WO2007097169A1 - materiau de plaque lithographique, procede de production et procede d'impression - Google Patents

materiau de plaque lithographique, procede de production et procede d'impression Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
acid
printing
mass
printing plate
plate material
Prior art date
Application number
PCT/JP2007/051680
Other languages
English (en)
Japanese (ja)
Inventor
Kazuyoshi Suzuki
Original Assignee
Konica Minolta Medical & Graphic, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Medical & Graphic, Inc. filed Critical Konica Minolta Medical & Graphic, Inc.
Publication of WO2007097169A1 publication Critical patent/WO2007097169A1/fr

Links

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!

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention a pour objet un matériau de plaque lithographique qui possède d'excellentes propriétés en termes d'aptitude à l'enduction, de résistance à l'eau de mouillage et à la décoloration après développement, tout en présentant une durabilité d'impression élevée, et qui convient à un développement sur machine à imprimer, un procédé de production dudit matériau et un procédé d'impression. Le matériau de plaque lithographique comprend un matériau de base et au moins une couche hydrophile et une couche de formation d'image thermique recouvrant le matériau de base, il est caractérisé en ce qu'au moins la couche hydrophile contient un pigment exerçant une fonction de conversion photothermique, le rapport molaire de la composition du pigment étant fer : titane = 1 : 1,1 à 6.
PCT/JP2007/051680 2006-02-24 2007-02-01 materiau de plaque lithographique, procede de production et procede d'impression WO2007097169A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006048118 2006-02-24
JP2006-048118 2006-02-24

Publications (1)

Publication Number Publication Date
WO2007097169A1 true WO2007097169A1 (fr) 2007-08-30

Family

ID=38437208

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/051680 WO2007097169A1 (fr) 2006-02-24 2007-02-01 materiau de plaque lithographique, procede de production et procede d'impression

Country Status (1)

Country Link
WO (1) WO2007097169A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05139068A (ja) * 1990-05-10 1993-06-08 Hoechst Ag オフセツト印刷用湿し水
JP2002370465A (ja) * 2001-06-14 2002-12-24 Konica Corp 印刷版材料、印刷版材料の画像形成方法及び印刷方法
JP2004341289A (ja) * 2003-05-16 2004-12-02 Fuji Photo Film Co Ltd 平版印刷版原版

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05139068A (ja) * 1990-05-10 1993-06-08 Hoechst Ag オフセツト印刷用湿し水
JP2002370465A (ja) * 2001-06-14 2002-12-24 Konica Corp 印刷版材料、印刷版材料の画像形成方法及び印刷方法
JP2004341289A (ja) * 2003-05-16 2004-12-02 Fuji Photo Film Co Ltd 平版印刷版原版

Similar Documents

Publication Publication Date Title
US20090095184A1 (en) Negative working, heat-sensitive lithographic printing plate precursor
JP2006150605A (ja) プロセスレス印刷版材料を用いた印刷方法
JP4244757B2 (ja) ロール状に巻回された形態で市場に流通される機上現像型印刷版材料
WO2007097169A1 (fr) materiau de plaque lithographique, procede de production et procede d'impression
JP2006321089A (ja) 平版印刷方法および湿し水
JP2006321090A (ja) 平版印刷方法および湿し水
JP2006327136A (ja) 平版印刷方法
EP1208974B1 (fr) Plaque d'impression lithographique sans traitement
JP2005288931A (ja) 平版印刷版材料、画像記録方法及び印刷方法
US20080118859A1 (en) Planographic Printing Plate Material and Planographic Printing Process
JP2006231597A (ja) 印刷版材料の製版方法、印刷版材料および印刷方法
JP2006341483A (ja) 平版印刷版材料及びそれを用いた印刷方法
JP2006192832A (ja) 平版印刷方法及び平版印刷機
JP2007105902A (ja) 印刷版材料とそれを用いた印刷方法
JP2006181802A (ja) 平版印刷方法及び平版印刷機
JP2006231730A (ja) 印刷版材料および印刷方法
JP2005067014A (ja) 平版印刷版材料、画像記録方法、印刷版作製方法および印刷方法
JP2005231231A (ja) 印刷版材料
JP2009172855A (ja) 平板印刷版の製造方法、平版印刷版材料の露光方法、及び印刷方法
JP2009258348A (ja) 平版印刷版材料、平版印刷版材料の処理方法、および、平版印刷版の作製方法
JP2005305741A (ja) 平版印刷版材料及び平版印刷版、並びにそれを用いた印刷方法
JP2008149467A (ja) 平版印刷版材料および印刷方法
JP2007079110A (ja) 平版印刷版用の修正ペン及び平版印刷版材料の修正方法
JP2007196418A (ja) 平版印刷版材料の製造方法及び平版印刷版材料
JP2007015242A (ja) 印刷版材料及び印刷方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07707866

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP