US3902976A - Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like - Google Patents

Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like Download PDF

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US3902976A
US3902976A US510909A US51090974A US3902976A US 3902976 A US3902976 A US 3902976A US 510909 A US510909 A US 510909A US 51090974 A US51090974 A US 51090974A US 3902976 A US3902976 A US 3902976A
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Prior art keywords
aluminum
plate
web
plates
webs
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US510909A
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John E Walls
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S O Litho Corp
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S O Litho Corp
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Priority to US510909A priority Critical patent/US3902976A/en
Priority to FR7516704A priority patent/FR2286714A1/fr
Priority to GB2826075A priority patent/GB1461566A/en
Priority to CA231,868A priority patent/CA1056762A/en
Priority to DE19752532769 priority patent/DE2532769A1/de
Priority to JP50090998A priority patent/JPS5146206A/ja
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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
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B41N3/034—Chemical or electrical pretreatment characterised by the electrochemical treatment of the aluminum support, e.g. anodisation, electro-graining; Sealing of the anodised layer; Treatment of the anodic layer with inorganic compounds; Colouring of the anodic layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/04—Etching of light metals

Definitions

  • ABSTRACT A process for electrolytically forming on an aluminum or aluminum alloy sheet or plate a protective layer of film which is corrosionand abrasion-resistant and provided with a hydrophilic surface.
  • the process consists in first anodizing the aluminum or aluminum alloy sheet or plate in an electrolyte consisting of an aqueous solution of a mineral acid such as to form on the aluminum or aluminum alloy surface an aluminum oxide film, and subsequently electrolytically treating the film in an aqueous solution of sodium silicate, such as to form a durable abrasion-resistant and corrosionresistant barrier layer on the sheet or plate of aluminum or alluminum alloy which is hydrophilic and which prevents deterioration of a light sensitive diazo resin, or the like, placed as a photosensitive coating on the sheet or plate so as to form a presensitized lithographic plate.
  • the present invention belongs to the field of methods and processes for forming on the surface of aluminum and aluminum alloy metallic elements a protective layer which is corrosion and abrasion resistant, which acts as a barrier layer preventing spontaneous interreaction between the material of the elements and a coat ing disposed thereon, and which is endowed with specific physical characteristics or qualities different from those of the base material.
  • products obtained by way of the present invention have a general usefulness as a result of being provided with a corrosion, abrasion and electrical resistant surface film, they are particularly useful as support members for photolitho graphic plates and the like, and more particularly presensitized lithographic plates.
  • the protective surface layer is obtained by a two-step anodic electrolytic process.
  • Photolithographic plates currently in use today often include a metallic support member having, for example, aluminum as its principal component, a surface of which has been silicated by chemical or electrochemical methods to provide a barrier layer which prevents interreaction between the photosensitive diazonium salts, or other photosensitive and non-photosensitive coatings, placed upon the support member and the metal surface of the support member. Silication of the metal surface provides a chemical pacification which increases the shelf life of the lithographic plate, facilitates the processing of the plate after exposure, and improves the length of printing run and the quality of print.
  • Thc barrier layer is obtained, according to the prior art, by subjecting the metallic surface to the action ofa solution of one or several of a plurality of compounds, examples of which include hydrolized cellulose ester, sodium phosphate glass, alkali metal silicates, sodium metaborate, phosphomolybdate, sodium silicate, silicomolybdate, water'soluble alkylated methylomelamine formaldehyde, polyalkylene-polyamime-melamine-formaldehyde resins, urea-formaldehyde resin plus polyamide, polyacrylic acid, polymethacrylic acid, sodium salts of carboxymethylcellulose, carboxymethyl-hydroxyethylcellulose, zirconium hexafluoride, etc.
  • hydrolized cellulose ester sodium phosphate glass
  • alkali metal silicates sodium metaborate
  • phosphomolybdate sodium silicate
  • silicomolybdate water'soluble alkylated methylomelamine formaldehyde
  • An often used solution in the prior art is an aqueous solution of sodium silicate in which the metallic plate, forming the lithographic plate support member, is dipped, or which is applied to a surface of the plate
  • the solution is preferably heated before dipping the plate therein and before applying to the surface of the plate, and the plate surface is optionally washed with an acidic medium in order to harden the silicated surface and neutralize any alkali that may remain on the surface.
  • the silicated surface forms a hydrophilic surface which partially acts as an initial water-carrying surface when the processed plate is placed in a printing press.
  • the hydrophilic surface thus formed is desirably relatively insoluble in the fountain solutions used in a printing press in order to prevent undercutting or hydration of the image areas.
  • Al A10 SiO (Al SiO )2x The aluminum silicate surface layer thus formed is substantially insoluble, although it may be dissolved to some extent is strong reagents, and it has been postulated that it is in the form of large super crystals having an endless chain-like structure as follows:
  • aluminum silicate in addition to aluminum silicate, other compounds may be formed and included in the surface layer, which often result in differences in the qualities of the surface layer.
  • Some of the compounds that may be present in the film of aluminum silicate including Al- (OI-I) hydrated A1 0 and hydrated sodium aluminum silicate, such as, for example Na- O.Al. O .2SiO- .6- H O, could present varied degrees of solubility in fountain solutions used on printing presses.
  • varied cations such as Ca, Mg, etc., they may also form complex double silicates with the alumi num, which may cause further loss in quality of the formed layer.
  • Silication of aluminum plates by the processes of the prior art requires control of the purity of the solution and of the process variables as closely as feasible, such process variables being the pH of the solution, the duration of the operation, the amount of grain of the plate, the plate surface cleanliness, the degreasing or desmutting processes utilized, etc. If all the process variables are closely controlled in the prior art processes, it is possible to obtain silicated aluminum plates of acceptable quality for use as support members for photolithographic plates.
  • the most important of the desirable qualities to be achieved consist in an adequate chemically inert surface layer which does not deteriorate with age and is uniform and well bonded to the aluminum base material and which protects the aluminum surface in such manner that it is prevented from interreacting with the acidic diazo resin and will be only slowly etched by the acidic fountain solutions, and in providing an appropriate anchorage for the light exposed diazo resin which permits the developing lacquer to build up on the image area and to supply long lasting oleophilicity to the image areas, thus insuring long runs of the plates in the printing press.
  • Such qualities are difficult to obtain in a repetitive manner by way of the chemical processes of the prior art.
  • the invention disclosed in said patent provides an electrolytic process for forming on the surface of a metallic plate, such as is generally used as a support member for a coating of diazonium salts or the like in photo- Iithographic plates, a pacified, corrosion-resistant, hydrophilic surface layer greatly enhancing lithographic and printing performances as compared to the surface layer obtained by strictly chemical processes.
  • silication obtained by prior art chemical methods provides a barrier layer between the metallic plate and the diazonium salt compounds or the like utilized as the I photosensitive coating in photolithographic plates,
  • electrolytically formed surface layers are much improved as far as lithographic hardness, and continuity and uniformity of the layers or films are concerned.
  • the electrolytic process of said patent also produces surface layers which are intimately bonded to the underlying metal, which have high hydrophilic qualities and which result in an important improvement in the fine grain of the plate surface.
  • the electrolytically formed surface layer has a much improved anchoring quality for adhesion of the diazo resin thus re ducing any tendency to image failure and resulting in improved printing runs.
  • the improved surface grain and the increase in bonding quality of the electrolytically treated surface also result in more retained diazo, more retained lacquer and a more oleophilic image, leading to longer running and higher quality press performances, as compared to conventional lithographic plates.
  • the advantages provided by the surface treatment obtained by the method of the present invention relative to photolithographic plates and printing press cylinder, rollers and other support members are less propensity to attack from the printing press fountain solutions, a marked decrease in soluble film remaining on the lithographic plate after rinsing, improved hydrophilic quality of the plate background surface, a lithographically harder surface and a decrease in deterioration of the plate as a result of wear.
  • the hard, compact surface film-or layer obtained by the present invention on the surface of aluminum or aluminum alloy elements because of its corrosion-resistant characteristics, its bonding and anchoring qualities with respect to decorative or protective films which may subsequently be applied thereto and the increase in electrical resistivity as compared to the resistivity of the base material, presents the added advantage of providing articles having general usefulness in the industry.
  • the present invention therefore is an improvement upon the method disclosed in US. Pat. No. 3,658,662 which consists in electrolytically anodizing a sheet or plate of aluminum or aluminum alloy in an acidic electrolyte so as to provide on the surface of the sheet or plate a film of aluminum oxide which after being subjected to a further anodic treatment in an electrolyte bath of an alkaline metal salt, such as sodium silicate, provides an effective barrier film, an anchoring surface for paint, varnish and the like, or for a coating of photosensitive material when the sheet or plate is used as a support member for a lithographic plate.
  • an alkaline metal salt such as sodium silicate
  • FIG. 1 is a schematic representation of an example of arrangement for practicing the electrolytic process of the present invention
  • FIG. 2 is a schematic representation of a modification thereof
  • FIG. 3 is a schematic representation of a further modification thereof
  • FIG. 4 is a schematic representation of a further modification thereof
  • FIG. 5 is a schematic representation of a continuous line process for manufacturing a photolithographic plate according to the present invention.
  • FIG. 6 is a view similar to FIG. 5 but showing a modification of the method for manufacturing photolithographic plates according to the present invention
  • FIG. 7 is a schematic sectional view of an aluminum or aluminum alloy plate having been subjected to the process of the invention.
  • FIG. 8 is a schematic sectional view of the plate of FIG. 7 provided with a coating or photosensitive material such as a diazo resin or the like.
  • the conductive electrode 16 may be in the form of a solid metallic plate, or in the shape of a grid or mesh made of the same material as the metallic plate 10, or made of a dissimilar material.
  • the DC power supply 18 may be a bank of storage batteries, an AC-DC dynamo-electric or a static converter, an AC-DC rectifier or any other convenient source of DC power.
  • a pulsed DC current power supply may be used, and it does not seem material whether the DC voltage across the terminals of the power supply is constant and steady or includes an AC ripple.
  • An AC power supply may be also used, which is arranged to operate on that portion of the cycle when the metal lic element is substantially anodic.
  • EXAMPLE 1 Plates of 1 100 aluminum, having an area of 25 sq. in. and .009 in. thick were prepared by having a surface of a continuous web of the aluminum material grained at a line speed of 12 feet per minute using a sand slurry. The web was then cut so as to provide plates of the indicated area.
  • the plates were electrolytically anodized according to the arrangement of FIG. 1, by dipping each plate in the electrolyte at a predetermined distance from a cathode 16 consisting of a stainless steel grid, having an area matching that of the plate 10, the grained surface of the plate 10 being disposed opposite the cathode 16.
  • the spacing between the plate and the cathode was three inches.
  • the electrolyte 12 used was an aqueous solution of 8% sulfuric acid.
  • a DC power supply 18 of 18 volts at 50 amps was used.
  • the plates 10 were rinsed with water and dried.
  • the penetration of the stannous chloride through the pores of the aluminum oxide layer obtained by anodization is noticeable as a plurality of dark points, and the reaction is complete when the plate ceases to darken.
  • i 1 provides a good indication of the amount of porosity of 2 Li of the prccbding f z i i f' the anodized surface and of the thickness of the anodi l e sg igg z l s g l cc n ff 40 ized oxide layer.
  • the strokes are applied repetitively to the same area of i 9 H2591 55 C the plates and the moment at which the anodized layer Duratlon of Anodlzation T:me tor SnCl to react 6O (5cm (mm) 15 broken through is recognized by the surface of the eraser turning black.
  • the other comparative test consists of pouring a satu- M) rated solution of stannous chloride over the surface of :2 if 6 the plates and, with an even pressure, in stroking an ordinary bristle brush across the surface of the plates.
  • the bristles of the brush abrade the anodized oxide film on the surface of the plates, and the reaction of the stannous chloride with the aluminum indicates towhat extent the surface is damaged.
  • Both tests may be effected by means of an appropriate fixture for the purpose of removing human error in applying the eraser or the brush with an even pressure over the surface of the plates.
  • the plates are placed on the table of a machine tool such as a milling machine, and the eraser or the brush is mounted on the tool holder.
  • the table is reciprocated by way of the table slides, the eraser end or the brush bristles being engaged with the surface of the plates being tested.
  • a spring loaded holder is preferably used for mounting the eraser and applying the eraser with a constant pressure to the plate surfaces.
  • the stannous chloride test, the eraser test and the brush test are indicative of the mechanical quality of the plate anodized surface, namely the degree of porosity of the anodized barrier film, its hardness, and its resistance to abrasion. They are not indicative of a further desirable quality for lithographic plates, namely the hydrophilic quality of the plate surface.
  • the hydrophilicity of the plate surface is tested by means of a dry ink test and by means of a wet ink test.
  • the dry ink test consists in rubbing the surface of the plate with a rag impregnated with printers ink which has been allowed to dry.
  • the wet ink test consists in rubbing the surface of the plate with wet printers ink.
  • the surface should not smudge when subjected to the wet ink test, and it should not ink readily when subjected to the more stringent dry ink test.
  • EXAMPLE 5 Plates of l 100 aluminum were prepared by being cut from a web of aluminum material grained at a line speed of 12 feet per minute using a sand slurry. After rinsing, the plates were electrolytically anodized according to the arrangement 'of FIG. 1, by dipping each plate in the electrolyte at a distance of 3 inches from the cathode 16 consisting of a stainless steel plate having the same area as that of the plate 10. The grained surface of the plate was disposed opposite the cathode 16.
  • the anodized oxide layer obtained with nitric acid electrolytes was thin, non-resistant to any of the mechanical tests and accepted ink readily in the course of the wet ink test as well as the dry ink test.
  • the anodized layer obtained by anodizing with a hydrochloric acid electrolyte was also relatively thin and not very resistant to the abrasion tests.
  • the sample plates did not pass the dry ink test, but were found to be acceptable when subjected to the wet ink test.
  • Plates anodized with acetic acid electrolytes were provided with a surface anodized film which was fairly resistant to abrasion.
  • the film was not at all dark in appearance, contrary to the surface film obtained by anodization with other electrolytes.
  • the anodized surface was not receptive to ink when subjected to the dry ink test.
  • the anodized suface layers obtained by using electrolytes of chromic acid and of boric acid were comparable in lack of resistance to the abrasion test, and therefore were considered unacceptable for the purpose intended as a support member for a lithographic plate.
  • the anodized surface layers obtained by electrolytes of phosphoric acid were in all points comparable with those obtained with the sulfuric acid electrolytes of Examples l-4, from the point of view of lithographic quality, and they even appeared to be slightly superior when subjected to the stannous chloride penetration test and the diverse abrasion tests.
  • the quality of the surface layers obtained with phosphoric acid electrolytes is apparently not as affected by the temperature of the electrolytes as is the case when using sulfuric acid electrolytes. Phosphoric acid electrolytes would therefore be quite acceptable for anodizing aluminum and aluminum alloy plates for support members for lithographic plates, if the price of phosphoric acid was not two times the price of sulfuric acid.
  • FIG. I for batch anodizing of aluminum or aluminum alloy plates or sheets may be modified to anodize a pair of plates 10 by placing a second plate 10 a predetermined distance from the cathode 16 in the tank 14, such as three inches away from the cathode, on the other side of the cathode and connecting both plates 10 to the negative terminal of the power supply 18. If it is desired to anodize both surfaces of a plate l0,-the arrangement of FIG. 2 is used, a pair of cathodes 16 and 16 being disposed each on one side of the plate 10 and connected to the negative terminal of the power supply 18.
  • an AC power supply may be used, as shown at 18 at FIG. 3, each terminal of the power supply being connected to one of the two aluminum or aluminum alloy plates 10 and 10'.
  • the arrangement of FIG. 4 may be used, utilizing an AC power supply 18', and the diverse plates being connected electrically as shown, with the results that plates 10a, 10b, 10b and 10c are anodized on both surfaces, and the plates 10a and 10c are anodized on the surface disposed respectively towards plates 10a and 100.
  • the present invention contemplates manufacturing presensitized lithographic plates by a method which includes as one of its steps an anodization step prior to subjecting the aluminum or aluminum alloy plate memher to electrosilication according to the method disclosed in said US. Pat. No. 3,658,662, thus obtaining a support member which, once coated with a photosensitive material, provides a presensitized lithographic plate of high quality, not subject to the formation of black spots, and provided with an effective barrier layer between the subjaccnt metal of the support mem ber and the photosensitive coating preventing spontaneous reaction between the two until the photolithographic plate is removed from its wrapper, exposed and developed.
  • the conditions of operation for the electrosilieation step in the method may be any one of those disclosed in the aforesaid US. Patent and consist generally in anodically treating the anodized plates by means of DC, AC or pulse current in an alkaline electrolyte made of an aqueous solution of sodium silicate containing from about 0.5% to about 37% by weight of sodium silicate, the electrolyte being maintained at a temperature between 20C and the boiling temperature of the electrolyte, the plate to be treated and the other electrode in the electrolytic bath being in close proximity to each other, the voltage being anywhere between 6 and 220,
  • the duration of the electrosilieation step being only a few seconds.
  • EXAMPLE 6 A plurality of plates of l 100 aluminum were grained in a sand slurry and anodized in an electrolyte made of a aqueous solution of sulfuric acid, using 18 volts DC, passing the current for seconds and maintaining the temperature of the electrolyte at C.
  • the plates were then rinsed and placed in a tank containing an aqeous solution of 17% sodium silicate by weight.
  • the plates were connected to the positive terminal of a 36 volt DC power supply, and the temperature of the electrolyte was maintained at 70C.
  • the period of time during which the current was turned on was varied from plate to plate, the minimum duration being 2 seconds and the maximum duration being 60 seconds.
  • the diverse plates having been subjected to an anodization step followed by an electrosilieation step showed no attack by the test solution in a duration of more than an hour.
  • Plates having been subjected to anodization alone were used as control plates in the eraser comparision test with plates having been subjected to the electrosilieation step following the anodization step.
  • the number of eraser strokes necessary to break through the layer of film formed on the plates having been subjected to both the anodizing the electrosilieation steps were between 2.7 and 3.1 times greater than the number of strokes required to break through the surface layer film of the plates having been only anodized.
  • the comparative brush test yielded the same results. Repetitively, the plates provided with an anodized surface were affected by the brush test, while the plates anodized and electrosilicated remained unaffected.
  • EXAMPLE 7 Plates which had been anodized and electrosilicated according to the process disclosed relative to Example 6 were coated, on their face provided with a barrier film, with a conventional diazo resin according to conventional methods in the lithographic plate manufacturing industry. A 6% solution of type L diazo manufactured by Fairmount Chemical Company was used for coating the plates. Control plates subjected only to anodizing were coated in the same manner. After drying of the coating, both types of plates were exposed to a mercury vapor light source for 30 seconds and developed with a subtractive developer, such as the subtractive developer in copending application Ser. No. 500,475. After development, the image area of both types of plates was subjected to the eraser test. The plates having received only the anodizing treatment were abraded at the image area in half as many strokes as were required to abrade the image area of the plates which had received both the anodizing and the electrosilieation treatments.
  • Electrosilieation of aluminum and aluminum alloy plates following anodization may be effected by batches, under the condition of operation disclosed in the aforesaid US. Patent and according to any one of the arrangements of FIGS. 14, substituting for the acid electrolyte 12 a sodium silicate alkaline electrolyte, connecting the plate 10 as an anode to the positive terminal of a DC power supply 18, using a stainless steel or other conductive cathode 16 connected to the negative terminal of the power supply (FIG. 1). If both faces of plate 10 have been anodized previously, both faces may be electrosilicated by using a pair of cathode electrodes l6 and 16, connected as shown at FIG. 2. Using an AC power supply 18, the arrangement of FIG. 3 or FIG. 4 may be used.
  • FIG. 5 there is schematically illustrated a continuous process for making photolithographic plates according to the present invention.
  • web 20 of aluminum or aluminum alloy foil is unwound from a coil 22 mounted on an appropriate support 24.
  • the web 20 is continuously fed in the direction of the arrows, appropriate feed means, such as shown at 26, being disposed at appropriate locations along the manufacturing line.
  • appropriate rollers By means of appropriate rollers, the continuously traveling web 20 is deflected into successive sive tanks in which appropriate steps of the process are accomplished.
  • the web 20 is first cleaned in the cleaning tank 28, containing an appropriate cleaning or de greasing fluid such as triehloroethylene, perchlorethylene, or the like, and from the cleaning tank the web is passed into a graining tank 30 in which a surface of the web 20 is grained under the action of a sand slurry 32 contained in the tank and frictionally applied to a surface of the web by means of a rotating brush 34.
  • the web 20 is then rinsed, as shown at 36, and after rinsing the web is caused to pass through an anodizing tank 38 wherein it is linearly displaced in proximity to an electrode 16, the grained surface of the web being directed toward the electrode 16.
  • anodizing tank 38 wherein it is linearly displaced in proximity to an electrode 16, the grained surface of the web being directed toward the electrode 16.
  • the electrode 16 is connected to the negative terminal of a DC power supply 18, while the positive terminal of the power supply 18 is connected to the web 20 by way of appropriate electrical contact making rollers 40.
  • the anodizing tank contains an electrolyte 12 made of an aqueous solution of an appropriate acid such as sulfuric acid or the like, at the concentrations disclosed at Examples l-4 hereinbefore, and the other parameters of operation, such as voltage of the power supply 18 and temperature of the electrolyte, may be one of the parameters hereinbefore disclosed.
  • the power supply 18 has a voltage of 36 volts
  • the electrolyte 12 consists of a aqueous solution of sulfuric acid and is maintained, by 36 of appro priate cooling means, not shown, at a temperature of 25C.
  • the grained surface of the web 20 is translated at a distance of 3 inches (75 mm.) from the electrode 16, and the relative length of the electrode 16 and the speed of translation of the web 20 are chosen to provide anodization of the grained surface of the Web for about seconds.
  • the electrode 16 has a length of 36 inches (91.5 cm.).
  • the web 20 is conveninetly obtained in 29 /2 inches (75 cm.), and the width of the electrode 16 is at least the width of the web 20.
  • the electrode 16 is a stainless steel plate or grid.
  • the web 20 having been now provided with a grained and an anodized surface, is subsequently passed through a rinsing tank 42 for removing traces of the acid electrolyte and is subsequently passed through an electrosilication tank 44.
  • the Web 20 is translated with its grained and anodized face disposed, for example, 3 inches (75 mm.) away from an electrode 46, made of stainless steel, for example, connected to the negative terminal of the power supply 18.
  • the web is maintained connected to the positive terminal of the power supply by means of electrical contact establishing rollers 40.
  • the electrolyte 48 in the electrosilication tank 44 consists of an appropriate aqueous solution of sodium silicate, as disclosed in the hereinbefore referred to US. Patent, for example an aqueous solution of l7% by weight of sodium silicate, such as the Star Brand sodium silicate marketed by Philadelphia Quartz Company, and the temperature of the electrolytc 48 is maintained at, for example, 70C by means of appropriate thermostatically controlled heating coils, not shown.
  • the grained and anodized surface of the web 20 is subjected to electrosilication for about 15 seconds, although other durations may be used, which necessitates providing the electrode 46 with a length of 36 inches (9L5 cm.).
  • the continuous web 20 After emerging from the electrosilication tank 44, the continuous web 20 is passed through a rinsing tank 50, and then dried by being passed through a tunnel oven 52 or the like.
  • the grained, anodized and electrosilicated surface of the web 20, after drying of the web, is coated with an appropriate photosensitive material such as a conventional aqueous solution of diazonum resin.
  • the coating operation is effected 'by any conventional means such as roller coating 54 or spraying followed by calendering.
  • the web After coating of its grained, anodized and electrosilieated surface, the web is passed through a drying oven 56 for drying the coating of photosensitive material, and the coated web is fed to a cutting station 58 where it is cut to appropriate lengths, thus providing presensitized photolithographic plates 60 which, after further cutting to appropriate sizes if so required, are appropriately packaged and shipped to the user.
  • the coating and subsequent steps are effected under yellow light which is nonactinic to diazo type photosensitive materials.
  • an AC power supply may be used for accomplishing the anodizing step and, as disclosed in the aforementioned patent, alternating current may be used for electrosilication of aluminum and aluminum alloys.
  • alternating current may be used for electrosilication of aluminum and aluminum alloys.
  • RMS alternating current at volts
  • FIG. 6 When utilizing an AC power supply, it is further advantageous to utilize the arrangement schematically illustrated at FIG. 6, comprising two continuous lines of aluminum or aluminum alloy webs as shown at 20 and 20, respectively, adapted to be translated parallel to each other, in the same direction as shown, or in opposite directions to each other.
  • the first web 20 is obtained from a coil 22, and the second web 20' is obtained from a second coil 22'.
  • Each web, while being translated, is successively passed through a cleaning tank 28, 28, a graining station 30, 30' to provide a surface of each web with a grained surface, and subsequently to graining each web is passed through a rinsing station as shown at 36 and 36, respectively.
  • the surface of the web 20 which is grained and the surface of the web 20 which is grained are caused to pass through the anodizing bath in the anodizing tank 38 facing one another.
  • the two webs 20 and 20 are displaced through the anodizing tank 38, parallel to each other, in close relative proximity, 3 inches for example, through an appropriate electrolyte 12, made for example of an aqueous solution of sulfuric acid, having the concentration hereinbefore indicated, preferably maintained at a temperature of 25C by means of appropriate cooling coils, not shown.
  • One of the webs is connected to a terminal of an AC power supply 18, and the other web is connected to the other terminal of the power supply by means of appropriate contact making rollers 40 and 40', respectively.
  • the webs and 20 are rinsed by being passed through a rinsing tank 42, and are passed through an electrosilication tank 48, being maintained parallel to each other with the grained and anodized faces opposite to each other and separated by a distance of, for example, 3 inches.
  • electrosilication in the eleetrosilication tank 44 for a period of time substantially equal to the period of time during which they are subjected to anodization, for example, 15 seconds, the two webs 20 and 20 are passed through a rinsing tank, as shown at 50, and they are dried in an oven, as shown at 52.
  • Each of the webs are then caused to pass separately through a coating station, as shown respectively at 54 and 54', where the grained, anodized and silicated surface of each web is coated with a coating of photosensitive material, such as a diazo resin, as previously explained.
  • the coating of photosensitive material is subsequently dried in the drying oven, as shown at 56 and 56', respectively.
  • the coated webs are then cut at a cutting station. 58 and 58, respectively, to appropriate lengths for providing presensitizcd photolithographic plates 60 and 60'.
  • FIG. 7 schematically illustrates, is a grossly exaggerated manner, a section through an aluminum or aluminum alloy plate 10 provided with an anodized oxide film 62 on a surface thereof.
  • the anodized film 62 is, as previously mentioned, hard and corrosion resistant, although not endowed with highly hydrophilic qualities.
  • the anodized layer 62 is substantially porous and, if its surface was provided with a coating of, for example, photosensitive material such as a diazo resin, the oxide layer 62 would be easily penetrated in view of its porosity by the coating material, which may result in a spontaneous reaction occurring between the metal of the support base 10 and the material of the coating.
  • a simply anodized aluminum plate is utilized as a support member for photosensitive coatings such as diazo resins for the purpose of providing a presensitizcd lithographic plate.
  • a lithographic plate has a very short shelf life, as the reaction betweeen the diazo resin having transpired through the oxide film 62 to the subjacent aluminum of the support base 10 tends to spontaneously react and spontaneously form black spots, that is spots resulting from areas of the diazo resin having spontaneously chemically reacted with the subjacent aluminum, the resultant material being highly oleophilic and incapable of being dissolved in the course of developing the lithographic plate following exposure.
  • the elcctrosilication step actually seals the pores of the oxide layer 62, in addition to electrolytically transforming the surface 64 of the oxide layer 62 from a mildly hydrophilic to a highly hydrophilic surface.
  • the result achieved is that an effective chemical barrier is created between the subjacent metallic support base 10 and a coating, such as a coating of diazo resin 66 (FIG. 8) which is subsequently applied to the surface 64 of the oxide layer 62.
  • the resulting presensitizcd lithographic plate has a long shelf life because, as a result of the electrosilication step, the oxide layer 62 provided by the anodization step has been effectively sealed, thus creating an effective barrier preventing spontaneous reaction between the diazo resin and the metal of the subjacent support base 10.
  • the resulting lithographic plate after exposure and processing, is provided with hydrophilic non-image areas as the surface 64 of the oxide layer 62 has been, in the course of the electrosilication step, further modified from a slightly hydrophilic surface to a highly hydrophilic surface, without any loss in the quality of the oxide layer to provide a corrosion and abrasion resistant film.
  • a method of manufacturing presensitizcd lithographic plates comprising the steps of graining a surface of an aluminum or aluminum alloy plate, anodizing the grained surface electrolytically in an aqueous acidic solution, anodically treating the anodized surface in an alkaline aqueous solution of sodium silicate, and coating the treated surface with a photosensitive material.
  • each of the steps of anodizing and anodically treating said plate is effected by connecting said plate and an electrode across a source of electrical energy such that said plate is anodic at least part of the time.
  • aqueous acidic solution is a solution of sulfuric acid having a concentration in acid of 5% to 15%.
  • said source of electrical energy is an AC source and said electrode is a second aluminum or aluminum alloy plate having a grained surface disposed proximate to the grained surface of the first plate.
  • a method of manufacturing presensitizcd lithographic plates from a continuous web of aluminum or aluminum alloy comprising the successive steps of cleaning said web, anodizing the grained sur face of said web electrolytically in an aqueous acid solution, anodically treating the anodized surface in an alkaline aqueous solution of sodium silicate, rinsing said web, drying said web, coating the treated surface of said web with a photosensitive material, drying said coating and cutting said web to appropriate size.
  • each of the steps of anodizing and anodically treating said web is effected by connecting said web and an electrode across a source of electrical energy such that said web is anodic at least part of the time.
  • aqueous acidic solution is a solution of sulfuric acid having a concentration in acid of to 11.
  • said aqueous acidic solution is maintained at a temperature of about C.
  • a method of manufacturing presensitized lithographic plates from a pair of continuous webs of aluminum or aluminum alloy comprising the successive steps of cleaning of said webs, graining a surface of each of said webs, anodizing the grained surface of each of said webs electrolytically in an aqueous acidic solution, anodically treating the anodized surface in an alkaline aqueous solution of sodium silicate,
  • aqueous acidic solution is a solution of sulfuric acid having a concentration in acid of 5% to 15%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
US510909A 1974-10-01 1974-10-01 Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like Expired - Lifetime US3902976A (en)

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US510909A US3902976A (en) 1974-10-01 1974-10-01 Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photolithographic plates and the like
FR7516704A FR2286714A1 (fr) 1974-10-01 1975-05-28 Procede de fabrication de plaques lithographiques pre-sensibilisees
GB2826075A GB1461566A (en) 1974-10-01 1975-07-04 Presensitised lithographic plates
CA231,868A CA1056762A (en) 1974-10-01 1975-07-21 Corrosion and abrasion resistant aluminum and aluminum alloy plates particularly useful as support members for photo-lithographic plates and the like
DE19752532769 DE2532769A1 (de) 1974-10-01 1975-07-22 Verfahren zur herstellung von vorsensibilisierten lithographischen platten
JP50090998A JPS5146206A (en) 1974-10-01 1975-07-25 Insatsuyoheibanseizoho

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Cited By (43)

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FR2418059A1 (fr) * 1978-02-28 1979-09-21 Fromson H A Procede destine a rendre des surfaces rugueuses et articles obtenus par mise en oeuvre de ce procede
US4211619A (en) * 1978-03-16 1980-07-08 Hoechst Aktiengesellschaft Process for anodically oxidizing aluminum and use of the material so prepared as a printing plate support
US4225398A (en) * 1977-03-30 1980-09-30 Yoshida Kogyo K.K. Method of improving the corrosion resistance of an anodically oxidized surface film on aluminum articles
US4229266A (en) * 1978-08-23 1980-10-21 Hoechst Aktiengesellschaft Process for anodically oxidizing aluminum and use of the material so prepared as a printing plate support
US4427766A (en) 1981-07-06 1984-01-24 Hoechst Aktiengesellschaft Hydrophilic coating of salt type nitrogen polymer on aluminum support materials for offset printing plates and process for manufacture and use with light sensitive layer thereon
US4427765A (en) 1981-07-06 1984-01-24 Hoechst Aktiengesellschaft Hydrophilic coating of salt-type phosphorus or sulfur polymer on aluminum support materials for offset printing plates and process for manufacture and use with light sensitive layer thereon
US4458005A (en) * 1981-07-06 1984-07-03 Hoechst Aktiengesellschaft Polyvinylmethylphosphinic acid, process for its manufacture and use
US4492616A (en) * 1982-09-01 1985-01-08 Hoechst Aktiengesellschaft Process for treating aluminum oxide layers and use in the manufacture of offset-printing plates
US4554057A (en) * 1982-02-23 1985-11-19 Hoechst Aktiengesellschaft Process for manufacturing support materials for offset printing plates
US4554216A (en) * 1982-02-23 1985-11-19 Hoechst Aktiengesellschaft Process for manufacturing support materials for offset printing plates
US4605480A (en) * 1983-06-13 1986-08-12 Hoechst Aktiengesellschaft Device for continuously anodically oxidizing aluminum strips on one surface thereof and use of these aluminum strips in the production of offset printing plates
US4689272A (en) * 1984-02-21 1987-08-25 Hoechst Aktiengesellschaft Process for a two-stage hydrophilizing post-treatment of aluminum oxide layers with aqueous solutions and use thereof in the manufacture of supports for offset printing plates
EP0268790A2 (de) 1986-10-17 1988-06-01 Hoechst Aktiengesellschaft Verfahren zur abtragenden Modifizierung von mehrstufig aufgerauhten Trägermaterialien aus Aluminium oder dessen Legierungen und deren Verwendung bei der Herstellung von Offsetdruckplatten
US4749451A (en) * 1986-02-05 1988-06-07 Basf Aktiengesellschaft Electrochemical coating of carbon fibers
US4782000A (en) * 1986-08-16 1988-11-01 Basf Aktiengesellschaft Electrophotographic recording elements with hydrolyzed silane layer
US4833065A (en) * 1985-10-04 1989-05-23 Fuji Photo Film Co., Ltd. Process for producing support for presensitized lithographic printing plate using alkaline electrolyte
US4935332A (en) * 1986-08-16 1990-06-19 Basf Aktiengesellschaft Photosensitive element having an aluminum base and silane intermediate layer
US4983497A (en) * 1985-10-10 1991-01-08 Eastman Kodak Company Treated anodized aluminum support and lithographic printing plate containing same
US5156723A (en) * 1990-01-19 1992-10-20 Hoechst Aktiengesellschaft Process for electrochemical roughening of aluminum for printing plate supports
US5178961A (en) * 1990-07-21 1993-01-12 Hoechst Aktiengesellschaft Thermally crosslinkable hydrophilic copolymers and their use in reprography
US5178963A (en) * 1990-07-21 1993-01-12 Hoechst Aktiengesellschaft Hydrophilic copolymers and their use in reprography
US5187046A (en) * 1991-03-18 1993-02-16 Aluminum Company Of America Arc-grained lithoplate
US5219664A (en) * 1990-07-21 1993-06-15 Hoechst Aktiengesellschaft Hydrophilic copolymers and their use in reprography
US5262244A (en) * 1990-07-21 1993-11-16 Hoechst Aktiengesellschaft Hydrophilic copolymers and their use in reprography
US5302460A (en) * 1990-07-21 1994-04-12 Hoechst Aktiengesellschaft Support material for offset-printing plates in the form of a sheet, a foil or a web process for its production and offset-printing plate comprising said material
US5481084A (en) * 1991-03-18 1996-01-02 Aluminum Company Of America Method for treating a surface such as a metal surface and producing products embodying such including lithoplate
US5493971A (en) * 1994-04-13 1996-02-27 Presstek, Inc. Laser-imageable printing members and methods for wet lithographic printing
US5556531A (en) * 1994-05-21 1996-09-17 Agfa-Gevaert Ag Process for the aftertreatment of aluminum materials substrates of such materials and their use for offset printing plates
US6014929A (en) * 1998-03-09 2000-01-18 Teng; Gary Ganghui Lithographic printing plates having a thin releasable interlayer overlying a rough substrate
US6240846B1 (en) * 1998-08-29 2001-06-05 Agfa-Gevaert Recording material comprising a substrate and a ceramic layer applied to a surface of the substrate
US6417069B1 (en) * 1999-03-25 2002-07-09 Canon Kabushiki Kaisha Substrate processing method and manufacturing method, and anodizing apparatus
WO2002070258A1 (en) 2001-03-01 2002-09-12 Presstek, Inc. Lithographic imaging with printing members having multiphase laser-responsive layers
US20040140221A1 (en) * 2003-01-21 2004-07-22 Kinard John Tony Method of anodizing aluminum utilizing stabilized silicate solutions
US20050000815A1 (en) * 2002-01-29 2005-01-06 Arellano Gonzales Plate for offset printing and method for manufacturing said plate
US20060201815A1 (en) * 2005-03-11 2006-09-14 Dr. Ing. H.C.F. Porsche Ag Method for production of oxide and silicon layers on a metal surface
EP2265441A1 (de) 2008-03-18 2010-12-29 Metal Coating Technologies, Llc Schutzbeschichtungen für metalle
EP2636525A2 (de) 2012-03-06 2013-09-11 Presstek, Inc. Lithografische Abbildung und Drucken mit positiv arbeitenden fotoreaktiven Druckelementen
EP2728041A1 (de) * 2012-10-30 2014-05-07 Hydro Aluminium Rolled Products GmbH Beschichteter Aluminiumstreifen und Verfahren zur Herstellung
EP3132932A2 (de) 2015-07-24 2017-02-22 Presstek, LLC. Lithografische abbildung und drucken mit negativ arbeitenden fotoreaktiven druckelementen
EP3170663A1 (de) 2015-11-18 2017-05-24 Presstek, Inc Trockene lithografische bildgebung und drucken mit druckelementen mit aluminiumsubstraten
US20170241037A1 (en) * 2014-08-07 2017-08-24 Henkel Ag & Co. Kgaa Apparatus for electroceramic coating of high tension cable wire
WO2018132365A1 (en) 2017-01-11 2018-07-19 Presstek Llc Ablation-type lithographic printing members having improved exposure sensitivity and related methods
CN108517549A (zh) * 2018-02-27 2018-09-11 中国计量大学 一种铝合金复合阳极氧化膜的制备方法

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US3531381A (en) * 1964-03-23 1970-09-29 Olin Corp Method of improving the corrosion resistance of oxidized metal surfaces
US3658662A (en) * 1969-01-21 1972-04-25 Durolith Corp Corrosion resistant metallic plates particularly useful as support members for photo-lithographic plates and the like
US3775266A (en) * 1971-06-29 1973-11-27 Kuboko Paint Co Process for forming resinous films on anodized aluminum substrates
US3852124A (en) * 1972-09-22 1974-12-03 Philco Ford Corp Duplex sealing process

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US3531381A (en) * 1964-03-23 1970-09-29 Olin Corp Method of improving the corrosion resistance of oxidized metal surfaces
US3376205A (en) * 1964-07-15 1968-04-02 Samuel L Cohn Method of reviving silicate sealing solutions
US3658662A (en) * 1969-01-21 1972-04-25 Durolith Corp Corrosion resistant metallic plates particularly useful as support members for photo-lithographic plates and the like
US3775266A (en) * 1971-06-29 1973-11-27 Kuboko Paint Co Process for forming resinous films on anodized aluminum substrates
US3852124A (en) * 1972-09-22 1974-12-03 Philco Ford Corp Duplex sealing process

Cited By (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225398A (en) * 1977-03-30 1980-09-30 Yoshida Kogyo K.K. Method of improving the corrosion resistance of an anodically oxidized surface film on aluminum articles
FR2418059A1 (fr) * 1978-02-28 1979-09-21 Fromson H A Procede destine a rendre des surfaces rugueuses et articles obtenus par mise en oeuvre de ce procede
US4183788A (en) * 1978-02-28 1980-01-15 Howard A. Fromson Process for graining an aluminum base lithographic plate and article thereof
US4211619A (en) * 1978-03-16 1980-07-08 Hoechst Aktiengesellschaft Process for anodically oxidizing aluminum and use of the material so prepared as a printing plate support
US4229266A (en) * 1978-08-23 1980-10-21 Hoechst Aktiengesellschaft Process for anodically oxidizing aluminum and use of the material so prepared as a printing plate support
US4427766A (en) 1981-07-06 1984-01-24 Hoechst Aktiengesellschaft Hydrophilic coating of salt type nitrogen polymer on aluminum support materials for offset printing plates and process for manufacture and use with light sensitive layer thereon
US4427765A (en) 1981-07-06 1984-01-24 Hoechst Aktiengesellschaft Hydrophilic coating of salt-type phosphorus or sulfur polymer on aluminum support materials for offset printing plates and process for manufacture and use with light sensitive layer thereon
US4458005A (en) * 1981-07-06 1984-07-03 Hoechst Aktiengesellschaft Polyvinylmethylphosphinic acid, process for its manufacture and use
US4554057A (en) * 1982-02-23 1985-11-19 Hoechst Aktiengesellschaft Process for manufacturing support materials for offset printing plates
US4554216A (en) * 1982-02-23 1985-11-19 Hoechst Aktiengesellschaft Process for manufacturing support materials for offset printing plates
US4492616A (en) * 1982-09-01 1985-01-08 Hoechst Aktiengesellschaft Process for treating aluminum oxide layers and use in the manufacture of offset-printing plates
US4605480A (en) * 1983-06-13 1986-08-12 Hoechst Aktiengesellschaft Device for continuously anodically oxidizing aluminum strips on one surface thereof and use of these aluminum strips in the production of offset printing plates
US4689272A (en) * 1984-02-21 1987-08-25 Hoechst Aktiengesellschaft Process for a two-stage hydrophilizing post-treatment of aluminum oxide layers with aqueous solutions and use thereof in the manufacture of supports for offset printing plates
US4833065A (en) * 1985-10-04 1989-05-23 Fuji Photo Film Co., Ltd. Process for producing support for presensitized lithographic printing plate using alkaline electrolyte
US4983497A (en) * 1985-10-10 1991-01-08 Eastman Kodak Company Treated anodized aluminum support and lithographic printing plate containing same
US4749451A (en) * 1986-02-05 1988-06-07 Basf Aktiengesellschaft Electrochemical coating of carbon fibers
US4782000A (en) * 1986-08-16 1988-11-01 Basf Aktiengesellschaft Electrophotographic recording elements with hydrolyzed silane layer
US4935332A (en) * 1986-08-16 1990-06-19 Basf Aktiengesellschaft Photosensitive element having an aluminum base and silane intermediate layer
EP0268790A2 (de) 1986-10-17 1988-06-01 Hoechst Aktiengesellschaft Verfahren zur abtragenden Modifizierung von mehrstufig aufgerauhten Trägermaterialien aus Aluminium oder dessen Legierungen und deren Verwendung bei der Herstellung von Offsetdruckplatten
US5156723A (en) * 1990-01-19 1992-10-20 Hoechst Aktiengesellschaft Process for electrochemical roughening of aluminum for printing plate supports
US5178961A (en) * 1990-07-21 1993-01-12 Hoechst Aktiengesellschaft Thermally crosslinkable hydrophilic copolymers and their use in reprography
US5178963A (en) * 1990-07-21 1993-01-12 Hoechst Aktiengesellschaft Hydrophilic copolymers and their use in reprography
US5302460A (en) * 1990-07-21 1994-04-12 Hoechst Aktiengesellschaft Support material for offset-printing plates in the form of a sheet, a foil or a web process for its production and offset-printing plate comprising said material
US5219664A (en) * 1990-07-21 1993-06-15 Hoechst Aktiengesellschaft Hydrophilic copolymers and their use in reprography
US5262244A (en) * 1990-07-21 1993-11-16 Hoechst Aktiengesellschaft Hydrophilic copolymers and their use in reprography
US5462609A (en) * 1991-03-18 1995-10-31 Aluminum Company Of America Electric arc method for treating the surface of lithoplate and other metals
US5481084A (en) * 1991-03-18 1996-01-02 Aluminum Company Of America Method for treating a surface such as a metal surface and producing products embodying such including lithoplate
US5187046A (en) * 1991-03-18 1993-02-16 Aluminum Company Of America Arc-grained lithoplate
US5493971A (en) * 1994-04-13 1996-02-27 Presstek, Inc. Laser-imageable printing members and methods for wet lithographic printing
US5556531A (en) * 1994-05-21 1996-09-17 Agfa-Gevaert Ag Process for the aftertreatment of aluminum materials substrates of such materials and their use for offset printing plates
US5770315A (en) * 1994-05-21 1998-06-23 Agfa-Gevaert Ag Process for the aftertreatment of aluminum materials, substrates of such materials, and their use for offset printing plates
US6014929A (en) * 1998-03-09 2000-01-18 Teng; Gary Ganghui Lithographic printing plates having a thin releasable interlayer overlying a rough substrate
US6240846B1 (en) * 1998-08-29 2001-06-05 Agfa-Gevaert Recording material comprising a substrate and a ceramic layer applied to a surface of the substrate
US6417069B1 (en) * 1999-03-25 2002-07-09 Canon Kabushiki Kaisha Substrate processing method and manufacturing method, and anodizing apparatus
WO2002070258A1 (en) 2001-03-01 2002-09-12 Presstek, Inc. Lithographic imaging with printing members having multiphase laser-responsive layers
US20050000815A1 (en) * 2002-01-29 2005-01-06 Arellano Gonzales Plate for offset printing and method for manufacturing said plate
US20080280153A1 (en) * 2003-01-21 2008-11-13 John Tony Kinard Method of Anodizing Aluminum Utilizing Stabilized Silicate Solutions
US20050103640A1 (en) * 2003-01-21 2005-05-19 Kinard John T. Method of anodizing aluminum utilizing stabilized silicate solutions
US20040140221A1 (en) * 2003-01-21 2004-07-22 Kinard John Tony Method of anodizing aluminum utilizing stabilized silicate solutions
US20060201815A1 (en) * 2005-03-11 2006-09-14 Dr. Ing. H.C.F. Porsche Ag Method for production of oxide and silicon layers on a metal surface
EP1700934A3 (de) * 2005-03-11 2008-08-06 Dr. Ing. h.c. F. Porsche Aktiengesellschaft Verfahren zur Herstellung von Oxyd- und Silikatschichten auf Metalloberflächen
EP2265441A1 (de) 2008-03-18 2010-12-29 Metal Coating Technologies, Llc Schutzbeschichtungen für metalle
US20120196119A1 (en) * 2008-03-18 2012-08-02 Mct Research And Developement Protective coatings for metals
EP2636525A2 (de) 2012-03-06 2013-09-11 Presstek, Inc. Lithografische Abbildung und Drucken mit positiv arbeitenden fotoreaktiven Druckelementen
WO2014067937A1 (en) * 2012-10-30 2014-05-08 Hydro Aluminium Rolled Products Gmbh Coated aluminum strip and method for manufacturing
EP2728041A1 (de) * 2012-10-30 2014-05-07 Hydro Aluminium Rolled Products GmbH Beschichteter Aluminiumstreifen und Verfahren zur Herstellung
CN104822865A (zh) * 2012-10-30 2015-08-05 海德鲁铝业钢材有限公司 涂覆铝带材及其制造方法
CN104822865B (zh) * 2012-10-30 2017-02-22 海德鲁铝业钢材有限公司 涂覆铝带材及其制造方法
RU2639166C2 (ru) * 2012-10-30 2017-12-20 Гидро Алюминиум Ролд Продактс Гмбх Алюминиевая полоса с покрытием и способ ее производства
US20170241037A1 (en) * 2014-08-07 2017-08-24 Henkel Ag & Co. Kgaa Apparatus for electroceramic coating of high tension cable wire
EP3132932A2 (de) 2015-07-24 2017-02-22 Presstek, LLC. Lithografische abbildung und drucken mit negativ arbeitenden fotoreaktiven druckelementen
EP3170663A1 (de) 2015-11-18 2017-05-24 Presstek, Inc Trockene lithografische bildgebung und drucken mit druckelementen mit aluminiumsubstraten
WO2018132365A1 (en) 2017-01-11 2018-07-19 Presstek Llc Ablation-type lithographic printing members having improved exposure sensitivity and related methods
CN108517549A (zh) * 2018-02-27 2018-09-11 中国计量大学 一种铝合金复合阳极氧化膜的制备方法
CN108517549B (zh) * 2018-02-27 2019-10-18 中国计量大学 一种铝合金复合阳极氧化膜的制备方法

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CA1056762A (en) 1979-06-19
JPS5146206A (en) 1976-04-20
GB1461566A (en) 1977-01-13
FR2286714A1 (fr) 1976-04-30
DE2532769A1 (de) 1976-04-15

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