EP1543899A2 - Substrat aus Aluminium-Legierung für lithographische Druckplatten und Verfahren zu seiner Herstellung - Google Patents

Substrat aus Aluminium-Legierung für lithographische Druckplatten und Verfahren zu seiner Herstellung Download PDF

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Publication number
EP1543899A2
EP1543899A2 EP04078437A EP04078437A EP1543899A2 EP 1543899 A2 EP1543899 A2 EP 1543899A2 EP 04078437 A EP04078437 A EP 04078437A EP 04078437 A EP04078437 A EP 04078437A EP 1543899 A2 EP1543899 A2 EP 1543899A2
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EP
European Patent Office
Prior art keywords
weight
support
printing plate
aluminium
graining
Prior art date
Legal status (The legal status 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 status listed.)
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EP04078437A
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English (en)
French (fr)
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EP1543899A3 (de
Inventor
Ronaldus Johannes Theodor Hermanus Wiegers
Toshiyuki Sekiya
Sipke Jan Koopmans
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Fujifilm Manufacturing Europe BV
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Fujifilm Manufacturing Europe BV
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Priority claimed from EP03079025A external-priority patent/EP1543898A1/de
Application filed by Fujifilm Manufacturing Europe BV filed Critical Fujifilm Manufacturing Europe BV
Priority to EP04078437A priority Critical patent/EP1543899A3/de
Publication of EP1543899A2 publication Critical patent/EP1543899A2/de
Publication of EP1543899A3 publication Critical patent/EP1543899A3/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
    • B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0605—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two belts, e.g. Hazelett-process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0622—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two casting wheels
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B1/30—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a non-continuous process
    • B21B1/32—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a non-continuous process in reversing single stand mills, e.g. with intermediate storage reels for accumulating work
    • B21B1/36—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a non-continuous process in reversing single stand mills, e.g. with intermediate storage reels for accumulating work by cold-rolling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B2003/001—Aluminium or its alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B3/003—Rolling non-ferrous metals immediately subsequent to continuous casting, i.e. in-line rolling
    • 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
    • B41M2205/12—Preparation of material for subsequent imaging, e.g. corona treatment, simultaneous coating, pre-treatments

Definitions

  • the present invention relates to a method of producing a support for lithographic printing plates and more particularly relates to a method of producing an aluminium support which is superior for the production of digitally imageable lithographic printing plates (computer-to-plate imaging).
  • the invention also relates to plates obtainable by that method.
  • EP-A-1 162 063 describes a positive acting IR-sensitive lithographic printing plate, based on a xylenol containing novolak.
  • distinction between the image and the non-image part of the printing plate is made based upon the increase in dissolution speed of the novolak containing coating layer in the developing liquid when this coating layer is exposed with infra-red radiation.
  • EP-A-0 672 954 describes a negative working IR-sensitive lithographic printing plate.
  • the image is being formed through heat-induced insolubilisation of the coating layer.
  • This type of plate usually requires a heating step between the IR-light exposure and the development step, in order to enhance the difference in dissolution speed between the image and the non-image area in the developer liquid.
  • Photopolymer plates generally contain a polymerizable monomer, a binder, a photoinitiator and a sensitising dye.
  • EP-A-0 985 683 describes a composition comprising a titanocene compound as a photoinitiator in a photopolymerizable composition that hardens upon exposure to light.
  • specific dyes By using specific dyes, the spectral sensitivity of the plate can be changed.
  • a wide range of dyes for the wavelength range from 300 to 1200 nm is disclosed in EP-A-1 091 247.
  • DTR process The principle of the silver complex diffusion transfer process (hereinafter referred to as DTR process) is well known, see e.g. US-A-2 352 014 and "Photographic Silver Halide Diffusion Processes" by Andre Rott and Edith Weyde--The Focal Press--London and New York, (1972).
  • the silver complex is imagewise transferred by diffusion from a silver halide emulsion layer to an image receptive layer and transformed therein into a silver image generally in the presence of physical development nuclei.
  • the imagewise exposed silver halide emulsion layer is arranged so as to be in contact with or is brought into contact with the image receptive layer in the presence of a developing agent and a solvent for the silver halide, thereby to convert the unexposed silver halide into a soluble silver complex.
  • the silver halide is developed into silver which is insoluble and, hence, cannot diffuse.
  • the silver halide In the unexposed areas of the silver halide emulsion layer, the silver halide is converted into a soluble silver complex and is transferred to an image receptive layer wherein the silver complex forms a silver image generally in the presence of physical development nuclei.
  • One means of reducing problems with the above mentioned poor development latitude is to lower the surface roughness of the roughened aluminium substrate. This may be done by omitting the usual mechanical graining process from the normal sequence of lithographic printing plate production or adjusting the settings of said process. In most cases this is sufficient to generate a plate which has sufficient development latitude to be practically usable.
  • Conventional aluminium alloy substrates as a support for a lithographic printing plate are generally provided in the form of a 0.1 to 0.5 mm thick cold-rolled sheet made of an aluminium alloy such as JIS A1050, A1100, A3003, or the like.
  • Such aluminium alloy cold-rolled sheets are generally produced by machining the surface of a semi-continuous-cast Direct Chill (DC) slab or billet, homogenisation heat-treating the billet when necessary, heating the billet to a selected temperature, hot-rolling the heated billet to a hot-rolled strip, cold-rolling the hot-rolled strip with an optional intermediate annealing between the cold rolling passes when necessary, and final cold rolling the strip to a cold-rolled sheet.
  • DC Direct Chill
  • An alternative method for the preparation of an aluminium support for lithographic printing plates is continuously supplying molten aluminium metal to cooled rollers or to a cooled belt, thus yielding a strip of aluminium. This method is also known as continuous casting (CC).
  • EP-A-0 415 238 and EP-A-0 615 801 describe the usage of this method for the manufacturing of conventionally imageable lithographic printing plates.
  • aluminium based lithographic printing plates that are digitally imageable so that they are suitable for computer to plate application, which plates have a good developable latitude and a low amount of defects. It has been found that such plates can be produced by a process comprising the step of continuous casting of molten aluminium.
  • the present invention is directed to a process for producing a digitally imageable lithographic printing plate, comprising forming a support by carrying out the subsequent steps of: continuously casting molten aluminium to form a strip having a thickness less than 30 mm; cold rolling said strip to form a plate; optionally a heat treatment step of said plate; correction of the plate; and mildly graining said plate; followed by providing a digitally imageable coating on said support, whereby said printing plate is obtained.
  • the continuous aluminium casting process provides for a support that is exceptionally suitable for providing plates for digitally imageable lithographic printing processes.
  • a further object of the invention is to provide a digitally imageable lithographic printing plate, comprising a support and a digitally imageable coating, which support may be prepared by the above-mentioned process of continuously casting molten aluminium to form a strip having a thickness less than 30 mm, followed by cold rolling, optional heat treatment, correction of the plate and then graining the aluminium support.
  • the support for the plates of the present invention have an average surface roughness R a of between 0.1 and 0.7 ⁇ m.
  • graining step means that the mechanical graining step, if carried out is carried out such that the average surface roughness R a of the resulting plates is less than 0.7 ⁇ m, preferably below 0.5 ⁇ m and more preferably below 0.4 ⁇ m.
  • any substantial mechanical surface graining is omitted in the preparation process of the supports for the plates of the present invention. It was found that in this way supports having a surface roughness that makes them very suitable for the applications of the present invention can be produced.
  • a digitally imageable lithographic offset plate is provided by a process comprising the steps of continuous casting molten aluminium so as to directly form a plate from the molten aluminium, cold-rolling and optionally heat-treating the plate to obtain an aluminium support, correction of the aluminium support, and surface-graining the aluminium support where the surface graining comprises an electrochemical graining process in dilute nitric acid, resulting in a support that has a centre line average surface roughness R a of less than 0.4 micrometer or in dilute hydrochloric acid, resulting in a support that has a centre line average surface roughness R a of less than 0.6 micrometer.
  • the supports thus produced are also excellent for use as supports for plates according to the present invention.
  • the supports prepared with the process in accordance with the present invention may be used to prepare printing plates. These plates are thus based on a support having a good developable latitude and a low amount of defects, which makes them structurally different from the plates known from the prior art.
  • a suitable method for continuously cast rolling a tabular plate directly from molten aluminium alloy is a method employing a cooling belt, such as the Hazelett method or a method employing a cooling roller, such as the Hunter method and the 3C method. Since the Hazelett method continuously casts a thick plate, a hot rolling is subsequently conducted to make the thickness reelable. On the other hand, since the Hunter method or the 3C method makes it possible to directly cast a plate having the thickness of 10 mm or lower, a hot rolling machine is not necessary.
  • JP-A-60-238001, JP-A-60-240360, and other publications disclose a method for preparing a coil of thin sheet. A twin roller continuous casting method, such as the Hunter method, is preferred.
  • the molten aluminium alloy is rapidly cooled by the continuous casting.
  • the reference number 1 refers to a melt holding furnace in which an aluminium ingot is melted and retained.
  • the molten aluminium is then fed to a twin-roller continuous casting machine 2, then wound on coiler 3.
  • a continuous casting method using a cooling belt and a hot rolling may be applied, as shown schematically in Fig. 1(B).
  • the coil wound on coiler 3 is cold rolled to a thin plate of 0.3 to 3.0 mm thickness using a cold rolling machine 4.
  • an intermediate annealing may be conducted using heating machine 5 when necessary.
  • heating (annealing) machine 5 there are various types, such as a batch type, a continuous annealing type or an induced heating type.
  • the temperature is elevated at a rate of 0.5 °C/sec or more and the preferred temperature is 300 °C or more.
  • the resulting thin plate is rolled again to a thickness of 0.1 to 0.5 mm using a cold rolling machine.
  • correction is conducted using correcting machine 6.
  • the correction may be conducted together with a finishing rolling.
  • a suitable alloy composition is as follows.
  • the preferred Fe content in the alloy is between 0.15 and 0.50 weight%, more preferably between 0.22 and 0.26 weight%.
  • the Fe content is less than 0.15 weight%, mechanical strength of the sheet may become insufficient.
  • Fe content is more than 0.50 weight%, electrical graining structure may become uneven.
  • the preferred Si content is between 0.05 and 0.20 weight%, more preferably between 0.10 and 0.18 weight%. When the Si content is less than 0.05 weight%, response to electrical graining becomes weak. When the Si content is more than 0.20 weight%, toning characteristics of the printing plate may become unacceptable.
  • the preferred Cu content is between 0.005 and 0.040 weight%, more preferably between 0.005 and 0.025 weight%.
  • Cu content is less than 0.005 weight%, response to electrical graining becomes weak.
  • Cu content is more than 0.040 weight%, resulting electrical graining structure becomes too coarse leading the printing plate having worse toning characteristic.
  • the support for lithographic printing plate according to the present invention preferably no mechanical graining is used. It is important to obtain a low surface roughness in the case of digitally imageable lithographic printing plates, since this provides for a correspondingly good development latitude.
  • Mechanical graining can be used when executed under mild conditions. Examples of mechanical graining methods include ball graining, wire graining, brush graining, and liquid honing.
  • electrochemical graining is used, preferably in the substantial absence of any mechanical graining.
  • electrochemical graining method there is normally used AC electrolytic etching method.
  • electric current there is used a normal alternating current such as sine waveform or a special alternating current such as square waveform, and the like.
  • etching may be conducted, for example with caustic soda.
  • electrochemical graining is conducted, it is preferably conducted with an alternating current in an aqueous solution comprising hydrochloric acid or nitric acid.
  • aqueous solution comprising hydrochloric acid or nitric acid.
  • the aluminium support Prior to the electrolytical graining, the aluminium support is etched with an alkaline agent.
  • alkaline agents include caustic soda, caustic potash, sodium metasilicate, sodium carbonate, sodium aluminate, sodium gluconate, etc.
  • concentration of the alkaline agent, the temperature of the alkaline agent and the etching time are preferably selected from 0.01 to 25%, 20 to 90 °C and 5 sec. to 5 min., respectively.
  • the preferred etching rate is in the range of 0.1 to 15 g/m 2 .
  • the aluminium plate is preferably subsequently subjected to AC electrolytic etching in an electrolyte mainly composed of hydrochloric acid or nitric acid.
  • the frequency of the AC electrolytic current is suitably in the range of 0.1 to 100 Hz, preferably 0.1 to 1.0 Hz or 10 to 60 Hz.
  • the concentration of dissolved aluminium in the etching solution is suitably in the range of 3 to 150 g/dm 3 , preferably 5 to 50 g/ dm 3 .
  • the solubility of aluminium in the etching bath is preferably in the range of not more than 50 g/ dm 3 , more preferably 2 to 20 g/ dm 3 .
  • the etching bath may contain additives as necessary. However, in mass production, it is difficult to control the concentration of such an etching bath.
  • the electric current density in the etching bath is preferably in the range of 5 to 100 A/dm 2 , more preferably 10 to 80 A/dm 2 .
  • the waveform of electric current can be properly selected depending on the required quality and components of aluminium support used, but the waveform is preferably the special alternating waveform described in US-A-4 087 341 (corresponding to JP-B-56-19280) and JP-B-55-19191. (The term "JP-B" as used herein means an "examined Japanese patent publication").
  • the waveform of electric current and the liquid conditions are properly selected depending on required electricity as well as required quality and components of aluminium support used.
  • the aluminium plate which has been subjected to electrolytic graining is then preferably subjected to dipping in an alkaline solution as a part of desmutting treatment to dissolve smuts away.
  • an alkaline agent there may be used caustic soda or the like.
  • the desmutting treatment is preferably effected at a pH value of not lower than 10 and a temperature of 25 to 60 °C for a dipping time as extremely short as 1 to 10 seconds.
  • the aluminium plate thus etched is then suitably dipped in a solution mainly composed of sulfuric acid.
  • the sulfuric acid solution is in the concentration range of 50 to 400 g/l, and the temperature range of 20 to 70 °C. If the concentration of sulfuric acid is more than 400 g/l or the temperature of sulfuric acid is more than 70 °C, the processing bath is more liable to corrosion. Further, if the aluminium plate is etched by more than 0.4 g/m 2 , the printing durability may be reduced. Thus, the etching rate is preferably controlled to not more than 0.4 g/m 2 , more preferably not more than 0.2 g/m 2 .
  • the aluminium plate preferably forms an anodised film thereon in an amount of 0.1 to 10 g/m 2 , more preferably 0.3 to 5 g/m 2 .
  • the anodising conditions vary with the electrolyte used and thus are not specifically determined. In general, it is appropriate that the electrolyte concentration is in the range of 1 to 80% by weight, the electrolyte temperature is in the range of 5 to 70 °C, the electric current density is in the range of 0.5 to 60 A/dm 2 , the voltage is in the range of 1 to 100 V, and the electrolysis time is in the range of 1 second to 5 minutes.
  • the grained aluminium plate having an anodised film thus obtained is stable and excellent in hydrophilicity itself and thus can directly be provided with a heat- or photosensitive coating thereon. If necessary, the aluminium plate may be further subjected to a surface treatment.
  • a silicate layer formed by the meta silicate of alkaline metal or an undercoating layer formed by a hydrophilic polymeric compound may be formed on the aluminium plate.
  • the surface roughness of the support obtained according to the present invention is of importance, since a too high surface roughness of the support will lead to a poor development latitude.
  • the surface roughness is suitably measured according to JIS B060.
  • the stylus radius for measurements of surface roughness R a is typically 5 ⁇ m, and with this stylus, the following limits have been established.
  • the centre line average surface roughness Ra of the thus obtained support has a value of 0.2 - 1.0 ⁇ m.
  • the surface roughness is preferably 0.15 - 0.40 ⁇ m when nitric acid is used in the electrolytical graining process. In the case hydrochloric acid is used in the electrolytical graining process, the preferred centre line average surface roughness R a lies between 0.40 and 0.65 ⁇ m.
  • an undercoating layer Before applying the main coating layer, an undercoating layer may be applied.
  • the coating amount of the undercoating layer is preferably in the range of 5 to 150 mg/m 2 .
  • a heat- and/or light sensitive coating is then formed on the aluminium plate thus treated.
  • This heat or photosensitive coating can be positive or negative working.
  • the heat- or light sensitive coating can be sensitive for electromagnetic radiation with a wavelength ranging between 380 and 1100 nm.
  • Specific wavelengths of laser diodes or solid state lasers that can be used for the imagewise exposure of the lithographic printing of the present invention include 405 nm (violet laser), 488 nm (Ar-ion laser), 532 nm (FD-YAG laser), 633 (He-Ne laser), 670, 675, 680 nm (red laser diodes), 760, 780 nm (IR laser diodes), 830 nm (IR laser), 1064 nm (YAG-laser).
  • Examples of the photosensitive coating for digitally imageable lithographic offset plates for which the present invention is useful are: negative working photopolymerizable systems, comprising one or more photoinitiators and mono- and/or oligomers; negative working thermal printing plates; positive working thermal printing plates; printing plates based on the silver salt diffusion transfer process; and the like.
  • the thus obtained lithographic printing plate precursor may then be imagewise exposed to digitally controlled (laser) light.
  • the plate After exposure, the plate can be subjected to a heat treatment if the nature of the printing plate requires so.
  • the plate can be developed in a developing liquid.
  • This liquid can be an aqueous alkaline solution, but also other solutions are known in the art.
  • the resulting plate has almost no copper defects, while the development latitude is excellent.
  • an aluminium strip (alloy AA1050) having a thickness of 5.0 mm was formed and coiled.
  • the strip was cold rolled to a thickness of 2.2 mm, then annealed at 380 °C for 4 hours, and further cold rolled to form a test material of a thickness of 0.278 mm.
  • the molten aluminium alloy had the following composition:
  • the thus produced aluminium strip was etched with a 25% aqueous solution of sodium hydroxide at 50 °C such that the etched amount was 5 g/m 2 .
  • the strip was immersed in an aqueous sulphuric acid of 180 g/dm 3 at 50 °C during 20 seconds to desmut the strip, and the strip was washed with water.
  • the support was electrochemically grained in 9 g/dm 3 of an aqueous nitric acid solution using the alternating (wave form) electric current described in Japanese Patent No. JP-B-55-19191).
  • An anode surface oxide coating of 2.5 g/m 2 was formed on the support in a 20% sulfuric acid, and then dried. Furthermore a silicate layer was formed on the surface by dipping in an 2.5 wt% aqueous sodium metasilicate solution at 25 °C. After these steps, the centre line average surface roughness R a was measured and found to be 0.32 ⁇ m.
  • composition was coated on the support thus-prepared in a dry coated weight of 1.3 g/m 2 to provide a positive working, thermal photosensitive layer.
  • a lithographic offset plate imageable with a digitally controlled 830 nm laser and having a good development latitude can be obtained.
  • Cyanine dye A (having the structure shown below) 0.01 Megafac F177 manufactured by DAINIPPON INK & 0.05 CHEMICALS, INC. 20.1 Ethyl violet 2.7 Methyl ethyl ketone 1-Methoxy-2-propanol
  • Example 1 a lithographic offset plate was made with the exception, that before the electrolytic graining a coarse mechanical graining step was included, carried out with a nylon brush (No. 8) and an aqueous suspension of 800 mesh pumice stone. This mechanical graining step resulted in an average surface roughness Ra of 0.75 ⁇ m. This was followed by thorough rinsing with water. The development latitude of the resulting offset plate was found to be insufficient.
  • a substrate for lithographic offset plate was made with the following alloy composition: Al 99.2%, Fe 0.7 wt%, Si 0.2 wt%, Cu 0.010 wt%.
  • the appearance of the grained substrate was streaky, and not sufficient for usage as substrate for a lithographic printing plate.
  • a lithographic offset plate was made in the same way as described for Example 1 except, that hydrogen chloride was used as an electrolyte during electrochemical etching. A good development latitude and no copper defects were obtained.
  • Example 2 In the same way as for Example 2 a lithographic offset plate was manufactured but instead of a continuous cast coil a DC coil was used.
  • DC cast aluminium coils were prepared from an aluminium ingot through a process including melting, holding, slab casting, scalping and soaking. The aluminium was hot-rolled, cold-rolled, annealed, corrected and grained to yield a strip that was chemically and dimensionally comparable to the continuously cast strip that is mentioned above. The development latitude was poor.
  • a lithographic offset plate was manufactured in the same way as for Example 1 except, that a DC casted aluminium coil was used. The development latitude was good, but the defect level was too high.
  • An aluminium coil (grade 1050AA) was prepared by twin-roll continuous casting of molten aluminium alloy (composition Al 99.5 wt%, Fe 0.26 wt%, Si 0.14 wt%, Cu 0.020 wt%) into a strip of 6 mm thickness. This strip was then cold rolled, annealed at 520 °C during 8 hours, again cold rolled and corrected to yield a coil of 0.30 mm thickness. The thus obtained coil was etched by immersing in a 10% aqueous solution of sodium hydroxide at 70 °C during 60 seconds, followed by successively washing with running water, a 20% nitric acid solution for neutralization, and water.
  • the surface of the aluminium plate was then electrolytically roughened in a 1% aqueous solution of nitric acid by the application of an alternating current in the form of a sinusoidal wave at the applied voltage (Va) of 12.7 V.
  • the electrical charge was set to 300 C/dm at the anode side.
  • the surface roughness of the aluminium plate was measured and found to be 0.29 ⁇ m in terms of Ra units.
  • the aluminium plate was immersed in a 30% aqueous solution of sulfuric acid at 55 °C during 2 minutes to desmut the plate.
  • the aluminium plate was then anodised in a 20% aqueous solution of sulfuric acid at 33 °C during 50 seconds at a current density of 5 A/dm 2 , with the surface-grained surface of the aluminium plate serving as a cathode.
  • the result was that the anodised layer with a thickness of 2.7 g/m 2 was deposited on the anode.
  • the coating amount was measured to be 1.5 g/m 2 .
  • a topcoating containing 3% aqueous solution of polyvinyl alcohol with a degree of saponification of 98 mol% and a degree of polymerisation of 500 was coated on the photosensitive layer so that the coating amount was 2.5 g/m 2 on a dry basis and dried at 120 °C.
  • the coil was automatically inspected with an automated laser inspection system. On this coil, no copper related defects were found.
  • the thus obtained plate was exposed with a 532 nm FD-YAG laser ("PlateJet 4" (trademark), made by Cymbolic Sciences, Inc.) with an intensity of 100 mW.
  • a solid image and dot images With an increased dot percent from 1 to 99% by 1%) were subjected to scanning using the above-mentioned light sources at a density of 4000 dpi and 175 rays/inch.
  • each PS plate was subjected to development under the standard conditions using a commercially available automatic processor ("LP-850P2" (trade name), made by Fuji Photo Film Co., Ltd.) containing LP-DS, a developer for photopolymerizable plates commercially available from Fuji Photo Film Co, Ltd.. A good, solid image was obtained, and the non-image area was free from coating residues.
  • LP-850P2 commercially available automatic processor
  • Molten aluminium (AA1050, same alloy composition as Example 7) was cast according to the DC method into slabs of 450 mm x 1200 mm x 3500 mm. These slabs were subjected to 7 mm scalping per surface, soaking at 550 °C for 12 hours, and were then hot-rolled at 500 °C to produce a plate of 5 mm thickness. This plate was cold rolled, annealed at 520 °C for 8 hours, again cold rolled and corrected to yield a coil of aluminium of 0.30 mm thickness.
  • This coil was grained mechanically with a nylon brush (No. 8) and an aqueous suspension of 800 mesh pumice stone, followed by thorough rinsing with water.
  • the coil was etched, grained and anodised in the fashion of Example 7, yielding a substrate with a centre line average surface roughness R a of 0.60 ⁇ m.
  • a coil was produced in the fashion of Example 7, this time without applying the mechanical graining.
  • the centre line average surface roughness R a after the completion of the anodising step was 0.31 ⁇ m. Exposure and development showed a good image area and a clean non-image area.
  • An aluminium coil (grade AA1050, alloy composition as in Example 1) was prepared by twin-roll casting of molten aluminium alloy into a strip of 3 mm thickness. This strip was then cold rolled, annealed at 380 °C for 4 hours, again cold rolled and corrected to yield a coil of 0.15 mm thickness.
  • an etching and graining process was carried out comprising the steps of treatment with 20% sodium hydroxide solution at 70 °C which removes 5 g/m 2 of the surface, treatment with 20% nitric acid, electrolytic graining in a 1% hydrochloric acid solution, using a 12.7 V sinusoidal alternating current with a total charge application of 160 Cb/dm 2 , treatment with 30% sulfuric acid at 55 °C, and anodising in 20% sulfuric acid to yield an aluminium oxide layer of 2.7 g/m 2 .
  • the substrate was treated with a 5% 40 °C phosphoric acid solution during 30 seconds.
  • the centre line average surface roughness R a of the substrate was 0.45 ⁇ m.
  • a silver nuclei containing hydrosol was prepared in the following way: Solution A: Trisodium Citrate (40%) 3.5 g FeSO4 7H 2 O (30 wt%) 2.5 g Solution B: AgNO 3 (10%) 2.5 g
  • the solutions A and B were mixed after adding solution B to A at a rate of 100 cc/min.
  • the excess citrate, iron and sodium ions were removed by ultra-filtration, and an Ag-sol was obtained.
  • This Ag sol was coated onto the substrate obtained above, yielding a image acceptance layer containing 2 mg/m 2 Ag.
  • a silver-halide emulsion layer was prepared in the following way:
  • a silver nitrate solution containing 1.0 mol/dm 3 AgNO 3 and 3x10 -7 mol/l rhodium ammonium chloride was prepared.
  • a halide solution containing KBr (0.1 mol/l) and NaCl (0.9 mol/l) was prepared.
  • the silver nitrate and the halide solutions were added to a solution containing 0.1 mol/l NaCl, 5x10 -7 mol/l iridium hexachlorate, and 1x10 -4 mol/l 1,3-dimethyl-2-imidazolinethione, at 45 °C during 30 minutes in a double jet process under continuous agitation.
  • the size of the silver halide crystals was 0.28 ⁇ m, and the crystals contained 90 mol% of AgCl.
  • the crystals were flocculated according to a well-know method, and after rinsing gelatine was added. The emulsion was then adjusted to pH 6.5 and pAg 7.5. 5 mg sodium thiosulfate and 8 mg chloroauric acid were added per mol silver. The chemical sensitisation process was carried out for 60 minutes at 60 °C, using 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene as a stabilizer.
  • the thus obtained emulsion was coated onto the substrate carrying the Ag-nuclei, resulting in a silver content of 1.5 g/m 2 and a gelatine coated weight of 1.5 g/m 2 .
  • the thus obtained printing plate precursor of the diffusion transfer type (DTR) was exposed by a digitally controlled semiconductor laser with a wavelength of 670 nm, and developed at 21°C during 25 seconds in a developing solution of the following composition: Developing solution for DTR plates Amount Sodium Hydroxide 16 g Sodium Sulfate (anhydr) 140 g Hydroquinone 27 g 1-phenyl-1-methyl-3-pyrazolidinone 3.5 g Sodium Thiosulfate (anhydr) 13 g 2-methylaminoethanol 28 g Glycerol 54 g De-ionised water 1000 g
  • finishing solution for DTR plates Amount Gum Arabic (10% in water) 25 ml Polystyrene sulfonate (20% in water) 100 ml Citric acid 20 g 1-octyl-5-mercaptotetrazole 2 g Sodium Hydroxide 5.5 g Water 1000 g
  • the thus obtained printing plate was of good quality with regards to scumming of the non-image area and dot-quality, and 50000 copies could be obtained.
  • Molten aluminium (AA1050, alloy composition Al 99.55 wt%, Fe 0.23 wt%, Si 0.17 wt%, Cu 0.010 wt%) was cast according to the DC method into slabs of 450mm x 1200 mm x 3500 mm. These slabs were subjected to 7 mm scalping per surface, soaking at 550 °C for 12 hours, and were then hot-rolled at 500 °C to produce a plate of 5 mm thickness. This plate was cold rolled, annealed at 380 °C for 4 hours, again cold rolled and corrected to yield a coil of aluminium of 0.15 mm thickness.
  • the aluminium coil was mechanically grained by a nylon brush and a water suspension of pumice stone 400 mesh). Then, the etching and graining treatment of Example 10 was applied, yielding a centre line average surface roughness R a of 0.75 ⁇ m.
  • the thus obtained support was coated with the same photosensitive layers as described in Example 10.
  • the inspection of the coil showed a low number of copper related defects: 2/1000 m 2 .
  • a support was made in the same way as comparative Example 11, this time omitting the mechanical graining process.
  • the centre line average surface roughness R a obtained was 0.44 ⁇ m.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
EP04078437A 2003-12-17 2004-12-17 Substrat aus Aluminium-Legierung für lithographische Druckplatten und Verfahren zu seiner Herstellung Withdrawn EP1543899A3 (de)

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EP03079025 2003-12-17
EP04078437A EP1543899A3 (de) 2003-12-17 2004-12-17 Substrat aus Aluminium-Legierung für lithographische Druckplatten und Verfahren zu seiner Herstellung

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1837091A1 (de) * 2006-03-23 2007-09-26 Hydro Aluminium Deutschland GmbH Funktionale Direktbeschichtung einer Aluminiumfolie
WO2007107030A1 (de) * 2006-03-21 2007-09-27 Xpose Holding Ag Innentrommelbelichter
GB2461240A (en) * 2008-06-24 2009-12-30 Bridgnorth Aluminium Ltd Aluminium alloy for lithographic sheet
CN104264011A (zh) * 2014-09-30 2015-01-07 石家庄新日锌业有限公司 一种铝丝
EP1859954B2 (de) † 2006-05-25 2017-11-08 FUJIFILM Corporation Flachdruckplattenvorläufer und Stapel daraus
CN110802892A (zh) * 2019-11-25 2020-02-18 兰州理工大学 一种表面沉积铜原子的多层铝/铜复合板叠制方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0415238A2 (de) * 1989-08-22 1991-03-06 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung eines Trägers für Flachdruckplatten
EP0615801A1 (de) * 1993-03-09 1994-09-21 Fuji Photo Film Co., Ltd. Verfahren zum Herstellen eines Trägers für eine Flachdruckplatte
US5547522A (en) * 1992-11-20 1996-08-20 Fuji Photo Film Co., Ltd. Support for a planographic printing plate and method for producing same
EP1106381A1 (de) * 1999-12-09 2001-06-13 Fuji Photo Film Co., Ltd. Flachdruckplattenvorstufe
US20010018159A1 (en) * 2000-01-14 2001-08-30 Kazuo Maemoto Lithographic printing plate precursor
EP1293579A2 (de) * 2001-09-12 2003-03-19 Fuji Photo Film Co., Ltd. Flachdruckplattenträger und vorsensibilisierte Druckplatte
US20030194642A1 (en) * 2002-03-13 2003-10-16 Fuji Photo Film Co., Ltd. Presensitized plate
EP1486348A2 (de) * 2003-06-12 2004-12-15 Fuji Photo Film B.V. Substrat aus Aluminium-Legierung für lithographische Druckplatten und Verfahren zu seiner Herstellung

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0415238A2 (de) * 1989-08-22 1991-03-06 Fuji Photo Film Co., Ltd. Verfahren zur Herstellung eines Trägers für Flachdruckplatten
US5547522A (en) * 1992-11-20 1996-08-20 Fuji Photo Film Co., Ltd. Support for a planographic printing plate and method for producing same
EP0615801A1 (de) * 1993-03-09 1994-09-21 Fuji Photo Film Co., Ltd. Verfahren zum Herstellen eines Trägers für eine Flachdruckplatte
EP1106381A1 (de) * 1999-12-09 2001-06-13 Fuji Photo Film Co., Ltd. Flachdruckplattenvorstufe
US20010018159A1 (en) * 2000-01-14 2001-08-30 Kazuo Maemoto Lithographic printing plate precursor
EP1132200A2 (de) * 2000-01-14 2001-09-12 Fuji Photo Film Co., Ltd. Lithographische Druckplattenvorstufe
EP1293579A2 (de) * 2001-09-12 2003-03-19 Fuji Photo Film Co., Ltd. Flachdruckplattenträger und vorsensibilisierte Druckplatte
US20030194642A1 (en) * 2002-03-13 2003-10-16 Fuji Photo Film Co., Ltd. Presensitized plate
EP1486348A2 (de) * 2003-06-12 2004-12-15 Fuji Photo Film B.V. Substrat aus Aluminium-Legierung für lithographische Druckplatten und Verfahren zu seiner Herstellung

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007107030A1 (de) * 2006-03-21 2007-09-27 Xpose Holding Ag Innentrommelbelichter
KR101017545B1 (ko) * 2006-03-21 2011-02-28 엑스포제 홀딩 아게 내부 드럼 이미지 세터
CN101406033B (zh) * 2006-03-21 2012-08-08 Xpose控股有限公司 内滚筒式图像集成机
EP1837091A1 (de) * 2006-03-23 2007-09-26 Hydro Aluminium Deutschland GmbH Funktionale Direktbeschichtung einer Aluminiumfolie
EP1859954B2 (de) † 2006-05-25 2017-11-08 FUJIFILM Corporation Flachdruckplattenvorläufer und Stapel daraus
GB2461240A (en) * 2008-06-24 2009-12-30 Bridgnorth Aluminium Ltd Aluminium alloy for lithographic sheet
CN104264011A (zh) * 2014-09-30 2015-01-07 石家庄新日锌业有限公司 一种铝丝
CN110802892A (zh) * 2019-11-25 2020-02-18 兰州理工大学 一种表面沉积铜原子的多层铝/铜复合板叠制方法

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