WO2007097169A1 - Lithographic printing plate material, method for manufacturing the same, and printing method - Google Patents

Lithographic printing plate material, method for manufacturing the same, and printing method Download PDF

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Publication number
WO2007097169A1
WO2007097169A1 PCT/JP2007/051680 JP2007051680W WO2007097169A1 WO 2007097169 A1 WO2007097169 A1 WO 2007097169A1 JP 2007051680 W JP2007051680 W JP 2007051680W WO 2007097169 A1 WO2007097169 A1 WO 2007097169A1
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WIPO (PCT)
Prior art keywords
acid
printing
mass
printing plate
plate material
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PCT/JP2007/051680
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French (fr)
Japanese (ja)
Inventor
Kazuyoshi Suzuki
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 WO2007097169A1 publication Critical patent/WO2007097169A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
    • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/06—Backcoats; Back layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/10—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by inorganic compounds, e.g. pigments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
    • B41C2201/14—Location, type or constituents of the non-imaging layers in lithographic printing formes characterised by macromolecular organic compounds, e.g. binder, adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/08—Developable by water or the fountain solution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/20—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by inorganic additives, e.g. pigments, salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
    • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer

Definitions

  • Planographic printing plate material manufacturing method thereof, and printing method
  • the present invention relates to a lithographic printing plate material used in a so-called computer-to-plate (hereinafter referred to as "CTP") system, which is developed on a printing press.
  • CTP computer-to-plate
  • the present invention relates to a planographic printing plate material, a method for producing the same, and a printing method using the same.
  • the printing plate material used for CTP is a type that uses an aluminum support as in the case of the conventional PS plate and a flexible plate that has various functional layers as a printing plate on a film substrate. is there.
  • a lipophilic layer each of which is laminated as a surface layer, and the surface layer is ablated by laser exposure to form a printing plate, or disclosed in JP-A-2001-96710
  • a hydrophilic layer and a heat-sensitive image forming layer are provided on such a film substrate, and the image forming layer is melt-fixed on the hydrophilic layer by heating the hydrophilic layer or the image forming layer in an image-like manner by laser exposure. And the like.
  • Infrared absorbers generally include inorganic pigments such as carbon black and iron oxide, cyanine dyes, methine dyes, naphthoquinone dyes, substituted allylbenzo (thio) pyrylium salts, trimethine thiapyrylium salts, Organic dyes such as pyrylium compounds are used.
  • black acid metal pigments such as acid iron, which are preferable from the viewpoints of hydrophilicity and coating properties necessary for printing plate performance, are used relatively frequently.
  • the conventional black acid metal has a problem in that the printing durability is deteriorated by the dampening water because the dampening water used for printing, which is weak in acidity, is acidic.
  • Patent Document 1 Japanese Patent Laid-Open No. 9-123387
  • Patent Document 2 JP-A-9-123388
  • the present invention has been made in view of the above problems, and its purpose is excellent in coating properties, dampening water resistance, decoloration resistance after development, and high printing durability on a printing press.
  • a lithographic printing plate material having at least a hydrophilic layer and a heat-sensitive image forming layer on a substrate, at least the hydrophilic layer contains a pigment having a photothermal conversion function, and the pigment contains iron
  • a lithographic printing plate material comprising: titanium as a component, wherein the composition molar ratio is 1.1 to 6 with respect to iron 1.
  • a method for producing a lithographic printing plate material comprising producing the lithographic printing plate material described in 1 or 2 above.
  • a printing method comprising printing using the lithographic printing plate material according to 1 or 2 above and a fountain solution having a pH of 4 to 6.5 at a temperature of 20 ° C.
  • a lithographic printing plate material having excellent coating properties, dampening water resistance, decoloration resistance after development, and high printing durability, suitable for development on a printing press, and production thereof Methods and printing methods can be provided.
  • the lithographic printing plate material of the present invention comprises an infrared absorbing dye, an inorganic organic material as a photothermal conversion base material on a hydrophilic layer or a hydrophilic lower layer provided between a hydrophilic layer and a support.
  • Various photothermal conversion raw materials such as pigments can be contained, and a metal oxide pigment having a photothermal conversion function (also simply referred to as a pigment) is particularly contained as a photothermal conversion material.
  • a metal oxide pigment having a photothermal conversion function also simply referred to as a pigment
  • the composition of the metal oxide pigment it contains at least iron and titanium as constituent components, and in this case, the molar ratio of these components is 1.1 to 6 with respect to iron 1.
  • iron oxide is particularly preferred for its photothermal conversion ability.
  • iron oxide has high magnetism and high cohesiveness, which causes problems such as coating failure.
  • a black composite oxide in which an acid iron is coated with an acid iron or a mixture of iron and titanium is preferred.
  • the pigment according to the present invention may be obtained by, for example, coating iron oxide titanium with iron oxide iron and firing it.
  • a TiO phase is formed. Then, using both hydrogen gas and carbon dioxide, Fe TiO is returned to Fe TiO.
  • the composition molar ratio of the pigment to be formed depends on the added amount of titanium oxide and iron oxide before the reaction, the composition molar ratio of iron to titanium per single particle is 1. It is preferably 1-6. Further preferably 1.5 to 5.
  • these pigments can use a sintering inhibitor such as aluminum and silicon, and can be subjected to a surface modification treatment.
  • the magnetization value of the pigment according to the present invention is preferably 0.5 to 10 emuZg, more preferably 2 to lOemuZg. If the magnetization value is less than 0.5 emuZg, the film strength is weak and poor printing durability occurs, and if it is greater than lOemuZg, secondary agglomeration and the like occur, resulting in poor coating properties.
  • the magnetic field value can be measured with a magnetometer (for example, a vibrating sample magnetometer VSM-P7-15 manufactured by Toei Kogyo Co., Ltd.).
  • a magnetometer for example, a vibrating sample magnetometer VSM-P7-15 manufactured by Toei Kogyo Co., Ltd.
  • a core material (BaSO, TiO, 9A1 ⁇ ⁇ 2 ⁇ 0, K O 'nTiO
  • the content of the metal oxide pigment according to the present invention is 10 to 60% by mass, preferably 15 to 50% by mass, with respect to the mass of all solid components of the hydrophilic layer. A mass% is more preferred.
  • the metal oxide pigment according to the present invention can also be contained in the lower layer or the like.
  • a known material can be used as the base material.
  • a metal plate, a plastic film, paper treated with polyolefin, a composite base material obtained by appropriately bonding the above materials, and the like can also be mentioned.
  • the thickness of the substrate is preferably 100 to 300 / ⁇ ⁇ , particularly preferably 150 to 200 ⁇ m.
  • aluminum an aluminum alloy (hereinafter referred to as “aluminum”) is particularly preferable as the relational force between force specific gravity and rigidity, such as iron, stainless steel, and aluminum.
  • the aluminum plate is usually used after degreasing with alkali, acid, solvent, etc. to remove the oil used during rolling * scraping existing on the surface.
  • degreasing treatment degreasing with an aqueous alkali solution is particularly preferable.
  • Adhesiveness with coating layer In order to improve, it is preferable to perform an easily bonding process and undercoat layer application
  • an aluminum plate roughened by a known method and a support combined with the above-mentioned easy adhesion treatment can be used, and the surface is roughened by a known method and anodized. It can also be used as a support, so-called aluminum grain that has been surface-treated if necessary.
  • plastic film examples include polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide, polycarbonate, polysulfone, polyphenylene oxide, cellulose ester, and the like. Particularly preferred are polyethylene terephthalate and polyethylene naphthalate. Further, it is preferable to use a support obtained by the method described in JP-A-10-10676 and having a thermal dimensional change rate at 120 ° C. for 30 seconds of 0.001% or more and 0.04% or less. In order to improve the adhesion of the plastic film to the coating layer, an easy adhesion treatment or undercoat layer coating is applied to the coated surface.
  • Examples of the easy adhesion treatment include corona discharge treatment, flame treatment, plasma treatment, and ultraviolet irradiation treatment.
  • Examples of the undercoat layer include layers containing gelatin and latex, and among them, the antistatic undercoat layer described in JP-A-7-191433, paragraph numbers 0044 to 0116 is preferably used.
  • a compound having a hydroxyl group such as PVA or acrylic latex can be used.
  • the hydrophilic layer of the lithographic printing plate material according to the present invention is mainly composed of a hydrophilic matrix component that forms the layer, a fine particle component that controls the surface shape, a mat material, and the like as components.
  • the metal oxide pigment according to the present invention in the hydrophilic layer as a photothermal conversion material.
  • the material forming the hydrophilic matrix is preferably a metal oxide, more preferably metal oxide fine particles.
  • Examples of the metal oxide fine particles include colloidal silica, alumina sol, titania sol, Examples of other metal oxide sols include spheres, feathers, and other forms of metal oxides, and an average particle size of 3 to LOONm is preferable. Several kinds of metal oxide fine particles having different average particle diameters can be used in combination. In addition, surface treatment may be applied to the particle surface.
  • the metal oxide particles can be used as a binder by utilizing the film-forming property.
  • hydrophilic layer in which the decrease in hydrophilicity is smaller than when an organic binder is used.
  • colloidal silica can be preferably used in the present invention.
  • 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 necklace-like colloidal silica combined with spherical silica having a primary particle diameter of the order of nm, and fine colloidal silica having an average particle diameter of 20 nm or less.
  • Colloidal silica is preferably alkaline as a colloidal solution.
  • necklace-shaped colloidal silica examples include “Snowtex PS” series manufactured by Nissan Chemical Industries.
  • Colloidal silica having an average particle size of 20 nm or less is particularly preferable because it can be further improved in strength while maintaining the porosity of the layer by using in combination with the aforementioned necklace-like colloidal silica force. .
  • Porous metal oxide particles having a particle size of less than 1 ⁇ m can be contained as the porous matrix of the hydrophilic layer matrix according to the present invention.
  • porous metal oxide particles porous silica, porous aluminosilicate particles or zeolite particles described later can be preferably used.
  • the porosity of the particles is preferably 0.5 mlZg or more in terms of pore volume, more preferably 0.8 ml / g or more. 1.0 to 2.5 mlZg or less Further preferred.
  • the pore volume is closely related to the water retention of the coating film, and the larger the pore volume, the better the water retention and the greater the water amount latitude that is difficult to get smeared during printing. When it becomes large, the particles themselves become very brittle, and the durability of the coating film decreases. When the pore volume is less than 0.5 mlZg, the water retention is lowered and stains are likely to occur during printing.
  • Zeolites can also be used as the porous material according to the present invention.
  • Zeolite is a crystalline aluminokeate and is a porous body having pores with a regular three-dimensional network structure with a pore diameter of 0.3 to Lnm.
  • the general formula combining natural and synthetic zeolite is expressed as follows. Where M 2 is an exchange ⁇ 3 ⁇ 4 cation and M 1 is Li +, Na +, K +, Tl +, Me ⁇ + ( ⁇
  • M 2 is Ca 2+ , Mg 2
  • n ⁇ m, and the value of m / n, that is, the Al / Si ratio is 1 or less.
  • the preferred AlZSi ratio is 0.4 to 1.0, more preferably ⁇ to 0.8 to 1.0. ⁇ represents an integer.
  • zeolite particles used in the present invention synthetic zeolite having a stable AlZSi ratio and a relatively sharp particle size distribution is preferred.
  • zeolite A Na (AlSiO) ' 27H 2 O; AlZSi ratio 1 ⁇
  • Zeolite X Na (Al 2 Si O) ⁇ 264 ⁇ ⁇ ; ⁇ 1
  • the surface of the hydrophilic layer preferably has a concavo-convex structure with a pitch of 0.1 to 20 m like the aluminum grain of the PS plate, and this concavo-convex improves water retention and image area retention. .
  • Such a concavo-convex structure can be formed by containing an appropriate amount of filler having an appropriate particle size in the hydrophilic layer matrix.
  • the above-mentioned alkaline colloidal silica can be used in the hydrophilic layer coating solution. It is preferable that a structure having better printability can be obtained by containing the above-mentioned water-soluble polysaccharide and forming it by causing phase separation when the hydrophilic layer is applied and dried.
  • the shape of the concavo-convex structure depends on the type of alkaline colloidal silica and It is possible to appropriately control the amount of addition, the type and amount of water-soluble polysaccharide, the type and amount of other additives, the solid content concentration of the coating liquid, the wet film thickness, and the drying conditions.
  • the water-soluble coagulum added to the hydrophilic matrix in the present invention is present in a state in which at least a part thereof is water-soluble and can be eluted in water. 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 polypropylene polyamine or derivatives thereof, tertiary amino groups and quaternary compounds. Examples thereof include acrylic resin having an ammonium group and diacrylamine. Cationic rosin may be added in the form of fine particles. Examples thereof include a cationic microgel described in JP-A-6-161101.
  • the hydrophilic layer coating solution of the present invention may contain a water-soluble surfactant for the purpose of improving coating properties.
  • a surfactant such as S-type or F-type can be used, but it is particularly preferable to use a surfactant containing Si element because there is no concern of causing printing stains.
  • the content of the surfactant is preferably from 0.01 to 3% by mass, more preferably from 0.03 to 1% by mass, based on the entire hydrophilic layer (solid content as the coating solution).
  • the hydrophilic layer according to the present invention may contain a phosphate.
  • the coating solution for the hydrophilic layer 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 amount of phosphate added is preferably 0.1 to 5% by mass, and more preferably 0.5 to 2% by mass, as an effective amount excluding hydrates.
  • the present invention at least one mat material that satisfies the following conditions is contained.
  • the mat material protrudes from 0.5 to 10. O / zm from the surface of the coated film after the thermal image forming layer is laminated, and the content of the mat material is 1,600-4,800 pieces Zmm 2 ,
  • the standard deviation of the center distance between adjacent mat members is preferably 20 m or less.
  • the material of the mat material may be any of porous, non-porous, organic resin particles, and inorganic fine particles.
  • examples of the inorganic mat material that can be used include silica, alumina, zirconium, titanium dioxide, carbon black.
  • the inorganic filler include particles in which a core of organic particles combined with PMMA, polystyrene, and melamine is coated with inorganic particles having a particle diameter smaller than that of the core particles.
  • the particle size of the inorganic particles is preferably about 1/10 to 1Z100 of the core particles.
  • known metal oxide particles such as silica, alumina, titania, zirconia can be used.
  • the coating method various known methods can be used.
  • the core particles and the coating material particles are collided at high speed in the air like a hybridizer, and the coating material particles bite into the surface of the core material particles. Further, a dry coating method of fixing and coating can be preferably used.
  • two or more different types of mat materials and particle sizes can be used in combination.
  • the average particle diameter of the mat member is preferably 1.0 to 20 ⁇ m, more preferably 3.0 to 8.0 ⁇ m.
  • the average particle size is less than 1.0 m, the printing durability and scratch resistance are lowered, and when it exceeds 20 ⁇ m, the on-press developability and resolution may be lowered.
  • the addition amount of the mat material is preferably 10% by mass to 80% by mass of the hydrophilic layer, more preferably 1
  • a hydrophilic lower layer may be provided between the hydrophilic layer and the support.
  • the material used for the hydrophilic lower layer the same material as the hydrophilic layer described above can be used.
  • a photothermal conversion agent can be added to the hydrophilic layer as described above.
  • the photothermal conversion agent in addition to the above-described metal oxide pigment according to the present invention, a known material may be used as long as it can absorb laser light for image formation and change into heat.
  • Possible Forces Preferred compounds include carbon black, graphite, colloidal silver, black iron oxide (Fe 2 O 3), and black complex metal oxides containing two or more metals.
  • black complex metal oxide examples include SnO doped with Sb (ATO) and Sn
  • TiO titanium oxynitride, generally titanium
  • These metal oxides can also be used as a core material (BaSO, TiO, 9A1 ⁇ ⁇ 2
  • / z m or less preferably lOOnm or less, more preferably 50 nm or less.
  • black composite metal oxides containing two or more metals are more preferred.
  • it is a composite metal oxide composed of two or more metals selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, and Ba. These are produced by the methods disclosed in JP-A-8-27393, JP-A-9-25126, JP-A-9-237570, JP-A-9-241529, JP-A-10-231441, and the like. can do.
  • the composite metal oxide used in the present invention is particularly preferably a Cu-Cr-Mn-based or Cu-Fe-Mn-based composite metal oxide.
  • a Cu—Cr—Mn system it is preferable to perform the treatment disclosed in JP-A-8-273393 in order to reduce elution of hexavalent chromium.
  • These composite metal oxides are colored with respect to the amount added, that is, they have good photothermal conversion efficiency.
  • These composite metal oxides preferably have an average primary particle diameter of 1 ⁇ m or less, and more preferably have an average primary particle diameter in the range of 0.01 to 0.5 m. .
  • the average primary particle size force Sl m or less By making the average primary particle size force Sl m or less, the photothermal conversion capacity with respect to the added amount becomes better, and by making the average primary particle size within the range of 0.01-0. The conversion ability is better.
  • the photothermal conversion ability with respect to the addition amount is greatly influenced 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 0.01 to 5% by mass, more preferably 0.1 to 2% by mass with respect to the composite metal oxide particles.
  • the amount of these composite metal oxides added is 0.01 to 5 with respect to the total solid content of the hydrophilic layer. 0.1% to 3% by mass is more preferable.
  • an infrared absorbing dye is used as the photothermal conversion agent
  • specific examples include the following compounds.
  • Common infrared absorbing dyes such as cyanine dyes, croconium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes
  • organic compounds such as organic and anthraquinone dyes, phthalocyanine, naphthalocyanine, azo, thiamid, dithiol, and indoor-phosphorus organometallic complexes.
  • the addition amount of these infrared absorbing dyes is preferably 0.01 to 2% by mass based on the total solid content of the hydrophilic layer, more preferably 0.1 to 1% by mass.
  • the heat-sensitive image forming layer according to the present invention is present in the layer in a state where the heat-meltable compound is finely divided.
  • the on-press developability by heat of the image forming portion (the property of being peeled and removed from the hydrophilic layer by dampening water and printing ink on the printing press) is reduced.
  • the heat-meltable composite is preferably a material generally classified as a wax having a low viscosity when melted, among thermoplastic materials.
  • the melting point is preferably 60 to 140 ° C. If the melting point is less than 60 ° C, storage stability is a problem. If the melting point is higher than 140 ° C, the sensitivity and print quality may be reduced.
  • Materials that can be used as a heat-meltable compound include carnauba wax, nophine tussus, montan wax, microcrystalline wax, candelilla wax, fatty acid-based wax, Fischer-Tropsch wax, polyethylene wax, and fatty acid. Ester base Tas, fatty acid amides and the like.
  • these waxes are acidified, and polar groups such as hydroxyl groups, ester groups, carboxyl groups, aldehyde groups, and peroxide groups are introduced. Monkey.
  • carnauba wax it is preferable to contain any of carnauba wax, paraffin wax, microcrystalline, fatty acid ester, fatty acid amide, and fatty acid.
  • carnauba wax has a relatively low melting point and a low melt viscosity, and therefore can form a highly sensitive image.
  • the average particle size of the heat-meltable particles which are preferably present as the heat-meltable particles, is preferably 0.1 to 1.
  • O / zm force more preferably 0. 3-0. 0: Less than L m, the on-press developability deteriorates, and if it exceeds 1.0 m, the printing durability may deteriorate.
  • the hot-melt compound is used by being dispersed in an appropriate dispersion medium.
  • the dispersion medium water, an organic solvent, or a mixture of both is appropriately used. In the present invention, it is preferable to contain 50% or more of water.
  • a dispersant may be added to the dispersion medium as necessary.
  • the dispersing agent include surfactants such as polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ester, polypropylene glycol-no-polyethylene glycol block copolymer, polyoxyethylene polyoxypropylene block copolymer, alkylbenzene sodium sulfonate, Examples thereof include water-soluble resin such as polyvinyl alcohol resin.
  • the amount of the dispersant added is 0.5 to 10%, preferably 1 to 5%.
  • potassium hydroxide, morpholine, triethanolamine is used as a dispersion stabilizer.
  • Alkaline agents such as can be added.
  • the amount of the alkaline agent to be added is determined as appropriate depending on the nature of the dispersoid.
  • the pH of the dispersion is preferably in the range of 7.5 to L1.
  • Dispersion in the dispersion medium is performed by a media dispersion method such as a ball mill, a sand mill, or an attritor.
  • a known dispersion technique such as a dropping stirring method can be used.
  • a method of dispersing with a ball mill while controlling the dispersion temperature below the melting temperature, and stirring the heat-meltable compound in a heated and melted state in the dispersion medium while controlling the temperature is particularly preferred.
  • thermomeltable particles include thermoplastic hydrophobic polymer polymer fine particles, and there is no specific upper limit to the softening temperature of the thermoplastic hydrophobic polymer polymer particles, but the temperature is It is preferable that the temperature is lower than the decomposition temperature of the polymer fine particles.
  • the weight average molecular weight (Mw) of the high molecular weight polymer is preferably in the range of 10,000 to 1,000,000.
  • polymer constituting the polymer fine particles include, for example, gen (co) polymers such as polypropylene, polybutadiene, polyisoprene, and ethylene butadiene copolymer, styrene-acrylic copolymer.
  • gen (co) polymers such as polypropylene, polybutadiene, polyisoprene, and ethylene butadiene copolymer, styrene-acrylic copolymer.
  • Copolymers styrene butadiene copolymers, methyl methacrylate-butadiene copolymers, synthetic rubbers such as atta-tolyl butadiene copolymers, polymethyl methacrylate and methyl methacrylate (2-ethylhexyl acrylate) Polymer, methyl methacrylate-methacrylic acid copolymer, methyl acrylate (N-methylolacrylamide) copolymer, (meth) acrylic acid ester such as polyacrylonitrile, (meth) acrylic acid (co) polymer, poly Vinyl acetate, vinyl acetate, vinyl pionate copolymer, vinyl acetate Examples include vinyl ester (co) polymers such as ethylene copolymers, butyl acetate (2-ethylhexyl acrylate) copolymers, polybutyl chloride, polyvinylidene chloride, polystyrene, and copolymers thereof.
  • styrene-acrylic copolymers (meth) acrylic acid esters, (meth) acrylic acid (co) polymers, berylester (co) polymers, polystyrene, and synthetic rubbers are preferably used.
  • the heat-meltable particles formed as described above are preferably contained in an amount of 50% by mass or more based on the solid content of the heat-sensitive image forming layer. By containing 50% by mass or more, the function of the hot-melt particles can be fully expressed.
  • the heat-sensitive image forming layer further contains an organic dye having a solubility of 0.1% by mass or more in a heat-meltable compound in a dispersed state with a particle size of 0.05 m or more.
  • the organic dye particles exist independently of the heat-meltable compound fine particles before image formation, and do not contribute much to the coloring of the image forming layer. Melting when writing images with heat By dissolving in the heat-meltable compound, the color density increases and the image area and the non-image area can be identified.
  • Organic dyes preferably used in the present invention include acid dyes, direct dyes, disperse dyes, oil-soluble dyes, metal-containing oil-soluble dyes, and the like. These coloring materials may be used alone or in combination of two or more as required.
  • the wavelength of the maximum absorbance of the organic dye dissolved in the hot-melt compound is preferably 450 to 75 Onm, more preferably 600 to 750 nm.
  • organic dyes include Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Blue # 613, Oil Black BY, Oil Black BS, Oil Black T-505 (above, manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI52015), and the like.
  • the organic dye can be appropriately dispersed by a known method in a heat-sensitive image forming layer coating solvent serving as a dispersion medium.
  • a dispersion method include a media disperser such as a sand mill, a dyno mill, an attritor and a ball mill, an internal shear disperser such as a homogenizer, a high-speed stirrer such as a dissolver, and an ultrasonic disperser.
  • the organic dye can be dispersed alone in the dispersion medium, but an appropriate dispersant can also be used in combination.
  • the dispersing agent include polyoxyethylene glycol ether, polyoxyethylene alcohol ester, polypropylene glycol 'polyethylene glycol block copolymer, polyoxyethylene / polyoxypropylene block copolymer, alkylbenzene sulfonic acid soda, etc.
  • Surfactants and water-soluble resin such as polyvinyl alcohol resin.
  • an oil drop dispersion method in which an organic dye dissolved at a high concentration in a water-insoluble solvent is dispersed in a water-soluble dispersion medium and then the organic solvent is removed by a reduced pressure treatment.
  • the average particle size of the organic dye is preferably from 0.75 to 0.5 ⁇ m, more preferably from 0.75 to 0.05.
  • the range is 2 ⁇ m. If it is less than 0.05 ⁇ m, the discoloration contrast is insufficient and Developability and printing stains in non-image areas deteriorate. Above 0.5 m, the discoloration contrast is insufficient.
  • the addition amount of the organic dye fine particles is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the entire thermosensitive image forming layer.
  • the heat-sensitive image forming layer of the present invention may contain known heat-meltable compound particles and thermoplastic compound particles, in addition to the above-described components, as long as the function is not impaired.
  • the heat-sensitive image forming layer may further contain a water-soluble material.
  • a water-soluble material By including the water-soluble material, it is possible to improve the removability when the image forming functional layer in the unexposed area is removed using dampening water or ink on the printing press.
  • the water-soluble rosins listed as materials that can be contained in the hydrophilic layer can also be used.
  • the water-soluble resin that can be used in the image-forming functional layer of the present invention is selected from hydrophilic natural polymers and synthetic polymers.
  • synthetic polymers such as modified products, white dextrin, pullulan, enzymatically-decomposed etherified dextrin, polyvinyl alcohol (preferably having an acidity of 70 mol% or more), polyacrylic acid, alkali metal salts or amines thereof Salt, polyacrylic acid copolymer, alkali metal salt or amine salt thereof, polymethacrylic acid, alkali metal salt or amine salt thereof, butyl alcohol Z acrylic acid copolymer and alkali metal salt or amine salt thereof, polyacrylamide , Its copolymers, polyhydroxyethyl acrylate, poly Vinyl pyrrolidone, its copolymer, polybulu methyl ether, burmethyl ether Z male
  • the content of the water-soluble rosin in the heat-sensitive image forming layer is preferably 1 to 50% by mass, more preferably 2 to 10% by mass of the entire layer. [0100] ⁇ Other layers>
  • At least one backing layer can be provided on the side of the support opposite to the image-forming functional layer in order to prevent handling and change in physical properties during storage.
  • the backing layer preferably contains a hydrophilic binder, especially if the surface of the printing plate material is hydrophobic, paragraphs 0033 to 0038 of JP-A-2002-258469. It can be obtained from the power of water-dispersed resin (polymer latex).
  • the hydrophilic binder is not particularly limited as long as it is hydrophilic, but polybutal alcohol (PVA), which is a resin having a hydroxyl group as a hydrophilic structural unit, cellulose-based resin (methylcellulose (MC ), Ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.), chitins, and starch; polyethylene oxide (PEO) which is a resin having an ether bond, Examples thereof include polypropylene oxide (PPO), polyethylene glycol (PEG), and polybule ether (PVE); polyacrylamide (PAAM) and polybulurpyrrolidone (PVP), which are amide groups or oxalic resins having an amide bond.
  • PVA polybutal alcohol
  • PAAM polyacrylamide
  • PVP polybulurpyrrolidone
  • polyacrylates having carboxyl groups as dissociable groups, maleic oxalates, alginates and gelatins; polystyrene sulfonates having sulfone groups; amino groups, imino groups, tertiary amines and quaternary ammonias Mention may be made of polyallylamine (PAA), polyethyleneimine (PEI), epoxidized polyamide (EP Am), polyburpyridine and gelatins having a humic salt.
  • the hydrophobic binder is not particularly limited as long as it is hydrophobic as a binder, but ex, for example,
  • Polymers derived from ethylenically unsaturated compounds such as polysalt vinyl, post monochlorinated polysalt bull, salt bull and salt vinylidene copolymer, bull chloride and vinyl acetate Copolymers, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polybulul alcohol made from polybulal alcohol as a starting material, and only a portion of the repeating butal alcohol units can react with aldehydes Examples include acetals, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene, or mixtures thereof.
  • the backing layer preferably contains a matting agent.
  • the matting agent can be used regardless of whether it is porous, non-porous, organic resin particles, or inorganic fine particles.
  • examples of inorganic matting agents that can be used include silica, alumina, zirconium oxide, titanium, carbon black, graphite, and TiO. , BaSO, ZnS, MgCO, CaCO, ZnO, C
  • organic matting agents polyethylene fine particles, fluorine resin particles, guanamine resin particles, acrylic resin particles, silicon resin particles, melamine resin particles Etc.
  • organic matting agents polyethylene fine particles, fluorine resin particles, guanamine resin particles, acrylic resin particles, silicon resin particles, melamine resin particles Etc.
  • the inorganic clothing matting agent include PMMA, polystyrene, and melamine, and particles obtained by coating a core of organic particles with inorganic particles having a smaller relay than the core particles.
  • the particle size of the inorganic particles is preferably about 1Z10 to 1Z100 of the core particles.
  • known metal oxide particles such as silica, alumina, titer, and zirconium oxide can be used.
  • a coating method various known methods can be used. Core material particles and coating material particles are collided at high speed in the air such as a force noblerizer, and the coating material particles are eaten on the surface of the core material particles. It is preferable to use a dry coating method in which it is fixed and covered.
  • any matting agent satisfying the scope of the present invention can exert its effect without any particular limitation.
  • the mat of the knock coating layer is used. Since the agent suppresses scratches on the heat-sensitive image forming layer, it is preferable to use organic resin particles.
  • the average particle size of the matting agent in the present invention can be obtained by calculating a circle equivalent from the projected area using an electron microscope.
  • the particle size is preferably 1 to 12 ⁇ m, more preferably 5 to 8 ⁇ m, and even more preferably 2 to 7 ⁇ m. If the particle size exceeds 12 m, scratches are likely to occur on the thermal image-forming layer. Conversely, if the particle size is 1 ⁇ m, the plate floats on the plate cylinder.
  • the ⁇ Ka ⁇ of [0107] matting agent, and more preferably be 0.2 to 10 weight 0/0 of the total back coating layer is preferably tool 1 to 10 wt%.
  • the laser recording device or the processless printing machine has a sensor for controlling the conveyance of the printing plate inside the device, and in order to perform these controls without delay, in the present invention,
  • the constituent layer preferably contains a dye and a pigment.
  • the dye and pigment black pigments such as infrared absorbing dyes and carbon black used for the above-mentioned photothermal conversion materials are preferably used.
  • the constituent layer can contain a known surfactant.
  • Image formation using the printing plate material of the present invention can be carried out by causing a physical change due to heat in the thermal image forming layer using a thermal head or a thermal laser.
  • a gas laser may be used as the laser, but it is particularly preferable to use a semiconductor laser that emits light in the near infrared region.
  • any system can be used as long as it can form an image on the surface of a printing plate material in accordance with an image signal from a computer camera using the semiconductor laser. Even a device.
  • the printing plate material held along the cylindrical surface inside the fixed cylindrical holding mechanism is used in the circumferential direction of the cylinder (main scanning) using one or more laser beams from the inside of the cylinder. Scanning) in the direction) and moving in the direction perpendicular to the circumferential direction (sub-scanning direction) to expose the entire surface of the printing plate material,
  • the printing plate material held on the surface of the cylindrical drum that rotates about the axis as a rotating body is rotated in the circumferential direction by rotating the drum using one or more laser beams from the outside of the cylinder (
  • the scanning exposure method (3) is particularly preferred, and the exposure method (3) is used particularly for an apparatus that performs exposure on a printing apparatus.
  • the lithographic printing plate material according to the present invention has a structure having an image forming layer on a support having a hydrophilic layer, and after image formation is performed by the image exposure described above, particularly wet development processing is performed. It has the feature that can be printed without any problems. That is, it is preferable that after forming an image on the printing plate material of the present invention using a thermal head or a thermal laser, development is performed with dampening water or dampening water and printing ink on a lithographic printing machine, and printing is performed. It is a state.
  • the printing plate material after image exposure is directly attached to the plate cylinder of the printing press or printing.
  • the non-image area of the image forming functional layer is removed by bringing the water supply roller and Z or ink supply roller into contact with the printing plate material while rotating the plate cylinder. Is possible.
  • the removal of the non-image area (unexposed area) of the image forming functional layer on the printing machine can be performed by contacting a watering roller or an ink roller while rotating the plate cylinder. It can be performed by various sequences as shown in FIG. In that case, the water amount adjustment that can be adjusted to increase or decrease the amount of dampening water required for printing is divided into multiple stages, or Let's change to the infinite step.
  • the water roller and the ink roller are brought into contact with each other at substantially the same time to rotate the plate cylinder one to several tens of times, and then printing is started.
  • a printing machine used for printing generally known lithographic offset printing machines using dampening water and lithographic printing ink can be used.
  • the lithographic printing plate material according to the present invention after imagewise exposure as described above, is developed with dampening water or dampening water and printing ink on a lithographic printing machine, and is then printed as a printing plate To be used.
  • water containing various preparations can be used as the dampening water supplied from the water supply roller.
  • the pH value of the fountain solution according to the present invention is preferably used in the range of 4 to 6.5 at 20 ° C.
  • the dampening water preferably contains an alcohol having 2 to 5 carbon atoms.
  • the content of the alcohol having 2 to 5 carbon atoms is 0.1% by mass or less based on the total amount of the dampening water. It is preferable that
  • the fountain solution according to the present invention is preferably a fountain solution having a phosphate compound content of 0.005 mol or more and less than 0.04 mol per liter of the fountain solution. Better!/,.
  • Examples of the phosphoric acid compound used in the fountain solution according to the present invention include phosphates, organic phosphorylated compounds, phosphites, hypophosphites, condensed phosphates, phytic acid compounds, and phosphones. Examples include acid compounds.
  • the phosphate is not particularly limited as long as it is a compound that releases phosphate ions in an aqueous solution.
  • phosphoric acid and ammonium salts of phosphoric acid (3 ammonium phosphate, hydrogen phosphate) 2 ammonium, ammonium dihydrogen phosphate, etc.
  • alkali metal salts of phosphoric acid (3 sodium phosphate, 2 sodium phosphate, 2 sodium phosphate, 3 potassium phosphate, etc.)
  • phosphorus Acid alkaline earth metal salts such as zinc phosphate, potassium phosphate, magnesium phosphate
  • iron phosphate phosphoric acid
  • Examples include manganese and phosphomolybdic acid.
  • Examples of the organic phosphoric acid compound include phenylphosphonic acid, phenylphosphoric acid, naphthylphosphonic acid, naphthylphosphonic acid, glycephospholic acid, glycephospholic acid, phenylphosphinic acid, naphthylphosphinic acid, diphenyl.
  • Examples include phosphinic acid, dimethylphosphinic acid, ⁇ -trifluorophosphinic acid, p-methoxyphenylphosphinic acid, and the like.
  • the phosphite is not particularly limited as long as it is a compound that releases phosphite ions in an aqueous solution.
  • phosphorous acid ammonium phosphite, sodium phosphite, rhodium phosphite Etc.
  • the hypophosphite is not particularly limited as long as it is a compound that releases hypophosphite ions in an aqueous solution.
  • hypophosphorous acid ammonium hypophosphite, sodium hypophosphite, hypophosphorous acid, and the like.
  • potassium phosphite examples include potassium phosphite.
  • the condensed phosphate is not particularly limited as long as it is a compound that releases condensed phosphate ions in an aqueous solution.
  • condensed phosphates such as polyphosphoric acid, piceric acid, metaphosphoric acid, ultraphosphoric acid, or the like.
  • Ammonium salts, alkali metal salts, alkaline earth metal salts and the like can be mentioned.
  • the phytic acid compound is not particularly limited as long as it is a compound capable of releasing phytate ions in an aqueous solution.
  • phytic acid ammonium salt of phytic acid, alkali Metal salts etc. are mentioned.
  • the phosphonic acid compound is not particularly limited as long as it is a compound capable of releasing phosphonic acid ions in an aqueous solution.
  • aminotri methylenephosphonic acid
  • phosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) and dimethyltriaminepenta (methylenephosphonic acid), ammonium salts thereof, and alkali metal salts.
  • the present invention is characterized in that the content of the phosphate compound is not less than 0.005 mol and less than 0.04 mol per liter of dampening water. More preferably, the content of the phosphoric acid compound is not less than 0.01 mol and less than 0.04 mol per liter of dampening water.
  • the phosphate when the phosphate is in the range of 0.005 mol or more and less than 0.04 mol, the fat-sensitive component that the phosphate has entered into the anodized film formed on the aluminum support, etc. This is considered to facilitate dissolution and removal together with a part of the film. On the other hand, if the amount of phosphate compound is as large as 0.04 mol or more, it will easily become dirty.
  • the printing plate material having a photosensitive layer formed on a substrate having a hydrophilic surface used for so-called processless printing in which on-press development processing is performed, the phosphate concentration in dampening water is adjusted to the above-mentioned range. By adjusting the range, it is possible to improve the initial ink fillability and improve the quality of the printed image.
  • the fountain solution used in the present invention is preferably a combination of the following.
  • the (a) pH adjuster used in the fountain solution according to the present invention at least one selected from water-soluble organic acids, inorganic acids and their salt strength can be used. These compounds are moist It is effective for pH adjustment or buffering of water and appropriate etching or anticorrosion of lithographic printing plate support.
  • Preferred organic acids include, for example, citrate, ascorbic acid, malic acid, tartaric acid, lactic acid, acetic acid, darconic acid, hydroxyacetic acid, succinic acid, malonic acid, levulinic acid, sulfuric acid, p-toluenesulfonic acid and the like.
  • examples of inorganic acids include nitric acid
  • alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts of these organic acids and Z or inorganic acids are also preferably used.
  • One of these organic acids, inorganic acids, and salts thereof may be used alone, or a mixture of two or more may be used.
  • the addition amount of these pH adjusting agents to the fountain solution is suitably in the range of 0.001% by mass or more and 0.1% by mass or less of the organic acid, inorganic acid and salts thereof.
  • the content is 0.001% by mass or more, the stain during printing is good due to the etching force of aluminum which is the support of the planographic printing plate.
  • it is 0.1% by mass or less, it is preferable from the point of view of the printing press.
  • the pH value of the fountain solution according to the present invention is preferably used in the range of 4 to 6.5 at 20 ° C as described above.
  • a surfactant or other solvent can be used as an aid for improving wettability.
  • anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfonates, linear alkyl benzene sulfonates, branched chains.
  • Polyoxyethylene alkyl ether phosphates polyoxyethylene alcohol
  • examples thereof include kiln ether ether phosphate salts, partial saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate and the like.
  • dialkyl sulfosuccinates, alkyl sulfate esters and alkyl naphthalene sulfonates are particularly preferably used.
  • cationic surfactants include primary amine salts, acyl aminoethylamine salts, N alkyl polyalkylene polyamine salts, fatty acid polyethylene polyamides, amides, and salts thereof, amine salts, and the like.
  • Quaternary ammonium salts or amide-bonded amide salts Esters such as ruhydroxyethyl ammonium salt and alkyloxymethylpyridium salt, ammonium salts having an ether bond; alkylimidazoline, 1 hydroxyethyl 2-alkylimidazoline, 1 acylaminoethyl-2 —Imidazolines such as alkyl imidazolium salts, imidazolium salts; alkyl polyoxyethylene amines, N-alkylaminopropylamines, N acyl polyethylene polyamines, acyl acyl polyamines, fatty acid triethanolamine esters, etc. Other fatty derivatives, biosurfactants, oligo soaps, and at least one of these can be used.
  • Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, Glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters , Polyethylene glycol fatty acid esters, poly Liglycerin fatty acid partial esters, polyoxyethylene coconut oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N bis 2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters , Polyoxyethylene polyoxypropylene block polymers, trialkylamine oxide
  • fluorine surfactants and silicon surfactants can also be used.
  • a surfactant the content thereof is 1% by mass or less, preferably 0.001-0. 5% by mass in consideration of foaming. Two or more types can be used in combination.
  • auxiliaries include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl eno-enoate, ethylene glycol mono-ethyl eno-enoate, diethylene glycerine.
  • Cornoremonochinenoatenore triethyleneglycolenomonochinenoatenore, tetraethyleneglycolenolemonochinenoatenore, ethyleneglycolenomonopropinoreatenore, jetylene glycolenolemonopropenoatenore, Triethyleneglycol monopropinore etherenole, tetraethylenedarlicol monopropyl ether, ethylene dalcol monoisopropyl etherenole, diethylenegnoleconole monoisopropino Etherenole, triethylene glycolenole monoisopropyl ether, tetraethylene dalcol monoisopropyl ether, ethylene glycol nore monobutinoreateoret, diethylene glycolenomonobutinoreatenore, triethylene glycolenoremonobutenoreatenore, tetra Ethylene glycol monobutino oleate
  • polypropylene glycols having a molecular weight of 200 to 1000 and their monomethyl ethers.
  • Methyl 1 butanol and 1 butoxy 2 propanol are preferred! These solvents may be used alone or in combination of two or more. These solvents are appropriately used in a range of from 0.002 to 1% by weight based on the total weight of the dampening water, preferably 0.005 to 0.5 mass 0/0.
  • the water-soluble polymer compound (c) used in the dampening solution used in the present invention includes, for example, arabic gum, starch derivatives (for example, dextrin, enzymatically decomposed dextrin, hydroxypropyl Hydrolytic enzyme dextrin, carboxymethylated starch, phosphate starch, otaturic starch, alginates, fibrin derivatives (for example, carboxymethylcellulose, carboxykisenoresenorelose, methinoresenorelose, hydroxyethinoresenorelose) ) And other natural products, polyethylene glycol and copolymers thereof, polybutyl alcohol and derivatives thereof, polyacrylamide and copolymers thereof, polyacrylic acid and copolymers thereof, butyl methyl ether and maleic anhydride copolymer.
  • arabic gum for example, arabic gum, starch derivatives (for example, dextrin, enzymatically decomposed dextrin, hydroxypropyl Hydrolytic enzyme dextri
  • Examples thereof include a polymer, vinyl acetate Z maleic anhydride copolymer, polystyrene sulfonic acid and a synthetic product of the copolymer, and polyvinylpyrrolidone.
  • carboxymethyl cellulose and hydroxyethyl cellulose are particularly preferable.
  • the content of the water-soluble polymer compound is 0.0 with respect to the fountain solution.
  • 01-0.5% by mass is suitable, more preferably 0.005-0.2% by mass.
  • Odor masking agents include esters that have been known to be used as perfumes. For example, there is one represented by the following general formula (I).
  • R is carbon
  • R is an alkyl group or an alkenyl group
  • an aralkyl group when it represents an aralkyl group, they may be linear or branched.
  • An alkenyl group having one double bond is particularly suitable.
  • the aralkyl group include a benzyl group and a ferroethyl group.
  • R is an alkyl group having 3 to 10 carbon atoms, an aralkyl group, or
  • a phenyl group which may be linear or branched.
  • the number of carbon atoms is preferably 3 to 9.
  • the aralkyl group include a benzyl group and a ferroethyl group.
  • (d) odor masking agents that can be used include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethylbutyric acid, valeric acid, isovaleric acid, 2-methylvaleric acid, hexanoic acid ( Proproic acid), 4-methylpentanoic acid (isohexanoic acid), 2 hexenoic acid, 4 pentenoic acid, heptanoic acid, 2-methylheptanoic acid, octanoic acid (forced prillic acid), nonanoic acid, decanoic acid ( Strength purine acid), 2-decenoic acid, lauric acid or myristic acid esters.
  • Proproic acid 4-methylpentanoic acid (isohexanoic acid), 2 hexenoic acid, 4 pentenoic acid, heptanoic acid, 2-methylheptanoic acid, octanoic acid (forced pri
  • acetoacetates such as benzyl phenylacetate, ethyl acetate, and 2-hexyl acetate.
  • n-pentyl acetate, isopentyl acetate, n-butyl butyrate, n pentyl butyrate and isopentyl butyrate are preferable, and n-butyl butyrate, n pentyl butyrate and isopentyl butyrate are particularly preferable.
  • the content of these odor masking agents (d) in the fountain solution is suitably from 0.001 to 0.5% by mass, more preferably from 0.002 to 0.2%, based on the total mass of the fountain solution. % By mass. By using these, the working environment can be further improved.
  • Vanillin, ethyl valine or the like may be used in combination.
  • Preservative used in the fountain solution according to the present invention includes phenol or a derivative thereof, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazoline-3-one derivative, benztriazole derivative, amidine Or guanidine derivatives, quaternary ammonium salts, pyridine, quinoline or guanidine derivatives, diazine or triazonole derivatives, oxazole or oxazine derivatives, bromonitroalcohol-based bromonitropropanols, 1 , 1 Jib mouth mo 1 12 tallow 2 Ethanol, 3 Bromo 3-tropentane 1, 2 diol and the like.
  • the preferred amount of applied force is the amount that exerts stability against bacteria, mold, yeast, etc., and it varies depending on the type of bacteria, mold, yeast, but is 0. A range of 001 to 0.5% by mass is preferred, and it is preferable to use two or more preservatives that are effective against various strengths of bacteria, bacteria, and yeast.
  • the fountain solution according to the present invention may further contain Sarakoko (f) a chelating agent.
  • the fountain solution is usually prepared by adding tap water, well water, etc. to the fountain solution concentrated composition at the time of use. 1S At this time, calcium ions contained in the tap water or well water to be diluted. It may adversely affect printing and cause the printed matter to become dirty easily. In such a case, the above disadvantages can be eliminated by adding a chelating agent.
  • Preferred chelating agents include, for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt, Hydroxyethyl ethylenediamine triacetic acid , Its potassium salt, its sodium salt; utrilotriacetic acid, its sodium salt; 1-hydroxyethane 1,1-diphosphonic acid, its potassium salt, its sodium salt; aminotri (methylenephosphonic acid), its potassium salt, its sodium salt, etc. And organic phosphonic acids such as phosphonoalkanetricarboxylic acids.
  • an organic amine salt is also effective.
  • These chelating agents are selected so that they are stably present in the fountain solution during use and do not impair the printability.
  • the content of the fountain Kiretoi ⁇ of water in use 0. 0001-0. Is suitably 5% by weight, preferably 0.0005 to 0.2 mass 0/0.
  • Food coloring agents and the like can be preferably used as the colorant (g) used in the fountain solution according to the present invention.
  • the colorant (g) used in the fountain solution according to the present invention CINo. 19140 and 15985 as yellow pigments, CINo. 16185, 45430, 16255, 45380 and 45100 as red pigments, CINo. 42640 as purple pigments, CINo. 42090 and 73015 as blue pigments, and green pigments Is CINo. 42095, with equal strength.
  • the content of the colorant in the fountain solution used is preferably 0.0001-0.
  • Examples of the antifungal agent (h) used in the fountain solution used in the present invention include benzotriazole, 5-methylbenzotriazole, thiosalicylic acid, benzimidazole and derivatives thereof.
  • a silicon antifoaming agent is preferred, and both an emulsified dispersion type and a soluble type can be used.
  • the content of the fungicide in the fountain solution is preferably from 0.0001 to 0.5% by mass.
  • the dampening water of the present invention may be supplemented with alcohols in order to improve the printability by adjusting the surface tension and viscosity.
  • alcohols that can be added include methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol.
  • the remainder of the fountain solution composition according to the present invention is water.
  • the fountain solution composition is usually concentrated and commercialized when commercialized. Therefore, a concentrated fountain solution composition can be obtained as an aqueous solution in which the above various components are dissolved using water, preferably demineralized water, that is, pure water.
  • a concentrated fountain solution composition Dilute to about 10 to 200 times with tap water, well water, etc. to make a fountain solution at the time of use.
  • the dampening water according to the present invention can also be used in the water supply system of the calling water supply system, the continuous water supply system! /, Or the dampening water of the misalignment, but particularly in the dampening water supply apparatus of the continuous water supply system. It is preferable that It can also be used on any printing press with Mitsubishi Diamatic Dampner, Komorimatic, Dahllen Dampner or Heidelberg Alcala Dampner.
  • the ink that can be used in printing according to the present invention may be any ink that can be used for lithographic printing.
  • rosin-modified phenol resin and vegetable oils ama oil, tung oil
  • Oil oil and acrylic oligomers, acrylic monomers, photopolymerization initiators, pigments, etc. composed of components such as petroleum solvents, pigments, oxidation polymerization catalysts (cobalt, manganese, lead, iron, zinc, etc.)
  • undercoat coating solution a On one side of the substrate obtained by the above method, apply the following undercoat coating solution a to a dry film thickness of 0.8 m while performing corona discharge treatment under the condition of 8 W / m 2 ⁇ min. Further, an undercoat coating solution b was applied to the dry film thickness of 0.1 ⁇ m while performing corona discharge treatment (8 WZm 2 .min) (undercoat surface A). Also, on the opposite side, apply the following undercoat coating solution c to a dry film thickness of 0.06 m while performing corona discharge treatment under the condition of 8 WZm 2 ′, and dry at 140 ° C. Next, apply the undercoating solution d so that the dry film thickness is 0. And dried at 140 ° C (undercoating surface B) to obtain an undercoated substrate
  • Mat material (silica, average particle size 3.5 m) 0.02 parts by mass
  • Antifungal agent F— 1 0. 01 parts by mass
  • Modified water-based polyester A (solid content 18%) 21.5 parts by weight Anionic surfactant 0.04 parts by weight Spherical silica matting agent Sea Hoster KE-P60 (Nippon Shokubai Co., Ltd.) Water
  • the hydrophilic layer coating solution shown below (preparation method is shown below) on the surface A of the undercoated support using a wire bar so that the dry weight is 3 g / m 2 and 120 ° C. After drying for 3 minutes, it was heated at 60 ° C for 48 hours. Furthermore, the image forming functional layer coating solution was applied onto the hydrophilic layer using a wire bar so that the drying weight was 0.5 gZm 2 and dried at 50 ° C. for 1 minute, and then at 50 ° C. for 24 minutes. The plate was subjected to heat treatment for a period of time, rolled 670 mm in width and 30.5 m in length, and produced lithographic printing plate materials 1 to 5 as shown in Table 1 below.
  • Colloidal silica alkaline
  • Snowtex- xs Snowtex- xs (Nissan Chemical Co., Ltd., solid content 20% by mass) 48 parts by mass
  • Colloidal silica alkaline
  • Snowtex-ZL Snowtex-ZL (Nissan Chemical Co., Ltd., solid content 40% by mass) 4 parts by mass
  • Porous Metal Oxide Particles SILTON JC-50 (Mizusawa Chemical Co., Ltd., porous aluminosilicate particles, average particle size 5 ⁇ m) 11. 1 part by mass
  • Silicone surfactant FZ-2161 (manufactured by Nippon Car Co., Ltd.) 0.16 parts by mass
  • the magnetic value of the pigment used in this example is 397.9 kAZm using VSM manufactured by Toei Kogyo Co., Ltd. Force measured in a magnetic field of (5 kOe)
  • the magnetic field value of the pigment according to the invention was in the range of 0.5 to LOemuZg.
  • Microcrystalline wax A—206 (Gifu Shellac Co., Ltd.) Solid content 40%
  • Polyethylene wax A- 514 (Gifu Shellac Co., Ltd.) 40% solids 15 parts by mass of sodium polyacrylate 30 mass 0/0 aqueous DL-522 (manufactured by Nippon Shokubai Co., Ltd.)
  • a lithographic printing plate material packaged in a roll of 670mm width and 30.5m roll on the exposure drum is cut to a length of 560mm, wound and fixed, and then a laser beam with a wavelength of 830nm and a spot diameter of about 18m is used.
  • the exposure energy is 200mjZcm 2 , 2400dpi (dpi is the number of dots per 2.54cm), 1751pi (lpi is the number of lines per 2.54cm) Prepared and exposed.
  • Komori Corporation's LITHRONE26 was used, and after inserting the above printing plate notch into the printing machine pin, coated paper (Oji Paper, 636x468) and Astro Mark 3 (Nikken A 2 mass% aqueous solution (pH 4.8) of Togoku Ink Co., Ltd.), and four inks of high yellow, indigo, red and black made by Toyo Ink Co., Ltd., and printing speed of 9000 sheets At Z, printing was performed using a Sumitomo Dunlop blanket o [0171] ⁇ Print life>
  • the printing durability was evaluated by obtaining the force at which part of the 2% halftone dot was missing on the printed material or the number of printed sheets when the non-image area was stained.
  • the printing plate after on-press development was immersed in a 2% by weight first mouth mark 3 aqueous solution (pH 4.8) for lh, and the change from the concentration before immersion was visually evaluated.
  • the number of aggregates in the hydrophilic layer coated product lm 2 was visually evaluated.
  • the printing plate material of the present invention is excellent in printing durability, decoloration resistance and coating property.
  • An aluminum plate (material 1050, tempered H16) with a thickness of 0.24 mm was immersed in a 1% by weight sodium hydroxide aqueous solution at 50 ° C, dissolved to a dissolution rate of 2 g / m 2 and washed with water. Thereafter, it was immersed in a 5 mass% nitric acid aqueous solution at 25 ° C for 30 seconds, neutralized, and then washed with water.
  • this aluminum plate was electrolytically roughened with an electrolytic solution containing 1 lgZL of hydrochloric acid, 10 gZL of acetic acid and 8 gZL of aluminum, using a sinusoidal alternating current at a peak current density of 80 AZdm 2. Processed. The distance between the electrode and the sample surface at this time was 10 mm. Electrolytic rough The chamfering process was divided into 8 times, and the amount of electricity processed at one time (at the time of anode) was 40 CZdm 2 , and the total amount of electricity processed (at the time of anode) was 320 CZdm 2 . In addition, a pause of 3 seconds was provided between each treatment.
  • the substrate was immersed in an aqueous solution of 5% by mass of lithium silicate (LSS45, manufactured by Nissan Chemical Co., Ltd.) for 15 seconds, washed with water and then dried at 80 ° C. for 5 minutes to obtain a support.
  • LSS45 lithium silicate
  • Polymer particles 1 (solid content 50%) 7.5 parts by mass
  • the printing plate material of the present invention is excellent in printing durability, decoloration resistance and coating property!

Abstract

This invention provides a lithographic printing plate material, which is excellent in coatability, dampening water resistance, and resistance to decolorization after development, and, at the same time, has high printing durability, and is suitable for development on a printing machine, a method for manufacturing the same, and a printing method. The lithographic printing plate material comprises a base material and at least a hydrophilic layer and a thermal image forming layer provided on the base material and is characterized in that at least the hydrophilic layer contains a pigment having a photothermal conversion function, the composition molar ratio of the pigment is iron : titanium = 1 : 1.1 to 6.

Description

明 細 書  Specification
平版印刷版材料、その製造方法、及び印刷方法  Planographic printing plate material, manufacturing method thereof, and printing method
技術分野  Technical field
[0001] 本発明は、いわゆるコンピュータ^ ~·トウ'プレート（computer— to—plate :以下に おいて、「CTP」という。）システムに用いられる平版印刷版材料に関し、印刷機上で 現像される平版印刷版材料、その製造方法、及びそれを用いた印刷方法に関する。 背景技術  [0001] The present invention relates to a lithographic printing plate material used in a so-called computer-to-plate (hereinafter referred to as "CTP") system, which is developed on a printing press. The present invention relates to a planographic printing plate material, a method for producing the same, and a printing method using the same. Background art
[0002] 近年、画像情報をコンピューターを用いて電子的に処理、蓄積、出力する、デジタ ルイ匕技術が広く普及し、オフセット印刷用の印刷版の作製技術においては、デジタ ル化された画像情報に従って、指向性の高いレーザー光を走査し、直接平版印刷 版に記録する、いわゆる CTPシステムが開発され、実用化が進展している。  [0002] In recent years, digital processing technology that electronically processes, stores, and outputs image information using a computer has become widespread, and digital image information has been used in the preparation of printing plates for offset printing. Therefore, a so-called CTP system that scans with a highly directional laser beam and records directly on a lithographic printing plate has been developed and is in practical use.
[0003] 一般に、 CTPに使用される印刷版材料は、従来の PS版と同様にアルミ支持体を使 用するタイプとフィルム基材上に印刷版としての各種機能層を設けたフレキシブルタ イブがある。  [0003] In general, the printing plate material used for CTP is a type that uses an aluminum support as in the case of the conventional PS plate and a flexible plate that has various functional layers as a printing plate on a film substrate. is there.
[0004] 近年、商業印刷分野においては、印刷の少量多品種ィ匕の傾向が進み、巿場では 高品質で、かつ低価格な印刷版材料への要望が強まってきている。従来のフレキシ ブルタイプの印刷版材料としては、例えば、特開平 5— 66564号公報に開示されるよ うなフィルム基材上に銀塩拡散転写方式の感光層を設けたもの、あるいは特開平 8 — 507727号、同 6— 186750号、同 6— 199064号、同 7— 314934号、同 10— 58 636号、同 10— 244773号の各公報に開示されるようなフィルム基材上に親水性層 と親油性層とを 、ずれかの層を表層として積層し、表層をレーザー露光でアブレーシ ヨンさせて印刷版を形成するように構成されたもの、あるいは特開 2001— 96710号 公報に開示されるようなフィルム基材上に親水性層と感熱画像形成層を設け、レー ザ一露光により親水性層あるいは画像形成層を画像様に発熱させることで画像形成 層を親水性層上に溶融固着させるもの等が挙げられる。  [0004] In recent years, in the field of commercial printing, there has been a tendency for a small amount of various types of printing, and there is an increasing demand for high-quality and low-cost printing plate materials in the factory. As a conventional flexible type printing plate material, for example, one having a silver salt diffusion transfer type photosensitive layer on a film base as disclosed in JP-A-5-66564, or JP-A-8- No. 507727, 6-186750, 6-199064, 7-314934, 10-58 636, 10-244773 And a lipophilic layer, each of which is laminated as a surface layer, and the surface layer is ablated by laser exposure to form a printing plate, or disclosed in JP-A-2001-96710 A hydrophilic layer and a heat-sensitive image forming layer are provided on such a film substrate, and the image forming layer is melt-fixed on the hydrophilic layer by heating the hydrophilic layer or the image forming layer in an image-like manner by laser exposure. And the like.
[0005] 一方、印刷用の画像形成方法として、環境適性等の観点より画像データ書き込み（ 画像様露光)後の印刷版を直接オフセット印刷機で印刷することにより湿し水で非画 像部の画像形成層のみ膨潤、溶解して印刷初期の印刷紙 (損紙)上に転写除去する 所謂印刷機上で現像を行う方法 (例えば、特許文献 1及び 2参照。）が知られている。 これらの印刷機上現像可能な印刷版材料は、鮮鋭なドット形状、高精細な画像が得 られ、又露光後の現像プロセスを必要とせず、環境適性にも優れている。 [0005] On the other hand, as an image forming method for printing, from the viewpoint of environmental suitability and the like, a printing plate after image data writing (image-like exposure) is directly printed with an offset printing machine, so that it is non-imaged with dampening water. A method of developing on a so-called printing machine in which only the image forming layer in the image area swells and dissolves and is transferred and removed onto printing paper (waste paper) at the initial printing stage is known (see, for example, Patent Documents 1 and 2). Yes. These printing plate materials that can be developed on a printing press can provide sharp dot shapes and high-definition images, and do not require a development process after exposure, and are excellent in environmental suitability.
[0006] 近年、これらの印刷機上現像可能な印刷版材料にぉ ヽては、近赤外域の波長の 光を吸収して発熱する、即ち、光熱変換機能を有する赤外線吸収剤を利用した平版 印刷版材料が実用化されている。赤外線吸収剤としては一般的に、カーボンブラック や酸化鉄のような無機顔料や、シァニン染料、メチン染料、ナフトキノン染料、置換さ れたァリールべンゾ (チォ)ピリリウム塩、トリメチンチアピリリウム塩、ピリリウム系化合 物、等の有機染料が用いられている。  [0006] In recent years, for these printing plate materials that can be developed on a printing press, lithographic printing using an infrared absorbent that absorbs light in the near-infrared region and generates heat, that is, has a photothermal conversion function. Printing plate materials are in practical use. Infrared absorbers generally include inorganic pigments such as carbon black and iron oxide, cyanine dyes, methine dyes, naphthoquinone dyes, substituted allylbenzo (thio) pyrylium salts, trimethine thiapyrylium salts, Organic dyes such as pyrylium compounds are used.
[0007] しかし、これらの赤外吸収剤のうち、印刷版性能に必要な親水性や塗布性などの観 点から好ましい酸ィ匕鉄のような黒色酸ィ匕金属顔料が比較的よく使用されているが、従 来使用されている黒色酸ィ匕金属は酸性に弱ぐ印刷に用いられる湿し水が酸性であ るため湿し水により耐刷性が劣化させられるという問題あった。  [0007] However, among these infrared absorbers, black acid metal pigments such as acid iron, which are preferable from the viewpoints of hydrophilicity and coating properties necessary for printing plate performance, are used relatively frequently. However, the conventional black acid metal has a problem in that the printing durability is deteriorated by the dampening water because the dampening water used for printing, which is weak in acidity, is acidic.
特許文献 1：特開平 9— 123387号公報  Patent Document 1: Japanese Patent Laid-Open No. 9-123387
特許文献 2：特開平 9— 123388号公報  Patent Document 2: JP-A-9-123388
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
[0008] 本発明は、上記課題に鑑みてなされたものであり、その目的は、塗布性、湿し水耐 性、現像後の耐脱色性に優れ、かつ高い耐刷性を持ち印刷機上現像に適した平版 印刷版材料、その製造方法及び印刷方法を提供することにある。 [0008] The present invention has been made in view of the above problems, and its purpose is excellent in coating properties, dampening water resistance, decoloration resistance after development, and high printing durability on a printing press. A planographic printing plate material suitable for development, a method for producing the same, and a printing method.
課題を解決するための手段  Means for solving the problem
[0009] 本発明の上記課題は、以下の手段により解決された。 The above-described problems of the present invention have been solved by the following means.
[0010] 1.基材上に少なくとも親水性層及び感熱画像形成層を有する平版印刷版材料に おいて、少なくとも該親水性層が光熱変換機能を有する顔料を含有し、かつ該顔料 は、鉄およびチタンを成分として有し、その場合の組成モル比が鉄 1に対し、チタン が 1. 1〜6であることを特徴とする平版印刷版材料。  [0010] 1. In a lithographic printing plate material having at least a hydrophilic layer and a heat-sensitive image forming layer on a substrate, at least the hydrophilic layer contains a pigment having a photothermal conversion function, and the pigment contains iron A lithographic printing plate material comprising: titanium as a component, wherein the composition molar ratio is 1.1 to 6 with respect to iron 1.
[0011] 2.前記顔料の磁化値が 0. 5〜10emuZgであることを特徴とする前記 1に記載の 平版印刷版材料。 [0011] 2. The magnetization value of the pigment according to 1 above, wherein the pigment has a magnetization value of 0.5 to 10 emuZg. Planographic printing plate material.
[0012] 3.前記 1又は 2に記載の平版印刷版材料を製造することを特徴とする平版印刷版 材料の製造方法。  [0012] 3. A method for producing a lithographic printing plate material, comprising producing the lithographic printing plate material described in 1 or 2 above.
[0013] 4.前記 1又は 2に記載の平版印刷版材料及び温度 20°Cにおいて pH4〜6. 5であ る湿し水を用いて印刷することを特徴とする印刷方法。  [0013] 4. A printing method comprising printing using the lithographic printing plate material according to 1 or 2 above and a fountain solution having a pH of 4 to 6.5 at a temperature of 20 ° C.
[0014] 5.前記湿し水に含有される炭素数 2〜5のアルコールの含有量が 0. 1質量％以下 であることを特徴とする前記 4に記載の印刷方法。 [0014] 5. The printing method as described in 4 above, wherein the content of the alcohol having 2 to 5 carbon atoms contained in the fountain solution is 0.1% by mass or less.
発明の効果  The invention's effect
[0015] 本発明の上記構成により、塗布性、湿し水耐性、現像後の耐脱色性に優れ、かつ 高!ヽ耐刷性を持ち印刷機上現像に適した平版印刷版材料、その製造方法及び印刷 方法を提供することができる。  [0015] According to the above configuration of the present invention, a lithographic printing plate material having excellent coating properties, dampening water resistance, decoloration resistance after development, and high printing durability, suitable for development on a printing press, and production thereof Methods and printing methods can be provided.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0016] 以下、本発明とその構成要素等について詳細な説明をする。 [0016] Hereinafter, the present invention and its components will be described in detail.
[0017] 〈光熱変換機能を有する顔料〉 <Pigment having photothermal conversion function>
本発明の平版印刷版材料は、後述するように、親水性層又は親水性層と支持体と の間に設けた親水性の下層等に、光熱変換素剤として赤外吸収色素、無機'有機顔 料等の種々の光熱変換素剤を含有することができるが、特に光熱変換素材として、 光熱変換機能を有する金属酸化物顔料 (単に、顔料とも呼ぶ)を含有することを特徴 とする。また、当該金属酸化物顔料の組成において、少なくとも、鉄及びチタンを構 成成分として含有し、かつその場合のこれらの組成モル比が鉄 1に対し、チタンが 1. 1〜6であることを特徴とする。  As will be described later, the lithographic printing plate material of the present invention comprises an infrared absorbing dye, an inorganic organic material as a photothermal conversion base material on a hydrophilic layer or a hydrophilic lower layer provided between a hydrophilic layer and a support. Various photothermal conversion raw materials such as pigments can be contained, and a metal oxide pigment having a photothermal conversion function (also simply referred to as a pigment) is particularly contained as a photothermal conversion material. Further, in the composition of the metal oxide pigment, it contains at least iron and titanium as constituent components, and in this case, the molar ratio of these components is 1.1 to 6 with respect to iron 1. Features.
[0018] 金属酸ィ匕物顔料の中では、酸化鉄が光熱変換能に特に優れ好まれているが、酸 化鉄では磁性が高く凝集性が高いため、塗布故障などの問題が起こるため、酸ィ匕チ タンに酸ィ匕鉄を被覆させたり、鉄とチタンとを混合組成させた黒色複合酸ィ匕物が好ま しい。 [0018] Among metal oxide pigments, iron oxide is particularly preferred for its photothermal conversion ability. However, iron oxide has high magnetism and high cohesiveness, which causes problems such as coating failure. A black composite oxide in which an acid iron is coated with an acid iron or a mixture of iron and titanium is preferred.
[0019] 本発明に係る顔料は、例えば、酸ィ匕チタンに酸ィ匕鉄を被覆させたあと焼成して Fe  [0019] The pigment according to the present invention may be obtained by, for example, coating iron oxide titanium with iron oxide iron and firing it.
2 2
TiO相を形成させる。その後水素ガスと炭酸ガスを併用し Fe TiOを Fe TiO へ還A TiO phase is formed. Then, using both hydrogen gas and carbon dioxide, Fe TiO is returned to Fe TiO.
5 2 5 2 4 元し製造することができる。 [0020] 反応させる前の酸化チタンと酸化鉄の添加量に生成する顔料の組成モル比は依 存し、単粒子あたりの鉄とチタンの組成モル比が鉄 1に対して、チタンが 1. 1〜6であ ることが好ましい。さらに 1. 5〜5であることがさらに好ましい。 5 2 5 2 4 Yuan can be manufactured. [0020] The composition molar ratio of the pigment to be formed depends on the added amount of titanium oxide and iron oxide before the reaction, the composition molar ratio of iron to titanium per single particle is 1. It is preferably 1-6. Further preferably 1.5 to 5.
[0021] またこれら顔料は、アルミニウムやケィ素等の焼結防止剤を使用でき、表面改質処 理を行うことができる。  In addition, these pigments can use a sintering inhibitor such as aluminum and silicon, and can be subjected to a surface modification treatment.
[0022] また、本発明に係る顔料の磁化値は、 0. 5〜10emuZgであることが好ましぐ 2〜 lOemuZgがさらに好ましい。磁化値が 0. 5emuZgより小さいと膜強度が弱く耐刷 不良を起こし、 lOemuZgより大きいと 2次凝集等を起こし塗布性が劣化する。  [0022] The magnetization value of the pigment according to the present invention is preferably 0.5 to 10 emuZg, more preferably 2 to lOemuZg. If the magnetization value is less than 0.5 emuZg, the film strength is weak and poor printing durability occurs, and if it is greater than lOemuZg, secondary agglomeration and the like occur, resulting in poor coating properties.
[0023] 上記磁ィ匕値は、磁力計 (例えば、東英工業株式会社製振動試料型磁力計 VSM— P7— 15型）により測定することができる。  [0023] The magnetic field value can be measured with a magnetometer (for example, a vibrating sample magnetometer VSM-P7-15 manufactured by Toei Kogyo Co., Ltd.).
[0024] さらに、これらの金属酸化物で芯材（BaSO、 TiO、 9A1 Ο · 2Β 0、 K O 'nTiO  [0024] Furthermore, a core material (BaSO, TiO, 9A1 Ο · 2Β 0, K O 'nTiO
4 2 2 3 2 2 2 等）を被覆したものも使用することができる。  4 2 2 3 2 2 2 etc.) can also be used.
[0025] これら本発明に係る金属酸化物顔料の含有量としては、親水性層の全固形成分の 質量に対して 10〜60質量％であり、 15〜50質量％が好ましぐ 20〜45質量％がよ り好ましい。  [0025] The content of the metal oxide pigment according to the present invention is 10 to 60% by mass, preferably 15 to 50% by mass, with respect to the mass of all solid components of the hydrophilic layer. A mass% is more preferred.
[0026] なお、親水性層と支持体との間に層を有する場合、係る下層等にも、同様に、本発 明に係る金属酸化物顔料を含有させることもできる。  [0026] When a layer is provided between the hydrophilic layer and the support, the metal oxide pigment according to the present invention can also be contained in the lower layer or the like.
[0027] また、本発明に係る顔料の他に、光熱変換素剤として併用することができる種々の 赤外吸収色素、無機'有機顔料については後述する。  [0027] In addition to the pigment according to the present invention, various infrared absorbing dyes and inorganic'organic pigments that can be used in combination as a photothermal conversion element will be described later.
[0028] <基材:支持体 >  [0028] <Substrate: Support>
基材としては、公知の材料を使用することができる。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基材等も 挙げられる。基材の厚みとしては 100〜300 /ζ πιが好ましぐ特に好ましくは 150〜2 00 μ mである。金属板としては、鉄、ステンレス、アルミニウム等が挙げられる力 比 重と剛性との関係力も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）が好ましい。アルミニウム板は、通常その表面に存在する圧延 *卷取り時に使用 されたオイルを除去するためにアルカリ、酸、溶剤等で脱脂した後に使用される。脱 脂処理としては特にアルカリ水溶液による脱脂が好ましい。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。陽極酸化処理も易接着処 理の一種と考えられ、使用することができる。また、陽極酸化処理と上記浸漬または 塗布処理を組み合わせて使用することもできる。また、公知の方法で粗面化されたァ ルミ-ゥム板や、それに上記の易接着処理を組み合わせた支持体も使用することが でき、公知の方法で粗面化し陽極酸化処理を行い、必要に応じて表面処理を行った 、いわゆるアルミ砂目を支持体として用いることもできる。 A known material can be used as the base material. For example, a metal plate, a plastic film, paper treated with polyolefin, a composite base material obtained by appropriately bonding the above materials, and the like can also be mentioned. The thickness of the substrate is preferably 100 to 300 / ζ πι, particularly preferably 150 to 200 μm. As the metal plate, aluminum, an aluminum alloy (hereinafter referred to as “aluminum”) is particularly preferable as the relational force between force specific gravity and rigidity, such as iron, stainless steel, and aluminum. The aluminum plate is usually used after degreasing with alkali, acid, solvent, etc. to remove the oil used during rolling * scraping existing on the surface. As the degreasing treatment, degreasing with an aqueous alkali solution is particularly preferable. Adhesiveness with coating layer In order to improve, it is preferable to perform an easily bonding process and undercoat layer application | coating to an application surface. For example, a method of performing sufficient drying after immersing in a liquid containing a coupling agent such as a silane coupling agent or applying a liquid. Anodization is also considered as a kind of easy adhesion treatment and can be used. Also, a combination of anodizing treatment and the above immersion or coating treatment can be used. In addition, an aluminum plate roughened by a known method and a support combined with the above-mentioned easy adhesion treatment can be used, and the surface is roughened by a known method and anodized. It can also be used as a support, so-called aluminum grain that has been surface-treated if necessary.
[0029] 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-レンオキサイド、セ ルロースエステル類等を挙げることができる。特に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が好ましい。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 、。これらプラスチックフィルムは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引き層塗布を行う。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。また、下引き層として は、ゼラチンやラテックスを含む層等が挙げられ、その中でも特開平 7— 191433号 段落番号 0044〜0116に記載の帯電防止下引き層が好ましく用いられる。  [0029] Examples of the plastic film include polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamide, polycarbonate, polysulfone, polyphenylene oxide, cellulose ester, and the like. Particularly preferred are polyethylene terephthalate and polyethylene naphthalate. Further, it is preferable to use a support obtained by the method described in JP-A-10-10676 and having a thermal dimensional change rate at 120 ° C. for 30 seconds of 0.001% or more and 0.04% or less. In order to improve the adhesion of the plastic film to the coating layer, an easy adhesion treatment or undercoat layer coating is applied to the coated surface. Examples of the easy adhesion treatment include corona discharge treatment, flame treatment, plasma treatment, and ultraviolet irradiation treatment. Examples of the undercoat layer include layers containing gelatin and latex, and among them, the antistatic undercoat layer described in JP-A-7-191433, paragraph numbers 0044 to 0116 is preferably used.
[0030] また下引き層には PVA、アクリルラテックスのような水酸基を有する化合物を用いる ことができる。  [0030] For the undercoat layer, a compound having a hydroxyl group such as PVA or acrylic latex can be used.
[0031] <親水性層 >  [0031] <Hydrophilic layer>
本発明に係る平版印刷版材料の親水性層は、主として層を形成する親水性マトリツ タス成分、表面形状を制御する微粒子成分、マット材などを成分として構成される。  The hydrophilic layer of the lithographic printing plate material according to the present invention is mainly composed of a hydrophilic matrix component that forms the layer, a fine particle component that controls the surface shape, a mat material, and the like as components.
[0032] なお、上述のように、光熱変換素材として、本発明に係る金属酸化物顔料を当該親 水性層に含有させることが好ま 、。  [0032] As described above, it is preferable to include the metal oxide pigment according to the present invention in the hydrophilic layer as a photothermal conversion material.
[0033] 親水性マトリックスを形成する素材としては金属酸化物が好ましぐ更に好ましくは 金属酸化物微粒子を含むことが好まし ヽ。  [0033] The material forming the hydrophilic matrix is preferably a metal oxide, more preferably metal oxide fine particles.
[0034] 金属酸化物微粒子としては、例えばコロイダルシリカ、アルミナゾル、チタニアゾル、 その他の金属酸ィ匕物のゾルが挙げられ、金属酸ィ匕物の形態としては、球状、羽毛状 その他の 、ずれの形態でもよぐ平均粒径としては 3〜： LOOnmであることが好ましく、 平均粒径が異なる数種の金属酸ィ匕物微粒子を併用することもできる。また、粒子表 面に表面処理がなされて 、てもよ 、。 [0034] Examples of the metal oxide fine particles include colloidal silica, alumina sol, titania sol, Examples of other metal oxide sols include spheres, feathers, and other forms of metal oxides, and an average particle size of 3 to LOONm is preferable. Several kinds of metal oxide fine particles having different average particle diameters can be used in combination. In addition, surface treatment may be applied to the particle surface.
[0035] 上記金属酸ィ匕物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。 [0035] The metal oxide particles can be used as a binder by utilizing the film-forming property.
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。  It is suitable for use in a hydrophilic layer in which the decrease in hydrophilicity is smaller than when an organic binder is used.
[0036] 本発明には、上記の中でも特にコロイダルシリカが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有り、良好な 強度を得ることが出来る。  [0036] Among the above, colloidal silica can be preferably used in the present invention. Colloidal silica has the advantage of high film-forming properties even under relatively low temperature drying conditions, and can provide good strength.
[0037] 上記コロイダルシリカとしては、 1次粒子径が nmのオーダーである球形シリカが結 合したネックレス状コロイダルシリカ、平均粒径 20nm以下の微粒子コロイダルシリカ を含む事が好ましぐさら〖こ、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。  [0037] The colloidal silica preferably includes necklace-like colloidal silica combined with spherical silica having a primary particle diameter of the order of nm, and fine colloidal silica having an average particle diameter of 20 nm or less. Colloidal silica is preferably alkaline as a colloidal solution.
[0038] 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 PS」シリーズなどが挙げられる。  [0038] Specific examples of the necklace-shaped colloidal silica include "Snowtex PS" series manufactured by Nissan Chemical Industries.
[0039] 平均粒径が 20nm以下であるコロイダルシリカは前述のネックレス状コロイダルシリ 力と併用することで、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。 [0039] Colloidal silica having an average particle size of 20 nm or less is particularly preferable because it can be further improved in strength while maintaining the porosity of the layer by using in combination with the aforementioned necklace-like colloidal silica force. .
[0040] 平均粒径が 20nm以下であるコロイダルシリカ Zネックレス状コロイダルシリカの比 率 ίま 95/5〜5/95力 S好ましく、 70/30〜20/80力 Sより好ましく、 60/40〜30/[0040] Ratio of colloidal silica Z necklace-shaped colloidal silica having an average particle diameter of 20 nm or less ί 95/5 to 5/95 force S, preferably 70/30 to 20/80 force S, more preferably 60/40 to 30 /
70が更に好ましい。 70 is more preferred.
[0041] 本発明に係る親水性層マトリックスの多孔質ィ匕材として粒径が 1 μ m未満の多孔質 金属酸化物粒子を含有することが出来る。多孔質金属酸ィ匕物粒子としては、後述す る多孔質シリカまたは多孔質アルミノシリケート粒子もしくはゼォライト粒子を好ましく 用いることが出来る。  [0041] Porous metal oxide particles having a particle size of less than 1 µm can be contained as the porous matrix of the hydrophilic layer matrix according to the present invention. As the porous metal oxide particles, porous silica, porous aluminosilicate particles or zeolite particles described later can be preferably used.
[0042] 粒子の多孔性としては細孔容積で 0. 5mlZg以上であることが好ましぐ 0. 8ml/ g以上であることがより好ましぐ 1. 0〜2. 5mlZg以下であることが更に好ましい。 [0043] 細孔容積は塗膜の保水性と密接に関連しており、細孔容積が大きいほど保水性が 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. 5mlZg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。細孔容積が 0. 5mlZg未満の場合には、保水性が低下して印刷時に汚れが発生し易くなる。 [0042] The porosity of the particles is preferably 0.5 mlZg or more in terms of pore volume, more preferably 0.8 ml / g or more. 1.0 to 2.5 mlZg or less Further preferred. [0043] The pore volume is closely related to the water retention of the coating film, and the larger the pore volume, the better the water retention and the greater the water amount latitude that is difficult to get smeared during printing. When it becomes large, the particles themselves become very brittle, and the durability of the coating film decreases. When the pore volume is less than 0.5 mlZg, the water retention is lowered and stains are likely to occur during printing.
[0044] 本発明に係る多孔質ィ匕材としてはゼオライトも使用できる。ゼォライトは結晶性のァ ルミノケィ酸塩であり、細孔径が 0. 3〜： Lnmの規則正しい三次元網目構造の空隙を 有する多孔質体である。天然及び合成ゼォライトを合わせた一般式は、次のように表 される。
Figure imgf000008_0001
ここで、 M2は交換†¾のカチオンであって、 M1は Li+、 Na+、 K+、 Tl+、 Me Ν+ (Τ[0044] Zeolites can also be used as the porous material according to the present invention. Zeolite is a crystalline aluminokeate and is a porous body having pores with a regular three-dimensional network structure with a pore diameter of 0.3 to Lnm. The general formula combining natural and synthetic zeolite is expressed as follows.
Figure imgf000008_0001
Where M 2 is an exchange † ¾ cation and M 1 is Li +, Na +, K +, Tl +, Me Ν + (Τ
MA)、 Et N+ (TEA)、 Pr N+ (TPA)、 C H N +、 C H N+等であり、 M2は Ca2+、 Mg2 MA), Et N + (TEA), Pr N + (TPA), CHN +, CH N +, etc., M 2 is Ca 2+ , Mg 2
、 Ba 、 Sr 、 C H N 等である。又、 n≥mであり、 m/nの値つまりは Al/Si比率 は 1以下となる。 Al/Si比率が高いほど交換性カチオンの量が多く含まれるため極 性が高ぐ従って親水性も高い。好ましい AlZSi比率は 0. 4〜1. 0であり、更に好ま しく ίま 0. 8〜1. 0である。 χίま整数を表す。 Ba, Sr, C H N and the like. In addition, n≥m, and the value of m / n, that is, the Al / Si ratio is 1 or less. The higher the Al / Si ratio, the greater the amount of exchangeable cations and the higher the polarity and therefore the higher the hydrophilicity. The preferred AlZSi ratio is 0.4 to 1.0, more preferably ί to 0.8 to 1.0. χί represents an integer.
[0046] 本発明で使用するゼオライト粒子としては、 AlZSi比率が安定しており、又粒径分 布も比較的シャープである合成ゼォライトが好ましぐ例えばゼォライト A: Na (Al S i O ) ' 27H O ;AlZSi比率 1 · 0、ゼォライト X: Na (Al Si O ) · 264Η Ο ;Α1[0046] As the zeolite particles used in the present invention, synthetic zeolite having a stable AlZSi ratio and a relatively sharp particle size distribution is preferred. For example, zeolite A: Na (AlSiO) ' 27H 2 O; AlZSi ratio 1 · 0, Zeolite X: Na (Al 2 Si O) · 264Η Ο; Ο1
ZSi比率 0· 811、ゼォライト Y: Na (Al Si O ) · 250Η 0 ;AlZSi比率 0· 412 等が挙げられる。 ZSi ratio 0 · 811, Zeolite Y: Na (Al 2 Si 2 O 3) · 250Al 0; AlZSi ratio 0 · 412
[0047] 親水性層の表面は、 PS版のアルミ砂目のように 0. 1〜 20 mピッチの凹凸構造を 有することが好ましぐこの凹凸により保水性や画像部の保持性が向上する。  [0047] The surface of the hydrophilic layer preferably has a concavo-convex structure with a pitch of 0.1 to 20 m like the aluminum grain of the PS plate, and this concavo-convex improves water retention and image area retention. .
[0048] このような凹凸構造は、親水性層マトリッ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。  Such a concavo-convex structure can be formed by containing an appropriate amount of filler having an appropriate particle size in the hydrophilic layer matrix. The above-mentioned alkaline colloidal silica can be used in the hydrophilic layer coating solution. It is preferable that a structure having better printability can be obtained by containing the above-mentioned water-soluble polysaccharide and forming it by causing phase separation when the hydrophilic layer is applied and dried.
[0049] 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。 [0049] The shape of the concavo-convex structure (such as pitch and surface roughness) depends on the type of alkaline colloidal silica and It is possible to appropriately control the amount of addition, the type and amount of water-soluble polysaccharide, the type and amount of other additives, the solid content concentration of the coating liquid, the wet film thickness, and the drying conditions.
[0050] 本発明で親水性マトリックスに添加される水溶性榭脂は、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。  [0050] It is preferable that the water-soluble coagulum added to the hydrophilic matrix in the present invention is present in a state in which at least a part thereof is water-soluble and can be eluted in water. 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.
[0051] 又、さらにカチオン性榭脂を含有しても良ぐカチオン性榭脂としては、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級アミノ基ゃ第 4級アンモニゥム基を有するアクリル榭脂、ジアクリルァミン等が 挙げられる。カチオン性榭脂は微粒子状の形態で添加しても良い。これは、例えば 特開平 6— 161101号に記載のカチオン性マイクロゲルが挙げられる。  [0051] In addition, examples of the cationic resin that may further contain a cationic resin include polyalkylene polyamines such as polyethyleneamine and polypropylene polyamine or derivatives thereof, tertiary amino groups and quaternary compounds. Examples thereof include acrylic resin having an ammonium group and diacrylamine. Cationic rosin may be added in the form of fine particles. Examples thereof include a cationic microgel described in JP-A-6-161101.
[0052] また、本発明の親水性層の塗布液には、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る。 S係、又は F系等の界面活性剤を使用することがで きるが、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く 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 1〜3質量％が好ましぐ 0. 03〜1質量％が更に好ましい。  [0052] The hydrophilic layer coating solution of the present invention may contain a water-soluble surfactant for the purpose of improving coating properties. A surfactant such as S-type or F-type can be used, but it is particularly preferable to use a surfactant containing Si element because there is no concern of causing printing stains. The content of the surfactant is preferably from 0.01 to 3% by mass, more preferably from 0.03 to 1% by mass, based on the entire hydrophilic layer (solid content as the coating solution).
[0053] また、本発明に係る親水性層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 、。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. 1〜5質量％が好ましぐ 0. 5〜2質量％が更に好ましい。  [0053] Further, the hydrophilic layer according to the present invention may contain a phosphate. In the present invention, since the coating solution for the hydrophilic layer 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 amount of phosphate added is preferably 0.1 to 5% by mass, and more preferably 0.5 to 2% by mass, as an effective amount excluding hydrates.
[0054] 本発明では、以下の条件を満足するような、マット材を少なくとも 1種含有する。マツ ト材は、感熱画像形成層積層後の塗膜面から 0. 5〜10. O /z m突出しており、かつ 該マット材の含有量が 1, 600-4, 800個 Zmm2であり、かつ隣接する該マット材間 中心距離の標準偏差が 20 m以下に存在することが好ましい。 [0054] In the present invention, at least one mat material that satisfies the following conditions is contained. The mat material protrudes from 0.5 to 10. O / zm from the surface of the coated film after the thermal image forming layer is laminated, and the content of the mat material is 1,600-4,800 pieces Zmm 2 , The standard deviation of the center distance between adjacent mat members is preferably 20 m or less.
[0055] マット材の材質としては、多孔質、無孔質、有機榭脂粒子、無機微粒子を問わず用 いても良ぐ無機マット材としてはシリカ、アルミナ、ジルコユア、チタ二了、カーボンブ ラック、グラフアイト、 TiO、 BaSO、 ZnSゝ MgCO、 CaCO、 ZnO、 CaO、 WS、 M [0055] The material of the mat material may be any of porous, non-porous, organic resin particles, and inorganic fine particles. Examples of the inorganic mat material that can be used include silica, alumina, zirconium, titanium dioxide, carbon black. Rack, Graphite, TiO, BaSO, ZnS ゝ MgCO, CaCO, ZnO, CaO, WS, M
2 4 3 3 2 oS、 MgO、 SnO、 Al O、 a— Fe O、 a— FeOOH、 SiC、 CeO、 BN、 SiN、 M 2 4 3 3 2 oS, MgO, SnO, Al 2 O, a—Fe 2 O, a—FeOOH, SiC, CeO, BN, SiN, M
2 2 2 3 2 3 2 2 2 2 3 2 3 2
oC、 BC、 WC、チタンカーバイド、コランダム、人造ダイアモンド、ザクロ石、ガーネッ ト、ケィ石、トリボリ、ケイソゥ土、ドロマイト等、有機フイラ一としてはポリエチレン微粒 子、フッ素榭脂粒子、グアナミン榭脂粒子、アクリル榭脂粒子、シリコン榭脂粒子、メラ ミン榭脂粒子等を挙げることが出来る。また無機被服フィラーとしてはたとえば PMM Aやポリスチレン、メラミンと ヽつた有機粒子の芯剤を芯剤粒子よりも粒径の小さな無 機粒子で被覆した粒子が挙げられる。無機粒子の粒径としては芯材粒子の 1/10〜 1Z100程度であることが好ましい。また、無機粒子としては、同様にシリカ、アルミナ 、チタニア、ジルコニァなど公知の金属酸ィ匕物粒子を用いることができる。被覆方法と しては、種々の公知の方法を用いることができる力 ハイブリダィザのような空気中で 芯材粒子と被覆材粒子とを高速に衝突させて芯材粒子表面に被覆材粒子を食い込 ませて固定、被覆する乾式の被覆方法を好ましく用いることができる。  oC, BC, WC, titanium carbide, corundum, artificial diamond, garnet, garnet, keystone, triboli, diatomaceous earth, dolomite, etc. Examples thereof include acrylic resin particles, silicon resin particles, and melamine resin particles. Examples of the inorganic filler include particles in which a core of organic particles combined with PMMA, polystyrene, and melamine is coated with inorganic particles having a particle diameter smaller than that of the core particles. The particle size of the inorganic particles is preferably about 1/10 to 1Z100 of the core particles. In addition, as the inorganic particles, known metal oxide particles such as silica, alumina, titania, zirconia can be used. As the coating method, various known methods can be used. The core particles and the coating material particles are collided at high speed in the air like a hybridizer, and the coating material particles bite into the surface of the core material particles. Further, a dry coating method of fixing and coating can be preferably used.
[0056] 本発明では、マット材の種類、粒子経は 2種以上の異なるものを併用できる。 In the present invention, two or more different types of mat materials and particle sizes can be used in combination.
[0057] マット材の平均粒子径 ίま、 1. 0〜20 μ m力好ましく、より好ましく ίま、 3. 0〜8. 0 μ mである。 [0057] The average particle diameter of the mat member is preferably 1.0 to 20 μm, more preferably 3.0 to 8.0 μm.
[0058] 平均粒子経が 1. 0 m未満の場合は、耐刷性、耐傷性が低下し、 20 μ mを超える 場合は機上現像性、解像度が低下する可能性がある。  [0058] When the average particle size is less than 1.0 m, the printing durability and scratch resistance are lowered, and when it exceeds 20 μm, the on-press developability and resolution may be lowered.
[0059] マット材の添加量は親水性層の 10質量％〜80質量％が好ましぐより好ましくは 1[0059] The addition amount of the mat material is preferably 10% by mass to 80% by mass of the hydrophilic layer, more preferably 1
5〜50質量％である。 5 to 50% by mass.
[0060] 親水性層と支持体との間に親水性の下層を設けてもよい。親水性の下層に用いる 素材としては、前述の親水性層と同様の素材を用いることができる。  [0060] A hydrophilic lower layer may be provided between the hydrophilic layer and the support. As the material used for the hydrophilic lower layer, the same material as the hydrophilic layer described above can be used.
[0061] 本発明に係る平版印刷版材料は、上述のように親水性層に光熱変換剤を添加する ことができる。光熱変換剤は、上述の本発明に係る金属酸化物顔料の他に、画像形 成用のレーザ光を吸収して熱に変化することのできるものであれば公知の材料を使 用することが可能である力 好ましい化合物としては、カーボンブラック、グラフアイト、 コロイド銀、黒色酸化鉄 (Fe O )や、二種以上の金属を含有する黒色複合金属酸ィ匕  [0061] In the lithographic printing plate material according to the present invention, a photothermal conversion agent can be added to the hydrophilic layer as described above. As the photothermal conversion agent, in addition to the above-described metal oxide pigment according to the present invention, a known material may be used as long as it can absorb laser light for image formation and change into heat. Possible Forces Preferred compounds include carbon black, graphite, colloidal silver, black iron oxide (Fe 2 O 3), and black complex metal oxides containing two or more metals.
3 4  3 4
物、及び赤外線吸収色素が挙げられる。 [0062] 黒色複合金属酸化物としては、例えば Sbをドープした SnO (ATO)、 Snを添カロし And infrared absorbing dyes. [0062] Examples of the black complex metal oxide include SnO doped with Sb (ATO) and Sn
2  2
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 In O (ITO), TiO, TiO reduced TiO (titanium oxynitride, generally titanium
2 3 2 2 2 3 2 2
ラック）などが挙げられる。又、これらの金属酸化物で芯材（BaSO、 TiO、 9A1 Ο · 2  Rack). These metal oxides can also be used as a core material (BaSO, TiO, 9A1 Ο · 2
4 2 2 3 4 2 2 3
Β 0、 Κ O 'nTiO等）を被覆したものも使用することができる。これらの粒径は、 0. 5Those coated with Β0, ΚO'nTiO etc. can also be used. Their particle size is 0.5
2 2 2 2 2 2
/z m以下、好ましくは lOOnm以下、更に好ましくは 50nm以下である。  / z m or less, preferably lOOnm or less, more preferably 50 nm or less.
[0063] これらの光熱変換剤のうち、二種以上の金属を含有する黒色複合金属酸化物がよ り好ましい。 [0063] Of these photothermal conversion agents, black composite metal oxides containing two or more metals are more preferred.
[0064] 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号公報、 特開平 9— 25126号公報、特開平 9 237570号公報、特開平 9— 241529号公報 、特開平 10— 231441号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。  [0064] Specifically, it is a composite metal oxide composed of two or more metals selected from Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, and Ba. These are produced by the methods disclosed in JP-A-8-27393, JP-A-9-25126, JP-A-9-237570, JP-A-9-241529, JP-A-10-231441, and the like. can do.
[0065] 本発明に用いる複合金属酸ィ匕物としては、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— 273393号公報に開示されている処理 を施すことが好ましい。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。  [0065] The composite metal oxide 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 disclosed in JP-A-8-273393 in order to reduce elution of hexavalent chromium. These composite metal oxides are colored with respect to the amount added, that is, they have good photothermal conversion efficiency.
[0066] これらの複合金属酸化物は平均 1次粒子径が 1 μ m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の範囲にあることがより好ましい。平均 1次粒子径 力 Sl 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。  [0066] These composite metal oxides preferably have an average primary particle diameter of 1 µm or less, and more preferably have an average primary particle diameter in the range of 0.01 to 0.5 m. . By making the average primary particle size force Sl m or less, the photothermal conversion capacity with respect to the added amount becomes better, and by making the average primary particle size within the range of 0.01-0. The conversion ability is better.
[0067] ただし、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。したがって、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. 01〜5質量％が好ましぐ 0. 1〜2質量％がより好ましい。  [0067] However, the photothermal conversion ability with respect to the addition amount is greatly influenced 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 0.01 to 5% by mass, more preferably 0.1 to 2% by mass with respect to the composite metal oxide particles.
[0068] これらの複合金属酸ィ匕物の添加量としては、親水性層全固形分に対して 0. 01〜5 質量％が好ましぐ 0. 1〜 3質量％がより好ましい。 [0068] The amount of these composite metal oxides added is 0.01 to 5 with respect to the total solid content of the hydrophilic layer. 0.1% to 3% by mass is more preferable.
[0069] 光熱変換剤として赤外線吸収色素を使用する場合、具体的には以下の化合物を 挙げることができる。 [0069] When an infrared absorbing dye is used as the photothermal conversion agent, specific examples include the following compounds.
[0070] 一般的な赤外吸収色素であるシァニン系色素、クロコニゥム系色素、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  [0070] Common infrared absorbing dyes such as cyanine dyes, croconium dyes, polymethine dyes, azurenium dyes, squalium dyes, thiopyrylium dyes, naphthoquinone dyes
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-リン系の有機金属錯体などが挙げら れる。具体的には、特開昭 63— 139191号、特開昭 64— 33547号、特開平 1— 16 0683号、特開平 1— 280750号、特開平 1— 293342号、特開平 2— 2074号、特開 平 3— 26593号、特開平 3— 30991号、特開平 3— 34891号、特開平 3— 36093号 、特開平 3— 94号、特開平 3— 95号、特開平 3— 42281号、特開平 3— 97 589号、特開平 3— 103476号等の各公報に記載の化合物が挙げられる。これらは 一種又は二種以上を組み合わせて用いることができる。  And organic compounds such as organic and anthraquinone dyes, phthalocyanine, naphthalocyanine, azo, thiamid, dithiol, and indoor-phosphorus organometallic complexes. Specifically, JP-A-63-139191, JP-A-64-33547, JP-A-1-160683, JP-A-1-280750, JP-A-1-293342, JP-A-2-2074, JP-A-3-26593, JP-A-3-30991, JP-A-3-34891, JP-A-3-36093, JP-A-3-94, JP-A-3-95, JP-A-3-42281, Examples thereof include compounds described in JP-A-3-97589 and JP-A-3-103476. These can be used alone or in combination of two or more.
[0071] これらの赤外吸収染料の添加量としては、親水性層全固形分に対して 0. 01〜2質 量％が好ましぐ 0. 1〜1質量％がより好ましい。  [0071] The addition amount of these infrared absorbing dyes is preferably 0.01 to 2% by mass based on the total solid content of the hydrophilic layer, more preferably 0.1 to 1% by mass.
[0072] <感熱画像形成層 >  <Thermal imaging layer>
本発明に係る感熱画像形成層は、熱溶融性化合物を微粒子化した状態で層内に 存在せしめている。これにより画像形成部の熱による機上現像性 (印刷機上に於いて 、湿し水と印刷インキにより親水性層から剥離除去する性質)を減少させる特性を持 たしている。  The heat-sensitive image forming layer according to the present invention is present in the layer in a state where the heat-meltable compound is finely divided. As a result, the on-press developability by heat of the image forming portion (the property of being peeled and removed from the hydrophilic layer by dampening water and printing ink on the printing press) is reduced.
[0073] 熱溶融性ィ匕合物とは、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が好ましい。物性としては、融点が 60〜140°Cで あることが好ましい。融点が 60°C未満では保存性が問題であり、融点が 140°Cよりも 高 、場合は感度、印刷品質が低下する可能性がある。  [0073] The heat-meltable composite is preferably a material generally classified as a wax having a low viscosity when melted, among thermoplastic materials. As a physical property, the melting point is preferably 60 to 140 ° C. If the melting point is less than 60 ° C, storage stability is a problem. If the melting point is higher than 140 ° C, the sensitivity and print quality may be reduced.
[0074] 熱溶融性ィ匕合物として使用可能な素材としては、カルナゥバワックス、ノ フィンヮ ッタス、モンタンワックス、マイクロクリスタリンワックス、キャンデリラワックス、脂肪酸系 ワックス、フィッシャートロプシュワックス、ポリエチレンワックス、脂肪酸エステル系ヮッ タス、脂肪酸アミド、等が挙げられる。 [0074] Materials that can be used as a heat-meltable compound include carnauba wax, nophine tussus, montan wax, microcrystalline wax, candelilla wax, fatty acid-based wax, Fischer-Tropsch wax, polyethylene wax, and fatty acid. Ester base Tas, fatty acid amides and the like.
[0075] 更に、分散媒との親和性を制御するために、これらのワックスを酸ィ匕し、水酸基、ェ 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 ことちでさる。 [0075] Further, in order to control the affinity with the dispersion medium, these waxes are acidified, and polar groups such as hydroxyl groups, ester groups, carboxyl groups, aldehyde groups, and peroxide groups are introduced. Monkey.
[0076] これらの中でもカルナゥバワックス、パラフィンワックス、マイクロクリスタリン、脂肪酸 エステル、脂肪酸アミド、脂肪酸の何れかを含有することが好ましい。特にカルナゥバ ワックスは、融点が比較的低ぐ溶融粘度も低いため、高感度の画像形成を行うこと ができる。  Among these, it is preferable to contain any of carnauba wax, paraffin wax, microcrystalline, fatty acid ester, fatty acid amide, and fatty acid. In particular, carnauba wax has a relatively low melting point and a low melt viscosity, and therefore can form a highly sensitive image.
[0077] 熱溶融性ィヒ合物は熱溶融性粒子として存在させることが好ましぐ熱溶融性粒子の 平均粒子経は、 0. 1〜1. O /z m力好ましく、より好ましくは 0. 3〜0. である。 0 . ： L m未満では、機上現像性が低下し、 1. 0 mを超えると耐刷性が低下すること がある。これらの粒子径分布の微粒子を全粒子中の 50%以上、より好ましくは 60% 以上含有することが好ま U、。  [0077] The average particle size of the heat-meltable particles, which are preferably present as the heat-meltable particles, is preferably 0.1 to 1. O / zm force, more preferably 0. 3-0. 0: Less than L m, the on-press developability deteriorates, and if it exceeds 1.0 m, the printing durability may deteriorate. It is preferable to contain fine particles having a particle size distribution of 50% or more, more preferably 60% or more of all particles.
[0078] 熱溶融性ィ匕合物は、適当な分散媒に分散して使用される。分散媒としては、水、又 は有機溶剤、あるいは両者の混合物が適宜用いられる。本発明においては、水を 50 %以上含有することが好ま Uヽ。  [0078] The hot-melt compound is used by being dispersed in an appropriate dispersion medium. As the dispersion medium, water, an organic solvent, or a mixture of both is appropriately used. In the present invention, it is preferable to contain 50% or more of water.
[0079] 分散媒中には必要に応じて分散剤を添加することができる。分散剤の具体例として は、ポリオキシエチレンノニルフエニルエーテル、ポリオキシエチレンアルキルエステ ル、ポリプロピレングリコーノレポリエチレングリコールブロックコポリマー、ポリオキシェ チレンポリオキシプロピレンブロックコポリマー、アルキルベンゼンスルフォン酸ソーダ 、等の界面活性剤、ポリビニルアルコール榭脂等の水溶性榭脂、を挙げることができ る。分散剤の添加量は 0. 5〜10%、好ましくは 1〜5%である。  [0079] A dispersant may be added to the dispersion medium as necessary. Specific examples of the dispersing agent include surfactants such as polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ester, polypropylene glycol-no-polyethylene glycol block copolymer, polyoxyethylene polyoxypropylene block copolymer, alkylbenzene sodium sulfonate, Examples thereof include water-soluble resin such as polyvinyl alcohol resin. The amount of the dispersant added is 0.5 to 10%, preferably 1 to 5%.
[0080] 更に、ワックス、榭脂の酸ィ匕部分を中和して親水基にすることにより、分散'乳化性 を高めるために、分散安定化剤として水酸化カリウム、モルホリン、トリエタノールアミ ン等のアルカリ剤を添加することができる。  [0080] Further, in order to increase the dispersion and emulsifiability by neutralizing the acid part of the wax and rosin to form a hydrophilic group, potassium hydroxide, morpholine, triethanolamine is used as a dispersion stabilizer. Alkaline agents such as can be added.
[0081] アルカリ剤の添加量は分散質の性質により適宜決定される力 本発明において、分 散液の pHとしては、 7. 5〜： L 1の範囲にあることが好ましい。  [0081] The amount of the alkaline agent to be added is determined as appropriate depending on the nature of the dispersoid. In the present invention, the pH of the dispersion is preferably in the range of 7.5 to L1.
[0082] 分散媒への分散は、ボールミル、サンドミル、アトライター等のメディア分散法、溶融 滴下撹拌法等、公知の分散技術を使用することができる。粒子経分布の均一な粒子 を得るためには、分散液温度を溶融温度以下に制御しながらボールミルで分散する 方法、加熱溶融状態の熱溶融性化合物を、温度を制御して分散媒中に撹拌しなが ら滴下することで分散状態を形成する溶融滴下撹拌法が特に好ましい。 [0082] Dispersion in the dispersion medium is performed by a media dispersion method such as a ball mill, a sand mill, or an attritor. A known dispersion technique such as a dropping stirring method can be used. In order to obtain particles having a uniform particle size distribution, a method of dispersing with a ball mill while controlling the dispersion temperature below the melting temperature, and stirring the heat-meltable compound in a heated and melted state in the dispersion medium while controlling the temperature. However, a melt dropping stirring method in which a dispersion state is formed by dropping is particularly preferred.
[0083] また、熱溶融性粒子としては、熱可塑性疎水性高分子重合体微粒子が挙げられ、 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!、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の範囲であることが好ましい。  [0083] Further, examples of the thermomeltable particles include thermoplastic hydrophobic polymer polymer fine particles, and there is no specific upper limit to the softening temperature of the thermoplastic hydrophobic polymer polymer particles, but the temperature is It is preferable that the temperature is lower than the decomposition temperature of the polymer fine particles. Further, the weight average molecular weight (Mw) of the high molecular weight polymer is preferably in the range of 10,000 to 1,000,000.
[0084] 高分子重合体微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 アクリル共重合体、スチレン ブタジエン共重合体、メチ ルメタクリレートーブタジエン共重合体、アタリ口-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、ポリ酢酸ビニル、酢酸ビニループ口ピオン酸ビ二 ル共重合体、酢酸ビニルーエチレン共重合体等のビニルエステル（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 ユリデン、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、スチレン アクリル共重合体、（メタ)アクリル酸エステル、（メタ)アクリル酸 (共)重合体、ビ- 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。  [0084] Specific examples of the polymer constituting the polymer fine particles include, for example, gen (co) polymers such as polypropylene, polybutadiene, polyisoprene, and ethylene butadiene copolymer, styrene-acrylic copolymer. Copolymers, styrene butadiene copolymers, methyl methacrylate-butadiene copolymers, synthetic rubbers such as atta-tolyl butadiene copolymers, polymethyl methacrylate and methyl methacrylate (2-ethylhexyl acrylate) Polymer, methyl methacrylate-methacrylic acid copolymer, methyl acrylate (N-methylolacrylamide) copolymer, (meth) acrylic acid ester such as polyacrylonitrile, (meth) acrylic acid (co) polymer, poly Vinyl acetate, vinyl acetate, vinyl pionate copolymer, vinyl acetate Examples include vinyl ester (co) polymers such as ethylene copolymers, butyl acetate (2-ethylhexyl acrylate) copolymers, polybutyl chloride, polyvinylidene chloride, polystyrene, and copolymers thereof. It is done. Of these, styrene-acrylic copolymers, (meth) acrylic acid esters, (meth) acrylic acid (co) polymers, berylester (co) polymers, polystyrene, and synthetic rubbers are preferably used.
[0085] 上述のように形成した熱溶融性粒子は、感熱画像形成層の固形分に対して 50質 量％以上含有せしめることが好ましい。 50質量％以上含有することで、熱溶融性粒 子の機能を十分に発現することができる。  [0085] The heat-meltable particles formed as described above are preferably contained in an amount of 50% by mass or more based on the solid content of the heat-sensitive image forming layer. By containing 50% by mass or more, the function of the hot-melt particles can be fully expressed.
[0086] 感熱画像形成層には、更に熱溶融性化合物に 0. 1質量％以上の溶解性を有する 有機染料を、粒子径 0. 05 m以上の分散状態で含有する。 [0086] The heat-sensitive image forming layer further contains an organic dye having a solubility of 0.1% by mass or more in a heat-meltable compound in a dispersed state with a particle size of 0.05 m or more.
[0087] 有機染料粒子は、画像形成前は前記熱溶融性化合物微粒子と独立して存在して おり、画像形成層の着色にはあまり寄与していない。熱による画像書き込み際に溶融 した熱溶融性化合物中に溶解することで発色濃度が上がり、画像部と非画像部を識 別できるようになる。 [0087] The organic dye particles exist independently of the heat-meltable compound fine particles before image formation, and do not contribute much to the coloring of the image forming layer. Melting when writing images with heat By dissolving in the heat-meltable compound, the color density increases and the image area and the non-image area can be identified.
[0088] 本発明で好ましく用いられる有機染料は、酸性染料、直接染料、分散染料、油溶 性染料および含金属油溶性染料などが挙げられる。これらの色材は、一種単独で使 用してもよいし、必要に応じて、二種以上を併用してもよい。  [0088] Organic dyes preferably used in the present invention include acid dyes, direct dyes, disperse dyes, oil-soluble dyes, metal-containing oil-soluble dyes, and the like. These coloring materials may be used alone or in combination of two or more as required.
[0089] 有機染料は、熱溶融性化合物に溶解した状態で最大吸光度の波長が、 450〜75 Onmにあることが好ましぐより好ましくは 600〜750nmの範囲である。  [0089] The wavelength of the maximum absorbance of the organic dye dissolved in the hot-melt compound is preferably 450 to 75 Onm, more preferably 600 to 750 nm.
[0090] 熱溶融性化合物に、前述のワックス類を使用する場合、有機染料の具体例としては 、オイルイェロー # 101、オイルイェロー # 130、オイルピンク # 312、オイルグリーン BG、オイルブルー BOS、オイルブルー # 603、オイルブルー # 613、オイルブラック BY、オイルブラック BS、オイルブラック T— 505 (以上、オリエント化学工業株式会社 製）、ビクトリアピュアブルー、クリスタルバイオレット（CI42555)、メチルバイオレット（ CI42535)、ローダミン B (CI45170B)、マラカイトグリーン（CI42000)、メチレンブ ルー（CI52015)等が挙げられる。  [0090] When the above-mentioned waxes are used for the heat-meltable compound, specific examples of organic dyes include Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Blue # 613, Oil Black BY, Oil Black BS, Oil Black T-505 (above, manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI52015), and the like.
[0091] 有機染料は、分散媒となる感熱画像形成層塗布溶媒中に公知の方法で適宜分散 することができる。分散方法としては、サンドミル、ダイノミル、アトライター、ボールミル 等のメディア分散機、ホモジナイザー等の内部剪断型分散機、ディゾルバ一等の高 速攪拌機、超音波分散機、等が挙げられる。  [0091] The organic dye can be appropriately dispersed by a known method in a heat-sensitive image forming layer coating solvent serving as a dispersion medium. Examples of the dispersion method include a media disperser such as a sand mill, a dyno mill, an attritor and a ball mill, an internal shear disperser such as a homogenizer, a high-speed stirrer such as a dissolver, and an ultrasonic disperser.
[0092] 有機染料は、単独で分散媒中に分散することもできるが、適当な分散剤を併用する こともできる。分散剤の具体例としては、ポリオキシエチレンノユルフェ-ルエーテル、 ポリオキシエチレンァノレキノレエステル、ポリプロピレングリコール 'ポリエチレングリコー ルブロックコポリマー、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、 アルキルベンゼンスルフォン酸ソーダ、等の界面活性剤、ポリビニルアルコール榭脂 等の水溶性榭脂、が挙げられる。  [0092] The organic dye can be dispersed alone in the dispersion medium, but an appropriate dispersant can also be used in combination. Specific examples of the dispersing agent include polyoxyethylene glycol ether, polyoxyethylene alcohol ester, polypropylene glycol 'polyethylene glycol block copolymer, polyoxyethylene / polyoxypropylene block copolymer, alkylbenzene sulfonic acid soda, etc. Surfactants and water-soluble resin such as polyvinyl alcohol resin.
[0093] 又、有機染料を非水溶性溶剤中に高濃度に溶解したものを、水溶性分散媒中に分 散した後、減圧処理により有機溶剤を除去するオイルドロップ分散法も適用できる。  [0093] Further, an oil drop dispersion method in which an organic dye dissolved at a high concentration in a water-insoluble solvent is dispersed in a water-soluble dispersion medium and then the organic solvent is removed by a reduced pressure treatment.
[0094] 有機染料の平均粒子径 ίま、 0. 05〜0. 5 μ m力好ましく、より好ましく ίま 0. 05〜0.  [0094] The average particle size of the organic dye is preferably from 0.75 to 0.5 μm, more preferably from 0.75 to 0.05.
2 μ mの範囲である。 0. 05 μ m未満では、変色のコントラストが不十分で、かつ機上 現像性、非画像部の印刷汚れが劣化する。 0. 5 m超では、変色のコントラストが不 十分である。 The range is 2 μm. If it is less than 0.05 μm, the discoloration contrast is insufficient and Developability and printing stains in non-image areas deteriorate. Above 0.5 m, the discoloration contrast is insufficient.
[0095] 有機染料微粒子の添加量は、感熱画像形成層全体の 0. 5〜10質量％が好ましく 、より好ましくは 1〜5質量％である。  [0095] The addition amount of the organic dye fine particles is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, based on the entire thermosensitive image forming layer.
[0096] 本発明の感熱画像形成層は、上述の成分以外に、機能を損なわない範囲で、公 知の熱溶融性化合物粒子、熱可塑性化合物粒子、を含有することができる。  [0096] The heat-sensitive image forming layer of the present invention may contain known heat-meltable compound particles and thermoplastic compound particles, in addition to the above-described components, as long as the function is not impaired.
[0097] 感熱画像形成層にはさらに水溶性素材を含有することができる。水溶性素材を含 有することにより、印刷機上で湿し水やインクを用いて未露光部の画像形成機能層を 除去する際に、その除去性を向上させることができる。  [0097] The heat-sensitive image forming layer may further contain a water-soluble material. By including the water-soluble material, it is possible to improve the removability when the image forming functional layer in the unexposed area is removed using dampening water or ink on the printing press.
[0098] 水溶性素材としては、親水性層に含有可能な素材として挙げた水溶性榭脂を用い ることもできる。本発明の画像形成機能層で使用できる水溶性榭脂は、親水性の天 然高分子及び合成高分子から選ばれる。本発明に好ましく用いられる水溶性榭脂の 具体例としては、天然高分子では、アラビアガム、水溶性大豆多糖類、繊維素誘導 体（例えば、カルボキシメチルセルローズ、カルボキシェチルセルローズ、メチルセル ローズ等）、その変性体、ホワイトデキストリン、プルラン、酵素分解エーテル化デキス トリン等、合成高分子では、ポリビニルアルコール (好ましくは酸ィ匕度 70モル％以上 のもの）、ポリアクリル酸、そのアルカリ金属塩またはアミン塩、ポリアクリル酸共重合体 、そのアルカリ金属塩またはアミン塩、ポリメタクリル酸、そのアルカリ金属塩またはァ ミン塩、ビュルアルコール Zアクリル酸共重合体及びそのアルカリ金属塩またはアミ ン塩、ポリアクリルアミド、その共重合体、ポリヒドロキシェチルアタリレート、ポリビニル ピロリドン、その共重合体、ポリビュルメチルエーテル、ビュルメチルエーテル Z無水 マレイン酸共重合体、ポリ 2—アクリルアミド 2—メチル 1 プロパンスルホン酸 、そのアルカリ金属塩またはアミン塩、ポリ 2—アクリルアミドー 2—メチルー 1 プロ パンスルホン酸共重合体、そのアルカリ金属塩またはアミン塩等を挙げることができる 。また、 目的に応じて、これらを二種以上混合して用いることもできる。しかし、本発明 はこれらの例に限定されるものではない。  [0098] As the water-soluble material, the water-soluble rosins listed as materials that can be contained in the hydrophilic layer can also be used. The water-soluble resin that can be used in the image-forming functional layer of the present invention is selected from hydrophilic natural polymers and synthetic polymers. Specific examples of the water-soluble sucrose preferably used in the present invention include natural gums such as gum arabic, water-soluble soybean polysaccharides, fibrin derivatives (for example, carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, etc.) In the case of synthetic polymers such as modified products, white dextrin, pullulan, enzymatically-decomposed etherified dextrin, polyvinyl alcohol (preferably having an acidity of 70 mol% or more), polyacrylic acid, alkali metal salts or amines thereof Salt, polyacrylic acid copolymer, alkali metal salt or amine salt thereof, polymethacrylic acid, alkali metal salt or amine salt thereof, butyl alcohol Z acrylic acid copolymer and alkali metal salt or amine salt thereof, polyacrylamide , Its copolymers, polyhydroxyethyl acrylate, poly Vinyl pyrrolidone, its copolymer, polybulu methyl ether, burmethyl ether Z maleic anhydride copolymer, poly 2-acrylamide 2-methyl 1 propanesulfonic acid, its alkali metal salt or amine salt, poly 2-acrylamide 2 —Methyl-1-propanosulfonic acid copolymer, its alkali metal salt or amine salt. Also, depending on the purpose, two or more of these may be used in combination. However, the present invention is not limited to these examples.
[0099] 感熱画像形成層中の水溶性榭脂の含有量としては、層全体の 1〜50質量％が好 ましぐ 2〜 10質量％がさらに好ましい。 [0100] <その他の層 > [0099] The content of the water-soluble rosin in the heat-sensitive image forming layer is preferably 1 to 50% by mass, more preferably 2 to 10% by mass of the entire layer. [0100] <Other layers>
本発明においては、取り扱い性及び保管時の物性変化防止のために、支持体の 画像形成機能層の反対側に少なくとも 1層の裏塗り層を有することができる。裏塗り 層としては、親水性結合剤を含有していることが好ましぐ特に印刷版材料表面が疎 水'性であれ ίま、特開 2002— 258469号公報の段落 0033〜0038【こ記載されて!ヽる 水分散系榭脂 (ポリマーラテックス)力ら得られたものでもよ 、。  In the present invention, at least one backing layer can be provided on the side of the support opposite to the image-forming functional layer in order to prevent handling and change in physical properties during storage. The backing layer preferably contains a hydrophilic binder, especially if the surface of the printing plate material is hydrophobic, paragraphs 0033 to 0038 of JP-A-2002-258469. It can be obtained from the power of water-dispersed resin (polymer latex).
[0101] 親水性結合剤としては、親水性のものなら特に限定はされないが、親水性構造単 位としてヒドロキシル基を有する榭脂であるポリビュルアルコール（PVA)、セルロース 系榭脂（メチルセルロース（MC)、ェチルセルロース（EC)、ヒドロキシェチルセル口 ース（HEC)、カルボキシメチルセルロース（CMC)等）、キチン類、及びデンプン；ェ 一テル結合を有する榭脂であるポリエチレンオキサイド (PEO)、ポリプロピレンォキ サイド（PPO)、ポリエチレングリコール（PEG)及びポリビュルエーテル（PVE)；アミド 基又はアミド結合を有する榭脂であるポリアクリルアミド (PAAM)及びポリビュルピロ リドン (PVP)等を挙げることができる。又、解離性基としてカルボキシル基を有するポ リアクリル酸塩、マレイン酸榭脂、アルギン酸塩及びゼラチン類;スルホン基を有する ポリスチレンスルホン酸塩;アミノ基、イミノ基、第 3ァミン及び第 4級アンモ-ゥム塩を 有するポリアリルアミン（PAA)、ポリエチレンィミン（PEI)、エポキシ化ポリアミド (EP Am)、ポリビュルピリジン及びゼラチン類を挙げることができる。  [0101] The hydrophilic binder is not particularly limited as long as it is hydrophilic, but polybutal alcohol (PVA), which is a resin having a hydroxyl group as a hydrophilic structural unit, cellulose-based resin (methylcellulose (MC ), Ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), etc.), chitins, and starch; polyethylene oxide (PEO) which is a resin having an ether bond, Examples thereof include polypropylene oxide (PPO), polyethylene glycol (PEG), and polybule ether (PVE); polyacrylamide (PAAM) and polybulurpyrrolidone (PVP), which are amide groups or oxalic resins having an amide bond. In addition, polyacrylates having carboxyl groups as dissociable groups, maleic oxalates, alginates and gelatins; polystyrene sulfonates having sulfone groups; amino groups, imino groups, tertiary amines and quaternary ammonias Mention may be made of polyallylamine (PAA), polyethyleneimine (PEI), epoxidized polyamide (EP Am), polyburpyridine and gelatins having a humic salt.
[0102] 疎水性結合剤は、結合剤として疎水性のものなら特に限定されな 、が、例えば ex、  [0102] The hydrophobic binder is not particularly limited as long as it is hydrophobic as a binder, but ex, for example,
β エチレン性不飽和化合物に由来するポリマー、例えばポリ塩ィ匕ビニル、後一塩 素化ポリ塩ィ匕ビュル、塩ィ匕ビュルと塩ィ匕ビ -リデンのコポリマー、塩化ビュルと酢酸ビ 二ルのコポリマー、ポリ酢酸ビニル及び部分的に加水分解されたポリ酢酸ビニル、出 発材料としてポリビュルアルコールから作られ、繰り返しビュルアルコール単位の一 部のみがアルデヒドと反応して 、ることができるポリビュルァセタール、好ましくはポリ ビニルブチラール、アクリロニトリルとアクリルアミドのコポリマー、ポリアクリル酸エステ ル、ポリメタクリル酸エステル、ポリスチレン及びポリエチレン又はそれらの混合物等が 挙げられる。  β Polymers derived from ethylenically unsaturated compounds, such as polysalt vinyl, post monochlorinated polysalt bull, salt bull and salt vinylidene copolymer, bull chloride and vinyl acetate Copolymers, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polybulul alcohol made from polybulal alcohol as a starting material, and only a portion of the repeating butal alcohol units can react with aldehydes Examples include acetals, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene, or mixtures thereof.
[0103] 本発明においては、印刷機への取り付け易さ、及び、印刷中における印刷版の位 置ズレによるカラー印刷での色ズレを防止するために、裏塗り層にはマット剤を含有 することが好ましい。含有するマット剤は多孔質、無孔質、有機榭脂粒子、無機微粒 子を問わず用いても良ぐ無機マット剤としてはシリカ、アルミナ、ジルコユア、チタ- ァ、カーボンブラック、グラフアイト、 TiO 、 BaSO 、 ZnS、 MgCO 、 CaCO 、 ZnO、 C [0103] In the present invention, it is easy to attach to a printing press and the position of the printing plate during printing. In order to prevent color misregistration in color printing due to misalignment, the backing layer preferably contains a matting agent. The matting agent can be used regardless of whether it is porous, non-porous, organic resin particles, or inorganic fine particles. Examples of inorganic matting agents that can be used include silica, alumina, zirconium oxide, titanium, carbon black, graphite, and TiO. , BaSO, ZnS, MgCO, CaCO, ZnO, C
2 4 3 3 aO、 WS 、 MoS 、 MgO、 SnO 、 Al O 、 a Fe O 、 a FeOOH  2 4 3 3 aO, WS, MoS, MgO, SnO, AlO, aFeO, aFeOOH
2 2 2 2 3 2 3  2 2 2 2 3 2 3
、 SiC、 CeO 、 BN、 SiN、 MoC、 BC、 WC、チタンカーバイド、コランダム、人造ダイ  SiC, CeO, BN, SiN, MoC, BC, WC, titanium carbide, corundum, artificial die
2  2
ァモンド、ザクロ石、ガーネット、ケィ石、トリボリ、ケイソゥ土、ドロマイト等、有機マット 剤としてはポリエチレン微粒子、フッ素榭脂粒子、グアナミン榭脂粒子、アクリル榭脂 粒子、シリコン榭脂粒子、メラミン榭脂粒子等を挙げることが出来る。また無機被服マ ット剤としてはたとえば PMMAやポリスチレン、メラミンと 、つた有機粒子の芯剤を芯 剤粒子よりも中継の小さな無機粒子で被覆した粒子が挙げられる。無機粒子の粒径 としては芯材粒子の 1Z10〜1Z100程度であることが好ましい。また、無機粒子とし ては、同様にシリカ、アルミナ、チタ-ァ、ジルコユアなど公知の金属酸ィ匕物粒子を用 いることができる。被覆方法としては、種々の公知の方法を用いることができる力 ノヽ イブリダィザのような空気中で芯材粒子と被覆材粒子とを高速に衝突させて芯材粒 子表面に被覆材粒子を食 、込ませて固定、被覆する乾式の被覆方法を好ましく用い ることがでさる。  Almond, garnet, garnet, keystone, triboli, diatomaceous earth, dolomite, etc. As organic matting agents, polyethylene fine particles, fluorine resin particles, guanamine resin particles, acrylic resin particles, silicon resin particles, melamine resin particles Etc. Examples of the inorganic clothing matting agent include PMMA, polystyrene, and melamine, and particles obtained by coating a core of organic particles with inorganic particles having a smaller relay than the core particles. The particle size of the inorganic particles is preferably about 1Z10 to 1Z100 of the core particles. In addition, as the inorganic particles, known metal oxide particles such as silica, alumina, titer, and zirconium oxide can be used. As a coating method, various known methods can be used. Core material particles and coating material particles are collided at high speed in the air such as a force noblerizer, and the coating material particles are eaten on the surface of the core material particles. It is preferable to use a dry coating method in which it is fixed and covered.
[0104] 本発明にお 、ては、本発明の範囲を満たすマット剤であれば特に制限無く効果が 発揮できるが、特にロール状に卷回された製品形態での場合、ノックコーティング層 のマット剤が、感熱画像形成層へのキズを抑制するため、有機榭脂粒子を用いるの が好ましい。  [0104] In the present invention, any matting agent satisfying the scope of the present invention can exert its effect without any particular limitation. However, particularly in the form of a product wound in a roll, the mat of the knock coating layer is used. Since the agent suppresses scratches on the heat-sensitive image forming layer, it is preferable to use organic resin particles.
[0105] なお、本発明おけるマット剤の平均粒径は電子顕微鏡を用い、投影面積から円相 当軽を算出して求められる。  [0105] The average particle size of the matting agent in the present invention can be obtained by calculating a circle equivalent from the projected area using an electron microscope.
[0106] 粒径は 1〜12 μ mが好ましぐ 1. 5〜8 μ mがより好ましぐ 2〜7 μ mがさらに好ま しい。粒径が 12 mを超えると、感熱画像形成層へのキズが生じやすくなり、逆に 1 μ mの粒子では、版胴上で版浮きが発生してしまう。 [0106] The particle size is preferably 1 to 12 μm, more preferably 5 to 8 μm, and even more preferably 2 to 7 μm. If the particle size exceeds 12 m, scratches are likely to occur on the thermal image-forming layer. Conversely, if the particle size is 1 μm, the plate floats on the plate cylinder.
[0107] マット剤の添カ卩量としては、バックコーティング層全体の 0. 2〜10質量0 /0であること が好ましぐ 1〜10質量％であることがより好ましい。 [0108] さらに、レーザー記録装置あるいはプロセスレス印刷機には、装置内部において印 刷版の搬送を制御するためのセンサーを有しており、これらの制御を滞りなく行うため に、本発明において、該構成層には、色素及び顔料を含有させることが好ましい。色 素及び顔料としては、前述の光熱変換素材に用いられる赤外吸収色素及びカーボ ンブラック等の黒色顔料が好ましく用いられる。又、更に、該構成層には公知の界面 活性剤を含有させることができる。 The添Ka卩量of [0107] matting agent, and more preferably be 0.2 to 10 weight 0/0 of the total back coating layer is preferably tool 1 to 10 wt%. [0108] Further, the laser recording device or the processless printing machine has a sensor for controlling the conveyance of the printing plate inside the device, and in order to perform these controls without delay, in the present invention, The constituent layer preferably contains a dye and a pigment. As the dye and pigment, black pigments such as infrared absorbing dyes and carbon black used for the above-mentioned photothermal conversion materials are preferably used. Further, the constituent layer can contain a known surfactant.
[0109] <画像形成方法 >  <Image forming method>
本発明の印刷版材料を用いた画像形成は、サーマルヘッドもしくはサーマルレ一 ザ一を用いて、上記感熱画像形成層に熱による物理ィ匕学的変化を起こすことにより 行うことができる。特に、サーマルレーザーとしての赤外線レーザーによる露光によつ て画像形成を行うことが好ましい。より具体的には、赤外および Zまたは近赤外領域 で発光する、すなわち 700〜 1500nmの波長範囲で発光するレーザーを使用した 走査露光が好ましい。レーザーとしてはガスレーザーを用いてもよいが、近赤外領域 で発光する半導体レーザーを使用することが特に好ましい。  Image formation using the printing plate material of the present invention can be carried out by causing a physical change due to heat in the thermal image forming layer using a thermal head or a thermal laser. In particular, it is preferable to perform image formation by exposure with an infrared laser as a thermal laser. More specifically, scanning exposure using a laser that emits light in the infrared and Z or near infrared region, that is, emits light in a wavelength range of 700 to 1500 nm is preferable. A gas laser may be used as the laser, but it is particularly preferable to use a semiconductor laser that emits light in the near infrared region.
[0110] 本発明の走査露光に好適な装置としては、該半導体レーザーを用いてコンビユー タカゝらの画像信号に応じて印刷版材料表面に画像を形成可能な装置であればどの ような方式の装置であってもよ 、。  [0110] As an apparatus suitable for scanning exposure according to the present invention, any system can be used as long as it can form an image on the surface of a printing plate material in accordance with an image signal from a computer camera using the semiconductor laser. Even a device.
[0111] 一般的には、  [0111] In general,
(1)平板状保持機構に保持された印刷版材料に一本もしくは複数本のレーザービ ームを用いて 2次元的な走査を行って印刷版材料全面を露光する方式、  (1) A method of exposing the entire surface of the printing plate material by performing two-dimensional scanning using one or more laser beams on the printing plate material held by the plate-like holding mechanism,
(2)固定された円筒状の保持機構の内側に、円筒面に沿って保持された印刷版材 料に、円筒内部から一本もしくは複数本のレーザービームを用いて円筒の周方向（ 主走査方向）に走査しつつ、周方向に直角な方向（副走査方向）に移動させて印刷 版材料全面を露光する方式、  (2) The printing plate material held along the cylindrical surface inside the fixed cylindrical holding mechanism is used in the circumferential direction of the cylinder (main scanning) using one or more laser beams from the inside of the cylinder. Scanning) in the direction) and moving in the direction perpendicular to the circumferential direction (sub-scanning direction) to expose the entire surface of the printing plate material,
(3)回転体としての軸を中心に回転する円筒状ドラム表面に保持された印刷版材 料に、円筒外部から一本もしくは複数本のレーザービームを用いてドラムの回転によ つて周方向（主走査方向）に走査しつつ、周方向に直角な方向（副走査方向）に移動 させて印刷版材料全面を露光する方式があげられる。 [0112] 本発明に関しては特に（3)の走査露光方式が好ましぐ特に印刷装置上で露光を 行う装置にぉ 、ては、（3)の露光方式が用いられる。 (3) The printing plate material held on the surface of the cylindrical drum that rotates about the axis as a rotating body is rotated in the circumferential direction by rotating the drum using one or more laser beams from the outside of the cylinder ( There is a method in which the entire surface of the printing plate material is exposed by moving in the direction perpendicular to the circumferential direction (sub-scanning direction) while scanning in the main scanning direction. In the present invention, the scanning exposure method (3) is particularly preferred, and the exposure method (3) is used particularly for an apparatus that performs exposure on a printing apparatus.
[0113] <印刷方法 >  [0113] <Printing method>
本発明に係る平版印刷版材料は、親水性層を有する支持体上に画像形成層を有 する構成であり、上記の画像露光により画像形成がなされた後、特に湿式の現像処 理を行うことなく印刷を行うことができる特徴を有する。即ち、本発明の印刷版材料に サーマルヘッドもしくはサーマルレーザーを用いて画像を形成した後に、平版印刷 機上で湿し水または湿し水と印刷インクにより現像を行 、、印刷することが好ま 、態 様である。  The lithographic printing plate material according to the present invention has a structure having an image forming layer on a support having a hydrophilic layer, and after image formation is performed by the image exposure described above, particularly wet development processing is performed. It has the feature that can be printed without any problems. That is, it is preferable that after forming an image on the printing plate material of the present invention using a thermal head or a thermal laser, development is performed with dampening water or dampening water and printing ink on a lithographic printing machine, and printing is performed. It is a state.
[0114] 即ち、画像露光後の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  [0114] That is, the printing plate material after image exposure is directly attached to the plate cylinder of the printing press or printing.
版材料を印刷機の版胴に取り付けた後に、版胴を回転させながら水供給ローラー及 び Zまたはインク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機能層の 非画像部を除去することが可能である。  After attaching the plate material to the plate cylinder of the printing press, the non-image area of the image forming functional layer is removed by bringing the water supply roller and Z or ink supply roller into contact with the printing plate material while rotating the plate cylinder. Is possible.
[0115] 印刷機上での画像形成機能層の非画像部 (未露光部)の除去は、版胴を回転させ ながら水付けローラーやインクローラーを接触させて行うことができるが、下記に挙げ る例のような、もしくは、それ以外の種々のシークェンスによって行うことができる。ま た、その際には、印刷時に必要な湿し水水量に対して、水量を増加させたり、減少さ せたりといった水量調整を行ってもよぐ水量調整を多段階に分けて、もしくは、無段 階に変化させて行ってもょ 、。  [0115] The removal of the non-image area (unexposed area) of the image forming functional layer on the printing machine can be performed by contacting a watering roller or an ink roller while rotating the plate cylinder. It can be performed by various sequences as shown in FIG. In that case, the water amount adjustment that can be adjusted to increase or decrease the amount of dampening water required for printing is divided into multiple stages, or Let's change to the infinite step.
[0116] (1)印刷開始のシークェンスとして、水付けローラーを接触させて版胴を 1回転〜 数十回転させ、次いで、インクローラーを接触させて版胴を 1回転〜数十回転回転さ せ、次いで、印刷を開始する。  [0116] (1) As a sequence for starting printing, contact the water roller to rotate the plate cylinder 1 to several tens of revolutions, then contact the ink roller to rotate the plate cylinder 1 to several tens of rotations. Then, printing is started.
[0117] (2)印刷開始のシークェンスとして、インクローラーを接触させて版胴を 1回転〜数 十回転させ、次いで、水付けローラーを接触させて版胴を 1回転〜数十回転させ、次 いで、印刷を開始する。  [0117] (2) As a sequence for starting printing, contact the ink roller to rotate the plate cylinder 1 to several tens of turns, then contact the watering roller to rotate the plate cylinder 1 to several tens of times, and then Start printing.
[0118] (3)印刷開始のシークェンスとして、水付けローラーとインクローラーとを実質的に 同時に接触させて版胴を 1回転〜数十回転させ、次いで、印刷を開始する。 [0119] 印刷に用いられる印刷機としては、一般に公知の、湿し水及び平版印刷インクを用 いる平版オフセット印刷機が使用できる。 (3) As a sequence for starting printing, the water roller and the ink roller are brought into contact with each other at substantially the same time to rotate the plate cylinder one to several tens of times, and then printing is started. [0119] As a printing machine used for printing, generally known lithographic offset printing machines using dampening water and lithographic printing ink can be used.
[0120] 本発明に係る平版印刷版材料は、上記のように画像様露光した後に、平版印刷機 上で湿し水または湿し水と印刷インクにより現像を行 、、印刷版とした後印刷に供せ られる。 [0120] The lithographic printing plate material according to the present invention, after imagewise exposure as described above, is developed with dampening water or dampening water and printing ink on a lithographic printing machine, and is then printed as a printing plate To be used.
[0121] 本発明に係る印刷版材料を用いた上記印刷方法にぉ 、ては、下にお 、て述べるよ うに、一般的な湿し水とプロセスインクとを使用することができる。  [0121] In the printing method using the printing plate material according to the present invention, general dampening water and process ink can be used as described below.
[0122] 〈湿し水〉 [0122] <Dampening water>
本発明に係る平版印刷版材料を用いた印刷方法にぉ ヽては、前記水供給ローラ 一から供給される前記湿し水としては、種々の調製剤を加えた水を使用することがで きるが、本発明に係る湿し水の pH値は 20°Cにおいて 4〜6. 5の範囲で用いることが 好ましい。また、湿し水中には炭素数 2〜5のアルコールを含有することが好ましぐ 含有される炭素数 2〜5のアルコール含有量は湿し水全体量に対して 0. 1質量％以 下であることが好ましい。  For the printing method using the planographic printing plate material according to the present invention, water containing various preparations can be used as the dampening water supplied from the water supply roller. However, the pH value of the fountain solution according to the present invention is preferably used in the range of 4 to 6.5 at 20 ° C. The dampening water preferably contains an alcohol having 2 to 5 carbon atoms. The content of the alcohol having 2 to 5 carbon atoms is 0.1% by mass or less based on the total amount of the dampening water. It is preferable that
[0123] 本発明に係る湿し水としては、リン酸ィ匕合物の含有量が湿し水 1リットルあたり 0. 00 5モル以上 0. 04モル未満である湿し水であることが好まし!/、。  [0123] The fountain solution according to the present invention is preferably a fountain solution having a phosphate compound content of 0.005 mol or more and less than 0.04 mol per liter of the fountain solution. Better!/,.
[0124] 本発明に係るプロセスレス印刷版材料を用いた印刷方法にぉ 、ては、この様にリン 酸ィ匕合物の含有量を上記の量の範囲とすることにより、特にアルミニウム支持体を用 いた印刷版材料の機上現像処理において、初期インキ着肉性と印刷画質を向上さ せることが出来る。  [0124] In the printing method using the processless printing plate material according to the present invention, by setting the content of the phosphoric acid compound in the above range, in particular, an aluminum support. In the on-press development processing of printing plate materials using, it is possible to improve the initial ink fillability and print image quality.
[0125] 本発明に係る湿し水に使用するリン酸化合物としては、リン酸塩、有機リン酸化合 物、亜リン酸塩、次亜リン酸塩、縮合リン酸塩類、フィチン酸化合物およびホスホン酸 化合物が挙げられる。  [0125] Examples of the phosphoric acid compound used in the fountain solution according to the present invention include phosphates, organic phosphorylated compounds, phosphites, hypophosphites, condensed phosphates, phytic acid compounds, and phosphones. Examples include acid compounds.
[0126] リン酸塩としては、水溶液中でリン酸イオンを放出する化合物であれば特に限定は なぐ例えばリン酸、リン酸のアンモ-ゥム塩類（リン酸 3アンモ-ゥム、リン酸水素 2ァ ンモ-ゥム、リン酸 2水素アンモ-ゥム等）、リン酸のアルカリ金属塩類（リン酸 3ナトリウ ム、リン水素 2ナトリウム、リン酸 2水素ナトリウム、リン酸 3カリウム等）、リン酸のアルカリ 土類金属塩類 (リン酸亜鉛、リン酸カリウム、リン酸マグネシウム等）、リン酸鉄、リン酸 マンガン、リンモリブデン酸等が挙げられる。 [0126] The phosphate is not particularly limited as long as it is a compound that releases phosphate ions in an aqueous solution. For example, phosphoric acid and ammonium salts of phosphoric acid (3 ammonium phosphate, hydrogen phosphate) 2 ammonium, ammonium dihydrogen phosphate, etc.), alkali metal salts of phosphoric acid (3 sodium phosphate, 2 sodium phosphate, 2 sodium phosphate, 3 potassium phosphate, etc.), phosphorus Acid alkaline earth metal salts (such as zinc phosphate, potassium phosphate, magnesium phosphate), iron phosphate, phosphoric acid Examples include manganese and phosphomolybdic acid.
[0127] また有機リン酸化合物の例としては、フエニルホスホン酸、フエ-ルリン酸、ナフチル ホスホン酸、ナフチルリン酸、グリセ口ホスホン酸、グリセ口リン酸、フエニルホスフィン 酸、ナフチルホスフィン酸、ジフエ-ルホスフィン酸、ジメチルホスフィン酸、 ρ -トロ フエ-ルホスフィン酸、 p—メトキシフエ-ルホスフィン酸等が挙げられる。  [0127] Examples of the organic phosphoric acid compound include phenylphosphonic acid, phenylphosphoric acid, naphthylphosphonic acid, naphthylphosphonic acid, glycephospholic acid, glycephospholic acid, phenylphosphinic acid, naphthylphosphinic acid, diphenyl. Examples include phosphinic acid, dimethylphosphinic acid, ρ-trifluorophosphinic acid, p-methoxyphenylphosphinic acid, and the like.
[0128] 亜リン酸塩としては、水溶液中で亜リン酸イオンを放出する化合物であれば特に限 定はなぐ例えば亜リン酸、亜リン酸アンモニゥム、亜リン酸ナトリウム、亜リン酸力リウ ム等が挙げられる。  [0128] The phosphite is not particularly limited as long as it is a compound that releases phosphite ions in an aqueous solution. For example, phosphorous acid, ammonium phosphite, sodium phosphite, rhodium phosphite Etc.
[0129] 次亜リン酸塩としては、水溶液中で次亜リン酸イオンを放出する化合物であれば特 に限定はなぐ例えば次亜リン酸、次亜リン酸アンモニゥム、次亜リン酸ナトリウム、次 亜リン酸カリウム等が挙げられる。  [0129] The hypophosphite is not particularly limited as long as it is a compound that releases hypophosphite ions in an aqueous solution. For example, hypophosphorous acid, ammonium hypophosphite, sodium hypophosphite, hypophosphorous acid, and the like. Examples include potassium phosphite.
[0130] 縮合リン酸塩としては、水溶液中で縮合リン酸イオンを放出する化合物であれば特 に限定はなぐ例えばポリリン酸、ピケリン酸、メタリン酸、ウルトラリン酸等の縮合リン 酸類またはこれらのアンモ-ゥム塩類、アルカリ金属塩類、アルカリ土類金属塩等が 挙げられる。  [0130] The condensed phosphate is not particularly limited as long as it is a compound that releases condensed phosphate ions in an aqueous solution. For example, condensed phosphates such as polyphosphoric acid, piceric acid, metaphosphoric acid, ultraphosphoric acid, or the like. Ammonium salts, alkali metal salts, alkaline earth metal salts and the like can be mentioned.
[0131] フィチン酸ィ匕合物としては、水溶液中でフィチン酸イオンを放出することができるィ匕 合物であれば特に限定はなぐ例えばフィチン酸、フィチン酸のアンモ-ゥム塩、アル カリ金属塩類等が挙げられる。  [0131] The phytic acid compound is not particularly limited as long as it is a compound capable of releasing phytate ions in an aqueous solution. For example, phytic acid, ammonium salt of phytic acid, alkali Metal salts etc. are mentioned.
[0132] ホスホン酸ィ匕合物としては、水溶液中でホスホン酸イオンを放出することができる化 合物であれば特に限定はなぐ例えばアミノトリ (メチレンホスホン酸）、 1ーヒドロキシ ェチリデン 1, 1ージホスホン酸、エチレンジアミンテトラ（メチレンホスホン酸）、ジェ チレントリァミンペンタ (メチレンホスホン酸）等のホスホン酸またはそのアンモニゥム塩 類、アルカリ金属塩等が挙げられる。  [0132] The phosphonic acid compound is not particularly limited as long as it is a compound capable of releasing phosphonic acid ions in an aqueous solution. For example, aminotri (methylenephosphonic acid), 1-hydroxyethylidene 1,1-diphosphonic acid And phosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) and dimethyltriaminepenta (methylenephosphonic acid), ammonium salts thereof, and alkali metal salts.
[0133] 本発明においては、リン酸ィ匕合物の含有量が湿し水 1リットルあたり 0. 005モル以 上、 0. 04モル未満あることが特徴である。さらに好ましくは、リン酸化合物の含有量 は湿し水 1リットルあたり 0. 01モル以上 0. 04モル未満である。  [0133] The present invention is characterized in that the content of the phosphate compound is not less than 0.005 mol and less than 0.04 mol per liter of dampening water. More preferably, the content of the phosphoric acid compound is not less than 0.01 mol and less than 0.04 mol per liter of dampening water.
[0134] 例えば、アルミニウム支持体を有する印刷版材料を、機上現像する場合、湿し水中 のリン酸ィ匕合物が 0. 005モル未満であると、非画像部である親水性部分に機上現 像工程において発生する感脂成分が付着し、特に初期インク着肉性に問題を生じる 。即ち、非画像部においての汚れがとれず、機上現像が不十分になって刷りだし時 の損紙の枚数が増えてしまう。アルミニウム支持体上には通常、親水化処理として、 陽極酸ィ匕膜が形成されており、ここに入り込んだ感脂成分が除去されないで残るた めと考えられる。しかしながら、リン酸塩が 0. 005モル以上、 0. 04モル未満の範囲 にある場合、リン酸塩がアルミニウム支持体上に形成されている陽極酸ィ匕膜中に入り 込んだ感脂成分等を、膜の一部と共に溶解除去しやすくするためと考えている。一 方リン酸化合物が 0. 04モル以上と多い場合には、また逆に汚れやすくなつてしまう。 [0134] For example, when a printing plate material having an aluminum support is developed on-press, if the phosphoric acid compound in the dampening water is less than 0.005 mol, the hydrophilic portion which is a non-image portion is formed. Present The oil-sensitive component generated in the image process is adhered, and particularly, there is a problem in initial ink setting. That is, the non-image area is not soiled, and the on-machine development becomes insufficient, resulting in an increase in the number of damaged paper at the time of printing. This is probably because an anodic acid film is usually formed on the aluminum support as a hydrophilization treatment, and the oil-sensitive component that has entered here remains without being removed. However, when the phosphate is in the range of 0.005 mol or more and less than 0.04 mol, the fat-sensitive component that the phosphate has entered into the anodized film formed on the aluminum support, etc. This is considered to facilitate dissolution and removal together with a part of the film. On the other hand, if the amount of phosphate compound is as large as 0.04 mol or more, it will easily become dirty.
[0135] また、この範囲にあると機上現像による非画像部における感脂成分による汚れ等が 少な 、 (機上現像が充分に行われる）ためか初期インク着肉性のみでなぐその後の 印刷、特に多数の印刷を行った場合においても、印刷画質の劣化がなく高品質の画 像を得ることが出来る。網点画像の品質の劣化が少な 、。  [0135] In addition, if it is within this range, the non-image area due to on-press development is less likely to be contaminated with grease-sensitive components (sufficient on-press development is performed), or the subsequent printing that is based only on initial ink fillability. In particular, even when a large number of printings are performed, it is possible to obtain a high-quality image without deterioration in printing image quality. There is little degradation in the quality of halftone images.
[0136] 機上現像処理を行う所謂プロセスレス印刷に用いる親水性表面を有する基材上に 形成された感光層を有する印刷版材料にぉ ヽて、湿し水中のリン酸塩濃度を前記範 囲に調整することによりこの様に初期インキ着肉性の改良や、印刷画像の品質の向 上をは力ることができる。  The printing plate material having a photosensitive layer formed on a substrate having a hydrophilic surface used for so-called processless printing in which on-press development processing is performed, the phosphate concentration in dampening water is adjusted to the above-mentioned range. By adjusting the range, it is possible to improve the initial ink fillability and improve the quality of the printed image.
[0137] 本発明で用いる湿し水には、以下のものを複数組み合わせることが好ましい。  [0137] The fountain solution used in the present invention is preferably a combination of the following.
(a) pH調整剤  (a) pH adjuster
(b)濡れ性向上のための助剤  (b) Auxiliary agent for improving wettability
(c)水溶性高分子化合物  (c) Water-soluble polymer compound
(d)臭気マスキング剤  (d) Odor masking agent
(e)防腐剤  (e) Preservative
(f)キレート化剤  (f) chelating agent
(g)着色剤  (g) Colorant
( )防鲭剤  () Antifungal agent
(i)消泡剤  (i) Antifoam agent
本発明に係る湿し水に用いられる（a) pH調整剤としては、水溶性の有機酸、無機 酸及びそれらの塩類力 選ばれる少なくとも 1種が使用できる。これらの化合物は湿 し水の pH調整あるいは pH緩衝、平版印刷版支持体の適度なエッチング又は防腐 食に効果がある。好ましい有機酸としては、例えばクェン酸、ァスコルビン酸、リンゴ 酸、酒石酸、乳酸、酢酸、ダルコン酸、ヒドロキシ酢酸、蓚酸、マロン酸、レブリン酸、 スルファ-ル酸、 p—トルエンスルホン酸等が挙げられる。無機酸としては例えば硝酸As the (a) pH adjuster used in the fountain solution according to the present invention, at least one selected from water-soluble organic acids, inorganic acids and their salt strength can be used. These compounds are moist It is effective for pH adjustment or buffering of water and appropriate etching or anticorrosion of lithographic printing plate support. Preferred organic acids include, for example, citrate, ascorbic acid, malic acid, tartaric acid, lactic acid, acetic acid, darconic acid, hydroxyacetic acid, succinic acid, malonic acid, levulinic acid, sulfuric acid, p-toluenesulfonic acid and the like. . Examples of inorganic acids include nitric acid
、硫酸が挙げられる。更にこれら有機酸及び Z又は無機酸のアルカリ金属塩、アル力 リ土類金属塩あるいはアンモ-ゥム塩、有機アミン塩も好適に用いられる。これらの有 機酸、無機酸及びこれらの塩類から 1種を単独で使用しても、あるいは 2種以上の混 合物として使用してもよい。 And sulfuric acid. Furthermore, alkali metal salts, alkaline earth metal salts, ammonium salts, and organic amine salts of these organic acids and Z or inorganic acids are also preferably used. One of these organic acids, inorganic acids, and salts thereof may be used alone, or a mixture of two or more may be used.
[0138] これら pH調整剤の湿し水への添加量は有機酸、無機酸及びこれらの塩類を合わ せて 0. 001質量％以上 0. 1質量％以下の範囲が適当である。 0. 001質量％以上 であると、平版印刷版の支持体であるアルミニウムのエッチング力により印刷時の汚 れが良好である。一方、 0. 1質量％以下であれば、印刷機の鲭びの点において好ま しい。 [0138] The addition amount of these pH adjusting agents to the fountain solution is suitably in the range of 0.001% by mass or more and 0.1% by mass or less of the organic acid, inorganic acid and salts thereof. When the content is 0.001% by mass or more, the stain during printing is good due to the etching force of aluminum which is the support of the planographic printing plate. On the other hand, if it is 0.1% by mass or less, it is preferable from the point of view of the printing press.
[0139] 本発明に係る湿し水の pH値は、前述のように 20°Cにおいて 4〜6. 5の範囲で用い ることが好ましい。  [0139] The pH value of the fountain solution according to the present invention is preferably used in the range of 4 to 6.5 at 20 ° C as described above.
[0140] (b)濡れ性向上の助剤として、界面活性剤や他の溶剤を使用することができる。界 面活性剤のうち、例えばァニオン型界面活性剤としては、脂肪酸塩類、ァビエチン酸 塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスル ホ琥珀酸塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンス ルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルフエノキシポリオキシェ チレンプロピルスルホン酸塩類、ポリオキシエチレンアルキルスルフエ-ルエーテル 塩類、 N—メチルー N—ォレイルタウリンナトリウム塩類、 N—アルキルスルホ琥珀酸 モノアミドニナトリウム塩類、石油スルホン酸塩類、硫酸化ひまし油、硫酸化牛脂油、 脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硫酸エステル塩類、ポリオ キシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステ ル塩類、ポリオキシエチレンアルキルフエ-ルエーテル硫酸エステル塩類、ポリオキ シエチレンスチリルフエ-ルエーテル硫酸エステル塩類、アルキル燐酸エステル塩類 [0140] (b) A surfactant or other solvent can be used as an aid for improving wettability. Among the surfactants, for example, anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfonates, linear alkyl benzene sulfonates, branched chains. Alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylphenoxypolyoxyethylenepropylsulfonates, polyoxyethylene alkylsulfurether salts, N-methyl-N-oleyl taurine sodium salts, N-alkylsulfones Succinic acid Monoamido sodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef tallow oil, sulfate esters of fatty acid alkyl esters, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fats Acid monoglyceride sulfate esters, polyoxyethylene alkylphenol ether sulfates, polyoxyethylene styryl ether sulfate sulfates, alkyl phosphate esters
、ポリオキシエチレンアルキルエーテル燐酸エステル塩類、ポリオキシエチレンアル キルフエ-ルエーテル燐酸エステル塩類、スチレン 無水マレイン酸共重合物の部 分けん化物類、ォレフィン 無水マレイン酸共重合物の部分けん化物類、ナフタレン スルホン酸塩ホルマリン縮合物類等が挙げられる。これらの中でもジアルキルスルホ 琥珀酸塩類、アルキル硫酸エステル塩類及びアルキルナフタレンスルホン酸塩類が 特に好ましく用いられる。 , Polyoxyethylene alkyl ether phosphates, polyoxyethylene alcohol Examples thereof include kiln ether ether phosphate salts, partial saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, naphthalene sulfonate formalin condensate and the like. Of these, dialkyl sulfosuccinates, alkyl sulfate esters and alkyl naphthalene sulfonates are particularly preferably used.
[0141] カチオン性界面活性剤としては、第一級ァミン塩、ァシルアミノエチルァミン塩、 N アルキルポリアルキレンポリアミン塩、脂肪酸ポリエチリンポリアミド類、アミド類、お よびその塩類、アミン塩などのアルキルァミン、ァシルァミンの塩類；アルキルトリメチ ルアンモ -ゥム塩、ジアルキルジメチルアンモ -ゥム塩、アルキルジメチルベンジルァ ンモ -ゥム塩、アルキルピリジゥム塩、ァシルアミノエチルメチルジェチルアンモ-ゥ ム塩、ァシルァミノプロピルジメチルベンジルアンモ -ゥム塩、ァシルァミノプロピヒル ジェチルヒドロキシェチルアンモ -ゥム塩、ァシルアミノエチルピリジゥム塩、ジァシル アミノエチルアンモ-ゥム塩等の第四級アンモ-ゥム塩若しくはアミド結合を有するァ ンモ-ゥム塩；ジァシ口キシェチルメチルヒドロキシェチルアンモ -ゥム塩、アルキル ォキシメチルピリジゥム塩等のエステル、エーテル結合を有するアンモ-ゥム塩；アル キルイミダゾリン、 1 ヒドロキシェチル 2—アルキルイミダゾリン、 1 ァシルアミノエ チル— 2—アルキルイミダゾリゥム塩等のイミダゾリン、イミダゾリゥム塩；アルキルポリ ォキシエチレンァミン、 N—アルキルアミノプロピルァミン、 N ァシルポリエチレンポ リアミン、ァシルポリエチレンポリアミン、脂肪酸トリエタノールァミンエステル等のアミ ン誘導体;その他脂肪系、バイオサーファクタント、オリゴソープが挙げられ、これらの 少なくとも一種が使用できる。  [0141] Examples of cationic surfactants include primary amine salts, acyl aminoethylamine salts, N alkyl polyalkylene polyamine salts, fatty acid polyethylene polyamides, amides, and salts thereof, amine salts, and the like. Alkylamine, acylamine salts; alkyltrimethyl ammonium salts, dialkyldimethyl ammonium salts, alkyldimethylbenzyl ammonium salts, alkyl pyridinium salts, acylaminoethyl methyl jetyl ammonium Salt, acylaminopropyldimethylbenzyl ammonium salt, acylaminopropyl diethyl diethylethyl ammonium salt, acyl aminoethyl pyridinium salt, diacyl aminoethyl ammonium salt, etc. Quaternary ammonium salts or amide-bonded amide salts; Esters such as ruhydroxyethyl ammonium salt and alkyloxymethylpyridium salt, ammonium salts having an ether bond; alkylimidazoline, 1 hydroxyethyl 2-alkylimidazoline, 1 acylaminoethyl-2 —Imidazolines such as alkyl imidazolium salts, imidazolium salts; alkyl polyoxyethylene amines, N-alkylaminopropylamines, N acyl polyethylene polyamines, acyl acyl polyamines, fatty acid triethanolamine esters, etc. Other fatty derivatives, biosurfactants, oligo soaps, and at least one of these can be used.
[0142] 非イオン型界面活性剤としては、ポリオキシエチレンアルキルエーテル類、ポリオキ シエチレンアルキルフエニルエーテル類、ポリオキシエチレンポリスチリルフエニルェ 一テル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル類、グリセリン 脂肪酸部分エステル類、ソルビタン脂肪酸部分エステル類、ペンタエリスリトール脂 肪酸部分エステル類、プロピレングリコールモノ脂肪酸エステル類、蔗糖脂肪酸部分 エステル類、ポリオキシエチレンソルビタン脂肪酸部分エステル類、ポリオキシェチレ ンソルビトール脂肪酸部分エステル類、ポリエチレングリコール脂肪酸エステル類、ポ リグリセリン脂肪酸部分エステル類、ポリオキシエチレンィ匕ひまし油類、ポリオキシェ チレングリセリン脂肪酸部分エステル類、脂肪酸ジエタノールアミド類、 N, N ビス 2—ヒドロキシアルキルアミン類、ポリオキシエチレンアルキルアミン類、トリエタノー ルァミン脂肪酸エステル類、ポリオキシエチレン ポリオキシプロピレンブロックポリマ 一類、トリアルキルアミンォキシド類などが挙げられる。その他、弗素系界面活性剤、 シリコン系界面活性剤も使用することができる。界面活性剤を使用する場合、その含 有量は発泡の点を考慮すると、 1質量％以下、好ましくは 0. 001-0. 5質量％が適 当である。また、 2種以上併用することもできる。 [0142] Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, Glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters , Polyethylene glycol fatty acid esters, poly Liglycerin fatty acid partial esters, polyoxyethylene coconut oils, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamides, N, N bis 2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters , Polyoxyethylene polyoxypropylene block polymers, trialkylamine oxides, and the like. In addition, fluorine surfactants and silicon surfactants can also be used. When a surfactant is used, the content thereof is 1% by mass or less, preferably 0.001-0. 5% by mass in consideration of foaming. Two or more types can be used in combination.
[0143] 助剤としてはその他に、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 ルモノメチルエーテル、トリエチレングリコールモノメチルエーテル、テトラエチレンダリ コーノレモノメチノレエーテノレ、エチレングリコーノレモノェチノレエーテノレ、ジエチレングリ コーノレモノェチノレエーテノレ、トリエチレングリコーノレモノェチノレエーテノレ、テトラエチレ ングリコーノレモノェチノレエーテノレ、エチレングリコーノレモノプロピノレエーテノレ、ジェチ レングリコーノレモノプロピノレエーテノレ、トリエチレングリコーノレモノプロピノレエーテノレ、 テトラエチレンダリコールモノプロピルエーテル、エチレンダルコールモノイソプロピル エーテノレ、ジエチレングノレコーノレモノイソプロピノレエーテノレ、 トリエチレングノレコーノレ モノイソプロピルエーテル、テトラエチレンダルコールモノイソプロピルエーテル、ェチ レングリコーノレモノブチノレエーテノレ、ジエチレングリコーノレモノブチノレエーテノレ、 トリエ チレングリコーノレモノブチノレエーテノレ、テトラエチレングリコーノレモノブチノレエーテノレ 、エチレングリコーノレモノイソブチノレエーテル、ジエチレングリコーノレモノイソブチノレエ 一テル、トリエチレングリコーノレモノイソブチノレエーテル、テトラエチレングリコーノレモノ イソブチノレエーテル、エチレングリコーノレモノターシヤリブチノレエ一テル、ジエチレン グリコールモノターシャリブチルエーテル、トリエチレングリコールモノターシヤリブチ ルエーテル、テトラエチレンダリコールモノターシヤリブチルエーテルが挙げられる。  [0143] Other auxiliaries include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl eno-enoate, ethylene glycol mono-ethyl eno-enoate, diethylene glycerine. Cornoremonochinenoatenore, triethyleneglycolenomonochinenoatenore, tetraethyleneglycolenolemonochinenoatenore, ethyleneglycolenomonopropinoreatenore, jetylene glycolenolemonopropenoatenore, Triethyleneglycol monopropinore etherenole, tetraethylenedarlicol monopropyl ether, ethylene dalcol monoisopropyl etherenole, diethylenegnoleconole monoisopropino Etherenole, triethylene glycolenole monoisopropyl ether, tetraethylene dalcol monoisopropyl ether, ethylene glycol nore monobutinoreateoret, diethylene glycolenomonobutinoreatenore, triethylene glycolenoremonobutenoreatenore, tetra Ethylene glycol monobutino oleate, ethylene glycol mono isobutino ole ether, diethylene glycol mono isobutino oleate, triethylene glycol monoisobutino oleate, tetraethylene glycol monoisobutino oleate, ethylene Glycol monomono tert-butyl ether ether, diethylene glycol monotertiary butyl ether, triethylene glycol monotertiary butyl ether, tetra Chi render Recall monobutyl Tashiya-butyl ether and the like.
[0144] さらに、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチル エーテル、トリプロピレングリコーノレモノメチノレエーテル、プロピレングリコーノレモノェ チノレエーテノレ、ジプロピレングリコーノレモノェチノレエーテノレ、トリプロピレングリコーノレ モノエチノレエーテノレ、テトラプロピレングリコールモノェチルエーテル、プロピレングリ コーノレモノプロピノレエーテノレ、ジプロピレングリコーノレモノプロピノレエーテノレ、トリプロ ピレンダリコールモノプロピルエーテル、プロピレングリコールモノイソプロピルエーテ ル、ジプロピレングリコーノレモノイソプロピノレエ一テル、トリプロピレングリコーノレモノィ ソプロピノレエ一テル、ジプロピレングリコーノレモノブチノレエーテル、トリプロピレングリ コーノレモノブチノレエーテノレ、プロピレングリコーノレモノイソブチノレエーテノレ、ジプロピ レングリコーノレモノイソブチノレエーテル、トリプロピレングリコーノレモノイソブチノレエー テル、プロピレングリコーノレモノターシヤリブチノレエーテノレ、ジプロピレングリコールモ ノターシヤリブチノレエーテノレ、トリプロピレングリコールモノターシヤリブチルエーテル[0144] Further, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol methanol monomethyl ether, propylene glycol monomer mono enoate, dipropylene glycol monomer mono ethenore, tripropylene glycol mono mono ethinore Etherol, tetrapropylene glycol monoethyl ether, propylene glycol Cornole monopropenoate ethere, dipropylene glycolenomonopropinoreatenore, tripropylene glycol monopropyl ether, propylene glycol monoisopropyl ether, dipropylene glycol monomonopropynole ether, tripropylene glycolenoremono Sopropylene ether, dipropylene glycol monomono butyl ether, tripropylene glycol mono mono butylate ethere, propylene glycol mono mono butino enoate, dipropylene glycol mono monobutyno ether, tripropylene glycol monomono ether Butinoreether, Propylene Glycol Monomono Shea Rib Chinore Ete Nore, Dipropylene Glycol Monochate Rib Chinore Ete Nore, Tripropylene Glyco Mono-tertiary butyl ether
、分子量 200〜1000のポリプロピレングリコール及びそれらのモノメチルエーテルが 挙げられる。 And polypropylene glycols having a molecular weight of 200 to 1000 and their monomethyl ethers.
[0145] また、さらに、モノェチルエーテル、モノプロピルエーテル、モノイソプロピルエーテ ル及びモノブチルエーテル、プロピレングリコール、ジプロピレングリコール、トリプロ ピレンダリコール、テトラプロピレングリコール及びペンタプロピレングリコール、ェチレ ングリコール、ジエチレングリコール、トリエチレングリコール、ブチレングリコーノレ、へ キシレングリコール、 2 ェチルー 1, 3 へキサンジオール、 3—メトキシー 3 メチル 1ーブタノール、 1 ブトキシー2—プロパノール、グリセリン、ジグリセリン、ポリダリ セリン、トリメチロールプロパン、 1—位が炭素原子数 1〜8のアルキル基で置換され た 2 ピロリドン誘導体、 3, 5 ジメチル— 1—へキシン— 3—オール、 2, 4, 7, 9— テトラメチルー 5 デシン—4, 7 ジオール、プロパルギルアルコール（2 プロピン 1 オール）、 3 ブチン 1 オール、 1ーブチン 3 オール、 2 ブチン 1, 4ージオール、 3, 6—ジメチルー 4ーォクチン 3, 6—ジオールなどが挙げられる。  [0145] In addition, monoethyl ether, monopropyl ether, monoisopropyl ether and monobutyl ether, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and pentapropylene glycol, ethylene glycol, diethylene glycol, Triethylene glycol, butylene glycol, hexylene glycol, 2-ethyl-1,3-hexanediol, 3-methoxy-3-methyl 1-butanol, 1-butoxy-2-propanol, glycerin, diglycerin, polydaririne, trimethylolpropane, 1-position Pyrrolidone derivatives substituted with an alkyl group of 1 to 8 carbon atoms, 3, 5 dimethyl- 1-hexyne-3-ol, 2, 4, 7, 9- tetramethyl-5 decyne-4, 7 diol Propargyl alcohol (2-propyn 1-ol), 3-butyn 1-ol, 1 Buchin 3-ol, 2-butyne 1, 4 Jioru, 3, 6-dimethyl-4 Okuchin 3, such as 6 diols.
[0146] これらの中でも特にエチレングリコールモノターシヤリブチルエーテル、 3—メトキシ  [0146] Among these, especially ethylene glycol monotertiary butyl ether, 3-methoxy
3 メチル 1 ブタノール及び 1 ブトキシ 2 プロパノールが好まし!/、。これら の溶剤は単独で用いても、 2種以上を併用してもよい。一般にこれらの溶剤は、湿し 水の全質量に基づいて 0. 002〜1質量％の範囲で使用するのが適当で、好ましくは 0. 005〜0. 5質量0 /0である。 3 Methyl 1 butanol and 1 butoxy 2 propanol are preferred! These solvents may be used alone or in combination of two or more. These solvents are appropriately used in a range of from 0.002 to 1% by weight based on the total weight of the dampening water, preferably 0.005 to 0.5 mass 0/0.
[0147] 本発明で用いる湿し水に使用する（c)水溶性高分子化合物としては、例えばァラビ ァガム、澱粉誘導体 (例えば、デキストリン、酵素分解デキストリン、ヒドロキシプロピル 化酵素分解デキストリン、カルボキシメチル化澱粉、リン酸澱粉、オタテュルコハク化 澱粉）、アルギン酸塩、繊維素誘導体 (例えば、カルボキシメチルセルロース、カルボ キシェチノレセノレロース、メチノレセノレロース、ヒドロキシェチノレセノレロース）等の天然物 及びその変性体、ポリエチレングリコール及びその共重合体、ポリビュルアルコール 及びその誘導体、ポリアクリルアミド及びその共重合体、ポリアクリル酸及びその共重 合体、ビュルメチルエーテル z無水マレイン酸共重合体、酢酸ビニル Z無水マレイ ン酸共重合体、ポリスチレンスルホン酸及びその共重合体の合成物、ポリビニルピロ リドン等が挙げられる。これらの中でもカルボキシメチルセルロース、ヒドロキシェチル セルロースは特に好ましい。水溶性高分子化合物の含有量は、湿し水に対して 0. 0[0147] The water-soluble polymer compound (c) used in the dampening solution used in the present invention includes, for example, arabic gum, starch derivatives (for example, dextrin, enzymatically decomposed dextrin, hydroxypropyl Hydrolytic enzyme dextrin, carboxymethylated starch, phosphate starch, otaturic starch, alginates, fibrin derivatives (for example, carboxymethylcellulose, carboxykisenoresenorelose, methinoresenorelose, hydroxyethinoresenorelose) ) And other natural products, polyethylene glycol and copolymers thereof, polybutyl alcohol and derivatives thereof, polyacrylamide and copolymers thereof, polyacrylic acid and copolymers thereof, butyl methyl ether and maleic anhydride copolymer. Examples thereof include a polymer, vinyl acetate Z maleic anhydride copolymer, polystyrene sulfonic acid and a synthetic product of the copolymer, and polyvinylpyrrolidone. Among these, carboxymethyl cellulose and hydroxyethyl cellulose are particularly preferable. The content of the water-soluble polymer compound is 0.0 with respect to the fountain solution.
01-0. 5質量％が適しており、より好ましくは、 0. 005-0. 2質量％である。 01-0.5% by mass is suitable, more preferably 0.005-0.2% by mass.
[0148] (d)臭気マスキング剤としては、従来香料としての用途が知られて ヽるエステルを含 む。例えば下記一般式 (I)で示されるものがある。 [0148] (d) Odor masking agents include esters that have been known to be used as perfumes. For example, there is one represented by the following general formula (I).
[0149] R -COOR (I) [0149] R -COOR (I)
1 2  1 2
一般式 (I)の化合物において、式中 Rは炭素  In the compound of general formula (I), R is carbon
1 原子数 1〜15のアルキル基、ァルケ 1 Alkyl group with 1 to 15 atoms, alkke
-ル基又はァラルキル基、あるいはフエ-ル基である。アルキル基又はアルケニル基 の場合、その炭素原子数は好ましくは 4〜8である。 Rがアルキル基、アルケニル基 -Group or aralkyl group or phenol group. In the case of an alkyl group or an alkenyl group, the number of carbon atoms is preferably 4-8. R is an alkyl group or an alkenyl group
1  1
又はァラルキル基を表す場合、それらは直鎖でも分岐鎖でもよい。アルケニル基は 特に二重結合を 1個有するものが適当である。ァラルキル基としては、ベンジル基や フエ-ルェチル基が挙げられる。なお、 Rで示されるアルキル基、ァルケ-ル基又は  Or when it represents an aralkyl group, they may be linear or branched. An alkenyl group having one double bond is particularly suitable. Examples of the aralkyl group include a benzyl group and a ferroethyl group. In addition, an alkyl group represented by R, an alkyl group or
1  1
ァラルキル基、あるいはフ -ル基の 1以上の水素原子力、水酸基又はァセチル基 で置換されていてもよい。 Rは炭素原子数 3〜 10のアルキル基、ァラルキル基又は  It may be substituted with one or more hydrogen atom, hydroxyl group or acetyl group of the aralkyl group or the full group. R is an alkyl group having 3 to 10 carbon atoms, an aralkyl group, or
2  2
フエニル基であって、それらは直鎖でも分岐鎖でもよい。アルキル基の場合、その炭 素原子数は好ましくは 3個から 9個である。ァラルキル基としては、ベンジル基やフエ -ルェチル基が挙げられる。  A phenyl group, which may be linear or branched. In the case of an alkyl group, the number of carbon atoms is preferably 3 to 9. Examples of the aralkyl group include a benzyl group and a ferroethyl group.
[0150] 使用できる（d)臭気マスキング剤として具体的に、蟻酸、酢酸、プロピオン酸、酪酸 、イソ酪酸、 2—ェチル酪酸、吉草酸、イソ吉草酸、 2—メチル吉草酸、へキサン酸 (力 プロン酸）、 4ーメチルペンタン酸（イソへキサン酸）、 2 へキセン酸、 4 ペンテン酸 、ヘプタン酸、 2—メチルヘプタン酸、オクタン酸（力プリル酸）、ノナン酸、デカン酸（ 力プリン酸）、 2—デセン酸、ラウリン酸又はミリスチン酸のエステルが挙げられる。そ の他、フヱ-ル酢酸ベンジル、ァセト酢酸ェチルやァセト酢酸 2—へキシルといったァ セト酢酸エステル等もある。中でも好ましいものとして、酢酸 n—ペンチル、酢酸イソべ ンチル、酪酸 n—ブチル、酪酸 n ペンチル及び酪酸イソペンチルが挙げられ、特に 酪酸 n—ブチル、酪酸 n ペンチル及び酪酸イソペンチルが好適である。これらの臭 気マスキング剤（d)の湿し水における含有量は、湿し水の全質量に基づいて 0. 001 〜0. 5質量％が適当で、より好ましくは 0. 002-0. 2質量％である。これらを使用す ることにより、作業環境をより改善することができる。また。バニリン、ェチルバ-リン等 を併用してもよい。 Specific examples of (d) odor masking agents that can be used include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, 2-ethylbutyric acid, valeric acid, isovaleric acid, 2-methylvaleric acid, hexanoic acid ( Proproic acid), 4-methylpentanoic acid (isohexanoic acid), 2 hexenoic acid, 4 pentenoic acid, heptanoic acid, 2-methylheptanoic acid, octanoic acid (forced prillic acid), nonanoic acid, decanoic acid ( Strength purine acid), 2-decenoic acid, lauric acid or myristic acid esters. In addition, there are acetoacetates such as benzyl phenylacetate, ethyl acetate, and 2-hexyl acetate. Among these, n-pentyl acetate, isopentyl acetate, n-butyl butyrate, n pentyl butyrate and isopentyl butyrate are preferable, and n-butyl butyrate, n pentyl butyrate and isopentyl butyrate are particularly preferable. The content of these odor masking agents (d) in the fountain solution is suitably from 0.001 to 0.5% by mass, more preferably from 0.002 to 0.2%, based on the total mass of the fountain solution. % By mass. By using these, the working environment can be further improved. Also. Vanillin, ethyl valine or the like may be used in combination.
[0151] 本発明に係る湿し水に使用する（e)防腐剤としては、フエノール又はその誘導体、 ホルマリン、イミダゾール誘導体、デヒドロ酢酸ナトリウム、 4—イソチアゾリン— 3—ォ ン誘導体、ベンズトリアゾール誘導体、アミジン又はグァ-ジンの誘導体、四級アンモ -ゥム塩類、ピリジン、キノリン又はグァ-ジンの誘導体、ダイアジン又はトリァゾーノレ の誘導体、ォキサゾール又はォキサジンの誘導体、ブロモニトロアルコール系のブロ モニトロプロパノーノレ、 1, 1 ジブ口モー 1一二トロー 2 エタノーノレ、 3 ブロモー 3 -トロペンタン一 2, 4 ジオール等が挙げられる。好ましい添力卩量は細菌、カビ、 酵母等に対して、安定に効力を発揮する量であって、細菌、カビ、酵母の種類によつ ても異なるが、湿し水に対し、 0. 001〜0. 5質量％の範囲が好ましぐまた種々の力 ビ、細菌、酵母に対して効力のあるような 2種以上の防腐剤を併用することが好ましい  [0151] (e) Preservative used in the fountain solution according to the present invention includes phenol or a derivative thereof, formalin, imidazole derivative, sodium dehydroacetate, 4-isothiazoline-3-one derivative, benztriazole derivative, amidine Or guanidine derivatives, quaternary ammonium salts, pyridine, quinoline or guanidine derivatives, diazine or triazonole derivatives, oxazole or oxazine derivatives, bromonitroalcohol-based bromonitropropanols, 1 , 1 Jib mouth mo 1 12 tallow 2 Ethanol, 3 Bromo 3-tropentane 1, 2 diol and the like. The preferred amount of applied force is the amount that exerts stability against bacteria, mold, yeast, etc., and it varies depending on the type of bacteria, mold, yeast, but is 0. A range of 001 to 0.5% by mass is preferred, and it is preferable to use two or more preservatives that are effective against various strengths of bacteria, bacteria, and yeast.
[0152] 本発明に係る湿し水は、さら〖こ、 （f)キレート化剤を含んでいてもよい。湿し水は、使 用時に通常湿し水濃縮組成物に、水道水、井戸水などを加えて希釈して調製される 1S この際、希釈する水道水や井戸水に含まれているカルシウムイオン等が印刷に 悪影響を与え、印刷物を汚れ易くする原因となることもある。このような場合、キレート ィ匕剤を添加しておくことにより、上記欠点を解消することができる。好ましいキレートイ匕 剤としては例えば、エチレンジアミンテトラ酢酸、そのカリウム塩、そのナトリウム塩;ジ エチレントリァミンペンタ酢酸、そのカリウム塩、ナトリウム塩；トリエチレンテトラミンへキ サ酢酸、そのカリウム塩、そのナトリウム塩、ヒドロキシェチルエチレンジァミントリ酢酸 、そのカリウム塩、そのナトリウム塩;ユトリロトリ酢酸、そのナトリウム塩； 1ーヒドロキシ ェタン一 1, 1—ジホスホン酸、そのカリウム塩、そのナトリウム塩;アミノトリ（メチレンホ スホン酸）、そのカリウム塩、そのナトリウム塩などのような有機ホスホン酸類あるいは ホスホノアルカントリカルボン酸類を挙げることができる。上記のキレート剤のナトリウ ム塩あるいはカリウム塩の代わりに、有機ァミンの塩も有効である。これらのキレート化 剤は使用時の湿し水中に安定に存在し、印刷性を阻害しないものが選ばれる。使用 時の湿し水中のキレートイ匕合物の含有量としては、 0. 0001-0. 5質量％が適当で 、好ましくは 0. 0005〜0. 2質量0 /0である。 [0152] The fountain solution according to the present invention may further contain Sarakoko (f) a chelating agent. The fountain solution is usually prepared by adding tap water, well water, etc. to the fountain solution concentrated composition at the time of use. 1S At this time, calcium ions contained in the tap water or well water to be diluted. It may adversely affect printing and cause the printed matter to become dirty easily. In such a case, the above disadvantages can be eliminated by adding a chelating agent. Preferred chelating agents include, for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt, Hydroxyethyl ethylenediamine triacetic acid , Its potassium salt, its sodium salt; utrilotriacetic acid, its sodium salt; 1-hydroxyethane 1,1-diphosphonic acid, its potassium salt, its sodium salt; aminotri (methylenephosphonic acid), its potassium salt, its sodium salt, etc. And organic phosphonic acids such as phosphonoalkanetricarboxylic acids. Instead of the sodium salt or potassium salt of the chelating agent, an organic amine salt is also effective. These chelating agents are selected so that they are stably present in the fountain solution during use and do not impair the printability. The content of the fountain Kiretoi匕合of water in use, 0. 0001-0. Is suitably 5% by weight, preferably 0.0005 to 0.2 mass 0/0.
[0153] 本発明に係る湿し水に使用する (g)着色剤としては、食品用色素等が好ましく使用 できる。例えば、黄色色素としては CINo. 19140、 15985、赤色色素としては CINo . 16185、 45430、 16255、 45380、 45100、紫色色素としては CINo. 42640、青 色色素としては CINo. 42090、 73015、緑色色素としては CINo. 42095、等力 ^挙 げられる。使用する湿し水中の着色剤の含有量としては 0. 0001-0. 5質量％が好 ましい。 [0153] Food coloring agents and the like can be preferably used as the colorant (g) used in the fountain solution according to the present invention. For example, CINo. 19140 and 15985 as yellow pigments, CINo. 16185, 45430, 16255, 45380 and 45100 as red pigments, CINo. 42640 as purple pigments, CINo. 42090 and 73015 as blue pigments, and green pigments Is CINo. 42095, with equal strength. The content of the colorant in the fountain solution used is preferably 0.0001-0.
[0154] 本発明で用いる湿し水に使用する（h)防鲭剤としては、例えばべンゾトリァゾール、 5—メチルベンゾトリァゾール、チォサリチル酸、ベンゾイミダゾール及びその誘導体 等が挙げられる。本発明で用いる湿し水に使用する（i)消泡剤としてはシリコン消泡 剤が好ましぐその中で乳化分散型及び可溶ィ匕型等いずれも使用することができる。 使用する場合の湿し水中の防鲭剤の含有量としては、 0. 0001〜0. 5質量％が好ま しい。  [0154] Examples of the antifungal agent (h) used in the fountain solution used in the present invention include benzotriazole, 5-methylbenzotriazole, thiosalicylic acid, benzimidazole and derivatives thereof. As the antifoaming agent used in the fountain solution used in the present invention, a silicon antifoaming agent is preferred, and both an emulsified dispersion type and a soluble type can be used. When used, the content of the fungicide in the fountain solution is preferably from 0.0001 to 0.5% by mass.
[0155] さらに本発明の湿し水は、表面張力及び粘度を調整して印刷適性を向上するため にアルコール類を添カ卩しても良い。添カ卩できるアルコールの例としては、メチルアルコ ール、エチルアルコール、プロピルアルコール、イソプロピルアルコール等が挙げら れる。  [0155] Further, the dampening water of the present invention may be supplemented with alcohols in order to improve the printability by adjusting the surface tension and viscosity. Examples of alcohols that can be added include methyl alcohol, ethyl alcohol, propyl alcohol, and isopropyl alcohol.
[0156] 本発明に係る湿し水組成物の成分として残余は、水である。湿し水組成物は、通常 商業ベースとするときは濃縮ィ匕して商品化するのが一般的である。従って、水、好ま しくは脱塩水、即ち、純水を使用して、上記の各種成分を溶解した水溶液として濃縮 湿し水組成物を得ることができる。このような濃縮液を使用するときに、通常使用時に 水道水、井戸水等で 10〜200倍程度に希釈し、使用時の湿し水組成物とする。 [0156] The remainder of the fountain solution composition according to the present invention is water. The fountain solution composition is usually concentrated and commercialized when commercialized. Therefore, a concentrated fountain solution composition can be obtained as an aqueous solution in which the above various components are dissolved using water, preferably demineralized water, that is, pure water. When using such a concentrated solution, Dilute to about 10 to 200 times with tap water, well water, etc. to make a fountain solution at the time of use.
[0157] 本発明に係る湿し水は、呼び出し給水方式、連続給水方式の!/、ずれの湿し水の供 給装置でも使用できるが、特に連続給水方式の湿し水の供給装置で用いられること が好ましい。三菱ダイヤマチックダンプナー、コモリマチック、ダールグレンダンプナ 一やハイデルベルグのアルカラ一ダンプナ一といつた印刷機でも使用することができ る。 [0157] The dampening water according to the present invention can also be used in the water supply system of the calling water supply system, the continuous water supply system! /, Or the dampening water of the misalignment, but particularly in the dampening water supply apparatus of the continuous water supply system. It is preferable that It can also be used on any printing press with Mitsubishi Diamatic Dampner, Komorimatic, Dahllen Dampner or Heidelberg Alcala Dampner.
[0158] <インク >  [0158] <Ink>
本発明に係る印刷で用 、ることができるインクは、平版印刷に使用できるインクであ ればいずれのインクでも良いが、具体的には、ロジン変性フエノール榭脂と植物油（ アマ-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クとアクリル系オリゴマー、アクリルモノマ 一、光重合開始剤、顔料等の成分よりなる放射線紫外線硬化型のインクであり、さら に、油性インクの性質と UVインクの性質を併せ持つハイブリッドインクも使用できる。 実施例  The ink that can be used in printing according to the present invention may be any ink that can be used for lithographic printing. Specifically, rosin-modified phenol resin and vegetable oils (ama oil, tung oil) Oil oil and acrylic oligomers, acrylic monomers, photopolymerization initiators, pigments, etc. composed of components such as petroleum solvents, pigments, oxidation polymerization catalysts (cobalt, manganese, lead, iron, zinc, etc.) It is a radiation ultraviolet curable ink consisting of these components, and hybrid inks that combine the properties of oil-based inks and UV inks can also be used. Example
[0159] 以下、実施例を挙げて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 るのもではない。  [0159] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
[0160] 《支持体の作製》：プラスチックフィルムの作製  [0160] <Production of support>: Production of plastic film
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. 66 (フエ ノール Zテトラクロロェタン = 6Z4 (質量比）中 25°Cで測定）の PETを得た。これをぺ レツトイ匕した後 130°Cで 4時間乾燥し、 300°Cで溶融後 T型ダイ力も押し出し、 50°C の冷却ドラム上で急冷し熱固定した未延伸フィルムを 2軸で熱延伸し作製した。  Using terephthalic acid and ethylene glycol, a PET with IV (inherent viscosity) = 0.66 (measured in phenol Z tetrachloroethane = 6Z4 (mass ratio) at 25 ° C) was obtained according to a conventional method. Pelletized, dried at 130 ° C for 4 hours, melted at 300 ° C, extruded T-die force, rapidly cooled on a 50 ° C cooling drum, and heat-set unstretched film biaxially. And made.
[0161] 《支持体の下引き処理》  [0161] <Support subtraction process>
上記の方法で得られた基材の一方の面に、 8W/m2 ·分の条件でコロナ放電処理 を行いながら下記下引き塗布液 aを乾燥膜厚 0. 8 mになるように塗設し、更にその 上にコロナ放電処理 (8WZm2.分)を行いながら下引き塗布液 bを乾燥膜厚 0. 1 μ mになるように塗設した（下引き面 A)。また反対側の面に、 8WZm2'分の条件でコロ ナ放電処理を行いながら下記下引き塗布液 cを乾燥膜厚 0. 06 mになるように塗 設し、 140°Cで乾燥し、続いて下引き塗布液 dを乾燥膜厚 0. になるように塗設 し、 140°Cで乾燥 (下引き面 B)して下引き済み基材を得た On one side of the substrate obtained by the above method, apply the following undercoat coating solution a to a dry film thickness of 0.8 m while performing corona discharge treatment under the condition of 8 W / m 2 · min. Further, an undercoat coating solution b was applied to the dry film thickness of 0.1 μm while performing corona discharge treatment (8 WZm 2 .min) (undercoat surface A). Also, on the opposite side, apply the following undercoat coating solution c to a dry film thickness of 0.06 m while performing corona discharge treatment under the condition of 8 WZm 2 ′, and dry at 140 ° C. Next, apply the undercoating solution d so that the dry film thickness is 0. And dried at 140 ° C (undercoating surface B) to obtain an undercoated substrate
《下引き塗布液 a》  << Undercoat liquid a >>
ート Zブチルアタリレート = 60Z39Zlの 3元系共重 合ラテックス (Tg = 75°C) 6. 3質量部  Z-Butyl Atylate = 60Z39Zl Ternary Copolymer Latex (Tg = 75 ° C) 6. 3 parts by mass
一卜 Ζブチルァクジレー卜 = 20Ζ40Ζ40の 3元 系共重合ラテックス 1. 6質量部  1-Butyl Axylate = 20 ~ 40 ~ 40 ternary copolymer latex 1.6 parts by mass
ァニオン系界面活性剤 S— 1 0. 1質 I  Anionic surfactant S— 1 0. 1 quality I
水 92. 0質量部  92.0 parts by weight of water
《下引き塗布液 b》  <Undercoat coating solution b>
ゼラチン 1質量部  1 part by weight of gelatin
PVA 0. 5質量部  0.5 parts by mass of PVA
ァニオン系界面活性剤 S— 1 0. 05質 I  Anionic surfactant S— 1 0. 05 Quality I
硬膜剤 H—1 0. 20質量部  Hardener H-1 0.20 parts by mass
マット材（シリカ，平均粒径 3. 5 m) 0. 02質量部  Mat material (silica, average particle size 3.5 m) 0.02 parts by mass
防黴剤 F— 1 0. 01質量部  Antifungal agent F— 1 0. 01 parts by mass
水 98. 22質量咅  Water 98.22
《下引き塗布液 c》  <Undercoat liquid c>
スチレン Zグリシジルメタタリレート Zブチルアタリレート（20Z20Z40)の共 重合ポリマーラテックス（固形分 30%) 1. 6質量部  Styrene Z Glycidyl metatalylate Copolymer polymer latex of Z butyl acrylate (20Z20Z40) (solid content 30%) 1.6 parts by mass
スチレン Zブチルアタリレート Zヒドロキシメチルメタタリレート（25Z45Z30 )の共重合ポリマーラテックス（固形分 30%) 0. 4質量部  Styrene Z-Butyl Atallate Copolymer latex of Z-hydroxymethyl metatalylate (25Z45Z30) (solid content 30%) 0.4 parts by mass
SnOゾル（固形分 10%) (特開平 10— 059720号公報記載の方法で合成) SnO sol (solid content 10%) (synthesized by the method described in JP-A-10-059720)
2 2
9. 1質量％  9. 1% by mass
ァニオン系界面活性剤 S— 1 0. 05質量部  Anionic surfactant S— 1 0. 05 parts by mass
水 88. 85質量咅  Water 88.85 mass
《下引き塗布液 d》  <Undercoat coating solution d>
変性水性ポリエステル A (固形分 18%) 21. 5質量部 ァニオン系界面活性剤 0. 04質量部 真球状シリカマット剤 シーホスター KE- P60 (日本触媒 (株)社製) 水 Modified water-based polyester A (solid content 18%) 21.5 parts by weight Anionic surfactant 0.04 parts by weight Spherical silica matting agent Sea Hoster KE-P60 (Nippon Shokubai Co., Ltd.) Water
[0163] [化 1]  [0163] [Chemical 1]
S一 1
Figure imgf000033_0001
S 1
Figure imgf000033_0001
CHCO-N N-COCH = CH CHCO-N N-COCH = CH
COCH=CH,  COCH = CH,
Figure imgf000033_0002
Figure imgf000033_0002
(成分 A) (成分 (成分 C>  (Component A) (Component (Component C>
成分 A:成分 B:成分 C = S0:46:4(モル比）  Component A: Component B: Component C = S0: 46: 4 (Molar ratio)
[0164] <変 '性水'性ポリエステノレ Aの合成 > [0164] <Synthesis of modified 'water'-related polyesterol A>
重縮合用反応容器に、テレフタル酸ジメチル 35. 4質量部、イソフタル酸ジメチル 3 3. 63質量部、 5—スルホーイソフタル酸ジメチルナトリウム塩 17. 92質量部、ェチレ ングリコール 62質量部、酢酸カルシウム一水塩 0. 065質量部、酢酸マンガン四水塩 0. 022質量部を投入し、窒素気流下において、 170〜220°Cでメタノールを留去し ながらエステル交換反応を行った後、リン酸トリメチル 0. 04質量部、重縮合触媒とし て三酸化アンチモン 0. 04質量部及び 1, 4ーシクロへキサンジカルボン酸 6. 8質量 部をカ卩え、 220〜235°Cの反応温度で、ほぼ理論量の水を留去し、エステル化を行 つた。その後、更に反応系内を約 1時間かけて減圧、昇温し最終的に 280°C、 133P a以下で約 1時間重縮合を行!ヽ、変性水性ポリエステル Aの前駆体を得た。  In a reaction vessel for polycondensation, 35.4 parts by weight of dimethyl terephthalate, 3 3.63 parts by weight of dimethyl isophthalate, 17.92 parts by weight of dimethyl sodium sulfo-isophthalate, 62 parts by weight of ethylene glycol, calcium acetate After adding 0.065 parts by mass of monohydrate and 0.022 parts by mass of manganese acetate tetrahydrate and carrying out a transesterification reaction while distilling off methanol at 170 to 220 ° C under a nitrogen stream, phosphoric acid was added. 0.04 parts by mass of trimethyl, 0.04 parts by mass of antimony trioxide as a polycondensation catalyst and 6.8 parts by mass of 1,4-cyclohexanedicarboxylic acid were added, and at a reaction temperature of 220 to 235 ° C, The theoretical amount of water was distilled off for esterification. Thereafter, the reaction system was further depressurized and heated for about 1 hour, and finally subjected to polycondensation at 280 ° C. and 133 Pa or less for about 1 hour to obtain a precursor of modified aqueous polyester A.
[0165] 攪拌翼、環流冷却管、温度計を付した 2Lの三つ口フラスコに、純水 850mlを入れ 、攪拌翼を回転させながら、 150gの上記前駆体を徐々に添加した。室温でこのまま 30分間攪拌した後、 1. 5時間かけて内温が 98°Cになるように加熱し、この温度で 3 時間加熱溶解した。加熱終了後、 1時間かけて室温まで冷却し、一夜放置して、固形 分濃度が 15質量％の前駆体の溶液を調製した。 [0165] 850 ml of pure water was placed in a 2 L three-necked flask equipped with a stirring blade, a reflux condenser, and a thermometer, and 150 g of the above precursor was gradually added while rotating the stirring blade. After stirring at room temperature for 30 minutes, 1. Heat to an internal temperature of 98 ° C over 5 hours. Dissolved by heating for hours. After the heating, the mixture was cooled to room temperature over 1 hour and allowed to stand overnight to prepare a precursor solution having a solid concentration of 15% by mass.
[0166] 攪拌翼、環流冷却管、温度計、滴下ロートを付した 3Lの四つ口フラスコに、上記前 駆体の溶液 1900mlを入れ、攪拌翼を回転させながら、内温度を 80°Cまで加熱した 。この中に、過酸化アンモ-ゥムの 24%水溶液を 6. 52ml加え、単量体混合液 (メタ クリル酸グリシジル 28. 5g、アクリル酸ェチル 21. 4g、メタクリル酸メチル 21. 4g)を 3 0分間かけて滴下し、更に 3時間反応を続けた。その後、 30°C以下まで冷却し、濾過 して、固形分濃度が 18質量％の変性水性ポリエステル Aの溶液を調製した。  [0166] Into a 3L four-necked flask equipped with a stirring blade, a reflux condenser, a thermometer, and a dropping funnel, put 1900ml of the above precursor solution, and turn the stirring blade to an internal temperature of 80 ° C. Heated. To this, 6.52 ml of a 24% aqueous solution of ammonium peroxide was added, and a monomer mixture (28.5 g of glycidyl methacrylate, 21.4 g of ethyl acrylate, 21.4 g of methyl methacrylate) was added. The solution was added dropwise over 0 minutes, and the reaction was continued for another 3 hours. Thereafter, the mixture was cooled to 30 ° C. or lower and filtered to prepare a modified aqueous polyester A solution having a solid concentration of 18% by mass.
[0167] <平版印刷版材料の作製 >  [0167] <Preparation of planographic printing plate material>
下記に示す親水性層塗布液 (調製方法は下記に示す)を下引き済み支持体の A面 上にワイヤーバーを用いて乾燥付量が 3g/m2になるように塗布し、 120°Cで 3分間 乾燥したのちに 60°Cで 48時間の加熱処理を施した。さらに、画像形成機能層塗布 液をワイヤーバーを用いて乾燥付量が 0. 5gZm2になるように親水層上に塗布して 5 0°Cで 1分間乾燥したのちに、 50°Cで 24時間の加熱処理を施して、幅 670mm、長さ 30. 5m卷回させ、下記表 1示す様に平版印刷版材料 1〜5を作製した。 Apply the hydrophilic layer coating solution shown below (preparation method is shown below) on the surface A of the undercoated support using a wire bar so that the dry weight is 3 g / m 2 and 120 ° C. After drying for 3 minutes, it was heated at 60 ° C for 48 hours. Furthermore, the image forming functional layer coating solution was applied onto the hydrophilic layer using a wire bar so that the drying weight was 0.5 gZm 2 and dried at 50 ° C. for 1 minute, and then at 50 ° C. for 24 minutes. The plate was subjected to heat treatment for a period of time, rolled 670 mm in width and 30.5 m in length, and produced lithographic printing plate materials 1 to 5 as shown in Table 1 below.
[0168] 《親水性層塗布液の調製》  <Preparation of hydrophilic layer coating solution>
コロイダルシリカ（アルカリ系）、スノーテックス— xs (日産化学社製、固形分 20 質量％) 48質量部 Colloidal silica (alkaline), Snowtex- xs (Nissan Chemical Co., Ltd., solid content 20% by mass) 48 parts by mass
コロイダルシリカ（アルカリ系）、スノーテックス— ZL (日産化学社製、固形分 40 質量％) 4質量部  Colloidal silica (alkaline), Snowtex-ZL (Nissan Chemical Co., Ltd., solid content 40% by mass) 4 parts by mass
多孔質金属酸ィ匕物粒子シルトン JC— 50 (水澤ィ匕学社製、多孔質アルミノシリケート 粒子、平均粒径 5 ^ m) 11. 1質量部  Porous Metal Oxide Particles SILTON JC-50 (Mizusawa Chemical Co., Ltd., porous aluminosilicate particles, average particle size 5 ^ m) 11. 1 part by mass
表 1に記載の顔料 30質量部  30 parts by mass of pigments listed in Table 1
カルボキシメチルセルロースナトリウム（関東ィ匕学社製)の 4質量％の水溶液 4% by weight aqueous solution of sodium carboxymethylcellulose (Kantoi Sogakusha)
0. 56質量部 0.56 parts by mass
層状鉱物粒子モンモリロナイト、ミネラルコロイド MO (Southern Clay Products社製、平均粒径 0. 1 μ m程度）をホモジナイザで強攪拌して 5質量 %の水膨潤ゲルとしたもの 1. 11質量部 リン酸三ナトリウム · 12水（関東ィ匕学社製)の 10質量％の水溶液 Layered mineral particle montmorillonite, mineral colloid MO (manufactured by Southern Clay Products, average particle size of about 0.1 μm) was vigorously stirred with a homogenizer to form a 5% water-swelled gel 1. 11 parts by mass 10% by mass aqueous solution of trisodium phosphate · 12 water (manufactured by Kantoi Sogakusha)
0. 28質量部  0.28 parts by mass
シリコーン系界面活性剤 FZ— 2161 (日本ュ-カー社製） 0. 16質量部 なお、本実施例において用いた顔料の磁ィ匕値は顔料粉末を東英工業製 VSMによ り 397. 9kAZm(5kOe)の磁場において測定した力 本発明に係る顔料の磁ィ匕値 は 0. 5〜： LOemuZgの範囲内にあった。  Silicone surfactant FZ-2161 (manufactured by Nippon Car Co., Ltd.) 0.16 parts by mass The magnetic value of the pigment used in this example is 397.9 kAZm using VSM manufactured by Toei Kogyo Co., Ltd. Force measured in a magnetic field of (5 kOe) The magnetic field value of the pigment according to the invention was in the range of 0.5 to LOemuZg.
[0169] 《感熱画像形成層塗布液の調製》 <Preparation of thermal image forming layer coating solution>
カルナバワックスェマルジヨン A118 (岐阜セラック社製）固形分 40%  Carnauba Wax Marzipon A118 (Gifu Shellac Co., Ltd.) Solid content 40%
45質量部  45 parts by mass
マイクロクリスタリンワックス A— 206 (岐阜セラック社製）固形分 40%  Microcrystalline wax A—206 (Gifu Shellac Co., Ltd.) Solid content 40%
25質量部  25 parts by mass
ポリエチレンワックス A— 514 (岐阜セラック社製）固形分 40% 15質量部 ポリアクリル酸ナトリウム 30質量0 /0水溶液 DL— 522 (日本触媒社製） Polyethylene wax A- 514 (Gifu Shellac Co., Ltd.) 40% solids 15 parts by mass of sodium polyacrylate 30 mass 0/0 aqueous DL-522 (manufactured by Nippon Shokubai Co., Ltd.)
10質量部  10 parts by mass
イソプロパノール 1質量部  1 part by weight of isopropanol
<露光方法 >  <Exposure method>
露光ドラムに 670mm幅 30. 5m巻きのロール状に包装形態された平版印刷版材 料を 560mmの長さに断裁し、巻き付け固定した後、波長 830nm、スポット径約 18 mのレーザービームを用い、露光エネルギーを 200mjZcm2、 2400dpi (dpiとは、 2 . 54cm当たりのドット数を表す。）、 1751pi (lpiとは、 2. 54cmあたりの線数を表す。 ) でベタ及び 2%小点画像を作製し、露光した。 A lithographic printing plate material packaged in a roll of 670mm width and 30.5m roll on the exposure drum is cut to a length of 560mm, wound and fixed, and then a laser beam with a wavelength of 830nm and a spot diameter of about 18m is used. The exposure energy is 200mjZcm 2 , 2400dpi (dpi is the number of dots per 2.54cm), 1751pi (lpi is the number of lines per 2.54cm) Prepared and exposed.
[0170] <印刷方法 > [0170] <Printing method>
印刷装置としては、小森コーポレーション製の LITHRONE26を用いて、上記印刷 版の切り込みを印刷機のピンに差し込んだ後に、コート紙 (王子製紙製、 636x468) と、湿し水としてァストロマーク 3 (日研ィ匕学研究所製)の 2質量部％水溶液 (pH 4. 8)、インキとして東洋インキ社製のハイュ-ティ黄、藍、紅、墨の 4色のインキを使用 して、印刷スピード 9000枚 Z時、住友ダンロップ製のブランケットを用いて印刷を行 つた o [0171] <耐刷性> As a printing device, Komori Corporation's LITHRONE26 was used, and after inserting the above printing plate notch into the printing machine pin, coated paper (Oji Paper, 636x468) and Astro Mark 3 (Nikken A 2 mass% aqueous solution (pH 4.8) of Togoku Ink Co., Ltd.), and four inks of high yellow, indigo, red and black made by Toyo Ink Co., Ltd., and printing speed of 9000 sheets At Z, printing was performed using a Sumitomo Dunlop blanket o [0171] <Print life>
印刷物上で 2%の網点の一部が欠ける力 もしくは、非画線部に汚れが生じた時点 での印刷枚数を求め、耐刷性の評価とした。  The printing durability was evaluated by obtaining the force at which part of the 2% halftone dot was missing on the printed material or the number of printed sheets when the non-image area was stained.
[0172] <耐脱色性 > [0172] <Decolorization resistance>
機上現像後の印刷版を 2質量部％ァスト口マーク 3水溶液 (pH 4. 8)中に lh浸漬 させ、浸漬前の濃度との変化を目視評価した。  The printing plate after on-press development was immersed in a 2% by weight first mouth mark 3 aqueous solution (pH 4.8) for lh, and the change from the concentration before immersion was visually evaluated.
〇：脱色がみられない  ○: No decolorization
△:わずかに脱色が見られる  Δ: Slight decolorization is observed
X：完全に脱色している  X: Completely decolorized
ぐ塗布性 >  Applicability>
親水性層塗布品 lm2中の凝集体の個数を目視評価した。 The number of aggregates in the hydrophilic layer coated product lm 2 was visually evaluated.
[0173] 上記の評価結果を表 1にまとめて示す。 [0173] The above evaluation results are summarized in Table 1.
[0174] [表 1] [0174] [Table 1]
Figure imgf000036_0001
Figure imgf000036_0001
[0175] 表 1から明らかなように、本発明の印刷版材料は、耐刷性、耐脱色性及び塗布性に ぉ 、て優れて 、ることが分かる。 As is apparent from Table 1, it can be seen that the printing plate material of the present invention is excellent in printing durability, decoloration resistance and coating property.
[0176] 次に、 A1支持体を用いた実施例を示す。  [0176] Next, an example using an A1 support is shown.
[0177] 〈く A1支持体の作製》  [0177] <Production of A1 support>
厚さ 0.24mmのアルミニウム板（材質 1050、調質 H16)を、 50°Cの 1質量％水酸化 ナトリウム水溶液中に浸漬し、溶解量が 2g/m2になるように溶解処理を行ない水洗 した後、 25°Cの 5質量％硝酸水溶液中に 30秒間浸漬し、中和処理した後水洗した。 An aluminum plate (material 1050, tempered H16) with a thickness of 0.24 mm was immersed in a 1% by weight sodium hydroxide aqueous solution at 50 ° C, dissolved to a dissolution rate of 2 g / m 2 and washed with water. Thereafter, it was immersed in a 5 mass% nitric acid aqueous solution at 25 ° C for 30 seconds, neutralized, and then washed with water.
[0178] 次 、でこのアルミニウム板を、塩酸 1 lgZL、酢酸 10gZL、アルミ 8gZLを含有す る電解液により、正弦波の交流を用いて、ピーク電流密度が 80AZdm2の条件で電 解粗面化処理を行った。この際の電極と試料表面との距離は 10mmとした。電解粗 面化処理は、 8回に分割して行ない、一回の処理電気量（陽極時)を 40CZdm2、合 計の処理電気量（陽極時)を 320CZdm2とした。また、各回の処理の間に 3秒間の 休止時間を設けた。 [0178] Next, this aluminum plate was electrolytically roughened with an electrolytic solution containing 1 lgZL of hydrochloric acid, 10 gZL of acetic acid and 8 gZL of aluminum, using a sinusoidal alternating current at a peak current density of 80 AZdm 2. Processed. The distance between the electrode and the sample surface at this time was 10 mm. Electrolytic rough The chamfering process was divided into 8 times, and the amount of electricity processed at one time (at the time of anode) was 40 CZdm 2 , and the total amount of electricity processed (at the time of anode) was 320 CZdm 2 . In addition, a pause of 3 seconds was provided between each treatment.
[0179] 電解粗面化後は、 50°Cに保たれた 10質量％リン酸水溶液中に浸漬して、粗面化 された面のスマット含めた溶解量が 0.65g/m2になるようにエッチングし、水洗した。 次いで、 20%硫酸水溶液中で、 5AZdm2の電流密度で付量 2.5gZm2の陽極酸ィ匕 皮膜を形成させる条件で陽極酸化処理を行な ヽ、さらに水洗した。 [0179] After electrolytic surface roughening, it is immersed in a 10 mass% phosphoric acid aqueous solution maintained at 50 ° C so that the amount of dissolution including the smut of the roughened surface becomes 0.65 g / m 2. Etched and washed with water. Then, in a 20% aqueous solution of sulfuric acid, row anodizing treatment under the conditions for forming the anode Sani匕film biasing amount 2.5GZm 2 at a current density of 5AZdm 2ヽwas further washed with water.
[0180] 次いで、水洗後の表面水をスクイーズした後、 50°Cに保たれた、 SiO成分として 0.  [0180] Next, after squeezing the surface water after washing with water, it was maintained at 50 ° C as the SiO component.
2  2
5質量％のリチウムシリケート (LSS45、日産化学社製)水溶液に 15秒間浸漬し、水洗 を行った後に 80°Cで 5分間乾燥し、支持体を得た。  The substrate was immersed in an aqueous solution of 5% by mass of lithium silicate (LSS45, manufactured by Nissan Chemical Co., Ltd.) for 15 seconds, washed with water and then dried at 80 ° C. for 5 minutes to obtain a support.
[0181] 《ポリマー粒子の作製》 [0181] <Production of polymer particles>
2リットルの 4つ口フラスコに脱イオン水 312質量部、 Newcol 707SF (日本乳ィ匕剤 製、固形分 30質量％) 2.3質量部を加え、窒素置換後、 80°Cに保つ。下記組成のプ レエマルジヨンを滴下する直前に 0.7質量部の過硫酸アンモ-ゥムをカ卩え、プレエマ ルジョンを 3時間にわたつて滴下した。  Add 312 parts by weight of deionized water and 2.3 parts by weight of Newcol 707SF (manufactured by Nippon Milky Co., Ltd., solid content: 30% by mass) to a 2-liter 4-neck flask, and maintain at 80 ° C after purging with nitrogen. Immediately before dropping a pre-margin with the following composition, 0.7 parts by mass of ammonium persulfate was added and pre-emulsion was dropped over 3 hours.
[0182] 脱イオン水 350質量部 [0182] 350 parts by weight of deionized water
ダイアセトンアクリルアミド 65質量部  65 parts by mass of diacetone acrylamide
アクリル酸 65質量部  65 parts by mass of acrylic acid
スチレン 98質量部  98 parts by mass of styrene
メチルメタタリレート 370質量部  Methyl metatalylate 370 parts by mass
2—ェチルへキシルアタリレート 52質量部  2-Ethylhexyl acrylate 52 parts by mass
Newcol707SF 60質量部  Newcol707SF 60 parts by mass
過硫酸アンモニゥム 1.2質量部  Ammonium persulfate 1.2 parts by mass
滴下終了後 30分より、 30分間 0.7質量部の過硫酸アンモニゥムを 7質量部の脱ィ オン水に溶力した溶液を滴下し、さらに 2時間 80°Cに保持し、その後約 50°Cに降温 した後、アンモニア水で pHを 8〜9の範囲内に調整し、固形分 50質量％、平均粒子 径 lOOnmのポリマー粒子 1のエマルシヨンを得た。  From 30 minutes after the completion of the dropwise addition, a solution of 0.7 parts by weight of ammonium persulfate dissolved in 7 parts by weight of deionized water is added dropwise for 30 minutes. After the temperature was lowered, the pH was adjusted within the range of 8 to 9 with aqueous ammonia, and an emulsion of polymer particles 1 having a solid content of 50% by mass and an average particle size of lOOnm was obtained.
[0183] 《平版印刷版材料の作製》 下記画像形成層塗布液をワイヤーバーを用いて乾燥付量が 0. 5g/m2になるよう に上記平版印刷版材料 3 (チタンモル比 3)で用いた親水層塗布液を塗布し形成した 親水性層上に塗布して 50°Cで 1分間乾燥したのちに、 50°Cで 24時間の加熱処理を 施して、幅 670mm、長さ 30. 5m卷回させ、下記表 2示す様に平版印刷版材料 6を 作製した。 [0183] << Preparation of planographic printing plate material >> The following image forming layer coating solution was formed by applying the hydrophilic layer coating solution used in the above lithographic printing plate material 3 (titanium molar ratio 3) to a dry weight of 0.5 g / m 2 using a wire bar. After coating on the adhesive layer and drying at 50 ° C for 1 minute, heat treatment was performed at 50 ° C for 24 hours, and the plate was rolled up to 670 mm in width and 30.5 m in length, as shown in Table 2 below. Printing plate material 6 was prepared.
[0184] 《感熱画像形成層塗布液の調製》  <Preparation of thermal image forming layer coating solution>
ポリマー粒子 1 (固形分 50%) 7. 5質量部  Polymer particles 1 (solid content 50%) 7.5 parts by mass
シァニン色素 1 (固形分 1%) 50. 0質量部  Cyanine dye 1 (solid content 1%) 50.0 parts by mass
ポリアクリル酸 Na (固形分 30%) 1. 17質量部  Polyacrylic acid Na (solid content 30%) 1.17 parts by mass
リン酸グァニジン（固形分 30%) 1. 17質量部  Guanidine phosphate (solid content 30%) 1. 17 parts by mass
純水 37. 33質量咅  Pure water 37.33 mass
[0185] [表 2]  [0185] [Table 2]
Figure imgf000038_0001
表 2から明らかなように、本発明の印刷版材料は、耐刷性、耐脱色性及び塗布性に お!、て優れて!/、ることが分かる。
Figure imgf000038_0001
As is apparent from Table 2, the printing plate material of the present invention is excellent in printing durability, decoloration resistance and coating property!

Claims

請求の範囲 The scope of the claims
[1] 基材上に少なくとも親水性層及び感熱画像形成層を有する平版印刷版材料にお いて、少なくとも該親水性層が光熱変換機能を有する顔料を含有し、かつ該顔料は [1] In a lithographic printing plate material having at least a hydrophilic layer and a heat-sensitive image forming layer on a substrate, at least the hydrophilic layer contains a pigment having a photothermal conversion function, and the pigment
、鉄およびチタンを成分として有し、その場合の組成モル比が鉄 1に対し、チタンが 1, With iron and titanium as components, in which case the compositional molar ratio of iron is 1 with respect to titanium
. 1〜6であることを特徴とする平版印刷版材料。 A lithographic printing plate material characterized by being 1-6.
[2] 前記顔料の磁化値が 0. 5〜10emuZgであることを特徴とする請求の範囲第 1項 に記載の平版印刷版材料。 [2] The lithographic printing plate material according to claim 1, wherein the pigment has a magnetization value of 0.5 to 10 emuZg.
[3] 請求の範囲第 1項又は第 2項に記載の平版印刷版材料を製造することを特徴とす る平版印刷版材料の製造方法。 [3] A method for producing a lithographic printing plate material, characterized in that the lithographic printing plate material according to claim 1 or 2 is produced.
[4] 請求の範囲第 1項又は第 2項に記載の平版印刷版材料及び温度 20°Cにおいて p[4] Lithographic printing plate material as claimed in claim 1 or 2 and p at 20 ° C
H4〜6. 5である湿し水を用いて印刷することを特徴とする印刷方法。 The printing method characterized by printing using the dampening water which is H4-6.5.
[5] 前記湿し水に含有される炭素数 2〜5のアルコールの含有量が 0. 1質量％以下で あることを特徴とする請求の範囲第 4項に記載の印刷方法。 [5] The printing method according to claim 4, wherein the content of the alcohol having 2 to 5 carbon atoms contained in the dampening water is 0.1% by mass or less.
PCT/JP2007/051680 2006-02-24 2007-02-01 Lithographic printing plate material, method for manufacturing the same, and printing method WO2007097169A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05139068A (en) * 1990-05-10 1993-06-08 Hoechst Ag Wetting water for offset printing
JP2002370465A (en) * 2001-06-14 2002-12-24 Konica Corp Printing plate material, method for forming image on printing plate material and method for printing
JP2004341289A (en) * 2003-05-16 2004-12-02 Fuji Photo Film Co Ltd Lithographic printing original plate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05139068A (en) * 1990-05-10 1993-06-08 Hoechst Ag Wetting water for offset printing
JP2002370465A (en) * 2001-06-14 2002-12-24 Konica Corp Printing plate material, method for forming image on printing plate material and method for printing
JP2004341289A (en) * 2003-05-16 2004-12-02 Fuji Photo Film Co Ltd Lithographic printing original plate

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