WO2008032511A1 - Image forming method, platen manufacturing method, engraving device, printing system, and platen material - Google Patents

Image forming method, platen manufacturing method, engraving device, printing system, and platen material Download PDF

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Publication number
WO2008032511A1
WO2008032511A1 PCT/JP2007/065425 JP2007065425W WO2008032511A1 WO 2008032511 A1 WO2008032511 A1 WO 2008032511A1 JP 2007065425 W JP2007065425 W JP 2007065425W WO 2008032511 A1 WO2008032511 A1 WO 2008032511A1
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Prior art keywords
image forming
printing
printing plate
image
particles
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PCT/JP2007/065425
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French (fr)
Japanese (ja)
Inventor
Masayuki Muraoka
Original Assignee
Konica Minolta Medical & Graphic, Inc.
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Application filed by Konica Minolta Medical & Graphic, Inc. filed Critical Konica Minolta Medical & Graphic, Inc.
Publication of WO2008032511A1 publication Critical patent/WO2008032511A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1066—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by spraying with powders, by using a nozzle, e.g. an ink jet system, by fusing a previously coated powder, e.g. with a laser

Definitions

  • Image forming method printing plate preparation method, plate making apparatus, printing system, and printing plate material
  • the present invention relates to a method for producing a printing plate, and more particularly to a method for producing a lithographic printing plate capable of on-press development.
  • CTP computer to plate
  • Printing plate materials used in CTP systems do not require development processing with processing solutions containing special chemicals (for example, alkalis, acids, solvents, etc.), and can be applied to conventional printing presses.
  • a phase change type printing plate material that does not require development processing at all
  • a printing plate material that is processed with water or a substantially neutral processing liquid mainly composed of water and a printing press.
  • printing plate materials called chemical-free type printing plate materials and processless type printing plate materials, such as V and printing plate materials that are developed at an early stage of printing and require a developing step in particular.
  • an on-machine development type in which a non-image portion of an image forming layer is removed using dampening water or ink on a printing machine.
  • Printing plate material provided with thermal image forming layer containing thermoplastic fine particles, water-soluble binder, photothermal conversion material on hydrophilic layer or aluminum grain as disclosed in No. 2938397 and Patent 2938398 Is known! These printing plate materials are used as a printing plate by forming an image by irradiating an actinic ray such as a laser imagewise and removing a non-image portion on a printing machine.
  • Processless printing plates using ink jet recording generally have a hydrophilic surface.
  • An oleophilic image forming material is applied image-wise to the printing plate material by an inkjet recording method, and the oleophilic image forming material applied image-wise is used as an image portion.
  • a hot melt type ink is supplied onto a support to form an image to produce a printing plate (see Patent Document 1), and an oil-based ink is used.
  • the plate making method (see Patent Document 3) is known!
  • Patent Document 1 JP-A-9 58144
  • Patent Document 2 JP-A-10-272753
  • Patent Document 3 Japanese Patent Laid-Open No. 5-204138
  • a printing plate material having an image forming layer that can be developed on-machine on a substrate having a hydrophilic surface, and a liquid containing an adhesive component is supplied imagewise to form an image.
  • Image forming method
  • a printing plate material characterized by being used in the image forming method described in 1 above;
  • a plate-making apparatus characterized by being used in the image forming method according to item 1;
  • a printing plate preparation method capable of obtaining a printing plate having excellent printing durability and halftone dot reproducibility, an image forming method, a printing plate material, and a plate making apparatus.
  • FIG. 1 is a schematic view showing an example of a plate making apparatus used in the image forming method of the present invention.
  • FIG. 2 is a schematic view showing the main part of the printing system of the present invention.
  • the present invention relates to an image forming method for producing a printing plate material, which comprises an adhesive component on a printing plate material having an on-machine developable image forming layer on a substrate having a hydrophilic surface.
  • An image is formed by supplying a liquid containing a liquid in an image-like manner.
  • a liquid containing an adhesive component is applied to an ink jet recording system on a printing plate material having an image forming layer that can be developed on-machine on a substrate having a hydrophilic surface.
  • a printing plate having excellent printing durability can be easily obtained at a low cost by supplying an image using the toner, forming an image, and performing on-press development on the printing press.
  • the hydrophilic surface according to the present invention is a surface in which the portion from which the image forming layer has been removed during printing can be a non-image portion having water retention and printing ink repellency, and the hydrophilic surface according to the present invention.
  • the substrate having a surface can be obtained by a method of hydrophilizing the surface of the substrate or a method of providing a hydrophilic layer containing a hydrophilic substance on the substrate.
  • the printing plate material according to the present invention may have an image forming layer on the side having a hydrophilic surface, and may have a backing layer or the like on the other side as necessary.
  • the base material according to the present invention a known base material used for a conventional printing plate material is used.
  • the base material for example, a metal plate, a plastic film, a polyolefin or the like is used. And a composite support obtained by appropriately bonding the above materials.
  • the thickness of the base material is not particularly limited as long as it can be attached to a printing press. Generally, a thickness of 50 to 500 ⁇ m is handled! /, Easy! / ⁇ .
  • plastic film As a substrate.
  • the plastic film include polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide, polycarbonate, polysulfone, polyphenylene oxide, and cellulose esters. And the like.
  • polyester films such as polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polyethylene naphthalate (hereinafter sometimes abbreviated as PEN) are used as the base material.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • a preferable polyester film is an unstretched polyester film, a uniaxially stretched polyester film, or a biaxially stretched polyester film.
  • a longitudinally stretched polyester film uniaxially stretched in the film extrusion direction (longitudinal direction) is particularly preferred.
  • PET is polymerized with terephthalic acid and ethylene glycol
  • PEN polymerized with naphthalenedicarboxylic acid and ethylene glycol as constituent components.
  • the dicarboxylic acid or diol constituting PET or PEN may be polymerized by mixing other suitable one type or two or more third components.
  • a suitable third component is a compound having a divalent ester-forming functional group. Examples of the dicarboxylic acid include the following.
  • terephthalic acid isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid, cyclo Hexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioether dicarboxylic acid, diphenylketone dicarboxylic acid, phenylindanedicarboxylic acid, and the like.
  • glycols examples include propylene glycol, tetramethylene glycol, and succinate.
  • Oral hexanedimethanol, 2,2-bis (4-hydroxyphenenole) propane, 2,2-bis (4-hydroxyethoxyphenol) propane, bis (4-hydroxyphenolinosulfone), bisphenol Examples include nore orange hydroxyethinoreethenole, diethyleneglycolole, neopentinoleglycol, hydroquinone, cyclohexanediol and the like.
  • a polyfunctional carboxylic acid or a polyhydric alcohol can also be mixed, and these can be mixed in an amount of about 0.00; .
  • the intrinsic viscosity of the polyester film is preferably 0.5 to 0.8. In addition, different intrinsic viscosities may be mixed and used.
  • the method for polymerizing the polyester film is not particularly limited, and can be produced according to a conventionally known method for polymerizing a polyester.
  • polymerization is performed by directly esterifying a dicarboxylic acid component with a diol component, diesterifying one hydroxyl group of the diol to a dicarboxylic acid, and heating one of the diols under reduced pressure to distill off the excess diol.
  • Direct esterification method or using a dialkyl ester (for example, dimethyl ester) as a dicarboxylic acid component, and transesterifying with the diol component to distill alkyl alcohol (for example, methanol) to distill the diol. It is possible to use a transesterification method in which one hydroxyl group is esterified to a dicarboxylic acid, and the excess diol component is polymerized by heating and distilling off under reduced pressure.
  • a dialkyl ester for example, dimethyl ester
  • alkyl alcohol for example, methanol
  • a transesterification catalyst As the catalyst, a transesterification catalyst, a polymerization reaction catalyst, and a heat-resistant stabilizer that are used for the synthesis of ordinary polyester can be used.
  • transesterification catalysts Ca (OAc) .HO, Zn (OAc) .2H 2 O, Mn (OAc) .4H 2 O, Mg (OAc) 4 Sb 2 0 3 and Ge 0 2 can be mentioned as catalysts.
  • examples of the heat resistant stabilizer include phosphoric acid, phosphorous acid, PO (OH) (CH 3), PO (OC H), P (OC H) and the like.
  • Stabilizers may be added.
  • the heat treatment should be accomplished by the following means after cooling and winding after completion of heat setting and then unwinding in a separate step.
  • a transport method in which both ends of a film such as a tenter are gripped with pins or clips, a roll transport method using a plurality of roll groups, a method of transporting air by blowing air onto the film, and the like Method of spraying heated air from one or both sides of a film surface from a plurality of slits
  • a method of using radiant heat by an infrared heater a method of heat-treating a method of contacting with a plurality of heated rolls singly or in combination
  • the tension of the heat treatment can be adjusted by adjusting the torque of the take-up roll and / or the delivery roll and / or by installing a dancer roll in the process and adjusting the load applied thereto.
  • Ding ⁇ + 50 ° Ji ⁇ Ding ⁇ + 0.99 ° Ji temperature range preferred instrument temperature range of poly E ester film as the processing temperature, preferably from preferably tool is 5Pa ⁇ lMPa as conveying tension Is from 5 Pa to 500 kPa, more preferably from 5 Pa to 200 kPa, and the treatment day interval is preferably from 30 to 30 minutes, more preferably from 30 seconds to 15 minutes.
  • the above temperature range, conveyance tension range, and treatment time fine scratches due to friction with the conveyance roll, etc., which do not deteriorate the flatness of the support due to partial differences in the thermal contraction of the support during heat treatment, are possible. Occurrence of etc. The force to avoid being pressed.
  • the heat-treated polyester film is cooled from a temperature near Tg to room temperature and then wound up. In order to prevent deterioration of flatness due to cooling at this time, at least 5 ° C / It is preferable to cool at a speed of more than a second! /.
  • the water content of the substrate is preferably 0.5% by mass or less.
  • the moisture content of the substrate is D ′ represented by the following formula.
  • W ' is the mass of the support in humidity conditioning equilibrium at 25 ° C and 60% relative humidity, and is the moisture content of the support in humidity conditioning equilibrium at 25 ° C and 60% relative humidity. Represents content.
  • the water content of the base material is preferably 0.5% by mass or less, more preferably 0.01-0.5% by mass, particularly preferably 0.01-0.3% by mass. %.
  • Means for controlling the moisture content of the base material to 0.5% by mass or less are as follows: (1) The support is heat-treated at 100 ° C or higher immediately before applying the coating liquid for the hydrophilic layer and other layers. (2) Control the relative humidity in the process of applying the coating solution for the hydrophilic layer and other layers. (3) Prior to applying the coating solution for the hydrophilic layer and other layers, the support should be 100 ° C. For example, heat treatment, cover with a moisture-proof sheet, store, and apply immediately after opening. Two or more of these may be combined.
  • the particles may be organic or inorganic! /, Or may be misaligned! /.
  • organic substances silica described in Swiss Patent No. 330, 158 and the like, glass powder described in French Patent No. 1,296, 995 and the like, British Patent No. 1, 173, It is possible to use alkaline earth metals or carbonates such as cadmium and zinc described in No.181.
  • Organic substances include starch described in U.S. Pat.No. 2,322,037, etc., starch derivatives described in Belgian Patent 625,451 and British Patent 981,198, etc. Polybulual alcohol described in Japanese Patent Publication No. 44-3643, etc. Polystyrene or polymethacrylate as described in US Patent No. 330,158, etc., polyacrylonitrile as described in US Pat. No. 3,079,257, US Pat. No. 3, 02 2,169, etc. Organic fine particles such as polycarbonates described in the documents can be used. The shape of the particles may be either regular or irregular.
  • polyester film substrate easy adhesion treatment or undercoat layer coating can be performed to give various functions.
  • Examples of the easy adhesion treatment include corona discharge treatment, flame treatment, plasma treatment, and ultraviolet irradiation treatment.
  • the undercoat layer a layer containing gelatin or latex or the like is preferably provided on the polyester film support.
  • the antistatic undercoat layer described in paragraph Nos. 0044 to 0116 of JP-A-7-191433 is preferably used.
  • the conductive polymer-containing layer described in JP-A-7-20596, step number 003;! To 0073 is conductive like the metal oxide-containing layer described in paragraph Nos. 0074 to 0081 of JP-A-7-20596. It is preferable to have a layer! As long as the conductive layer is on the polyester film support, it may be coated on the side of displacement, but it is preferably coated on the opposite side of the image forming layer with respect to the support. When this conductive layer is provided, the charging property is improved, the adhesion of dust and the like is reduced, and white spots failure during printing is greatly reduced.
  • the plastic film as described above when used as the substrate, it is preferable to provide a hydrophilic layer on the substrate to provide a substrate having a hydrophilic surface.
  • the hydrophilic layer preferably has a porous structure.
  • hydrophilic layer having a porous structure In order to form a hydrophilic layer having a porous structure, the following materials for forming a hydrophilic matrix are preferably used.
  • the material for forming the hydrophilic matrix is preferably a metal oxide.
  • Examples of the metal oxide preferably include metal oxide fine particles include colloidal silica, alumina sol, titania sol, and other metal oxide sols.
  • the money The form of the metal oxide fine particles may be spherical, needle-like, feather-like, or any other form, and the average particle diameter is 3 to; several types with different average particle diameters preferably in the range of OOnm. These metal oxide fine particles can also be used in combination. Further, the surface of the particles may be surface-treated.
  • the metal oxide fine particles can be used as a binder by utilizing the film-forming property. It is suitable for use in a hydrophilic layer where the decrease in hydrophilicity is less than when an organic binder is used.
  • colloidal silica can be particularly preferably used.
  • Colloidal silica has the advantage of high film forming properties even under relatively low temperature drying conditions, and can provide good strength.
  • the colloidal silica preferably includes a necklace-shaped colloidal silica, which will be described later, and a fine particle colloidal silica having an average particle size of 20 ⁇ m or less. Further, the colloidal silica preferably exhibits alkalinity as a colloid solution.
  • Necklace-shaped colloidal silica is a general term for an aqueous dispersion of spherical silica having a primary particle diameter of the order of nm, and spherical colloidal silica having a primary particle diameter of 10 to 50 nm has a length of 50 to 400 nm. It means the combined “pearl necklace” colloidal silica.
  • the pearl necklace shape (that is, the pearl necklace shape) means an image power in a state in which the silica particles of colloidal silica are joined together and shaped like a pearl necklace! /.
  • the bonding between the silica particles constituting the pearl necklace-like colloidal silica is presumed to be Si—O—Si in which SiOH groups present on the surface of the silica particles are dehydrated.
  • colloidal silica in the form of pearl necklace include the “Snowtex 1? 3” series manufactured by Nissan Chemical Industries, Ltd., and the product name is “Snowtex 1 PS-S (average particles in a connected state).
  • colloidal silica has a stronger binding force as the particle size is smaller.
  • colloidal silica having an average particle size of 20 nm or less. 3 to; 15 nm.
  • colloidal silica is particularly preferable because it is alkaline and has an effect of suppressing the occurrence of soiling.
  • alkaline colloidal silica having an average particle size in this range include ⁇ Snowtex 20 (particle size 10-20 nm) '' and ⁇ Snotex 30 (particle size 10-20 nm) manufactured by Nissan Chemical Co., Ltd. ), “Snowtex 1 40 (particle size 10-20 nm)”, “Snowtex 1 N (particle size 10-20 nm)”, “Snowtex 1 S (particle size 8; l lnm)”, “Snowtex XS (particle diameter 4-6 nm) ”.
  • Colloidal silica having an average particle size of 20 nm or less can be used in combination with the aforementioned pearl necklace-like colloidal silica to further improve the strength while maintaining the porosity of the layer to be formed. Is particularly preferred.
  • the ratio of colloidal silica / pearl necklace-shaped colloidal silica having an average particle diameter of 20 nm or less is preferably in the range of 95/5 to 5/95, more preferably in the range of 70 / 30-20 / 80. The more preferable range is 60/40 to 30/70.
  • the porous metal oxide particles having a particle size of less than 111 m can be contained as the porous material having a hydrophilic layer matrix structure.
  • porous metal oxide particles the following porous silica, porous aluminosilicate particles, or zeolite particles can be preferably used.
  • the porous silica particles are generally produced by a wet method or a dry method.
  • the gel obtained by neutralizing the aqueous silicate solution is dried, ground, or neutralized and precipitated. It is possible to obtain force S by grinding the sediment.
  • silicon tetrachloride is burned with hydrogen and oxygen, and silica is deposited.
  • the porosity and particle size of these particles can be controlled by adjusting the production conditions.
  • the porous silica particles those obtained from a wet gel are particularly preferred.
  • Porous aluminosilicate particles are produced, for example, by the method described in JP-A-10-71764. That is, amorphous composite particles synthesized by hydrolysis using aluminum alkoxide and silicon alkoxide as main components. The ratio of alumina to silica in the particles can be synthesized in the range of 1: 4 to 4: 1. In addition, particles produced by adding other metal alkoxides at the time of production as composite particles of three or more components can also be used in the present invention. The porosity and particle size of these composite particles can also be controlled by adjusting the production conditions.
  • the porosity of the particles is preferably 0.5 ml / g or more in terms of pore volume, more preferably 0.8 ml / g or more, and 1.0 to 2.5 ml / g. More preferably it is.
  • the pore volume is closely related to the water retention of the coating film. The larger the pore volume, the better the water retention and the greater the water volume latitude that is difficult to get smudged during printing. If the particle size is larger than 1, the particle itself becomes very brittle, and the durability of the coating film is lowered. Conversely, if the pore volume is less than 0.5 ml / g, the printing performance may be slightly insufficient.
  • the pore volume is measured by using Auto Soap 1 (manufactured by Cantachrome), and the powder voids are filled with nitrogen by nitrogen adsorption measurement using a constant volume method.
  • the relative pressure is calculated from the nitrogen adsorption amount at 0.998.
  • Zeolite is a crystalline aluminosilicate, and has a pore size of 0.3 nm or more; a porous body having regular regular LV of Inm and voids of a three-dimensional network structure.
  • the hydrophilic layer matrix structure constituting the hydrophilic layer can contain layered clay mineral particles.
  • the layered mineral particles include kaolinite, halloysite, talc, smetite (montmorillonite, piderite, hectorite, sabonite, etc.), clay minerals such as vermiculite, my strength (mica), chlorite, and hyde mouth tar.
  • Site layered polycaic acid Salt (such as kanemite, macatite, eyelite, magadiite, kenyaite).
  • the higher the charge density of the unit layer (unit layer) the higher the polarity and the higher the hydrophilicity.
  • the charge density is preferably 0.25 or more, more preferably 0.6 or more.
  • the layered mineral having such a charge density include smectite (charge density of 0.25 to 0.6; negative charge), vermiculite (charge density of 0.6 to 0.9; negative charge) and the like.
  • synthetic fluorine mica is preferable because it can be obtained with a stable quality such as particle size. Further, among the synthetic fluorine mica, those that are swellable are preferable, and those that are free swell are more preferable.
  • the layered mineral intercalation compounds such as billard crystals
  • surface treatment silane coupling treatment, compounding treatment with organic binder, etc.
  • the size of the plate-like layered mineral particles is less than the average particle size (maximum particle length) force, im in the state of being contained in the layer (including the case of undergoing the swelling process and dispersion peeling process).
  • the aspect ratio is 50 or more.
  • the particle size is in the above range, the continuity and flexibility in the planar direction, which are the characteristics of thin layered particles, are imparted to the coating film, and the cracking force S can be reduced to make it a tough coating film in a dry state. it can.
  • sedimentation of the particulate matter can be suppressed by the thickening effect of the layered clay mineral.
  • the coating film may become non-uniform and the strength may be locally reduced.
  • the aspect ratio is not more than the above range, the number of tabular grains relative to the added amount is decreased, the thickening is insufficient, and the effect of suppressing the sedimentation of the particles is reduced.
  • the content of the layered mineral particles is preferably 0.;! To 30% by mass of the entire layer.
  • swellable synthetic fluoromica is preferred because smectite is effective even when added in a small amount.
  • the layered mineral particles may be added to the coating solution in powder form! /, But good dispersion can be obtained by a simple preparation method (requiring no dispersion step such as media dispersion! /). Therefore, it is preferable to prepare a gel in which lamellar mineral particles are swelled alone in water and then add it to the coating solution.
  • the hydrophilic layer in the matrix other additives material constituting the hydrophilic layer, it can be force s to be used Kei salt water solution. Alkali metal silicates such as Na, Ca and Li are preferred.
  • the SiO / MO ratio is such that the pH of the entire coating solution does not exceed 13 when the caate is added. It is preferable to select it in order to prevent dissolution of inorganic particles.
  • an inorganic polymer or an organic-inorganic hybrid polymer by a so-called sol-gel method using a metal alkoxide can also be used.
  • sol-gel method for example, the force described in “Application of the sol-gel method” (published by Sakuo Sakuo / Agne Jofusha) or cited in this book Known methods described in the published literature can be used.
  • a water-soluble resin may be contained!
  • the water-soluble resin include polysaccharides, polyethylene oxide, polypropylene oxide, polybutyl alcohol, polyethylene glycol (PEG), polybutyl ether, styrene butadiene copolymer, and conjugated methyl methacrylate / butadiene copolymer.
  • examples include resins such as gen-based polymer latex, acrylic polymer latex, bulle polymer latex, polyacrylamide, and polybulurpyrrolidone, and the water-soluble resin used in the present invention uses polysaccharides. It is preferable.
  • polysaccharides starches, celluloses, polyuronic acids, pullulans, and the like can be used, and cellulose derivatives such as methyl cellulose salts, carboxymethyl cellulose salts, and hydroxyethyl cellulose salts are particularly preferable. Sodium salt and ammonium salt are more preferable. This is because the effect of forming the surface shape of the hydrophilic layer in a favorable state can be obtained by incorporating the polysaccharide into the hydrophilic layer.
  • the surface of the hydrophilic layer should have an uneven structure with a pitch of 0.;! To 20 m, like the aluminum grain of the PS plate. S Preferably, the unevenness improves water retention and image area retention. To do.
  • a concavo-convex structure can be formed by adding an appropriate amount of a filler having an appropriate particle size to the hydrophilic layer matrix, and the alkaline colloidal silica described above and the above-described alkaline colloidal silica in the hydrophilic layer coating solution. Contains water-soluble polysaccharides and causes phase separation when the hydrophilic layer is applied and dried A structure having better printability can be obtained.
  • the shape of the concavo-convex structure depends on the type and amount of alkaline colloidal silica, the type and amount of water-soluble polysaccharides, the type and amount of other additives, and the solid content of the coating liquid. It is possible to appropriately control the concentration, wet film thickness, drying conditions, and the like.
  • the water-soluble resin to be added to the hydrophilic matrix structure part may exist in a state where at least a part thereof is water-soluble and can be eluted in water. preferable. This is because even if a water-soluble material is cross-linked by a cross-linking agent or the like and becomes insoluble in water, its hydrophilicity is lowered and printability may be deteriorated.
  • examples of the cationic resin that may further contain a cationic resin include polyalkylene polyamines such as polyethyleneamine and polypropylenepolyamine or derivatives thereof, tertiary amino groups, and quaternary ammonia. Examples thereof include an acrylic resin having a group and diacrylamine.
  • the force thione resin may be added in the form of fine particles, for example, a cationic microgel described in JP-A-6-161101.
  • the coating liquid used for coating the hydrophilic layer may contain a water-soluble surfactant for the purpose of improving the coating property, and the interface of Si system or F system etc.
  • a surfactant containing Si element in particular, because there is no fear of causing printing stains.
  • the content of the surfactant is preferably 0.0;! To 3% by mass, more preferably 0.03 to 1% by mass of the entire hydrophilic layer (solid component as the coating solution).
  • the hydrophilic layer may contain a phosphate.
  • the hydrophilic layer coating solution is preferably alkaline, it is preferable to add the phosphate as trisodium phosphate or disodium hydrogen phosphate. By adding phosphate, the effect of improving the mesh opening during printing can be obtained.
  • the addition amount of phosphate is preferably 0.5 to 5% by mass, more preferably 0.5 to 2% by mass, as an effective amount excluding hydrates.
  • aluminum or an aluminum alloy (hereinafter referred to as aluminum) is particularly preferred because of the relationship between the force S that can be used for iron, stainless steel, aluminum, etc., and the specific gravity and rigidity. ,.
  • the aluminum substrate is not roughened or anodized to form a hydrophilic surface. It is preferable to use it after applying it.
  • the aluminum substrate is preferably subjected to a degreasing treatment in order to remove the rolling oil on the aluminum surface prior to the roughening treatment.
  • a degreasing treatment using a solvent such as trichlene or thinner an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used.
  • an aqueous alkali solution such as sodium hydroxide, lithium hydroxide, sodium carbonate, or sodium phosphate can also be used.
  • an alkaline aqueous solution is used for the degreasing treatment, it cannot be removed only by the above degreasing treatment! /, And dirt and oxide film can also be removed.
  • the roughening of the substrate can be performed by chemical roughening, mechanical roughening, or roughening by appropriately combining these.
  • an anodizing treatment is preferably performed.
  • a known method without particular limitation can be used for the method of anodizing treatment.
  • the anodized base material may be subjected to a sealing treatment as necessary.
  • These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, steam treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.
  • the anodized base material can be appropriately subjected to a surface treatment other than the above-described sealing treatment.
  • the surface treatment include known treatments such as silicate treatment, phosphate treatment, various organic acid treatments, PVP A treatment, and boehmite treatment.
  • the treatment with an aqueous solution containing a bicarbonate described in JP-A-8-314157 or the treatment with an aqueous solution containing a bicarbonate may be followed by an organic acid treatment such as citrate.
  • an easy adhesion treatment or undercoat layer coating on the coated surface.
  • a method of performing sufficient drying after dipping in a liquid containing a coupling agent such as a silane coupling agent or applying a liquid for example, a method of performing sufficient drying after dipping in a liquid containing a coupling agent such as a silane coupling agent or applying a liquid.
  • the image forming layer according to the present invention is a layer that can be developed on a printing press, and is described in, for example, JP-A-8-507727 or JP-A-6-186750 in which thermal laser recording or thermal head recording is performed.
  • Printing plate materials of an ablation type such as those described above and a development type and a thermal melting transfer type on a thermal fusion image layer as described in JP-A-9 123387 The image forming layer used for the material can be used.
  • a layer that can be developed on a printing press is an image forming layer formed by supplying dampening water or dampening water and printing ink onto a printing plate material and printing on the printing press after forming an image. This is a layer from which the non-image area can be removed.
  • the image forming layer is particularly preferably a layer containing a lipophilic component and a water-soluble binder, preferably a layer containing a lipophilic component! /.
  • the oleophilic component is one that can be made to accept printing ink when the image forming layer is printed, and is particularly preferably in the form of particles and contained in the image forming layer.
  • thermoplastic polymer particles are preferably used, and examples thereof include lipophilic heat-fusible particles or heat-fusible particles.
  • a softening point of 40 ° C or higher preferably a softening point of 40 ° C or higher and 120 ° C or lower, and a melting point of 60 ° C or higher and 150 ° C or lower, in terms of storage stability and ink deposition properties. More preferably, the temperature is 100 ° C or lower and the melting point is 60 ° C or higher and 120 ° C or lower.
  • Examples of materials that can be used include paraffin, polyolefin, polyethylene wax, microcrystalline wax, and fatty acid wax. These have a molecular weight of about 800 to 10,000, and in order to facilitate emulsification, these waxes may be oxidized to introduce polar groups such as hydroxyl groups, ester groups, carboxyl groups, aldehyde groups, and peroxide groups. it can. Furthermore, in order to lower the softening point and improve workability, these waxes include, for example, stearamide, linolenamide, laurylamide, myristenoreamide, hardened beef fatty acid amide, palmitoamide, oleic acid amide, rice sugar fatty acid.
  • amides coconut fatty acid amides, methylolated products of these fatty acid amides, methylene bissteraroamide, ethylene bissteraroamide, and the like.
  • Coumarone indene resin, rosin-modified phenol resin, terpene-modified phenol resin, xylene resin, ketone resin, acrylic resin, ionomer, and copolymers of these resins can also be used. [0105] Among these, it is preferable to contain any of polyethylene, microcrystalline, fatty acid ester, and fatty acid.
  • These heat-meltable particles are preferably dispersible in water, and the average particle diameter is preferably 0 ⁇ 0;! To 10 m from the viewpoint of on-machine developability. Is 0 ⁇ 05-3111.
  • a nonionic surfactant an anionic surfactant, a cationic surfactant, or a polymer surfactant.
  • composition of the heat-meltable particles may vary continuously between the inside and the surface layer, or may be coated with a different material.
  • a coating method a known microcapsule formation method, a sol-gel method, or the like can be used.
  • the content of the heat-meltable particles in the image forming layer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass of the entire layer.
  • thermoplastic hydrophobic polymer particles examples include thermoplastic hydrophobic polymer particles, and there is no specific upper limit for the softening temperature of the thermoplastic hydrophobic polymer particles. It is preferable that it is lower than the decomposition temperature.
  • the weight average molecular weight (Mw) of the polymer is preferably in the range of 10,000-1, 000,000.
  • thermoplastic hydrophobic polymer particles include, for example, gen (co) polymers such as polypropylene, polybutadiene, polyisoprene, and ethylene butadiene copolymer, styrene.
  • gen (co) polymers such as polypropylene, polybutadiene, polyisoprene, and ethylene butadiene copolymer, styrene.
  • Synthetic rubbers such as butadiene copolymer, methyl methacrylate-butadiene copolymer, acrylonitrile-butadiene copolymer, polymethyl methacrylate, methyl methacrylate (2-ethylhexyl acrylate) copolymer, methyl Methacrylate-methacrylic acid copolymer, methyl acrylate (N methylol acrylamide) copolymer, (meth) acrylic acid ester such as polyacrylonitrile, (meth) acrylic acid (co) polymer, polyacetic acid butyl, acetic acid butyl Propionate butyl copolymer, butyl acetate / ethylene copolymer Bulle ester (co) polymer of the polymer such as, acetic Bulle one (2 Ethyl hexyl acrylate) copolymer, polybutyl chloride, polyvinylidene chloride, polystyrene and the like, and copoly
  • the thermoplastic hydrophobic polymer particles may be made of a polymer polymer polymerized by any known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a gas phase polymerization method.
  • the polymer polymerized by the solution polymerization method or the gas phase polymerization method is made into fine particles by spraying a solution in an organic solvent of the polymer polymer into an inert gas and drying it. And a method in which a polymer is dissolved in an organic solvent immiscible in water, this solution is dispersed in water or an aqueous medium, and the organic solvent is distilled off to form fine particles.
  • the heat-meltable particles and the heat-fusible particles may be used as a dispersant or a stabilizer, for example, sodium lauryl sulfate, dodecylbenzenesulfone, or the like when polymerized or finely divided.
  • a surfactant such as sodium acid or polyethylene glycol or a water-soluble resin such as polybutyl alcohol may be used.
  • the heat-fusible particles are dispersible in water.
  • the average particle size is preferably 0.01 to 10 ⁇ m from the viewpoint of on-image development and resolution. More preferably 0.;! ⁇ 3 ⁇ m ⁇ ).
  • composition of the heat-fusible particles may vary continuously between the inside and the surface layer, or may be coated with a different material.
  • a coating method a known microcapsule formation method, a sol-gel method, or the like can be used.
  • the content of the heat-fusible particles in the image forming layer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass of the entire layer.
  • Water-soluble binders that can be used in the image forming layer include polysaccharides, polyethylene oxide, polypropylene oxide, polybutyl alcohol, polyethylene glycol (PEG), polybutyl ether, styrene butadiene copolymer, methyl metatalylate butadiene copolymer Conjugated Conjugated Polymer Latex, Acrylic Polymer Latex And resin such as bulle polymer latex, polyacrylamide, polyacrylic acid or salts thereof, and polyvinylpyrrolidone. Among them, it is preferable to use polyataryl acid or a salt or polysaccharide thereof that does not deteriorate the printing performance.
  • the content of the water-soluble binder in the image forming layer is preferably 1.0% by mass to 30% by mass, particularly preferably 5% by mass to 20% by mass.
  • the image-forming layer according to the present invention may contain a photothermal conversion material described later.
  • the dry coating weight of the image forming layer is preferably 0 .;! To 1.5 g / m 2 , more preferably 0.15 to. Og / m.
  • the printing plate material according to the present invention preferably contains a photothermal conversion material in the image forming layer because it can also be used as a heat-sensitive image forming material.
  • an infrared absorbing dye or pigment can be used as the photothermal conversion material.
  • infrared absorbing dyes examples include cyanine dyes, chromium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyridium dyes, naphthoquinone dyes, anthraquinone dyes, which are general infrared absorbing dyes. And organic metal complexes of phthalocyanine, naphthalocyanine, azo, thiamide, dithiol, and indoor diphosphorus.
  • Examples of the pigment include carbon, graphite, metal, metal oxide and the like.
  • the particle size (d50) is preferably lOOnm or less, more preferably 50 nm or less.
  • the particle size of the graphite is 0.5 111 or less, preferably lOOnm or less, more preferably
  • Fine particles of 50 nm or less can be used.
  • any metal can be used as long as the particle diameter is 0.5 ⁇ m or less, preferably lOOnm or less, more preferably 50 nm or less.
  • the shape may be any shape such as a sphere, a piece, or a needle. Colloidal metal fine particles (Ag, Au, etc.) are particularly preferred.
  • the metal oxide it is possible to use a material that exhibits black color in a visible light castle! /, A material that is electrically conductive, or that is a semiconductor.
  • Materials that are black in the visible light range include black iron oxide (Fe 2 O 3) and black containing two or more of the aforementioned metals.
  • the metal oxide is a black complex metal oxide composed of two or more kinds of metal oxides. Specifically, it is a complex metal oxide composed of two or more metals selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, and Ba. These can be produced by the methods disclosed in JP-A-8-27393, JP-A-9-25126, JP-A-9-237570, JP-A-9-241529 and JP-A-10-231441. .
  • the composite metal oxide that can be used in the present invention is particularly preferably a Cu-Cr-Mn-based or Cu-Fe-Mn-based composite metal oxide.
  • composite metal oxides have good coloration with respect to the amount added, that is, good photothermal conversion efficiency.
  • These composite metal oxides preferably have an average primary particle size of 1 in or less, and an average primary particle size in the range of 0.01 to 0.5 m is preferable. When the average primary particle size is 1 m or less, the photothermal conversion capacity with respect to the added amount becomes better, and when the average primary particle size is within the range of 0.01 to 0.5 m, the light heat with respect to the added amount is increased. The conversion ability becomes better.
  • the photothermal conversion ability with respect to the amount added is greatly affected by the degree of dispersion of the particles, and the better the dispersion, the better. Therefore, it is preferable to disperse these composite metal oxide particles by a known method separately before adding them to the layer coating solution to prepare a dispersion (paste).
  • An average primary particle size of less than 0.01 is not preferable because dispersion becomes difficult.
  • a dispersing agent can be appropriately used for the dispersion.
  • the addition amount of the dispersant is preferably 0.0 ;! to 5% by mass with respect to the composite metal oxide particles 0.;! To 2 The mass% is more preferable.
  • the type of dispersant is not particularly limited, but it is preferable to use a Si-based surfactant containing Si elements.
  • Examples of materials that have conductivity or are semiconductors include, for example, SnO doped with Sb (ATO), In O with added Sn (ITO), TiO, and TiO. Examples thereof include TiO (titanium oxynitride, generally titanium black). In addition, it is possible to use those metal oxides coated with a core material (BaSO, TiO, 9A1 2 ⁇ 20, KO-nTiO, etc.). Their particle size is 0.5 111 or less, preferably 10 nm or less, more preferably 50 nm or less.
  • the addition amount of these light-to-heat conversion materials is preferably 0.;! To 50% by mass with respect to the image forming layer. S is preferable. Furthermore,! To 30% by mass is preferable. % Is more particularly preferred
  • an image is formed by supplying a liquid containing an adhesive component onto the image forming layer of the printing plate material in an image-like manner.
  • the liquid containing the adhesive component according to the present invention is supplied onto the image forming layer and penetrates into the image forming layer.
  • the adhesive component refers to an image forming layer, that is, an image portion to which a liquid containing the adhesive component is supplied by increasing the adhesive force between the image forming layer and the hydrophilic layer surface of the base material after penetrating the image forming layer. It can be prevented from being removed by on-press development. Adhesive strength can be increased by the presence of the adhesive component at the interface between the substrate surface and the image forming layer. In addition, the adhesion between the oleophilic component and the water-soluble binder in the image forming layer is also increased, which makes it difficult to remove by on-press development.
  • Adhesive components include natural adhesive components such as casein, natural latex, starch and gelatin, acrylic acid and its derivatives, acrylic resin, polyester resin, copolymer resin of ⁇ -olefin and maleic anhydride, urethane resin , Polyol isocyanate with a hydroxyl group at the terminal, ethylene 'bule acetate resin, epoxy resin precursor, chloride resin, acetate resin, cyanoacrylate, silicone, styrene' butadiene rubber copolymer, nitrocellulose , Phenolic resin, petital resin and the like S, among which urethane resin, acrylic resin, polyester resin, butyral
  • the power at which a polyol resin is used More preferably, a polyester resin and a petital resin are preferable from the viewpoint of printing durability, and a petital resin is particularly preferable.
  • the content of the adhesive component with respect to the entire liquid is preferably 0.5 to 80% by mass, more preferably 2 to 50% by mass, and particularly preferably 2 to 25% by mass.
  • the solvent of the liquid containing the adhesive component it is preferable to use various solvents in which the adhesive component dissolves.
  • the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol), polyhydric alcohols (eg, ethylene glycol, ethylene glycol) Nore, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexane dianol, pentanediol, glycerin, hexane triol, thioglycol) , Glycol ethers (e.g., ethylene glycol monomethyl ether, diethylene glycol monomethino ethenore, triethylene glycol monomono methinore Tenole, diethylene glycol monobutyl ether,
  • alcohols eg
  • the above solvent is preferably one that is supplied onto the image forming layer and then removed from the image forming layer by volatilization or the like.
  • dipropylene glycol monomethyl ether and ethyl acetate are used.
  • Preferred are a mixed solvent of N-glycoleno retino enoate, a mixed solvent of diethylene glucono-resin methino reetenole and propylene carbonate, and the like.
  • the content of the solvent with respect to the entire liquid is preferably 20 to 99% by mass, more preferably 50 to 98% by mass.
  • the method of supplying the liquid containing the adhesive component in an image-like manner includes a method of supplying fine droplets from an inkjet nozzle by handwriting using a brush, an inkjet recording method, and the like.
  • a method of supplying an image by an ink jet recording method is more preferably used.
  • liquid containing the adhesive component is a droplet by an ink jet recording method is a preferred embodiment.
  • liquid containing the adhesive component is an inkjet ink used in the inkjet recording method.
  • the preferred viscosity of the liquid containing the adhesive component is 2 to 25 ° C, more preferably lOOmPa's, more preferably , 4-80mPa's.
  • the pigment conventionally known organic and inorganic colored pigments can be preferably used, and as the colored pigment, for example, azo pigments such as azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment, phthalocyanine pigment, perylene. And perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinophthaloni pigments, etc., dye lakes such as acid dye lakes, nitro pigments, nitroso pigments, aniline Examples thereof include organic pigments such as black and daylight fluorescent pigments, and inorganic pigments such as carbon black. In the present invention, carbon black is particularly preferable from the viewpoint of visible image quality.
  • azo pigments such as azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment, phthalocyanine pigment, perylene.
  • perylene pigments anthraquinone
  • Styrene acrylic acid acrylic acid alkyl ester copolymer styrene acrylic acid copolymer, styrene maleic acid copolymer, styrene maleic acid acrylic acid alkyl ester copolymer, which are preferably used as the water-soluble resin, Water-soluble such as styrene-methacrylic acid copolymer, styrene-methacrylic acid acrylic acid alkyl ester copolymer, styrene maleic acid half ester copolymer, urunaphthalene acrylic acid copolymer, urunaphthalene maleic acid copolymer, etc. Resin.
  • the content of the water-soluble resin with respect to the total amount of the ink is preferably 0.;! To 10% by mass, and more preferably 0.3 to 5% by mass. Two or more of these water-soluble resins can be used in combination.
  • the average particle diameter of the pigment dispersion used in the inkjet ink is preferably 500 nm or less, more preferably 200 nm or less, more preferably lOnm or more and 200 nm or less, from the viewpoint of the storage stability of the ink, preferably lOnm or more. 150 nm or less is particularly preferable.
  • a method for dispersing the pigment various methods such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker can be used.
  • the dye examples include water-soluble dyes such as acidic dyes, direct dyes, and reactive dyes, and disperse dyes that are not particularly limited.
  • water-soluble dyes examples include azo dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, phthalocyanine dyes, triphenylmethane dyes, diphenylmethane dyes, and the like.
  • Ink-jet inks may contain surfactants such as alkyl sulfates, alkyl ester sulfates, dialkyl sulfosuccinates, alkyl naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates.
  • surfactants such as alkyl sulfates, alkyl ester sulfates, dialkyl sulfosuccinates, alkyl naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates.
  • Anionic surfactants such as salts and fatty acid salts
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, acetylene glycols and polyoxyethylene polyoxypropylene block copolymers
  • Surfactants such as glycerin esters, sorbitan esters, polyoxyethylene fatty acid amides and amines, and cationic surfactants such as alkylamine salts and quaternary ammonium salts.
  • the ink-jet ink can contain other conventionally known additives.
  • fluorescent brighteners for example, fluorescent brighteners, antifoaming agents, lubricants, preservatives, thickeners, antistatic agents, matting agents, water-soluble polyvalent metal salts, acid bases, buffer solutions, etc.pH adjusters, antioxidants, surfaces
  • tension adjusters specific resistance adjusters, and antifungal agents.
  • ink jet ink is supplied to a printer head having ink ejection nozzles of an inkjet recording system printer, and an image-like image is formed from the ink ejection nozzles of the printer head. Then, it is discharged onto the surface of the image forming layer. After that, it is preferable to carry out an actinic ray irradiation treatment using ultraviolet rays, infrared rays, etc., or a heat treatment for drying the discharged droplets.
  • the ink-jet ink preferably has a viscosity at 25 ° C adjusted to 4 to 80 mPa's from the viewpoint of ejection stability.
  • Ink-jet inks are preferred to have an electrical conductivity of 10 S / cm or less in the piezo head, without electrical corrosion inside the head! /, And ink! / ⁇ .
  • In the continuous type it is necessary to adjust the conductivity with an electrolyte. In this case, it is preferable to adjust the conductivity to 0.5 mS / cm or more.
  • the plate making apparatus of the present invention is a plate making apparatus used in the image forming method of the present invention, and has an image recording means for supplying the liquid containing the adhesive component according to the present invention imagewise, and a drying means for performing drying. .
  • the image recording means there are preferably used nozzles used in the ink jet recording method as described above, and nozzles used in the ink jet recording method.
  • the drying means a means for contacting with heated air, such as a means for contacting with heated air, a means for contacting with a medium such as a heated drum, is preferably used.
  • FIG. 1 shows an example of a plate making apparatus used in the image forming method of the present invention.
  • the printing plate material 1 is conveyed through the roller 2 from the printing plate material roll 7 in which the printing plate material is wound in a roll shape.
  • the conveyed printing plate material is cut by cutter 3 into a size that can be used as a printing plate.
  • the liquid containing the adhesive component is supplied in droplets via an inkjet head 4, which is an image recording means for supplying the liquid containing the adhesive component in an image-like manner. Is done. After the liquid containing the adhesive component is supplied onto the printing plate material, it is dried by the drying means 5. The printing plate material thus image-formed is subjected to on-machine image formation by a printing machine to produce a printing plate.
  • a general lithographic printing machine is used as a printing machine used in the method for preparing a printing plate of the present invention.
  • the lithographic printing machine has a dampening water supply device and a printing ink supply device.
  • Development on the printing press according to the present invention is performed by supplying dampening water or dampening water and printing ink onto the printing plate material on which an image is formed.
  • the development on the printing press according to the present invention can be performed in a normal printing sequence using a PS plate, and is preferably a process performed by so-called on-press development processing. It is.
  • the printing plate production method of the present invention can be performed by a system having the plate making apparatus and the lithographic printing machine of the present invention, and the plate making apparatus and the lithographic printing machine of the present invention are arranged in series.
  • a printing system or a system in which a plate making apparatus is installed in a lithographic printing machine can be used.
  • FIG. 2 shows an example of a system in which a plate making apparatus is installed in a lithographic printing machine, that is, a printing system having an image recording means and a drying means in a lithographic printing machine.
  • a liquid containing an adhesive component is supplied in an image-like manner from an inkjet recording head 4 as image recording means onto a printing plate material 27 mounted on the plate cylinder 21, and dried by the drying means 5.
  • printing ink is supplied from the dampening water supply roller 22 on the printing press from the dampening water supply roller 22 and the on-press development is carried out to produce a printing plate.
  • the printing ink that can be used in the method for preparing a printing plate of the present invention may be any ink that can be used for lithographic printing. Specifically, rosin-modified phenolic resin and vegetable oil (Amani oil) , Tung oil, soybean oil, etc.), petroleum-based solvents, pigments, oxidative polymerization catalysts (cobalt, manganese, lead, iron, zinc, etc.) and other oil-based inks, acrylic oligomers, acrylic monomers, photopolymerization initiators UV curable UV inks composed of components such as pigments, and hybrid inks that combine the properties of oil-based inks and UV inks.
  • rosin-modified phenolic resin and vegetable oil Mani oil
  • Tung oil, soybean oil, etc. petroleum-based solvents
  • pigments oxidative polymerization catalysts (cobalt, manganese, lead, iron, zinc, etc.) and other oil-based inks
  • acrylic oligomers acrylic monomers
  • fountain solution a general fountain solution used for lithographic printing can be used.
  • the fountain solution contains a water-soluble organic solvent such as an alkylene glycol monoalkyl ether compound, a pH adjuster, an auxiliary agent for improving wettability, a water-soluble polymer compound, a chelating agent, and a preservative. I prefer to use it.
  • a water-soluble organic solvent such as an alkylene glycol monoalkyl ether compound, a pH adjuster, an auxiliary agent for improving wettability, a water-soluble polymer compound, a chelating agent, and a preservative. I prefer to use it.
  • part represents “part by mass” unless otherwise specified.
  • a corona discharge treatment of 8 W / m 2 / min was applied to both sides of the support film obtained above.
  • the undercoat coating solution a shown in Table 1 below was applied on one surface so that the coating solution film thickness was 10 m, and then dried at 180 ° C. for 4 minutes.
  • the undercoat coating solution b in Table 2 below was applied on top of it, apply the undercoat coating solution b in Table 2 below to a coating solution film thickness of 11 m, and dry at 180 ° C for 4 minutes. It was.
  • Porous gold oxide Shilton JC— 40
  • Porous metal oxide Shilton JC-1 7Q
  • Cu Fe ttn metal oxide black pigment TS-50 black powder
  • Trinatto phosphate Vum '12 hydrate (manufactured by Kanto Chemical Co.) 0 quality 3 ⁇ 4% aqueous solution 0,32 parts Titanium oxide-containing iron oxide: £ TB-300 (Ako Kasei Co., Ltd. average particle size 200M) 22.00 parts Spherical silica soot particles: Pipe resiliency FQ
  • the lower hydrophilic layer coating solution is applied onto the substrate coated with the undercoat layer using wire bar # 5 and the drying zone set at 100 ° C with a length of 15m is transported at a conveyance speed of 15m / It was passed at a rate of minutes. Subsequently, the upper layer hydrophilic layer coating solution was applied using wire bar # 4, and the substrate having a hydrophilic surface was obtained by passing the drying zone set at 100 ° C of 30 m length at a conveyance speed of 15 m / min. Produced.
  • the applied amounts of the lower hydrophilic layer and the upper hydrophilic layer were 3. Og / m 2 and 1.8 g / m 2 , respectively.
  • the coated sample was aged at 60 ° C for 1 day.
  • the image forming layer coating solution having the composition shown in Table 5 below is applied on the upper hydrophilic layer provided as described above using wire bar # 4, and dried at 70 ° C with a length of 30 m.
  • a lithographic printing plate material was prepared by passing through the zone at a conveyance speed of 15 m / min.
  • the weight of the image forming layer was 0.5 g / m 2 . After application, aging was performed at 50 ° C for 2 days.
  • Polyacrylic bowl 8a 0L-522
  • the above lithographic printing plate material is cut to a width of 660mm and wound 30m around a paper core with an outer diameter of 76rmm.
  • a rolled lithographic printing plate material was obtained.
  • the present invention is a.
  • the present invention i: (tree) ⁇ powder powder) bully (power)
  • FIG. 1 A schematic diagram of a plate making apparatus for image formation is shown in FIG. 1
  • the lithographic printing plate material 1 produced as described above is conveyed by a roller 2 and cut into a predetermined size, and then the liquid containing the adhesive component adjusted as described above is used as an inkjet ink. From the inkjet head 4 of the inkjet printer (not shown) The lithographic printing plate material 1 was supplied as droplets.
  • the inkjet head a piezo-type head having a nozzle diameter of 25 m, a driving frequency of 12 kHz, a nozzle number of 128, and a nozzle density of 180 dpi (where dpi represents the number of dots per 2.54 cm) was used.
  • the drying temperature is 50 ° C by means of drying means 5.
  • Drying was performed under the condition of a drying time of 5 seconds.
  • Printing apparatus On-press development was performed using Lithlon 26P manufactured by Komori Corporation, and printing was performed. Printing evaluation was performed with OK top coat for printing paper, Fast mouth mark 3 for fountain solution (Niken Chemical Laboratory Co., Ltd.) 2% by mass, and ink with Fusion-G made by Dainippon Ink and Chemicals.
  • the minimum percentage of halftone dots that were normally reproduced on the 100th printed sheet was determined, and small dot reproducibility was evaluated as an index of halftone dot reproducibility.
  • the stage at which a decrease in the solid density of the printed material was confirmed was regarded as the printing end point, and the number of sheets obtained was determined as an index of printing durability.

Abstract

Provided are a platen manufacturing method for acquiring such a platen easily at a low cost as can perform an on-printer development and as is excellent in printing endurance and dot reproducibility, and an image forming method, a platen material and an engraving device, which are used in the platen manufacturing method. The image forming method is characterized in that a liquid containing an adhesive component is fed in conformity to an image onto the engraving material having an on-printer developable image forming layer on a substrate having a hydrophilic surface, thereby to form an image.

Description

明 細 書  Specification
画像形成方法、印刷版の作製方法、製版装置、印刷システムおよび印刷 版材料  Image forming method, printing plate preparation method, plate making apparatus, printing system, and printing plate material
技術分野  Technical field
[0001] 本発明は、印刷版の作製方法に関するものであり、特に機上現像可能な平版印刷 版の作製方法に関する。  TECHNICAL FIELD [0001] The present invention relates to a method for producing a printing plate, and more particularly to a method for producing a lithographic printing plate capable of on-press development.
背景技術  Background art
[0002] 近年、オフセット印刷用の印刷版の作製技術において、画像のデジタルデータをレ 一ザ一光源で直接印刷版材料に記録する CTP (コンピューター .トゥー'プレート)シ ステムが普及してきた。  [0002] In recent years, CTP (computer to plate) systems that record digital image data directly on a printing plate material with a laser light source have become widespread in the technology for producing printing plates for offset printing.
[0003] CTPシステムに使用される印刷版材料として、特別な薬剤（例えばアルカリ、酸、溶 媒など）を含む処理液による現像処理を必要とせず、従来の印刷機に適用可能であ る印刷版材料が求められており、例えば、全く現像処理を必要としない相変化タイプ の印刷版材料、水もしくは水を主体とした実質的に中性の処理液で処理をする印刷 版材料、印刷機上で印刷の初期段階で現像処理を行い特に現像工程を必要としな V、印刷版材料などの、ケミカルフリータイプ印刷版材料やプロセスレスタイプ印刷版 材料と呼ばれる印刷版材料が知られている。  [0003] Printing plate materials used in CTP systems do not require development processing with processing solutions containing special chemicals (for example, alkalis, acids, solvents, etc.), and can be applied to conventional printing presses. For example, a phase change type printing plate material that does not require development processing at all, a printing plate material that is processed with water or a substantially neutral processing liquid mainly composed of water, and a printing press. There are known printing plate materials called chemical-free type printing plate materials and processless type printing plate materials, such as V and printing plate materials that are developed at an early stage of printing and require a developing step in particular.
[0004] これらのプロセスレス CTPとしては、印刷機上で湿し水やインキを用いて画像形成 層の非画像部を除去する、機上現像タイプが知られており、この例として例えば、特 許 2938397号や特許 2938398号に開示されているような、親水性層もしくはアルミ 砂目上に熱可塑性微粒子、水溶性の結合剤、光熱変換素材を含有する感熱画像形 成層を設けた印刷版材料が知られて!/、る。これらの印刷版材料はレーザなどの活性 光線を画像様に照射することにより画像が形成され、印刷機上で非画像部が除去さ れて印刷版として利用される。  [0004] As these processless CTPs, an on-machine development type is known in which a non-image portion of an image forming layer is removed using dampening water or ink on a printing machine. Printing plate material provided with thermal image forming layer containing thermoplastic fine particles, water-soluble binder, photothermal conversion material on hydrophilic layer or aluminum grain as disclosed in No. 2938397 and Patent 2938398 Is known! These printing plate materials are used as a printing plate by forming an image by irradiating an actinic ray such as a laser imagewise and removing a non-image portion on a printing machine.
[0005] 一方、プロセスレスタイプの印刷版材料を用いる画像形成方法としては、インクジェ ット記録方式も有力な手段のひとつとして提案されている。  On the other hand, as an image forming method using a processless type printing plate material, an inkjet recording method has been proposed as one of the effective means.
[0006] インクジェット記録方式によるプロセスレス印刷版は、一般的には親水性表面を有 する印刷版材料に、インクジェット記録方式により親油性の画像形成素材を画像様に 付与し、画像様に付与された親油性の画像形成素材を画像部とするものである。 [0006] Processless printing plates using ink jet recording generally have a hydrophilic surface. An oleophilic image forming material is applied image-wise to the printing plate material by an inkjet recording method, and the oleophilic image forming material applied image-wise is used as an image portion.
[0007] インクジェット記録方式を利用した印刷版の作製方法としては、ホットメルト型インク を支持体上に供給し画像を形成して印刷版を作製する方法 (特許文献 1参照）、油 性インクを静電界を利用して吐出させてインクジェット方式で画像を形成する製版方 法（特許文献 2参照）、あるいは光重合性インク組成物をインク吸収層を有する支持 体上に供給して画像を形成する製版方法 (特許文献 3参照）などが知られて!/、る。  [0007] As a method for producing a printing plate using an ink jet recording method, a hot melt type ink is supplied onto a support to form an image to produce a printing plate (see Patent Document 1), and an oil-based ink is used. A plate making method in which an electrostatic field is used to form an image by an ink jet method (see Patent Document 2), or a photopolymerizable ink composition is supplied onto a support having an ink absorbing layer to form an image. The plate making method (see Patent Document 3) is known!
[0008] しかしながら、上記の感熱画像形成層を設けた印刷版材料を使用する場合には、 露光に比較的高価な露光装置を必要とする、耐刷性が不充分な場合がある、網点 再現性が不充分な場合があると!/、つた問題があり、またインクジェット記録方式を用 V、た製版方法では耐刷性が不充分である、と!/、つた問題があった。  However, when using the printing plate material provided with the thermal image forming layer, a halftone dot which requires a relatively expensive exposure apparatus for exposure and may have insufficient printing durability. In some cases, the reproducibility is insufficient! /, And there are other problems, and the plate making method using the ink jet recording method has insufficient printing durability! /.
特許文献 1 :特開平 9 58144号公報  Patent Document 1: JP-A-9 58144
特許文献 2 :特開平 10— 272753号公報  Patent Document 2: JP-A-10-272753
特許文献 3：特開平 5— 204138号公報  Patent Document 3: Japanese Patent Laid-Open No. 5-204138
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0009] 本発明の目的は、印刷機上現像が可能であって、安価なコストで、簡易に、耐刷性 に優れ、網点再現性に優れた印刷版が得られる印刷版の作製方法、それに用いら れる画像形成方法、印刷版材料、製版装置を提供することにある。 [0009] An object of the present invention is a method for producing a printing plate that can be developed on a printing press, can be obtained at a low cost, simply, with excellent printing durability, and with excellent halftone dot reproducibility. Another object of the present invention is to provide an image forming method, a printing plate material, and a plate making apparatus used therefor.
課題を解決するための手段  Means for solving the problem
[0010] 本発明の上記目的は、下記構成により達成される。 [0010] The object of the present invention is achieved by the following constitution.
1.親水性表面を有する基材上に機上現像可能な画像形成層を有する印刷版材料 上に、接着成分を含有する液を、画像様に供給し、画像を形成することを特徴とする 画像形成方法。  1. A printing plate material having an image forming layer that can be developed on-machine on a substrate having a hydrophilic surface, and a liquid containing an adhesive component is supplied imagewise to form an image. Image forming method.
2.前記接着成分がプチラール樹脂であることを特徴とする 1に記載の画像形成方法  2. The image forming method according to 1, wherein the adhesive component is a petal resin.
3.前記画像形成層が親油性成分を含有することを特徴とする 1または 2に記載の画 像形成方法。 4.前記接着成分を含有する液が、インクジェット記録方式による液滴であることを特 徴とする;!〜 3のいずれか 1項に記載の画像形成方法。 3. The image forming method according to 1 or 2, wherein the image forming layer contains a lipophilic component. 4. The image forming method according to any one of [1] to [3] above, wherein the liquid containing the adhesive component is a droplet by an ink jet recording method.
5.前記接着成分を含有する液が有色顔料を含有することを特徴とする 1〜4のいず れか 1項に記載の画像形成方法。  5. The image forming method according to any one of 1 to 4, wherein the liquid containing the adhesive component contains a colored pigment.
6.前記有色顔料がカーボンブラックであることを特徴とする 5に記載の画像形成方 法。 7.；!〜 6のいずれ力、 1項に記載の画像形成方法により得られた、画像を有する印 刷版材料、を印刷機上で現像し印刷版を作製することを特徴とする印刷版の作製方 法。  6. The image forming method according to 5, wherein the colored pigment is carbon black. 7. A printing plate obtained by developing on a printing machine a printing plate material having an image obtained by the image forming method according to 1 above, which is any force of! How to make
8.；!〜 6のいずれ力、 1項に記載の画像形成方法に用いられることを特徴とする印刷 版材料。  8. A printing plate material characterized by being used in the image forming method described in 1 above;
9.；!〜 6のいずれ力、 1項に記載の画像形成方法に用いられることを特徴とする製版 装置。  9. A plate-making apparatus characterized by being used in the image forming method according to item 1;
10. 7に記載の印刷版の作製方法に用いられる印刷システムであって、 9に記載の 製版装置及び平版印刷機を有することを特徴とする印刷システム。  10. A printing system for use in the method for producing a printing plate as described in 7, comprising the plate making apparatus and the lithographic printing machine as described in 9.
発明の効果  The invention's effect
[0011] 本発明の上記構成により、印刷機上現像が可能であって、安価なコストで、簡易に [0011] According to the above configuration of the present invention, development on a printing press is possible, and it is simple and inexpensive.
、耐刷性に優れ、網点再現性に優れた印刷版が得られる印刷版の作製方法、それ に用いられる画像形成方法、印刷版材料、製版装置が提供できる。 In addition, it is possible to provide a printing plate preparation method capable of obtaining a printing plate having excellent printing durability and halftone dot reproducibility, an image forming method, a printing plate material, and a plate making apparatus.
図面の簡単な説明  Brief Description of Drawings
[0012] [図 1]本発明の画像形成方法に用いられる製版装置の例を示す概略図である。  FIG. 1 is a schematic view showing an example of a plate making apparatus used in the image forming method of the present invention.
[図 2]本発明の印刷システムの主要部を示す概略図である。  FIG. 2 is a schematic view showing the main part of the printing system of the present invention.
符号の説明  Explanation of symbols
[0013] 1 印刷版材料 [0013] 1 Printing plate material
2 ローラ  2 Roller
3 カッター  3 Cutter
4 インクジェット記録ヘッド  4 Inkjet recording head
5 乾燥手段  5 Drying means
6 集積トレィ 7 印刷版材料ロール 6 Integrated tray 7 Printing plate material roll
21 版胴  21 plate cylinder
22 湿し水供給ローラ  22 Dampening water supply roller
23 印刷インキ供給ローラ  23 Printing ink supply roller
25 圧胴 25 impression cylinder
26 印刷用紙  26 Printing paper
27 印刷版材料  27 Printing plate materials
31 印刷機  31 Printing machine
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0014] 本発明は、印刷版材料を作製するための画像形成方法であって、親水性表面を有 する基材上に機上現像可能な画像形成層を有する印刷版材料上に、接着成分を含 有する液を、画像様に供給し、画像を形成することを特徴とする。 [0014] The present invention relates to an image forming method for producing a printing plate material, which comprises an adhesive component on a printing plate material having an on-machine developable image forming layer on a substrate having a hydrophilic surface. An image is formed by supplying a liquid containing a liquid in an image-like manner.
[0015] 本発明にお!/、ては、特に、親水性表面を有する基材上に機上現像可能な画像形 成層を有する印刷版材料上に、接着成分を含有する液をインクジェット記録方式を 用いて供給し、画像を形成し、印刷機上で、機上現像を行うことにより、安価なコスト で、簡易に、耐刷性に優れた印刷版が得られる。 [0015] In the present invention, in particular, a liquid containing an adhesive component is applied to an ink jet recording system on a printing plate material having an image forming layer that can be developed on-machine on a substrate having a hydrophilic surface. A printing plate having excellent printing durability can be easily obtained at a low cost by supplying an image using the toner, forming an image, and performing on-press development on the printing press.
[0016] [印刷版材料] [0016] [Printing plate materials]
本発明に係る親水性表面とは、印刷時に、画像形成層が除去された部分が水保持 性を有し印刷インキ反撥性を有する非画像部、となりうる表面であり、本発明に係る 親水性表面を有する基材は、基材の表面を親水化処理する方法あるいは基材上に 親水性物質を含む親水性層を設ける方法により得られる。  The hydrophilic surface according to the present invention is a surface in which the portion from which the image forming layer has been removed during printing can be a non-image portion having water retention and printing ink repellency, and the hydrophilic surface according to the present invention. The substrate having a surface can be obtained by a method of hydrophilizing the surface of the substrate or a method of providing a hydrophilic layer containing a hydrophilic substance on the substrate.
[0017] 本発明に係る印刷版材料は、親水性表面を有する側に画像形成層を有し、他方の 面に必要に応じ裏塗り層等を有してもよい。 [0017] The printing plate material according to the present invention may have an image forming layer on the side having a hydrophilic surface, and may have a backing layer or the like on the other side as necessary.
[0018] [基材] [0018] [Substrate]
本発明に係わる基材としては、従来の印刷版材料に用いられる公知の基材を使用 すること力 Sでさる。  As the base material according to the present invention, a known base material used for a conventional printing plate material is used.
[0019] 基材としては、例えば、金属板、プラスチックフィルム、ポリオレフイン等で処理され た紙、上記材料を適宜貼り合わせた複合支持体等が挙げられる。 [0019] As the base material, for example, a metal plate, a plastic film, a polyolefin or the like is used. And a composite support obtained by appropriately bonding the above materials.
[0020] 基材の厚さとしては、印刷機に取り付け可能であれば特に制限されるものではない 、通常 50〜500 μ mのものが一般的に取り扱!/、やす!/ヽ。 [0020] The thickness of the base material is not particularly limited as long as it can be attached to a printing press. Generally, a thickness of 50 to 500 μm is handled! /, Easy! / ヽ.
[0021] 本発明においては、基材としてプラスチックフィルムを用いることが好ましぐプラス チックフィルムとしては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリイ ミド、ポリアミド、ポリカーボネート、ポリスルホン、ポリフエ二レンオキサイド、セルロース エステル類等のフィルムを挙げることができる。 [0021] In the present invention, it is preferable to use a plastic film as a substrate. Examples of the plastic film include polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide, polycarbonate, polysulfone, polyphenylene oxide, and cellulose esters. And the like.
[0022] 本発明では、これらのプラスチックフィルムのうち、特にポリエチレンテレフタレート（ 以降、略して PETという場合がある）、ポリエチレンナフタレート（以降、 PENと略すこ とがある）などのポリエステルフィルムが基材として好ましく用いられる。 In the present invention, among these plastic films, polyester films such as polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polyethylene naphthalate (hereinafter sometimes abbreviated as PEN) are used as the base material. Are preferably used.
[0023] さらに特開平 10— 10676号に記載の方法で得られた 120°C30秒での熱寸法変 化率が 0. 001 %以上 0. 04%以下の支持体を用いることが好ましい。 [0023] Furthermore, it is preferable to use a support obtained by the method described in JP-A-10-10676 and having a thermal dimensional change at 120 ° C for 30 seconds of from 0.001% to 0.04%.
[0024] 好ましいポリエステルフィルムとしては、未延伸ポリエステルフィルム、一軸延伸ポリ エステルフィルムまたは二軸延伸ポリエステルフィルムである。 [0024] A preferable polyester film is an unstretched polyester film, a uniaxially stretched polyester film, or a biaxially stretched polyester film.
[0025] このうちフィルムの押出し方向（縦方向）に一軸延伸した縦延伸ポリエステルフィル ムが特に好ましい。 Of these, a longitudinally stretched polyester film uniaxially stretched in the film extrusion direction (longitudinal direction) is particularly preferred.
[0026] PETはテレフタル酸とエチレングリコール、また PENはナフタレンジカルボン酸とェ チレングリコールを構成成分として重合されたものである。  [0026] PET is polymerized with terephthalic acid and ethylene glycol, and PEN polymerized with naphthalenedicarboxylic acid and ethylene glycol as constituent components.
[0027] PETまたは PENを構成するジカルボン酸またはジオールを他の適当な 1種、また は 2種以上の第 3成分を混合して重合したものでもよい。適当な第 3成分としては、 2 価のエステル形成官能基を有する化合物で、例えば、ジカルボン酸の例として次の ようなものを挙げることができる。  [0027] The dicarboxylic acid or diol constituting PET or PEN may be polymerized by mixing other suitable one type or two or more third components. A suitable third component is a compound having a divalent ester-forming functional group. Examples of the dicarboxylic acid include the following.
[0028] テレフタル酸、イソフタル酸、フタル酸、 2, 6—ナフタレンジカルボン酸、 2, 7—ナフ タレンジカルボン酸、ジフエニルスルホンジカルボン酸、ジフエニルエーテルジカルボ ン酸、ジフエニルエタンジカルボン酸、シクロへキサンジカルボン酸、ジフエ二ルジカ ノレボン酸、ジフエ二ルチオエーテルジカルボン酸、ジフエ二ルケトンジカルボン酸、フ ェニルインダンジカルボン酸等を挙げることができる。  [0028] terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid, cyclo Hexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioether dicarboxylic acid, diphenylketone dicarboxylic acid, phenylindanedicarboxylic acid, and the like.
[0029] また、グリコールの例としては、プロピレングリコール、テトラメチレングリコール、シク 口へキサンジメタノーノレ、 2, 2—ビス（4—ヒドロキシフエニノレ）プロパン、 2, 2—ビス（4 ーヒドロキシエトキシフエ二ノレ）プロパン、ビス（4ーヒドロキシフエ二ノレ）スルホン、ビス フエノーノレフノレオレンジヒドロキシェチノレエーテノレ、ジエチレングリコーノレ、ネオペン チノレグリコール、ハイドロキノン、シクロへキサンジオール等を挙げることができる。 [0029] Examples of glycols include propylene glycol, tetramethylene glycol, and succinate. Oral hexanedimethanol, 2,2-bis (4-hydroxyphenenole) propane, 2,2-bis (4-hydroxyethoxyphenol) propane, bis (4-hydroxyphenolinosulfone), bisphenol Examples include nore orange hydroxyethinoreethenole, diethyleneglycolole, neopentinoleglycol, hydroquinone, cyclohexanediol and the like.
[0030] 第 3成分としては多官能性カルボン酸や多価アルコールも混合することができるが 、これらは全ポリエステル構成成分に対して 0. 00；!〜 5質量％程度混合することがで きる。 [0030] As the third component, a polyfunctional carboxylic acid or a polyhydric alcohol can also be mixed, and these can be mixed in an amount of about 0.00; .
[0031] ポリエステルフィルムの固有粘度は 0. 5〜0. 8であることが好ましい。また、固有粘 度の異なるものを混合して使用してもよい。  [0031] The intrinsic viscosity of the polyester film is preferably 0.5 to 0.8. In addition, different intrinsic viscosities may be mixed and used.
[0032] ポリエステルフィルムの重合方法は特に限定があるわけではなぐ従来公知のポリ エステルの重合方法に従って製造できる。  [0032] The method for polymerizing the polyester film is not particularly limited, and can be produced according to a conventionally known method for polymerizing a polyester.
[0033] 例えば、ジカルボン酸成分をジオール成分と直接エステル化反応させ、ジオール の片方の水酸基をジカルボン酸にジエステル化し、更に一方のジオールを減圧下加 熱して余剰のジオールを留去することにより重合させる直接エステル化法、またジカ ルボン酸成分としてジアルキルエステル（例えば、ジメチルエステル）を用いて、これ とジオール成分とでエステル交換反応させてアルキルアルコール（例えば、メタノー ノレ）を留出させてジオールの片方の水酸基をジカルボン酸にエステル化し、更に余 剰のジオール成分を減圧下で加熱して留去することにより重合させるエステル交換 法を用いることができる。  [0033] For example, polymerization is performed by directly esterifying a dicarboxylic acid component with a diol component, diesterifying one hydroxyl group of the diol to a dicarboxylic acid, and heating one of the diols under reduced pressure to distill off the excess diol. Direct esterification method, or using a dialkyl ester (for example, dimethyl ester) as a dicarboxylic acid component, and transesterifying with the diol component to distill alkyl alcohol (for example, methanol) to distill the diol. It is possible to use a transesterification method in which one hydroxyl group is esterified to a dicarboxylic acid, and the excess diol component is polymerized by heating and distilling off under reduced pressure.
[0034] 触媒としては、通常のポリエステルの合成に使用するエステル交換触媒、重合反応 触媒及び耐熱安定剤を用いることができる。例えば、エステル交換触媒としては、 Ca (OAc) .H O、Zn (OAc) .2H O、Mn (OAc) .4H O、Mg (OAc) ·4Η O等を挙 げること力 Sでき、重合反応触媒としては Sb2〇3、 Ge〇2を挙げること力 Sできる。また、耐 熱安定剤としてはリン酸、亜リン酸、 PO (OH) (CH ) 、 PO (OC H ) 、 P (OC H ) 等を挙げること力 Sできる。また、合成時の各過程で着色防止剤、結晶核剤、すべり剤[0034] As the catalyst, a transesterification catalyst, a polymerization reaction catalyst, and a heat-resistant stabilizer that are used for the synthesis of ordinary polyester can be used. For example, as transesterification catalysts, Ca (OAc) .HO, Zn (OAc) .2H 2 O, Mn (OAc) .4H 2 O, Mg (OAc) 4 Sb 2 0 3 and Ge 0 2 can be mentioned as catalysts. Further, examples of the heat resistant stabilizer include phosphoric acid, phosphorous acid, PO (OH) (CH 3), PO (OC H), P (OC H) and the like. In addition, anti-coloring agent, crystal nucleating agent, slip agent in each process during synthesis
、安定剤、ブロッキング防止剤、紫外線吸収剤、粘度調節剤、透明化剤、帯電防止 剤、 pH調整剤、染料、顔料等を添加させてもよい。 Stabilizers, anti-blocking agents, UV absorbers, viscosity modifiers, clearing agents, antistatic agents, pH adjusters, dyes, pigments, etc. may be added.
[0035] 印刷時の寸法を安定化させカラー印刷時の色ズレを防ぐために、延伸及び熱固定 後のポリエステルフィルムについては熱処理をすることが好ましい。 [0035] Stretching and heat setting to stabilize printing dimensions and prevent color misregistration during color printing The subsequent polyester film is preferably subjected to heat treatment.
[0036] 熱処理は熱固定終了後冷却して巻き取った後に、別工程で巻きほぐしてから、以 下のような手段で達成するのがよレ、。 [0036] The heat treatment should be accomplished by the following means after cooling and winding after completion of heat setting and then unwinding in a separate step.
[0037] 熱処理する方法としては、テンターのようなフィルムの両端をピンやクリップで把持 する搬送方法、複数のロール群によるロール搬送方法、空気をフィルムに吹き付けて 浮揚させるエアー搬送等により搬送させる方法 (複数のスリットから加熱空気をフィル ム面の片面あるいは両面に吹き付ける方法）、赤外線ヒーター等による輻射熱を利用 する方法、加熱した複数のロールと接触させる方法等を単独または複数組み合わせ て熱処理する方法、またフィルムを自重で垂れ下がらせ、下方で巻き取る搬送方法 等を単独あるいは複数組み合わせて用いることが好ましレ、。 [0037] As a method of heat treatment, a transport method in which both ends of a film such as a tenter are gripped with pins or clips, a roll transport method using a plurality of roll groups, a method of transporting air by blowing air onto the film, and the like. (Method of spraying heated air from one or both sides of a film surface from a plurality of slits), a method of using radiant heat by an infrared heater, a method of heat-treating a method of contacting with a plurality of heated rolls singly or in combination, It is also preferable to use a single or a combination of transport methods that hang the film under its own weight and wind it underneath.
[0038] 熱処理の張力調整は、巻き取りロール及び/または送り出しロールのトルクを調整 すること、及び/または工程内にダンサーロールを設置し、これに加える荷重を調整 することで達成できる。 [0038] The tension of the heat treatment can be adjusted by adjusting the torque of the take-up roll and / or the delivery roll and / or by installing a dancer roll in the process and adjusting the load applied thereto.
[0039] 熱処理中及び/または熱処理後の冷却時に張力を変化させる場合、これらの工程 前後及び/または工程内にダンサーロールを設置し、それらの荷重を調整すること で所望の張力状態を設定してもよい。また、振動的に搬送張力を変化させるには、熱 処理ロール間スパンを小さくすることにより有効に行うことができる。  [0039] When the tension is changed during the heat treatment and / or during the cooling after the heat treatment, a dancer roll is installed before and after these processes and / or in the process, and a desired tension state is set by adjusting their loads. May be. In addition, it is possible to effectively change the conveyance tension by vibration by reducing the span between the heat treatment rolls.
[0040] 熱処理は熱収縮の進行を妨げずに、その後の熱処理（熱現像）時の寸法変化を小 さくする上で、できるだけ搬送張力を低くし、熱処理時間を長くすることが望ましい。  [0040] In order to reduce the dimensional change during the subsequent heat treatment (heat development) without hindering the progress of heat shrinkage, it is desirable that the conveyance tension is as low as possible and the heat treatment time is lengthened.
[0041] 処理温度としてはポリェステルフィルムの丁§+ 50°じ〜丁§+ 150°じの温度範囲が 好ましぐその温度範囲で、搬送張力としては 5Pa〜lMPaが好ましぐより好ましくは 5Pa〜500kPa、更に好ましくは 5Pa〜200kPaであり、処理日寺間としては 30禾少〜 30 分が好ましくより好ましくは 30秒〜 15分である。上記の温度範囲、搬送張力範囲及 び処理時間にすることにより、熱処理時に支持体の熱収縮の部分的な差により支持 体の平面性が劣化することもなぐ搬送ロールとの摩擦等により細かいキズ等の発生 あ押さ免ること力 Sでさる。 [0041] In Ding § + 50 ° Ji ~ Ding § + 0.99 ° Ji temperature range preferred instrument temperature range of poly E ester film as the processing temperature, preferably from preferably tool is 5Pa~lMPa as conveying tension Is from 5 Pa to 500 kPa, more preferably from 5 Pa to 200 kPa, and the treatment day interval is preferably from 30 to 30 minutes, more preferably from 30 seconds to 15 minutes. By using the above temperature range, conveyance tension range, and treatment time, fine scratches due to friction with the conveyance roll, etc., which do not deteriorate the flatness of the support due to partial differences in the thermal contraction of the support during heat treatment, are possible. Occurrence of etc. The force to avoid being pressed.
[0042] 熱処理は所望の寸法変化率を得るために少なくとも 1回は行うことが好ましぐ必要 に応じて 2回以上実施することも可能である。 [0043] 熱処理したポリエステルフィルムを Tg付近の温度から常温まで冷却してから巻き取 り、この時の冷却による平面性の劣化を防ぐために、 Tgを跨いで常温まで下げるまで に少なくとも 5°C/秒以上の速度で冷却するのが好まし!/、。 [0042] It is preferable to perform the heat treatment at least once in order to obtain a desired dimensional change rate. It is also possible to carry out the heat treatment twice or more as necessary. [0043] The heat-treated polyester film is cooled from a temperature near Tg to room temperature and then wound up. In order to prevent deterioration of flatness due to cooling at this time, at least 5 ° C / It is preferable to cool at a speed of more than a second! /.
[0044] ポリエステルフィルム基材の場合、露光装置等における搬送を良好に行うためには[0044] In the case of a polyester film substrate, in order to satisfactorily carry in an exposure apparatus or the like
、基材の含水率は 0. 5質量％以下であることが好ましい。基材の含水率とは下記式 で表される D' である。 The water content of the substrate is preferably 0.5% by mass or less. The moisture content of the substrate is D ′ represented by the following formula.
[0045] Ό' (質量％) = (w' / ) X 100 [0045] Ό '(mass%) = (w' /) X 100
式中、 W' は 25°C、 60%相対湿度の雰囲気下で調湿平衡にある支持体の質量、 は 25°C、 60%相対湿度の雰囲気下で調湿平衡にある支持体の水分含量を表 す。  Where W 'is the mass of the support in humidity conditioning equilibrium at 25 ° C and 60% relative humidity, and is the moisture content of the support in humidity conditioning equilibrium at 25 ° C and 60% relative humidity. Represents content.
[0046] 基材の含水率は 0. 5質量％以下であることが好ましぐ 0. 01 -0. 5質量％である ことが更に好ましぐ特に好ましくは 0. 01 -0. 3質量％である。  [0046] The water content of the base material is preferably 0.5% by mass or less, more preferably 0.01-0.5% by mass, particularly preferably 0.01-0.3% by mass. %.
[0047] 基材の含水率を 0. 5質量％以下に制御する手段としては、（1)親水性層及びその 他の層の塗布液を塗布する直前に支持体を 100°C以上で熱処理する、（2)親水性 層及びその他の層の塗布液を塗布する工程の相対湿度を制御する、（3)親水性層 及びその他の層の塗布液を塗布する前に支持体を 100°C以上で熱処理し、防湿シ ートでカバーして保管し、開封後直ちに塗布する等が挙げられる。これらを 2以上組 み合わせて行ってもよい。  [0047] Means for controlling the moisture content of the base material to 0.5% by mass or less are as follows: (1) The support is heat-treated at 100 ° C or higher immediately before applying the coating liquid for the hydrophilic layer and other layers. (2) Control the relative humidity in the process of applying the coating solution for the hydrophilic layer and other layers. (3) Prior to applying the coating solution for the hydrophilic layer and other layers, the support should be 100 ° C. For example, heat treatment, cover with a moisture-proof sheet, store, and apply immediately after opening. Two or more of these may be combined.
[0048] (微粒子）  [0048] (Fine particles)
ポリエステル基材中にはハンドリング性向上のため、 0. 01〜； 10〃 mの粒子を；!〜 1 OOOppm添加することが好まし!/、。  In order to improve the handling property, it is preferable to add particles of 0.01 to 10 μm;! To 1 OOOppm in the polyester base!
[0049] この粒子としては有機物及び無機物の!/、ずれでもよ!/、。 [0049] The particles may be organic or inorganic! /, Or may be misaligned! /.
[0050] 例えば、無機物としては、スイス特許第 330, 158号明細書等に記載のシリカ、仏 国特許第 1 , 296, 995号明細書等に記載のガラス粉、英国特許第 1 , 173, 181号 明細書等に記載のアルカリ土類金属またはカドミウム、亜鉛等の炭酸塩等を用いるこ と力できる。有機物としては、米国特許第 2, 322, 037号明細書等に記載の澱粉、 ベルギー特許第 625, 451号明細書や英国特許第 981 , 198号明細書等に記載さ れた澱粉誘導体、特公昭 44— 3643号公報等に記載のポリビュルアルコール、スィ ス特許第 330, 158号明細書等に記載のポリスチレン或いはポリメタアタリレート、米 国特許第 3, 079, 257号明細書等に記載のポリアクリロニトリル、米国特許第 3, 02 2, 169号明細書等に記載されたポリカーボネートのような有機微粒子を用いることが できる。粒子の形状は定形、不定形どちらでもよい。 [0050] For example, as inorganic substances, silica described in Swiss Patent No. 330, 158 and the like, glass powder described in French Patent No. 1,296, 995 and the like, British Patent No. 1, 173, It is possible to use alkaline earth metals or carbonates such as cadmium and zinc described in No.181. Organic substances include starch described in U.S. Pat.No. 2,322,037, etc., starch derivatives described in Belgian Patent 625,451 and British Patent 981,198, etc. Polybulual alcohol described in Japanese Patent Publication No. 44-3643, etc. Polystyrene or polymethacrylate as described in US Patent No. 330,158, etc., polyacrylonitrile as described in US Pat. No. 3,079,257, US Pat. No. 3, 02 2,169, etc. Organic fine particles such as polycarbonates described in the documents can be used. The shape of the particles may be either regular or irregular.
[0051] (基材への下引き層塗布） [0051] (Applying undercoat layer to substrate)
ポリエステルフィルム基材においては、各種の機能を持たせるために易接着処理や 下引き層塗布を行うことができる。  In the polyester film substrate, easy adhesion treatment or undercoat layer coating can be performed to give various functions.
[0052] 易接着処理としては、コロナ放電処理や火炎処理、プラズマ処理、紫外線照射処 理等が挙げられる。 [0052] Examples of the easy adhesion treatment include corona discharge treatment, flame treatment, plasma treatment, and ultraviolet irradiation treatment.
[0053] 下引き層としては、ゼラチンやラテックスを含む層等をポリエステルフィルム支持体 上に設けること等が好ましい。その中でも特開平 7— 191433号段落番号 0044〜01 16に記載の帯電防止下塗り層が好ましく用いられる。又特開平 7— 20596号公報段 落番号 003；!〜 0073に記載の導電性ポリマー含有層ゃ特開平 7— 20596号公報 段落番号 0074〜0081に記載の金属酸化物含有層のような導電性層を設けること が好まし!/、。導電性層はポリエステルフィルム支持体上であれば!/、ずれの側に塗設 されてもよいが、好ましくは支持体に対し画像形成層の反対側に塗設するのが好まし い。この導電性層を設けると帯電性が改良されてゴミなどの付着が減少し、印刷時の 白抜け故障などが大幅に減少する。  [0053] As the undercoat layer, a layer containing gelatin or latex or the like is preferably provided on the polyester film support. Among them, the antistatic undercoat layer described in paragraph Nos. 0044 to 0116 of JP-A-7-191433 is preferably used. In addition, the conductive polymer-containing layer described in JP-A-7-20596, step number 003;! To 0073 is conductive like the metal oxide-containing layer described in paragraph Nos. 0074 to 0081 of JP-A-7-20596. It is preferable to have a layer! As long as the conductive layer is on the polyester film support, it may be coated on the side of displacement, but it is preferably coated on the opposite side of the image forming layer with respect to the support. When this conductive layer is provided, the charging property is improved, the adhesion of dust and the like is reduced, and white spots failure during printing is greatly reduced.
[0054] (親水性層）  [0054] (Hydrophilic layer)
本発明にお!/、ては、基材として上記のようなプラスチックフィルムを用いる場合には 、基材上に親水性層を設けて親水性表面を有する基材とすることが好ましい。  In the present invention, when the plastic film as described above is used as the substrate, it is preferable to provide a hydrophilic layer on the substrate to provide a substrate having a hydrophilic surface.
[0055] この場合、親水性層は、多孔質構造を有することが好ましい。  [0055] In this case, the hydrophilic layer preferably has a porous structure.
[0056] 多孔質構造を有する親水性層を形成するためには、下記に記載の親水性マトリク スを形成する素材が好ましく用いられる。  [0056] In order to form a hydrophilic layer having a porous structure, the following materials for forming a hydrophilic matrix are preferably used.
[0057] 親水性マトリクスを形成する素材としては、金属酸化物が好ましい。  [0057] The material for forming the hydrophilic matrix is preferably a metal oxide.
[0058] (金属酸化物）  [0058] (Metal oxide)
金属酸化物としては、金属酸化物微粒子を含むことが好ましぐ例えば、コロイダル シリカ、アルミナゾル、チタニアゾル、その他の金属酸化物のゾルが挙げられる。該金 属酸化物微粒子の形態としては、球状、針状、羽毛状、その他の何れの形態でも良 く、平均粒径としては、 3〜； !OOnmの範囲が好ましぐ平均粒径が異なる数種の金属 酸化物微粒子を併用することもできる。又、粒子表面に表面処理がなされていても良 い。 Examples of the metal oxide preferably include metal oxide fine particles include colloidal silica, alumina sol, titania sol, and other metal oxide sols. The money The form of the metal oxide fine particles may be spherical, needle-like, feather-like, or any other form, and the average particle diameter is 3 to; several types with different average particle diameters preferably in the range of OOnm. These metal oxide fine particles can also be used in combination. Further, the surface of the particles may be surface-treated.
[0059] 上記金属酸化物微粒子は、その造膜性を利用して結合剤としての使用が可能であ る。有機の結合剤を用いるよりも親水性の低下が少なぐ親水性層への使用に適して いる。  [0059] The metal oxide fine particles can be used as a binder by utilizing the film-forming property. It is suitable for use in a hydrophilic layer where the decrease in hydrophilicity is less than when an organic binder is used.
[0060] (コロイダルシリカ）  [0060] (Colloidal silica)
中でも、コロイダルシリカが特に好ましく使用できる。コロイダルシリカは、比較的低 温の乾燥条件であっても造膜性が高いという利点があり、良好な強度を得ることがで きる。コロイダルシリカとしては、後述するネックレス状コロイダルシリカ、平均粒径 20η m以下の微粒子コロイダルシリカを含むことが好ましぐ更に、コロイダルシリカはコロ イド溶液としてアルカリ性を呈することが好ましい。  Among these, colloidal silica can be particularly preferably used. Colloidal silica has the advantage of high film forming properties even under relatively low temperature drying conditions, and can provide good strength. The colloidal silica preferably includes a necklace-shaped colloidal silica, which will be described later, and a fine particle colloidal silica having an average particle size of 20 ηm or less. Further, the colloidal silica preferably exhibits alkalinity as a colloid solution.
[0061] ネックレス状コロイダルシリカとは、一次粒子径が nmのオーダーである球状シリカの 水分散系の総称であり、一次粒粒子径が 10〜50nmの球状コロイダルシリカが 50〜 400nmの長さに結合した「パールネックレス状」のコロイダルシリカを意味する。  [0061] Necklace-shaped colloidal silica is a general term for an aqueous dispersion of spherical silica having a primary particle diameter of the order of nm, and spherical colloidal silica having a primary particle diameter of 10 to 50 nm has a length of 50 to 400 nm. It means the combined “pearl necklace” colloidal silica.
[0062] パールネックレス状（即ち真珠ネックレス状）とは、コロイダルシリカのシリカ粒子が連 なって結合した状態のイメージ力 真珠ネックレスの様な形状をして!/、ることを意味し ている。  [0062] The pearl necklace shape (that is, the pearl necklace shape) means an image power in a state in which the silica particles of colloidal silica are joined together and shaped like a pearl necklace! /.
[0063] パールネックレス状コロイダルシリカを構成するシリカ粒子同士の結合は、シリカ粒 子表面に存在する SiOH基が脱水結合した Si— O— Si と推定される。パール ネックレス状のコロイダルシリカとしては、具体的には日産化学工業社製の「スノーテ ックス一？3」シリーズなどが挙げられ、製品名としては「スノーテックス一 PS— S (連結 した状態の平均粒子径は 11 Onm程度）」、「スノーテックス— PS— M (連結した状態 の平均粒子径は 120nm程度）」及び「スノーテックス— PS— L (連結した状態の平均 粒子径は 170nm程度）」があり、これらに各々対応する酸性の製品が「スノーテックス — PS— S 〇」、 「スノーテックス一 PS— M 〇」及び「スノーテックス一 PS— L— OJ である。 [0064] パールネックレス状コロイダルシリカを添加することにより、層の多孔性を確保しつ つ、強度を維持することが可能となり、親水性層マトリクスの多孔質化材として好ましく 使用できる。これらの中でも、アルカリ性である「スノーテックス PS— S」、「スノーテック ス PS— M」、 「スノーテックス PS— L」を用いると、親水性層の強度が向上し、又、印 刷枚数が多!/、場合でも地汚れの発生が抑制され、特に好まし!/、。 [0063] The bonding between the silica particles constituting the pearl necklace-like colloidal silica is presumed to be Si—O—Si in which SiOH groups present on the surface of the silica particles are dehydrated. Specific examples of colloidal silica in the form of pearl necklace include the “Snowtex 1? 3” series manufactured by Nissan Chemical Industries, Ltd., and the product name is “Snowtex 1 PS-S (average particles in a connected state). "Snowtex-PS-M (the average particle size in the connected state is about 120 nm)" and "Snowtex-PS-L (the average particle size in the connected state is about 170 nm)" The corresponding acidic products are “Snowtex — PS—S 〇”, “Snowtex One PS—M 〇” and “Snowtex One PS— L—OJ”. [0064] By adding pearl necklace-shaped colloidal silica, it becomes possible to maintain the strength of the layer while securing the porosity, and it can be preferably used as a porous material for the hydrophilic layer matrix. Of these, the use of alkaline "Snowtex PS-S", "Snowtex PS-M", and "Snowtex PS-L" improves the strength of the hydrophilic layer and reduces the number of printed sheets. Many! /, Even in cases where the occurrence of dirt is suppressed, especially preferred! /.
[0065] 又、コロイダルシリカは、粒子径が小さいほど結合力が強くなることが知られており、 本発明では平均粒径が 20nm以下であるコロイダルシリカを用いることが好ましぐ更 に好ましくは、 3〜； 15nmのものである。  [0065] Further, it is known that the colloidal silica has a stronger binding force as the particle size is smaller. In the present invention, it is preferable to use colloidal silica having an average particle size of 20 nm or less. 3 to; 15 nm.
[0066] 前述のようにコロイダルシリカの中ではアルカリ性のもの力 地汚れ発生を抑制する 効果が高く特に好ましい。平均粒径がこの範囲にあるアルカリ性のコロイダルシリカと しては、例えば、 日産化学社製の「スノーテックス一 20 (粒子径 10〜20nm)」、「スノ 一テックス一 30 (粒子径 10〜20nm)」、 「スノーテックス一 40 (粒子径 10〜20nm)」 、 「スノーテックス一 N (粒子径 10〜20nm)」、 「スノーテックス一 S (粒子径 8〜； l lnm )」、 「スノーテックス XS (粒子径 4〜6nm)」が挙げられる。  [0066] As mentioned above, colloidal silica is particularly preferable because it is alkaline and has an effect of suppressing the occurrence of soiling. Examples of alkaline colloidal silica having an average particle size in this range include `` Snowtex 20 (particle size 10-20 nm) '' and `` Snotex 30 (particle size 10-20 nm) manufactured by Nissan Chemical Co., Ltd. ), “Snowtex 1 40 (particle size 10-20 nm)”, “Snowtex 1 N (particle size 10-20 nm)”, “Snowtex 1 S (particle size 8; l lnm)”, “Snowtex XS (particle diameter 4-6 nm) ”.
[0067] 平均粒径が 20nm以下であるコロイダルシリカは、前述のパールネックレス状コロイ ダルシリカと併用することで、形成する層の多孔質性を維持しながら、強度をさらに向 上させることが可能となり、特に好ましい。  [0067] Colloidal silica having an average particle size of 20 nm or less can be used in combination with the aforementioned pearl necklace-like colloidal silica to further improve the strength while maintaining the porosity of the layer to be formed. Is particularly preferred.
[0068] 平均粒径が 20nm以下であるコロイダルシリカ/パールネックレス状コロイダルシリ 力の比率は 95/5〜5/95の範囲が好ましぐ更に好ましくは、 70/30-20/80 の範囲がより好ましぐ 60/40〜30/70の範囲が更に好ましい。  [0068] The ratio of colloidal silica / pearl necklace-shaped colloidal silica having an average particle diameter of 20 nm or less is preferably in the range of 95/5 to 5/95, more preferably in the range of 70 / 30-20 / 80. The more preferable range is 60/40 to 30/70.
[0069] 本発明において、親水性層マトリクス構造の多孔質化材として、粒径が 1 11 m未満 の多孔質金属酸化物粒子を含有することができる。  [0069] In the present invention, the porous metal oxide particles having a particle size of less than 111 m can be contained as the porous material having a hydrophilic layer matrix structure.
[0070] (多孔質金属酸化物粒子）  [0070] (Porous metal oxide particles)
多孔質金属酸化物粒子としては、以下に記載の多孔質シリカ、多孔質アルミノシリ ケート粒子又は、ゼォライト粒子を好ましく用いることができる。  As the porous metal oxide particles, the following porous silica, porous aluminosilicate particles, or zeolite particles can be preferably used.
[0071] (多孔質シリカ多孔質シリカ、多孔質アルミノシリケート粒子）  [0071] (Porous Silica, Porous Silica, Porous Aluminosilicate Particles)
多孔質シリカ粒子は、一般に湿式法又は、乾式法により製造される。湿式法では、 ケィ酸塩水溶液を中和して得られるゲルを乾燥、粉砕するか、もしくは中和して析出 した沈降物を粉砕することで得ること力 Sできる。乾式法では、四塩化珪素を水素と酸 素と共に燃焼し、シリカを析出することで得られる。これらの粒子は製造条件の調整 により、多孔性や粒径を制御することが可能である。多孔質シリカ粒子としては、湿式 法のゲルから得られるものが特に好ましレ、。 The porous silica particles are generally produced by a wet method or a dry method. In the wet method, the gel obtained by neutralizing the aqueous silicate solution is dried, ground, or neutralized and precipitated. It is possible to obtain force S by grinding the sediment. In the dry method, silicon tetrachloride is burned with hydrogen and oxygen, and silica is deposited. The porosity and particle size of these particles can be controlled by adjusting the production conditions. As the porous silica particles, those obtained from a wet gel are particularly preferred.
[0072] 多孔質アルミノシリケート粒子は、例えば、特開平 10— 71764号公報に記載されて いる方法により製造される。即ち、アルミニウムアルコキシドと珪素アルコキシドを主成 分として加水分解法により合成された非晶質な複合体粒子である。粒子中のアルミ ナとシリカの比率は 1 : 4〜4： 1の範囲で合成することが可能である。又、製造時にそ の他の金属のアルコキシドを添加して 3成分以上の複合体粒子として製造したものも 本発明に使用できる。これらの複合体粒子も製造条件の調整により多孔性や粒径を 制御することが可能である。  [0072] Porous aluminosilicate particles are produced, for example, by the method described in JP-A-10-71764. That is, amorphous composite particles synthesized by hydrolysis using aluminum alkoxide and silicon alkoxide as main components. The ratio of alumina to silica in the particles can be synthesized in the range of 1: 4 to 4: 1. In addition, particles produced by adding other metal alkoxides at the time of production as composite particles of three or more components can also be used in the present invention. The porosity and particle size of these composite particles can also be controlled by adjusting the production conditions.
[0073] 粒子の多孔性としては、細孔容積で 0. 5ml/g以上であることが好ましぐ 0. 8ml /g以上であること力 り好ましく、 1. 0〜2. 5ml/gであることが更に好ましい。細孔 容積は、塗膜の保水性と密接に関連しており、細孔容積が大きレ、ほど保水性が良好 となって印刷時に汚れにくぐ水量ラチチュードも広くなるが、 2. 5ml/gよりも大きく なると粒子自体が非常に脆くなるため塗膜の耐久性が低下する。逆に、細孔容積が 0. 5ml/g未満の場合には、印刷性能がやや不十分となる場合がある。  [0073] The porosity of the particles is preferably 0.5 ml / g or more in terms of pore volume, more preferably 0.8 ml / g or more, and 1.0 to 2.5 ml / g. More preferably it is. The pore volume is closely related to the water retention of the coating film. The larger the pore volume, the better the water retention and the greater the water volume latitude that is difficult to get smudged during printing. If the particle size is larger than 1, the particle itself becomes very brittle, and the durability of the coating film is lowered. Conversely, if the pore volume is less than 0.5 ml / g, the printing performance may be slightly insufficient.
[0074] (細孔容積の測定方法）  [0074] (Measurement method of pore volume)
ここで、上記の細孔容積の測定は、オートソープ 1 (カンタクローム社製）を使用し 、定容法を用いた窒素吸着測定により、粉体の空隙が窒素により、充填されていると 仮定して相対圧力が 0. 998における窒素吸着量から算出されるものである。  Here, it is assumed that the pore volume is measured by using Auto Soap 1 (manufactured by Cantachrome), and the powder voids are filled with nitrogen by nitrogen adsorption measurement using a constant volume method. Thus, the relative pressure is calculated from the nitrogen adsorption amount at 0.998.
[0075] (ゼオライト粒子）  [0075] (Zeolite particles)
ゼォライトは、結晶性のアルミノケィ酸塩であり、細孔径が 0. 3nm〜； Inmの規則正 LV、三次元網目構造の空隙を有する多孔質体である。  Zeolite is a crystalline aluminosilicate, and has a pore size of 0.3 nm or more; a porous body having regular regular LV of Inm and voids of a three-dimensional network structure.
[0076] 又、親水層を構成する親水性層マトリクス構造は、層状粘土鉱物粒子を含有するこ とができる。該層状鉱物粒子としては、例えば、カオリナイト、ハロイサイト、タルク、ス メタタイト (モンモリロナイト、パイデライト、ヘクトライト、サボナイト等）、バーミキユライト 、マイ力（雲母）、クロライトといった粘土鉱物及び、ハイド口タルサイト、層状ポリケィ酸 塩 (カネマイト、マカタイト、アイァライト、マガディアイト、ケニヤアイト等）等が挙げられ る。特に、単位層（ユニットレイヤー）の電荷密度が高いほど極性が高ぐ親水性も高 いと考えられる。好ましい電荷密度としては 0. 25以上、更に好ましくは 0. 6以上であ る。このような電荷密度を有する層状鉱物としては、スメクタイト（電荷密度 0. 25〜0. 6 ;陰電荷）、バーミキユライト (電荷密度 0. 6〜0. 9 ;陰電荷)等が挙げられる。特に、 合成フッ素雲母は粒径等安定した品質のものを入手することができ好ましい。又、合 成フッ素雲母の中でも、膨潤性のものが好ましく、自由膨潤であるものが更に好まし い。 [0076] Further, the hydrophilic layer matrix structure constituting the hydrophilic layer can contain layered clay mineral particles. Examples of the layered mineral particles include kaolinite, halloysite, talc, smetite (montmorillonite, piderite, hectorite, sabonite, etc.), clay minerals such as vermiculite, my strength (mica), chlorite, and hyde mouth tar. Site, layered polycaic acid Salt (such as kanemite, macatite, eyelite, magadiite, kenyaite). In particular, the higher the charge density of the unit layer (unit layer), the higher the polarity and the higher the hydrophilicity. The charge density is preferably 0.25 or more, more preferably 0.6 or more. Examples of the layered mineral having such a charge density include smectite (charge density of 0.25 to 0.6; negative charge), vermiculite (charge density of 0.6 to 0.9; negative charge) and the like. In particular, synthetic fluorine mica is preferable because it can be obtained with a stable quality such as particle size. Further, among the synthetic fluorine mica, those that are swellable are preferable, and those that are free swell are more preferable.
[0077] 又、上記の層状鉱物のインターカレーシヨン化合物（ビラードクリスタル等）や、ィォ ン交換処理を施したもの、表面処理 (シランカップリング処理、有機バインダとの複合 化処理等）を施したものも使用することができる。  [0077] In addition, the layered mineral intercalation compounds (such as billard crystals), those subjected to ion exchange treatment, surface treatment (silane coupling treatment, compounding treatment with organic binder, etc.) The applied one can also be used.
[0078] 平板状層状鉱物粒子のサイズとしては、層中に含有されている状態で (膨潤工程、 分散剥離工程を経た場合も含めて）、平均粒径 (粒子の最大長）力 ,i m未満であり[0078] The size of the plate-like layered mineral particles is less than the average particle size (maximum particle length) force, im in the state of being contained in the layer (including the case of undergoing the swelling process and dispersion peeling process). And
、平均ァ , Average
スぺタト比が 50以上であることが好ましい。粒子サイズが上記範囲にある場合、薄層 状粒子の特徴である平面方向の連続性及び柔軟性が塗膜に付与され、クラック力 S入 りに《乾燥状態で強靭な塗膜とすることができる。又、粒子物を多く含有する塗布液 においては、層状粘土鉱物の増粘効果によって、粒子物の沈降を抑制することがで きる。粒子径が上記範囲より大きくなると、塗膜に不均一性が生じて、局所的に強度 が弱くなる場合がある。又、アスペクト比が上記範囲以下である場合、添加量に対す る平板状の粒子数が少なくなり、増粘性が不充分となり、粒子物の沈降を抑制する効 果が低減する。  It is preferable that the aspect ratio is 50 or more. When the particle size is in the above range, the continuity and flexibility in the planar direction, which are the characteristics of thin layered particles, are imparted to the coating film, and the cracking force S can be reduced to make it a tough coating film in a dry state. it can. In a coating solution containing a large amount of particulate matter, sedimentation of the particulate matter can be suppressed by the thickening effect of the layered clay mineral. If the particle diameter is larger than the above range, the coating film may become non-uniform and the strength may be locally reduced. On the other hand, when the aspect ratio is not more than the above range, the number of tabular grains relative to the added amount is decreased, the thickening is insufficient, and the effect of suppressing the sedimentation of the particles is reduced.
[0079] 層状鉱物粒子の含有量としては、層全体の 0. ；!〜 30質量％であることが好ましぐ  [0079] The content of the layered mineral particles is preferably 0.;! To 30% by mass of the entire layer.
1〜； 10質量％であることがより好ましい。特に膨潤性合成フッ素雲母ゃスメクタイトは 少量の添加でも効果が見られるため好ましい。層状鉱物粒子は、塗布液に粉体で添 カロしてもよ!/、が、簡便な調液方法 (メディア分散等の分散工程を必要としな!/、)でも良 好な分散度を得るために、層状鉱物粒子を単独で水に膨潤させたゲルを調製した後 、塗布液に添加することが好ましい。 [0080] 親水層を構成する親水性層マトリクスにはその他の添加素材として、ケィ酸塩水溶 液も使用すること力 sできる。ケィ酸 Na、ケィ酸 K、ケィ酸 Liといったアルカリ金属ケィ 酸塩が好ましぐその SiO /M O比率はケィ酸塩を添加した際の塗布液全体の pH が 13を超えない範囲となるように選択することが無機粒子の溶解を防止する上で好 ましい。 1 to 10% by mass is more preferable. In particular, swellable synthetic fluoromica is preferred because smectite is effective even when added in a small amount. The layered mineral particles may be added to the coating solution in powder form! /, But good dispersion can be obtained by a simple preparation method (requiring no dispersion step such as media dispersion! /). Therefore, it is preferable to prepare a gel in which lamellar mineral particles are swelled alone in water and then add it to the coating solution. [0080] As the hydrophilic layer in the matrix other additives material constituting the hydrophilic layer, it can be force s to be used Kei salt water solution. Alkali metal silicates such as Na, Ca and Li are preferred. The SiO / MO ratio is such that the pH of the entire coating solution does not exceed 13 when the caate is added. It is preferable to select it in order to prevent dissolution of inorganic particles.
[0081] 又、金属アルコキシドを用いた、いわゆるゾルーゲル法による無機ポリマーもしくは 有機 無機ハイブリッドポリマーも使用することができる。ゾルーゲル法による無機ポ リマーもしくは有機 無機ハイブリッドポリマーの形成については、例えば、「ゾルー ゲル法の応用」（作花済夫著/ァグネ承風社発行）に記載されている力、、又は本書に 引用されている文献に記載されている公知の方法を使用することができる。  [0081] Further, an inorganic polymer or an organic-inorganic hybrid polymer by a so-called sol-gel method using a metal alkoxide can also be used. For the formation of inorganic polymers or organic-inorganic hybrid polymers by the sol-gel method, for example, the force described in “Application of the sol-gel method” (published by Sakuo Sakuo / Agne Jofusha) or cited in this book Known methods described in the published literature can be used.
[0082] 又、本発明では、水溶性樹脂を含有してもよ!/、。水溶性樹脂としては、例えば、多 糖類、ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリビュルアルコール、ポリ エチレングリコール（PEG)、ポリビュルエーテル、スチレン ブタジエン共重合体、メ チルメタタリレート—ブタジエン共重合体の共役ジェン系重合体ラテックス、アクリル 系重合体ラテックス、ビュル系重合体ラテックス、ポリアクリルアミド、ポリビュルピロリド ン等の樹脂が挙げられるが、本発明に用いられる水溶性樹脂としては、多糖類を用 いることが好ましい。  [0082] In the present invention, a water-soluble resin may be contained! Examples of the water-soluble resin include polysaccharides, polyethylene oxide, polypropylene oxide, polybutyl alcohol, polyethylene glycol (PEG), polybutyl ether, styrene butadiene copolymer, and conjugated methyl methacrylate / butadiene copolymer. Examples include resins such as gen-based polymer latex, acrylic polymer latex, bulle polymer latex, polyacrylamide, and polybulurpyrrolidone, and the water-soluble resin used in the present invention uses polysaccharides. It is preferable.
[0083] 多糖類としては、デンプン類、セルロース類、ポリウロン酸、プルランなどが使用可 能であるが、特にメチルセルロース塩、カルボキシメチルセルロース塩、ヒドロキシェ チルセルロース塩等のセルロース誘導体が好ましく、カルボキシメチルセルロースの ナトリウム塩やアンモニゥム塩がより好ましい。これは、親水性層に多糖類を含有させ ることにより、親水性層の表面形状を好ましい状態形成する効果が得られるためであ  [0083] As polysaccharides, starches, celluloses, polyuronic acids, pullulans, and the like can be used, and cellulose derivatives such as methyl cellulose salts, carboxymethyl cellulose salts, and hydroxyethyl cellulose salts are particularly preferable. Sodium salt and ammonium salt are more preferable. This is because the effect of forming the surface shape of the hydrophilic layer in a favorable state can be obtained by incorporating the polysaccharide into the hydrophilic layer.
[0084] 親水性層の表面は、 PS版のアルミ砂目のように 0. ；!〜 20 mピッチの凹凸構造を 有すること力 S好ましく、この凹凸により保水性や画像部の保持性が向上する。このよう な凹凸構造は、親水性層マトリクスに適切な粒径のフィラーを適切な量含有させて形 成することも可能である力、親水性層の塗布液に前述のアルカリ性コロイダルシリカと 前述の水溶性多糖類とを含有させ、親水性層を塗布、乾燥させる際に相分離を生じ させて形成することがより良好な印刷適性を有する構造を得ることができ、好ましい。 [0084] The surface of the hydrophilic layer should have an uneven structure with a pitch of 0.;! To 20 m, like the aluminum grain of the PS plate. S Preferably, the unevenness improves water retention and image area retention. To do. Such a concavo-convex structure can be formed by adding an appropriate amount of a filler having an appropriate particle size to the hydrophilic layer matrix, and the alkaline colloidal silica described above and the above-described alkaline colloidal silica in the hydrophilic layer coating solution. Contains water-soluble polysaccharides and causes phase separation when the hydrophilic layer is applied and dried A structure having better printability can be obtained.
[0085] 凹凸構造の形態（ピッチ及び表面粗さなど）は、アルカリ性コロイダルシリカの種類 及び添加量、水溶性多糖類の種類及び添加量、その他添加材の種類及び添加量、 塗布液の固形分濃度、ウエット膜厚、乾燥条件等で適宜コントロールすることが可能 である。 [0085] The shape of the concavo-convex structure (pitch, surface roughness, etc.) depends on the type and amount of alkaline colloidal silica, the type and amount of water-soluble polysaccharides, the type and amount of other additives, and the solid content of the coating liquid. It is possible to appropriately control the concentration, wet film thickness, drying conditions, and the like.
[0086] 本発明にお!/、て、親水性マトリクス構造部に添加される水溶性樹脂は、少なくともそ の一部が水溶性の状態のまま、水に溶出可能な状態で存在することが好ましい。水 溶性の素材であっても、架橋剤等によって架橋し、水に不溶の状態になると、その親 水性は低下して印刷適性を劣化させる懸念があるためである。又、さらにカチオン性 樹脂を含有しても良ぐカチオン性樹脂としては、例えば、ポリエチレンァミン、ポリプ ロピレンポリアミン等のようなポリアルキレンポリアミン類又はその誘導体、第 3級ァミノ 基や第 4級アンモニゥム基を有するアクリル樹脂、ジアクリルァミン等が挙げられる。力 チオン性樹脂は、微粒子状の形態で添加しても良ぐ例えば、特開平 6— 161101号 公報に記載のカチオン性マイクロゲルが挙げられる。  [0086] In the present invention, the water-soluble resin to be added to the hydrophilic matrix structure part may exist in a state where at least a part thereof is water-soluble and can be eluted in water. preferable. This is because even if a water-soluble material is cross-linked by a cross-linking agent or the like and becomes insoluble in water, its hydrophilicity is lowered and printability may be deteriorated. In addition, examples of the cationic resin that may further contain a cationic resin include polyalkylene polyamines such as polyethyleneamine and polypropylenepolyamine or derivatives thereof, tertiary amino groups, and quaternary ammonia. Examples thereof include an acrylic resin having a group and diacrylamine. The force thione resin may be added in the form of fine particles, for example, a cationic microgel described in JP-A-6-161101.
[0087] 又、親水性層を塗設する為に用いられる塗布液には、塗布性改善等の目的で水溶 性の界面活性剤を含有させることができ、 Si系又は、 F系等の界面活性剤を使用す ること力 Sできる力 特に Si元素を含む界面活性剤を使用することが印刷汚れを生じる 懸念がなぐ好ましい。該界面活性剤の含有量は、親水性層全体 (塗布液としては固 形分）の 0. 0；!〜 3質量％が好ましぐ 0. 03〜1質量％が更に好ましい。  [0087] The coating liquid used for coating the hydrophilic layer may contain a water-soluble surfactant for the purpose of improving the coating property, and the interface of Si system or F system etc. The ability to use an activator A force that can be used S It is preferable to use a surfactant containing Si element, in particular, because there is no fear of causing printing stains. The content of the surfactant is preferably 0.0;! To 3% by mass, more preferably 0.03 to 1% by mass of the entire hydrophilic layer (solid component as the coating solution).
[0088] 又、親水性層には、リン酸塩を含むことができる。本発明では、親水性層の塗布液 がアルカリ性であることが好ましいため、リン酸塩としてはリン酸三ナトリウムやリン酸 水素ニナトリウムとして添加することが好ましい。リン酸塩を添加することで、印刷時の 網の目開きを改善する効果が得られる。リン酸塩の添加量としては、水和物を除いた 有効量として、 0.；!〜 5質量％が好ましぐ 0. 5〜2質量％が更に好ましい。  [0088] The hydrophilic layer may contain a phosphate. In the present invention, since the hydrophilic layer coating solution is preferably alkaline, it is preferable to add the phosphate as trisodium phosphate or disodium hydrogen phosphate. By adding phosphate, the effect of improving the mesh opening during printing can be obtained. The addition amount of phosphate is preferably 0.5 to 5% by mass, more preferably 0.5 to 2% by mass, as an effective amount excluding hydrates.
[0089] 基材として用いられる金属板の金属としては、鉄、ステンレス、アルミニウム等が挙 げられる力 S、比重と剛性との関係から特にアルミニウムまたはアルミニウム合金（以下 アルミニウムとする）が好ましレ、。  [0089] As the metal of the metal plate used as the substrate, aluminum or an aluminum alloy (hereinafter referred to as aluminum) is particularly preferred because of the relationship between the force S that can be used for iron, stainless steel, aluminum, etc., and the specific gravity and rigidity. ,.
[0090] アルミニウム基材は、親水性表面を形成するために粗面化処理、陽極酸化処理な どを施されて使用されるのが好ましい。 [0090] The aluminum substrate is not roughened or anodized to form a hydrophilic surface. It is preferable to use it after applying it.
[0091] アルミニウム基材は、粗面化処理に先立ってアルミニウム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ェマルジヨンを用いたェマルジ ヨン脱脂処理等が用いられる。また、脱脂処理には、水酸化ナトリウム、水酸化力リウ ム、炭酸ナトリウム、リン酸ナトリウム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!/、汚れや 酸化皮膜も除去することができる。  [0091] The aluminum substrate is preferably subjected to a degreasing treatment in order to remove the rolling oil on the aluminum surface prior to the roughening treatment. As the degreasing treatment, a degreasing treatment using a solvent such as trichlene or thinner, an emulsion degreasing treatment using an emulsion such as kesilon or triethanol, or the like is used. In the degreasing treatment, an aqueous alkali solution such as sodium hydroxide, lithium hydroxide, sodium carbonate, or sodium phosphate can also be used. When an alkaline aqueous solution is used for the degreasing treatment, it cannot be removed only by the above degreasing treatment! /, And dirt and oxide film can also be removed.
[0092] 基材の粗面化としては化学的粗面化処理や機械的粗面化あるいは、これらを適宜 組み合わせた粗面化処理により行うことができる。  [0092] The roughening of the substrate can be performed by chemical roughening, mechanical roughening, or roughening by appropriately combining these.
[0093] 粗面化処理の次に、陽極酸化処理を行うことが好ましい。  [0093] Following the roughening treatment, an anodizing treatment is preferably performed.
[0094] 陽極酸化処理の方法には特に制限はなぐ公知の方法を用いることができる。  [0094] A known method without particular limitation can be used for the method of anodizing treatment.
[0095] 陽極酸化処理された基材は、必要に応じ封孔処理を施してもよい。これら封孔処理 は、熱水処理、沸騰水処理、水蒸気処理、重クロム酸塩水溶液処理、亜硝酸塩処理 、酢酸アンモニゥム処理等公知の方法を用いて行うことができる。  [0095] The anodized base material may be subjected to a sealing treatment as necessary. These sealing treatments can be performed using known methods such as hot water treatment, boiling water treatment, steam treatment, dichromate aqueous solution treatment, nitrite treatment, and ammonium acetate treatment.
[0096] また、陽極酸化処理された基材は適宜、上記封孔処理以外の表面処理を行うこと もできる。表面処理としては、ケィ酸塩処理、リン酸塩処理、各種有機酸処理、 PVP A処理、ベーマイト化処理といった公知の処理が挙げられる。また、特開平 8— 3141 57号に記載の炭酸水素塩を含有する水溶液による処理や、炭酸水素塩を含有する 水溶液による処理に続けてクェン酸のような有機酸処理を行ってもよい。  [0096] Further, the anodized base material can be appropriately subjected to a surface treatment other than the above-described sealing treatment. Examples of the surface treatment include known treatments such as silicate treatment, phosphate treatment, various organic acid treatments, PVP A treatment, and boehmite treatment. Further, the treatment with an aqueous solution containing a bicarbonate described in JP-A-8-314157 or the treatment with an aqueous solution containing a bicarbonate may be followed by an organic acid treatment such as citrate.
[0097] また、塗布層との接着性を向上させるために、塗布面に易接着処理や下塗り層塗 布を行うことが好ましい。例えば、ケィ酸塩ゃシランカップリング剤等のカップリング剤 を含有する液に浸漬するか、液を塗布した後、十分な乾燥を行う方法が挙げられる。  [0097] In order to improve the adhesion to the coating layer, it is preferable to perform an easy adhesion treatment or undercoat layer coating on the coated surface. For example, a method of performing sufficient drying after dipping in a liquid containing a coupling agent such as a silane coupling agent or applying a liquid.
[0098] (画像形成層）  [0098] (Image forming layer)
本発明に係る画像形成層は、印刷機上現像可能な層であり、例えば、サーマルレ 一ザ一記録またはサーマルヘッド記録される特表平 8— 507727号公報ゃ特開平 6 — 186750号公報に記載のようなアブレーシヨンタイプと、特開平 9 123387号公 報に記載のような熱融着画像層機上現像タイプ及び熱溶融転写タイプの印刷版材 料に用いられる画像形成層を用いることができる。 The image forming layer according to the present invention is a layer that can be developed on a printing press, and is described in, for example, JP-A-8-507727 or JP-A-6-186750 in which thermal laser recording or thermal head recording is performed. Printing plate materials of an ablation type such as those described above and a development type and a thermal melting transfer type on a thermal fusion image layer as described in JP-A-9 123387 The image forming layer used for the material can be used.
[0099] 印刷機上現像可能な層とは、画像を形成後、印刷機上で湿し水、あるいは湿し水と 印刷インキを印刷版材料上に供給し印刷することで、画像形成層の非画像部となる 部分が除去され得る層である。 [0099] A layer that can be developed on a printing press is an image forming layer formed by supplying dampening water or dampening water and printing ink onto a printing plate material and printing on the printing press after forming an image. This is a layer from which the non-image area can be removed.
[0100] 画像形成層としては、親油性成分を含有する層であることが好ましぐ親油性成分 および水溶性バインダーを含有する層であることが特に好まし!/、。親油性成分とは、 画像形成層を印刷時、印刷インキ受容性となし得るものであり、特に、粒子状で画像 形成層に含まれることが好ましレ、態様である。 [0100] The image forming layer is particularly preferably a layer containing a lipophilic component and a water-soluble binder, preferably a layer containing a lipophilic component! /. The oleophilic component is one that can be made to accept printing ink when the image forming layer is printed, and is particularly preferably in the form of particles and contained in the image forming layer.
[0101] 粒子状の親油性成分としては、熱可塑性のポリマー粒子が好ましく用いられ、たと えば親油性の熱溶融性粒子または熱融着性粒子があげられる。 [0101] As the particulate lipophilic component, thermoplastic polymer particles are preferably used, and examples thereof include lipophilic heat-fusible particles or heat-fusible particles.
[0102] (熱溶融性粒子）  [0102] (Heat-meltable particles)
画像形成層に用いることができる熱溶融性粒子としては、熱可塑性素材の中でも特 に溶融した際の粘度が低ぐ一般的にワックスとして分類される素材で形成された粒 子があげられる。  Examples of the heat-meltable particles that can be used in the image forming layer include particles formed of a material generally classified as a wax that has a low viscosity when melted, among thermoplastic materials.
[0103] 物性としては、保存性、インキ着肉性の面から軟化点 40°C以上 120°C以下、融点 6 0°C以上 150°C以下であることが好ましぐ軟化点 40°C以上 100°C以下、融点 60°C 以上 120°C以下であることが更に好ましい。  [0103] With regard to physical properties, a softening point of 40 ° C or higher, preferably a softening point of 40 ° C or higher and 120 ° C or lower, and a melting point of 60 ° C or higher and 150 ° C or lower, in terms of storage stability and ink deposition properties. More preferably, the temperature is 100 ° C or lower and the melting point is 60 ° C or higher and 120 ° C or lower.
[0104] 使用できる素材としては、パラフィン、ポリオレフイン、ポリエチレンワックス、マイクロ クリスタリンワックス、脂肪酸系ワックスが挙げられる。これらは分子量 800〜10000程 度のものであり、また乳化しやすくするためにこれらのワックスを酸化し、水酸基、エス テル基、カルボキシル基、アルデヒド基、ペルォキシド基などの極性基を導入すること もできる。更には軟化点を下げたり作業性を向上させたりするためにこれらのワックス に、例えば、ステアロアミド、リノレンアミド、ラウリルアミド、ミリステノレアミド、硬化牛脂 肪酸アミド、パルミトアミド、ォレイン酸アミド、米糖脂肪酸アミド、ヤシ脂肪酸アミドまた はこれらの脂肪酸アミドのメチロール化物、メチレンビスステラロアミド、エチレンビスス テラロアミドなどを添加することも可能である。また、クマロン インデン樹脂、ロジン 変性フエノール樹脂、テルペン変性フエノール樹脂、キシレン樹脂、ケトン樹脂、ァク リル樹脂、アイオノマー、これらの樹脂の共重合体も使用することができる。 [0105] これらの中でも、ポリエチレン、マイクロクリスタリン、脂肪酸エステル、脂肪酸の何れ かを含有することが好ましい。 [0104] Examples of materials that can be used include paraffin, polyolefin, polyethylene wax, microcrystalline wax, and fatty acid wax. These have a molecular weight of about 800 to 10,000, and in order to facilitate emulsification, these waxes may be oxidized to introduce polar groups such as hydroxyl groups, ester groups, carboxyl groups, aldehyde groups, and peroxide groups. it can. Furthermore, in order to lower the softening point and improve workability, these waxes include, for example, stearamide, linolenamide, laurylamide, myristenoreamide, hardened beef fatty acid amide, palmitoamide, oleic acid amide, rice sugar fatty acid. It is also possible to add amides, coconut fatty acid amides, methylolated products of these fatty acid amides, methylene bissteraroamide, ethylene bissteraroamide, and the like. Coumarone indene resin, rosin-modified phenol resin, terpene-modified phenol resin, xylene resin, ketone resin, acrylic resin, ionomer, and copolymers of these resins can also be used. [0105] Among these, it is preferable to contain any of polyethylene, microcrystalline, fatty acid ester, and fatty acid.
[0106] これらの熱溶融性粒子は水に分散可能であることが好ましぐその平均粒径は機上 現像性の面から 0· 0；!〜 10 mであることが好ましぐより好ましくは 0· 05〜3 111で ある。 [0106] These heat-meltable particles are preferably dispersible in water, and the average particle diameter is preferably 0 · 0;! To 10 m from the viewpoint of on-machine developability. Is 0 · 05-3111.
[0107] これらの熱溶融性粒子を水に分散するには、非イオン性界面活性剤、ァニオン性 界面活性剤、カチオン性界面活性剤または高分子界面活性剤を用いることが好まし い。これらの化合物を用いることで熱溶融性微粒子の水分散物を安定化でき、かつ 故障がなレ、均一な塗布物を得ることができる。  [0107] In order to disperse these heat-meltable particles in water, it is preferable to use a nonionic surfactant, an anionic surfactant, a cationic surfactant, or a polymer surfactant. By using these compounds, it is possible to stabilize an aqueous dispersion of heat-meltable fine particles, and to obtain a uniform coating with no failure.
[0108] また、熱溶融性粒子は内部と表層との組成が連続的に変化していたり、もしくは異 なる素材で被覆されていてもよい。被覆方法は公知のマイクロカプセル形成方法、ゾ ルゲル法等が使用できる。  [0108] Further, the composition of the heat-meltable particles may vary continuously between the inside and the surface layer, or may be coated with a different material. As a coating method, a known microcapsule formation method, a sol-gel method, or the like can be used.
[0109] 画像形成層中での熱溶融性粒子の含有量としては、層全体の 1〜90質量％が好 ましぐ 5〜80質量％が更に好ましい。  [0109] The content of the heat-meltable particles in the image forming layer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass of the entire layer.
[0110] (熱融着性粒子）  [0110] (Heat-fusion particles)
熱融着性粒子としては、熱可塑性疎水性高分子重合体粒子が挙げられ、該熱可 塑性疎水性高分子重合体粒子の軟化温度に特定の上限はないが、温度は高分子 重合体微粒子の分解温度より低いことが好ましい。また、高分子重合体の重量平均 分子量（Mw)は 10, 000—1 , 000, 000の範囲であること力《好ましい。  Examples of the heat-fusible particles include thermoplastic hydrophobic polymer particles, and there is no specific upper limit for the softening temperature of the thermoplastic hydrophobic polymer particles. It is preferable that it is lower than the decomposition temperature. The weight average molecular weight (Mw) of the polymer is preferably in the range of 10,000-1, 000,000.
[0111] 熱可塑性疎水性高分子重合体粒子を構成する高分子重合体の具体例としては、 例えば、ポリプロピレン、ポリブタジエン、ポリイソプレン、エチレン ブタジエン共重 合体等のジェン (共）重合体類、スチレン ブタジエン共重合体、メチルメタタリレート —ブタジエン共重合体、アクリロニトリル—ブタジエン共重合体等の合成ゴム類、ポリ メチルメタタリレート、メチルメタクリレートー（2—ェチルへキシルアタリレート）共重合 体、メチルメタクリレートーメタクリル酸共重合体、メチルアタリレート一（N メチロー ルアクリルアミド）共重合体、ポリアクリロニトリル等の（メタ）アクリル酸エステル、 （メタ） アクリル酸（共）重合体、ポリ酢酸ビュル、酢酸ビュル プロピオン酸ビュル共重合体 、酢酸ビュル一エチレン共重合体等のビュルエステル（共）重合体、酢酸ビュル一（2 ェチルへキシルアタリレート）共重合体、ポリ塩化ビュル、ポリ塩化ビニリデン、ポリ スチレン等及びそれらの共重合体が挙げられる。これらのうち、（メタ）アクリル酸エス テル、（メタ）アクリル酸 (共）重合体、ビュルエステル (共）重合体、ポリスチレン、合成 ゴム類が好ましく用いられる。 [0111] Specific examples of the polymer constituting the thermoplastic hydrophobic polymer particles include, for example, gen (co) polymers such as polypropylene, polybutadiene, polyisoprene, and ethylene butadiene copolymer, styrene. Synthetic rubbers such as butadiene copolymer, methyl methacrylate-butadiene copolymer, acrylonitrile-butadiene copolymer, polymethyl methacrylate, methyl methacrylate (2-ethylhexyl acrylate) copolymer, methyl Methacrylate-methacrylic acid copolymer, methyl acrylate (N methylol acrylamide) copolymer, (meth) acrylic acid ester such as polyacrylonitrile, (meth) acrylic acid (co) polymer, polyacetic acid butyl, acetic acid butyl Propionate butyl copolymer, butyl acetate / ethylene copolymer Bulle ester (co) polymer of the polymer such as, acetic Bulle one (2 Ethyl hexyl acrylate) copolymer, polybutyl chloride, polyvinylidene chloride, polystyrene and the like, and copolymers thereof. Of these, (meth) acrylic acid ester, (meth) acrylic acid (co) polymer, bull ester (co) polymer, polystyrene, and synthetic rubbers are preferably used.
[0112] 熱可塑性疎水性高分子重合体粒子は、乳化重合法、懸濁重合法、溶液重合法、 気相重合法等、公知の何れの方法で重合された高分子重合体からなるものでもよレヽ 。溶液重合法または気相重合法で重合された高分子重合体を微粒子化する方法と しては、高分子重合体の有機溶媒に溶解液を不活性ガス中に噴霧、乾燥して微粒 子化する方法、高分子重合体を水に非混和性の有機溶媒に溶解し、この溶液を水 または水性媒体に分散、有機溶媒を留去して微粒子化する方法等が挙げられる。  [0112] The thermoplastic hydrophobic polymer particles may be made of a polymer polymer polymerized by any known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a gas phase polymerization method. Yo! The polymer polymerized by the solution polymerization method or the gas phase polymerization method is made into fine particles by spraying a solution in an organic solvent of the polymer polymer into an inert gas and drying it. And a method in which a polymer is dissolved in an organic solvent immiscible in water, this solution is dispersed in water or an aqueous medium, and the organic solvent is distilled off to form fine particles.
[0113] また、熱溶融性粒子、熱融着性粒子は、何れの方法においても、必要に応じ重合 あるいは微粒子化の際に分散剤、安定剤として、例えば、ラウリル硫酸ナトリウム、ド デシルベンゼンスルホン酸ナトリウム、ポリエチレングリコール等の界面活性剤やポリ ビュルアルコール等の水溶性樹脂を用いてもよい。また、トリェチルァミン、トリェタノ ールァミン等を含有させてもょレ、。  [0113] Further, in any of the methods, the heat-meltable particles and the heat-fusible particles may be used as a dispersant or a stabilizer, for example, sodium lauryl sulfate, dodecylbenzenesulfone, or the like when polymerized or finely divided. A surfactant such as sodium acid or polyethylene glycol or a water-soluble resin such as polybutyl alcohol may be used. Also, add triethylamine, triethanolamine, etc.
[0114] また、熱融着性粒子は水に分散可能であることが好ましぐその平均粒径は機上現 像性、解像度の面から 0. 01〜； 10 ^ mであることが好ましぐより好ましくは 0. ；!〜 3 μ mであ^)。 [0114] Further, it is preferable that the heat-fusible particles are dispersible in water. The average particle size is preferably 0.01 to 10 ^ m from the viewpoint of on-image development and resolution. More preferably 0.;! ~ 3 μm ^).
[0115] また、熱融着性粒子は内部と表層との組成が連続的に変化していたり、もしくは異 なる素材で被覆されていてもよい。被覆方法は公知のマイクロカプセル形成方法、ゾ ルゲル法等が使用できる。  [0115] In addition, the composition of the heat-fusible particles may vary continuously between the inside and the surface layer, or may be coated with a different material. As a coating method, a known microcapsule formation method, a sol-gel method, or the like can be used.
[0116] 画像形成層中の熱融着性粒子の含有量としては、層全体の 1〜90質量％が好まし く、 5〜80質量％が更に好ましい。  [0116] The content of the heat-fusible particles in the image forming layer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass of the entire layer.
[0117] (水溶性バインダー）  [0117] (Water-soluble binder)
画像形成層に用いることができる水溶性バインダーとしては、多糖類、ポリエチレン オキサイド、ポリプロピレンオキサイド、ポリビュルアルコール、ポリエチレングリコール (PEG)、ポリビュルエーテル、スチレン ブタジエン共重合体、メチルメタタリレート ブタジエン共重合体の共役ジェン系重合体ラテックス、アクリル系重合体ラテックス 、ビュル系重合体ラテックス、ポリアクリルアミド、ポリアクリル酸あるいはその塩、ポリビ ニルピロリドン等の樹脂が挙げられる。その中でも印刷性能を劣化させないポリアタリ ル酸あるいはその塩又は多糖類を用いることが好ましレ、。 Water-soluble binders that can be used in the image forming layer include polysaccharides, polyethylene oxide, polypropylene oxide, polybutyl alcohol, polyethylene glycol (PEG), polybutyl ether, styrene butadiene copolymer, methyl metatalylate butadiene copolymer Conjugated Conjugated Polymer Latex, Acrylic Polymer Latex And resin such as bulle polymer latex, polyacrylamide, polyacrylic acid or salts thereof, and polyvinylpyrrolidone. Among them, it is preferable to use polyataryl acid or a salt or polysaccharide thereof that does not deteriorate the printing performance.
[0118] 水溶性バインダーの画像形成層に対する含有量としては、 1. 0質量％〜30質量 %が好ましぐ特に 5質量％〜20質量％が好ましい。  [0118] The content of the water-soluble binder in the image forming layer is preferably 1.0% by mass to 30% by mass, particularly preferably 5% by mass to 20% by mass.
[0119] 本発明に係る画像形成層には、後述する光熱変換素材を含有させることできる。  [0119] The image-forming layer according to the present invention may contain a photothermal conversion material described later.
[0120] 画像形成層の乾燥塗布質量は好ましくは 0. ；!〜 1. 5g/m2、より好ましくは 0. 15 〜 . Og/ mである。 [0120] The dry coating weight of the image forming layer is preferably 0 .;! To 1.5 g / m 2 , more preferably 0.15 to. Og / m.
[0121] (光熱変換素材）  [0121] (Photothermal conversion material)
本発明に係る印刷版材料は、画像形成層に、光熱変換素材を含有することが、感 熱画像形成材料としても用いることができるため好ましレ、。  The printing plate material according to the present invention preferably contains a photothermal conversion material in the image forming layer because it can also be used as a heat-sensitive image forming material.
[0122] 光熱変換素材としては赤外吸収色素または顔料を用いることができる。  [0122] As the photothermal conversion material, an infrared absorbing dye or pigment can be used.
[0123] (赤外吸収色素）  [0123] (Infrared absorbing dye)
赤外吸収色素としては、一般的な赤外吸収色素であるシァニン系色素、クロコユウ ム系色素、ポリメチン系色素、ァズレニウム系色素、スクヮリウム系色素、チォピリリウ ム系色素、ナフトキノン系色素、アントラキノン系色素などの有機化合物、フタロシア ニン系、ナフタロシアニン系、ァゾ系、チォアミド系、ジチオール系、インドア二リン系 の有機金属錯体などが挙げられる。  Examples of infrared absorbing dyes include cyanine dyes, chromium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyridium dyes, naphthoquinone dyes, anthraquinone dyes, which are general infrared absorbing dyes. And organic metal complexes of phthalocyanine, naphthalocyanine, azo, thiamide, dithiol, and indoor diphosphorus.
[0124] 具体的には、特開昭 63— 139191号、同 64— 33547号、特開平； 1— 160683号、 同 1— 280750号、同 1— 293342号、同 2— 2074号、同 3— 26593号、同 3— 309 91号、同 3— 34891号、同 3— 36093号、同 3— 36094号、同 3— 36095号、同 3 — 42281号、同 3— 97589号、同 3— 103476号、同 7— 43851号、同 7— 102179 号、特開 2001— 117201の各公報等に記載の化合物が挙げられる。これらは一種 または二種以上を組み合わせて用いることができる。  [0124] Specifically, JP-A-63-139191, JP-A-64-33547, JP-A-Hei; 1-160683, 1-280750, 1-293342, 2-2074, 3 — 26593, 3—309 91, 3—34891, 3—36093, 3—36094, 3—36095, 3—42281, 3—97589, 3— No. 103476, No. 7-43851, No. 7-102179, JP-A-2001-117201, and the like. These can be used alone or in combination of two or more.
[0125] 顔料としては、カーボン、グラフアイト、金属、金属酸化物等が挙げられる。  [0125] Examples of the pigment include carbon, graphite, metal, metal oxide and the like.
[0126] カーボンとしては特にファーネスブラックやアセチレンブラックの使用が好ましい。粒 度（d50)は lOOnm以下であることが好ましぐ 50nm以下であることが更に好ましい [0127] グラフアイトとしては粒径が 0. 5 111以下、好ましくは lOOnm以下、更に好ましくは[0126] As carbon, furnace black or acetylene black is particularly preferable. The particle size (d50) is preferably lOOnm or less, more preferably 50 nm or less. [0127] The particle size of the graphite is 0.5 111 or less, preferably lOOnm or less, more preferably
50nm以下の微粒子を使用することができる。 Fine particles of 50 nm or less can be used.
[0128] 金属としては粒径が 0. 5〃m以下、好ましくは lOOnm以下、更に好ましくは 50nm 以下の微粒子であれば何れの金属であっても使用することができる。形状としては球 状、片状、針状等何れの形状でもよい。特にコロイド状金属微粒子 (Ag、 Au等）が好 ましい。 [0128] As the metal, any metal can be used as long as the particle diameter is 0.5 μm or less, preferably lOOnm or less, more preferably 50 nm or less. The shape may be any shape such as a sphere, a piece, or a needle. Colloidal metal fine particles (Ag, Au, etc.) are particularly preferred.
[0129] 金属酸化物としては、可視光城で黒色を呈して!/、る素材または素材自体が導電性 を有するか、半導体であるような素材を使用することができる。可視光域で黒色を呈 している素材しては、黒色酸化鉄 (Fe O )や、前述の二種以上の金属を含有する黒  [0129] As the metal oxide, it is possible to use a material that exhibits black color in a visible light castle! /, A material that is electrically conductive, or that is a semiconductor. Materials that are black in the visible light range include black iron oxide (Fe 2 O 3) and black containing two or more of the aforementioned metals.
3 4  3 4
色複合金属酸化物が挙げられる。金属酸化物が二種以上の金属の酸化物からなる 黒色複合金属酸化物であることである。具体的には、 Al、 Ti、 Cr、 Mn、 Fe、 Co、 Ni 、 Cu、 Zn、 Sb、 Baから選ばれる二種以上の金属からなる複合金属酸化物である。こ れらは特開平 8— 27393号、同 9— 25126号、同 9— 237570号、同 9— 241529号 、同 10— 231441号の各公報等に開示されている方法により製造することができる。 本発明に用いることができる複合金属酸化物としては、特に Cu— Cr— Mn系または Cu— Fe— Mn系の複合金属酸化物であることが好ましい。 Cu— Cr Mn系の場合 には、 6価クロムの溶出を低減させるために、特開平 8— 27393号公報に開示されて V、る処理を施すことが好まし!/、。これらの複合金属酸化物は添加量に対する着色、 つまり光熱変換効率が良好である。これらの複合金属酸化物は平均 1次粒子径が 1 in以下であることが好ましぐ平均 1次粒子径が 0. 01-0. 5 mの範囲にあること 力はり好ましい。平均 1次粒子径が 1 m以下とすることで、添加量に対する光熱変換 能がより良好となり、平均 1次粒子径が 0. 01-0. 5 mの範囲とすることで添加量に 対する光熱変換能がより良好となる。但し、添加量に対する光熱変換能は粒子の分 散度にも大きく影響を受け、分散が良好であるほど良好となる。従って、これらの複合 金属酸化物粒子は層の塗布液に添加する前に、別途公知の方法により分散して、分 散液 (ペースト）としておくことが好ましい。平均 1次粒子径が 0. 01未満となると、分散 が困難となるため好ましくない。分散には適宜分散剤を使用することができる。分散 剤の添加量は複合金属酸化物粒子に対して 0. 0；!〜 5質量％が好ましぐ 0.；!〜 2 質量％がより好ましい。分散剤の種類は特に限定しないが、 Si元素を含む Si系界面 活性剤を用いることが好ましレ、。 Color composite metal oxides may be mentioned. The metal oxide is a black complex metal oxide composed of two or more kinds of metal oxides. Specifically, it is a complex metal oxide composed of two or more metals selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, and Ba. These can be produced by the methods disclosed in JP-A-8-27393, JP-A-9-25126, JP-A-9-237570, JP-A-9-241529 and JP-A-10-231441. . The composite metal oxide that can be used in the present invention is particularly preferably a Cu-Cr-Mn-based or Cu-Fe-Mn-based composite metal oxide. In the case of a Cu—Cr Mn system, it is preferable to perform the treatment V disclosed in JP-A-8-27393 in order to reduce elution of hexavalent chromium! These composite metal oxides have good coloration with respect to the amount added, that is, good photothermal conversion efficiency. These composite metal oxides preferably have an average primary particle size of 1 in or less, and an average primary particle size in the range of 0.01 to 0.5 m is preferable. When the average primary particle size is 1 m or less, the photothermal conversion capacity with respect to the added amount becomes better, and when the average primary particle size is within the range of 0.01 to 0.5 m, the light heat with respect to the added amount is increased. The conversion ability becomes better. However, the photothermal conversion ability with respect to the amount added is greatly affected by the degree of dispersion of the particles, and the better the dispersion, the better. Therefore, it is preferable to disperse these composite metal oxide particles by a known method separately before adding them to the layer coating solution to prepare a dispersion (paste). An average primary particle size of less than 0.01 is not preferable because dispersion becomes difficult. A dispersing agent can be appropriately used for the dispersion. The addition amount of the dispersant is preferably 0.0 ;! to 5% by mass with respect to the composite metal oxide particles 0.;! To 2 The mass% is more preferable. The type of dispersant is not particularly limited, but it is preferable to use a Si-based surfactant containing Si elements.
[0130] 素材自体が導電性を有するか、半導体であるような素材としては、例えば、 Sbをド ープした SnO (ATO)、 Snを添加した In O (ITO)、 TiO、 TiOを還元した TiO (酸 化窒化チタン、一般的にはチタンブラック）などが挙げられる。また、これらの金属酸 化物で芯材（BaSO、 TiO、 9A1 Ο · 2Β 0、 K O-nTiO等）を被覆したものも使用 すること力 Sできる。これらの粒径は 0. 5 111以下、好ましくは lOOnm以下、更に好ま しくは 50nm以下である。  [0130] Examples of materials that have conductivity or are semiconductors include, for example, SnO doped with Sb (ATO), In O with added Sn (ITO), TiO, and TiO. Examples thereof include TiO (titanium oxynitride, generally titanium black). In addition, it is possible to use those metal oxides coated with a core material (BaSO, TiO, 9A1 2 · 20, KO-nTiO, etc.). Their particle size is 0.5 111 or less, preferably 10 nm or less, more preferably 50 nm or less.
[0131] これらの光熱変換素材の添加量としては、画像形成層に対して 0. ；!〜 50質量％で あること力 S好ましく、さらに；!〜 30質量％が好ましぐ 3〜25質量％がより特に好ましい [0131] The addition amount of these light-to-heat conversion materials is preferably 0.;! To 50% by mass with respect to the image forming layer. S is preferable. Furthermore,! To 30% by mass is preferable. % Is more particularly preferred
〇 Yes
[0132] (接着成分を含有する液）  [0132] (Liquid containing adhesive component)
本発明にお!/、ては、接着成分を含有する液を画像様に印刷版材料の画像形成層 上に供給して画像を形成する。本発明に係る接着成分を含有する液は、画像形成層 上に供給され、画像形成層に浸透する。  In the present invention, an image is formed by supplying a liquid containing an adhesive component onto the image forming layer of the printing plate material in an image-like manner. The liquid containing the adhesive component according to the present invention is supplied onto the image forming layer and penetrates into the image forming layer.
[0133] 接着成分とは、画像形成層に浸透した後、画像形成層と基材の親水層表面との接 着力を高め、接着成分を含有する液が供給された画像形成層すなわち画像部を、 機上現像で除去されないようにし得るものである。接着成分が基材表面と画像形成 層との界面に存在することにより接着力を高めることができる。また画像形成層中の 親油性成分と水溶性バインダーとの接着力も高めることにより、さらに機上現像で除 去されにくくなる。  [0133] The adhesive component refers to an image forming layer, that is, an image portion to which a liquid containing the adhesive component is supplied by increasing the adhesive force between the image forming layer and the hydrophilic layer surface of the base material after penetrating the image forming layer. It can be prevented from being removed by on-press development. Adhesive strength can be increased by the presence of the adhesive component at the interface between the substrate surface and the image forming layer. In addition, the adhesion between the oleophilic component and the water-soluble binder in the image forming layer is also increased, which makes it difficult to remove by on-press development.
[0134] 接着成分としては、カゼイン、天然ラテックス、デンプン、ゼラチンなどの天然接着 成分、アクリル酸およびその誘導体、アクリル樹脂、ポリエステル樹脂、 α—ォレフィ ンと無水マレイン酸との共重合樹脂、ウレタン樹脂、末端に水酸基を持つポリオール とポリイソシァネートの混合物、エチレン '酢酸ビュル樹脂、エポキシ樹脂プレボリマ 一、塩化ビュル樹脂、酢酸ビュル樹脂、シァノアクリレート、シリコーン、スチレン'ブタ ジェンゴム共重合体、ニトロセルロース、フエノール樹脂、プチラール樹脂などが挙げ られる力 S、この中で好ましくはウレタン樹脂、アクリル樹脂、ポリエステル樹脂、ブチラ ール樹脂が用いられる力 さらに好ましくはポリエステル樹脂、プチラール樹脂が耐 刷面の観点から好ましぐ特にプチラール樹脂が好ましい。 [0134] Adhesive components include natural adhesive components such as casein, natural latex, starch and gelatin, acrylic acid and its derivatives, acrylic resin, polyester resin, copolymer resin of α-olefin and maleic anhydride, urethane resin , Polyol isocyanate with a hydroxyl group at the terminal, ethylene 'bule acetate resin, epoxy resin precursor, chloride resin, acetate resin, cyanoacrylate, silicone, styrene' butadiene rubber copolymer, nitrocellulose , Phenolic resin, petital resin and the like S, among which urethane resin, acrylic resin, polyester resin, butyral The power at which a polyol resin is used More preferably, a polyester resin and a petital resin are preferable from the viewpoint of printing durability, and a petital resin is particularly preferable.
[0135] 接着成分の液全体に対する含有量としては、 0. 5〜80質量％が好ましぐ更に好 ましくは 2〜50質量％であり、特に 2〜25質量％が好ましい。  [0135] The content of the adhesive component with respect to the entire liquid is preferably 0.5 to 80% by mass, more preferably 2 to 50% by mass, and particularly preferably 2 to 25% by mass.
[0136] 接着成分を含有する液の溶媒としては、接着成分が溶解する各種溶媒を用いるこ とが好ましい。溶媒の具体例としては、アルコール類（例えば、メタノール、エタノーノレ 、プロパノーノレ、イソプロパノーノレ、ブタノーノレ、イソブタノーノレ、セカンダリーブタノー ノレ、ターシャリーブタノール）、多価アルコール類（例えば、エチレングリコール、ジェ チレングリコーノレ、トリエチレングリコーノレ、ポリエチレングリコーノレ、プロピレングリコー ノレ、ジプロピレングリコーノレ、ポリプロピレングリコーノレ、ブチレングリコーノレ、へキサン ジォーノレ、ペンタンジォーノレ、グリセリン、へキサントリオ一ノレ、チォジグリコーノレ）、グ リコールエーテル類（例えば、エチレングリコールモノメチルエーテル、ジエチレングリ コーノレモノメチノレエーテノレ、トリエチレングリコーノレモノメチノレエーテノレ、ジエチレング リコールモノブチルエーテル、エチレングリコールモノメチルアセテート、プロピレング リコーノレモノメチノレエーテノレ、ジプロピレングリコーノレモノメチノレエーテノレ、エチレング リコールモノフエニルエーテル、エチレングリコールジメチルエーテル、ジエチレングリ コーノレジメチノレエーテノレ、トリエチレングリコーノレジメチノレエーテノレ、テトラエチレング リコールジメチルエーテル、ジエチレングリコールジェチルエーテル、ジエチレングリ コーノレジブチノレエーテノレ、ジエチレングリコーノレェチノレメチノレエーテノレ、ジエチレン グリコーノレイソプロピノレメチノレエーテノレ、ジエチレングリコーノレブチノレメチノレエーテノレ 、トリエチレングリコーノレブチノレメチノレエーテノレ、プロピレングリコーノレジメチノレエーテ ノレ、ジプロピレングリコーノレジメチノレエーテノレ、トリプロピレングリコーノレジメチノレエ一 テル）、環状エステル類（例えば、プロピレンカーボネート、 /3—プロピオラタトン、 β ブチロラタトン、 α—メチノレー β ブチロラタトン、 γ ブチロラタトン、 γ バレロラ タトン、 δ ノ レ口ラタトン、 ε 一力プロラタトン、 γ—力プロラタトン、 γ ヘプタノラタ トン）、がある。  [0136] As the solvent of the liquid containing the adhesive component, it is preferable to use various solvents in which the adhesive component dissolves. Specific examples of the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol), polyhydric alcohols (eg, ethylene glycol, ethylene glycol) Nore, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexane dianol, pentanediol, glycerin, hexane triol, thioglycol) , Glycol ethers (e.g., ethylene glycol monomethyl ether, diethylene glycol monomethino ethenore, triethylene glycol monomono methinore Tenole, diethylene glycol monobutyl ether, ethylene glycol monomethyl acetate, propylene glycol monomethino ethenore, dipropylene glycol monomethino ethenore, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, diethylene glycolone methinoreate tenole , Triethylene glycolenoresimethinoateolate, tetraethyleneglycoldimethylether, diethyleneglycoljetylether, diethyleneglycolosebutinoreatenore, diethyleneglycolenoretinoremethinoreatenore, diethyleneglycolenoisopropinoremethinoreatenore , Diethyleneglycololebutinoremethinoleethenore, triethyleneglycolenobutenole Chinoleatenore, propylene glycolenoresimethinoleate, dipropylene glyconoresimethinoleateore, tripropyleneglyconoresimethinoleate), cyclic esters (eg, propylene carbonate, / 3-propiolatatane, β-butyrolatatone, α-methinolate β butyrolatataton, γ butyrolatataton, γ valerolatataton, δ north-mouth ratataton, ε-one-protalataton, γ-force prolatataton, and γ-heptanolataton).
[0137] 上記溶媒は、画像形成層上に供給された後、揮発などにより画像形成層から除去 されるものカ好ましく、例えば、ジプロピレングリコールモノメチルエーテルとジェチレ ングリコーノレジェチノレエーテノレの混合溶媒、ジエチレングリコーノレジメチノレエーテノレ とプロピレンカーボネートの混合溶媒、などが好ましく用いられる。 [0137] The above solvent is preferably one that is supplied onto the image forming layer and then removed from the image forming layer by volatilization or the like. For example, dipropylene glycol monomethyl ether and ethyl acetate are used. Preferred are a mixed solvent of N-glycoleno retino enoate, a mixed solvent of diethylene glucono-resin methino reetenole and propylene carbonate, and the like.
[0138] 該溶媒の液全体に対する含有量としては、 20〜99質量％が好ましぐ更に好ましく は 50〜98質量％である。 [0138] The content of the solvent with respect to the entire liquid is preferably 20 to 99% by mass, more preferably 50 to 98% by mass.
[0139] 本発明において、接着成分を含有する液を画像様に供給する方法としては、筆な どを用いる手書き、インクジェット記録方式により、微小液滴をインクジェットノズルから 供給する方法などがあるが、インクジェット記録方式により画像様に供給する方法が より好ましく用いられる。 [0139] In the present invention, the method of supplying the liquid containing the adhesive component in an image-like manner includes a method of supplying fine droplets from an inkjet nozzle by handwriting using a brush, an inkjet recording method, and the like. A method of supplying an image by an ink jet recording method is more preferably used.
[0140] 即ち、接着成分を含有する液が、インクジェット記録方式による液滴である態様が 好ましい態様である。 That is, an embodiment in which the liquid containing the adhesive component is a droplet by an ink jet recording method is a preferred embodiment.
[0141] 以下、接着成分を含有する液が、インクジェット記録方式に用いられるインクジェット インクである場合につ!/、て説明する。  [0141] Hereinafter, the case where the liquid containing the adhesive component is an inkjet ink used in the inkjet recording method will be described.
[0142] インクジェット記録方式により画像様に接着成分を含有する液を供給する場合、接 着成分を含有する液の好ましい粘度としては、 25°Cにおいて 2〜； lOOmPa ' sであり、 更に好ましくは、 4〜80mPa ' sである。 [0142] When supplying a liquid containing an adhesive component in an image-like manner by an ink jet recording method, the preferred viscosity of the liquid containing the adhesive component is 2 to 25 ° C, more preferably lOOmPa's, more preferably , 4-80mPa's.
[0143] また、インクジェット記録方式により画像様に液供給する場合、接着成分を含有する 液には色剤を含むことが可視画性の面から好ましぐ色剤として公知の各種顔料又 は染料を用いることカできる。 [0143] In addition, when an image-like liquid is supplied by the ink jet recording method, various pigments or dyes known as colorants that are preferred from the viewpoint of visible image quality that the liquid containing an adhesive component contains a colorant. Can be used.
[0144] (顔料） [0144] (Pigment)
顔料としては、従来公知の有機及び無機の有色顔料が好ましく使用でき、有色顔 料としては、例えばァゾレーキ、不溶性ァゾ顔料、縮合ァゾ顔料、キレートァゾ顔料等 のァゾ顔料や、フタロシアニン顔料、ペリレン及びペリレン顔料、アントラキノン顔料、 キナクリドン顔料、ジォキサンジン顔料、チォインジゴ顔料、イソインドリノン顔料、キノ フタロニ顔料等の多環式顔料や、酸性染料型レーキ等の染料レーキや、ニトロ顔料、 ニトロソ顔料、ァニリンブラック、昼光蛍光顔料等の有機顔料、カーボンブラック等の 無機顔料が挙げられる。本発明においては、可視画性の面から特にカーボンブラッ クが好ましい。  As the pigment, conventionally known organic and inorganic colored pigments can be preferably used, and as the colored pigment, for example, azo pigments such as azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment, phthalocyanine pigment, perylene. And perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinophthaloni pigments, etc., dye lakes such as acid dye lakes, nitro pigments, nitroso pigments, aniline Examples thereof include organic pigments such as black and daylight fluorescent pigments, and inorganic pigments such as carbon black. In the present invention, carbon black is particularly preferable from the viewpoint of visible image quality.
[0145] (分散剤） 顔料をインクジェットインク中に安定に分散するためには、水溶性高分子分散剤とし て、下記の水溶性樹脂を用いることが好ましレ、。 [0145] (Dispersant) In order to stably disperse the pigment in the inkjet ink, it is preferable to use the following water-soluble resin as the water-soluble polymer dispersant.
[0146] 水溶性樹脂として好ましく用いられるのは、スチレン アクリル酸 アクリル酸アル キルエステル共重合体、スチレン アクリル酸共重合体、スチレン マレイン酸共重 合体、スチレン マレイン酸 アクリル酸アルキルエステル共重合体、スチレン メタ クリル酸共重合体、スチレンーメタクリル酸 アクリル酸アルキルエステル共重合体、 スチレン マレイン酸ハーフエステル共重合体、ビュルナフタレン アクリル酸共重 合体、ビュルナフタレン マレイン酸共重合体等のような水溶性樹脂である。 [0146] Styrene acrylic acid acrylic acid alkyl ester copolymer, styrene acrylic acid copolymer, styrene maleic acid copolymer, styrene maleic acid acrylic acid alkyl ester copolymer, which are preferably used as the water-soluble resin, Water-soluble such as styrene-methacrylic acid copolymer, styrene-methacrylic acid acrylic acid alkyl ester copolymer, styrene maleic acid half ester copolymer, urunaphthalene acrylic acid copolymer, urunaphthalene maleic acid copolymer, etc. Resin.
[0147] 水溶性樹脂のインク全量に対する含有量としては、 0. ；!〜 10質量％が好ましぐ更 に好ましくは、 0. 3〜5質量％である。これらの水溶性樹脂は二種以上併用すること も可能である。 [0147] The content of the water-soluble resin with respect to the total amount of the ink is preferably 0.;! To 10% by mass, and more preferably 0.3 to 5% by mass. Two or more of these water-soluble resins can be used in combination.
[0148] インクジェットインクに使用する顔料分散体の平均粒径は、インクの保存安定性の 面から 500nm以下が好ましく 200nm以下がより好ましぐ lOnm以上、 200nm以下 であること力 り好ましく、 lOnm以上、 150nm以下が特に好ましい。  [0148] The average particle diameter of the pigment dispersion used in the inkjet ink is preferably 500 nm or less, more preferably 200 nm or less, more preferably lOnm or more and 200 nm or less, from the viewpoint of the storage stability of the ink, preferably lOnm or more. 150 nm or less is particularly preferable.
[0149] 顔料の分散方法としては、ボールミル、サンドミル、アトライター、ロールミル、アジテ ータ、ヘンシェルミキサ、コロイドミル、超音波ホモジナイザー、パールミル、湿式ジェ ットミル、ペイントシェーカー等各種を用いることができる。  [0149] As a method for dispersing the pigment, various methods such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, and a paint shaker can be used.
[0150] (染料）  [0150] (Dye)
染料としては、特に制限はなぐ酸性染料、直接染料、反応性染料等の水溶性染 料、分散染料等が挙げられる。  Examples of the dye include water-soluble dyes such as acidic dyes, direct dyes, and reactive dyes, and disperse dyes that are not particularly limited.
[0151] (水溶性染料） [0151] (Water-soluble dye)
水溶性染料としては、例えば、ァゾ染料、メチン染料、ァゾメチン染料、キサンテン 染料、キノン染料、フタロシアニン染料、トリフエニルメタン染料、ジフエニルメタン染料 等を挙げること力 Sでさる。  Examples of water-soluble dyes include azo dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, phthalocyanine dyes, triphenylmethane dyes, diphenylmethane dyes, and the like.
[0152] (界面活性剤） [0152] (Surfactant)
インクジェットインクは界面活性剤を含んでもよぐ界面活性剤としては、アルキル硫 酸塩、アルキルエステル硫酸塩、ジアルキルスルホコハク酸塩類、アルキルナフタレ ンスルホン酸塩類、アルキルリン酸塩、ポリオキシアルキレンアルキルエーテルリン酸 塩、脂肪酸塩類等のァニオン性界面活性剤、ポリオキシエチレンアルキルエーテル 類、ポリオキシアルキレンアルキルフエニルエーテル類、アセチレングリコール類、ポ リオキシエチレン ポリオキシプロピレンブロックコポリマー類等のノニオン性界面活 性剤、グリセリンエステル、ソルビタンエステル、ポリオキシエチレン脂肪酸アミド、アミ ンォキシド等の活性剤、アルキルアミン塩類、第四級アンモニゥム塩類等のカチオン 性界面活性剤が挙げられる。 Ink-jet inks may contain surfactants such as alkyl sulfates, alkyl ester sulfates, dialkyl sulfosuccinates, alkyl naphthalene sulfonates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates. acid Anionic surfactants such as salts and fatty acid salts, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, acetylene glycols and polyoxyethylene polyoxypropylene block copolymers , Surfactants such as glycerin esters, sorbitan esters, polyoxyethylene fatty acid amides and amines, and cationic surfactants such as alkylamine salts and quaternary ammonium salts.
[0153] (各種添加剤）  [0153] (Various additives)
インクジェットインクは、その他に従来公知の添加剤を含有することができる。例え ば蛍光増白剤、消泡剤、潤滑剤、防腐剤、増粘剤、帯電防止剤、マット剤、水溶性多 価金属塩、酸塩基、緩衝液等 pH調整剤、酸化防止剤、表面張力調整剤、比抵抗調 整剤、防鯖剤料等である。  The ink-jet ink can contain other conventionally known additives. For example, fluorescent brighteners, antifoaming agents, lubricants, preservatives, thickeners, antistatic agents, matting agents, water-soluble polyvalent metal salts, acid bases, buffer solutions, etc.pH adjusters, antioxidants, surfaces These are tension adjusters, specific resistance adjusters, and antifungal agents.
[0154] (インクジェット記録方式による画像形成方法）  [0154] (Image Forming Method Using Inkjet Recording Method)
インクジェット記録方式による液滴を用いる画像形成方法にぉレ、ては、まずインクジ エツトインクをインクジェット記録方式用プリンタの、インク吐出ノズルを有するプリンタ ヘッドに供給し、このプリンタヘッドのインク吐出ノズルから画像様に、画像形成層表 面に吐出する。その後、吐出した液滴の乾燥のために、紫外線、赤外線、などによる 活性光線の照射処理、あるレ、は加熱処理などを行うことが好ましレ、。  First, ink jet ink is supplied to a printer head having ink ejection nozzles of an inkjet recording system printer, and an image-like image is formed from the ink ejection nozzles of the printer head. Then, it is discharged onto the surface of the image forming layer. After that, it is preferable to carry out an actinic ray irradiation treatment using ultraviolet rays, infrared rays, etc., or a heat treatment for drying the discharged droplets.
[0155] インクジェットインクは、 25°Cでの粘度を、吐出の安定性の面から 4〜80mPa ' sに 調整することが好ましい。インクジェットインクは、ピエゾヘッドにおいては、 10 S/c m以下の電導度とし、ヘッド内部での電気的な腐食のな!/、インクとすることが好まし!/ヽ 。また、コンティニユアスタイプにおいては、電解質による電導度の調整が必要であり 、この場合には、 0. 5mS/cm以上の電導度に調整することが好ましい。  [0155] The ink-jet ink preferably has a viscosity at 25 ° C adjusted to 4 to 80 mPa's from the viewpoint of ejection stability. Ink-jet inks are preferred to have an electrical conductivity of 10 S / cm or less in the piezo head, without electrical corrosion inside the head! /, And ink! / ヽ. In the continuous type, it is necessary to adjust the conductivity with an electrolyte. In this case, it is preferable to adjust the conductivity to 0.5 mS / cm or more.
[0156] (製版装置）  [0156] (Plate making equipment)
本発明の製版装置は、本発明の画像形成方法に用いられる製版装置であって、本 発明に係る接着成分を含有する液を画像様に供給する画像記録手段、及び乾燥を 行う乾燥手段を有する。画像記録手段としては、上記のようなインクジェット記録方式 に用いられるノズル、印刷方式に用いられるドラムなどがある力 インクジェット記録方 式に用いられるノズルが好ましく用いられる。 [0157] 乾燥手段としては、加熱された空気に接触させる手段、加熱されたドラムなどの媒 体に接触させる手段などがある力 加熱された空気に接触させる手段が好ましく用い られる。 The plate making apparatus of the present invention is a plate making apparatus used in the image forming method of the present invention, and has an image recording means for supplying the liquid containing the adhesive component according to the present invention imagewise, and a drying means for performing drying. . As the image recording means, there are preferably used nozzles used in the ink jet recording method as described above, and nozzles used in the ink jet recording method. [0157] As the drying means, a means for contacting with heated air, such as a means for contacting with heated air, a means for contacting with a medium such as a heated drum, is preferably used.
[0158] 図 1に本発明の画像形成方法に用いられる製版装置の例の示す。  FIG. 1 shows an example of a plate making apparatus used in the image forming method of the present invention.
[0159] 印刷版材料がロール状に巻回された印刷版材料ロール 7から印刷版材料 1がロー ラ 2を介して、搬送される。搬送された印刷版材料はカッター 3により、印刷版として使 用される大きさに断裁される。  The printing plate material 1 is conveyed through the roller 2 from the printing plate material roll 7 in which the printing plate material is wound in a roll shape. The conveyed printing plate material is cut by cutter 3 into a size that can be used as a printing plate.
[0160] 断裁された印刷版材料上に、接着成分を含有する液が画像様に、接着成分を含 有する液を画像様に供給する画像記録手段であるインクジェットヘッド 4を介して液 滴で供給される。接着成分を含有する液が印刷版材料上に供給された後、乾燥手 段 5により乾燥される。このように画像形成された印刷版材料は、印刷機により機上現 像が行われ印刷版が作製される。 [0160] On the cut printing plate material, the liquid containing the adhesive component is supplied in droplets via an inkjet head 4, which is an image recording means for supplying the liquid containing the adhesive component in an image-like manner. Is done. After the liquid containing the adhesive component is supplied onto the printing plate material, it is dried by the drying means 5. The printing plate material thus image-formed is subjected to on-machine image formation by a printing machine to produce a printing plate.
[0161] (印刷版の作製方法） [0161] (Preparation method of printing plate)
本発明の印刷版の作製方法に用いられる印刷機としては、一般的な平版印刷機が 用いられる。平版印刷機は、湿し水供給装置および印刷インキ供給装置を有してい  A general lithographic printing machine is used as a printing machine used in the method for preparing a printing plate of the present invention. The lithographic printing machine has a dampening water supply device and a printing ink supply device.
[0162] 本発明に係る印刷機上での現像は、湿し水、または湿し水および印刷インキを画 像が形成された印刷版材料上に供給することにより行われる。 [0162] Development on the printing press according to the present invention is performed by supplying dampening water or dampening water and printing ink onto the printing plate material on which an image is formed.
[0163] 画像形成された印刷版材料をそのまま印刷機の版胴に取り付ける力、、あるいは印 刷版材料を印刷機の版胴に取り付けた後に画像形成を行い、版胴を回転させながら 水供給ローラー及び/またはインキ供給ローラーを印刷版材料に接触させることで 画像形成層の非画像部を除去することが可能である。 [0163] Force to attach the imaged printing plate material directly to the plate cylinder of the printing machine, or image formation after attaching the printing plate material to the plate cylinder of the printing machine, and supply water while rotating the plate cylinder The non-image area of the image forming layer can be removed by bringing the roller and / or the ink supply roller into contact with the printing plate material.
[0164] 本発明に係る印刷機上での現像は、 PS版を使用した通常の印刷シークェンスで 行うことができるものであり、いわゆる機上現像処理によりなされる工程であることが好 ましい態様である。 [0164] The development on the printing press according to the present invention can be performed in a normal printing sequence using a PS plate, and is preferably a process performed by so-called on-press development processing. It is.
[0165] (印刷システム） [0165] (Printing system)
本発明の印刷版の作製方法は、本発明の製版装置及び平版印刷機を有するシス テムにより行うことができ、本発明の製版装置および平版印刷機が直列に配置された 印刷システム、または平版印刷機内に製版装置を装着したシステムを用いることがで きる。 The printing plate production method of the present invention can be performed by a system having the plate making apparatus and the lithographic printing machine of the present invention, and the plate making apparatus and the lithographic printing machine of the present invention are arranged in series. A printing system or a system in which a plate making apparatus is installed in a lithographic printing machine can be used.
[0166] 図 2に平版印刷機内に、製版装置を装着したシステム、即ち、平版印刷機内に、画 像記録手段、乾燥手段を有する印刷システムの例を示す。  FIG. 2 shows an example of a system in which a plate making apparatus is installed in a lithographic printing machine, that is, a printing system having an image recording means and a drying means in a lithographic printing machine.
[0167] 版胴 21に装着された印刷版材料 27上に画像記録手段であるインクジェット記録へ ッド 4から接着成分を含有する液が画像様に供給され、乾燥手段 5により乾燥される。 乾燥された印刷版材料 27上に、印刷機上で湿し水供給ローラ 22から湿し水力 印 刷インキ供給ローラ 23から印刷インキが供給され、機上現像が行われ、印刷版が作 製される。  A liquid containing an adhesive component is supplied in an image-like manner from an inkjet recording head 4 as image recording means onto a printing plate material 27 mounted on the plate cylinder 21, and dried by the drying means 5. On the printing plate material 27 that has been dried, printing ink is supplied from the dampening water supply roller 22 on the printing press from the dampening water supply roller 22 and the on-press development is carried out to produce a printing plate. The
[0168] (インキ）  [0168] (Ink)
本発明の印刷版の作製方法に用いることができる印刷インキとしては、平版印刷に 使用できるインキであればいずれのインキでも良いが、具体的には、ロジン変性フエ ノール樹脂と植物油（アマ二油、桐油、大豆油等）、石油系溶剤、顔料、酸化重合触 媒 (コバルト、マンガン、鉛、鉄、亜鉛等）等の成分よりなる油性インキ、及びアクリル 系オリゴマー、アクリルモノマー、光重合開始剤、顔料等の成分よりなる紫外線硬化 型の UVインキ、さらに、油性インキの性質と UVインキの性質を併せ持つハイブリッド インキが挙げられる。  The printing ink that can be used in the method for preparing a printing plate of the present invention may be any ink that can be used for lithographic printing. Specifically, rosin-modified phenolic resin and vegetable oil (Amani oil) , Tung oil, soybean oil, etc.), petroleum-based solvents, pigments, oxidative polymerization catalysts (cobalt, manganese, lead, iron, zinc, etc.) and other oil-based inks, acrylic oligomers, acrylic monomers, photopolymerization initiators UV curable UV inks composed of components such as pigments, and hybrid inks that combine the properties of oil-based inks and UV inks.
[0169] (湿し水） [0169] (Dampening water)
湿し水としては、平版印刷に用いられる一般的な湿し水を用いることができる。  As the fountain solution, a general fountain solution used for lithographic printing can be used.
[0170] 湿し水は、アルキレングリコールモノアルキルエーテル化合物などの水溶性有機溶 剤、 pH調整剤、濡れ性向上のための助剤、水溶性高分子化合物、キレート化剤、防 腐剤などを用いることが好ましレ、。 [0170] The fountain solution contains a water-soluble organic solvent such as an alkylene glycol monoalkyl ether compound, a pH adjuster, an auxiliary agent for improving wettability, a water-soluble polymer compound, a chelating agent, and a preservative. I prefer to use it.
実施例  Example
[0171] 以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されない [0171] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
。尚、実施例中「部」は特に断りのないかぎり「質量部」を表す。 . In the examples, “part” represents “part by mass” unless otherwise specified.
[0172] 印刷版材料の作製 [0172] Preparation of printing plate materials
(基材の作製）  (Preparation of base material)
テレフタル酸とエチレングリコールを用い、常法に従い IV (固有粘度） =0· 66dl/ g (フエノール/テトラクロルェタン = 6/4 (質量比）中 25°Cで測定）のポリエチレンテ レフタレートを得た。これをペレット化した後 130°Cで 4時間乾燥し、 300°Cで溶融後 T型ダイから押し出し、 50°Cの冷却ドラム上で急冷し未延伸フィルムを作製した。これ を、延伸温度は前段延伸が 102°Cで 1. 3倍に、後段延伸は 110°Cで 2. 6倍に縦延 伸した。次いで、テンターで 120°Cで 4. 5倍に横延伸した。この後、 240°Cで 20秒間 熱固定後これと同じ温度で横方向に 4%緩和した。この後、テンターのチャック部をス リットした後、両端にナーリング加工を行い、 40°Cに冷却後 47. lN/mで巻き取った 。このようにして厚さ 175 μ mの二軸延伸ポリエチレンテレフタレートフィルムを得た。 この二軸延伸ポリエチレンテレフタレートフィルムのガラス転移温度（Tg)は 79°Cであ つた。得られたポリエチレンテレフタレートフィルムの幅（製膜幅）は 2· 5mであった。 なお、得られた支持体の厚み分布は 3%であった。 Using terephthalic acid and ethylene glycol, IV (Intrinsic Viscosity) = 0 · 66dl / Polyethylene terephthalate of g (measured in phenol / tetrachloroethane = 6/4 (mass ratio) at 25 ° C.) was obtained. This was pelletized, dried at 130 ° C for 4 hours, melted at 300 ° C, extruded from a T-die, and rapidly cooled on a 50 ° C cooling drum to produce an unstretched film. The stretching temperature was stretched 1.3 times at 102 ° C in the former stage and 2.6 times at 110 ° C in the latter stage. Next, the film was stretched 4.5 times at 120 ° C with a tenter. After that, after heat setting at 240 ° C for 20 seconds, it was relaxed 4% laterally at the same temperature. Then, after slitting the chuck part of the tenter, knurling was performed on both ends, and after cooling to 40 ° C, it was wound at 47. lN / m. Thus, a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm was obtained. This biaxially stretched polyethylene terephthalate film had a glass transition temperature (Tg) of 79 ° C. The resulting polyethylene terephthalate film had a width (film forming width) of 2.5 m. The thickness distribution of the obtained support was 3%.
[0173] 《下引き済み基材の作製》 [0173] << Preparation of Substrated Substrate >>
上記で得られた支持体のフィルムの両面に、 8W/m2/minのコロナ放電処理を 施 A corona discharge treatment of 8 W / m 2 / min was applied to both sides of the support film obtained above.
し、次いで、一方の面に下記表 1の下引き塗布液 aを塗布液膜厚として 10 mになる ように塗設した後に 180°C、 4分間乾燥させた。ついでその上にコロナ放電処理（8W /m2/min)を行いながら下記表 2の下引き塗布液 bを塗布液膜厚として 11 mに なるように塗布し、 180°C、 4分間乾燥させた。 Then, the undercoat coating solution a shown in Table 1 below was applied on one surface so that the coating solution film thickness was 10 m, and then dried at 180 ° C. for 4 minutes. Next, while applying corona discharge treatment (8W / m 2 / min) on top of it, apply the undercoat coating solution b in Table 2 below to a coating solution film thickness of 11 m, and dry at 180 ° C for 4 minutes. It was.
[0174] <下引き塗布液 a〉  [0174] <Undercoat liquid a>
[0175] [表 1]  [0175] [Table 1]
Figure imgf000030_0001
Figure imgf000030_0001
[0176] <下引き塗布液 b〉 [0176] <Undercoat coating solution b>
[0177] [表 2] 素材 [0177] [Table 2] Material
ポリビニルアルコール固形分 5質量％ 平均分子最 1 KHD S .76部  Polyvinyl alcohol solid content 5% by weight Average molecule 1 KHD S .76 parts
水溶性'コポ .リエステルノアクリル成分 =&4/36':の Soluble '. Copolyarylene Li ester Roh acrylic component = &4/36': the
部  Part
7クリル変性ポリエステル 固形分 21 J質量％  7 Krill modified polyester Solid content 21 J mass%
ァニ才ン某界面活性剤 S—i Ο'.Οί部  Anniversary Surfactant S—i Ο'.Οί Department
マット剤 ·〈シリ力平均粒後 0.5 μ s) Q .004gp  Matting agent (<0.5 μs after squeezing force average grain) Q .004 gp
硬腠剤 H— 2 0.058部  Hardener H-2 0.058 parts
純水 91 ,06部  91,06 parts of pure water
[0178] [化 1]
Figure imgf000031_0001
[0178] [Chemical 1]
Figure imgf000031_0001
H -  H-
Figure imgf000031_0002
Figure imgf000031_0002
の 3種の浪合物  The three kinds of seaweed
[0179] 《親水性表面を有する基材の作製》 [0179] << Production of Substrate Having a Hydrophilic Surface >>
下記表 3に記載の成分をホモジナイザを用いて十分に攪拌混合した後、濾過して 下層親水性層塗布液を調製した。  The components listed in Table 3 below were sufficiently stirred and mixed using a homogenizer, and then filtered to prepare a lower hydrophilic layer coating solution.
[0180] <下層親水性層塗布液〉 [0180] <Lower hydrophilic layer coating solution>
[0181] [表 3] 素材 添加量 [0181] [Table 3] Material addition amount
コロイダルシリ力 (：ァル力 ·)系〉 ： スノ一テックス -XS  Colloidal Siri Force (: Al Force ·) System>: Sno-Tex -XS
372, 90部  372, 90 parts
(日産化学社製 固形分 20冀量％〉  (Nissan Chemical Co., Ltd., 20% solid content)
コロイダルシリカ（ァル力リ系）： W - 4540S  Colloidal silica (Al power system): W-4540S
•99..00部  • 99..00 copies
(日産化学社製、 固形分 4な質萤％) (Nissan Chemical Co., Ltd., solid content 4 %)
多孔質金厲酸化物： シルトン JC— 40  Porous gold oxide: Shilton JC— 40
r. 部  r.
(水沢化学社製、 多孔質ァルミノシリケ一ト粒子、 平均粒径 4 μ Β  (Mizusawa Chemical Co., Ltd., porous aluminum silicate particles, average particle size 4 μΒ
多孔質金属酸化物： シルトン JC一 7Q  Porous metal oxide: Shilton JC-1 7Q
Π.00部  Π.00
(水沢化学社製、 多孔質アルミノシリケ一ト粒子、 平均粒径 7 ίί )  (Mizusawa Chemical Co., Ltd., porous aluminosilicate particles, average particle size 7 ίί)
攛状粘土鉱物モンモリ £3ナイ ト ： ミネラルコロイ ド «δ  Soil-like clay mineral Montmorry £ 3 Night: Mineral Colloid «δ
(Souther is Clay Produets社製、 平均粒.径 0·. 1 Π 部 をホモジナイザで強攪拌レて S質爨％ 水膨潤ゲルとしたもの  (Made by Souther is Clay Produets, average grain. Diameter 0 ·. 1 部 part was stirred vigorously with a homogenizer and made into S mass% water swollen gel.
Cu Fe ttn系金属酸化物黒色顔料： TS— 50ブラツク粉体  Cu Fe ttn metal oxide black pigment: TS-50 black powder
(大日精化工業社製、 粒径 0 J 程度）  (Daiichi Seika Kogyo Co., Ltd., particle size around 0 J)
の固形分4 うち 0.2%質量％は分散材)水分散物 4 % of the solid content is 0.2% by mass.
力ルボキ'シメチ:ルセ'ル口一スナト リ 'ゥム  Force Ruboki 'Simechi: Ruse'
1.4:8部  1.4: 8 parts
(関東化学社製試薬)の 4賀鱟 %の水溶液  4% aqueous solution of (Kanto Chemical Co., Ltd.)
リン酸三ナト Vゥム ' 12水和物（関東化学社製)の 0質 ¾%の水溶液 0,32部 酸化チタン含有酸化鉄： £TB— 300(赤穂化成社製、 平均粒径 200M) 22.00部 球形シリカ徽粒子：パイプレシ力 FQ  Trinatto phosphate Vum '12 hydrate (manufactured by Kanto Chemical Co.) 0 quality ¾% aqueous solution 0,32 parts Titanium oxide-containing iron oxide: £ TB-300 (Ako Kasei Co., Ltd. average particle size 200M) 22.00 parts Spherical silica soot particles: Pipe resiliency FQ
2·2.·00部  2.2.00 copies
(宇部日東化成社製、 平均粒後 6.0 μ )  (Ube Nitto Kasei Co., Ltd., average grain size 6.0 μ)
表面被 メラミン樹腺粒子： —  Surface melamine gland particles: —
8.80'部  8.80 'part
(日産化学社製、 平均粒径 3.5 )  (Nissan Chemical Co., Ltd., average particle size 3.5)
撒69部 固形分瀵度 [質量％]  撒 69 parts Solid content [mass%]
[0182] 下記表 4に記載の成分をホモジナイザを用いて十分に攪拌混合した後、濾過して 上層親水性層塗布液を調製した。 [0182] The components described in Table 4 below were sufficiently stirred and mixed using a homogenizer, and then filtered to prepare an upper hydrophilic layer coating solution.
[0183] <上層親水性層塗布液〉 [0183] <Upper hydrophilic layer coating solution>
[0184] [表 4] [0184] [Table 4]
Figure imgf000033_0001
Figure imgf000033_0001
[0185] 下層親水性層塗布液を上記下引き層塗布済み基材の上にワイヤーバー # 5を用 いて塗布し 15mの長さの 100°Cに設定押された乾燥ゾーンを搬送スピード 15m/分 の速度で通過させた。引き続き上層親水層塗布液をワイヤーバー # 4を用いて塗布 し 30mの長さの 100°Cに設定された乾燥ゾーンを搬送スピード 15m/分の速度で通 過させ親水性表面を有する基材を作製した。 [0185] The lower hydrophilic layer coating solution is applied onto the substrate coated with the undercoat layer using wire bar # 5 and the drying zone set at 100 ° C with a length of 15m is transported at a conveyance speed of 15m / It was passed at a rate of minutes. Subsequently, the upper layer hydrophilic layer coating solution was applied using wire bar # 4, and the substrate having a hydrophilic surface was obtained by passing the drying zone set at 100 ° C of 30 m length at a conveyance speed of 15 m / min. Produced.
[0186] 下層親水性層、上層親水性層のそれぞれの付量は 3. Og/m2、 1. 8g/m2であつ た。塗布後のサンプルは 60°Cで 1日間のエイジングを行なった。 [0186] The applied amounts of the lower hydrophilic layer and the upper hydrophilic layer were 3. Og / m 2 and 1.8 g / m 2 , respectively. The coated sample was aged at 60 ° C for 1 day.
[0187] 《平版印刷版材料の作製》  [0187] << Preparation of planographic printing plate material >>
下記表 5に示す組成の画像形成層塗布液を、上記のように設けた上層親水性層の 上にワイヤーバー # 4を用いて塗布し、 30mの長さの 70°Cに設定された乾燥ゾーン を搬送スピード 15m/分の速度で通過させ、平版印刷版材料を作製した。画像形成 層の付量は 0. 5g/m2であった。塗布後は 50°Cで 2日間のエイジングを行なった。 The image forming layer coating solution having the composition shown in Table 5 below is applied on the upper hydrophilic layer provided as described above using wire bar # 4, and dried at 70 ° C with a length of 30 m. A lithographic printing plate material was prepared by passing through the zone at a conveyance speed of 15 m / min. The weight of the image forming layer was 0.5 g / m 2 . After application, aging was performed at 50 ° C for 2 days.
[0188] <画像形成層塗布液 >  [0188] <Image forming layer coating solution>
[0189] [表 5] 素材 添加量 [0189] [Table 5] Material addition amount
カルナバヮ ·ツクスエマルジ'ヨン A1 IS  Carnauba ヮ Tsukusu Maruji 'Yon A1 IS
(岐阜セラ' ク社製、 平均粒径 軟化点 65 、 融点 8(TC：、 140¾ 84.3部' での溶驗粘度 、 固形分 40質资％) (Gifu Sera Co., Ltd., average particle size, softening point 65, melting point 8 (TC: molten iron viscosity at 140¾ 84.3 parts', solid content 40 %)
マイクロクリスタリン ッ'クスェマルジョン  Micro Crystallin
30.8都  30.8 capital
(岐阜セラヅク社製、 平均粒子径 0.5# ¾、 固形分 40賓麓％)  (Gifu Ceramics, average particle size 0.5 # ¾, solid content 40%)
ポ Uエチレンワックス .ェマルジヨン ASi4  PO U Ethylene Wax Emulsion ASi4
部  Part
(岐阜セラ、 yク社製、 平均粒子径 ί < ο ^、 固形分 40質楚％)  (Gifu Sera, manufactured by y-ku, average particle size ί <ο ^, solid content 40%)
ポリアクリ疆 8a： 0L - 522  Polyacrylic bowl 8a ： 0L-522
33, 3鄧  33, 3 鄧
(日本触媒社製、 平均分子量 Π万、 固形分 3G¾S%)  (Nippon Shokubai Co., Ltd., average molecular weight 10,000, solid content 3G¾S%)
変性デキストリン ： ぺノン JE— 66  Modified dextrin: Penon JE- 66
2.0部  2.0 copies
師化学社製）  Shishi Chemical Co., Ltd.)
赤外染料：· ADS830AT  Infrared dye: ADS830AT
2.0部  2.0 copies
(日本シ一ペルへグナ一ネ i製〉  (Nippon Shippel Hegnane i made)
純水 747.6部 固形分濂度 [質量％] 10.00%  747.6 parts of pure water Solid content [mass%] 10.00%
[0190] 上記平版印刷版材料を 660mm幅に断裁し、外径 76rmmの紙コアに 30m巻回し[0190] The above lithographic printing plate material is cut to a width of 660mm and wound 30m around a paper core with an outer diameter of 76rmm.
、ロール状平版印刷版材料を得た。 A rolled lithographic printing plate material was obtained.
[0191] 《接着成分を含有する液の調製》 [0191] <Preparation of liquid containing adhesive component>
下記表 6に示す成分をホモジナイザを用いて十分に攪拌混合した後、濾過して接 着成分を含有する液を調製した。  The components shown in Table 6 below were sufficiently stirred and mixed using a homogenizer, and then filtered to prepare a solution containing an adhesive component.
[0192] [表 6] [0192] [Table 6]
m m
m * ： 菱化学社製プジピチグモ！ i三ンリテル ·αレルメルコノェ ·一一 '  m *: Phi Pig Spider made by Ryo Chemicals! iSan Littel · α Lermerkonoe ·
部 i  Part i
|粉体ブ） (ジクカボラチルジングリチエレコルテルェェッー一一 .  | Powder B) (1)
ΐλ  ΐλ
部 | 50  50
|積水学化製ブおジビレグリチメチルコモェル αンノ ·ルー一 I  | Sekisui Gakka's bu jiregigiri methyl comoell α Nno Lu I
翳 部ク Bエスレ 5ZLッ—. m  翳 部 ク B ス レ 5ZL
本発明  The present invention
(ブ脂樹分チ子〉ラ髦ジグリチジルル 3200ルチテ0レンコェルエ X；一一™、  (Bubricum tree chico) La Digiglycidyl 3200 Lucite 0 Lenkorue X; Ichiichi ™,
部 50部 so■. 一  50 parts so ■.
i積水化学社製プグジピリ Hチテルレルメル Qンコモノエー一I ¾ 5  i Sekisui Chemical Co., Ltd.
Iレク部ス 8エZ |ぉし 5ッ .-. I Lek Club 8 D Z |
(プ旗チ樹分子リラジグルジチチルテ |レンルェルコエェーー一 '、.  (Pu flag Chi-tree molecule Lirajigurdi Chitilte | Renruerukoyeichi ',.
|部9  | Part 9
I穰水化学社製菱学社製化チジグジチ三リメレテルエンルルェコー一  I Suisui Chemical Co., Ltd.
ク部スレ BおエL！ッ—  Kube Thread B Oe L! -
| | (プ樹分ク粉体プ脂(ボ）力チ子 ¾)力ラブラネル9000ボ1ピレ卜ンロンッ一一一一、.  | | (Pow tree powder powder (bolt) force ¾) force Labranel 9000 Bo 1 pyrene long 11
|部部8部 250  | Part 8 Part 250
社製脔松油脂  Jade pine oil
(ゥポタ）レリスルジンテエマルンェヨ  (UPOTA) Relisur Jinte Emaruneyo
1 j製大菱日業お製イ学プ本化キ三 ；ピン工ジメチテレグリルモンコノルルロ工一ー.  1 j Obishi Nikko Co., Ltd.
1クデ部リァク A 45ィッ—  1 KUDA Department Raku A 45
本発明 i： (樹）嗨粉体ク）ブァリ (力クグルボラジチリジチテレンルンエコルルェェッ一一一  The present invention i: (tree) 嗨 powder powder) bully (power)
¾ |部部 9部 18θ ;025'.,  ¾ | part 9 part 18θ; 025 '.,
i i
襖  sliding screen
ί ！ I i ί! I i
撈  撈
[0193] 《画像形成、印刷方法》 [0193] << Image formation and printing method >>
画像形成に用レ、た製版装置の概略図を図 1に示す。  A schematic diagram of a plate making apparatus for image formation is shown in FIG.
[0194] 上記のように作製した平版印刷版材料 1を、ローラ 2により搬送し、所定の大きさに 断裁した後に、上記のように調整した接着成分を含有する液をインクジェットインクと して用いたインクジェットプリンター（図示せず）のインクジェットヘッド 4から画像様に 液滴として平版印刷版材料 1上に供給した。 [0194] The lithographic printing plate material 1 produced as described above is conveyed by a roller 2 and cut into a predetermined size, and then the liquid containing the adhesive component adjusted as described above is used as an inkjet ink. From the inkjet head 4 of the inkjet printer (not shown) The lithographic printing plate material 1 was supplied as droplets.
[0195] インクジェットヘッドとしては、ノズノレ口径 25 m、駆動周波数 12kHz、ノズノレ数 12 8、ノズル密度 180dpi (なお、 dpiは 2· 54cm当たりのドット数を表す）であるピエゾ型 ヘッドを用いた。 [0195] As the inkjet head, a piezo-type head having a nozzle diameter of 25 m, a driving frequency of 12 kHz, a nozzle number of 128, and a nozzle density of 180 dpi (where dpi represents the number of dots per 2.54 cm) was used.
[0196] 接着成分を含有する液を画像様に供給した後、乾燥手段 5により、乾燥温度 50°C [0196] After supplying the liquid containing the adhesive component in an image-like manner, the drying temperature is 50 ° C by means of drying means 5.
、乾燥時間 5秒の条件で、乾燥を行った。 Drying was performed under the condition of a drying time of 5 seconds.
[0197] 上記のように画像形成された印刷版材料を下記の印刷条件で印刷し評価を行った [0197] The printing plate material imaged as described above was printed and evaluated under the following printing conditions.
[0198] 印刷装置：小森コーポレーション (株)製リスロン 26Pを用いて、機上現像を行い、印 刷した。印刷用紙は OKトップコート、湿し水はァスト口マーク 3 (日研化学研究所社製 ) 2質量％、インキは大日本インキ化学工業社製 Fusion— Gで印刷評価を行った。 [0198] Printing apparatus: On-press development was performed using Lithlon 26P manufactured by Komori Corporation, and printing was performed. Printing evaluation was performed with OK top coat for printing paper, Fast mouth mark 3 for fountain solution (Niken Chemical Laboratory Co., Ltd.) 2% by mass, and ink with Fusion-G made by Dainippon Ink and Chemicals.
[0199] 《小点再現の評価》 [0199] 《Evaluation of small dot reproduction》
印刷 100枚目で、正常に再現される網点の最小％を求め、小点再現性を評価して 、網点再現性の指標とした。  The minimum percentage of halftone dots that were normally reproduced on the 100th printed sheet was determined, and small dot reproducibility was evaluated as an index of halftone dot reproducibility.
[0200] 《耐刷性の評価》 [0200] << Evaluation of printing durability >>
印刷物のベタ部濃度低下が確認された段階を耐刷終点とし、その枚数を求め、耐 刷性の指標とした。  The stage at which a decrease in the solid density of the printed material was confirmed was regarded as the printing end point, and the number of sheets obtained was determined as an index of printing durability.
[0201] 結果を表 7に示す。表 7から、本発明の画像形成方法は、特に高価な露光機を必 要とすることなぐ印刷版を作製することができ、本発明の画像形成方法を用いて得 られた印刷版は、小点再現性が良好で網点再現性に優れ、耐刷性に優れて!/、ること 力 s カゝる。 [0201] The results are shown in Table 7. From Table 7, the image forming method of the present invention can produce a printing plate that does not particularly require an expensive exposure machine, and the printing plate obtained using the image forming method of the present invention is small. point reproducibility is excellent to good dot reproduction, excellent printing durability! /, Rukoto force s Such.
[0202] [表 7] 耐繊 小点再現 備 考  [0202] [Table 7] Reproduction of fiber-resistant small dots Remarks
液〜 1 譲枚■ 5% 比 較  Liquid-1 transfer ■ 5% comparison
液— 2 25000枚 2% 本発明  Liquid-2 25,000 sheets 2% The present invention
液— 3 ■25000敉 2% 本発明  Liquid 3 ■ 25000 敉 2% The present invention
液— 4 ■2棚。教 2% 本発萌  Liquid — 4 ■ 2 shelves. Teaching 2%
液一 5 20麵教 2% 本発明  Liquid 1 5 20 Confucianism 2% The present invention
■液— 6 200G0枚 3 ?4 本発明  ■ Liquid— 6 200G0 3-4

Claims

請求の範囲 The scope of the claims
[1] 親水性表面を有する基材上に機上現像可能な画像形成層を有する印刷版材料上 に、接着成分を含有する液を、画像様に供給し、画像を形成することを特徴とする画 像形成方法。  [1] An image is formed by supplying an image-like liquid containing an adhesive component onto a printing plate material having an image forming layer that can be developed on-machine on a substrate having a hydrophilic surface. Image forming method.
[2] 前記接着成分がプチラール樹脂であることを特徴とする請求の範囲第 1項に記載の 画像形成方法。  [2] The image forming method according to [1], wherein the adhesive component is a peticular resin.
[3] 前記画像形成層が親油性成分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項に記載の画像形成方法。  [3] The image forming method according to [1] or [2], wherein the image forming layer contains a lipophilic component.
[4] 前記接着成分を含有する液が、インクジェット記録方式による液滴であることを特徴と する請求の範囲第 1項〜第 3項のいずれか 1項に記載の画像形成方法。 [4] The image forming method according to any one of [1] to [3], wherein the liquid containing the adhesive component is a liquid droplet by an ink jet recording method.
[5] 前記接着成分を含有する液が有色顔料を含有することを特徴とする請求の範囲第 1 項〜第 4項のいずれか 1項に記載の画像形成方法。 5. The image forming method according to any one of claims 1 to 4, wherein the liquid containing the adhesive component contains a colored pigment.
[6] 前記有色顔料がカーボンブラックであることを特徴とする請求の範囲第 5項に記載の 画像形成方法。 6. The image forming method according to claim 5, wherein the colored pigment is carbon black.
[7] 請求の範囲第 1項〜第 6項のいずれか 1項に記載の画像形成方法により得られた、 画像を有する印刷版材料、を印刷機上で現像し印刷版を作製することを特徴とする 印刷版の作製方法。  [7] A printing plate material having an image obtained by the image forming method according to any one of claims 1 to 6 is developed on a printing machine to produce a printing plate. A method for producing a printing plate.
[8] 請求の範囲第 1項〜第 6項のいずれか 1項に記載の画像形成方法に用いられること を特徴とする印刷版材料。  [8] A printing plate material used in the image forming method according to any one of claims 1 to 6.
[9] 請求の範囲第 1項〜第 6項のいずれか 1項に記載の画像形成方法に用いられること を特徴とする製版装置。 [9] A plate-making apparatus, which is used in the image forming method according to any one of claims 1 to 6.
[10] 請求の範囲第 7項に記載の印刷版の作製方法に用いられる印刷システムであって、 請求の範囲第 9項に記載の製版装置及び平版印刷機を有することを特徴とする印刷 システム。 [10] A printing system for use in the method for producing a printing plate according to claim 7, comprising the plate making apparatus and the planographic printing machine according to claim 9. .
PCT/JP2007/065425 2006-09-13 2007-08-07 Image forming method, platen manufacturing method, engraving device, printing system, and platen material WO2008032511A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08324145A (en) * 1995-05-29 1996-12-10 Nikken Kagaku Kenkyusho:Kk Direct lithographic printing plate
JP2000043439A (en) * 1998-07-27 2000-02-15 Eastman Kodak Co Image forming method for forming image forming element protected from fingerprint
JP2001232746A (en) * 1999-12-17 2001-08-28 Konica Corp Method for manufacturing printing plate
JP2003094597A (en) * 2001-06-15 2003-04-03 Agfa Gevaert Nv Method for manufacturing lithographic printing plate
JP2004528201A (en) * 2001-04-03 2004-09-16 ピッセス−プリント イメージング サイエンス，インク． Chemical imaging of lithographic printing plates.
JP2006231597A (en) * 2005-02-23 2006-09-07 Konica Minolta Medical & Graphic Inc Method for manufacturing printing plate using printing plate material, printing plate material and printing method
JP2007260987A (en) * 2006-03-27 2007-10-11 Fujifilm Corp Manufacturing method of lithographic printing plate
JP2007261248A (en) * 2006-03-03 2007-10-11 Fujifilm Corp Medium to be recorded, lithographic printing plate using it, and its manufacturing method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08324145A (en) * 1995-05-29 1996-12-10 Nikken Kagaku Kenkyusho:Kk Direct lithographic printing plate
JP2000043439A (en) * 1998-07-27 2000-02-15 Eastman Kodak Co Image forming method for forming image forming element protected from fingerprint
JP2001232746A (en) * 1999-12-17 2001-08-28 Konica Corp Method for manufacturing printing plate
JP2004528201A (en) * 2001-04-03 2004-09-16 ピッセス−プリント イメージング サイエンス，インク． Chemical imaging of lithographic printing plates.
JP2003094597A (en) * 2001-06-15 2003-04-03 Agfa Gevaert Nv Method for manufacturing lithographic printing plate
JP2006231597A (en) * 2005-02-23 2006-09-07 Konica Minolta Medical & Graphic Inc Method for manufacturing printing plate using printing plate material, printing plate material and printing method
JP2007261248A (en) * 2006-03-03 2007-10-11 Fujifilm Corp Medium to be recorded, lithographic printing plate using it, and its manufacturing method
JP2007260987A (en) * 2006-03-27 2007-10-11 Fujifilm Corp Manufacturing method of lithographic printing plate

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