EP0170045B1 - Procédé pour le décapage et le chromage simultanés de plaques d'acier comme supports pour des utilisations lithographiques - Google Patents

Procédé pour le décapage et le chromage simultanés de plaques d'acier comme supports pour des utilisations lithographiques Download PDF

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Publication number
EP0170045B1
EP0170045B1 EP85107827A EP85107827A EP0170045B1 EP 0170045 B1 EP0170045 B1 EP 0170045B1 EP 85107827 A EP85107827 A EP 85107827A EP 85107827 A EP85107827 A EP 85107827A EP 0170045 B1 EP0170045 B1 EP 0170045B1
Authority
EP
European Patent Office
Prior art keywords
ions
chromium
treatment
plates
electrolyte
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
EP85107827A
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German (de)
English (en)
Other versions
EP0170045A1 (fr
Inventor
Engelbert 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
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 EP0170045A1 publication Critical patent/EP0170045A1/fr
Application granted granted Critical
Publication of EP0170045B1 publication Critical patent/EP0170045B1/fr
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N1/00—Printing plates or foils; Materials therefor
    • B41N1/04—Printing plates or foils; Materials therefor metallic
    • B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
    • 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
    • C25F3/06—Etching of iron or steel
    • 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
    • Y10S205/00—Electrolysis: processes, compositions used therein, and methods of preparing the compositions
    • Y10S205/921—Electrolytic coating of printing member, other than selected area coating

Definitions

  • the present invention relates to a method for roughening and chroming steel plates for lithographic applications (offset printing plate support) in one and the same electrolyte.
  • Offset printing plates which in the following are referred to as printing plates for the sake of simplicity, generally consist of a support on which at least one radiation-sensitive reproduction layer is applied, with this either on the support in the case of non-precoated plates by the consumer or in the case of precoated (presensitized) plates by the industrial manufacturer is applied.
  • Metallic materials are mainly used as the printing plate carrier, mainly aluminum and its alloys being used. But carrier plates made of normal carbon steel or steel alloys (chrome-nickel steels, manganese steels etc.) are also used.
  • the printing plate In order to achieve certain properties necessary for a printing plate, such as adhesion to the layer, differentiation of hydrophilic and hydrophobic areas with specific behavior, corrosion properties, hardness of the surface, which is important for the print run, the printing plate is generally subjected to a pretreatment. These include, for example, modification by mechanical, chemical, electrochemical roughening, which is also called graining or etching, chemical or electrochemical oxidation of the surface, treatment with hydrophilizing agents or temperature hardening.
  • the modification usually consists of a combination of mechanical and / or electrochemical roughening and an anodic oxidation, optionally with a subsequent hydrophilization step.
  • Base plates based on aluminum are used extensively and have largely proven themselves, even if they have a lower mechanical strength and abrasion resistance than steel plates due to the material. However, they are not accessible to an advantageous magnetic attachment on the printing cylinders. The desirable property of magnetic fastening is of particular interest in high-speed reel machines.
  • multilayer plates which consist of a base support made of aluminum or steel, on which are made of two different metals, printing and non-printing areas are available.
  • the printing areas are mainly made of copper, the non-printing areas are made of chrome.
  • the roughening is carried out in a solution of bifluorides, the cathodic chromium plating in a bath of chromium oxide and sulfuric acid.
  • the conditions for the rinsing processes in particular become critical, since otherwise no uniform plates are formed.
  • the pre-chromium plating is carried out in a bath of chromic acid and nitric acid, the main chromium plating in a bath of chromic acid and sulfuric acid, the current density and the temperature in the second bath being higher.
  • the aftertreatment is carried out by treatment with a solution of a water-soluble polymer such as. B. gum arabic and a water-soluble salt, such as. B. zinc acetate.
  • a water-soluble polymer such as. B. gum arabic
  • a water-soluble salt such as. B. zinc acetate
  • EP-A 0 097 503. A similar multi-stage treatment for the production of chrome-plated steel plates is known from EP-A 0 097 503.
  • the main difference to EP-A 0 097 502 lies in the individual bath compositions.
  • the above object is achieved by a process for the production of chrome-plated steel plates for use in lithography, the steel plate being treated electrochemically in an acid bath containing chromium ions, the characteristic feature of which is that the steel plate is in a 10 to 300 g / l Chromium ions 1-50 g / I chloride ions, sulfate ions and optionally electrolytes containing up to 100 g / I strontium ions are first roughened with alternating current and partially chromed and then finally chromed in the same bath using direct current, with a current treatment time of 5 to 300 seconds being selected.
  • the concentration of the chromium ions is between 10 and 300 g / l, especially between 30 and 100 g / l, that of the chloride ions between 1 and 50 g / l, that of the sulfate ions between 0.1 and 10 g / l and that of the strontium ions between 0 and 100 g / l.
  • the alternating current density is between 10 and 150 Ndm2. especially between 30-100 A / dm 2 .
  • the direct current density is between 10 and 70 A / dm 2 . If necessary, a defoaming agent can also be added.
  • the process according to the invention is carried out either discontinuously or preferably continuously with strips or formats made of steel or its alloys.
  • the process parameters in continuous processes during the treatment are in the following ranges: the temperature of the electrolyte between 20 and 60 ° C, the residence time of a material point in the electrolyte between 10 and 300 sec and the electrolyte flow rate on the surface of the material between 5 and 100 cm / sec.
  • the current densities mentioned are in the lower part and the dwell times are in the upper part of the ranges specified; the flow of the electrolyte can also be dispensed with.
  • the electrochemical roughening and chrome plating stage for producing the printing plate support material from steel can also be followed by one or more post-treatment stages.
  • Aftertreatment is understood to mean in particular a hydrophilizing chemical or electrochemical treatment of the steel beam, for example an electrochemical treatment (anodization) in an aqueous alkali silicate solution according to DE-A 25 32 769, an immersion treatment in an aqueous alkali silicate solution according to DE-A 14 71 707 or an immersion treatment of the material in an aqueous polyvinylphosphonic acid solution according to DE-A 16 21 478.
  • These post-treatment stages serve in particular to additionally increase the hydrophilicity of the carrier material, which is already sufficient for many areas of application, while at least the other desired properties are retained.
  • steel should be understood to mean all steels which can be roughened and chromed in the specified electrolyte, i.e. H. Both unalloyed and correspondingly alloyed steels can be used according to the invention. If the process is also effective for steels with a higher C content, particularly uniform roughening is achieved, especially for steels whose C content does not exceed 0.1%.
  • all layers are suitable as photosensitive reproduction layers which can be applied and which, after exposure - possibly 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 a template. 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 usual carrier materials using known methods.
  • the light-sensitive reproduction layers include such as z. B. in “Light-Sensitive Systems by Jaromir Kosar, John Wiley & Sons Verlag, New York 1965. Layers containing unsaturated compounds in which these compounds are isomerized, rearranged, cyclized or crosslinked during exposure (Kosar, Chapter 4); Layers containing photopolymerizable compounds, in which monomers or prepolymers optionally polymerize during exposure by means of an initiator (Kosar, Chapter 5), and layers containing o-diazoquinones such as naphthoquinonediazides, p-diazoquinones or diazonium salt condensates (Kosar, Chapter 7) .
  • Suitable layers also include the electrophotographic layers, i.e. H. those containing an inorganic or organic photoconductor.
  • negative-working mixed condensation products of aromatic diazonium compounds can be used, for example those according to DE-A 20 24 244, which each have at least one unit of the general types (AD) n and B-linked 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 condensation with an active carbonyl compound in at least one position in an acid medium.
  • D is a diazonium salt group bonded to an aromatic carbon atom of A, n is an integer from 1 to 10 and B is the remainder of a diazonium group-free compound capable of condensing with an active carbonyl compound in at least one position of the molecule in an acidic medium.
  • Positive-working layers such as those according to DE-A-2610 842, which contain a compound which cleaves off on irradiation, a compound which has at least one CoC group which can be cleaved by acid (for example an orthocarboxylic acid ester group or a carboxylic acid amide acetal group) and optionally a binder contain, can be used.
  • Negative-working layers of photopolymerizable monomers, photoinitiators, binders and optionally other additives can also be used.
  • the monomers used here 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. 2760863 and 3060023 and DE-A-2 064 079 and 2361 041.
  • Suitable photoinitiators include Benzoin, benzoin ethers, multinuclear quinones, acridine derivatives, phenazine derivatives, quinoxaline derivatives or synergistic mixtures of different ketones.
  • soluble organic polymers can be used as binders, e.g. B. polyacetal resins, polyamides, polyesters, alkyd resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin or cellulose ether.
  • 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.
  • photoconductive layers such as z. B. in DE-A 1 117 391, 1 522497. 1 572 312, 2322046 and 2 322 047 are described, are applied to the support materials, whereby highly light-sensitive, electrophotographic layers are formed.
  • the roughened and chrome-plated printing plate supports according to the method of the invention have a uniform surface topography, which has a positive influence on the support stability and the water flow when printing printing forms made from these supports. There are few “scars” (marked depressions compared to the roughening of the surroundings); these can even be almost completely suppressed. In addition, the roughness depth values achieved are particularly favorable for the application of copy layers. These surface properties can be achieved without particularly great procedural and apparatus expenditure.
  • the sheets were roughened and chrome-plated under the conditions given in the table.
  • the quality of the roughening was determined visually using a microscope.
  • a classification into 10 quality levels was carried out, whereby a completely homogeneously roughened and scar-free surface was given quality level “1”.
  • the quality level «10 received a completely unevenly roughened surface (very different roughness depths) and / or a surface that had thick scars of more than 100 ⁇ m depth.
  • the roughness depth was determined with a roughness depth measuring device (Perth-o-meter C5D).
  • the specified average roughness (R z ) resulted from measurements at 10 different points on the sample.
  • both the surface topography and the roughness depth values in the case of the AC / DC treatment in the same electrolyte are significantly improved compared to a pure DC treatment.
  • a plate treated according to Example 1 was subjected to a water rinse to remove the adhering electrolyte and dried.
  • the roughened and chrome-plated plate was provided with a positive working layer.
  • the copy layer consisted of
  • cresol-formaldehyde novolak (with a softening range of 105-120 ° C according to DIN 53 181).
  • the plate thus produced was able to produce approximately 80,000 prints without any interferences.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Claims (7)

1. Procédé de préparation de plaques d'acier chromées pour l'emploi dans des buts lithographiques, la plaque d'acier étant traitée électrochimiquement dans un bain acide contenant des ions chrome caractérisé en ce que l'on fait tout d'abord par emploi de courant alternatif un grainage et un chromage partiel de la plaque d'acier dans un électrolyte contenant 10 à 300 g/I d'ions chrome, 1 à 50 g/1 d'ions chlorure, des ions sulfate et éventuellement jusqu'à 100 g/l d'ions strontium et ensuite, par emploi de courant continu, dans le même bain, un chromage final en choisissant une durée de traitement par le courant de 5 à 300 secondes.
2. Procédé selon la revendication 1, caractérisé en ce que l'on ajuste la concentration des ions chrome à une valeur de 30 à 100 g/I.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on ajuste la concentration des ions sulfate à une valeur de 0,1 à 10 g/I.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'on opère avec une densité de courant alternatif comprise entre 10 et 150 A/dm2, de préférence entre 30 et 100 A/dm2.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'on opère avec une densité de courant continu comprise entre 10 et 100 A/dm2, de préférence entre 10 et 70 A/dm2.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'on maintient la température de l'électrolyte pendant le traitement à un niveau de 20 à 60 °C.
7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on ajuste la vitesse d'écoulement de l'électrolyte à la surface du matériau à une valeur de 5 à 100 cm/s.
EP85107827A 1984-07-04 1985-06-24 Procédé pour le décapage et le chromage simultanés de plaques d'acier comme supports pour des utilisations lithographiques Expired EP0170045B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3424528 1984-07-04
DE19843424528 DE3424528A1 (de) 1984-07-04 1984-07-04 Verfahren zum gleichzeitigen aufrauhen und verchromen von stahlplatten als traeger fuer lithographische anwendungen

Publications (2)

Publication Number Publication Date
EP0170045A1 EP0170045A1 (fr) 1986-02-05
EP0170045B1 true EP0170045B1 (fr) 1988-03-02

Family

ID=6239772

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85107827A Expired EP0170045B1 (fr) 1984-07-04 1985-06-24 Procédé pour le décapage et le chromage simultanés de plaques d'acier comme supports pour des utilisations lithographiques

Country Status (5)

Country Link
US (1) US4619742A (fr)
EP (1) EP0170045B1 (fr)
JP (1) JPS6135289A (fr)
DE (2) DE3424528A1 (fr)
ZA (1) ZA854980B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4711705A (en) * 1987-01-15 1987-12-08 M&T Chemicals Inc. Activation composition and method for forming adherent chromium electrodeposits on ferrous metal substrates from high energy efficient baths
IL107544A0 (en) * 1993-11-09 1994-02-27 Golan Galvanics Ltd Electrolyte for electroplating of chromium based coating having improved wear resistance corrosion resistance and plasticity
DE19828545C1 (de) * 1998-06-26 1999-08-12 Cromotec Oberflaechentechnik G Galvanisches Bad, Verfahren zur Erzeugung strukturierter Hartchromschichten und Verwendung
EP1157853A3 (fr) * 2000-05-24 2005-01-05 Hydro Aluminium Deutschland GmbH Procédé de grainage d'un support pour plaques d'impréssion
CA2448753A1 (fr) * 2001-05-29 2002-12-05 Texas Tech University Health Sciences Center Quantification de l'etat de surface de formes posologiques pharmaceutiques, a base d'herbes, nutritionnelles et preparations cosmetiques
DE10215285A1 (de) * 2002-04-07 2003-10-16 Christian Erker Sitzschale mit Neigungs-Konturkoppelungsmechanismus
JP4932370B2 (ja) * 2006-07-28 2012-05-16 日本マクダーミッド株式会社 電解めっき方法、プリント配線板及び半導体ウェハー

Family Cites Families (16)

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Publication number Priority date Publication date Assignee Title
US2907656A (en) * 1953-11-12 1959-10-06 Chrome Steel Plate Corp Lithographic plates
US2939826A (en) * 1956-04-05 1960-06-07 Graham L Gulick Method of cleaning ferrous metal objects
US3041257A (en) * 1960-08-25 1962-06-26 Westinghouse Electric Corp Chromium electroplating
US3303113A (en) * 1963-10-18 1967-02-07 Udylite Corp Chromium plating
AU428636B2 (en) * 1967-05-26 1972-09-29 Recherche Et Industrie Therapeutiques R. I. T Beta phenylalanine derivatives
FR2081148A1 (en) * 1970-03-10 1971-12-03 Nobel Bozel Matt chromium plating - for offset printing plates of enhanced hydrophilic character
GB1492702A (en) * 1974-01-23 1977-11-23 Vintage Curacao Nv Electroplating process for chrome
CH610599A5 (en) * 1974-06-12 1979-04-30 Rotel Holding Ag Chromium-electroplating bath and use thereof
US3929591A (en) * 1974-08-26 1975-12-30 Polychrome Corp Novel lithographic plate and method
US3979212A (en) * 1974-10-04 1976-09-07 Printing Developments, Inc. Laminated lithographic printing plate
US4234396A (en) * 1978-03-08 1980-11-18 Mark Perakh Chromium plating
US4371430A (en) * 1979-04-27 1983-02-01 Printing Developments, Inc. Electrodeposition of chromium on metal base lithographic sheet
US4445998A (en) * 1981-12-02 1984-05-01 Toyo Kohan Co., Ltd. Method for producing a steel lithographic plate
JPS5928640B2 (ja) * 1981-12-22 1984-07-14 知也 「峰」岸 複合クロムめつき法
JPS58220797A (ja) * 1982-06-18 1983-12-22 Konishiroku Photo Ind Co Ltd 平版印刷版用支持体およびその製造方法
US4492740A (en) * 1982-06-18 1985-01-08 Konishiroku Photo Industry Co., Ltd. Support for lithographic printing plate

Also Published As

Publication number Publication date
DE3424528A1 (de) 1986-01-09
DE3561750D1 (en) 1988-04-07
US4619742A (en) 1986-10-28
JPS6135289A (ja) 1986-02-19
ZA854980B (en) 1986-02-26
EP0170045A1 (fr) 1986-02-05

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