EP1110631A1 - Method for producing an aluminium strip for lithographic printing plates - Google Patents
Method for producing an aluminium strip for lithographic printing plates Download PDFInfo
- Publication number
- EP1110631A1 EP1110631A1 EP99811203A EP99811203A EP1110631A1 EP 1110631 A1 EP1110631 A1 EP 1110631A1 EP 99811203 A EP99811203 A EP 99811203A EP 99811203 A EP99811203 A EP 99811203A EP 1110631 A1 EP1110631 A1 EP 1110631A1
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- EP
- European Patent Office
- Prior art keywords
- strip
- thickness
- cast
- rolled
- lithographic printing
- 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.)
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- 239000004411 aluminium Substances 0.000 title 1
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 238000005266 casting Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 230000007423 decrease Effects 0.000 claims abstract description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 9
- 239000003973 paint Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 abstract description 8
- 238000005530 etching Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005097 cold rolling Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 238000007712 rapid solidification Methods 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Images
Classifications
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- 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
- B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B3/003—Rolling non-ferrous metals immediately subsequent to continuous casting, i.e. in-line rolling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/001—Aluminium or its alloys
-
- 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
-
- 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
- B41N3/04—Graining or abrasion by mechanical means
Definitions
- the invention relates to a method for producing a strip from aluminum or an aluminum alloy for electrolytically roughened lithographic printing plates, the metal being continuously cast into a strip and the cast strip subsequently being cold-rolled to final thickness (d e ).
- the scope of the invention also includes lithographic printing plates with an electrolytically roughened surface.
- Aluminum tapes are predominantly used today for the production of lithographic printing plates used by hot and cold rolling - with engagement an intermediate annealing - be made from continuous cast ingots.
- an intermediate annealing - be made from continuous cast ingots.
- Various attempts have been made in recent years to to process strip cast aluminum materials to lithographic printing plates.
- EP-A-0 821 074 describes a process for producing an aluminum strip disclosed for lithographic printing plates in which the metal is continuous in the casting roll gap between the cooled rolls of a strip casting machine cast into a strip and the cast strip subsequently without intermediate annealing is rolled to final thickness. Often include specifications for litho sheets maximum values for the strength, which only then without intermediate annealing can be observed if the thickness of the cast Band is significantly less than 3 mm. Such small cast strip thicknesses are however in good use with conventional band casting machines in practice Quality is not easy to manufacture.
- EP-A-0 653 497 describes a process for producing an aluminum strip known for lithographic printing plates, in which initially a cast strip with a thickness of max. 3 mm also by means of a casting and rolling system will be produced.
- the cast strip produced in this way is annealed annealed recrystallizing during cold rolling. This glow is at a temperature of at least 300 ° C and with a heating up time of at least 1 ° C / sec stationary in an oven on the coil or, preferably at temperatures from 400 to 550 ° C, carried out in a continuous annealing furnace. After this annealing, the cast strip is directly to a maximum final thickness 0.5 mm cold rolled.
- the invention has for its object a method of the aforementioned Art to create, which without a costly investment to one Litho tape with good strength even after a paint bake cycle leads the lithographic printing plates produced.
- the core of the method which is essential to the invention, is intermediate annealing, which only serves to restore the structure and not to form new grains leads, as in the usual recrystallizing intermediate annealing the state of the art.
- Aluminum strips with the recovery annealing according to the invention lead to less drop in strength after a paint baking cycle than tapes, which have been annealed to recrystallize.
- the method according to the invention thus leads to lithographic printing plates, which also in connection with high paint baking temperatures of up to 300 ° C advantages over conventionally manufactured litho sheets offer their ultimate strength.
- the metal is preferably to a thickness of max. 3.5 mm, especially 2.0 up to 3.0 mm, preferably 2.4 to 2.8 mm, cast. This gives the cast Tape an ideal microstructure in a near-surface area that in Combination with the recovery annealing according to the invention to the final thickness rolled strip to a surface structure with excellent etching behavior.
- any strip casting process can be used to produce the cast strip are used, ideally a rapid solidification simultaneous hot forming in the casting roll gap is desired.
- the two the latter properties are fulfilled, for example, by the casting and rolling process, in which the metal in the casting roll gap between cooled rolls to the Tape is poured.
- the cast strip cold rolling with non-recrystallizing intermediate annealing remains the advantageous one Microstructure in the areas near the surface as a result of faster Preserve solidification.
- the continuous casting process also enables high solidification speeds and very fine grain sizes in areas near the surface through dynamic recovery immediately after the cast Strip from the casting roll nip.
- the further processing of the cast tape is done by reeling the cast tape into a bundle of the desired size.
- Processing step is for producing the tape in one Litho sheet suitable cold rolling mill to the desired intermediate thickness and after the recovery annealing continue to the desired final thickness in the usual way Rolled range of about 150 to 300 microns.
- the intermediate thickness at which the recovery annealing is carried out, the temperature as well as the duration of the relaxation glow depends on the one hand the initial thickness of the cast strip and, on the other hand, the composition of the material used. Using a simple series of experiments however, the person skilled in the art can readily generate the desired one Determine recovery parameters required.
- the cast tape is at least 50% of the total Thickness-reduced intermediate thickness rolled, the appropriate intermediate thickness is about 1.0 to 1.6 mm.
- the annealing of the strip rolled down to the intermediate thickness takes place preferably in a temperature range from 260 to 300 ° C, expediently in a temperature range of about 270 to 290 ° C, which on Intermediate-thickness rolled strip annealed for a period of about 2 to 5 hours becomes.
- one according to the invention manufactured tape on excellent mechanical properties, so e.g. high strength, even during the baking of a photosensitive Lacquer in the production of lithographic printing plates only insignificantly decreases.
- the tape produced according to the invention is equally suitable for etching in HCI and HNO 3 electrolytes, the advantages of the microstructure obtained being particularly apparent when etching in an HNO 3 electrolyte.
- alloys for the production of the strip according to the invention all commonly used to make lithographic printing plates used aluminum materials are used. Particularly preferred are alloys from the AA 1xxx, AA 3xxx or AA 8xxx series, for example the alloys AA 1050, AA 1200 or AA 3103.
- the above-mentioned advantageous microstructure in the area of the belt near the surface essentially results from the rapid solidification on the surface.
- the secondary phase particles are separated out in the microstructure in a very fine form and in high density.
- These particles act as the first points of attack for the etching, especially when the electrochemical roughening is carried out in an HNO 3 electrolyte.
- the particles mentioned have an average distance of less than 5 ⁇ m and thereby form a coherent network of uniform surface attack points. Starting from these first points of attack, distributed uniformly and in high density over the entire strip surface, the growth of the actual three-dimensional roughness pattern begins.
- the small size of the intermetallic phases mentioned has the further advantage that they considerably shorten the period of electrochemical dissolution in the initial phase of the etching, as a result of which electrical energy can be saved. Since the rapid solidification in the surface areas of the belt preferably results in imbalance phases, the dissolution rate of the fine particles mentioned is high.
- the tape produced is the small grain size that occurs during tape casting in the areas near the surface.
- the high density of the Penetration points of the grain boundaries on the surface lead along with a high density of defects in the grains even at chemically active points of attack for the continuous formation of new etch pits.
- Electrolytes made from dilute hydrochloric acid (HCI) and electrolytes made from dilute nitric acid (HNO 3 ) are used for this purpose.
- etching is now carried out in the nitric acid electrolyte, it shows the practice that a uniform etching structure only if certain Etching parameters can be achieved. For example, for economic reasons if the charge (coulomb) is too small, irregular results Etch images with mostly strip-like areas where no etching attack took place. If etching takes place under these critical conditions, then come all subtle differences in the structure of the substrate (litho tape) to the fore and you can get a classification of the litho materials used determine.
- the advantage of the invention is evident with the interposition of a recovery annealing manufactured strip material compared to a tape material with a recrystallizing Intermediate annealing, especially for lithographic printing plates after a Paint baking cycle at temperatures in the range of about 270 to 300 ° C.
- the temperature and time information refer to the duration of the annealing at metal temperature after the tape at a heating rate of 100 ° C / h has been heated to the annealing temperature. As more characteristic The elongation at break (Rm) was determined.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Printing Plates And Materials Therefor (AREA)
- Continuous Casting (AREA)
- Metal Rolling (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung eines Bandes aus Aluminium oder einer Aluminiumlegierung für elektrolytisch aufgerauhte lithographische Druckplatten, wobei das Metall kontinuierlich zu einem Band gegossen und das gegossene Band nachfolgend auf Enddicke (de) kaltgewalzt wird. Im Rahmen der Erfindung liegen auch lithographische Druckplatten mit elektrolytisch aufgerauhter Oberfläche.The invention relates to a method for producing a strip from aluminum or an aluminum alloy for electrolytically roughened lithographic printing plates, the metal being continuously cast into a strip and the cast strip subsequently being cold-rolled to final thickness (d e ). The scope of the invention also includes lithographic printing plates with an electrolytically roughened surface.
Lithographische Druckplatten aus Aluminium, die typischerweise eine Dicke von etwa 0,3 mm aufweisen, haben gegenüber Platten aus anderen Werkstoffen Vorteile, von denen hier nur einige genannt sind:
- Eine gleichmässige Oberfläche, die sich gut zur mechanischen, chemischen und elektrochemischen Aufrauhung eignet.
- Eine harte Oberfläche nach dem Anodisieren, was eine grosse Zahl von Abdrucken ermöglicht.
- Leichtes Gewicht.
- Niedrige Gestehungskosten.
- A uniform surface that is well suited for mechanical, chemical and electrochemical roughening.
- A hard surface after anodizing, which enables a large number of impressions.
- Lightweight.
- Low production costs.
Der Artikel ALUMINIUM ALLOYS AS SUBSTRATES FOR LITHOGRAPHIC PLATES von F. Wehner und R.J. Dean, 8. Internationale Leichtmetalltagung Leoben-Wien 1987, gibt einen Überblick über die Herstellung und Eigenschaften von Bändern für lithographische Druckplatten.The article ALUMINUM ALLOYS AS SUBSTRATES FOR LITHOGRAPHIC PLATES by F. Wehner and R.J. Dean, 8th International Light Metal Conference Leoben-Vienna 1987, gives an overview of the production and properties of tapes for lithographic printing plates.
Zur Herstellung lithographischer Druckplatten werden heute überwiegend Aluminiumbänder eingesetzt, die durch Warm- und Kaltwalzen -- unter Einschaltung einer Zwischenglühung -- aus Stranggussbarren gefertigt werden. In den letzten Jahren sind auch verschiedentlich Versuche unternommen worden, bandgegossene Aluminiumwerkstoffe zu lithographischen Druckplatten zu verarbeiten.Aluminum tapes are predominantly used today for the production of lithographic printing plates used by hot and cold rolling - with engagement an intermediate annealing - be made from continuous cast ingots. In the Various attempts have been made in recent years to to process strip cast aluminum materials to lithographic printing plates.
In der EP-A-0 821 074 ist ein Verfahren zur Herstellung eines Aluminiumbandes für lithographische Druckplatten offenbart, bei dem das Metall kontinuierlich im Giesswalzspalt zwischen gekühlten Walzen einer Bandgiessmaschine zu einem Band gegossen und das gegossene Band nachfolgend ohne Zwischenglühung auf Enddicke gewalzt wird. Oftmals beinhalten Spezifikationen für Lithobleche Maximalwerte für die Festigkeit, welche nur dann ohne Zwischenglühung eingehalten werden können, wenn die Dicke des gegossenen Bandes wesentlich weniger als 3 mm beträgt. Derart geringe Gussbanddicken sind jedoch mit herkömmlichen Bandgiessmaschinen im Praxisbetrieb in guter Qualität nicht einfach herzustellen.EP-A-0 821 074 describes a process for producing an aluminum strip disclosed for lithographic printing plates in which the metal is continuous in the casting roll gap between the cooled rolls of a strip casting machine cast into a strip and the cast strip subsequently without intermediate annealing is rolled to final thickness. Often include specifications for litho sheets maximum values for the strength, which only then without intermediate annealing can be observed if the thickness of the cast Band is significantly less than 3 mm. Such small cast strip thicknesses are however in good use with conventional band casting machines in practice Quality is not easy to manufacture.
Aus der EP-A-0 653 497 ist ein Verfahren zur Herstellung eines Aluminiumbandes für lithographische Druckplatten bekannt, bei der zunächst ein Gussband mit einer Dicke von max. 3 mm ebenfalls mittels einer Giesswalzanlage hergestellt wird. Das so gefertigte Gussband wird im Rahmen einer Zwischenglühung während des Kaltwalzens rekristallisierend geglüht. Diese Glühung wird bei einer Temperatur von mindestens 300° C und bei einer Aufheizzeit von mindestens 1° C/sec stationär in einem Ofen am Coil oder, bevorzugt bei Temperaturen von 400 bis 550° C, in einem Banddurchlaufglühofen durchgeführt. Nach dieser Glühung wird das Gussband direkt auf eine Enddicke von maximal 0.5 mm kaltgewalzt.EP-A-0 653 497 describes a process for producing an aluminum strip known for lithographic printing plates, in which initially a cast strip with a thickness of max. 3 mm also by means of a casting and rolling system will be produced. The cast strip produced in this way is annealed annealed recrystallizing during cold rolling. This glow is at a temperature of at least 300 ° C and with a heating up time of at least 1 ° C / sec stationary in an oven on the coil or, preferably at temperatures from 400 to 550 ° C, carried out in a continuous annealing furnace. After this annealing, the cast strip is directly to a maximum final thickness 0.5 mm cold rolled.
Beim Kaltwalzen von Aluminiumbändern ist zudem allgemein bekannt, insbesondere bei Abwalzgraden von insgesamt mehr als 90 %, in einem Temperaturbereich von üblicherweise 300 - 400° C eine rekristallisierende Zwischenglühung vorzunehmen. When cold rolling aluminum strips, it is also generally known, in particular with degrees of rolling of more than 90% in total, in a temperature range a recrystallizing intermediate annealing of usually 300 - 400 ° C to make.
Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art zu schaffen, welches ohne kostenintensive Anlagen zu einem Lithoband mit guter Festigkeit auch nach einem Lackeinbrennzyklus an aus dem Band hergestellten lithographischen Druckplatten führt.The invention has for its object a method of the aforementioned Art to create, which without a costly investment to one Litho tape with good strength even after a paint bake cycle leads the lithographic printing plates produced.
Zur erfindungsgemässen Lösung der Aufgabe führt, dass
"Ohne weitere Wärmezufuhr" bedeutet hier, dass dem gegossenen Band nach dem Verlassen des Giesswalzspaltes bis zum erfolgten Abwalzen auf die Zwischendicke von aussen keine Wärme zugeführt wird. Wird das gegossene Band, welches nach dem Austritt aus dem Giesswalzspalt noch während einer gewissen Zeitdauer eine verhältnismässig hohe Temperatur aufweist, bereits kurze Zeit nach seiner Herstellung auf die Zwischendicke gewalzt, so kann die Starttemperatur beim Walzen, insbesondere bei grossen Banddicken, erhöht sein. Bei geringen Banddicken entspricht die Verarbeitung auf die Zwischendicke einem Kaltwalzen."Without further heat supply" means here that the cast tape leaving the casting roll gap until rolling to the intermediate thickness no heat is supplied from the outside. Will the cast Belt which, after emerging from the casting roll gap, still during a has a relatively high temperature for a certain period of time rolled to the intermediate thickness a short time after its production, so the Starting temperature during rolling, especially with large strip thicknesses, increased his. With small strip thicknesses, processing corresponds to the intermediate thickness a cold rolling.
Der erfindungswesentliche Kern des Verfahrens liegt in der Zwischenglühung, die nur der Erholung des Gefüges dient und nicht zu einer Kornneubildung führt, wie sie bei den üblichen rekristallisierenden Zwischenglühungen nach dem Stand der Technik eintritt. The core of the method, which is essential to the invention, is intermediate annealing, which only serves to restore the structure and not to form new grains leads, as in the usual recrystallizing intermediate annealing the state of the art.
Aluminiumbänder mit der erfindungsgemässen Erholungsglühung führen zu einem geringeren Festigkeitsabfall nach einem Lackeinbrennzyklus als Bänder, die rekristallisierend zwischengeglüht worden sind.Aluminum strips with the recovery annealing according to the invention lead to less drop in strength after a paint baking cycle than tapes, which have been annealed to recrystallize.
Das erfindungsgemässe Verfahren führt damit zu lithographischen Druckplatten, die auch in Verbindung mit hohen Lackeinbrenntemperaturen von bis zu 300° C gegenüber konventionell hergestellten Lithoblechen Vorteile bezüglich ihrer Endfestigkeit bieten.The method according to the invention thus leads to lithographic printing plates, which also in connection with high paint baking temperatures of up to 300 ° C advantages over conventionally manufactured litho sheets offer their ultimate strength.
Bevorzugt wird das Metall auf eine Dicke von max. 3.5 mm, insbesondere 2.0 bis 3.0 mm, vorzugsweise 2.4 bis 2.8 mm, gegossen. Damit erhält das gegossene Band eine ideale Mikrostruktur in einem oberflächennahen Bereich, die in Kombination mit der erfindungsgemässen Erholungsglühung an dem auf Enddicke gewalzten Band zu einer Oberflächenstruktur mit ausgezeichnetem Ätzverhalten.The metal is preferably to a thickness of max. 3.5 mm, especially 2.0 up to 3.0 mm, preferably 2.4 to 2.8 mm, cast. This gives the cast Tape an ideal microstructure in a near-surface area that in Combination with the recovery annealing according to the invention to the final thickness rolled strip to a surface structure with excellent etching behavior.
Grundsätzlich kann zur Herstellung des gegossenen Bandes jedes Bandgiessverfahren eingesetzt werden, wobei im Idealfall eine rasche Erstarrung bei gleichzeitiger Warmverformung im Giesswalzspalt erwünscht ist. Die beiden letztgenannten Eigenschaften erfüllt beispielsweise das Giesswalzverfahren, bei dem das Metall im Giesswalzspalt zwischen gekühlten Walzen zu dem Band gegossen wird. Durch die Weiterverarbeitung des gegossenen Bandes durch Kaltwalzen mit nicht rekristallisierender Zwischenglühung bleibt die vorteilhafte Gefügestruktur in den oberflächennahen Bereichen infolge rascher Erstarrung erhalten.In principle, any strip casting process can be used to produce the cast strip are used, ideally a rapid solidification simultaneous hot forming in the casting roll gap is desired. The two the latter properties are fulfilled, for example, by the casting and rolling process, in which the metal in the casting roll gap between cooled rolls to the Tape is poured. By further processing the cast strip cold rolling with non-recrystallizing intermediate annealing remains the advantageous one Microstructure in the areas near the surface as a result of faster Preserve solidification.
Das kontinuierliche Giessverfahren ermöglicht gleichzeitig hohe Erstarrungsgeschwindigkeiten und sehr feine Korngrössen in oberflächennahen Bereichen durch dynamische Erholung unmittelbar nach dem Austritt des gegossenen Bandes aus dem Giesswalzspalt. The continuous casting process also enables high solidification speeds and very fine grain sizes in areas near the surface through dynamic recovery immediately after the cast Strip from the casting roll nip.
Die weitere Verarbeitung des gegossenen Bandes erfolgt durch Aufhaspeln des gegossenen Bandes zu einem Bund gewünschter Grösse. Im darauffolgenden Verarbeitungsschritt wird das Band in einem für die Herstellung von Lithoblechen geeigneten Kaltwalzwerk zur gewünschten Zwischendicke und nach der Erholungsglühung weiter auf die gewünschte Enddicke im üblichen Bereich von etwa 150 bis 300 µm gewalzt.The further processing of the cast tape is done by reeling the cast tape into a bundle of the desired size. In the following Processing step is for producing the tape in one Litho sheet suitable cold rolling mill to the desired intermediate thickness and after the recovery annealing continue to the desired final thickness in the usual way Rolled range of about 150 to 300 microns.
Die Zwischendicke, bei der die Erholungsglühung durchgeführt wird, die Temperatur sowie die Zeitdauer der Erholungsglühung richtet sich einerseits nach der Ausgangsdicke des Gussbandes und andererseits nach der Zusammensetzung des eingesetzten Werkstoffes. Anhand einer einfachen Versuchsreihe kann jedoch der Fachmann ohne weiteres die zur Erzeugung des gewünschten Erholungszustandes erforderlichen Parameter ermitteln.The intermediate thickness at which the recovery annealing is carried out, the temperature as well as the duration of the relaxation glow depends on the one hand the initial thickness of the cast strip and, on the other hand, the composition of the material used. Using a simple series of experiments however, the person skilled in the art can readily generate the desired one Determine recovery parameters required.
Bevorzugt wird das gegossene Band auf eine mindestens 50 % der gesamten Dickenabnahme betragende Zwischendicke gewalzt, wobei die geeignete Zwischendicke etwa 1.0 bis 1.6 mm beträgt.Preferably, the cast tape is at least 50% of the total Thickness-reduced intermediate thickness rolled, the appropriate intermediate thickness is about 1.0 to 1.6 mm.
Die Erholungsglühung des auf die Zwischendicke abgewalzten Bandes erfolgt bevorzugt in einem Temperaturbereich von 260 bis 300° C, zweckmässigerweise in einem Temperaturbereich von etwa 270 bis 290° C, wobei das auf Zwischendicke gewalzte Band während einer Zeitdauer von etwa 2 bis 5 h geglüht wird.The annealing of the strip rolled down to the intermediate thickness takes place preferably in a temperature range from 260 to 300 ° C, expediently in a temperature range of about 270 to 290 ° C, which on Intermediate-thickness rolled strip annealed for a period of about 2 to 5 hours becomes.
Neben dem Vorteil eines gleichmässigen Ätzangriffs weist ein erfindungsgemäss hergestelltes Band ausgezeichnete mechanische Eigenschaften auf, so z.B. eine hohe Festigkeit, die auch während dem Einbrennen eines photosensitiven Lackes bei der Herstellung lithographischer Druckplatten nur unwesentlich abnimmt. In addition to the advantage of a uniform etching attack, one according to the invention manufactured tape on excellent mechanical properties, so e.g. high strength, even during the baking of a photosensitive Lacquer in the production of lithographic printing plates only insignificantly decreases.
Das erfindungsgemäss hergestellte Band ist zur Ätzung in HCI- und HNO3- Elektrolyten gleichermassen geeignet, wobei die Vorzüge der erzielten Mikrostruktur in besonderem Masse beim Ätzen in einem HNO3-Elektrolyten hervortreten.The tape produced according to the invention is equally suitable for etching in HCI and HNO 3 electrolytes, the advantages of the microstructure obtained being particularly apparent when etching in an HNO 3 electrolyte.
Als Legierung zur Herstellung des erfindungsgemässen Bandes können grundsätzlich
alle zur Herstellung von lithographischen Druckplatten üblicherweise
verwendeten Aluminiumwerkstoffe eingesetzt werden. Besonders bevorzugt
sind hierbei Legierungen aus der Reihe AA 1xxx, AA 3xxx oder AA 8xxx, beispielsweise
die Legierungen AA 1050, AA 1200 oder AA 3103.Basically, as an alloy for the production of the strip according to the invention
all commonly used to make lithographic printing plates
used aluminum materials are used. Particularly preferred
are alloys from the AA 1xxx, AA 3xxx or AA 8xxx series, for example
the
Die vorstehend erwähnte vorteilhafte Mikrostruktur im oberflächennahen Bereich des Bandes entsteht im wesentlichen durch die schnelle Erstarrung an der Oberfläche. Als Folge der hohen Erstarrungsgeschwindigkeit erfolgt die Ausscheidung der Sekundärphasenpartikel in der Mikrostruktur in sehr feiner Form und in hoher Dichte. Diese Teilchen wirken als erste Angriffsstellen für das Ätzen, insbesondere wenn das elektrochemische Aufrauhen in einem HNO3-Elektrolyten durchgeführt wird. Die genannten Partikel weisen bei schneller Erstarrung des Bandes auf der Oberfläche einen mittleren Abstand von weniger als 5 µm auf und bilden dadurch ein zusammenhängendes Netz gleichmässiger Oberflächenangriffspunkte. Ausgehend von diesen ersten, gleichmässig und in hoher Dichte über die gesamte Bandoberfläche verteilten Angriffspunkten beginnt das Wachstum des eigentlichen dreidimensionalen Rauheitsmusters. Die geringe Grösse der genannten intermetallischen Phasen hat den weiteren Vorteil, dass sie die Zeitspanne der elektrochemischen Auflösung in der Anfangsphase des Ätzens erheblich verkürzen, wodurch elektrische Energie eingespart werden kann. Da mit der raschen Erstarrung in den Oberflächenbereichen des Bandes bevorzugt Ungleichgewichtsphasen auftreten, ist die Auflösungsgeschwindigkeit der genannten feinen Partikel hoch.The above-mentioned advantageous microstructure in the area of the belt near the surface essentially results from the rapid solidification on the surface. As a result of the high solidification rate, the secondary phase particles are separated out in the microstructure in a very fine form and in high density. These particles act as the first points of attack for the etching, especially when the electrochemical roughening is carried out in an HNO 3 electrolyte. When the band solidifies rapidly on the surface, the particles mentioned have an average distance of less than 5 μm and thereby form a coherent network of uniform surface attack points. Starting from these first points of attack, distributed uniformly and in high density over the entire strip surface, the growth of the actual three-dimensional roughness pattern begins. The small size of the intermetallic phases mentioned has the further advantage that they considerably shorten the period of electrochemical dissolution in the initial phase of the etching, as a result of which electrical energy can be saved. Since the rapid solidification in the surface areas of the belt preferably results in imbalance phases, the dissolution rate of the fine particles mentioned is high.
Ein weiteres wesentliches mikrostrukturelles Merkmal des erfindungsgemäss hergestellten Bandes ist die geringe Korngrösse, die sich während des Bandgiessens in den oberflächennahen Bereichen ergibt. Die hohe Dichte der Durchstosspunkte der Korngrenzen an der Oberfläche führt zusammen mit einer hohen Fehlstellendichte in den Körnern selbst zu chemisch aktiven Angriffspunkten für eine kontinuierliche Bildung neuer Ätzgrübchen.Another essential microstructural feature of the invention The tape produced is the small grain size that occurs during tape casting in the areas near the surface. The high density of the Penetration points of the grain boundaries on the surface lead along with a high density of defects in the grains even at chemically active points of attack for the continuous formation of new etch pits.
Die vorstehend beschriebene Mikrostruktur in der Bandoberfläche führt beim elektrochemischen Ätzvorgang zur Ausbildung des bei lithographischen Druckplatten geforderten gleichmässigen Rauheitsmusters. Die Vorteile, die sich bei Verwendung des erfindungsgemäss hergestellten Bandes ergeben, sind die folgenden:
- Gleichmässige Ätzstruktur als Folge einer hohen Dichte möglicher Ätzangriffspunkte an der Oberfläche
- Ätzen in einem HNO3-Elektrolyten unter kritischen elektrochemischen Prozessbedingungen
- Ausdehnung der Ätzparameter in den Bereich niedriger Ladungsdichte und damit Einsparung von elektrischer Energie
- Verhinderung von Ätzfehlern in HNO3-Elektrolyten als Folge unerwünschter Passivierungsreaktionen
- Bildung eines dichten Netzes von Rissen in der Oxidschicht im Passivitätsbereich des anodischen Potentials durch eine hohe Dichte kleiner intermetallischer Partikel mit Ungleichgewichtsstrukturen
- Bildung eines dichten Netzes von Fehlstellen in der natürlichen Oxidschicht im Passivitätsbereich des anodischen Potentials als Folge einer geringen Korngrösse mit vielen Korngrenzendurchstosspunkten in der Oxidschicht.
- Uniform etching structure as a result of a high density of possible etching points on the surface
- Etching in an HNO 3 electrolyte under critical electrochemical process conditions
- Extension of the etching parameters in the area of low charge density and thus saving of electrical energy
- Prevention of etching errors in HNO 3 electrolytes as a result of undesired passivation reactions
- Formation of a dense network of cracks in the oxide layer in the passivity range of the anodic potential due to a high density of small intermetallic particles with imbalance structures
- Formation of a dense network of defects in the natural oxide layer in the passivity range of the anodic potential as a result of a small grain size with many grain boundary penetration points in the oxide layer.
Eine wesentliche Eigenschaft des auf die gewünschte Enddicke im Dickenbereich von 0.2 bis 0.3 mm gewalzten Lithobandes ergibt sich nun aus dem nachfolgenden Prozessschritt, der elektrochemischen Aufrauhung, welche eine möglichst gleichmässige Ätzstruktur auf der Oberfläche erzeugen sollte. Dafür werden einerseits Elektrolyte aus verdünnter Salzsäure (HCI) und andererseits Elektrolyte aus verdünnter Salpetersäure (HNO3) verwendet, die je nach dem gewünschten Plattentyp ein charakteristisches Ätzbild unter Einwirkung von Wechselstrom erzeugen.An essential property of the litho tape rolled to the desired final thickness in the thickness range from 0.2 to 0.3 mm now results from the subsequent process step, the electrochemical roughening, which should produce a uniform etching structure on the surface. Electrolytes made from dilute hydrochloric acid (HCI) and electrolytes made from dilute nitric acid (HNO 3 ) are used for this purpose.
Wird nun eine Ätzung im Salpetersäure-Elektrolyten vorgenommen, so zeigt die Praxis, dass eine gleichmässige Ätzstruktur nur unter Einhaltung gewisser Ätzparameter zu erreichen ist. Wird zum Beispiel aus wirtschaftlichen Gründen eine zu geringe Ladungsmenge (Coulomb) aufgewendet, so ergeben sich unregelmässige Ätzbilder mit meist streifenartigen Stellen, an denen kein Ätzangriff stattfand. Wird unter diesen kritischen Bedingungen geätzt, so kommen alle feinen Unterschiede in der Gefügestruktur des Substrates (Lithobandes) zum Vorschein und man kann eine Klassierung der verwendeten Lithowerkstoffe feststellen.If etching is now carried out in the nitric acid electrolyte, it shows the practice that a uniform etching structure only if certain Etching parameters can be achieved. For example, for economic reasons if the charge (coulomb) is too small, irregular results Etch images with mostly strip-like areas where no etching attack took place. If etching takes place under these critical conditions, then come all subtle differences in the structure of the substrate (litho tape) to the fore and you can get a classification of the litho materials used determine.
Die Ursache für die Empfindlichkeit des HNO3-Elektrolyten auf das elektrochemische Ätzverhalten von Aluminium liegt in seinem anodischen Passivbereich (Passivoxid) und der damit verbundenen erschwerten Keimbildung von Ätzgrübchen (pits). Erst bei einem anodischen Durchbruchspotential von +1,65 V (SCE) wird dieser Passivbereich durch die Bildung von Ätzgrübchen überwunden, während die pit-Bildung in HCI bereits am Korrosionspotential von -0,65 V (SCE) einsetzt. Dies hat bei anodischer Strombelastung im HNO3-Elektrolyten zur Folge, dass die im Gefüge vorhandenen intermetallischen Phasen zuerst im Potentialbereich -0,5 bis -0,3 V (SCE) aufgelöst werden, bevor die Aluminium-Matrix angegriffen wird und "pitting" entsteht. Die Verteilung dieser intermetallischen Phase bildet nun ein erstes Netzwerk von pits auf der geätzten Oberfläche, und es ist deshalb wesentlich, in welcher Flächendichte diese Phasen auf der Oberfläche vorhanden sind.The reason for the sensitivity of the HNO 3 electrolyte to the electrochemical etching behavior of aluminum lies in its anodic passive area (passive oxide) and the associated difficult nucleation of etching pits. Only at an anodic breakdown potential of +1.65 V (SCE) is this passive area overcome by the formation of caustic pits, while the pit formation in HCI already starts at the corrosion potential of -0.65 V (SCE). With anodic current load in the HNO 3 electrolyte, this means that the intermetallic phases in the structure are first dissolved in the potential range -0.5 to -0.3 V (SCE) before the aluminum matrix is attacked and "pitting" arises. The distribution of this intermetallic phase now forms a first network of pits on the etched surface, and it is therefore important in which area density these phases are present on the surface.
Wie bereits oben erwähnt, zeigt sich die Vorteilhaftigkeit des erfindungsgemäss unter Zwischenschaltung einer Erholungsglühung hergestellten Bandmaterials im Vergleich zu einem Bandmaterial mit einer rekristallisierenden Zwischenglühung vor allem bei lithographischen Druckplatten nach einem Lackeinbrennzyklus bei Temperaturen im Bereich von etwa 270 bis 300° C.As already mentioned above, the advantage of the invention is evident with the interposition of a recovery annealing manufactured strip material compared to a tape material with a recrystallizing Intermediate annealing, especially for lithographic printing plates after a Paint baking cycle at temperatures in the range of about 270 to 300 ° C.
Die Vorteilhaftigkeit des erfindungsgemäss hergestellten Bandmaterials gegenüber
einem Bandmaterial mit konventioneller rekristallisierender Zwischenglühung
ergibt sich aus den nachfolgend in Tabelle 1 dargestellten Festigkeitswerten
bei der Enddicke im kaltgewalzenen Zustand sowie nach verschiedenen
Lackeinbrennsimulationen für die Legierungen AA 1050 und AA 1200.
Die Ergebnisse aus der Tabelle 1 sind in Figur 1 graphisch dargestellt.The advantage of the strip material produced according to the invention compared to
a strip material with conventional recrystallizing intermediate annealing
results from the strength values shown in Table 1 below
in the final thickness in the cold-rolled state and according to various
Paint burn-in simulations for the
Als Ausgangsmaterial für die Untersuchungen diente ein 4.5 mm dickes, auf einer Giesswalzmaschine hergestelltes Gussband. Dieses wurde kalt auf eine Zwischendicke von 1.5 mm gewalzt und nach erfolgter Zwischenglühung auf eine Enddicke von 0.28 mm weiter kaltgewalzt.A 4.5 mm thick, served as the starting material for the investigations cast strip produced by a casting and rolling machine. This got cold on one Rolled to an intermediate thickness of 1.5 mm and after intermediate annealing cold rolled to a final thickness of 0.28 mm.
Die folgenden Zwischenglühbedingungen wurden angewandt:
- R
- (Rekristallisierende Glühung) 380° C x 2h
- E
- (Erholungsglühung) 300° C x 2h
- R
- (Recrystallizing annealing) 380 ° C x 2h
- E
- (Relaxation annealing) 300 ° C x 2h
Die Temperatur- und Zeitangaben beziehen sich auf die Dauer der Glühung bei Metalltemperatur, nachdem das Band mit einer Aufheizgeschwindigkeit von 100° C/h auf die Glühtemperatur aufgeheizt worden ist. Als charakteristischer Festigkeitswert wurde die Bruchdehnung (Rm) bestimmt.The temperature and time information refer to the duration of the annealing at metal temperature after the tape at a heating rate of 100 ° C / h has been heated to the annealing temperature. As more characteristic The elongation at break (Rm) was determined.
Das Einbrennen eines photosensitiven Lackes wurde durch Eintauchen in ein
Salzbad während einer Zeitdauer von 10 min. simuliert.
Claims (10)
dadurch gekennzeichnet, dass
characterized in that
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99811203A EP1110631A1 (en) | 1999-12-23 | 1999-12-23 | Method for producing an aluminium strip for lithographic printing plates |
AU18635/01A AU1863501A (en) | 1999-12-23 | 2000-12-13 | Method for producing an aluminium strip for lithographic printing plates |
PCT/EP2000/012649 WO2001047649A1 (en) | 1999-12-23 | 2000-12-13 | Method for producing an aluminium strip for lithographic printing plates |
JP2001548230A JP2003518554A (en) | 1999-12-23 | 2000-12-13 | Method of manufacturing aluminum strip for lithographic printing plate |
US10/149,420 US20020189725A1 (en) | 1999-12-23 | 2000-12-13 | Method for producing an aluminium strip for lithographic printing plates |
HU0203748A HUP0203748A2 (en) | 1999-12-23 | 2000-12-13 | Method for producing an aluminium strip for lithographic printing plates |
CA002395166A CA2395166A1 (en) | 1999-12-23 | 2000-12-13 | Method for producing an aluminium strip for lithographic printing plates |
NO20023046A NO20023046L (en) | 1999-12-23 | 2002-06-21 | Process for producing an aluminum strip for lithographic printing plates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99811203A EP1110631A1 (en) | 1999-12-23 | 1999-12-23 | Method for producing an aluminium strip for lithographic printing plates |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1110631A1 true EP1110631A1 (en) | 2001-06-27 |
Family
ID=8243212
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99811203A Withdrawn EP1110631A1 (en) | 1999-12-23 | 1999-12-23 | Method for producing an aluminium strip for lithographic printing plates |
Country Status (8)
Country | Link |
---|---|
US (1) | US20020189725A1 (en) |
EP (1) | EP1110631A1 (en) |
JP (1) | JP2003518554A (en) |
AU (1) | AU1863501A (en) |
CA (1) | CA2395166A1 (en) |
HU (1) | HUP0203748A2 (en) |
NO (1) | NO20023046L (en) |
WO (1) | WO2001047649A1 (en) |
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CN113770180B (en) * | 2021-08-19 | 2023-01-10 | 山东理工大学 | Hot rolling method for refining 7000 series aluminum alloy thick plate grains |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0603476A2 (en) * | 1992-11-20 | 1994-06-29 | Fuji Photo Film Co., Ltd. | Support for a planographic printing plate and method for producing same |
EP0640694A1 (en) * | 1993-08-31 | 1995-03-01 | Nippon Light Metal Co., Ltd. | Aluminium alloy substrate for lithographic printing plate and process of producing same |
EP0653497A1 (en) * | 1993-11-15 | 1995-05-17 | Fuji Photo Film Co., Ltd. | Method of producing support for planographic printing plate |
EP0821074A1 (en) * | 1996-07-25 | 1998-01-28 | Alusuisse Technology & Management AG | Process for producing a strip of an aluminium alloy for lithographic printing plates |
-
1999
- 1999-12-23 EP EP99811203A patent/EP1110631A1/en not_active Withdrawn
-
2000
- 2000-12-13 US US10/149,420 patent/US20020189725A1/en not_active Abandoned
- 2000-12-13 WO PCT/EP2000/012649 patent/WO2001047649A1/en active Application Filing
- 2000-12-13 HU HU0203748A patent/HUP0203748A2/en unknown
- 2000-12-13 CA CA002395166A patent/CA2395166A1/en not_active Abandoned
- 2000-12-13 JP JP2001548230A patent/JP2003518554A/en active Pending
- 2000-12-13 AU AU18635/01A patent/AU1863501A/en not_active Abandoned
-
2002
- 2002-06-21 NO NO20023046A patent/NO20023046L/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0603476A2 (en) * | 1992-11-20 | 1994-06-29 | Fuji Photo Film Co., Ltd. | Support for a planographic printing plate and method for producing same |
EP0640694A1 (en) * | 1993-08-31 | 1995-03-01 | Nippon Light Metal Co., Ltd. | Aluminium alloy substrate for lithographic printing plate and process of producing same |
EP0653497A1 (en) * | 1993-11-15 | 1995-05-17 | Fuji Photo Film Co., Ltd. | Method of producing support for planographic printing plate |
EP0821074A1 (en) * | 1996-07-25 | 1998-01-28 | Alusuisse Technology & Management AG | Process for producing a strip of an aluminium alloy for lithographic printing plates |
Also Published As
Publication number | Publication date |
---|---|
HUP0203748A2 (en) | 2003-03-28 |
CA2395166A1 (en) | 2001-07-05 |
NO20023046L (en) | 2002-07-01 |
US20020189725A1 (en) | 2002-12-19 |
JP2003518554A (en) | 2003-06-10 |
AU1863501A (en) | 2001-07-09 |
NO20023046D0 (en) | 2002-06-21 |
WO2001047649A1 (en) | 2001-07-05 |
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