Abstract:
Disclosed is a process for electrochemically roughening aluminum or alloys thereof, in an aqueous electrolyte, under the action of an alternating current which is generated by superimposing at least two types of alternating current of different frequencies. The materials roughened in this manner are used as supports for radiation-sensitive reproduction coatings in the field of manufacturing offset-printing plates. Also disclosed are roughened aluminum supports and printing plates produced by the above process.

Description:
BACKGROUND OF THE INVENTION 
     The present invention relates to a process for electrochemically roughening aluminum for use as printing plate supports. In particular, roughening of the aluminum support which is present in an acid and/or salt electrolyte is effected by an alternating current. 
     Printing plates, used herein to refer to offset-printing plates, usually comprise a support and at least one radiation-sensitive (photosensitive) reproduction coating arranged thereon. The reproduction coating is applied to the support either by the user, in the case of plates which are not pre-coated, or by the industrial manufacturer, in the case of pre-coated plates. Aluminum or an alloy thereof has gained acceptance as a support material in the field of printing plates. In principle, it is possible to use the supports without pretreatment and modification; however, they are generally modified in or on their surfaces, for example, by a mechanical, chemical and/or electrochemical roughening process, sometimes referred to as graining or etching in literature, a chemical or electrochemical oxidation process and/or a treatment with hydrophilizing agents. In modern continuously working high-speed equipment employed by the manufacturers of printing plate supports and/or pre-coated printing plates, a combination of the aforementioned modifying methods is frequently used, particularly a combination of electrochemical roughening and anodic oxidation, optionally followed by a hydrophilizing step. Roughening is, for example, carried out in aqueous acids, such as aqueous solutions of HCl or HNO 3  or in aqueous salt solutions, such as aqueous solutions of NaCl or Al(NO 3 ) 3 , using alternating current. The peak-to-valley roughnesses of the roughened surface, which are defined as mean peak-to-valley roughnesses, R z , are in the range from about 1 to 15 μm, particularly from 2 to 8 μm. The peak-to-valley roughness is determined according to DIN 4768, October 1970, as the arithmetic mean of the individual peak-to-valley roughness values of five mutually adjacent individual measurement lengths. 
     Roughening is carried out, inter alia, in order to enhance the adhesion of the reproduction coating to the support and to improve the water acceptance of the printing form, which results from irradiating and developing the printing plate. By irradiating and developing, or decoating in the case of electrophotographically working reproduction coatings, the ink-receptive image areas and the water-retaining non-image areas, the latter generally being the uncovered support surface, are produced on the printing plate in the subsequent printing operation, thus producing the actual printing form. The final topography of the aluminum surface which is to be roughened is influenced by various parameters, as is explained, by way of example, in the text which follows. 
     The paper, &#34;The Alternating Current Etching of Aluminum Lithographic Sheet&#34;, by A. J. Dowell, published in Transactions of the Institute of Metal Finishing, 1979, Vol. 57, pages 138 to 144, presents basic comments on the roughening of aluminum in aqueous solutions of hydrochloric acid, based on variations of the following process parameters and an investigation of the corresponding effects. The electrolyte composition is changed during repeated use of the electrolyte, for example, in view of the H +  (H 3  O 30 ) ion concentration (measurable by means of the pH) and the Al 3+   ion concentration. As a result of these changes, influences on the surface topography are observed. Temperature variations between 16° C. and 90° C. do not effect changes until temperatures are 50° C. or higher. The effect becoming apparent, for example, as a significant decrease in film formation on the surface. Variations in roughening time between 2 and 25 minutes lead to an increasing metal dissolution with increasing duration of action. Variations in current density between about 2 and 8 A/dm 2  result in higher roughness values with rising current density. If the acid concentration is in the range from about 0.17 to 3.3% of HCl, only negligible changes in pit structure occur between about 0.5 and 2% of HCl. Below 0.5% of HCl, the surface is only locally attacked and at the high values, an irregular dissolution of Al takes place. An addition of SO 4   2-   ions or Cl -   ions in the form of salts, e.g., by adding Al 2  (SO 4 ) 3  or NaCl, can also influence the topography of the roughened aluminum. Rectification of the alternating current shows that both half-wave types are necessary to obtain a uniform roughening. The influence of frequency changes or of superpositions of currents of different frequencies are not investigated; a constant frequency of about 50 Hz was utilized. 
     The influence of the electrolyte composition on the quality of roughening is, for example, also described in the following publications, in which standard alternating current having a frequency from about 50 to 60 Hz is used: 
     German Offenlegungsschrift No. 2,250,275 (=British Pat. No. 1,400,918) specifies aqueous solutions containing from 1.0 to 1.5% by weight of HNO 3  or from 0.4 to 0.6% by weight of HCl and optionally from 0.4 to 0.6% by weight of H 3  PO 4 , for use as electrolytes in the roughening of aluminum for printing plate supports by means of an alternating current, 
     German Offenlegungsschrift No. 2,810,308 (=U.S. Pat. No. 4,072,589) mentions aqueous solutions containing from about 0.2 to 1.0% by weight of HCl and from 0.8 to 6.0% by weight of HNO 3  as electrolytes in the roughening of aluminum with alternating current, 
     German Auslegeschrift No. 1,238,049 (=U.S. Pat. No. 3,330,743) mentions protective colloids acting as inhibitors, for example, lignin, benzaldehyde, acetophenone or pine needle oil, as additional components in aqueous HNO 3  solutions used in the roughening of aluminum for printing plate supports with alternating current, 
     U.S. Pat. No. 3,963,594 specifies aqueous solutions containing HCl and gluconic acid as electrolytes in the electrochemical roughening of aluminum for printing plate supports. 
     Admittedly, the use of aqueous solutions comprising several components to roughen aluminum may lead to more or less uniformly roughened surfaces, but monitoring the bath composition is very expensive, particularly in the case of the presently preferred continuously working high-speed processing equipment for strips. This measure, however, is necessary in practice, since the composition of the electrolyte often changes in the course of the process. 
     Another known possibility for improving the uniformity of electrochemical roughening comprises a modification of the type of electric current employed, including, for example, 
     using an alternating current, in which the anodic voltage and the anodic coulombic input are higher than the cathodic voltage and the cathodic coulombic input, according to German Auslegeschrift No. 2,650,762 (=U.S. Pat. No. 4,087,341), the anodic half-cycle period of the alternating current being generally adjusted to be less than the cathodic half-cycle period. This method is, for example, also referred to in German Offenlegungsschrift No. 2,912,060 (=U.S. Pat. No. 4,301,229), German Offenlegungsschrift No. 3,012,135 (=published UK Patent Application No. 2,047,274) or German Offenlegungsschrift No. 3,030,815 (=U.S. Pat. No. 4,272,342), 
     using an alternating current, in which the anodic voltage is markedly increased compared with the cathodic voltage, according to German Offenlegungsschrift No. 1,446,026 (=U.S. Pat. No. 3,193,485), 
     interrupting the current flow for 10 to 120 seconds and re-applying current for 30 to 300 seconds, using alternating current and, as the electrolyte, and aqueous solution of 0.75 to 2.0N HCl, with the addition of NaCl or MgCl 2 , according to British Pat. No. 879,768. A similar process comprising an interruption of current flow in the anodic or cathodic phase is also disclosed in German Offenlegungsschrift No. 3,020,420 (=U.S. Pat. No. 4,294,672). 
     The aforementioned methods may lead to relatively uniformly roughened aluminum surfaces, but each requires a comparatively great equipment expenditure and, in addition, are applicable only within closely limited parameters. 
     SUMMARY OF THE INVENTION 
     It is therefore an object of the present invention to provide a process for electrochemically roughening aluminum, which is carried out using an alternating current and which leads to a roughening structure of a uniformity such that the aluminum can be used as a printing plate support. 
     It is another object of the present invention to provide a process for producing a printing plate having a uniformly roughened aluminum support. 
     It is yet another object of the present invention to provide a process for electrochemically roughening aluminum which can be performed in various electrolytes. 
     It is still another object of the present invention to provide a process for electrochemically roughening aluminum which can be performed using alternating currents having widely varying frequencies. 
     In accomplishing the foregoing objects, there has been provided in accordance with one aspect of the present invention a process for electrochemically roughening aluminum or alloys thereof for use as printing plate supports, comprising the step of electrochemically roughening aluminum or an aluminum alloy in a aqueous electrolyte with an alternating current generated by superimposing at least two types of alternating current having different frequencies. Preferably, the frequency or frequencies of the higher-frequency alternating current(s) is/are about 3 to 100 times the lowest frequency, the alternating current with the lowest frequency may be referred to as the carrier current. 
     In accordance with another aspect of the present invention, there has been provided a roughened aluminum support produced by the above-mentioned process. 
     In accordance with still another aspect of the present invention, there has been provided a process for producing printing plates, comprising the steps of providing an aluminum or aluminum alloy support, contacting the support with an aqueous electrolyte, applying to the support an alternating current generated by superimposing at least two types of alternating current having different frequencies to produce a roughened aluminum support, and coating the roughened support with a radiation-sensitive reproduction coating. 
     In accordance with yet another aspect of the present invention, there has been provided a printing plate produced by the above-mentioned process. 
    
    
     Further objects, features and advantages of the present invention will become apparent from the detailed description of preferred embodiments which follows. 
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
     The process of the invention can be carried out either continuously or discontinuously; however, a continuous process is preferred. The process utilizes strips of aluminum or aluminum alloys. In continuous processes, the process parameters during roughening are generally within the following ranges: temperature of the electrolyte between about 20° and 60° C., electrolyte (acid and/or salt) concentration between about 1 and 250 g/l, particularly between about 5 and 100 g/l, current density between about 3 and 130 A/dm 2 , dwell time of a material spot to be roughened in the electrolyte between about 10 and 300 seconds, and rate of flow of the electrolyte on the surface of the material to be roughened between about 5 and 100 cm/second. In a preferred embodiment, the ratio of the amplitudes of the higher-frequency superimposing alternating current(s) to the lowest-frequency alternating current ranges between about 0.1 and 10, particularly between about 0.2 and 2. Appropriately, only two alternating currents with different frequencies are superimposed upon each other in the process of the invention. The type of alternating current used may have a rectangular, trapezoidal or sinusoidal shape, a combination of rectangular shape for the alternating current having the lower frequency and sinusoidal shape for the alternating current having the higher frequency being preferred in the process according to the invention. In discontinuous processes, the required current densities are in the lower region and the dwell times in the upper region of the ranges indicated in each case. Additionally, a flow of the electrolyte can even be dispensed with in these processes. In addition to the electrolytes, for example aqueous solutions of HCl and/or HNO 3 , which have been previously mentioned, it is also possible to use aqueous salt solutions, for example, as described in German Pat. No. 2,537,724 (=British Pat. No. 1,532,303) or in German Pat. No. 2,527,725 (=U.S. Pat. No. 4,166,015). Suitable apparatus for the continuous performance of the process according to the invention are, for example, disclosed in German Pat. No. 2,234,365 (=U.S. Pat. No. 3,880,744) or in German Pat. No. 2,234,424 (=U.S. Pat. No. 3,871,982). 
     The following materials which may be in the form of a sheet, a foil or a strip and which were employed in the examples which follow are, for example, used for roughening in the process of the invention: 
     &#34;Pure aluminum&#34; (DIN Material No. 3.0255), i.e., composed of not less than 99.5% Al, and the following permissible admixtures (maximum total 0.5%) of 0.3% Si, 0.4% Fe, 0.03% Ti, 0.02% Cu, 0.07% Zn and 0.03% of other substances, or 
     &#34;Al-alloy 3003&#34; (comparable to DIN Material No. 3.0515), i.e, composed of not less than 98.5% Al, 0 to 0.3% Mg and 0.8 to 1.5% Mn, as alloying constituents, and 0.5% Si, 0.5% Fe, 0.2% Ti, 0.2% Zn, 0.1% Cu and 0.15% of other substances, as permissible admixtures. 
     The electrochemical roughening process according to the present invention may be followed by an anodic oxidation of the aluminum in a further process step, in order to improve, for example, the abrasive and adhesive properties of the surface of the support material. Conventional electrolytes, such as H 2  SO 4 , H 3  PO 4 , H 2  C 2  O 4 , amidosulfonic acid, sulfosuccinic acid, sulfosalicylic acid or mixtures thereof, may be used for the anodic oxidation. The following are standard methods for the use of aqueous, H 2  SO 4  -containing electrolytes for the anodic oxidation of aluminum (see, in this regard, e.g. M. Schenk, Werkstoff Aluminium und seine anodische Oxydation (The Material Aluminum and its Anodic Oxidation), Francke Verlag, Bern, 1948, page 760; Praktische Galvanotechnik (Practical Electroplating), Eugen G. Leuze Verlag, Saulgua, 1970, pages 395 et seq., and pages 518/519; W. Huebner and C. T. Speiser, Die Praxis der anodischen Oxidation des Aluminiums (Practical Technology of the Anodic Oxidation of Aluminum), Aluminium Verlag, Duesseldorf, 1977, 3rd Edition, pages 137 et seq.): 
     The direct current sulfuric acid process refers to a process in which anodic oxidation is carried out in an aqueous electrolyte which conventionally contains approximately 230 g of H 2  SO 4  per 1 liter of solution, for 10 to 60 minutes at 10° to 22° C., and at a current density of 0.5 to 2.5 A/dm 2 . In this process, the sulfuric acid concentration in the aqueous electrolyte solution can also be reduced to 8 to 10% by weight of H 2  SO 4  (about 100 g of H 2  SO 4  per liter), or it can also be increased to 30% by weight (365 g of H 2  SO 4  per liter), or more. 
     The &#34;hard-anodizing process&#34; is carried out using an aqueous electrolyte, containing H 2  SO 4  in a concentration of 166 g of H 2  SO 4  per liter (or about 230 g of H 2  SO 4  per liter), at an operating temperature of 0° to 5° C., and at a current density of 2 to 3 A/dm 2 , for 30 to 200 minutes, at a voltage which rises from approximately 25 to 30 V at the beginning of the treatment, to approximately 40 to 100 V toward the end of the treatment. 
     In addition to the processes for the anodic oxidation of printing plate support materials which have already been mentioned in the preceding paragraph, the following processes can, for example, also be used: the anodic oxidation of aluminum in an aqueous, H 2  SO 4  -containing electrolyte, in which the content of Al 3+   ions is adjusted to values exceeding 12 g/l (according to German Offenlegungsschrift No. 2,811,396=U.S. Pat. No. 4,211,619), in an aqueous electrolyte containing H 2  SO 4  and H 3  PO 4  (according to German Offenlegungsschrift No. 2,707,810=U.S. Pat. No. 4,049,504), or in an aqueous electrolyte containing H 2  SO 4 , H 3  PO 4  and Al 3+   ions (according to German Offenlegungsschrift No. 2,836,803=U.S. Pat. No. 4,229,226). Direct current is preferably used for the anodic oxidation, but it is also possible to use alternating current or a combination of these types of current (for example, direct current with superimposed alternating current). The layer weights of aluminum oxide range from about 1 to 10 g/m 2 , which corresponds to layer thicknesses from about 0.3 to 3.0 μm. After the electrochemical roughening step and prior to an anodic oxidation step, an abrasive modification of the roughened surface may additionally be performed, as described, for example, in German Offenlegungsschrift No. 3,009,103. A modifying intermediate treatment of this kind can, inter alia, enable the formation of abrasion-resistant oxide layers and reduce the tendency to scumming in the subsequent printing operation. 
     The anodic oxidation of the aluminum support material for printing plates is optionally followed by one or more post-treating steps. Post-treating is particularly understood to be a hydrophilizing chemical or electrochemical treatment of the aluminum oxide layer, for example, an immersion treatment of the material in an aqueous solution of polyvinyl phosphonic acid according to German Pat. No. 1,621,478 (=British Pat. No. 1,230,447), an immersion treatment in an aqueous solution of an alkali-metal silicate according to German Auslegeschrift No. 1,471,707 (=U.S. Pat. No. 3,181,461), or an electrochemical treatment (anodization) in an aqueous solution of an alkali-metal silicate according to German Offenlegungsschrift No. 3,532,769 (=U.S. Pat. No. 3,902,976). These post-treatment steps serve, in particular, to even further improve the hydrophilic properties of the aluminum oxide layer, which are already sufficient for many fields of application, while maintaining the other well-known properties of the layer. 
     Suitable photosensitive reproduction coatings basically comprise any coatings which, after exposure, optionally followed by development and/or fixing, yield a surface in image configuration, which can be used for printing and/or which represents a relief image of an original. The coatings are applied to one of the support materials roughened according to the present invention, either by the manufacturers of presensitized printing plates or so-called dry resists or directly by the user. The photosensitive reproduction coatings include those which are described, for example, in &#34;Light-Sensitive Systems&#34;, by Jaromir Kosar, published by John Wiley &amp; Sons, New York, 1965. These include coatings containing unsaturated compounds, which, upon exposure, are isomerized, rearranged, cyclized, or cross-linked (Kosar, Chapter 4); coatings containing compounds, e.g. monomers or prepolymers, which can be photopolymerized, which, on being exposed, undergo polymerization, optionally with the aid of an initiator (Kosar, Chapter 5); and coatings containing o-diazoquinones, such as naphthoquinonediazides, p-diazoquinones, or condensation products of diazonium salts (Kosar, Chapter 7). 
     Other suitable coatings include the electrophotographic coatings, i.e. coatings which contain an inorganic or organic photoconductor. In addition to the photosensitive substances, these coatings can, of course, also contain other constituents, such as for example, resins, dyes, pigments, wetting agents, sensitizers, adhesion promoters, indicators, plasticizers or other conventional auxiliary agents. In particular, the following photosensitive compositions or compounds can be employed in the coating of support materials: 
     positive-working o-quinone diazide compounds, preferably o-naphthoquinone diazide compounds, which are described, for example, in German Pat. Nos. 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 formed from diphenylaminediazonium salts and formaldehyde, which are described, for example, in German Pat. Nos. 596,731, 1,138,399, 1,138,400, 1,138,401, 1,142,871, and 1,154,123, U.S. Pat. Nos. 2,679,498 and 3,050,502 and British Pat. No. 712,606; 
     negative-working co-condensation products of aromatic diazonium compounds, for example, according to German Offenlegungsschrift No. 2,024,244, which possess, in each case, at least one unit of the general types A(-D) n  and B, connected by a divalent linking member derived from a carbonyl compound which is capable of participating in a condensation reaction. In this context, these symbols are defined as follows: A is the radical of a compound which contains at least two aromatic carbocyclic and/or heterocyclic nuclei, and which is capable, in an acid medium, of participating in a condensation reaction with an active carbonyl compound, at one or more positions. D is a diazonium salt group which is bonded to an aromatic carbon atom of A; n is an integer from 1 to 10, and B is the radical of a compound which contains no diazonium groups and which is capable, in an acid medium, of participating in a condensation reaction with an active carbonyl compound, at one or more positions on the molecule; 
     positive-working coatings according to German Offenlegungsschrift No. 2,610,842, which contain a compound which, on being irradiated, splits off an acid, a compound which possesses at least one C--O--C group, which can be split off by acid (e.g., an orthocarboxylic acid ester group, or a carboxamideacetal group), and, if appropriate, a binder; 
     negative-working coatings, composed of photopolymerizable monomers, photo-initiators, binders and, if appropriate, further additives. In these coatings, for example, acrylic and methacrylic acid esters, or reaction products of diisocyanates with partial esters of polyhydric alcohols are employed as monomers, as described, for example, in U.S. Pat. Nos. 2,760,863 and 3,060,023, and in German Offenlegungsschrift No. 2,064,079 and No. 2,361,041. Suitable photo-initiators are, inter alia, benzoin, benzoin ethers, polynuclear quinones, acridine derivatives, phenazine derivatives, quinoxaline derivatives, quinazoline derivatives, or synergistic mixtures of various ketones. A large number of soluble organic polymers can be employed as binders, for example, polyamides, polyesters, alkyd resins, polyvinyl alcohol, polyvinyl-pyrrolidone, polyethylene oxide, gelatin or cellulose ethers; 
     negative-working coatings according to German Offenlegungsschrift No. 3,036,077, which contain, as the photosensitive compound, a diazonium salt polycondensation product, or an organic azido compound, and which contain, as the binder, a high-molecular weight polymer with alkenylsulfonylurethane or cycloalkenylsulfonylurethane side groups. 
     It is also possible to apply photosemiconducting coatings to the support materials, such as described, for example, in German Pat. Nos. 1,117,391, 1,522,497, 1,572,312, 2,322,046 and 2,322,047, as a result of which highly photosensitive electrophotographic coatings are produced. 
     The materials for printing plate supports, which have been roughened according to the process of the invention, exhibit a uniform topography, which positively influences the stability of print runs and the water acceptance during printing with printing forms manufactured from these supports. Compared with the use of only one type of alternating current, &#34;pitting&#34; (pronounced depressions, in comparison to the surrounding roughening) occurs less frequently and can even be completely suppressed. These surface characteristics can be produced without great equipment expenditure and without continuously monitoring the quality and quantity of the bath. Possibly, the formation of a more uniform roughening can be ascribed to the fact that the gas bubbles which are formed on the aluminum surface in the electrochemical reaction can more easily detach from the surface. 
     The present invention is explained in further detail by the following non-limiting examples wherein percentages denote percentages by weight, unless otherwise stated. Parts by weight are related to parts by volume as the g is related to the cm 3 . 
     EXAMPLES 1 TO 35 AND COMPARATIVE EXAMPLES C1 TO C8 
     In the examples and comparative examples which follow, the alternating carrier current used was, with the exception of Example 7, a rectangular current and the superimposing alternating current was a sinusoidal current. In Example 7 a sinusoidal current was also used as the alternating carrier current. 
     An aluminum sheet was first pickled in an aqueous solution containing 20 g/l of NaOH, at room temperature, for a duration of 60 seconds, and was then freed from any alkaline residue which may have been present, by briefly dipping into a solution corresponding to the electrolyte used for roughening. Roughening was carried out in the specified electrolytes, either with galvanostatic or potentiostatic control, in the latter case, the reference electrode was either the saturated system Ag/AgCl (Examples 32, C8, 34 and 35) or the counter electrode (Example 33). Examples 1 to 31 and C1 to C7 were galvanostatically controlled (Table I) and Examples 32 to 35 and C8 (Table II) were potentiostatically controlled. 
     Classification into quality grades (surface topography) was made by visual assessment under a microscope, a homogeneously roughened surface which was free from pitting was assigned quality grade &#34;1&#34;. A surface with severe pitting of a size exceeding 100 μm or with an extremely nonuniformly roughened surface was assigned quality grade &#34;10&#34;. The electrolytes used in the examples had the following composition: 
     Electrolyte A: 1.0 part by weight of HNO 3  and 5.0 parts by weight of Al(NO 3 ) 3 .9H 2  O per 100 parts by volume of aqueous solution; 
     Electrolyte B: 1.5 parts by weight of HNO 3  and 7.0 parts by weight of Al(NO 3 ) 3 .9H 2  O per 100 parts by volume of aqueous solution; 
     Electrolyte C: 2.0 parts by weight of HNO 3  and 9.0 parts by weight of Al(NO 3 ) 3 .9H 2  O per 100 parts by volume of aqueous solution; 
     Electrolyte D: 3% strength aqueous solution of HCl; 
     Electrolyte E: 3% strength aqueous solution of HCl containing 1.0 part by weight of AlCl 3  per 100 parts by volume of solution; and 
     Electrolyte F: 5% strength aqueous solution of HCl. 
     Electrolysis was started with the electrolyte being at room temperature. A comparison of surfaces treated with an alternating current comprising a carrier current and superimposing current of higher frequency with surfaces treated with only one type of alternating current of uniform frequency, under process conditions which are otherwise identical, clearly showed a more homogeneously roughened surface in the former surface. 
     
                                           TABLE I__________________________________________________________________________            Carrier AC Superimposing Current      Time of            Current    CurrentExample    Electrolysis            Density                 Frequency                       Density                             Frequency                                   SurfaceNo.  Electrolyte      (seconds)            (A/dm.sup.2)                 (Hz)  (A/dm.sup.2)                             (Hz)  Quality__________________________________________________________________________C1   B     75    8    5     --    --    51    B     75    8    5     8     50    2C2   B     150   8    5     --    --    32    B     150   8    5     8     50    13    B     200   8    0.5   10     5    1C3   E     275   8    5     --    --    84    E     275   8    5     8     50    55    A     90    12   5     12    50    16    A     120   12   5     12    50    27    B     120   12   5     12    50    28    A     150   12   5     12    50    2C4   A     90    12   0.5   --    --    49    A     90    12   0.5   12     5    310   A     90    12   0.5   12    50    211   B     130   12   0.5   10     5    212   C     150   12   5     12    50    113   B     75    16   5     8     50    114   B     75    16   5     12    50    115   B     100   16   5     10    50    116   B     75    16   0.5   8      5    117   C     112   16   5     8     50    118   C     112   16   5     16    50    119   B     60    20   5     6     50    220   B     80    20   5     8     50    121   B     80    20   50    10    500   222   C     60    20   5     20    50    123   C     90    20   5     20    50    124   C     120   20   5     20    50    2C5   F     30    24   5     --    --    1025   F     30    24   5     8     50    626   F     30    24   5     16    50    527   B     38    32   5     12    50    128   B     38    32   5     16    50    1C6   D     60    32   500   --    --    429   D     60    32   500   16    5000  230   B     44    36   5     10    50    2C7   F     61    36   5     --    --    731   F     61    36   5     8     50    4__________________________________________________________________________ 
    
     
                                           TABLE II__________________________________________________________________________      Time of            Carrier AC Superimposing CurrentExample    Electrolysis            Voltage                 Frequency                       Voltage                             Frequency                                   SurfaceNo.  Electrolyte      (seconds)            (V)  (Hz)  (V)   (Hz)  Quality__________________________________________________________________________32   B     60    5    5     2.5   50    233   B     60    5    5     2.5   50    2C8   B     45    7    5     --    --    434   B     45    7    5     2.5   50    335   B     45    7    5     5.0   50    2__________________________________________________________________________ 
    
     EXAMPLE 36 
     An aluminum sheet which had been roughened in accordance with Example 2 was anodically oxidized in an electrolyte comprising H 2  SO 4  and Al 2  (SO 4 ) 3 , as specified in German Offenlegungsschrift No. 2,811,396,  until a 2.8 μm thick oxide layer was obtained. The roughened and anodically oxidized aluminum support was then coated with the following negative-working photo-sensitive coating. 
     0.70 part by weight of the polycondensation product of 1 mole of 3-methoxy-diphenylamine-4-diazonium sulfate and 1 mole of 4,4&#39;-bis-methoxymethyl-diphenyl ether, precipitated as the mesitylene sulfonate, 
     3.40 parts by weight of 85% strength H 3  PO 4 , 
     3.00 parts by weight of a modified epoxide resin, obtained by reacting 50 parts by weight of an epoxide resin having a molecular weight of less than 1,000 and 12.8 parts by weight of benzoic acid in ethylene glycol monomethyl ether, in the presence of benzyltrimethylammonium hydroxide, 
     0.44 part by weight of finely-ground Heliogen Blue G (C.I. 74 100), 
     62.00 parts by volume of ethylene glycol monomethyl ether, 
     30.60 parts by volume of tetrahydrofuran, and 
     8.00 parts by volume of butyl acetate. 
     After imagewise exposure, the coating was developed with a solution of 2.80 parts by weight of Na 2  SO 4 .10H 2  O, 2.80 parts by weight of MgSO 4 .7H 2  O, 0.90 part by weight of 85% strength H 3  PO 4 , 0.08 part by weight of H 3  PO 3 , 1.60 parts by weight of a non-ionic wetting agent, 10.00 parts by weight of benzyl alcohol, 20.00 parts by weight of n-propanol, and 60.00 parts by weight of water. 
     It was possible to print 125,000 copies from this printing form. 
     COMPARATIVE EXAMPLE C9 
     A printing plate which was anodically oxidized and coated as specified in Example 36, but which was roughened at 50 Hz, upon development, resulted in a printing form which yielded a print run of only 75,000 copies.