EP0162281B1 - Procédé de grainage électrochimique d'aluminium pour supports de plaques d'impression dans un électrolyte composite aqueux - Google Patents

Procédé de grainage électrochimique d'aluminium pour supports de plaques d'impression dans un électrolyte composite aqueux Download PDF

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Publication number
EP0162281B1
EP0162281B1 EP85104603A EP85104603A EP0162281B1 EP 0162281 B1 EP0162281 B1 EP 0162281B1 EP 85104603 A EP85104603 A EP 85104603A EP 85104603 A EP85104603 A EP 85104603A EP 0162281 B1 EP0162281 B1 EP 0162281B1
Authority
EP
European Patent Office
Prior art keywords
acid
aqueous
aluminum
roughening
printing plate
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
EP85104603A
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German (de)
English (en)
Other versions
EP0162281A2 (fr
EP0162281A3 (en
Inventor
Dieter Dr. Dipl.-Chem. Mohr
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0162281A2 publication Critical patent/EP0162281A2/fr
Publication of EP0162281A3 publication Critical patent/EP0162281A3/de
Application granted granted Critical
Publication of EP0162281B1 publication Critical patent/EP0162281B1/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

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 support 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 HCI or HN0 3 solutions, in aqueous salt solutions such as aqueous NaCl or Al (N0 3 ) 3 solutions or in a combination of these components 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 Lithography Sheet” by AJ Dowell in Transactions of the Institute of Metal Finishing, 1979, Vol. 57, pp. 138 to 144 contains basic explanations made for roughening aluminum in aqueous hydrochloric acid solutions, the following process parameters being varied and the corresponding effects being investigated.
  • the electrolyte composition is changed when the electrolyte is used several times, for example with regard to the H + (H 3 O + ) ion concentration (measurable via the pH value) of the Al 3 + 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 only minor changes occur 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.
  • S0 4 2- ions or CI ions in salt form [eg by adding Al 2 (SO 4 ) 3 or NaC11 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 used in the previously known electrolyte solutions based on aqueous HCL solutions in modern, high-speed, high-performance systems can only be achieved under difficult conditions; For example - what is always difficult to control in terms of process - the process parameters must be kept within very narrow limits.
  • the previously 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 A1 3+ ions to dissolve the aluminum and thereby increase 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 organic carboxylic acid under the action of alternating current.
  • the aqueous electrolyte solution contains 0.5 to 10.0%, in particular 0.8 to 5.0%, of HCl and 0.1 to 8.0%, in particular 0.2 to 5.0%, of haloalkanoic acid (n).
  • 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 particular with continuous process control tion, in the electrochemical roughening stage in the following areas: 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 roughened material point in the electrolyte between 1 and 300 sec and the electrolyte flow rate on 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 with a frequency of 50 to 60 Hz is 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 frequencies and waveforms 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% 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.
  • 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 which essentially only have a rinsing and / or. have a cleaning effect and serve, for example, to remove deposits ( «Schmant») formed during roughening or simply to remove 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.
  • 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 washing out of the non-image areas with a developer, for example an aqueous alkaline developer solution.
  • a developer for example an aqueous alkaline developer solution.
  • % data always mean% by weight, unless stated otherwise. Parts by weight relate to parts by volume in the ratio of g to c m3 .
  • An aluminum sheet is first pickled for 60 seconds in an aqueous solution of 20 g NaOH per 1 at room temperature and then freed of any alkali residues that may be present by briefly immersing it 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 takes place by visual assessment under the microscope, whereby the quality level «1 (best value) is assigned to a homogeneously roughened and scar-free surface.
  • the quality pencil "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 example Games are carried out with symmetrical alternating current with a frequency of 50 Hz, one electrode being the aluminum sheet and the other a graphite plate.
  • An aluminum sheet prepared according to Example 12 is immersed at 40 ° C. for 30 seconds in an aqueous solution containing 5 g / l of polyvinylphosphonic acid and then rinsed with fully demineralized 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 18 is coated with the following solution in order to produce an electrophotographically operated offset printing plate:
  • 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 is obtained by dispersing 3.0 parts by weight of magnesium sulfate in a solution of 7.5 parts by weight of pentaerythritol resin ester 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, the areas of the photoconductor layer not covered with toner being removed.
  • the printing form is then ready for printing.

Landscapes

  • 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 d'impression, dans une solution électrolytique aqueuse mixte contenant HCI et au moins un acide organique carboxylique, sous l'effet d'un courant alternatif, caractérisé en ce que l'acide organique carboxylique est un acide halogéno-alcanoïque de formule générale HalxHy-xCz-COOH, dans laquelle Hal représente un atome d'halogène, z est un nombre entier valant de 1 à 5, y = 2z + 1 et x représente un nombre entier allant de 1 à y.
2. Procédé selon la revendication 1, caractérisé en ce que l'électrolyte mixte contient de 0, 5 à 10,0% en poids de HCI et 0, 1 à 8,0% en poids d'acideis) halogéno-alcanoïque(s).
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'électrolyte mixte contient de 0,8 à 5,0% en poids de HCI et 0,2 à 5,0% en poids d'acide(s) halogéno-alcanoïque(s).
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que, dans la formule générale, z représente 1 ou 2, x = 1 à 3 et Hal représente F ou CI.
5. Utilisation du procédé selon l'une des revendications 1 à 4, dans la fabrication de plaques d'impression offset portant une couche sensible aux radiations.
EP85104603A 1984-04-25 1985-04-16 Procédé de grainage électrochimique d'aluminium pour supports de plaques d'impression dans un électrolyte composite aqueux Expired EP0162281B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3415338 1984-04-25
DE19843415338 DE3415338A1 (de) 1984-04-25 1984-04-25 Verfahren zur elektrochemischen aufrauhung von aluminium fuer druckplattentraeger in einem waessrigen mischelektrolyten

Publications (3)

Publication Number Publication Date
EP0162281A2 EP0162281A2 (fr) 1985-11-27
EP0162281A3 EP0162281A3 (en) 1986-01-15
EP0162281B1 true EP0162281B1 (fr) 1987-09-16

Family

ID=6234306

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85104603A Expired EP0162281B1 (fr) 1984-04-25 1985-04-16 Procédé de grainage électrochimique d'aluminium pour supports de plaques d'impression dans un électrolyte composite aqueux

Country Status (4)

Country Link
US (1) US4600482A (fr)
EP (1) EP0162281B1 (fr)
JP (1) JPS60234895A (fr)
DE (2) DE3415338A1 (fr)

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JPS6399992A (ja) * 1986-05-07 1988-05-02 Fuji Photo Film Co Ltd 平版印刷版用支持体の製造方法
US4818300A (en) * 1986-12-08 1989-04-04 Aluminum Company Of America Method for making lithoplate
US5028276A (en) * 1990-02-16 1991-07-02 Aluminum Company Of America Method for making lithoplate having improved grainability
US5176763A (en) * 1991-07-01 1993-01-05 Aluminum Company Of America Method for making lithoplate having improved grainability
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
JPH0665934U (ja) * 1993-02-10 1994-09-16 日新工機株式会社 テンキー一体型マウス
CN102460749A (zh) 2009-06-26 2012-05-16 富士胶片株式会社 光反射基板及其制造方法
DE102009033368B4 (de) * 2009-07-16 2023-01-26 Bruker Daltonics GmbH & Co. KG Massenspektrometrische Sepsisdiagnose
JP2012033853A (ja) 2010-04-28 2012-02-16 Fujifilm Corp 絶縁性光反射基板
CN103085523B (zh) 2011-10-28 2016-12-21 富士胶片株式会社 用于平版印刷版的载体的制备方法和制备装置
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
CN105277653A (zh) * 2014-06-25 2016-01-27 上海宝钢化工有限公司 一种检测粘油中水分含量的方法
WO2017150099A1 (fr) 2016-02-29 2017-09-08 富士フイルム株式会社 Corps composite
WO2017163913A1 (fr) 2016-03-25 2017-09-28 富士フイルム株式会社 Procédé de fabrication de feuille d'aluminium et appareil de fabrication de feuille d'aluminium
KR20190111115A (ko) 2017-03-13 2019-10-01 후지필름 가부시키가이샤 전자파 실드 부재
JP6757462B2 (ja) 2017-03-27 2020-09-16 富士フイルム株式会社 防音構造体、ならびに、吸音パネルおよび調音パネル
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
CN111033608A (zh) 2017-08-22 2020-04-17 富士胶片株式会社 隔音结构体及吸音面板
WO2019044589A1 (fr) 2017-08-28 2019-03-07 富士フイルム株式会社 Structure et corps insonorisés
EP3689595A1 (fr) 2017-09-29 2020-08-05 FUJIFILM Corporation Stratifié

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GB1006207A (en) * 1963-10-09 1965-09-29 Reynolds Metals Co Improvements in the treatment of aluminium and aluminium base alloy surfaces
JPS517081B1 (fr) * 1971-04-17 1976-03-04
GB1392191A (en) * 1971-07-09 1975-04-30 Alcan Res & Dev Process for electrograining aluminium
DE2250275A1 (de) * 1972-10-13 1974-04-25 Oce Van Der Grinten Nv Verfahren zur elektrochemischen behandlung von aluminium zur herstellung lithographischer druckplatten
FR2241633B1 (fr) * 1973-07-13 1976-06-18 Ugine Kuhlmann
US4052275A (en) * 1976-12-02 1977-10-04 Polychrome Corporation Process for electrolytic graining of aluminum sheet
GB1598701A (en) * 1977-04-16 1981-09-23 Vickers Ltd Electrolytic graining of aluminium or aluminium alloy surfaces
JPS56135095A (en) * 1980-03-26 1981-10-22 Mitsubishi Chem Ind Ltd Manufacture of supporter for planographic process block
JPS5724294A (en) * 1980-07-18 1982-02-08 Mitsubishi Chem Ind Ltd Production of support for planographic printing plate

Also Published As

Publication number Publication date
DE3415338A1 (de) 1985-10-31
JPH054236B2 (fr) 1993-01-19
EP0162281A2 (fr) 1985-11-27
JPS60234895A (ja) 1985-11-21
DE3560642D1 (en) 1987-10-22
US4600482A (en) 1986-07-15
EP0162281A3 (en) 1986-01-15

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