DE1696108C3 - Process for the production of a non-metallic layer support plated with copper, nickel and / or silver - Google Patents

Description

^y 3 4

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 Cellulosic 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 metal, so much the same

Examples of synthetic bespoke that can be used according to the invention adheres to the substrate, the harder the wax materials are homopolymers and copolymers of is. ".

Ethylenically unsaturated aliphatic, acyclic The support can have various shapes

and aromatic hydrocarbons such as Polyäthy- io have z. B. They can be used as compacts, foils, rods, len polypropylene, polybutylene, ethylene-propylene fibers or as a fabric. Copolymers, copolymers of ethylene or in the first stage of the inventive method

Propvi'en with other olefins, polybutadiene, poly- rene, it is preferred to use the layer support .nit elementameris'ate 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 pentene, hexene, heptene, octene, 2-methyl- in the vapor phase, as a liquid or dissolved in one

_open 4-methylhexene-1, bicyclo-12,2,1) -hepten-2. Solvents, can be used. PentaJien, hexadiene, 2,3-dimethylbutadiene, vinyl- Suitable solvents or diluents

cvclor -'- xen. Cyclopentadiene and methyl styrene. Others for phosphorus are solvents, the elementary polymers are polyindene, luden- 20 phosphorus dissolve and the preferably dte Ubertiacne Cunwon resins, polymers of acrylic acid - a plastic without destruction for swelling brin- and V'.ethacrylic acid esters, acrylic acid and meth - gen. Such solvents include the naiogeacry acid ester resins, eg made from ethyl acrylate. Nated hydrocarbons, such as chloroform, 1,1-methyl-methyl-methyl-ester, isobutyl-methacrylic chloroethane, benzotrichloride, dichloroethylene, ethyl methacrylate and ethyl methacrylate. Perchlorates, trichloroethane, chlorpromethoxide, alkyd resins, cellulose derivatives, such as cellulose, ethylene dibromide, ethylene chlorobromide, P ™ py ^ n-Sctai, cellulose acetate butyrate. Cellulose nitrate, dibromide, chlorobenzene, monochlorotol and arorna-ethy cellulose, hydroxyethyl cellulose. Methyl celhilic hydrocarbons, such as Be ^nzo' - ^loluO1 ; ~ ^yi """and" sodium carboxymethyl cellulose, epoxy resins, fu-ethylbenzene and naphthalene. The preferred L ₀ - "n resins (furfuryl alcohol or / f-acyl-ethenyl-furan), solvents are trichlorethylene, ^ Jl? ™ ^" ^ ¹ Petroleum hydrocarbon resins, benzene isobutylene resins. Solvent mixtures can also be used - (Polvisobutylene), isocyanate resins (Polyurethanes), Medicated. - ,, one hears

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

Urea-formaldehyde condensates, oleoresins. Phenolic with concentrations in the range of ^{about 0} J ¹ TT | V * resin ": such as phenol-formaldehyde condensates, phenol percent by weight phosphorus up to a total of lots of ash elastomers, phenolic epoxy resins, phenol and preferably with concentrations of about 1.5 before polyamides and phenolic vinyl acetate. Poly to 2.5 Before the elementary phospho ^ aU Ga,! «! Polymers such as super polyamides, polyamide liquids or solutions with ££ * ££« £ ^ epoxy resins and, in particular, long-lasting superpolymers, you should dte , _t ^b ° ™ ^ _n f _L aside with carbonamide groups as part of the main carrier 40 clean se.n. If, '' Site ^ne, polyester resins such as unsaturated polyester two- the solvent in alfeinen for basic acids and dihydroxy compounds is used, and If gaseous polyester elastomer and resorcinol resins, such as resorcinol phosphorus, are used, the surface becomes formaldehyde, resorcinol furfural, resorcinol phenol, preferably formaldehyde, resorcinol -Polyamide- and resorcinol- 45 wash, however, needs not specially treated, e.g. ti. Urea condensates, rubbers, such as natural etched or polished to be _eewohr . _Uc h at

fschuk butadiene-acrylonitrile, butadiene-styrene, butyl-Sch.chtträgers and -

ss? st: ai =? f ¹

thermoplastic polymers of bisphenols and 60 ie de ^ Pj ⁰ ^^ _t et or under the surface epichlorohydrin, graft polymers and -copolymer «- in the ⁰ ^ ** ^^ deposited. The kind de sate and polymers of unsaturated carbon in ^^^^^^^ A

TÄfr ⁿ PÄ =: _n ; w-rvTÄÄ _to ι

or carbon dioxide, or by means of radiant heat ovens or normal ovens. The dry seasons vary considerably, e.g. From 1 second to 30 minutes or more. Drying times of 5 seconds to 10 minutes, in particular, are preferred from 5 to 120 seconds. Rinsing and drying are optional.

In the second treatment stage of the preferred embodiment of the method according to the invention if the layer substrate treated with phosphorus is treated with a solution of a metal salt or a metal salt complex, which can react with the phosphorus to form a metal phosphide, brought into contact. The term "metal phosphide" means the metal phosphorus coating that is applied to the surface of the layer "5 carrier is formed. As already mentioned, the metals are copper, nickel and / or silver.

The metal salts used in the process according to the invention can contain a large number of anions, z. B. the anions of mineral acids, such as sulfate, chloride, bromide, iodide, fluoride, nitrate, phosphate, Chlorate, perchlorate, borate, carbonate or cyanide ions. The anions can also be derived from organic acids, e.g. B. Ant, vinegar, lemon, Butter, valerian, capron, heptane, octane, naphthene, 2-ethylcaproone, cinnamon, stearin, oil or Palmitic acid and dimethylglyoxime. In general, the anions of organic acids contain 1 to 18 carbon atoms. Specific examples of usable metal salts are copper sulfate, copper chloride, silver nitrate and nickel cyanide.

The metal salts can be complexed with a complexing agent, which forms a solution with a pH value> 7. The amine complexes of the above metal salts with 1 to 6 ammonia molecules in the complex are particularly useful. Typical examples are NiSO ₄ -ONH, NiCl ₂ -6NH ₃ , Ni (CH ₃ COO) ₂ -6NH ₁ , CuSO ₄ -ONH ₃ , CuCl ₂ -ONH ₃ , AgNO ₃ -ONH ₃ , NiSO ₄ -3 NH _S , CuSO ₄ -4NH ₃ and Ni (NO ₃ ) ₂ -4NH ₃ . Other useful complexing agents are quinoline, amines and pyridine. Usable complexes are e.g. B. also compounds of the general formula MX ₂ Q ₂ , in which M is the metal ion, X is a chlorine or bromine atom and Q is a quinoline molecule.

Typical examples are NiCl ₂ Q ₂ , NiBr ₂ Q ₂ , NiJ ₂ Q ₂ , CuCl ₂ Q ₂ and CuBr ₂ Q ₂ . The corresponding monoquinoline complexes can also be used. Suitable amine complexes are the mono- (ethylenediamine), bis (ethylenediamine), tris (ethylenediamine), bis (1,2-propanediamine) and bis (1,3-propanediamine) complexes of salts, z. B. of copper sulfate. Typical pyridine complexes are NiCl ₂ (py) ₂ and CuCl ₂ (py) ₂ , where py is pyridine.

The aforementioned metal salts and their complexes are preferably used in polar or ionic media in aqueous solutions, used. However, non-aqueous media such as alcohols can also be used be e.g. B. methanol, ethanol, butanol, heptanol or Decancl. Mixtures of alcohol and Water can also be used. Furthermore, polar mixtures of alcohol with others are with it Miscible solvents of the aforementioned type can be used. The concentration of the solution is in generally in a range of about 0.1 percent by weight of metal salt or complex, based on the Total weight of the solution, to a saturated solution, and is preferably about 1 to about 10 weight percent metal salt or complex. The pH of the metal salt or complex solution can be in are in the range of about 4 to 14, but are generally in the basic range; H. over 7, and preferably from about 10 to about 13.

The support treated with phosphorus is brought into contact with the metal salt solution generally at a temperature below its softening point and below the boiling point of the solvent, if such is used. In general, the temperature is in the range from about 30 to 110 ^° C., preferably from about 50 to 100 ^° C. The contact time fluctuates considerably and depends on the type of substrate material, the properties of the metal salts used and the contact temperature generally about 0.1 to 30 minutes, preferably about 5 to 10 minutes.

As already mentioned, the metal phosphide can also be formed on the surface in that the Layer support is first brought into contact with the metal salt or complex salt solution to form the metal compound deposit on the substrate surface. The metal salts described above and complexes can be used under the conditions described above. So treated Layer support is then coated with white phosphorus as a vapor or liquid or in solution in one of the Treated the aforementioned solvent. The conditions described above also apply here. The surface obtained can then be electrolessly and / or electrolytically plated.

Depending on the conditions used in the two treatment stages, the duration of the treatment and the type of substrate treated, the treated surface obtained can either

1. be conductive so that the surface can be clektroplated by known methods, or

2. Be non-conductive.

In the latter case, the treated surface contains active or catalytic sites that the surface is responsible for exposes another electroless plating process in which a conductive coating is applied to the plastic surface. Such a conductive coating can then be applied by known methods be electroplated.

In a typical electroless plating process, a surface containing catalytic sites is contacted with a metal salt solution under conditions in which the metal ion of the metal salt is reduced to the metallic stage and deposited on the surface. The catalytic sites on the surface that result from the treatment with the metal salt or complex salt solution are essential. To apply a nickel coating to the surface having catalytic sites produced according to the invention, z. B. a solution of a nickel salt in an aqueous hypophosphite solution. Common hypophosphites are the alkali metal hypophosphites, such as sodium hypophosphite and potassium hypophosphite, and the alkaline earth metal hypophosphites. such as calcium hypophosphite and barium hypophosphite. Other metal salts suitable for use as a chemical treatment bath are those described above with regard to the metal salt treatment of phosphor-treated substrates. Other reducing agents are formaldehyde, hydroquinone and hydrazine. Other additives such as buffers unc

S "

Complexing agents, can be included in the chemical plating 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 Metal is usually dissolved in an aqueous plating bath, but other media can also be used will. In general, a salt solution of the metal to be plated can be used. One can also use an anode made from the metal to be plated. In some cases, however, a Carbon anode or another inert anode is used. Those suitable for electroplating Metals, solutions, and terms are listed in the Metal Finishing Guidebook Directory for 1967 by Metals and Plastics Publications, Inc., Westwood, N.J., V. St. Α.

The examples illustrate the invention. Refer to parts based on weight, unless otherwise specified.

Examples 1 to 7

Polyvinyl chloride, polyethylene and polypropylene pieces (plastic pieces) have been treated with solutions of phosphorus in various solvents. After being removed from the phosphorus solutions, the plastic pieces were immersed in a bath of the same solvent for 3 seconds. The adhering solvent was then allowed to evaporate, after which the plastic void was immersed in ammoniacal nickel sulfate solutions. In each case, the surface quality was assessed.
The various plastics and solvents used, 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 listed in Table I.

Several of the treated plastic pieces were then electroplated by placing each as a cathode in a nickel chloride plating bath. A current of 1 ampere, corresponding to a current density of 5.38 A / dm ² , was passed through the plating bath for 30 minutes. The electroplated pieces of polyvinyl chloride produced according to Example 10 were subjected to a warm-cold test in which the plastic was immersed in water at 50 to 55 ^° C. for 1 minute

ao was then immersed in crushed dry ice at -7O ^{0 C for 1 minute.} This thermal cycle treatment was repeated eight times in a row. After that, no cracks could be found on the nickel-plated layer.

The nickel-plated polyethylene pieces prepared in Example 5 became five of the above Subjected to hot-cold treatment cycles. In the After that, no cracks could be found in the nickel-plated layer.

Table I.

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

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

The nickel-plated polypropylene pieces produced according to Example 7 were subjected to a peel and lift test where it was observed that a force of 1.3 kgf was required to pass a 12.7 mm peel off a wide metal strip from the plastic surface. This corresponds to a joint strength of 1.02 kgf / cm.

Example 8

A polyethylene film was first treated with a solution of yellow phosphorus in trichlorethylene for 2 minutes at 55 ° C, 15 seconds at room temperature in air dried and then placed for 10 minutes at 90 ⁰ C in a 10 ° / _o strength nickel sulfate solution, which strongly with ammonia had been made alkaline.

The polyethylene film treated in this way was electroplated with copper by inserting the plastic film as a cathode in a copper plating bath made of copper sulfate, sulfuric acid and hydrochloric acid and copper-plating it with a current density of 2.15 A / dm * for 30 minutes. After an approximately 12.7 μm thick copper layer had deposited, the plated polyethylene film was used as a cathode in a nickel plating bath and ^{nickel-plated for 30 minutes at a current density of 2.15 A / dm s} until an approximately 12.7 μm thick nickel layer was deposited . The composite copper-nickel plating had a joint strength of about 1.4 kgf / cm.

409629 / 26C

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 had been set to 13.

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

10

Examples 10 to 44

Various plastics have been made with solutions of yellow phosphorus in a variety of solvents treated. The plastic pieces treated with phosphorus were then treated with an aqueous ammoniacal saline solution for 10 minutes and then according to the »Metal Finishing Guide

ίο Book ", 1966, pp. 260 to 262, known processes or using a galvanic bath of the type described by Dorl, a so-called "Watts bath" galvanically nickel-plated (this method of electroplating with nickel is hereinafter referred to as »Watts Nickel plating «). The joint strength of the nickel plating layer obtained was determined in each case.

Table II

plastic Solvent for
phosphorus Temperature of 86 Contact time Joint strength at
game Phosphorus solution 80 Minutes kp / cm Polypropylene Trichlorethylene "C 85 2 4.39 10 Polypropylene benzene 118 2 5.36 11th Polyethylene (high density) Trichlorethylene 80 5 8.27 12th Polyethylene (high density) Perchlorethylene 53 10 1.68 13th Polyethylene (high density) benzene 55 2 6.96 14th Polyethylene (high density) chloroform 80 2 0.95 15th Polyethylene (low density) Monochlorobenzene 55 2 1.54 16 Polystyrene benzene 121 2 0.29 17th Polyvinyl chloride Trichlorethylene 53 0.5 8.48 18th Polyvinyl chloride Perchlorethylene 53 1 6.25 19th Polyvinyl chloride benzene 53 2 7.32 20th Polyvinyl chloride Monochlorobenzene 74 2 2.52 21 Polyvinyl chloride chloroform 53 2 0.95 22nd Polyvinyl chloride Methyl chloroform 2 0.54 23 Polyvinyl chloride with 10% poly Perchlorethylene 53 2 7.50 24 vinyl acetate Polyvinyl chloride with 10% poly benzene 50 to 55 1 6.91 25th vinyl acetate Acrylic acid polyvinyl chloride poly Trichlorethylene 2 3.02 26th merisat 50 to 60 ABS polyvinyl chloride polymer Trichlorethylene 87 0.29 27 ABS resin Trichlorethylene 60 0.05 1.05 28 Polycarbonate Trichlorethylene 60 0.5 0.29 29 Diallyl phthalate resin Trichlorethylene 47 5 30th Phenol formaldehyde Trichlorethylene 53 5 31 Phenol formaldehyde Carbon disulfide 74 5 32 Polystyrene acrylonitrile benzene 73 0.083 1.32 33 Polymethacrylic acid methyl ester Methyl chloroform 45 5 1.68 34 Polymethacrylic acid methyl ester Monochlorobenzene 50 5 0.50 35 Polyphenylene oxide Trichlorethylene 0.033 3.1 36 modified thermoplastic Trichlorethylene 50 0.033 37 Phenylene oxide resin Modified soft tube Trichlorethylene 50 0.05 *) 38 made of polyvinyl chloride Hose made of filler included Trichlorethylene 50 0.83 *) 39 the rubber 70 to 75 rubber tube Trichlorethylene 60 to 73 0.25 *) 40 Cotton fabric Trichlorethylene 60 2 *) 41 Acetate silk fabric Trichlorethylene 60 10 *) 42 Nylon fabric Trichlorethylene 5 *) 43 Polyvinylidene resin fabric Trichlorethylene 5 *) 44

·) The peeling and lifting tests could not be carried out on the hoses and fabrics, but they stuck onDlated metal films very well.

In Table II, the plastics used for the respective examples, solvents for the Phosphorus, phosphorus solution temperatures and the contact times with the plastic are given. For the The second treatment stage in Examples 26, 27 and 37 to 40 was an ammoniacal nickel acetate solution, in Examples 30 and 31 an ammoniacal nickel cyanide solution, in all other examples an ammoniacal nickel sulfate solution is used. On the treated plastics of Examples 30 to Catalytic nickel phosphide had deposited on 32. 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 with a saturated solution of phosphorus in trichlorethylene (Example 45) or with treated a 50% saturated solution of phosphorus in trichlorethylene (Example 46). It was the polypropylene is treated with the phosphorus solution for 2 minutes at 80 to 85 ° C, then dried and then 10 minutes at 90 ° C in one

immersed in ammoniacal nickel sulfate solution. The treated plastics were electroplated in a Watts bath, a current of 5.38 A / dm ^{2 being used for} 30 minutes in Example 45 and 40 minutes in Example 46. The joint strengths of the nickel layers obtained were 2.52 kp / cm (Example 45) and 3.14 kp / cm (Example 46).

ίο B e i s ρ i e 1 e 47 to 57

In Examples 47 to 56, polyethylene pieces were used 1 to 7 minutes at temperatures in the range of 56 to 65 ° C with a saturated solution of

treated with yellow phosphorus in trichlorethylene. Irish In Example 57, a piece of polyvinyl chloride containing 10% polyvinyl acetate was prepared in an analogous manner 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 by Watts nickel plating with Nick «! electroplated. In Table III are the used th metal salts, the salt solution temperatures, the contact times of the plastic pieces with the salt solution: the joint strengths of the nickel layers are listed

Table 111

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

·) Joint strength in kp / cm.

Examples 58 to 63

In Examples 58 to 63 Folyäthylenstücke 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, which were complexed with different pyridines, amines, and quinolines. This treatment stage resulted in lea ting layers on the plastic surfaces, on which galvanically firmly adhering metal layers could be plated. In Example 63, a nickel phosphide layer was obtained which catalyzes the deposition of nickel from an electroless plating bath. Table IV lists the metal salts, the complexing agents, the salt solution temperatures and contact times.

Table IV

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

Example 64

A phenol-formaldehyde resin molding was treated with sodium hydroxide for 12 minutes at 90 ^° C., then for a few minutes at about 60 ^° C. with a saturated solution of yellow phosphorus in trichlorethylene and then for 5 minutes at 80 ^° C. with an aqueous ammoniacal nickel sulfate solution. 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 was conductive. Finally, the shaped body was provided with a further nickel layer by means of Watts nickel-plating.

Example 65

A Polyäthylenpreßling was dipped for 3 minutes at 72 ⁰ C in a mixture of yellow phosphorus, trichlorethylene, ethanol and nickel nitrate. Sufficient ammonia was then added to the mixture to make it strongly alkaline. The polyethylene compact was left in the ammoniacal solution for 10 minutes. After that, its surface was covered with a light gray nickel phosphide layer, onto which firmly adhering MetaM layers could be plated.

Example 66

Polypropylene was immersed in a 10% nickel acetate solution at 60 ° C. for 6 minutes, which was then dissolved of nickel acetate in a solvent made up of 1 volume of ethanol and 3 volumes Trichlorethylene and a small amount of ethylene diamine to form a dark blue color Complex existed. The thus treated polypropylene was air-dried and poured into a saturated one Solution of yellow phosphorus in a mixture of 5 parts of trichlorethylene and 1 part of ethylenediamine submerged. The temperature of the phosphor solution was 60 ° C. The polypropylene was quickly immersed and taken out of the solution ten times in a row and the solvent evaporated. The treated like that 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 ° / "solution of phosphorus in trichlorethylene and then at 90 ⁰ C with a 10 ° / o NickehuUatlösung with excess ammonia at 60 ⁰ C with ίο. The supports and contact times are given in Table V.
Table V

example

67
68

69

₇₀

71
72

Support

wood

cardboard

cork

Porous clay
Asbestos cement
porcelain
(unglazed)

Time in the
Phosphorus solution

Minutes

Time in the nickel sulfate solution

Minutes

The substrates of Examples 67 to 70 treated in this way and some of those from 71 were ^{electroplated with nickel at 55 ° C. and a current density of 5.38 A / dm 2} and thus provided with an adhesive nickel coating. The treated substrate of Example 72 and the remainder of the treated substrate of Be ^! - Spiels 71 were electrolessly nickel-plated according to the process known from US Pat. No. 3,649,713, with a conductive nickel layer being applied.

Example 73

A piece of leather was treated with a 2 ° / _o by weight phosphorus solution in trichlorethylene for 3 minutes at 60 ⁰ C and then for 5 minutes at 60 ° C with a solution of nickel acetate and excess ammonia. The treated piece was conductive and had a shiny nickel coating after it was electroplated ^{at 55 ° C and a current density of about 5.38 A / dm 2.}

Example 74

A piece of porous glass was treated with a 2 ° / _o solution of phosphorus in trichlorethylene at 60 ° C and then immersed in a nickel sulphate solution with excess ammonia at 90 ⁰ C. The glass treated in this way was electroplated with nickel at 55 ° C. and at a current density of about 5.38 A / dm ^2.

Claims (3)

1 2 In this process typical of the state of the art in terms of its complexity and time-consuming process, the nickel deposition bath and the 1. Process for the production of a copper, nickel plating bath no pure nickel layers, but nickel and / or silver-plated non-metallic 5 which deposit nickel-phosphorus alloy layers, see layer base, thereby identifying the traces not only because of their conductivity, that either the following galvanic copper plating is possible, but a) the substrate surface with a the a firm anchoring of Kupferplattie solvent dissolved or vapor ^run 8 ^b ^ ^'strength' ·. ^The \ f N.ckel ^{rtl-phosphorus} Leg.erun- or liquid white phosphorus and subsequent ^1O gene and its property of being thin films or closing with a solution of metal salts * layers process or in this form making or enter into a metal salt complex of copper ^{to Iassen S0Wle mlt} Melallschichten a fixed versus nickel and / or Silher or ^lateral 8 ^e anchoring , are also from the nickel and / or silver or USA.-Patent 3 282 737, the magazine "Metall", b) the layer carrier surface first with a _{i5 17} q _{963) h 5 s 4} 5i _{un {} j456 and the German Aus solution of the metal salt concerned or Weschrift 1 059 738 known. Eraturstelle from the last-mentioned metal salt complex and then corresponds _Lit is however also known that such by not having dissolved in a solvent _electroless deposition on plastic plates or or vapor or liquid we.ßem _N i _chlme Tailen layers produced nickel-phosphorus treated and then de-energized and _{2 <J and / or} cobalt-phosphorus alloys only poorly or electrolytically _{adhere to copper, stainless steel and / to non-metallic layer carriers} because they are plated or silver-plated. _{without tearing easily as fo} | _{ien from the} substrate 2. The method according to claim 1, characterized in this way. shows that the metal salt complex is an amine- The invention is therefore based on the object complex of nickel sulfate, nickel chloride, nickel-25 to create a process by which on layer substrates acetal, 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 characterized in that a substrate 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 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 a layer support plated with copper, nickel and / or silver initially with vaporous, liquid non-metallic substrate. 40 or white Phos-Es dissolved in a solvent There is a growing demand for with phor and then with a solution of a copper, nickel metal plated objects, e.g. B. plastic and / or silver salt or salt complexes subject matter with a metal-like appearance. Such delts or vice versa, before one can recognize it in objects that are known in themselves are, for example, in vehicle construction, galvanically or electrolessly copper-plated, verfür Household, radio and television sets and for ornamental 45 nickel and / or silver-plated. container required. So far, the metal plate required - the invention thus provides a method of plastics, there are many process stages, and of the type described at the beginning, which is characterized by in general, such procedures were only for one person or that one is either applicable to a few similar substrates. _{} the} substrate surface with in a solution * 1 £ J « ^{example els} _f ^w ? ^{se from the} USA patent _{specification 5} oj,, _ö * _{O (kr vaporous or liquid} . 3 154 478 a process for copper-plating non- ⁸ _{ßem Ph hor and} then with a metallic layers known, in which the to * -; Metal salt or a metal salt verkupfernde first surface by sandblasting, _komp LLS of copper, nickel and / or silver Steam blasting, brushing, grinding, etching or the like. refreshed or roughened, under certain conditions 55 ,,,. ".,,",.
carefully rinsed conditions, then ^the Sch.churageroberflache ^b steam) first with "" he degreased again carefully cleaned, acidified ^{of the} relevant metal salt or metallic acid with sulfuric ^Loslin 8, again thoroughly rinsed, then salt-complex, and then either in with an activating Solution of a salt from the group ^{dissolved in a} solvent or in vapor form, in particular a platinum group metal ^{salt, 60 B en} ? "The liquid white phosphorus treated like palladium chloride, treated, dried / electrolytic plated in one and then de-energized and or reducing, for example hypophosphite corresponds ^Ku P ^fer · ^Nickel ^ ά / οά ^ τ silver,
holding solution dipped, rinsed again, in a nickel deposit bath, rinsed again, z. B. one-sided mirrors, water and liquid stripped with sulfuric acid, in a chemical collecting device, protective coatings on houses, nickel-plating bath electrolessly nickel-plated, thoroughly dried by a motor vehicle, boat, power pole and street-long heat treatment and lighting and the heat insulation of degassed and then finally galvanic is copper-plated. Improve fabrics and homes.