CA1077434A - Roughening aluminum plate electrochemically in aluminum salt solution - Google Patents

Roughening aluminum plate electrochemically in aluminum salt solution

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Publication number
CA1077434A
CA1077434A CA259,615A CA259615A CA1077434A CA 1077434 A CA1077434 A CA 1077434A CA 259615 A CA259615 A CA 259615A CA 1077434 A CA1077434 A CA 1077434A
Authority
CA
Canada
Prior art keywords
aluminum
roughening
electrolyte
aluminum salt
support
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
CA259,615A
Other languages
French (fr)
Inventor
Siegfried Raether
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
Application granted granted Critical
Publication of CA1077434A publication Critical patent/CA1077434A/en
Expired legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41NPRINTING 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
    • B41N3/00Preparing for use and conserving printing surfaces
    • B41N3/03Chemical or electrical pretreatment
    • B41N3/034Chemical 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Process for the Manufacture of Aluminum Supports for Planographic Printing Plates by Electrochemical Roughening of the Plate Surfaces Abstract of the Disclosure This invention relates to an improvement in the process for the manufacture of aluminum supports for planographic printing plates by electrochemical roughening of the surfaces in agitated aqueous electro-lyte solutions, the improvement comprising that the electrolyte used is an aqueous solution of an aluminum salt.

Description

Process for the Manufacture of Aluminum Supports for Planographic Printing Plates by Electrochemical Roughening of the Plate Surfaces The present invention relates to a process for the electrochemi-cal roughening of the surfaces of aluminum plates which are to be used as supporting materials for planographic printing plates.
The use of aluminum supports for planographic printing plates generally has been accepted and proved to be advantageous.
It is known to subject the surfaces of aluminum supports for planographic printing plates to a pretreatment in order to improve the adhesion of the image-carrying layer and the hydrophilic properties of the aluminum support.
Thus, mechanical treatments have been proposed, for example brushing with wire brushes or wet-brushing with abrasives. Recently, electrochemical roughening, followed, if desired, by anodic oxidation, has increasingly gained importance. Preferably, the roughening process is continuously operated, i.e. the materials to be roughened are in the form of webs.
Satisfactory qualities are achieved by mechanical roughening processes. Among the known processes, wire brushing yields a direc-tionally oriented surface which still has a silvery luster. Brushing with the aid of graining abrasives and water produces a dull gray surface which in only exceptional cases shows a directional orientation. By far the most favorable results are produced by electrochemical roughen-ing in acid baths. The uniformity of the roughening thus produced is achieved by no other known method.
As a rule, acid-containing electrolytes are used for roughening.
The rinsing solutions and spent baths resulting from this treatment must be decontaminated at considerable expense. Handling, storage, and ... . ,. ....................... ....
.. . .
.
.
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.. . . . .

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equipment must be adapted to the corrosive media, which also causes large costs.
Further, it has been proposed to manufacture foils for electro-lytic condensers by subjecting aluminum surfaces to an electrochemical treatment with neutral or only slightly corrosive solutions. Being in-tended for a different purpose, these foils require surfaces which are quite different from those of planographic printing plates, however.
In a process for the manufacture of a condenser foil disclosed in GermanAuslegeschrift No. 1,262,721, for example, sodium chloride is used together with sodium bisulfate in an anodic circuit arrangement at a low pH value and high temperatures, the desired pH range being ad-~usted by the continuous addition of sulfuric acid. In this Auslegeschrift, reference is made to another prior art process in which an aqueous alumi-num chloride solution IS used as the electrolyte and the aluminum is subjected to an anodic treatment.
It is the object of all these prior art processes to modify the aluminum in a manner such that pores of maximum depth are formed by which a maximum increase of the aluminum surface is produced. A sur-face treated in this manner is not very suitable, however, for use as a support for planographic printing plates. Too deep, and often irregularly distributed, depressions impede processing at all stages.
Normally, a very uniform, directionally unoriented roughening of medium depth is desired for planographic printing plate supports.
Above all, it should guarantee a good adhesion of the light-sensitive layer to be applied thereto and good hydrophilic properties during the printing process.
On the other hand, however, it is desirable in the manufacture of planographic printing plate supports to have available, in addition to "~ 107743~

types of surfaces which may be used for many purposes, also such surfaces which are adapted to special purposes and which differ from each other in a characteristic manner, for example by the depth of roughening, the number and size of their pores, the distribution of the pore sizes, and other parameters. The de-mand for such different types of surfaces is determined by the nature of the light-sensitive layer, the run to be printed, the printing technique to be employed, etc. So far it was known only that for producing surfaces of different types, electrolyte solutions of different compositions had to be selected. This means that time-consuming changeover operations were invariably necessary if it was desired to successively produce, in one and the same plant, aluminum webs with different types of roughening.
The present invention is directed at providing a pro-cess for the electrochemical roughening of aluminum surfaces which may be operated with as little environmental pollution as possible and which renders it possible to produce surfaces with different types of roughening by changing easily variable pro-cess parameters.
The present invention provides a process for the manu-facture of a printing plate that can be processed into a plano-graphic printing form which process comprises:
(a) electrochemically roughening a surface of a sup-port comprising aluminum in an electrolyte comprising an aqueous solution of an aluminum salt, in a concentration from 200 g per litre to the saturation point, the support being the cathode or the anode and either a direct or an alternating electrolysis current being used, provided that when the support is the cath-ode and a direct current is used the electrolyte also contains, in solution, an alkali metal salt; and ~ _ ~...... ~, .

, 107743~

(b) applying a light sensitive layer to at least one roughened surface of the support. -The inventive process has the advantage that only very little of the electrolyte used is consumed. Consequently, it has the further advantage that only small quantities of spent electrolyte solution result to be disposed of, without damage to the environment. The aluminum dissolved during the electro-chemical roughening process precipitates in the form of aluminum hydroxide or aluminum oxide hydrate and thus may be continuously removed from the mixture by filtration or centrifuging.

,~ ., ~ - 3a -` 1077434 K-2407 Prior to electrochemical roughening, the aluminum is normally pickled in the conventional manner with an aqueous-alkaline solution in order to clean and degrease the surface thereof.
The usability of the electrolyte solutions employed according to the present invention is practically unlimited. Other than in the case of acid-containing electrolytes, only those components must be replaced which are lost by entrainment. This means a considerable rationaliza-tion in the storage and handling of the chemicals used. -~
Depending upon the anion and further additives which may be used, the pH of the electrolyte is between about 1 and 5. It remains practically unchanged during operation of the process.
Aluminum chloride or aluminum nitrate are preferably used as electrolytes. The salts are normally used in concentrations of from about 50 g, preferably from 200 g per llter, to the saturation point. ~ -Good results also may be obtained when using other halides or salts of oxygen-containing halogen acids, especially the bromides and chlorates, but also the nitrites. In addition to the aluminum salts, the electrolytes also may contain alkali or ammonium salts of the same anions .
Different degrees and types of roughening may be produced by selecting an appropriate type of current and circuit arrangement. Either direct current or alternating current may be applied, and in the case of direct current the aluminu may be connected in the circuit either as o~e,~
the anode or the cathode . ~If electrolytes are used which contain only aluminum salts, no roughening occurs with direct current and a cathodic circuit arrangement, but may be caused by adding alkali salts to the electrolytes .

1~'7743~

When the anion is responsible for the roughening action, either pure aluminum salt electrolytes or mixed electrolytes con-taining aluminum salts and alkali salts may be used.
If a direct current is applied and the circuit arrange-ment is cathodic, the aluminum plate is first degreased by means of an alkaline pickling solution and then treated for about 30 to 60 seconds with a current density between 2,000 and 9,000 C/dm2, which corresponds to about 70 - 150 A/dm2. A silvery sur-face with a dull finish is produced which very much resembles that of a directionally unoriented, wire-brushed surface (Type A). The depth of roughening of the material thus obtained ranges from about 9 to 12 ~m. The good contrast between the support and the light-sensitive layer applied thereto allows an effective visual control during processing of the resulting printing plates. When the process described for Type A is ap-plied, using, however, direct current in an anodic circuit arrangement, a dull gray, visually uniform surface is produced which resembles known surfaces produced by electrochemical treat-ment with acid-containing electrolytes (Type B). The depth of roughening of surfaces of this type may range from about 7 to about 20 ~m, depending on the electrolyte selected, the current density, and the like.
If alternating current is applied, a more pitted sur-face results which does not appear as uniform to the eye but is nevertheless very suitable for the manufacture of an offset printing plate (Type C). In this case, the depth of roughening ranges from about 15 to 20 ~m. (In all cases, the depth of roughening was measured by means of a "Perthometer", type S 10 D.) - 1077~34 If a surface of Type A is to be produced, it is necessary to add alkali cations, especially Na or K cations, in concentrations ranging from about 30 g per liter to the point of saturation.
With an anodic arrangement or alternating current, ammonium salts may be used to increase the concentration of the -desired anion after the saturation limit of the aluminum salt has been reached.
Urea, for example in the form of the chloride or nitrate, was found to be suitable as the anion carrier. The inhibiting action of this compound, which is known from con-ventional corrosion tests, is not so effective in the electro-chemical treatment of aluminum as to prevent roughening.
The inventive process may be applied to single sheets, in a simple trough equipped with the necessary circulating and current supply devices, or to webs in appropriately designed, continuously operating plants. The current transfer in these plants may be either by contact rollers or by the neutral-wire method.
Suitable apparatuses for performing the process of the invention are described, for example, in German Offenlegungs-schriften No. 2,234,424, published on January 31, 1974 to Idstein, and No. 2,228,424, published December 20, 1973 to Stroszynski.
Of course, these apparatuses must be provided with temperature control and adjusting devices. The working r~nge of the process of the present invention extends normally from room temperature (20 C) to the boiling point of the solutions used. The application of lower temperatures, even those approach-ing the solidifying point of the solutions, is possible but not recommended in view of the high cooling costs.
In the case of a cathodic circuit arrangement, a relatively high reaction temperature within the range stated, i.e. between about 40 and 80C, preferably between 50 and 60 C, is normally of advantage.

- 6a -- `` 107743~ K-2 4 07 In the case of an anodic arrangement and an alternating current circuit, temperatures between 20 and 35 C are generally preferred.
In order to facilitate the heat exchange and flow of material at the aluminum surface, the electrolyte is stirred or circulated by pump-ing. The velocity of flow is advantageously maintained between about 0.1 and 5 m per second, preferably between 0.8 and 1.5 m/sec. These values refer to an operation of the inventive process on a technical scale, especially in a continuous operation and treating continuously fed webs of aluminum. Some of the experiments described were made on a laboratory scale, so that the values stated in the examples may deviate from the optimum values.
If the current densities applied fall substantially below the values stated above and an equivalent quantity of current is achieved by prolonging the reaction time, poorer results are normally achieved.
Likewise, it is not always advisable to increase the current density while simultaneously shortening the reaction time. In most cases, this results in a heavy removal of metal and produces very smooth, almost electro-polished surfaces.
The voltage required depends largely upon the distance between the electrodes. For this reason, this distance should be made as small as possible. In order to guarantee the necessary exchange of material, distances ranging from about 0.5 to 5 cm, preferably from 0.6 to 1.5 cm, are preferred. Wider distances are possible, but require higher voltages. The examples below describe a number of experiments using testing plants in which the distance between electrodes did not corre-spond to the optimum values stated above.
The surfaces roughened by the process according to the invention may be either directly provided with a light-sensitive layer or first ano-dized .

.-.

1~743~

If copying layers based on diazo compounds are used, non-anodized surfaces of Type A yield 10,000 to 30,000 copies of good quality, and non-anodized surfaces of Type B and C yield about 50,000 copies. Subsequently anodized plates yield runs which correspond to a multiple of the above values, the increase being more conspicuous in the case of Types B and C than in the case of surfaces of Type A.
Like the roughening process, anodization may be per-formed in known manner, treating either individual sheets or endless webs. Suitable apparatuses are described, for example, in German Offenlegungsschriften No. 2,420,704, published on December 5, 1974 to Fromson, and No. 1,906,538, published on November 20, 1967 to Suzuki and Hamabe. -The following examples describe the inventive roughen- -ing of aluminum in different electrolyte solutions. In all examples, a web of smooth rolled aluminum with an aluminum con- -tent of 99.5 per cent was used. Prior to electrochemical roughening, the web was subjected for 30 seconds, at a tempera-ture of 50 to 60 C, to an alkaline pickling treatment in an aqueous solution containing 20 g of NaOH per liter of water.
About 3 g of aluminum per square meter were removed by this treatment.
In the following examples, all percentages are by weight unless otherwise stated.
Example 1 Electrolyte: 200 g of sodium chloride and 300 g of AlC13 6H2O per liter of softened water.

_~ _ 1~7743~

CircuitCurrent Temperature Time Appearance ArrangementDensity (C) (secs) ~ _,(A/dm2) Anodic 70 30 30 dull dark gray Cathodic 100 50 60 dull silvery :
finish Alternating current (50 Hz) 70 30 30 dull dark gray - 8a -' 107743~ K - 2 4 0 7 Distance between electrodes: 5 cm.
Flow velocity of electrolyte: 0.3 - 0.4 m/sec.
pH value of the solution: 2 If a solution containing 200 g of sodium nitrate and 200 g of Al(NO3)3 9H2O per liter is used, the same alteration of the aluminum surface results. In the case of an anodic circuit arrangement and alter-nating current, however, the resulting surfaces are of a lighter shade of gray.
Example 2 i Electrolyte: 200 g of Al(NO3)3 9H2O per liter of softened water. , Circuit Current Tempe- Time, Appearance Arrangement Density rature, (secs.) (A/dm2) ( C ) ,,,,,,_ Anodic 100 30 30 dull light gray Cathodic 100 60 30 no corrosion, for-mation of oxide deposit Alternating -current (50 Hz) 100 30 30 dull gray . .

Distance between electrodes: 5 cm.
20 Flow velocity of electrolyte: 0.3 m/sec.
pH value of solution: approximately 3 It will be obvious to those skilled in the art that many modifi-cations may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications .

_ g _

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the manufacture of a printing plate that can be processed into a planographic printing form which process comprises:
(a) electrochemically roughening a surface of a sup-port comprising aluminum in an electrolyte comprising an aqueous solution of an aluminum salt, in a concentration from 200 g per litre to the saturation point, the support being the cathode or the anode and either a direct or an alternating electrolysis current being used, provided that when the support is the cath-ode and a direct current is used the electrolyte also contains, in solution, an alkali metal salt; and (b) applying a light sensitive layer to at least one roughened surface of the support.
2. A process according to claim 1 in which the electrolyte has a pH value from 1 to 5.
3. A process according to claim 1 in which the aluminum salt is an aluminum halide, nitrite, or nitrate or an aluminum salt of an oxygen-containing halogen acid.
4. A process according to claim 3 in which the aluminum salt is an aluminum halide or nitrate.
CA259,615A 1975-08-25 1976-08-23 Roughening aluminum plate electrochemically in aluminum salt solution Expired CA1077434A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19752537725 DE2537725C3 (en) 1975-08-25 1975-08-25 Use of a process for the electrochemical roughening of aluminum in the production of planographic printing plate carriers

Publications (1)

Publication Number Publication Date
CA1077434A true CA1077434A (en) 1980-05-13

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ID=5954763

Family Applications (1)

Application Number Title Priority Date Filing Date
CA259,615A Expired CA1077434A (en) 1975-08-25 1976-08-23 Roughening aluminum plate electrochemically in aluminum salt solution

Country Status (11)

Country Link
JP (1) JPS60236B2 (en)
AT (1) AT352150B (en)
BE (1) BE845431A (en)
BR (1) BR7605510A (en)
CA (1) CA1077434A (en)
CH (1) CH622466A5 (en)
DE (1) DE2537725C3 (en)
FR (1) FR2322015A1 (en)
GB (1) GB1532304A (en)
NL (1) NL187107C (en)
SE (1) SE7609309L (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4201836A (en) * 1978-08-28 1980-05-06 Polychrome Corporation Aluminum substrates grained with a saturated solution of aluminum salts of mineral acids
US4242417A (en) * 1979-08-24 1980-12-30 Polychrome Corporation Lithographic substrates
DE3222967A1 (en) * 1982-06-19 1983-12-22 Hoechst Ag, 6230 Frankfurt METHOD FOR REMOVING MODIFICATION OF ELECTROCHEMICALLY Roughened SUPPORT MATERIALS MADE OF ALUMINUM AND THE USE THEREOF IN THE PRODUCTION OF OFFSET PRINTING PLATES
DE3118151A1 (en) * 1981-05-07 1982-12-02 Siemens AG, 1000 Berlin und 8000 München METHOD FOR ETCHING A RECRYSTALLIZED ALUMINUM FILM FOR ELECTROLYTE CAPACITORS
DE3635303A1 (en) * 1986-10-17 1988-04-28 Hoechst Ag METHOD FOR REMOVING MODIFICATION OF CARRIER MATERIALS MADE OF ALUMINUM OR ITS ALLOYS, AND THEIR ALLOYS AND THEIR USE IN THE PRODUCTION OF OFFSET PRINTING PLATES
JPH028640U (en) * 1988-06-30 1990-01-19

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE756216C (en) * 1936-12-19 1952-10-13 Siemens & Halske A G Electrolytic process for roughening the surface of an electrode, especially for electrolytic capacitors
US2209712A (en) * 1937-05-06 1940-07-30 Joseph B Brennan Method of treating aluminum
GB896563A (en) * 1959-12-10 1962-05-16 Algraphy Ltd Improvements in or relating to the graining of lithographic plates
US3193485A (en) * 1960-09-20 1965-07-06 Plessey Co Ltd Electrolytic treatment of aluminium for increasing the effective surface

Also Published As

Publication number Publication date
FR2322015A1 (en) 1977-03-25
JPS5226905A (en) 1977-02-28
NL7609348A (en) 1977-03-01
DE2537725A1 (en) 1977-03-10
DE2537725B2 (en) 1980-06-19
NL187107C (en) 1991-06-03
GB1532304A (en) 1978-11-15
AT352150B (en) 1979-09-10
JPS60236B2 (en) 1985-01-07
DE2537725C3 (en) 1981-02-19
SE7609309L (en) 1977-02-26
BR7605510A (en) 1977-08-16
CH622466A5 (en) 1981-04-15
ATA623576A (en) 1979-02-15
FR2322015B1 (en) 1982-10-22
BE845431A (en) 1977-02-23

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