Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0053—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor combined with a final operation, e.g. shaping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/16—Making multilayered or multicoloured articles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1635—Composition of the substrate
  • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
  • C23C18/1641—Organic substrates, e.g. resin, plastic
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1646—Characteristics of the product obtained
  • C23C18/165—Multilayered product
  • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/285—Sensitising or activating with tin based compound or composition
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating
  • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/16—Making multilayered or multicoloured articles
  • B29C2045/169—Making multilayered or multicoloured articles injecting electrical circuits, e.g. one layer being made of conductive material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
  • B29L2031/3493—Moulded interconnect devices, i.e. moulded articles provided with integrated circuit traces

Definitions

• the invention relates to metallizable molded parts, processes for their production and their use as a component with integrated electrically conductive sections for electrical applications.
• thermoplastic materials with integrated electrically conductive sections are known in principle.
• PA 12 in particular was used here as a non-metallizable component and polyamides based on ⁇ -caprolactam and / or hexamethylenediamine and adipic acid as a metallizable component, both components being used in most cases in the form of glass-fiber reinforced compounds.
• DE 44 16 986 describes a method for producing a special component from a plastic Kl from the group that is difficult or impossible to metallize
• the following cannot be metallized under the conditions typical for PA6, e.g. partially aromatic polyamides.
• the Durethan T40 (commercial product from Bayer AG, partially aromatic polyamide, molding compound set according to ISO 1874: PA6I, MT, 12-030), which cannot be metallized under the conditions customary for PA6, is partially galvanized by melt compounding with 30% glass fibers, so that the material is not considered as Alternative for PA 12 comes into question.
• partially aromatic polyesters such as, for example, polybutylene terephthalate (PBT) and polyamides (PA) are insoluble in one another in the melt and therefore do not show any miscibility. Due to this incompatibility, no blends of polyester (including PBT) and PA (including PA6) of commercial importance are known to date (Z. Xiaochuan et al, Polymers and Polymer Composites, Vol. 5, No. 7, 1997, S 501 - 505). Probably for this reason, PBT / PA blends are not mentioned in the plastic manual polyamide (plastic manual polyamide 3/4, Carl Hanser Verlag, 1998, ISBN 3-446-16486-3, p. 131 - 165). Therefore, it has previously been assumed that combinations of PBT and PA in two-component injection molding are unsuitable for 3-D MID applications.
• PBT polybutylene terephthalate
• PA polyamides
• the preferred metallization method is the Baygamid® method (Bayer AG method).
• plastic (s) K (I) and the plastic (s) K (II) are present in a macroscopically phase-separated manner in relation to the respective type of plastic to more than 90% by weight.
• the partially aromatic polyester according to the invention is selected from the group of derivatives of polyalkyliderephthalates, preferably selected from the group of polyethylene terephthalates, polytrimethylene terephthalates and polybutylene terephthalates, particularly preferably polybutylene terephthalates, very particularly preferably polybutylene terephthalate.
• Partially aromatic polyester is understood to mean materials which, in addition to aromatic molecular parts, also contain aliphatic molecular parts.
• polyalkylene terephthalates are reaction products made from aromatic dicarboxylic acid or its 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 from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Kunststoff 1973 ).
• Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, 1,3-ethylene glycol and / or propanediol and / or butanediol-1,4-residues.
• the preferred polyalkylene terephthalates can contain up to 20 mol% residues of other aromatic dicarboxylic acids with 8 to 14 C atoms or aliphatic dicarboxylic acids with 4 to 12 C atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
• the preferred polyalkylene terephthalates can contain up to 20 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 Contain carbon atoms, e.g.
• the polyalkylene terephthalates can be branched by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acid, as described, for example, in DE-OS 19 00 270 and US Pat. No. 3,692,744.
• Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethyl ether and propane and pentaerythritol.
• polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (eg its dialkyl esters) and ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol (polyethylene and polybutylene terephthalate), and mixtures of these polyalkylene terephthalates.
• Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.
• the polyalkylene terephthalates generally have an intrinsic viscosity of approximately 0.4 to 1.5, preferably 0.5 to 1.3, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
• the partially aromatic polyester additives such as Fillers and reinforcing materials such as Contain glass fibers or mineral fillers, flame retardants, processing aids, stabilizers, flow aids, antistatic agents, dyes, pigments and other common additives.
• glass fibers As fiber or particulate fillers and reinforcing materials for the molding compositions according to the invention, glass fibers, glass balls, glass fabric, glass mats,
• Carbon fibers, aramid fibers, potassium titanate fibers, natural fibers, amorphous Silicic acid, magnesium carbonate, barium sulfate, feldspar, mica, silicates, quartz, talc, kaolin, titanium dioxide, wollastonite, etc. can be added, which can also be surface-treated.
• Preferred reinforcing materials are commercially available glass fibers.
• the glass fibers which generally have a fiber diameter between 8 and 18 ⁇ m, can be in the form of continuous fibers or cut or ground
• Glass fibers are added, the fibers with a suitable sizing system and an adhesion promoter or adhesion promoter system e.g. can be equipped on a silane basis.
• acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character. Needle-shaped wollastonite is an example.
• the mineral preferably has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 1 1: 1.
• the mineral filler can optionally be surface-treated.
• the polyester molding composition preferably contains 0 to 50 parts by weight, preferably 0-40, in particular 10-30 parts by weight of fillers and / or reinforcing materials. Polyester molding compositions without fillers and / or reinforcing materials can also be used.
• organic compounds or halogen compounds with synergists or commercially available organic nitrogen compounds or organic / inorganic phosphorus compounds are suitable as flame retardants.
• Mineral flame retardant additives such as magnesium hydroxide or Ca-Mg carbonate
• halogen-containing, in particular brominated and chlorinated, compounds are: ethylene-1,2-bistetrabromophthalimide, epoxidized tetrabromobisphenol A resin, tetrabromobisphenol A oligocarbonate, tetrachlorobisphenol A oligocarbonate, pentabromopolyacrylate, brominated polystyrene.
• the phosphorus compounds according to WO98 / 17720 are suitable, for example Triphenyl phosphate (TPP), resorcinol bis (diphenyl phosphate) including oligomers (RDP) and bisphenol A bis bis diphenyl phosphate including oligomers (BDP), melamine phosphate, melamine pyrophosphate, melamine polyphosphate and mixtures thereof.
• TPP Triphenyl phosphate
• RDP resorcinol bis
• BDP bisphenol A bis bis diphenyl phosphate including oligomers
• melamine phosphate melamine pyrophosphate
• melamine polyphosphate and mixtures thereof.
• suitable synergists are antimony compounds, in particular antimony trioxide and antimony pentoxide, zinc compounds, tin compounds such as zinc stannate and borates. Carbon formers and tetrafluoroethylene polymers can be added.
• the partially aromatic polyesters according to the invention can contain conventional additives such as
• Agents against heat decomposition agents against heat crosslinking, agents against damage by ultraviolet light, plasticizers, lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers and dyes and pigments.
• oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
• UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition.
• Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can also be added as colorants and other colorants.
• organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones
• sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc can be used as nucleating agents.
• Lubricants and mold release agents which are usually used in amounts of up to 1% by weight, are preferably ester waxes, penterithryt stearate (PETS), long-chain fatty acids (for example stearic acid or behenic acid), their salts (for example Ca or Zn stearate) and amide derivatives (eg ethylene-bis-stearylamide) or montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) as well as low molecular weight polyethylene or polypropylene waxes.
• PETS penterithryt stearate
• long-chain fatty acids for example stearic acid or behenic acid
• their salts for example Ca or Zn stearate
• amide derivatives eg ethylene-bis-stearylamide
• montan waxes mixturetures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms
• plasticizers are phthalic acid dioctyl esters, phthalic acid dibenzyl esters, phthalic acid butyl benzyl esters, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.
• rubber-elastic polymers (often also referred to as impact modifier, elastomer or rubber) is particularly preferred.
• these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene,
• EPM ethylene-propylene
• EPDM ethylene-propylene-diene
• EPM rubbers generally have practically no more double bonds, while EPDM rubbers can have 1 to 20 double bonds per 100 carbon atoms.
• diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-l, 4-diene, hexa- 1, 4-diene, hexa-l, 5 -diene, 2,5-dimethylhexa-l, 5-diene and octa-
• cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5 -norbornene and tricyclodienes such as 3-methyl-tricyclo- (5.2.1.0.2.6) -3,8-decadiene or their mixtures. Hexa-l, 5-diene, 5-ethylidene norbornene and dicyclopentadiene are preferred.
• the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8,% by weight, based on the total weight of the rubber.
• EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives.
• reactive carboxylic acids or their derivatives e.g. Acrylic acid.
• 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 also contain dicarboxylic acids such as maleic acid and fumaric acid
• R 1 to R 9 represent hydrogen or alkyl groups having 1 to 6 carbon 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.
• the radicals R 1 to R 9 are preferably hydrogen, where m is 0 or 1 and g is 1.
• the corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.
• Preferred compounds of the formulas (I), (II) and (IV) are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior comes close to that of the free acids and is therefore referred to as monomers with latent carboxyl groups.
• the copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or monomers containing methacrylic acid and / or monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.
• Copolymers of are particularly preferred
• I to 45 in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
• esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
• vinyl esters and vinyl ethers can also be used as comonomers.
• the ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.
• Preferred elastomers are also emulsion polymers, the preparation of which is described, for example, by Blackley in the monograph "Emulsion Polymerization".
• the emulsifiers and catalysts which can be used are known per se.
• homogeneous elastomers or those with a shell structure can be used.
• the shell-like structure is determined by the order of addition of the individual monomers;
• the morphology of the polymers is also influenced by this order of addition.
• acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
• monomers for the production of the rubber part of the elastomers acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
• monomers can be combined with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.
• the soft or rubber phase (with a glass transition temperature of 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 two shells); with multi-layer
• Elastomers can also consist of several shells from a rubber phase.
• one or more hard components are involved in the construction of the elastomer, these are generally made by polymerizing styrene, acrylonitrile,
• acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as main monomers.
• methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as main monomers.
• smaller proportions of other comonomers can also be used here.
• emulsion polymers which have reactive groups on the surface.
• groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups as well as functional groups which are obtained by using monomers of the general formula
• R 10 is hydrogen or a C j to C 4 alkyl group
• R 1 1 is hydrogen, a C to Cg alkyl group or an aryl group, in particular phenyl,
• R 12 is hydrogen, a Ci to Cj Q alkyl, a C 6 to C 2 aryl group or -OR13,
• R 13 is a C j to Cg alkyl or Cg to C aryl group, optionally with
• O- or N-containing groups can be substituted
• X is a chemical bond, a Ci to C 10 alkylene, a C 6 to C j2 arylene group or
• Z is a C j to C j o-alkylene or a C ⁇ to C ⁇ arylene group.
• the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
• Further examples are acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (Nt-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) called ethyl acrylate.
• the particles of the rubber phase can also be crosslinked.
• Monomers acting as crosslinking agents are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265.
• graft-linking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds, which react at different rates during the polymerization. Those compounds are preferably used in which at least one reactive group has approximately the same rate as the others
• Monomers polymerize while the other reactive group (or reactive groups) e.g. polymerizes much slower (polymerize).
• the different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, i.e. the grafted phase is at least partially linked to the graft base via chemical bonds.
• graft-crosslinking monomers examples include those containing allyl groups
• Monomers especially 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.
• graft-crosslinking monomers for further details, reference is made here, for example, to US Pat. No. 4,148,846.
• 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-modifying polymer.
• graft polymers with a core and at least one outer shell are to be mentioned, which have the following structure:
• graft polymers in particular ABS and / or ASA polymers, are preferably used for impact modification of PBT, if appropriate in a mixture.
• homogeneous, ie single-layer elastomers composed of buta- 1,3-diene, isoprene and n-butyl acrylate or their copolymers can also be used. These products can also be prepared by using crosslinking monomers or monomers with reactive groups.
• emulsion polymers examples include 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 made of n-butyl acrylate or based on butadiene and an outer shell of the above
• Copolymers and copolymers of ethylene with comonomers that provide reactive groups are also known as copolymers and copolymers of ethylene with comonomers that provide reactive groups.
• the elastomers described can also be made by other conventional methods, e.g. by suspension polymerization.
• Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290 are also preferred.
• the polyester molding composition preferably contains 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 partially aromatic polyester molding compositions according to the invention are produced by mixing the respective constituents in a known manner and converting them into conventional units such as, for example, at temperatures from 200 ° C. to 330 ° C. Internal kneading, extruders, twin-shaft screws melt-compounded or melt-extruded.
• Melt compounding or melt extruding step can be added to other additives such as reinforcing materials, rubber-elastic polymers, stabilizers, dyes, pigments, lubricants and mold release agents, nucleating agents, compatibalizers and other additives.
• the polyamide according to the invention is preferably selected from the group of derivatives of polyamides in which 3 to 8 methylene groups are contained in the polymer chain per polyamide group, particularly preferably selected from the group formed from PA6 and PA66, very particularly preferably from the group of PA6 and its copolymers .
• the polyamides according to the invention can be produced by various processes and synthesized from very different building blocks and, in special applications, alone or in combination with processing aids, stabilizers, polymeric alloy partners (e.g. elastomers) or also reinforcing materials (such as mineral fillers or glass fibers) to form materials be equipped with specially set combinations of properties. Blends are also suitable, e.g. with parts of polyethylene, polypropylene, ABS.
• the properties of the polyamides can be improved by adding elastomers, e.g. B. with regard to the impact strength of z. B. reinforced polyamides. The variety of possible combinations enables a very large number of products with different properties.
• Preferred polyamides for the combinations K (I) / K (II) according to the invention are partially crystalline polyamides which start from diamines and dicarboxylic acids and or Lactams with at least 5 ring members or corresponding amino acids can be produced.
• the starting products 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 2,4,4-trimethylhexamethylene diamine, the isomeric diamino-dicyclohexylmethane, diamino-dicyclohexylpropane, bis-aminomethyl-cyclohexane, aminocarboxylic acids such as aminocaproic acid, or the corresponding lactams. Copolyamides from several of the monomers mentioned are included.
• Caprolactams are particularly preferably used, very particularly preferably ⁇ -caprolactam.
• Polyamide 6 or polyamide 6.6 or polyamide 4.6 or polyamide 6.10 or a copolyamide from the units of the homopolyamides mentioned or a copolyamide of caprolactam units and units derived from hexamethylene diamine and adipic acid are particularly preferably used.
• Polyamide 6 or copolyamides with polyamide 6 are very particularly preferably used.
• polyamides produced according to the invention can also be mixed with others
• Polyamides and / or other polymers are used.
• the polyamide molding compositions according to the invention can contain additives, for example rubber-elastic polymers, as already described above for the polyester molding compositions.
• the polyamide molding compounds can still fire retardants such.
• B. contain rubbers or polyolefins and the like.
• carbon fibers, aramid fibers, mineral fibers and whiskers can be considered as fibrous reinforcing materials.
• suitable mineral fillers are calcium carbonate, dolomite, calcium sulfate, mica, fluorine mica, wollastonite, talc and kaolin.
• other oxides or hydrated oxides of an element selected from the group consisting of boron, aluminum, gallium, indium, silicon, tin, titanium, zirconium, zinc, ytrium or iron can also be used.
• the fibrous reinforcing materials and the mineral fillers can be surface-treated.
• conductive polyamides In order to obtain conductive polyamides, conductive carbon blacks, carbon fibrils, conductive polymers, metal fibers and conventional additives to increase the conductivity can be added.
• the polyamide molding composition according to the invention preferably contains fillers and / or reinforcing materials, preferably in amounts of 1-50% by weight, particularly preferably between 2-40% by weight, particularly preferably between 5-35% by weight, based on the Total mass of the polyamide molding compound.
• fillers and / or reinforcing materials preferably in amounts of 1-50% by weight, particularly preferably between 2-40% by weight, particularly preferably between 5-35% by weight, based on the Total mass of the polyamide molding compound.
• PA molding compounds without fillers and / or reinforcing materials can also be used.
• the fillers can be added before, during or after the polymerization of the monomers to give the polyamide. If the fillers according to the invention are added after the polymerization, they are preferably added to the polyamide melt in an extruder.
• the fillers according to the invention are added before or during the polymerization, the polymerization can comprise phases in which work is carried out in the presence of 1 to 50 percent by weight of water.
• the fillers can already be present as particles with the particle size ultimately occurring in the molding composition.
• the fillers in the molding composition can already be present as particles with the particle size ultimately occurring in the molding composition.
• the fillers in the molding composition can already be present as particles with the particle size ultimately occurring in the molding composition.
• Diphenyls or diphenyl ethers in combination with antimony trioxide and chlorinated cycloaliphatic hydrocarbons (Dechlorane ® plus from Occidental Chemical
• brominated styrene oligomers e.g. in DE-A-2 703 419
• core brominated styrene oligomers e.g. in DE-A-2 703 419
• Polystyrenes eg Pyro-Chek 68 ® from FERRO Chemicals
• Zinc compounds or iron oxides are also used as synergists with the halogen compounds mentioned.
• melamine salts in particular have proven themselves as flame retardants, especially for unstable, poor polyamides.
• magnesium hydroxide has long proven itself as a flame retardant for polyamide.
• polyamide molding compositions which, in addition to glass fibers, additionally contain rubber-elastic polymers (often also as an impact modifier, elastomer or
• Rubber-elastic polymers are understood here as already described above for the polyester molding compositions.
• the polyamide molding composition preferably contains 0-40, preferably 0-30, particularly preferably 3-20 parts by weight of impact modifier, elastomer or rubber.
• Graft polymers with a core based on acrylates and a shell based on styrene and acrylates are particularly suitable.
• Polyamide molding compositions which are both glass-fiber reinforced and elastomer-modified are particularly preferred.
• MID is generally understood to mean the following:
• MID Molded Interconnect Devices
• MID has been an internationally introduced term since the early 1990s to refer to spatially injection-molded circuit boards. The idea behind this is to produce electrical connecting elements based on thermoplastic materials in a three-dimensional, spatial arrangement. MIDs carry electricity, form shielding or transmitting surfaces, carry electronic components and integrate mechanical elements. The MID technology extends the conventional circuit board technology, which is limited to one room level, and is partly in competition with it.
• MIDs One of the most frequently used manufacturing processes for MIDs is the two-component injection molding technique followed by wet chemical metallization of a plastic component. This process enables the greatest geometrical design freedom in the manufacture of MIDs.
• a composite body is produced from two thermoplastics, one component of which can be metallized, while the other component remains completely unaffected by the chemical action of the metallization electrolytes.
• the metallizable plastic can be structured in the form of electrical conductor tracks. However, it can also be structured over a large area and thus, after metallization, contribute to the shielding of electromagnetic interference fields, specifically dissipate frictional heat or become more wear-resistant.
• the structural fineness for example the width of electronic conductor tracks, can be reduced to about 500 ⁇ m.
• Such fine conductor track structures are achieved if the metallizable plastic is injected in the first shot and the non-metallizable plastic is extrusion-coated in the second shot. But the reverse order is also possible.
• the location and number of sprues, the material costs and the adhesion between the two plastic components depend on the type of sequence.
• the adherent metallizability of plastics is a crucial point in the manufacture of MIDs.
• AHC, Kerpen, a provider of functional surface technology uses a process (Baygamid® process etc.) for adhesive metallization especially for polyamides.
• the coating is carried out by wet chemical means by immersing the workpieces in suitable electrolytes. First, an approximately 2 ⁇ m thick metallic stop layer is applied. It can be further reinforced chemically (for example with chemical nickel) or glavanically (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 fiber or mineral fiber filling up to 40% can be metallized.
• the adhesive strength of the applied metal layers is more than 1 N / mm.
• Individual chemically nickel-plated polyamide types pass temperature cycling tests, for example a three cycle from + 140 ° C to -40 ° C. There is no shifting of the layer.
• the manufacturing costs of a car door lock carrier using this MID technology could be reduced to almost half the costs for conventional manufacturing.
• the door lock carrier is located in the car door behind the door handle. Depending on the equipment of the vehicle, it is equipped with a lock heater, the control for the central locking and the activation of the automatic interior lighting.
• Current-carrying strands, microswitches and resistance wire have to be mounted in a conventional manner on an aluminum die-cast body.
• the support structure generated in the first shot already contains all the storage and storage facilities relevant for the later function
• the metallizable component is overmolded in the second shot and, after the metallization, replaces the current-carrying strands of conventional production.
• Another application is the production of a car sunroof control as a MID based on polyamide.
• fine conductor track structures are created, but also later plug contacts in the first shot.
• the second shot creates the non-metallizable body from another type of polyamide. It contains all mechanical components. After the metallization of the two-component polyamide, assembly is limited to assembling the electrical components and soldering them. Compared to the conventional PCB solution the number of mechanical components is reduced and the assembly effort is minimized. However, the conventional assembly technology, especially in the area of assembly and soldering, can be retained. Special advantages are:
• thermoplastic materials for the production of circuit carriers offers the almost unlimited freedom of design for the construction of electronic assemblies, as is made possible by injection molding technology.
• the miniaturized and lighter MID assemblies allow new functions and the design of any shape.
• the miniaturized MID assemblies reduce the otherwise necessary use of materials.
• the MID technology is characterized by a number of improvements in terms of its environmental compatibility. During the pretreatment of the most important MID-suitable plastics, strongly oxidizing acids are avoided. In addition to environmentally friendly production, reducing the variety of materials also plays a decisive role. This favors the recycling of basic materials and the uncritical disposal of residual materials. By using thermoplastics, many can
• thermosets
• the molded parts can be produced by a process in which (A) is first
• Plastic K (I) or K (II) is brought into a mold so that a partial molding T (I) or T (II) is formed and then (B) at least one point on the surface of the partial molding, the other plastic K (II) or K (I) is attached.
• the molded parts are produced by two-component injection molding.
• a part of the surface is preferably of the molding metallized by the known to those skilled in conventional wet chemical, electrolytic processes, particularly preferably by the Baygamid ® - method (Bayer AG), wherein this additional step between steps (A) and ( B) or is preferably carried out after the two steps.
• the metallization step of the metallizable plastic K (II) can preferably contain the following steps: Chemical roughening of the surface e.g. with a calcium chloride solution. Deposit of a
• Activator eg palladium ions. Sensitization eg by reducing the palla dium cations to palladium. Chemical deposition of a conductive material such as nickel or copper through, for example, palladium-catalyzed reduction of soluble nickel or copper ion complexes. Electrochemical conversion (electroplating, possibly with a multi-layer structure). All of this, as described for example in DE 43 28 883 or EP 146 723 or EP 146 724, which are hereby incorporated by reference into this document. Further descriptions of this or a similar process can be found in the literature (GD Wolf, F. Funenger, Metallized Polyamide Injection Moldings, Bayer SN 19038, May 1989; U. Tyszka, The standard, large-scale galvanic metallization of injection molded parts made of polyamide, Galvanotechnik 80, 1989, pp. 2 ff; and literature cited there).
• the metallization of plastic surfaces can be achieved by physical metallization (preferably metal vapor deposition, vacuum metallization) or chemical metallization, preferably wet-chemical electroless or wet-chemical electro-galvanic metallization (galvanization), chemical metallization in particular, in particular wet-chemical (electroless or electro-galvanic) for this invention.
• Metallization is preferred.
• organometallic activators that have been developed for use in novel metallization processes.
• organometallic activators that have been developed for use in novel metallization processes.
• These are complex compounds of noble metals, preferably palladium or platinum, with different organic ligands.
• the organic ligands were chosen so that there is a special affinity for the polyamide surface, which makes a significant contribution to the adhesive strength of the metal layer to be applied. Because of this novel activation principle, it was possible to achieve that only a very slight roughening of the polyamide surface has to be carried out as an additional measure for very good metal adhesion.
• the entire pretreatment before chemical nickel plating consists of the following stages:
• the dwell time in the baths is 5 to 10 minutes at approx. 40 ° C.
• the first metal layer can then be immediately deposited in any chemical nickel bath. After a first adherent conductive metal layer has been applied, the usual electroplating process, e.g. connect the galvanic layer structure of nickel / copper / nickel / chrome without any problems.
• the process enables the adherent metallization of different commercially available polyamides.
• the application of the method is not restricted to polyamide 6 types.
• Injection molded parts made of polyamide 66 can also be metallized without any problems while observing the optimized process parameters.
• tailor-made metallizable polyamide types are available, which are reinforced with glass fibers for the requirements for high rigidity and heat resistance or for setting a reduced tendency to warp with mineral fillers. Flame retardant products are also available in this way.
• polyamide types with special elastomer modification have been developed.
• the class of elastomer-modified, glass fiber-reinforced polyamides is particularly suitable for components that have to meet at most requirements with regard to dimensional stability, dynamic fatigue strength and heat resistance, for example when used in the motor vehicle engine compartment.
• the glass fiber reinforcement significantly reduces the thermal expansion coefficient of the injection molded parts, so that the adhesive bond between the metal surface and the plastic substrate remains guaranteed even with extreme temperature changes.
• the electroplating step preferably of the metalizable plastic K (II) comprises the following steps: G (I) disintegrating the surface by dissolving baths, preferably containing calcium salts, G (II) chemical deposition of metals, preferably palladium, to produce a conductive one
• a 90 x 150 x 3 mm thick glass fiber reinforced (30% glass fibers) plate made of polyamide-6 was placed in a pretreatment bath with a flash point> 110 ° C of the following composition:
• the adhesive strength is according to DIN 53 494 60N / 25 mm.
• a molded part made of a polyamide-6 reinforced with 30% by weight glass fiber was pretreated according to Example 1, activated, sensitized, chemically nickel-plated and then galvanically reinforced.
• the galvanic layer structure Ni / Cu / Ni / Cr was obtained as follows:
• the cheapest process for producing the molded parts is carried out using a two-component injection molding process and subsequent galvanization.
• two-component injection molding was only used to describe the process in which two materials are injected into one another. In the present case, however, it is about two plastics being sprayed onto one another. This process was previously called two-color injection molding.
• Typewriter keys, switch buttons and the like were preferably produced with it by first injection-molding a cap with a recess in the form of the character to be represented. This was then back-injected with a different colored material, whereby the recess for the sign was filled.
• Plastic used The MID's trace geometry is shown in relief. In the second shot, the areas between the conductor tracks are filled with a plastic that cannot be metallized.
• the conductor track structure can be injected as a depression from the non-metallizable component in the first shot and filled with the metallizable component in the second shot.
• the MID base part 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 molding offers the greatest geometric freedom of all MID manufacturing processes. Difficult conductor track geometries and plated-through holes can be realized in this process. The structuring of the conductor track geometry takes place during the injection molding. The smallest trace width is 0.25 mm. It depends on the flow properties of the plastic and the
• Structuring is carried out using two tool cavities, high currents can be realized, short process chain, low unit costs for large series through-plating without problems
• the components with integrated electrically conductive sections can preferably be used for electrical applications, particularly preferably in vehicle technology, mechanical engineering, computer technology, household electronics, electrical household appliances, lighting technology and installation technology.
• electrical applications particularly preferably in vehicle technology, mechanical engineering, computer technology, household electronics, electrical household appliances, lighting technology and installation technology.
• plastic parts with the molded parts according to the invention and the methods according to the invention including metal surfaces and conductor tracks, for example also snap and locking elements, for example snap hooks for fastening microswitches etc.
• the two components were processed under the conditions customary for the respective molding compositions (PA: ISO 1874; PBT: ISO 7792).
• Polyester grades that were tested for the ability to be galvanized using the Baygamid method using the injection-molded test specimens (60 * 40 * 4 mm 3 ) under the conditions customary for PA and show good results:
• Pocan B3235 30% glass fiber (PBT, MHMR, 10 - 100, GF 30)
• Pocan B4235 30% glass fiber, flame retardant (PBT, MFHR, 10 - 110, GF 30)
• Pocan KU2-7033 30% glass fiber, elastomer modified (PBT, MHPR, - 080, GF 30) None of the three types can be galvanized. AFM images do not indicate serious changes in the surface.
• Pocan B3215 10% glass fiber (PBT, MHMR, 10 - 070, GF 10) Pocan KL 1-7265: 15% glass fiber (PBT, MHMR, 10 -0 60, GF 15) Pocan B3225: 20% glass fiber (PBT, MHMR , 10 - 070, GF 20) Pocan B4225: 20% glass fiber, flame retardant (PBT, MFHR, 10 - 070, GF 20)
• Pocan B1305 Medium viscosity (PBT, MHMR, 10 - 030, N)
• Pocan B1505 Medium to high viscosity (PBT, MHMR, 14 - 030, N)
• Pocan B 1800 High viscosity (PBT, EN, 16 - 030)
• Durethan BKV 130 30% glass fiber, elastomer modified; Molding compound set according to ISO 1874: PA6, MPR, 14-090, GF30
• Durethan BKV 115 15% glass fiber, elastomer modified, molding compound set according to ISO 1874: PA6, MPR, 14-060, GF15
• Durethan BKV 230 PA 6 injection molding grade with 30% glass fibers, elastomer modified, molding compound set according to ISO 1874: PA6, MPR, 14-080, GF30
• Durethan BKV 215 PA 6 injection molding grade with 15% glass fibers, elastomer modified, molding compound set according to ISO 1874: PA6, MPR, 14-040, GF15
• Durethan BKV 30 H1.0 PA 6 injection molding grade with 30% glass fibers, heat stabilized, molding compound set according to ISO 1874: PA6, MHR, 14-100, GF30
• Durethan AKV 30 PA 66 injection molding grade with 30% glass fibers; Molding compound set according to ISO 1874: PA66, MR, 14-090, GF30
• Durethan B 30 S PA 6 standard injection molding type, good flow, easy release, quick setting; ; Molding compound set according to ISO 1874: PA6, MR, 14-030, N
• Durethan A 30 S PA 66 standard injection molding type, unreinforced, very good release properties; Molding compound set according to ISO 1874: PA66, MR, 14-040N
• the molded parts according to the invention show advantages in three established tests for MID.
• the layer system 2 ⁇ m chemical nickel (stop layer) and 10 ⁇ m chemical nickel (top layer) were examined under different conditions. Scoring test

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Metallurgy (AREA)
• Manufacturing & Machinery (AREA)
• Inorganic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Injection Moulding Of Plastics Or The Like (AREA)
• Chemically Coating (AREA)
• Other Surface Treatments For Metallic Materials (AREA)
• Reinforced Plastic Materials (AREA)
• Thermistors And Varistors (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

Priority Applications (7)

Applications Claiming Priority (4)

Publications (2)

Family

ID=26051642

Family Applications (1)

Country Status (11)

Cited By (1)

Families Citing this family (7)

Citations (4)

• 2000
  • 2000-01-21 KR KR1020017009742A patent/KR20010101932A/ko not_active Application Discontinuation
  • 2000-01-21 EP EP00902624A patent/EP1155162A2/de not_active Withdrawn
  • 2000-01-21 JP JP2000597476A patent/JP2002536503A/ja active Pending
  • 2000-01-21 BR BR0008005-5A patent/BR0008005A/pt not_active IP Right Cessation
  • 2000-01-21 WO PCT/EP2000/000445 patent/WO2000046419A2/de not_active Application Discontinuation
  • 2000-01-21 PL PL00350124A patent/PL350124A1/xx unknown
  • 2000-01-21 CN CN00805634A patent/CN1345383A/zh active Pending
  • 2000-01-21 AU AU24394/00A patent/AU2439400A/en not_active Abandoned
  • 2000-01-21 CZ CZ20012837A patent/CZ20012837A3/cs unknown
  • 2000-01-21 CA CA002361399A patent/CA2361399A1/en not_active Abandoned
• 2002
  • 2002-09-10 HK HK02106644.5A patent/HK1044969A1/zh unknown

Patent Citations (4)

Also Published As

Similar Documents

Legal Events