CA2361399A1 - Metallizable moulded part - Google Patents

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.

Description

~ CA 02361399 2001-07-31 -1- , 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 ' CA 02361399 2001-07-31

-2-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.

' CA 02361399 2001-07-31

-3- , 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.

" CA 02361399 2001-07-31

-4- , 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 ' CA 02361399 2001-07-31

-5- , 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 ' CA 02361399 2001-07-31

-6- , 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-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, ' CA 02361399 2001-07-31 ~ WO 00/46419 PCT/EP00/00445 _7_ 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.

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445 -8_ 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.

' CA 02361399 2001-07-31 -9- , Diene monomers which may be mentioned for EPDM rubbers are, for example, conjugated dimes, such as isoprene and butadiene, non-conjugated dimes having 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) RFC CSR
CO~ ~~O
O

. , WO 00/46419 PCT/EP00/00445 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, -11- , 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.

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 _ 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, -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 - 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

-15- , 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

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, - 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 -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

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

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

Ultramid A3 EG BASF 30% GF

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

-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

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 -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 -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 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.

-30- , 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 -31 - , 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.

CA 02361399 2001-07-31 pCT/EP00/00445 -32- , 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.

WO 00/46419 CA 02361399 2001-07-31 pCTBP00/00445 -33- , 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.

. WO 00/46419 PCT/EP00/00445 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 -35- , 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 ' WO 00/46419 CA 02361399 2001-07-31 pCT1EP00/00445 -36- , 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.

WO 00/46419 CA 02361399 2001-07-31 pCT/EP00/00445 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 - 3g _ , 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-and BKV 115 have very similar shrinkage values because of the same glass fibre e' contents.

Claims (18)

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%.

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.

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 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.