EP0318820B1 - Verfahren zur anodischen Oxidation der Oberfläche von Aluminium oder Aluminiumlegierungen - Google Patents

Verfahren zur anodischen Oxidation der Oberfläche von Aluminium oder Aluminiumlegierungen Download PDF

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Publication number
EP0318820B1
EP0318820B1 EP88119523A EP88119523A EP0318820B1 EP 0318820 B1 EP0318820 B1 EP 0318820B1 EP 88119523 A EP88119523 A EP 88119523A EP 88119523 A EP88119523 A EP 88119523A EP 0318820 B1 EP0318820 B1 EP 0318820B1
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EP
European Patent Office
Prior art keywords
recording layer
aluminum
plates
silanes
anodic oxidation
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EP88119523A
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German (de)
English (en)
French (fr)
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EP0318820A2 (de
EP0318820A3 (en
Inventor
Harald Dr. Lauke
Bernhard Dr. Nick
Reinhold J. Dr. Leyrer
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BASF SE
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BASF SE
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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
    • 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

Definitions

  • the invention relates to a new process for the anodic oxidation of the surface of plates, foils or strips made of aluminum or aluminum alloys in an aqueous electrolyte containing one or more acids and one or more additives.
  • the invention also relates to the use of the process products obtained with the aid of the new process for the production of photosensitive lithographic printing plates or offset printing plates.
  • Parts made of aluminum or aluminum alloys are used in various forms in a wide variety of technical fields due to their advantageous property profile.
  • they are used for architectural purposes, are used for the construction of light engines or serve in the form of plates, foils or tapes as supports for printing plates, in particular lithographic printing plates, which are also generally referred to as offset printing plates.
  • This surface layer mainly defines the application properties and thus the usability of the molded parts made of aluminum or aluminum alloys.
  • the most important properties that this surface layer must have include, for example, high corrosion resistance, good appearance, precisely adjustable density, high hardness, good wear resistance, high absorption capacity and adhesion for paints, synthetic resins and light-sensitive mixtures, good colorability , high gloss or good hydrophilicity.
  • these surface layers essentially composed of aluminum oxides are produced by the anodic oxidation of molded parts made of aluminum or aluminum alloys in an aqueous electrolyte containing sulfuric acid or phosphoric acid.
  • the quality of the surface layers produced in this way depends above all on the preselection of the process parameters such as the duration of the electrolysis, electrolysis voltage, current density, electrolyte temperature and acid concentration. With a skilful choice of parameters, usable surface layers can be produced. However, these do not fully meet the high demands that are placed in practice on the surface layers of the plates, foils or tapes used for printing purposes.
  • lithographic printing plates or offset printing plates produced from these photosensitive lithographic printing plates or offset printing plates, imagewise exposed to actinic light and washed out with developer solvents also offer certain advantages with regard to the hydrophilicity of their carrier surface and with regard to the high number of good printed products.
  • the known method still has disadvantages.
  • the polyvinylphosphonic acid which is particularly preferably used in the context of this process frequently leads to the deposition of poorly soluble polyvinylphosphonic acid-aluminum complexes on the surfaces to be anodized in the course of the electrolysis, which leads to disturbances in the layer structure.
  • this results in sensitive wetting disturbances in the lithographic printing plates or offset printing plates, which are imagewise exposed to actinic light and washed out with developer solvents, which leads to poor color guidance or even breakouts in the printing areas of the printing plates during printing, as a result of which both the quality of the printed products and whose circulation will be reduced.
  • the object of the present invention is to propose a new process for the anodic oxidation of plates, foils or strips made of aluminum or aluminum alloys, which no longer has the disadvantages of the prior art both with regard to its implementation and with regard to its process products and their secondary products.
  • radicals R 1 and R 2 in the silanes I to be used according to the invention are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, Heptyl, octyl, iso-octyl, nonyl, phenyl, benzyl, o-, m- and p-tolyl, 2,4-dimethylphen-1-yl, 3,5-dimethylphen-1-yl, naphth-1-yl and Naphth-2-yl.
  • the radicals R1 and R2 in the silanes I used in each case are the same or different from one another.
  • Suitable radicals X in the silanes I to be used according to the invention are the radicals X 1 to X 11.
  • radicals X 1 are those in which Z represents a hydrogen atom or a lithium, sodium or potassium cation and R 3 is one of the alkyl radicals R 1 mentioned above, a carboxyl group, a methane carboxylic acid, ethan-1-yl-2-carboxylic acid, Propan-1-yl-3-carboxylic acid, n-butan-1-yl-2-, -3- or -4-carboxylic acid, n-pentan-1-yl-2-, -3-, -4- or - 5-carboxylic acid, n-hexan-1-yl-6-carboxylic acid, n-heptan-1-yl-7-carboxylic acid, n-octan-1-yl-8-carboxylic acid or an n-nonan-1 -yl-9-carboxylic acid residue or a carboxylic acid anhydride ring, which consists of one of the abovementioned alkane carboxylic acid
  • Suitable radicals X2 are those in which R4 represents one of the radicals R1 mentioned above.
  • Suitable radicals X3 are those in which Z has the meaning given above and R5 represents one of the radicals R1 mentioned above.
  • Another suitable radical X is the maleic anhydride radical X5.
  • radicals X6 are those in which R6 represents a hydrogen atom or one of the radicals R1 mentioned above.
  • the suitable radicals X7 are the dichloro, dibromo and chlorobromophosphonyl groups.
  • the suitable radicals X8 are the sulfonic acid group and the lithium, sodium and potassium sulfonate groups.
  • the suitable radicals X9 are the sulfochloride and sulfobromide groups.
  • radicals X10 are phen-1-yl-2-, -3- and -4-sulfonic acid, 2-methyl-phen-1-yl-3-, -4-, -5- and -6-sulfonic acid, 4 -Methyl-phen-1-yl-2-and -3-sulfonic acid, benzyl-2-, -3- and -4-sulfonic acid, naphth-1-yl-2-, -3-, -4-, -5 -, -6-, -7- and -8-sulfonic acid, naphth-2-yl-1-, -3-, -4-, -5-, -6-, -7- and -8-sulfonic acid and the Lithium, sodium and potassium salts of these sulfonic acids.
  • radicals X11 are the chlorides and bromides of the aforementioned sulfonic acids X10.
  • y stands for an integer from 1 to 4, and n stands independently of y for 0, 1 or 2.
  • silanes I which are used with particular advantage in the process according to the invention are (2-tripropoxisilylethyl) carboxylic acid, (3-trimethoxisilylpropyl) carboxylic acid and (4-trimethoxisilylbutyl) carboxylic acid as well as their methyl, ethyl, propyl and butyl esters, (3-triethoxisilylpropyl) succinic anhydride, (3-triethoxisilylpropyl) maleic anhydride, (2-trimethoxisilylethyl) phosphonic acid, (2-trimethoxisilylethyl) phosphonic acid dimethylesteryl ethylsilyl-3-ethylpropylate , (2-Trimethoxisilylmethyl) phosphonic acid dichloride, (3-Trimethoxisilylpropyl) phosphonic acid dichloride, (3-Trimethoxisilylpropyl) phosphonic acid, 2- (4-chlor
  • the silanes I are well-known compounds which are synthesized in a simple manner from commercially available compounds using the customary and known methods of silicon chemistry.
  • silicon halides and the corresponding organic compounds are used, for example, which contain the desired radicals - (CH2) y -X, R1 and R2 of the silanes I or the precursors of these radicals.
  • the hydrolysis of the silanes I takes place when the silanes I are dissolved in the aqueous electrolyte. As is known, this sets in motion the condensation of the silanes I, which takes place with the elimination of alcohol. Depending on the silane I used, the condensation reaction proceeds more or less completely and therefore leads to mixtures of hydrolyzed, condensed silanes I of different molecular weights, i.e. different degrees of condensation. In the hydrolysis of silanes I, the corresponding free acid groups are of course formed from the ester, anhydride or acid halide groups. The degree of reaction, i.e. the degree of hydrolysis, depending on the particular silane I used.
  • the degree of hydrolysis can be low, but the degree of condensation can be high.
  • the reverse can also occur, i.e. the degree of hydrolysis is high, whereas the degree of condensation is low.
  • both reactions, both hydrolysis and condensation are to a high degree, i.e. almost complete or almost complete, expired.
  • the hydrolysis and condensation of the silanes I takes place by dissolving the silanes I in water or aqueous alcoholic solutions before adding these solutions to the electrolyte.
  • the advantages of the process according to the invention are always reliable. If the silanes I are hydrolyzed and / or condensed separately before addition to the aqueous electrolyte, of course only so much solvent is used for this that the desired silane I concentration is established after the addition of the silane I solution to the aqueous electrolyte.
  • the silanes I to be used according to the invention fulfill the function of additives in the aqueous electrolyte, which additives are added to the aqueous electrolyte in addition to one or more acids.
  • the silanes I are also used together with other additives which generally serve to modify or color the surface layer which is formed, which is mainly composed of aluminum oxides, during the anodic oxidation, or to coat another layer on this surface layer to deposit from, for example, organic material.
  • the silanes I have acid groups or form acid groups during their hydrolysis and condensation, they simultaneously fulfill the function of the single acid or the function of one of several acids in the aqueous electrolyte.
  • the acids in the aqueous electrolyte serve to increase its conductivity, and they are known to have a considerable influence on the physico-chemical and application properties of the surface layers, which are mainly composed of aluminum oxides and which form during the anodic oxidation.
  • the effect of the silanes I should rather be regarded as additives or as acids cannot be determined precisely because the silanes I perform both functions in an advantageous manner in the process according to the invention, i.e. the silanes I have an application-related property profile, which otherwise can only be achieved at best by combining several different substances at best.
  • the aqueous electrolyte advantageously contains the silanes I in an amount of 0.001 to 50% by weight, based on the electrolyte. If the aqueous electrolyte contains less than 0.001% by weight of the silanes I, their advantageous technical effect cannot be reliably reproduced in all cases. On the other hand, it is not necessary because of the advantageous technical effect of the silanes I to increase their content in the aqueous electrolyte to over 50% by weight, because the additional advantages which can still be achieved thereby do not increase the higher consumption of silanes I. absolutely justify.
  • the content of 0.001 to 50% by weight of silanes I in the aqueous electrolyte is an optimal range, both from an application point of view and for economic reasons, within which the silane I concentration varies widely and both the technical problems to be solved and the apparatus conditions is adapted in a simple and advantageous manner.
  • silane I content 0.05 to 30, preferably 0.1 to 25 and in particular 1 to 10% by weight, based on the electrolyte, proves to be special advantageous.
  • silanes I are used together with an acid or with several acids in the aqueous electrolyte, a silane I content of 0.005 to 25, preferably 0.05 to 20 and in particular 0.08 to 10% by weight, based on the electrolyte, is of particular advantage. It is of additional advantage here if the content of the aqueous electrolyte in the acid (s) used is 0.5 to 50, preferably 1 to 35 and in particular 3 to 30% by weight.
  • the acids used are selected from the group of inorganic mineral acids, low molecular weight, mono- and polyfunctional organic carboxylic, sulfonic and phosphonic acids as well as oligomeric and high molecular weight, polyfunctional carbon, sulfonic and phosphonic acids. Suitable acids are known from EP-A-0 048 909 and EP-A-0 050 216 as well as from the prior art dealt with extensively in these patents.
  • customary and known additives are added to the aqueous electrolyte in a molecularly dispersed or colloidal solution, their amount depends primarily on their solubility in the aqueous electrolyte and on the extent to which they influence the solubility of the silanes I. Accordingly, the customary and known additives can be added in the amounts which are necessary for achieving the respective technical effect usually caused by them, as long as they do not cause the aqueous electrolyte to be de-homogenized, for example by forming separate liquid phases or insoluble precipitates.
  • the usual and known additives are generally selected from the group of inorganic and organic salts and of low molecular weight, oligomeric and high molecular weight non-acidic organic compounds. Examples of suitable additives are also known from EP-A-0 048 909 and EP-A-0 050 216 as well as from the prior art dealt with extensively therein.
  • an aqueous electrolyte in the process according to the invention which, in addition to the silanes I, contains sulfuric acid and / or phosphoric acid.
  • the process according to the invention is carried out in apparatus or plants as are customary and known for the anodic oxidation of aluminum.
  • the method according to the invention therefore does not require any new investments in equipment and systems to be specially developed for this purpose, on the contrary, it does not even require major modifications to existing equipment and systems.
  • the apparatuses and plants in which the process according to the invention is carried out essentially comprise electrolysis troughs, controllable current and voltage sources, heat exchanges for the plates, foils or tapes and the customary and known regulating and measuring devices.
  • the electrolysis troughs can contain agitators, cooling devices and devices for supplying and removing the aqueous electrolyte and for cleaning it.
  • the brackets are of course connected to the respective current and voltage sources.
  • the process according to the invention is carried out discontinuously, some or all of its process parameters change from a preselected initial state to a desired final state during its course.
  • the temperature of the aqueous electrolyte, the voltage, the current density and / or the acid and additive concentration are changed in a predetermined manner during the anodic oxidation in order to achieve a very particularly advantageous technical effect.
  • the process according to the invention is also carried out continuously, the process parameters in the desired range being forced, as corresponds to the nature of a continuous process is kept constant and the plates, foils or strips of aluminum or aluminum alloys are continuously passed through the aqueous electrolyte.
  • the temperature of the electrolyte to be used according to the invention is in the range from -2 to + 60.degree.
  • the method according to the invention uses direct voltage, alternating voltage or direct voltage superimposed by alternating voltage of 1 to 75 V in both continuous and discontinuous operation.
  • amounts of electricity in the range from 2 to 100 kC / m2 have proven to be advantageous.
  • Particularly advantageous process results are obtained when the anodic oxidation lasts from 4 seconds to 5 minutes.
  • process parameters of the process according to the invention are selected from the ranges specified above. It is particularly advantageous to select all process parameters from these areas. After the selection and setting of the process parameters, the majority of the process parameters in the process according to the invention are kept constant over the entire course of the anodic oxidation in the range specified above. Or these process parameters are selected and set, after which some or all of the process parameters change in the course of the anodic oxidation, starting from the initial state, until the desired final state is reached. This change is carried out according to a specific program or results automatically from the interaction of the changing process parameters with one another and with the changing nature of the surface to be oxidized. It is particularly advantageous if the process parameters are within the ranges specified above when the desired final state is reached.
  • the process according to the invention in which the anodic oxidation is carried out at temperatures from -2 to + 60 ° C. with a direct voltage of 1 to 75 V and a current of 2 to 100 kC / m 2 within a period of 4 seconds to 5, delivers particularly excellent process results Minutes using an aqueous electrolyte which, based on its total amount, contains 0.05 to 50% by weight of the silanes I.
  • the process according to the invention can be preceded by a cleaning of the surface of the plates, foils or strips made of aluminum or aluminum alloys which is customary and known in this technical field.
  • Suitable cleaning methods are rinsing with water, aqueous alkaline solutions, acids and organic solvents.
  • the known cleaning methods can also be combined with one another in a suitable manner. For this purpose, reference is made, for example, to DE-B-29 12 060.
  • the method according to the invention can also be preceded by a mechanical, chemical and / or electrochemical roughening of the surface of the plates, foils or strips made of aluminum or aluminum alloys which is customary and known in this technical field.
  • This roughening usually follows the cleaning and is usually followed by a further cleaning step. Examples of suitable roughening methods are known from DE-A-25 57 222, DE-A-26 50 762 or DE-B-29 12 060.
  • the process according to the invention can be followed by customary and known aftertreatment processes for the surface layer essentially composed of aluminum oxides.
  • suitable post-treatment methods are sealing, hardening and hydrophilizing the surface layer.
  • treatment with hot steam is used for sealing, and chemical and electrochemical aftertreatment with halides and acids is known to be considered for hardening and / or hydrophilizing.
  • This aftertreatment can also be followed by a drying step.
  • silanes I can be applied to the surface layer then present, which is essentially composed of aluminum oxides, in order to further improve its already excellent profile of properties.
  • the process according to the invention has numerous special advantages which were not to be expected in this abundance.
  • the process according to the invention can be carried out in apparatuses and plants as are customary and known for anodic oxidation.
  • the method according to the invention reliably delivers method products with excellent application properties in a simple manner.
  • the method according to the invention therefore does not require any new investments in equipment and systems to be specially developed for this.
  • the surface layers on the molded parts made of aluminum or aluminum alloys which are essentially made of aluminum oxides and which are produced with the aid of the method according to the invention, have a good appearance, particularly high corrosion resistance, excellent hardness, very good wear resistance and very good dyeability, so that the relevant ones Molded parts also for architectural purposes, e.g. can be used with advantage as window frames, door panels or cover plates or for light machine construction. It proves to be a further very special advantage of the method according to the invention that the density and the structure of the surface layers concerned vary in a simple manner on the one hand broadly and on the other hand very precisely in a thickness range of 0.1 to 150 g / m2, which is approximately Corresponds to 0.1 to 200 ⁇ m, can be set.
  • the method according to the invention is used with particular preference for the production of light-sensitive lithographic printing plates or offset printing plates, because its numerous advantages come to light in a particularly high degree.
  • the surface layers of the anodized plates, foils or strips made of aluminum or aluminum alloys which are essentially made of aluminum oxides and are produced by the process according to the invention, have, in addition to the advantages listed above, a particularly high absorption capacity and adhesion for paints, synthetic resins and light-sensitive mixtures of the most varied compositions .
  • the surface layers are hard, wear and abrasion-resistant and also very tough and unbreakable.
  • they are very hydrophilic and have a high chemical and physical stability during storage and excellent color guide properties during printing.
  • the density, thickness and structure of the surface layers can be varied widely and can be adapted to the light-sensitive mixtures to be applied and the printing requirements.
  • the 0.05 to 1.5 mm thick anodized plates, foils or strips made of aluminum and aluminum alloys which are produced with the aid of the method according to the invention, which are referred to below as "supports", with light-sensitive mixtures of various compositions in a thickness of 0.1 to 20 microns, in particular 0.5 to 5 microns can be covered and in this way provide photosensitive lithographic printing plates or offset printing plates, which both the rapid image-wise exposure with computer-controlled lasers, ie coherent actinic light, as well as conventional imagewise exposure with incoherent actinic light through a negative original are accessible.
  • the light-sensitive recording layers (a1) to (a8) of light-sensitive lithographic printing plates or offset printing plates are insoluble in the imagewise exposure to incoherent actinic light through a negative original or with laser light in their exposed areas and take therein the typical for offset printing Oil-in-water inks, whereas their unexposed areas can be washed out with developer fluids.
  • the hydrophilic and ink-repellent surface of the support of the lithographic printing plates or offset printing plates anodically oxidized by the method according to the invention is exposed, whereby the surface of the printing plates is differentiated into color-guiding image areas and color-repelling non-image areas.
  • the photosensitive recording layers (b1) to (b3) of the photosensitive lithographic printing plates or offset printing plates become soluble in the exposed areas during imagewise exposure to incoherent actinic light or with laser light in their exposed areas, after which these can be washed out with developer liquids.
  • the hydrophilic and therefore ink-repellent surface of the support of the lithographic printing plates or offset printing plates anodized by the process according to the invention is exposed.
  • the unexposed areas on the other hand, remain insoluble and take on the "oil-in-water” printing inks typical of offset printing, as a result of which here, too, the differentiation of the printing plate surfaces into color-guiding image areas and ink-repellent non-image areas is ultimately achieved.
  • Typical examples of photosensitive recording layers of photosensitive lithographic printing plates of the type mentioned under point (c) are generally referred to as electrophotographic recording layers and essentially consist of at least one readily dispersible binder which is soluble in developer liquids, at least one photoconductor and at least one sensitizer.
  • These electrophotographic recording layers are loaded by means of a high-voltage corona with a surface potential of several hundred volts and then exposed imagewise with incoherent actinic light through a negative original or with laser light, as a result of which they become electrically conductive in their exposed areas, so that the surface potential is greater than that according to the invention Process anodized oxidized carrier can drain.
  • the light-sensitive recording layer (a7) or (a8) produced in this way can then be matted in a customary and known manner, coated with a smooth or matt top layer which is soluble or easily dispersible in the developer solvents for (a7) or (a8), or with a easily removable, smooth or matt cover film are covered.
  • the cover layer and the cover film can also be used together, the cover layer of the respective light-sensitive recording layer being directly in contact.
  • Suitable binders for the production of the light-sensitive recording layers (a7) are methyl methacrylate / methacrylic acid copolymers, styrene / methacrylic acid copolymers, methacrylic acid / acrylic acid copolymers, polyurethanes or unsaturated polyesters and polyester urethanes.
  • Examples of suitable monomers with photopolymerizable olefinically unsaturated groups for the production of the light-sensitive recording layers (a7) are mono-, di- or poly (meth) acrylates as obtained by the esterification of monoalcohols, diols and polyols with acrylic acid and methacrylic acid or their derivatives .
  • Suitable initiators of photopolymerization are benzoin, benzoin ethers, benzil acetals, acylphosphine oxides, Michler's ketone, anthraquinones, aryl-substituted imidazoles, acridines, phenazines or compounds which easily release halogen atoms on exposure.
  • inhibitors of thermal polymerization dyes, pigments, photochromic compounds or systems, sensitometric regulators, plasticizers, flow control agents, matting agents or lubricants can also be used for the production of the light-sensitive recording layers (a7).
  • Suitable diazo resins for the production of the light-sensitive recording layers (a8) are the condensation products of diphenylamine-4-diazonium sulfate, -hexafluorophosphate, -tetrafluorophosphate or -tetrafluoroborate with formaldehyde or the condensation products of 3-methoxidiphenylamine-4-diazonium sulfate with 4,4'-ethyl-bismethyl -diphenyl ethers, which are isolated as mesitylene sulfonate or methanesulfonate salts.
  • Suitable binders for the production of the light-sensitive recording layers (a8) are copolymers of acrylic acid, methacrylic acid and / or crotonic acid as an essential component with acrylonitrile, alkyl (meth) acrylates such as ethyl methacrylate and with hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl methacrylate.
  • Suitable solvents for the components of the light-sensitive recording layers (a8) are those mentioned in DE-A-36 27 585, of which diacetone alcohol is very particularly preferred, contrary to the statements made there.
  • organic oligocarboxylic acids such as tartaric acids, dyes, pigments, flow control agents, plasticizers and the customary and known stabilizers for diazo resins can be used for the production of the light-sensitive recording layers (a7).
  • Suitable binders for the production of the electrophotographic recording layers (c) are cellulose ethers, polyester resins, polyvinyl chlorides, polycarbonates or copolymers such as styrene / maleic anhydride, vinyl chloride / maleic anhydride, styrene / maleic anhydride / (meth) acrylic acid or styrene / (meth) acrylic acid Copolymers.
  • Examples of suitable photoconductors for the production of the electrophotographic recording layers (C) are the customary and known oxazoles, oxdiazoles, triazoles, azomethines, pyrazolines, imidazoles, arylamines, 1,3-dithiols, benzotriazoles, triazolylpyridines, pyrazolotriazoles, triphenyltriazoles, hydrazones, poly ( N-vinyl carbazole) or arylamine polymers.
  • Suitable sensitizers for the preparation of the electrophotographic recording layers (c) are the dyes from the classes of triarylmethane, cyanine, xanthene, azo, phthalocyanine, naphtholactam or isoindolenine dyes.
  • leveling aids plasticizers, adhesion promoters, fillers or metal complexes such as metal acetylacetonates can also be used for the production of the electrophotographic recording layers (c).
  • photosensitive lithographic printing plates or offset printing plates with a support which has been anodically oxidized by the process according to the invention and the photosensitive recording layer (a7), (a8) or (c) provide excellent exposure and development, which are typical and customary for them lithographic printing plates or offset printing plates, which again document the particular advantages of the method according to the invention.
  • lithographic printing plates or offset printing plates which have been produced using the supports anodically oxidized by the process according to the invention are distinguished in particular by an excellent hydrophilicity in their non-image areas and by an excellent adhesion of their image areas to the supports. In addition, they deliver excellent print products in very large print runs.
  • Aluminum sheets measuring 280x250x0.3 mm were cleaned alkaline, electrochemically roughened in hydrochloric acid at a concentration of 20 g / l at a current density of 60 A / dm2 for 15 seconds, then cleaned again alkaline and then anodized.
  • an aqueous electrolyte consisting of 30% sulfuric acid was used, which contained 0.1% by weight of 3- (triethoxisilylpropyl) succinic anhydride, the amount of electricity was 20 kC / m2, the electrolysis temperature was 30 ° C. and the electrolysis time was 40 seconds.
  • the plates were covered with a dense, uniform, good-looking surface layer, which was mainly made up of aluminum oxides. Further advantages were evident when the plates were used as supports for offset printing plates.
  • Example 1 was repeated, except that instead of (3-triethoxisilylpropyl) succinic anhydride (2-trimethoxisilylethyl) phosphonic acid was used.
  • the same advantageous results as in Example 1 were obtained. Further advantages were evident when the plates were used as supports for offset printing plates.
  • Example 1 was repeated, except that 1% by weight of polyvinylphosphonic acid was used instead of 0.1% by weight of (3-triethoxisilylpropyl) succinic anhydride.
  • Example 1 was repeated without silane I and without polyvinylphosphonic acid.
  • the surface layer obtained in this way was less dense, non-uniform and less good-looking than that from example 1 or 2. Further defects were revealed when using the plates as supports for offset printing plates.
  • Three photosensitive mixtures (a7), (a8) and (c) were prepared by dissolving the relevant components in a suitable solvent. The solutions were poured onto the supports and then dried in such a way that the light-sensitive recording layers (a7), (a8) and (c) resulted in the desired thickness and the desired composition.
  • the light-sensitive lithographic printing plates or offset printing plates obtained in this way were exposed in the typical, customary and known manner for each of them imagewise to incoherent actinic light through a standard negative (UGRA test wedge) and then developed.
  • UGRA test wedge standard negative
  • the photosensitive recording layer (a7) was used. This consisted of the total amount 59% by weight a copolymer made from methyl methacrylate and methacrylic acid (binder), 30% by weight 1,4-butanediol diglycidyl ether diacrylate (monomer), 2% by weight Michler's ketone (photoinitiator), 6% by weight 2- (4′-methoxinaphth-1′-yl) -4,6-bis- (trichloromethyl) -s-triazine (coinitiator that releases chlorine atoms), 1% by weight Georgia pure blue (CI BB7) and 2% by weight Benzenesulfonic acid-n-butylamide (plasticizer).
  • binder methyl methacrylate and methacrylic acid
  • 1,4-butanediol diglycidyl ether diacrylate monomer
  • Michler's ketone photoinitiator
  • the layer weight of the light-sensitive recording layer (a7) was 2 g / m2. It was exposed with the help of a high-pressure mercury lamp for 25 seconds (power consumption: 3 kW) and then with developed an aqueous alkaline developer in a developing machine of the brand ®nylolith 650-W2 from BASF AG.
  • the photosensitive recording layer (a8) was used. This consisted of the total amount 86% by weight a copolymer made from 2-hydroxyethyl methacrylate, acrylonitrile, ethyl methacrylate and methacrylic acid (binder), 2% by weight Tartaric acid, 11.9% by weight the condensation product of diphenylamine-4-diazonium hexafluorophosphate with formaldehyde (diazonium salt) and 0.1% by weight renovated pure blue (CI BB7).
  • the layer weight of the light-sensitive recording layer (a8) was 2.5 g / m2.
  • the exposure and development conditions correspond to those of Example 3, except that an exposure time of 45 seconds was selected (power consumption: 3 kW).
  • the electrophotographic recording layer (c) was used. This consisted of the total amount 54.6% by weight a copolymer of styrene and methacrylic acid (binder), 45% by weight 2,5-bis (4'-N, N-diethylamino-phen-1'-yl) -1,3,4-oxdiazole (photoconductor) and 0.4% by weight CI Basis Red 1 (sensitizer).
  • the recording layer (c) was loaded with a surface potential of -850 V using a high-voltage corona of -6.75 kV from a distance of 1 cm. Thereafter, it was exposed with the aid of a repro camera with four halogen spotlights of 1000 W each for 15 seconds, whereby a latent electrostatic charge image was generated, which was toned with a commercially available toner. This toner image was fixed by heating, and then the fixed toner image on the recording layer (c) was developed in the manner as in Example 3.

Landscapes

  • 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)
  • Laminated Bodies (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP88119523A 1987-12-01 1988-11-24 Verfahren zur anodischen Oxidation der Oberfläche von Aluminium oder Aluminiumlegierungen Expired - Lifetime EP0318820B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3740698 1987-12-01
DE19873740698 DE3740698A1 (de) 1987-12-01 1987-12-01 Verfahren zur anodischen oxidation der oberflaeche von aluminium oder aluminiumlegierungen

Publications (3)

Publication Number Publication Date
EP0318820A2 EP0318820A2 (de) 1989-06-07
EP0318820A3 EP0318820A3 (en) 1989-07-05
EP0318820B1 true EP0318820B1 (de) 1992-03-18

Family

ID=6341657

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88119523A Expired - Lifetime EP0318820B1 (de) 1987-12-01 1988-11-24 Verfahren zur anodischen Oxidation der Oberfläche von Aluminium oder Aluminiumlegierungen

Country Status (6)

Country Link
US (1) US4939068A (fi)
EP (1) EP0318820B1 (fi)
JP (1) JPH01188694A (fi)
DE (2) DE3740698A1 (fi)
ES (1) ES2030145T3 (fi)
FI (1) FI885590A (fi)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3928794A1 (de) * 1989-08-31 1991-03-07 Basf Ag Verfahren zur herstellung von platten-, folien- oder bandfoermigen materialien sowie verfahren zur herstellung von sensibilisierten flachdruckplatten
JP2907643B2 (ja) * 1992-07-16 1999-06-21 富士写真フイルム株式会社 感光性平版印刷版およびその処理方法
US6999824B2 (en) * 1997-08-21 2006-02-14 Fieldbus Foundation System and method for implementing safety instrumented systems in a fieldbus architecture
GB9825043D0 (en) * 1998-11-16 1999-01-13 Agfa Gevaert Ltd Production of support for lithographic printing plate
EP2048266A1 (en) * 2007-10-10 2009-04-15 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Corrosion protective layer
CN102964372B (zh) * 2012-09-24 2015-09-30 中国科学院广州能源研究所 卤硅烷功能化碳酸酯电解质材料,其制备方法及在锂离子电池电解液中的应用
WO2021055076A1 (en) * 2019-09-18 2021-03-25 Novelis Inc. Metal surface coatings for improving bond performance and methods of making the same
JP6764517B1 (ja) * 2019-11-08 2020-09-30 ドングァン ディーエスピー テクノロジー カンパニー リミテッド アルミニウム表面処理方法
CN113755922A (zh) * 2020-07-29 2021-12-07 英迪那米(徐州)半导体科技有限公司 一种铝合金阳极氧化电解液制备工艺

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3945899A (en) * 1973-07-06 1976-03-23 Kansai Paint Company, Limited Process for coating aluminum or aluminum alloy
JPS5134007A (ja) * 1974-09-12 1976-03-23 Fuji Photo Film Co Ltd Insatsubanyoshijitainosetozohoho
US3935080A (en) * 1974-10-02 1976-01-27 Polychrome Corporation Method of producing an aluminum base sheet for a printing plate
GB1548689A (en) * 1975-11-06 1979-07-18 Nippon Light Metal Res Labor Process for electrograining aluminum substrates for lithographic printing
DE2607207C2 (de) * 1976-02-23 1983-07-14 Hoechst Ag, 6230 Frankfurt Verfahren zur Herstellung von Flachdruckformen mit Laserstrahlen
JPS5926480B2 (ja) * 1978-03-27 1984-06-27 富士写真フイルム株式会社 平版印刷版用支持体
US4452674A (en) * 1980-09-26 1984-06-05 American Hoechst Corporation Electrolytes for electrochemically treated metal plates
US4448647A (en) * 1980-09-26 1984-05-15 American Hoechst Corporation Electrochemically treated metal plates
US4399021A (en) * 1980-09-26 1983-08-16 American Hoechst Corporation Novel electrolytes for electrochemically treated metal plates
JPS5852036B2 (ja) * 1980-12-13 1983-11-19 株式会社フジクラ 陽極酸化処理方法
US4542088A (en) * 1982-03-18 1985-09-17 Konishiroku Photo Industry Co., Ltd. Photopolymerizable compositions and image-forming materials using said compositions
JPS6238471A (ja) * 1985-08-14 1987-02-19 Fuji Photo Film Co Ltd 感光性平版印刷版の製造方法
DE3627757A1 (de) * 1986-08-16 1988-02-18 Basf Ag Verfahren zur herstellung von flachdruckplatten

Also Published As

Publication number Publication date
FI885590A0 (fi) 1988-12-01
DE3740698A1 (de) 1989-06-15
FI885590A (fi) 1989-06-02
EP0318820A2 (de) 1989-06-07
DE3869346D1 (de) 1992-04-23
US4939068A (en) 1990-07-03
JPH01188694A (ja) 1989-07-27
ES2030145T3 (es) 1992-10-16
EP0318820A3 (en) 1989-07-05

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