WO2010001631A1 - Lithographic printing plate material - Google Patents

Lithographic printing plate material Download PDF

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Publication number
WO2010001631A1
WO2010001631A1 PCT/JP2009/052653 JP2009052653W WO2010001631A1 WO 2010001631 A1 WO2010001631 A1 WO 2010001631A1 JP 2009052653 W JP2009052653 W JP 2009052653W WO 2010001631 A1 WO2010001631 A1 WO 2010001631A1
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WO
WIPO (PCT)
Prior art keywords
acid
printing plate
lithographic printing
plate material
forming layer
Prior art date
Application number
PCT/JP2009/052653
Other languages
French (fr)
Japanese (ja)
Inventor
平林　和彦
Original Assignee
コニカミノルタエムジー株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by コニカミノルタエムジー株式会社 filed Critical コニカミノルタエムジー株式会社
Publication of WO2010001631A1 publication Critical patent/WO2010001631A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
    • B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
    • 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
    • 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
    • B41C2210/06—Developable by an alkaline 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
    • B41C2210/10—Developable by an acidic 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
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • 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
    • 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
    • B41C2210/26—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 not involving carbon-to-carbon unsaturated bonds
    • B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
    • 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
    • B41C2210/26—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 not involving carbon-to-carbon unsaturated bonds
    • B41C2210/266—Polyurethanes; Polyureas

Definitions

  • the present invention relates to a lithographic printing plate material, and more particularly, to a lithographic printing plate material that can obtain a lithographic printing plate having good printing durability without deterioration of dot dot quality.
  • CTP computer-to-plate
  • Patent Document 2 a negative CTP lithographic printing plate material having a polymerization type photosensitive layer containing a polymerizable compound has been proposed (for example, see Patent Document 2).
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-100408 JP 2007-269887 A
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a lithographic printing plate material which can obtain a lithographic printing plate having good printing durability without deterioration of dot quality. .
  • the surface shape parameter Rz ( ⁇ m) on the surface side having the image forming layer of the aluminum support is 1.0 ⁇ m or more, 4 0.04 ⁇ m or less
  • an anodic oxide coating amount ADT (g / m 2 ) is 0.10 g / m 2 or more and 8.0 g / m 2 or less
  • the surface shape parameter Rz ( ⁇ m) and the anodic oxide coating amount ADT ( g / m 2 ) The product [Rz ⁇ ADT] is 0.11 ( ⁇ m ⁇ g / m 2 ) or more and 5.0 ( ⁇ m ⁇ g / m 2 ) or less. material.
  • the said photosensitive composition contains A) the ethylenic double bond containing monomer which can be addition-polymerized, B) a photoinitiator composition, and C) polymeric binder, Said 1 characterized by the above-mentioned. Lithographic printing plate material.
  • a lithographic printing plate material capable of obtaining a lithographic printing plate having good dot durability without deterioration of dot dot quality.
  • the present invention relates to a lithographic printing plate material having an image forming layer containing a photosensitive composition on an aluminum support, the surface shape parameter Rz ( ⁇ m) of the surface having the image forming layer of the aluminum support and anodization.
  • the product [Rz ⁇ ADT] with the coating amount ADT (g / m 2 ) is 0.11 ( ⁇ m ⁇ g / m 2 ) or more and 5.0 ( ⁇ m ⁇ g / m 2 ) or less.
  • the present inventor has obtained the product of the surface shape parameter Rz ( ⁇ m) on the surface side having the image forming layer of the aluminum support and the amount of anodized film ADT (g / m 2 ).
  • the inventors have found that a lithographic printing plate material excellent in halftone dot quality, high image quality and good printing durability can be obtained by controlling within the range specified by the invention, and the present invention has been achieved.
  • the aluminum support according to the present invention is a support used for providing an image forming layer containing a photosensitive composition, and is preferably subjected to roughening and anodized film formation, and further if necessary. Thus, a sealing treatment or a post-treatment may be performed.
  • the aluminum support according to the present invention has a surface shape parameter Rz ( ⁇ m) on the side having an image forming layer of 1.0 ⁇ m or more and 4.0 ⁇ m or less, and an anodic oxide film amount ADT (g / m 2 ) of 0.2. 10 g / m 2 or more and 8.0 g / m 2 or less, and the product [Rz ⁇ ADT] of the surface shape parameter Rz ( ⁇ m) and the amount of anodized film ADT (g / m 2 ) is 0.11 ( ⁇ m ⁇ g / m 2 ) or more and 5.0 ( ⁇ m ⁇ g / m 2 ) or less.
  • the surface shape parameter Rz ( ⁇ m) of the aluminum support referred to in the present invention indicates a so-called surface roughness Ra, meaning “ten-point average roughness”, and a cross-sectional curve (surface perpendicular to the surface).
  • the average line (the square sum of the deviation from the measured surface to the cross-section curve) is minimized.
  • the difference between the average value of the highest elevation of the peak from the highest to the fifth and the average elevation of the bottom of the valley from the deepest to the fifth measured in the direction of the vertical magnification from the straight line that is parallel to the line and does not cross the section curve. (Refer to JIS B 0601).
  • the surface shape parameter Rz ( ⁇ m) can be measured using a commercially available stylus type or non-contact type surface roughness meter.
  • the surface shape parameter Rz according to the present invention is 1.0 ⁇ m or more and 4.0 ⁇ m or less, more preferably 1.7 ⁇ m or more and 4.0 ⁇ m or less, and most preferably Is 2.3 ⁇ m or more and 3.7 ⁇ m or less.
  • the surface shape parameter Rz can be adjusted to the above range by roughening, anodic oxide film formation, sealing treatment or post-treatment, among which roughening (graining treatment) described later is performed. Therefore, it is preferable to adjust.
  • the anodic oxide film amount ADT (g / m 2 ) in the present invention is an aluminum plate prepared by dissolving a chromic phosphate solution (85% phosphoric acid solution: 35 ml, chromium (IV) oxide: 20 g in 1 L of water). It is a value obtained by immersing the substrate in a melt, dissolving the oxide film, and measuring the change in mass before and after dissolution of the aluminum plate film.
  • the anodic oxide coating amount ADT is 0.10 g / m 2 or more and 8.0 g / m 2 or less, more preferably 0.1 g / m 2 or more and 2.5 g / m. 2 or less, and most preferably 0.1 g / m 2 or more and 0.9 g / m 2 or less.
  • the amount of anodic oxide film ADT defined in the present invention can be adjusted to the preferred range defined above by performing an anodic oxidation treatment and an anodized film described later.
  • Rz and ADT are appropriately adjusted as described above, and Rz ⁇ ADT is 0.11 ( ⁇ m ⁇ g / m 2 ) or more and 5.0 ( ⁇ m ⁇ g / m 2 ) or less.
  • Rz ⁇ ADT is preferably 0.6 ( ⁇ m ⁇ g / m 2 ) or more and 4.0 ( ⁇ m ⁇ g / m 2 ) or less.
  • the support according to the present invention uses an aluminum substrate having a hydrophilic surface, and in this case, pure aluminum or an aluminum alloy may be used.
  • Various aluminum alloys can be used as the support, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. .
  • the support Prior to roughening (graining treatment), the support is preferably subjected to a degreasing treatment to remove rolling oil on the surface.
  • a degreasing treatment a degreasing treatment using a solvent such as trichrene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like can be used.
  • an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment.
  • an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed.
  • smut is generated on the surface of the support.
  • an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof, It is preferable to perform a desmut treatment.
  • roughening is carried out by electrolysis.
  • mechanical roughening treatment electrolytic roughening mainly composed of nitric acid is performed.
  • Pre-roughening by surface treatment or the like may be performed.
  • the mechanical pre-roughening method is not particularly limited, but a brush polishing method and a honing polishing method are preferable.
  • the roughening by the brush polishing method is performed, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and, for example, volcanic ash particles having a particle size of 10 to 100 ⁇ m on water. While supplying the uniformly dispersed slurry, the brush can be pressed.
  • For roughening by honing for example, volcanic ash particles having a particle size of 10 to 100 ⁇ m are uniformly dispersed in water, and this dispersion is pressurized from a nozzle and sprayed and collided with the surface of the aluminum support at an angle.
  • abrasive particles having a particle size of 10 to 100 ⁇ m are present on the surface of the aluminum support at a density of 2.5 ⁇ 10 3 to 10 ⁇ 10 3 particles / cm 2 at intervals of 100 to 200 ⁇ m.
  • Roughening can also be performed by laminating the coated sheet and applying a pressure to transfer the rough surface pattern of the sheet.
  • the surface is roughened by the above-described mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the aluminum support, the generated aluminum scraps, and the like.
  • the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like.
  • the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide.
  • the amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m 2 .
  • the pre-electrolytic roughening treatment mainly composed of nitric acid can be performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts.
  • Current density may be in the range of 10 ⁇ 200A / dm 2, preferably selected from the range of 20 ⁇ 100A / dm 2.
  • the quantity of electricity may be in the range of 100 ⁇ 5000C / dm 2, preferably selected from the range of 100 ⁇ 2000C / dm 2.
  • the temperature at which the electrochemical surface roughening method is carried out can be in the range of 10 to 50 ° C., but is preferably selected from the range of 15 to 45 ° C.
  • the concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass.
  • nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, aluminum ions, and the like can be added to the electrolytic solution.
  • the electrolytic surface-roughening treatment mainly composed of nitric acid
  • it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface.
  • the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like.
  • the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution.
  • the amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m 2 .
  • neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
  • electrochemical surface roughening treatment it is preferable to perform an AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid.
  • the concentration of hydrochloric acid is generally in the range of 5 to 20 g / L, preferably 6.5 to 16 g / L.
  • the temperature of the electrolytic solution is generally in the range of 15 to 35 ° C, preferably 18 to 38 ° C.
  • the aluminum ion concentration in the electrolytic solution is generally in the range of 0.5 to 15 g / L, preferably 0.7 to 10 g / L.
  • the electrolytic solution preferably contains acetic acid or boric acid, and the concentration is generally in the range of 1 to 20 g / L, preferably 3 to 15 g / L.
  • the ratio to the hydrochloric acid concentration is preferably 0.5 to 1.5.
  • the current density is approximately 15 to 120 A / dm 2 , preferably 20 to 90 A / dm 2 .
  • the quantity of electricity is generally the range of 400 ⁇ 2000C / dm 2, preferably 500 ⁇ 1200C / dm 2.
  • the frequency is preferably in the range of 40 to 150 Hz.
  • the support for a lithographic printing plate material according to the present invention can be obtained by adjusting the electrolysis conditions for the electrochemical surface roughening treatment within the above range.
  • the aluminum ion concentration in the electrolytic solution is 3
  • the concentration of acetic acid or boric acid in the electrolyte is in the range of 7 to 13 g / L
  • the ratio of acetic acid or boric acid concentration to the hydrochloric acid concentration is in the range of 0.7 to 1.2
  • the current density Is in the range of 15 to 90 A / dm 2
  • the amount of electricity is preferably in the range of 500 to 1200 C / dm 2 , and is preferably adjusted to the optimum condition within each condition range.
  • the amount of electricity in the first half can be achieved by electrolytic surface roughening under conditions of two-bath electrolysis using an electrolytic treatment or an electrolytic solution having a high hydrochloric acid concentration in the first half and an electrolytic solution having a high acetic acid concentration or high boric acid concentration in the second half.
  • the aluminum support body which has can be obtained.
  • the AC electrolytic treatment may be divided into several stages. For example, the method of changing the current density in multiple stages, the method of changing the AC waveform in multiple stages, the method of changing the frequency in multiple stages, and the acidic electrolyte concentration A method of changing in multiple stages can be applied.
  • the electrolytic surface roughening treatment is performed in the above-described electrolytic solution mainly composed of hydrochloric acid, it is preferably immersed in an aqueous solution of acid or alkali in order to remove aluminum scraps on the surface.
  • the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like.
  • the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous solution of phosphoric acid or sodium hydroxide.
  • the amount of aluminum dissolved on the surface is preferably 0.1 to 2 g / m 2 .
  • neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
  • the mechanical pre-roughening method described above is a brush polishing method.
  • the aluminum support according to the present invention is preferably subjected to an anodizing treatment following the electrochemical surface roughening treatment.
  • the method of anodizing treatment is not particularly limited, and a known method can be used. By performing this anodizing treatment, an oxide film is formed on the aluminum support.
  • the anodizing treatment is generally performed by direct current electrolysis using sulfuric acid or phosphoric acid or a mixed aqueous solution of both as the electrolytic solution.
  • the anodic oxidation treatment is preferably performed using sulfuric acid as the electrolytic solution.
  • the concentration of sulfuric acid is preferably in the range of 5 to 50% by mass, particularly preferably 10 to 35% by mass.
  • the temperature is preferably in the range of 10 to 50 ° C.
  • the treatment voltage is preferably 18V or more, and more preferably 20V or more.
  • the current density is preferably in the range of 1 to 30 A / dm 2 .
  • the amount of electricity is preferably in the range of 100 to 500 C / dm 2 .
  • the amount of the anodized film adjusted under the above conditions is 0.1 g / m 2 or more and 8.0 g / m 2 or less. 1 g / m 2 or more and 2.5 g / m 2 or less, and most preferably 0.1 g / m 2 or more and 0.9 g / m 2 or less.
  • Micropores are generated in the anodic oxide film, and the density of the micropores is preferably 400 to 700 / ⁇ m 2, and more preferably 400 to 600 / ⁇ m 2 .
  • the method for controlling the anodic oxide film amount ADT under the conditions defined in the present invention is not particularly limited, but it can be preferably achieved by adjusting the current density and the electric quantity.
  • the current density is preferably in the range of 1 to 30 A / dm 2 .
  • the amount of electricity is preferably in the range of 100 to 500 C / dm 2 .
  • the anodized aluminum support may be sealed as necessary.
  • known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment and ammonium acetate treatment can be used.
  • the aluminum support is coated with a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, It is also suitable to apply zinc borate), or a yellow dye, an amine salt or the like as an undercoat layer.
  • a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, It is also suitable to apply zinc borate), or a yellow dye, an amine salt or the like as an undercoat layer.
  • a sol-gel treatment in which a functional group capable of causing an addition reaction by a radical is covalently bonded as disclosed in JP-A-5-304358 is also preferably used.
  • the image forming layer containing the photosensitive composition according to the present invention is a layer capable of forming an image by image exposure, and is either a negative type or a positive type conventionally used as an image forming layer of a lithographic printing plate material.
  • An image forming layer of the above system can be used.
  • the image forming layer according to the present invention is preferably a heat-sensitive image forming layer or a polymerizable image forming layer, and particularly preferably a polymerizable image forming layer.
  • heat-sensitive image forming layer a layer causing a change capable of forming an image using heat generated by infrared laser exposure is preferably used.
  • these heat-sensitive image forming layers those described in paragraphs [0036] to [0175] of WO 2007/083542 can be preferably used.
  • the photosensitive composition may contain A) an ethylenic double bond-containing monomer capable of addition polymerization, B) a photopolymerization initiator composition, and C) a polymer binder.
  • A) an ethylenic double bond-containing monomer capable of addition polymerization B) a photopolymerization initiator composition
  • C) a polymer binder preferable.
  • the image forming layer will be described in detail as an example of the polymerizable image forming layer.
  • the photosensitive composition may contain A) an addition-polymerizable ethylenic double bond-containing monomer, B) a photopolymerization initiator composition, and C) a polymer binder. preferable.
  • the addition-polymerizable ethylenic double bond-containing monomer is a polymerizable monomer and is a compound (monomer) that can be polymerized with the reaction product of a photopolymerization initiator by image exposure as an opportunity.
  • a wide range of compounds that can initiate a polymerization reaction triggered by a reaction with a radical species generated from a photopolymerization initiator can be used.
  • the compound preferably used as the addition-polymerizable ethylenic double bond-containing monomer according to the present invention is an ethylenically unsaturated bond-containing compound, which is a polymerizable compound, and is a general radical-polymerizable monomer.
  • polyfunctional monomers having a plurality of addition-polymerizable ethylenic double bonds in the molecule generally used for ultraviolet curable resins, polyfunctional oligomers, and the like.
  • Preferred examples of the polymerizable monomer according to the present invention include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydro Furfuryloxyhexanolide acrylate, acrylate of ⁇ -caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid ester such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid esters such as ethylene glycol Acrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinon
  • prepolymers can be used in the same manner as described above.
  • examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can also be suitably used.
  • These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.
  • prepolymer examples include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, and pimelic acid.
  • Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, tri Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by the combination of polyhydric alcohols such as methylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Acrylates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol Adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, poly(
  • the image forming layer according to the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane benzoic acid benzoate.
  • a phosphazene monomer triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane benzoic acid benzoate.
  • Addition-polymerizable oligomers and prepolymers having monomers such as acid esters, alkylene glycol type acrylic acid-modified, urethane-modified acrylates, and structural units formed from the monomers can be contained.
  • examples of the ethylenic monomer that can be used in combination with the present invention include a phosphoric ester compound containing at least one (meth) acryloyl group.
  • the compound is not particularly limited as long as at least a part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.
  • the compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.
  • an addition-polymerizable ethylenic double bond-containing compound containing a tertiary amino group in the molecule which is a tertiary amine monomer is preferably used.
  • a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used.
  • polymerizable compounds described in JP-A-1-165613, 1-203413 and 1-1197213 are preferably used.
  • a tertiary amine monomer a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule are used. It is preferred to use a reaction product.
  • polyhydric alcohol containing a tertiary amino group in the molecule examples include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, N , N-di (hydroxyethyl) aniline, N, N, N ′, N′-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N ′, N′-tetra-2-hydroxyethylethylenediamine N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol, N, N-di (n- Propyl) amino-2,3-propanediol, N, N- (An iso-propyl) amino-2,3-propane
  • diisocyanate compound examples include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, and 1,3-diisocyanate methyl.
  • Examples of the compound containing a hydroxyl group and addition-polymerizable ethylenic double bond in the molecule include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1, Examples include 3-dimethacrylate and 2-hydroxypropylene-1-methacrylate-3-acrylate.
  • a polyhydric alcohol containing a tertiary amino group in the molecule a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule are as follows.
  • a reaction product As a reaction product. These reactions can be carried out in the same manner as the method of synthesizing urethane acrylate by the reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.
  • M-1 Reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol)
  • M-2 Triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol)
  • M-3 Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) Reaction product of benzene (2 mol) and 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol)
  • M-4 Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) ) Reaction of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol)
  • the product M-5 N-methyldiethanolamine (1 mole), tolylene-2,4-diisocyanate (2 moles),
  • acrylates or alkyl acrylates described in JP-A-1-105238 and JP-A-2-127404 can be used.
  • the photopolymerization initiator composition according to the present invention is capable of initiating polymerization of a polymerizable monomer by image exposure, and preferably contains a bisimidazole compound as a photopolymerization initiator composition, and a hexaarylbiimidazole compound. It is more preferable to contain.
  • HABI hexaarylbiimidazole
  • triaryl-imidazole dimer triaryl-imidazole dimer
  • Their use in such compositions is described in European Patent No. 24,629, European Patent No. 107,792, US Pat. No. 4,410,621, European Patent No. 215,453 and German Patent No. 3, It is described in each specification of No. 211,312.
  • polymerization initiator as a polymerization initiator, other types of polymerization initiators can be used in combination with hexaarylbiimidazole.
  • titanocene compounds, monoalkyltriaryl borate compounds, iron arene complex compounds, and polyhalogen compounds are preferably used.
  • titanocene compound examples include compounds described in JP-A-63-41483 and JP-A-2-291. Specific examples include bis (cyclopentadienyl) -Ti-di-chloride. Bis (cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti -Bis-2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2 , 6-Difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-ch
  • Examples of the monoalkyl triaryl borate compound include compounds described in JP-A Nos. 62-150242 and 62-143044, and specific examples thereof include tetra-n-butylammonium / n-butyl- Trinaphthalen-1-yl-borate, tetra-n-butylammonium / n-butyl-triphenyl-borate, tetra-n-butylammonium / n-butyl-tri- (4-t-butylphenyl) -borate, tetra -N-butylammonium ⁇ n-hexyl-tri- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium ⁇ n-hexyl-tri- (3-fluorophenyl) -borate, etc. .
  • iron arene complex compound examples include compounds described in JP-A-59-219307, and specific examples include ⁇ -benzene- ( ⁇ -cyclopentadienyl) iron hexafluorophosphate, ⁇ -cumene- ( ⁇ -cyclopentadienyl) iron hexafluorophosphate, ⁇ -fluorene- ( ⁇ -cyclopentadienyl) iron hexafluorophosphate, ⁇ -naphthalene- ( ⁇ -cyclopentadienyl) iron hexafluorophosphate, ⁇ -xylene -( ⁇ -cyclopentadienyl) iron hexafluorophosphate, ⁇ -benzene- ( ⁇ -cyclopentadienyl) iron tetrafluoroborate, and the like.
  • a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalomethylene group is preferably used, and in particular, the halogen compound represented by the following general formula (PIH1) and the above group are substituted on the oxadiazole ring.
  • the compound obtained is preferably used.
  • a halogen compound represented by the following general formula (PIH2) is particularly preferably used.
  • R 1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an iminosulfonyl group, or a cyano group.
  • R 2 represents a monovalent substituent.
  • R 1 and R 2 may combine to form a ring.
  • Y 2 represents a halogen atom.
  • R 3 represents a monovalent substituent.
  • X represents —O— or —NR 4 —.
  • R 4 represents a hydrogen atom or an alkyl group.
  • R 3 and R 4 may be bonded to form a ring.
  • Y 3 represents a halogen atom.
  • those having a polyhalogen acetylamide group are particularly preferably used.
  • the biimidazole compound is a derivative of biimidazole, and examples thereof include compounds described in JP-A No. 2003-295426.
  • photopolymerization initiators can be used in combination.
  • J. et al. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. More specific compounds are disclosed in GB 1,459,563.
  • photopolymerization initiator that can be used in combination, the following can be used.
  • benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis Benzophenone derivatives such as (dimethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone and N-butylacrylic Acridone derivatives such as dong; ⁇ , ⁇ -diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, Japanese Patent Publication Nos.
  • transition metal complex containing transition metal such as ruthenium described in “Coordination Chemistry Review”, 84, 85-277 (1988) and JP-A-2-182701; -2,4,5-trio described in JP-A-209477 Reel imidazole dimer; carbon tetrabromide, organic halogen compounds in JP 59-107344 JP, and the like.
  • the content of the photopolymerization initiator according to the present invention is preferably from 0.1 to 20% by mass, particularly preferably from 0.5 to 15% by mass, based on the polymerizable monomer.
  • the polymer binder according to the present invention is capable of supporting the components contained in the image forming layer on an aluminum support.
  • the polymer binder include acrylic polymers, polyvinyl butyral resins, and polyurethane resins.
  • Polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and other natural resins can be used. Two or more of these may be used in combination.
  • the copolymer composition of the polymer binder is preferably a copolymer of (a) carboxyl group-containing monomer, (b) methacrylic acid alkyl ester, or acrylic acid alkyl ester.
  • carboxyl group-containing monomer examples include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like.
  • carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferred.
  • alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate.
  • the monomers described in 1) to 14) shown below can be used as copolymerization monomers.
  • Monomers having an aromatic hydroxyl group such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate, etc.
  • Monomers having an aliphatic hydroxyl group such as 2 -Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl Methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether, etc.
  • Monomer having an aminosulfonyl group eg For example, m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide, etc.
  • Monomers having sulfonamide groups such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide 5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N-phenylacrylamide, N- (4-hydro Siphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, etc.
  • Monomers containing alkyl fluoride groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoro Pentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.
  • Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc.
  • Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate
  • Styrenes such as styrene, methyl styrene, chloromethyl styrene
  • Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone 11)
  • Olefins such as ethylene and propylene I-butylene, butadiene, isoprene, etc.
  • N-vinylpyrrolidone N-vinylcarbazole, 4-vinylpyridine, etc. 13) Monomer having a cyano group, For example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene, etc.
  • the polymer binder is preferably a vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain.
  • a vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain For example, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Is also preferred as a polymer binder.
  • the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969.
  • an unsaturated bond-containing vinyl copolymer obtained by adding a compound having a (meth) acryloyl group and an isocyanate group in the molecule to the hydroxyl group present in the molecule of the vinyl polymer is also high. Preferred as a molecular binder.
  • Examples of the compound having both an unsaturated bond and an isocyanate group in the molecule include vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or p-isopropenyl- ⁇ , ⁇ '- Dimethylbenzyl isocyanate is preferred, and examples include (meth) acrylic isocyanate and 2- (meth) acryloyloxyethyl isocyanate.
  • the vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain is preferably 50 to 100% by mass, more preferably 100% by mass in the total polymer binder.
  • the content of the polymer binder in the image forming layer is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and use in the range of 20 to 50% by mass in terms of sensitivity. Is particularly preferred.
  • the image forming layer according to the present invention can contain a spectral sensitizer having a maximum absorption wavelength of 350 to 900 nm, preferably 350 to 450 nm as a spectral sensitizer, and further having an absorption maximum wavelength of 350 to 450 nm. It is preferable to contain a certain spectral sensitizer.
  • spectral sensitizer examples include cyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, acridine, acridone, azo compound, diphenylmethane, triphenylmethane, triphenylamine, Coumarin derivatives, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, ketoalcohol borate complexes, and the like.
  • Examples of the coumarin derivative include B-1 to B-22 coumarin derivatives of JP-A-8-129258, D-1 to D-32 coumarin derivatives of JP-A-2003-21901, and JP-A-2002.
  • No. 1-363206 of coumarin derivatives JP-A No. 2002-363207 No. 1 to 40 coumarin derivatives, JP-A No. 2002-363208 No. 1 to 34 coumarin derivatives, JP-A No. 2002-363209
  • Examples thereof include 1 to 56 coumarin derivatives and can be preferably used.
  • Examples of other dyes that can be preferably used include, for example, JP-A Nos. 2000-98605, 2000-147773, 2000-206690, 2000-258910, 2000-309724, 2001-042524, And spectral sensitizers described in JP-A Nos. 2002-202598 and 2000-221790.
  • the image forming layer according to the present invention is a polymerization inhibitor in order to prevent unnecessary polymerization of an ethylenic double bond monomer that can be polymerized during the production or storage of a lithographic printing plate material. It is desirable to add an agent.
  • Suitable polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t -Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2- And hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.
  • the addition amount of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the image forming layer.
  • higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition by oxygen, and unevenly distributed on the surface of the photosensitive layer in the drying process after coating. Good.
  • the addition amount of the higher fatty acid derivative is preferably 0.5 to 10% by mass of the total composition.
  • a coloring agent can also be used and a conventionally well-known thing can be used conveniently as a coloring agent including a commercially available thing.
  • a coloring agent can also be used and a conventionally well-known thing can be used conveniently as a coloring agent including a commercially available thing.
  • pigments include black pigments, yellow pigments, red pigments, brown pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and metal powder pigments.
  • inorganic pigments titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates
  • organic pigments azo-based, thioindigo
  • Anthraquinone, anthanthrone, and triphendioxazine pigments vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.
  • the pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used.
  • an integrating sphere at the laser wavelength to be used is used.
  • the reflection absorption of the used pigment is 0.05 or less.
  • the addition amount of the pigment is preferably from 0.1 to 10% by mass, more preferably from 0.2 to 5% by mass, based on the solid content of the composition.
  • a purple pigment or a blue pigment such as, for example, cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue first sky blue, indanthrene blue, indico, dioxane violet, Examples include isoviolanthrone violet, indanthrone blue, and indanthrone BC. Among these, phthalocyanine blue and dioxane violet are more preferable.
  • the image forming layer can contain a surfactant as a coating property improving agent as long as the object and effects of the present invention are not impaired.
  • a surfactant as a coating property improving agent as long as the object and effects of the present invention are not impaired.
  • fluorine-based surfactants are preferred.
  • ⁇ Plasticizer> In order to improve the physical properties of the cured film, additives such as an inorganic filler, a plasticizer such as dioctyl phthalate, dimethyl phthalate, and tricresyl phosphate may be added. These addition amounts are preferably 10% by mass or less based on the total solid content.
  • solvent used in preparing the image forming layer coating solution of the image forming layer according to the present invention examples include, for example, alcohol: polyhydric alcohol derivatives: sec-butanol, isobutanol, n-hexanol, benzyl Alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, and ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone alcohol Preferred examples include cyclohexanone, methylcyclohexanone and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.
  • alcohol polyhydric alcohol derivatives: sec-butanol, isobutanol, n-hexanol, benzyl Alcohol, diethylene glycol, triethylene glycol,
  • the image forming layer according to the present invention is constituted by coating on a support using this.
  • the weight on the aluminum support is preferably from 0.1 to 10 g / m 2 , particularly preferably from 0.5 to 5 g / m 2 .
  • an oxygen blocking layer having an oxygen blocking function and other protective functions as required can be provided.
  • an oxygen blocking layer it is preferable to provide an oxygen blocking layer.
  • the oxygen blocking layer is preferably highly soluble in an aqueous solution that removes the aforementioned unexposed image portion, and for that purpose, it preferably contains polyvinyl alcohol.
  • Polyvinyl alcohol has an effect of suppressing permeation of oxygen.
  • polysaccharides polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required
  • Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.
  • the peel force between the image forming layer and the oxygen barrier layer is preferably 35 mN / mm or more, more preferably 50 mN / mm or more, and even more preferably 75 mN / mm. That's it.
  • Preferable oxygen barrier layer compositions include those described in JP-A-10-10742.
  • the above-mentioned peeling force is applied with an adhesive tape having a predetermined width having a sufficiently large adhesive force on the oxygen barrier layer and peeled off with the oxygen barrier layer at an angle of 90 degrees with respect to the plane of the planographic printing plate material. It can be determined by measuring the force of time.
  • the oxygen barrier layer can further contain a surfactant, a matting agent and the like as required.
  • the oxygen barrier layer composition is dissolved in a suitable solvent, applied onto the image forming layer and dried to form an oxygen barrier layer.
  • the main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol and i-propanol.
  • the thickness is preferably 0.1 to 5.0 ⁇ m, particularly preferably 0.5 to 3.0 ⁇ m.
  • coating methods for the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion coater method Etc.
  • the drying temperature of the image forming layer is preferably 60 to 160 ° C., more preferably 80 to 140 ° C., and particularly preferably 90 to 120 ° C.
  • a laser light source As a light source for image exposure on the lithographic printing plate material, for example, a laser light source is used.
  • the laser light source an argon laser, a He—Ne gas laser, a YAG laser, a semiconductor laser, or the like can be preferably used.
  • a laser light source having an emission wavelength in a region from 350 nm to 900 nm can be used.
  • a laser light source having an emission wavelength of 350 nm to 450 nm is particularly preferably used.
  • a laser light source used for exposure for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid laser, KNbO 3 as a semiconductor laser system, a ring resonator ( 430 nm), AlGaInN (350 to 450 nm), AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm), and the like.
  • a He—Cd laser 441 nm
  • a combination of Cr: LiSAF and SHG crystal 430 nm
  • KNbO 3 as a semiconductor laser system
  • a ring resonator 430 nm
  • AlGaInN 350 to 450 nm
  • AlGaInN semiconductor laser commercially available InGaN-based semiconductor laser 400 to 410 nm
  • the lithographic printing plate material of the present invention is suitable for direct writing without using a mask material because light can be reduced in a beam shape and scanning exposure according to image data is possible.
  • a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.
  • Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning.
  • cylindrical outer surface scanning laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is set as main scanning, and the movement of laser light is set as sub scanning.
  • cylindrical inner surface scanning a recording material is fixed to the inner surface of a drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis.
  • main scanning of laser light is performed by combining a polygon mirror or galvanometer mirror and an f ⁇ lens, and sub scanning is performed by moving a recording medium.
  • Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.
  • Preheating includes, for example, a method of heating with a preheating roller that heats a lithographic printing plate material carried during development processing to a predetermined temperature range before development in an automatic developing apparatus that develops the lithographic printing plate material.
  • the preheat roller is composed of a pair of rollers including at least one roller having heating means therein, and the roller having the heating means is a hollow made of a metal having high thermal conductivity (for example, aluminum, iron, etc.). It is possible to use a pipe in which a nichrome wire or the like is embedded as a heating element and the outer surface of the metal pipe is covered with a plastic sheet such as polyethylene, polystyrene, or Teflon (registered trademark).
  • JP-A No. 64-80962 JP-A No. 64-80962.
  • the preheating is preferably performed at 70 to 180 ° C. for about 3 to 240 seconds.
  • sodium silicate same potassium, same ammonium
  • dibasic sodium phosphate same potassium, same ammonium
  • sodium bicarbonate same potassium, same ammonium
  • sodium carbonate same potassium, same ammonium
  • sodium bicarbonate same potassium, same Ammonium
  • sodium borate potassium, ammonium
  • alkaline developers using an inorganic alkaline agent such as sodium hydroxide, potassium, ammonium, and lithium.
  • Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.
  • alkali agents are used alone or in combination of two or more.
  • an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer as necessary.
  • the lithographic printing plate material of the present invention uses an aqueous solution having a low pH as a treatment liquid in an unexposed portion (non-image portion) after exposing / recording image information with a laser light source when producing a lithographic printing plate.
  • a development processing method that removes them can also be applied.
  • the lithographic printing plate material of the present invention is prepared by exposing and recording image information with a laser light source having a light emission wavelength in the range of 350 nm to 450 nm when preparing a lithographic printing plate.
  • Development processing can be performed using an aqueous solution containing a resin and a surfactant and having a pH of 2.0 to 9.0 at 25 ° C. as a processing solution.
  • it is effective in the case of a lithographic printing plate material having a polymerizable image forming layer.
  • the surfactant includes an anionic surfactant and a nonionic surfactant.
  • anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfones.
  • Acid salts alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, polyoxyethylene aryl ether sulfonates, polyoxyethylene naphthyl ether sulfonates, N-methyl-N-oleyl taurine sodium salts N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, nitrated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, Rualkyl nitrates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ethers Phosphoric acid ester salts
  • Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene aryl ethers, polyoxyethylene naphthyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxy Propylene alkyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid moiety Esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenation Bran oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine
  • polyoxyethylene alkylphenyl ethers polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used.
  • Fluorine-based and silicon-based anions and nonionic surfactants can also be used.
  • preferable surfactants include surfactants added to the lithographic printing plate surface protecting agents described in JP-A Nos. 2004-167903, 2004-230650, and 2005-43393. . Two or more of these surfactants can be used in combination. For example, two or more different from each other can be used in combination.
  • a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant is preferable.
  • the amount of the surfactant used is not particularly limited, but is preferably 0.01 to 20% by mass of the post-treatment liquid.
  • the mineral solution is added to the aqueous solution. Adjust by adding acid, organic acid or inorganic salt. The addition amount is preferably 0.01 to 2% by mass.
  • mineral acids include nitric acid, sulfuric acid, phosphoric acid, and metaphosphoric acid.
  • organic acids include citric acid, acetic acid, succinic acid, malonic acid, p-toluenesulfonic acid, tartaric acid, malic acid, lactic acid, levulinic acid, phytic acid, and organic phosphonic acid.
  • examples of the inorganic salt include magnesium nitrate, primary sodium phosphate, secondary sodium phosphate, nickel sulfate, sodium hexamethanoate, sodium tripolyphosphate, and the like. You may use together at least 1 sort (s) or 2 or more types, such as a mineral acid, an organic acid, or an inorganic salt. When used in the basic region pH 8 to 9, it can be adjusted to the pH by adding a water-soluble organic base or inorganic base.
  • a water-soluble organic base is preferable, and examples include triethanolamine, diethanolamine, and ethanolamine.
  • preservatives, antifoaming agents and the like can be added to the aqueous solution.
  • phenol or a derivative thereof o-phenylphenol, p-chlorometacresol, hydroxybenzoic acid alkyl ester, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazolin-3-one derivative, benzoisothiazoline-3 -Derivatives such as ones, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyridine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives, and the like.
  • a preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the type of bacteria, molds, yeasts, but 0.01% with respect to the plate surface protective agent at the time of use.
  • the range of ⁇ 4% by mass is preferable, and two or more kinds of preservatives are preferably used in combination so as to be effective against various molds and sterilization.
  • As the antifoaming agent a silicon antifoaming agent is preferable. Among them, emulsification dispersion type and solubilization can be used. The range of 0.01 to 1.0% by mass is optimal.
  • a chelate compound may be added.
  • Preferred chelate compounds include, for example, ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, sodium salt thereof; ethylenediamine disuccinic acid, potassium salt thereof.
  • An organic amine salt is also effective in place of the sodium salt and potassium salt of the chelating agent. These chelating agents are selected so that they are stably present in the gum solution composition and do not impair the printability. The addition amount is suitably 0.001 to 1.0% by mass.
  • a sensitizer can be added if necessary.
  • hydrocarbons such as turpentine oil, xylene, toluene, low heptane, solvent naphtha, kerosene, mineral spirit, petroleum fraction having a boiling point of about 120 ° C.
  • dibutyl phthalate, dihebutyl phthalate, di-n -Phthalic acid diester agents such as octyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl benzyl phthalate, such as dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate
  • Aliphatic dibasic acid esters such as di (2-ethylhexyl) sebacate, dioctyl sebacate, epoxidized triglycerides such as epoxidized soybean oil, tricresyl phosphate, trioctyl Contains a plasticizer having a freezing point of 15 ° C.
  • phosphate esters such as phosphate and trischlorethyl phosphate
  • benzoate esters such as benzyl benzoate
  • fatty acids which are liquid at 50 ° C., more preferred are those having 5 to 25 carbon atoms, and most preferred are those having 8 to 21 carbon atoms.
  • These sensitizers can be used alone or in combination of two or more.
  • a preferable range of the amount used is 0.01 to 10% by mass, and a more preferable range is 0.05 to 5% by mass.
  • the unexposed portion after exposing and recording image information with a laser light source having an emission wavelength in the range of 350 nm to 450 nm is water-soluble.
  • a development processing method that removes with an aqueous solution containing a resin and a surfactant and having a pH of 3.0 to 9.0 at 25 ° C.
  • Various measures can be taken.
  • the unexposed portion can be removed by selecting an appropriate condition for the type and content of the polymerizable monomer contained in the image forming layer of the lithographic printing plate material.
  • a polymerizable compound having at least a hydroxyl group in the molecule is selected as the polymerizable monomer to be contained in the image forming layer, and a homopolymer or copolymer of at least N-vinylpyrrolidone is used as the polymer binder. It is preferable to select the combination from the viewpoint of solving the problem according to the present invention.
  • Example 1 ⁇ Production of support> [Preparation of Support 1]
  • a JIS A 1050 aluminum plate having a thickness of 0.30 mm and a width of 1030 mm, treatment was continuously performed according to the following steps to produce a support 1 that was an aluminum support.
  • An anodizing apparatus of an existing two-stage feed electrolytic treatment method (the length of the first electrolysis part and the second electrolysis part is 6 m, the length of the first feed part is 3 m, the length of the second feed part is 3 m, The length of each of the feeding electrode and the second feeding electrode is 2.4 m), and an aqueous solution having a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions) is used in the electrolysis section.
  • Anodization was performed at 0 ° C. The current density was adjusted so that the amount of anodized film ADT was 0.10 g / m 2 . Then, water washing by spraying was performed.
  • the film was immersed in an aqueous solution containing 0.4% by mass of polyvinylphosphonic acid for 30 seconds to be hydrophilized.
  • the liquid temperature was 85 ° C. Thereafter, it was washed with spray water and dried with an infrared heater to obtain a support 1.
  • the surface shape parameter Rz is 2.31 ⁇ m, except that 1% by mass of nitric acid is used instead of hydrochloric acid and acetic acid as the composition of the electrolytic solution used in step c.
  • a support 12 having an oxide film amount ADT of 0.88 g / m 2 was produced.
  • the process in this process c is called the grain processing N.
  • the surface shape parameter Rz is 3.34 ⁇ m, except that 1% by mass of nitric acid is used instead of hydrochloric acid and acetic acid as the composition of the electrolytic solution used in step c.
  • a support 13 having an oxide film amount ADT of 0.88 g / m 2 was produced.
  • the process in this process c is called the grain processing N.
  • the surface shape parameter Rz ( ⁇ m) and the amount of anodized film ADT (g / m 2 ) of each support shown in Table 1 were measured according to the following methods.
  • Preparation of a negative lithographic printing plate material having a polymerizable image forming layer >> [Preparation of planographic printing plate material 1]
  • the following photopolymerizable image-forming layer coating solution 1 is applied on the prepared support 1 using a wire bar so that the solid content after drying is 1.5 g / m 2, and 1.5% at 95 ° C.
  • the photopolymerizable image forming layer 1 was formed by drying for a minute.
  • an oxygen barrier layer coating liquid 1 having the following composition was applied on the polymerizable image forming layer 1 using a wire bar so that the solid content after drying was 1.8 g / m 2 , Drying for 5 minutes produced a lithographic printing plate material 1 having an image forming layer and an oxygen blocking layer on a support.
  • Ethylene double bond-containing monomer 1 27.0 parts by mass Ethylene double bond-containing monomer (NK ester 4G: Shin-Nakamura Chemical Co., Ltd.) 14.0 parts by mass Initiator-based additive ⁇ 1>: ( ⁇ 6-cumene) ( ⁇ 5-cyclopentadienyl) iron (2) hexafluorophosphate 4.0 parts by mass ⁇ 2>: spectral sensitizer 1 0 parts by mass ⁇ 3>: tribromoacetylamide compound 2.0 parts by mass Acrylic copolymer 1 42.0 parts by mass Phthalocyanine pigment (MHI454: manufactured by Mikuni Dye Co., Ltd.) 6.0 parts by mass 2-t-butyl-6 -(3-t-Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M) 0.5 parts by mass Fluorine-based surfactant (FC-4430; manufactured by Sumi
  • Acrylic copolymer 1 (polymer binder) was synthesized as follows.
  • Polyvinyl alcohol (GL-05: manufactured by Nippon Synthetic Chemical Co., Ltd.) 79 parts by mass Polyvinylpyrrolidone (PVP K-30: manufactured by ASP Japan) 10 parts by mass Polyethyleneimine (Lupazole WF: manufactured by BASF) 5 parts by mass Cation-modified polyvinyl alcohol (Kuraray C polymer: manufactured by Kuraray) 5 parts by mass Surfactant (Surfinol 465: manufactured by Nisshin Chemical Industry Co., Ltd.) 0.5 Mass parts Water 900 parts by mass [Preparation of planographic printing plate materials 2 to 8] In the production of the lithographic printing plate material 1, the lithographic printing plate materials 2 to 8 were produced in the same manner except that the supports 2 to 8 were used in place of the support 1, respectively.
  • planographic printing plate material 9 In the production of the lithographic printing plate material 1, the support 9 is used in place of the support 1, and the following photopolymerizable image forming layer coating liquid 2 is used in place of the photopolymerizable image forming layer coating liquid 1. A lithographic printing plate material 9 was produced in the same manner except that.
  • lithographic printing plate material produced above was subjected to 2540 dpi (dpi represents the number of dots per 2.54 cm) and 175 lpi using a Prosetter (manufactured by HEIDELBERG) equipped with a 405 nm semiconductor laser head light source. The exposure was performed.
  • the exposed lithographic printing plate material is inserted into the preheating part of a Raptor Polymer 85 automatic developing machine (speed: 114 cm / min) manufactured by Glunz & Jensen, heated at a temperature setting at which the back side of the plate surface becomes 90 ° C., and subjected to oxygen in the pre-water washing step.
  • the blocking layer was removed, and then the unexposed portion was removed at the developing portion containing the following processing solution 1 (new solution).
  • a gum solution was applied and dried at 50 ° C. to prepare lithographic printing plates 1 to 14.
  • As the gum solution 840 Plate Finisher manufactured by Konica Minolta was used.
  • a lithographic printing plate produced in the same manner as the dot gain evaluation described above was applied to a coated paper, printing ink (Toyo Ink Co., Ltd., Toyo King High Co., Ltd.) using a printing machine (Mitsubishi Heavy Industries, Ltd., DAIYA1F-1). Echo M Red) and dampening water (manufactured by Tokyo Ink Co., Ltd., H liquid SG-51 density 1.5% by mass), and under the condition of exposure amount that 2% dots reproduce 2%.
  • the plate surface was wiped with a cleaner, the number of prints in which the highlight portion was thinned and the shadow portion was entangled was used as an index of printing durability.
  • One printing durability refers to an operation of continually printing 600 sheets and then wiping with a cleaner. The higher the printing frequency, the better the printing durability.
  • the cleaner used was an Ultra Plate Cleaner (Distributor: Dainichi Seika).
  • Table 1 shows the results obtained as described above.
  • the lithographic printing plate produced using the lithographic printing plate material having the support having the characteristics specified in the present invention has a dot dot quality deterioration as compared with the comparative example. It can be seen that the printing durability is excellent.
  • Example 2 ⁇ Production of support> [Preparation of Support 15]
  • the current density and the amount of electricity (in the range of 2 to 12 C / cm 2 ) in step c are controlled so that the surface shape parameter Rz is 2.31 ( ⁇ m).
  • the support body 15 was produced similarly except having controlled the current density in the process e so that the amount of anodic oxide films ADT might be 0.89 g / m ⁇ 2 >.
  • the surface shape parameter Rz ( ⁇ m) and the anodic oxide film amount ADT (g / m 2 ) of each support described in Table 2 were measured in the same manner as in the method described in Example 1.
  • Preparation of a negative lithographic printing plate material having a polymerizable image forming layer [Preparation of planographic printing plate material 15]
  • the following photopolymerizable image-forming layer coating solution 3 is applied to the prepared support 15 using a wire bar so that the solid content after drying is 1.5 g / m 2, and is 1.5 at 95 ° C.
  • the photopolymerizable image forming layer 3 was formed by drying for a minute.
  • an oxygen barrier layer coating liquid 2 having the following composition was applied on the polymerizable image forming layer 3 using a wire bar so that the solid content after drying was 1.5 g / m 2. Drying for 0 minute produced a lithographic printing plate material 15 having an image forming layer and an oxygen blocking layer on a support.
  • (Oxygen barrier layer coating solution 2) 400 parts by weight of the following mica dispersion 1
  • Polyvinyl alcohol (Mowiol 4-98: degree of saponification 98, manufactured by Klares Specialties Europe) 90 parts by weight Poly (N-vinylpyrrolidone) Rubytec K30 (manufactured by BASF) 5 parts by weight polyethyleneimine (Lupazole WF: manufactured by BASF) 5 parts by mass Surfactant (Surfinol 465: manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 parts by mass Water 900 parts by mass ⁇ Preparation of Mica Dispersion 1>
  • 32 g of synthetic mica (Sofshima ME-100, manufactured by Co-op Chemical Co., Ltd., aspect ratio of 1000 or more) is added and dispersed using a homogenizer until the average particle size (laser diffusion method) becomes 0.5 ⁇ m. 1 was obtained.
  • a lithographic printing plate material 16 was produced in the same manner as in the production of the lithographic printing plate material 15 except that the support 16 was used instead of the support 15.
  • lithographic printing plate materials 15 and 16 were exposed and developed in the same manner as in Example 1 except that the lithographic printing plate materials 15 and 16 were developed using the following treatment liquids 2A to 2F to produce lithographic printing plates 15 to 26.
  • the treatment liquid with pH adjusted to 1.5 is treatment liquid 2A
  • the treatment liquid with pH adjusted to 2.0 is treatment liquid 2B
  • the treatment liquid with pH adjusted to 3.0 is treatment liquid 2C
  • the treatment liquid with pH adjusted to 5.0 was treated liquid 2D
  • the treatment liquid with pH adjusted to 9.0 was treated liquid 2E
  • the treatment liquid with pH adjusted to 10.0 was treated liquid 2F.
  • the lithographic printing plate produced using the lithographic printing plate material having the support having the characteristics defined in the present invention has no deterioration of dot dot quality and printing durability. Furthermore, it can be seen that the above effects can be further exhibited and the environmental suitability is excellent by developing with a processing solution having a pH of 2.0 or more and 9.0 or less.
  • Example 3 ⁇ Production of support> [Production of Supports 17 to 20]
  • the current density and the amount of electricity in step c (range of 200 to 1200 C / dm 2 ) were controlled so as to be the surface shape parameter Rz ( ⁇ m) described in Table 3.
  • the surface shape parameter Rz ( ⁇ m) and the anode listed in Table 3 are the same except that the current density in step e is controlled to be the amount of anodized film ADT (g / m 2 ) listed in Table 3.
  • Supports 17 to 20 having an oxide film amount ADT (g / m 2 ) were produced.
  • the surface shape parameter Rz ( ⁇ m) and the anodic oxide film amount ADT (g / m 2 ) of each support described in Table 3 were measured in the same manner as in the method described in Example 1.
  • Each prepared lithographic printing plate was coated with a printing machine (Mitsubishi Heavy Industries, Ltd., DAIYA1F-1), coated paper, printing ink (manufactured by Dainippon Ink & Chemicals, soybean oil ink: Naturalis 100) and dampening. Printing was performed using water (H liquid SG-51 concentration 1.5%, manufactured by Tokyo Ink Co., Ltd.). The plate surface is wiped with a plate cleaner (Ultra Plate Cleaner (Distributor: Dainichi Seika Kogyo Co., Ltd.)) every 500 prints, and 3% under the condition of the exposure amount that 2% dots reproduce 2% on the printed matter. The number of times the plate cleaner was wiped until the missing of a small dot occurred was used as an indicator of printing durability. The larger the number of plate cleaner wipes, the better the printing durability.
  • Table 3 shows the evaluation results obtained as described above.
  • the lithographic printing plate produced using the lithographic printing plate material having the support having the characteristics specified in the present invention has a dot dot deterioration compared to the comparative example. It can be seen that the printing durability is excellent.

Abstract

Disclosed is a lithographic printing plate material which enables formation of a lithographic printing plate having good printing durability without deterioration of dot quality. The lithographic printing plate material has a structure wherein an image-forming layer containing a photosensitive composition is arranged on an aluminum support. The lithographic printing plate material is characterized in that the aluminum support has a surface shape parameter Rz (μm) of not less than 1.0 μm but not more than 4.0 μm on the side where the image-forming layer is arranged, while having an anodic oxide coating amount ADT (g/m2) of not less than 0.10 g/m2 but not more than 8.0 g/m2. The lithographic printing plate material is also characterized in that the product of the surface shape parameter Rz (μm) and the anodic oxide coating amount ADT (g/m2), namely [Rz × ADT] is not less than 0.11 μm ⋅ g/m2 but not more than 6.3 μm ⋅ g/m2.

Description

平版印刷版材料Planographic printing plate material
　本発明は、平版印刷版材料に関し、詳しくは網点点質の劣化がなく、耐刷性が良好な平版印刷版を得ることができる平版印刷版材料に関する。 The present invention relates to a lithographic printing plate material, and more particularly, to a lithographic printing plate material that can obtain a lithographic printing plate having good printing durability without deterioration of dot dot quality.
　近年、製版データのデジタル化に伴い、デジタルデータを直接レーザ信号に変調し、平版印刷版材料を露光する、いわゆるコンピューター・トゥー・プレート（以下、ＣＴＰと称す）システムが普及している。 In recent years, with the digitization of plate-making data, a so-called computer-to-plate (hereinafter referred to as CTP) system that modulates digital data directly into a laser signal and exposes a lithographic printing plate material has become widespread.
　これらのうち、比較的高い耐刷力が要求される印刷分野においては、アルミニウム板を支持体として、その上に画像形成層を有する平版印刷版材料を用いることが知られている。 Among these, in the printing field where a relatively high printing durability is required, it is known to use a lithographic printing plate material having an aluminum plate as a support and an image forming layer thereon.
　近年、印刷物の画質に対する要望は高くなってきており、前記の比較的高い耐刷力が要求される平版印刷版材料においても、より高品質な画像再現性が求められてきており、様々な技術が提案されている（例えば、特許文献１参照。）。 In recent years, there has been an increasing demand for image quality of printed materials, and higher quality image reproducibility has been demanded for the above-described lithographic printing plate materials that require relatively high printing durability. Has been proposed (see, for example, Patent Document 1).
　しかしながら、従来のアルミニウム板を支持体とする平版印刷版材料では、高い耐刷力と高品質な画像再現性の性能を両立できる技術が不十分であり、これらを解決できる技術が要望されていた。 However, conventional lithographic printing plate materials that use an aluminum plate as a support have insufficient technology capable of achieving both high printing durability and high-quality image reproducibility, and there has been a demand for technology that can solve these problems. .
　特に、重合可能な化合物を含む重合型の感光層を有するネガ型ＣＴＰ平版印刷版材料の提案がなされている（例えば、特許文献２参照。）。しかしながら、特許文献２で提案されている方法では、画質と耐刷性能の両立できる技術が不十分であり、これらを改良する技術がより強く求められているのが現状である。
特開２００１－１００４０８号公報 特開２００７－２６９８８７号公報 In particular, a negative CTP lithographic printing plate material having a polymerization type photosensitive layer containing a polymerizable compound has been proposed (for example, see Patent Document 2). However, in the method proposed in Patent Document 2, there is insufficient technology that can achieve both image quality and printing durability, and there is a strong demand for a technique for improving these techniques.
Japanese Patent Laid-Open No. 2001-100408 JP 2007-269887 A
　本発明は、上記課題に鑑みなされたものであり、その目的は、網点点質の劣化がなく、耐刷性が良好な平版印刷版を得ることができる平版印刷版材料を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a lithographic printing plate material which can obtain a lithographic printing plate having good printing durability without deterioration of dot quality. .
　本発明の上記目的は、下記の構成により達成される。 The above object of the present invention is achieved by the following configuration.
　１．アルミニウム支持体上に感光性組成物を含有する画像形成層を有する平版印刷版材料において、該アルミニウム支持体の画像形成層を有する面側の表面形状パラメータＲｚ（μｍ）が１．０μｍ以上、４．０μｍ以下で、陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）が０．１０ｇ／ｍ２以上、８．０ｇ／ｍ２以下であり、かつ表面形状パラメータＲｚ（μｍ）と陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）との積〔Ｒｚ×ＡＤＴ〕が、０．１１（μｍ・ｇ／ｍ２）以上、５．０（μｍ・ｇ／ｍ２）以下であることを特徴とする平版印刷版材料。 1. In a lithographic printing plate material having an image forming layer containing a photosensitive composition on an aluminum support, the surface shape parameter Rz (μm) on the surface side having the image forming layer of the aluminum support is 1.0 μm or more, 4 0.04 μm or less, an anodic oxide coating amount ADT (g / m 2 ) is 0.10 g / m 2 or more and 8.0 g / m 2 or less, and the surface shape parameter Rz (μm) and the anodic oxide coating amount ADT ( g / m 2 ) The product [Rz × ADT] is 0.11 (μm · g / m 2 ) or more and 5.0 (μm · g / m 2 ) or less. material.
　２．前記感光性組成物が、Ａ）付加重合可能なエチレン性二重結合含有単量体、Ｂ）光重合開始剤組成物及びＣ）高分子結合材を含有することを特徴とする前記１に記載の平版印刷版材料。 2. The said photosensitive composition contains A) the ethylenic double bond containing monomer which can be addition-polymerized, B) a photoinitiator composition, and C) polymeric binder, Said 1 characterized by the above-mentioned. Lithographic printing plate material.
　３．前記感光性組成物が、ビスイミダゾール化合物を含有することを特徴とする前記１または２に記載の平版印刷版材料。 3. 3. The lithographic printing plate material as described in 1 or 2 above, wherein the photosensitive composition contains a bisimidazole compound.
　４．ｐＨが２．０以上、９．０以下の処理液で現像処理されることを特徴とする前記１から３のいずれか１項に記載の平版印刷版材料。 4. The lithographic printing plate material as described in any one of 1 to 3 above, which is developed with a processing solution having a pH of 2.0 or more and 9.0 or less.
　５．波長が３５０ｎｍ以上、４５０ｎｍ以下のレーザで露光されることを特徴とする前記１から４のいずれか１項に記載の平版印刷版材料。 5. The lithographic printing plate material as described in any one of 1 to 4 above, which is exposed with a laser having a wavelength of 350 nm or more and 450 nm or less.
　本発明によれば、網点点質の劣化がなく、耐刷性が良好な平版印刷版を得ることができる平版印刷版材料を提供することができる。 According to the present invention, it is possible to provide a lithographic printing plate material capable of obtaining a lithographic printing plate having good dot durability without deterioration of dot dot quality.
　以下、本発明を実施するための最良の形態について説明するが、本発明はこれらに限定されない。 Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.
　本発明は、アルミニウム支持体上に感光性組成物を含有する画像形成層を有する平版印刷版材料において、該アルミニウム支持体の画像形成層を有する面側の表面形状パラメータＲｚ（μｍ）と陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）との積〔Ｒｚ×ＡＤＴ〕が、０．１１（μｍ・ｇ／ｍ２）以上、５．０（μｍ・ｇ／ｍ２）以下であることを特徴とする。 The present invention relates to a lithographic printing plate material having an image forming layer containing a photosensitive composition on an aluminum support, the surface shape parameter Rz (μm) of the surface having the image forming layer of the aluminum support and anodization. The product [Rz × ADT] with the coating amount ADT (g / m 2 ) is 0.11 (μm · g / m 2 ) or more and 5.0 (μm · g / m 2 ) or less. To do.
　本発明者は、上記課題に鑑み鋭意検討した結果、アルミニウム支持体の画像形成層を有する面側の表面形状パラメータＲｚ（μｍ）と陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）と積を、本発明で規定する範囲に制御することにより、網点点質に優れ、高画質で耐刷性も良好な平版印刷版材料が得えられることを見出し、本発明に至ったものである。 As a result of intensive studies in view of the above problems, the present inventor has obtained the product of the surface shape parameter Rz (μm) on the surface side having the image forming layer of the aluminum support and the amount of anodized film ADT (g / m 2 ). The inventors have found that a lithographic printing plate material excellent in halftone dot quality, high image quality and good printing durability can be obtained by controlling within the range specified by the invention, and the present invention has been achieved.
　以下、本発明の平版印刷版材料の各構成要素の詳細について説明する。 Hereinafter, details of each component of the planographic printing plate material of the present invention will be described.
　《アルミニウム支持体》
　はじめに、本発明の平版印刷版材料に適用するアルミニウム支持体について説明する。 <Aluminum support>
First, the aluminum support applied to the planographic printing plate material of the present invention will be described.
　本発明に係るアルミニウム支持体とは、感光性組成物を含有する画像形成層を設けるのに用いる支持体であり、粗面化、陽極酸化皮膜形成が施されることが好ましく、さらに必要に応じて封孔処理や後処理が施されてもよい。 The aluminum support according to the present invention is a support used for providing an image forming layer containing a photosensitive composition, and is preferably subjected to roughening and anodized film formation, and further if necessary. Thus, a sealing treatment or a post-treatment may be performed.
　本発明に係るアルミニウム支持体は、画像形成層を有する面側の表面形状パラメータＲｚ（μｍ）が１．０μｍ以上、４．０μｍ以下で、陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）が０．１０ｇ／ｍ２以上、８．０ｇ／ｍ２以下であり、かつ表面形状パラメータＲｚ（μｍ）と陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）の積〔Ｒｚ×ＡＤＴ〕が０．１１（μｍ・ｇ／ｍ２）以上、５．０（μｍ・ｇ／ｍ２）以下であることを特徴とする。 The aluminum support according to the present invention has a surface shape parameter Rz (μm) on the side having an image forming layer of 1.0 μm or more and 4.0 μm or less, and an anodic oxide film amount ADT (g / m 2 ) of 0.2. 10 g / m 2 or more and 8.0 g / m 2 or less, and the product [Rz × ADT] of the surface shape parameter Rz (μm) and the amount of anodized film ADT (g / m 2 ) is 0.11 (μm · g / m 2 ) or more and 5.0 (μm · g / m 2 ) or less.
　本発明でいうアルミニウム支持体の表面形状パラメータＲｚ（μｍ）とは、いわゆる表面粗さＲaを示すものであり、「十点平均粗さ」のことを意味し、断面曲線（表面をそれに直角な平面で切った切り口を考えた場合の凹凸のある曲線）から抜き取った一定の長さ（基準長さ）を用い、その平均線（被測定面から断面曲線までの偏差の自乗和が最小になる線）に平行且つ断面曲線を横切らない直線から縦倍率の方向に測定した最高から５番目までの山頂の標高の平均値と最深から５番目までの谷底の標高の平均値との差をミクロン単位で表したものをいう（ＪＩＳ　Ｂ　０６０１参照）。表面形状パラメータＲｚ（μｍ）は、市販されている触針式あるいは非接触型の表面粗さ計を用いて測定することができる。 The surface shape parameter Rz (μm) of the aluminum support referred to in the present invention indicates a so-called surface roughness Ra, meaning “ten-point average roughness”, and a cross-sectional curve (surface perpendicular to the surface). Using a fixed length (reference length) extracted from a rough curve when considering a cut surface cut in a plane, the average line (the square sum of the deviation from the measured surface to the cross-section curve) is minimized. The difference between the average value of the highest elevation of the peak from the highest to the fifth and the average elevation of the bottom of the valley from the deepest to the fifth measured in the direction of the vertical magnification from the straight line that is parallel to the line and does not cross the section curve. (Refer to JIS B 0601). The surface shape parameter Rz (μm) can be measured using a commercially available stylus type or non-contact type surface roughness meter.
　本発明においては、本発明に係る表面形状パラメータＲｚは、１．０μｍ以上、４．０μｍ以下であることを特徴とするが、さらに好ましくは１．７μｍ以上、４．０μｍ以下であり、最も好ましくは、２．３μｍ以上、３．７μｍ以下である。 In the present invention, the surface shape parameter Rz according to the present invention is 1.0 μm or more and 4.0 μm or less, more preferably 1.7 μm or more and 4.0 μm or less, and most preferably Is 2.3 μm or more and 3.7 μm or less.
　表面形状パラメータＲｚは、粗面化、陽極酸化皮膜形成、封孔処理や後処理などの処理によって上記の範囲に調整することができるが、その中でも後述の粗面化（砂目立て処理）を行うことにより、調整することが好ましい。 The surface shape parameter Rz can be adjusted to the above range by roughening, anodic oxide film formation, sealing treatment or post-treatment, among which roughening (graining treatment) described later is performed. Therefore, it is preferable to adjust.
　本発明でいう陽極酸化膜量ＡＤＴ（ｇ／ｍ２）とは、アルミニウム板を燐酸クロム酸溶液（燐酸８５％液：３５ｍｌ、酸化クロム（IV）：２０ｇを１Ｌの水に溶解して調製）に浸漬し、酸化皮膜を溶解し、アルミニウム板の皮膜溶解前後における質量変化を測定して求められる値である。 The anodic oxide film amount ADT (g / m 2 ) in the present invention is an aluminum plate prepared by dissolving a chromic phosphate solution (85% phosphoric acid solution: 35 ml, chromium (IV) oxide: 20 g in 1 L of water). It is a value obtained by immersing the substrate in a melt, dissolving the oxide film, and measuring the change in mass before and after dissolution of the aluminum plate film.
　本発明において、陽極酸化皮膜量ＡＤＴとしては０．１０ｇ／ｍ２以上、８．０ｇ／ｍ２以下であることを特徴とし、更に好ましくは、０．１ｇ／ｍ２以上、２．５ｇ／ｍ２以下であり、最も好ましくは０．１ｇ／ｍ２以上、０．９ｇ／ｍ２以下である。 In the present invention, the anodic oxide coating amount ADT is 0.10 g / m 2 or more and 8.0 g / m 2 or less, more preferably 0.1 g / m 2 or more and 2.5 g / m. 2 or less, and most preferably 0.1 g / m 2 or more and 0.9 g / m 2 or less.
　本発明で規定する陽極酸化膜量ＡＤＴは、後述の陽極酸化処理、陽極酸化皮膜の形成を行うことによって、上記で規定する好ましい範囲に調整することができる。 The amount of anodic oxide film ADT defined in the present invention can be adjusted to the preferred range defined above by performing an anodic oxidation treatment and an anodized film described later.
　本発明においては、ＲｚとＡＤＴとを上記のようにそれぞれを適宜調整して、Ｒｚ×ＡＤＴを０．１１（μｍ・ｇ／ｍ２）以上、５．０（μｍ・ｇ／ｍ２）以下にする。Ｒｚ×ＡＤＴは好ましくは、０．６（μｍ・ｇ／ｍ２）以上、４．０（μｍ・ｇ／ｍ２）以下である。 In the present invention, Rz and ADT are appropriately adjusted as described above, and Rz × ADT is 0.11 (μm · g / m 2 ) or more and 5.0 (μm · g / m 2 ) or less. To. Rz × ADT is preferably 0.6 (μm · g / m 2 ) or more and 4.0 (μm · g / m 2 ) or less.
　（粗面化（砂目立て処理））
　本発明に係る支持体は、親水性表面を有するアルミニウム基材が使用され、この場合、純アルミニウム又はアルミニウム合金であってもよい。 (Roughening (graining treatment))
The support according to the present invention uses an aluminum substrate having a hydrophilic surface, and in this case, pure aluminum or an aluminum alloy may be used.
　支持体のアルミニウム合金としては、種々のものが使用でき、例えば、珪素、銅、マンガン、マグネシウム、クロム、亜鉛、鉛、ビスマス、ニッケル、チタン、ナトリウム、鉄等の金属とアルミニウムの合金が用いられる。 Various aluminum alloys can be used as the support, and for example, alloys of metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel, titanium, sodium, iron, and aluminum are used. .
　支持体は、粗面化（砂目立て処理）するに先立って、表面の圧延油を除去するために脱脂処理を施すことが好ましい。脱脂処理としては、トリクレン、シンナー等の溶剤を用いる脱脂処理、ケシロン、トリエタノール等のエマルジョンを用いたエマルジョン脱脂処理等を用いることができる。又、脱脂処理には、苛性ソーダ等のアルカリの水溶液を用いることもできる。脱脂処理に苛性ソーダ等のアルカリ水溶液を用いた場合、上記脱脂処理のみでは除去できない汚れや酸化皮膜も除去することができる。脱脂処理に苛性ソーダ等のアルカリ水溶液を用いた場合、支持体の表面にはスマットが生成するので、この場合には、燐酸、硝酸、硫酸、クロム酸等の酸、或いはそれらの混酸に浸漬し、デスマット処理を施すことが好ましい。 Prior to roughening (graining treatment), the support is preferably subjected to a degreasing treatment to remove rolling oil on the surface. As the degreasing treatment, a degreasing treatment using a solvent such as trichrene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like can be used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, dirt and oxide film that cannot be removed only by the degreasing treatment can be removed. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, smut is generated on the surface of the support. In this case, it is immersed in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid, or a mixed acid thereof, It is preferable to perform a desmut treatment.
　本発明に用いられるアルミニウム支持体の粗面化の方法としては、電解により粗面化を行うが、電気化学的粗面化処理に先立ち、機械的粗面化処理、硝酸を主体とする電解粗面化処理などによるプレ粗面化を施しても良い。 As a method for roughening the aluminum support used in the present invention, roughening is carried out by electrolysis. Prior to the electrochemical roughening treatment, mechanical roughening treatment, electrolytic roughening mainly composed of nitric acid is performed. Pre-roughening by surface treatment or the like may be performed.
　機械的プレ粗面化方法は、特に限定されるものではないが、ブラシ研磨法、ホーニング研磨法が好ましい。ブラシ研磨法による粗面化は、例えば、直径０．２～０．８ｍｍのブラシ毛を使用した回転ブラシを回転させ、アルミニウム支持体表面に、例えば、粒径１０～１００μｍの火山灰粒子を水に均一に分散させたスラリーを供給しながら、ブラシを押し付けて行うことができる。ホーニング研磨による粗面化は、例えば、粒径１０～１００μｍの火山灰粒子を水に均一に分散させ、この分散液をノズルより圧力をかけて、アルミニウム支持体表面に斜めから噴射、衝突させて粗面化を行うことができる。また、例えば、アルミニウム支持体表面に、粒径が１０～１００μｍの研磨剤粒子を、１００～２００μｍの間隔で、２．５×１０３～１０×１０３個／ｃｍ２の密度で存在するように塗布したシートを張り合わせ、圧力をかけてシートの粗面パターンを転写することにより粗面化を行うこともできる。 The mechanical pre-roughening method is not particularly limited, but a brush polishing method and a honing polishing method are preferable. The roughening by the brush polishing method is performed, for example, by rotating a rotating brush using a bristle having a diameter of 0.2 to 0.8 mm, and, for example, volcanic ash particles having a particle size of 10 to 100 μm on water. While supplying the uniformly dispersed slurry, the brush can be pressed. For roughening by honing, for example, volcanic ash particles having a particle size of 10 to 100 μm are uniformly dispersed in water, and this dispersion is pressurized from a nozzle and sprayed and collided with the surface of the aluminum support at an angle. Surfaceization can be performed. Further, for example, abrasive particles having a particle size of 10 to 100 μm are present on the surface of the aluminum support at a density of 2.5 × 10 3 to 10 × 10 3 particles / cm 2 at intervals of 100 to 200 μm. Roughening can also be performed by laminating the coated sheet and applying a pressure to transfer the rough surface pattern of the sheet.
　上記の機械的粗面化法で粗面化した後は、アルミニウム支持体の表面に食い込んだ研磨剤、発生したアルミニウム屑等を取り除くため、酸又はアルカリの水溶液に浸漬することが好ましい。酸としては、例えば、硫酸、過硫酸、弗酸、燐酸、硝酸、塩酸等が用いられ、塩基としては、例えば、水酸化ナトリウム、水酸化カリウム等が用いられる。これらの中でも、水酸化ナトリウム等のアルカリ水溶液を用いるのが好ましい。表面のアルミニウムの溶解量としては、０．５～５ｇ／ｍ２が好ましい。アルカリ水溶液で浸漬処理を行った後、燐酸、硝酸、硫酸、クロム酸等の酸或いはそれらの混酸に浸漬して中和処理を施すことが好ましい。 After the surface is roughened by the above-described mechanical surface roughening method, it is preferable to immerse in an aqueous solution of acid or alkali in order to remove the abrasive that has digged into the surface of the aluminum support, the generated aluminum scraps, and the like. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous alkali solution such as sodium hydroxide. The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m 2 . After the immersion treatment with an alkaline aqueous solution, it is preferable to carry out a neutralization treatment by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
　硝酸を主体とするプレ電解粗面化処理は、１～５０ボルトの範囲の電圧を印加することによって行うことができるが、１０～３０ボルトの範囲から選ぶのが好ましい。 The pre-electrolytic roughening treatment mainly composed of nitric acid can be performed by applying a voltage in the range of 1 to 50 volts, but is preferably selected from the range of 10 to 30 volts.
　電流密度は、１０～２００Ａ／ｄｍ２の範囲を用いることができるが、２０～１００Ａ／ｄｍ２の範囲から選ぶのが好ましい。電気量は、１００～５０００Ｃ／ｄｍ２の範囲を用いることができるが、１００～２０００Ｃ／ｄｍ２の範囲から選ぶのが好ましい。電気化学的粗面化法を行う温度は、１０～５０℃の範囲とすることができるが、１５～４５℃の範囲から選ぶのが好ましい。電解液における硝酸濃度は０．１～５質量％とすることが好ましい。電解液には、必要に応じて、硝酸塩、塩化物、アミン類、アルデヒド類、燐酸、クロム酸、ホウ酸、酢酸、しゅう酸、アルミニウムイオン等を加えることができる。 Current density may be in the range of 10 ~ 200A / dm 2, preferably selected from the range of 20 ~ 100A / dm 2. The quantity of electricity, may be in the range of 100 ~ 5000C / dm 2, preferably selected from the range of 100 ~ 2000C / dm 2. The temperature at which the electrochemical surface roughening method is carried out can be in the range of 10 to 50 ° C., but is preferably selected from the range of 15 to 45 ° C. The concentration of nitric acid in the electrolytic solution is preferably 0.1 to 5% by mass. If necessary, nitrates, chlorides, amines, aldehydes, phosphoric acid, chromic acid, boric acid, acetic acid, oxalic acid, aluminum ions, and the like can be added to the electrolytic solution.
　上記の硝酸を主体とする電解粗面化処理後は、表面のアルミニウム屑等を取り除くため、酸又はアルカリの水溶液に浸漬することが好ましい。酸としては、例えば、硫酸、過硫酸、弗酸、燐酸、硝酸、塩酸等が用いられ、塩基としては、例えば、水酸化ナトリウム、水酸化カリウム等が用いられる。これらの中でもアルカリの水溶液を用いるのが好ましい。 After the electrolytic surface-roughening treatment mainly composed of nitric acid, it is preferably immersed in an acid or alkali aqueous solution in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an alkaline aqueous solution.
　表面のアルミニウムの溶解量としては、０．５～５ｇ／ｍ２が好ましい。又、アルカリの水溶液で浸漬処理を行った後、燐酸、硝酸、硫酸、クロム酸等の酸或いはそれらの混酸に浸漬して中和処理を施すことが好ましい。 The amount of aluminum dissolved on the surface is preferably 0.5 to 5 g / m 2 . In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
　本発明に係る電気化学的粗面化処理としては、塩酸を主体とする電解液中での交流電解粗面化処理を施すことが好ましい。 As the electrochemical surface roughening treatment according to the present invention, it is preferable to perform an AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid.
　塩酸を主体とする電解液中での交流電解粗面化処理は、塩酸濃度は概ね５～２０ｇ／Ｌの範囲であり、好ましくは６．５～１６ｇ／Ｌである。電解液の温度は概ね１５～３５℃の範囲であり、好ましくは１８～３８℃である。 In the AC electrolytic surface roughening treatment in an electrolytic solution mainly composed of hydrochloric acid, the concentration of hydrochloric acid is generally in the range of 5 to 20 g / L, preferably 6.5 to 16 g / L. The temperature of the electrolytic solution is generally in the range of 15 to 35 ° C, preferably 18 to 38 ° C.
　電解液中のアルミニウムイオン濃度は概ね０．５～１５ｇ／Ｌの範囲であり、好ましくは０．７～１０ｇ／Ｌである。電解液中には酢酸または硼酸を含有することが好ましく、その濃度としては概ね１～２０ｇ／Ｌの範囲であり、好ましくは３～１５ｇ／Ｌである。また塩酸濃度との比（酢酸または硼酸濃度／塩酸濃度）は０．５～１．５が好ましい。電流密度は概ね１５～１２０Ａ／ｄｍ２であり、好ましくは２０～９０Ａ／ｄｍ２である。電気量は概ね４００～２０００Ｃ／ｄｍ２の範囲であり、好ましくは５００～１２００Ｃ／ｄｍ２である。周波数は４０～１５０Ｈｚの範囲で行うことが好ましい。 The aluminum ion concentration in the electrolytic solution is generally in the range of 0.5 to 15 g / L, preferably 0.7 to 10 g / L. The electrolytic solution preferably contains acetic acid or boric acid, and the concentration is generally in the range of 1 to 20 g / L, preferably 3 to 15 g / L. The ratio to the hydrochloric acid concentration (acetic acid or boric acid concentration / hydrochloric acid concentration) is preferably 0.5 to 1.5. The current density is approximately 15 to 120 A / dm 2 , preferably 20 to 90 A / dm 2 . The quantity of electricity is generally the range of 400 ~ 2000C / dm 2, preferably 500 ~ 1200C / dm 2. The frequency is preferably in the range of 40 to 150 Hz.
　本発明に係る平版印刷版材料用支持体は、上記の電気化学的粗面化処理の電解条件を上記の範囲の中で調整することにより得られ、例えば、電解液中のアルミニウムイオン濃度を３～７ｇ／Ｌの範囲とし、電解液中の酢酸または硼酸の濃度を７～１３ｇ／Ｌの範囲とし、塩酸濃度に対する酢酸または硼酸濃度の比を０．７～１．２の範囲とし、電流密度を１５～９０Ａ／ｄｍ２の範囲とし、電気量を５００～１２００Ｃ／ｄｍ２の範囲として、それぞれの条件範囲内で最適条件に調整することが好ましい。 The support for a lithographic printing plate material according to the present invention can be obtained by adjusting the electrolysis conditions for the electrochemical surface roughening treatment within the above range. For example, the aluminum ion concentration in the electrolytic solution is 3 The concentration of acetic acid or boric acid in the electrolyte is in the range of 7 to 13 g / L, the ratio of acetic acid or boric acid concentration to the hydrochloric acid concentration is in the range of 0.7 to 1.2, and the current density Is in the range of 15 to 90 A / dm 2 , and the amount of electricity is preferably in the range of 500 to 1200 C / dm 2 , and is preferably adjusted to the optimum condition within each condition range.
　特に、前半で電流密度４０Ａ／ｄｍ２以上での電解処理、後半で電流密度３５Ａ／ｄｍ２以下での電解処理の２段階電流密度電解処理、前半の電気量＞後半の電気量の条件での電解処理、あるいは、前半に高塩酸濃度の電解液、後半に高酢酸濃度または高硼酸濃度の電解液を用いる２浴電解の条件で電解粗面化することにより、本発明に係る粗面特性を有するアルミニウム支持体を得ることができる。 Particularly, in the first half, electrolytic treatment at a current density of 40 A / dm 2 or more, in the latter half, a two-stage current density electrolytic treatment of current treatment at a current density of 35 A / dm 2 or less, the amount of electricity in the first half> the amount of electricity in the second half The rough surface characteristics according to the present invention can be achieved by electrolytic surface roughening under conditions of two-bath electrolysis using an electrolytic treatment or an electrolytic solution having a high hydrochloric acid concentration in the first half and an electrolytic solution having a high acetic acid concentration or high boric acid concentration in the second half. The aluminum support body which has can be obtained.
　交流電解処理は、数段階に分けてもよく、例えば、電流密度を多段階的に変化させる方法、交流波形を多段階に変化させる方法、周波数を多段階に変化させる方法、酸性電解液濃度を多段階に変化させる方法等、が適用できる。 The AC electrolytic treatment may be divided into several stages. For example, the method of changing the current density in multiple stages, the method of changing the AC waveform in multiple stages, the method of changing the frequency in multiple stages, and the acidic electrolyte concentration A method of changing in multiple stages can be applied.
　上記の塩酸を主体とする電解液中で電解粗面化処理を施した後は、表面のアルミニウム屑等を取り除くため、酸又はアルカリの水溶液に浸漬することが好ましい。酸としては、例えば、硫酸、過硫酸、弗酸、燐酸、硝酸、塩酸等が用いられ、塩基としては、例えば、水酸化ナトリウム、水酸化カリウム等が用いられる。これらの中でも燐酸または水酸化ナトリウムの水溶液を用いるのが好ましい。表面のアルミニウムの溶解量としては、０．１～２ｇ／ｍ２が好ましい。又、アルカリの水溶液で浸漬処理を行った後、燐酸、硝酸、硫酸、クロム酸等の酸或いはそれらの混酸に浸漬し中和処理を施すことが好ましい。 After the electrolytic surface roughening treatment is performed in the above-described electrolytic solution mainly composed of hydrochloric acid, it is preferably immersed in an aqueous solution of acid or alkali in order to remove aluminum scraps on the surface. Examples of the acid include sulfuric acid, persulfuric acid, hydrofluoric acid, phosphoric acid, nitric acid, hydrochloric acid, and the like. Examples of the base include sodium hydroxide and potassium hydroxide. Among these, it is preferable to use an aqueous solution of phosphoric acid or sodium hydroxide. The amount of aluminum dissolved on the surface is preferably 0.1 to 2 g / m 2 . In addition, it is preferable that after the immersion treatment with an alkaline aqueous solution, neutralization treatment is performed by immersion in an acid such as phosphoric acid, nitric acid, sulfuric acid, chromic acid or a mixed acid thereof.
　本発明において、アルミニウム支持体表面を本発明で規定する表面形状パラメータＲｚ（μｍ）の範囲に制御する具体的な方法としては、上記説明した機械的プレ粗面化方法においては、ブラシ研磨法でのブラシの押しつけ量を調整する手段、ホーニング研磨法での使用する粒子の平均粒径を調整する手段、また、上記説明した電解粗面化方法においては、電気量及び電流密度を調整する手段、電解液組成及び電解温度を調整する手段、周波数を調整する手段等が挙げられ、各手段を単独、あるいは組み合わせて用いることにより、所望の表面形状パラメータＲｚ（μｍ）を得ることができる。 In the present invention, as a specific method for controlling the aluminum support surface within the range of the surface shape parameter Rz (μm) defined in the present invention, the mechanical pre-roughening method described above is a brush polishing method. Means for adjusting the pressing amount of the brush, means for adjusting the average particle size of the particles used in the honing polishing method, and means for adjusting the amount of electricity and current density in the electrolytic surface-roughening method described above, Examples include means for adjusting the electrolyte composition and electrolysis temperature, means for adjusting the frequency, and the like. By using each means alone or in combination, a desired surface shape parameter Rz (μm) can be obtained.
　（陽極酸化皮膜）
　本発明に係るアルミニウム支持体は、電気化学的粗面化処理に続き、陽極酸化処理を施すことが好ましい。 (Anodized film)
The aluminum support according to the present invention is preferably subjected to an anodizing treatment following the electrochemical surface roughening treatment.
　陽極酸化処理の方法は、特に制限はなく、公知の方法を用いることができる。この陽極酸化処理を施すことにより、アルミニウム支持体上に酸化皮膜が形成される。陽極酸化処理は、一般的には、電解液として、硫酸またはリン酸、あるいは両者の混合水溶液を用い、直流電解することにより行われる。本発明においては、陽極酸化処理は、電解液として硫酸を用いて行うことが好ましい。硫酸の濃度は、５～５０質量％の範囲が好ましく、１０～３５質量％が特に好ましい。温度は１０～５０℃の範囲が好ましい。処理電圧は１８Ｖ以上であることが好ましく、２０Ｖ以上であることが更に好ましい。電流密度は１～３０Ａ／ｄｍ２の範囲で行うことが好ましい。電気量は１００～５００Ｃ／ｄｍ２の範囲で行うことが好ましい。 The method of anodizing treatment is not particularly limited, and a known method can be used. By performing this anodizing treatment, an oxide film is formed on the aluminum support. The anodizing treatment is generally performed by direct current electrolysis using sulfuric acid or phosphoric acid or a mixed aqueous solution of both as the electrolytic solution. In the present invention, the anodic oxidation treatment is preferably performed using sulfuric acid as the electrolytic solution. The concentration of sulfuric acid is preferably in the range of 5 to 50% by mass, particularly preferably 10 to 35% by mass. The temperature is preferably in the range of 10 to 50 ° C. The treatment voltage is preferably 18V or more, and more preferably 20V or more. The current density is preferably in the range of 1 to 30 A / dm 2 . The amount of electricity is preferably in the range of 100 to 500 C / dm 2 .
　上記条件で調整された陽極酸化皮膜量は、前述の通り、０．１ｇ／ｍ２以上、８．０ｇ／ｍ２以下であることを特徴とするが、上述の通り、更に好ましくは、０．１ｇ／ｍ２以上、２．５ｇ／ｍ２以下であり、最も好ましくは０．１ｇ／ｍ２以上０．９ｇ／ｍ２以下である。陽極酸化皮膜にはマイクロポアが生成されるが、マイクロポアの密度は、４００～７００個／μｍ２が好ましく、４００～６００個／μｍ２が更に好ましい。 As described above, the amount of the anodized film adjusted under the above conditions is 0.1 g / m 2 or more and 8.0 g / m 2 or less. 1 g / m 2 or more and 2.5 g / m 2 or less, and most preferably 0.1 g / m 2 or more and 0.9 g / m 2 or less. Micropores are generated in the anodic oxide film, and the density of the micropores is preferably 400 to 700 / μm 2, and more preferably 400 to 600 / μm 2 .
　本発明において、陽極酸化皮膜量ＡＤＴを本発明で規定する条件の制御する方法としては、特に制限はないが、好ましくは電流密度及び電気量を調整することにより達成することができる。電流密度としては１～３０Ａ／ｄｍ２の範囲で行うことが好ましい。電気量としては１００～５００Ｃ／ｄｍ２の範囲で行うことが好ましい。 In the present invention, the method for controlling the anodic oxide film amount ADT under the conditions defined in the present invention is not particularly limited, but it can be preferably achieved by adjusting the current density and the electric quantity. The current density is preferably in the range of 1 to 30 A / dm 2 . The amount of electricity is preferably in the range of 100 to 500 C / dm 2 .
　陽極酸化処理されたアルミニウム支持体は、必要に応じ封孔処理を施してもよい。封孔処理としては、熱水処理、沸騰水処理、水蒸気処理、珪酸ソーダ処理、重クロム酸塩水溶液処理、亜硝酸塩処理、酢酸アンモニウム処理等の公知の方法を用いて行うことができる。 The anodized aluminum support may be sealed as necessary. As the sealing treatment, known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment and ammonium acetate treatment can be used.
　更に、上記処理を行った後、アルミニウム支持体に、水溶性樹脂、例えば、ポリビニルホスホン酸、スルホン酸基を側鎖に有する重合体及び共重合体、ポリアクリル酸、水溶性金属塩（例えば、ホウ酸亜鉛）、もしくは黄色染料、アミン塩等を下塗り層として付与することも好適である。更に、特開平５－３０４３５８号公報に開示されているような、ラジカルによって付加反応を起し得る官能基を共有結合させたゾル－ゲル処理を施したアルミニウム支持体も好適に用いられる。 Further, after performing the above treatment, the aluminum support is coated with a water-soluble resin such as polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, It is also suitable to apply zinc borate), or a yellow dye, an amine salt or the like as an undercoat layer. Furthermore, an aluminum support subjected to a sol-gel treatment in which a functional group capable of causing an addition reaction by a radical is covalently bonded as disclosed in JP-A-5-304358 is also preferably used.
　《画像形成層》
　本発明に係る感光性組成物を含有する画像形成層は、画像露光によって画像を形成し得る層であり、従来、平版印刷版材料の画像形成層として用いられているネガ型、ポジ型のいずれの方式の画像形成層を用いることができる。 <Image forming layer>
The image forming layer containing the photosensitive composition according to the present invention is a layer capable of forming an image by image exposure, and is either a negative type or a positive type conventionally used as an image forming layer of a lithographic printing plate material. An image forming layer of the above system can be used.
　本発明に係る画像形成層としては、感熱性画像形成層あるいは重合性画像形成層であることが本発明においては好ましく、特に、重合性画像形成層であることが特に好ましい。 In the present invention, the image forming layer according to the present invention is preferably a heat-sensitive image forming layer or a polymerizable image forming layer, and particularly preferably a polymerizable image forming layer.
　感熱性画像形成層としては、赤外レーザ露光により生じた熱を利用して画像形成可能な変化を生じるものが好ましく用いられる。これらの感熱性画像形成層としては、国際公開第２００７／０８３５４２号明細書の段落［００３６］～［０１７５］に記載されたものを好ましく用いることができる。 As the heat-sensitive image forming layer, a layer causing a change capable of forming an image using heat generated by infrared laser exposure is preferably used. As these heat-sensitive image forming layers, those described in paragraphs [0036] to [0175] of WO 2007/083542 can be preferably used.
　重合性画像形成層としては、感光性組成物が、Ａ）付加重合可能なエチレン性二重結合含有単量体、Ｂ）光重合開始剤組成物、Ｃ）高分子結合材を含有することが好ましい。以下、画像形成層について、重合性画像形成層の一例として、その詳細を説明する。 As the polymerizable image forming layer, the photosensitive composition may contain A) an ethylenic double bond-containing monomer capable of addition polymerization, B) a photopolymerization initiator composition, and C) a polymer binder. preferable. Hereinafter, the image forming layer will be described in detail as an example of the polymerizable image forming layer.
　〔重合性画像形成層〕
　重合性画像形成層としては、感光性組成物が、Ａ）付加重合可能なエチレン性二重結合含有単量体、Ｂ）光重合開始剤組成物及びＣ）高分子結合材を含有することが好ましい。 (Polymerizable image forming layer)
As the polymerizable image forming layer, the photosensitive composition may contain A) an addition-polymerizable ethylenic double bond-containing monomer, B) a photopolymerization initiator composition, and C) a polymer binder. preferable.
　（Ａ）付加重合可能なエチレン性二重結合含有単量体）
　付加重合可能なエチレン性二重結合含有単量体とは、重合性モノマーであり、画像露光による光重合開始剤の反応生成物を契機として重合し得る化合物（単量体）である。本発明においては、光重合開始剤から生成するラジカル種等との反応を契機として重合反応が開始し得る広範囲の化合物が使用できる。 (A) Ethylenic double bond-containing monomer capable of addition polymerization)
The addition-polymerizable ethylenic double bond-containing monomer is a polymerizable monomer and is a compound (monomer) that can be polymerized with the reaction product of a photopolymerization initiator by image exposure as an opportunity. In the present invention, a wide range of compounds that can initiate a polymerization reaction triggered by a reaction with a radical species generated from a photopolymerization initiator can be used.
　本発明に係る付加重合可能なエチレン性二重結合含有単量体として好ましく用いられる化合物は、エチレン性不飽和結合含有化合物で、重合可能な化合物であって、一般的なラジカル重合性のモノマー類、紫外線硬化樹脂に一般的に用いられる分子内に付加重合可能なエチレン性二重結合を複数有する多官能モノマー類や、多官能オリゴマー類等を挙げることができる。 The compound preferably used as the addition-polymerizable ethylenic double bond-containing monomer according to the present invention is an ethylenically unsaturated bond-containing compound, which is a polymerizable compound, and is a general radical-polymerizable monomer. And polyfunctional monomers having a plurality of addition-polymerizable ethylenic double bonds in the molecule generally used for ultraviolet curable resins, polyfunctional oligomers, and the like.
　本発明に係る重合性モノマーの好ましいものとして、例えば、２－エチルヘキシルアクリレート、２－ヒドロキシプロピルアクリレート、グリセロールアクリレート、テトラヒドロフルフリルアクリレート、フェノキシエチルアクリレート、ノニルフェノキシエチルアクリレート、テトラヒドロフルフリルオキシエチルアクリレート、テトラヒドロフルフリルオキシヘキサノリドアクリレート、１，３－ジオキサンアルコールのε－カプロラクトン付加物のアクリレート、１，３－ジオキソランアクリレート等の単官能アクリル酸エステル類、あるいはこれらのアクリレートをメタクリレート、イタコネート、クロトネート、マレエートに代えたメタクリル酸、イタコン酸、クロトン酸、マレイン酸エステル、例えば、エチレングリコールジアクリレート、トリエチレングルコールジアクリレート、ペンタエリスリトールジアクリレート、ハイドロキノンジアクリレート、レゾルシンジアクリレート、ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、トリプロピレングリコールジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールのジアクリレート、ネオペンチルグリコールアジペートのジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールのε－カプロラクトン付加物のジアクリレート、２－（２－ヒドロキシ－１，１－ジメチルエチル）－５－ヒドロキシメチル－５－エチル－１，３－ジオキサンジアクリレート、トリシクロデカンジメチロールアクリレート、トリシクロデカンジメチロールアクリレートのε－カプロラクトン付加物、１，６－ヘキサンジオールのジグリシジルエーテルのジアクリレート等の２官能アクリル酸エステル類、あるいはこれらのアクリレートをメタクリレート、イタコネート、クロトネート、マレエートに代えたメタクリル酸、イタコン酸、クロトン酸、マレイン酸エステル、例えば、トリメチロールプロパントリアクリレート、ジトリメチロールプロパンテトラアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサアクリレートのε－カプロラクトン付加物、ピロガロールトリアクリレート、プロピオン酸・ジペンタエリスリトールトリアクリレート、プロピオン酸・ジペンタエリスリトールテトラアクリレート、ヒドロキシピバリルアルデヒド変性ジメチロールプロパントリアクリレート等の多官能アクリル酸エステル酸、あるいはこれらのアクリレートをメタクリレート、イタコネート、クロトネート、マレエートに代えたメタクリル酸、イタコン酸、クロトン酸、マレイン酸エステル等を挙げることができる。 Preferred examples of the polymerizable monomer according to the present invention include 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydro Furfuryloxyhexanolide acrylate, acrylate of ε-caprolactone adduct of 1,3-dioxane alcohol, monofunctional acrylic acid ester such as 1,3-dioxolane acrylate, or these acrylates as methacrylate, itaconate, crotonate, maleate Methacrylic acid, itaconic acid, crotonic acid, maleic acid esters such as ethylene glycol Acrylate, triethylene glycol diacrylate, pentaerythritol diacrylate, hydroquinone diacrylate, resorcin diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, diacrylate of hydroxypivalate neopentyl glycol, neo Diacrylate of pentyl glycol adipate, diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3 -Ε-caprolactate of dioxane diacrylate, tricyclodecane dimethylol acrylate, tricyclodecane dimethylol acrylate Adducts, bifunctional acrylic esters such as diacrylate of diglycidyl ether of 1,6-hexanediol, or methacrylic acid, itaconic acid, crotonic acid, maleate in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Acid esters such as trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , Ε-caprolactone adduct of dipentaerythritol hexaacrylate, pyrogallol Multifunctional acrylic acid ester acid such as acrylate, propionic acid / dipentaerythritol triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalylaldehyde-modified dimethylolpropane triacrylate, or acrylate of these, methacrylate, itaconate, crotonate And methacrylic acid, itaconic acid, crotonic acid, maleic acid ester, etc., instead of maleate.
　また、プレポリマーも上記と同様に使用することができる。プレポリマーとしては、後述するような化合物等を挙げることができ、また適当な分子量のオリゴマーにアクリル酸、またはメタクリル酸を導入し、光重合性を付与したプレポリマーも好適に使用できる。これらプレポリマーは１種または２種以上を併用してもよいし、上述のモノマー及び／またはオリゴマーと混合して用いてもよい。 Also, prepolymers can be used in the same manner as described above. Examples of the prepolymer include compounds as described below, and a prepolymer obtained by introducing acrylic acid or methacrylic acid into an oligomer having an appropriate molecular weight and imparting photopolymerizability can also be suitably used. These prepolymers may be used alone or in combination of two or more, and may be used by mixing with the above-mentioned monomers and / or oligomers.
　プレポリマーとしては、例えば、アジピン酸、トリメリット酸、マレイン酸、フタル酸、テレフタル酸、ハイミック酸、マロン酸、コハク酸、グルタール酸、イタコン酸、ピロメリット酸、フマル酸、グルタール酸、ピメリン酸、セバシン酸、ドデカン酸、テトラヒドロフタル酸等の多塩基酸と、エチレングリコール、プロピレングルコール、ジエチレングリコール、プロピレンオキサイド、１，４－ブタンジオール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、１，６－ヘキサンジオール、１，２，６－ヘキサントリオール等の多価のアルコールの結合で得られるポリエステルに（メタ）アクリル酸を導入したポリエステルアクリレート類、例えば、ビスフェノールＡ・エピクロルヒドリン・（メタ）アクリル酸、フェノールノボラック・エピクロルヒドリン・（メタ）アクリル酸のようにエポキシ樹脂に（メタ）アクリル酸を導入したエポキシアクリレート類、例えば、エチレングリコール・アジピン酸・トリレンジイソシアネート・２－ヒドロキシエチルアクリレート、ポリエチレングリコール・トリレンジイソシアネート・２－ヒドロキシエチルアクリレート、ヒドロキシエチルフタリルメタクリレート・キシレンジイソシアネート、１，２－ポリブタジエングリコール・トリレンジイソシアネート・２－ヒドロキシエチルアクリレート、トリメチロールプロパン・プロピレングリコール・トリレンジイソシアネート・２－ヒドロキシエチルアクリレートのように、ウレタン樹脂に（メタ）アクリル酸を導入したウレタンアクリレート、例えば、ポリシロキサンアクリレート、ポリシロキサン・ジイソシアネート・２－ヒドロキシエチルアクリレート等のシリコン樹脂アクリレート類、その他、油変性アルキッド樹脂に（メタ）アクリロイル基を導入したアルキッド変性アクリレート類、スピラン樹脂アクリレート類等のプレポリマーが挙げられる。 Examples of the prepolymer include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, and pimelic acid. , Polybasic acids such as sebacic acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, tri Polyester obtained by introducing (meth) acrylic acid into a polyester obtained by the combination of polyhydric alcohols such as methylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Acrylates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol Adipic acid, tolylene diisocyanate, 2-hydroxyethyl acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate, hydroxyethyl phthalyl methacrylate, xylene diisocyanate, 1,2-polybutadiene glycol, tolylene diisocyanate, 2-hydroxyethyl Acrylate, trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate As described above, urethane acrylate in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, and other oil-modified alkyd resins (meth ) Prepolymers such as alkyd-modified acrylates and spirane resin acrylates introduced with acryloyl groups.
　本発明に係る画像形成層には、ホスファゼンモノマー、トリエチレングリコール、イソシアヌール酸ＥＯ（エチレンオキシド）変性ジアクリレート、イソシアヌール酸ＥＯ変性トリアクリレート、ジメチロールトリシクロデカンジアクリレート、トリメチロールプロパンアクリル酸安息香酸エステル、アルキレングリコールタイプアクリル酸変性、ウレタン変性アクリレート等の単量体及び該単量体から形成される構成単位を有する付加重合性のオリゴマー及びプレポリマーを含有することができる。 The image forming layer according to the present invention includes a phosphazene monomer, triethylene glycol, isocyanuric acid EO (ethylene oxide) modified diacrylate, isocyanuric acid EO modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane benzoic acid benzoate. Addition-polymerizable oligomers and prepolymers having monomers such as acid esters, alkylene glycol type acrylic acid-modified, urethane-modified acrylates, and structural units formed from the monomers can be contained.
　更に、本発明に併用可能なエチレン性単量体として、少なくとも一つの（メタ）アクリロイル基を含有する燐酸エステル化合物が挙げられる。該化合物は燐酸の水酸基の少なくとも一部がエステル化された化合物であり、しかも（メタ）アクリロイル基を有する限り特に限定はされない。 Furthermore, examples of the ethylenic monomer that can be used in combination with the present invention include a phosphoric ester compound containing at least one (meth) acryloyl group. The compound is not particularly limited as long as at least a part of the hydroxyl group of phosphoric acid is esterified and has a (meth) acryloyl group.
　その他に、特開昭５８－２１２９９４号、同６１－６６４９号、同６２－４６６８８号、同６２－４８５８９号、同６２－１７３２９５号、同６２－１８７０９２号、同６３－６７１８９号、特開平１－２４４８９１号の各公報等に記載の化合物などを挙げることができ、更に「１１２９０の化学商品」化学工業日報社、ｐ．２８６～ｐ．２９４に記載の化合物、「ＵＶ・ＥＢ硬化ハンドブック（原料編）」高分子刊行会、ｐ．１１～６５に記載の化合物なども本発明においては好適に用いることができる。これらの中で、分子内に２以上のアクリル基またはメタクリル基を有する化合物が本発明においては好ましく、更に分子量が１０，０００以下、より好ましくは５，０００以下のものが好ましい。 In addition, JP 58-212994, 61-6649, 62-46688, 62-48589, 62-173295, 62-187092, 63-67189, JP-A 1 -244891 publications, etc., and "11290 Chemical Products", Chemical Industry Daily, p. 286-p. 294, “UV / EB Curing Handbook (raw material)”, Kobunshi Publishing Co., p. The compounds described in 11 to 65 can also be suitably used in the present invention. Of these, compounds having two or more acrylic groups or methacryl groups in the molecule are preferred in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are preferred.
　また、本発明に係る画像形成層には、三級アミンモノマーである分子内に三級アミノ基を含有する付加重合可能なエチレン性二重結合含有化合物を使用することが好ましい。構造上の限定は特にないが、水酸基を有する三級アミン化合物をグリシジルメタクリレート、メタクリル酸クロリド、アクリル酸クロリド等で変性したものが好ましく用いられる。具体的には、特開平１－１６５６１３号、同１－２０３４１３号、同１－１９７２１３号の各公報に記載の重合可能な化合物が好ましく用いられる。 In the image forming layer according to the present invention, it is preferable to use an addition-polymerizable ethylenic double bond-containing compound containing a tertiary amino group in the molecule which is a tertiary amine monomer. Although there is no particular limitation on the structure, a tertiary amine compound having a hydroxyl group modified with glycidyl methacrylate, methacrylic acid chloride, acrylic acid chloride or the like is preferably used. Specifically, polymerizable compounds described in JP-A-1-165613, 1-203413 and 1-1197213 are preferably used.
　更に本発明では、三級アミンモノマーである、分子内に三級アミノ基を含有する多価アルコール、ジイソシアネート化合物、及び分子内にヒドロキシル基と付加重合可能なエチレン性二重結合を含有する化合物の反応生成物を使用することが好ましい。 Furthermore, in the present invention, a tertiary amine monomer, a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule are used. It is preferred to use a reaction product.
　ここで言う分子内に三級アミノ基を含有する多価アルコールとしては、例えば、トリエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン、Ｎ－ｎ－ブチルジエタノールアミン、Ｎ－ｔ－ブチルジエタノールアミン、Ｎ，Ｎ－ジ（ヒドロキシエチル）アニリン、Ｎ，Ｎ，Ｎ′，Ｎ′－テトラ－２－ヒドロキシプロピルエチレンジアミン、ｐ－トリルジエタノールアミン、Ｎ，Ｎ，Ｎ′，Ｎ′－テトラ－２－ヒドロキシエチルエチレンジアミン、Ｎ，Ｎ－ビス（２－ヒドロキシプロピル）アニリン、アリルジエタノールアミン、３－（ジメチルアミノ）－１，２－プロパンジオール、３－ジエチルアミノ－１，２－プロパンジオール、Ｎ，Ｎ－ジ（ｎ－プロピル）アミノ－２，３－プロパンジオール、Ｎ，Ｎ－ジ（ｉｓｏ－プロピル）アミノ－２，３－プロパンジオール、３－（Ｎ－メチル－Ｎ－ベンジルアミノ）－１，２－プロパンジオール等が挙げられるが、これに限定されない。 Examples of the polyhydric alcohol containing a tertiary amino group in the molecule include triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, N , N-di (hydroxyethyl) aniline, N, N, N ′, N′-tetra-2-hydroxypropylethylenediamine, p-tolyldiethanolamine, N, N, N ′, N′-tetra-2-hydroxyethylethylenediamine N, N-bis (2-hydroxypropyl) aniline, allyldiethanolamine, 3- (dimethylamino) -1,2-propanediol, 3-diethylamino-1,2-propanediol, N, N-di (n- Propyl) amino-2,3-propanediol, N, N- (An iso-propyl) amino-2,3-propanediol, 3- (N-methyl--N- benzylamino) -1,2-propane diol, and the like, but is not limited thereto.
　ジイソシアネート化合物としては、例えば、ブタン－１，４－ジイソシアネート、ヘキサン－１，６－ジイソシアネート、２－メチルペンタン－１，５－ジイソシアネート、オクタン－１，８－ジイソシアネート、１，３－ジイソシアナートメチル－シクロヘキサノン、２，２，４－トリメチルヘキサン－１，６－ジイソシアネート、イソホロンジイソシアネート、１，２－フェニレンジイソシアネート、１，３－フェニレンジイソシアネート、１，４－フェニレンジイソシアネート、トリレン－２，４－ジイソシアネート、トリレン－２，５－ジイソシアネート、トリレン－２，６－ジイソシアネート、１，３－ジ（イソシアナートメチル）ベンゼン、１，３－ビス（１－イソシアナート－１－メチルエチル）ベンゼン等が挙げられるが、これに限定されない。 Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexane-1,6-diisocyanate, 2-methylpentane-1,5-diisocyanate, octane-1,8-diisocyanate, and 1,3-diisocyanate methyl. -Cyclohexanone, 2,2,4-trimethylhexane-1,6-diisocyanate, isophorone diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene-2,4-diisocyanate, Examples include tolylene-2,5-diisocyanate, tolylene-2,6-diisocyanate, 1,3-di (isocyanatomethyl) benzene, 1,3-bis (1-isocyanato-1-methylethyl) benzene. But it is not limited to this.
　分子内にヒドロキシル基と付加重合可能なエチレン性二重結合とを含有する化合物としては、例えば、２－ヒドロキシエチルメタクリレート、２－ヒドロキシエチルアクリレート、４－ヒドロキシブチルアクリレート、２－ヒドロキシプロピレン－１，３－ジメタクリレート、２－ヒドロキシプロピレン－１－メタクリレート－３－アクリレート等が挙げられる。 Examples of the compound containing a hydroxyl group and addition-polymerizable ethylenic double bond in the molecule include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropylene-1, Examples include 3-dimethacrylate and 2-hydroxypropylene-1-methacrylate-3-acrylate.
　以下に、分子内に三級アミノ基を含有する多価アルコール、ジイソシアネート化合物、及び分子内にヒドロキシル基と付加重合可能なエチレン性二重結合を含有する化合物の具体例を、下記の化合物を原料とする反応生成物として示す。これらの反応は、通常のジオール化合物、ジイソシアネート化合物、ヒドロキシル基含有アクリレート化合物の反応で、ウレタンアクリレートを合成する方法と同様に行うことができる。 Specific examples of a polyhydric alcohol containing a tertiary amino group in the molecule, a diisocyanate compound, and a compound containing an ethylenic double bond capable of addition polymerization with a hydroxyl group in the molecule are as follows. As a reaction product. These reactions can be carried out in the same manner as the method of synthesizing urethane acrylate by the reaction of a normal diol compound, diisocyanate compound, and hydroxyl group-containing acrylate compound.
　Ｍ－１：トリエタノールアミン（１モル）、ヘキサン－１，６－ジイソシアネート（３モル）、２－ヒドロキシエチルメタクリレート（３モル）の反応生成物
　Ｍ－２：トリエタノールアミン（１モル）、イソホロンジイソシアネート（３モル）、２－ヒドロキシエチルアクリレート（３モル）の反応生成物
　Ｍ－３：Ｎ－ｎ－ブチルジエタノールアミン（１モル）、１，３－ビス（１－イソシアナート－１－メチルエチル）ベンゼン（２モル）、２－ヒドロキシプロピレン－１－メタクリレート－３－アクリレート（２モル）の反応生成物
　Ｍ－４：Ｎ－ｎ－ブチルジエタノールアミン（１モル）、１，３－ジ（イソシアナートメチル）ベンゼン（２モル）、２－ヒドロキシプロピレン－１－メタクリレート－３－アクリレート（２モル）の反応生成物
　Ｍ－５：Ｎ－メチルジエタノールアミン（１モル）、トリレン－２，４－ジイソシアネート（２モル）、２－ヒドロキシプロピレン－１，３－ジメタクリレート（２モル）の反応生成物。 M-1: Reaction product of triethanolamine (1 mol), hexane-1,6-diisocyanate (3 mol), 2-hydroxyethyl methacrylate (3 mol) M-2: Triethanolamine (1 mol), isophorone Reaction product of diisocyanate (3 mol) and 2-hydroxyethyl acrylate (3 mol) M-3: Nn-butyldiethanolamine (1 mol), 1,3-bis (1-isocyanato-1-methylethyl) Reaction product of benzene (2 mol) and 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) M-4: Nn-butyldiethanolamine (1 mol), 1,3-di (isocyanatomethyl) ) Reaction of benzene (2 mol), 2-hydroxypropylene-1-methacrylate-3-acrylate (2 mol) The product M-5: N-methyldiethanolamine (1 mole), tolylene-2,4-diisocyanate (2 moles), 2-hydroxypropylene-1,3-dimethacrylate reaction product of (2 moles).
　この他にも、特開平１－１０５２３８号、同２－１２７４０４号の各公報に記載のアクリレートまたはアルキルアクリレートが用いることができる。 In addition, acrylates or alkyl acrylates described in JP-A-1-105238 and JP-A-2-127404 can be used.
　（Ｂ）光重合開始剤組成物）
　本発明に係る光重合開始剤組成物は、画像露光により重合性モノマーの重合を開始し得るものであり、光重合開始剤組成物としてビスイミダゾール化合物を含有することが好ましく、ヘキサアリールビイミダゾール化合物を含有することがより好ましい。 (B) Photopolymerization initiator composition)
The photopolymerization initiator composition according to the present invention is capable of initiating polymerization of a polymerizable monomer by image exposure, and preferably contains a bisimidazole compound as a photopolymerization initiator composition, and a hexaarylbiimidazole compound. It is more preferable to contain.
　本発明において用いられるヘキサアリールビイミダゾール（ＨＡＢＩ、トリアリール－イミダゾールの二量体）化合物類の製造方法は、西独国特許第１，４７０，１５４号明細書に記載されており、そして光重合可能な組成物中でのそれらの使用は欧州特許第２４，６２９号、欧州特許第１０７，７９２号、米国特許第４，４１０，６２１号、欧州特許第２１５，４５３号及び西独国特許第３，２１１，３１２号の各明細書に記述されている。 The process for producing hexaarylbiimidazole (HABI, triaryl-imidazole dimer) compounds used in the present invention is described in West German Patent 1,470,154 and is photopolymerizable. Their use in such compositions is described in European Patent No. 24,629, European Patent No. 107,792, US Pat. No. 4,410,621, European Patent No. 215,453 and German Patent No. 3, It is described in each specification of No. 211,312.
　例えば、２，４，５，２′，４′，５′－ヘキサフェニルビイミダゾール、２，２′－ビス（２－クロロフェニル）－４，５，４′，５′－テトラフェニルビイミダゾール、２，２′－ビス（２－ブロモフェニル）－４，５，４′，５′－テトラフェニルビイミダゾール、２，２′－ビス（２，４－ジクロロフェニル）－４，５，４′，５′－テトラフェニルビイミダゾール、２，２′－ビス（２－クロロフェニル）－４，５，４′，５′－テトラキス（３－メトキシフェニル）ビイミダゾール、２，２′－ビス（２－クロロフェニル）－４，５，４′，５′－テトラキス（３，４，５－トリメトキシフェニル）－ビイミダゾール、２，５，２′，５′－テトラキス（２－クロロフェニル）－４，４′－ビス（３，４－ジメトキシフェニル）ビイミダゾール、２，２′－ビス（２，６－ジクロロフェニル）－４，５，４′，５′－テトラフェニルビイミダゾール、２，２′－ビス（２－ニトロフェニル）－４，５，４′，５′－テトラフェニルビイミダゾール、２，２′－ジ－ｏ－トリル－４，５，４′，５′－テトラフェニルビイミダゾール、２，２′－ビス（２－エトキシフェニル）－４，５，４′，５′－テトラフェニルビイミダゾール及び２，２′－ビス（２，６－ジフルオロフェニル）－４，５，４′，５′－テトラフェニルビイミダゾール等を挙げることができる。 For example, 2,4,5,2 ′, 4 ′, 5′-hexaphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenylbiimidazole, 2 , 2'-bis (2-bromophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4', 5 ' -Tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetrakis (3-methoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl)- 4,5,4 ', 5'-tetrakis (3,4,5-trimethoxyphenyl) -biimidazole, 2,5,2', 5'-tetrakis (2-chlorophenyl) -4,4'-bis ( 3,4-dimethoxyphenyl Biimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2-nitrophenyl) -4,5,4 ', 5'-tetraphenylbiimidazole, 2,2'-di-o-tolyl-4,5,4', 5'-tetraphenylbiimidazole, 2,2'-bis (2-ethoxyphenyl) -4 , 5,4 ', 5'-tetraphenylbiimidazole, 2,2'-bis (2,6-difluorophenyl) -4,5,4', 5'-tetraphenylbiimidazole, and the like.
　本発明においては、重合開始剤として、ヘキサアリールビイミダゾールに加えて他種の重合開始剤を併用することもできる。例えば、チタノセン化合物、モノアルキルトリアリールボレート化合物、鉄アレーン錯体化合物、ポリハロゲン化合物が好ましく用いられる。 In the present invention, as a polymerization initiator, other types of polymerization initiators can be used in combination with hexaarylbiimidazole. For example, titanocene compounds, monoalkyltriaryl borate compounds, iron arene complex compounds, and polyhalogen compounds are preferably used.
　チタノセン化合物としては、特開昭６３－４１４８３号、特開平２－２９１号の各公報に記載される化合物等が挙げられ、具体例としては、ビス（シクロペンタジエニル）－Ｔｉ－ジ－クロライド、ビス（シクロペンタジエニル）－Ｔｉ－ビス－フェニル、ビス（シクロペンタジエニル）－Ｔｉ－ビス－２，３，４，５，６－ペンタフルオロフェニル、ビス（シクロペンタジエニル）－Ｔｉ－ビス－２，３，５，６－テトラフルオロフェニル、ビス（シクロペンタジエニル）－Ｔｉ－ビス－２，４，６－トリフルオロフェニル、ビス（シクロペンタジエニル）－Ｔｉ－ビス－２，６－ジフルオロフェニル、ビス（シクロペンタジエニル）－Ｔｉ－ビス－２，４－ジフルオロフェニル、ビス（メチルシクロペンタジエニル）－Ｔｉ－ビス－２，３，４，５，６－ペンタフルオロフェニル、ビス（メチルシクロペンタジエニル）－Ｔｉ－ビス－２，３，５，６－テトラフルオロフェニル、ビス（メチルシクロペンタジエニル）－Ｔｉ－ビス－２，６－ジフルオロフェニル（ＩＲＧＡＣＵＲＥ７２７Ｌ：チバ・ジャパン製）、ビス（シクロペンタジエニル）－ビス（２，６－ジフルオロ－３－（ピリ－１－イル）フェニル）チタニウム（ＩＲＧＡＣＵＲＥ７８４：チバ・ジャパン製）、ビス（シクロペンタジエニル）－ビス（２，４，６－トリフルオロ－３－（ピリ－１－イル）フェニル）チタニウムビス（シクロペンタジエニル）－ビス（２，４，６－トリフルオロ－３－（２－５－ジメチルピリ－１－イル）フェニル）チタニウム等が挙げられる。 Examples of the titanocene compound include compounds described in JP-A-63-41483 and JP-A-2-291. Specific examples include bis (cyclopentadienyl) -Ti-di-chloride. Bis (cyclopentadienyl) -Ti-bis-phenyl, bis (cyclopentadienyl) -Ti-bis-2,3,4,5,6-pentafluorophenyl, bis (cyclopentadienyl) -Ti -Bis-2,3,5,6-tetrafluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4,6-trifluorophenyl, bis (cyclopentadienyl) -Ti-bis-2 , 6-Difluorophenyl, bis (cyclopentadienyl) -Ti-bis-2,4-difluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2 3,4,5,6-pentafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis-2,3,5,6-tetrafluorophenyl, bis (methylcyclopentadienyl) -Ti-bis- 2,6-difluorophenyl (IRGACURE727L: manufactured by Ciba Japan), bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium (IRGACURE784: manufactured by Ciba Japan) ), Bis (cyclopentadienyl) -bis (2,4,6-trifluoro-3- (pyridin-1-yl) phenyl) titanium bis (cyclopentadienyl) -bis (2,4,6-tri And fluoro-3- (2-5-dimethylpyridinyl) phenyl) titanium.
　モノアルキルトリアリールボレート化合物としては、特開昭６２－１５０２４２号、同６２－１４３０４４号の各公報に記載される化合物等挙げられ、具体例としては、テトラ－ｎ－ブチルアンモニウム・ｎ－ブチル－トリナフタレン－１－イル－ボレート、テトラ－ｎ－ブチルアンモニウム・ｎ－ブチル－トリフェニル－ボレート、テトラ－ｎ－ブチルアンモニウム・ｎ－ブチル－トリ－（４－ｔ－ブチルフェニル）－ボレート、テトラ－ｎ－ブチルアンモニウム・ｎ－ヘキシル－トリ－（３－クロロ－４－メチルフェニル）－ボレート、テトラ－ｎ－ブチルアンモニウム・ｎ－ヘキシル－トリ－（３－フルオロフェニル）－ボレート等が挙げられる。 Examples of the monoalkyl triaryl borate compound include compounds described in JP-A Nos. 62-150242 and 62-143044, and specific examples thereof include tetra-n-butylammonium / n-butyl- Trinaphthalen-1-yl-borate, tetra-n-butylammonium / n-butyl-triphenyl-borate, tetra-n-butylammonium / n-butyl-tri- (4-t-butylphenyl) -borate, tetra -N-butylammonium · n-hexyl-tri- (3-chloro-4-methylphenyl) -borate, tetra-n-butylammonium · n-hexyl-tri- (3-fluorophenyl) -borate, etc. .
　鉄アレーン錯体化合物としては、特開昭５９－２１９３０７号公報に記載される化合物等挙げられ、具体例としては、η－ベンゼン－（η－シクロペンタジエニル）鉄ヘキサフルオロホスフェート、η－クメン－（η－シクロペンタジエニル）鉄ヘキサフルオロホスフェート、η－フルオレン－（η－シクロペンタジエニル）鉄ヘキサフルオロホスフェート、η－ナフタレン－（η－シクロペンタジエニル）鉄ヘキサフルオロホスフェート、η－キシレン－（η－シクロペンタジエニル）鉄ヘキサフルオロホスフェート、η－ベンゼン－（η－シクロペンタジエニル）鉄テトラフルオロボレート等が挙げられる。 Examples of the iron arene complex compound include compounds described in JP-A-59-219307, and specific examples include η-benzene- (η-cyclopentadienyl) iron hexafluorophosphate, η-cumene- (Η-cyclopentadienyl) iron hexafluorophosphate, η-fluorene- (η-cyclopentadienyl) iron hexafluorophosphate, η-naphthalene- (η-cyclopentadienyl) iron hexafluorophosphate, η-xylene -(Η-cyclopentadienyl) iron hexafluorophosphate, η-benzene- (η-cyclopentadienyl) iron tetrafluoroborate, and the like.
　ポリハロゲン化合物としては、トリハロゲンメチル基、ジハロゲンメチル基またはジハロゲンメチレン基を有する化合物が好ましく用いられ、特に、下記一般式（ＰＩＨ１）で表されるハロゲン化合物及び上記基がオキサジアゾール環に置換した化合物が好ましく用いられる。この中でも、更に下記一般式（ＰＩＨ２）で表されるハロゲン化合物が特に好ましく用いられる。 As the polyhalogen compound, a compound having a trihalogenmethyl group, a dihalogenmethyl group or a dihalomethylene group is preferably used, and in particular, the halogen compound represented by the following general formula (PIH1) and the above group are substituted on the oxadiazole ring. The compound obtained is preferably used. Among these, a halogen compound represented by the following general formula (PIH2) is particularly preferably used.
　一般式（ＰＩＨ１）
　　　Ｒ１－ＣＹ２－（Ｃ＝Ｏ）－Ｒ２
　式中、Ｒ１は水素原子、ハロゲン原子、アルキル基、アリール基、アシル基、アルキルスルホニル基、アリールスルホニル基、イミノスルホニル基またはシアノ基を表す。Ｒ２は一価の置換基を表す。Ｒ１とＲ２が結合して環を形成しても構わない。Ｙ２はハロゲン原子を表す。 General formula (PIH1)
R 1 —CY 2 — (C═O) —R 2
In the formula, R 1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an iminosulfonyl group, or a cyano group. R 2 represents a monovalent substituent. R 1 and R 2 may combine to form a ring. Y 2 represents a halogen atom.
　一般式（ＰＩＨ２）
　　　ＣＹ３－（Ｃ＝Ｏ）－Ｘ－Ｒ３
　式中、Ｒ３は一価の置換基を表す。Ｘは－Ｏ－または－ＮＲ４－を表す。Ｒ４は水素原子またはアルキル基を表す。Ｒ３とＲ４が結合して環を形成しても構わない。Ｙ３はハロゲン原子を表す。これらの中でも、特に、ポリハロゲンアセチルアミド基を有するものが好ましく用いられる。 General formula (PIH2)
CY 3 — (C═O) —XR 3
In the formula, R 3 represents a monovalent substituent. X represents —O— or —NR 4 —. R 4 represents a hydrogen atom or an alkyl group. R 3 and R 4 may be bonded to form a ring. Y 3 represents a halogen atom. Among these, those having a polyhalogen acetylamide group are particularly preferably used.
　また、ポリハロゲンメチル基がオキサジアゾール環に置換した化合物も好ましく用いられる。更に、特開平５－３４９０４号、同－４５８７５号、同８－２４０９０９号の各公報に記載のオキサジアゾール化合物も好ましく用いられる。 In addition, compounds in which a polyhalogen methyl group is substituted with an oxadiazole ring are also preferably used. Furthermore, oxadiazole compounds described in JP-A-5-34904, JP-A-45875 and JP-A-8-240909 are also preferably used.
　ビイミダゾール化合物はビイミダゾールの誘導体であり、例えば、特開２００３－２９５４２６号公報に記載される化合物等が挙げられる。 The biimidazole compound is a derivative of biimidazole, and examples thereof include compounds described in JP-A No. 2003-295426.
　その他に任意の光重合開始剤の併用が可能である。例えば、Ｊ．コーサー（Ｊ．Ｋｏｓａｒ）著「ライト・センシテイブ・システムズ」第５章に記載されるようなカルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾ並びにジアゾ化合物、ハロゲン化合物、光還元性色素などが挙げられる。更に具体的な化合物は英国特許第１，４５９，５６３号明細書に開示されている。 Other optional photopolymerization initiators can be used in combination. For example, J. et al. Carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo, diazo compounds, halogen compounds, and photoreductive dyes as described in Chapter 5 of “Light Sensitive Systems” by J. Kosar Etc. More specific compounds are disclosed in GB 1,459,563.
　即ち、併用が可能な光重合開始剤としては、次のようなものを使用することができる。 That is, as a photopolymerization initiator that can be used in combination, the following can be used.
　例えば、ベンゾインメチルエーテル、ベンゾイン－ｉ－プロピルエーテル、α，α－ジメトキシ－α－フェニルアセトフェノン等のベンゾイン誘導体；ベンゾフェノン、２，４－ジクロロベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４，４′－ビス（ジメチルアミノ）ベンゾフェノン等のベンゾフェノン誘導体；２－クロロチオキサントン、２－ｉ－プロピルチオキサントン等のチオキサントン誘導体；２－クロロアントラキノン、２－メチルアントラキノン等のアントラキノン誘導体；Ｎ－メチルアクリドン、Ｎ－ブチルアクリドン等のアクリドン誘導体；α，α－ジエトキシアセトフェノン、ベンジル、フルオレノン、キサントン、ウラニル化合物の他、特公昭５９－１２８１号、同６１－９６２１号並びに特開昭６０－６０１０４号の各公報記載のトリアジン誘導体；特開昭５９－１５０４号、同６１－２４３８０７号の各公報記載の有機過酸化物；特公昭４３－２３６８４号、同４４－６４１３号、同４４－６４１３号、同４７－１６０４号の各公報並びに米国特許第３，５６７，４５３号明細書記載のジアゾニウム化合物；米国特許第２，８４８，３２８号、同２，８５２，３７９号並びに同２，９４０，８５３号の各明細書記載の有機アジド化合物；特公昭３６－２２０６２ｂ号、同３７－１３１０９号、同３８－１８０１５号並びに同４５－９６１０号の各公報記載のｏ－キノンジアジド類；特公昭５５－３９１６２号、特開昭５９－１４０２３号の各公報並びに「マクロモレキュルス（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ）」１０巻，１３０７頁（１９７７年）記載の各種オニウム化合物；特開昭５９－１４２２０５号公報記載のアゾ化合物；特開平１－５４４４０号公報、欧州特許第１０９，８５１号、同１２６，７１２号の各明細書並びに「ジャーナル・オブ・イメージング・サイエンス（Ｊ．Ｉｍａｇ．Ｓｃｉ．）」３０巻，１７４頁（１９８６年）記載の金属アレーン錯体；特開平５－２１３８９１号号、同５－２５５３４７号の各公報記載の（オキソ）スルホニウム有機硼素錯体；「コーディネーション・ケミストリー・レビュー（Ｃｏｏｒｄｉｎａｔｉｏｎ　Ｃｈｅｍｉｓｔｒｙ　Ｒｅｖｉｅｗ）」８４巻，８５～２７７頁（１９８８年）並びに特開平２－１８２７０１号公報記載のルテニウム等の遷移金属を含有する遷移金属錯体；特開平３－２０９４７７号公報記載の２，４，５－トリアリールイミダゾール二量体；四臭化炭素、特開昭５９－１０７３４４号公報記載の有機ハロゲン化合物等が挙げられる。 For example, benzoin derivatives such as benzoin methyl ether, benzoin-i-propyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis Benzophenone derivatives such as (dimethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-i-propylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methylacridone and N-butylacrylic Acridone derivatives such as dong; α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, Japanese Patent Publication Nos. 59-1281, 61-9621, and JP-A-60-60104 Triazine derivatives described in JP-A-59-1504 and JP-A-61-243807; JP-B-43-23684, JP-A-44-6413, JP-A-44-6413 Nos. 47-1604 and U.S. Pat. No. 3,567,453; diazonium compounds; U.S. Pat. Nos. 2,848,328, 2,852,379 and 2,940,853. No. 36-22062b, 37-13109, 38-18015 and 45-9610, o-quinonediazides described in JP-B Nos. 36-22062b, 45-9610; No. 1, JP-A-59-14023 and “Macromolecules”, Vol. 10, p. 1307 (1977) Various onium compounds; azo compounds described in JP-A-59-142205; JP-A-1-54440, European Patent Nos. 109,851 and 126,712, and “Journal of Imaging” • Metal arene complexes described in Science (J. Imag. Sci.), 30, 174 (1986); (oxo) sulfonium organoboron described in JP-A Nos. 5-213891 and 5-255347 Complex; transition metal complex containing transition metal such as ruthenium described in “Coordination Chemistry Review”, 84, 85-277 (1988) and JP-A-2-182701; -2,4,5-trio described in JP-A-209477 Reel imidazole dimer; carbon tetrabromide, organic halogen compounds in JP 59-107344 JP, and the like.
　本発明に係る光重合開始剤の含有量（光重合開始剤の総量）は、重合性モノマーに対して、０．１～２０質量％が好ましく、０．５～１５質量％が特に好ましい。 The content of the photopolymerization initiator according to the present invention (total amount of photopolymerization initiator) is preferably from 0.1 to 20% by mass, particularly preferably from 0.5 to 15% by mass, based on the polymerizable monomer.
　（Ｃ）高分子結合材）
　本発明に係る高分子結合材は、画像形成層に含まれる成分をアルミニウム支持体上に担持し得るものであり、高分子結合材としては、例えば、アクリル系重合体、ポリビニルブチラール樹脂、ポリウレタン樹脂、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、ポリカーボネート樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、シェラック、その他の天然樹脂等が使用できる。また、これらを２種以上併用しても構わない。 (C) Polymer binder)
The polymer binder according to the present invention is capable of supporting the components contained in the image forming layer on an aluminum support. Examples of the polymer binder include acrylic polymers, polyvinyl butyral resins, and polyurethane resins. Polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, and other natural resins can be used. Two or more of these may be used in combination.
　好ましくは、アクリル系のモノマーの共重合によって得られるビニル系共重合である。更に、高分子結合材の共重合組成として、（ａ）カルボキシル基含有モノマー、（ｂ）メタクリル酸アルキルエステル、またはアクリル酸アルキルエステルの共重合体であることが好ましい。 Preferably, it is a vinyl copolymer obtained by copolymerization of an acrylic monomer. Furthermore, the copolymer composition of the polymer binder is preferably a copolymer of (a) carboxyl group-containing monomer, (b) methacrylic acid alkyl ester, or acrylic acid alkyl ester.
　カルボキシル基含有モノマーの具体例としては、α，β－不飽和カルボン酸類、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸等が挙げられる。その他、フタル酸と２－ヒドロキシメタクリレートのハーフエステル等のカルボン酸も好ましい。 Specific examples of the carboxyl group-containing monomer include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and the like. In addition, carboxylic acids such as phthalic acid and 2-hydroxymethacrylate half ester are also preferred.
　メタクリル酸アルキルエステル、アクリル酸アルキルエステルの具体例としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸アミル、メタクリル酸ヘキシル、メタクリル酸ヘプチル、メタクリル酸オクチル、メタクリル酸ノニル、メタクリル酸デシル、メタクリル酸ウンデシル、メタクリル酸ドデシル、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸アミル、アクリル酸ヘキシル、アクリル酸ヘプチル、アクリル酸オクチル、アクリル酸ノニル、アクリル酸デシル、アクリル酸ウンデシル、アクリル酸ドデシル等の無置換アルキルエステルの他、メタクリル酸シクロヘキシル、アクリル酸シクロヘキシル等の環状アルキルエステルや、メタクリル酸ベンジル、メタクリル酸－２－クロロエチル、Ｎ，Ｎ－ジメチルアミノエチルメタクリレート、グリシジルメタクリレート、アクリル酸ベンジル、アクリル酸－２－クロロエチル、Ｎ，Ｎ－ジメチルアミノエチルアクリレート、グリシジルアクリレート等の置換アルキルエステルが挙げられる。 Specific examples of alkyl methacrylates and alkyl esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate. , Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, acrylic Cyclic alkyl esters such as cyclohexyl methacrylate and cyclohexyl acrylate, in addition to unsubstituted alkyl esters such as decyl acid, undecyl acrylate, and dodecyl acrylate Substituted alkyl such as benzyl methacrylate, 2-chloroethyl methacrylate, N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, benzyl acrylate, 2-chloroethyl acrylate, N, N-dimethylaminoethyl acrylate, glycidyl acrylate, etc. Examples include esters.
　更に高分子結合材は、共重合モノマーとして、下記に示す１）～１４）に記載のモノマー等を用いることができる。 Further, in the polymer binder, the monomers described in 1) to 14) shown below can be used as copolymerization monomers.
　１）芳香族水酸基を有するモノマー、例えば、ｏ－（またはｐ－，ｍ－）ヒドロキシスチレン、ｏ－（またはｐ－、ｍ－）ヒドロキシフェニルアクリレート等
　２）脂肪族水酸基を有するモノマー、例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、４－ヒドロキシブチルメタクリレート、５－ヒドロキシペンチルアクリレート、５－ヒドロキシペンチルメタクリレート、６－ヒドロキシヘキシルアクリレート、６－ヒドロキシヘキシルメタクリレート、Ｎ－（２－ヒドロキシエチル）アクリルアミド、Ｎ－（２－ヒドロキシエチル）メタクリルアミド、ヒドロキシエチルビニルエーテル等
　３）アミノスルホニル基を有するモノマー、例えば、ｍ－（またはｐ－）アミノスルホニルフェニルメタクリレート、ｍ－（またはｐ－）アミノスルホニルフェニルアクリレート、Ｎ－（ｐ－アミノスルホニルフェニル）メタクリルアミド、Ｎ－（ｐ－アミノスルホニルフェニル）アクリルアミド等
　４）スルホンアミド基を有するモノマー、例えば、Ｎ－（ｐ－トルエンスルホニル）アクリルアミド、Ｎ－（ｐ－トルエンスルホニル）メタクリルアミド等
　５）アクリルアミドまたはメタクリルアミド類、例えば、アクリルアミド、メタクリルアミド、Ｎ－エチルアクリルアミド、Ｎ－ヘキシルアクリルアミド、Ｎ－シクロヘキシルアクリルアミド、Ｎ－フェニルアクリルアミド、Ｎ－（４－ニトロフェニル）アクリルアミド、Ｎ－エチル－Ｎ－フェニルアクリルアミド、Ｎ－（４－ヒドロキシフェニル）アクリルアミド、Ｎ－（４－ヒドロキシフェニル）メタクリルアミド等
　６）弗化アルキル基を含有するモノマー、例えば、トリフルオロエチルアクリレート、トリフルオロエチルメタクリレート、テトラフルオロプロピルメタクリレート、ヘキサフルオロプロピルメタクリレート、オクタフルオロペンチルアクリレート、オクタフルオロペンチルメタクリレート、ヘプタデカフルオロデシルメタクリレート、Ｎ－ブチル－Ｎ－（２－アクリロキシエチル）ヘプタデカフルオロオクチルスルホンアミド等。 1) Monomers having an aromatic hydroxyl group, such as o- (or p-, m-) hydroxystyrene, o- (or p-, m-) hydroxyphenyl acrylate, etc. 2) Monomers having an aliphatic hydroxyl group, such as 2 -Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 4-hydroxybutyl methacrylate, 5-hydroxypentyl acrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl Methacrylate, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, hydroxyethyl vinyl ether, etc. 3) Monomer having an aminosulfonyl group, eg For example, m- (or p-) aminosulfonylphenyl methacrylate, m- (or p-) aminosulfonylphenyl acrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) acrylamide, etc. 4 ) Monomers having sulfonamide groups such as N- (p-toluenesulfonyl) acrylamide, N- (p-toluenesulfonyl) methacrylamide 5) Acrylamide or methacrylamides such as acrylamide, methacrylamide, N-ethylacrylamide N-hexylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (4-nitrophenyl) acrylamide, N-ethyl-N-phenylacrylamide, N- (4-hydro Siphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, etc. 6) Monomers containing alkyl fluoride groups such as trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluoropropyl methacrylate, octafluoro Pentyl acrylate, octafluoropentyl methacrylate, heptadecafluorodecyl methacrylate, N-butyl-N- (2-acryloxyethyl) heptadecafluorooctylsulfonamide and the like.
　７）ビニルエーテル類、例えば、エチルビニルエーテル、２－クロロエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、オクチルビニルエーテル、フェニルビニルエーテル等
　８）ビニルエステル類、例えば、ビニルアセテート、ビニルクロロアセテート、ビニルブチレート、安息香酸ビニル等
　９）スチレン類、例えば、スチレン、メチルスチレン、クロロメチルスチレン等
　１０）ビニルケトン類、例えば、メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトン等
　１１）オレフィン類、例えば、エチレン、プロピレン、ｉ－ブチレン、ブタジエン、イソプレン等
　１２）Ｎ－ビニルピロリドン、Ｎ－ビニルカルバゾール、４－ビニルピリジン等
　１３）シアノ基を有するモノマー、例えば、アクリロニトリル、メタクリロニトリル、２－ペンテンニトリル、２－メチル－３－ブテンニトリル、２－シアノエチルアクリレート、ｏ－（またはｍ－、ｐ－）シアノスチレン等
　１４）アミノ基を有するモノマー、例えば、Ｎ，Ｎ－ジエチルアミノエチルメタクリレート、Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノエチルメタクリレート、ポリブタジエンウレタンアクリレート、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、アクリロイルモルホリン、Ｎ－ｉ－プロピルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド等。 7) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. 8) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate 9) Styrenes such as styrene, methyl styrene, chloromethyl styrene 10) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone 11) Olefins such as ethylene and propylene I-butylene, butadiene, isoprene, etc. 12) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc. 13) Monomer having a cyano group, For example, acrylonitrile, methacrylonitrile, 2-pentenenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o- (or m-, p-) cyanostyrene, etc. 14) monomers having amino groups, for example N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, polybutadiene urethane acrylate, N, N-dimethylaminopropylacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N -I-propylacrylamide, N, N-diethylacrylamide, etc.
　更にこれらのモノマーと共重合し得る他のモノマーを共重合してもよい。 Further, other monomers that can be copolymerized with these monomers may be copolymerized.
　更に、高分子結合材は、側鎖にカルボキシル基及び重合性二重結合を有するビニル系重合体であることが好ましい。例えば、上記ビニル系共重合体の分子内に存在するカルボキシル基に、分子内に（メタ）アクリロイル基とエポキシ基を有する化合物を付加反応させることによって得られる、不飽和結合含有ビニル系共重合体も高分子結合材として好ましい。 Furthermore, the polymer binder is preferably a vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain. For example, an unsaturated bond-containing vinyl copolymer obtained by addition-reacting a compound having a (meth) acryloyl group and an epoxy group in the molecule to a carboxyl group present in the molecule of the vinyl copolymer. Is also preferred as a polymer binder.
　分子内に不飽和結合とエポキシ基を共に含有する化合物としては、具体的にはグリシジルアクリレート、グリシジルメタクリレート、特開平１１－２７１９６９号公報に記載のあるエポキシ基含有不飽和化合物等が挙げられる。また、上記ビニル系重合体の分子内に存在する水酸基に、分子内に（メタ）アクリロイル基とイソシアネート基を有する化合物を付加反応させることによって得られる、不飽和結合含有ビニル系共重合体も高分子結合材として好ましい。 Specific examples of the compound containing both an unsaturated bond and an epoxy group in the molecule include glycidyl acrylate, glycidyl methacrylate, and an epoxy group-containing unsaturated compound described in JP-A No. 11-271969. Also, an unsaturated bond-containing vinyl copolymer obtained by adding a compound having a (meth) acryloyl group and an isocyanate group in the molecule to the hydroxyl group present in the molecule of the vinyl polymer is also high. Preferred as a molecular binder.
　分子内に不飽和結合とイソシアネート基を共に有する化合物としては、例えば、ビニルイソシアネート、（メタ）アクリルイソシアネート、２－（メタ）アクリロイルオキシエチルイソシアネート、ｍ－またはｐ－イソプロペニル－α，α′－ジメチルベンジルイソシアネートが好ましく、（メタ）アクリルイソシアネート、２－（メタ）アクリロイルオキシエチルイソシアネート等が挙げられる。 Examples of the compound having both an unsaturated bond and an isocyanate group in the molecule include vinyl isocyanate, (meth) acrylic isocyanate, 2- (meth) acryloyloxyethyl isocyanate, m- or p-isopropenyl-α, α'- Dimethylbenzyl isocyanate is preferred, and examples include (meth) acrylic isocyanate and 2- (meth) acryloyloxyethyl isocyanate.
　側鎖にカルボキシル基及び重合性二重結合を有するビニル系重合体は、全高分子結合材において、５０～１００質量％であることが好ましく、１００質量％であることがより好ましい。 The vinyl polymer having a carboxyl group and a polymerizable double bond in the side chain is preferably 50 to 100% by mass, more preferably 100% by mass in the total polymer binder.
　画像形成層中における高分子結合材の含有量は、１０～９０質量％の範囲が好ましく、１５～７０質量％の範囲が更に好ましく、２０～５０質量％の範囲で使用することが感度の面から特に好ましい。 The content of the polymer binder in the image forming layer is preferably in the range of 10 to 90% by mass, more preferably in the range of 15 to 70% by mass, and use in the range of 20 to 50% by mass in terms of sensitivity. Is particularly preferred.
　（分光増感剤）
　本発明に係る画像形成層は、分光増感剤として吸収極大波長が３５０～９００ｎｍ、好ましくは３５０～４５０ｎｍにある分光増感剤を含有することができ、更には吸収極大波長が３５０～４５０ｎｍにある分光増感剤を含有することが好ましい。 (Spectral sensitizer)
The image forming layer according to the present invention can contain a spectral sensitizer having a maximum absorption wavelength of 350 to 900 nm, preferably 350 to 450 nm as a spectral sensitizer, and further having an absorption maximum wavelength of 350 to 450 nm. It is preferable to contain a certain spectral sensitizer.
　当該分光増感剤としては、例えば、シアニン、メロシアニン、ポルフィリン、スピロ化合物、フェロセン、フルオレン、フルギド、イミダゾール、ペリレン、フェナジン、フェノチアジン、アクリジン、アクリドン、アゾ化合物、ジフェニルメタン、トリフェニルメタン、トリフェニルアミン、クマリン誘導体、キナクリドン、インジゴ、スチリル、ピリリウム化合物、ピロメテン化合物、ピラゾロトリアゾール化合物、ベンゾチアゾール化合部、バルビツール酸誘導体、チオバルビツール酸誘導体、ケトアルコールボレート錯体、等が挙げられる。 Examples of the spectral sensitizer include cyanine, merocyanine, porphyrin, spiro compound, ferrocene, fluorene, fulgide, imidazole, perylene, phenazine, phenothiazine, acridine, acridone, azo compound, diphenylmethane, triphenylmethane, triphenylamine, Coumarin derivatives, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, ketoalcohol borate complexes, and the like.
　上記のクマリン誘導体としては、例えば、特開平８－１２９２５８号公報のＢ－１からＢ－２２のクマリン誘導体、特開２００３－２１９０１号公報のＤ－１からＤ－３２のクマリン誘導体、特開２００２－３６３２０６号公報の１から２１のクマリン誘導体、特開２００２－３６３２０７号公報の１から４０のクマリン誘導体、特開２００２－３６３２０８号公報の１から３４のクマリン誘導体、特開２００２－３６３２０９号公報の１から５６のクマリン誘導体等が挙げられ、好ましく使用可能である。 Examples of the coumarin derivative include B-1 to B-22 coumarin derivatives of JP-A-8-129258, D-1 to D-32 coumarin derivatives of JP-A-2003-21901, and JP-A-2002. No. 1-363206 of coumarin derivatives, JP-A No. 2002-363207 No. 1 to 40 coumarin derivatives, JP-A No. 2002-363208 No. 1 to 34 coumarin derivatives, JP-A No. 2002-363209 Examples thereof include 1 to 56 coumarin derivatives and can be preferably used.
　また、他の好ましく使用できる色素としては、例えば、特開２０００－９８６０５号、同２０００－１４７７６３号、同２０００－２０６６９０号、同２０００－２５８９１０号、同２０００－３０９７２４号、同２００１－０４２５２４号、同２００２－２０２５９８号、同２０００－２２１７９０号の各公報に記載の分光増感剤等が挙げられる。 Examples of other dyes that can be preferably used include, for example, JP-A Nos. 2000-98605, 2000-147773, 2000-206690, 2000-258910, 2000-309724, 2001-042524, And spectral sensitizers described in JP-A Nos. 2002-202598 and 2000-221790.
　（各種添加剤）
　〈重合防止剤〉
　本発明に係る画像形成層には、上記各種成分の他に平版印刷版材料の製造中あるいは保存中において重合可能なエチレン性二重結合単量体の不要な重合を阻止するために、重合防止剤を添加することが望ましい。 (Various additives)
<Polymerization inhibitor>
In addition to the above-mentioned various components, the image forming layer according to the present invention is a polymerization inhibitor in order to prevent unnecessary polymerization of an ethylenic double bond monomer that can be polymerized during the production or storage of a lithographic printing plate material. It is desirable to add an agent.
　適当な重合防止剤としては、例えば、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔ－ブチルカテコール、ベンゾキノン、４，４′－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２′－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシルアミン第一セリウム塩、２－ｔ－ブチル－６－（３－ｔ－ブチル－２－ヒドロキシ－５－メチルベンジル）－４－メチルフェニルアクリレート等が挙げられる。 Suitable polymerization inhibitors include, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t -Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, 2-t-butyl-6- (3-t-butyl-2- And hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.
　重合防止剤の添加量は、画像形成層の全固形分の質量に対して０．０１～５質量％が好ましい。また、必要に応じて、酸素による重合阻害を防止するためにベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体等を添加し、塗布後の乾燥の過程で感光性層の表面に偏在させてもよい。高級脂肪酸誘導体の添加量は、全組成物の０．５～１０質量％が好ましい。 The addition amount of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the image forming layer. Also, if necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition by oxygen, and unevenly distributed on the surface of the photosensitive layer in the drying process after coating. Good. The addition amount of the higher fatty acid derivative is preferably 0.5 to 10% by mass of the total composition.
　〈着色剤〉
　また、着色剤も使用することができ、着色剤としては市販のものを含め従来公知のものが好適に使用できる。例えば、改訂新版「顔料便覧」日本顔料技術協会編（誠文堂新光社）、カラーインデックス便覧等に述べられているものが挙げられる。 <Colorant>
Moreover, a coloring agent can also be used and a conventionally well-known thing can be used conveniently as a coloring agent including a commercially available thing. For example, those described in the revised new edition “Pigment Handbook” edited by Japan Pigment Technology Association (Seikodo Shinkosha), Color Index Handbook, and the like.
　顔料の種類としては、黒色顔料、黄色顔料、赤色顔料、褐色顔料、紫色顔料、青色顔料、緑色顔料、蛍光顔料、金属粉顔料等が挙げられる。具体的には、無機顔料（二酸化チタン、カーボンブラック、グラファイト、酸化亜鉛、プルシアンブルー、硫化カドミウム、酸化鉄、並びに鉛、亜鉛、バリウム及びカルシウムのクロム酸塩等）及び有機顔料（アゾ系、チオインジゴ系、アントラキノン系、アントアンスロン系、トリフェンジオキサジン系の顔料、バット染料顔料、フタロシアニン顔料及びその誘導体、キナクリドン顔料等）が挙げられる。 Examples of pigments include black pigments, yellow pigments, red pigments, brown pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, and metal powder pigments. Specifically, inorganic pigments (titanium dioxide, carbon black, graphite, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and lead, zinc, barium and calcium chromates) and organic pigments (azo-based, thioindigo) , Anthraquinone, anthanthrone, and triphendioxazine pigments, vat dye pigments, phthalocyanine pigments and derivatives thereof, quinacridone pigments, and the like.
　これらの中でも、使用する露光レーザに対応した分光増感色素の吸収波長域に実質的に吸収を持たない顔料を選択して使用することが好ましく、この場合、使用するレーザ波長での積分球を用いた顔料の反射吸収が０．０５以下であることが好ましい。また、顔料の添加量としては、上記組成物の固形分に対し０．１～１０質量％が好ましく、より好ましくは０．２～５質量％である。 Among these, it is preferable to select and use a pigment having substantially no absorption in the absorption wavelength region of the spectral sensitizing dye corresponding to the exposure laser to be used. In this case, an integrating sphere at the laser wavelength to be used is used. It is preferable that the reflection absorption of the used pigment is 0.05 or less. The addition amount of the pigment is preferably from 0.1 to 10% by mass, more preferably from 0.2 to 5% by mass, based on the solid content of the composition.
　上記の感光波長領域での顔料吸収及び現像後の可視画性の観点から、紫色顔料、青色顔料を用いるのが好ましい。このようなものとしては、例えば、コバルトブルー、セルリアンブルー、アルカリブルーレーキ、フォナトーンブルー６Ｇ、ビクトリアブルーレーキ、無金属フタロシアニンブルー、フタロシアニンブルーファーストスカイブルー、インダンスレンブルー、インジコ、ジオキサンバイオレット、イソビオランスロンバイオレット、インダンスロンブルー、インダンスロンＢＣ等を挙げることができる。これらの中で、より好ましくはフタロシアニンブルー、ジオキサンバイオレットである。 From the viewpoints of pigment absorption in the above-mentioned photosensitive wavelength region and visible image properties after development, it is preferable to use a purple pigment or a blue pigment. Such as, for example, cobalt blue, cerulean blue, alkali blue lake, phonatone blue 6G, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue first sky blue, indanthrene blue, indico, dioxane violet, Examples include isoviolanthrone violet, indanthrone blue, and indanthrone BC. Among these, phthalocyanine blue and dioxane violet are more preferable.
　〈界面活性剤〉
　また、画像形成層は、本発明の目的効果を損なわない範囲で、界面活性剤を塗布性改良剤として含有することができる。その中でも好ましいのはフッ素系界面活性剤である。 <Surfactant>
In addition, the image forming layer can contain a surfactant as a coating property improving agent as long as the object and effects of the present invention are not impaired. Of these, fluorine-based surfactants are preferred.
　〈可塑剤〉
　また、硬化皮膜の物性を改良するために、無機充填剤やジオクチルフタレート、ジメチルフタレート、トリクレジルホスフェート等の可塑剤等の添加剤を加えてもよい。これらの添加量は全固形分の１０質量％以下が好ましい。 <Plasticizer>
In order to improve the physical properties of the cured film, additives such as an inorganic filler, a plasticizer such as dioctyl phthalate, dimethyl phthalate, and tricresyl phosphate may be added. These addition amounts are preferably 10% by mass or less based on the total solid content.
　〈溶剤〉
　また、本発明に係る画像形成層の画像形成層塗布液を調製する際に使用する溶剤としては、例えば、アルコール：多価アルコールの誘導体類では、ｓｅｃ－ブタノール、イソブタノール、ｎ－ヘキサノール、ベンジルアルコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，５－ペンタンジオール、またエーテル類：プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、またケトン類、アルデヒド類：ジアセトンアルコール、シクロヘキサノン、メチルシクロヘキサノン、またエステル類：乳酸エチル、乳酸ブチル、蓚酸ジエチル、安息香酸メチル等が好ましく挙げられる。 <solvent>
Examples of the solvent used in preparing the image forming layer coating solution of the image forming layer according to the present invention include, for example, alcohol: polyhydric alcohol derivatives: sec-butanol, isobutanol, n-hexanol, benzyl Alcohol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, and ethers: propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ketones, aldehydes: diacetone alcohol Preferred examples include cyclohexanone, methylcyclohexanone and esters: ethyl lactate, butyl lactate, diethyl oxalate, methyl benzoate and the like.
　以上画像形成層塗布液について説明したが、本発明に係る画像形成層はこれを用いて支持体上に塗設することにより構成される。 Although the image forming layer coating solution has been described above, the image forming layer according to the present invention is constituted by coating on a support using this.
　本発明に係る画像形成層は、アルミニウム支持体上の付き量としては、０．１～１０ｇ／ｍ２が好ましく、特に０．５～５ｇ／ｍ２が好ましい。 In the image forming layer according to the present invention, the weight on the aluminum support is preferably from 0.1 to 10 g / m 2 , particularly preferably from 0.5 to 5 g / m 2 .
　《酸素遮断層》
　本発明に係る画像形成層の上側には、酸素遮断及び必要に応じその他の保護的機能を備えた酸素遮断層を設けることができる。特に、重合性画像形成層を有する場合には、酸素遮断層を設けることが好ましい。 《Oxygen barrier layer》
On the upper side of the image forming layer according to the present invention, an oxygen blocking layer having an oxygen blocking function and other protective functions as required can be provided. In particular, when a polymerizable image forming layer is provided, it is preferable to provide an oxygen blocking layer.
　酸素遮断層は、前述の画像未露光部を除去する水溶液への溶解性が高いことが好ましく、そのためにはポリビニルアルコールを含有することが好ましい。ポリビニルアルコールは、酸素の透過を抑制する効果を有する。なお、隣接する画像形成層との接着性を確保する効果を有するポリビニルピロリドンを併用することが好ましい。 The oxygen blocking layer is preferably highly soluble in an aqueous solution that removes the aforementioned unexposed image portion, and for that purpose, it preferably contains polyvinyl alcohol. Polyvinyl alcohol has an effect of suppressing permeation of oxygen. In addition, it is preferable to use together polyvinyl pyrrolidone which has the effect of ensuring adhesiveness with an adjacent image forming layer.
　上記２種のポリマーの他に、必要に応じ、ポリサッカライド、ポリエチレングリコール、ゼラチン、膠、カゼイン、ヒドロキシエチルセルロース、カルボキシメチルセルロース、メチルセルロース、ヒドロキシエチル澱粉、アラビアゴム、サクローズオクタアセテート、アルギン酸アンモニウム、アルギン酸ナトリウム、ポリビニルアミン、ポリエチレンオキシド、ポリスチレンスルホン酸、ポリアクリル酸、水溶性ポリアミド等の水溶性ポリマーを併用することもできる。 In addition to the above two polymers, polysaccharides, polyethylene glycol, gelatin, glue, casein, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl starch, gum arabic, sucrose octaacetate, ammonium alginate, sodium alginate as required Water-soluble polymers such as polyvinylamine, polyethylene oxide, polystyrene sulfonic acid, polyacrylic acid, and water-soluble polyamide can also be used in combination.
　本発明の平版印刷版材料に酸素遮断層を設ける際、画像形成層と酸素遮断層間の剥離力が３５ｍＮ／ｍｍ以上であることが好ましく、より好ましくは５０ｍＮ／ｍｍ以上、更に好ましくは７５ｍＮ／ｍｍ以上である。好ましい酸素遮断層の組成としては、特開平１０－１０７４２号公報に記載されるものが挙げられる。 When an oxygen barrier layer is provided on the planographic printing plate material of the present invention, the peel force between the image forming layer and the oxygen barrier layer is preferably 35 mN / mm or more, more preferably 50 mN / mm or more, and even more preferably 75 mN / mm. That's it. Preferable oxygen barrier layer compositions include those described in JP-A-10-10742.
　本発明でいう上記剥離力は、酸素遮断層上に十分大きい粘着力を有する所定幅の粘着テープを貼り、それを平版印刷版材料の平面に対して９０度の角度で酸素遮断層と共に剥離する時の力を測定することにより求めることができる。 In the present invention, the above-mentioned peeling force is applied with an adhesive tape having a predetermined width having a sufficiently large adhesive force on the oxygen barrier layer and peeled off with the oxygen barrier layer at an angle of 90 degrees with respect to the plane of the planographic printing plate material. It can be determined by measuring the force of time.
　酸素遮断層には、更に必要に応じて界面活性剤、マット剤等を含有することができる。上記酸素遮断層組成物を適当な溶剤に溶解し、画像形成層上に塗布、乾燥して酸素遮断層を形成する。塗布溶剤の主成分は、水、あるいはメタノール、エタノール、ｉ－プロパノール等のアルコール類であることが特に好ましい。 The oxygen barrier layer can further contain a surfactant, a matting agent and the like as required. The oxygen barrier layer composition is dissolved in a suitable solvent, applied onto the image forming layer and dried to form an oxygen barrier layer. The main component of the coating solvent is particularly preferably water or alcohols such as methanol, ethanol and i-propanol.
　酸素遮断層を設ける場合、その厚みは０．１～５．０μｍが好ましく、特に好ましくは０．５～３．０μｍである。 When the oxygen barrier layer is provided, the thickness is preferably 0.1 to 5.0 μm, particularly preferably 0.5 to 3.0 μm.
　《塗布》
　上記の画像形成層塗布液、あるいは必要に応じて設ける酸素遮断層塗布液を従来公知の方法で支持体上に塗布し、乾燥し、平版印刷版材料を作製することができる。 <Application>
The above-mentioned image forming layer coating solution or an oxygen barrier layer coating solution provided as necessary can be coated on a support by a conventionally known method and dried to prepare a lithographic printing plate material.
　塗布液の塗布方法としては、例えば、エアドクタコータ法、ブレードコータ法、ワイヤーバー法、ナイフコータ法、ディップコータ法、リバースロールコータ法、グラビヤコータ法、キャストコーティング法、カーテンコータ法及び押し出しコータ法等を挙げることができる。 Examples of coating methods for the coating liquid include air doctor coater method, blade coater method, wire bar method, knife coater method, dip coater method, reverse roll coater method, gravure coater method, cast coating method, curtain coater method and extrusion coater method Etc.
　画像形成層の乾燥温度は６０～１６０℃の範囲が好ましく、より好ましくは８０～１４０℃、特に好ましくは９０～１２０℃の範囲で乾燥することが好ましい。 The drying temperature of the image forming layer is preferably 60 to 160 ° C., more preferably 80 to 140 ° C., and particularly preferably 90 to 120 ° C.
　《平版印刷版の作製》
　〔画像記録〕
　平版印刷版材料に画像露光する光源としては、例えば、レーザ光源を用いる。レーザ光源としては、アルゴンレーザ、Ｈｅ－Ｎｅガスレーザ、ＹＡＧレーザ、半導体レーザ等を何れも好適に用いることが可能である。本発明では、３５０ｎｍから９００ｎｍの領域に発光波長を有するレーザ光源を用いることができる。その中でも特に３５０ｎｍから４５０ｎｍに発光波長を有するレーザ光源が好ましく用いられる。その場合には、露光に用いるレーザ光源としては、例えば、Ｈｅ－Ｃｄレーザ（４４１ｎｍ）、固体レーザとしてＣｒ：ＬｉＳＡＦとＳＨＧ結晶の組み合わせ（４３０ｎｍ）、半導体レーザ系として、ＫＮｂＯ３、リング共振器（４３０ｎｍ）、ＡｌＧａＩｎＮ（３５０～４５０ｎｍ）、ＡｌＧａＩｎＮ半導体レーザ（市販ＩｎＧａＮ系半導体レーザ４００～４１０ｎｍ）等を挙げることができる。 << Preparation of lithographic printing plate >>
[Image recording]
As a light source for image exposure on the lithographic printing plate material, for example, a laser light source is used. As the laser light source, an argon laser, a He—Ne gas laser, a YAG laser, a semiconductor laser, or the like can be preferably used. In the present invention, a laser light source having an emission wavelength in a region from 350 nm to 900 nm can be used. Among these, a laser light source having an emission wavelength of 350 nm to 450 nm is particularly preferably used. In that case, as a laser light source used for exposure, for example, a He—Cd laser (441 nm), a combination of Cr: LiSAF and SHG crystal (430 nm) as a solid laser, KNbO 3 as a semiconductor laser system, a ring resonator ( 430 nm), AlGaInN (350 to 450 nm), AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm), and the like.
　本発明の平版印刷版材料は、レーザ露光の場合には、光をビーム状に絞り画像データに応じた走査露光が可能なので、マスク材料を使用せず、直接書込みを行うのに適している。また、レーザを光源として用いる場合には、露光面積を微小サイズに絞ることが容易であり、高解像度の画像形成が可能となる。 In the case of laser exposure, the lithographic printing plate material of the present invention is suitable for direct writing without using a mask material because light can be reduced in a beam shape and scanning exposure according to image data is possible. When a laser is used as a light source, it is easy to reduce the exposure area to a very small size, and high-resolution image formation is possible.
　レーザの走査方法としては、円筒外面走査、円筒内面走査、平面走査などがある。円筒外面走査では、記録材料を外面に巻き付けたドラムを回転させながらレーザ露光を行い、ドラムの回転を主走査としレーザ光の移動を副走査とする。円筒内面走査では、ドラムの内面に記録材料を固定し、レーザビームを内側から照射し、光学系の一部又は全部を回転させることにより円周方向に主走査を行い、光学系の一部又は全部をドラムの軸に平行に直線移動させることにより軸方向に副走査を行う。平面走査では、ポリゴンミラーやガルバノミラーとｆθレンズ等を組み合わせてレーザ光の主走査を行い、記録媒体の移動により副走査を行う。円筒外面走査及び円筒内面走査の方が光学系の精度を高め易く、高密度記録には適している。 Laser scanning methods include cylindrical outer surface scanning, cylindrical inner surface scanning, and planar scanning. In the cylindrical outer surface scanning, laser exposure is performed while rotating a drum around which the recording material is wound, and the rotation of the drum is set as main scanning, and the movement of laser light is set as sub scanning. In cylindrical inner surface scanning, a recording material is fixed to the inner surface of a drum, a laser beam is irradiated from the inside, and a main scanning is performed in the circumferential direction by rotating a part or all of the optical system. Sub scanning is performed in the axial direction by linearly moving all of them in parallel with the drum axis. In planar scanning, main scanning of laser light is performed by combining a polygon mirror or galvanometer mirror and an fθ lens, and sub scanning is performed by moving a recording medium. Cylindrical outer surface scanning and cylindrical inner surface scanning are easier to increase the accuracy of the optical system and are suitable for high-density recording.
　〔プレヒート〕
　本発明においては、平版印刷版材料に画像を露光した後、現像処理する前又は現像処理しながら平版印刷版材料を加熱処理することが好ましい。この様に加熱処理することで、画像形成層とアルミニウム支持体の接着性が向上し、本発明に係る発明の効果を向上させることができる。 [Preheat]
In the present invention, it is preferable to heat-treat the lithographic printing plate material after exposing the image to the lithographic printing plate material and before or during development. By performing the heat treatment in this manner, the adhesion between the image forming layer and the aluminum support is improved, and the effects of the invention according to the present invention can be improved.
　プレヒートは、例えば、平版印刷版材料を現像処理する自動現像装置において、現像処理時に搬走される平版印刷版材料を現像前に所定の温度範囲に加熱するプレヒートローラによる加熱する方法を挙げることができる。例えば、プレヒートローラは、内部に加熱手段を有する少なくとも１つのローラを含む１対のローラからなり、加熱手段を有するローラとしては、熱伝導率の高い金属（例えば、アルミニウム、鉄等）からなる中空パイプの内部に発熱体としてニクロム線等を埋設し、該金属パイプの外側面をポリエチレン、ポリスチレン、テフロン（登録商標）等のプラスチックシートで被覆したものを使用することができる。また、こうしたプレヒートローラの詳細については、特開昭６４－８０９６２号公報を参照することができる。 Preheating includes, for example, a method of heating with a preheating roller that heats a lithographic printing plate material carried during development processing to a predetermined temperature range before development in an automatic developing apparatus that develops the lithographic printing plate material. it can. For example, the preheat roller is composed of a pair of rollers including at least one roller having heating means therein, and the roller having the heating means is a hollow made of a metal having high thermal conductivity (for example, aluminum, iron, etc.). It is possible to use a pipe in which a nichrome wire or the like is embedded as a heating element and the outer surface of the metal pipe is covered with a plastic sheet such as polyethylene, polystyrene, or Teflon (registered trademark). For details of the preheat roller, reference can be made to JP-A No. 64-80962.
　当該プレヒートは、７０～１８０℃で、３～２４０秒程度行うことが好ましい。 The preheating is preferably performed at 70 to 180 ° C. for about 3 to 240 seconds.
　〔現像処理〕
　画像形成層は、画像露光を施すことにより露光部が硬化する。画像露光を行った後、アルカリ現像液を処理液として現像処理することにより、未露光部が除去され画像形成が可能となり平版印刷版が得られる。この様な現像液としては、従来から知られているアルカリ水溶液（通常ｐＨが１０．０～１３．５）が使用できる。例えば、ケイ酸ナトリウム、同カリウム、同アンモニウム；第二燐酸ナトリウム、同カリウム、同アンモニウム；重炭酸ナトリウム、同カリウム、同アンモニウム；炭酸ナトリウム、同カリウム、同アンモニウム；炭酸水素ナトリウム、同カリウム、同アンモニウム；ホウ酸ナトリウム、同カリウム、同アンモニウム；水酸化ナトリウム、同カリウム、同アンモニウム及び同リチウム等の無機アルカリ剤を使用するアルカリ現像液が挙げられる。 [Development processing]
The exposed portion of the image forming layer is cured by image exposure. After image exposure, development processing is performed using an alkaline developer as a processing solution, whereby unexposed portions are removed, image formation is possible, and a lithographic printing plate is obtained. As such a developer, a conventionally known alkaline aqueous solution (usually pH is 10.0 to 13.5) can be used. For example, sodium silicate, same potassium, same ammonium; dibasic sodium phosphate, same potassium, same ammonium; sodium bicarbonate, same potassium, same ammonium; sodium carbonate, same potassium, same ammonium; sodium bicarbonate, same potassium, same Ammonium; sodium borate, potassium, ammonium; alkaline developers using an inorganic alkaline agent such as sodium hydroxide, potassium, ammonium, and lithium.
　また、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノ－ｉ－プロピルアミン、ジ－ｉ－プロピルアミン、トリ－ｉ－プロピルアミン、ブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノ－ｉ－プロパノールアミン、ジ－ｉ－プロパノールアミン、エチレンイミン、エチレンジアミン、ピリジン等の有機アルカリ剤も用いることができる。 Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono-i-propylamine, di-i-propylamine, tri-i-propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, Organic alkali agents such as mono-i-propanolamine, di-i-propanolamine, ethyleneimine, ethylenediamine, and pyridine can also be used.
　これらのアルカリ剤は、単独又は２種以上組合せて用いられる。また、該現像液には、必要に応じてアニオン性界面活性剤、両性活性剤やアルコール等の有機溶媒を加えることができる。 These alkali agents are used alone or in combination of two or more. In addition, an organic solvent such as an anionic surfactant, an amphoteric surfactant or alcohol can be added to the developer as necessary.
　（低ｐＨ現像処理）
　また、本発明の平版印刷版材料は、平版印刷版の作製の際、レーザ光源により画像情報を露光・記録した後、未露光部（非画像部）が、低ｐＨの水溶液を処理液として用いて除去する現像処理方法も適用することができる。 (Low pH development processing)
Further, the lithographic printing plate material of the present invention uses an aqueous solution having a low pH as a treatment liquid in an unexposed portion (non-image portion) after exposing / recording image information with a laser light source when producing a lithographic printing plate. A development processing method that removes them can also be applied.
　本発明の平版印刷版材料は、平版印刷版作製の際、３５０ｎｍから４５０ｎｍの範囲に発光波長を持つレーザ光源により画像情報を露光・記録した後、未露光部（非画像部）を、水溶性樹脂及び界面活性剤を含有し、温度２５℃でのｐＨが２．０～９．０の範囲にある水溶液を処理液として用いて現像処理することができる。特に、重合性画像形成層を有する平版印刷版材料の場合には有効である。 The lithographic printing plate material of the present invention is prepared by exposing and recording image information with a laser light source having a light emission wavelength in the range of 350 nm to 450 nm when preparing a lithographic printing plate. Development processing can be performed using an aqueous solution containing a resin and a surfactant and having a pH of 2.0 to 9.0 at 25 ° C. as a processing solution. In particular, it is effective in the case of a lithographic printing plate material having a polymerizable image forming layer.
　上記界面活性剤としては、アニオン界面活性剤又はノニオン界面活性剤が挙げられる。例えば、アニオン型界面活性剤としては、脂肪酸塩類、アビエチン酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホコハク酸塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルフェノキシポリオキシエチレンプロピルスルホン酸塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、ポリオキシエチレンアリールエーテルスルホン酸塩、ポリオキシエチレンナフチルエーテルスルホン酸塩、Ｎ－メチル－Ｎ－オレイルタウリンナトリウム類、Ｎ－アルキルスルホコハク酸モノアミドニナトリウム塩類、石油スルホン酸塩類、硝酸化ヒマシ油、硫酸化牛脂油、脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硝酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ポリオキシエチレンスチリルフェニルエーテル硫酸エステル塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸エステル塩類、スチレン－無水マレイン酸共重合物の部分ケン化物類、オレフィン－無水マレイン酸共重合物の部分ケン化物類、ナフタレンスルホン酸塩ホルマリン縮合物類等が挙げられる。これらの中でもジアルキルスルホコハク酸塩類、アルキル硫酸エステル塩類及びアルキルナフタレンスルホン酸塩類が特に好ましく用いられる。 The surfactant includes an anionic surfactant and a nonionic surfactant. For example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, linear alkyl benzene sulfonates, branched alkyl benzene sulfonates, alkyl naphthalene sulfones. Acid salts, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, polyoxyethylene aryl ether sulfonates, polyoxyethylene naphthyl ether sulfonates, N-methyl-N-oleyl taurine sodium salts N-alkylsulfosuccinic acid monoamide disodium salts, petroleum sulfonates, nitrated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, Rualkyl nitrates, polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl phosphate esters, polyoxyethylene alkyl ethers Phosphoric acid ester salts, polyoxyethylene alkylphenyl ether phosphoric acid ester salts, partially saponified products of styrene-maleic anhydride copolymer, partially saponified products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensates Etc. Among these, dialkyl sulfosuccinates, alkyl sulfate esters, and alkyl naphthalene sulfonates are particularly preferably used.
　又、ノニオン界面活性剤としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアリールエーテル類、ポリオキシエチレンナフチルエーテル、ポリオキシエチレンポリスチリルフェニルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、グリセリン脂肪酸部分エステル類、ソルビタン脂肪酸部分エステル類、ペンタエリスリトール脂肪酸部分エステル類、プロピレングリコールモノ脂肪酸エステル、ショ糖脂肪酸部分エステル、ポリオキシエチレンソルビタン脂肪酸部分エステル類、ポリオキシエチレンソルビトール脂肪酸部分エステル類、ポリエチレングリコール脂肪酸エステル類、ポリグリセリン脂肪酸部分エステル類、ポリオキシエチレン化ひまし油類、ポリオキシエチレングリセリン脂肪酸部分エステル類、脂肪酸ジエタノールアミド類、Ｎ，Ｎ－ビス－２－ヒドロキシアルキルアミン類、ポリオキシエチレンアルキルアミン、トリエタノールアミン脂肪酸エステル、トリアルキルアミンオキシド等が挙げられる。その中でもポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンポリエキシプロピレンアルキルエーテル、ポリオキシエチレン－ポリオキシプロピレンブロックポリマー類等が好ましく用いられる。又、弗素系、シリコン系のアニオン、ノニオン界面活性剤も同様に使用することができる。また、好ましい界面活性剤の例として、特開２００４－１６７９０３号、特開２００４－２３０６５０号、特開２００５－４３３９３号公報に記載の平版印刷版用版面保護剤に添加する界面活性剤が挙げられる。これら界面活性剤は２種以上併用することもできる。例えば互いに異なる２種以上を併用することもできる。例えば互いに異なる２種以上のアニオン界面活性剤の併用やアニオン界面活性剤とノニオン界面活性剤の併用が好ましい。上記界面活性剤の使用量は特に限定する必要はないが、好ましくは後処理液の０．０１～２０質量％である。 Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene aryl ethers, polyoxyethylene naphthyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxy Propylene alkyl ether, glycerin fatty acid partial ester, sorbitan fatty acid partial ester, pentaerythritol fatty acid partial ester, propylene glycol mono fatty acid ester, sucrose fatty acid partial ester, polyoxyethylene sorbitan fatty acid partial ester, polyoxyethylene sorbitol fatty acid moiety Esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters, polyoxyethylenation Bran oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, etc. It is done. Of these, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene-polyoxypropylene block polymers and the like are preferably used. Fluorine-based and silicon-based anions and nonionic surfactants can also be used. Examples of preferable surfactants include surfactants added to the lithographic printing plate surface protecting agents described in JP-A Nos. 2004-167903, 2004-230650, and 2005-43393. . Two or more of these surfactants can be used in combination. For example, two or more different from each other can be used in combination. For example, a combination of two or more different anionic surfactants or a combination of an anionic surfactant and a nonionic surfactant is preferable. The amount of the surfactant used is not particularly limited, but is preferably 0.01 to 20% by mass of the post-treatment liquid.
　上記、ｐＨが２．０～９．０の範囲にある水溶液を処理液として用いて現像処理する場合に、酸性領域であるｐＨ２．０～６の範囲で使用する場合には、水溶液中に鉱酸、有機酸又は無機塩等を添加して調節する。その添加量は０．０１～２質量％が好ましい。例えば、鉱酸としては硝酸、硫酸、リン酸及びメタリン酸等が挙げられる。又、有機酸としては、クエン酸、酢酸、蓚酸、マロン酸、ｐ－トルエンスルホン酸、酒石酸、リンゴ酸、乳酸、レブリン酸、フィチン酸及び有機ホスホン酸等が挙げられる。更に無機塩としては、硝酸マグネシウム、第１リン酸ナトリウム、第２リン酸ナトリウム、硫酸ニッケル、ヘキサメタン酸ナトリウム、トリポリリン酸ナトリウム等が挙げられる。鉱酸、有機酸又は無機塩等の少なくとも１種もしくは２種以上を併用してもよい。塩基性領域ｐＨ８～９で用いる場合には、水溶性有機塩基、無機塩基を添加して該ｐＨに調節することが出来る。好ましいのは水溶性有機塩基で、トリエタノールアミン、ジエタノールアミン、エタノールアミン等が挙げられる。 When the above aqueous solution having a pH in the range of 2.0 to 9.0 is used as a processing solution and development is performed, when the acidic solution is used in the pH range of 2.0 to 6, the mineral solution is added to the aqueous solution. Adjust by adding acid, organic acid or inorganic salt. The addition amount is preferably 0.01 to 2% by mass. Examples of mineral acids include nitric acid, sulfuric acid, phosphoric acid, and metaphosphoric acid. Examples of organic acids include citric acid, acetic acid, succinic acid, malonic acid, p-toluenesulfonic acid, tartaric acid, malic acid, lactic acid, levulinic acid, phytic acid, and organic phosphonic acid. Further, examples of the inorganic salt include magnesium nitrate, primary sodium phosphate, secondary sodium phosphate, nickel sulfate, sodium hexamethanoate, sodium tripolyphosphate, and the like. You may use together at least 1 sort (s) or 2 or more types, such as a mineral acid, an organic acid, or an inorganic salt. When used in the basic region pH 8 to 9, it can be adjusted to the pH by adding a water-soluble organic base or inorganic base. A water-soluble organic base is preferable, and examples include triethanolamine, diethanolamine, and ethanolamine.
　また上記水溶液には、防腐剤、消泡剤等を添加することができる。例えば、防腐剤としてはフェノール又はその誘導体、ｏ－フェニルフェノール、ｐ－クロロメタクレゾール、ヒドロキシ安息香酸アルキルエステル、ホルマリン、イミダゾール誘導体、デヒドロ酢酸ナトリウム、４－イソチアゾリン－３－オン誘導体、ベンゾイソチアゾリン－３－オン、ベンズトリアゾール誘導体、アミジングアニジン誘導体、四級アンモニウム塩類、ピリジン、キノリン、グアニジン等の誘導体、ダイアジン、トリアゾール誘導体、オキサゾール、オキサジン誘導体等が挙げられる。好ましい添加量は、細菌、カビ、酵母等に対して、安定に効力を発揮する量であって、細菌、カビ、酵母の種類によっても異なるが、使用時の版面保護剤に対して０．０１～４質量％の範囲が好ましく、又種々のカビ、殺菌に対して効力のある様に２種以上の防腐剤を併用することが好ましい。又、消泡剤としてはシリコン消泡剤が好ましい。その中で乳化分散型及び可溶化等が何れも使用できる。好ましくは０．０１～１．０質量％の範囲が最適である。 Also, preservatives, antifoaming agents and the like can be added to the aqueous solution. For example, as a preservative, phenol or a derivative thereof, o-phenylphenol, p-chlorometacresol, hydroxybenzoic acid alkyl ester, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazolin-3-one derivative, benzoisothiazoline-3 -Derivatives such as ones, benztriazole derivatives, amiding anidine derivatives, quaternary ammonium salts, pyridine, quinoline, guanidine, diazine, triazole derivatives, oxazole, oxazine derivatives, and the like. A preferable addition amount is an amount that exerts a stable effect on bacteria, molds, yeasts, etc., and varies depending on the type of bacteria, molds, yeasts, but 0.01% with respect to the plate surface protective agent at the time of use. The range of ˜4% by mass is preferable, and two or more kinds of preservatives are preferably used in combination so as to be effective against various molds and sterilization. As the antifoaming agent, a silicon antifoaming agent is preferable. Among them, emulsification dispersion type and solubilization can be used. The range of 0.01 to 1.0% by mass is optimal.
　更に、キレート化合物を添加してもよい。好ましいキレート化合物としては、例えば、エチレンジアミンテトラ酢酸、そのカリウム塩、そのナトリウム塩；ジエチレントリアミンペンタ酢酸、そのカリウム塩、そのナトリウム塩；トリエチレンテトラミンヘキサ酢酸、そのナトリウム塩；エチレンジアミンジコハク酸、そのカリウム塩、そのナトリウム塩；トリエチレンテトラミンヘキサ酢酸、そのカリウム塩、そのナトリウム塩、ヒドロキシエチルエチレンジアミントリ酢酸、そのカリウム塩、そのナトリウム塩：ニトリロトリ酢酸、そのナトリウム塩；１－ヒドロキシエタン－１，１－ジホスホン酸、そのカリウム塩、そのナトリウム塩；アミノトリ（メチレンホスホン酸）、そのカリウム塩、そのナトリウム塩等の様な有機ホスホン酸類或いはホスホノアルカントリカルボン酸類を挙げることが出来る。上記キレート剤のナトリウム塩、カリウム塩の代わりに有機アミンの塩も有効である。これらキレート剤はガム液組成中に安定に存在し、印刷性を阻害しないものが選ばれる。添加量としては０．００１～１．０質量％が適当である。 Furthermore, a chelate compound may be added. Preferred chelate compounds include, for example, ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof; diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof; triethylenetetraminehexaacetic acid, sodium salt thereof; ethylenediamine disuccinic acid, potassium salt thereof. Triethylenetetramine hexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof: nitrilotriacetic acid, sodium salt thereof; 1-hydroxyethane-1,1-diphosphone Acids, potassium salts, sodium salts; organic phosphonic acids or phosphonoalkanetricarboxylic acids such as aminotri (methylenephosphonic acid), potassium salts, sodium salts, etc. It can be mentioned. An organic amine salt is also effective in place of the sodium salt and potassium salt of the chelating agent. These chelating agents are selected so that they are stably present in the gum solution composition and do not impair the printability. The addition amount is suitably 0.001 to 1.0% by mass.
　上記成分の他、必要により感脂化剤も添加することができる。例えば、テレピン油、キシレン、トルエン、ローヘプタン、ソルベントナフサ、ケロシン、ミネラルスピリット、沸点が約１２０℃～約２５０℃の石油留分等の炭化水素類、例えば、ジブチルフタレート、ジヘブチルフタレート、ジ－ｎ－オクチルフタレート、ジ（２－エチルヘキシル）フタレート、ジノニルフタレート、ジデシルフタレート、ジラウリルフタレート、ブチルベンジルフタレート等のフタル酸ジエステル剤、例えば、ジオクチルアジペート、ブチルグリコールアジペート、ジオクチルアゼレート、ジブチルセバケート、ジ（２－エチルヘキシル）セバケート、ジオクチルセバケート等の脂肪族二塩基酸エステル類、例えばエポキシ化大豆油等のエポキシ化トリグリセリド類、例えば、トリクレジルホスフェート、トリオクチルフォスフェート、トリスクロルエチルフォスフェート等のリン酸エステル類、例えば安息香酸ベンジル等の安息香酸エステル類等の凝固点が１５℃以下で、１気圧下での沸点が３００℃以上の可塑剤が含まれる。更にカプロン酸、エナント酸、カプリル酸、ヘラルゴン酸、カプリン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコサン酸、モンタン酸、メリシン酸、ラクセル酸、イソ吉草酸等の飽和脂肪酸とアクリル酸、クロトン酸、イソクロトン酸、ウンデシレン酸、オレイン酸、エライジン酸、セトレイン酸、ニルカ酸、ブテシジン酸、ソルビン酸、リノール酸、リノレン酸、アラキドン酸、プロピオール酸、ステアロール酸、イワシ酸、タリリン酸、リカン酸等の不飽和脂肪酸も挙げられる。より好ましくは５０℃において液体である脂肪酸であり、更に好ましくは炭素数が５～２５であり、最も好ましくは炭素数が８～２１である。これらの感脂化剤は１種もしくは２種以上併用することもできる。使用量として好ましい範囲は０．０１～１０質量％、より好ましい範囲は０．０５～５質量％である。 In addition to the above components, a sensitizer can be added if necessary. For example, hydrocarbons such as turpentine oil, xylene, toluene, low heptane, solvent naphtha, kerosene, mineral spirit, petroleum fraction having a boiling point of about 120 ° C. to about 250 ° C., for example, dibutyl phthalate, dihebutyl phthalate, di-n -Phthalic acid diester agents such as octyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate, butyl benzyl phthalate, such as dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate Aliphatic dibasic acid esters such as di (2-ethylhexyl) sebacate, dioctyl sebacate, epoxidized triglycerides such as epoxidized soybean oil, tricresyl phosphate, trioctyl Contains a plasticizer having a freezing point of 15 ° C. or lower and a boiling point of 300 ° C. or higher at 1 atm, such as phosphate esters such as phosphate and trischlorethyl phosphate, for example, benzoate esters such as benzyl benzoate . In addition, caproic acid, enanthic acid, caprylic acid, helargonic acid, capric acid, undecyl acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, lignoserine Saturated fatty acids such as acid, serotic acid, heptacosanoic acid, montanic acid, melicinic acid, lactelic acid, isovaleric acid, and acrylic acid, crotonic acid, isocrotonic acid, undecylenic acid, oleic acid, elaidic acid, celetic acid, nillic acid, buteticidin Examples also include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid, sardine acid, talylic acid and licanoic acid. More preferred are fatty acids which are liquid at 50 ° C., more preferred are those having 5 to 25 carbon atoms, and most preferred are those having 8 to 21 carbon atoms. These sensitizers can be used alone or in combination of two or more. A preferable range of the amount used is 0.01 to 10% by mass, and a more preferable range is 0.05 to 5% by mass.
　なお、本発明の平版印刷版材料は、平版印刷版を作製する際に、３５０ｎｍから４５０ｎｍの範囲内に発光波長を持つレーザ光源により画像情報を露光・記録した後の未露光部が、水溶性樹脂及び界面活性剤を含有し温度２５℃でのｐＨが３．０～９．０である水溶液により除去する現像処理方法を適用することができるが、未露光部分を除去できるようにするためには、種々の手段が採り得る。 In the lithographic printing plate material of the present invention, when the lithographic printing plate is prepared, the unexposed portion after exposing and recording image information with a laser light source having an emission wavelength in the range of 350 nm to 450 nm is water-soluble. In order to be able to remove the unexposed portion, it is possible to apply a development processing method that removes with an aqueous solution containing a resin and a surfactant and having a pH of 3.0 to 9.0 at 25 ° C. Various measures can be taken.
　例えば、本発明においては、平版印刷版材料の画像形成層に含有させる重合性モノマーの種類や含有量の適切条件の選択によって未露光部分の除去を可能とすることが好ましい態様の一つである。この態様の例としては、画像形成層に含有させる重合性モノマーとして、少なくとも分子内にヒドロキシル基を有する重合性化合物を選ぶこと、高分子結合材として、少なくともＮ－ビニルピロリドンのホモポリマー又は共重合体を選ぶことが、本発明に係る課題解決の観点から好ましい。 For example, in the present invention, it is one of the preferred embodiments that the unexposed portion can be removed by selecting an appropriate condition for the type and content of the polymerizable monomer contained in the image forming layer of the lithographic printing plate material. . As an example of this embodiment, a polymerizable compound having at least a hydroxyl group in the molecule is selected as the polymerizable monomer to be contained in the image forming layer, and a homopolymer or copolymer of at least N-vinylpyrrolidone is used as the polymer binder. It is preferable to select the combination from the viewpoint of solving the problem according to the present invention.
　以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれらに限定されない。尚、特に断りない限り、実施例中の「部」あるいは「％」の表示は、「質量部」あるいは「質量％」を表す。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “part” or “%” in the examples represents “part by mass” or “% by mass”.
　実施例１
　《支持体の作製》
　〔支持体１の作製〕
　厚さ０．３０ｍｍ、幅１０３０ｍｍのＪＩＳ　Ａ　１０５０アルミニウム板を用いて以下の各工程に従い連続的に処理を行って、アルミニウム支持体である支持体１を作製した。 Example 1
<Production of support>
[Preparation of Support 1]
By using a JIS A 1050 aluminum plate having a thickness of 0.30 mm and a width of 1030 mm, treatment was continuously performed according to the following steps to produce a support 1 that was an aluminum support.
　（工程ａ）
　アルミニウム板を、苛性ソーダ濃度が２．６質量％、アルミニウムイオン濃度が６．５質量％の水溶液を用い、液温７０℃でスプレーによるエッチング処理を行い、アルミニウム板を０．３ｇ／ｍ２溶解した。その後スプレーによる水洗を行った。 (Process a)
The aluminum plate was subjected to an etching process by spraying at a liquid temperature of 70 ° C. using an aqueous solution having a caustic soda concentration of 2.6 mass% and an aluminum ion concentration of 6.5 mass% to dissolve 0.3 g / m 2 of the aluminum plate. . Thereafter, washing with water was performed by spraying.
　（工程ｂ）
　温度３０℃の硝酸濃度が１質量％の水溶液（アルミニウムイオン０．５質量％含む）で、スプレーによるデスマット処理を行い、その後スプレーで水洗した。 (Process b)
Desmutting treatment was performed by spraying with an aqueous solution (containing 0.5% by weight of aluminum ions) having a nitric acid concentration of 30% at a temperature of 30 ° C., and then washed with water by spraying.
　（工程ｃ）
　６０Ｈｚの交流電圧を用いて、連続的に電気化学的な粗面化処理を行った。この時の電解液は、塩酸を１．１質量％、アルミニウムイオンを０．５質量％、酢酸を０．５質量％含む水溶液で、液温は２１℃であった。交流電源は、電流値がゼロからピークに達するまでの時間ＴＰが２ｍｓｅｃの正弦波交流を用いて、カーボン電極を対極として電気化学的な粗面化処理を行った。電流密度を表面形状パラメータＲｚが１．０μｍとなるよう調整し、電気量は３００Ｃ／ｄｍ２であった。その後、スプレーによる水洗を行った。この塩酸及び酢酸を含む電解液を用いた処理を、砂目処理Ｃｌと称す。 (Process c)
Using an alternating voltage of 60 Hz, electrochemical surface roughening was continuously performed. The electrolytic solution at this time was an aqueous solution containing 1.1% by mass of hydrochloric acid, 0.5% by mass of aluminum ions, and 0.5% by mass of acetic acid, and the liquid temperature was 21 ° C. The AC power source was subjected to an electrochemical surface roughening treatment using a sine wave alternating current with a time TP of 2 msec until the current value reached a peak from zero, using a carbon electrode as a counter electrode. The current density was adjusted so that the surface shape parameter Rz was 1.0 μm, and the amount of electricity was 300 C / dm 2 . Then, water washing by spraying was performed. The treatment using the electrolytic solution containing hydrochloric acid and acetic acid is referred to as grain-treated Cl.
　（工程ｄ）
　液温が６０℃で燐酸濃度が２０質量％の水溶液（アルミニウムイオンを０．５質量％含む）で、１０秒間デスマット処理を行い、その後スプレーによる水洗を行った。 (Process d)
A desmut treatment was performed for 10 seconds with an aqueous solution (containing 0.5 mass% of aluminum ions) having a liquid temperature of 60 ° C. and a phosphoric acid concentration of 20 mass%, and then washed with water by spraying.
　（工程ｅ）
　既存の二段給電電解処理法の陽極酸化装置（第一電解部および第二電解部の長さが各６ｍ、第一給電部の長さが３ｍ、第二給電部の長さが３ｍ、第一給電電極及び第二給電電極の長さが各２．４ｍ）を使って、電解部に硫酸濃度が１７０ｇ／リットル（アルミニウムイオンを０．５質量％含む）の水溶液を用いて、液温３８℃で陽極酸化処理を行った。陽極酸化皮膜量ＡＤＴが、０．１０ｇ／ｍ２となるように電流密度を調整した。その後、スプレーによる水洗を行った。 (Process e)
An anodizing apparatus of an existing two-stage feed electrolytic treatment method (the length of the first electrolysis part and the second electrolysis part is 6 m, the length of the first feed part is 3 m, the length of the second feed part is 3 m, The length of each of the feeding electrode and the second feeding electrode is 2.4 m), and an aqueous solution having a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions) is used in the electrolysis section. Anodization was performed at 0 ° C. The current density was adjusted so that the amount of anodized film ADT was 0.10 g / m 2 . Then, water washing by spraying was performed.
　スプレー水洗後、０．４質量％のポリビニルホスホン酸を含む水溶液中に３０秒浸漬し、親水化処理をした。液温は８５℃であった。その後スプレー水洗し、赤外線ヒーターで乾燥して、支持体１を得た。 After washing with spray water, the film was immersed in an aqueous solution containing 0.4% by mass of polyvinylphosphonic acid for 30 seconds to be hydrophilized. The liquid temperature was 85 ° C. Thereafter, it was washed with spray water and dried with an infrared heater to obtain a support 1.
　〔支持体２～１１の作製〕
　上記支持体１の作製において、工程ｃにおける電流密度及び電気量（２００～１２００Ｃ／ｄｍ２の範囲）を表１に記載の表面形状パラメータＲｚ（μｍ）となる様に制御し、かつ工程ｅにおける電流密度を表１に記載の陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）となる様に制御した以外は同様にして、表１に記載の表面形状パラメータＲｚ（μｍ）及び陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）を有する支持体２～１１を作製した。 [Preparation of Supports 2 to 11]
In the production of the support 1, the current density and the amount of electricity (in the range of 200 to 1200 C / dm 2 ) in step c are controlled to be the surface shape parameter Rz (μm) described in Table 1, and in step e The surface shape parameter Rz (μm) and the anodic oxide film amount ADT (Table 1) shown in Table 1 were similarly used except that the current density was controlled to be the anodic oxide film amount ADT (g / m 2 ) described in Table 1. Supports 2 to 11 having g / m 2 ) were produced.
　〔支持体１２の作製〕
　上記支持体１０の作製において、工程ｃで用いた電解液の組成として、塩酸及び酢酸に代えて、１質量％の硝酸を用いた以外は同様にして、表面形状パラメータＲｚが２．３１μｍ、陽極酸化皮膜量ＡＤＴが０．８８ｇ／ｍ２の支持体１２を作製した。なお、この工程ｃにおける処理を、砂目処理Ｎと称す。 [Preparation of Support 12]
In the production of the support 10, the surface shape parameter Rz is 2.31 μm, except that 1% by mass of nitric acid is used instead of hydrochloric acid and acetic acid as the composition of the electrolytic solution used in step c. A support 12 having an oxide film amount ADT of 0.88 g / m 2 was produced. In addition, the process in this process c is called the grain processing N.
　〔支持体１３の作製〕
　上記支持体１０の作製において、工程ｃで用いた電解液の組成として、塩酸及び酢酸に代えて、１質量％の硝酸を用いた以外は同様にして、表面形状パラメータＲｚが３．３４μｍ、陽極酸化皮膜量ＡＤＴが０．８８ｇ／ｍ２の支持体１３を作製した。なお、この工程ｃにおける処理を、砂目処理Ｎと称す。 [Preparation of Support 13]
In the production of the support 10, the surface shape parameter Rz is 3.34 μm, except that 1% by mass of nitric acid is used instead of hydrochloric acid and acetic acid as the composition of the electrolytic solution used in step c. A support 13 having an oxide film amount ADT of 0.88 g / m 2 was produced. In addition, the process in this process c is called the grain processing N.
　〔支持体１４の作製〕
　特開２００２－２１３２号公報の実施例の段落番号〔００５５〕に記載の実施例４と同様の方法により、表面形状パラメータＲｚが４．２０μｍ、陽極酸化皮膜量ＡＤＴが１．２０ｇ／ｍ２の支持体１４を作製した。 [Preparation of Support 14]
According to the same method as in Example 4 described in paragraph No. [0055] of the example of Japanese Patent Laid-Open No. 2002-2132, the surface shape parameter Rz is 4.20 μm and the anodic oxide film amount ADT is 1.20 g / m 2 . A support 14 was produced.
　なお、表１に記載の各支持体の表面形状パラメータＲｚ（μｍ）及び陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）は、下記の方法に従って測定した。 The surface shape parameter Rz (μm) and the amount of anodized film ADT (g / m 2 ) of each support shown in Table 1 were measured according to the following methods.
　（陽極酸化皮膜量ＡＤＴの測定）
　得られた各支持体を１０ｃｍ×５ｃｍにカットし、裏面をメッキ用テープでマスクした。９３℃に保たれた燐酸クロム酸溶液（燐酸８５質量％液：３５ｍｌ、酸化クロム（IV）：２０ｇ、を１Ｌの水に溶解して調製）に５分間浸漬し、陽極酸化皮膜を溶解し、水洗、乾燥した。陽極酸化皮膜溶解の前後における質量変化測定を測定し、これを支持体表面の陽極酸化皮膜量（ｇ／ｍ２）とした。 (Measurement of anodized film amount ADT)
Each obtained support was cut into 10 cm × 5 cm, and the back surface was masked with a plating tape. Immerse in a chromic phosphate solution kept at 93 ° C. (prepared by dissolving 85 mass% phosphoric acid solution: 35 ml, chromium (IV) oxide: 20 g in 1 L of water) for 5 minutes to dissolve the anodized film, Washed with water and dried. The mass change measurement before and after dissolution of the anodic oxide film was measured, and this was defined as the amount of anodic oxide film (g / m 2 ) on the support surface.
　（表面形状パラメータＲｚの測定）
　得られた各支持体の画像形成層を塗布する面側の表面を、ＳＥ１７００α（小坂研究所（株）製）の接触式粗さ計を用いて表面粗さを測定し、表面形状パラメータＲｚを求めた。 (Measurement of surface shape parameter Rz)
The surface of the surface of each support on which the image forming layer is applied is measured for surface roughness using a contact type roughness meter of SE1700α (manufactured by Kosaka Laboratory Co., Ltd.), and the surface shape parameter Rz is set. Asked.
　《重合性画像形成層を有するネガ型の平版印刷版材料の作製》
　〔平版印刷版材料１の作製〕
　上記作製した支持体１上に、下記光重合性画像形成層塗工液１を乾燥後の固形分量が１．５ｇ／ｍ２となるようワイヤーバーを用いて塗布し、９５℃で１．５分間乾燥して光重合性画像形成層１を形成した。次いで、重合性画像形成層１上に、下記組成の酸素遮断層塗工液１を、乾燥後の固形分量が１．８ｇ／ｍ２となるようワイヤーバーを用いて塗布し、７５℃で１．５分間乾燥して、支持体上に画像形成層及び酸素遮断層を有する平版印刷版材料１を作製した。 << Preparation of a negative lithographic printing plate material having a polymerizable image forming layer >>
[Preparation of planographic printing plate material 1]
The following photopolymerizable image-forming layer coating solution 1 is applied on the prepared support 1 using a wire bar so that the solid content after drying is 1.5 g / m 2, and 1.5% at 95 ° C. The photopolymerizable image forming layer 1 was formed by drying for a minute. Next, an oxygen barrier layer coating liquid 1 having the following composition was applied on the polymerizable image forming layer 1 using a wire bar so that the solid content after drying was 1.8 g / m 2 , Drying for 5 minutes produced a lithographic printing plate material 1 having an image forming layer and an oxygen blocking layer on a support.
　（光重合性画像形成層塗工液１の調製）
　下記各添加剤を順次、混合、溶解して、光重合性画像形成層塗工液１を調製した。 (Preparation of photopolymerizable image-forming layer coating solution 1)
The following additives were sequentially mixed and dissolved to prepare a photopolymerizable image forming layer coating solution 1.
　エチレン性二重結合含有単量体１　　　　　　　　　　　　　　　２７．０質量部
　エチレン性二重結合含有単量体（ＮＫエステル４Ｇ：新中村化学工業（株））
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１４．０質量部
　開始剤系添加剤
　〈１〉：（η６－クメン）（η５－シクロペンタジエニル）鉄（２）ヘキサフルオロホスフェート　　　　　　　　　　　　　　　　　　　　　　　　　　４．０質量部
　〈２〉：分光増感剤１　　　　　　　　　　　　　　　　　　　　　３．０質量部
　〈３〉：トリブロモアセチルアミド化合物　　　　　　　　　　　　２．０質量部
　アクリル系共重合体１　　　　　　　　　　　　　　　　　　　　４２．０質量部
　フタロシアニン顔料（ＭＨＩ４５４：御国色素社製）　　　　　　　６．０質量部
　２－ｔ－ブチル－６－（３－ｔ－ブチル－２－ヒドロキシ－５－メチルベンジル）－４－メチルフェニルアクリレート（スミライザーＧＳ：住友３Ｍ社製）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．５質量部
　弗素系界面活性剤（ＦＣ－４４３０；住友スリーエム社製）　　　　０．５質量部
　シロキサン系界面活性剤（ＢＹＫ３３７；ビックケミー社製）　　　０．９質量部
　メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　　　８０質量部
　プロピレングリコールメチルエーテル　　　　　　　　　　　　　　８２０質量部
　なお、上記光重合性画像形成層塗工液１の調製に用いた各添加剤の詳細は、以下の通りである。 Ethylene double bond-containing monomer 1 27.0 parts by mass Ethylene double bond-containing monomer (NK ester 4G: Shin-Nakamura Chemical Co., Ltd.)
14.0 parts by mass Initiator-based additive <1>: (η6-cumene) (η5-cyclopentadienyl) iron (2) hexafluorophosphate 4.0 parts by mass <2>: spectral sensitizer 1 0 parts by mass <3>: tribromoacetylamide compound 2.0 parts by mass Acrylic copolymer 1 42.0 parts by mass Phthalocyanine pigment (MHI454: manufactured by Mikuni Dye Co., Ltd.) 6.0 parts by mass 2-t-butyl-6 -(3-t-Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GS: manufactured by Sumitomo 3M)
0.5 parts by mass Fluorine-based surfactant (FC-4430; manufactured by Sumitomo 3M) 0.5 parts by mass Siloxane-based surfactant (BYK337; manufactured by BYK Chemie) 0.9 parts by mass Methyl ethyl ketone 80 parts by mass Propylene glycol methyl ether 820 parts by mass The details of each additive used in the preparation of the photopolymerizable image-forming layer coating solution 1 are as follows.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　アクリル系共重合体１：アクリル系共重合体１（高分子結合材）は、下記のようにして合成した。 Acrylic copolymer 1: Acrylic copolymer 1 (polymer binder) was synthesized as follows.
　〈アクリル系共重合体１の合成〉
　窒素気流下の三ツ口フラスコに、メタクリル酸３０部、メタクリル酸メチル５０部、メタクリル酸エチル２０部、イソプロピルアルコール５００部及びα，α′－アゾビスイソブチロニトリル３部を入れ、窒素気流中８０℃のオイルバスで６時間反応させた。その後、イソプロピルアルコールの沸点で１時間還流を行った後、トリエチルアンモニウムクロライド３部及びグリシジルメタクリレート２５部を加えて３時間反応させ、アクリル系共重合体１を得た。ＧＰＣを用いて測定した重量平均分子量は約３５，０００、ＤＳＣ（示差熱分析法）を用いて測定したガラス転移温度（Ｔｇ）は約８５℃であった。 <Synthesis of acrylic copolymer 1>
In a three-necked flask under a nitrogen stream, 30 parts of methacrylic acid, 50 parts of methyl methacrylate, 20 parts of ethyl methacrylate, 500 parts of isopropyl alcohol and 3 parts of α, α'-azobisisobutyronitrile are placed in a nitrogen stream. The reaction was carried out in an oil bath at 0 ° C. for 6 hours. Then, after refluxing at the boiling point of isopropyl alcohol for 1 hour, 3 parts of triethylammonium chloride and 25 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1. The weight average molecular weight measured using GPC was about 35,000, and the glass transition temperature (Tg) measured using DSC (differential thermal analysis) was about 85 ° C.
　（酸素遮断層塗工液１の調製）
　下記各添加剤を順次、混合、溶解して、酸素遮断層塗工液１を調製した。 (Preparation of oxygen barrier layer coating solution 1)
The following additives were sequentially mixed and dissolved to prepare an oxygen barrier layer coating solution 1.
　ポリビニルアルコール（ＧＬ－０５：日本合成化学社製）　　　　　　７９質量部
　ポリビニルピロリドン（ＰＶＰ　Ｋ－３０：アイエスピー・ジャパン社製）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１０質量部
　ポリエチレンイミン（ルパゾールＷＦ：ＢＡＳＦ社製）　　　　　　　　５質量部
　カチオン変性ポリビニルアルコール（クラレＣポリマー：クラレ社製）　５質量部
　界面活性剤（サーフィノール４６５：日信化学工業社製）　　　　　０．５質量部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　９００質量部
　〔平版印刷版材料２～８の作製〕
　上記平版印刷版材料１の作製において、支持体１に代えて、それぞれ支持体２～８を用いた以外は同様にして、平版印刷版材料２～８を作製した。 Polyvinyl alcohol (GL-05: manufactured by Nippon Synthetic Chemical Co., Ltd.) 79 parts by mass Polyvinylpyrrolidone (PVP K-30: manufactured by ASP Japan)
10 parts by mass Polyethyleneimine (Lupazole WF: manufactured by BASF) 5 parts by mass Cation-modified polyvinyl alcohol (Kuraray C polymer: manufactured by Kuraray) 5 parts by mass Surfactant (Surfinol 465: manufactured by Nisshin Chemical Industry Co., Ltd.) 0.5 Mass parts Water 900 parts by mass [Preparation of planographic printing plate materials 2 to 8]
In the production of the lithographic printing plate material 1, the lithographic printing plate materials 2 to 8 were produced in the same manner except that the supports 2 to 8 were used in place of the support 1, respectively.
　〔平版印刷版材料９の作製〕
　上記平版印刷版材料１の作製において、支持体１に代えて支持体９を用い、かつ光重合性画像形成層塗工液１に代えて、下記光重合性画像形成層塗工液２を用いた以外は同様にして、平版印刷版材料９を作製した。 [Preparation of planographic printing plate material 9]
In the production of the lithographic printing plate material 1, the support 9 is used in place of the support 1, and the following photopolymerizable image forming layer coating liquid 2 is used in place of the photopolymerizable image forming layer coating liquid 1. A lithographic printing plate material 9 was produced in the same manner except that.
　（光重合性画像形成層塗工液２の調製）
　光重合性画像形成層塗工液１の調製において、〈１〉：（η６－クメン）（η５－シクロペンタジエニル）鉄（２）ヘキサフルオロホスフェートに代えて、同量の下記分光増感剤２を、〈２〉：分光増感剤１に代えて、同量の下記ビスイミダゾール化合物を、〈３〉：トリブロモアセチルアミド化合物に代えて、同量の下記メルカプト化合物を用いた以外は同様にして、光重合性画像形成層塗工液２を調製した。 (Preparation of photopolymerizable image forming layer coating solution 2)
In the preparation of the photopolymerizable image-forming layer coating solution 1, <1>: (η6-cumene) (η5-cyclopentadienyl) iron (2) instead of hexafluorophosphate, the same amount of the following spectral sensitizer <2>: The same amount of the following bisimidazole compound was used instead of the spectral sensitizer 1, and <3>: the same amount of the following mercapto compound was used instead of the tribromoacetylamide compound. Thus, a photopolymerizable image forming layer coating solution 2 was prepared.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　〔平版印刷版材料１０～１４の作製〕
　上記平版印刷版材料９の作製において、支持体９に代えて、それぞれ支持体１０～１４を用いた以外は同様にして、平版印刷版材料１０～１４を作製した。 [Preparation of planographic printing plate materials 10 to 14]
In the production of the lithographic printing plate material 9, the lithographic printing plate materials 10 to 14 were produced in the same manner except that the supports 10 to 14 were used in place of the support 9, respectively.
　《平版印刷版の作製》
　上記作製した各平版印刷版材料を、４０５ｎｍの半導体レーザヘッド光源を備えたＰｒｏｓｅｔｔｅｒ（ＨＥＩＤＥＬＢＥＲＧ社製）を用いて、２５４０ｄｐｉ（ｄｐｉとは、２．５４ｃｍ当たりのドット数を表す。）、１７５ｌｐｉの条件で露光を行った。 << Preparation of lithographic printing plate >>
Each lithographic printing plate material produced above was subjected to 2540 dpi (dpi represents the number of dots per 2.54 cm) and 175 lpi using a Prosetter (manufactured by HEIDELBERG) equipped with a 405 nm semiconductor laser head light source. The exposure was performed.
　露光後の平版印刷版材料を、Ｇｌｕｎｚ＆Ｊｅｎｓｅｎ社製のＲａｐｔｏｒ　Ｐｏｌｙｍｅｒ　８５自動現像機（速度１１４ｃｍ／ｍｉｎ）のプレヒート部に挿入し、版面裏面が９０℃となる温度設定で加熱し、プレ水洗工程で酸素遮断層を除去し、次いで下記処理液１（新液）を入れた現像部で未露光部を除去した。自動現像機内で現像し、水洗した後、ガム液を塗布し、５０℃で乾燥して、平版印刷版１～１４を作製した。ガム液は、コニカミノルタ社製の８４０　Ｐｌａｔｅ　Ｆｉｎｉｓｈｅｒを用いた。 The exposed lithographic printing plate material is inserted into the preheating part of a Raptor Polymer 85 automatic developing machine (speed: 114 cm / min) manufactured by Glunz & Jensen, heated at a temperature setting at which the back side of the plate surface becomes 90 ° C., and subjected to oxygen in the pre-water washing step. The blocking layer was removed, and then the unexposed portion was removed at the developing portion containing the following processing solution 1 (new solution). After developing in an automatic processor and washing with water, a gum solution was applied and dried at 50 ° C. to prepare lithographic printing plates 1 to 14. As the gum solution, 840 Plate Finisher manufactured by Konica Minolta was used.
　〔現像液組成〕
　（処理液１）
　Ａケイ酸カリウム　　　　　　　　　　　　　　　　　　　　　　　　８．０質量％
　ニューコールＢ－１３ＳＮ（日本乳化剤社製）　　　　　　　　　　　２．０質量％
　プロノン＃２０４（日本油脂社性）　　　　　　　　　　　　　　　　１．０質量％
　苛性カリ　　　　　　　　　　　　　　　　　　　　　ｐＨ＝１２．５となる添加量
　《平版印刷版の評価》
　〔ドットゲインの評価〕
　上記作製した各平版印刷版において、２％のドットが２％を再現する露光量の条件で、５０％を再現すべき網点画像の網％を測定し、その差をドットゲインの評価を示す指標として、その測定値を表１に示した。数値が０に近いほど良い。なお、網％測定は、Ｘ－ｒｉｔｅ社製のｉＣＰｌａｔｅIIを使用した。 [Developer composition]
(Processing liquid 1)
A Potassium silicate 8.0 mass%
New Coal B-13SN (Nippon Emulsifier Co., Ltd.) 2.0% by mass
Pronon # 204 (Nippon Yushi Co., Ltd.) 1.0% by mass
Caustic potash pH = 12.5 <Evaluation of planographic printing plate>
[Evaluation of dot gain]
In each lithographic printing plate produced as described above, halftone dots of a halftone image to be reproduced at 50% are measured under the condition of an exposure amount at which 2% of dots reproduce 2%, and the difference indicates dot gain evaluation. The measured value is shown in Table 1 as an index. The closer the value is to 0, the better. The net% measurement was performed using iCPlate II manufactured by X-rite.
　〔耐刷性の評価〕
　上記ドットゲインの評価の場合と同様にして作製した平版印刷版を、印刷機（三菱重工業（株）製、ＤＡＩＹＡ１Ｆ－１）で、コート紙、印刷インキ（東洋インク（株）製、トーヨーキングハイエコーＭ紅）及び湿し水（東京インク（株）製、Ｈ液ＳＧ－５１濃度１．５質量％）を用いて印刷を行い、２％のドットが２％を再現する露光量の条件で、６００枚連続印刷後、クリーナーで版面をふき、ハイライト部の点細り、シャドウ部の絡みの発生する印刷枚数を耐刷力の指標とした。耐刷性の１回は６００枚連続印刷した後クリーナーで拭き取る作業を指し、回数が多いほど耐刷性に優れていることを表す。クリーナーは、ウルトラプレートクリーナー（発売元：大日精化）を使用した。 [Evaluation of printing durability]
A lithographic printing plate produced in the same manner as the dot gain evaluation described above was applied to a coated paper, printing ink (Toyo Ink Co., Ltd., Toyo King High Co., Ltd.) using a printing machine (Mitsubishi Heavy Industries, Ltd., DAIYA1F-1). Echo M Red) and dampening water (manufactured by Tokyo Ink Co., Ltd., H liquid SG-51 density 1.5% by mass), and under the condition of exposure amount that 2% dots reproduce 2%. After continuous printing of 600 sheets, the plate surface was wiped with a cleaner, the number of prints in which the highlight portion was thinned and the shadow portion was entangled was used as an index of printing durability. One printing durability refers to an operation of continually printing 600 sheets and then wiping with a cleaner. The higher the printing frequency, the better the printing durability. The cleaner used was an Ultra Plate Cleaner (Distributor: Dainichi Seika).
　以上により得られた結果を、表１に示す。 Table 1 shows the results obtained as described above.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１に記載の結果より明らかなように、本発明で規定する特性を備えた支持体を有する平版印刷版材料を用いて作製した平版印刷版は、比較例に対し、網点点質の劣化がなく、耐刷性に優れていることが分かる。 As is clear from the results shown in Table 1, the lithographic printing plate produced using the lithographic printing plate material having the support having the characteristics specified in the present invention has a dot dot quality deterioration as compared with the comparative example. It can be seen that the printing durability is excellent.
　実施例２
　《支持体の作製》
　〔支持体１５の作製〕
　実施例１に記載の支持体１の作製において、工程ｃにおける電流密度及び電気量（２～１２Ｃ／ｃｍ２の範囲）を、表面形状パラメータＲｚが２．３１（μｍ）となる様に制御し、かつ工程ｅにおける電流密度を、陽極酸化皮膜量ＡＤＴが０．８９ｇ／ｍ２となる様に制御した以外は同様にして、支持体１５を作製した。 Example 2
<Production of support>
[Preparation of Support 15]
In the production of the support 1 described in Example 1, the current density and the amount of electricity (in the range of 2 to 12 C / cm 2 ) in step c are controlled so that the surface shape parameter Rz is 2.31 (μm). And the support body 15 was produced similarly except having controlled the current density in the process e so that the amount of anodic oxide films ADT might be 0.89 g / m < 2 >.
　〔支持体１６の作製〕
　実施例１に記載の支持体１の作製において、工程ｃにおける電流密度及び電気量（２００～１２００Ｃ／ｄｍ２の範囲）を、表面形状パラメータＲｚが３．３４（μｍ）となる様に制御し、かつ工程ｅにおける電流密度を、陽極酸化皮膜量ＡＤＴが０．８９ｇ／ｍ２となる様に制御した以外は同様にして、支持体１６を作製した。 [Preparation of Support 16]
In the production of the support 1 described in Example 1, the current density and the electric quantity (in the range of 200 to 1200 C / dm 2 ) in the step c are controlled so that the surface shape parameter Rz is 3.34 (μm). And the support body 16 was produced similarly except having controlled the current density in the process e so that the amount of anodic oxide films ADT might be 0.89 g / m < 2 >.
　なお、表２に記載の各支持体の表面形状パラメータＲｚ（μｍ）及び陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）は、実施例１に記載の方法と同様にして測定した。 The surface shape parameter Rz (μm) and the anodic oxide film amount ADT (g / m 2 ) of each support described in Table 2 were measured in the same manner as in the method described in Example 1.
　《重合性画像形成層を有するネガ型の平版印刷版材料の作製》
　〔平版印刷版材料１５の作製〕
　上記作製した支持体１５上に、下記光重合性画像形成層塗工液３を乾燥後の固形分量が１．５ｇ／ｍ２となるようワイヤーバーを用いて塗布し、９５℃で１．５分間乾燥して光重合性画像形成層３を形成した。次いで、重合性画像形成層３上に、下記組成の酸素遮断層塗工液２を、乾燥後の固形分量が１．５ｇ／ｍ２となるようワイヤーバーを用いて塗布し、８５℃で１．０分間乾燥して、支持体上に画像形成層及び酸素遮断層を有する平版印刷版材料１５を作製した。 << Preparation of a negative lithographic printing plate material having a polymerizable image forming layer >>
[Preparation of planographic printing plate material 15]
The following photopolymerizable image-forming layer coating solution 3 is applied to the prepared support 15 using a wire bar so that the solid content after drying is 1.5 g / m 2, and is 1.5 at 95 ° C. The photopolymerizable image forming layer 3 was formed by drying for a minute. Next, an oxygen barrier layer coating liquid 2 having the following composition was applied on the polymerizable image forming layer 3 using a wire bar so that the solid content after drying was 1.5 g / m 2. Drying for 0 minute produced a lithographic printing plate material 15 having an image forming layer and an oxygen blocking layer on a support.
　（光重合性画像形成層塗工液３の調製）
　マルカリンカーＣＨＭ（丸善石油化学）　　　　　　　　　　　　４０．０質量部
　重合性モノマー１　　　　　　　　　　　　　　　　　　　　　　　５．０質量部
　重合性モノマー２　　　　　　　　　　　　　　　　　　　　　　２２．０質量部
　重合性モノマー３　　　　　　　　　　　　　　　　　　　　　　２２．０質量部
　分光増感剤２（前出）　　　　　　　　　　　　　　　　　　　　　３．５質量部
　ビスイミダゾール化合物（前出）　　　　　　　　　　　　　　　　３．５質量部
　メルカプト化合物（前出）　　　　　　　　　　　　　　　　　　　１．０質量部
　弗素系界面活性剤（ＦＣ－４４３０；住友スリーエム社製）　　　　０．５質量部
　シロキサン系界面活性剤（ＢＹＫ３３７；ビックケミー社製）　　　０．５質量部
　フタロシアニン顔料分散液ＭＨＩ＃４５４（御国色素製）　　　　　３．０質量部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　２５０質量部
　エタノール　　　　　　　　　　　　　　　　　　　　　　　　　　２５０質量部
　メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　　２００質量部
　プロピレングリコールメチルエーテル　　　　　　　　　　　　　　２００質量部 (Preparation of photopolymerizable image-forming layer coating solution 3)
Marcalinker CHM (Maruzen Petrochemical) 40.0 parts by mass Polymerizable monomer 1 5.0 parts by mass Polymerizable monomer 2 22.0 parts by mass Polymerizable monomer 3 22.0 parts by mass Spectral sensitizer 2 (supra) 3 0.5 parts by mass Bisimidazole compound (supra) 3.5 parts by mass Mercapto compound (supra) 1.0 part by mass Fluorosurfactant (FC-4430; manufactured by Sumitomo 3M) 0.5 part by mass Siloxane interface Activator (BYK337; manufactured by Big Chemie) 0.5 parts by weight Phthalocyanine pigment dispersion MHI # 454 (manufactured by Gokoku Dye) 3.0 parts by weight Water 250 parts by weight Ethanol 250 parts by weight Methyl ethyl ketone 200 quality Parts of propylene glycol methyl ether 200 parts by weight
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　（酸素遮断層塗工液２）
　下記雲母分散液１　　　　　　　　　　　　　　　　　　　　　　　４００質量部
　ポリビニルアルコール（Ｍｏｗｉｏｌ　４－９８：ケン化度９８、クラレスペシャリティーズヨーロッパ社製）　　　　　　　　　　　　　　　　　　　　　９０質量部
　ポリ（Ｎ－ビニルピロリドン）　ルビテックＫ３０（ＢＡＳＦ社製）　　５質量部
　ポリエチレンイミン（ルパゾールＷＦ：ＢＡＳＦ社製）　　　　　　　　５質量部
　界面活性剤（サーフィノール４６５：日信化学工業社製）　　　　　０．５質量部
　水　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　９００質量部
　〈雲母分散液１の調製〉
　水３６８ｇに合成雲母（ソフシマＭＥ－１００：コープケミカル社製、アスペクト比１０００以上）３２ｇを添加し、ホモジナイザーを用いて平均粒径（レーザ拡散法）０．５μｍになるまで分散し、雲母分散液１を得た。 (Oxygen barrier layer coating solution 2)
400 parts by weight of the following mica dispersion 1 Polyvinyl alcohol (Mowiol 4-98: degree of saponification 98, manufactured by Klares Specialties Europe) 90 parts by weight Poly (N-vinylpyrrolidone) Rubytec K30 (manufactured by BASF) 5 parts by weight polyethyleneimine (Lupazole WF: manufactured by BASF) 5 parts by mass Surfactant (Surfinol 465: manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 parts by mass Water 900 parts by mass <Preparation of Mica Dispersion 1>
To 368 g of water, 32 g of synthetic mica (Sofshima ME-100, manufactured by Co-op Chemical Co., Ltd., aspect ratio of 1000 or more) is added and dispersed using a homogenizer until the average particle size (laser diffusion method) becomes 0.5 μm. 1 was obtained.
　〔平版印刷版材料１６の作製〕
　上記平版印刷版材料１５の作製において、支持体１５に代えて支持体１６を用いた以外は同様にして、平版印刷版材料１６を作製した。 [Preparation of planographic printing plate material 16]
A lithographic printing plate material 16 was produced in the same manner as in the production of the lithographic printing plate material 15 except that the support 16 was used instead of the support 15.
　《平版印刷版の作製》
　上記作製した平版印刷版材料１５、１６を、下記処理液２Ａ～２Ｆを用いて現像処理した以外は、実施例１と同様にして露光、現像を行い、平版印刷版１５～２６を作製した。 << Preparation of lithographic printing plate >>
The lithographic printing plate materials 15 and 16 were exposed and developed in the same manner as in Example 1 except that the lithographic printing plate materials 15 and 16 were developed using the following treatment liquids 2A to 2F to produce lithographic printing plates 15 to 26.
　〔現像液組成〕
　（処理液２）
　界面活性剤：Ｎｅｗｃｏｌ　Ｂ１３ＳＮ（日本乳化剤株式会社製）　　　５ｇ／Ｌ
　シクロデキストリン　　　　　　　　　　　　　　　　　　　　　　　　１ｇ／Ｌ
　でんぷん（プリバイン：日殿化学株式会社）　　　　　　　　　　　　２０ｇ／Ｌ
　Ｇｌｏｂｅ　Ｐｌｕｓ　１０ＤＥ（Ｃｏｒｎ　Ｐｒｏｄｕｃｔｓ社製）　５ｇ／Ｌ
　ＣＭＣ　ＤＡＩＣＥＬ　１２０５（Ｄａｉｃｅｌ　Ｃｈｅｍｉｃａｌｓ社製）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　２ｇ／Ｌ
　殺菌剤Ｋａｔｈｏｎ　ＣＧ／ＩＣＰ（Ｒｏａｍ＆Ｈａａａｓ社製）　　　１ｇ／Ｌ
　リン酸　８５質量％溶液（Ｐｒａｙｏｎ社製）　　　　　　　　　　０．２ｇ／Ｌ
　硫酸（東京化成）　　　　　　　　　　　　表２記載の処理液ｐＨになるよう添加
　水で１Ｌに仕上げた。 [Developer composition]
(Processing liquid 2)
Surfactant: Newcol B13SN (manufactured by Nippon Emulsifier Co., Ltd.) 5g / L
Cyclodextrin 1g / L
Starch (Previne: Hita Chemical Co., Ltd.) 20g / L
Globe Plus 10DE (Corn Products) 5g / L
CMC DAICEL 1205 (manufactured by Daicel Chemicals)
2g / L
Disinfectant Kathon CG / ICP (Roam & Haaas) 1g / L
Phosphoric acid 85 mass% solution (manufactured by Playon) 0.2 g / L
Sulfuric acid (Tokyo Kasei) It was made up to 1 L with added water so that the pH of the treatment solution described in Table 2 was reached.
　上記処理液２において、ｐＨを１．５に調整した処理液を処理液２Ａ、ｐＨを２．０に調整した処理液を処理液２Ｂ、ｐＨを３．０に調整した処理液を処理液２Ｃ、ｐＨを５．０に調整した処理液を処理液２Ｄ、ｐＨを９．０に調整した処理液を処理液２Ｅ、ｐＨを１０．０に調整した処理液を処理液２Ｆとした。 In the above treatment liquid 2, the treatment liquid with pH adjusted to 1.5 is treatment liquid 2A, the treatment liquid with pH adjusted to 2.0 is treatment liquid 2B, and the treatment liquid with pH adjusted to 3.0 is treatment liquid 2C. The treatment liquid with pH adjusted to 5.0 was treated liquid 2D, the treatment liquid with pH adjusted to 9.0 was treated liquid 2E, and the treatment liquid with pH adjusted to 10.0 was treated liquid 2F.
　《平版印刷版の評価》
　実施例１に記載の方法と同様にして、ドットゲイン（％）の測定と耐刷性（回）の評価を行い、得られた結果を表２に示す。 << Evaluation of planographic printing plates >>
In the same manner as in the method described in Example 1, measurement of dot gain (%) and evaluation of printing durability (times) were performed, and the obtained results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表２に記載の結果より明らかなように、本発明で規定する特性を備えた支持体を有する平版印刷版材料を用いて作製した平版印刷版は、網点点質の劣化がなく、耐刷性に優れており、更には、ｐＨが２．０以上、９．０以下の処理液で現像処理することにより、上記効果をより奏することができ、かつ環境適性にも優れていることが分かる。 As is clear from the results shown in Table 2, the lithographic printing plate produced using the lithographic printing plate material having the support having the characteristics defined in the present invention has no deterioration of dot dot quality and printing durability. Furthermore, it can be seen that the above effects can be further exhibited and the environmental suitability is excellent by developing with a processing solution having a pH of 2.0 or more and 9.0 or less.
　実施例３
　《支持体の作製》
　〔支持体１７～２０の作製〕
　実施例１に記載の支持体１の作製において、工程ｃにおける電流密度及び電気量（２００～１２００Ｃ／ｄｍ２の範囲）を表３に記載の表面形状パラメータＲｚ（μｍ）となる様に制御し、かつ工程ｅにおける電流密度を表３に記載の陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）となる様に制御した以外は同様にして、表３に記載の表面形状パラメータＲｚ（μｍ）及び陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）を有する支持体１７～２０を作製した。 Example 3
<Production of support>
[Production of Supports 17 to 20]
In the production of the support 1 described in Example 1, the current density and the amount of electricity in step c (range of 200 to 1200 C / dm 2 ) were controlled so as to be the surface shape parameter Rz (μm) described in Table 3. The surface shape parameter Rz (μm) and the anode listed in Table 3 are the same except that the current density in step e is controlled to be the amount of anodized film ADT (g / m 2 ) listed in Table 3. Supports 17 to 20 having an oxide film amount ADT (g / m 2 ) were produced.
　〔支持体２１の作製〕
　実施例１に記載の支持体１２の作製において、工程ｃにおける電流密度及び電気量（２００～１２００Ｃ／ｄｍ２の範囲）を、表面形状パラメータＲｚが１．７５（μｍ）となる様に制御し、かつ工程ｅにおける電流密度を、陽極酸化皮膜量ＡＤＴが１．２０ｇ／ｍ２となる様に制御した以外は同様にして、支持体２１を作製した。 [Preparation of Support 21]
In the production of the support 12 described in Example 1, the current density and the electric quantity (in the range of 200 to 1200 C / dm 2 ) in step c are controlled so that the surface shape parameter Rz is 1.75 (μm). And the support body 21 was produced similarly except having controlled the current density in the process e so that the amount of anodic oxide films ADT might be 1.20 g / m < 2 >.
　なお、表３に記載の各支持体の表面形状パラメータＲｚ（μｍ）及び陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）は、実施例１に記載の方法と同様にして測定した。 The surface shape parameter Rz (μm) and the anodic oxide film amount ADT (g / m 2 ) of each support described in Table 3 were measured in the same manner as in the method described in Example 1.
　《感熱性画像形成層を有するネガ型の平版印刷版材料の作製》
　〔平版印刷版材料１７の作製〕
　上記作製した支持体１７上に、下記組成から成る感熱性画像形成層塗工液１（ネガ型感光性組成物）を、ワイヤーバーを用いて乾燥後の固形分量が１．４ｇ／ｍ２になるように塗布し、８０℃の温風循環型ドライヤー中に６０秒保持して乾燥させ、感熱性画像形成層を有するネガ型の平版印刷版材料である平版印刷版材料１７を作製した。 << Preparation of a negative planographic printing plate material having a heat-sensitive image forming layer >>
[Preparation of planographic printing plate material 17]
On the prepared support 17, the heat-sensitive image forming layer coating liquid 1 (negative photosensitive composition) having the following composition is dried to 1.4 g / m 2 using a wire bar. The lithographic printing plate material 17, which is a negative lithographic printing plate material having a heat-sensitive image forming layer, was produced by applying the coating solution in a warm air circulating dryer at 80 ° C. for 60 seconds.
　（感熱性画像形成層塗工液１）
　ノボラック樹脂（フェノールとｍ－，ｐ－混合クレゾールとホルムアルデヒドとの共縮合化合物）（Ｍｎ＝５００、Ｍｗ＝２５００、フェノールとｍ－，Ｐ－，クレゾールの割合は、５０：３０：２０（フェノール：ｍ：ｐ）（モル比））　　　８２質量部
　メラミン架橋剤（Ｍ－１）　　　　　　　　　　　　　　　　　　　　　８質量部
　酸発生剤（ＴＺ－１）　　　　　　　　　　　　　　　　　　　　　　　７質量部
　赤外線吸収色素（ＩＲ－１）　　　　　　　　　　　　　　　　　　１．６質量部
　可視画染料（ＤＹ－１）　　　　　　　　　　　　　　　　　　　　１．３質量部
　フッ素系界面活性剤（ＦＳ－１）　　　　　　　　　　　　　　　　０．１質量部
　プロピレングルコールモノメチルエーテル　　　　　　　　　　　　８００質量部
　メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　　２００質量部 (Thermosensitive image forming layer coating solution 1)
Novolac resin (co-condensation compound of phenol, m-, p-mixed cresol and formaldehyde) (Mn = 500, Mw = 2500, the ratio of phenol to m-, P-, cresol is 50:30:20 (phenol: m: p) (molar ratio)) 82 parts by mass Melamine crosslinking agent (M-1) 8 parts by mass Acid generator (TZ-1) 7 parts by mass Infrared absorbing dye (IR-1) 1.6 parts by mass Visible dye (DY-1) 1.3 parts by mass Fluorosurfactant (FS-1) 0.1 parts by mass Propylene glycol monomethyl ether 800 parts by mass Methyl ethyl ketone 200 parts by mass
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　〔平版印刷版材料１８～２１の作製〕
　上記平版印刷版材料１７の作製において、支持体１７に代えて、それぞれ支持体１８～２１を用いた以外は同様にして、平版印刷版材料１８～２１を作製した。 [Preparation of planographic printing plate materials 18-21]
In the production of the lithographic printing plate material 17, the lithographic printing plate materials 18 to 21 were produced in the same manner except that the supports 18 to 21 were used in place of the support 17, respectively.
　《平版印刷版の作製》
　上記作製した各平版印刷版材料を、８０８ｎｍの半導体レーザヘッドを搭載した市販のＣＴＰセッター（大日本スクリーン製造株式会社製、ＰＴＲ－４３００）を用い、ドラム回転数１０００ｒｐｍ、レーザ出力を３０～１００％に変化させて、解像度２４００ｄｐｉ（ｄｐｉとは１インチ即ち２．５４ｃｍ当たりのドット数を表す。）で１７５線相当の網点画像露光を行った。露光後の版を、１０５℃のオーブンで３分間加熱した後、自動現像機（ＰＫ－９１０、コダックポリクロームグラフィックス（株）製）および下記処理液ＰＤ－１を用いて３０℃で２５秒間、現像処理を行って、平版印刷版２７～３１を作製した。 << Preparation of lithographic printing plate >>
Each of the produced lithographic printing plate materials was used with a commercially available CTP setter (manufactured by Dainippon Screen Mfg. Co., Ltd., PTR-4300) equipped with a 808 nm semiconductor laser head, with a drum rotation speed of 1000 rpm and a laser output of 30 to 100%. The halftone image exposure corresponding to 175 lines was performed at a resolution of 2400 dpi (dpi represents the number of dots per inch, that is, 2.54 cm). The exposed plate was heated in an oven at 105 ° C. for 3 minutes, and then for 25 seconds at 30 ° C. using an automatic processor (PK-910, manufactured by Kodak Polychrome Graphics Co., Ltd.) and the following processing solution PD-1. Then, development processing was performed to prepare lithographic printing plates 27-31.
　〔現像液組成〕
　（処理液ＰＤ－１）
　珪酸カリウム水溶液（ＳｉＯ２：２９．１質量％）　　　　　　　 ２００質量部
　メタ珪酸ナトリウム　　　　　　　　　　　　　　　　　　　　　　２０質量部
　Ｄ－ソリビトール　　　　　　　　　　　　　　　　　　　　　　　３０質量部
　水酸化カリウム　　　　　（使用液１０００部としたときにｐＨ１３．４になる量）
　水で全体を１０００部とした。 [Developer composition]
(Processing liquid PD-1)
Potassium silicate aqueous solution (SiO 2 : 29.1% by mass) 200 parts by mass Sodium metasilicate 20 parts by mass D-Sorbitol 30 parts by mass Potassium hydroxide (amount that gives a pH of 13.4 when the used solution is 1000 parts)
The whole was made up to 1000 parts with water.
　《平版印刷版の評価》
　（画質評価：ドットゲインの評価）
　上記作製した各平版印刷版において、２％のドットが２％を再現する露光量の条件で、５０％を再現すべき網点画像の網％を測定し、その差をドットゲインの評価を示す指標として、その測定値を表３に示した。数値が０に近いほど良い。なお、網％測定は、Ｘ－ｒｉｔｅ社製のｉＣＰｌａｔｅIIを使用した。 << Evaluation of planographic printing plates >>
(Image quality evaluation: dot gain evaluation)
In each of the lithographic printing plates produced above, halftone dots of a halftone image to be reproduced 50% are measured under the condition of an exposure amount at which 2% dots reproduce 2%, and the difference indicates dot gain evaluation. The measured values are shown in Table 3 as an index. The closer the value is to 0, the better. The net% measurement was performed using iCPlate II manufactured by X-rite.
　（耐刷性の評価）
　作製した各平版印刷版を、印刷機（三菱重工業（株）製、ＤＡＩＹＡ１Ｆ－１）で、コート紙、印刷インキ（大日本インキ化学工業社製の、大豆油インキ：ナチュラリス１００）及び湿し水（東京インク（株）製Ｈ液ＳＧ－５１濃度１．５％）を用いて印刷を行った。印刷５００枚毎にプレートクリーナー（ウルトラプレートクリーナー（販売元：大日精化工業株式会社））で版面を拭き、印刷物上で、２％のドットが２％を再現する露光量の条件で、３％小点の欠落が発生するまでのプレートクリーナー拭き取り回数を耐刷性の指標とした。プレートクリーナー拭き取り回数が多いほど、耐刷性に優れていることを示す。 (Evaluation of printing durability)
Each prepared lithographic printing plate was coated with a printing machine (Mitsubishi Heavy Industries, Ltd., DAIYA1F-1), coated paper, printing ink (manufactured by Dainippon Ink & Chemicals, soybean oil ink: Naturalis 100) and dampening. Printing was performed using water (H liquid SG-51 concentration 1.5%, manufactured by Tokyo Ink Co., Ltd.). The plate surface is wiped with a plate cleaner (Ultra Plate Cleaner (Distributor: Dainichi Seika Kogyo Co., Ltd.)) every 500 prints, and 3% under the condition of the exposure amount that 2% dots reproduce 2% on the printed matter. The number of times the plate cleaner was wiped until the missing of a small dot occurred was used as an indicator of printing durability. The larger the number of plate cleaner wipes, the better the printing durability.
　以上により得られた各評価結果を、表３に示す。 Table 3 shows the evaluation results obtained as described above.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表３に記載の結果より明らかなように、本発明で規定する特性を備えた支持体を有する平版印刷版材料を用いて作製した平版印刷版は、比較例に対し、網点点質の劣化がなく、耐刷性に優れていることが分かる。 As is clear from the results shown in Table 3, the lithographic printing plate produced using the lithographic printing plate material having the support having the characteristics specified in the present invention has a dot dot deterioration compared to the comparative example. It can be seen that the printing durability is excellent.

Claims (5)

  1. 　アルミニウム支持体上に感光性組成物を含有する画像形成層を有する平版印刷版材料において、該アルミニウム支持体の画像形成層を有する面側の表面形状パラメータＲｚ（μｍ）が１．０μｍ以上、４．０μｍ以下で、陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）が０．１０ｇ／ｍ２以上、８．０ｇ／ｍ２以下であり、かつ表面形状パラメータＲｚ（μｍ）と陽極酸化皮膜量ＡＤＴ（ｇ／ｍ２）との積〔Ｒｚ×ＡＤＴ〕が、０．１１（μｍ・ｇ／ｍ２）以上、５．０（μｍ・ｇ／ｍ２）以下であることを特徴とする平版印刷版材料。 In a lithographic printing plate material having an image forming layer containing a photosensitive composition on an aluminum support, the surface shape parameter Rz (μm) on the surface side of the aluminum support having the image forming layer is 1.0 μm or more, 4 0.04 μm or less, an anodic oxide coating amount ADT (g / m 2 ) is 0.10 g / m 2 or more and 8.0 g / m 2 or less, and the surface shape parameter Rz (μm) and the anodic oxide coating amount ADT ( g / m 2 ) The product [Rz × ADT] is 0.11 (μm · g / m 2 ) or more and 5.0 (μm · g / m 2 ) or less. material.
  2. 　前記感光性組成物が、Ａ）付加重合可能なエチレン性二重結合含有単量体、Ｂ）光重合開始剤組成物及びＣ）高分子結合材を含有することを特徴とする請求の範囲第１項に記載の平版印刷版材料。 The photosensitive composition contains A) an ethylenic double bond-containing monomer capable of addition polymerization, B) a photopolymerization initiator composition, and C) a polymer binder. 2. The lithographic printing plate material according to item 1.
  3. 　前記感光性組成物が、ビスイミダゾール化合物を含有することを特徴とする請求の範囲第１項または第２項に記載の平版印刷版材料。 The lithographic printing plate material according to claim 1 or 2, wherein the photosensitive composition contains a bisimidazole compound.
  4. 　ｐＨが２．０以上、９．０以下の処理液で現像処理されることを特徴とする請求の範囲第１項から第３項のいずれか１項に記載の平版印刷版材料。 The lithographic printing plate material according to any one of claims 1 to 3, which is developed with a processing solution having a pH of 2.0 or more and 9.0 or less.
  5. 　波長が３５０ｎｍ以上、４５０ｎｍ以下のレーザで露光されることを特徴とする請求の範囲第１項から第４項のいずれか１項に記載の平版印刷版材料。 The lithographic printing plate material according to any one of claims 1 to 4, wherein the lithographic printing plate material is exposed with a laser having a wavelength of 350 nm or more and 450 nm or less.
PCT/JP2009/052653 2008-07-01 2009-02-17 Lithographic printing plate material WO2010001631A1 (en)

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JP2013064034A (en) * 2011-09-15 2013-04-11 Fujifilm Corp Coating composition, and image-forming material, planographic printing plate precursor and oxygen-barrier film, each using the composition
JP2018162348A (en) * 2017-03-24 2018-10-18 セイコーエプソン株式会社 Aqueous ink composition for inkjet recording and colorant liquid

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JPH09226263A (en) * 1995-12-04 1997-09-02 Bayer Corp Lithographic printing plate having smooth and lustrous surface
JPH1165105A (en) * 1997-06-13 1999-03-05 Konica Corp Image forming material and image forming method
JPH11286183A (en) * 1998-04-02 1999-10-19 Fuji Photo Film Co Ltd Aluminum support for lithographic printing plate and method for roughing it
JP2003103949A (en) * 2001-09-28 2003-04-09 Fuji Photo Film Co Ltd Support for lithographic printing plate and lithographic printing original plate using the support
JP2007538279A (en) * 2004-05-19 2007-12-27 アグファ・ゲヴェルト・ナームロゼ・ベンノートチャップ Method for producing photosensitive polymer printing plate
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013064034A (en) * 2011-09-15 2013-04-11 Fujifilm Corp Coating composition, and image-forming material, planographic printing plate precursor and oxygen-barrier film, each using the composition
JP2018162348A (en) * 2017-03-24 2018-10-18 セイコーエプソン株式会社 Aqueous ink composition for inkjet recording and colorant liquid

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