DE1249048B - Process for electroplating molded structures made of plastics - Google Patents
Process for electroplating molded structures made of plasticsInfo
- Publication number
- DE1249048B DE1249048B DED47901A DE1249048DA DE1249048B DE 1249048 B DE1249048 B DE 1249048B DE D47901 A DED47901 A DE D47901A DE 1249048D A DE1249048D A DE 1249048DA DE 1249048 B DE1249048 B DE 1249048B
- Authority
- DE
- Germany
- Prior art keywords
- electroplating
- plastics
- copper
- structures made
- salt solutions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004033 plastic Substances 0.000 title claims description 8
- 229920003023 plastic Polymers 0.000 title claims description 8
- 238000009713 electroplating Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 title claims description 3
- 239000002253 acid Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 230000000875 corresponding Effects 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-M Sodium 2-anthraquinonesulfonate Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)[O-])=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-M 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L Nickel(II) chloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 1
- 101710043771 PDCL Proteins 0.000 description 1
- 229940074439 POTASSIUM SODIUM TARTRATE Drugs 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- LJCNRYVRMXRIQR-UHFFFAOYSA-L Potassium sodium tartrate Chemical compound [Na+].[K+].[O-]C(=O)C(O)C(O)C([O-])=O LJCNRYVRMXRIQR-UHFFFAOYSA-L 0.000 description 1
- ZGKNDXOLMOFEJH-UHFFFAOYSA-M Sodium hypophosphite Chemical compound [Na+].[O-]P=O ZGKNDXOLMOFEJH-UHFFFAOYSA-M 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K Trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M laurate Chemical class CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000003638 reducing agent Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229940013123 stannous chloride Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin dichloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000011778 trisodium citrate Substances 0.000 description 1
Classifications
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Chemically Coating (AREA)
Description
(UNDESREPUBLIK DEUTSCHLAND(UNDESREPUBLIC OF GERMANY
IEUTSCHESIEUTSCHES
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. Cl.:Int. Cl .:
C23bC23b
Deutsche Kl.: 48 a - 5/64German class: 48 a - 5/64
Nummer: 1 249 048Number: 1 249 048
Aktenzeichen: D 47901 VI b/48 aFile number: D 47901 VI b / 48 a
Anmeldetag: 5. August 1965Filing date: August 5, 1965
Auslegetag: 31. August 1967Opened on August 31, 1967
€250 5-56€ 250 5-56
Es ist bekannt, sogenannte ABS-Polymerisate, d. h. Polymerisate aus Acrylnitril, Butadien und Styrol, in der Weise zu metallisieren, daß man auf die vorbehandelten KunststofToberflächen chemisch einen dünnen Metallfilm aus Kupfer und/oder Nickel aufbringt und anschließend auf galvanischem Wege einen Überzug aus den gleichen oder anderen gewünschten Metallen aufbringt. Versucht man jedoch, auf die gleiche Art und Weise Erzeugnisse aus Polyvinylchlorid, Polyvinylidenchlorid, Polyolefinen, wie Poly- ίο äthylen und Polypropylen, Polystyrol, Polymethacrylsäureestern oder entsprechenden Mischpolymerisaten galvanisch mit Metall zu überziehen, so stellt man fest, daß bereits die chemisch erzeugte Grundierung eine nicht genügende Haftfestigkeit aufweist.It is known that so-called ABS polymers, d. H. Polymers of acrylonitrile, butadiene and styrene, to be metallized in such a way that one is on the pretreated Plastics surfaces chemically applies a thin metal film made of copper and / or nickel and then galvanically a coating of the same or different ones as desired Applies metals. However, if one tries in the same way to produce products made of polyvinyl chloride, Polyvinylidene chloride, polyolefins such as polyethylene and polypropylene, polystyrene, polymethacrylic acid esters or corresponding copolymers to be galvanically coated with metal, it is found that that even the chemically produced primer does not have sufficient adhesive strength.
Es wurde nun gefunden, daß man die erwähnten Schwierigkeiten vermeiden kann, wenn man in die Kunststoffe der genannten Art vor der Formgebung Kupfersalze von Oxykarbonsäuren in einer Menge von 0,1 bis 2 Gewichtsprozent, vorzugsweise etwa 0,4 bis etwa 1,6 Gewichtsprozent, berechnet als Kupfer, neben bekannten Stabilisatoren und Gleitmitteln einarbeitet. Es kommen Kupfersalze folgender Oxykarbonsäuren in Frage:It has now been found that the difficulties mentioned can be avoided by going into the Plastics of the type mentioned before shaping Copper salts of oxycarboxylic acids in an amount from 0.1 to 2 weight percent, preferably about 0.4 to about 1.6 weight percent, calculated as Copper, in addition to known stabilizers and lubricants. There are copper salts as follows Oxycarboxylic acids in question:
1. Glykolsäure,1. glycolic acid,
2. Milchsäure,2. lactic acid,
3. Oxystearinsäure,3. oxystearic acid,
4. Zitronensäure,4. citric acid,
5. Weinsäure,5. tartaric acid,
6. Karboxylgruppen enthaltende Polyacrolein- Formaldehyd-Anlagerungsprodukte gemäß der belgischen Patentschrift 611 797,6. Polyacrolein-formaldehyde addition products containing carboxyl groups according to Belgian patent 611 797,
7. Produkte einer Cannizzaro-Reaktion von Polyacrolein, 7. products of a Cannizzaro reaction of polyacrolein,
8. Salicylsäure,8. salicylic acid,
9. m-Oxybenzoesäure,
10. p-Oxybenzoesäure.9. m-oxybenzoic acid,
10. p-oxybenzoic acid.
Besonders vorteilhaft verwendet man aus der genannten Reihe die Säuren 4 bis 6.It is particularly advantageous to use acids 4 to 6 from the series mentioned.
Die Vorbehandlung der Kunststofferzeugnisse, z. B. Folien, Filme, Platten, Bänder, Becher, geformter kompakter Gebilde od. dgl., erfolgt in an sich bekannter Weise, indem man wie folgt arbeitet:The pretreatment of plastic products, e.g. B. foils, films, plates, tapes, cups, shaped compact structure or the like, takes place in a manner known per se by working as follows:
1. Entfetten mit 40°/0iger Natronlauge,1. degreasing with 40 ° / 0 sodium hydroxide solution,
2. Neutralisieren mit 20°/oiger wäßriger NaHSO3-Lösung, 2. neutralizing with 20 ° / o aqueous NaHSO 3 solution,
3. chemisches Aufrauhen mit Chromschwefelsäure (40 g K2Cr2O7 + 20 g H2O + 500 ml konzentrierte Schwefelsäure),3. chemical roughening with chromosulfuric acid (40 g K 2 Cr 2 O 7 + 20 g H 2 O + 500 ml concentrated sulfuric acid),
Verfahren zum Galvanisieren von geformten Gebilden aus KunststoffenProcess for electroplating molded structures made of plastics
Anmelder:Applicant:
Dynamit Nobel Aktiengesellschaft, Troisdorf (Bez. Köln)Dynamit Nobel Aktiengesellschaft, Troisdorf (District Cologne)
Als Erfinder benannt:Named as inventor:
Dr. Ilse Ursula Nebel,Dr. Ilse Ursula Nebel,
Dr. Heinz Hartel, Oberlar;Dr. Heinz Hartel, Oberlar;
Dr. Gerhard Bier, Troisdorf (Bez. Köln)Dr. Gerhard Bier, Troisdorf (District Cologne)
4. Sensibilisieren mit Stannochloridlösung (10 g SnCl2 + 40 ml konzentrierte HCl + 1000 ml H2O),4. Sensitize with stannous chloride solution (10 g SnCl 2 + 40 ml concentrated HCl + 1000 ml H 2 O),
5. Aktivieren mit Palladiumchlorid lösung (250 mg PdCL2 + 2,5 ml konzentrierte HCl + 1000 ml H2O).5. Activation with palladium chloride solution (250 mg PdCL 2 + 2.5 ml concentrated HCl + 1000 ml H 2 O).
Die chemische Erzeugnug der Grundschicht erfolgt z. B. durch Zusammengeben folgender Lösungen im Verhältnis 1:1 und nachfolgendes Eintauchen des Kunststoffes:The chemical production of the base layer takes place e.g. B. by combining the following solutions in Ratio 1: 1 and subsequent immersion of the plastic:
Lösung ASolution a
31.8 g Kupfersulfat,
8,2 g Nickelchlorid,31.8 g copper sulfate,
8.2 g nickel chloride,
78,6 g 37O/Oige wäßrige Formaldehydlösung, 532 ml Wasser;78.6 g 37 O / O aqueous formaldehyde solution, 532 ml water;
Lösung BSolution b
23.9 g NaOH,23.9 g NaOH,
95,5 g Kalium-natrium-tartrat,95.5 g potassium sodium tartrate,
8,2 g Na2CO3,
532 ml Wasser.8.2 g Na 2 CO 3 ,
532 ml of water.
Die chemische Erzeugung der Nickelgrundschicht erfolgt z. B. bei 900C durch Eintauchen des Kunststoffes in folgende Lösung:The chemical production of the nickel base layer takes place, for. B. at 90 0 C by immersing the plastic in the following solution:
30 g Nickelchlorid,
10 g Natriumhypophosphit,
100 g Natriumeitrat,
50 g Ammoniumchlorid,30 g nickel chloride,
10 g sodium hypophosphite,
100 g sodium citrate,
50 g ammonium chloride,
auf 1000 ml Wasser aufgefüllt, mit NH4OH auf pH 8 bis 10 eingestellt. Die chemische Erzeugung der Silbergrundschicht erfolgt z. B. in an sich bekannter Weise durch Eintauchen des Gegenstandes in eine Silbersalzlösung, der ein Reduktionsmittel beigemischt ist.made up to 1000 ml of water, adjusted to pH 8 to 10 with NH 4 OH. The chemical production of the silver base layer takes place, for. B. in a known manner by immersing the object in a silver salt solution to which a reducing agent is added.
709 639/442709 639/442
Die galvanische Verkupferung erfolgt ζ. B. in einem sauren Kupfersulfatbad aus 250 g CuSO4 und 100 g H2SO4 auf LOOO ml Wasser bei einer Spannung von 0,5 Volt. In entsprechender Weise können auf die Grundschicht aus Kupfer und/oder Nickel und/oder Silberauch andere Metalle, z. B. Ag, Au,Ni,Crod.dgl., galvanisch aufgebracht werden.The galvanic copper plating takes place ζ. B. in an acidic copper sulfate bath of 250 g CuSO 4 and 100 g H 2 SO 4 on LOOO ml of water at a voltage of 0.5 volts. In a corresponding manner, other metals, e.g. B. Ag, Au, Ni, Crod. The like., Electroplated.
Als Stabilisatoren bzw. Gleitmittel können z. B. Alkyl-Zinn-Thioverbindungen oder Gemische aus Ba- und Cd-Lauraten verwendet werden.As stabilizers or lubricants, for. B. alkyl tin thio compounds or mixtures of Ba- and Cd laurates can be used.
In allen Fällen war die erzielte Haftfestigkeit bereits der Grundierschicht sehr gut. Eine Vergleichsprobe, z. B. aus Polyvinylchlorid ohne Zusatz der erwähnten Kupfersalze, war für eine Galvanisierung nicht brauchbar.In all cases, the adhesive strength achieved was already very good for the primer layer. A comparative sample, z. B. from polyvinyl chloride without the addition of the copper salts mentioned, was not for electroplating useful.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1249048B true DE1249048B (en) | 1967-08-31 |
Family
ID=603280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED47901A Pending DE1249048B (en) | Process for electroplating molded structures made of plastics |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1249048B (en) |
-
0
- DE DED47901A patent/DE1249048B/en active Pending
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