EP0151304B1 - Verfahren zur elektrochemischen Aufrauhung von Aluminium für Druckplattenträger in einem wässrigen Mischelektrolyten - Google Patents

Verfahren zur elektrochemischen Aufrauhung von Aluminium für Druckplattenträger in einem wässrigen Mischelektrolyten Download PDF

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Publication number
EP0151304B1
EP0151304B1 EP84116021A EP84116021A EP0151304B1 EP 0151304 B1 EP0151304 B1 EP 0151304B1 EP 84116021 A EP84116021 A EP 84116021A EP 84116021 A EP84116021 A EP 84116021A EP 0151304 B1 EP0151304 B1 EP 0151304B1
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EP
European Patent Office
Prior art keywords
aluminum
aqueous
weight
compound
roughening
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.)
Expired
Application number
EP84116021A
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German (de)
English (en)
French (fr)
Other versions
EP0151304A3 (en
EP0151304A2 (de
Inventor
Dieter Dr. Dipl.-Chem. Mohr
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Hoechst AG
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Hoechst AG
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Filing date
Publication date
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Publication of EP0151304A2 publication Critical patent/EP0151304A2/de
Publication of EP0151304A3 publication Critical patent/EP0151304A3/de
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Publication of EP0151304B1 publication Critical patent/EP0151304B1/de
Expired legal-status Critical Current

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Classifications

    • 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
    • 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

  • the invention relates to a method for the electrochemical roughening of aluminum for printing plate supports, which is carried out with alternating current in an aqueous mixed electrolyte.
  • Printing plates generally consist of a support and at least one radiation-sensitive reproduction layer arranged thereon, this layer either by the consumer (in the case of non-precoated plates) or is applied by the industrial manufacturer (in the case of pre-coated boards) to the layer support.
  • Aluminum or one of its alloys has established itself as a layer material in the printing plate field.
  • these substrates can also be used without a modifying pretreatment, but they are generally modified in or on the surface, for example by mechanical, chemical and / or electrochemical roughening (sometimes also called grain or etching in the literature), chemical or electrochemical Oxidation and / or treatment with hydrophilizing agents.
  • a combination of the above-mentioned types of modification is often used, in particular a combination of electrochemical roughening and anodic oxidation, optionally with a subsequent hydrophilization step.
  • the roughening is carried out, for example, in aqueous acids such as aqueous HCI or HN0 3 solutions or in aqueous salt solutions such as aqueous NaCI or Al (N0 3 ) 3 solutions using alternating current.
  • the roughness depths that can be achieved in this way are in the range from about 1 to 15 ⁇ m, in particular in the range from 2 to 8 ⁇ m.
  • the roughness depth is determined in accordance with DIN 4768 in the version from October 1970, the roughness depth R z is then the arithmetic mean of the individual roughness depths of five adjacent individual measuring sections.
  • the roughening is therefore carried out in order to improve the adhesion of the reproduction layer on the layer support and the water flow of the printing plate resulting from the printing plate by irradiation (exposure) and development.
  • irradiation and development or de-coating in the case of reproduction layers working electrophotographically
  • the image points which carry color during later printing and the water-bearing non-image points are produced on the printing plate, as a result of which the actual printing form is created.
  • Various parameters have an influence on the later topography of the aluminum surface to be roughened, which may be exemplified by the following explanations of the prior art:
  • the essay "The Alternating Current Etching of Aluminum Lithographie Sheet” by AJ Dowell in Transactions ofthe Institute of Metal Finishing, 1979, Vol. 57, pp. 138 to 144 contains basic explanations Aluminum is roughened in aqueous hydrochloric acid solutions, the following process parameters being varied and the corresponding effects being examined.
  • the electrolyte composition is changed with repeated use of the electrolyte, for example with regard to the H + (H 3 O + ) ion concentration (measurable via the pH value) and the AI3 + ion concentration, effects on the surface topography being observed.
  • the temperature variation between 16 ° C and 90 ° C shows a changing influence only from around 50 ° C, which is expressed, for example, by the sharp decline in the formation of layers on the surface.
  • the roughening time change between 2 and 25 min also leads to an increasing metal dissolution with increasing exposure time.
  • the variation of the current density between 2 and 8 A / dm 2 results in higher roughness values with increasing current density. If the acid concentration is in the range 0.17 to 3.3% of HCI, then between 0.5 and 2% of HCI there are only insignificant changes in the hole structure, below 0.5% of HCI there is only a local attack on the Surface and at the high values an irregular dissolution of AI instead.
  • the addition of SO 4 1- ions or CI ions in salt form [eg by adding Al 2 / SO 4 ) 3 or NaCl] can also influence the topography of the roughened aluminum. The rectification of the alternating current shows that both types of half-wave are obviously required for a uniform roughening.
  • aqueous HCI solutions as an electrolyte solution for the electrochemical roughening of carrier materials made of aluminum must therefore be assumed to be known. It can be obtained - as many examples of commercial printing plates show - a uniform grain size that is particularly suitable for the field of application of lithography and is within a roughness range that is generally useful in practice. For certain areas of application of printing plates (e.g. with certain negative working reproduction layers), a uniform and relatively «flat» roughened surface topography is required, which, however, is only available in the previously known electrolyte solutions based on aqueous HCI solutions in modern, high-speed, high-performance systems difficult conditions can be achieved; For example, what is always difficult to control in percentage terms, the process parameters must be kept within very narrow limits.
  • the known organic additives to aqueous acid electrolytes such as HCI or HN0 3 solutions have the disadvantage that they become electrochemically unstable and at least partially decompose at high current loads (voltage) in modern continuously operating conveyor systems.
  • the known inorganic additives such as phosphoric, chromic or boric acid have the disadvantage that the intended protective effect often breaks down locally and individual, particularly pronounced scars then develop there.
  • the previously known complexing additives generally accelerate the "trapping" of released AI 3 + ions to dissolve the aluminum and thus lead to an increase in the roughening attack; However, this often leads to the fact that no additional hole nuclei are created, but that already formed nuclei and holes continue to grow, ie there is an increased formation of scars.
  • the previously known inhibitory additives generally have the effect that the hole growth of individual holes is stopped relatively soon and new hole nuclei can arise; However, they have the decisive disadvantage that this protective effect is caused by imperfections, alloy components and the like. can collapse; this then leads to deep holes in an otherwise flat and evenly roughened surface. Backing materials with such imperfections are unsuitable for lithographic purposes.
  • the object of the present invention is therefore to propose a method for the electrochemical roughening of aluminum for printing plate supports, which makes it possible to achieve a uniformly roughened surface topography with a wide range in the mean roughness depth values and to achieve long bath service lives.
  • the invention is based on the known method for the electrochemical roughening of aluminum or its alloys for printing plate supports in an aqueous mixed electrolyte solution containing HCl and at least one further ionic halogen compound under the action of alternating current.
  • the process according to the invention is then characterized in that the ionic halogen compound is an inorganic fluorine compound which is present as an acid or alkali metal salt and whose anion contains fluorine and at least one further element.
  • the aqueous electrolyte solution contains 0.5 to 10% by weight, in particular 0.8 to 5.0% by weight, of HCI and 0.05 to 5.0% by weight, in particular 0.1 1 to 2.0% by weight, of the fluorine compound.
  • the inorganic ionic fluorine compound is in particular a complex-like compound or a compound comparable to it.
  • Preferred examples of such fluorine compounds are acids or alkali salts (including the ammonium salts) with the anions: SiF 6 2 ⁇ , TiF62-, ZrF 6 2 ⁇ , BF 4- , PF 6 - and P0 3 F 2- ;
  • compounds with the following anions can also be used: NbF 6 , TaF 6 , FeF 6 3 -, SbF 6 -, HfF 6 2- and SO 3 F - .
  • the compounds are preferably used individually, but can be used as a mixture of several.
  • Suitable base materials for the material to be roughened according to the invention include those made of aluminum or one of its alloys, which have, for example, a content of more than 98.5% by weight of Al and proportions of Si, Fe, Ti, Cu and Zn.
  • These aluminum carrier materials can also be roughened mechanically (e.g. by brushing and / or with abrasive treatments) before the electrochemical stage, if necessary after pre-cleaning. All process steps can be carried out discontinuously with plates or foils, but they are preferably carried out continuously with tapes.
  • the process parameters are in the following ranges: the temperature of the electrolyte between 20 and 60 ° C, the current density between 3 and 200 A / dm 2 , the residence time of a material point to be roughened in the electrolyte between 3 and 100 sec and the electrolyte flow rate at the surface of the material to be roughened between 5 and 100 cm / sec; in the batchwise process, the required current densities tend to be in the lower part and the dwell times are in the upper part of the ranges specified, and the flow of the electrolyte can also be dispensed with.
  • alternating current of a frequency of 50 to 60 Hz is usually used as the type of current, but modified types of current such as alternating current with different amplitudes of the current strength for the anode and cathode current, lower frequencies, current interruptions or superimposition of two currents of different frequency and waveform are also possible.
  • the average roughness depth R z of the roughened surface is in the range from 1 to 15 ⁇ m, in particular from 1.5 to 8.0 ⁇ m.
  • aluminum ions in the form of aluminum salts in particular 0.5 to 5.0% by weight of AICI 3, can also be added to the aqueous electrolyte.
  • Pre-cleaning includes, for example, treatment with aqueous NaOH solution with or without degreasing agents and / or complexing agents, trichlorethylene, acetone, methanol or other commercially available aluminum stains.
  • the roughening or, in the case of several roughening stages, also between the individual stages, an abrasive treatment can additionally be carried out, in particular a maximum of 2 g / m 2 being removed (up to 5 g / m 2 between the stages);
  • aqueous solutions of alkali metal hydroxide or aqueous solutions of alkaline salts or aqueous acid solutions based on HN0 3 , H 2 SO 4 or H 3 PO 4 are used as abrasive solutions.
  • non-electrochemical treatments are also known which essentially have only a rinsing and / or cleaning effect and, for example, for removing deposits formed during roughening ("Schmant") or simply for Serve removal of electrolyte residues; For example, dilute aqueous alkali hydroxide solutions or water are used for these purposes.
  • an anodic oxidation of the aluminum can then preferably follow in a further process step to be used, for example to improve the abrasion and adhesion properties of the surface of the carrier material.
  • the usual electrolytes such as H 2 S0 4 , H 3 P0 4 , H 2 C 2 0 4 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof can be used for anodic oxidation; in particular, H 2 S0 4 and H 3 P0 4 are used alone, in a mixture and / or in a multi-stage anodizing process.
  • the stage of anodic oxidation of the aluminum support material can also be followed by one or more post-treatment stages.
  • These post-treatment stages serve in particular to additionally increase the hydrophilicity of the aluminum oxide layer, which is often sufficient, while at least the other known properties of this layer are retained.
  • the materials produced according to the invention are used as supports for offset printing plates, i.e. a radiation-sensitive coating is applied to one or both sides of the carrier material either by the manufacturer of presensitized printing plates or directly by the consumer.
  • a radiation-sensitive coating is applied to one or both sides of the carrier material either by the manufacturer of presensitized printing plates or directly by the consumer.
  • all layers are suitable as radiation (light) sensitive layers which, after irradiation (exposure), possibly with subsequent development and / or fixation, provide an imagewise surface from which printing can take place.
  • the suitable layers also include the electrophotographic layers, ie those which contain an inorganic or organic photoconductor.
  • these layers can of course also contain other constituents such as resins, dyes or plasticizers.
  • the following light-sensitive compositions or compounds can be used in the coating of the carrier materials produced by the process according to the invention:
  • o-quinonediazides in particular o-naphthoquinonediazides such as naphthoquinone- (1,2) -diazid- (2) -sulfonic acid esters or amides, which can be of low or higher molecular weight, as a photosensitive compound-containing reproduction layers, for example in the DE-C 854 890, 865 109, 879 203, 894 959, 938 233, 1 109 521, 1 144 705, 1 118606, 1 120 273, 1 124 817 and 2 331 377 and EP-A 0 021 428 and 0 055 814;
  • o-naphthoquinonediazides such as naphthoquinone- (1,2) -diazid- (2) -sulfonic acid esters or amides, which can be of low or higher molecular weight, as a photosensitive compound-containing reproduction layers, for example in the DE-C 854 890, 865
  • condensation products from aromatic diazonium salts and compounds with active carbonyl groups preferably condensation products from diphenylamine diazonium salts and formaldehyde, which are described, for example, in DE-C 596 731, 1 138 399, 1 138 400, 1 138 401, 1 142 871, 1 154 123, U.S. 2,679,498 and 3,050,502 and GB 712,606;
  • Reproductive layers containing negative-working, mixed condensation products of armoatic diazonium compounds for example according to DE-C 2 065 732, the products with at least one unit each of a) a condensable aromatic diazonium salt compound and b) a condensable compound such as a phenol ether or an aromatic thioether, connected by have a double bonded intermediate derived from a condensable carbonyl compound such as a methylene group;
  • positive-working layers according to DE-A 2 610 842, DE-C 2 718 254 or DE-A 2 928 636, which contain a compound which cleaves off on irradiation, a monomeric or polymeric compound which has at least one COC which can be cleaved by acid Group (for example an orthocarboxylic acid ester group or a carboxamide acetal group) and optionally contain a binder;
  • acid Group for example an orthocarboxylic acid ester group or a carboxamide acetal group
  • the monomers used are, for example, acrylic and methacrylic acid esters or reaction products of diisocyanates with partial esters of polyhydric alcohols, as described, for example, in US Pat. Nos. 2,760,863 and 3,060,023 and DE-A 2,064,079 and 2,361,041;
  • Negative-working layers according to DE-A 3 036 077, which contain a diazonium salt polycondensation product or an organic azido compound as the photosensitive compound and a high molecular weight polymer with pendant alkenylsulfonyl or cycloalkenylsulfonylurethane groups as the binder.
  • photo-semiconducting layers such as e.g. in DE-C 1 117 391, 1 522 497, 1 572 312, 2 322 046 and 2 322 047 are described, are applied to the carrier materials produced according to the invention, thereby producing highly light-sensitive, electrophotographic printing plates.
  • coated offset printing plates obtained from the carrier materials produced by the process according to the invention are converted into the desired printing form in a known manner by imagewise exposure or irradiation and growth of the non-image areas with a developer, for example an aqueous alkaline developer solution.
  • a developer for example an aqueous alkaline developer solution.
  • An aluminum sheet is initially in an aqueous solution with a content of 60 sec 20 g NaOH per pickled at room temperature and then freed from any alkali residues by briefly immersing them in a solution corresponding to the roughening electrolyte.
  • the roughening takes place in the electrolyte systems shown in the following tables and under the conditions listed there.
  • an anodic oxidation is carried out in an aqueous electrolyte containing H 2 S0 4 and Al 3+ ions up to a layer weight of 3.0 g / m 2 .
  • the classification into the quality classes is carried out by visual assessment under a microscope, whereby a homogeneously roughened and scar-free surface is assigned quality level «1» (best value).
  • Quality level “10” (worst value) is assigned to a surface with thick scars of a size of more than 100 ⁇ m or an extremely unevenly roughened or almost rolled surface.
  • Intermediate qualities are rated "2" to "9". All examples and the comparative examples are carried out with symmetrical alternating current at a frequency of 50 Hz, one electrode being the aluminum sheet and the other a graphite plate.
  • An aluminum sheet prepared according to Example 21 is immersed at 40 ° C. for 30 seconds in an aqueous solution containing 5 g / 1 of polyvinylphosphonic acid and then rinsed with deionized water and dried. To produce a lithographic printing plate, the sheet is coated with the following negative-working light-sensitive solution.
  • a carrier material produced according to Example 4 is coated with the following solution in order to produce an electrophotographic offset printing plate: 300.00 parts by weight of ethylene glycol monomethyl ether.
  • the layer is negatively charged to about 400 V in the dark by means of a corona.
  • the charged plate is exposed imagewise in a repro camera and then with an electrophotographic suspension developer, which by dispersing 3.0 parts by weight of magnesium sulfate in a solution of 7.5 parts by weight of pentaerythritol resin in 1200 parts by volume of an isoparaffin mixture with a Boiling range of 185 to 210 ° C was obtained.
  • the developer is fixed and the plate in a solution of 35 parts by weight of sodium metasilicate for 60 seconds.
  • 9 H 2 0, 140 parts by weight of glycerol, 550 parts by weight of ethylene glycol and 140 parts by weight of ethanol immersed.
  • the plate is then rinsed off with a powerful jet of water, removing the areas of the photoconductor layer not covered with toner.
  • the printing form is then ready for printing.

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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)
EP84116021A 1984-01-05 1984-12-21 Verfahren zur elektrochemischen Aufrauhung von Aluminium für Druckplattenträger in einem wässrigen Mischelektrolyten Expired EP0151304B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843400248 DE3400248A1 (de) 1984-01-05 1984-01-05 Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger in einem waessrigen mischelektrolyten
DE3400248 1984-01-05

Publications (3)

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EP0151304A2 EP0151304A2 (de) 1985-08-14
EP0151304A3 EP0151304A3 (en) 1985-09-11
EP0151304B1 true EP0151304B1 (de) 1987-05-13

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EP84116021A Expired EP0151304B1 (de) 1984-01-05 1984-12-21 Verfahren zur elektrochemischen Aufrauhung von Aluminium für Druckplattenträger in einem wässrigen Mischelektrolyten

Country Status (8)

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US (1) US4566959A (es)
EP (1) EP0151304B1 (es)
JP (1) JPS60159093A (es)
BR (1) BR8500015A (es)
CA (1) CA1256059A (es)
DE (2) DE3400248A1 (es)
ES (1) ES8700338A1 (es)
ZA (1) ZA8590B (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101229518B1 (ko) * 2006-02-03 2013-02-04 퀄컴 인코포레이티드 무선 통신에서의 콘텐츠 보호 방법 및 장치

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3503927A1 (de) * 1985-02-06 1986-08-07 Hoechst Ag, 6230 Frankfurt Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger
GB9113214D0 (en) * 1991-06-19 1991-08-07 Alcan Int Ltd Treating al sheet
DE4129909A1 (de) * 1991-09-09 1993-03-11 Hoechst Ag Verfahren zum aufrauhen von aluminium bzw. von aluminiumlegierungen als traegermaterial fuer druckplatten und eine druckplatte
US5432046A (en) * 1993-09-29 1995-07-11 Hoechst Celanese Corporation Process for preparing improved lithographic printing plates by brushgraining with alumina/quartz slurry
BRPI0802427A2 (pt) * 2008-08-05 2010-03-23 Ibf Ind Brasileira De Filmes L processo para o tratamento das superfÍcies de chapas de alumÍnio para uso em impressço de imagens digitalizadas, processo para a produÇço de chapas de alumÍnio prÉ-sensibilizada e chapa
US20120091495A1 (en) 2009-06-26 2012-04-19 Fujifilm Corporation Light reflecting substrate and process for manufacture thereof
JP2012033853A (ja) 2010-04-28 2012-02-16 Fujifilm Corp 絶縁性光反射基板
US9573404B2 (en) 2011-10-28 2017-02-21 Fujifilm Corporation Manufacturing method and manufacturing apparatus of support for planographic printing plate
JP6199416B2 (ja) 2014-01-31 2017-09-20 富士フイルム株式会社 アルミニウム板の製造方法、アルミニウム板、蓄電デバイス用集電体、蓄電デバイス、防音・吸音材、電磁波シールドおよび建築用材料
WO2017150099A1 (ja) 2016-02-29 2017-09-08 富士フイルム株式会社 複合体
JP6636612B2 (ja) 2016-03-25 2020-01-29 富士フイルム株式会社 アルミニウム板の製造方法、及び、アルミニウム板の製造装置
JPWO2018168786A1 (ja) 2017-03-13 2020-01-16 富士フイルム株式会社 電磁波シールド部材
EP3605525B1 (en) 2017-03-27 2022-03-30 FUJIFILM Corporation Soundproof structure
JPWO2018235659A1 (ja) 2017-06-21 2020-04-16 富士フイルム株式会社 アルミニウム複合材料
JP6866480B2 (ja) 2017-06-21 2021-04-28 富士フイルム株式会社 加飾フィルム
JPWO2019039469A1 (ja) 2017-08-22 2020-10-15 富士フイルム株式会社 防音構造体および吸音パネル
WO2019044589A1 (ja) 2017-08-28 2019-03-07 富士フイルム株式会社 防音構造、及び防音構造体
KR20200044057A (ko) 2017-09-29 2020-04-28 후지필름 가부시키가이샤 적층체

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE120061C (es) * 1900-02-05
GB294237A (en) * 1927-07-22 1929-09-12 Electrolux Ltd A process for treating aluminium or other light metals
US2336846A (en) * 1938-01-03 1943-12-14 Gen Electric Etching of capacitor armatures
DE695182C (de) * 1939-01-25 1940-08-19 Mahle Kg Verfahren zur Erzeugung von Poren auf Laufflaechentmaschinen
US2775553A (en) * 1952-12-31 1956-12-25 Sprague Electric Co Electrolytic etching process for electrolytic capacitors
US3330745A (en) * 1964-08-11 1967-07-11 Grace W R & Co Electrolytic process for graft polymerization
DE1496825A1 (de) * 1965-04-13 1969-04-10 Fischer Dr Wilhelm Anton Verfahren zur elektrochemischen Behandlung von als Anode geschalteten Werkstuecken
US3445355A (en) * 1966-07-15 1969-05-20 Ibm Method and composition for the electrolytic etching of beryllium-copper alloys
DE1621115C3 (de) * 1967-10-17 1981-06-25 Metalloxyd GmbH, 5000 Köln Verfahren zur Herstellung eines Trägers aus Aluminium für lithographische Druckplatten
JPS517081B1 (es) * 1971-04-17 1976-03-04
DE2250275A1 (de) * 1972-10-13 1974-04-25 Oce Van Der Grinten Nv Verfahren zur elektrochemischen behandlung von aluminium zur herstellung lithographischer druckplatten
FR2241633B1 (es) * 1973-07-13 1976-06-18 Ugine Kuhlmann
US3963594A (en) * 1975-06-03 1976-06-15 Aluminum Company Of America Electrochemical treatment of aluminum surfaces with an aqueous solution of hydrochloric acid and gluconic acid
JPS5317580A (en) * 1976-08-02 1978-02-17 Yuuroku Dev Ab Method of increasing filtration and sedimentation of suspension of macromolecular biological substances
US4072589A (en) * 1977-04-13 1978-02-07 Polychrome Corporation Process for electrolytic graining of aluminum sheet
US4502925A (en) * 1984-06-11 1985-03-05 American Hoechst Corporation Process for aluminum surface preparation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101229518B1 (ko) * 2006-02-03 2013-02-04 퀄컴 인코포레이티드 무선 통신에서의 콘텐츠 보호 방법 및 장치

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BR8500015A (pt) 1985-08-13
ES8700338A1 (es) 1986-10-01
US4566959A (en) 1986-01-28
EP0151304A3 (en) 1985-09-11
DE3400248A1 (de) 1985-07-18
JPH0462279B2 (es) 1992-10-05
EP0151304A2 (de) 1985-08-14
DE3463681D1 (en) 1987-06-19
CA1256059A (en) 1989-06-20
ZA8590B (en) 1985-08-28
JPS60159093A (ja) 1985-08-20
ES539251A0 (es) 1986-10-01

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