CZ20012837A3 - 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

Metallizable shaped part

Technical field

BACKGROUND OF THE INVENTION The present invention relates to metallizable moldings, a process for their manufacture and their use as components with integrated electrically conductive components for use in electrical engineering.

BACKGROUND OF THE INVENTION

The molded parts, method and use of thermoplastic components with integrated electrically conductive parts are known in principle.

These components are known from the literature as MID (molded interconnection device). Some patents also deal with a similar technique.

In the manufacture of three-dimensional components (3-D

In recent years, the combination of metallizable (electroless wet chemically, electrogalvanizers) and non-metallizable polyamide has been used in recent years. In particular, PA 12 is used here as a non-metallable component and polyamides based on ε-caprolactam and / or hexamethylenediamine and adipic acid as metallizable components, both of which are in most cases used in the form of glass fiber reinforced compounds.

Thus, DE 44 16 986 describes a production process

-2 · ··· · ············································· • a special component made of non-metallic or poorly metallizable plastic material K1 of PA 6, PA 66,

PA 11, PA 12, PPA and metallizable plastics K2 from the group PA 6, PA 66, PA 66/6, PMMA, ABS, PVC, PUR, UP.

This technical solution shows various shortcomings. Among other things, the uptake of water by the polyamide, as the case may be, leads to the formation of bubbles during infrared soldering and to insufficient dimensional stability and heat resistance, especially at temperatures of about 50 ° C. A further disadvantage is that PA 12 in molded parts produced, for example, by 2-component injection molding, often does not sufficiently adhere to the boundary surfaces of the second polyamide component. Therefore, the higher cost of PA 12 over PA 6 is a disadvantage of said combination of materials for use in 3-D MID. In addition, components with a combination of PA 12 / PA 6 materials can cause unwanted uptake of water or moisture, which in some cases adversely affects the joints on the boundary surfaces of both materials. For these reasons, alternatives for non-galvanizable components, in particular PA 12, are sought. Constant electrical and mechanical properties (e.g. stiffness), as well as stability towards chemicals, for example, play a particularly important role.

Under the conditions typical of PA6, partially aromatic polyamides, for example, are not metalizable. However, the glass fiber reinforcement of polyamides of this type, which is required to achieve sufficient rigidity and shrinkage similar to that of glass fiber reinforced PA 6, however, leads to the gradual galvanization of the corresponding surfaces of the moldings. Thus, under the conditions usual for PA 6, the non-metalizable durethane T 40 (commercial product of Bayer AG, partially aromatic polyamide) is a proportion of the molding composition according to ISO 1874: PA

61, MT, 12-030) by melt compounding with 30% glass fiber gradually galvanizable, so that the material is not a substitute for PA 12.

Furthermore, it is known that partially aromatic polyesters such as polybutylene terephthalate (PBT) and polyamides (PA) are insoluble in the melt and therefore exhibit no miscibility. Because of this intolerance, no blends of polyesters (including PBT) and PA (including PA 6) of commercial interest are known to date (Y.Xiaochuan et al., Polymers and Polymer Composites, Vol. 5, No. 7, 1997, pages 501- 505). Certainly, therefore, PBT / PA mixtures are not mentioned in the Kunststoff Handbuch Polyamide 3/4, Carl Hanser Verlag, 1998, ISBN 3-446-16486-3, pages 131-165. Therefore, it has hitherto been assumed that PBT and PA combinations are not suitable for use in 2-component 3-D-MID injection molding.

SUMMARY OF THE INVENTION

Surprisingly, it has been discovered that a combination of PBT as a non-metalizable component and PA 6 as a metalizable component in two-component injection molding for components

3-D-MID does not have the above disadvantages. The preferred method of metallization is the Baygamid® process (Bayer AG process).

Accordingly, the present invention provides a molding comprising at least two thermoplastic materials K (I) and K (II), wherein at least one plastic material K (I) is a partially aromatic polyester and at least one plastic material K (II) is a polyamide.

···· · · · · ·

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-Η · »- - - · · · · · · · · · · · · · · · ·

In this case, it is particularly important that both plastics do not mix with each other and do not produce fuzzy boundary surfaces under the usual process conditions of plastics processing. This would significantly affect the metallization accuracy. Therefore, it is preferable that the plastic or plastics K (I) and the plastic or plastics K (II) are macroscopically phase separated by more than 90% by weight, based on the respective types of plastics.

The partially aromatic polyesters according to the invention are selected from the group of polyalkylene terephthalate derivatives, in particular selected from the group of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate, particularly preferably polybutylene terephthalate, very particularly preferably polybutylene terephthalate.

Partially aromatic polyesters are substances which, in addition to the aromatic moieties of the molecule, also contain aliphatic moieties of the molecule.

Polyalkylene terephthalates within the meaning of the invention are the reaction products of aromatic dicarboxylic acids or their reactive derivatives (for example dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.

Preferred polyalkylene terephthalates can be prepared by known methods from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms (Kunststoff-Handbuch, Bd. VIII, page 695 et seq., Karl-Hanser-Verlag, Munchen 1973) .

Preferred polyalkylene terephthalates contain at least 80,

Preferably 90 mole%, based on dicarboxylic acid, terephthalic acid residues, and at least 80, preferably at least 90 mole%, based on the diol component, ethylene glycol, 1,3-propanediol and / or or

1,4-butanediol residues.

Preferred polyalkylene terephthalates may contain, in addition to the terephthalic acid residues, up to 20 mol% of residues of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as phthalic acid, isophthalic acid, naphthalene-2,6 dicarboxylic acids, 4,4-diphenyldicarboxylic acids, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.

Preferred polyalkylene terephthalates may contain, in addition to the propanediol 1,3-glycol or butanediol 1,4-glycol residues, up to 20 mol% of the residues of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, for example propanediol residues. 1,3, 2-ethylpropanediol-1,3, neopentylglycol, pentanediol-1,5, hexanediol-1,6, cyclohexane dimethanol-1,4,3-methylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3 and -1,6,2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3, hexanediol-2,5, 1,4-di- (β- hydroxyethoxy) benzene, 2,2-bis- (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis- (3-phydroxyethoxyphenyl) -propane and 2, 2-bis- (4-hydroxypropoxyphenyl) -propane (DE-OS 24 07 674, 24 07 776, 27 15 932).

Polyalkylene terephthalates may be incorporated by the incorporation of relatively small amounts of 3- or 4-valent alcohols or 3- or 4-alcohols

-6 • ·

4-fold of the basic carboxylic acids, for example as described in DE-OS 19 00 744. Examples of suitable agents for trimesic acid, trimellitic acid, trimethylolpropane and pentaerythritol.

270 and in U.S. Pat. No. 3,692 branches are trimethylolethane a

It is suitable for branching, not to use more than 1 mol% based on the acid component.

polyalkylene terephthalates which are preferred

In particular, they are themselves made from terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and / or propanediol-1,3 and / or butanediol-1,4 (polyethylene and polybutylene terephthalate), and mixtures of these polyalkylene terephthalate.

Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the above-mentioned acid components and / or at least two of the above-mentioned alcohol components. Particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) -terephthalates.

Polyalkylene terephthalates generally have an intrinsic viscosity of about 0.4-1.5, preferably 0.5-1.3, each measured in phenol / o-dichlorobenzene (1: 1, parts by weight) at 25 ° C.

In addition, the partially aromatic polyesters may contain additives such as fillers and reinforcing agents such as glass fibers or mineral fillers, flame retardants, processing aids, stabilizers, leveling aids, antistatic agents, dyes, pigments and other conventional additives .

Glass fibers, glass spheres, glass cloth, glass mats, carbon fibers, aramid fibers, potassium titanate fibers, natural fibers, amorphous silica, magnesium carbonate, sulfate can be added as fillers and reinforcing agents in the form of fibers or particles for the molding compositions of the invention. barium, feldspar, mica, silicates, quartz, talc, kaolin, titanium dioxide, Wolastonite and the like, which can also be surface treated. Preferred reinforcing materials are commercially available glass fibers. Glass fibers generally having a fiber diameter generally between 8 and 18 gm may be added as continuous filament or as chopped or ground glass fibers, wherein the fibers may be provided with a suitable sizing system and an adhesion promoter or adhesion promoter, e.g. silanes.

Needle-shaped mineral fillers are also suitable. For the purposes of the present invention, needle-shaped mineral fillers are understood to be mineral fillers with a distinct acicular character. An example is needle-like wolastonite. Preferably, the mineral has an L / D ratio (length-diameter) of 8: 1 to 35: 1, preferably 8: 1 to 11: 1. The mineral filler can be surface treated, for example.

Preferably, the polyester molding composition comprises 0 to 50 parts by weight, preferably 0 to 4 parts by weight, in particular 10 to 30 parts by weight of fillers and / or reinforcing agents. Polyester compositions without fillers and / or reinforcing agents may also be used.

Commercially available organic compounds or halogen are suitable as flame retardants.

The compounds are synergistic or commercially available organic nitrogen compounds or organic / inorganic phosphorus compounds. Mineral flame retardant additives such as magnesium hydroxide or calcium-magnesium carbonate hydrates can also be used (for example DE-OS 4,236,122). Examples of halogen-containing compounds, in particular the tracer and chlorinated compounds, are: ethylene-1,2-bis-tetrabromophthalimide, epoxidized tetrabromobisphenol A-resin, tetrabromobisphenol-A-oligocarbonate, tetrachlorobisphenol-A-oligocarbonate, pentabromopolyacrylate, thickened polysrtyrene. Suitable phosphorus compounds are the phosphorus compounds of WO 98/17720 (PCT / EP / 05705), for example trienylphosphate (TPP), resorcinol bis (diphenylphosphate) including oligomers (RDP) as well as bisphenol A-bis-diphenyl phenyl phosphate including oligomers (BDP), melamine phosphate, melamine pyrophosphate, melamine polyphosphate and mixtures thereof. Suitable nitrogen compounds are, in particular, melamine and melamine cyanurate. Suitable synergists are, for example, antimony compounds, in particular antimony trioxide and antimony trioxide, zinc compounds, tin compounds such as zinc stearate and borates. Carbon releasing agents and tetrafluoroethylene polymers may be added.

The partially aromatic polyesters according to the invention may contain conventional additives such as heat decomposition agents, heat crosslinking agents, ultraviolet light damage agents, plasticizers, glidants and mold release aids, nucleating agents, antistatic agents, stabilizers as well as dyes and pigments .

Examples of antioxidants and heat stress stabilizers are sterically shielded

-9 ···· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · Phenols and / or phosphites, hydroquinone, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations up to 1% by weight, based on to the weight of the thermoplastic molding material.

UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition, are various substituted resorcinols, sylicylates, benzotriazoles and benzophenones.

Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxides and carbon black, organic pigments such as phthalocyanines, quinacridone, perylene and dyes such as nigrosine and anthraquinone, as well as other coloring agents can be added as coloring agents.

Sodium phenylphosphinate, alumina, silica and also preferably talc may be added as antifungal agents.

Glidants and mold release agents typically used in amounts up to 1% by weight are preferably esterified waxes, pentaerythritol stearate (PETS), long chain fatty acids (e.g., stearic acid or behenic acid), salts thereof (e.g. calcium or zinc stearates) as well as amide derivatives (for example ethylene-bis-stearylamide) or wax assembly (straight chain saturated carboxylic acid mixtures having a chain length of 28 to 32 carbon atoms) as well as low molecular weight polyethylene or polypropylene waxes.

Examples of plasticizers include dioctyl ester

-10 phthalic acids, phthalic acid dibenzyl ester, phthalic acid benzyl ester, hydrocarbon oils,

N- (n-butyl) benzenesulfonamide.

Especially preferred is the additional addition of rubber-elastic polymers (often referred to as impact modifiers, elastomers or rubbers).

In general, they are copolymers which are preferably constructed from at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and esters of acrylic or methacrylic acid and 1 to 18 carbon atoms in the alcoholic folder.

Polymers of this kind are described, for example, in Houben-Veyl, Methoden der organischen Chemie, Bd. 14/1, (Georg-Thieme-Verlag, Stuttgart, 1961), pages 392-406, and in the monograph by C. Bucknall, Toughened Plastics (Applied Science Publishers, London, 1977).

Some preferred types of such elastomers will be presented below.

Preferred types of such elastomers are so-called ethylene-propylene (EPM) or ethylene-propylene-marrow (EPDM) rubbers.

EPM rubbers generally have virtually no double bonds, while EPDM rubbers may have 1 to 20 double bonds per 100 carbon atoms.

-114 4 4 4 * tt 4 4 4 4 4 4 «4 4 4 44 4444444 4444 44 44 44 44

Diene monomers for EPDM rubbers include, for example, conjugated marrows such as isoprene and butadiene, unconjugated dienes of 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4-diene, hexa-1,5-diene, 2 , 5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene as well as alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5 -norbornene, 2-isoprenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) 3,8-decadiene or mixtures thereof. Preferred are hexa-1,5diene, 5-ethylidennorbornene and dicyclopentadiene. The diene content of the EPDM rubber is preferably from 0.5 to 50% by weight, in particular from 1 to 8% by weight, based on the total weight of the rubber.

The EPM or EPDM rubbers may also preferably be grafted with reactive carboxylic acids or derivatives thereof. Examples which may be mentioned are acrylic acid, methacrylic acid and derivatives thereof, for example glycidyl (meth) acrylate and also maleic anhydride.

Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or esters thereof. In addition, the rubbers may also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives thereof, for example esters and anhydrides, and / or monomers containing epoxy groups. These dicarboxylic acid derivatives or epoxy-containing monomers are incorporated into the rubber, preferably by adding dicarboxylic acid monomers or epoxy-containing monomers of formula (I) or (II) or (III) or (IV) to the monomer mixture, · • ·

-12R ^! C (COOR ²⁾ = C ^{(COOR3) R4}

(II), co ^ _z co

(III),

CH ₂ --CR - where represents

(IV),

R ³ and hydrogen or alkyl groups having 1 to 6 carbon atoms,

m whole number from 0 to 20, G whole number from 0 to 10 a P whole number from 0 to 5.

Preferably, the radicals R ³ to R ³ are hydrogen, with M being 0 or 1 and g being 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether. Preferred compounds of formula (I), (II) and (IV) ) are

-13 maleic acid, maleic anhydride and acrylic and / or methacrylic acid esters containing epoxy groups such as glycidyl acrylate, glycidyl methacrylate and esters with tertiary alcohols such as t-butyl acrylate. The latter have no free carboxyl groups, but by their behavior they approach free acids and are referred to as monomers with latent cyrboxyl groups.

Preferably the copolymers consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing acid anhydride groups, as well as residual amounts of (meth) acrylic acid esters.

Particularly preferred are copolymers of up to 98,

0.1 to 40 to 45, in particular 55 to 95% by weight of ethylene, in particular 0.3 to 20% by weight of glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydrides and in particular 10 to 40% % of n-butyl acrylate and / or 2-ethylhexyl acrylate.

Other preferred acrylic and / or methacrylic esters are the methyl, ethyl, propyl and i-tert-butyl esters.

In addition, vinyl ester and vinyl ether can also be used as comonomers.

• 444 4 4 4 · · 4 4 · · · · · · · · · · · · · · · · · · · · · · · · »444 44

The ethylene copolymers described above can be produced by known methods, preferably by random copolymerization at high pressure and elevated temperature. Corresponding processes are well known.

Emulsion polymers are also preferred elastomers, the preparation of which is described, for example, by Blackley in the monograph Emulsion Polymerization. Useful emulsifiers and catalysts are generally known.

In principle, however, homogeneously constructed elastomers or the like can be replaced by a shell structure. The shell structure is formed by the order of addition of the individual monomers, also the morphology of the polymers is influenced by this order of addition.

Only marginally mention may be made here of acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene, as well as mixtures thereof, as monomers for the production of the rubber parts of the elastomers. These monomers can be copolymerized with other monomers such as styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate.

The soft or rubber phase of the elastomers (with a glass transition temperature less than 0 ° C) may be a core, an outer shell, or a middle layer (in the case of elastomers, with more than a two-layer structure); in the case of a plurality of layered elastomers, a plurality of layers may consist of the rubber phase.

If, in addition to the rubber phase, one or more hard constituents (with a glass transition temperature of more than 20 ° C) participate in the construction of the elastomer, these constituents are generally produced by polymerizing styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, acrylic acid esters, methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as major monomers.

In some cases, it has proven advantageous to use emulsion polymers having surface reactive groups. Such groups are, for example, epoxide, carboxyl, latent carboxyl, amine or amide groups as well as functional groups which can be introduced by the simultaneous action of the monomers of the general formula:

R ¹⁰ R ”

CH 2 = C-X-N-CR ¹²

Wherein the substituents may have the following meanings:

hydrogen or alkyl having 1 to 4 carbon atoms,

R ¹¹ is hydrogen, alkyl of 1-8 carbon atoms or aryl, especially phenyl; _"7

R is hydrogen, (C 1 -C 10) alkyl, (C 6 -C 12) aryl or OR ³³ ,

R ^{13 is} C 1 -C 8 alkyl or C 6 -C 12 aryl which may optionally also be substituted with

-16 containing 0- or N-,

X a chemical bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a group

O

Y is O-Z or NH-Z;

Z is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 12 carbon atoms.

The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups to the surface.

Further examples include acrylamide, methacrylamide and substituted acrylic or methacrylic esters such as (N-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate, (N, N-diethylamino) ) ethyl acrylate.

Furthermore, the rubber phase particles can also be crosslinked. Crosslinking monomers include, but are not limited to, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, as well as the compounds described in EP-A 50 265.

In addition, so-called graftlinking monomers, i.e. monomers having two or more polymerizable double bonds, which react at different rates during polymerization, may also be used. Preferably

-17 · · 17 17 17 · 17 17 17 17 17 17 17 · 17 17 17 17 17 17 Use 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), for example, polymerize (polymerize) significantly more slowly. Different polymerization rates bring about a certain proportion of unsaturated double bonds in the rubber. When other phases are grafted onto such rubber, the double bonds present in the rubber react at least partially with the grafted monomers to form chemical bonds, i.e. the grafted phase is at least partially bonded by chemical bond to the graft base.

Examples of such grafting crosslinking monomers are monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated cyrboxylic acids such as allyl acrylate, allyl methacrylate, diallymethacrylate, diallyl fumarate, diallylitaconate or the corresponding monoallyl compounds of these dicarboxylic acids. In addition, there are a number of other suitable grafting crosslinking monomers, for details see, for example, US-PS 4,148,846.

In general, the proportion of these crosslinking monomers in the impact-modified polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modified polymer.

Some preferred emulsion polymers are listed below. First, graft polymers having a core and at least one outer shell having the following structure are listed:

-18Table

Type Core monomers Monomers for envelope AND Buta-1,3-diene, isoprene, n-butyl acrylate, ethylhexyl acrylate or mixtures thereof Styrene, acrylonitrile, methyl methacrylate II Like I, but using crosslinking agents J as I III As I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, buta-1,3-diene, isoprene, ethylhexyl acrylate IV As II or III As I or III, but using monomers with reactive groups as described herein in Styrene, acrylonitrile, methyl methacrylate or mixtures thereof The first envelope of the monomers described under I and II for the core, a second envelope as described for envelope ad I or IV

These graft polymers, especially ABS and / or ASA polymers, are preferably used to modify the impact strength of PBTs, optionally in admixture.

Homogeneous, i.e. monolayer elastomers of buta-1,3-diene, isoprene and n-butyl acrylate, or copolymers thereof, can also be used in place of the graft polymers with a multilayer structure. Also, these products can be produced by the simultaneous use of 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 copolymers or n-butyl acrylate / glycidyl methacrylate copolymers, n-butyl acrylate inner-core or butadiene-based graft polymers mentioned above and outer envelope of the above and copolymers of ethylene with comonomers that provide reactive groups.

The elastomers described can also be prepared by other conventional methods, for example by suspension polymerization.

Also preferred are silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290.

Of course, mixtures of the abovementioned types of rubbers may also be used.

Preferably, the polyester molding composition comprises between 0 and 40% by weight, preferably between 0 and 30% by weight and particularly preferably between 0 and 20% by weight of rubber elastic polymers.

The polyester, partially aromatic molding compositions according to the invention are prepared by mixing the ingredients in a known manner and compounding or melt-extruding at 200 to 330 ° C in conventional aggregates such as internal kneaders, extruders, twin screws. For compounding or melt extrusion, other additives such as reinforcing components, rubber elastic polymers, stabilizers, dyes, pigments, glidants, mold release aids, nucleating agents, compatibilizers and other additives can be added.

The polyamide according to the invention is preferably selected from the group of polyamide derivatives in which 3 to 8 methylene groups are present per polyamide group in the polymer chain, particularly preferably selected from the group consisting of PA 6 and PA 66, very particularly preferably from PA 6 and of its copolymers.

In this case, the polyamides according to the invention can be produced in different ways and synthesized from very different building elements and, for specific applications, can be used to form particularly well-defined combinations of properties of the polyamides themselves, or in combination with processing aids, stabilizers, polymeric alloying components (e.g. elastomers) or reinforcing agents. materials (such as mineral fibers or glass fibers). Mixtures with, for example, polyethylene, polypropylene, ABS proportions are also suitable. The properties of polyamides can be improved by the addition of elastomers, for example with respect to the impact toughness of the exemplary crosslinked polyamides. A large number of combination options allows a very high number of products with the most varied properties.

A number of process processes are known for the production of polyamides, depending on the desired end product, different monomeric building blocks, different chain length regulators to set the desired molecular weight, or also monomers with reactive groups of the later intended treatment.

Technically important processes for the production of polyamides proceed without melt polycondensation. In this context, polycondensation also includes hydrolytic polymerization of lactams.

Preferred polyamides for the K (I) / K (II) combinations of the invention are partially crystalline polyamides which can be prepared from starting diamines and dicarboxylic acids and / or lactams with at least five ring members or corresponding amino acids.

Suitable starting materials are preferably aliphatic dicarboxylic acids such as adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, aliphatic diamines such as hexamethylenediamine, 2,2,4- and 2-carboxylic acids. 4,4-trimethylhexamethylenediamine, isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bis-aminomethylcyclohexane, aminocarboxylic acids such as aminocaproic acid, or the corresponding lactams. Included are copolyamides of the aforementioned monomers.

Caprolactam is particularly preferably used, very particularly preferably β-caprolactam.

Compounds based on PA 6, PA 66 and other aliphatic polyamides or copolyamides in which 3 to 8 methylene groups per polyamide group in the polymer chain are particularly suitable.

Particular preference is given to using polyamide 6 or polyamide 66 or polyamide 4,6 or polyamide 6,10 or copolyamites from the units of said homopolyamides or copolyamides from caprolactam units and units derived from hexamethylenediamine and adipic acid. Very particularly preferably polyamide 6 or copolyamides with polyamide 6 are used.

The polyamides produced according to the invention can also be used

-22 ···· · · · · · · • · • · • · • · • · • ·

In admixture with other polyamides and / or other polymers. Ve Φ ve ve ve ve směsi směsi směsi směsi směsi směsi směsi

The polyamide molding compositions according to the invention may contain additives, for example rubber elastic polymers, as described above for polyester molding compositions.

In addition, the polyamide molding compositions may comprise flame retardants, such as phosphorus compounds, organic halogenated compounds, nitrogen compounds and / or magnesium hydroxide, stabilizers, dyes or pigments, processing aids such as lubricants, nucleating agents, stabilizers, impact modifying agents such as rubbers or polyolefins and other substances.

In addition to glass fibers, carbon fibers, aramid fibers, mineral fibers and whiskers are suitable as reinforcing fibers. Suitable mineral fillers are, for example, calcium carbonate, dolomite, calcium sulfate, mica, fluorine mica, wolastonite, talc and kaolin. However, other oxides or hydrates of oxides of any element selected from the group of boron, aluminum, gallium, indium, silicon, tin, titanium, zirconium, zinc yttrium or iron may also be used. To improve the mechanical properties, the fibrous reinforcing materials and mineral fillers can be surface treated.

To obtain conductive polyamides, conductive carbon black, carbon fibers, conductive polymers, metal fibers, as well as conventional conductivity enhancers may be added.

Preferably, the polyamide molding compositions comprise fillers

Or reinforcing materials, preferably in an amount of 1-50% by weight, particularly preferably between 2-40% by weight, particularly preferably between 5-35% by weight, based on the total weight of the polyamide molding material. PA-molding materials without fillers and / or reinforcing materials can also be used.

The addition of filler can be carried out before, during or after the polymerization of the monomers to the polyamide. If the addition of the fillers according to the invention is carried out after polymerization, it is preferably carried out by adding to the polyamide melt in an extruder. If the filler according to the invention is added before or after polymerization, the polymerization may comprise phases in which 1 to 50% by weight of water is used.

The fillers may already be present in the form of particles having a size which is ultimately present in the molding material during the addition. Alternatively, the fillers may be added in the form of precursors, from which the ultimately present particles in the molding material are only formed during the addition or incorporation.

Suitable flame retardants and flame-retardants are, for example, red phosphorus (DE-A 3,713,746 A1 (= US-A 4,877,823) and EP-A 299,444 (= US-A 5,081,222), accumulated diphenyls or diphenyl ethers in combination with antimony trioxide and chlorinated cycoaliphatic hydrocarbons (Dechlorane ® plus from Occidental Chemical Co.), thickened styrene oligomers (e.g. DE-A 2 703 419) and polystyrenes

R accumulated on the core (for example Pyro-Chek from FERRO Chemicals).

As synergistic substances to the mentioned halogenated 00 00 0 0 0 0 0 0 0 0 0 0

-24Λ · · · · «« 0 · 0

Zinc compounds or iron oxides can also be used for the compounds.

In particular, melamine salts, especially for unpaved polyamides, have proved to be a flame retardant.

Furthermore, magnesium hydroxide has long been proven to be a flame retardant for polyamide.

Preferred are polyamide molding compositions which, in addition to glass fibers, additionally contain rubber elastic polymers (often referred to as impact modifiers, elastomers or rubbers). By rubber elastic polymers is meant herein as described above for polyester molding compositions.

Advantageously, the polyamide molding compositions contain 0-40, preferably 0-30, particularly preferably 3-20% by weight parts of impact modifiers, elastomers or rubbers. Particularly suitable are graft polymers having an acrylate-based core and a styrene-acrylate-based envelope.

Particularly preferred are polyamide molding compositions which are both reinforced with glass fibers and elastically molded.

For example, the types of polyamides listed in the following table are suitable:

Table

Type of polyamide Manufacturer Fiber content PA 46 TV 300 F0-F6 DSM 0-30% GF PA 6 Durethan BKV 115 Bayer 15% GF event. Durethan BKV 130 Bayer 30% GF PA 6 copoly- Durethan BKV 30 H Bayer 30% GF amid Durethan BM-240 Bayer 40% M Ultramid B3 EG 6 BASF 15% GF Ultramid B3 EG 6 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 Grilon XE 3524 Ems-Chemie 30% GF Grillon PMV-5H VO Ems-Chemie 15% GF + M PA 66 AKV 30 Bayer 30% GF Ultramid A3 VG 6 BASF 30% GF Ultramid A3 XI G5 BASF 25% GF Ultramid A3 X2 G5 BASF 24% GF Ultramid A3 X3 G5 BASF 25% GF Ultramid A3 EG 3 BASF 15% GF Ultramid A3 EG 6 BASF 30% GF Minlon 13 T 1 DuPont 30% M Minlon 13 T 2 DuPont 30% M Minlon 11C140 DuPont 40% M Bergamid A70 Bergmann 15% GK Grill TV - 3H Ems-Chemie 30% GF PA 66 + FR Grilon XE 3525 Ems-Chemie 20% GF Ultramid A3 XI G5 BASF 25% GF Ultramid A3 X2 G5 BASF 25% GF Ultramid A3 X3 G5 BASF 25% GF PA 66/6 72 G 30 L DuPont 30% GF C 3 ZM 6 BASF 30% GF

GF

M glass fibers mineral fibers

-26 ···· · · · · »· · · · 4 4 4 4 4 4 4 φ 4 φ φ 4 · ·· «

MID is generally understood as follows:

Molded Interconnect Devices, MID for short

An internationally established term for the design of spatially injection molded interconnection carriers. The idea is to produce electrical fasteners based on thermoplastics in a three-dimensional, spatial arrangement. MIDs conduct current, create shielding or transmitting surfaces, carry electronic components and integrate mechanical elements. MID technology expands the possibilities of conventional PCB technology into a spatial arrangement. It represents partially competitive technology.

There are a number of MID manufacturing processes. These include hot stamping of electrically conductive films, structuring of laser conducting paths in combination with a wet chemical metallization process, or spraying of preformed metal structures with a thermoplastic plastic.

One of the most commonly used manufacturing processes for MID is a two-component injection molding technique followed by metallization of the plastic component by a wet chemical process. This method allows the greatest possible geometry creation in MID production. A combined body is made of two thermoplastic materials, one of which is a metallizable component, while the other remains completely unaffected by the chemical effect of the metallizing electrolyte.

Thus, it is possible to produce plastic components which, by suitable coating, can partially obtain the properties of the metal. The metallizable plastic may be structured to form an electrical conductive outlet. But it can also be

Structured over a large area to contribute to shielding of electromagnetic disturbing fields, controlled to dissipate frictional heat or to contribute to abrasion resistance. The degree of detail of the structure, for example the width of the electrically conductive track, can be reduced to about 500 gm.

Such fine conductive structures are obtained when the metallizable plastic is injected in a first step and is oversprayed with a metallizable plastic. However, the reverse order is also possible. The position and number of inlets, the cost of material and the adhesion between the two plastic components depend, among other things, on the kind of order.

Most of the MIDs so far produced are based on high-quality plastics such as polyethersulfones (PES), polyetherimides (PEI) or liquid crystalline polymers (LCP). They have been selected to withstand temperatures from the brazing process, which can reach up to 260 ° C in the short term. Currently, polyamides, which are high quality plastics, are preferred as MID material. There are several types of soldering polyprocesses which are suitable for the production of MIDs for the amides to be applied at a significantly more cost effective than available.

High adhesion of metallization on plastics is a decisive factor in MID production. Especially for polyamides, a solid metalization process is performed by AHC, Kerpen, which offers a functional surface treatment technique (Baygamide process, etc.). Coating is performed by wet chemical treatment by immersing the component in a suitable electrolyte. First, about 2 gm of base metal layer is applied. This can be further reinforced chemically (for example, nickel chemically) or galvanically (for example, copper). Chemical and galvanic layers are possible

-28 φ · φ φ · také φ · také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také také.

PA 6, PA 66, PA 66/6 and PA 46 polyamides and copolyamides with glass fiber or mineral fiber filler up to 40% are metallizable. The adhesion of the applied metal layers is more than 1 N / mm. Individual chemically nickel-plated polyamides are subjected to a temperature change test, for example, a triple cycle of + 140 ° C to -40 ° C. There are no cracks in the layer.

Production of MID based on polyamides using two-component injection molding technique and subsequent wet chemical metallization is therefore an interesting alternative to other MID manufacturing methods due to the high freedom of geometric form, low material costs and low number of manufacturing steps. Two applications from the automotive industry prove this statement.

The manufacturing cost of a car door lock beam using this MID technique could be reduced to almost half the cost of conventional manufacturing. The door lock beam is located in the car door behind the door handle. Depending on the vehicle equipment, it is fitted with a heating system for the lock, central locking control and automatic lighting control. The current conductors, microswitches and resistance wire must be costly mounted on an aluminum die-cast in a conventional manufacturing process.

In the polyamide-based MID process, the carrier structure produced in the first step already contains all the important bearings and clamping elements for other functions.

The metallizable component is oversprayed in the second step and, after metallization, replaces the conventional conductor conductors

-29 ···· · 9 · 9 99 9 · 9 9 9 9 · 9 99

9 9 9 9 9 9 99

999 99 Μ ····· production.

Another application is the production of sliding roof control of a passenger car as MID based on polyamides. Here, first, the structure of the conductive plate, as well as later plug-in contacts, are first produced. In a second step, a non-metalizable base body is produced from another type of polyamide. It contains all mechanical components. After metallization of the two-component polyamide, the assembly is limited only to the installation of electrical components and their soldering. Compared to a conventional conductive plate solution, the number of mechanical components is reduced and assembly costs are minimized. However, conventional assembly technology, especially in the field of stocking and soldering, can be maintained.

The specific advantages are:

1. Freedom to create

The use of thermoplastic plastics for the production of fasteners offers virtually unlimited freedom of creation in the construction of electronic building blocks, as is possible with the injection molding technique. The miniaturized and lighter MID construction claddings allow for new functions and the creation of any shape.

2. Significant rationalization effect

The rationalizing effect of this innovative technology and the high efficiency associated with it are convincing:

- By reducing the number of parts, material, purchasing and logistics costs are replaced

-30ΦΦΦΦ φ φφ φφ · φ

ΦΦΦ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ

Mechan φφ φ φ φ · · · · · mechan mechan mechan mechan φ mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan mechan

- miniaturized MIDs reduce the otherwise necessary use of materials.

- by eliminating the subsequent processing steps, in particular, the production of through holes shortens the sequence of the production process and thus achieves significant savings. More than 30% savings can be achieved compared to conventional production methods.

3. Less burden on the environment

MID technology has a number of improvements in terms of environmental burden. In the pre-treatment of the most important plastics suitable for MID, strongly oxidizing acids can be partially eliminated. In addition to environmentally friendly production, reducing the frequency of materials plays a decisive role. This has a beneficial effect on the recycling of basic materials and the uncritical disposal of residual materials. The use of thermoplastics has made it possible to exclude the use of thermosets in many applications.

Method :

The molded parts can be produced by a process in which (A) the plastic K (I) or K (II) is first blown into the mold, so that a T-part (T) or T (II) is formed and then (B) ) at least one point of the surface of the molded part is applied with another plastics material K (II) or K (I). The production of shaped parts is carried out by a preferred two-component injection molding process.

Preferably, in an additional step, a portion of the surface of the molding is metallized chemically, electrolytically, in a conventional manner known to those skilled in the art, particularly preferably by the Baygamid® process (Bayer AG), this additional step being carried out between steps (A) and (B); preferably after both steps.

In one particular embodiment, the metallization of the metallizable plastic K (II) may advantageously comprise the following steps: chemical roughening of the surface, for example calcium chloride solution, deposition of an activator of for example palladium ions, sensitization, for example by reduction of palladium cations to palladium for example, nickel or copper by means of, for example, palladium catalyzed reduction of soluble nickel or copper ion complexes, electrochemical reaction (electroplating, possibly in multiple layers). All of this, as exemplified in DE 43 28 883 or EP 146 723 or EP 146 724, incorporated herein by reference. Further descriptions of this or similar procedures are given in the literature (GDVolf, F.Funger, Metallisierte Polyamide-Spritzgussteile, Bayer SN 19038, May 1989; U.Tyszka, Die Serienmássige, Grosstechnische Galvanische Metallisierung von Spritzgussteilen aus Polyamide, Galvanotechnik 80, 1989, p. 2 et al.

Metallization of plastic surfaces can be accomplished by physical metallization (preferably metal vapor deposition, vacuum metallization) or chemical metallization, preferably wet current metallization without current or wet chemical electrogalvanic metallization (electroplating), particularly preferred chemical metallization for the present invention,

-32 especially wet chemical (electroless or electrogalvanic) metallization.

For polyamide moldings, a special process has been developed that takes into account the chemical nature of polyamides in the etching / roughening process and performs the activation step with complex palladium and platinum compounds and complexing agents that guarantee high affinity for the polyamide surface. Hereinafter, an embodiment is described.

The core of the process is a relatively simple pre-treatment process with organometallic activators that have been developed for use in new metallization processes. They are complex noble metal compounds, preferably palladium or platinum, with different organic ligands.

The organic ligands are selected such that a particular affinity for the surface of the polyamide is created, thereby making a significant contribution to the adhesion of the deposited metal layer. Due to this new activation principle, it is possible to achieve only a very limited roughening of the polyamide surface as an additional measure for a very good metal adhesion.

All pre-treatment prior to chemical nickel plating consists in detail of the following stages:

roughening the surface of the polyamide in the pretreatment bath, activation in the activation bath containing a palladium complex sensitizing the activated substrate surface.

-33 Delay in the bath is 5-10 minutes at temperature

After activation and sensitization always do well

It can then be immediately in any chemical

Once it is

Time about 40 ° C.

rinses.

nickel bath eliminate the first metal layer.

The first well-adhering conductive metal layer can be applied without any problems, the conventional electroplating process or the electroplating of nickel / copper / nickel / chromium layers can be carried out without problems.

In this way, well adhering metallization of the different commercially available polyamides is possible. For example, the use of the process is not limited to polyamide 6 types. Also, injection molded parts of polyamide 66 can be metallized perfectly, while maintaining optimized process parameters.

Specially prepared metallizable types of polyamides are currently available, which are reinforced with glass fibers for the requirements of high rigidity and shape stability or to adjust the reduced tendency to flow with mineral fillers. Flame retardant products are also available.

construction aspects

In order to achieve a particularly good galvanizing ability, polyamide types with special modification of elastomers have been developed. The class of polyamides modified with elastomers and fiberglass reinforcement is particularly suited for components that have to meet the highest requirements of dimensional stability, dynamic durability and heat resistance, for example when used in automotive engine compartments. Fiberglass reinforcement significantly reduces the thermal expansion coefficient of injection molded parts, so that a strong bond between and

-34 ···· · ·

metal surface and plastic substrate even at extreme temperature changes.

In one particular embodiment, the electroplating step of preferably metallizable plastic K (II) comprises the following steps: G (I) for etching the surface of a dissolving bath containing preferably calcium salts, G (II) chemically eliminating metals, preferably palladium, to produce conductive surface activators, particularly preferably activators and G (III) electrogalvanization, optionally with multilayer formation, as described, for example, in DE 43 28 883 or EP 146 723 or EP 146 724, to which reference is made in this specification. By way of example, the partial molding or the molding is processed analogously to the following process:

A 90 x 150 x 3 mm glass fiber reinforced polyamide 6 board (30% glass fiber) is treated in a pretreatment bath with a flash point> 110 ° C as follows:

parts by weight

100 parts by volume

100 parts by volume

800 parts by volume (CaCl2 anhydrous, dissolved in water, for this

HCl 37%), and ethylene glycol (glycol) for 10 minutes at 40 ° C.

This is followed by rinsing in glycol at room temperature (RT) followed by activation in a bath consisting of

0.7 parts by weight

1000 parts by volume

PdCl ₂ ,

CaCl ₂ anhydrous and glycol.

-35 ·· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · φ · ·· ···

The residence time in this bath is 5 minutes at room temperature. The flash point of the activation solution is> 100 ° C.

After rinsing in gylcol at room temperature, sensitization is carried out at room temperature in a bath of the following composition:

1.5 parts by weight of dimethylaminoborane crystals. (DMAB)

1.5 parts by weight of NaOH furnace and

1000 parts by volume of glycol.

It is then thoroughly purged in water at room temperature and subsequently nickel plated in a commercially available hypophosphite nickel-plating bath from Blasberg AG, Solingen at 30 ° C for 15 minutes. Nickel plating is very even. The adhesive strength of the metal layer, determined by the pulling force according to DIN 53 494, is > 60 N / 25 mm. The galvanic amplification of the above polyamide plate to determine the pulling force is performed as follows:

a) half a minute of etching in 10% sulfuric acid,

(b) rinsing,

(c) 5 minutes in a semi-gloss nickel-plated bath, 9 Volt, bath temperature 60 ºC,

d) rinsing,

e) half a minute etching,

f) 90 minutes in a copper bath, 1.9 Volt, 28 ° C bath temperature,

g) rinsing.

A metallic coating with excellent adhesion is obtained. The connection strength is 60 N / 15 mm according to DIN 53 494.

-36ΦΦΦΦ · φ φ • · · · · · φ φ φ · · · • φ φ • • • • • • • • • •

Alternatively:

The polyamide 6 molding reinforced with 30% glass fiber is subjected to a pretreatment as described in Example 1, activated, sensitized, nickel-plated by chemical means, and then galvanically consolidated. Electroplating with the sequence Ni / Cu / Ni / Cr is obtained as follows:

a) half a minute of etching in 10% sulfuric acid,

(b) rinsing,

(c) 5 minutes in a semi-gloss nickel-plated bath, 4 Volt, bath temperature 60 ° C, precipitated semi-gloss nickel layer approximately 4 to 5 μ,

d) rinsing,

e) half a minute etching,

f) 30 minutes in a copper bath, voltage 1.9 Volt, bath temperature 28 ° C, deposited copper layer about 15 to 16 μ,

g) rinsing,

h) half a minute of etching,

(i) 8 minutes in a shiny nickel-plating bath, 5.5 Volt, bath temperature 52 ° C, deposited nickel layer about 20 μ,

j) rinsing,

(k) immersion in oxalic acid (0,5% aqueous solution);

(l) 3 minutes in a shiny chrome bath, 4.5 Volt, bath temperature 40 ° C, deposited chromium layer about 0,3 μ,

m) rinsing,

n) decontamination in 40% bisulfite solution,

(o) rinsing in distilled water.

The metallized molded body is subjected to an alternating temperature load test according to DIN 53 496, the hot deposition being carried out at a temperature of + 110 ° C and the deposition.

-37in cold at -40 ° C. The metal coating holds so firmly on the surface of the molding that there are no changes.

In a preferred method of producing shaped parts, a two-stage injection molding process and subsequent galvanization are employed.

Previously, only a two-shot molding process was referred to as a two-component injection molding process. The present case, however, is that two plastics are sprayed onto each other. This method was formerly referred to as two-color injection molding. In this way, typewriter buttons, switch buttons and the like were advantageously produced in such a way that the shaped piece with free space in the shape of the desired sign was first injection molded. This was then sprayed with a material of different color to fill the shape cavity for this sign.

The process described herein follows a similar procedure. Typically, a metallizable, non-electrically conductive plastic is used in the first spraying. In doing so, the geometry of the MID conductive paths is created. In the second injection, the areas between the conducting tracks are filled with a non-metallic plastic.

Alternatively, in the first step, the structure of the conductive tracks may be sprayed as a depression of the non-metalizable components and in the second step may be supplemented with a metallizable component. After the second injection, the MID base has a final biometric form and the metallizable component is metallized in the following steps.

···· »1 ·· »« 00 • • · • 0 • · ·· • * • * • · • · • · • • · and • · ·· ··· ·· ·· ·· ··

Two-component injection molding offers maximum geometrical freedom in all MID manufacturing processes. In this way, difficult geometrical forms of conductive tracks and interconnecting contacts are feasible. The structuring of the conductive path geometry is performed during injection molding. The smallest conductive track width is 0.25 mm. It is dependent on the creep properties of the plastic and the creep lengths in the tool. Thanks to the short process chains, even small series costs result in low unit costs. Different cavities are required for spraying the first and second bars. The plastics used here must have a very good so-called melt compatibility in order to achieve good adhesion when sprayed together.

Two-component injection molding is characterized as follows:

Highest geometric freedom of all processes MID geometric freedom limited only by injection molding Structuring is performed by two tool cavities Feasibility of high currents Short process chains Low unit cost For large series Seamless connection Possible limitations Fine Pitch Limited possible decorative surfaces ^ _.

DETAILED DESCRIPTION OF THE INVENTION

Performing experiments (injection molding, metallization) on common two-component molded bodies

-39 · β β β β β β β β β β β β β β β β β β β β β · ·· β injection molding for use in 3D-MID as an example connector plate (Plastics in Practice 1/98, Bayer AG Leverkusen, edition 30.04.98, KU 11501-9804 d, e / 4822818 page 17), sliding control plate roofs (Der Vorgriff auf die Zukunft: Bayer Thermoplastic for die 3-D MID-Technology, Bayer AG Leverkusen, KU 46052d / 4260437, edition 03.97, page 7) or light support plates.

The processing of both components is carried out under the usual conditions for these molding compositions (PA: ISO 1874; PBT: ISO 7792).

In general for PA 6 : temperature of the mass 260 to 280 ° C, temperature tools about 70-90 ° C. In general for PBT: temperature of matter 240 to 280 ° C, temperature tools about 70-90 ° C. In general for PET: temperature of matter 270 to 310 ° C, temperature tools about 80-140 Deň: 32 ° C.

Types of polyesters based on injection - molded and

The test specimens (60 x 40 x 4 mm ^a ) were tested for galvanizability by the Baygamid method under PA conditions and showed good results:

B3235 beeper 30)  30% glass fiber (PBT, MHMR, 10 - 100, Pocan B4235 : 30% glass fiber, protection against flame (PBT, MHMR, 10-110, GF 30)

Pocan KU2-7033: 30% glass fiber, elasto-40mer modified (PBT, MHPR, - 080, GF 30)

None of these three types can be galvanized.

AFM images do not indicate significant surface changes.

Reinforced polyester types that also show good results:

Pocan B3215: 10% glass fiber (PBT, MHMR, 10 - 070, GF

10)

Pocan KL1-7265: 15% glass fiber, (PBT, MHMR, 10 - 060, GF 15)

Pocan B3225 : 20 % of glass fibers (PBT, MHMR, 10-070, GF 20) Pocan B4225 : 20 % fiberglass, flame protection (PBT, MFMR, 10 - 070, GF 20) Unpaved types of polyesters that are in in principle also

acceptable:

Pocan B1305 medium viscosity, (PBT, MHMR, 10 - 030, N)

Pocan B1505: medium to high viscosity (PBT, MHMR, 14 - 030, N)

Pocan B1800 highly viscous (PBT, EN, 16 - 030).

Metallization or galvanization of types n

polyamide or durethane by the Baygamid method:

-41 • 4 4 · 9 · · 44 4 · · 4 · 4 · «* 4 · · · · · 4

The following types of polyamide or durethane, for example, exhibit excellent galvanizability (particularly good bond strength between metal and polyamide):

Durethan BKV 130: 30% glass fiber, elastomer modified, using molding material according to ISO 1874: PA 6, MPR, 14 - 090, GF 30

Durethan BKV 115: 15% glass fiber, elastomer modified, using molding material according to ISO 1874: PA 6, MPR, 14 - 060, GF 15

The following types of polyamide or durethane show very good galvanization:

Durethan BKV 230: Type PA 6 for injection molding, 30% glass fiber, elastomer modified, use of molding material according to ISO 1874: PA 6, MPR, 14 - 080, GF 30

Durethan BKV 215: Type PA 6 for injection molding, 15% glass fiber, elastomer modified, use of molding material according to ISO 1874: PA 6, MPR, 14 - 040, GF 15

Durethan BKV 30 Η 1.0: type PA 6 for injection molding, 30% glass fiber, heat stabilized, use of molding material according to ISO 1874: PA 6, MHR, 14 - 100, GF 30

Durethan AKV 30: Type PA 66 for injection molding, 30% fiberglass glass, heat stabilized, use of molding material according to ISO 1874: PA 66, MR, 14 - 090, GF 30

Durethan B 30 S: standard type PA 6 for injection molding, well flowing, easily removable from mold, quick setting, use of molding material according to ISO 1874: PA 6, MR, 14

030, N

-42 Durethane A 30 S: standard type PA 66 for injection molding, unpaved, very easy to remove from mold, quick setting, use of molding material according to ISO 1874: PA 66, MR, 14 - 040, N.

The molded parts according to the invention demonstrate advantages in three established MID tests.

Bond strength

Adhesion of a layer consisting of 2 µm of chemically deposited nickel (base layer) and 40 µm of galvanically deposited copper according to DIN 53 494. The adhesion strength of metallic layers is tested on plastics according to this standard. In the present case, the test directly reports the adhesion of chemically deposited nickel to the polyamide component. The grip is more than 40 N / 25 mm.

AC temperature test

A laminate system of 2 µm chemically deposited nickel (base layer) and 10 µm chemically deposited nickel (coating) was tested under different conditions.

Grid engraving test

Two parallel lines are engraved on the carbide line at a distance of 2 mm, and two others are engraved perpendicular to them at the same distance. The quadrilateral lines must not be released in this test.

Layered system of 2 pm chemically deposited nickel (Ac-43-

10 μιη of chemically deposited nickel (coating) passed the test.

Particular advantages result from 2K injection molding tests of the following material combinations:

no. Component K (l) Component K (II) Galvanizovatelnost K (I) Galvanizovatelnost K (II) Compatible ntt border area 1 Pocan B 3225 Durethan BKV 115 G 1 G 2 K 1 2 Pocan B 3225 Durethan BKV 115 G 1 G 2 K 1 3 Pocan B 3225 Durethan BKV 115 black G 1 G 2 K 1 4 Pocan B 3225 Durethan BKV 115 black G 1 G 2 K 1 5 Pocan KL 1-7265 Durethan BKV 115 G 1 G 2 K 1 Srv. 1 Grilamid LV-3H5 Durethan BKV 115 G 1 G 2 K 2

G1 after galvanization unchanged surface

G2 very good envelope strength 1 N / mm

K1 no squeaking noises when the shaped part is torsion

K2 strong squeaking noises when the shaped part is torsion

Particular advantages of the method are within the examples

-44 Φ 9 9 9 9 9 9 9 9 Φ «Φ

Φ · ΦΦ · · · Φ · ·

Ukáz Φ · · · · · · · · ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz ukáz

100% non-galvanizing of Pocan by the Baygamid process, both unpaved and reinforced, elastomer-modified and / or flame-protected types, compared to PA 12, the very low water intake of polyesters (PBT) of the PBT / PA 6 combination does not show PBT- and PBT- PA 6 with similar shrinkage values (possible fill quantity adjustment) no mold removal problems with 2K injection molding and no creaking noises when the molded body is torsion, indicating a particularly good bonding of materials. This also prevents undesirable penetration of the metallization bath components in the contact zone between K (I) and K (II). Combination 5 of the table is particularly preferred because Pocan KL-1-7265 and BKV 115 exhibit very similar shrinkage values based on the same glass fiber content.

Industrial applicability

Components with integrated electrically conductive components can be used advantageously for electrical circuits, particularly preferably in automotive, mechanical engineering, computer technology, consumer electronics, electrical household appliances, lighting and installation technology.

In principle, however, it is possible, with the aid of the shaped parts according to the invention and with the method according to the invention, to realize all possible design alternatives and thus also to utilize all

-45 ♦ · ·· ♦ 9 the possibilities that are possible for plastics, including metal surfaces and conductive tracks, for example latches and stops, for example latching hinges for fastening microswitches and the like.

Claims (18)

PATENT CLAIMS Molding comprising at least two thermoplastic materials K (I) and K (II), characterized in that at least one plastic material K (I) is a partially aromatic polyester and at least one plastic material K (II) is a polyamide. Molding according to claim 1, characterized in that the plastics material (s) K (I) and the plastics material (s) K (II) are macroscopically phase separated by more than 90% by weight, based on the respective plastics. Molding according to at least one of the preceding claims, characterized in that the partially aromatic polyester is selected from the group of polyalkylene terephthalate derivatives, in particular selected from polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate, particularly preferably polybutylene terephthalate, very particularly preferably polybutylene terephthalate. Molding according to at least one of the preceding claims, characterized in that the polyamide is selected from the group of polyamide derivatives in which 3 to 8 methylene groups are present per polyamide group in the polymer chain, particularly preferably selected from the group consisting of PA 6 and PA 66, very particularly preferably from the group PA 6 and its copolymers. Molding according to at least one of claims 1 to 9, 9 99 9 9 9 9 9 99 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 99 9 9 9 9 99 9 «is metallized and / or galvanized, preferably wet-chemically metallised without wet, particularly preferably chemically and subsequently electrogalvanically metallised, preferably less than 98%, particularly preferably less more than 70%, very particularly preferably less than 40%. Molded part 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 wet-current metallized, particularly preferably wet-free, and subsequently metallizes electrogalvanically, preferably plastic K (II), particularly preferably polyamide part of plastic K (II). Molded part according to at least one of the preceding claims, characterized in that the weight ratio between the plastics K (I) and K (II) is greater than 10: 90, preferably greater than 50: 50, particularly preferably greater than 70: 30 and very particularly preferably between 80: 20 and 99: 1. Molding according to at least one of the preceding claims, characterized in that one or both of the plastics or the plastics mixture K (I) or K (II) comprise one or more reinforcing agents V (I) in plastic K (I) or one or more reinforcing agents V (II) in plastic K (II), preferably in an amount between 1 to 50% by weight, preferably between 2 and 40% by weight, particularly preferably between 5 and 35% by weight, in each case based on the total weight of the plastic molding compositions in question. 9. Molded part according to at least one of the foregoing Claims, characterized in that the two plastics comprise a reinforcing agent, preferably in a weight ratio V (I) to V (II) between 90: 10 and 10: 90, particularly preferably between 70: 30 and 30: 70, completely particularly preferably between 60: 40 and 40: 60 and particularly preferably between 55: 45 and 45: 55. Molding according to at least one of the preceding claims, characterized in that the two plastics also comprise glass fibers, preferably in a weight ratio V (I) to V (II) between 90: 10 and 10: 90, particularly preferably between 70 : 30 and 30: 70, very particularly preferably between 60: 40 and 40: 60 and particularly preferably between 55: 45 and 45: 55. Molded part according to at least one of the preceding claims, characterized in that one or both of the plastics or the plastics mixture K (I) or K (II) comprise one or more elastomeric modifiers E (I) in plastic K (I) or one or more elastomeric modifiers E (II) in plastic K (II), preferably in an amount between 0 to 40% by weight, preferably between 0 and 30% by weight, particularly preferably between 3 and 20% by weight, in each case based on the total weight of said plastic molding compositions. Molding according to at least one of the preceding claims, characterized in that the plastic K (I) is glass-fiber-reinforced PBT and the plastic K (II) is glass-fiber reinforced and elastomer-modified PA, the plastics K (I) and K (II) each preferably contain 10 to 30% by weight of glass fibers and the plastics K (II) preferably contain 3 to 30% by weight of glass fibers. -4910% by weight of the elastomeric modifier based on the total weight of said plastic molding compositions. Molding according to at least one of the preceding claims, characterized in that further conventional additives are additionally present in either plastic K (I) and / or in plastic K (II) in an amount of up to 5% by weight, based on for the given plastics. Method for producing a molded part according to at least one of Claims 1 to 13, characterized in that (A) the plastics K (I) or the plastics K (II) are first molded, so that a partial molding T (I) is formed. ) or T (II) and thereafter another plastics material K (II) or K (I) is applied to at least one point of the surface of the molding, the process preferably being a two-component injection molding. Method according to claim 14, characterized in that in an additional step a portion of the surface of the molding is metallized, preferably wet-chemically metallized, particularly preferably wet-chemically metallized, and subsequently electrogalvanized, the additional step being carried out between steps (A) and (B), or preferably after both steps. Method according to at least one of the preceding claims 14 and / or 15, characterized in that the metallization process of the metallizable plastic K (II) comprises the following steps: chemical roughening of the surface with preferably calcium chloride solution, deposition of an activator of preferably palladium ions , sensitization preferably by reduction of palladium cations to palladium, chemical deposition of conductive material preferably nickel or copper, electrochemical reaction (galvani -50) and possibly the formation of additional layers. Method according to one of the preceding claims 14 to 16, characterized in that the process is carried out by means of at least one two-component injection molding process and subsequent metallization. Use of one of the moldings according to at least one of claims 1 to 13 and / or of at least one product of the process according to at least one of claims 14 to 17 as a component with integrated electrically conductive components, preferably in automotive construction, mechanical engineering, computer technology , consumer electronics, electrical household appliances, lighting and installation technology.