DE2045081A1 - Process for the production of Me tallbildern on carriers - Google Patents

Description

Process for the production of metal images on carriers

One already knows processes for generating permanent,

lightfast I-markings on permanent metal supports, e.g. 3 _o for identification badges. If, for example, according to US Pat. No. 3,108,932, a porous surface of an aluminum sheet, such as, for example, 3. an anodized surface with no pore filler, treated with a reducing agent and then printed or described with a solution of a reducible metal ion, an image of the reduced metal is formed almost immediately. This method is based on the formation of an oxidation-reduction system in the image areas with the creation of νου images of consistently uniform density. However, this method is practically not calibrated for the generation of images with different densities and also has other "laughable" ones be removed from the Pertiger testimony, especially

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werm its oxidized form unwanted Pax-be to V / ei;. "... The reducing Metallioneniöaungen, including silver, mercury or Kupferionenlösic.gen that the" form ink "f.'ir -ILj imaging, must turn against reducing substances are protected and also offer some SChv; _ierl;;. in the manner of -ites Hailtierur .. ;; that ilberionenlösungen the IVchinann especially in ^ are vertrauu the US Patent 3 '-17 · ί-03 describes a similar process , in which the permanent writing or printing takes place on anodized aluminum surfaces provided with a pore filler, ur.d: Ias üie same ITacht that errors that occur when printing or writing: - of the picture cannot easily be repaired, which leads to the waste of aluminum sheets and the V ^.; isderholur.g of an already partially finished work process.

Other methods of making permanent markings on -Iuin in ium use mechanical means or the ciier.ischor. Etching, as they are known to those skilled in the art, and provide images, who are unsatisfactory in many relationships and are wrong. Compare to the methods mentioned above, especially in comparison to the oxidation-reduction process of the United States patent 3 108 932, not easy to manufacture.

Furthermore, one knows photograph! See processes for the production of

ψ? lachdruckforrnen einschliesulich printing plates * ■ When aie ^ it. Method, a photosensitive layer on einerr, -rager, s.Bo on aluminum panels, the desired image r.iit belieh ^ ex, "then v / ith a metal image, Z.3 _6, a silver or copper image, developed, and finally v / ird the plate enOspreciiend ^ ..;. · ". intended use ^r eck "treated as iichter.pfirii.liche layers can in this case the üb'lichen photographiooi;.. ^ layers aB _o silver halide, use, v / es ie in the U ^ .- Patents 2,115,339, 2,126,017 and 2,766,119, British published patent application

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1 Cu, 725 describes the use before. aromatic diazosuiionaton as a light-sensitive Hatr.rial for the production of 'Printing plates and electrical circuits.

Originally, lithographic plates were made with certain Steiner, produced that have oleophilic and hydrophilic properties. Lie surface of such stones will be covered with greasy Strand it, and printing is done by wetting the Stone and then 'coloring it, with the printing ink is only absorbed by the image areas. If ciar / Λ pressing a copy sheet against the stone becomes the greasy one Image reproduced on it. In view of further developments In lithography, this method no longer has any technical significance.

The present method is particularly suitable for manufacture of full metal images on metal support ^ in view of the light weight Feasibility of the necessary procedural steps, especially for the production of printing plates, printed electrical circuits and lianas or nameplates, in particular for Manufacture of ornate nameplates.

The invention is a method for the production of Metal images on carriers, which is characterized by that one records an image on a carrier with a nucleating image recording medium (imaging material) and by treating the carrier provided with the recording with an image-forming material a metal image is generated on the areas of the carrier provided with the recording. Preferably the treatment is.-R. With the metal image-forming agent continued until the resulting metal image adheres firmly to the carrier, especially if it is a metal carrier, e.g. made of aluminum or iron. You can do anything for the new products use supports common in photography and lithography; however, a ketallic carrier is preferably used

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ger. ^ ol a uevor: ". ^a: 7Üi": n digestion verwonuet you as me, ^{'allbilderzeugendes} means the selective electrolytic U2tallabseht-i-amg or photographic physical developer, iie products gomäss the invention are particularly ale; ITamonscuilder, printing plates, printed electrical circuits, slides and for decorative purposes *

Manufacture of the new products is carried out by recording the desired image on a carrier with the aid of a ko!;. forming imaging agent. "Record" The Ausdi'ucik the purposes of the invention, each Z-Iothode includes the h.ufschreibens countries (by hand or with a typewriter), recording, or otherwise supports Aufdruckend ^ of BiI- W, letters or other images, including the imprinting of images in the recording surface »Ler j.usdruclc" record "does not have the meaning of the p!: o jographic application of such images; this is η loht within the scope of the invention.

The expression “nucleating image recording agent” encompasses, within the scope of the invention, substances which are preferably coated by the metal image-forming agent. When the metal imaging agent ZoB. a physical developer i., t, the silver ions and a reducing agent for the same, the nucleating image recording agent can consist of; jo'jom material, aas in the reduction of the physical Ε; -; - w / ickler preferably by metallic Plating silver. ¹ Irh. Such nucleating image recording means sine; known in photographic chemistry; to them belong material, vio f. houo graphic chemistry are well known. One preferred ;; Boron: .. of home-forming image recording media for the bovorzu-; t ·: - :. Metal carriers are electrically conductive Bilaaufaufnahme..mantel, which due to their electrically conductive connection with the.

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Metal supports can be easily metallized by dao metal-forming agents. To the conductive Bildaufzeiohmingsmituolr. goliören. the abovementioned key figures in ■ "■:". α em gooijfl · -ten binder, which er..io ^ iioht the recording, and preferably carbon, metals and metal compounds. The preferred conductive BildaufzeicririUii ^ G ^ ittil are different forms of carbon that and are easy & best 'available oind for the recording process a.. Storage agents made of carbon are available in various l-'orine and physical states, e.g. as carbon pencils with hardness H3, 3, 43 and 23. Other common trade names for carbon pencils are "libony" and "Carbon Othello (46/2)". Han can also use the usual graphite and pencils. Metals can also be used in suitable binders, for example colloidal silver in polyvinyl alcohol, polymethacrylic acid esters, gelatin or similar binders known in the photographic art. These binders should not run on the support, but should instead retain the originally recorded form, which does not present any difficulties with regard to the selection of the suitable ily properties of the image recording medium.

The choice of recording medium is up to the person skilled in the art and depends on the desired effect, the respective metal image-forming agent and other considerations, which can be determined with a minimum of routine tests with regard to the most favorable conditions. The common ones Precautionary measures or special considerations that may be required are within the scope of the general Expertise. Y / erm the nucleating image records! ttel is.Bo contains hydrophobic substances, as is the case with many coal, Lead and graphite pencils, especially the softer types that contain a wacha-like or oil-like ingredient, the If so, the hydrophobic substances can be used as protective

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act over the metal imaging agent, which is usually an aqueous agent. This difficulty can be eliminated by using non-water-miscible organic ingredients, and the chemist is familiar with the fact that he only needs to add acetone or lower alkanols in this pail. Surface-active agents, for example non-ionic surface-active agents, can also be used instead of organic compounds.

Suitable imaging media can easily be found on G-runa Easier to pick out experiments by taking small test strips dos to be used carrier with a record from do; .. Imaging means and then dipping them in a physical developer containing silver ion and a reducing agent for the same contains. A picture recording: ;;. '.! ttel, developed by such a physical developer, doh. is coated with metallic silver, is suitable for the present process. You can use the test strips also in a suitable metallization bath, such as a copper plating bath, immersing an imaging agent suitable for the purposes of the invention selectively with the metal is coated »

As carrier one may within the scope of the "invention Z ₀ B ₀ paper, plastics, wood and the like to use, but preferably used metal support, the non-metallic support may consist of any suitable plastics are made, which is preferably cellulose acetate, and polyester, especially polyethylene terephthalate, include. , "The support may in existing, liebiger shape, Z ₀ B. in'Porm of sheets, tapes, rolls and the like, be used. The carrier must of course be strong and durable enough to be used as a lithographic support or image carrier If the carrier consists of a plastic, especially a polyester such as polyethylene terephthalate, it is advantageous to use an adhesive layer in order to adhere the desired image.

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des to ensure the carrier. ·

Any suitable metallic or substantially metallic support which has the strength and durability required for an image support can be used for the preferred supports. The carrier may be in any form, "B z ₀ in PorITi of 31echeri, tapes, 'rollers, etc., are present. The sheet metal can be made of any suitable metal or any suitable metal alloy, for example of hydrophilic ketals such as chromium, nickel, lead, stainless steel, liagncsiurn or "~~~" ~ "" aluminum, "or of . oleophilic He tall s, such as copper or zinc aluminum is, due to its physical and chemical properties as well as its cost preferably "Sine non-anodized surface is for the aluminum exchanger special λ dera preferred; however, one can also operate with anodized aluminum, is preferably the non-anodized aluminum surface for best results, for example, "coated with sodium silicate. Coating with sodium silicate avoids the difficulty of haze formation on uncoated aluminum in the presence of the metal-image-forming compound, which can arise with highly reactive systems". This difficulty However, it can also be used by sor Avoid careful control of the process stage of ketallic imaging. . ,

In the case of supports made of plastics, especially transparent λ

Plastics such as cellulose acetate or polyester, in particular Polyethylene terephthalate, it is sometimes useful to use the Cover the surface with a layer zi *, which improves the adhesion of the resulting image to the plastic film. Such intermediate layers are referred to in photography as adhesive layers. Usually exist Adhesive layers made of materials that are attached to both deia plastic and also adhere to the image recording medium. In general the adhesive layers consist of gelatin; but they can too

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from different Polymei-isat'latices, such as Vinylici.enpoly:.; erisater, Polyvinylforrcalen, Poly \ ^r iny! "butyral and similar borrowed substances, Des parts _o Gelatins, and which improve the efficiency of ketallic imaging.

The carrier is advantageously physically, chemically or otherwise roughened so that the metal image is produced in Ilittel ar:. cling to the "rager. Physically roughened! suitable for the purposes of the invention have granular, porous or matt surfaces «chemically roughened substrates meaning with suitable acids or bases, with acting as adhesives Primers and the like have been treated,

t so that there is a chemical bond between the imaging agents and the carrier surface. In addition, additives such as cadmium and / or zinc salts can be added to the image-forming agents, as described in the French additional patent carift 77 556, in order to improve the adhesion of the metal image to the carrier. Certain alloys, such as magnesium-aluminum alloys, also cause the deposited metal image to adhere well. The term "roughened carrier" includes · therefore physically glatjc carriers that have been, ^'r ege treated by chemical or other ^T so that an adhesive bond with the metal deposited thereon image comes off. But also with beams with a smooth surface, especially aluminum beams that are not anodized

Have become P, excellent results are obtained.

To the "metal image-forming agents which can be used according to the invention Agents include the usual physical developers such as those in U.S. Patent 3,152,903, British published patent application 1,043,250 and British Patent Specification 1,064-725 ". These image-forming Gowns preferably contain an oxidizing agent and a reducing agent. Such imaging gowns are used in in technology often referred to as electroless plating baths.

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net. One 'can also use electrolytic development' as described in US Pat. No. 3,152,969 "int. The oxidizing agent is generally the image-related component" of the image-forming agent. Organic or inorganic oxidizing agents can be used as the oxidizing component of the imaging agent. The oxidizing and reducing agents can be combined in a single bath or used in separate baths, or one or both of these ingredients can be incorporated into the imaging medium prior to exposure. Preferred oxidizing agents are reducible metal ions which have at least the oxidizing power of the copper (II) ion; 'These include metal ions such as Ag, Kg, Pb, Au', 'Au ⁺⁵ , Pt ⁺² , Pt ⁺⁴ , Ii ⁺² , Sn ⁺² , Pb ⁺² , -Cu "!" ¹ and Cu ⁺² .

Can be used as a reducing component of the image-forming agent one compounds such as the oxalates, pormates and the ethylenediaminetetraacetate complex compounds of metals with multiple valencies, as well as organic compounds such as dihydroxybenzenes, Use aminophenols and aminoanilines. Further reducing agents which can be used according to the invention are polyvinylpyrrolidone, Hydrazine and ascorbic acid. Particular, suitable reducing agents are hydroquinone or derivatives thereof, ο- and p-aminophenol, p-methylaminophenol sulfate, p-hydroxyphenylglycine, o- and p-phenylenediamine, i-phenyl-3-pyrazolidone, Alkali and alkaline earth oxalates and formates.

? Lüüoige physical developers are excellent because of the Results obtained with them are preferred as imaging agents. Any suitable solvent can be used. Aqueous treatment baths are preferred, however. The pH of the developer is not particularly important; However, it has been found that, with metallic carriers, the best results are obtained with acidic developers, especially those with pH values between about 2 and 5 and ■ especially with organic acids such as citric acid,

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Gluconic acid, maleic acid and oxalic acid that act as complexing agents work for metals. pH levels of around 2 to 3 are special preferred. It is believed that the acid dissolves the oxide layer on the metal, such as aluminum, and thereby the adhesive strength and the electrically conductive connection between the image and the metallic carrier are improved.

In addition, the image-forming agents or physical Developers contain organic acids or alkali salts thereof which form complex metal anions with metal ions. Furthermore, the developers can use other complexing agents and 'Contain similar substances that improve image generation and other technically valuable properties »

Further developers that can be used in the context of the invention are contained in the USA patent applications Serial Nos. 743 981, 743 932 and 743 983 dated July 11, 1968.

The action of the physical developer on the Image carrier provided with recording is preferably continued until an image is obtained which adheres to the carrier and, in the case of a metal carrier, conducts it with it. is bound. This length of time depends on the substrate, the conductive image recording medium and the activity of the physical developer. To determine the respective günfe A simple experiment can be used for the longest period of time. The adhesion of the metal image to the carrier can be determined empirically with an adhesive tape strip. The adhesive tape is pressed firmly against the picture and then quickly removed, e.g. by hand, which can be followed by inspection determines how well the image adheres to the carrier. »If the tape has accepted little or no metal, so this means excellent adhesive strength, while a complete peeling of the image areas through the adhesive tape proves that the image does not adhere to the carrier.

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The: -UVuaHüilaerKeu.3ung is preferably carried out by I-Iet & llicie- Timr, - either by electrolytic lietallabucheidun> öäor by electroless metallization, eg "copper plating. The r.tronloce I metallization is preferred. Such strornlocen Xetallisicrung; jverfahren based on the displacement of the ions of the coated metal from the solution, Z.3 _o on the displacement of copper ions from the solution by the aetalli-dche of aluminum Prägers provided with the recording. Such baths normally contain substances which attack the metal of the carrier, for example acids, complexing agents or pickling agents, and the like. Electroless metallization baths therefore contain a starting material for the ions of the metal to be coated, an acid and / or a complexing agent for the ketal of the image carrier.

Preferred electroless plating baths contain copper srions and a pickling agent for the metallic substrate as described in U.S. Patent Application Serial Ivo. 744 661 of July 15 Is described in 1968;

Electroless plating baths of this kind are suitable for "carriers" in which the recorded image is in conductive contact with the metal surface of the carrier. because the recorded image 'can itself then in electrical contact with the conductive metal are when ₀ as an aluminum oxide layer, is separated on an aluminum carrier of the same by a thin layer, Z ₀ Excellent results are obtained with aluminum supports which are not anodized are, Z ₀ B ₀ with non-anodized aluminum sheet, which has a thin aluminum oxide coating, or with silicate coated aluminum sheets. In view of these results, the theory of electrically conductive contact between the recorded image and the conductive one should be believed

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Metal support must be well founded. The further observation of the ■ Spontaneous metal deposition in the image areas when the image carrier with the recording is immersed in aas Metallization bath also speaks in favor of this theoretical explanation. In any case, an electroless metallization takes place only takes place when the recorded 'image is in close proximity Adjacent to or in physical contact with the metal of the carrier.

The electroless plating bath only works when the carrier metal is exposed to the action of the solution of plating ions. This means that the fresh or cleaned metal is in contact with the solution. W The conductive metals of the substrate include metals, either under normal conditions easy a protective coating form> such as aluminum, which coats in the air with his / i oxide, or which have been particularly provided with a protective coating ', Z ₆ B ₀ by galvanizing iron or steel or by anodizing aluminum. In order for the plating baths to work satisfactorily, the conductive metal should be exposed to the action of the bath by removing any coatings from the surface thereof, preferably while the surface is in contact with the plating bath. For this purpose, an agent is preferably added to the bath which removes the protective coating, that is to say a solvent for the protective coating and preferably a pickling agent for the surface of the conductive metal. Such solvents and pickling agents are known in the art; They include non-oxidizing acids such as dilute sulfuric acid, bases and salts that attack the protective coating. Complexing agents are particularly effective for the ions of the conductive metal, which attack the protective coating and at the same time bring the ions of the conductive metal into solution and thereby prevent possible precipitation from the metallization bath. ' Aluminum ions that result from the oxidation of a

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Aluminiumträsers-have formed, e.g. as hydrated ' tea oxide, i.e. hydroxide, on the metal surface again, off, fall when the plating bath is alkaline, causing the efficiency of the metallization process is reduced. Such a precipitation is avoided by the complexing agent. -.

The protective coatings can also be removed from the metal supports by known methods before the supports are exposed to the action of the metallization bath. So 'the coating ζ _β Β »can be removed from the surface with the aid of an abrasive. Mechanical scraping or similar processes can also be used.

The treatment with a mordant can also be carried out before immersion in the plating bath .. An aluminum support with, a metal seed image already formed thereon may be, for _a B "by known means, such as oxalic acid, acetic acid, citric acid, Grlucoheptansäure or caustic alkali such as sodium hydroxide, prior to Metallization are pickled. Such a process must, however, be carried out in an inert atmosphere, because otherwise oxide coatings will immediately form again when the atmosphere acts on the freshly exposed metallic aluminum. Such a precaution. is in. In view of the high prior reactivity of the conductive metal, and because of this high chemical reactivity, prior removal of the protective coating is not preferred, especially in view of the high efficiency of removing the protective coating in the preferred plating bath described herein.

One does not need to remove all of the protective coating from the conductive metal, but only part of it, like this that enough metal can be oxidized to produce the desired To bring about a degree of reduction of the ions of the metallizing metal. There is no absolute requirement for purely practical purposes.

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There is a need for the quantity of the pickling agent, as the most favorable quantities can easily be determined. If the efficiency decrease of Metallisierungsvorganges, it can be the amount of the seed treatment, even if the Metallisierungsverfahreh is already operating for some time, increase and & en desired efficiency by controlling the concentration of the etchant (preferred \ ^ else a complexing agent) in de ::, Maintain the metallization bath. Such a control is familiar to the person skilled in the art and does not need to be described in detail. · ·

The preferred electroless plating bath according to the invention contains a starting material for the ions of the metallizing metal and a complexing agent for the ions of the conductive metal of the carrier, in particular a complexing agent, which also acts as a pickling agent for the protective coating acts on the conductive carrier metal. If the carrier with the picture is immersed in the plating bath, the ions of the metallizing metal on the recorded image are reduced to the metal, and the conductive Metal is oxidized to the corresponding ions, which are converted into complex ions in the solution, and the process continues through the oxidation-reduction reaction. The process is continuous because the metallization is so takes place as long as there are still enough ions of the metallizing metal in the solution.

Any common source for such ions can be used as the starting material for the ions of the metallizing metal. Since the bath is preferably an aqueous bath, the starting material should be water-soluble or at least, Z ₀ B ₄ , should be able to be made soluble in water by the formation of complex ions. The best results are obtained when the ions of the metallizing metal are in the form of complex ions. The use of complex ions offers the further advantage that this allows the separation of undesired sludge or foam

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avoided on the surface of the image carrier to be coated, the metal deposit on the conductive metal support limited to a minimum, so a high degree of selectivity for the preferred metallization of the recorded image and in general the overall efficiency of the Metallization process, especially in terms of the duration of immersion in the bath, is improved.

The metallizing metal only needs to be below the metal of the carrier in the series of voltages . To achieve the best results are used as metallizing metals preferably the so-called "precious metals" ·, that is copper and metals that are in the voltage range from copper, 'for example, ₀ silver, gold, platinum, palladium and mercury. silver »Of these, copper and silver are preferred for most purposes. These metals can be nitrate in Ketallisierungsbad in the form of their soluble salts, such as _o in I? Orm of silver nitrate, copper (II), mercury (II) nitrate, "acid PlatinchlorwasBerstoff," Palladium or chi id, etc., or as a soluble complex compounds are used, many examples of which are described in the literature. The soluble complex ions of the metallizing metal are the preferred form from which the metallizing metal is reduced in the process according to the invention. The complex ion should be relatively stable in solution if the advantages of the invention are to be achieved. In particular, the cumulative or total stability constant of the complexion should not be less than about 7 if the ion is to be usable in the process according to the invention in 'the work "Stability Gonstants of Metal-Ion Complexes, · with Solubility Product of Inorganic Substances", Part I & II, compiled by Jannik Bjerrum, Verlag Metcalfe & Cooper, Limited, 10-24 Scrutton St., London, EC2, The preferred metal complex compounds are generally

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the ones who are at least as stable as the known ones Ammonia complex compounds of copper ions. Under a constant or stable complex ion of the metallizing Me- ■ Tail is understood here to mean a complex ion whose total or "cumulative stability constant" is at least about 7.

If the metallizing solution does not contain a complexing agent for the ions of the metallizing metal, the metallizing bath works generally not effective ', because then also in the places where there is no picture (the so-called Background areas) a certain metallization can occur, which leads to an undesirable background metallite ■ leads so that the metallization does not proceed with the selectivity as it is for the complexes mentioned above Metal ions is characteristic. In other cases it takes place in normal working hours, even if the bath is a pickling agent contains, hardly any metallization, so that one has to work with longer immersion times, what 'compared to the short ones Immersion times, which are required when metallizing with complex ions, is uneconomical.

In general, complexing agents, which the MetallisierungsvVorgang affect, to be avoided. In itself, for example, Ascorbic acid can be used as a complexing agent for copper ions in copper plating; this is preferably used Fe acid, however, not, although copper plating can be carried out with it is because it acts at the same time as a reducing agent for copper ions and consequently in the method according to the invention to a reduction in the selectivity of the copper deposition results in that metallic copper is also noticeably deposited on the background. Therefore complexing agents are preferred, which do not cause secondary or competing reactions which would produce the desired result among the Affect working conditions «,

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Complexing agents or pickling agents for the ions of the conductive metal are also known in leohnik]. Uranil-li, H-diacetic acid, ethylenedianiintetraacetic acid and its homologues and analogues, 1,8-I) ihyäröxy-2-phenylazonap ^> hthalin-3,5-disulfonic acid, citric acid, tartaric acid, glueonic acids, such as gluoic acid and glucoheptanoic acid, and use sodium Suitable complexing agents for the purposes of the invention and the stability of the complex compounds formed from within are described in the above-cited work by Jannik Bjerrum

The ions of the metallizing metal should preferably be in the form of soluble complex ions. Such complex compounds are easily formed in solution by adding a suitable complex ion former to a solution of ions of the metallizing metal or to a solution of an ion former of the metallizing metal. Preferably, the starting material used for the ions of the complexing agent is one which dissolves easily in the respective solvent and dissociates therein. If the ion of the complexing agent z / B. which is ethylenediaminetetraacetate ion, a soluble salt of the corresponding acid is preferably used as the starting material for the ion of the complexing agent and not the free acid, which dissociates only weakly in the preferred aqueous medium. Instead of acetic acid, citric acid, gluconic acid and the like, soluble salts of these acids, such as ammonium, potassium or sodium, are also used. . ' ·

Complexing agents for copper ions, the preferred metallization ions, are known and described in the above-mentioned ¹ work. Examples of such compounds are formic acid, oxalic acid, methylamine, acetic acid, glycolic acid, biguanide,

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Ethylenediarain, chloroacetic acid, bromoacetic acid, glycine, " Ethanolamine, propionic acid, lactic acid, 3-hydroxypropionic acid, 1,3-Maminopropane, N-methylethylenediamine, 2-methylthioethyl-amine, Maleic acid, fumaric acid, succinic acid, tartaric acid, Iminodiacetic acid, ethylenediaminetetraacetic acid and their Analogs and homologues, pyridine, catechol, citric acid. re, gluconic acid, o-aminophenol, nitrilotriacetic acid, salicylaldehyde and salicylic acid.

Many complexing agents for copper ions are at the same time complexing agents for aluminum ions, which are capable of pickling the metal surface and of forming complex compounds with the ketallic ions in question. For aluminum can be in the Fc sem meaning z _t B, citric acid, acetic acid, gluconic acid, water soluble salts of nitrilotriacetic acid and Äthylendiamintetraes3igsäure use. If the complexing agent is also a pickling agent for the conductive metal, there is no need to add a special pickling agent, since the complexing agent takes on both tasks in this case. Although it is not necessary, it is usually preferred to add the complexing agent in excess in order to increase the pickling effect, although the effect can still be observed if the ions of the metallizing metal and the complexing agent are used only in stoichiometric proportions.

The preferred plating baths can be used within a wide range of pH values determined solely by stability the respective metal ion complex compounds is limited. For example, the pH of the solution should be above that pH value at which the metal ion complex compound dissociates into its individual ions. Determining the appropriate and the most favorable pH ranges can be done through routine experimentation. Of course, both the cheapest are aimed as well as the generally applicable pH ranges according to the Type of complexing agent. For general purposes, the pH value, of the metallization bath in the range of about 4 to 10

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ries; with many complex compounds one can also work at pH values of 2 or even less »The best results are achieved at pH values in the range of around 5

till 9. ·

If the pH of the bath is in the alkaline range, there is always the risk of precipitation of the ions of the metallizing Metal, e.g. as hydroxide or hydrated Oxide, and therefore these ions are preferably kept in solution in the porin of relatively stable complex ions. The complex., Formers for the ions of the conductive metal also prevent " if so, the formation of soluble or hydrated hydroxides Oxides on the surface of the conductive metal, on which ions of the same are formed by oxidation. The accumulation Such insoluble substances on the surface of the metal subject to oxidation can reduce the Efficiency or even lead to a complete standstill of the metallization process.

In a preferred metallization bath, especially for manufacture of printing plates, the ion of the metallizing metal is the copper (II) ion in the form of a complex compound with a complex-forming organic acid, such as e.g. Glucoheptanoic acid, citric acid, ethylenediaminetetraacetic acid or nitrilotriacetic acid. In addition, the bath preferably contains another 'complexing agent for the ions of the conductive metal, preferably for aluminum ions. The bathroom can e.g. from a solution of copper ClIJ-ethylenediamine tetraacetate, a soluble salt of ethylenediaminetetraacetic acid as a grain

plexing agent for the aluminum ions and a solvent exist for the oxide coating on the sheet metal.

The plating bath can be supplemented by adding the necessary components by simply adding them as required dissolves in the bath, even when the bath is in operation «This is possible because the metallization bath is so simple is composed.

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The temperature of the plating bath is not very important and can reach the boiling point. As with all metallization baths, the temperature influences the Metallization speed and to a “lesser extent also the nature of the metallization layer; At higher temperatures, the metallization proceeds faster themselves. If you have ZoB. works at the boiling point of the bath, one usually gets a strong, adherent copper " topping in just 30 seconds; at 5-0-55 ° C you get a good one Topping in 2 minutes, and at 70 ° G you get an even thicker topping in 2 minutes. . ■

The metal image that forms is. A. Coherent, electrical conductive metal image as opposed to the non-conductive metal image composed of individual particles that one usually obtained in photographic processing. The coherent metal image is made up of large, one another neighboring particles of the metal and has the appearance of a continuous layer. The picture has a characteristic Shine; e.g., silver images are glossy, and this is the preferred form of metal for those in question Applications, namely for printing plates and electric Circuit parts, as opposed to the fine, particulate, black, non-conductive metal deposits that are used for characteristic of most metal photographic images, e.g., the black deposits of metallic silver on silver halide photography, which are generally not electrically conductive.

In the manufacture of printed electrical circuits, the products can be used as such after being developed, or they can be used with metal supports and so on. be treated that the electrical circuit is created by chemical detachment of the metallic circuit that has formed on the metallic carrier. All reagents that attack the carrier but act against the

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JFS-8366 KJ

tall of the image can be used to separate the metallic circuit, e.g. alkali, such as diluted caustic soda, or acids such as dilute sulfuric acid, for silver or copper pictures on an aluminum carrier. Other reagents that can be used for this purpose are familiar to the person skilled in the art .. If necessary, the metallic First embed the circuit in a suitable carrier before removing it from the aluminum carrier; the in The circuit is then embedded in the substrate Removed aluminum support as described. ·

Image carriers with adhering metal images are preferably used as printing plates. As soon as the adhering metal image has formed, the developed image carrier is used for the purpose. Making a printing plate treated. As part of a sol 'chen treatment, it is usually advisable to increase the differentiation between the oleophilic and hydrophilic properties of the image areas and background areas of the plate ·. In the case of a silver image deposited on an aluminum support, this can be done, for example, by treatment with substances such as mercaptans. adhere to the silver image areas and make them more oleophilic, and these agents can be used alone or in combination with phosphoric acid, which adheres to the background areas and makes them more hydrophilic. In addition, a lithographic preparation can be applied which contains a polymer, such as gum arabic or carboxymethyl cellulose, in order to improve the hydrophilic character of the background parts of the plate. Furthermore, the useful life of the plate and its oleophilic character can be improved by coating the plate with varnishes that selectively adhere to the image areas but not to the background areas. Further compounds for improving the printing capacity of these metal plates are described in French supplementary paibentso pen 77 556. A silver image can be made stronger by strengthening it in a metal ion bath, which is a

- 21. '■ -,

BATH

taiX image, which is more oleophilic than the silver image, e.g. a copper picture.

• ■ ·

If the products having a metal image are to be used as liarn signs or generally for decorative purposes, the metal image is preferably coated with a varnish that selectively adheres to the image, is a clear varnish and can be colored to achieve aesthetic effects .. But you can also use a colored developer to produce the metal image in order to give the metal image a color. D. The panels can then be coated with an ordinary clear coating *

According to another embodiment of the invention, you can Support provided with a photosensitive layer on which by exposure before or after writing or printing photographic images can be formed with the conductive recording medium. So can the photosensitive Layer before the image is recorded, a 'latent or have visible photographic image, or one can Generate additional images on the carrier provided with the recording by exposure, which expediently appear simultaneously let develop with the physical development described above. If you have a photosensitive support of course, care must be taken that it is not exposed to actinic light. the light-sensitive layer, can also be applied to the support after the metal image has been developed.

In most cases the photosensitive layer should be on the same side of the support on which the image is recorded. In one transparent carriers, however, the same results obtained essentially _r when the photosensitive layer is located on the back.

The photosensitive material can be used in photography common substances, such as silver halides, ferro-ferric

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^Turns: Diazosulfonate- and photoconductor used. The photoconductors are particularly / preferred because they can be handled with the least amount of care. If the photoconductor is accidentally exposed to the action of actinic light, its activation can be _{easily reversed, for example,} by adapting to conceit, corona discharge or heating. if after; If a photographic image is to be generated before the recorded image is generated, one of the treatments described above can be used to reverse an unintentional photoactivation. ·

If the photosensitive layer is there, you can Image recording means, as described above, · immediately bring this up. '

The method can be used to produce imaged supports which can be used as replacements for lithographic stones, printing plates, nameplates and encrypted signs such as vehicle registration plates, for decorative purposes, as electrical circuits, for direct reading in computers such as one of a Computer operated typewriter, can be used as relief _{images, Z 0} Bo for relief letters as a substitute for Braille, and for similar purposes. The method is also suitable for _ "* -. | Electrolytic or electroless metal deposition on a wide variety of carriers, including metals that are covered with protective layers such as oxide coatings.

According to a technical embodiment, the invention a simple equipment pack that includes a metal plate, preferably made of aluminum, the dry chemicals required for electroless metallization and one Pen or other recording device with a

109830711 U

_BAD original.

Includes instructions for use. Such a pack is suitable for professional and amateur craftsmen and contains for the latter also a simple printing press with accessories.

Because of its simplicity and high level of effectiveness, the invention has a wide range of uses. In view of the ease with which errors that occur during recording, can be corrected, for example, ₀ through erasing, when trying to use a pencil, has the method according to the invention a greater practical V / ert than similar known methods.

example 1

An aluminum sheet measuring 25 cm χ 40 cm (alloy 1100) is degreased, cleaned and then grained with a brush. The grain · comes with an automatic vibrating burst. device such as is commercially available from Puller Brush Company. After graining, the aluminum is preserved a mild alkaline caustic treatment (Pennsalt AE 21) and will then rinsed and cleaned in 30 percent nitric acid. The sheet is then placed in 25 percent sulfuric acid at a current density of 1.29 A / dm and a voltage for 5 minutes anodized from 16 T, then rinsed again and dried * Las Sheet metal is now suitable for labeling.

The sheet metal is used to record an engineering drawing. The drawing is carried out with a soft pencil (Dixon Ticonderoga 1388-2). The one grained with the brush, Anodized and imaged carrier is then immersed for 2 minutes in a bath of the following composition: .

- 24 109830/1 IU

. 2045081 g ; 78.4 G '33, 2 G 80 / O G 1.0. G ■ 1.0

JFS-8366. ZS

solution I - ferroammonium sulfate
Perrinitrate
■ citric acid
Made up to 1 liter with water

Solution II - "Armac D"

"Lissapol N"

Made up to 1 liter with water

Solution III - 3n silver nitrate solution.

125 ml of the solution I’re mixed with 25 ml of the. Solution II and 6 ml the solution III mixed. After 2 "to 3 minutes of immersion the plate is removed from this mixture and rinsed. The recorded image is. now in silver on metal— lizes and can no longer be rubbed off. The picture is firmly attached to the metallic carrier. ·

The sheet is now treated with a: dispersion of the following composition:

■ 2-mercaptobenzothiazole. 1.0 g

85 percent phosphoric acid ■ 1.0 g

Water ... . 80.0 g.

The dispersion is applied to the recorded, metallized image painted on, making the image areas selective for printing ink become receptive. By means of "this product one obtains first-class impressions of the recorded in an offset press th picture. . ,

Example 2

A non-anodized aluminum sheet that has been cleaned according to Example 1 and imaged by recording is immersed in the following aqueous solution: *

- 25- -10983Q / 1 UA

_BA D

200 ml CuSO ₄ (i-molar)

300 ml trisodium salt of nitrilotriacetic acid (1 molar)
12 ml NaOL (5 molar)
Filled up to 1 1 with V / ater

After 10 minutes the picture surfaces are copper-plated.

Example 3

A silver image produced according to Example 1 on an aluminum support is treated with the following dispersion: "V / estern PN" developer (red) 100.0 g mercaptothiazalin (2-MT) 0.8 g 85 percent phosphoric acid 2.0 g N _f N-dimethylförmaraid 2.0 g

The silver picture takes on a red color.

Example 4

Following the procedure of Example 1, a firmly bonded metal image is obtained on a non-anodized, granular aluminum silicate coated with sodium silicate (available from Harold Pitman Company, New Jersey, V ₀ St, A _0).

'The picture is a drawing of a ship on the high seas that recorded by an artist with a charcoal pencil.

After treating the silver image with that described in Example 1 Solution of mercaptobenzothiazole and phosphoric acid, the image is colored and used for making impressions used in the drawing. The printed images show α Ig the same clarity and line sharpness as the recorded one Original.

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r ■ ■

jps-8366 -

Example 5

On grained, chemically grained, ball-grained with the brush •respectively. Aluminum plates machined with your sandblasting machine ■ is made with a, graphite pencil (Dixon Ticonderoga 1388-2 soft) recorded one image each. The recorded images are then made by immersing them in the following solution for 60 seconds copper-plated: '■

Rupfer (I) chloride (Cu ₂ Cl ₂ ) 31 g

■ Hydrochloric acid (37-38.5 "/ <>) 32 cm ³ ·

■ .. ■■ · 3

Isopropyl alcohol '1000 cm.

B el'8 pi.el '6 .

A grained aluminum plate is labeled with a graphite pen (Futura-soft 2) and then with a commercially available copper plating bath ("Lith-Ken-Ko copper base") for aluminum (Litho Chemical and Supply Company, Inc., Lynbrook, Long Iceland) copper-plated »·

- ' Example 7

Smooth aluminum sheets are bound with a pencil (bound Lead Uro. 3 - Boston Co. - 'Boston, Massachusetts, V.StoAo) labeled and, as described above, copper-plated.

If the copper-coated pictures produced according to Examples 5 to 7 are rubbed off with the help of a cotton swab with 5 percent phosphoric acid and then colored with conventional offset printing inks or varnishes, first-class prints of the pictures in question are obtained. ',

If you prepared according to the previous examples Plates used for printing in an offset press are obtained True-to-page copies of the recorded original image. If · the prints are made directly with the plate, they are Mirror images of the original image.

• -27 - -.
1: 09B30./i: U4

• ORIGINAL BATHROOM ·

Example 8

On an aluminum sheet grained with the brush, carbon and graphite pencils of different hardnesses recorded an image with broad shading and toning effects. the The finished drawing is washed thoroughly with denatured alcohol using a polyethylene squirt bottle. Then it will be the plate in the example; 2 described copper plating bath immersed. Subject to the copper plating of the image areas, the copper image is treated with 5 percent phosphoric acid and then colored. Using the lithographic stone method one obtains true-to-page reproductions of the original picture "

Example 9

An aluminum sheet grained with the brush is recorded with a graphite pen (Dixon Ticonderoga 1388 Wr * 2 "5). Then the plate is in an electroplating bath! which contains 1.5 ^c / o copper sulfate, 'connected as an anode. After electrolysis for 120 seconds at a voltage of 5.0 V, a dense, shiny copper coating has selectively deposited on the image areas.

Example 10

Mari works according to example 2, but does not draw the picture directly on, but transfers a charcoal image from a transfer sheet, as described in U.S. Patents 2,588,803 and 3,131,106, and finally receives a copper-plated one Image on the carrier. When using the carbon image on an aluminum sheet by printing with a printing press an ink containing carbon particles or by using an ink containing carbon particles electrical or xerographic toning agent applied after developing according to Example 2, a similar copper-plated image is obtained.

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The metal plates thus provided with images are used for production of printed productions of the recorded *

■ ■ ■ * · "

Images are used and these are made with printed reproductions of the same image compared, but using the known method of the photograph production of a lithographic plate have been made. With the photographic The highlighted areas of the image have been lost, and attempts to remove the highlighted areas to improve lead to undesirable changes in density in the remaining parts of the image. The differences between the prints produced by the process according to the invention and the photographically produced prints lead to the photographic Chemists conclude that photographic dodging or shielding must be used in order to be · photographic to receive printed impressions relating to ' their clarity and line sharpness those produced according to the invention Resemble prints.

When the new plates are used for printing, it receives a mirror image of the recorded one can be obtained by direct printing Image, while offset printing provides an exact duplicate of the originally recorded image.

With those produced by the process according to the invention Plates are obtained with an almost completely correct tonal value Playback of the recorded original image. "

For the purposes of the invention, the recording medium special for metal supports, the shape of the usual "pencils" 'have, which include those who have the recording medium made of bound lead (oxides of lead), made of graphite or consists of other carbonaceous substances.

3TAAtIU _ba d

Claims (11)

• September 11, 1970 Itek Corporation. JPS-8366 Patent application back • ——————————. — __— ■ _——— Process for the production of metal pictures on carriers, characterized in that an image is recorded on a support with a nucleating image recording medium and by treating the carrier provided with the recording with a metal image-forming agent Metal image generated on the carrier provided with the recording. 2. The method according to claim 1, · characterized in that the image recording agent used is carbon or printing ink used. 3. The method according to claim 1 or 2, characterized by dadurck, the treatment with the imaging agent is the same • continues for a long time until the resulting metal image attaches to the Carrier adheres. 4. The method according to claim 1 to 3, characterized in that a plastic carrier or a metal carrier used. · " 5. The method according to claim 1 to 4, characterized in that that a metallizing bath is used as the imaging agent used. - 30 - 109830/114 4 '· BAD ORIGINAL JFS-8366 ■ ■ 6. The method according to claim 1 to 4, characterized in that that one contains a metal ion as an imaging agent endd solution used. .. · 7. The method according to claim 1 to 4, characterized in that that a streamless ketallizing bath is used as the imaging agent used. 8. The method according to claim 5 to 7, characterized in that the metallization is carried out with silver or copper • leads. "' 9. The method according to claim 7 »characterized in that one with a metallizing bath containing copper (II) ions is working. 10. The method according to claim 7, characterized in that one works with a metallization bath, which is complex Contains copper (II) anions. 11. The method according to claim 10, characterized in that one works with a metallization bath, which copper (II) ethylenediarainetraacetate or copper (II) nitrilotriacetate contains. ■. · 12. The method according to claim 1 to 11, characterized in that a metal carrier is used. 13. The method according to claim 12, characterized in that an aluminum carrier is used. 14. The method according to claim 12, characterized in that a carrier with a grained, porous or matt surface is used. .'.- .. ■ 15. The method according to claim 14, characterized in that an aluminum support is used, the porous surface of which is made of aluminum oxide. ■ - 31- ■ '.. · 109830/1 TU • ■ ■ ■. ·. ·· ■■■ - ■. _BATH ORIGINAL 16. Ancestors according to claim -1 to 15, characterized in that that you can paint the picture with a pencil, with a typewriter or by printing. 17ο method according to claim 1 to 16 ,. characterized, that a conductive image recording medium is used, 18. The method according to claim 1 to 17, characterized in that the process product is processed into a printing plate. 19 · Image medium, characterized in that it consists of a :; 2ragor and a metal image which is recorded on the support with a conductive image recording medium Share corresponds. 20. Medium according to claim 19, characterized in that the Tr: ig he is a metal wearer. 21. Hedium according to claim 20, characterized in that the Metal image is bound to the carrier. 22. Medium according to claim 19 'ois 21, characterized in that the carrier consists of aluminum _c 23. Medium nach'Anspruch 19 to 22, characterized in that ■ that the conductive image recording medium made of carbon "Substance consists and through. treatment with. an electroless η Motaliisierungslösung to a coherent metal picture lets develop. ο Mod ium lu-ch claim 19 "^ is 23, thereby g ^ markzeiclme ^, c .-. ss the TrM.'er has a granular, porous or matt-Cb ^ r- £ 1 ache. .25 ,. MtciiuE according to claim 19 Oi · 3 24, characterized in that gc ^ .- rin the Keta-11 is at least as noble as copper f Π 9 ° J '/ 11U BATH ORIGINAL 26. Medium according to claim 25, characterized in that daoa aas Metal is silver or copper. . ' - '53' - 109830/1 UA BAD ORlQiNAL