EP0167087B1 - Procédé pour le décapage électrochimique de plaques d'acier pour l'utilisation comme supports pour plaques d'impression offset ainsi qu'une solution électrolytique appropriée à ce procédé - Google Patents

Procédé pour le décapage électrochimique de plaques d'acier pour l'utilisation comme supports pour plaques d'impression offset ainsi qu'une solution électrolytique appropriée à ce procédé Download PDF

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Publication number
EP0167087B1
EP0167087B1 EP85107826A EP85107826A EP0167087B1 EP 0167087 B1 EP0167087 B1 EP 0167087B1 EP 85107826 A EP85107826 A EP 85107826A EP 85107826 A EP85107826 A EP 85107826A EP 0167087 B1 EP0167087 B1 EP 0167087B1
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EP
European Patent Office
Prior art keywords
electrolyte
graining
wetting agent
compounds
plates
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
EP85107826A
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German (de)
English (en)
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EP0167087A1 (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
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Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0167087A1 publication Critical patent/EP0167087A1/fr
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Publication of EP0167087B1 publication Critical patent/EP0167087B1/fr
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
    • B41N3/038—Treatment with a chromium compound, a silicon compound, a phophorus compound or a compound of a metal of group IVB; Hydrophilic coatings obtained by hydrolysis of organometallic compounds
    • 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

Definitions

  • the present invention relates to a method for the electrochemical roughening of printing plate supports based on steel in an aqueous electrolyte containing chloride ions and additives, a corrosion protection effect being achieved in addition to a uniform roughening of the surface.
  • the invention also relates to the use of an aqueous electrolyte solution containing chloride ions and additives for the electrochemical roughening of printing plate supports based on steel.
  • 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 reproduction layer sensitive to radiation is applied, this being applied to the support either by the consumer in the case of non-pre-coated plates or by the industrial manufacturer in the case of pre-coated (pre-sensitized) plates 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.
  • Carrier plates based on aluminum are used to a large extent 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.
  • the printing plate supports have been designed as multi-layer plates.
  • Multi-layer 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.
  • the printing areas are mainly made of copper, the non-printing areas are made of chrome.
  • Such multilayer boards have the advantage in terms of magnetic fastening and have strength, kink resistance and surface hardness.
  • a disadvantage of multi-layer boards is, among others, in their technically complicated manufacture.
  • a pressure plate based on steel was developed according to DE-A 31 00 630.
  • Steel as a lithographic base material is sufficiently hydrophilic to form non-image area directly, but it has the disadvantage of being highly susceptible to corrosion.
  • the steel plates are electro-roughened in a chloride solution with an inhibiting salt solution, e.g. a sodium nitrite solution. The copy layer is then applied. Hexacyanoferrates or cobaltates are used as hydrophilizing agents.
  • Such printing plates have the advantages of strength, kink resistance, magnetic adhesion in the printing press and a certain corrosion resistance when storing and / or developing the exposed plates and / or developing the exposed plates and / or compared to the previously mentioned printing plates Printing process.
  • the object is achieved according to the invention by a process for the electrochemical roughening of printing plate supports based on steel in an aqueous electrolyte containing chloride ions and additives, the characteristic feature of which is that the printing plate support is electrochemically contained in an electrolyte containing 1 to 100 g / l hydrochloric acid and Roughening 1 to 50 g / l of at least one neutral or nitrogen-containing corrosion inhibitor with a wetting agent effect (wetting agent inhibitor).
  • the electrolyte composed of hydrochloric acid and a corrosion inhibitor with wetting agent properties may optionally contain compounds which form fluoride ions and are soluble in the electrolyte.
  • steel is to be understood to mean all steels which can be etched with hydrochloric acid, i.e. 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 with steels whose C content does not exceed 0.1%.
  • wetting agent inhibitors which delay the formation of scars when etched by hydrochloric acid.
  • neutral reacting compounds such as Nonylphenol polyglycol, especially N-containing compounds.
  • Amines, imines and ammonium compounds are particularly suitable.
  • Fluoride ions bring about an improved surface attack with finer structuring, particularly in the case of steels with a coarse grain structure.
  • hydrofluoric acid and soluble fluorine compounds in particular alkali metal fluorides such as sodium fluoride or else double fluorides, have proven themselves as compounds which form fluoride ions in the electrolyte.
  • the concentrations of the hydrochloric acid and the compounds forming the fluoride ions are between 10 and 100 g / l.
  • iron compounds preferably FeCl 3 , of 10 to 50 g / l can be added without any negative effects on the roughening pattern.
  • direct current is used in such a way that the sheet to be roughened is switched as an anode. 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 made of steel or its alloys.
  • the process parameters in continuous processes during roughening lie in the following ranges: the temperature of the electrolyte between 20 and 60 ° C, 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 Electrolyte flow rate on the surface of the material to be roughened between 5 and 100 cm / sec.
  • the current densities required tend to be in the lower part and the residence times are in the upper part of the ranges specified; the flow of the electrolyte can also be dispensed with.
  • the stage of electrochemical roughening of the printing plate support material made of 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 2532769, 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 polyvinylphos Phonic acid solution according to DE-A 16 21 478.
  • These post-treatment stages serve in particular to additionally increase the hydrophilicity of the iron carrier material, which is already sufficient for many areas of application, with the other desired properties of this layer being at least retained.
  • all layers are suitable as light-sensitive reproduction layers which, after exposure, optionally with a 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 those as e.g. 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 electrophotographic layers, i.e. those containing an inorganic or organic photoconductor.
  • Negative-working mixed condensation products of aromatic diazonium compounds can furthermore 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 - connected by a double-bonded intermediate member derived from a condensable carbonyl compound.
  • the symbols are defined as follows: 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 26 10 842, which contain a compound which cleaves off on irradiation, a compound which has at least one C-0-C group which can be cleaved by acid (for example an orthocarboxylic acid ester group or a carboxylic acid amide acetal group) and optionally contain a binder can be used.
  • acid for example an orthocarboxylic acid ester group or a carboxylic acid amide acetal group
  • binder optionally contain a binder
  • 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. 2,760,863 and 30,60023 and DE-A 20 64 079 and 23 61 041.
  • 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. Polyacetal resins, polyamides, polyesters, alkyd resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin or cellulose ether.
  • binders e.g. Polyacetal resins, polyamides, polyesters, alkyd resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin or cellulose ether.
  • negative-working layers 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-A 11 17 391, 15 22 497, 15 72 312, 23 22 046 and 23 22 047 are described, to which support materials are applied, which results in highly light-sensitive, electrophotographic layers.
  • the materials roughened by the method according to the invention for printing plate supports have a uniform surface topography, which has a positive effect on the support stability and the water flow when printing printing forms made from these supports influenced. There are few “scars” (distinctive depressions compared to the roughening of the surroundings); these can even be almost completely suppressed. These surface properties can be achieved without any great expenditure on equipment.
  • the simultaneous action of chloride ions and a wetting agent inhibitor may accelerate hole passivation and induce a finer surface structure.
  • the addition of fluorine compounds can intensify this effect, so that such an addition is a preferred embodiment.
  • the sheets were roughened with direct current 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”.
  • 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 flm depth.
  • the plates roughened according to the examples according to the invention were subjected to a conventional stress test in distilled water at room temperature for 17 hours. A rust attack could not be found after this time.
  • the panels were also subjected to a corrosion test at room temperature with an aqueous NaCl solution of 50 g / l for 5 hours. Even at bending points, no trace of rust could be detected after this time.
  • the plates produced according to the comparative examples without a wetting agent inhibitor showed marked rust attack in distilled water after 17 hours in the above-mentioned tests. Significant traces of rust appeared after about 2 hours in the NaCI test. After five hours of treatment, the sheets were completely rusty.
  • a steel plate was treated in an electrolyte solution consisting of 40 g / l hydrochloric acid, 10 g / l sodium fluoride, 5 g / l dodecor 2725 and 27 g / l iron chloride.
  • the plate was roughened with direct current with a current density of 60 A / dm 2 within a period of 30 seconds.
  • the thus treated plate was rinsed with water to remove the adhering electrolyte and dried.
  • the roughened plate was provided with a positive working copy layer.
  • the copy layer consisted of
  • cresol-formaldehyde novolak (with a softening range of 105-120 ° C according to DIN 53181)
  • the plate produced in this way was able to produce about 25,000 prints without any interference.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Printing Plates And Materials Therefor (AREA)

Claims (18)

1. Procédé pour le grainage électrochimique de supports à base d'acier pour plaques d'impression, dans un électrolyte aqueux contenant des ions chlorure et des additifs, caractérisé en ce que l'on effectue le grainage électrochimique des supports de plaques d'impression dans un électrolyte contenant 1 à 100 g/litre d'acide chlorhydrique et 1 à 50 g/litre d'au moins un inhibiteur de corrosion, azoté ou à réaction neutre, à effet d'agent mouillant (inhibiteur-agent mouillant).
2. Procédé selon la revendication 1, caractérisé en ce que l'on effectue le grainage avec un électrolyte auquel on ajoute, en plus, des composés solubles dans l'électrolyte, générateurs d'ions fluorure.
3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que l'on effectue le grainage avec un électrolyte auquel on ajoute, en plus, des composés à base de fer, solubles dans l'eau.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'on ajuste à 10-100 g/litre la concentration du composé générateur d'ions fluorure.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'on ajuste à 10-50 g/litre la concentration du composé à base de fer.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'on utilise au moins un inhibiteur-agent mouillant azoté.
7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on effectue le grainage avec du courant continu.
8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce que l'on règle la densité de courant à 3-130 A/dm2.
9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que, pendant le grainage, on maintient la température de l'électrolyte à 20-60 °C.
10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que l'on effectue le grainage pendant une durée de 5 à 300 secondes.
11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce que l'on ajuste à 5-100 cm/s la vitesse d'écoulement de l'électrolyte à la surface du matériau à grainer.
12. Utilisation d'une solution électrolytique aqueuse contenant des ions chlorure et des additifs, pour le grainage électrochimique de supports à base d'acier pour plaques d'impression, caractérisée en ce qu'elle est constituée de 1 à 100 g/litre d'acide chlorhydrique et de 1 à 50 g/litre d'au moins un inhibiteur de corrosion azoté ou à réaction neutre, à effet d'agent mouillant (inhibiteur-agent mouillant).
13. Utilisation selon la revendication 12, caractérisé en ce que la solution électrolytique contient en outre au moins un composé soluble dans l'é- lèctrolyte, générateur d'ions fluorure.
14. Utilisation selon l'une des revendications 12 ou 13, caractérisée en ce que la solution électrolytique contient en outre au moins un composé à base de fer, soluble dans l'électrolyte.
15. Utilisation selon l'une des revendications 12 à 14, caractérisée en ce que la concentration du composé générateur d'ions fluorure va de 10 à 100 g/litre.
16. Utilisation selon l'une des revendications 12 à 15, caractérisée en ce que la concentration du composé à base de fer va de 10 à 50 g/litre.
17. Utilisation selon l'une des revendications 12 à 16, caractérisée en ce que la solution électrolytique contient, en tant qu'inhibiteur-agent mouillant, des composés azotés basiques.
18. Utilisation selon la revendication 17, caractérisée en ce que la solution électrolytique contient, en tant qu'inhibiteur-agent mouillant, des composés d'ammonium quaternaire ou des amines ou imines, aliphatiques ou aromatiques.
EP85107826A 1984-07-04 1985-06-24 Procédé pour le décapage électrochimique de plaques d'acier pour l'utilisation comme supports pour plaques d'impression offset ainsi qu'une solution électrolytique appropriée à ce procédé Expired EP0167087B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843424529 DE3424529A1 (de) 1984-07-04 1984-07-04 Verfahren zur elektrochemischen aufrauhung von stahlplatten zur verwendung als offsetdruckplattentraeger sowie eine fuer das verfahren geeignete elektrolytloesung
DE3424529 1984-07-04

Publications (2)

Publication Number Publication Date
EP0167087A1 EP0167087A1 (fr) 1986-01-08
EP0167087B1 true EP0167087B1 (fr) 1988-08-03

Family

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EP85107826A Expired EP0167087B1 (fr) 1984-07-04 1985-06-24 Procédé pour le décapage électrochimique de plaques d'acier pour l'utilisation comme supports pour plaques d'impression offset ainsi qu'une solution électrolytique appropriée à ce procédé

Country Status (4)

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US (1) US4614571A (fr)
EP (1) EP0167087B1 (fr)
JP (1) JPS6125887A (fr)
DE (2) DE3424529A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2356870A (en) * 1999-12-01 2001-06-06 Secr Defence Dissolution of metal structures
US6716569B2 (en) * 2000-07-07 2004-04-06 Fuji Photo Film Co., Ltd. Preparation method for lithographic printing plate
RU2242543C2 (ru) * 2003-02-11 2004-12-20 Воронежский государственный технический университет Способ электрохимического травления стальной ленты

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6905522A (fr) * 1968-04-12 1969-10-14
US3979212A (en) * 1974-10-04 1976-09-07 Printing Developments, Inc. Laminated lithographic printing plate
SE409474B (sv) * 1975-05-13 1979-08-20 Wennborg Ab C J Sett vid kontinuerlig och diskontinuerlig elektrokemisk rengoring av legerade stal, serskilt rostfritt stal i form av band, stang, profiler, trad, ror och styckegods med ytor bemengda av mineraloljor och syntetiska ...
SE415891B (sv) * 1979-02-19 1980-11-10 Blomsterberg Karl Ingemar Sett att anodiskt avgrada och/eller polera ett stalforemal i ett elektrolytiskt bad samt bad for utforande av settet
JPS55158298A (en) * 1979-05-30 1980-12-09 Fuji Photo Film Co Ltd Manufacture of support for lithographic plate
US4431724A (en) * 1981-01-07 1984-02-14 Ovchinnikov Jury M Offset printing plate and process for making same

Also Published As

Publication number Publication date
US4614571A (en) 1986-09-30
DE3424529A1 (de) 1986-01-09
EP0167087A1 (fr) 1986-01-08
DE3564137D1 (en) 1988-09-08
JPS6125887A (ja) 1986-02-04

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