DE1696108B2 - Process for the production of a non-metallic substrate coated with copper, nickel and / or silver - Google Patents

Description

or a metal salt complex of copper, ™. ⁸⁵⁵⁶ H ^SOT f "* metal layers a fete opposite

NiHrpl imritaHn- «iirhm · ™ W ⁸⁰⁰ SB anchoring are also based on the NickdundjoderSaeroder US ^ patent 3 282 737, the magazine "Metall",

b) the scarf carrier surface first only one 17 (1963), issue 5, pp.451 and 456, and the German> aiAui-

Solution of the metal salt concerned or _legeschr jf _t γ ₀₅ 9 738 known. From the latter Metal salt complex and then uterature site _is also known that by

_{neither with electroless} deposition on plastic plates dissolved in a solvent or

or vapor or flussigem white _N j _chlme metals produced layers of such nickel-phosphorus treated and then de-energized and _{ao υαά [οάα} cobalt-phosphorous alloys poorly

or electrolytically with copper. Nickel and / _on non-metallic substrates adhere because they are

or silver plated. _without ^^ β ^ i _{calibrates a! s fo} ii _en from the substrate

2. The method according to claim 1, characterized thereby.

records that the metal salt complex is an amine- The invention is therefore based on the object

complex of nickel sulfate, nickel chloride, nickel- as creating a process by which on layer substrates acc tat, copper sulfate, copper chloride or silver - of various kinds, especially thermoplastic nitrate is used. Polymerizates, fixed in a simple and rational way

3. The method according to claim 1 and 2, thereby adhesive coatings of copper, nickel and / or silver geken'zeich that a layer support made of poly with good joint strength, resistance to propylene initially applied with a solution of white 30 temperature fluctuations and corrosion Phosphorus in trichlorethylene and then with one that are electrically conductive so that elek amine complex is treated by nickel sulfate. Trostatic charges quickly from surfaces

be derived, protect the substrate from abrasion and scratching, reduce their porosity and

35 improve their thermal conductivity.

It has now been found that this problem can be achieved, surprisingly, by the

The invention relates to a method of manufacturing with copper, nickel and / or silver to be plated one with copper, nod! and / or silver-plated support initially with vaporous, liquid non-metallic substrate. 40 or white phosphorus dissolved in a solvent

There is a growing demand for objects plated with phor and then with a solution of a copper, nickel metal, e.g. B. plastic and / or silver salt or salt complex pre-existing objects with a metal-like appearance. Such delts or vice versa, before they are known in themselves, objects are, for example in vehicle construction, galvanically or currentlessly copper-plated, nickel-plated and / or silver-plated for household, radio and television sets and for decorative 45.

container required. So far, the metal plate required - the invention thus provides a method

ren of plastics many process stages, and in the type described at the beginning, the more general. were such processes only for one or it is possible to use them for a few similar substrates. _{} the} substrate surface with in a solution

1 1 ä £ « ^b ? ^sp ' ^e iT ^{Se from} ** USA patent _{specification 50 middle} , _dissolved * ^ _{steam-powder or flü} ^ _

¹ JV ⁷ κ "" AS " ^to . Yerkupfern von mcht- _we f _{ßem ph hor U} J _αηχ ^ ηά with a

metallic carrier known, in which the to ^ _{0 d} metal salt or a metal salt

copper-plating surface initially by sandblasting, _comp , | _{xes of} copper, nickel and / or silver

Steam blasting, brushing, grinding, etching or the like. Or

refreshed or roughened, under certain conditions- 55 .... ",., .., _a . ,

gungen carefully rinsed, then with steam ^b ) ^dl 5 layer support surface first degreased with a, carefully cleaned again, ^{acidified with sulfur-L} ° ^sun 8 of ^the metal salt or metal acid in question, again thoroughly rinsed, then salt complex and then either with m

with an activating solution of a salt from the group ^{dissolved in a} solvent or in vapor form

VIIIa, in particular a platinum group ^{metal salt, 60 8 em} °, ^the liquid white phosphorus treated like palladium chloride, treated, dried, in a " ^nd , ^daim _t . Currentless and / or electrolytic groove

reducing, for example hypophosphite corresponds ^Ku P ^{fer> Nlckd} and / or silver plated,

holding solution immersed, rinsed again, in a After the method according to the invention one can

Nickel precipitation bath immersed, rinsed again, e.g. B. one-sided mirrors, water and liquids stripped with sulfuric acid, ia a chemical 65 collection devices, protective coatings on houses, Nickel plating bath electrolessly nickel-plated, thoroughly dried by means of a motor vehicle, boat,! relieved and then finally galvanically copper-plated. Improve fabrics and homes.

Before the substances used in the process according to the invention, such as glass fibers, glass powder, glass beads, asbestos, Layer supports can be plastics or other in talc or other mineral fillers, wood flour be essential non-metallic substrates, e.g. B, and other vegetable fillers, carbon in its CeDulose material and ceramics, such as fabrics, various shapes, dyes, pigments and Paper, wood, cork, cardboard, clay, porcelain, leather, 5 waxes, can be used. It was found that porous glass or asbestos cement in the case of wax as filler the metal all the more so

Examples of synthetic synthetic base according to the invention adheres better to the substrate, the harder the wax materials are homopolymers and copolymers of ^

Ethylenically unsaturated aliphatic, alicyclic The support can have various shapes

and aromatic hydrocarbons such as Polyäthy- iq have z. B. They can be used as compacts, foils, rods; fen, polypropylene, polybutylene, ethylene-propylene fibers or as a fabric. Copolymers, copolymers of ethylene or in the first stage of the process according to the invention

Propylene with other olefins, polybutadiene, poly- rene, it is preferred to use elementatnerisate on the support of butadiene, of both natural and rem white phosphorus to treat that also as also synthetic polyisoprene, polystyrene and poly- 15 yellow phosphorus is called. The phosphorus can merisaie of pents. Witches. Hepten, Octene. 2-methyl- in the vapor phase, as a liquid or dissolved in a propene, 4-Met'.vlhexen-1, bicyclo- (2,2.1) -hepten-2, solvent, can be used. Pentadiene, hexadiene, 2,3-dimethylbutadiene vinyl- Suitable solvents or diluents

cyclohexene. Cyclopentadiene and methyl styrene. Others for phosphorus are solvents, the elementary ones Usable polymers are polyindene, indene ao phosphorus and which preferably dissolve the surface Coumarone resins, polymers of acrylic acid - a plastic that swells without being destroyed - and methacrylic acid esters, acrylic acid and meth- gen. Such solvents include the halogenated acrylic acid ester resins, z. Building; Acrylic acid ethyl ester, nated hydrocarbons such as chloroform, 1,1,1-tri-methacrylic acid n-butyl ester. N'lethacrylic acid isobutyl chloroethane. Benzo chloride, dichloroethylene, trichloro ester, Methacrylic acid ethyl ester and methacrylic acid as ethyien. Perchlorethylene, trichloroethane, dichloropromethyl ester, Alkyd resins, cellulose derivatives, such as cellulose, ethylene dibromide, ethylene chlorobromide, propylenelose acetate, Cellulose acetate butyrate, cellulose nitrate, dibromide, chlorobenzene, monochlorotoluene and aromatic ethyl cellulose, Hydroxyethyl cellulose, methyl cellulose table hydrocarbons, such as benzoJ, toluene, xylene, and sodium carboxy diethyl cellulose. Epoxy resins, fu-ethylbenzene and naphthalene. The preferred Loran resins (Furfuryl alcohol cder / S-Acy'-ethenyl-furan), 30 solvents are trichlorethylene, perchlorethylene and Hydrocarbon resins made from earth> ', isobutylene resins benzene. Solvent mixtures can also be used (polyisobutylene), Isocyanate resins (polyurethanes), mediated.

amine resins such as melamine-formaldehyde and melamine. If you use phosphorus solutions, you work

Urea-formaldehyde condensates, oleoresins. Phenol with concentrations in the range of about 0.0001 u resins, such as phenol-formaldehyde condensates, phenol 35 weight percent phosphorus up to saturated solutions, elastic elastomers, phenol: he epoxy resins, phenol and preferably with concentrations of about 1.5 polyamides and phenolic V'inylacetale, poly- to 2.5 ° / _0th Before the elementary phosphorus is brought as a gas, amide polymer, such as super polyamides, polyamide liquid or solution with the plastic in con-epoxy resins and especially long-chain super polytact, the surface of the layer amide with carbonamide groups as part of the main carrier should be clean be. If a solution is used, such as chain, polyester resins, such as unsaturated polyesters, the solvent is generally used to clean basic acids and dihydroxy compounds, and the surface. If gaseous or liquid polyester elastomers and resorcinol resins such as resorcinol phosphorus are used, the formaldehyde, resorcinol furfural, resorcinol phenol surface to be treated is preferably treated with a solvent. «Wash, but does not need special treatment, r .. B. urea condensates, rubbers, such as natural etching or polishing. Rubber, synthetic polyisopropene, regenerated- The treatment with phosphorus is usually used in

rubber. Chlorinated rubber, polybutadiene, Cyclokau- a temperature below the softening point of the chuk, butadiene-acrylonitrile-, butadiene-styrene, butyl substrate and - if a solvent is used and polychlorobutadiene rubber, polysulfide, ter- 50 - below the boiling point of the Solution resins, urea resins, vinyl resins, such as polymer resins. In general, the Tempesate is vinyl acetate or vinyl alcohol-vinyl acetate temperature in the range of about 30 to 135 ° C and preferential copolymers, polymers of vinyl alcohol, vinyl, between about 50 and 100 ⁰ C. The contact time chloride, vinyl butyral, vinyl chloride Vinyl acetate-Co depends on the type of support material, the polymer. Vinylpyrrolidone and vinylidene chloride solvent and the temperature, but copolymers, polyoxymethylenes, polyphenylene generally about 1 second to 1 hour or more, oxides, polymers of diallyl phthalates and preferably about 1 to 10 minutes. Phthalic acids, polycarbonates made from phosgene or thio- After the first treatment stage, phosphorus is aui

phosgene and dihydroxy compounds, such as bisphenols, are applied to the surface of the substrate, thermoplastic polymers of bisphenols and 60 d. i.e., the phosphor is applied to the surface, Epichlorohydrin, graft polymers and copolymers! - embedded in the surface or below the surface sate and polymerizate of unsaturated carbon embedded in the support material. The kind of Hydrogen and an unsaturated monomer, application depends on when a solvent is used such as B. graft polymers of polybutadiene, of its effect on the surface of the Styroi and Actylnitril, which generally come under the name 6 * base material from.

ABS resins are known, ABS polyvinylchloridelpoly- After the first stage of treatment, the layer-

merisate and acrylic-polyvinylcMorid-Polymerisaite, rinsed with a solvent and then on

These polymers can with or without filling the air or in an inert atmosphere, eg. B. in nitrogen

or carbon dioxide, or by means of radiant heaters or
can be dried in normal ovens. The dry seasons

vary considerably, e.g. B. from 1 second to general in basic nerciwu, **. «. -., - 30 minutes or more. Drying times of 5 seconds to 10 minutes, in particular 5, are preferred, preferably at about 10 to about 13. The layer substrate treated with phosphorus lasts from 5 to 120 seconds. Rinsing and drying are generally optional for the metaL solution at a temperature. rature below its softening point and below the

In the second treatment stage, the preferred boiling point of the solvent, if such an embodiment of the process according to the invention is used, is brought into contact. In general, the layer substrate treated with phosphorus is the temperature in the range from ~ 30 to 10 ⁰ C, a solution of a metal salt or a metal salt - preferably about 50 to 100 ° C. The contact time complex, the one with The phosphorus in one varies considerably and depends on the kind of metal phosphide which can react with which it is brought into contact. The term "MetaHphosphidi" means the metal and metal salts and the contact temperature, the phosphoric coating that is formed on the surface of the layer is generally about 0.1 to 30 minutes, however. The metals are, as already mentioned, preferably about 5 to 10 minutes. Copper, nickel and / or silver. The metal phosphide can, as already mentioned, at

The surface used in the process according to the invention can also be formed in that the metal salts can contain a large number of anions. 7 .. B. the anions of mineral acids, such as sulfate, 20 saline solution is brought into contact with the metal chloride, bromide. Iodide, fluoride, nitrate, phosphate, compound on the layer support surface to beat down to chlorate, perchlorate, borate, carbonate or cyanide. The metal salts described above are ions. Likewise, the anions of organic and complexes can be derived from the acids described above, z. B. Ant, vinegar, citric conditions can be used. The so treated nen-. Butter-. Valerian, Capron, Heptane. Octane, »5 layer support is then coated with white phosphorus as naphthene, 2-ethylcapron, cinnamon, stearic, oil or vapor or liquid or ^; n Solution in one of the palmitic acid and dimethylglyoxime. In general, the aforementioned solvent treated. The conditions described above contain the anions of organic acids 1 to 18 carbon atoms can also be used here. Specific examples of useful surfaces can then be electrolytically plated and / or metal salts are copper sulfate, copper chloride, silver, nitrate and nickel cyanide. according to the two treatment stages

The metal salts know the conditions applied with a complexing agent, the duration of the treatment be complexed, which can be a solution with a pH and the type of substrate treated Who forms> 7. Particularly useful are the amine-obtained treated surfaces either complexes of the above metal salts with 1 to 35

6 ammonia molecules in the complex. Typical examples are 1 · conductive, so that the surface according to known games are NiSO ₄ -ONH ₃ . NiCl ₂ -ONH ₃ , Ni (CH ₃ COO) V methods can be electroplated, or

6NH ₃ , CuSO ₄ -6NHj, CuCVoMH ₃ , AgNO ₃ -ONH ₃ , 2 be non-conductive.

NiSO ₄ -3NH ₃ . CuSO ₄ -4NH ₃ and Ni (NO ₃ V 4 NH ₃ .

Other useful complexing agents are quinoline, 40 In the latter case, the treated surface contains amines and pyridine. Usable complexes are e.g. B. active or catalytic sites that make the surface accessible for compounds of the general formula MXjQ ₄ , a further treatment after electroless Plattierverin the M drive the metal ion, X a chlorine or bromine atom, in which a conductive coating and Q mean a quinoline molecule . is applied to the plastic surface. Such

Typical examples are NiCl ₂ Q ₂ , NiBr ₂ Q ₄ , NiJ ₂ Q ₂ , 45 a conductive coating can then according to known Ver-CuCl ₂ Q ₂ and CuBr ₂ Q ₂ . Likewise, the corresponding drives are to be electroplated. Monoquinoline complexes useful. Suitable amine- In a typical electroless plating process

The complexes are the mono- (ethylenediamine) -, bis- (ethylenediamine), tris- (ethylenediamine), bis- (1,2-propane and a metal salt solution under conditions) in Kondiamine) and bis (1,3-propanediamine) complexes of 50 cycles, in which the metal ion of the metal salt salts, e.g. of head sulfate. Typical Pyridinkom- to the metallic stage reduces unc ¹ on the surface complexes are NiCl ₂ (py) _a ^ and CuCl (Py) _2, wherein py is pyridine depressed. Essential ^; ch are the catalytic means. see spots on the surface that are

The aforementioned metal salts and their complexes development with the metal salt or complex salt solution in polar or ionic media. Stir preferably. For applying a nickel coating to the wisely used in aqueous solutions. However, catalytic sites produced according to the invention can be found surfaces that use non-aqueous media such as alcohols are also suitable, e.g. B. a solution of a be det, z. B. methanol, ethanol, butanol, Hep nickel salt in an aqueous hypophosphite solution. tanol or decanol. Mixtures of alcohol and suitable hypophosphites are the alkali metal hypo-water can also be used. Furthermore, 60 are phosphites, ν ie sodium hypophosphite and potassium polar Mixtures of alcohol with others with hypophosphite, and the alkaline earth metal hypophosphites, miscible solvents of the aforementioned type such as calcium hypophosphite and barium hypophosphii. useful. The concentration of the solution is in general for use other than chemical treatment Metal salts suitable in a range of about 0.1 weight bath are those above percent metal salt or complex, based on the 65 with regard to the metal salt treatment of total phos weight the solution, up to a saturated phosphor-treated support. Solution and is preferably about 1 to about their reducing agents are formaldehyde, Hydrochi-10 Weight percent metal salt or complex. The non and hydrazine. Other additives such as buffers and

Complexing agents can be contained in the chemical flatting solutions or baths.

The treated substrates, which are conductive, can be electroplated by known methods will. The article is usually used as a cathode that used for electroplating Mutall is usually done in an aqueous plating bath solved, but other media can also be used. Generally one can use a saline solution of the metal to be plated. One can also use an anode made from the metal to be plated use. In some cases, however, a carbon anode or other inert anode is used. Those suitable for electroplating Metals, solutions, and conditions are in the Metal Finishing Guidebook Directory for 1967. issued by Metals and Plastics Publications, Inc., Westwood, N.J., V. St. Α., described.

The examples illustrate the invention. Unless otherwise stated, parts are by weight is.

Examples Ibis7

Polyvinyl chloride, polyethylene and polypropylene pieces (plastic pieces) were with solutions of Phosphorus treated in different solvents after being removed from the phosphorus solutions the plastic pieces were immersed in a bath of the same solvent for 3 seconds. Then one left evaporate the adhering solvent, whereupon the plastic pieces were immersed in ammoniacal nickel sulfate solutions. In any case, the Surface quality appraised S The various plastics used and Solvent, the temperature of the phosphorus solution, the contact time with the phosphorus solution and with the Nickel sulfate solution and the properties of the layer formed on the plastic surface are in Ta Belle I listed.

Several of the treated plastic pieces were then electroplated, each serving as a cathode in a nickel chloride plating bath was used. A current was passed through the plating bath for 30 minutes at a time of 1 ampere, corresponding to a current density of 5.38 A / dm *. The electroplated polyvinyl chloride pieces prepared in Example 10 were made subjected to a hot-cold test in which the plastic was immersed in water at 50 to 55 ° C for 1 minute and

ao then 1 minute in crushed dry ice at -70 ° C was dived. This thermal cycle treatment was repeated eight times in succession. Thereafter no cracks could be found on the nickel-plated layer.

as The nickel-plated prepared according to Example 5 Polyethylene pieces were subjected to five of the above warm-cold treatment cycles. In the After that, no cracks could be found after the nickel-plated layer.

Table I.

at
game plastic solvent
for phosphorus Temperature of
Phosphorus solution
⁰ C Time of one
diving into the
Phosphorus solution
Minutes Time of the
tauchciu in the
Nickel sulfate
solution
Minutes nature
the treated
Plastic-
surface 1
2
3
4th
5
6th
7th Polyvinyl chloride
Polyvinyl chloride
Polyvinyl chloride
Polyvinyl chloride
Polyethylene
Polyethylene
Polypropylene chloroform
chloroform
benzene
1,1,1-trichloro
ethane
chloroform
chloroform
benzene 55
55
55
74
55
55
80 1
2
2
2
1
2
2 5
10
10
10
10
10
10 conductive
conductive
conductive
conductive
conductive
conductive
smooth, shiny,
conductive,
metallic
Aasseben

The pieces were then subjected to a peeling and lifting test, which determined that a force of 0.3 kp is required to move a Peel 12.7 mm wide metal strips from the plastic surface. This corresponds to a joint strength of 0.232 kp / cm.

The nickel-plated fulypropylene pieces produced according to Example 7 were subjected to a peeling and lifting test, during which it was observed that a force of 13 kp is required to make a 12.7 mm peel metal strips from the plastic surface. This corresponds to a joint strength of 1.02 kgf / cm.

Example 8

- A polyethylene sheet was first coated with a solution of yellow phosphorus ^; n Trchlorethylene 2 minutes treated at 55 ° C, 15 seconds at Raumtemperatui dried in air and then for 10 minutes at 90 ⁰ C in a 10 ° / ^ ge nickel sulfate solution brought the mi

Ammonia had been made strongly alkaline.

The polyethylene film treated in this way was coated with Kunfei electroplated by using the plastic film as a cathode in a copper plating bath on copper sulfate, sulfur acid and hydrochloric acid used and with a stream density of 2.15 A / dm * was copper-plated for 30 minutes After an approximately 12.7 μτη thick copper layer had deposited, the plated polyethylene film was used as a cathode in a nickel plating bath and 30 minutes at a current density of 2.15 A / dm nickel-plated, up to about 12.7 (in a thick nickel layer was secluded. The composite head he-Nickel-Plai Tjerung had a joint strength of about 1.4 kgf / ct on.

209553/44

28? Fi

Example 9

A polyvinyl chloride sheet was placed, treated with trichlene of yellow phosphorus 0.5 minutes at 55 ° C, then at room temperature for 15 seconds and finally air dried for 10 minutes at 60 ⁰ C in a 10% nickel acetate whose pH value with ammonia was set to ¹ .3.

The polyvinyl chloride film treated in this way was initially electroplated with copper for 45 minutes as in Example 8, an approximately 19.05 μm thick copper layer deposited, and then galvanically nickel-plated for about 30 minutes, with an approximately 12.7 μm thick nickel layer deposited. The joint strength of the copper-nickel plating obtained was 1.87 kg / cm.

10

ß e i s ρ i e 1 e 10 to 44

Various plastics have been treated with solutions of yellow phosphorus in a variety of solvents. Those treated with phosphorus Plastic pieces were then treated with an aqueous ammoniacal salt solution for 10 minutes and then according to the method known from the "Metal Finishing Guide jo Book", 1966, pp. 260 to 262, or using a galvanic bath of the type described there, a so-called "Watts bath", Electroplated nickel-plated (this method of electroplating with nickel is hereinafter referred to for short as »Watts-Vemickelni). The joint strength is preserved The nickel plating layer was determined in each case.

Table II

at
game plastic Solvent for
phosphorus Temperature of
Phosphorus solution 86 Contact time Joint strength ⁰ C 80 Minutes kp / cm 10 Polypropylene Trichlorethylene 85 2 «, 39 11th Polypropylene benzene 118 2 5 ^ 6 i2 Polyethylene (high density) Trichlorethylene 80 5 8.27 13th Polyethylene (high density) Perchlorethylene 53 10 1.68 14th Polyethylene (high density) benzene 55 2 6.96 15th Polyethylene (high density) chloroform 80 2 0.95 16 Polyethylene (low density) Monochlorobenzene 55 2 1.54 17th Polystyrene benzene 121 2 0.29 18th Pnlwtnvirhinrirf Trirhlnrätiwi '* - ¹ ' 53 05 8 4R 19th Polyvinyl chloride Perchlorethylene 53 1 OyTO
6.25 20th Polyvinyl chloride benzene 53 2 7.32 21 Polyvinyl chloride Monochlorobenzene 74 2 2.52 22nd Polyvinyl chloride chloroform 53 2 0.95 23 Polyvinyl chloride Methyl chloroform 53 2 0.54 24 Polyvinyl chloride with 10% poly
vt η vl α c * f * \ si t Perchlorethylene 50 to 55 2 7.50 25th YllljrlawClal
Polyvinyl chloride with 10% poly benzene 1 6.91 26th vinyiaceuxi
Acrylic acid polyvinyl chloride poly Trichlorethylene 2 3.02 merisat 50 to 60 27 ABS polyvinyl chloride polymer Trichlorethylene 87 0.29 28 ABS resin Trichlorethylene 6L 0.05 1.05 29 Polycarbonate Trichlorethylene 60 0.5 0.29 30th Diallyl phthalate resin Trichlorethylene 47 5 Ά Pheaol formaldehyde Trichlorethylene 53 S. 32 Phenol formaldehyde Carbon disulfide 74 5 33 Polystyrene acrylonitrile benzene 73 0.083 1.32 34 Polymethacrylic acid methyl ester Methyl chloroform 45 5 1.68 35 Methyl methacrylate Monochlorobenzene 50 5 0.50 36 Polyphenylene oxide Trichlorethylene 0.033 3.1 37 modified thermoplastic Trichlorethylene 50 0.033 Phenylene oxide resin 38 Hose made of modified soft Trichlorethylene 50 0.05 *) made of polyvinyl chloride 39 Hose made of filler included Trichlorethylene 50 0.83 *) the rubber 70 to 75 40 rubber tube Trichlorethylene 60 to 73 0.25 *) 41 Cotton fabric Trichlorethylene 60 2 *) 42 Acetate silk fabric Trichloroethyias 60 10 *) 43 Nylon fabric Trichlorethylene 5 *) 44 Polyvinyl flooring resin fabric Trichlorethylene 5

- *) The peeling and lifting could be carried out on the hoses and guns, but they stuck aurplated MetalKL '-. ie very good;. . ·

In table It are those for the respective examples used plastics, solvents for the phosphorus, phosphorus solution temperatures and the Contact times with the plastic are given. For the second treatment stage in Examples 26.27 and 37 to 40 an ammoniacal nickel acetate solution, in Examples 30 and 31 an ammoniacal one Nickel cyanide solution »in all other examples an ammoniacal nickel sulfate solution is used. On the treated plastics of Examples 30 to 32 catalytic nickel phosphide had deposited. These plastic surfaces became electroless plated. The joint strengths of the electroplated plastic articles other than those of the examples 38 to 44 are given in Table II.

Examples 45 and 46

Polypropylene was treated with a saturated solution of phosphorus in trichlorethylene (Example 45) or with a 50% saturated solution of phosphorus in trichlorethylene (Example 46). In this case, the polypropylene was each treated with the phosphorus solution for 2 minutes at 80 to 85 ⁰ C, then dried and then immersed for 10 minutes at 9O ⁰ C in an ammoniacal solution of nickel sulfate. The treated plastics were electroplated in a Watts bath, a current of 5.38 A / dm ^{2 being applied for} 30 minutes in Example 45 and 40 minutes in Example 46. The joint strengths of the nickel layers obtained were 2.52 kg / cm (Example 45) and 3.14 kg / cm (Example 46).

At sρ iele 47 to 57

In Examples 47 to 56, polyethylene pieces were given for 1 to 7 minutes at temperatures in the range Treated from 56 to 65 ° C with a saturated solution of yellow phosphorus in trichlorethylene. in the Example 57 prepared a piece of polyvinyl chloride containing 10% polyvinyl acetate in an analogous manner treated with a solution of yellow phosphorus in benzene. The pieces of plastic treated with phosphorus were treated with various aqueous ammoniacal solutions of nickel salts and then electroplated with nickel by Watts nickel plating. In Table III are those used Metal salts, the salt solution temperatures, the contact times of the plastic pieces with the salt solution and the joint strengths of the nickel layers are listed

Table III

Nickel salt temperature Contact time
Minutes Properties of plating 2.5 *) at
game acetate the
Saline solution
⁰ C 4th 0.87 *) 47 nitrate 70 6th black conductive deposit,
electroplated
black conductive deposit, 48 Carbonate 80 10 electroplated 49 iodide 70 3 4.29 *) 50 73 3.48 *) chloride 5 black conductive deposit 51 bromide 70 5 black conductive deposit, 52 Cyanide 70 5 electroplated 53 Citrate 72 5 black conductive deposit,
electroplated
black conductive deposit, 54 75 electroplated Perchlorate 5 3.75 *) 55 Dimethyl glyoxime 85 10 56 Formate 5 57 70

*) Fngenfestigkit in kp / cm.

Examples 58 to 6 ~

In Examples 58 to 63 Polyäthylenstücke treated with saturated solutions of yellow phosphorus in trichlorethylene for 2 minutes at 60 ⁰ C and then treated with aqueous solutions of metal salts with different pyridines, amines and Cbinolinen were complexed. This treatment level resulted in Ie tending layers on the plastic surfaces, plated onto the galvanically adhering metal layers could become. In example 63 there was a nod phosphide layer obtained, which ve the deposit

6s nickel as catalyzed in an electroless plating bath In Table IV the metal salts are the following: bildnur, the Salzlörongstempcratoren and Kontals times listed.

Table TV

at
game Nickel salt Complexing agents Pyridine Temperature of
Saline solution
"C Contact time
Minutes 58 acetate Lauryl pyridinium chloride 92 35 59 acetate Pyridine and ammonia 92 60 60 acetate Laurylpyridinium chloride and 90 30th 61 acetate ammonia 90 70 Ethylenediamite 62 chloride Quinoline in aqueous ethanol 90 10 63 chloride solution 90 5

Example 64

A Püenolformaldehydharzformkörper was treated with sodium hydroxide for 12 minutes at 9O ⁰ C, then a few minutes at about 60 ⁰ C with a saturated solution of yellow phosphorus in trichlorethylene and then 5 minutes at 80 ° C with an aqueous ammoniacal solution of nickel sulfate. The surfaces of the shaped body treated in this way contained a catalytically active deposit of nickel phosphide. The shaped body was then electrolessly nickel-plated using the process known from US Pat. No. 3,649,713. The nickel layer applied in the process was conductive. Finally, the shaped body was provided with a further nickel layer by means of Watts nickel-plating.

Example 65

A polyethylene molding was for 3 minutes at 72 ° C in a mixture of yellow phosphorus, trichlorethylene, Submerged in ethanol and nickel nitrate. Sufficient ammonia was then added to the mixture, to make them highly alkaline. The polyethylene compact was 10 minutes in the ammoniacal Solution left. After that, its surface was coated with a light gray layer of nickel phosphide the firmly adhering metal layers could be plated on.

Example 66

Polypropylene was immersed for 6 minutes at 60 ⁰ C in a 10% Nickelacütarlösung, which had been prepared by dissolving nickel in a solvent. which consisted of 1 volume of ethanol and 3 volumes of trichlorethylene and also a small amount of ethylenediamine to form a dark blue complex. The treated polypropylene was air-dried and immersed in a saturated solution of yellow phosphorus in a mixture of 5 parts of trichlorethylene and 1 part of ethylenediamine Solvent evaporated. The treated surface was conductive.

Nickel was plated on the treated surface, using an electroless nickel plating bath.

Examples 67 to 72

Various substrate treated a 2 ° / o solution of phosphorus in trichlorethylene and then at 90 ⁰ C with a 10 ° / o nickel sulfate solution with excess ammonia at 6O ⁰ C and ao. The supports and contact times are given in Table V.
Table V

at
game Support Time in the
phosphorus
solution
Vf iniilpn Time in the
Nickel sulfate
solution
Minutes 67 wood 6th 5 68
69
³⁵ 70 Pantie 1
1
1 5
5
5 71
72 cork 1
1 5
5 Porous clay Asbestzemr it porcelain
(unglazed)

The substrates treated in this way from Examples 67 to 70 and some of those 71 were electroplated with nickel at 55 ° C. and a current density of 5.38 A / dm ^a and thus provided with an adhesive nickel coating. The treated substrate of Example 72 and the remainder of the treated substrate of Example 71 were electrolessly nickel-plated using the method known from U.S. Pat. No. 3,649,713, a conductive nickel layer being applied.

_so ^: Example 73

A piece of leather wasto treated with a 2% phosphorus solution in trichlorethylene for 3 minutes at 60 ° C and then for 5 minutes at 60 ° C with a solution of nickel acetate and excess ammonia at 55 ° C and a current density of about 5.38AZdIn ¹ .

Example 74

A piece of porous Olas was treated with a 2 ° / oigea solution of phosphorus in Trichloräthyfen at 60 ° C and then immersed in a nickel sulphate solution with Oberschüssigem ammonia at 90 ⁰ C. The thus loading "5 acted glass was bä 55 ⁰ C and at a Current density of about 5.38 A / dm ¹ electroplated with nickel

2826

Claims (1)

1 2 With this in its complexity and elaborate patient claims: keh typical for the state of the art process should be aimed at the nickel precipitation bath and the 1. Process for the production of a copier, nickel-plated bath ken * e pure nickel layers, son-nickel and / or silver-plated non-metal layers are deposited from the Mckel-phosphorus alloy layers, see the layer carrier, characterized by the fact that the following galvanic copper plating is possible, but not nor- a) the substrate surface with in eiuem ^dem ? «*« «ί ^^^^^^ Solvent-dinosaur or vaporous ™ !
or liquid.Γ white phospho? and an- ^1O f «. ¹ ° Sp