US20080035488A1 - Manufacturing process to produce litho sheet - Google Patents

Manufacturing process to produce litho sheet Download PDF

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US20080035488A1
US20080035488A1 US11/694,116 US69411607A US2008035488A1 US 20080035488 A1 US20080035488 A1 US 20080035488A1 US 69411607 A US69411607 A US 69411607A US 2008035488 A1 US2008035488 A1 US 2008035488A1
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less
equal
alloy
current
sheet
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Juan Francisco Martin
Ricardo Miralles
Gemma Azuar
Jose Fuster
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Howmet Aerospace Inc
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Alcoa Inc
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Priority to US11/694,116 priority Critical patent/US20080035488A1/en
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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
    • 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
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N3/00—Preparing for use and conserving printing surfaces
    • B41N3/03—Chemical or electrical pretreatment
    • B41N3/034—Chemical 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon

Definitions

  • This invention in one embodiment relates to an Al alloy and yet in another embodiment relates to a process suitable for producing lithographic sheet having increased strength and improved electro-graining response.
  • Lithographic sheet manufacturing places high requirements on purity and uniformity of litho strip surfaces.
  • Lithographic sheet manufacturing typically includes a roughening process step. It is standard practice to perform electrochemical (EC) roughening, also referred to as electrograining. It is desirable for electro-graining of the lithographic sheet to result in a plate that is rough across its entire surface and exhibits a very uniform non-directional appearance (no streakiness effects).
  • EC electrochemical
  • a finished printing plate formed of lithographic sheet is inserted into the printing machine, wherein the exact clamping of the plate on the printing cylinder so that no play will result during the printing process.
  • plate cracking occurs according to practical experience in the fast running rotary offset printing machines.
  • the reason for plate cracking is fatigue fracture, and the result is an immediate interruption of the printing process. Therefore, Al-materials for offset printing plates must exhibit sufficiently high fatigue strength or reversed bending fatigue strength so that plate cracking can be prevented.
  • the present invention provides an alloy suitable for lithographic sheet applications that provides increased strength and suitable graining response performance.
  • the aluminum alloy includes:
  • the aluminum alloy includes:
  • a method for forming a lithographic sheet including a electrolytic pre-etching step includes:
  • the current having a non-sinusoidal wave form with substantially constant peaks may be obtained from a thyristor power supply which conducts in either one or both directions to provide a desired current density applied to the aluminum sheet by controlling the phase angle of the switching point of the power supply.
  • FIG. 1 shows the sinusoidal wave form of current used in the prior art and the non-sinusoidal wave form with constant peak values here disclosed, in accordance with the present invention.
  • FIGS. 2 a - 2 c represent micrographs of a lithographic sheet surface formed using the alloy and process of the invention, wherein the sheet was treated to an electrograining treatment with 8% HN0 3 acid and current densities of 10 A/dm 2 for a period of 90 seconds.
  • FIGS. 3 a - 3 c represent micrographs of a lithographic sheet surface formed of an alloy outside the scope of the present invention, which includes 0.2 wt % Mg, wherein the sheet was treated to an electro-graining treatment with 8% HNO 3 acid and current densities of 10 A/dm 2 for a period of 90 seconds.
  • FIGS. 4 a - 4 c represent micrographs of a lithographic sheet surface formed an alloy outside the scope of the present invention, which includes 0.2 wt % Mg and 0.07 wt % Mn, wherein the sheet was treated to an electro-graining step with 8% HNO 3 acid and current densities of 10 A/dm 2 for a period of 90 seconds.
  • FIGS. 5 a - 5 c represent micrographs of a lithographic sheet surface formed using the alloy and process of the present invention, wherein the sheet was treated to an electrograining treatment with 8% HCl acid and current densities of 15 A/dm 2 for a period of 20 seconds.
  • an aluminum alloy for forming lithographic sheet that provides increased strength and suitable electro-graining performance.
  • Lithographic sheet is used in printing applications to provide a printing plate.
  • the term aluminum alloy means an aluminum metal with soluble alloying elements either in the aluminum lattice or in a phase with aluminum. All component percentages herein are by weight percent unless otherwise indicated. When referring to any numerical range of values, such ranges are understood to include each and every number and/or fraction between the stated range minimum and maximum. A range of about 5-15 wt. % Si, for example, would expressly include all intermediate values of about 5.1, 5.2, 5.3 and 5.5%, all the way up to and including 14.5, 14.7 and 14.9% Si. The same applies to each other numerical property, relative thickness and/or elemental range set forth herein.
  • the alloy of the present invention includes:
  • the Mg content may range from 0.31 wt % to about 0.35 wt %.
  • the Si content may range from about 0.05 wt % to about 0.25 wt %. In yet another embodiment, the Si content may range from about 0.8 wt % to about 0.12 wt %.
  • Si in solution may alter the reactivity of the lithographic sheet during electro-graining. If the Si content is too low, a low pitting density may disadvantageously occur during electro-graining, which may render the surface not suitable for lithographic sheet.
  • Low pitting density may be have a surface characterized as including flat areas, which may be referred to as plateaus, that may be detected by scanning electron microscopy (SEM), wherein in one embodiment a low pitting density may have a negative skewness (S) value, with absolute values being higher than 0.4. If the Si content is too great, too few pits may form during electro-graining, in which the size of the individual pits may be too large. In one embodiment, excess pitting may be characterized as a surfacing having at least two pits with a diameter greater than 10 ⁇ m, as observed in a 100 ⁇ 60 ⁇ m scanning electron microscopy (SEM) image.
  • SEM scanning electron microscopy
  • the Fe content may range from about 0.25 wt % to about 0.4 wt % Fe. In yet another embodiment, the Fe content may range from about 0.28 wt % to about 0.32 wt %. Similar to Si, Fe in solution may alter the reactivity of the lithographic sheet during electro-graining, wherein excess pitting may occur if the Fe content is too low or insufficient pitting may occur when the Fe content is too great. Additionally, increasing the Fe content above the specified range may result in increased intermetallic phases present as particles within the sheet, which are detrimental to the sheet's electro-graining performance.
  • Mg present ranging from 0.31 wt % to approximately 0.40 wt %, in accordance with the present invention, provides for an electrograining response that may provide a topography of round pits having a diameter of less than five microns when processed with acids, such as HNO 3 , HCl or combinations thereof, and mixtures further including additives selected from the group including but not limited to acetic acid and boric acid.
  • the Mg content may range from 0.31 wt % to approximately 0.35 wt %.
  • Mg is one element in the alloy that may provide for strengthening in work hardening. The Mg content of the present alloy surprisingly helped attained improved mechanical strength, while maintaining electro-graining performance. Prior to the present invention, a suitable electrograining response was not achievable in alloys having the Mg content of the present alloy with commercial electrograining acids, such as HNO 3 or HCl.
  • the term increased mechanical strength means that a lithographic sheet formed from the inventive alloy and work hardened to H18 temper has a greater ultimate tensile strength (UTS) and yield strength (YS) being at least about 20 Mpa higher than similarly prepared lithographic sheets of AA 1050.
  • the lithographic sheet formed in accordance with the present invention and work hardened to H18 may have an ultimate tensile strength greater than about 165 MPa, in another embodiment being greater than about 175 MPa, and a yield strength greater than about 155 MPa, in another embodiment being greater than about 160 MPa.
  • the inventive aluminum alloy has a higher ultimate tensile strength and yield strength than AA 1050 when heat treated following working.
  • the H18 designation means that the material was cold rolled at a temperature not exceeding about 50° C. for significant periods of time to a reduction of about 74% or more as the last processing step, thereby producing a hard material.
  • a hard material denotes a Brinell hardness greater than about 50.
  • Zn may be present in less than or equal to about 0.03 wt %. In another embodiment, the Zn content may range from 0.01 wt % to 0.03 wt %. In some embodiments, Zn is advantageous for electro-graining in nitric acid. In one embodiment, Zn is electrochemically anodic with respect to aluminum and functions as the initiator for pit formation during electrograining.
  • Ti may be present in less than or equal to about 0.03 wt %, preferably being less than about 0.014 wt %.
  • a lower Ti content favors graining in producing a homogeneous finish, in which 100 ⁇ 60 ⁇ m SEM micrographs do not include isolated pits having a diameter greater than about 10 ⁇ m in diameter or flat areas (plateaus) having a topography with a surface area greater than about 25 ⁇ m 2 .
  • Grain refiner such as TiB 2 , may or may not be present. Ti combined with B is not detrimental to graining.
  • Mn is present in less than about 0.25 wt %, preferably being less that 0.02 wt %. In some embodiments, Mn may have a strengthening effect. In one embodiment, Mn may be present within a range of about 0.01 wt % to about 0.25 wt %. In one embodiment, Mn may be present from about 0.05 wt % to about 0.25 wt % to take advantage of Mn's presence in solid solution or intermetallic particles.
  • Cu may be present in up to about 0.04 %, and in one embodiment of the present invention is limited to about 0.007 wt % or less.
  • incidental impurities refers to elements that are not purposeful additions to the alloy, but that due to impurities and/or leaching from contact with manufacturing equipment, trace quantities of such elements being no greater than about 0.05 wt % each and in combination no greater than about 0.15 wt % of the final alloy, which may nevertheless find their way into the final alloy product.
  • the alloy includes about 0.8 wt % to about 0.12 wt % Si; about 0.28 wt % to about 0.32 wt % Fe; less than or equal to about 0.007 wt % Cu; less than or equal to about 0.02 wt % Mn; 0.31 wt % to 0.35 wt % Mg; less than or equal to about 0.03 wt % Zn; less than or equal to about 0.0 14 wt % Ti; and a balance of Al and incidental impurities.
  • a method for processing an aluminum alloy, such as the alloy described-above, for producing a lithographic sheet.
  • the lithographic sheet forming process begins with providing a direct cast ingot preferably in accordance with the above compositions.
  • titanium boride may be employed as a grain refiner.
  • the ingot is scalped in a machining step to remove the non-uniformities from the ingot's surface that are typically formed during the casting process.
  • the ingot is treated by a pre-heat step.
  • the pre-heat step prepares the ingot for hot rolling and provides for a uniform microstructure throughout ingot.
  • the pre-heat step is conducted in a gas/electric furnace at a temperature between 500° C. to 600° C.
  • the pre-heat time may range from 2-20 hours depending on the heat up cycle of the furnace.
  • the ingot is then hot rolled to a thickness ranging from about 7.5 mm to about 10 mm.
  • the hot rolling apparatus may be single stand or multi-stand hot mill.
  • the strip is then coiled, in which the coiling temperature is maintained between about about 320° C. to about about 360° C. to obtain a grain re-crystallized structure (fine grain structure).
  • the coiling temperature is maintained between about 320° C. and about 360° C. by cooling sprays. If the temperature drops below about 320° C. undesirable cold working effects may be observed. In one embodiment, temperatures drops to below about 320° C. adversely effect recrystallization of the structure, which may result in streaking during electrograining. If the temperature is greater than 360° C. the sheet may experience surface defects including but not limited to welding laps, damages or pick ups that may result in physical defects on the lithographic sheet product.
  • the strip is cold rolled to a thickness ranging from about 1.0 mm to about 5.0 mm, in yet another embodiment to a thickness ranging from about 1.5 mm to about 3.0 mm, and then annealed for approximately 2 to approximately 6 hours at a temperature ranging from about 280° C. to about 500° C., in winch the annealing atmosphere may or may not be an inert atmosphere.
  • the strip is then cold rolled to a final gauge, i.e. ranging from about 0.1 mm to about 0.5 mm, with a minimal reduction of about 74%. Once cold rolled to its final gauge, the strip is then trimmed and tension leveled.
  • the aluminum strip is then treated with an electrolytic pre-etching or degreasing step, hereafter referred to as an electrolytic pre-etching step, including a combination of chemical and electrical treatments that produce an anodized coating on the sheet's surface, which provides for greater graining response.
  • the electro-graining response provided by the present invention is characterized as a topography having fine round pits of a diameter of less than about 5 microns.
  • the anodized coating may be an aluminum oxide having a thickness of about 100 nm or less, and in yet another embodiment may be a thickness ranging from about 1 nm to about 30 nm. It is noted that other thickness for the anodized coating have been contemplated and are within the scope of the present invention, so long as the thickness of the anodized coating should provide protection from oxidation, yet be thin enough to be easily removed in subsequent operations.
  • the electrolytic pre-etching step includes passing the aluminum strip through a mineral acid bath (electrolyte), and applying a current density ranging from about 4 A/dm 2 to about 12 A/dm 2 for dwell times of about 0.5 to about 3.0 seconds using silicon controller rectifier (SCR) pulse waves.
  • the charge density is about 3000 Qm ⁇ 2 .
  • the electrolytic pre-etching step is a continuous in-line process, wherein the aluminum strip enters the mineral acid bath, a current is applied and the aluminum strip is removed with an anodized coating.
  • the mineral acid bath may include any mineral acid in a concentration of less than about 35%, and in another embodiment the mineral acid is in a concentration of about 5% to about 35%, and yet in an even further embodiment the mineral acid bath may be about 15% to about 25%.
  • the mineral acid includes sulfuric, phosphoric, or sulfuric-phosphoric mixtures.
  • the aluminum content of the electrolyte should be kept below about 15 g/l (of Al ion) in phosphoric acid electrolytes, and below about 20 g/l in sulphuric acid, wherein higher levels may decrease conductivity.
  • the mineral acid bath includes phosphoric acid ranging from about 10% to about 30%, and in yet another embodiment approximately 20% phosphoric acid, and containing about 2 g/l to about 15 g/l aluminum, wherein the aluminum concentration may be equal to approximately 0 g/l during start up operations.
  • the temperature of the mineral acid bath may range from about 40° C. to about 100° C., and in another embodiment may range from about 50° C. to about 80° C.
  • the mineral acid bath may include chromic, boric, and tartaric acids and combinations thereof.
  • FIG. 1 shows the non-sinusoidal wave form 10 of the current generated by a thyristor power supply which is used during pre-etching when practicing this invention as compared to the sinusoidal wave form 5 generated by a prior art AC autotransformer.
  • the operating frequency of the thyristor power supply is at least several cycles per second and is preferably at the commercial frequency.
  • the wave form of the current here disclosed is non-sinusoidal with constant peak voltage up to about 60 volts, can be symmetrical or asymmetrical and provide a selected charge density up to about 30,000 Qcm. to the minus 2 which depends upon the strip width or final product requirements. As depicted in FIG.
  • current with non-sinusoidal wave form 10 here disclosed can be generated by a thyristor power supply where the conduction angle is selected for the exact current density applied to the aluminum sheet.
  • the peak voltage ranges from about 35 to about 60 volts.
  • the thyristor power supply maintains a constant peak voltage. Degreasing of the aluminum sheet requires cathodic and anodic current. Cathodic current provides mechanical cleaning of oil, debris, and fines from the aluminum sheet. Anodic current provides the generation of thin aluminum oxide coating (anodized coating). Operating with a current having a wave form here disclosed provides increase cathodic current and anodic current. Peak current is related to peak voltage. By maintaining a constant peak voltage and employing a current having a non-sinusoidal wave form 10 , uniformity to the cathodic and anodic current is obtained.
  • the current having a non-sinusoidal wave form 10 provides uniformity to mechanical cleaning of the aluminum strip through gas generation and uniformity to the formation of the anodized coating, resulting in a more reactive degreasing step than is possible with a current having a sinusoidal wave form 5 from an AC autotransformer.
  • the aluminum strip may be roughened by electrograining and may be treated by similar processes used to provide lithographic sheet and plates. Suitable electrograining response may be achieved with the alloy and method of the invention using Hydrochloric or Nitric acid.
  • the present alloy and processing method provides a lithographic sheet having higher mechanical properties than AA1050, better fatigue behavior, and allows for longer press runs.
  • a method of processing a lithographic sheet in which the current has a non-sinusoidal wave form 10 which can be asymmetrical or symmetrical and has a constant peak voltage.
  • Table 1 below shows the composition of an alloy within the scope of the present invention, designated “ALLOY”, which is hereafter referred to as the inventive alloy, and an alloy representative of Aluminum Associations (AA) 1050, which is hereafter referred to as the comparative example.
  • Lithographic sheets were formed using the alloy representative of the invention and the alloy representative of AA 1050. Each sheet was prepared from a DC cast ingot, pre-heat treated, hot rolled, coiled, cold rolled with intermediate anneal steps to a final gauge, and trimmed.
  • the sheet formed of the inventive alloy is degreased with a pre-etching step.
  • the pre-etching step included a sulphuric acid bath and a current having a non-sinusoidal wave form with constant peak voltage to provide a current density ranging from about 4 A/dm 2 to about 12 A/dm 2 for dwell times of about 0.5 to 3.0 seconds.
  • the comparison sheet formed from AA 1050 was not treated with the pre-etching step and was processed with a prior art sinusoidal AC wave form current from an AC autotransformer.
  • inventive alloy sheet and comparison sheet were then tested for ultimate tensile strength (UTS), yield strength (YS), and Elongation (%) after being worked to H18 temper. Samples were also tested for ultimate tensile strength (UTS), yield strength (YS), and Elongation (%) following a heat treatment at a temperature of 280° C. for a period of 4 minutes. TABLE 2 TEMPER H18 BAKING 280 C./4 MINUTES UTS YS el. UTS YS el. COMP (MPa) (MPa) (%) (MPa (MPa) (%) ALLOY >165 >155 >1.0 >115 >115 >1.5 AA 1050 >145 >135 >1.5 >105 >100 >1.5
  • Table 2 shows the mechanical strength advantages of the inventive alloy having increased Mg content and processed with the inventive pre-etching step, when compared to a conventionally processed AA 1050 sheet.
  • the sheets comprising the inventive alloy displayed greater than a 10% increase in ultimate tensile strength (UTS) and yield strength (YS) when compared to similarly prepared AA 1050, wherein the samples had been worked to H18 temper. Similar results were observed in the samples that had been heat treated.
  • (baking test) sheets prepared in accordance with the present invention displayed greater than an 8% increase in ultimate tensile strength and greater than a 13% increase in yield strength when compared to similarly prepared AA 1050.
  • An electro-graining step was conducted using about 8% HNO 3 acid with current densities of about 10 A/dm 2 for a time period of about 90 seconds.
  • FIGS. 2 a - 2 c represent micrographs of electrograin roughened lithographic sheet surface formed using the alloy and process in accordance with the present invention, as designated in Table 1.
  • FIGS. 3 a - 3 c represent micrographs of a comparative example of an electrograin roughened lithographic sheet surface formed from an alloy composition similar to AA 1050, which included about 0.2 wt % Mg.
  • the comparative example depicted in FIGS. 3 a - 3 c was formed from an alloy composition including 0.082 wt % Si, 0.40 wt % Fe, 0.001 wt % Cu, 0.004 wt % Mn, 0.02 wt % Mg, 0.001 wt % Cr, 0.002 wt % Ni, 0.015 wt % Zn, and 0.015 wt % Ti.
  • FIGS. 4 a - 4 c represent micrographs of a comparative example of an electrograin roughened lithographic sheet surface formed from an alloy composition similar to AA 1050, which included about 0.2 wt % Mg and about 0.07 wt % Mn.
  • the comparative example depicted in FIGS. 4 a - 4 c was formed from an alloy composition including 0.090 wt % Si, 0.34 wt % Fe, 0.004 wt % Cu, 0.071 wt % Mn, 0.018 wt % Mg, 0.001 wt % Cr, 0.002 wt % Ni, 0.013 wt % Zn, and 0.013 wt % Ti.
  • FIGS. 5 a - 5 c represent micrographs of a lithographic sheet surface formed using the alloy and process in accordance with the present invention, wherein the sheet was treated to an electrograining treatment with about 8% HCl acid and current density of about 15 A/dm 2 for a period of 20 seconds.
  • the alloy was composed of 0.096 wt % Si, 0.33 wt % Fe, 0.002 wt % Cu, 0.005 wt % Mn, 0.34 wt % Mg, 0.001 wt % Cr, 0.005 wt % Ni, 0.002 wt % Zn and 0.015 wt % Ti.
  • the electro-graining aspect for the lithographic sheet formed in accordance with the present invention was equal to the comparative examples of AA 1050.

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EP (1) EP2077949B1 (fr)
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Cited By (8)

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WO2009144108A1 (fr) * 2008-05-28 2009-12-03 Novelis Inc. Plaque lithographique en aluminium composite
US20090324994A1 (en) * 2006-07-21 2009-12-31 Hydro Aluminium Deutschland Gmbh Aluminum strip used for lithographic printing plate supports
WO2010057959A1 (fr) * 2008-11-21 2010-05-27 Hydro Aluminium Deutschland Gmbh Bande d'aluminium pour porte-plaque d'impression lithographique ayant une grande résistance à la flexion alternée
WO2010127903A1 (fr) 2009-05-08 2010-11-11 Novelis Inc. Plaque lithographique en aluminium
US20110039121A1 (en) * 2007-11-30 2011-02-17 Hydro Aluminium Deutschland Gmbh Aluminum strip for lithographic printing plate carriers and the production thereof
WO2011059341A1 (fr) * 2009-11-13 2011-05-19 Norsk Hydro Asa Procédé pour la production de matière en bande ou feuille continue d'aluminium contenant du magnésium présentant une adhérence améliorée
WO2012059362A1 (fr) 2010-11-04 2012-05-10 Novelis Inc. Feuille lithographique d'aluminium
US20170253952A1 (en) * 2007-11-30 2017-09-07 Hydro Aluminium Deutschland Gmbh Aluminum strip for lithographic printing plate carriers and the production thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2077949B1 (fr) 2006-03-31 2015-09-30 Aludium Transformación de Productos, S.L.U. Processus de fabrication de feuille lithographique
EP2495106B1 (fr) 2011-03-02 2015-05-13 Hydro Aluminium Rolled Products GmbH Bande en aluminium pour support de plaques d'impression lithographique doté de revêtements à base d'eau
KR102150366B1 (ko) 2020-03-20 2020-09-01 주식회사 창신 스포이트형 화장품 용기

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KR20080109058A (ko) 2008-12-16
WO2007115167A2 (fr) 2007-10-11
BRPI0709691A2 (pt) 2011-07-19
WO2007115167A3 (fr) 2008-11-13
EP2077949A2 (fr) 2009-07-15
KR101152169B1 (ko) 2012-06-15
CN101484322A (zh) 2009-07-15

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