EP0536531A2 - Procédé de grainage d'aluminium ou d'alliages d'aluminium pour supports plaques d'impression et une plaque d'impression - Google Patents

Procédé de grainage d'aluminium ou d'alliages d'aluminium pour supports plaques d'impression et une plaque d'impression Download PDF

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Publication number
EP0536531A2
EP0536531A2 EP92115022A EP92115022A EP0536531A2 EP 0536531 A2 EP0536531 A2 EP 0536531A2 EP 92115022 A EP92115022 A EP 92115022A EP 92115022 A EP92115022 A EP 92115022A EP 0536531 A2 EP0536531 A2 EP 0536531A2
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EP
European Patent Office
Prior art keywords
roughening
electrolyte
aluminum
acid
pickling
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.)
Granted
Application number
EP92115022A
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German (de)
English (en)
Other versions
EP0536531B1 (fr
EP0536531A3 (en
Inventor
Michael Dr. Brenk
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.)
Agfa Gevaert AG
Original Assignee
Hoechst AG
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Publication date
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Publication of EP0536531A3 publication Critical patent/EP0536531A3/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C3/00—Reproduction or duplicating of printing formes
    • B41C3/02—Stereotyping
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/04—Etching of light metals
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/08—AC plus DC

Definitions

  • the invention relates to a method for roughening aluminum or aluminum alloys as a carrier material for printing plates, in which two electrochemical roughening steps follow one after the other, and a printing plate made of a carrier material that is produced by the method.
  • Printing plates especially offset printing plates, generally consist of a support and at least one radiation-sensitive layer arranged thereon, this layer being applied by the consumer in the case of non-precoated plates or by the manufacturer in the case of precoated plates.
  • Aluminum or one of its alloys has established itself as a layer support in the printing plate field.
  • these substrates can also be used without a modifying pretreatment, but they are generally modified in or on the surface, for example by mechanical, chemical and / or electrochemical roughening, sometimes also called graining or etching, chemical or electrochemical oxidation and / or treatment with hydrophilizing agents.
  • the roughening can be carried out in aqueous acids, e.g. B. aqueous HCl or HNO3 solutions, or in aqueous salt solutions, for. B. aqueous NaCl or Al (NO3) 3 solutions, using alternating current.
  • aqueous acids e.g. B. aqueous HCl or HNO3 solutions
  • aqueous salt solutions for. B. aqueous NaCl or Al (NO3) 3 solutions
  • the roughness depths of the roughened surface which can be achieved in this way, given, for example, as mean roughness depths R z , are in the range from 1 to 15 ⁇ m, in particular in the range from 2 to 8 ⁇ m.
  • the roughness depth is determined in accordance with DIN 4768 in the version from October 1970.
  • the arithmetic mean of the individual roughness depths of five adjacent individual measuring sections is calculated as the average roughness depth R z .
  • the roughening takes place u. a. to improve the adhesion of the reproduction layer on the support and the dampening solution guide of the printing plate resulting from the printing plate by exposure and development.
  • the water flow is an important quality feature for offset printing plates. It is defined as the dosage and control in the document “Determining an optimal water flow to increase the performance of offset printing” (Albrecht, J .; Rebner, W., Wirz, B., West Germanr Verlag, Cologne and Opladen 1966, page 7) the moistening of the printing form during the print run.
  • the water flow also depends, among other things, on the surface roughness of the printing form, ie the grain size of the surface.
  • the problems of inadequate water supply are well known: If too much water is required to keep the non-printing parts of a printing form free of ink, more water can get into the ink emulsify, the pressure becomes flat. Watermarks may also occur, causing the paper to become damp.
  • the fountain solution consumption of a printing plate can be measured objectively with sufficient accuracy, but not the fountain solution guidance, since it is responsible for some of the above-mentioned disadvantageous phenomena, e.g. B. smearing, there is no objective measurement method (Decker, P., in "Contribution to Analysis ", page 18). Therefore the dampening solution guidance of a printing plate is assessed qualitatively with the adjectives "very good”, “good”, “satisfactory”, “sufficient”, “moderate”, “bad”, “very bad”. It will be described later in the context of the explanation of the examples under which conditions these adjectives are used as a basis for the assessment.
  • Another quality feature of an offset printing plate is the brightness and the uniformity of the brightness of the carrier material.
  • the brightness can be measured as described in the DIN standard 6174 in the version from January 1979. It also mentions how the uniformity of the color impression can be quantified.
  • the value ⁇ E ab * which can be calculated from the three color values L * , a * and b *, serves as a measure of the uniformity.
  • a support must not be too dark so that too much of the incident light is not absorbed by the support surface itself and is thus lost in the actual light-sensitive layer for photochemical reactions.
  • the surface should also be uniformly bright so that the sensitivity to light does not vary from place to place on the printing plate.
  • the image points that guide the color during later printing and the non-image points that carry the dampening agent which are generally the exposed carrier surface, and thus the actual printing form, are produced on the printing plate created.
  • Very different parameters influence the later topography and thus the dampening solution management of the surface to be roughened.
  • the following references provide information:
  • the temperature variation between 16 ° C and 90 ° C shows a changing influence only from about 50 ° C, which is noticeable, for example, by the sharp decline in the formation of layers on the surface.
  • the roughening time between 2 and 25 min leads to an increasing metal dissolution with increasing exposure time.
  • the variation of the current density between 2 and 8 A / dm2 results in higher roughness values with increasing current density.
  • the acid concentration is in the range of 0.5 and 2% HCl, there are only minor changes in the hole structure below 0.5% HCl, there is only a local attack on the surface and, at high values, an irregular dissolution of aluminum.
  • pulsed direct current is used instead of alternating current, it can be seen that both types of half-wave are obviously required for uniform roughening.
  • the addition of sulfate ions increasingly leads to undesired, coarse, non-homogeneous roughening structures which are not suitable for lithographic purposes.
  • DE-A 35 03 927 describes ammonium chloride as an inorganic additive to an HCl electrolyte.
  • JP-B 16 918/82 are the combination of a pre-structuring which takes place mechanically in the first step, followed by one chemical cleaning (pickling) which may take place with an electrochemical roughening by means of modified alternating current in electrolytes containing hydrochloric or nitric acid is described, it being possible for a further cleaning step to subsequently take place.
  • US-A 4 437 955 discloses a two-stage electrochemical roughening process for the production of capacitors with an electrolyte containing hydrochloric acid in the first step and an electrolyte containing chloride and sulfate ions in the second step.
  • the second stage electrolyte is not acidic, and DC is used in this stage.
  • DE-A 38 36 810 describes a process in which aluminum is also roughened in two steps for the production of printing plate supports. Pickling is carried out there between the first and the second roughening step. This method has the disadvantage that the plates, especially when chloride-containing electrolytes are used in the last pickling step, become superficially uneven and quite dark.
  • the object of the present invention is to improve a method for roughening aluminum for printing plate supports of the type described above in such a way that, in addition to a uniformly bright, very fine, grain-free, area-covering roughening structure of the aluminum surface of the printing plate supports, very good reprographic and printing properties, in particular high ones Print runs of the finished printing forms can be obtained.
  • This object is achieved in that the first electrochemical roughening step in an electrolyte containing hydrochloric, nitric or sulfuric acid and chloride ions or nitrate ions, the subsequent second electrochemical roughening step in an electrolyte with the same or different concentration proportions of the additives as in the first roughening step and that finally a pickling of the substrate surface is carried out.
  • the pickling step removes undesirable deposits that make the surface uneven and dark from the surface of the carrier material.
  • the process can be carried out discontinuously or continuously with strips made of aluminum or its alloys.
  • the process parameters in the continuous process during the roughening step are in the following ranges: the temperature of the electrolyte between 20 and 80 ° C, the current density between 3 and 180 A / dm2, the residence time of a material point to be roughened in the electrolyte between 5 and 300 s and Electrolyte flow rate on the surface of the material to be roughened between 5 and 200 cm / s. Due to the continuous driving style and the simultaneous release of Al ions and the consumption of H+, constant adjustment of the electrolyte composition by the corresponding diluted acids is necessary.
  • the required current densities are between 3 and 40 A / dm2 and the residence times between 30 and 300 s.
  • the flow of the electrolyte can also be dispensed with.
  • the process can also be used successfully with other aluminum alloys.
  • an anodic oxidation of the aluminum takes place, for example, which improves the abrasion and adhesion properties of the surface of the carrier material.
  • the following processes can also be used, for example: the anodic oxidation of aluminum in an aqueous electrolyte containing H2SO4, the Al3+ ion content of which is more than 12 g / l is set in an aqueous electrolyte containing H2SO4 and H3PO4 or in an aqueous electrolyte containing H2SO4, H3PO4 and Al3+ ions.
  • Direct current is preferably used for the anodic oxidation, but alternating current or a combination of these types of current (eg direct current with superimposed alternating current) can also be used.
  • the layer weights of aluminum oxide range from 1 to 10 g / m2, corresponding to a layer thickness of approximately 0.3 to 3.0 ⁇ m.
  • a modifying treatment which causes a surface removal from the roughened surface, can also be applied.
  • This treatment can be carried out in both acidic and basic media.
  • Such a modifying intermediate treatment provides by removing fine structures and. a. a uniformly bright surface, and the surface improves the water flow of the panels.
  • the anodic oxidation of the aluminum printing plate support material can be followed by one or more post-treatment stages.
  • Aftertreatment is understood to mean, in particular, a hydrophilizing chemical or electrochemical treatment of the aluminum oxide layer, for example immersion treatment of the material in an aqueous polyvinylphosphonic acid solution, immersion treatment in an aqueous alkali silicate solution or electrochemical treatment (anodization) in an aqueous alkali silicate solution.
  • post-treatment stages serve in particular to additionally increase the hydrophilicity of the aluminum oxide layer, which is already sufficient for many areas of application, without impairing the other known properties of this layer.
  • a carrier material produced by the method according to the invention becomes a printing plate by coating with a light-sensitive layer.
  • all layers are suitable as light-sensitive reproduction layers which, after exposure, subsequent development and / or fixing, provide an image-like area from which printing can take place and / or which represent a relief image of an original.
  • the reproduction layers are either at the manufacturer applied by presensitized printing plates or directly by the consumer on one of the usual carrier materials.
  • the light-sensitive reproduction layers include such as z. B. in "Light-Sensitive Systems” by Jaromir Kosar, John Wiley & Sons Verlag, New York 1965, are described: The layers containing unsaturated compounds in which these compounds are isomerized, rearranged, cyclized or crosslinked during exposure (Kosar, chapter 4) such as B.
  • Cinnamate the layers containing photopolymerizable compounds, in which monomers or prepolymers optionally polymerize during exposure by means of an initiator (Kosar, Chapter 5); and the layers containing o-diazo-quinones such as naphthoquinonediazides, p-diazo-quinones or diazonium salt condensates (Kosar, Chapter 7).
  • o-diazo-quinones such as naphthoquinonediazides, p-diazo-quinones or diazonium salt condensates
  • Suitable layers also include the electrophotographic layers, i.e. H. those containing an inorganic or organic photoconductor.
  • these layers can of course also contain other components, e.g. B. resins, dyes, pigments, wetting agents, sensitizers, adhesion promoters, indicators, plasticizers or other conventional auxiliaries.
  • photoconductive layers such as z. B. in DE-C 11 17 391, 15 22 497, 15 72 312, 23 22 046 and 23 22 047 are described, are applied to the support materials, whereby highly light-sensitive, electrophotographic layers are formed.
  • the materials for printing plate supports roughened by the process according to the invention have a uniform brightness and a very uniform topography, which has a positive influence on the print run stability and the dampening solution guidance when printing printing forms made from these supports.
  • Undesirable "scars" occur less frequently, which form distinctive depressions compared to the roughening of the surroundings; these can even be completely suppressed.
  • An aluminum support material is first pickled for 60 s in an aqueous solution containing 20 g / l NaOH at room temperature.
  • the roughening takes place in the specified electrolyte systems of the roughening stages A, B, C, D by combining two roughening steps, all possible combinations of the electrolyte systems of the roughening steps A to D, including the combination of one of the roughening steps with themselves, e.g. B. A-A, B-B, C-C, D-D, is possible.
  • the classification into the quality classes taking into account the surface topography with regard to uniformity, freedom from scars and area coverage, is carried out by visual assessment under a microscope, whereby a homogeneously roughened and scar-free surface is assigned quality level "10" (best value).
  • quality level "0" (worst value) is assigned to a surface with thick scars of a size of more than 30 ⁇ m and / or an extremely unevenly roughened or almost rolled surface.
  • Another criterion for the quality is the brightness and the uniformity of the brightness of the support surface, which are given as L-value and ⁇ E-value in the tables below.
  • L-value and ⁇ E-value are given as L-value and ⁇ E-value in the tables below. The greater the L value, the greater the brightness, and the greater the ⁇ E value, the more the brightness fluctuates from place to place on the carrier surface.
  • Column 2 of the following tables shows the roughening process used in the first step, columns 3 and 4 the roughening time and the current density, column 5 shows the roughening process used in the second step, columns 6 and 7 the roughening time and the current density, the column 8 contains the L value explained above, the one The measure of the brightness is, and column 9 contains the classification of the carrier in quality classes, which was explained in the previous section, column 10 shows the uniformity ⁇ E of the brightness.
  • the supports are still alkali pickled in a third step after both roughening steps.
  • an aqueous solution of 20 g / l NaOH and 2 g / l sodium carbonate (anhydrous) at room temperature of 20 to 24 ° C. is used as the pickling solution.
  • the concentration of both salt and acid can be varied.
  • the temperature or the pickling time may have to be adjusted.
  • the pickling time is 15 s, but can be between 5 and 120 s. Under no circumstances should it be longer than 300 s in this pickling solution.
  • Time s Current density A / dm2 method Time s Current density A / dm2 Brightness L * grade ⁇ E 1 A 20th 100 D 15 40 65.5 7 0.4 2nd A 20th 100 D 20th 40 69.2 7 0.3 3rd C. 10th 40 B 15 40 71.4 10th 0.3 4th C. 10th 40 B 20th 40 80.0 10th 0.6 5 B 30th 60 D 10th 40 83.4 7 0.8 6 C.
  • Table 2 contains comparative examples of supports that were not made by the methods of the invention. Except for the pickling step after the two roughening steps, the carriers were produced under identical conditions as the carriers in Table 1. Instead of the pickling step after the two roughening steps, a pickling step was inserted between the two roughening steps.
  • This pickling step not listed in Table 2 is an alkaline pickling. In this case, an aqueous solution of 20 g / l NaOH and 2 g / l sodium carbonate (anhydrous) at room temperature from 20 to 24 ° C. was used as the pickling solution. The diving time was 30 s. The poorer quality of the carriers can be seen from Table 2 in comparison to Table 1.
  • the carriers are darker than those produced according to the invention, the brightness is more irregular.
  • Table 2 1st roughening step 2nd roughening step 1 2nd 3rd 4th 5 6 7 8th 9 10th No. method Time s Current density A / dm2 method Time s Current density A / dm2 Brightness L * grade ⁇ E V1 A 20th 100 D 15 40 59.5 6 3.4 V2 A 20th 100 D 20th 40 59.2 5 2.3 V3 C. 10th 40 B 15 40 59.4 4th 2.3 V4 C. 10th 40 B 20th 40 60.0 5 6.6 V5 B 30th 60 D 10th 40 59.9 6 3.1 V6 C.
  • Table 3 again contains comparative examples which were not produced by the process according to the invention. Here no pickling was carried out between the two roughening steps nor after the roughening steps. The supports are overall more uneven than the comparative examples in Table 2, the supports of which were pickled after the first roughening step.
  • Table 3 1st roughening step 2nd roughening step 1 2nd 3rd 4th 5 6 7 8th 9 10th No.
  • Procedure time Current density Procedure time Current density
  • Examples V51 to V54 in the table above are supports which have been subjected to roughening in only one stage.
  • Table 4 shows the results of supports which were roughened in the same way as the supports in Table 1. They differ from those described in Table 1 by the pickling.
  • the carriers are pickled in a third processing step after both roughening steps.
  • an aqueous solution of 100 g / l H2SO4 and 5 g / l aluminum sulfate (anhydrous) at 45 ° C is used as the pickling solution.
  • the acid concentration can range from 10g / l to 500g / l, and the aluminum concentration can also be changed. With low acid concentrations, it is advisable to increase the temperature.
  • the pickling time is 60 s, but can be between 10 and 300 s.
  • Table 4 1st roughening step 2nd roughening step 1 2nd 3rd 4th 5 6 7 8th 9 10th No. method Time s Current density A / dm2 method Time s Current density A / dm2 Brightness L * grade ⁇ E 26 A 20th 100 D 15 40 64.5 7 0.6 27th A 20th 100 D 20th 40 68.2 7 0.4 28 C. 10th 40 B 15 40 69.8 10th 0.8 29 C. 10th 40 B 20th 40 79.5 10th 0.9 30th B 30th 60 D 10th 40 83.0 7 0.7 31 C.
  • the coated supports are dried in the drying tunnel at temperatures up to 120 ° C.
  • the printing plates thus produced are exposed under a positive template and developed with a developer of the following composition: 5.3 pbw Sodium metasilicate ⁇ 9H2O 3.4 pbw Trisodium phosphate 0.3 pbw Sodium dihydrogen phosphate (anhydrous) 91.0 pbw Water.
  • Table 6 shows the results of some printing forms which were produced from supports not according to the invention and which do not match the printing forms in Table 5 either in the print run or in the water supply.
  • Table 6 carrier Edition Water supply V1 80,000 satisfying V5 60,000 bad V31 150,000 very bad V21 30,000 Good V33 90,000 bad V38 30,000 bad V48 145,000 bad V51 120,000 bad V52 140,000 very bad V53 80,000 satisfying V54 60,000 satisfying

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Rotary Presses (AREA)
EP92115022A 1991-09-09 1992-09-03 Procédé de grainage d'aluminium ou d'alliages d'aluminium pour supports plaques d'impression et une plaque d'impression Expired - Lifetime EP0536531B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4129909 1991-09-09
DE4129909A DE4129909A1 (de) 1991-09-09 1991-09-09 Verfahren zum aufrauhen von aluminium bzw. von aluminiumlegierungen als traegermaterial fuer druckplatten und eine druckplatte

Publications (3)

Publication Number Publication Date
EP0536531A2 true EP0536531A2 (fr) 1993-04-14
EP0536531A3 EP0536531A3 (en) 1993-04-28
EP0536531B1 EP0536531B1 (fr) 1997-03-05

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EP92115022A Expired - Lifetime EP0536531B1 (fr) 1991-09-09 1992-09-03 Procédé de grainage d'aluminium ou d'alliages d'aluminium pour supports plaques d'impression et une plaque d'impression

Country Status (6)

Country Link
US (1) US5304298A (fr)
EP (1) EP0536531B1 (fr)
JP (1) JPH05278361A (fr)
KR (1) KR930005783A (fr)
CA (1) CA2077306A1 (fr)
DE (2) DE4129909A1 (fr)

Families Citing this family (6)

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Publication number Priority date Publication date Assignee Title
US5795541A (en) * 1996-01-05 1998-08-18 Kabushiki Kaisha Kobe Seiko Sho Aluminum alloy sheet for lithographic printing plates and method for manufacturing the same
JP3567402B2 (ja) * 1996-06-12 2004-09-22 コニカミノルタホールディングス株式会社 平版印刷版用支持体の製造方法、その製造方法で得られる平版印刷版用支持体及びその支持体を用いた感光性平版印刷版
US6048657A (en) * 1999-01-28 2000-04-11 Xerox Corporation Surface treatment method without external power source
EP1157853A3 (fr) * 2000-05-24 2005-01-05 Hydro Aluminium Deutschland GmbH Procédé de grainage d'un support pour plaques d'impréssion
KR101835178B1 (ko) 2015-01-05 2018-03-06 씨제이제일제당 (주) 즉석 조리용 생당면의 제조방법 및 이로부터 제조된 생당면
CN116065153A (zh) * 2022-11-17 2023-05-05 陕西华燕航空仪表有限公司 一种提升软磁合金片粘接强度的方法

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Also Published As

Publication number Publication date
DE4129909A1 (de) 1993-03-11
JPH05278361A (ja) 1993-10-26
EP0536531B1 (fr) 1997-03-05
US5304298A (en) 1994-04-19
EP0536531A3 (en) 1993-04-28
CA2077306A1 (fr) 1993-03-10
DE59208104D1 (de) 1997-04-10
KR930005783A (ko) 1993-04-20

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