EP0093961B1 - Procédé de grainage électrochimique de l'aluminium pour des supports de plaques d'impression - Google Patents

Procédé de grainage électrochimique de l'aluminium pour des supports de plaques d'impression Download PDF

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Publication number
EP0093961B1
EP0093961B1 EP83104146A EP83104146A EP0093961B1 EP 0093961 B1 EP0093961 B1 EP 0093961B1 EP 83104146 A EP83104146 A EP 83104146A EP 83104146 A EP83104146 A EP 83104146A EP 0093961 B1 EP0093961 B1 EP 0093961B1
Authority
EP
European Patent Office
Prior art keywords
alternating current
aluminum
current
printing plate
von
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
EP83104146A
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German (de)
English (en)
Other versions
EP0093961A1 (fr
Inventor
Engelbert Dr. Dipl.-Chem. Pliefke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0093961A1 publication Critical patent/EP0093961A1/fr
Application granted granted Critical
Publication of EP0093961B1 publication Critical patent/EP0093961B1/fr
Expired legal-status Critical Current

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Classifications

    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/09—Wave forms

Definitions

  • the invention relates to a process for the electrochemical roughening of aluminum or its alloys for printing plate supports, which is carried out with superimposed alternating current in one of the customary acid and / or salt electrolytes, and the use of the process for producing roughened aluminum for printing plate supports.
  • Printing plates generally consist of a support and at least one radiation-sensitive reproduction layer arranged thereon, this layer either from the consumer (in the case of non-precoated plates) or from the industrial one Manufacturer (for pre-coated boards) is applied to the substrate.
  • Aluminum or one of its alloys has established itself as a substrate 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 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 HCl or HNO 3 solutions or in aqueous salt solutions such as aqueous NaCl 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.
  • aqueous solutions with several components in the roughening of aluminum can lead to more or less uniformly roughened surfaces, but the monitoring of the bath composition, particularly in the case of the currently preferred continuous high-speed belt systems, is very complex, but necessary in practice, because the composition of the electrolyte changes frequently during the process.
  • the object of the present invention is therefore to propose a method for the electrochemical roughening of aluminum for printing plate supports, which can be carried out with superimposed alternating current of various frequencies in a wide variety of electrolytes and which results in a uniform and dense roughening structure which serves to ensure good water management.
  • the invention relates to a process for the electrochemical roughening of aluminum or its alloys for printing plate supports in an aqueous electrolyte under the action of superimposed alternating current, the alternating current consisting of at least two types of alternating current with different frequencies and the ratio of the amplitudes of the superimposed alternating current (Alternating currents) to the carrier alternating current is set to values between 0.1 and 10 and the frequency of the superimposed alternating current (alternating currents) is 3 to 100 times greater than the frequency of the carrier alternating current.
  • the AC type with the lowest frequency is referred to as the carrier current and the AC type (s) with the higher frequency (s) is referred to as the superimposed current.
  • the ratio of the amplitudes of superimposing alternating current to carrier alternating current is between 0.2 and 2. Only two types of alternating current are expediently superimposed on one another in the method according to the invention.
  • the shape of the alternating current - in the case of a graphical representation of the course of the current density or voltage as a function of time - can have, for example, a rectangular, trapezoidal or sine curve, in the method according to the invention a combination of rectangular shape for the carrier alternating current and sinusoidal shape for the superimposed alternating current is preferred .
  • the process according to the invention is carried out either discontinuously or preferably continuously with strips made of aluminum or its alloys.
  • the process parameters in continuous processes during roughening are in the following ranges: the temperature of the electrolyte between 20 and 60 ° C, the electrolyte (acid and / or salt) concentration between 1 and 250 g, in particular between 5 and 100 g / I, the current density between 3 and 130 A / dm 2 , the residence time of a material point to be roughened in the electrolyte between 10 and 300 sec and the electrolyte flow rate at the surface of the material to be roughened between 5 and 100 cm / sec.
  • Direct current is preferably used for the anodic oxidation, however alternating current or a combination of these types of current (eg direct current with superimposed alternating current) can also be used.
  • the layer weights of aluminum oxide range from 1 to 10 g / m 2 , corresponding to a layer thickness of approximately 0.3 to 3.0 ⁇ m.
  • a modification can also be applied which causes surface abrasion from the roughened surface, as described, for example, in DE-OS 30 09 103.
  • a modifying intermediate treatment can, among other things, enable the build-up of abrasion-resistant oxide layers and a lower tendency to tone during later printing.
  • the stage of anodic oxidation of the aluminum printing plate 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 already sufficient for many areas of application, the remaining known properties of this layer being at least retained.
  • all layers are suitable as light-sensitive reproduction layers which, after exposure, optionally with subsequent development and / or fixation, provide an image-like area from which printing can take place and / or which represent a relief image of an original. They are applied either by the manufacturer of presensitized printing plates or by so-called dry resists or directly by the consumer to one of the carrier materials roughened according to the invention.
  • the reproduction layers include those such as z. B.
  • Suitable layers also include the electrophotographic layers, i.e. H.
  • these layers can of course also other components such.
  • the following light-sensitive compositions or compounds can be used in the coating of the carrier materials:
  • Positive-working o-quinonediazide preferably o-naphthoquinonediazide compounds, which are described, for example, in DE-PS 854 890, 865 109, 879 203, 894 959, 938 233, 1 109 521, 1 144 705, 1 118 606, 1 120 273 and 1 124 817.
  • Negative-working 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-PS 596 731, 1 138 399, 1 138 400, 1 138 401, 1 142 871, 1 154 123 U.S. Patents 2,679,498 and 3,050,502 and British Patent 712,606.
  • Negative mixed condensation products of aromatic diazonium compounds for example according to DE-OS 20 24 244, which each have at least one unit of the general types A ⁇ -D) n and B connected by a double-bonded intermediate member derived from a condensable carbonyl compound.
  • A is the remainder of a compound containing at least two aromatic carbocyclic and / or heterocyclic nuclei, which is capable of condensing with an active carbonyl compound in an acidic medium at at least one position.
  • D is a diazonium salt group attached to an aromatic carbon atom of A; n is an integer from 1 to 10; and B is the remainder of a compound free of diazonium groups and capable of condensing with an active carbonyl compound in an acidic medium at at least one position on the molecule.
  • Positive-working layers according to DE-OS 26 10 842 which contain a compound which splits off acid when irradiated, a compound which has at least one C-O-C group which can be split off by acid (e.g. an orthocarboxylic acid ester group or a carboxylic acid amide acetal group) and, if appropriate, a binder.
  • acid e.g. an orthocarboxylic acid ester group or a carboxylic acid amide 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-OSes 20 64 079 and 23 61 041.
  • photoinitiators are u. a. Benzoin, benzoin ethers, multinuclear quinones, acridine derivatives, phenazine derivatives, quinoxaline derivatives, quinazoline derivatives or synergistic mixtures of different ketones.
  • soluble organic polymers can be used as binders, e.g. B. polyamides, polyesters, alkyd resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin or cellulose ether.
  • Negative working layers according to DE-OS 30 36 077 which contain a diazonium salt polycondensation product or an organic azido compound as a photosensitive compound and a high molecular weight polymer with pendant alkenylsulfonyl or cycloalkenylsulfonylurethane groups as a binder.
  • photoconductive layers such as z. B. in DE-PSs 11 17 391, 15 22 497, 15 72 312, 23 22 046 and 23 22 047 described, applied to the carrier materials. , which results in highly light-sensitive, electrophotographic layers.
  • the materials for printing plate supports roughened by the process according to the invention have a uniform topography, which has a positive influence on the support stability and the water flow during printing of printing forms made from these supports.
  • "scars" marked depressions compared to the roughening of the surroundings
  • These surface properties can be realized without particularly great expenditure on equipment and without continuous qualitative and quantitative bath monitoring.
  • the uniformity of the roughening may be due to the fact that the gas bubbles formed on the aluminum surface during the electrochemical reaction can be detached from the surface more easily in the process according to the invention.
  • Example 7 a rectangular current is always used as the carrier alternating current and a sinusoidal current as the superimposing alternating current; in example 7, a sinusoidal current is also used as the carrier alternating current.
  • An aluminum sheet is first pickled for 60 seconds in an aqueous solution of 20 g NaOH per liter at room temperature and then by briefly immersing it in the roughening electrolyte. Corresponding solution freed from any alkali residues that may be present.
  • the roughening takes place either under galvanostatic or potentiostatic control in the specified electrolytes, in the latter the reference electrode being either the Ag / AgCI system saturated (Ex. 32, V8, 34 and 35) or the counter electrode (Ex. 33).
  • Examples 1 to 31 and V1 to V7 are galvanostatically (Table 1) and Examples 32 to 35 and V8 (Table 11) controlled potentiostatically.
  • the electrolysis is started at room temperature of the electrolyte.
  • a printing plate which has been anodically oxidized and coated in accordance with Example 36, but which is roughened in accordance with Comparative Example V2, results in a printing form after development, of which only 75,000 sheets can be printed.

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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)

Claims (5)

1. Procédé pour le grainage électrochimique d'aluminium ou de ses alliages pour supports de plaques dimpression, au moyen de courant alternatif superposé, dans un électrolyte aqueux, le courant alternatif étant composé d'au moins deux types de courants alternatifs de fréquences différentes, et le rapport de l'amplitude du (des) courant(s) alternatif(s) superposé(s) à l'amplitude du courant alternatif porteur étant ajusté à des valeurs comprises entre 0,1 et 10, et la fréquence du (des) courant(s) alternatif(s) superposé(s) étant de 3 à 100 fois plus élevée que la fréquence du courant alternatif porteur.
2. Procédé selon la revendication 1, caractérisé en ce que le rapport de l'amplitude du courant alternatif superposé à l'amplitude du courant alternatif porteur est compris entre 0,2 et 2.
3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que le courant alternatif porteur présente une forme rectangulaire et le courant alternatif superposé présente une forme sinusoïdale.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'on utilise comme électrolyte des solutions aqueuses à base de HCI et/ou HN03.
5. Utilisation du procédé selon l'une des revendications 1 à 4, pour la préparation d'aluminium grainé ou de ses alliages grainés, pour supports de plaques d'impression.
EP83104146A 1982-05-10 1983-04-28 Procédé de grainage électrochimique de l'aluminium pour des supports de plaques d'impression Expired EP0093961B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3217499A DE3217499A1 (de) 1982-05-10 1982-05-10 Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger
DE3217499 1982-05-10

Publications (2)

Publication Number Publication Date
EP0093961A1 EP0093961A1 (fr) 1983-11-16
EP0093961B1 true EP0093961B1 (fr) 1987-06-10

Family

ID=6163182

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83104146A Expired EP0093961B1 (fr) 1982-05-10 1983-04-28 Procédé de grainage électrochimique de l'aluminium pour des supports de plaques d'impression

Country Status (7)

Country Link
US (1) US4468295A (fr)
EP (1) EP0093961B1 (fr)
JP (1) JPS58207374A (fr)
AU (1) AU550815B2 (fr)
BR (1) BR8302397A (fr)
CA (1) CA1209522A (fr)
DE (2) DE3217499A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6068997A (ja) * 1983-09-27 1985-04-19 Fuji Photo Film Co Ltd 平版印刷版用アルミニウム支持体の製造方法
US4525249A (en) * 1984-07-16 1985-06-25 North American Philips Corporation Two step electro chemical and chemical etch process for high volt aluminum anode foil
US4545875A (en) * 1984-08-06 1985-10-08 Polychrome Corporation Electrolytic graining
US4548683A (en) * 1984-09-28 1985-10-22 Polychrome Corp. Method of electrolytically graining a lithographic plate
DE3533532A1 (de) * 1985-09-20 1987-04-02 Hoechst Ag Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger
JPS6282089A (ja) * 1985-10-04 1987-04-15 Fuji Photo Film Co Ltd 平版印刷版用支持体の製造方法
DE3714059C3 (de) * 1987-04-28 1995-12-07 Vaw Ver Aluminium Werke Ag Material in Band- oder Plattenform und Verfahren zu seiner Herstellung sowie dessen Verwendung als Träger für Flachdruckformen
GB9112211D0 (en) * 1991-06-06 1991-07-24 Alcan Int Ltd Treating a1 sheet
JP3117322B2 (ja) * 1993-04-05 2000-12-11 富士写真フイルム株式会社 感光性平版印刷版およびその支持体の製造方法
GB9326150D0 (en) * 1993-12-22 1994-02-23 Alcan Int Ltd Electrochemical roughening method
US5500101A (en) * 1993-12-28 1996-03-19 Nihon Chikudenki Kogyo Kabushiki Kaisha Method of etching aluminum foil for electrolytic capacitor
DE69512321T2 (de) 1994-06-16 2000-05-11 Kodak Polychrome Graphics Llc, Norwalk Lithographische Druckplatten mit einer oleophilen bilderzeugenden Schicht
US20030032879A1 (en) * 1997-07-07 2003-02-13 Steven Quay Microbubble formation using ultrasound
US20030047464A1 (en) * 2001-07-27 2003-03-13 Applied Materials, Inc. Electrochemically roughened aluminum semiconductor processing apparatus surfaces
JP4654083B2 (ja) * 2005-07-20 2011-03-16 富士フイルム株式会社 金属粒子型反応触媒およびその製造方法、並びに該触媒を用いた有機合成反応装置
US20080253922A1 (en) * 2007-04-13 2008-10-16 General Electric Company Method for roughening metal surfaces and article manufactured thereby

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GB879768A (en) * 1958-11-19 1961-10-11 Algraphy Ltd Improvements in or relating to the production of lithographic plates
US3193485A (en) * 1960-09-20 1965-07-06 Plessey Co Ltd Electrolytic treatment of aluminium for increasing the effective surface
BE633210A (fr) * 1962-06-15
DE1496956A1 (de) * 1965-03-15 1969-11-27 Paehr Dr Hans Werner Verfahren zur AEtzung von Metallbaendern
GB1439127A (en) * 1972-06-08 1976-06-09 Alcan Res & Dev Production of lithographic plates
DE2250275A1 (de) * 1972-10-13 1974-04-25 Oce Van Der Grinten Nv Verfahren zur elektrochemischen behandlung von aluminium zur herstellung lithographischer druckplatten
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
US4140599A (en) * 1975-06-04 1979-02-20 Fujitsu Limited Process for producing porous aluminum anode element
GB1548689A (en) * 1975-11-06 1979-07-18 Nippon Light Metal Res Labor Process for electrograining aluminum substrates for lithographic printing
US4072589A (en) * 1977-04-13 1978-02-07 Polychrome Corporation Process for electrolytic graining of aluminum sheet
JPS5926480B2 (ja) * 1978-03-27 1984-06-27 富士写真フイルム株式会社 平版印刷版用支持体
US4177744A (en) * 1978-07-28 1979-12-11 The Singer Company Digital override control of bight and feed in a sewing machine
DE2836803A1 (de) * 1978-08-23 1980-03-06 Hoechst Ag Verfahren zur anodischen oxidation von aluminium und dessen verwendung als druckplatten-traegermaterial
DE3012135C2 (de) * 1979-03-29 1986-10-16 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Träger für lithographische Druckplatten, Verfahren zu seiner Herstellung und seine Verwendung zur Herstellung von vorsensibilisierten Druckplatten
JPS55158298A (en) * 1979-05-30 1980-12-09 Fuji Photo Film Co Ltd Manufacture of support for lithographic plate
JPS5629699A (en) * 1979-08-15 1981-03-25 Fuji Photo Film Co Ltd Surface roughening method by electrolysis
US4324841A (en) * 1979-08-24 1982-04-13 Polychrome Corporation Lithographic substrates
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US4396468A (en) * 1981-12-21 1983-08-02 American Hoechst Corporation Three phase graining of aluminum substrates

Also Published As

Publication number Publication date
EP0093961A1 (fr) 1983-11-16
JPS58207374A (ja) 1983-12-02
BR8302397A (pt) 1984-01-10
CA1209522A (fr) 1986-08-12
AU550815B2 (en) 1986-04-10
JPH0568560B2 (fr) 1993-09-29
DE3372001D1 (en) 1987-07-16
AU1430083A (en) 1983-11-17
US4468295A (en) 1984-08-28
DE3217499A1 (de) 1983-11-10

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