DK143948B - PROCEDURE FOR POWERFUL COPPER COVERING AND BATH FOR USE IN THE PROCEDURE - Google Patents
PROCEDURE FOR POWERFUL COPPER COVERING AND BATH FOR USE IN THE PROCEDURE Download PDFInfo
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- DK143948B DK143948B DK23573AA DK23573A DK143948B DK 143948 B DK143948 B DK 143948B DK 23573A A DK23573A A DK 23573AA DK 23573 A DK23573 A DK 23573A DK 143948 B DK143948 B DK 143948B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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Description
U3948U3948
Den foreliggende opfindelse angår en fremgangsmåde til strømløs kobberovertrækning af genstande og af den i krav l's indledning angivne art.BACKGROUND OF THE INVENTION The present invention relates to a method for the electroless copper coating of articles and of the kind set forth in the preamble of claim 1.
Yed strømløs kobberovertrækning kan man i en alkalisk rea-5 gerende opløsning anvende formaldehyd som reduktionsmiddel for cupriioner. Sådanne opløsninger er autokatalytiske og er derfor hyppigt ustabile, d.v.s. de har tilbøjelighed til at frigive kobber for tidligt. Der kendes mange metoder til at formindske autodekompositionen af strømløs kobberover-10 trækningsbade. Anvendelsen af stærke cheleringsmidler, såsom ethylendiaminotetraeddikesyre (EDTA), kan f.eks. medvirke til at formindske dekompositionshastigheden. En sådan fremgangsmåde kendes fra beskrivelsen til U.S.A. patent nr.For an electroless copper coating, in an alkaline reacting solution, formaldehyde can be used as a reducing agent for cup ions. Such solutions are autocatalytic and are therefore frequently unstable, i.e. they tend to release copper prematurely. Many methods are known for reducing the autodecomposition of powerless copper coating baths. The use of strong chelating agents, such as ethylenediaminotetraacetic acid (EDTA), can be e.g. help decrease the decomposition rate. Such a method is known from the disclosure to U.S.A. patent no.
3 119 709. Chelering giver dog ikke en fuldstændig tilfreds-15 stillende stabilisering,og i mange tilfælde formindskes udfældningshastigheden for metallet, hvorved overtrækningspro-cessen bliver teknisk værdiløs.However, chelation does not provide a fully satisfactory stabilization, and in many cases the precipitation rate of the metal is reduced, thereby rendering the coating process technically worthless.
Det har endvidere vist sig, at cuproionen er yderst aktiv til at fremkalde autodekomposition i strømløse kobberovertræk-20 ningsopløsninger. Til reduktion af cuproionkoncentrationen er det kendt at boble luft eller oxygen gennem strømløse overtrækningsopløsninger, se f.eks. U.S.A. patentskrift nr.Furthermore, it has been found that the cup ion is highly active in inducing autodeposition in powerless copper coating solutions. For reducing the cuprous ion concentration, it is known to bubble air or oxygen through powerless coating solutions, see e.g. U.S.A. patent specification no.
2 938 805. Ved denne metode omdannes cuproion til cupriion, hvilket benyttes almindeligt i praksis. Hvis denne metode anvendes 25 alene til stabilisering af badet, fremkommer to hovedulemper.2 938 805. This method converts cuproion into cupriion, which is commonly used in practice. If this method is used alone to stabilize the bath, two major drawbacks appear.
For eksempel har de udfældede overtræk sædvanligvis et mørkt og ikke-metallisk udseende, sandsynligvis som følge af et ydre lag af cuprioxid, og for det andet forflygtiges en stor mængde formaldehyd, når oxygenet passerer gennem opløsningen, 30 hvorved det er vanskeligt at opretholde konstante koncentrationer af kemikalierne.For example, the precipitated coatings usually have a dark and non-metallic appearance, probably due to an outer layer of cuprioxide, and secondly, a large amount of formaldehyde is volatile as the oxygen passes through the solution, making it difficult to maintain constant concentrations. of the chemicals.
Anvendelsen af små mængder af forskellige kemikalier, der kan gøre cuproionen komplex, er ligeledes velkendt til forøgelsen af stabiliteten af strømløse kobberovertrækningsop- 2 143948 løsninger. Typiske additiver er cyanider, nitriler, uorganiske sulfider og forskellige organiske divalente svovlforbindelser, se beskrivelsen til U.S.A. patent nr. 3 095 309 og 3 361 580. Sædvanligvis har også disse additiver flere ulemper. Ofte for-5 øger de kun i ringe grad anvendelsestiden for de strømløse kobberovertrækningsopløsninger, og hvis stabiliteten forøges væsentligt, bliver udfældningshastigheden og kvaliteten af det udfældede metal sædvanligvis forringet. Det har derfor været nødvendigt at indgå et kompromis mellem stabiliteten 10 af de strømløse opløsninger og kvaliteten og kvantiteten af det udfældede metal.The use of small amounts of various chemicals that can make the cuprous ion complex is also well known for the enhancement of the stability of powerless copper coating solutions. Typical additives are cyanides, nitriles, inorganic sulfides and various organic divalent sulfur compounds, see the description for U.S.A. Patent Nos. 3,095,309 and 3,361,580. Usually, these additives also have several disadvantages. Often, they only slightly increase the useful life of the copperless coating solutions, and if the stability is significantly increased, the precipitation rate and the quality of the precipitated metal are usually degraded. Therefore, it has been necessary to compromise between the stability 10 of the powerless solutions and the quality and quantity of the precipitated metal.
Ved fremgangsmåden ifølge den foreliggende opfindelse kan strømløse kobberovertrækningsopløsninger stabiliseres over et stort temperaturområde i overordentlig lang tid, uden at 15 det går ud over kvaliteten, farven eller hastigheden for metaludfældningen. Det omhandlede strømløse bad kan anvendes kontinuerligt og med høj effektivitet, når de ved overtrækningen forbrugte bestanddele erstattes til opretholdelse af uforandret koncentration.In the process of the present invention, copperless coating solutions can be stabilized over a large temperature range for an extremely long time without compromising the quality, color or speed of the metal precipitation. The present powerless bath can be used continuously and with high efficiency when the components consumed by the coating are replaced to maintain unchanged concentration.
20 De ved fremgangsmåden ifølge opfindelsen anvendte bade kan tåle gentagne opvarmninger og afkølinger og vil sædvanligvis virke effektivt ved stuetemperatur. De dannede kobberovertræk er klart lyserøde og består af rent kobbermetal. De er fri for mørke og kornede områder med kobberoxider, der sædvanlig-25 vis ses ved hidtil kendte udfældninger.The baths used in the process of the invention can withstand repeated heating and cooling and will usually operate effectively at room temperature. The copper coatings formed are clearly pink and consist of pure copper metal. They are free of dark and grainy areas with copper oxides, which are usually seen in previously known precipitates.
Fremgangsmåden ifølge opfindelsen er ejendommelig ved, at den til overtrækningen anvendte alkaliske vandige -opløsning indeholder en primær stabilisator med den almene formel: ^"(X) S \ " ^:p-(z)r* R(Y) hvor R og R'" er ens eller forskellige og betyder en alkyl-30 gruppe med 1-12 carbonatomer, fortrinsvis 1-4 carbon- atomer, en phenyl- eller naphthylgruppe, X, Y og Z er oxygen U3948 3 eller svovl, idet X og Y fortrinsvis er oxygen, og RT sammen med Z betyder en sur gruppe, der kan hydrolysere i den alkaliske opløsning. Opfindelsen angår endvidere et bad til brug ved udøvelse af fremgangsmåden, og af den i krav 5 8's indledning angivne art, hvilket bad er ejendommeligt ved det i den kendetegnende del af krav 8 anførte.The process according to the invention is characterized in that the alkaline aqueous solution used for the coating contains a primary stabilizer of the general formula: ^ (X) S ': p- (z) r * R (Y) where R and R "" is the same or different and means an alkyl group having 1-12 carbon atoms, preferably 1-4 carbon atoms, a phenyl or naphthyl group, X, Y and Z are oxygen or sulfur, X and Y being preferably The invention also relates to a bath for use in the practice of the process, and of the kind set forth in the preamble of claim 58, which bath is peculiar to it. in the characterizing part of claim 8.
Eksempler på typiske egnede stabilisatorer er følgende: diethyl-p-nitrophenyl-phosphat, diethyl-p-nitrophenyl-thiono-phosphat (Parathion), dimethyl-S-2-ethylthioethyl-thiolphos-10 phat, monomethylamid af 0,0-dimethyldithiophosphoryleddike-syre, diethylester af 0,0-dimethyldithiophosphoryl-ravsyre (Malathion), dimethyl-l-hydroxy-2,2,2-trichlorethyl-phosphonat og diethyl-2-isopropyl-4-methyl-pyrimid-6-yl-thionophosphat.Examples of typical suitable stabilizers are the following: diethyl p-nitrophenyl phosphate, diethyl p-nitrophenyl thiono phosphate (Parathion), dimethyl S-2-ethylthioethyl thiolphosphate, monomethyl amide of 0.0-dimethyldithiophosphoryl acetic acid. acid, diethyl ester of 0,0-dimethyldithiophosphoryl succinic acid (Malathion), dimethyl-1-hydroxy-2,2,2-trichloroethyl phosphonate and diethyl-2-isopropyl-4-methyl-pyrimid-6-yl-thionophosphate.
Særlig effektive primære stabilisatorer er diethyl-p-nitro-15 phenylthionophosphat og diethylester af 0,O-dimethyl-dithio-phosphoryl-ravsyre, kendt under trivialnavnene henholdsvis Parathion og Malathion.Particularly effective primary stabilizers are diethyl p-nitro-phenylthionophosphate and diethyl ester of O-dimethyl-dithio-phosphoryl succinic acid, known by the trivial names Parathion and Malathion, respectively.
For yderligere at forbedre stabiliteten af det strømløse overtrækningsbad og egenskaberne for det udfældede overtræk foretrækkes det ved den omhandlede fremgangsmåde at anvende 20 en alkalisk vandig opløsning, der yderligere indeholder en sekundær stabilisator med den almene formel:In order to further improve the stability of the electroless coating bath and the properties of the precipitated coating, it is preferred to use in the present process an alkaline aqueous solution which further contains a secondary stabilizer of the general formula:
R"X' - (CH2) .....-CHR "X" - (CH 2) .....- CH
hvor R" er en alkylgruppe med 1-12 carbonatomer, en phenyl-eller naphthylgruppe eller en substitueret phenyl- eller naphthylgruppe, X’ er en thio-, sulfonyl-, sulfoxid-, oxy-, 25 carbonyl- eller iminogruppe, n er 1, 2 eller 3, eller R*X* er imid eller en heterocyclisk ring, bestående af nitrogen og carbon, med eller uden oxygen. Den sekundære stabilisator er således en propargylforbindelse, og eksempler herpå er N-propargylphthalimid, N-propargyloxy-phthalimid, N-propar-30 gylmaleimid, N-propargylsuccinimid, N-alkyl-N-propargylamider, N,N-dialkyl-N-propargylaminer, aryl- og alkylpropargylethere, 143948 4 aryl- og alkylpropargylthioethere, aryl- og alkylpropargyl-ketoner og aryl- og alkylpropargylsulfoner.wherein R "is an alkyl group of 1-12 carbon atoms, a phenyl or naphthyl group or a substituted phenyl or naphthyl group, X 'is a thio, sulfonyl, sulfoxide, oxy, carbonyl or imino group, n is 1 , 2 or 3, or R * X * is imide or a heterocyclic ring consisting of nitrogen and carbon, with or without oxygen, thus the secondary stabilizer is a propargyl compound and examples thereof are N-propargylphthalimide, N-propargyloxy-phthalimide, N-propargylmaleimide, N-propargylsuccinimide, N-alkyl-N-propargylamides, N, N-dialkyl-N-propargylamines, aryl and alkylpropargyl ethers, aryl and alkylpropargylthioethers, aryl and alkylpropargyl ketones and aryl and alkyl propargyl sulfones.
De omhandlede strømløse kobberovertrækningsbade er alkaliske opløsninger indeholdende cupriioner, mindst ét komplexdan-5 nende middel for cupriioner og et aktivt reduktionsmiddel. Alkaliniteten kan opnås ved tilsætning af natrium- eller kaliumhydroxider, - carbonater eller -phosphater eller andre baser. Den foretrukne base er en blanding af et alkalimetal-hydroxid og -carbonat. Denne blanding er økonomisk og mulig-10 gør en sikker kontrol af pH-værdien. Natriumsaltene foretrækkes sædvanligvis på grund af deres lave pris.The present electroless copper coating baths are alkaline solutions containing cup rions, at least one complexing agent for cup rions, and an active reducing agent. The alkalinity can be obtained by the addition of sodium or potassium hydroxides, carbonates or phosphates or other bases. The preferred base is a mixture of an alkali metal hydroxide and carbonate. This mixture is economical and allows for a safe control of the pH. The sodium salts are usually preferred because of their low cost.
Egnede kilder for cupriion er vandopløselige cuprisalte, såsom cuprisulfat, cuprinitrat, cuprichlorid og cupriacetat.Suitable sources of cupri ion are water-soluble cupric salts such as cupris sulfate, cuprinitrate, cuprichloride and cupriacetate.
Ved fremgangsmåden ifølge opfindelsen foretrækkes cuprisulfat, 15 fordi det er billigt og let tilgængeligt.In the process of the invention, cupric sulfate is preferred because it is cheap and readily available.
Egnede komplexdannende midler for cupriionen er triethanol-amin, tetrakis-N,N,N,N-hydroxypropylethylendiamin, salte af nitrilotrieddikesyre, salte af ethylendiaminacetat og salte af hydroxycarboxylsyre, såsom gluconsyre, citronsyre eller 20 vinsyre. Blandinger af salte af ethylendiaminotetraeddikesyre og vinsyre er foretrukne komplexdannende midler, hvorved opnås optimal badstabilitet og udfældningsegenskaber af badet ifølge opfindelsen.Suitable complexing agents for the cupri ion are triethanolamine, tetrakis-N, N, N, N-hydroxypropylethylenediamine, salts of nitrilotriacetic acid, salts of ethylenediamine acetate, and salts of hydroxycarboxylic acid such as gluconic acid, citric acid or tartaric acid. Mixtures of salts of ethylenediaminotetraacetic acid and tartaric acid are preferred complexing agents, thereby achieving optimum bath stability and precipitation properties of the bath of the invention.
Egnede reduktionsmidler er formaldehyd eller derivater deraf, såsom paraformaldehyd. Formaldehydet anvendes fortrinsvis i 25 form af vandige opløsninger, da disse er billige og let tilgængelige.Suitable reducing agents are formaldehyde or derivatives thereof, such as paraformaldehyde. The formaldehyde is preferably used in the form of aqueous solutions as these are inexpensive and readily available.
Der kan anvendes andre additiver, såsom overflade-aktive stoffer, til forbedring af de omhandlede strømløse kobber-overtrækningsbade.Other additives, such as surfactants, can be used to improve the subjectless copper coating baths.
Sådanne bade kan pr. liter indeholde 0,002 - 0,15 mol, for- 5 143948 trinsvis 0,002 - 0,04 mol kobbersulfat. Alkaliindholdet skal være af en sådan størrelse, at pH-værdien bliver 10,5 - 14, fortrinsvis 13,0 - 13,5. Mængden af formaldehyd eller et derivat deraf bør være 0,06 - 1,3 mol, fortrinsvis 0,25 -5 0,50 mol. Mængden af komplexdannende middel bør være 1-4 gange så stor som indholdet af kobber udtrykt i mol, fortrinsvis 2 - 2,5 gange.Such baths can per. liters contain 0.002 - 0.15 mol, preferably 0.002 - 0.04 mol of copper sulfate. The alkali content should be such that the pH is 10.5 - 14, preferably 13.0 - 13.5. The amount of formaldehyde or a derivative thereof should be 0.06 - 1.3 mol, preferably 0.25 -5 0.50 mol. The amount of complexing agent should be 1-4 times the content of copper expressed in moles, preferably 2 - 2.5 times.
Som oven for anført er den omhandlede strømløse kobberovertræk-’ ningsopløsning stabil i lang tid ved stuetemperatur. Den kan endvidere modstå opvarmninger til 50°C eller derover og i nogle 10 tilfælde til kogepunktet uden skadelige virkninger.As mentioned above, the present electroless copper coating solution is stable for a long time at room temperature. It can also withstand heating to 50 ° C or above and in some 10 cases to the boiling point without harmful effects.
De omhandlede strømløse overtrækningsopløsninger holdes fortrinsvis på en vægtfylde på 1,04 - 1,05 ved en temperatur på 24 - 27° C. Under disse betingelser kan der opnås en udfældningshastighed svarende til en femogtyve milliontedel mm pr.Preferably, the streamless coating solutions in question are maintained at a density of 1.04 - 1.05 at a temperature of 24 - 27 ° C. Under these conditions, a precipitation rate corresponding to twenty-five millionths of a mm can be obtained.
15 minut. Ved højere temperatur vil udfældningshastigheden forøges.15 minutes. At higher temperature, the precipitation rate will increase.
I praksis kan den strømløse overtrækningsopløsning opretholdes i en plastbeholder eller en metalbeholder, der er plastbeklædt, ved en temperatur på 21 - 38°C, fortrinsvis under mekanisk omrøring. De genstande, som skal overtrækkes, 20 renses og sensibiliseres, hvis det er nødvendigt, på kendt måde. De genstande, der skal overtrækkes, neddykkes sædvanligvis i 10 - 30 minutter, hvilket er tilstrækkeligt til dannelse af den ønskede overtrækningstykkelse. Om ønsket kan man udfælde mere metal elektrolytisk.In practice, the powerless coating solution can be maintained in a plastic container or a metal container coated in plastic at a temperature of 21 - 38 ° C, preferably with mechanical stirring. The articles to be coated are cleaned and sensitized, if necessary, in known manner. The articles to be coated are usually submerged for 10 - 30 minutes, which is sufficient to form the desired coating thickness. If desired, more metal can be precipitated electrolytically.
25 Den overflade, der skal overtrækkes, må være fri for fedtstoffer og andre forureninger. Hvis en ikke-metallisk overflade skal overtrækkes, behandles overfladen hensigtsmæssigt først med sensibiliserings- og podeopløsninger, såsom stanno-chlorid (SnCl2), efterfulgt af en behandling med fortyndet 30 opløsning af palladiumchlorid (PdCl2). Hvis man skal behandle en metaloverflade, f.eks. rustfrit stål, må den affedtes og 143948 6 derefter behandles med en syre, såsom saltsyre eller phosphor-syre til at befri overfladen for ethvert spor af oxid. Hvis aflejringen skal ske på en genstand af plast eller keramik, der er imprægneret med cuprooxid (Cu^O), neddykkes den rensede 5 genstand i det strømløse overtrækningsbad, hvor den holdes, indtil.aflejringen er tilstrækkelig tyk.25 The surface to be coated must be free of grease and other contaminants. If a non-metallic surface is to be coated, the surface is suitably first treated with sensitization and grafting solutions, such as stannous chloride (SnCl2), followed by a diluted solution of palladium chloride (PdCl2). If one has to treat a metal surface, e.g. stainless steel, it must be degreased and then treated with an acid such as hydrochloric acid or phosphoric acid to free the surface of any trace of oxide. If the deposition is to be done on a plastic or ceramic article impregnated with cuprous oxide (Cu 2 O), the purified article is immersed in the powerless coating bath where it is held until the deposit is sufficiently thick.
Opfindelsen skal i det følgende illustreres nærmere ved hjælp af nogle eksempler: EKSEMPEL 1The invention will be further illustrated by the following examples: EXAMPLE 1
Der fremstilles strømløse kobberovertrækningsopløsninger.Copperless coating solutions are prepared.
10 Sammensætningen af disse opløsninger er følgende: Til ca. en halv liter vand sættes i den i efterfølgende tabel angivne rækkefølge de nævnte forbindelser. Forud for tilsætningen bliver stabilisatorerne solvatiseret med et hjælpeopløsningsmiddel, såsom glycolether, således som det vil forstås af fag-15 manden. Efter at alle komponenter er tilsat, tilsættes vand til et totalt rumfang på én liter. Hver af opløsningerne indeholder.9,25 gram CuS0^.5H20, 16 gram NaOH, 5 gram Na2C0^ og 30 gram 37% formaldehyd.The composition of these solutions is as follows: For approx. half a liter of water is added to the listed compounds in the order given in the following table. Prior to the addition, the stabilizers are solvated with an auxiliary solvent such as glycol ether, as will be understood by those skilled in the art. After all components are added, water is added to a total volume of one liter. Each of the solutions contains 9.25 grams of CuSO 2 .5H 2 O, 16 grams of NaOH, 5 grams of Na 2 CO 2, and 30 grams of 37% formaldehyde.
Af efterfølgende tabel fremgår indholdet af andre forbindelser i opløsningerne:The following table shows the content of other compounds in the solutions:
20 ’ TABEL A20 'TABLE A
Forbindelse OnTøsning nummer 1 2 3 4 5 6Connection OnSolution number 1 2 3 4 5 6
Rochelle- salt g 16,6 16,6 33,2 33,2 33,2 33,2Rochelle salt g 16.6 16.6 33.2 33.2 33.2 33.2
Na/EDTA.Na / EDTA.
2HJ0, g 16,6 16,6 - - 33,2 33,2 25 Malathion, g 0,005 0,005 0,0025 0,005 0,0025 0,0025 M-Propargyl- phthalimid,g 0,005 - 0,0025 - 0,0025 7 1439482HJO, g 16.6 16.6 - 33.2 33.2 25 Malathion, g 0.005 0.005 0.0025 0.005 0.0025 0.0025 M-Propargylphthalimide, g 0.005 - 0.0025 - 0.0025 143948
Accelererede stabilitetsprøver udføres ved at indføre ovennævnte opløsninger i tilsmeltede glasbeholdere, der opbevares ved 54° C i indtil 12 dage. Efterfølgende tabel viser tabet af cupriion udtrykt i procent efter forskellige opbevaringstider.Accelerated stability tests are carried out by introducing the above solutions into molten glass containers stored at 54 ° C for up to 12 days. The following table shows the loss of cupriion, expressed as a percentage after different storage times.
5 TABEL BTABLE B
Procent tab af cupriion Tid ved 54°C Opløsning nummer 1 2 3 4 5 6 Kontrol3*^ 1 time nd nd nd tr nd nd 20 10 2 tim r nd nd 10 10 nd nd 50.Percent loss of cupriion Time at 54 ° C Resolution number 1 2 3 4 5 6 Control3 * ^ 1 hour nd nd nd tr nd 20 10 2 h r nd nd 10 10 nd nd 50.
3 timer nd nd - - tr tr 75 4 timer nd nd 50 20 10 - 5 timer nd tr - - 10 100 6 timer tr - - 30 15 15 72 timer 15 15 100 100 12 dage 50 50 50 40 x) Samme som opløsning nr. 2 uden tr = Spor3 hours nd nd - - tr tr 75 4 h nd nd 50 20 10 - 5 h nd tr - - 10 100 6 h tr - - 30 15 15 72 hrs 15 15 100 100 12 days 50 50 50 40 x) Same as solution # 2 without tr = Trace
Malathion nd = ikke på viseligMalathion nd = not visibly
Af ovennævnte tabel fremgår det, at de omhandlede opløsninger 20 har en betydelig forbedret stabilitet i forhold til kontrolopløsningen. En opløsning svarende til opløsning 1 med den ændring, at man ikke tilsætter Malathion, har i det væsentlige samme stabilitet som kontrolprøven, selv om 0,005 gram phthalimid er tilsat. For at demonstrere effektiviteten af de omhandlede 25 kobberovertrækningsopløsninger anvendes hver af de syv opløsninger til at overtrække plader af epoxyplast. Pladerne skrubbes og sensibiliseres på i og for sig kendt måde. De sensibiliserede plader neddykkes i separate bægerglas, der hvert indeholder ovennævnte opløsning, ved 24°C og ved en pH-værdi på 13,3 i 30 10 minutter. Efterfølgende tabel viser den opnåede overtrækningstykkelse for hver af opløsningerne: 143948 8From the above table it can be seen that the present solutions 20 have a significantly improved stability over the control solution. A solution corresponding to solution 1 with the change of not adding Malathion has substantially the same stability as the control sample, although 0.005 grams of phthalimide is added. To demonstrate the effectiveness of the 25 copper coating solutions in question, each of the seven solutions is used to coat epoxy plastic sheets. The plates are scrubbed and sensitized in a manner known per se. The sensitized plates are immersed in separate beaters, each containing the above solution, at 24 ° C and at a pH of 13.3 for 30 minutes. The following table shows the obtained coating thickness for each of the solutions: 143948 8
TABEL CTABLE C
Opløsning nummer Tykkelse (udtrykt i/um) efter 10 minutter 1 0,305 2 0,330 3 0,251 4 0,193 5 5 0,269 6 0,307Resolution number Thickness (in µm) after 10 minutes 1 0.305 2 0.330 3 0.251 4 0.193 5 5 0.269 6 0.307
Kontrol 0,518 I hvert tilfælde, bortset fra kontrolopløsningen, opnåedes kobberlag med en tykkelse på 0,2 - 0,33 /um, svarende til en overtrækningshastighed på 20 - 33 nm pr. minut. Kobberlaget 10 er af en udmærket kvalitet, har en lyserød farve og er fri for urenheder. En særlig god kvalitet opnås, når der tilsættes en sekundær stabilisator.Control 0.518 In each case, except for the control solution, copper layers with a thickness of 0.2 - 0.33 µm were obtained, corresponding to a coating rate of 20 - 33 nm per minute. minute. The copper layer 10 is of excellent quality, has a pink color and is free of impurities. Particularly good quality is achieved when a secondary stabilizer is added.
Selvom overtrækningshastigheden for kontrolopløsningen er noget hurtigere, er kobberlaget ikke af en god kvalitet, 15 idet det indeholder dekomponeringsprodukter, som viser sig ved mørke og grålige områder på pladen.Although the coating speed of the control solution is somewhat faster, the copper layer is not of a good quality, as it contains decomposition products which appear in dark and gray areas on the plate.
Af denne sammenligning fremgår, at de omhandlede strømløse kobberovertrækningsopløsninger er stabile og giver overtræk af høj kvalitet med tilfredsstillende udfældningshastigheder.This comparison shows that the present copperless coating solutions are stable and provide high quality coatings with satisfactory precipitation rates.
20 De optimale betingelser kan variere noget efter arten af genstanden og overtrækningsbetingelserne.The optimal conditions may vary somewhat depending on the nature of the object and the coating conditions.
EKSEMPEL 2EXAMPLE 2
For at vise anvendelsen af andre stabilisatorer fremstilles flere opløsninger. Disse er identiske med den i eksempel 1 beskrevne opløsning nr, 5 med den ændring, at der som stabi-25 lisator anvendes 0,005 gram af forskellige dialkylmercapto-thionphosphater i stedet for Malathion. Ved at anvende de i eksempel 1 viste prøver fås følgende stabilitet og overtræk-* ningshastigheder: 9 143948To show the use of other stabilizers, several solutions are prepared. These are identical to Solution 5, described in Example 1, with the change that 0.005 grams of various dialkylmercaptothione phosphates are used instead of Malathion as a stabilizer. By using the samples shown in Example 1, the following stability and coating rates are obtained: 9 143948
TABEL DTABLE D
Overtrækningstykkelse % tab efter 72 Stabilisator_(i yum) efter 10 min._timer ved 54°CCoating thickness% loss after 72 Stabilizer (in yum) after 10 min_hours at 54 ° C
Dimethylmercapto- thionphosphat 0,358 15Dimethyl mercaptothione phosphate 0.358 15
Diethylmercapto- thionphosphat 0,358 15Diethylmercaptothione phosphate 0.358 15
Di-n-propylmercapto- thionphosphat 0,383 15 5 Ved hver af prøverne opnås kobberovertræk af en udmærket kvalitet, med lyserød farve og fri for urenheder.Di-n-propylmercaptothione phosphate 0.383 15 5 Copper coatings of excellent quality, pink in color and free of impurities are obtained for each of the samples.
EKSEMPEL 3EXAMPLE 3
Fremgangsmåden ifølge eksempel 1 gentages til fremstilling af en opløsning, som er identisk med opløsning nr. 1 med den ændring, at 0,005 gram N-propargyloxyphthalimid anvendes i 10 stedet for N-propargylphthalimid. Derved opnås tilsvarende resultater som ved anvendelse af opløsning nr. 1.The procedure of Example 1 is repeated to prepare a solution identical to solution # 1 with the change that 0.005 grams of N-propargyloxyphthalimide is used in place of N-propargylphthalimide. This results in similar results to that of solution # 1.
Claims (9)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21845972A | 1972-01-17 | 1972-01-17 | |
| US21845972 | 1972-01-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK143948B true DK143948B (en) | 1981-11-02 |
| DK143948C DK143948C (en) | 1982-04-19 |
Family
ID=22815208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK23573A DK143948C (en) | 1972-01-17 | 1973-01-16 | PROCEDURE FOR POWERFUL COPPER COVERING AND BATH FOR USE BY THE PROCEDURE |
Country Status (23)
| Country | Link |
|---|---|
| US (1) | US3790392A (en) |
| JP (1) | JPS5519983B2 (en) |
| AT (1) | AT320372B (en) |
| AU (1) | AU464729B2 (en) |
| BE (1) | BE794048A (en) |
| CH (1) | CH599981A5 (en) |
| DD (1) | DD107490A5 (en) |
| DE (1) | DE2300748C3 (en) |
| DK (1) | DK143948C (en) |
| ES (1) | ES410652A1 (en) |
| FI (1) | FI54500C (en) |
| FR (1) | FR2168364B1 (en) |
| GB (1) | GB1414896A (en) |
| HK (1) | HK65076A (en) |
| IL (1) | IL41331A (en) |
| IT (1) | IT980460B (en) |
| LU (1) | LU66834A1 (en) |
| NL (1) | NL177330C (en) |
| NO (1) | NO135188C (en) |
| PL (1) | PL94000B1 (en) |
| RO (1) | RO69172A (en) |
| SE (1) | SE387664B (en) |
| ZA (1) | ZA73328B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL164906C (en) * | 1975-08-19 | 1981-02-16 | Philips Nv | PROCESS FOR PREPARING AN AQUEOUS ALKALINE SELLER BATH. |
| JPS60159328U (en) * | 1984-03-31 | 1985-10-23 | 株式会社 高津製作所 | Oil level gauge with drain alarm |
| US4666858A (en) * | 1984-10-22 | 1987-05-19 | International Business Machines Corporation | Determination of amount of anionic material in a liquid sample |
| US5626736A (en) | 1996-01-19 | 1997-05-06 | Shipley Company, L.L.C. | Electroplating process |
| EP2639335B1 (en) | 2012-03-14 | 2015-09-16 | Atotech Deutschland GmbH | Alkaline plating bath for electroless deposition of cobalt alloys |
| CN103225092A (en) * | 2013-05-22 | 2013-07-31 | 南通鑫平制衣有限公司 | Plated copper for plastics |
| JP6176841B2 (en) * | 2013-07-19 | 2017-08-09 | ローム・アンド・ハース電子材料株式会社 | Electroless copper plating solution |
| US10060034B2 (en) | 2017-01-23 | 2018-08-28 | Rohm And Haas Electronic Materials Llc | Electroless copper plating compositions |
| US10655227B2 (en) | 2017-10-06 | 2020-05-19 | Rohm And Haas Electronic Materials Llc | Stable electroless copper plating compositions and methods for electroless plating copper on substrates |
| US10294569B2 (en) | 2017-10-06 | 2019-05-21 | Rohm And Haas Electronic Materials Llc | Stable electroless copper plating compositions and methods for electroless plating copper on substrates |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1192021B (en) * | 1963-01-12 | 1965-04-29 | Dehydag Gmbh | Galvanic baths |
| US3457089A (en) * | 1967-04-07 | 1969-07-22 | Shipley Co | Electroless copperplating |
| US3635758A (en) * | 1969-08-04 | 1972-01-18 | Photocircuits Corp | Electroless metal deposition |
-
0
- BE BE794048D patent/BE794048A/en not_active IP Right Cessation
-
1972
- 1972-01-17 US US00218459A patent/US3790392A/en not_active Expired - Lifetime
-
1973
- 1973-01-05 AU AU50768/73A patent/AU464729B2/en not_active Expired
- 1973-01-08 DE DE2300748A patent/DE2300748C3/en not_active Expired
- 1973-01-08 AT AT13573A patent/AT320372B/en not_active IP Right Cessation
- 1973-01-11 NO NO123/73A patent/NO135188C/no unknown
- 1973-01-12 SE SE7300440A patent/SE387664B/en unknown
- 1973-01-15 FR FR7301315A patent/FR2168364B1/fr not_active Expired
- 1973-01-15 CH CH52373A patent/CH599981A5/xx not_active IP Right Cessation
- 1973-01-15 GB GB207373A patent/GB1414896A/en not_active Expired
- 1973-01-15 LU LU66834A patent/LU66834A1/xx unknown
- 1973-01-16 DK DK23573A patent/DK143948C/en not_active IP Right Cessation
- 1973-01-16 DD DD168260A patent/DD107490A5/xx unknown
- 1973-01-16 ZA ZA730328A patent/ZA73328B/en unknown
- 1973-01-16 ES ES410652A patent/ES410652A1/en not_active Expired
- 1973-01-16 FI FI117/73A patent/FI54500C/en active
- 1973-01-16 IT IT67057/73A patent/IT980460B/en active
- 1973-01-16 NL NLAANVRAGE7300599,A patent/NL177330C/en not_active IP Right Cessation
- 1973-01-17 IL IL41331A patent/IL41331A/en unknown
- 1973-01-17 RO RO7373524A patent/RO69172A/en unknown
- 1973-01-17 PL PL1973160307A patent/PL94000B1/pl unknown
- 1973-01-17 JP JP774073A patent/JPS5519983B2/ja not_active Expired
-
1976
- 1976-10-14 HK HK650/76*UA patent/HK65076A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL41331A (en) | 1975-11-25 |
| NL177330C (en) | 1985-09-02 |
| SE387664B (en) | 1976-09-13 |
| NO135188C (en) | 1977-02-23 |
| HK65076A (en) | 1976-10-22 |
| IL41331A0 (en) | 1973-03-30 |
| DD107490A5 (en) | 1974-08-05 |
| FI54500C (en) | 1978-12-11 |
| NL7300599A (en) | 1973-07-19 |
| RO69172A (en) | 1980-01-15 |
| ES410652A1 (en) | 1976-01-01 |
| LU66834A1 (en) | 1973-03-19 |
| DE2300748C3 (en) | 1975-10-30 |
| GB1414896A (en) | 1975-11-19 |
| FR2168364A1 (en) | 1973-08-31 |
| NO135188B (en) | 1976-11-15 |
| CH599981A5 (en) | 1978-06-15 |
| FR2168364B1 (en) | 1975-03-28 |
| AT320372B (en) | 1975-02-10 |
| ZA73328B (en) | 1973-10-31 |
| AU464729B2 (en) | 1975-09-04 |
| AU5076873A (en) | 1974-07-11 |
| JPS5519983B2 (en) | 1980-05-30 |
| NL177330B (en) | 1985-04-01 |
| DE2300748A1 (en) | 1973-07-26 |
| BE794048A (en) | 1973-07-16 |
| FI54500B (en) | 1978-08-31 |
| DE2300748B2 (en) | 1975-03-13 |
| DK143948C (en) | 1982-04-19 |
| IT980460B (en) | 1974-09-30 |
| US3790392A (en) | 1974-02-05 |
| JPS4999934A (en) | 1974-09-20 |
| PL94000B1 (en) | 1977-07-30 |
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