EP1880861B1 - Aluminiumband für lithografische Druckplattenträger - Google Patents

Aluminiumband für lithografische Druckplattenträger Download PDF

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Publication number
EP1880861B1
EP1880861B1 EP06117701.0A EP06117701A EP1880861B1 EP 1880861 B1 EP1880861 B1 EP 1880861B1 EP 06117701 A EP06117701 A EP 06117701A EP 1880861 B1 EP1880861 B1 EP 1880861B1
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EP
European Patent Office
Prior art keywords
strip
surface layer
microcrystalline
bulk
avg
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.)
Active
Application number
EP06117701.0A
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German (de)
English (en)
French (fr)
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EP1880861A1 (de
Inventor
Bernhard Kernig
Henk-Jan Brinkman
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.)
Speira GmbH
Original Assignee
Hydro Aluminium Rolled Products GmbH
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
Priority to EP06117701.0A priority Critical patent/EP1880861B1/de
Application filed by Hydro Aluminium Rolled Products GmbH filed Critical Hydro Aluminium Rolled Products GmbH
Priority to EP15191870.3A priority patent/EP2998126A1/de
Priority to ES06117701.0T priority patent/ES2556166T3/es
Priority to US12/374,022 priority patent/US9206494B2/en
Priority to CN2007800275229A priority patent/CN101489798B/zh
Priority to BRPI0714809A priority patent/BRPI0714809B8/pt
Priority to PCT/EP2007/057532 priority patent/WO2008009747A1/de
Priority to JP2009519993A priority patent/JP5451386B2/ja
Publication of EP1880861A1 publication Critical patent/EP1880861A1/de
Priority to JP2013186601A priority patent/JP5684348B2/ja
Application granted granted Critical
Publication of EP1880861B1 publication Critical patent/EP1880861B1/de
Active legal-status Critical Current
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    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12993—Surface feature [e.g., rough, mirror]

Definitions

  • the invention relates to a belt for producing a support for lithographic printing plates consisting of aluminum or an aluminum alloy, wherein the strip at least partially has a microcrystalline surface layer due to hot and / or cold rolling passes. Moreover, the invention relates to a method for characterizing a surface of a belt for the production of lithographic printing plate supports.
  • Tapes for making lithographic printing plate supports are produced after casting a corresponding aluminum alloy by rolling.
  • the strip is produced by hot rolling a roll bar followed by cold rolling. After the tape has been made, it is degreased and wound onto a coil.
  • the coil is pretreated by the lithographic printing plate manufacturer and then electrochemically roughened.
  • the microcrystalline surface layer of the aluminum strip introduced by the rolling has largely been removed by the pretreatment, so that the microcrystalline surface layer no longer plays any role in terms of the subsequent electrochemical roughening.
  • the EP 1 136 280 A2 relates to a support for lithographic printing plates and its production, in which prior to anodizing the surface of an aluminum sheet is pickled alkaline.
  • the EP 0 795 048 B1 describes a method of cleaning the surface of aluminum workpieces by anodizing.
  • the EP 1598 138 A1 describes a method of texturing an aluminum sheet with a stamping die.
  • the object of the present invention is to provide a ribbon for the production of lithographic printing plate supports which has an improved microcrystalline surface layer, so that higher production speeds are possible in the production of lithographic printing plate supports.
  • the invention has for its object to propose a method for characterizing the surface quality of the microcrystalline surface layer of strips of aluminum or an aluminum alloy.
  • the above-derived object is achieved in that in a surface microprobe analysis after the mapping process of a surface region of the microcrystalline surface of the strip, the surface portion with an intensity ratio I / I bulk (avg) of greater than 3 in the spectral range the K ⁇ 1 line of the X-ray emission spectrum of oxygen of the measured microcrystalline surface layer is less than 10%, preferably less than 7%, wherein in the areal microprobe analysis an excitation voltage of 15 kV, a beam current of 50 nA and a beam cross section of 1 .mu.m, at a Increment of 16.75 microns is used for the electron beam.
  • the electrons incident on the surface of the band generate X-ray brake radiation and characteristic X-ray emission spectra whose wavelength identifies the element present in the sample and whose intensity gives information about the concentration or frequency of the corresponding element in the measuring region of the electron beam cross section impinging on the surface to be measured.
  • the highest intensities are found in the K ⁇ 1 lines of the X-ray emission spectra. Due to the excitation voltage of 15 kV, the penetration depth of the electrons is limited to 1 to 2 microns, so that only near-surface layers of the belt to the emission of the characteristic X-ray emission spectra excited become.
  • the penetration depth of the electrons coincides with the values known from the literature for the thickness of the microcrystalline surface layer which is produced during hot rolling of the rolling bar and after cold rolling at final strip thicknesses of 0.15 to 0.5 mm is typically 1 to 2 ⁇ m (see For this: Lindseth I., "Optical total reflectance, near surface microstructure, and topography of rolled aluminum materials", PhD thesis, NTNO, Trontheim, Norway, 1999 ).
  • the K ⁇ 1 line of the X-ray emission spectrum of oxygen now indicates the content of oxygen of oxidic compounds in the microcrystalline surface layer at the corresponding measurement point.
  • the intensity of the micro-sonic signal can thus be used as a measure of the size of the oxide particles.
  • rolled-in-oxide particles Due to the penetration depth of the electrons of about 1 to 2 .mu.m, rolled-in-oxide particles, which have been identified as problematic with respect to electrochemical roughening, are detected in particular by rolling. Due to the limitation of the surface portions with I / I bulk (avg) > 3 to less than 10%, preferably less than 7%, the tape according to the invention for the production of Therefore lithographic printing plate supports a distribution of relatively small oxide particles, so that the tape according to the invention has very good Aufraueigenschaften.
  • the thickness of the tape is 0.15 to 0.5 mm and the thickness of the microcrystalline surface layer of the tape is about 0.5 to 2.5 ⁇ m.
  • a further increase in the process speeds in the electrochemical roughening of the tape for lithographic printing plate support can be ensured by the tape according to the invention in that in area microprobe analysis by the mapping method of a surface portion of the tape, the area ratio with an intensity ratio I / I bulk (avg) of greater than 4 in the spectral range of the K ⁇ 1 line of the X-ray emission spectrum of oxygen of the measured microcrystalline surface layer is less than 3%, preferably less than 2%.
  • the microcrystalline surface layer of the strip according to the invention has an even smaller number of larger oxide particles which can disturb the electrochemical roughening or the preceding pretreatments.
  • the band is made of an aluminum alloy of the type AA1050, AA1100 or AA3103. These aluminum alloys have already found wide application in terms of their suitability for the production of lithographic printing plate supports.
  • a further improvement in terms of strength and Aufrauley tape for the production of lithographic printing plate supports can thereby That the aluminum strip consists of an aluminum alloy with the following proportions by weight of alloy components: 0.05% ⁇ Si ⁇ 0.1%, 0.4% ⁇ Fe ⁇ 1 %, Cu ⁇ 0.04%, Mn ⁇ 0.3%, 0.05% ⁇ Mg ⁇ 0.3%, Ti ⁇ 0.04%, Residual Al with unavoidable impurities individually a maximum of 0.005% in total maximum of 0.15%.
  • the above-described object is achieved by a method for characterizing a surface of a belt, in particular a belt for the production of lithographic printing plate carriers by performing a surface microprobe analysis of the microcrystalline surface layer according to the mapping method and the quality the surface of the band is evaluated on the basis of the measured intensity distribution in the spectral range of the K ⁇ 1 line of the X-ray emission spectrum of oxygen.
  • the areal microprobe analysis offers the possibility of examining the microcrystalline surface layer for its composition and, in particular, by the distribution of the intensity distribution of the K ⁇ 1 line of the X-ray emission spectrum of oxygen over the area of oxide particles in the microcrystalline surface layer.
  • a surface microprobe analysis according to the mapping of surfaces is already known.
  • a quality evaluation of the surface area of an aluminum or aluminum alloy strip based on the intensity distribution in the spectral region of the K ⁇ 1 line of the X-ray emission spectrum of oxygen with respect to the suitability for producing lithographic printing plate supports has not been performed hitherto.
  • the suitability of the strip in particular in downstream electrochemical roughening methods, can be reliably checked via the characterization method according to the invention.
  • the influence of the aluminum oxide film on the microcrystalline surface layer can, according to a first embodiment of the method according to the invention, be reduced in the measurement result by ascertaining from the measured intensity distribution of the surface layer an area fraction having a specific value for the intensity ratio I / I bulk (avg) .
  • a measure of the size of the oxide particles in the microcrystalline surface layer is provided by the intensity ratio I / I bulk (avg) and a measure of the frequency of the oxide particles over the surface portions with a specific intensity ratio I / I bulk (avg) posed. From the intensity ratio mentioned, this results in a combined measure of the size and area occupancy of the microcrystalline surface layer with oxide particles of a certain size. It has been found that in particular the combination of size and number of oxide particles in the microcrystalline surface layer, the subsequent electrochemical Can negatively influence Aufraurea, provided upstream pickling steps do not completely eliminate the microcrystalline surface layer or a roughened surface of bulk material is roughened.
  • an excitation voltage of 5 to 20 kV, preferably 15 kV, a beam current of 10 to 100 nA, preferably 50 nA and a beam cross section of 0.2 to 1.5 .mu.m, preferably 1 .mu.m used for the electron beam not only the penetration depth are limited to the electrons, but on the beam current and the beam cross-section excitation densities and X-ray emission intensities are achieved, which reduce measurement errors in the determination of the surface portions.
  • the measuring time per measuring point ensures that a sufficiently large strip surface section can be measured in an adequate time.
  • a linear focusing spectrometer with a crystal having a lattice plane distance 2d of 6 nm, preferably an LDE1H crystal.
  • the crystal is arranged in linear focusing spectrometers on a Rowlandnik with a small diameter, for example 100 mm.
  • the spectrometer on the one hand by the linear focusing that the X-ray emission spectrum, which is emitted from the sample spot, with sufficient intensity in the detector, preferably a designed as a counter tube detector for X-rays, is bundled.
  • Fig. 1 shows the typical structure of the spectrometer of a microprobe analysis, in the present case a JEOL JXA 8200 microprobe was used, in which an electron beam 1 is deflected onto a sample 2.
  • the electrons are excited with an excitation voltage of 15 kV, a beam current of 50 nA and a beam cross section of 1 micron to the sample 2 directed.
  • sample 2 the characteristic X-ray emission spectrum 3 is then generated, which is generated by electron transitions on the inner shells of the excited atoms.
  • the wavelength of the emitted spectrum is therefore characteristic of each atom. This in Fig.
  • the linearly focused spectrometer shown has a curved crystal 4 for wavelength analysis, which reflects the X-radiation emitted by the specimen 2 in a wavelength-selective manner into the slit of a detector 5.
  • the acceptance angle of the characteristic X-radiation ⁇ is 40 °.
  • the position of the crystal 4 on the Rowland circle 6, which here has a diameter of 100 mm, is adjusted so that only the K ⁇ 1 line of the characteristic X-ray spectrum of oxygen in the detector is diffracted by Bragg reflection. After the number of X-ray pulses has been counted in the detector over a measuring time of 0.6 s, the sample is transported further by the increment of 16.75 ⁇ m and a next measuring point is measured.
  • the spectrometer has a crystal specially adapted for measuring the K ⁇ 1 line of the X-ray emission spectrum of oxygen and oriented for maximum intensity of the oxygen spectrum, a type LDE1H crystal having a lattice plane distance 2d of 6 nm.
  • the penetration depth of the electrons into the sample 2 is about 1 to 2 ⁇ m at an excitation voltage of 15 kV.
  • a square area with an edge length of 5.025 mm was measured, with a step size of 16.75 ⁇ m being selected, so that a total of 900 measuring points were measured in the square surface.
  • FIG. 2 shows the measurement results of the surface microprobe analysis after the mapping process on a sample, each measuring point on the one hand a square area with an edge length of 16.75 microns and on the other hand, the measured intensity ratio I / I bulk (avg) is assigned. It can be seen in Fig. 2 the measured measured surface area intensity values converted into color values, which show the microscopic streaking in the rolling direction typical of the rolled strip surfaces investigated. This streakiness is attributed to a distribution of rolled surface particles in the rolling direction during rolling. Corresponding mappings were then evaluated with regard to their area occupation with certain intensity ratios I / I bulk (avg) .
  • each tape sample consisting of an AA1050 aluminum alloy.
  • the experimental setup for determining the size and frequency of the oxide particles in the microcrystalline surface layer was chosen as described above.
  • the microcrystalline surface layer was removed by ablating greater than 2 ⁇ m in a pickling step, the sample forming a typical aluminum oxide layer being about 1 Week stored, also carried out a two-dimensional microprobe analysis and a mean intensity signal for the bulk material I bulk (avg) determined.
  • 125 pulses were measured in 0.6 s at the above-mentioned excitation and detection conditions.
  • the intensity values of the K ⁇ 1 line of the X-ray emission spectrum of oxygen measured on the samples became divided by the mean intensity value of the bulk material and assigned in a corresponding mapping of a square measurement area with an edge length of 16.75 microns. Subsequently, the areas in the 5.025 mm ⁇ 5.025 mm total measurement area were summed up, which have an intensity ratio of I / I bulk (avg) greater than 3 or greater than 4.
  • the area proportions measured in samples Nos. 1 to 9 with an intensity ratio of I / I bulk (avg) greater than 3 or 4 are shown in Table 1 together with the averaged intensity values I avg measured on the samples. Table 1 Samples no.
  • samples 1-9 or the associated strips were subjected to an electrochemical roughening and their behavior during the electrochemical roughening was evaluated.
  • Sample Nos. 1, 2 and 3 caused electrochemical roughening errors and no increase in process speed during electrochemical Allow for confidence. While Sample Nos. 1 and 2 were considered to be very poor (-) in terms of electrochemical roughening, so that homogeneous roughening could be achieved only at very high charge carrier input, the roughening of Sample No. 3 improved. However, Sample No. 3 did not show satisfactory roughening. All samples were subjected to conventional degreasing prior to measurement.
  • the intensity ratio I / I bulk (avg) is a measure of the size of the oxide particles in the microcrystalline surface layer and their surface area corresponds to the frequency of oxide particles above a certain size.
  • the sample No. 5 corresponds to the previously examined sample No. 2, which has additionally undergone a surface pickling selectively applied to the rolled-in particles.
  • the surface of Sample No. 5 was pickled with a 10% H 3 PO 4 solution at 80 ° C for about 10 seconds. Since the phosphoric acid almost does not attack the aluminum matrix and selectively removes only the oxide particles, the area fraction with an intensity ratio I / I bulk (avg) greater than 4 could be reduced from 23.9% to 6.0%.
  • the measured values of the bulk sample 9 are shown in Table 1.
  • the measured values for the area proportions of I / I bulk (avg) are consistently zero and the roughening was very good.
  • the still measured intensity of the characteristic X-ray emission spectrum of the oxygen is attributed to the formation of a natural aluminum oxide layer on the surface.
  • the sample 9 after removal of the microcrystalline Surface layer stored for about 1 week, so that could form a sufficiently thick aluminum oxide layer.
  • an average intensity signal I bulk (avg) of 125 pulses was measured across the sample surface.
  • the improved electrochemical Aufraueigenschaften the inventive samples Nos. 4 to 8 are noticeable in particular in a reduced charge carrier entry for complete roughening during the electrochemical roughening of the surface of the samples.
  • a ribbon for lithographic printing plate supports can be provided, which allows higher process speeds in the electrochemical roughening or in the manufacture of lithographic printing plate supports.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Printing Plates And Materials Therefor (AREA)
EP06117701.0A 2006-07-21 2006-07-21 Aluminiumband für lithografische Druckplattenträger Active EP1880861B1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP15191870.3A EP2998126A1 (de) 2006-07-21 2006-07-21 Verfahren zur herstellung eines lithografischen druckplattenträgers
ES06117701.0T ES2556166T3 (es) 2006-07-21 2006-07-21 Banda de aluminio para soporte de placa de impresión litográfica
EP06117701.0A EP1880861B1 (de) 2006-07-21 2006-07-21 Aluminiumband für lithografische Druckplattenträger
CN2007800275229A CN101489798B (zh) 2006-07-21 2007-07-20 用于石印版基板的铝板条及表征其表面的方法
US12/374,022 US9206494B2 (en) 2006-07-21 2007-07-20 Aluminum strip used for lithographic printing plate supports
BRPI0714809A BRPI0714809B8 (pt) 2006-07-21 2007-07-20 Tira para a produção de um substrato para chapas de impressão litográfica e método para a definição de uma superfície de uma tira de alumínio ou uma liga de alumínio
PCT/EP2007/057532 WO2008009747A1 (de) 2006-07-21 2007-07-20 Aluminiumband für lithografische druckplattenträger
JP2009519993A JP5451386B2 (ja) 2006-07-21 2007-07-20 リソグラフ印刷プレート基板用のストリップ
JP2013186601A JP5684348B2 (ja) 2006-07-21 2013-09-09 リソグラフ印刷プレート基板用のストリップ

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP06117701.0A EP1880861B1 (de) 2006-07-21 2006-07-21 Aluminiumband für lithografische Druckplattenträger

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP15191870.3A Division EP2998126A1 (de) 2006-07-21 2006-07-21 Verfahren zur herstellung eines lithografischen druckplattenträgers

Publications (2)

Publication Number Publication Date
EP1880861A1 EP1880861A1 (de) 2008-01-23
EP1880861B1 true EP1880861B1 (de) 2015-11-04

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP06117701.0A Active EP1880861B1 (de) 2006-07-21 2006-07-21 Aluminiumband für lithografische Druckplattenträger
EP15191870.3A Withdrawn EP2998126A1 (de) 2006-07-21 2006-07-21 Verfahren zur herstellung eines lithografischen druckplattenträgers

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP15191870.3A Withdrawn EP2998126A1 (de) 2006-07-21 2006-07-21 Verfahren zur herstellung eines lithografischen druckplattenträgers

Country Status (7)

Country Link
US (1) US9206494B2 (ja)
EP (2) EP1880861B1 (ja)
JP (2) JP5451386B2 (ja)
CN (1) CN101489798B (ja)
BR (1) BRPI0714809B8 (ja)
ES (1) ES2556166T3 (ja)
WO (1) WO2008009747A1 (ja)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0617702B8 (pt) 2005-10-19 2023-01-10 Hydro Aluminium Deutschland Gmbh Processo para produção de uma fita de alumínio para suportes de placa de impressão litográfica
JP5487510B2 (ja) * 2008-07-30 2014-05-07 国立大学法人東北大学 Ａｌ合金部材、電子装置製造装置、および陽極酸化膜付きＡｌ合金部材の製造方法
EP2192202B2 (de) * 2008-11-21 2022-01-12 Speira GmbH Aluminiumband für lithographische Druckplattenträger mit hoher Biegewechselbeständigkeit

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0795048A1 (en) * 1994-12-19 1997-09-17 Alcan International Limited Cleaning aluminium workpieces

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62230946A (ja) 1986-04-01 1987-10-09 Furukawa Alum Co Ltd 平版印刷版用アルミニウム合金支持体
US6337136B1 (en) 1998-07-30 2002-01-08 Nippon Light Metal Company, Ltd. Aluminum alloy support for lithographic printing plate and process for producing substrate for support
JP4016310B2 (ja) * 1998-07-30 2007-12-05 日本軽金属株式会社 平版印刷版用アルミニウム合金支持体および該支持体用素板の製造方法
DE60128174T2 (de) * 2000-03-09 2007-12-27 Fujifilm Corp. Flachdruckplattenträger und sein Herstellungsverfahren
JP2001322362A (ja) * 2000-03-09 2001-11-20 Fuji Photo Film Co Ltd 平版印刷版用支持体
JP4098462B2 (ja) * 2000-03-24 2008-06-11 富士フイルム株式会社 平版印刷版用支持体の製造方法
JP3983611B2 (ja) 2002-07-05 2007-09-26 三菱アルミニウム株式会社 印刷版用アルミニウム合金板の製造方法
JP2005329451A (ja) * 2004-05-21 2005-12-02 Fuji Photo Film Co Ltd アルミニウム板の表面加工方法及び平版印刷版用支持体並びに平版印刷版
BRPI0617702B8 (pt) * 2005-10-19 2023-01-10 Hydro Aluminium Deutschland Gmbh Processo para produção de uma fita de alumínio para suportes de placa de impressão litográfica
CN101484322A (zh) * 2006-03-31 2009-07-15 美铝公司 生产平版印刷片材的制造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0795048A1 (en) * 1994-12-19 1997-09-17 Alcan International Limited Cleaning aluminium workpieces

Also Published As

Publication number Publication date
JP5684348B2 (ja) 2015-03-11
JP5451386B2 (ja) 2014-03-26
JP2014058156A (ja) 2014-04-03
EP2998126A1 (de) 2016-03-23
WO2008009747A1 (de) 2008-01-24
EP1880861A1 (de) 2008-01-23
BRPI0714809B8 (pt) 2023-01-10
CN101489798A (zh) 2009-07-22
ES2556166T3 (es) 2016-01-13
CN101489798B (zh) 2011-03-16
JP2009544486A (ja) 2009-12-17
US9206494B2 (en) 2015-12-08
BRPI0714809B1 (pt) 2020-08-04
BRPI0714809A2 (pt) 2016-05-24
US20090324994A1 (en) 2009-12-31

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