U.S. patent number 3,930,109 [Application Number 05/385,148] was granted by the patent office on 1975-12-30 for process for the manufacture of metallized shaped bodies of macromolecular material.
This patent grant is currently assigned to Hoechst Aktiengesellschaft. Invention is credited to Irmgard Bindrum, Wilhelm Brandt.
United States Patent |
3,930,109 |
Brandt , et al. |
December 30, 1975 |
Process for the manufacture of metallized shaped bodies of
macromolecular material
Abstract
This invention relates to a process for the deposition of a
metal coating on the surface of a shaped body of macromolecular
material which comprises forming a layer of a noble metal salt
solution or dispersion of a film-forming macromolecular material on
the surface of a solid support material, Heating the coated support
to remove the liquid and form a film, Treating the film with a
metallization liquid, and drying.
Inventors: |
Brandt; Wilhelm (Wertach,
DT), Bindrum; Irmgard (Wiesbaden-Biebrich,
DT) |
Assignee: |
Hoechst Aktiengesellschaft
(DT)
|
Family
ID: |
27431218 |
Appl.
No.: |
05/385,148 |
Filed: |
August 2, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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231825 |
Mar 6, 1972 |
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Foreign Application Priority Data
Current U.S.
Class: |
428/422; 427/306;
427/371; 427/443.1; 427/101; 427/305; 427/367; 427/383.1;
428/463 |
Current CPC
Class: |
C23C
18/34 (20130101); C23C 18/206 (20130101); D06Q
1/04 (20130101); H01B 1/00 (20130101); C23C
18/30 (20130101); Y10T 428/31699 (20150401); Y10T
428/31544 (20150401) |
Current International
Class: |
C23C
18/20 (20060101); C23C 18/31 (20060101); H01B
1/00 (20060101); D06Q 1/04 (20060101); D06Q
1/00 (20060101); C23C 18/34 (20060101); B05D
5/12 (20060101); B05D 7/02 (20060101); C23C
003/02 () |
Field of
Search: |
;117/47A,138.8UF,138.8UA,138.8PV,143B,13E,16R,213 ;428/421,422 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Willis, Jr.; P. E.
Attorney, Agent or Firm: Bryan; James E.
Parent Case Text
This is a division of application Ser. No. 231,825, filed Mar. 6,
1972.
Claims
What is claimed is:
1. A self-supporting film of polytetrafluoroethylene having a noble
metal salt dispersed therein and a metal coating selected from the
group consisting of copper and nickel on the surface of said
film.
2. A self-supporting film according to claim 1 in which the noble
metal salt is selected from the group consisting of palladium
chloride, platinum chloride or silver nitrate.
3. A self-supporting film according to claim 1 in which the weight
ratio of polytetrafluoroethylene to noble metal salt disposed
therein is in the range of about 5 : 1 to 25 : 1.
Description
The present invention relates to a process for the deposition of a
metal coating on the surface of a shaped body, particularly a
sheet, of macromolecular material. The invention also relates to
shaped bodies of macromolecular material with metallized surfaces,
particularly to sheet materials.
It is known to provide shaped bodies of non-electroconductive
plastics, e.g. of polystyrene, acrylonitrile/butadiene/styrene
copolymers, polyolefins, and polyesters, if desired after suitable
pretreatment, with thin metal coatings either by electroplating or
electroless plating.
In this connection, a process has proved particularly suitable in
which a very thin layer of noble metal nuclei is deposited on the
plastic surface, In this process, the surface is sensitized and a
noble metal salt solution and activated with a solution of a
reducing agent. BY means of electroplating or electroless plating
baths, continuous metal layers are deposited at the noble metal
nuclei.
In such a pretreatment, for example, the surface is first treated
with a palladium salt solution, e.g. PdCl.sub.2, and then with a
hydrazine hydrate solution, or first with a stannous chloride
solution and then with a silver nitrate solution. In each case,
small quantities of elemental noble metal are deposited on the
surface.
The present invention provides a process by which it is possible to
deposit, by electroless plating on the surface of a shaped body, a
metal coating firmly adhering to the polymer surface of the shaped
body and which eliminates the disadvantages of known processes.
In the present process for the deposition of a metal coating on the
surface of a shaped body of synthetic or natural macromolecular
material, a noble metal salt solution or dispersion of a
film-forming macromolecular material, which optionally may contain
a wetting agent, is spread on the surface of a solid support
material to form a layer and, for removing the liquid component of
the layer and for forming a continuous film on the support,
sufficient heat is caused to act on the coated support. Then,
optionally, an activating solution is caused to act thereon and, in
a further process step, metallization liquid is caused to act on
the film-carrying support. Optionally, the film then is stripped
from the support.
A shaped body of macromolecular material means in particular a
sheet material of macromolecular material which is self-supporting,
as well as a composite material comprising a mechanically stable
support sheet material and a film of macromolecular material firmly
adhering thereto.
A film capable of being stripped from the solid support without
leaving any residue is self-supporting.
The self-supporting film has two free surfaces and the film
adhering to the substrate one free surface accessible to
metallization.
The support material may have a continuous structured or
structureless surface.
It is also possible to use textile sheet materials as supports.
The layer of a liquid polymer dispersion or solution which is first
to be applied to the support according to the process of the
invention is applied by known processes to the surface of the
support material, e.g. by doctor devices, and levelled. The liquid
component of the layer is then removed, e.g. by subjecting the
coated support material to heat at a temperature sufficient to
remove the liquid component. This may be performed, for example, by
means of a drying cabinet operated with warm air or in a drying
channel.
For the production of a sintered film of polytetrafluoroethylene, a
liquid layer of an aqueous tetrafluoroethylene dispersion spread on
a sufficiently heat-resistant solid support is exposed in known
manner to heat at a temperature of about 100.degree.C; after
vaporizing the liquid component of the layer, heat in the
temperature range above 300.degree.C, preferably in the range
between 380.degree. and 400.degree.C, is applied to the coated
support material in order to form a sintered film of
polytetrafluoroethylene on the surface of the support. The time of
the heat action is not critical.
The invention further provides a modification of the said process
including, when using a polymer dispersion and a discontinuous
layer is produced on the surface of the support after vaporization
of the dispersing agent, heating the metallized layer sufficiently
to form a sintered film of the polymer.
In the following, the liquid containing the noble metal salt and
the film-forming macromolecular substances in dispersed or
dissolved form is called the "sensitized liquid containing
film-forming macromolecular material." The liquid used for
metallization of the shaped bodies, which contains ions reducible
to yield free metal and a reducing agent in an aqueous solution, is
called the "metallization liquid." Furthermore, the metal baths
generally contain substances forming complexes with the metal ions,
which complexes provide for the necessary stability of the bath and
which act on the structure of the metal layer to be formed, e.g. as
glossing agents.
The metallization liquid contains no dissolved noble metal
salt.
An aqueous solution of a chemical reducing agent is called the
"activating liquid".
Suitable aqueous noble metal salt solutions have a content of noble
metal salt in the range from 0.001 to 10 per cent by weight,
calculated on the total weight of the solution.
Suitable noble metal salts for the production of the sensitized
liquid containing film-forming macromolecular material are
palladium chloride, gold chloride, platinum chloride, and silver
nitrate.
Aqueous noble metal salt solutions may be ammoniacal or acidic.
Since the described noble metal salts dissolve in acidic media as
well as in ammoniacal aqueous media, the aqueous noble metal salt
solutions may be incorporated into ammoniacal as well as into
acidic aqueous polymer dispersions or solutions.
If permanent adhesion of the film of polymer material to the
support is desired, it is necessary to add to the polymer
dispersion or solution a suitable wetting agent, e.g. dodecyl
benzene sulfonate, in a quantity of at least 0.1 per cent by
weight, calculated on the total weight of the dispersion.
Polymer solutions or dispersions are those which contain natural or
synthetic film-forming macromolecular substances, particularly
those with a thermoplastic character, in a dissolved or dispersed
form.
The solvent or dispersing agent may be water or an organic
liquid.
Suitable macromolecular substances are: vinyl polymers and the
copolymers thereof, e.g. polyvinyl chloride, copolymers of vinyl
chloride and vinyl acetate, vinylidene chloride copolymers,
polytetrafluoroethylene, polystyrene, synthetic elastomers, e.g.
polyurethane or polyacrylates, polymethacrylates, as well as the
copolymers thereof, natural rubbers and synthetic rubbers,
polyolefins, cellulose derivatives, polycarbonates, epoxides,
polyesters, melamine condensates, urea condensation products,
phenol-formaldehyde condensation products, polyamides, and
polyphenyls.
If the liquid component of the sensitized liquid containing
film-forming macromolecular material is an organic liquid, the
noble metal salt is incorporated into the liquid in a manner such
that it is dissolved in a suitable solvent, e.g. in acetone or
butanone, and this solution is then added to the liquid containing
the polymer.
The metallization liquid has a solids content of metal salt in the
range from 5 to 20 g, preferably from 7 to 10 g, per liter of
copper salt-containing metallization liquid, and 10 to 50 g,
preferably from 20 to 30 g, per liter of nickel salt-containing
metallization liquid.
Suitable salts are CuSo.sub.4 and NiSO.sub.4.
It is particularly advantageous to use metallization liquids which
contain a chemical medium capable of complex formation with the
metal salt; these complex-forming agents maintain the concentration
of the metal ions in the metallization liquid low.
Chemical reducing agents in the metallization liquid are, for
example, sodium hypophosphite, sodium hydride or nitrogen diethyl
borane; formaldehyde, hydrazine hydrate as well as sodium bisulfite
are suitable for copper salt-containing liquids.
Particularly suitable for the production of the aqueous activating
liquid are stannous chloride combined with hydrochloric acid
dissolved in water and hydrazine hydrate in an alkaline
solution.
In some cases, it is advantageous to activate the palladium
chloride-containing plastic layers, prior to their metallization,
with hydrazine hydrate solution. It may be ascertained by simple
preliminary tests whether deposition of the metal salt from the
metallization liquid takes place sufficiently rapidly without
previous activation of the layer by the action of hydrazine hydrate
solution.
It is advantageous to use metallization liquids which contain a
stabilizer for the reducing agent, e.g. telluric acid in nickel
salt baths.
The stabilizer for the chemical reducing agent generally is
employed in a concentration in the range from 0.001 to 2 per cent
by weight, calculated on the total weight of the liquid. In special
cases, it is advantageous when copper-containing metallization
liquids contain a gloss-imparting additive, e.g. saccharin, in a
concentration of 0.01 g/l.
The ratio by weight of metal salt to chemical reducing agent in the
metallization liquid advantageously is so selected that the
reducing agent is in excess.
The metallization liquid in accordance with the process has a
temperature in the range from 30.degree. to 100.degree.C, in the
case of a nickel salt-containing liquid, and a temperature in the
range from 20.degree. to 50.degree.C in the case of a copper
salt-containing liquid.
The time of action of the metallization liquid upon the shaped body
depends upon the metal quantity to be deposited per unit area.
For depositing, for example, a 0.2 mm thick metal layer, a time in
the range from 1 to 10 minutes is required, depending on the
chemical composition of the metallization liquid or the metal salt
concentration thereof.
The metallized shaped bodies produced according to the process of
the invention have metal coatings of a thickness in the range
between 0.02 and 0.25 .mu..
The metal coatings are abrasion-resistant and firmly adherent to
the polymer surfaces of the shaped bodies.
A firmly adherent coating means a coating which cannot be separated
from its contact surface of polymer material by the adhesive tape
test.
The adhesive tape test is performed as follows:
A crisscross pattern is scratched into the surface of the metal
coating on the shaped body, which pattern is then covered with an
adhesive tape having a pressure-sensitive layer. The adhesive tape
is then stripped with a pull. The metal coating is firmly adherent
to its contact surface when the metal coating cannot be separated
from its contact surface under the aforementioned conditions.
The process of the invention is performed in a manner such that
first the solution of a noble metal salt is added to a polymer
dispersion or to a polymer solution. The solids content of the
polymer dispersion or of the polymer solution is not critical in
the usual viscosity range of easily spreadable or castable
solutions.
When preferably using as the aqueous polymer dispersion a
dispersion of polytetrafluoroethylene, this dispersion
advantageously has a polymer portion in the range from 1 to 10 per
cent by weight, calculated on the total weight of the dispersion,
particularly preferably, however, in the range from 5 to 8 per cent
by weight.
The ratio by weight of the polymer to the noble metal salt in the
liquid obtained after the mixing of the polymer dispersion or
solution with the noble metal salt solution is in the range between
2 : 1 and 100 : 1, preferably in the range between 5 : 1 and 25 :
1.
The liquid obtained by mixing the polymer dispersion or the polymer
solution with the noble metal salt solution is then applied in the
form of a layer to a self-supporting planar support of sufficient
inherent rigidity and sufficient strength. The material forming the
support must be chemically resistant to the liquid components of
the liquid layer applied to the support.
The support must be chemically resistant as well as sufficiently
mechanically stable in the temperature range in which vaporization
of the liquid component of the layer applied to the support takes
place.
Suitable supports are those of synthetic or natural organic
material as well as of inorganic material which fullfil the
above-mentioned conditions. For the production of preferable shaped
bodies of polytetrafluoroethylene with metallized surfaces,
supports particularly suitable are those of glass, steel, aluminum,
unglazed porous clay, unglazed ceramic material or roughened
polyimide film. All these supports are well wetted by aqueous
polytetrafluoroethylene dispersions containing wetting agents. The
support for a shaped body of polytetrafluoroethylene must be
thermally resistant in the range between 250.degree. and
400.degree.C.
After the application of the liquid layer to the support, the
coated support is exposed to heat sufficient to vaporize the liquid
components of the applied layer; the temperature to be maintained
during heating depends upon the boiling point of the liquid
component of the layer which must be vaporized.
The heating of the coated support may take place, for example, in a
drying cabinet operated with warm air.
If a copper layer is to be applied, it is advantageous, prior to
the action of the copper salt-containing metallization liquid, to
treat the surface of the polymer film with activating liquid.
Metallization liquid is then caused to act upon the support
provided with a polymer film. This may be performed by immersing
the support provided with a polymer film into a tank filled with
metallization liquid. After removal of the film-carrying support
from the tank, the shaped body with the metallized surface of the
polymer film is treated in a rinsing liquid, preferably water, and
liberated from the rinsing liquid by drying.
In accordance with the invention, the production of a
self-supporting film from polymer material, the surface of which is
metallized, is performed by using a planar sheet material as the
support, to the surface of which is applied the above-mentioned
liquid layer in the manner described above and, after the formation
of a metal layer on the film of polymer material, this film is
stripped as a self-supporting film from the support.
If the film to be metallized and united with a support or the
self-supporting film to be metallized is of
polytetrafluoroethylene, film formation must be performed by a
sintering process on a support. In this case, after the application
of the aqueous palladium chloride-containing
polytetrafluoroethylene dispersion to the support, first the liquid
component of the layer is removed by heating sufficient to vaporize
this component, and the coated support is then exposed to heat
sufficient to produce a sintered film of polytetrafluoroethylene on
the surface of the support.
A sintered film is a continuous voidless film in which, by the
action of heat, the plurality of discrete particles of
polytetrafluoroethylene on the surface of the support fuse to form
a continuous film.
Film formation on the support also may be performed continuously by
applying a liquid layer in known manner, for example by means of a
doctor knife, to the surface of a web support moving at a constant
speed, levelled, and then converted in the described manner into a
polymer film. In connection with the preferred production of
metallized shaped bodies of polytetrafluoroethylene, the following
should be borne in mind:
When the solid support has a rough surface, the film produced by
sintering the polytetrafluoroethylene particles on the support
adheres thereto in any case. The film, for example, adheres
inseparably to a surface of a glass plate roughened with silicon
carbide paste (depth of rougheness 11 .mu.), independently of
whether sintering of the film has occurred prior to or after the
action of the metallization liquid.
When the support has a surface of a smaller depth of roughness,
adhesion of the metallized polytetrafluoroethylene film depends
upon whether the layer has been sintered prior to or after
metallization.
When, for example, a palladium chloride-containing aqueous
polytetrafluoroethylene dispersion is applied to a grease-free
roughened surface of a steel plate (depth of roughness 3.5 .mu.),
the dispersion is dried, the layer of a plurality of discrete
particles is metallized by the action of the metallization liquid
and the layer is then sintered, the metallized film cannot be
stripped from the steel plate surface. When, however, the aqueous
polytetrafluoroethylene dispersion is applied to the polished
surface of the steel plate and the polytetrafluorroethylene layer
is dried, sintered and only then metallized by the action of the
metallization liquid, the metallized polytetrafluoroethylene film
can be stripped from the support without leaving any residue. In
this manner, it is possible to produce self-supporting films with
metallized surfaces.
When the palladium chloride-containing aqueous
polytetrafluoroethylene dispersion is coated onto a grease-free
polished surface of a glass plate or of a high-luster polished
steel plate (depth of roughness < 0.1 .mu.) and then dried, the
metallized film can be stripped from the support in the form of a
self-supporting film independently of whether the action of the
metallization liquid has taken place prior to or after
sintering.
If the production of self-supporting metallized films of
polytetrafluoroethylene is desired, the support to which the
polytetrafluoroethylene dispersion is applied must be so selected
that easy separation of the sintered metallized film therefrom
without any residue is guaranteed.
It is possible, for example, to apply the dispersion continuously
to the polished surface of a drum. At the periphery of the drum, is
a device for the application of the aqueous dispersion, a device
for drying the applied layer, a device by means of which it is
possible to cause the metallization liquid to act upon the dry
polytetrafluoroethylene layer, and a heating device for effecting
sintering of the layer to give a film. In this manner, it is
possible to continuously strip from the surface of the rotating
drum a self-supporting metallized film of polytetrafluoroethylene
in the form of a self-supporting web.
The metal coating applied to the polytetrafluoroethylene film,
self-supporting or not, may serve as an adhesive for substances
which, without the adhesive metal coating on the
polytetrafluoroethylene film, cannot be firmly united with a shaped
body of polytetrafluoroethylene.
Plastics adhering to the metal coating, for example, may be
sufficiently deposited from solutions, dispersions or melts in the
form of self-supporting sheet materials, e.g. by laminating while
hot, to the metallized surface of the polytetrafluoroethylene
layer.
For these cases, it is sufficient if the metal layer imparting
adhesion is very thin, e.g. has a thickness of 0.1 .mu..
In this manner, it is also possible to produce sandwiches
constructed from a plurality of alternately superimposed layers of
polytetrafluoroethylene and metal. The individual metal layers may
be similar or different.
The quantity og noble metal salt in the aqueous
polytetrafluoroethylene dispersion which is necessary to form a
continuous metal coating deposited by electroless plating on the
surface of the polytetrafluoroethylene layer determines:
1. the fluocculation of the dispersed plastic material or the
stability of the dispersion during drying of the layer on the
support,
2. the speed of deposition of the metal from the metallization
liquid on the layer of polytetrafluoroethylene, and
3. the continuity of the metal coating deposited on the surface of
the polytetrafluoroethylene layer.
The shaped bodies metallized according to the process of the
invention may be used as electrical resistance elements. When using
a shaped body of a metallized film of macromolecular material which
adheres to a support, the support must be an electrically
insulating material.
The invention will be further illustrated by reference to the
accompanying drawing, in which:
FIG. 1 shows a sheet material with a metallized surface (which
consists of a substrate with a continuous surface) of a noble metal
salt-containing layer of macromolecular material thereon and a
coating of metal on the surface and firmly adhering thereto,
and
FIG. 2 shows a noble metal salt-containing self-supporting film of
macromolecular material on the surface of which there is a firmly
adhering metal coating.
The self-supporting film with the metallized surface according to
FIG. 2 is obtained by stripping the film 2 with the metallized
surface from the substrate 1 according to FIG. 1.
Referring to FIG. 1, numeral 1 identifies the substrate, numeral 2
identifies the noble metal salt-containing film of macromolecular
material, numeral 3 the noble metal salt uniformly distributed over
the cross-section of the film, and numeral 4 identifies the metal
coating.
Referring to FIG. 2, numerals 2, 3, and 4 have the same meanings as
in FIG. 1.
The following examples further illustrate the invention:
EXAMPLE 1
A 60 percent by weight aqueous polytetrafluoroethylene dispersion
(e.g. Hostaflon TF 32, registered trade mark of Farbwerke Hoechst
AG, Frankfurt, Germany), which contains 5 percent by weight of a
non-ionic wetting agent, i.e. a reaction product of ethylene oxide
and nonyl phenol (Hostapal, a registered tade mark of Farbwerke
Hoechst AG, Frankfurt, Germany) and 0.04 percent by weight of
ammonia is diluted with water in a ratio of 1 : 12.
A 5 percent by weight aqueous polytetrafluoroethylene dispersion is
obtained thereby. To 86 ml of this diluted aqueous
polytetrafluoroethylene dispersion, there is added a solution of
0.2 g of palladium chloride dissolved in 10 ml of concentrated
ammonia and 0.8 g of the sodium salt of dodecylphenyl sulfonic acid
dissolved in 4 ml of water. The liquid thus prepared has a content
of 4.3 per cent by weight of polytetrafluoroethylene and 0.2 per
cent by weight of palladium chloride: the ratio of palladium
chloride to polytetrafluoroethylene in the dispersion is 1 :
21.5.
The pH value of the liquid is 8.0.
One support used for the liquid layer of the above-described
composition is an aluminum plate of a depth of roughness of 4.8
.mu., and another one a glass plate of a depth of roughness of 11
.mu..
A liquid layer of the above-described palladium chloride-containing
aqueous polytetrafluoroethylene dispersion is applied to each of
the two plates. The application is performed by casting the liquid
onto the surface of the support and levelling the layer thickness.
The coated plate is dried for 2 minutes in a drying cabinet at
90.degree.C. After removal from the drying cabinet, the plates are
placed into a liquid bath of the metallization liquid which is
prepared as follows: 25 g of NiSO.sub.4 .sup.. 7 H.sub.2 O are
dissolved in 200 ml of distilled water. A second solution is
prepared containing 24.4 g of Na.sub.2 H.sub.2 PO.sub.2 dissolved
in 200 ml of distilled water. Both salt solutions are combined and
27 g of d,1-lactic acid and 16.8 g of succinic acid, dissolved in
200 ml of distilled water, are added to the aqueous solution
containing the metal salt and the chemical reducing agent. The
solution is adjusted to a pH value of 6 by addition of caustic
soda. A small quantity of telluric acid is added to the solution,
which is then diluted with distilled water to 1,000 ml. The
metallization liquid has a temperature of 70.degree.C. The time of
action of the metallization liquid onto the supporting plates
coated with polytetrafluoroethylene is 1 minute. After this time of
action, the plates are removed from the bath and placed in a drying
cabinet heated to 380.degree.C. The plates remain in this drying
cabinet for 15 minutes. The sintered polytetrafluoroethylene layer
has a thickness of 1.1 .mu.; the nickel coating deposited by
electroless plating on its surface has a thickness of 0.2 .mu..
A crisscross pattern is scratched into the nickel coating by means
of a razor blade. A pressure-sensitive adhesive tape (e.g. a Tesa
tape marketed by Messrs. Beiersdorf, Hamburg, germany) is bonded
over the crisscross pattern and then stripped again with a pull.
The adhesive tape can be separated from the metal coating without
leaving any residue, i.e. the metal coating firmly adheres to the
polytetrafluoroethylene film.
Even after repeated sharp bending of the coated aluminum plate, the
plastic layer does not break; the nickel coating cannot be
separated.
EXAMPLE 2
A liquid layer of a palladium chloride-containing aqueous
polytetrafluoroethylene dispersion, as described in Example 1, is
applied to the surface of an unglazed porous clay plate and dried.
In contradistinction to Example 1, the plate is then placed for 5
minutes into a metallization liquid containing, instead of a nickel
salt, a 0.6 percent aqueous copper sulfate solution containing 1.5
percent of formaldehyde and 1.9 per cent of sodium hydrogen sulfite
(e.g. chemical copper deposition bath CP 70 of Messrs. Shipley).
Sintering takes place during 15 minutes at a temperature of
380.degree.C in a drying cabinet.
The metallization liquid has a temperature of 50.degree.C. The
copper coating on the film of polytetrafluoroethylene has a
thickness of 0.2 to 0.3 .mu.. Result of the adhesive tape test:
firm adhesion.
The polytetrafluoroethylene film provided with a copper coating
adheres firmly to the supporting plate. The thickness of the copper
coating applied to the polytetrafluoroethylene film by electroless
plating is then increased by electroplating to 10 .mu..
The 10 .mu. thick coating is subjected to the adhesive tape test.
Result: firm adhesion.
EXAMPLE 3
This example is similar to Example 1 with the exception that the
supporting plate used is a steel plate with a degreased high-luster
polished surface (depth of roughness 0.1 .mu.). The thickness of
the nickel coating deposited by electroless plating on the surface
of the polytetrafluoroethylene film is then increased to 10 .mu. by
electroplating with a further nickel layer. The film of
polytetrafluoroethylene has a thickness of 1 .mu..
The nickel-plated polytetrafluoroethylene layer can be easily
stripped from the support without leaving any rsidue.
The adhesion of the metal coating to the self-supporting
nickel-plated polytetrafluoroethylene layer is tested according to
the adhesive tape test. Result: firm adhesion.
EXAMPLE 4
An 8 percent aqueous solution of polyvinyl alcohol (e.g. Mowiol N
70-98 of Farbwerke Hoechst AG, Frankfurt, Germany) is prepared
which contains 0.1 percent of palladium chloride, calculated on the
solution weight, or 1.2 percent of palladium chloride, calculated
on the polyvinyl alcohol weight. A liquid layer of this solution is
applied to the roughened surface of a glass plate and dried for 5
minutes at 200.degree.C in a drying cabinet operated with warm air.
The dried polymer film has a thickness of 10 .mu.. The
film-carrying glass plate is then placed into a metallization
liquid of the composition described in Example 1. Duration: 1
minute. The plate is then removed from the bath and rinsed with
water. The nickel coating firmly adhering to the surface of the
polymer film has a thickness of about 0.2 .mu.. The thickness of
the applied nickel layer is then increased in known manner by
electroplating to 5 .mu., the time of action in the electroplating
bath is 20 minutes at a current density of 1 A/dm.sup.2, and the
electoplating bath has a temperature of 60.degree.C.
EXAMPLE 5
A 10 percent aqueous dispersion of a copolymer based on vinylidene
chloride/methyl methacrylate/methyl acrylate/itaconic acid which
contains an addition of 0.05 percent of palladium chloride,
calculated on the dispersion weight, or of 0.5 percent of palladium
chloride, calculated on the polymer component weight, is applied to
the surface of a textile fabric (cotton/nettle fabric) and dried
for 3 minutes at 130.degree.C. The layer thickness of the polymer
film formed on the support material is 10 .mu.. The polymer
film-carrying support material is then treated for 6 minutes in a
metallization liquid according to the procedure of Example 1. After
this treatment, a continuous nickel coating of a thickness of about
0.2 .mu. has formed on the surface of the polymer film to which it
firmly adheres.
EXAMPLE 6
The example is similar to Example 5 with the exception that the
coated textile material, after drying at 130.degree.C, is immersed
for 1 minute into a 0.6 percent aqueous hydrazine hydrate solution
containing 1.2 per cent of NaOH. The coated textile material is
then placed for 8 minutes into a metallization bath according to
example 2. A 0.2 .mu. thick copper coating is formed on the surface
of the polymer film on the support material.
EXAMPLE 7
A 10 percent aqueous dispersion of a copolymer based on acrylic
acid butyl ester is prepared which contains 0.1 per cent of
palladium chloride, calculated on the dispersion weight, or 1 per
cent of palladium chloride, calculated on the polymer component
weight. A layer of the liquid is applied to the surface of a
polyester film (e.g. Hostaphan, registered trade mark of Farbwerke
Hoechst AG, Frankfurt, Germany). The coated polyester film is dried
for 2 minutes at 130.degree.C in a drying cabinet operated with
warm air; the thickness of the dry layer of the copolymer film on
the surface of the polyester film is 7 .mu.. The coated polyester
film is bathed for 1 minute in a 0.6 percent aqueous hydrazine
hydrate solution containing 1.2 percent of NaOH and then rinsed
under running water.
a. One half of the coated polyester film is placed for 1 minute
into a metallization liquid of the composition described in Example
1. After treatment, a continuous, about 0.2 .mu. thick, nickel
coating has formed on the surface of the film of the copolymer.
b. The other half of the polyester supporting film coating with a
polymer is placed for 5 minutes into a metallization liquid
according to Example 2. After the indicated time of action, a 0.2
.mu. thick copper coating has formed on the surface of the film of
the polyacrylic ester copolymer.
The metal coatings produced are firmly adherent to the plastic film
surfaces.
The shaped body is suitable for use as an electrical resistance
element.
EXAMPLE 8
A 10 percent solution of polyvinyl acetate (e.g. Mowilith 50 of
Farbwerke Hoechst AG, Frankfurt, Germany) in acetone is prepared,
which contains 0.04 percent of palladium chloride, calculated on
the solution weight, or 0.4 percent of palladium chloride,
calculated on the polymer component weight, and applied to the
surface of a supporting film of cellulose acetate. The supporting
film coated with the liquid, is placed for 2 minutes into a drying
cabinet operated with warm air of 130.degree.C. After heat
treatment, the thickness of the polymer film on the supporting film
is 10 .mu..
The coated supporting film is divided into two parts of equal
size:
a. One part of the coated film is placed for 1 minute into a
metallization liquid according to the procedure of Example 1. A
continuous 0.2 .mu. thick nickel coating is formed on the surface
of the polyvinyl acetate film.
b. The other half of the coated film is bathed in a 0.5 per cent
aqueous stannous chloride solution and then rinsed under running
water. The thus treated film is then placed for 5 minutes into a
metallization liquid according to the procedure of Example 2. A 0.2
.mu. thick continuous copper coating is formed on the surface of
the polyvinyl acetate film.
In both cases, the metal coatings are firmly adherent to the
plastic film surfaces.
EXAMPLE 9
A 10 percent by weight solution of cellulose acetate in acetone is
prepared which contains 0.04 percent of palladium chloride,
calculated on the solution weight. For the preparation of this
acetone solution of cellulose acetate and palladium chloride, 0.2 g
of palladium chloride are dissolved in 1 ml of concentrated
hydrochloric acid at 70.degree.C. After cooling this solution to
room temperature, 15 ml of acetone are carefully added with
continuous stirring. With further stirring, the solution prepared
is heated to 40.degree. to 50.degree.C, whereby the total quantity
of palladium chloride is dissolved. This acetonic palladium
chloride solution is added to the acetonic cellulose acetate
solution.
The cellulose acetate has a fatty acid content of 72 percent, a K
value of 70 (e.g. Cellit 700 of Farbenfabriken Bayer, Leverkusen,
Germany, may be used). This solution is spread on the surface of a
cellulose acetate supporting film to produce a layer. The coated
cellulose acetate film is dried for 2 minutes at 130.degree.C. The
thickness of the film on the supporting film is 2 .mu.. The coated
film is bathed for 1 minute in a 0.6 percent aqueous hydrazine
solution and then rinsed for 1 minute in running water.
The pretreated coated film is then placed for 2 minutes into a
metallization liquid according to Example 2. After the time of
action, an about 0.2 .mu. thick continuous copper coating has
formed on the surface of the applied cellulose acetate film.
The metal coating is firmly adherent to its support.
EXAMPLE 10
A 10 percent by weight acetonic solution of a copolymer based on
polyvinyl chloride/acrylonitrile/itaconic acid, e.g. F 220 of
Messrs. Dow Chemical Company, Midland, U. S. A., having a content
of 0.04 percent of palladium chloride, calculated on the solution
weight, or of 0.4 percent of palladium chloride, calculated on the
copolymer component weight. The addition of the palladium chloride
is always performed in the manner described in Example 8. This
solution is spread in the form of a liquid layer on the surface of
a polyester film (e.g. Hostaphan, registered trade mark of
Farbwerke Hoechst AG, Frankfurt, Germany). The coated Hostaphan
film is dried for 2 minutes at 140.degree.C by placing it into a
drying cabinet operated with warm air. After drying, the applied
copolymer film has a layer thickness of 10 .mu.. The film sample is
divided into two pieces of equal size.
One half of the film is placed for 1 minute into a metallization
liquid according to the procedure of Example 1. After the time of
action, an about 02. .mu. thick coating of nickel has formed on the
surface of the copolymer film. The coating is firmly adherent to
its contact surface.
The second half of the film sample is bathed for 1 minute in 0.6
per cent aqueous hydrazine hydrate solution. The coated film is
then rinse for 1 minute in running water. The film is then placed
for 5 minutes into a metallization liquid according to the
procedure of Example 2. After the time of action of the
metallization bath, an about 0.2 .mu. thick continuous copper
coating has formed on the surface of the copolymer film on the
supporting film. The coating is firmly adherent to its contact
surface.
Shaped bodies produced in accordance with the invention may be used
as electrical resistance elements provided the metallized film has
a substrate of non-electroconductive material.
It will be obvious to those skilled in the art that many
modifications may be made within the scope of the present invention
without departing from the spirit thereof, and the invention
includes all such modifications.
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