EP0082454B1 - Procédé de traitement anodique de l'aluminium et son application comme support pour plaques d'impression - Google Patents

Procédé de traitement anodique de l'aluminium et son application comme support pour plaques d'impression Download PDF

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Publication number
EP0082454B1
EP0082454B1 EP82111545A EP82111545A EP0082454B1 EP 0082454 B1 EP0082454 B1 EP 0082454B1 EP 82111545 A EP82111545 A EP 82111545A EP 82111545 A EP82111545 A EP 82111545A EP 0082454 B1 EP0082454 B1 EP 0082454B1
Authority
EP
European Patent Office
Prior art keywords
acid
polybasic
monomeric
organic
electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82111545A
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German (de)
English (en)
Other versions
EP0082454A1 (fr
Inventor
Thomas Nicolas Gillich
John E. Walls
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.)
CNA Holdings LLC
Original Assignee
Hoechst Celanese Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst Celanese Corp filed Critical Hoechst Celanese Corp
Publication of EP0082454A1 publication Critical patent/EP0082454A1/fr
Application granted granted Critical
Publication of EP0082454B1 publication Critical patent/EP0082454B1/fr
Expired legal-status Critical Current

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Classifications

    • 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
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials

Definitions

  • the present invention relates to a process for the anodic treatment of aluminum in an electrolyte containing an organic phosphonic, sulfonic or carboxylic acid and the use of the process product as a printing plate support material.
  • Surfaces created in such a method are also suitable for capacitors, dielectric purposes, and other applications where a barrier layer is useful.
  • Anodized layers produced with phosphoric acid have many good properties that make them suitable for use in offset printing.
  • the film produced by anodic oxidation is rather «soft and has a relatively low abrasion resistance; this is a disadvantage when long print runs are required.
  • Anodized layers produced with sulfuric acid are much harder, have a relatively higher abrasion resistance and therefore result in mechanically more resistant offset printing plates, with which long print runs can be achieved. Both methods have found their way into practice, the respective plates are commercially successful in different sub-areas.
  • the sulfuric acid process is also easier to use for the production of thicker anodized layers than the phosphoric acid process, which shows a tendency towards self-limitation due to the greater solubility of the film produced by anodic oxidation in the electrolyte.
  • the sulfuric acid process also has certain disadvantages, so there are layers which are not always entirely satisfactory for offset printing substrates, since they tend to not delineate oleophilic and hydrophilic areas sharply enough, so that often with these layers, except for the thinnest, processes must be applied by the z. B. the color acceptance in the non-image areas is prevented.
  • This necessary treatment of the anodically produced layer can occasionally be problematic when, for example, it is necessary to produce presensitized offset printing plates in which the adhesion of the radiation-sensitive coating to the support is of primary importance during and after the development of the exposed layer. If such treatments which modify the surface of the carrier material are carried out on the layer produced by anodic oxidation, it is important to find a compromise between achieving sufficient hydrophilicity in the non-image areas and at the same time satisfactory behavior of the image areas. These treatments can thus give results which are desirable for offset printing, and they are known for both the planographic printing plates anodized with phosphoric acid and for the anodized with sulfuric acid and are customary in practice.
  • the older, non-prepublished EP-A 0 048 909 and 0 050 216 describe processes for the anodic oxidation of plate, sheet or strip material made of aluminum or its alloys, which are carried out in an aqueous electrolyte containing at least one polybasic organic acid be performed. If necessary, mechanical, chemical and / or electrochemical roughening can take place before the oxidation.
  • the polybasic organic acids include monomeric or polymeric phosphonic, sulfonic or organic carboxylic acids such as phytic acid, tridecylbenzenesulfonic acid, nitrilotriacetic acid, polyvinylphosphonic acid, polybenzenesulfonic acid or polyacrylic acid.
  • the electrolyte can also contain an inorganic acid such as phosphoric acid.
  • the process products are preferably used as a carrier material in the production of printing plates bearing a radiation-sensitive layer.
  • the invention is based on the process for the anodic treatment of plate, sheet or strip material made of aluminum or its alloys in an electrolyte containing at least one monomeric polybasic organic phosphonic, sulfonic or carboxylic acid, optionally after preceding mechanical, chemical and / or electrochemical roughening.
  • the nitrate contains free, non-aqueous electrolyte as solvent at least one organic solvent with a dipole moment of at least 1.5.
  • Organic acids from the group given above are also to be understood as meaning compounds in which, for example, one or more of the acid functions are esterified, as in the case of phosphoric acid monoesters, ie. H. polybasic then means that the relevant molecule still has at least two free acid functions.
  • Monomer then means that a basic molecular unit occurs only once and can no longer be broken down structurally into further, smaller, constant units.
  • the method thus relates to the electrolytic deposition of a layer on aluminum, the aluminum to be treated being switched as the anode and any inert metal (such as lead or steel) or graphite as the cathode.
  • a possibly pulsating direct voltage is then applied to the previously degreased and optionally roughened carrier through a non-aqueous electrolyte.
  • the electrolyte contains at least one of the acids, which is dissolved in the organic solvent or the solvent mixture, which allows a current to flow due to its dipole moment, but which does not undergo any electrochemical reactions at the anode or at the cathode.
  • non-aqueous electrolyte precludes the formation of oxides of aluminum and only allows the formation of a non-oxide layer in the manner of an "organometallic" complex.
  • a layer produced in this way is highly non-porous and very thin. This results in a very good surface on the aluminum base material, through which better adhesion of coatings to the aluminum support material is achieved than with conventionally anodized surfaces.
  • the plates usable in the practice of this invention can be made of aluminum or aluminum alloys such as those with more than 98.5% Al and components such as Mn, Fe, Si, Cu, Zn and / or Ti.
  • the aluminum strip or the aluminum plate or foil is first freed of its rolling fat, for which purpose it is treated with a suitable degreasing agent, e.g. B. by immersing it in a warm immersion bath with 1,1,1-trichloroethane, trichloroethene, methylene chloride or perchlorethylene or in an aqueous alkaline solution. Then, if necessary, chemical, electrochemical and / or mechanical roughening, for. B.
  • the surface is then rinsed with water and rinsed with the organic solvent to be used in the electrolysis bath. This is to prevent water from entering the electrolysis bath.
  • the carrier material is then treated electrolytically according to the invention.
  • Monomeric polybasic acids suitable for the process according to the invention are, for example: nitrilotriacetic acid, 1,2,4,5-benzene-tetracarboxylic acid, phytic acid, phosphoric acid mono (dodecyloxy polyoxyethylene) ester, dinonylnaphthalene disulfonic acid, 2,2'-dinitro-4, 4'-stilbene disulfonic acid, 2-ethylhexane phosphonic acid, dodecyl naphthalene disulfonic acid, di-n-butyl naphthalene disulfonic acid, diethylenetriaminepentaacetic acid, ethylenediamine-tetraacetic acid, hydroxyethylethylenediamine-triacetic acid and mixtures of the acids mentioned.
  • the most preferred acids are phytic acid and phosphoric acid mono (dodecyloxy polyoxyethylene) esters, i.e. H. in both cases, monoesters of phosphoric
  • Such organic solvents are suitable for the invention which have a dipole moment of at least 1.5, preferably of at least 1.7, including (dipole moment in brackets): formamide (3.22), dimethyl sulfoxide (3.96), aniline (1.53) dimethylformamide (3.82), mono- (2.27), di- (2.81 triethanolamine (3.57) and tetrahydrofuran (1.70).
  • Values for DMSO and DMF were obtained from CRC Handbook of Chemistry and Physics, CRC Press - Boca Raton (USA), 62nd edition 1981/82, pp. E-60 to E-62, and the other values from Physikalisch-Chemische Taschenbuch, Akademische Verlagsweger & Erler - Leipzig, 1945 , Volume I, p. 519 ff.
  • the acid can in principle be present in the non-aqueous solution in an amount of 0.01% to the saturation point, preferably in an amount of 0.8 to 5%.
  • the electrolysis temperature is generally kept at -5 to 60 ° C, in particular at 10 to 40 ° C and preferably at 20 to 30 ° C.
  • the voltage is expediently between 5 and 120 V, preferably between 10 and 60 V and in particular between 20 and 40 V.
  • the electrolysis time should be sufficient to give the carrier a charge of 1 to 150 C / dm 2 , preferably 30 to 90 C / dm 2 and in particular from 40 to 70 C / dm 2 supply.
  • the distance between the cathode and anode is generally 1 to 25 cm, preferably between 3 and 15 cm and in particular between about 4 and 10 cm.
  • the aluminum surface created according to the invention When the aluminum surface created according to the invention is examined under a scanning electron microscope at a magnification of 30,000 times, an essentially non-porous surface can be seen.
  • the surface is fundamentally free from oxide formation and shows excellent adhesion to later applied coatings suitable for offset printing.
  • anodically treated material is particularly suitable for use as a carrier material in the production of printing plates bearing a radiation-sensitive layer.
  • the carrier is coated by the consumer with one of the known radiation-sensitive compositions.
  • An aluminum plate in bright rolled condition is treated for 30 seconds at room temperature in an aqueous NaOH solution.
  • the plate cleaned and chemically roughened in this way, is rinsed well with water and, without drying, is then immediately rinsed with dimethyl sulfoxide (DMSO).
  • DMSO dimethyl sulfoxide
  • the plate is immersed in a solution containing DMSO and 20 g / l of 2-ethylhexanephosphonic acid.
  • DMSO dimethyl sulfoxide
  • the plate Compared to a comparison plate in which the aluminum is hydrophilized by thermal treatment, the plate likewise being roughened alkaline and then treated non-anodically with a 0.5% strength solution of a methyl vinyl ether / maleic anhydride copolymer in dimethyl sulfoxide at about 70 ° C. for 60 seconds the anodized plate achieves a 25% higher print run.
  • An aluminum plate is mechanically wet-roughened using a known method using abrasives / nylon brushes and then treated in an aqueous NaOH solution for 30 seconds.
  • the roughened plate is rinsed well with water and immediately rinsed thoroughly with formamide.
  • the plate coated with the organic solvent is immersed in a solution containing formamide and 25 g / l of 2,2'-dinitro-4,4'-stilbene disulfonic acid.
  • a lead electrode which acts as a cathode at a distance of about 5 cm from the aluminum plate.
  • the aluminum serves as an anode, to which a voltage of 20 V from rectified alternating current is applied for a period of 60 seconds at room temperature.
  • the anodized plate is rinsed well and patted dry.
  • the anodically produced layer When the anodically produced layer is removed, its layer weight is determined to be 109 mg / m 2 .
  • a plate produced in the same way shows a very hydrophilic surface both in the wet and in the dry coloring test.
  • the reaction time in the SnCig test is 93 sec
  • the reaction time in the zincate test is 137 sec.
  • An aluminum plate is roughened as indicated in Example 2. The rinsing is done with formamide. The plate covered with the solvent is immersed in a solution containing formamide and 15 g / l 1,2,4,5-benzene-tetracarboxylic acid. Located in the bathroom a lead electrode serving as a cathode is located at a distance of approximately 5 cm from the aluminum plate. The aluminum acts as an anode, to which a voltage of 20 V from rectified alternating current is applied for a period of 60 seconds at room temperature. The treated plate is rinsed well and patted dry. The layer weight is 89 mg / m 2 . A plate produced in the same way shows a very hydrophilic surface both in the wet and in the dry coloring test.
  • the reaction time in the SnCl 2 test is 81 seconds, the reaction time in the zincate test is 133 seconds.
  • the light-sensitive coating with the layer specified in Example 1 compared to a thermally treated comparison plate, in which the processing parameters specified in Example 1 are carried out on a mechanically roughened plate can also be used, with the anodized plate a 32% higher print run.
  • a wet and dry coloring test reveals a hydrophilic surface. The layer weight is measured at 87 mg / m 2 .
  • the reaction time for the SnC1 2 7 test is 104 sec, for the zincate test 157 sec.
  • the coated plate has good adhesion for the light-sensitive layer and provides an improvement of 20% in the print run compared to the corresponding comparison plate.

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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)
  • Printing Plates And Materials Therefor (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)

Claims (9)

1. Procédé pour le traitement anodique de matériau en forme de plaques, feuilles ou bandes, en aluminium ou en un de ses alliages, dans un électrolyte contenant au moins un polyacide phosphonique, sulfonique ou carboxylique organique monomère, éventuellement après grainage mécanique, chimique et/ou électrochimique préliminaire, l'électrolyte non aqueux, exempt de nitrates, contenant en tant que solvant au moins un solvant organique ayant un moment dipolaire d'au moins 1,5.
2. Procédé selon la revendication 1, caractérisé en ce que le solvant organique présente un moment dipolaire d'au moins 1,7.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'électrolyte contient le polyacide organique monomère en une concentration allant de 0,01 % en poids à la saturation.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que l'électrolyte contient le polyacide organique monomère en une concentration de 0,8 à 5 % en poids.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que l'électrolyte contient, en tant que solvant, du formamide, du diméthylsul- foxyde, de l'aniline, du diméthylformamide, de la mono-, di- ou triéthanolamine et/ou du tétrahydro- furanne.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'électrolyte contient, en tant que polyacide phosphonique monomère, de l'acide phytinique, du mono(dodécyloxy- polyoxyéthylène)ester de l'acide phosphorique ou de l'acide 2-éthylhexanephosphonique.
7. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'électrolyte contient, en tant que polyacide sulfonique monomère, de l'acide dinonyl-naphtalène-disulfonique, de l'acide 2,2'-dinitro-4,4'-stilbène-disulfonique, de l'acide dodécyl-naphtalène-disulfonique ou de l'acide di-n-butyl-naphtalène-disulfonique.
8. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'électrolyte contient, en tant qu'acide polycarboxylique organique monomère, de l'acide 1,2,4,5-benzène-tétracarboxyli- que, de l'acide diéthylène-triamine-pentaacéti- que, de l'acide nitrilotriacétique, de l'acide éthylène-diamine-tétraacétique ou de l'acide hydroxyé- thyl-éthylènediamine-triacétique.
9. Utilisation du procédé selon l'une des revendications 1 à 8, pour la préparation d'un matériau traité par anodisation, en tant que matériau de support dans la fabrication de plaques d'impression portant une couche sensible aux radiations.
EP82111545A 1981-12-23 1982-12-13 Procédé de traitement anodique de l'aluminium et son application comme support pour plaques d'impression Expired EP0082454B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US333586 1981-12-23
US06/333,586 US4388156A (en) 1981-12-23 1981-12-23 Aluminum electrolysis in non-aqueous monomeric organic acid

Publications (2)

Publication Number Publication Date
EP0082454A1 EP0082454A1 (fr) 1983-06-29
EP0082454B1 true EP0082454B1 (fr) 1988-05-04

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EP82111545A Expired EP0082454B1 (fr) 1981-12-23 1982-12-13 Procédé de traitement anodique de l'aluminium et son application comme support pour plaques d'impression

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US (1) US4388156A (fr)
EP (1) EP0082454B1 (fr)
JP (1) JPS58110692A (fr)
DE (1) DE3278428D1 (fr)

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US4439282A (en) * 1982-06-01 1984-03-27 Mcdonnell Douglas Corporation Treatment of metals to enhance adhesive bonding
US4467028A (en) * 1982-07-12 1984-08-21 Polychrome Corporation Acid interlayered planographic printing plate
US5124022A (en) * 1989-08-23 1992-06-23 Aluminum Company Of America Electrolytic capacitor and method of making same
US5032237A (en) * 1989-08-23 1991-07-16 Aluminum Company Of America Anodic phosphonic/phosphinic acid duplex coating on valve metal surface
US5126210A (en) * 1989-08-23 1992-06-30 Aluminum Company Of America Anodic phosphonic/phosphinic acid duplex coating on valve metal surface
US5059258A (en) * 1989-08-23 1991-10-22 Aluminum Company Of America Phosphonic/phosphinic acid bonded to aluminum hydroxide layer
US5102507A (en) * 1989-10-16 1992-04-07 Aluminum Company Of America Method of making an anodic phosphate ester duplex coating on a valve metal surface
US5103550A (en) * 1989-12-26 1992-04-14 Aluminum Company Of America Method of making a food or beverage container
US5837121A (en) * 1997-10-10 1998-11-17 Kemet Electronics Corporation Method for anodizing valve metals
US6149793A (en) * 1998-06-04 2000-11-21 Kemet Electronics Corporation Method and electrolyte for anodizing valve metals
GB2359823A (en) * 1998-08-28 2001-09-05 Kemet Electronics Corp Phosphate anodizing electrolyte and its use to prepare capacitors valve metal anodes produced from very fine metal powders
US6183618B1 (en) 1999-02-02 2001-02-06 Kemet Electronics Corporation Process for treating impregnated electrolytic capacitor anodes
US6235181B1 (en) 1999-03-10 2001-05-22 Kemet Electronics Corporation Method of operating process for anodizing valve metals
US6558873B1 (en) * 1999-10-05 2003-05-06 Fuji Photo Film Co., Ltd. Lithographic printing plate precursor
US6436268B1 (en) * 2000-08-02 2002-08-20 Kemet Electronics Corporation Non-aqueous electrolytes for anodizing
US6267861B1 (en) 2000-10-02 2001-07-31 Kemet Electronics Corporation Method of anodizing valve metals

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EP0050216B1 (fr) * 1980-09-26 1985-01-09 American Hoechst Corporation Procédé pour l'oxydation anodique d'aluminium et son utilisation comme support pour planches d'imprimerie

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Also Published As

Publication number Publication date
EP0082454A1 (fr) 1983-06-29
US4388156A (en) 1983-06-14
JPS58110692A (ja) 1983-07-01
DE3278428D1 (en) 1988-06-09

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