METALLIZABLE MOULDED PART

PIECE MOULEE METALLISABLE

English Abstract

The invention relates to metallizeable moulded parts, to methods for producing
them and to their use as a component with integrated electroconductive
sections for electrical applications.

French Abstract

L'invention concerne des pièces moulées métallisables, des procédés pour leur production, et leur utilisation comme composant dans des sections électroconductrices intégrées pour des applications électriques.

Claims

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claims
1. Moulding comprising at least two thermoplastics K (I) and K (II),
characterized in that at least one plastic K (I) is a partly aromatic
polyester
and at least one plastic K (II) is a polyamide.
2. Moulding according to claim 1, characterized in that the plastic or
plastics
K (I) and the plastic or plastics K (II) are present macroscopically in
separate
phases to the extent of more than 90 wt.%, based on the particular type of
plastic.
3. Moulding according to at least one of the preceding claims, characterized
in
that the partly aromatic polyester is chosen from the group consisting of
derivatives of polyalkylidene terephthalates, preferably chosen from the group
consisting of polyethylene terephthalates, polytrimethylene terephthalates and
polybutylene terephthalates, particularly preferably polybutylene
terephthalates, very particularly preferably polybutylene terephthalate.
4. Moulding according to at least one of the preceding claims, characterized
in
that the polyamide is chosen from the group consisting of derivatives of
polyamides which contain 3 to 8 methylene groups in the polymer chain per
polyamide group, particularly preferably chosen from the group formed by
PA6 and PA66, very particularly preferably from the group consisting of PA6
and its copolymers.
5. Moulding according to at least one of the preceding claims, characterized
in
that part of the surface is metallized and/or galvanized, preferably
metallized
by a currentless wet chemistry means, particularly preferably metallized by a
currentless wet chemistry means and then electrogalvanically, preferably less
than 98%, particularly preferably less than 70%, very particularly preferably
less than 40%.

-40-
6. Moulding according to at least one of the preceding claims, characterized
in
that only one of the two plastics K (I) and K (II) is metallized, preferably
metallized by a currentless wet chemistry means, particularly preferably
metallized by a currentless wet chemistry means and then electrogalvanically,
preferably plastic K (II), particularly preferably the polyamide part of
plastic
K (II).
7. Moulding according to at least one of the preceding claims, characterized
in
that the weight ratio between plastic K (I) and K (II) is greater than 10:90,
preferably greater than 50:50, particularly preferably greater than 70:30,
very
particularly preferably between 80:20 and 99:1.
8. Moulding according to at least one of the preceding claims, characterized
in
that one of the two or both plastics or mixtures of plastics K (I) or K (II)
comprise one or more reinforcing substances V (I) in plastic K (I), or one or
more reinforcing substances V (II) in plastic K (II), preferably in amounts of
between 1 and 50 wt.%, preferably between 2 and 40 wt.%, particularly
preferably between 5 and 35 wt.%, in each case based on the total weight of
the particular plastics moulding compositions.
9. Moulding according to at least one of the preceding claims, characterized
in
that the two plastics comprise reinforcing substances, preferably in a weight
ratio of V (I) to V (II) of between 90:10 and 10:90, particularly preferably
between 70:30 and 30:70, very particularly preferably between 60:40 and
40:60, and extremely preferably between 55:45 and 45:55.
10. Moulding according to at least one of the preceding claims, characterized
in
that the two plastics comprise glass fibres, preferably in a weight ratio of V
(I)
to V (II) of between 90:10 and 10:90, particularly preferably between 70:30
and 30:70, very particularly preferably between 60:40 and 40:60, and
extremely preferably between 55:45 and 45:55.

-41-
11. Moulding according to at least one of the preceding claims, characterized
in
that one of the two or both plastics or mixtures of plastics K (I) or K (II)
comprise one or more elastomer modifying agents E (I) in plastic K (I), or one
or more elastomer modifying agents E (II) in plastic K (II), preferably in
amounts of between 0 and 40 wt.%, preferably between 0 and 30 wt.%,
particularly preferably between 3 and 20 wt.%, in each case based on the total
weight of the particular plastics moulding compositions.
12. Moulding according to at least one of the preceding claims, characterized
in
that plastic K (I) is a glass fibre-reinforced PBT and plastic K (II) is a
glass
fibre-reinforced, elastomer-modified PA, plastic K (I) and K (II) in each case
preferably comprising 10 - 30 wt.% of glass fibres and plastic K (II)
preferably comprising 3 - 10 wt.% of elastomer modifying agent, based on the
total weight of the particular plastic moulding compositions.
13. Moulding according to at least one of the preceding claims, characterized
in
that either plastic K (I) and/or plastic K (II) also additionally comprises
further conventional additives in amounts of up to 5 wt.%, based on the
particular plastic.
14. Process for the production of a moulding according to at least one of
claims 1
to 13, characterized in that (A) a plastic K (I) or K (II) is first introduced
into
a mould so that a partial shaped article T (I) or T (II) is formed, and (B)
the
other plastic K (II) or K (I) is then applied at least at one point of the
surface
of the partial shaped article, the process preferably being two-component
injection moulding.
15. Process according to claim 14, characterized in that, in an additional
step, part
of the surface of the shaped article is metallized, preferably metallized by a
currentless wet chemistry means, particularly preferably metallized by a
currentless wet chemistry means and then metallized electrogalvanically, this

-42-
additional step being carried out between steps (A) and (B), or preferably
after
the two steps.
16. Process according to at least one of the preceding claims 14 and/or 15,
characterized in that the metallization step, preferably of the metallizable
plastic K (II), comprises the following steps: chemical roughening of the
surface, preferably with a calcium chloride solution, deposition of an
activator, preferably palladium ions, sensitization, preferably by reducing
the
palladium cations to palladium, chemical deposition of a conductive material,
preferably nickel or copper, electrochemical conversion (galvanization) and
possibly build-up of further layers.
.17. Process according to at least one of the preceding claims 14 to 16,
characterized in that it is carried out by at least one two-component
injection
moulding process and subsequent metallization.
18. Use of one of the mouldings according to at least one of claims 1 to 13
and/or
at least one process product according to at least one of claims 14 to 17 as a
component part with integrated electrically conductive sections, preferably in
vehicle engineering, machine construction, computer engineering, domestic
electronics, domestic electrical appliances, illumination engineering and
installation engineering.

Description

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Metallizable moulding
The invention relates to metallizable mouldings, processes for their
produciton and
S their use as a component part with integrated electically conductive
sections for
electrical applications.
Mouldings, processes and uses of component parts of thermoplastics with
integrated
electrically conductive sections are known in principle.
These component parts are known in the literature as Mm (moulded
interconnection
device). Some patents also relate to a similar technique.
The production of three-dimensional component parts (3-D Mm technology) in
recent years has chiefly been concentrated on combinations of metallizable (by
currentless wet chemistry, electrogalvanically) and non-metallizable
polyamides. ,-'
Materials which were used in particular here were PA12 as the non-metallizable
component and polyamides based on s-caprolactam and/or hexamethylenediamine
and adipic acid as the metallizable component, the two components being
employed
in the form of glass fibre-reinforced compounds in most cases.
DE 44 16 986 thus describes a process for the production of a specific
component
part of a non-metallizable or poorly metallizable plastic K1 from the group
consisting
of PA6, PA66, PA11, PA12 and PPA and a metallizable plastic K2 from the group
consisting of PA6, PA66, PA66/6, PMMA, ABS, PVC, PU and UP.
This technical solution has various disadvantages. Inter alia, the water
uptake of the
polyamide under certain circumstances lead to the formation of bubbles during
IR
soldering and a lack of dimensional stability and thermal dimensional
stability,
especially at temperatures of about 50°C. Another disadvantage is that
in mouldings
produced, for example, by 2-component injection moulding, PA12 often adheres

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inadequately at the interface to the second polyamide component. The higher
costs of
PA12 compared with PA6 are furthermore disadvantages of the above material
combination for 3-D MID. An undesirable uptake of water or moisture can also
occur
in component parts of the material combination of PA12/PA6, under certain
circumstances having an adverse influence on the anchoring at the interface of
the
two materials. For these reasons, alternatives are sought for the non-
galvanizable
component, in particular PA12. Constant electrical and mechanical properties
(e.g.
rigidity) and stability, e.g. to chemicals, play a prominent role here.
Partly aromatic polyamides e.g. are non-metallizable under the conditions
typical for
PA6. However, the reinforcement of such polyamides with glass fibres, which is
necessary to achieve an adequate rigidity and similar shrinkage ratios, such
as e.g. in
the case of glass fibre-reinforced PA6, leads to galvanizability in part of
corresponding moulding surfaces. Durethan T40 (commercial product from Bayer
AG, partly aromatic polyamide, moulding composition code according to ISO
1874:
PA6I,MT,12-030), which is not metallizable under the conventional conditions
for ,-'
PA6, thus becomes galvanizable in part by melt compounding with 30% glass
fibres,
so that the material is unsuitable as an alternative to PA12.
_ It is furthermore known that partly aromatic polyesters, such as, for
example,
polybutylene terep'hthalate (PBT), and polyamides (PA) are insoluble in one
another
in the melt and therefore show no miscibility. Because of this
incompatibility, no
blends of polyester (including PBT) and PA (including PA6) of commercial
importance are as yet known (Z. Xiaochuan et al, Polymers and Polymer
Composites,
vol. S, no. 7, 1997, p. 501 - 505). For this reason indeed, also no PBT / PA
blends
are mentioned in Kunststoff Handbuch Polyamide 3 / 4, Carl Hanser Verlag,
1998,
ISBN 3-446-16486-3, p. 131 - 165. It has therefore been assumed to date that
combinations of PBT and PA are unsuitable in two-component injection moulding
for 3-D MID applications.

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It has been found, surprisingly, that a combination of PBT as the non-
metallizable w
component and PA6 as the metallizable component does not have the
abovementioned disadvantages for 3-D MID components in the injection moudling
process. The preferred metallizing process here is the Baygamid~ process
(process of
Bayer AG).
The Application accordingly relates to a moulding comprising at least two
thermoplastics K (I) and K (II), at least one plastic K (I) being a partly
aromatic
polyester and at least one plastic K (II) being a polyamide.
It is a particular feature here that the two plastics do not mix with one
another and
form blurred interfaces under the conventional process conditions of plastics
processing. This would considerably impair the precision of the metallization.
It is
. therefore preferable if the plastic or plastics K (I) and the plastic or
plastics K (II) are
present macroscopically in separate phases to the extent of more than 90 wt.%,
based
on the particular type of plastic.
The partly aromatic polyester according to the invention is chosen from the
group
consisting of derivatives of polyalkylidene terephthalates, preferably chosen
from the
group consisting of polyethylene terephthalates, polytrimethylene
terephthalates and
polybutylene terephthalates, particularly preferably polybutylene
terephthalates, very
particularly preferably polybutylene terephthalate.
Partly aromatic polyesters is understood as meaning materials which also
contain
aliphatic molecular moieties in addition to aromatic molecular moities.
Polyalkylene terephthalates in the context of the invention are reaction
products of
aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl
esters or
anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of
these
reaction products.

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Preferred polyalkylene terephthalates can be prepared from terephthalic acid
(or its
reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 C
atoms by
known methods (Kunststoff Handbuch, vol. VIII, p. 695 et seq., Karl-Hanser-
Verlag,
Munich 1973).
Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%,
based
on the dicarboxylic acid, of terephthalic acid radicals and at least 80,
preferbaly at
least 90 mol%, based on the diol component, of ethylene glycol and/or propane-
1,3-
diol and/or butane-1,4-diol radicals.
In addition to terephthalic acid radicals, the preferred polyalkylene
terephthalates can
contain up to 20 mol% of radicals of other aromatic dicarboxylic acids having
8 to 14
C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms, such as
radicals of
. phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-
diphenyldicarboxylic acid, succinic, adipic, sebacic or azelaic acid or
cyclohexanediacetic acid.
In addition to ethylene glycol or propane-1,3-diol or butane-1,4-diol
radicals, the
preferred polyalkylene terephthalates can contain up to 20 mol% of other
aliphatic
diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms,
e.g.
radicals of propane-1,3-diol, 2-ethylpropane-1,3-diol, neopentylglycol,
pentane-1,5-
diol, hexane-1,6-diol, cyclohexane-1,4-dimethanol, 3-methylpentane-2,4-diol, 2-
methylpentane-2,4-diol, 2,2,4-trimethylpentane-1,3- and -1,6-diol, 2-
ethylhexane-1,3-
diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di-((3-hydroxyethoxy)-
benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-
tetramethyl-
cyclobutane, 2,2-bis-(3-13-hydroxyethoxyphenyl)-propane and 2,2-bis-(4-
hydroxypro-
poxyphenyl)-propane (DE-OS 24 07 674, 24 07 776, 27 15 932).
The polyalkylene terephthalates can be branched by incorporation of relatively
small
amounts of 3- or 4-hydric alcohols or 3- or 4-basic carboxylic acids, such as
are
described e.g. in DE-OS 19 00 270 and US-PS 3 692 744. Examples of preferred

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branching agents are trimesic acid, trimellitic acid, trimethylolethane and -
propane
and pentaerythritol.
It is advisable to use not more than 1 mol% of the branching agent, based on
the acid
component.
Polyalkylene terephthalates which have been prepared solely from terephthalic
acid
and reactive derivatives thereof (e.g. dialkyl esters thereof) and ethylene
glycol
and/or propane-1,3-diol and/or butane-1,4-diol (polyethylene terephthalate and
polybutylene terephpthalate) and mixtures of these polyalkylene terephthalates
are
particularly preferred.
Copolyesters which are prepared from at least two of the abovementioned acid
components and/or from at least two of the abovementioned alcohol components
are
1 S also preferred polyalkylene terephthalates, and particularly preferred
copolyesters are
poly-(ethylene glycol/butane-1,4-diol)-terephthalates. ,.
The polyalkylene terephthalates in general have an intrinsic viscosity of
approx. 0.4
to 1.5, preferably 0.5 to 1.3, in each case measured in phenol/o-
dichlorobenzene ( 1:1
parts by wt.) at 25°C.
The partly aromatic polyesters can furthermore comprise additives, such as e.g
fillers
and reinforcing substances, such as e.g. glass fibres or mineral fillers,
flameproofing
agents, processing auxiliaries, stabilizers, flow auxiliaries, antistatics,
dyestuffs,
pigments and other conventional additives.
Fibrous or particulate fillers and reinforcing substances which can be added
for the
moulding compositions according to the invention are glass fibres, glass
beads, glass
fabric, glass mats, carbon fibres, aramid fibres, potassium titanate fibres,
natural
fibres, amorphous silica, magnesium carbonate, barium sulfate, feldspar, mica,
silicates, quartz, talc, kaolin, titanium dioxide, wollastonite and the like,
which can

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also be treated on the surface. Commercially available glass fibres are
preferred
reinforcing substances. The glass fibres, which in general have a fibre
diameter of
between 8 and 18 pm, can be added as continuous fibres or as cut or ground
glass
fibres, it being possible for the fibres to be finished with a suitable size
system and an
adhesion promoter or adhesion promoter system, e.g. based on silane.
Needle-shaped mineral fillers are also suitable. Needle-shaped mineral fillers
is
understood in the context of the invention as meaning a mineral filler with a
highly
pronounced needle-shaped character. Needle-shaped wollastonite may be
mentioned
as an example. The mineral preferably has an L/D (length/diameter) ratio of
8:1 to
35:1, preferably 8:1 to 11:1. The mineral filler can optionally be treated on
the
surface.
The polyester moulding composition preferably comprises 0 to 50 parts by wt.,
preferaby 0 - 40, in particular 10 - 30 parts by wt. of added fillers and
reinforcing
substances. Polyester moulding compositions without fillers and/or reinforcing
.~
substances can also be used.
Suitable flameproofing agents are commercially available organic compounds or
_ halogen compounds with synergists or commercially available organic nitrogen
compounds or organic/inorganic phosphorus compounds. Mineral flameproofing
additives, such as rrlagnesium hydroxide or Ca-Mg carbonate hydrates (e.g. DE-
OS 4
236 122), can also be employed. Examples of halogen-containing, in particular
brominated and chlorinated compounds which may be mentioned are: ethylene-1,2-
bistetrabromophthalimide, epoxidized tetrabromobisphenol A resin, tetra-
bromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, penta-
bromopolyacrylate and brominated polystyrene. Suitable organic phopshorus
compounds are the phosphorus compounds according to W098/17720
(PCT/EP/05705), e.g. triphenyl phosphate (TPP), resorcinol bis-(diphenyl
phosphate), including oligomers (RDP), and bisphenol A bis-diphenyl phosphate,
including oligomers (BDP), melamine phosphate, melamine pyrophosphate,

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melamine polyphosphate and mixtures thereof. Possible nitrogen compounds are,
in
particular, melamine and melamine cyanurate. Suitable synergists are e.g.
antimony
compounds, in particular antimony trioxide and antimony pentoxide, zinc
compounds, tin compounds, such as e.g zinc stannate, and borates. Carbon-
forming
agents and tetrafluoroethylene polymers can be added.
The partly aromatic polyesters according to the invention can comprise
conventional
additives, such as agents against thermal decomposition, agents against
thermal
crosslinking, agents against damage caused by ultraviolet light, plasticizers,
lubricants and mould release agents, nucleating agents, antistatics,
stabilizers and
dyestuffs and pigments.
Examples of oxidation retardants and heat stabilizers which are mentioned are
sterically hindered phenols andlor phosphites, hydroquinones, aromatic
secondary
amines, such as diphenylamines, various substituted representatives of these
groups
and mixtures thereof, in concentrations of up to 1 wt.%, based on the weight
of the
,,
thermoplastic moulding compositions.
UV stabilizers, which are in general used in amounts of up to 2 wt.%, based on
the
20. moulding composition, which may be mentioned are various substituted
resorcinols,
salicylates, benzotriazoles and benzophenones.
Inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide and
carbon black, and furthermore organic pigments, such as phthalocyanines,
quinacridones, perylenes, and dyestuffs, such as nigrosin and anthraquinone,
as
colouring agents, and other colouring agents can be added.
Sodium phenyl-phosphinate, aluminium oxide, silicon dioxide and, preferably,
talc
can be employed e.g. as nucleating agents.

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Lubricants and mould release agents, which are conventionally employed in
amounts
of up to 1 wt.%, are preferably ester waxes, pentaerithrytol stearate (PETS),
long-
chain fatty acids (e.g. stearic acid or behenic acid), salts thereof (e.g. Ca
or Zn
stearate) and amide derivatives (e.g. ethylene-bis-stearylamide) or montan
waxes
(mixtures of straight-chain, saturated carboxylic acids having chain lengths
of 28 to
32 C atoms) and low molecular weight polyethylene waxes or polypropylene
waxes.
Examples of plasticizers which may be mentioned are dioctyl phthalate,
dibenzyl
phthalate, butyl benzyl phthalate, hydrocarbon oils and N-(n
butyl)benzenesulfonamide.
The additional use of rubber-elastic polymers (often also called impact
modifiers,
elastomer or rubber) is particularly preferred.
Quite generally, these are copolymers which are preferably built up from at
least two
of the following monomers: ethylene, propylene, butadiene, isobutene,
isoprene, ,.'
chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic
acid esters
having 1 to 18 C atoms in the alcohol component. ,
Such polymers are described e.g. in Houben-Weyl, Methoden der organischen
Chemie, vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, 1961), pages 392 to 406 and
in
the monograph by C.B. Bucknall, "Toughened Plastics" (Applied Science
Publishers,
London, 1977).
Some preferred types of such elastomers are described in the following.
Preferred types of such elastomers are the so-called ethylene/propylene (EPM)
or
ethylene/propylene/diene (EPDM) rubbers.
EPM rubbers in general have practically no more double bonds, while EPDM
rubbers
can contain 1 to 20 double bonds per 100 C atoms.

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Diene monomers which may be mentioned for EPDM rubbers are, for example,
conjugated dimes, such as isoprene and butadiene, non-conjugated dimes having
5
to 25 C atoms, such as penta-1,4-dime, hexa-1,4-dime, hexa-1,5-dime, 2,5-
dimethylhexa-1,5-diene and octa-1,4-dime, cyclic dimes, such as
cyclopentadiene,
cyclohexadienes, cyclooctadienes and dicyclopentadiene, and
alkenylnorbornenes,
such as S-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-
norbornene, 2-isopropenyl-5-norbornene, and tricyclodienes, such as 3-methyl-
tricyclo-(5.2.1Ø2.6)-3,8-decadiene, or mixtures thereof. Hexa-1,5-dime, 5-
ethylidenenorbornene and dicyclopentadiene are preferred. The dime content of
the
EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt.%, based on the
total
weight of the rubber.
EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic
acids
or derivatives thereof. There may be mentioned here e.g. acrylic acid,
methacrylic
acid and derivatives thereof, e.g. glycidyl (meth)acrylate, and malefic
anhydride.
Another group of preferred rubbers are copolymers of ethylene with acrylic
acid
and/or methacrylic acid and/or the esters of these acids. The rubbers can
additionally
also comprise dicarboxylic acids, such as malefic acid and fumaric acid, or
derivatives
_ of these acids, e.g. esters and anhydrides, and/or monomers containing
epoxide
groups. These dicarboxylic acid derivatives or monomers containing epoxide
groups
are preferably incorporated into the rubber by addition of monomers containing
dicarboxylic acid or epoxide groups, of the general formulae (I) or (II) or
(III) or (N),
to the monomer mixture
R1C(COOR2) = C(COOR3)R4 (I)
1 4
RFC CSR
CO~ ~~O
O

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O "'
CHR~CH (CH ) O- CHR6 -CH
2 m ( )q CHR
CHz CR9 COO-(-CH2)p-CH CHRe (N)
O
S
wherein R' to R9 represent hydrogen or alkyl groups having 1 to 6 C atoms and
m is
an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from
0 to 5.
Preferably, the radicals R' to R9 denote hydrogen, where m represents 0 or 1
and g
represents 1. The corresponding compounds are malefic acid, fumaric acid,
malefic
' anhydride, allyl glycidyl ether and vinyl glycidyl ether.
Preferred compounds of the formulae (17, (B) and (1V) are malefic acid,
malefic
anhydride and esters of acrylic acid and/or methacrylic acid containing
epoxide
groups, such as glycidyl acrylate and glycidyl methacrylate, and the esters
with
tertiary alcohols, such as t-butyl acrylate. The latter indeed contain no free
carboxyl
groups, but come close in their properties to the free acids and are therefore
called
monomers with latent carboxyl groups. -
The copolymers advantageously comprise 50 to 98 wt.% ethylene, 0.1 to 20 wt.%
monomers containing epoxide groups and/or methacrylic acid and/or monomers
containing acid anhydride goups and the the remaining amount as (meth)acrylic
acid
esters.
Particularly preferred copolymers are those of
50 to 98, in particular 55 to 95 wt.% ethylene,

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0.1 to 40, in particular 0.3 to 20 wt.% glycidyl acrylate and/or glycidyl
methacrylate, (meth)acrylic acid and/or malefic anhydride, and
1 to 45, in particular 10 to 40 wt.% n-butyl acrylate and/or 2-ethylhexyl
acrylate.
Further preferred esters of acrylic and/or methacrylic acid are the methyl,
ethyl,
propyl and i- or t-butyl ester.
In addition, vinyl esters and vinyl ethers can also be employed as comonomers.
The ethylene copolymers described above can be prepared by processes known per
se, preferably by random copolymerization under a high pressure and elevated
temperature. Corresponding processes are generally known.
Emulsion polymers, the preparation of which is described e.g. by Blackley in
the ,~'
monograph "Emulsion Polymerization", are also preferred. The emulsifiers and
catalysts which can be used are known per se.
In principle, homogeneously built up elastomers and also those with a shell
structure
can be employed. fihe shell structure is determined by the sequence of
addition of the
individual monomers; the morphology of the polymers is also influenced by this
sequence of addition.
Monomers which may be mentioned here merely representatively for the
preparation
of the rubber part of the elastomers are acrylates, such as e.g. n-butyl
acrylate and 2-
ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and
mixtures thereof. These monomers can be copolymerized with further monomers,
such as e.g. styrene, acrylonitrile, vinyl ethers and further acrylates or
methacrylates,
such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl
acrylate.

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The soft or rubber phase (with a glass transition temperature below
0°C) of the
elastomers can be the core, the outer shell or a middle shell (in the case of
elastomers
with more than a two-shell structure); in mufti-shell elastomers, it is also
possible for
several shells to consist of one rubber phase.
If one or more hard components (with glass transition temperatures above
20°C)
participate, in addtion to the rubber phase, in the build-up of the
elastomers, these are
in general prepared by polymerization of styrene, acrylonitrile,
methacrylonitrile, a-
methylstyrene, p-methylstyrene and acrylic acid esters and methacrylic acid
esters,
such as methyl acrylate, ethyl acrylate and methyl methacrylate, as the main
monomers. In addition, minor amounts of further comonomers can also be
employed
here.
In some cases it has proved advantageous to employ emulstion polymers which
have
reactive groups on the surface. Such groups are e.g. epoxide, carboxyl, latent
carboxyl, amino or amide groups and functional groups which can be introduced
by ,~
co-using monomers of the general formula
R' ° R"
CH- ~ -X ~ -C-R'z
O _
25
wherein the substituents can have the following meaning:
R'° hydrogen or a C1- to C4-alkyl group;
R' ~ hydrogen, a C~- to C8-alkyl group or an aryl group, in particular phenyl,
R~Z hydrogen, a C1- to Ci°-alkyl or a C6- to Clz-aryl group or -
OR~3,

CA 02361399 2001-07-31
WO 00/46419 PCT/EP00/00445
-13- ,
R13 a C1- to Cg-alkyl or C6- to Clz-aryl group, which can optionally be
substituted w
by O- or N-containing groups,
X a chemical bond, a C~- to Coo-alkylene or a C6- to C,2-arylene group or
O
-C-Y
Y O-Z or NH-Z and
Z a C1- to Cla-alkylene or a C6- to CIZ-arylene group.
The grafting monomers described in EP-A 208 187 are also suitable for
introducing
reactive groups on to the surface.
Further examples which may also be mentioned are acrylamide, methacrylamide
and
substituted esters of acrylic acid or methacrylic acid, such as (N-t-
butylamino)-ethyl
methacrylate, (N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)-methyl '~
acrylate and (N,N-diethylamino)ethyl acrylate.
The particles of the rubber phase may furthermore also be crosslinked.
Monomers
which act as crosslinking agents are, for example, buta-1,3-dime,
divinylbenzene,
diallyl phthalate and dihydrodicyclopentadienyl acrylate, as well as the
compounds
described in EP-A 50 265).
So-called graftlinking monomers can furthermore also be used, i.e. monomers
with
two or more polymerizable double bonds which react at different rates during
the
polymerization. Those compounds in which at least one reactive group
polymerizes
at about the same rate as the other monomers, while the other reactive group
(or
reactive groups) e.g. polymerizes (polymerize) significantly more slowly, are
preferably used. The different polymerization rates have the effect of a
certain
content of unsaturated double bonds in the rubber. If another phase is then
grafted on
to such a rubber, the double bonds present in the rubber thus at least partly
react with

CA 02361399 2001-07-31
WO 00/46419 PCT/EP00/00445
- 14- ,
the grafting monomers to form chemical bonds, i.e. the grafted-on phase is at
least
partly linked to the graft base via chemical bonds.
Examples of such graftlinking monomers are monomers containing allyl groups,
in
particular allyl esters of ethylenically unsaturated carboxylic acids, such as
allyl
acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl
itaconate or the
corresponding monoallyl compounds of these dicarboxylic acids. In addition,
there
are a large number of further suitable graftlinking monomers; for further
details
reference may be made here, for example, to US-PS 4 148 846.
The content of these crosslinking monomers in the impact-modifying polymer is
in
general up to 5 wt.%, preferably not more than 3 wt.%, based on the impact-
modifying polymer.
Some preferred emulsion polymers are listed in the following. Graft polymers
which
have a core and at least one outer shell and have the following build-up are
to be ,-
mentioned first here:
Type Monomers for the care Monomers for the shell
I buta-1,3-dime, isoprene, styrene, acrylonitrile,
n-butyl methyl methacrylate
acrylate, ethyl-hexyl acrylate
or
mixtures thereof
II as I, but with the co-use as I
of crosslinking
a ents
DI as I or II n-butyl acrylate, ethyl
acrylate, methyl
acrylate, buta-1,3-dime,
isoprene,
eth lhex 1 ac late
IV as I or II as I or III, but with the
co-use of
monomers with reactive groups
as
described herein
V styrene, acryloniMle, methylfirst shell of monomers
as described for
methacrylate or mixtures the core under I and II
thereof
second shell as described
for the shell
under I or IV

CA 02361399 2001-07-31
WO 00/46419 PCT/EP00/00445
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These graft polymers, in particular ABS and/or ASA polymers, are preferably "'
employed for impact modification of PBT, optionally as a mixture.
Instead of graft polymers with a mufti-shell build-up, homogeneous, i.e.
single-shell,
elastomers of buts-1,3-dime, isoprene and n-butyl acrylate or copolymers
thereof can
also be employed. These products can also be prepared by co-using crosslinking
monomers or monomers with reactive groups.
Examples of preferred emulsion polymers are n-butyl acrylate/(meth)acrylic
acid
copolymers, n-butyl acrylate/glycidyl acrylate or n-butyl acrylate/glycidyl
methacrylate copolymers, graft polymers with an inner core of n-butyl acrylate
or
based on butadiene and an outer shell of the abovementioned copolymers and
copolymers of ethylene with comonomers which provide reactive groups.
The elastomers described can also be prepared by other conventional processes,
e.g.
by suspension polymerization. ,~'
Silicone rubbers such as are described in DE-A 37 25 576, EP-A 235 690, DE-A
38
00 603 and EP-A 319 290 are also preferred.
It is of course also possible to employ mixtures of the rubber types listed
above.
,
The polyester moulding composition preferably comprises between 0 and 40 wt.%,
preferably between 0 and 30 wt.% and particularly preferably between 0 and 20
wt.%
of rubber-elastic polymers.
The partly aromatic polyester moulding compositions according to the invention
are
prepared by mixing the particular constituents in a known manner and
subjecting the
mixture to melt compounding or melt extrusion at temperatures of 200°C
to 330°C in
conventional units, such as e.g. internal kneaders, extruders or twin-screw
extruders.
Further additives, such as e.g. reinforcing substances, rubber-elastic
polymers,

CA 02361399 2001-07-31
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- 16- ,
stabilizers, dyestuffs, pigments, lubricants and mould release agents,
nucleating
agents, compatibilizing agents and other additives, can be added during the
melt
compounding or melt extrusion step.
The polyamide according to the invention is preferably chosen from the group
consisting of derivatives of polyamides which contain 3 to 8 methylene groups
in the
polymer chain per polyamide group, particularly preferably chosen from the
group
formed by PA6 and PA66, very particularly preferably from the group consisting
of
PA6 and its copolymers.
The polyamides according to the invention can be prepared here by various
processes
and synthesized from very different units, and in the specific instance of use
can be
finished, by themselves or in combination with processing auxiliaries,
stabilizers,
polymeric blending partners (e.g. elastomers) or also reinforcing materials
(such as
e.g. mineral fillers or glass fibres), to give materials with specifically
established
combinations of properties. Blends e.g. with contents of polyethylene,
polypropylene ,~
or ABS are also suitable. The properties of the polyamides can be improved,
e.g. in
respect of the impact strength of e.g. reinforced polyamides, by addition of
elastomers.
The large number of possible combinations allows a very large number of
products
with widely varying properties.
A large number of procedures have been disclosed for the preparation of
polyamides,
different monomer units, various chain regulators for establishing a required
molecular weight or also monomers with reactive groups for after-treatments
intended later being employed, depending on the desired end product.
The industrially relevant processes for the preparation of polyamides proceed
without
exception via polycondensation in the melt. In this context, the hydrolytic
polymerization of lactams is also understood as polycondensation.

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445
- 1~ -
Preferred polyamides for the combinations K(17/K(II) according to the
invention are
partly crystalline polyamides, which can be prepared starting from diamines
and
dicarboxylic acids and/or lactams having at least 5 ring members or
corresponding
amino acids.
Possible starting substances are, preferably aliphatic dicarboxylic acids,
such as
adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and sebacic
acid,
aliphatic diamines, such as hexamethylenediamine. 2.2.4- and 2_4_4-
trimethylhexamethylenediamine, the isomeric diamino-dicyclohexylinethanes and
diamino-dicyclohexylpropanes and bis-aminomethyl-cyclohexane, and
aminocarboxylic acids, such as aminocaproic acid, and the corresponding
lactams.
Copolyamides of several of the monomers mentioned are included.
Caprolactams are particularly preferably employed, very particularly
preferably s-
caprolactam.
,,
Most compounds based on PA6, PA66 and other aliphatic polyamides or
copolyamides in which 3 to 8 methylene groups are present in the polymer chain
per
one polyamide group are furthermore particularly suitable.
Polyamide 6 or polyamide 6,6 or polyamide 4,6 or polyamide 6,10 or a
copolyamide of
the units of the homopolyamides mentioned or a copolyamide of caprolactam
units and
units derived from hexamethylenediamine and adipic acid are particularly
preferably
used. Polyamide 6 or copolyamides with polyamide 6 are very particularly
preferably
used.
The polyamides prepared according to the invention can also be employed as a
mixture with other polyamides and/or further polymers.

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445
- 1g -
The polyamide moulding compositions according to the invention can comprise
additives, e.g. rubber-elastic polymers as already described above for the
polyester
moulding compositions.
The polyamide moulding compositions can additionally also comprise
fireproofing
agents, such as e.g. phosphorus compounds, organic halogen compounds, nitrogen
compounds and/or magnesium hydroxide, stabilizers, colouring agents, dyestuffs
or
pigments, processing auxiliaries, such as e.g. lubricants, nucleating agents,
stabilizers, impact modifiers, such as e.g. rubbers or polyolefins, and the
like.
Possible fibrous reinforcing substances are, in addition to glass fibres,
carbon fibres,
aramid fibres, mineral fibres and whisker. Suitable mineral fillers which may
be
mentioned by way of example are calcium carbonate, dolomite, calcium sulfate,
mica, fluorinated mica, wollastonite, talc and kaolin. However, other oxides
or oxide
hydrates of an element chosen from the group consisting of boron, aluminium,
gallium, indium, silicon, tin, titanium, zirconium, zinc, yttrium or iron can
also be ,~'
employed. The fibrous reinforcing substances and the mineral fillers can be
treated
on the surface to improve the mechanical properties.
_ To obtain conductive polyamides, conductive carbon blacks, carbon fibrils,
conductive polymers, metal fibres and conventional additives can be added to
increase the conductpity.
The polyester moulding composition according to the invention preferably
comprises
fillers and/or reinforcing substances, preferably in amounts of 1 - 50 wt.%,
particularly preferably between 2 - 40 wt.%, especially preferably between 5 -
wt.%, based on the total weight of the polyamide moulding composition. PA
moulding compositions without fillers and/or reinforcing substances can also
be
employed.

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445
-19- ,
The fillers can be added before, during or after the polymerization of the
monomers to w
give the polyamide. If the fillers according to the invention are added after
the
polymerization, the addition is preferably carried out by addition to the
polyamide melt
in an extruder. If the fillers according to the invention are added before or
during the
polymerization, the polymerization can include phases which are carried out in
the
presence of 1 to 50 per cent by weight of water.
During the addition, the fillers can already be present as particles with the
particle size
finally occurring in the moulding composition. Alternatively, the fillers can
be added in
the form of precursors, from which the particles finally occurring in the
moulding
composition are formed only in the course of the addition or incorporation.
Possible fire- or flameproofing agents are, for example, red phosphorus (DE-A-
3 713 746 A 1 (= US-A-4 877 823) and EP-A-299 444 (= US-A-5 081 222),
brominated diphenyls or diphenyl ethers in combination with antimony trioxide,
and
chlorinated cycloaliphatic hydrocarbons (Dechlorane~ plus from Occidental
Chemical ,-'
Co.), brominated styrene oligomers (e.g. in DE-A-2 703 419) and polystyrenes
brominated on the nucleus (e.g. Pyro-Chek 68~ from FERRO Chemicals).
. Zinc compounds or iron oxides are also employed as a synergist to the
halogen
compounds mentioned.
As further alternatives, melamine salts above all have proved to be suitable
flameproofing agents, especially for non-reinforced polyamides.
Magnesium hydroxide has moreover for a long time proved to be a suitable
flameproofing agent for polyamide.
Polyamide moulding compositions which, in addition to glass fibres,
additionally
comprise rubber-elastic polymers (often also called impact modifier, elastomer
or

CA 02361399 2001-07-31
WO 00/46419 PCT/EP00/00445
-20- ,
rubber) are preferred. Rubber-elastic polymers are understood here as already
described above for the polyester moulding compositions.
Preferably, the polyamide moulding composition comprises 0 - 40, preferably 0 -
30,
S particularly preferably 3 - 20 parts by wt. of impact modifier, elastomer or
rubber.
Graft polymers with a core based on acrylates and a shell based on styrene and
acrylates are very particularly suitable.
Polyamide moulding compositions which are both glass fibre-reinforced and
elastomer-modified are particularly preferred.
Possible polyamide types are, for example:
Polyamide type ManufacturerFibre content
PA 46 TW 300 FO-F6 DSM 0 - 30% GF
PA 6 or Durethan BKV 115 Bayer 15% GF
PA 6 copoly-Durethan BKV 130 Bayer 30% GF ,'
amides Durethan BKV 30 Bayer 30% GF
H
Durethan BM-240 Bayer 40% mineral
Ultramid B3 EG BASF 1 S% GF
3
Ultramid 6 EG 3 BASF 30% GF
Ultramid B3 M 6 BASF 30% GF
Grilon PVZ - 3H Ems-Chemie 30% GF
Grilon PVS - 3H Ems-Chemie 30% GF
PA 6 + FR GrilQn XE 3524 Ems-Chemie 30% GF
Grilon PMV-SH VO Ems-Chemie 15% GF+ mineral
PA 66 AKV 30 Bayer 30% GF
Ultramid A3 WG BASF 30% GF
6
Ultramid A3 X1 BASF 25% GF
GS
Ultramid A3 X2 BASF 24% GF
GS
Ultramid A3 X3 BASF 25% GF
GS
Ultramid A3 EG BASF 15% GF
3
Ultramid A3 EG BASF 30% GF
6
Minion 13 T 1 DuPont 30% mineral
Minion 13 T 2 DuPont 30% mineral
Minion 11 C 140 DuPont 40% mineral
(Blend)
Bergamid A70 Bergmann 15% GB
Grilon TV - 3H Ems-Chemie 30/a GF

CA 02361399 2001-07-31
WO 00/46419 PCT/EP00/00445
-21 - ,
Polyamide type ManufacturerFibre content
PA 66 + FR Grilon XE 3525 Ems-Chemie 20% GF
Ultramid A3 X1 BASF 25% GF
GS
Ultramid A3 X2 BASF 25% GF
G5
Ultramid A3 X3 BASF 25% GF
GS
PA 66/6 72 G 30 L DuPont 30% GF
C 3 ZM 6 BASF 30% GF
M>D is understood in general as meaning the following:
"Moulded interconnect devices", abbreviated to MID, is a term introduced
internationally since the beginning of the 1990s to describe three-
dimensionally
injection-moulded circuit carriers. They are based on the idea of producing
electrical
. connecting elements based on thermoplastics in a three-dimensional spatial
arrangement. MIDs conduct current, form shielding or emitting surfaces, carry
electronic component parts and integrate mechanical elements. The MID
technique
extends the conventional printed circuit board technique which is limited to
one '~
spatial plane. It competes with it in part.
There is now a wide range of MID production processes. These include hot
embossing of electrically conductive films, laser structuring of strip
conductcus in
combination with wet chemistry metallization processes or injection moulding
thermoplastic around'preformed metal structures.
One of the production processes used most frequently for MIDs is the two-
component injection moulding technique with subsequent wet chemistry
metallization of a component of plastic. This process allows the greatest
freedom of
geometrical shape in the production of MIl7s. A composite of two
thermoplastics is
produced, one component of which is metallizable, while the other component
remains completely unaffected by the chemical action of the metallizing
electrolytes.
Component parts of plastic to which partly metallic properties can be imparted
by a
suitable coating can be produced in this way. The metallizable plastic can be

' CA 02361399 2001-07-31
WO 00/46419 PCT/EP00/00445
-22- ,
structured in the form of electrical strip conductors. However, it can also be
w
structured with a large surface area and thus, after the metallization,
contribute
towards shielding of electromagnetic interference fields, remove heat of
friction in a
controlled manner or itself become more wear-resistant. The structure
fineness, that
is to say, for example, the width of electronic strip conductors, can be
reduced to
about 500 p.m. Such fine strip conductor structures are achieved if the
metallizable
plastic is injection moulded in the first shot and the non-metallizable
plastic is
injection moulded around it in the second shot. However, the reverse sequence
is also
possible. The position and number of sprues, the costs of the material and the
adhesion between the two components of plastic, inter alia, depend on the
nature of
the sequence.
Most of the MIDs series-produced to date are based on high performance
plastics,
such as polyether-sulfone (PES), polyether-imide (PEI) or liquid crystal
polymers
(LCP). They have been chosen in order to withstand the temperatures which
arise
during soldering processes, which can be up to 260°C in the short term.
Reinforced ,~
polyamides have recently moved into the foreground as an MID material, these
being
considerably less expensive than the high performance plastics. Some polyamide
types which are suitable for soldering processes such as are used for MIDs are
available.
Adhesive metallizability of plastics is a decisive point in the production of
Mms. A
process (Baygamid~ process, inter alia) for adhesive metallization is used
specifically
for polyamides by AHC, Kerpen, a supplier of functional surface technology.
Coating
is carried out by wet chemistry routes by dipping the workpieces in suitable
electrolytes. A metallic stop layer about 2 ~m thick is first applied. It can
be further
reinforced chemically (for example with chemical nickel) or galvanically (for
example with copper). Chemical and galvanic layers can also be combined with
one
another.
Polyamides of types PA 6, PA 66, PA 66/6 and PA 46 and copolyamides with a
glass fibre or mineral fibre filler content of up to 40% can be metallized.
The

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445
- 23 - ,
adhesive strength of the metal layers applied is more than 1 N/mm. Individual
w
chemically nickel-plated polyamide types pass temperature change tests, for
example .
three cycles from +140°C to -40°C. There is no flaking of the
layer at all in these.
The production of MIDs based on polyamide by means of the two-component
injection moulding technique and subsequent wet chemistry metallization is
therefore
an interesting alternative to the other MID production processes on the basis
of the
wide freedom of geometric shape, the low costs of the material and the small
number
of production steps. Two applications from the automobile industry demonstrate
this
statement.
It was possible to reduce the production costs of a car door lock support by
this MID
technique to almost half the costs of conventional production. The door lock
support
is in the car door behind the door handle. Depending on the extent to which
the
vehicle is fitted out, it is equipped with lock heating, central locking
control and
actuation of the automatic interior light. In conventional construction,
current- ,~'
conducting cords, microswitches and resistance wire must be mounted on an
aluminium diecasting in an expensive manner.
In production as an MID based on polyamide, the support structure produced in
the
first shot already comprises all the bearing and fixing elements relevant for
the later
function. The metallizable component is injection moulded around this in the
second
shot, and after the metallization replaces the current-conducting cords of
conventional production.
Another application is production of a car sliding roof control as an MID
based on
polyamide. Here, first fine strip conductor structures and later also plug
contacts are
produced in the first shot. The second shot produces the non-metallizable base
body
of another polyamide type. It comprises all the mechanical component parts.
After
metallization of the two-component polyamide, assembly is limited merely to
equipping with the electrical component parts and soldering thereof. Compared
with

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445
-24- ,
the conventional printed circuit board solution, the number of mechanical
component
elements is reduced and the expenditure on assembly is minimized. However, the
conventional assembly technology, in particular in the area of equipping and
soldering, can be retained.
' Particular advantages are accordingly:
1. Freedom in shape
The use of thermoplastics for the production of circuit carriers offers the
almost unlimited freedom of shape such as is rendered possible by the
injection moulding technique for construction of electronic component
groups. The miniaturized and lighter M>l7 component groups allow new
functions and shaping of any desired forms.
2. The huh rationalization effect ,a
The rationalization effect of this innovative technology and therefore the
high
profitability are convincing.
- By reducing the number of parts, the costs for material, production,
acquisition and logistics of the mechanical and electronic component
parts substituted are eliminated.
- The miniaturized Mm component groups reduce the amount of
material otherwise necessary.
- By the elimination of subsequent working steps, in particular the
previous introduction of through-holes, process chains for the
production are shortened, and significant savings are therefore

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445
-25- ,
achieved. Compared with conventional construction, cost advantages w
of more than 30% can result.
3. Environment friendliness
M>D technology is distinguished in respect of its environment friendliness by
a number of improvements. Highly oxidizing acids can in some cases be
omitted in the pretreatment of the most important plastics suitable for M>D.
In
addition to the environment-friendly production, the reduction in the
diversity
of the materials also plays a decisive role. Recycling of the base materials
and
non-critical disposal of residual materials are thereby favoured. By employing
thermoplastics, the use of thermosetting resins can be dispensed with in many
applications.
Process:
.,
The mouldings can be produced by a process in which (A) a plastic K (n or K
(I)] is
first introduced into a mould so that a partial shaped article T (17 or T (II)
is formed,
and (B) the other plastic K (In or K (17 is then applied at least at one point
of the
_ surface of the partial shaped article. In a preferred process, the mouldings
are
produced by two-component inj ection moulding.
Preferably, in an additional step, part of the surface of the shaped article
is metallized
by the conventional wet chemistry, electrolytic processes known to the expert,
particularly preferably by the Baygamid~ process (Bayer AG), this additional
step
being carned out between steps (A) and (B), or preferably after the two steps.
In a particular embodiment, the metallization step on the metallizable plastic
K (II)
can preferably comprise the following steps: Chemical roughening of the
surface, e.g.
with a calcium chloride solution. Deposition of an activator, e.g. palladium
ions.
Sensitization, e.g. by reducing the palladium cations to palladium. Chemical

CA 02361399 2001-07-31
WO 00/46419 PCT/EP00/00445
-26- ,
deposition of a conductive material, e.g. nickel or copper, by e.g. palladium-
catalysed
reduction of soluble nickel or copper ion complexes. Electrochemical
conversion
(electrogalvanization, optionally with a mufti-layer build-up). This is all
carried out
as is described e.g. in DE 43 28 883 or EP 146 723 or EP 146 724, which are
hereby
incorporated into this specification by reference. Further descriptions of
these or
similar processes are to be found in the literature (G. D. Wolf, F. Fiinger,
Metalli-
sierte Polyamid-Spritzgul3teile, Bayer SN 19038, May 1989; U. Tyszka, Die
serienmaf3ige, grol3technische galvanische Metallisierung von Spritzgul3teilen
aus
Polyamid, Galvanotechnik 80, 1989, p.2 et seq.; and the literature cited
there).
The metallization of surfaces of plastics can be achieved by physical
metallization
(preferably vapour deposition of metal, vacuum metallization) or chemical
metallization, preferably wet chemistry currentless or wet chemistry
electrogalvanic
metallization (galvanization), chemical metallization, in particular wet
chemistry
(currentless or electrogalvanic) metallization being particularly preferred
for this
invention.
l~
For mouldings of polyamides, a special process has been developed which takes
into
account the chemical character of the polyamide in the breakdown/roughening
step
- and carries out the activation step with complex compounds of palladium and
platinum and complexing agents which guarantee a high affinity for the
polyamide
surface. An embodirpent is described in the following.
The core of the process is a relatively simple pretreatment process with
organometallic activators which have been developed for use in novel
metallization
processes. They are complex compounds of noble metals, preferably of palladium
or
platinum, with various organic ligands.
The organic ligands have been chosen such that a particular affinity for the
polyamide surface results, which provides a considerable contribution towards
the
- adhesive strength of the metal layer to be applied. On the basis of this
novel

' WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445
activation principle, it has been possible to achieve the situation where only
a very w
slight roughening of the polyamide surface has to be carried out as an
additional
measure for a very good adhesion of the metal.
The total pretreatment before the chemical nickel-plating specifically
comprises the
following stages:
- roughening of the polyamide surface in a pretreatment bath,
- activation in an activating bath comprising the palladium complex,
- sensitization of the activated substrate surface.
The residence time in the baths is 5 to 10 minutes at approx. 40°C.
After activation
and sensitization, the substrate is in each case rinsed thoroughly.
Thereafter, the first
metal layer can be deposited directly in any desired chemical nickel bath.
When a
first adhesive conductive metal layer has been applied, the conventional
galvanizing
process, i.e. the galvanic layer build-up of nickel/copper/nickel/chromium,
can ,~'
follow without problems.
Adhesive metallization of various commercially available polyamides is
possible
with the process. For example, the use of the process is not linked to
polyamide 6
types. Injection-moulded components of polyamide 66 can also be metallized
without
problems by adhering to the optimized process parameters.
Tailor-made metallizable polyamide types which are reinforced with glass
fibres for
the requirements of high rigidity and heat distortion point or with mineral
fibres to
establish a reduced tendency to warp are now available. Products which have
been
rendered flame-retardant are also available in this way.
To achieve a particularly good galvanizability, polyamide types with a
specific
elastomer modification have been developed. The class of elastomer-modified,
glass
- fibre-reinforced polyamides is particularly suitable for components which
must meet

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445
_28_
the highest requirements in respect of dimensional stability, dynamic fatigue
strength
and heat distortion point, for example for use in motor vehicle engine spaces.
The
glass fibre reinforcement significantly reduces the thermal expansion
coefficients of
the injection-moulded components, so that the adhesive bond between the metal
surface and substrate of plastic is guaranteed even during extreme changes in
temperature.
In a particular embodiment, the galvanization step preferably on the
metallizable
plastic K (II] comprises the following steps: G(n Breaking down of the surface
by
superficially dissolving baths comprising preferably calcium salts, G(II)
chemical
deposition of metals, preferably palladium, to produce a conductive surface,
particularly preferably by activators and G(IIn electrogalvanization,
optionally with a
multi-layer build-up, such as is described e.g, in DE 43 28 883 or EP 146 723
or EP
146 724, which are hereby incorporated into this specification by reference.
For
example, a partial shaped article or a shaped article is treated analogously
to the
following process:
A 90 x 150 x 3 mm thick glass fibre-reinforced (30% glass fibres) sheet of
polyamide
6 was treated in a pretreatment bath with a flash point of >110°C of
the following
composition:
64 parts by wt. ~ CaCl2 (anhydrous, dissolved in
100 parts by vol. water) plus
100 parts by vol. HCl (37%) and
800 parts by vol. ethylene glycol (glycol)
for 10 minutes at 40°C.
This is followed by rinsing in glycol at room temperature (RT) and then
activation in
a bath comprising

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445
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0.7 part by wt. PdCl2,
7 part by wt. CaCl2 (anhydrous) and
1,000 parts by vol. glycol.
Residence time in this bath 5 minutes at RT. The flash point of the activation
solution is >_ 100°C.
After renewed rinsing in glycol at RT, the sensitization was carried out at RT
in a
bath of the following composition:
1.5 parts by wt. dimethylaminborane, cryst. (DMAB),
1.5 parts by wt. NaOH lozenges and
1000 parts by vol. glycol.
Thereafter, the sheet was rinsed very thoroughly in water at RT and then
nickel-
plated in a commercially available hypophosphite-containing nickel-plating
bath ,~
from Blasberg AG, Solingen at 30°C for 15 minutes. It was striking that
the nickel-
plating took place very uniformly. The adhesive strength of the metal deposit,
determined by the peel strength according to DIN 53 494, is >_ 60 N/25 mm. The
_ galvanic reinforcement of the abovementioned polyamide sheet for
determination of
the peel strength was carried out as follows:
a) pickling in 10% H2S04 for half a minute,
b) rinsing,
c) S minutes in semi-bright nickel bath, voltage 9 volt, bath temperature
60°C,
d) rinsing,
e) pickling for half a minute,
f) 90 minutes in a copper bath; voltage 1.9 volt, bath temperature
28°C,
g) rinsing.

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A metal coating with outstanding adhesion is obtained. The adhesive strength
according to DIN 53 494 is 60 N/25 mm.
Alternatively:
A moulding of a polyamide 6 reinforced with 30 wt.% glass fibres was
pretreated
according to example 1, activated, sensitized, nickel-plated by a chemical
route and
then reinforced galvanically. The galvanic layer build-up of Ni/Cu/Ni/Cr was
obtained as follows:
a) pickling in IO% H2S04 for half a minute,
b) rinsing,
c) 5 minutes in a semi-bright nickel bath, voltage 4 volt, bath temperature
60°C,
. semi-bright nickel layer deposited: approx. 4 to S p,
d) rinsing,
e) pickling for half a minute,
fj 30 minutes in a copper bath; voltage 1.9 volt, bath temperature
28°C, copper l'
layer applied 15 to 16 p.,
g) rinsing.
h) pickling for half a minute,
. i) 8 minutes in a bright nickel bath, voltage 5.5 volt, bath temperature
52°C,
nickel layer deposited: approx. 20 ~,,
j) rinsing, ,
k) dipping in oxalic acid (0.5% aqueous solution),
1) 3 minutes in a bright chromium bath, voltage 4.5 volt, bath temperature
40°C,
chromium layer deposited: approx. 0.3 p,
m) rinsing,
n) decontamination in a 40% bisulfate solution,
o) rinsing in distilled water.
The shaped article metallized in this way was exposed to the temperature
change test
according to DIN 53 496, the hot storage taking place at + 110°C and
the cold storage

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at -40°C. The metal deposit adheres so firmly to the surface of the
shaped article that °"
it shows no change.
The most favourable process for the production of the mouldings is carried out
by a
two-component injection moulding process and subsequent galvanization.
Previously, two-component injection moulding process designated only the
process
in which two materials are injection moulded into one another. In the present
case,
however, two plastics are injection moulded on to one another. This process in
turn
was previously called two-colour injection moulding. Typewriter keys,
gearswitch
knobs and the like have preferably been produced by this process by first
injection
moulding a cap with a blank area in the form of the symbol to be represented.
A
material of a different colour was then injection moulded behind this, the
blank area
for the symbol being filled.
The process to be described here is carried out in a similar manner. A
metallizable ,~'
plastic which is not electrically conductive is as a rule used for the first
"shot". The
strip conductor geometry of the MID is imaged in relief during this operation.
In the
second shot, the areas between the strip conductors are filled with a non-
. metallizable plastic.
Alternatively, the strip conductor structure can be injection-moulded as a
depression
from the non-metallizable component in the first shot, and filled with the
metallizable component in the second shot. After the second shot, the MID base
part
has its final geometric shape, and the metallizable component is metallized in
the
subsequent steps.
Two-component injection moulding offers the greatest geometric freedom of all
the
Mm production processes. Difficult strip conductor geometries and through-
platings
can be realized in this process. Structuring of the strip conductor geometry
takes
place during the injection moulding. The smallest strip conductor width is
0.25 mm.

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It depends on the flow properties of the plastic and the flow lengths in the
mould.
Because of the short process chains, low piece costs result for large series.
Different
cavities are necessary for injection of the first and second shot. The
plastics used here
must have a goad so-called melt compatibility so that a good adhesion results
when
S they are inj ection moulded on to ore another.
Two-component injection moulding is characterized by the following points:
- greatest geometric freedom of all the MID production processes
- geometric freedom limited only by the injection mouldability
- structuring takes place by two mould cavities
- high currents can be realized
- short process chain
- low piece costs for large series
- through-platings without problems
- fine pitch possible to a limited extent ,,
- decorative surfaces possible to a limited extent
Use
The component pmts with integrated electrically conductive sections can
preferably
be used for electrical applications, particularly preferably in vehicle
engineering,
machine construction, computer engineering, domestic electronics. domestic
electrical appliances, illumination engineering and installation engineering.
In principle, however, it is possible to realize all possible shape
possibilities and
therefore also all uses which exist for parts of plastic with the moulding
according to
the invention and the processes according to the invention, including metal
surfaces
and strip conductors, e.g. also snap and click elements, for example snap
hooks for
fixing microswitches etc.

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Examples
The experiments were carried out (injection moulding, metallization) on
conventional shaped articles produced by 2-component injection moulding for 3D
MID applications, such as, for example, plug boards (Plastics in Practice
1/98, Bayer
AG Leverkusen, issue 30.04.98, KU 11501-9804 d,e/4822818, p 17), boards for
controlling sliding roofs (Der Vorgriff auf die Zukunft: Bayer-Thermoplaste
fiir die
3-D MID-Technologie, Bayer AG Leverkusen, KU 46052d/4260437, issue 03.97, p.
7) or lamp carrier plates.
The two components were processed under the conventional conditions for the
particular moulding compositions (PA: ISO 1874; PBT: ISO 7792).
. Generally for PA6: material temperature 260 - 280°C, mould
temperature approx. 70
- 90°C.
Generally for PBT: material temperature 240 - 280°C, mould temperature
approx. 70 ~.~
- 90°C. Generally, for PET: material temperature 270 - 310°,
mould temperature 80 -
140°C.
Polyester types which have been investigated for galvanizability by the
Baygamid process under the conventional conditions for PA with the aid of
injection-moulded test specimens (60 * 40 * 4 mm3) and show good results:
Pocan B3235: 30% glass fibres (PBT, MHMR, 10 - 100, GF 30)
Pocan B4235: 30% glass fibres, flameproofed (PBT, MFHR, 10 - 110, GF 30)
Pocan KU2-7033: 30% glass fibres, elastomer-modified (PBT, MHPR, - 080, GF 30)
None of the three types can be galvanized. AFM photographs do not indicate
serious
changes to the surface.

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Reinforced polyester types which also show good results:
Pocan B3215: 10% glass fibres (PBT, MHMR, 10 - 070, GF 10)
Pocan KL1-7265: 15% glass fibres (PBT, MHMR, 10 -0 60, GF 15)
Pocan B3225: 20% glass fibres (PBT, MHMR, 10 - 070, GF 20)
Pocan B4225: 20% glass fibres, flameproofed (PBT, MFHR, 10 - 070, GF 20)
Non-reinforced polyester types which can also be taken in principle:
Pocan B 1305: medium viscosity (PBT, MHMR, 10 - 030, N)
Pocan B1505: medium to high viscosity (PBT, MHMR, 14 - 030, N)
Pocan B1800: high viscosity (PBT, EN, 16 - 030)
Metallizability or galvanizability of polyamide types or Durethan types by the
Baygamid~ process:
,,
Outstanding galvanizability (particularly good adhesive strength between the
metal
and polyamide) is shown e.g. by the following polyamide types or Durethan
types:
_ Durethan BKV 130: 30% glass fibres, elastomer-modified; moulding composition
code according to ISO 1874: PA6,MPR,14-090,GF30
Durethan BKV 115: IS% glass fibres, elastomer-modified, moulding composition
code according to ISO 1874: PA6,MPR,14-060,GF1 S
Very good galvanizability is shown e.g. by the following polyamide types or
Durethan types:
Durethan BKV 230: PA 6 injection moulding type with 30% glass fibres,
elastomer
modified, moulding composition code according to ISO 1874: PA6,MPR,14
080,GF30

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Durethan BKV 215: PA 6 injection moulding type with 15% glass fibres,
elastomer-
modified, moulding composition code according to ISO 1874: PA6,MPR,14-
040,GF 15
Durethan BKV 30 H1.0: PA 6 injection moulding type with 30% glass fibres, heat-
stabilized, moulding composition code according to ISO 1874: PA6,MHR,14-
1 OO,GF30
Durethan AKV 30: PA 66 injection moulding type with 30% glass fibres; moulding
composition code according to ISO 1874: PA66,MR,14-090,GF30
Durethan B 30 S: PA 6 injection moulding type, good flow properties, easily
removed from the mould, rapidly solidifying; moulding composition code
according
to ISO 1874: PA6,MR,14-030,N
Durethan A 30 S: PA 66 standard injection moulding type, non-reinforced, very
,~
easily removed from the mould; moulding composition code according to ISO
1874:
PA66, MR, 14-040N
_ The mouldings according to the invention show advantages in three
established tests
for M117. '
Adhesive strength
Adhesion of a layer comprising 2 p,m of chemical nickel (stop layer) and 40
p,m of
galvanic copper according to DIN 53 494. The adhesive strength of metal layers
on
plastics is tested according to this standard. In the present case, the test
indicates the
adhesive strength of chemical nickel on the polyamide component directly. The
adhesion was more than 40 N/25 mm

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Temperature char e~ests
The layer system of 2 ~,m of chemical nickel (stop layer) and 10 ~.m of
chemical
nickel (top layer) was investigated under various conditions.
Cross-hatch test
Using a carbide pin, two parallel lines are scratched in the surface two
millimetres
apart, and two further lines are scratched in perpendicular to these the same
distance
apart. The squares enclosed by the lines must not flake off in this test.
The layer system of 2 pm of chemical nickel (stop layer) and 10 pm of chemical
nickel (top layer) passed the test.

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Particular advantages resulted in the tests on shaped articles produced by 2C
injection
moulding of the following material combinations.
No. Component ComponentGalvanizabilityGalvanizabilityCompatibility
at
K(I) K(11) K(n K(I)7 the interface
1 Pocan B DurethanUnchanged Very good No grinding
3225 peel
BKV 115 surface afterstrength noises on
> 1
galvanizationN/mm twisting
the
moulding
2 Pocan B DurethanUnchanged Very good No grinding
3225 peel
BKV 115 surface afterstrength noises on
> 1
galvanizationN/mm twisting
the
moulding
3 Pocan B DurethanUnchanged Very good No grinding
3225 peel
BKV 115 surface afterstrength noises on
> 1
black galvanizationN/mm twisting
the
moulding
4 Pocan B DurethanUnchanged Very good No grinding
3225 peel
BKV 215 surface afterstrength noises on
> 1
black galvanizationN/mm twisting
the
moulding
Pocan , DurethanUnchanged Very good No grinding
peel
KL 1-7265 BKV 115 surface afterstrength noises -
> 1 on
' galvanizationN/mm twisting
the
moulding
Comp. Grilamid DurethanUnchanged Very good Severe grinding
1 LV- peel
3H (PA BKV 115 surface afterstrength noises on
12) > 1
galvanizationN/mm twisting
the
moulding
5

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Particular advantages of the process found in the context of the examples are:
- 100% non-galvanizability of Pocan by the Baygamid process, and in particular
both of non-reinforced, reinforced, elastomer-modified and/or flameproofed
S types.
- Compared with PA 12, only a very low uptake of water by polyesters (PBT).
- The combination PBT / PA6 shows, when using PBT and PA6 compounds with
similar shrinkage values (can be established by adjusting the amounts of
filler),
no problems in releasing from the mould in 2C injection moulding and no
grinding noises when the shaped articles are twisted, which indicates a
decidedly
good bonding of the materials. As a result, undesirable penetration of
constituents
of the metallizing baths into the contact zone between K (I) and K (I)) cannot
occur. Combination 5 of the table is particularly preferred, since Pocan KL1-
7265
and BKV 115 have very similar shrinkage values because of the same glass fibre
e'
contents.