CN101522956A - Method for applying a metal layer to a substrate - Google Patents

Abstract

The invention relates to a method for applying a metal layer to a substrate by chemical and/or galvanic deposition of a metal from a metal salt solution, an essential feature being that the substrate surface comprises carbon nanotubes. The invention further relates to the use of carbon nanotubes for applying a metal layer to a substrate.

Description

On matrix, apply the method for metal level

The present invention relates to apply on matrix from the metal of metal salt solution the method for metal level, and carbon nanotube is applying the purposes of metal level to the matrix by deposition.

The method that makes common non electrically conductive material such as plastic-metalization is known.These metallized parts such as metallized plastic components use in various fields, and for example their electric conductivity makes them be used as electric component.They also are widely used in the decoration field in addition, because when they had the outward appearance identical with the goods of being made by metal fully, their weight was lighter and production cost is lower.

Plastic-metalization there are a lot of methods, wherein need process chemistry or physics roughening method or chemistry or physical etch method that this frosting is carried out than complicated pretreatment, for example use chromic acid-sulfuric acid mixture, and/or apply prime coat or the adhesion promoting layer that for example comprises precious metal, as electricity and/or electrochemical plating deposition adheres to and the pre-treatment (for example referring to WO01/77419) of the metal level that firmly adheres to by not having.

The currently known methods that another kind is given plastics electric conductivity (this is the pre-treatment for the necessity of being undertaken by the electrochemical plating metal refining) is that carbon nanotube or carbon nanometer fibril are incorporated into plastics.The example of other advantage of these electric conductivity carbon nanotubes is that they have than the lighter weight of metal powder and they and give the toughness (for example referring to US 2006/0025515 A1) that plastics increase usually.

DE 102 59 498 A1 disclose and have not only comprised granular carbonization compound such as carbon black or graphite but also comprise carbon nanometer fibrillar electric conductivity thermoplastics.Plastic hybrid described in the document not only has electric conductivity but also has good flowability, favorable surface quality and high tenacity.They are particularly suitable for the electrostatic coating of plastics and improve the antistatic property of plastics.But when its surface resistivity when being undertaken being used as matrix in the metallized technology of disclosed electric conductivity thermoplastics in this specification sheets by electrochemical plating not enough.

The purpose of this invention is to provide by chemistry and/or electrochemical plating deposition and on matrix, apply improving one's methods of metal level from the metal of metal salt solution.This method should be feasible especially, and the metal level that wherein is deposited on the matrix can be in shorter electroplating time and this matrix excellent bonds, and cost is low and quality good, and the weight of the matrix that wherein metallizes is lighter.

Therefore the method described in the foreword of finding is used for applying metal level by chemistry and/or electrochemical plating deposition from the metal of metal salt solution on matrix, and the principal feature of these methods is to have carbon nanotube in stromal surface.

Find that in addition carbon nanotube is applying the purposes of metal level to the matrix.

The inventive method allows with improvement to apply metal level by chemistry and/or electrochemical plating deposition from the metal of metal salt solution on matrix.Especially can by the inventive method with the good adhesion of matrix, short electroplating time, low cost and good quality depositing metal layers on matrix.The metallization matrix weight of being produced is lighter.

The inventive method is described below, and other goods, methods and applications.

The important feature of the inventive method is that the stromal surface in the matrix of waiting to metallize exists carbon nanotube.This means or this matrix itself (thereby also comprising its surface) comprises carbon nanotube that perhaps being applied to wherein with the form of the form of mucoadhesive polymers coating or lacquer carbon nanotube, there is not the matrix of carbon nanotube in itself.The carbon nanotube that is positioned on stromal surface or the stromal surface brings electric conductivity, this for subsequently pass through chemistry and/or electrochemical plating technology of metal refining on matrix is necessary.For example except carbon nanotube, other conductive component such as metal-powder or carbon black pellet can be arranged in stromal surface or on the stromal surface, with the increase electric conductivity, but their existence is dispensable for the present invention.Carbon nanotube itself and preparation (B component or B ') thereof will be described in the back.

Therefore in the preferred embodiment of the inventive method, matrix used in the technology by chemistry and/or electrochemical plating metal refining is by the moulding compound production that comprises carbon nanotube, and the back can be described in more detail.In other preferred embodiment of the inventive method, by used matrix in the technology of chemistry and/or electrochemical plating metal refining provide the back described and comprise the dispersion of carbon nanotube and subsequently to small part dry and/or subsclerotic at least those.

The moulding compound that comprises carbon nanotube

In a preferred embodiment, the matrix that can use in the methods of the invention is based on thermoplastic composition, and based on the gross weight (100 weight %) of component A, B, C and D, this thermoplastic composition comprises:

A 20-99 weight %, preferred 55-95 weight %, the component A of preferred especially 60-92 weight %,

B 1-30 weight %, preferred 5-25 weight %, the B component of preferred especially 8-20 weight %,

C 0-10 weight %, preferred 0-8 weight %, the component C of preferred especially 0-5 weight %, and

D 0-40 weight %, preferred 0-30 weight %, the component D of preferred especially 0-10 weight %.

Each component of these moulding compounds is below described:

Component A

In principle, any thermoplastic polymer all is suitable as component A.Thermoplastic polymer normally its fracture tension strain is 10-1000%, preferred 20-700%, more preferably those of 50-500%.(mentioned these and other all fracture tension strain and tensile strength values all are to go up at 1BA type sample (the annex A of described standard: " small sample ") according to ISO 527-2:1996 tension test to measure in this application).

The example of suitable ingredients A is polyethylene, polypropylene, polyvinyl chloride, polystyrene (impact modification or non-impact modification), ABS (acrylonitrile-butadiene-styrene (ABS)), ASA (acrylonitrile-styrene-acrylic ester), MABS (transparent ABS comprises methacrylate unit), styrene-butadiene block copolymer (BASF Aktiengesellschaft for example

Or

, the K-ResinTM of CPC), polymeric amide, polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polybutylene terephthalate (PBT), aliphatic-aromatic copolyesters (BASF Aktiengesellschaft for example

), polycarbonate (Bayer AG for example ), polymethylmethacrylate (PMMA), poly-(ether) sulfone and polyphenylene oxide (PPO).

As component A, preferably use one or more to be selected from the polymkeric substance of impact modification vinyl aromatic copolymers, polyolefine, aliphatic-aromatic copolyesters, polycarbonate, thermoplastic polyurethane and styrenic based thermoplastic elastomer.

Polymeric amide can be used as preferred ingredients A equally.

The impact modification vinyl aromatic copolymers:

Preferred impact modification vinyl aromatic copolymers is the impact modification multipolymer of being made up of vi-ny l aromatic monomers and vinyl cyanide (SAN).The preferred impact modification SAN that uses preferably includes ASA polymkeric substance and/or abs polymer, perhaps (methyl) acrylic ester-acrylonitrile-butadiene-styrene polymkeric substance (" MABS ", transparent ABS), perhaps SAN, ABS, ASA and MABS and other thermoplastic material such as polycarbonate, polymeric amide, polyethylene terephthalate, polybutylene terephthalate, PVC or polyolefinic mixture.

Can be generally 10-300% as the ASA of component A and the fracture tension strain value of ABS, be preferably 15-250%, be preferably 20-200% especially.

The ASA polymkeric substance is generally the impact modification SAN polymkeric substance that comprises the elastomeric graft copolymers of vinyl aromatic compounds (particularly vinylbenzene) and vinyl cyanide (particularly vinyl cyanide) on the polyalkyl acrylate rubber in the polymer matrices of particularly being made up of vinylbenzene and/or alpha-methyl styrene and vinyl cyanide.

Thermoplastic composition comprises in the preferred embodiment of ASA polymkeric substance therein, the elastomeric graft copolymers A of component A ^RComposed of the following components:

A1 1-99 weight %, the particulate state graft bases A1 of preferred 55-80 weight %, particularly 55-65 weight %, its second-order transition temperature is lower than 0 ℃,

A2 1-99 weight %, the grafting A2 of preferred 20-45 weight %, particularly 35-45 weight %, grafting A2 is made up of following monomer:

A21 is 40-100 weight % based on A2, styrene units, substituted phenylethylene unit or (methyl) acrylic ester unit of preferred 65-85 weight %, and perhaps the mixture of these materials, particularly vinylbenzene and/or alpha-methyl styrene unit as component A21, reach

A22 is 60 weight % at the most based on A2, and vinyl cyanide or the methacrylonitrile unit, particularly acrylonitrile unit of preferred 15-35 weight % are as component A22.

Grafting this moment A2 is made up of at least one graft shell.

This moment, component A1 was made up of following monomer:

A11 80-99.99 weight %, at least a vinylformic acid C of 95-99.99 weight % ₁-C ₈Alkyl ester, preferred n-butyl acrylate and/or vinylformic acid (ethyl hexyl) ester, as component A11,

A12 0.01-20 weight %, at least a multifunctional cross-linking monomer of preferred 0.1-5.0 weight %, preferred Phthalic acid, diallyl ester and/or DCPA are as component A12.

According to one embodiment of the invention, component A ^RMean particle size be 50-1000nm, be unimodal distribution.

In another embodiment, component A ^RSize-grade distribution be bimodal, based on component A ^RGross weight, median size be 50-200nm account for 60-90 weight %, median size be 50-400nm account for 10-40 weight %.

Given mean particle size and size-grade distribution are the sizes by the accumulating weight measure of spread.Mean particle size under all situations is average particle size.This mensuration is based on W.Scholtan and H.Lange, and Kolloid-Z.und Z.-Polymere 250 (1972), the method for 782-796 page or leaf, operational analysis ultracentrifuge.The accumulating weight that the ultracentrifuge measurement provides the sample particle diameter distributes.Can release the particulate weight percentage that diameter is equal to or less than specific dimensions thus.Here median size (is also referred to as the d that accumulating weight distributes ₅₀) be defined as 50 weight % the particulate diameter less than corresponding to d ₅₀The particle diameter of diameter.Equally, the particulate diameter of 50 weight % is greater than d ₅₀For describing the width of rubber grain size-grade distribution, except d ₅₀(median size) also utilizes the d that is distributed and provided by accumulating weight ₁₀And d ₉₀Value.The d that accumulating weight distributes ₁₀And d ₉₀Definition and d ₅₀Similar, different is they separately based on the particle of 10 weight % and 90 weight %.Merchant (d ₉₀-d ₁₀)/d ₅₀=Q is measuring of size-grade distribution width.Preferred elastomeric graft copolymer A ^RThe Q value less than 0.5, particularly less than 0.35.

Acrylic elastomer A1 is preferably by one or more vinylformic acid C ₁-C ₈Alkyl ester, preferred vinylformic acid C ₄-C ₈The alkyl acrylate rubber that alkyl ester is formed preferably uses at least some butyl acrylates, own ester, monooctyl ester or 2-(ethyl hexyl) ester, particularly n-butyl acrylate and 2-(ethyl hexyl) ester.These alkyl acrylate rubber can comprise the monomer of the formation hard polymer of 30 weight % at the most such as vinyl-acetic ester, (methyl) vinyl cyanide, vinylbenzene, substituted phenylethylene, methyl methacrylate, vinyl ether as comonomer.

Acrylic elastomer also comprises 0.01-20 weight %, the crosslinked polyfunctional monomer (cross-linking monomer) of preferred 0.1-5 weight %.Example is the monomer that comprises two keys (preferably not being 1, the 3-conjugation) that two or more can copolymerization.

The example of suitable cross-linking monomer is Vinylstyrene, diallyl maleate, diallyl fumarate, Phthalic acid, diallyl ester, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, vinylformic acid tricyclodecenyl esters, vinylformic acid dihydro Dicyclopentadiene (DCPD) ester, triallyl phosphate, allyl acrylate, allyl methacrylate(AMA).Proved that vinylformic acid Dicyclopentadiene (DCPD) ester (DCPA) is specially suitable cross-linking monomer (referring to DE-C 12 60 135).

Component A ^RBe graft copolymer.These graft copolymers A ^RMean particle size d ₅₀Be 50-1000nm, be preferably 50-800nm, be preferably 50-600nm especially.If the granularity of used graft bases A1 is 50-800nm, be preferably 50-500nm, be preferably 50-250nm especially, then can realize these granularities.Graft copolymer A ^RUsually have one or more levels, promptly it is by examining the polymkeric substance of forming with one or more shells.This polymkeric substance is made up of the first step (grafting nuclear) A1 and one or a preferred a plurality of level A2 (grafting) who is grafted on this first step and is called grafting level or graft shell.

Can use simple grafting or multistep step by step grafting apply one or more graft shell to this rubber grain, each graft shell can have different compositions.Except grafted monomer, can also comprise multifunctional cross-linking monomer in the grafting process or contain the monomer (for example referring to EP-A 230 282, DE-B 36 01 419, EP-A 269 861) of reactive group.

In a preferred embodiment, component A ^RBy forming with the graft copolymer of two-stage or more multistage foundation, these grafting levels are usually by the monomer preparation that forms resin, and its second-order transition temperature T _gBe higher than 30 ℃, preferably be higher than 50 ℃.Wherein has two-stage or more multistage structure makes rubber grain A ^R(partly) compatible with thermoplastic matrix.

Graft copolymer A ^RPreparation method's example be that at least a monomer A of hereinafter listing 2 is grafted at least a graft bases listed above or the grafting nuclear matter A1.

In one embodiment of the invention, graft bases A1 is made up of one of described other monomer of the linking agent of the acrylic elastomer of 15-99 weight %, 0.1-5 weight % and 0-49.9 weight % or rubber.

The proper monomer that forms grafting A2 is vinylbenzene, alpha-methyl styrene, (methyl) acrylate, vinyl cyanide and methacrylonitrile, particularly vinyl cyanide.

In one embodiment of the invention, second-order transition temperature is lower than 0 ℃ crosslinked acrylate polymers as graft bases A1.The second-order transition temperature of crosslinked acrylate polymers preferably is lower than-20 ℃, particularly is lower than-30 ℃.

In a preferred embodiment, grafting A2 is made up of at least one graft shell, and the second-order transition temperature of outermost graft shell is higher than 30 ℃, and the second-order transition temperature of the polymkeric substance that is formed by the monomer of this grafting A2 is higher than 80 ℃.

Graft copolymer A ^RAppropriate preparation method be letex polymerization, solution polymerization, mass polymerization or suspension polymerization.Graft copolymer A ^RPreferably by under 20-90 ℃ in the presence of the latex of component A1, use water-soluble or oil-soluble initiator such as peroxydisulfate or Benzoyl Peroxide or prepare by means of redox initiator carries out free-radical emulsion polymerization.Redox initiator also is adapted at being lower than and carries out polymerization under 20 ℃.

Among DE-A 28 26 925,31 49 358 and the DE-C 12 60 135 suitable emulsion polymerisation process has been described.

Graft shell is preferably set up with the emulsion polymerisation process of describing among the DE-A 32 27 555,31 49 357,31 49 358,34 14 118.Limit by the method for describing in (1965) the 2929th pages of DE-C 12 60 135 and DE-A 28 26 925 and " applied polymer science " the 9th volumes preferably that granularity is set is 50-1000nm.For example has varigrained polymkeric substance by DE-A 28 26 925 and US-A 5 196 480 known uses.

The method of describing among the DE-C 12 60 135 is from preparation graft bases A1, graft bases A1 is by known method itself, if make acrylate used in one embodiment of the invention and multifunctional cross-linking monomer and suitable other monomer in water miscible liquid at 20-100 ℃, preferred 50-80 ℃ of following polymerization and preparing.Can use conventional emulsifier such as basic metal alkyl-or alkylaryl sulphonate, alkyl-sulphate, fatty alcohol sulfonate, have the salt or the sodium resinate of the higher fatty acid of 10-30 carbon atom.The preferred fatty acid sodium salt that uses mersolates or have 10-18 carbon atom.In one embodiment, the consumption of emulsifying agent is 0.5-5 weight %, particularly 1-2 weight % based on the used monomer of preparation graft bases A1.Usually operate with water and the monomer weight ratio of 2:1-0.7:1.Persulphate such as Potassium Persulphate that used polymerization starter is particularly commonly used.But, can also use redox system.The consumption of initiator is generally 0.1-1 weight % based on the used monomer of preparation graft bases A1.Operable other reagent and additive in polymerization is for can preferred pH being set to the conventional buffer substance of 6-9 between polymerization period, and example is sodium bicarbonate and trisodium phosphate, and the molecular weight regulator of 0-3 weight % such as mercaptan, terpinol or two poly alpha methylstyrenes.The amount of accurate polymerizing condition, especially character, charging parameter and emulsifying agent is respectively at the above-mentioned d that makes gained crosslinked acrylate polymers latex ₅₀Be about 50-800nm, preferred 50-500nm determines in the scope of preferred especially 80-250nm.This moment, the size-grade distribution of latex was preferably narrow.

In one embodiment of the invention, be preparation graftomer A ^RIn step subsequently, in the presence of gained crosslinked acrylate polymers latex, make the monomer mixture polymerization of forming by vinylbenzene and vinyl cyanide, this moment in a preferred embodiment of the invention, the weight ratio of vinylbenzene and vinyl cyanide should be 100:0-40:60 in the monomer mixture, is preferably 65:35-85:15.Advantageously in water miscible liquid, make vinylbenzene and acrylonitrile graft copolymer to being used as on the cross-linked polyacrylate polymer of graft bases under the above-mentioned normal condition once more.Graft copolymerization can be carried out effectively in the system that is used for emulsion polymerization prepared graft bases A1, wherein can add other emulsifying agent and initiator if desired.In one embodiment of the invention, treat the mixture of grafted vinylbenzene and acrylonitrile monemer can be once, in a more than step, in polymerization process, add in the reaction mixture continuously in batches or preferably.The graft copolymerization of carrying out vinylbenzene and acrylonitrile mixture in the presence of crosslinked acrylate polymers makes and obtains graft(ing) degree based on component A ^RGross weight be 1-99 weight %, the graft copolymer A of preferred 20-45 weight %, particularly 35-45 weight % ^RBecause the percentage of grafting in the graft copolymerization is not 100%, so the amount of the mixture of vinylbenzene that uses in graft copolymerization and acrylonitrile monemer is than more corresponding to the amount of required graft(ing) degree.The control of percentage of grafting and so gained graft copolymer A in the graft copolymerization ^RGraft(ing) degree control be that those skilled in the art are familiar with.For example this can realize by monomeric metering rate or by adding conditioning agent (ACS Polymer Preprints reaches page or leaf subsequently for the 15 (1974), the 329th page for Chauvel, Daniel).Emulsion graft copolymerization usually produces free, the grafted styrene-acrylonitrile copolymer not that is about 5-15 weight % based on this graft copolymer.Measure graft copolymer A in the graft copolymerization gained polymerisate by the method that above provides ^RRatio.Except above-mentioned technological method advantage, prepare graft copolymer A by emulsion process ^RAlso can produce the reproducible change of having of granularity, for example by particle is reunited at least to the degree that produces larger particle.This means graft copolymer A ^RIn also may exist and have varigrained polymkeric substance.The component A that forms by graft bases and graft shell ^REspecially can be ideally suited each and use, especially with regard to granularity.

Graft copolymer A ^RUsually comprise 1-99 weight %, preferred 55-80 weight %, the graft bases A1 of preferred especially 55-65 weight %, and 1-99 weight %, preferred 20-45 weight %, the grafting A2 of preferred especially 35-45 weight %, every kind of situation is all based on whole graft copolymer.

Abs polymer is generally understood as impact modification SAN polymkeric substance, and diene polymer wherein, particularly poly-1,3-butadiene are present in the polymer matrices of vinylbenzene particularly and/or alpha-methyl styrene and vinyl cyanide.

In a preferred embodiment, wherein thermoplastic composition comprises abs polymer, the elastomeric graft copolymers A of component A ^{R '}Have following composition: a1 ' 10-90 weight % can be lower than 0 ℃ at least a elasticity graft bases by the second-order transition temperature that the following monomer of polymerization obtains:

A11 ' is 60-100 weight % based on A1 ', at least a conjugated diolefine and/or the vinylformic acid C of preferred 70-100 weight % ₁-C ₁₀Alkyl ester, particularly divinyl, isoprene, n-butyl acrylate and/or 2-ethylhexyl acrylate,

A12 ' is 0-30 weight % based on A1 ', at least a other single ethylenically unsaturated monomers of preferred 0-25 weight %, particularly vinylbenzene, alpha-methyl styrene, n-butyl acrylate, methyl methacrylate or its mixture, especially butadiene-styrene copolymer and n-butyl acrylate-styrol copolymer among in the end enumerating, and

A13 ' is a 0-10 weight based on A1 ', at least a cross-linking monomer of preferred 0-6 weight %, preferred Vinylstyrene, diallyl maleate, (methyl) vinylformic acid diallyl, vinylformic acid dihydro Dicyclopentadiene (DCPD) ester, the divinyl ester of dicarboxylic acid such as succsinic acid and hexanodioic acid, and two functional alcohol such as ethylene glycol or 1, the diallyl ether of 4-butyleneglycol and divinyl ether

A2 ' 10-60 weight %, the grafting A2 ' of preferred 15-55 weight %, A2 ' has following composition:

A21 ' is 50-100 weight % based on A2 ', at least a vi-ny l aromatic monomers of preferred 55-90 weight %, and optimization styrene and/or alpha-methyl styrene,

A22 ' is 5-35 weight % based on A2 ', vinyl cyanide and/or the methacrylonitrile of preferred 10-30 weight %, and preferred vinyl cyanide,

A23 ' is 0-50 weight % based on A2 ', at least a other single ethylenically unsaturated monomers of preferred 0-30 weight %, preferable methyl methyl acrylate and n-butyl acrylate.

Thermoplastic composition comprises in another preferred embodiment of ABS therein, component A ^{R '}For having the graft rubber of bomodal size distribution, A ^{R '}Have following composition:

A1 " based on A ^{R '}Be 40-90 weight %, the elastic granule shape graft bases A1 that can obtain by the following monomer of polymerization of preferred 45-85 weight % ":

A11 " based on A1 " be 70-100 weight %, at least a conjugated diolefine, particularly divinyl and/or the isoprene of preferred 75-100 weight %,

A12 " based on A1 " be 0-30 weight %, at least a other single ethylenically unsaturated monomers, particularly vinylbenzene, alpha-methyl styrene, n-butyl acrylate or its mixture of preferred 0-25 weight %,

A2 " based on A ^{R '}Be 10-60 weight %, the grafting A2 of preferred 15-55 weight % ", A2 " have a following composition:

A21 " based on A2 " be 65-95 weight %, at least a vi-ny l aromatic monomers of 70-90 weight %, optimization styrene,

A22 " based on A2 " be 5-35 weight %, the vinyl cyanide of preferred 10-30 weight %,

A23 " based on A2 " be 0-30 weight %, at least a other single ethylenically unsaturated monomers of preferred 0-20 weight %, preferable methyl methyl acrylate and n-butyl acrylate.

Thermoplastic composition comprises in the preferred embodiment of ASA polymkeric substance as component A therein, the hard matrix A of component A ^MBe at least a unitary hard multipolymer that comprises derived from ethylene base aromatic monomer, and the unitary gross weight that comprises based on derived from ethylene base aromatic monomer is 0-100 weight %, preferred 40-100 weight %, the unit of preferred especially 60-100 weight % derived from alpha-methyl styrene, and comprise 0-100 weight %, preferred 0-60 weight %, preferred especially 0-40 weight % derived from cinnamic unit, A ^MHave following composition:

a ^M1 based on A ^MBe 40-100 weight %, the vinyl aromatic units of preferred 60-85 weight % is as component A ^M1,

a ^M2 based on A ^MBe 60 weight % at the most, acrylonitrile unit or the methacrylonitrile unit, particularly acrylonitrile unit of preferred 15-40 weight % are as component A ^M2.

Thermoplastic composition comprises in the preferred embodiment of ABS as component A therein, the hard matrix A of component A ^{M ＇}Be at least a unitary hard multipolymer that comprises derived from ethylene base aromatic monomer, and the unitary gross weight that comprises based on derived from ethylene base aromatic monomer is 0-100 weight %, preferred 40-100 weight %, the unit of preferred especially 60-100 weight % derived from alpha-methyl styrene, and comprise 0-100 weight %, preferred 0-60 weight %, preferred especially 0-40 weight % derived from cinnamic unit, A ^{M ＇}Have following composition:

a ^M1 ' based on A ^{M ＇}Be 50-100 weight %, the vi-ny l aromatic monomers of preferred 55-90 weight %,

a ^M2 ' based on A ^{M ＇}Be vinyl cyanide or methacrylonitrile or its mixture of 0-50 weight %,

a ^M3 ' based on A ^{M ＇}Be at least a other single ethylenically unsaturated monomers of 0-50 weight % such as methyl methacrylate and N-alkyl-or N-aryl maleimide, for example N-phenylmaleimide.

Thermoplastic composition comprises in ABS another preferred embodiment as component A therein, component A ^{M ＇}For at least a viscosity number VN (according to DIN 53726, in the dimethyl formamide solution of 0.5 weight % concentration, measuring under 25 ℃) be the hard multipolymer of 50-120ml/g, it comprises the unit of derived from ethylene base aromatic monomer, and the unitary gross weight that comprises based on derived from ethylene base aromatic monomer is 0-100 weight %, preferred 40-100 weight %, the unit of preferred especially 60-100 weight % derived from alpha-methyl styrene, and 0-100 weight %, preferred 0-60 weight %, preferred especially 0-40 weight % derived from cinnamic unit, A ^{M ＇}Have following composition:

a _M1 " based on A ^{M ＇}Be 69-81 weight %, the vi-ny l aromatic monomers of preferred 70-78 weight %,

a _M2 " based on A ^{M ＇}Be 19-31 weight %, the vinyl cyanide of preferred 22-30 weight %,

a _M3 " based on A ^{M ＇}Be 0-30 weight %, at least a other the single ethylenically unsaturated monomers of preferred 0-28 weight % such as methyl methacrylate or N-alkyl-or N-aryl maleimide, for example N-phenylmaleimide.

In one embodiment, abs polymer comprises the component A that viscosity number VN differs at least five units (ml/g) simultaneously ^{M ＇}, and/or acrylonitrile content differs the component A of five units (weight %) ^{M ＇}At last, except component A ^{M ＇}With other embodiment, the multipolymer that can also have (Alpha-Methyl) vinylbenzene and maleic anhydride or maleimide, the multipolymer of (Alpha-Methyl) vinylbenzene and maleimide and methyl methacrylate or vinyl cyanide, the perhaps multipolymer of (Alpha-Methyl) vinylbenzene and maleimide, methyl methacrylate and vinyl cyanide.

In these abs polymers, preferably obtain graftomer A by letex polymerization ^{R '}Usually mixed grafting polymer A in mixing equipment ^{R '}With component A ^{M ＇}If, produce basic melted polymer mixture with suitable other additive.Advantageously very rapidly cool off this molten polymer mixture.

In German patent application DE-A 19728629, describe the others of above-mentioned abs polymer in detail, preparation method and general embodiment and special embodiment, the document is incorporated the present invention into by reference clearly at this.

Described abs polymer can comprise other conventional auxiliary agent and filler.The example of these materials is lubricant and releasing agent, wax, pigment, dyestuff, fire retardant, antioxidant, light stabilizer and static inhibitor.

According to a preferred embodiment of the invention, the hard matrix A of component A ^MAnd A ^{M ＇}Viscosity number be respectively 50-90, be preferably 60-80.

The hard matrix A of component A ^MAnd A ^{M ＇}Be preferably amorphous polymer.According to one embodiment of the invention, the mixture of the mixture of vinylbenzene and acrylonitrile copolymer and the multipolymer be made up of alpha-methyl styrene and vinyl cyanide is used separately as the hard matrix A of component A ^MAnd A ^{M ＇}The content of vinyl cyanide is 0-60 weight % based on the gross weight of this hard matrix in the multipolymer of these hard matrixes, is preferably 15-40 weight %.The hard matrix A of component A ^MAnd A ^{M ＇}Also be included in respectively and be respectively preparation component A ^RAnd A ^{R ＇}And the free that produces during the graft copolymerization that carries out, grafted (Alpha-Methyl) styrene-acrylonitrile copolymer not.Depend on and be respectively preparation graft copolymer A ^RAnd A ^{R ＇}And selected condition during the graft copolymerization that carries out can form the hard matrix of enough ratios before graft copolymerization finishes.But the product that still needs usually to obtain during the graft copolymerization mixes with the extra hard matrix of preparation separately.

Can obtain the extra hard matrix A of preparation separately of component A by ordinary method respectively ^MAnd A ^{M ＇}For example, according to one embodiment of the invention, the copolyreaction of vinylbenzene and/or alpha-methyl styrene and vinyl cyanide can be carried out in body, solution, suspension or water miscible liquid.Component A ^MAnd A ^{M ＇}Viscosity number be preferably 40-100 respectively, be preferably 50-90, particularly 60-80.Viscosity number is measured the 0.5g material dissolves according to DIN 53726 in the 100ml dimethyl formamide at this moment.

Component A ^R(reach A respectively ^{R ＇}) and A ^M(reach A respectively ^{M ＇}) mixing can carry out in any required mode by any known method.For example, if these components then can be mixed with each other the resulting polymers dispersion, then with these polymkeric substance coprecipitations and this polymeric blends of aftertreatment by emulsion polymerization prepared.But preferably by these components being rolled together or kneading or extrude and mix these components, if desired, these components are separated the gained water dispersion or the aqueous solution during polyreaction in advance.Gained graft copolymerization product also can a partial dehydration in water dispersion, and mixes with hard matrix with the form of moist chip, so carry out the complete drying of graft copolymer in mixing process.

Styrenic based thermoplastic elastomer

Preferred styrenic based thermoplastic elastomer (S-TPE) for the fracture tension strain greater than 300%, be preferably greater than 500% especially, particularly greater than 500% to 600% those.Blended S-TPE especially preferably comprises linearity or the star styrene-butadiene block copolymer with outside polystyrene block S, and is to have irregular phenylethylene/divinyl distribute (S/B) between these blocks _RandomOr has a vinylbenzene gradient (S/B) _{Gradual change}The styrene-butadiene copolymer block (for example from BASFAktiengesellschaft's

Or

K-Resin from CPC ^TM).

The divinyl total content is preferably 15-50 weight %, is preferably 25-40 weight % especially, and corresponding vinylbenzene total content is preferably 50-85 weight %, is preferably 60-75 weight % especially.

Styrene butadiene block (S/B) preferably is made up of the vinylbenzene of 30-75 weight % and the divinyl of 25-70 weight %.(S/B) block especially preferably has the butadiene content of 35-70 weight % and the styrene content of 30-65 weight %.

Based on whole segmented copolymer, the content of polystyrene block S is preferably 5-40 weight %, particularly 25-35 weight %.The content of S/B copolymer block is preferably 60-95 weight %, particularly 65-75 weight %.

Preferred general especially structure is linear styrene-butadiene block copolymer of S-(S/B)-S, is one or more (S/B) that irregular phenylethylene/divinyl distributes that have between two S blocks wherein _RandomBlock.This segmented copolymer can obtain by anionoid polymerization in the non-polar solvent that has added polar co-solvent or sylvite, for example described in WO 95/35335 or the WO 97/40079.

Contents of ethylene is 1 of a diene units, and the 2-key is based on all 1,2-key and 1, and 4-is along key and 1, the relative content of 4-antibonding.In the styrene-butadiene copolymer block (S/B) 1, the 2-contents of ethylene preferably is lower than 20%, and particularly 10-18% is preferably 12-16% especially.

Polyolefine:

Can be generally 10-600% as the polyolefinic fracture tension strain of component A, be preferably 15-500%, be preferably 20-400% especially.

The example of suitable ingredients A is a semicrystalline polyolefins, as the homopolymer or the multipolymer of ethene, propylene, 1-butylene, 1-amylene, 1-hexene or 4-methyl-1-pentene, and the multipolymer of ethene and vinyl-acetic ester, vinyl alcohol, ethyl propenoate, butyl acrylate, Jia Jibingxisuanyizhi or butyl methacrylate.Used component A preferably includes high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), vinyl-vinyl acetate copolymer (EVA) or ethylene-acrylic acid copolymer.Particularly preferred component A is a polypropylene.

Polycarbonate

The fracture tension strain value that can be used as the polycarbonate of component A is generally 20-300%, is preferably 30-250%, is preferably 40-200% especially.

Be suitable as molar mass (the weight average M of the polycarbonate of component A _W, measure in tetrahydrofuran (THF) by gel permeation chromatography, with respect to polystyrene standard) and be preferably 10 000-60 000g/mol.For example, they can be obtained by interfacial polycondensation or be obtained by diphenyl carbonate and bis-phenol reaction by the method among the DE-A-1 495 730 by the method among the DE-B-1 300 266.Preferred bis-phenol is 2, and 2-two (4-hydroxyphenyl) propane is called dihydroxyphenyl propane usually and also hereinafter.

Replace dihydroxyphenyl propane, can also use other aromatic dihydroxy compound, particularly 2,2-two (4-hydroxyphenyl) pentane, 2, the 6-dihydroxy naphthlene, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxydiphenyl ether, sulfurous acid 4,4 '-dihydroxyl diphenyl ester, 4,4 '-dihydroxyl ditan, 1,1-two (4-hydroxyphenyl) ethane, 4,4-dihydroxybiphenyl or dihydroxy-phenyl cycloalkane, preferred dihydroxy-phenyl-cyclohexane or dihydroxyl pentamethylene, particularly 1,1-two (4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane, the perhaps mixture of above-mentioned dihydroxy compound.

Particularly preferred polycarbonate is based on dihydroxyphenyl propane or dihydroxyphenyl propane and those of the above-mentioned aromatic dihydroxy compound of 80mol% at the most.

The polycarbonate that is particularly suitable as component A be comprise derived from resorcinol or alkyl resorcinol ester unitary those, for example at described in WO 00/61664, WO 00/15718 or the WO 00/26274 those.These polycarbonate are for example sold by General Electric Corporation, and trade mark is

Can also use the polycarbonate according to US-A 3 737 409, this moment, the interested especially polycarbonate that is based on dihydroxyphenyl propane and two (3,5-dimethyl dihydroxyphenyl) sulfone is characterized in that high heat resistance.Can also use the mixture of different polycarbonate.

The average molar mass of polycarbonate (weight average M _W, measure in tetrahydrofuran (THF) by gel permeation chromatography, with respect to polystyrene standard) and be 10000-64000g/mol.They are preferably 15000-63000g/mol, particularly 15000-60000g/mol.The solution relative viscosity (measuring down at 25 ℃ in the 0.5 weight % concentration solution in methylene dichloride) that this means polycarbonate for 1.1-1.3, is preferably 1.15-1.33.Difference between the solution relative viscosity of used polycarbonate preferably is not more than 0.05, particularly is not more than 0.04.

Wherein the form of polycarbonate use can be polycarbonate particle or polycarbonate pellets.

Thermoplastic polyurethane:

Aromatics or aliphatic thermoplastic polyurethane are suitable as component A usually, and preferred suitable is transparent amorphous aliphatic thermoplastic polyurethane.Aliphatic thermoplastic polyurethane and preparation thereof are for example known by EP-B1 567 883 or DE-A 10321081 by those skilled in the art, and for example can be by BayerAktiengesellsch aft with trade mark

With

Commercial.

The Shore D of preferred aliphatic thermoplastic polyurethane is 45-70, and their fracture tension strain value is 30-800%, is preferably 50-600%, is preferably 80-500% especially.

Particularly preferred component A is a styrenic based thermoplastic elastomer.

B component

Thermoplastic composition comprises carbon nanotube as B component.Carbon nanotube and preparation thereof are known by those skilled in the art, and in the literature as describing to some extent among US 2005/0186378 A1.Carbon nanotube for example can synthesize (for example referring to US-A 5643502) in the reactor that comprises metal catalyst and carbonaceous gas.Carbon nanotube is for example sold by Hyperion Catalysis or Applied Sciences company.

That preferred carbon nanotube has usually is single-or the multi-walled pipes structure.Single Walled Carbon Nanotube (SWCN) is formed by single graphite carbon-coating, and multi-walled carbon nano-tubes (MWCN) is formed by a plurality of such graphite carbon-coatings.Graphite linings has around the concentric arrangement of cylindrical axle.The length-to-diameter ratio of carbon nanotube is at least 5 usually, preferably is at least 100, especially preferably is at least 1000.Nanotube typically have a diameter from 0.002-0.5 μ m, be preferably 0.005-0.08 μ m, be preferably 0.006-0.05 μ m especially.The length of carbon nanotube is generally 0.5-1000 μ m, is preferably 0.8-100 μ m, is preferably 1-10 μ m especially.Carbon nanotube has the hollow circuit cylinder forming core, and graphite linings is wound on around it in form.This cavity typically have a diameter from 0.001-0.1 μ m, be preferably 0.008-0.015 μ m.In a typical embodiments of carbon nanotube, form by for example 8 graphite sublevels around the tube wall of this cavity.This moment, carbon nanotube can take diameter to be at most 1000 μ m, preferably was at most the aggregate form of being made up of a plurality of nanotubes of 500 μ m.This aggregate can be taked the form of nest, heckling yarn or open mesh structure.

Carbon nanotube can be before monomer polymerization forms thermoplastic polymer components A, in the process or add afterwards.If carbon nanotube adds after polymerization, they preferably add by adding in the thermoplastic melt in forcing machine or preferred kneading machine.Combination process in forcing machine or kneading machine is particularly basic or even all pulverize and this carbon nanotube is dispersed in the thermoplastic matrix with above-mentioned aggregate.

In a preferred embodiment, carbon nanotube infeeds thermoplastics with highly enriched master batch form, and the latter is preferably selected from the thermoplastics as component A.The concentration of carbon nanotube is generally 5-50 weight % in the masterbatch, is preferably 8-30 weight %, is preferably 12-22 weight % especially.The preparation of masterbatch has for example been described in US-A5643502.The use of masterbatch can improve the pulverizing of aggregate especially.Owing to be processed into moulding compound or moulded product, the length distribution of the carbon nanotube in the moulding compound or in the moulded product is shorter than the carbon nanotube of original use.

Component C

In principle, anyly be described in the of the prior art and known dispersion agent that is used in the plastic hybrid of those skilled in the art and all be suitable as component C.Preferred dispersing agent is tensio-active agent or surfactant mixture, as negatively charged ion, positively charged ion, both sexes or nonionogenic tenside.Further preferred commercially available and known oligopolymer dispersion agent of those skilled in the art and polymeric dispersant are as at CD

Chemie Lexikon[CD

Chemical encyclopedia] the-the 3.0th edition, Stuttgart/ New York: Georg Thieme Verlag 2006 is described in the keyword " dispersion agent ".Salt, amine/amide functional polyester and polyacrylic ester, soybean lecithin, polyphosphate, modification casein that example is poly carboxylic acid, polyamines, be made up of long-chain polyamines and poly carboxylic acid.These polymeric dispersants can exist with the form of segmented copolymer, comb shaped polymer or random copolymers.

Cats product and anion surfactant are for example at " Encyclopedia ofPolymer Science and Technology ", J.Wiley ﹠amp; Sons (1966), the 5th volume, 816-818 page or leaf and " Emulsion Polymerisation and Emulsion Polymers ", editor P.Lovell and M.EI-Asser, Wiley ﹠amp; Sons publishes (1997), describes in the 224-226 page or leaf.

The example of anion surfactant is that chain length is 8-30, an alkali metal salt of the organic carboxyl acid of preferred 12-18 carbon atom.These are commonly referred to soap.Normally used salt is sodium, potassium or ammonium salt.Other operable anion surfactant is individual for having 8-30, the alkyl-sulphate of preferred 12-18 carbon atom or alkyl-or alkylaryl sulphonate.Specially suitable compound is basic metal dodecyl sulfate such as sodium lauryl sulphate or dodecyl sulphate potassium, and C ₁₂-C ₁₆An alkali metal salt of alkansulfonic acid.Other suitable compound is Sodium dodecylbenzene sulfonate and sulfo-succinic acid dioctyl ester sodium.

The example of suitable cation tensio-active agent is amine salt or two amine salt, quaternary ammonium salt such as cetyl trimethylammonium bromide, and the salt of long-chain substituted cyclic amine such as pyridine, morpholine, piperidines.Especially trialkylamine quaternary ammonium salt such as cetyl trimethylammonium bromide.This moment, alkyl preferably had 1-20 carbon atom.

Can use nonionogenic tenside as component C especially.Nonionogenic tenside is for example at CD

Chemie Lexikon-the 1.0th edition describes among Stuttgart/ New York: the Georg ThiemeVerlag 1995, keyword " Nichtionische Tenside " [nonionogenic tenside].

The example of suitable nonionogenic tenside is the material based on polyethylene oxide or poly(propylene oxide), as from BASF Aktiengesellschaft

Or

Be suitable as the molar mass M of the polyalkylene glycol of nonionogenic tenside _nBe generally 1000-15000g/mol, be preferably 2000-13000g/mol, be preferably 4000-11000g/mol especially.Preferred nonionic is a polyoxyethylene glycol.

Polyalkylene glycol be itself known maybe can be by known method itself, for example by using alkali metal hydroxide catalyzer such as sodium hydroxide or potassium hydroxide or using alkali metal alkoxide catalyst such as sodium methylate, sodium ethylate, potassium ethylate or potassium isopropoxide also add at least a 2-8 of a comprising hydrogen atoms, the starter molecules of preferred 2-6 hydrogen atoms is carried out anionoid polymerization and is prepared, perhaps by using lewis acid catalyst such as antimony pentachloride, boron fluoride etherate or Fuller's earth carry out cationoid polymerisation and prepare, and raw material is for having the alkylene oxide of 2-4 carbon atom in one or more alkylidene groups.

The example of suitable alkylene oxide is a tetrahydrofuran (THF), 1,2-or 1,3-butylene oxide ring, Styrene oxide 98min., optimization ethylene oxide and/or 1,2 epoxy prapane.Alkylene oxide can be separately, alternately or as mixture use one by one.The example of operable starter molecules is: water, organic dicarboxylic acid such as succsinic acid, hexanodioic acid, phthalic acid or terephthalic acid, have the aliphatic series of 1-4 carbon atom or aromatics in the alkyl, do not replace or N-single-or N, N-or N, the diamines that N '-dialkyl group replaces is not as replacing or single-or the quadrol that replaces of dialkyl group, diethylenetriamine, Triethylenetetramine (TETA), 1, the 3-propylene diamine, 1,3-or 1,4-butanediamine or 1,2-, 1,3-, 1,4-, 1,5-or 1,6-hexanediamine.

Other operable starter molecules is: alkanolamine such as thanomin, N-Mono Methyl Ethanol Amine and N-ehtylethanolamine, two alkanolamines such as diethanolamine and N methyldiethanol amine and N-ethyldiethanolamine, and trialkanolamine such as trolamine and ammonia.The preferred polyvalent alcohol that uses, particularly two or trivalent alcohol or functionality greater than 3 alcohol, for example ethylene glycol, 1,2-propylene glycol, 1, ammediol, glycol ether, dipropylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, sucrose and sorbyl alcohol.

Other suitable component C is the esterification polyalkylene glycol, as described can be by making the end OH base and the organic acid of described polyalkylene glycol, preferred hexanodioic acid or terephthalic acid with the list of the polyalkylene glycol of known method prepared in reaction itself-, two-, three-or polyester.Preferred polyethylene glycol adipate or the polyethylene terephthalate of using is as component C.

The material of specially suitable nonionogenic tenside for preparing by the compound alkoxylate that will have active hydrogen atom, for example oxyethane is added to the adducts on Fatty Alcohol(C12-C14 and C12-C18), oxo alcohol or the alkylphenol.For alkoxylation, preferably use oxyethane or 1,2 epoxy prapane.

Other preferred nonionic is alkoxylate or non-alkoxylate sugar ester or sugar ether.

Sugar ether is the alkylglycoside by Fatty Alcohol(C12-C14 and C12-C18) and sugar reaction are obtained, and sugar ester obtains by making sugar and fatty acid response.Sugar, Fatty Alcohol(C12-C14 and C12-C18) and the lipid acid for preparing described material demand is that those skilled in the art are known.

For example at Beyer/Walter, Lehrbuch der organischen Chemie[organic chemistry textbook], S.Hirzel Verlag Stuttgart, the 19th edition, 1981, the 392-425 pages or leaves have been described suitable sugar.Specially suitable sugar is D-sorbyl alcohol and the anhydro sorbitol by the dehydration of D-sorbyl alcohol is obtained.

Suitable fatty acids is for having 6-26 carbon atom, preferred 8-22 carbon atom, and preferred especially 10-20 carbon atom saturated or singly unsaturated or how unsaturated not branching or branched carboxylic acids are for example at CD

Chemie Lexikon-the 1.0th edition, Stuttgart/ New York: Georg ThiemeVerlag 1995, keyword

Described in [lipid acid].Preferred lipid acid is lauric acid, palmitinic acid, stearic acid and oleic acid.

The carbon skeleton of suitable Fatty Alcohol(C12-C14 and C12-C18) is identical with the compound of describing as suitable fatty acids.

Sugar ether, sugar ester and preparation method thereof are that those skilled in the art are known.Preferred sugar ether by currently known methods by making described sugar and described Fatty Alcohol(C12-C14 and C12-C18) prepared in reaction.Preferred sugar ester is prepared by making described sugar and described fatty acid response by currently known methods.Preferred sugar ester is the monoesters of anhydro sorbitol and lipid acid, diester and three esters, Arlacel-20 particularly, the anhydro sorbitol dilaurate, the anhydro sorbitol trilaurin, polyoxyethylene-sorbitan mono-oleate, the anhydro sorbitol dioleate, sorbitan trioleate, Arlacel-40, the anhydro sorbitol dipalmitate, the anhydro sorbitol tripalmitate, Arlacel-60, the anhydro sorbitol SUNSOFT Q-182S, Arlacel-65 and Arlacel-83, the mixture of polyoxyethylene-sorbitan mono-oleate and anhydro sorbitol dioleate.

Component D

Thermoplastic composition comprises fibrous or granulated filler except that B component or its mixture as component D.These are preferably commercially available product, as carbon fiber and glass fibre.

Operable glass fibre can be made up of E, A or C glass, and has preferably sticked with glue agent or coupling agent treatment.Their diameter is generally 6-20 μ m.Can use length to be 1-10mm, long filament (rove) or the segment glass fibre (staple fibre) of preferred 3-6mm.

Can also add filler or supporting material, as granulated glass sphere, mineral fibre, whiskers, sapphire whisker, mica, flint and wollastonite.

This thermoplastic composition can also comprise typical other conventional additive in the plastic hybrid in addition.

The example of these additives that can mention is: dyestuff, pigment, tinting material, static inhibitor, antioxidant, the stable on heating stablizer of raising, improve sunproof stablizer, improve stablizer, the antagonism pyrolysated reagent of resistance to hydrolysis and anti-chemical, particularly help producing the lubricant of moulded product.These other additives can be metered in any stage in process of production, but preferably add in early days, with the stabilization (or other special roles) that can utilize additive in early days.Thermo-stabilizer or oxidation retarder are generally the metal halide (muriate, bromide, iodide) of the metal (for example Li, Na, K, Cu) of period of element Table I family.

Suitable stabilizers is conventional sterically hindered phenol, but also can be the compound of vitamin E or similar structures.HALS stablizer (hindered amine light stabilizer), benzophenone, resorcin(ol), salicylate, benzotriazole as

RP (from UV absorption agent 2-(2H-benzotriazole-2-yl)-4-methylphenol of CIBA), and other compound is also suitable.Their consumption is generally 2 weight % (based on whole thermoplastic composition mixtures) at the most.

Examples of suitable lubricants and releasing agent are stearic acid, stearyl alcohol, stearate and general higher lipid acid and derivative thereof and the fatty acid mixt that has 12-30 carbon atom accordingly.The amount of these additives is 0.05-1 weight %.

Silicone oil, low polyisobutene or similar material also can be used as additive, and common consumption is 0.05-5 weight %.Can also use pigment, dyestuff, color brightening agent such as ultramarine blue, phthalocyanine, titanium dioxide, Cadmium Sulfide, perylene tetracarboxylic acid derivative.

The consumption of processing aid and stablizer such as UV stablizer, lubricant and static inhibitor is generally 0.01-5 weight %.

The production method of the matrix that can metallize

If thermoplastic composition is prepared by the procedure known to those skilled in the art by component A, B and suitable C and D, for example be generally 150-300 ℃, particularly each component of blend melt form under 200-280 ℃ the temperature (according to the character of used polymer A) by the known equipment of use those skilled in the art.This moment, each component all can be introduced in the mixing equipment with the form of pure substance.But, at first each component of pre-mixing such as A and B or A and C, and then they are mixed with other component A, B and/or C or with other component such as D.In one embodiment, at first in component A, prepare enriched material (known additives masterbatch), and then mix with the remaining ingredient of aequum by for example B component, C or D.Thermoplastic composition can carry out granulation by the procedure known to those skilled in the art, for example produces by extrusion molding, injection moulding, calendering or compression molding subsequently and can metallize moulded product (being matrix) as sheet or plate or layering composite sheet or layering composition board.But, they can also directly process (particularly extrusion molding or injection moulding) become to metallize moulded product such as sheet or plate after combination process, perhaps process (i.e. also preferably extrusion molding (preferably utilizing screw extrusion press) or injection moulding of blend melt simultaneously) in a program moulded product such as sheet or plate become to metallize with combination process.

In utilizing an embodiment preferred of extrusion process, screw extrusion press is designed to have the single screw extrusion machine of at least one distributivity mixing screw element.

In another embodiment preferred of this method, screw extrusion press is designed to have the twin screw extruder of at least one distributivity mixing screw element.

Can metallize the extrusion process of moulded product can be by describing in the prior art and the procedure known to those skilled in the art (for example slot extrusion (slot extrusion) of adaptor coextrusion (adaptor coextrusion) or mouthful pattern co-extrusion (die coextrusion) form) and using is described in the prior art and the known equipment of those skilled in the art carries out.Injection moulding, calendering or the compression molding technology of moulded product of can metallizing is known and be described in the prior art by those skilled in the art equally.

The total thickness of the metallized moulded product of sheet or plate form is generally 10 μ m-5mm, is preferably 10 μ m-3mm, is preferably 20 μ m-1.5mm, particularly 100-400 μ m especially.

The moulded product that can metallize can further carry out the conventional moulding process in the plastic processing.Can pass through the moulded product that further moulding process obtains:

Sheet or plate or layering composite sheet or the layering composition board of can metallizing can be used to produce other moulded product.Can obtain any required moulded product this moment, preferred plate shape moulded product, particularly high surface area moulded product.These sheets or plate and layering composite sheet or layering composition board are particularly preferred for producing other and have extraordinary toughness value, each layer adherent moulded product well each other, and good dimensional stability is important, thereby for example makes because the destruction that surfacial spalling causes minimizes.The back sheet (being applied to the back side of this material by injection moulding, foaming, casting or compression molding technology) that can have monolithic or layering composition board or layering composite sheet and form by the particularly preferred moulded product that further moulding process obtains by plastics.

Method known and that for example describe in WO 04/00935 can be used for by metallizing sheet or plate or by can metallized layering composite sheet or can metallized layering composition board produce these moulded products (hereinafter described the method for further processing layering composition board or layering composite sheet, but these methods also can be used for further processing sheet or plate).This material can not need other procedure of processing to be applied to the back side of layering composition board or layering composite sheet by injection moulding, foaming, casting or compression molding technology.Particularly, even the use of described layering composition board or layering composite sheet makes the production of slight three-dimensional micromodule also not need the preheating moulding.But layering composition board or layering composite sheet also can be carried out the preheating moulding process.

For example, can three-decker (by back sheet, middle layer and outer the composition) or the layering composition board of bilayer structure (by back sheet and outer the composition) or the assembly of layering composite sheet thermoforming production relative complex will be had.Both can use positive hot-forming method also can use negative hot-forming method this moment.Suitable method is that those skilled in the art are known.This moment, layering composition board or layering composite sheet were orientated in the thermoforming process.But because the surface quality of layering composition board or layering composite sheet and metal voltinism at high orientation ratio as not reducing, so about may be orientated almost without limits in thermoforming process up to orientation under the 1:5.After the thermoforming, layering composition board or sheet still can carry out other forming step, for example profile cut.

If suitable, after described thermoforming process, can also be by material be produced other moulded product that can metallize by the back side that injection moulding, foaming, casting or compression molding are applied to layering composition board or layering composite sheet.These methods are that those skilled in the art are known, and describe to some extent in for example DE-A1 100 55 190 or DE-A1 199 39 111.

With injection moulding, the plastic material that compression molding or casting method apply preferably includes the polymkeric substance based on ASA, abs polymer, the SAN polymkeric substance, poly-(methyl) acrylate, polyethersulfone, polybutylene terephthalate, polycarbonate, the thermoplastic composition of polypropylene (PP) or polyethylene (PE), perhaps mixture of forming by ASA polymkeric substance or abs polymer and polycarbonate or polybutylene terephthalate and the mixture of forming by polycarbonate and polybutylene terephthalate, if use PP and/or PE here, then obviously can on hypothallus, provide the tackifier layer in advance.Specially suitable material is amorphous thermoplastic plastic and composition thereof.The plastic material that is preferred for being applied to by injection moulding this material back side is abs polymer or SAN polymkeric substance.In another preferred embodiment, the known thermoset molding composition of those skilled in the art is used for being applied to by foaming or compression molding the back side of this material.In a preferred embodiment, these are glass fibre enhanced plastic materials, and suitable modification is particularly described in DE-A1 100 55 190 to some extent.For be applied to the back side of this material by foaming, preferably use polyurethane foam, for example at described in the DE-A1199 39 111 those.

In a preferred production methods, can metallized layering composition board or the thermoforming of layering composite sheet, place back side forming mould then, by injection moulding, casting or compression molding thermoplastics is applied to the back side of this material, perhaps thermosetting resin is applied to the back side of this material by foaming or compression molding.

After the thermoforming and place before the forming mould of the back side, layering composition board or layering composite sheet can be carried out profile cut.Profile cut also can postpone after taking out from the forming mould of the back side.The dispersion that comprises carbon nanotube

In another preferred embodiment, can be used for the matrix of the inventive method by chemistry and/or electrochemical plating metal refining be wherein before carrying out metallization step, provide by chemistry and/or electrochemical plating the dispersion that comprises carbon nanotube and this dispersion to small part dry and/or subsclerotic at least those matrix.

Based on the gross weight (it is 100 weight %) of component A ', B ' and C ', the dispersion that comprises carbon nanotube preferably comprises:

A ' 0.1-99.9 weight %, preferred 2-89.5 weight %, the component A ' of preferred especially 4-84 weight %,

B ' 0.1-30 weight %, preferred 0.5-20 weight %, the B component of preferred especially 1-10 weight % ' and

C ' 0-99.8 weight %, preferred 10-97.5 weight %, the component C ' of preferred especially 15-95 weight %.

Except described component A '-C ', this dispersion can comprise at least a following component:

D ' is 0.1-50 weight % based on the gross weight of component A '-C ' ', preferred 0.5-40 weight %, the dispersion agent component D ' of preferred especially 1-20 weight %; And

E ' is 0-50 weight % based on the gross weight of component A '-C ', preferred 0.1-40 weight %, preferred especially 0.5-30 weight % be different from B component ' filler component E.

Each component of this dispersion is hereinafter described:

Component A '

Organic binder bond component A ' is binding agent or binder mixtures.Possible binding agent is the binding agent that contains the conjugated group with pigment affinity, naturally occurring and synthetic polymkeric substance and derivative, naturally occurring resin and synthetic resins and derivative, natural rubber, synthetic rubber, protein, derivatived cellulose, siccative oil and non-drying oil etc.They can (but be not must) be the materials of chemistry or physical solidification, for example air curing, radiation curing or thermofixation material.

Binder component A ' is preferably polymkeric substance or polymeric blends.

Preferably the polymkeric substance as binding agent is ABS (acrylonitrile-butadiene-styrene (ABS)); ASA (acrylonitrile-styrene-acrylic ester); Propylene acidylate acrylate (acrylated acrylates); Synolac; Acetate alkyl vinyl ester; Alkene-vinyl acetate copolymer, particularly methylene radical-vinyl-acetic ester, ethylidene-vinyl-acetic ester, butylidene-vinyl-acetic ester; Alkene-vinyl chloride copolymer; Aminoresin; Aldehyde resin and ketone resin; Mierocrystalline cellulose and derivatived cellulose, particularly hydroxy alkyl cellulose, cellulose ester such as cellulose ethanoate, cellulose propionate, cellulose butylate, carboxyalkyl cellulose, cellulose nitrate; Epoxy acrylate; Resins, epoxy; Modified epoxy, for example two senses or multifunctional dihydroxyphenyl propane or Bisphenol F resin, epoxy-Novolak resin, brominated epoxy resin, cycloaliphatic epoxy resin; Aliphatic epoxy resin, glycidyl ether, vinyl ether, ethylene-acrylic acid copolymer; Hydrocarbon resin; MABS (transparent ABS that comprises the acrylic ester unit of existence); Melamine resin, copolymer-maleic anhydride; Methacrylic ester; Natural rubber; Synthetic rubber; Chlorinated rubber; Natural resin; Rosin; Lac; Resol; Polyester; Vibrin such as phenyl ester resin; Polysulfones; Polyethersulfone; Polymeric amide; Polyimide; Polyaniline; Polypyrrole; Polybutylene terephthalate (PBT); Polycarbonate is (as from Bayer AG

); Polyester acrylate; Polyether acrylate; Polyethylene; The polyethylene thiophene; PEN; Polyethylene terephthalate (PET); Polyethylene terephthalate glycol (PETG); Polypropylene; Polymethylmethacrylate (PMMA); Polyphenylene oxide (PPO); Polystyrene (PS), polytetrafluoroethylene (PTFE); Polytetrahydrofuran; Polyethers (for example polyoxyethylene glycol, polypropylene glycol), polyacrylic acid vinyl ester and polymethyl acrylic acid vinyl ester and multipolymer, polyacrylic ester and the polystyrene copolymer of polyvinyl compound, particularly polyvinyl chloride (PVC), PVC multipolymer, PVdC, polyvinyl acetate and multipolymer thereof, polyvinyl alcohol (if the suitable partial hydrolysis form that is), polyvinyl acetal, polyvinyl acetate, Polyvinylpyrolidone (PVP), polyvinyl ether, solution and dispersion form; Polystyrene (impact-resistant modified or non-impact-resistant modified); Urethane (uncrosslinked or with isocyanate-crosslinked); Urethane acrylate, the styrene-propene acid copolymer; Styrene-butadiene block copolymer is (for example from BASF AG's

Or

K-Resin from CPC ^TM, from Kraton D or the Kraton G of Kraton Polymers); Protein such as casein; SIS; Triazine resin, bismaleimides-cyanate resin (BT), cyanate ester resin (CE), allylation polyphenylene oxide (APPE).

Two or more mixture of polymers also can form organic binder component A '.

Be acrylate, acrylate resin, derivatived cellulose, methacrylic ester, methacrylate resin, trimeric cyanamide and aminoresin, polyalkenes hydrocarbon, polyimide, Resins, epoxy, modified epoxy such as difunctionality or multifunctional dihydroxyphenyl propane or Bisphenol F resin, epoxy-Novolak resin, brominated epoxy resin, cycloaliphatic epoxy resin preferably as the polymkeric substance of component A '; Aliphatic epoxy resin, glycidyl ether, vinyl ether and resol, urethane, polyester, polyvinyl acetal, polyvinyl acetate, polystyrene, polystyrene copolymer, polystyrene-acrylate, styrene-butadiene block copolymer, alkene-vinyl-acetic ester and vinyl chloride copolymer, polymeric amide and multipolymer thereof.

B component '

Above the carbon nanotube of describing as B component can be used as B component '.

In one embodiment of the invention, can be by at first carbon nanotube being introduced among the binder component A ' and carbon nanotube is added dispersion; As fruit component A ' is polymkeric substance or polymeric blends, and then this introducing can be carried out during monomer polymerization produces binder component A ' or afterwards.If add nanotube after polymerization, then they are preferably by at forcing machine or preferably add in kneading machine in the polymer melt and add.Combination process in kneading machine or forcing machine can with aggregate or carbon nanotube be gone up substantially or even pulverize fully and carbon nanotube is dispersed in the polymeric matrix.

In a preferred embodiment of carbon nanotube being introduced in advance among the binder component A ', wherein carbon nanotube is metered into binder component A ' and can takes be preferably selected from as the high density master batch form in the polymkeric substance of the polymkeric substance of component A '.The concentration of carbon nanotube in masterbatch is generally 5-50 weight %, is preferably 8-30 weight %, is preferably 12-22 weight % especially.The preparation of masterbatch has for example been described in US-A 5643502.The use of masterbatch can improve the pulverizing of aggregate especially.

Introduce in the dispersion or the result who introduces in advance among the component A ' is that the length distribution of carbon nanotube may be than the weak point of original use.

Component C '

Dispersion also comprises solvent composition C ' in addition.It is made up of solvent or solvent mixture.

The example of suitable solvent is an aliphatic series or aromatic hydrocarbon (octane for example, hexanaphthene, toluene, dimethylbenzene), alcohol (methyl alcohol for example, ethanol, the 1-propyl alcohol, the 2-propyl alcohol, the 1-butanols, the 2-butanols, amylalcohol), polyvalent alcohol such as glycerine, ethylene glycol, propylene glycol, neopentyl glycol, alkyl ester (methyl acetate for example, ethyl acetate, propyl acetate, butylacetate, isobutyl acetate, isopropyl acetate, the 3-methyl butanol), alkoxyl alcohol (methoxypropanol for example, methoxybutanol, the oxyethyl group propyl alcohol), alkylbenzene (ethylbenzene for example, isopropyl benzene, butyl glycol, butyldiglycol, alkyl glycol acetic ester (butyl glycol acetate for example, the butyldiglycol acetic ester), Pyranton, the glycol ether dialkyl ether, the diglycol monotertiary alkyl oxide, the dipropylene glycol dialkyl ether, the dipropylene glycol monoalky lether, glycol ether alkyl oxide acetic ester, dipropylene glycol alkyl oxide acetic ester diox, dipropylene glycol and dipropylene glycol, glycol ether and glycol ether ether, DBE (dibasic ester), ether (diethyl ether for example, tetrahydrofuran (THF)), vinylchlorid, ethylene glycol, the ethylene glycol ethyl ethers acid esters, ethylene glycol dimethyl ether, cresols, lactone (for example butyrolactone), ketone (acetone for example, 2-butanone, pimelinketone, methylethylketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK)), methyl glycol ether, methylene dichloride, methylene glycol, methyl glycol acetate, methylphenol (adjacent-, between-, p-cresol), pyrrolidone (for example N-methyl 2-Pyrrolidone), propylene glycol, Texacar PC, tetracol phenixin, toluene, TriMethylolPropane(TMP) (TMP), aromatic hydrocarbon and mixture, aliphatic hydrocrbon and mixture, pure formula monoterpene (for example terpinol), water, and by the mixture of two or more these solvent compositions.

Preferred solvent be pure (ethanol for example, the 1-propyl alcohol, the 2-propyl alcohol, butanols), alkoxyl alcohol (methoxypropanol for example, the oxyethyl group propyl alcohol, butyl glycol, butyldiglycol), butyrolactone, the glycol ether dialkyl ether, the diglycol monotertiary alkyl oxide, the dipropylene glycol dialkyl ether, the dipropylene glycol monoalky lether, ester (ethyl acetate for example, butylacetate, butyl glycol acetate, the butyldiglycol acetic ester, glycol ether alkyl oxide acetic ester, the dipropylene glycol acetic ester, DBE), ether (for example tetrahydrofuran (THF)), polyvalent alcohol such as glycerine, ethylene glycol, propylene glycol, neopentyl glycol, ketone (acetone for example, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone), hydrocarbon (hexanaphthene for example, ethylbenzene, toluene, dimethylbenzene), N-N-methyl-2-2-pyrrolidone N-, water, and their mixture.

Component D '

Dispersion also comprises above the dispersion agent described as component C as dispersion agent component D ' in addition.Component E '

Dispersion also comprises above the filler described as component D as filler component E ' in addition.

If except described component A ', B ', C ' and suitable D ' and/or E ', dispersion can also comprise other additive, as processing aid and stablizer, for example UV stablizer, lubricant, corrosion inhibitor and fire retardant.

Can also use other additive, as reagent with thixotropic effect, for example silica, silicate, for example Aerosil (a kind of silica gel of high dispersing) or wilkinite, the organic reagent and the thickening material that perhaps have thixotropic effect, for example polyacrylic acid, urethane, hydrogenated castor oil, dyestuff, lipid acid, fatty acid amide, softening agent, wetting agent, antifoams, lubricant, siccative, linking agent, light trigger, coordination agent, wax, pigment and conductive polymer particles.

Other content of additive is generally 0.01-30 weight % based on the gross weight of this dispersion.This content is preferably 0.1-10 weight %.

The preferred method for preparing this dispersion may further comprise the steps:

A ') if blending ingredients A '-B ' and at least a portion component C ' and suitable D ', E ' and other component,

B ') disperse this mixture,

C ') if suitable adding not at step a ') in the component C ' of the ratio used to regulate viscosity to adapt to each application method.

This dispersion can and use those skilled in the art's known devices to disperse to prepare by intense mixing.This is included in and mixes each component in strong diverting device such as kneading machine, ball mill, ball mill, dissolver, three-roll mill or the rotor-stator mixing machine.

All the required components that can in a step of this method, mix this dispersion.But, also can two or more components of pre-mixing, for example component A ' and B ', as mentioned above, and with the Mixed Delay of remaining ingredient to this method independent process subsequently.

The embodiment that the present invention produces the method for metal level at least a portion stromal surface may further comprise the steps:

A) dispersion that will comprise carbon nanotube is applied to matrix;

B) layer that will be applied to this matrix to small part dry and/or partially hardened at least; And

C) metal refining on and/or at least subsclerotic dispersion layer dry by chemistry and/or electrochemical plating to small part.

Non-electric conductivity material such as polymkeric substance are provided on suitable matrix.Suitable polymers is a Resins, epoxy, difunctionality or multifunctional for example, aromatic poly strengthens or glass fibre strengthens or paper enhanced Resins, epoxy (as FR4) glass filament reinforced plastics, liquid crystalline polymers (LCP), polyphenylene sulfide (PPS), polyoxymethylene (POM), PAEK (PAEK), polyether-ether-ketone (PEEK), polyamide (PA), polycarbonate (PC), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyimide (PI), polyimide resin, cyanate ester class, bismaleimides-cyanate resin, nylon, vinyl ester resin, polyester, vibrin, polymeric amide, polyaniline, resol, polypyrrole, poly terephthalic acid naphthalene ester, polymethylmethacrylate, poly-Ethylenedioxy Thiophene, the aramid paper that resol applies, polytetrafluoroethylene (PTFE), melamine resin, silicone resin, fluoro-resin, dielectric medium, APPE, polyetherimide (PEI), polyphenylene oxide (PPO), polypropylene (PP), polyethylene (PE), polysulfones (PSU), polyethersulfone (PES), polyarylamide (PAA), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene (ABS) (ABS), acrylonitrile-styrene-acrylic ester (ASA), styrene-acrylonitrile (SAN), and two or more above-mentioned mixture of polymers, it can take various forms.This matrix can comprise those skilled in the art's known additives, for example fire retardant.

In principle, can also use any polymkeric substance that is listed under the component A '.

Other suitable matrix is matrix material, the foam type polymkeric substance,

Paper, timber, mineral material, silicon, glass, plant tissue or the animal tissues of urethane (PU), ceramic surface, textiles, card board kai, cardboard, paper, polymer-coated or the saturated Woven fabric of resin are pressed into plate or volume.

For this embodiment of the present invention, the meaning of preferred " non-electric conductivity matrix " is that the surface resistivity of matrix is greater than 10 ⁹Ohm/cm.

This dispersion can the procedure known to those skilled in the art be applied to matrix/backing.

Can be applied to the one side of stromal surface or multiaspect more, and can extend at one dimension, two dimension or three-dimensional space.This matrix can have any required geometrical shape usually to be fit to predetermined purpose.

This dispersion can apply with structured form or non-structure form in step a).Preferably apply step [step a] with continuous program], drying and/or cure step [step b]] and metal deposition [step c]].This is owing to simply carry out step a), b) and c) but possible.But, in batches or semicontinuous method also be fine certainly.

Used coating method can comprise ordinary method and well-known method (casting, be coated with shop, blade coating, brushing, printing (intaglio, silk screen printing, offset printing, bat printing (pad print), ink-jet, offset printing, Method (as described in the DE10051850) etc., spraying, dip-coating, roll extrusion, efflorescence, fluidized-bed etc.).Bed thickness is preferably at 0.01-100 μ m, and more preferably 0.1-50 μ m changes in the preferred especially 1-25 μ m.These layers can apply with non-structure or structured form.

Use the dispersion that ordinary method is dry or sclerosis applies with structurizing or non-structure form.For example, this dispersion can for example be hardened via polymerization, addition polymerization or the polycondensation (for example by UV radiation, electron beam, microwave radiation, IR radiation or heating) of binding agent via chemistry route, perhaps hardens via the evaporation of solvent by pure physical route.Can also carry out drying in conjunction with physics and chemistry route.

Apply dispersion and layer dry and/or that obtain behind the partially hardened at least makes the metal refining on and/or at least subsclerotic dispersion layer dry to small part by chemistry and/or electrochemical plating subsequently to small part.

By electrochemical plating metal refining on matrix

Its surface exists the matrix of carbon nanotube as thermoplastic composition that comprises carbon nanotube or the matrix that is coated with the dispersion that comprises carbon nanotube, be particularly suitable for by the electrochemical plating depositing metal layers, promptly produce metallization matrix, and do not need stromal surface is carried out complicated pretreatment.

In principle, any those skilled in the art electrochemical plating of passing through known and that describe in the literature all are suitable as the method for producing metallization matrix in the method for frosting metal refining.(for example referring to people such as Harold Ebneth, Metallisieren von Kunststoffen:PraktischeErfahrungen mit physikalisch, the metallization of chemisch und galvanisch metallisiertenHochpolymeren[plastics: by physics, chemistry and the electrochemical plating metallized practical experience of superpolymer], Expert Verlag, Renningen-Malmsheim, 1995, ISBN3-8169-1037-8; People such as Kurt Heymann, the metallization of Kunststoffmetallisierung:Handbuchf ü r Theorie und Praxis[plastics: theory and practice handbook] Galvanotechnik und by name

In the Public Series of [electroplating technology and surface treatment] No. 22, Saulgau:Leuze, 1991; Mittal, K.L. (editor), metallized plastic three: Fundamental and Applied Aspects, Third Electrochemical SocietySymposium on Metallized Plastics:Proceedings, Phoenix, Arizona State, 13-18 day in October, 1991, New York, Plenum press).

Preferably after each final molding technology, the matrix that can metallize by applying electromotive force is arranged in negative electrode and makes it and contacts with the metal salt solution of tart, neutral or alkalescence, thereby the metal of this metal salt solution is deposited in the matrix that can metallize by electrochemical plating and comprises on the surface of carbon nanotube.Preferably being used for sedimentary metal is chromium, nickel, copper, Jin Heyin, particularly copper.Can also deposit multiple metal level in succession by electrochemical plating, the matrix that for example can metallize is introduced in the dip-coating bath of the solution that contains different metal, applies external voltage and electric current under every kind of situation.

Although before metallizing, do not need the stromal surface that can metallize is carried out special pre-treatment, can carry out surface active by the procedure known to those skilled in the art in principle by chemistry and/or electrochemical plating.The surface active of stromal surface can improve tack or quicken metal deposition by surface roughening being discharged from the teeth outwards carbon nanotube with control mode or use control method.Discharging carbon nanotube needs just can realize metallized advantage than small proportion in polymeric matrix in addition.

For example, surface active can pass through mechanical wear, particularly brush, grind or polishing or impact under from the pressure of water jet, sandblast or with supercritical co (dry ice) sandblast with abrasive material, perhaps by physical method such as heating, laser, UV light, corona or plasma discharge, and/or chemistry abrasion, particularly etching and/or oxidation and carry out.Carrying out mechanical wear and/or chemical abrasive method is the known and descriptions to some extent in the prior art of those skilled in the art.

The abrasive material that is used to polish can be the known any abrasive materials of those skilled in the art.The example of suitable abrasive material is a pumice sand.Be the superiors of ablation sclerosis dispersion, when using pressurized jet of water, water jet preferably comprises small amount of solid particle such as pumice sand (Al ₂O ₃), its average particle size distribution is 40-120 μ m, is preferably 60-80 μ m, perhaps particle diameter〉flint (SiO of 3 μ m ₂).

Surface active can also be undertaken by (also usually be called draw or the extend) matrix that can metallize that stretches, the 0.1-9 that particularly stretched doubly, preferred 0.2-4 doubly, preferred especially 0.3-2 is doubly.Be surface active, the application that can certainly be bonded to each other of described machinery and/or chemical abrasive embodiment and described tensile embodiment.

Stretching can be carried out in one or more directions.Under the situation of extruded profile, line or pipe, preferred unidirectional the carrying out that stretch, under the situation of tabular plastics, it is for example preferably multi-direction with blowing or thermoforming process on sheet material or sheet material to stretch, particularly two-way carrying out.Under multi-direction tensile situation, importantly reach described draw ratio at least one draw direction.Can be used on the tensile methodological principle be document describe with the known any drawing process of those skilled in the art.Example for the preferred drawing process of sheet material is a blow moulding.

Under the abrasive situation of chemistry, preferred chemical or the chemical mixture that is fit to this matrix polymer that use.Under the abrasive situation of chemistry, polymkeric substance for example can be partly dissolved by solvent at least on the surface, and perhaps the chemical structure of body material can be destroyed at least to a certain extent by suitable reagent, thereby discharges carbon nanotube.Make body material expansible reagent also be suitable for discharging carbon nanotube.Expand to produce and to treat that deposited metal ions can be from the cavity of electrolyte solution infiltration, thereby make relatively large carbon nano tube metalization.The carbon nanotube of relatively large release has improved the speed of metallization process.

If body material for example is Resins, epoxy, modified epoxy, epoxy-phenolic varnish, polyacrylic ester, ABS, styrene-butadiene copolymer or polyethers, then preferably realize the release of carbon nanotube by oxygenant.Oxygenant destroys the key of body material, discharges particle thereby make binding agent separate.The example of suitable oxidizers is manganate such as potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide, oxygen, oxygen under catalyzer exists, for example manganese salt, molybdenum salt, bismuth salt, tungsten salt and cobalt salt, ozone, Vanadium Pentoxide in FLAKES, tin anhydride, ammonium polysulfide solution, sulphur under ammonia or amine exist, Manganse Dioxide, potassium ferrate, dichromate/sulfuric acid, the chromic acid in the sulfuric acid or in the acetate or in the diacetyl oxide, nitric acid, hydroiodic acid HI, Hydrogen bromide, dichromic acid pyridine, chromic acid-pyrimidine title complex, chromic trioxide, chromic oxide (VI), Periodic acid, lead tetraacetate, quinone, the methyl quinone, anthraquinone, bromine, chlorine, fluorine, iron salt solutions, hydrosulfate solution, SPC-D, oxo halate such as oxymuriate or bromate or iodate, perhalide such as sodium periodate or sodium perchlorate, hyperbromic acid sodium, dichromate such as sodium dichromate 99, persulphate such as Potassium Persulfate, permonosulphuric acid potassium, pyridinium chlorochromate, hypohalite such as clorox, the methyl-sulphoxide under electrophilic reagent exists, t-butyl hydroperoxide, 3-chlorine peroxybenzoic acid, 2,2-dimethyl propionic aldehyde, Des-Martin-Periodinan, oxalyl chloride, urea-hydrogen peroxide adduct, urea peroxide, 2-iodine oxybenzene formic acid, permonosulphuric acid potassium, metachloroperbenzoic acid, N-methylmorpholine N-oxide compound, 2-methyl-prop-2-base hydroperoxide, peracetic acid, pivalyl aldehyde, perosmic anhydride, oxone, ruthenium (III) salt and ruthenium (IV) salt, 2,2,6, oxygen under 6-tetramethyl-piperidyl N-oxide compound exists, triacetyl oxygen base periodate (Triacetoxiperiodinan), trifluoroperacetic acid, trimethyl-acetaldehyde, ammonium nitrate.Choose in this technological process elevated temperature wantonly to improve release process.

Preferred manganate such as potassium permanganate, potassium manganate, sodium permanganate, sodium manganate; Hydrogen peroxide, N-methylmorpholine N-oxide compound, percarbonate such as SPC-D or antihypo; Perborate such as Sodium peroxoborate or potassium per(oxy)borate; Persulphate such as Sodium Persulfate or Potassium Persulphate; Sodium persulfate and permonosulphuric acid sodium, Potassium Persulfate and permonosulphuric acid potassium, ammonium peroxydisulfate and permonosulphuric acid ammonium, clorox, urea-hydrogen peroxide adduct, oxo halate such as oxymuriate or bromate or iodate, perhalide such as sodium periodate or sodium perchlorate, tetrabutyl ammonium peroxydisulfate, quinone, iron salt solutions, Vanadium Pentoxide in FLAKES, dichromic acid pyridine, hydrochloric acid, bromine, chlorine, dichromate.

Preferred especially potassium permanganate, potassium manganate, sodium permanganate, sodium manganate hydrogen peroxide and adducts, perborate, percarbonate, persulphate, peroxydisulfate, clorox and perchlorate.

For being released in the carbon nanotube that comprises as in the body material of ester structure such as vibrin, polyester acrylate, polyether acrylate, the polyester urethane, preferably use as acidity or alkaline chemical and/or chemical mixture.Preferred acidic chemical and/or chemical mixture for example are concentrated acid or diluted acid example hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.According to body material, organic acid also may be suitable, and example is formic acid or acetate.Suitable alkaline chemical and/or chemical mixture for example are alkali such as sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide or carbonate such as yellow soda ash or salt of wormwood.Choose in this technological process elevated temperature wantonly to improve release process.

Solvent also can be used for discharging the carbon nanotube of body material.Solvent must be suitably and the body material coupling, because body material must dissolve in solvent or by the solvent solvation.If use body material to dissolve in wherein solvent, then make bottom only contact the short time with solvent, thereby so that the body material upper strata by solvation and separation.In principle, can use above-mentioned any solvent.Preferred solvent is dimethylbenzene, toluene, halohydrocarbon, acetone, methylethylketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), diethylene glycol monobutyl ether.For improving solvent nature, can choose elevated temperature in dissolution process wantonly.

In the known normal ranges of those skilled in the art, and not critical to the present invention by chemistry and/or sedimentary one or more layers metal layer thickness of electrochemical plating.

The metallization matrix that is preferably used as electric conductivity assembly, particularly printed circuit board (PCB) especially has at least, and one deck passes through chemistry and/or the sedimentary metal level of electrochemical plating, particularly copper layer, silver layer or gold layer.

The metallization matrix of using particularly preferably in ornamental field has by chemistry and/or the sedimentary copper layer of electrochemical plating, has on it by chemistry and/or the sedimentary nickel dam of electrochemical plating, and deposits chromium layer, silver layer or gold layer on it.

Metallization matrix, if be suitably in by after the method and procedure known to those skilled in the art production conductor track structure described in the document, be suitable as conductivity group spare, printed circuit board (PCB) particularly, the RFID antenna, transponder antenna or other antenna structure, switch, transmitter and MID, EMI shielding material (promptly shielding to avoid electromagnetic interference) is as resorber, losser or ELECTROMAGNETIC RADIATION REFLECTION device, perhaps as gas shield or ornamental member, particularly at automotive field, health field, the toy field, the ornamental member in field of furniture and office field.

The example of these application is: the metallization ornamental tape on computer, electronic component, military affairs and non-military shielding, device, scraper accessory and toilet rack accessory, showerhead, shower cross bar, shower frame, metallization door handle and door knob, lavatory paper bowl frame, bathtub handle, furniture and the mirror and the framework of shower dividing plate.

What can also mention is the metallized plastic surface of automotive field, for example ornamental tape, outer visor, water tank, front end metallization, aerofoil, outside car body component, threshold, the pedal that resets, ornamental wheel cap.

Those that the parts that can be made by plastics are particularly partially or completely made by metal up to now.Here the example that can mention is an instrument, as pliers, screwdriver, rig, drill chuck, saw blade, ring spanner and open-ended spanner.

Metallization matrix (comprising under the situation of magnetizable metal) also is used for magnetisable functional component field, for example magnetic sheet, magnetic game, the magnetic surface in refrigerator door for example.They also are applied to wherein good heat conductivity is favourable field, for example the thin slice of seat heating system, floor heating system, insulating material.

The inventive method allows to apply metal level by chemistry and/or electrochemical plating deposition with improvement from the metal of metal salt solution on matrix.Particularly, the inventive method can be with short electroplating time, low-cost good tack and the measured metal level of matter that has with matrix that deposit on matrix.Gained metallization matrix weight is lighter.

Hereinafter the embodiment of Shi Yonging is used for further explaining the present invention.

Embodiment

Experimental section 1: the matrix of forming by the moulding compound that comprises carbon nanotube:

Below as component A:

2G66 is from the S-TPE of BASF Aktiengesellschaft.

A-ii is from the PP4821 polypropylene of Borealis, melt flow index 2.4g/10min (measuring under 230 ℃ and 2.16kg according to ISO 1133).

Below as B component:

C150P is from the multi-walled carbon nano-tubes of Bayer Material Science AG, carbon content〉95 weight %, median size is 13-16nm, length is 1-10 μ m.

Following component is used for non-contrast experiment of the present invention:

Comp-i:

XC 72R is from the graphitized carbon black of Cabot Corp.

The production of the matrix that can metallize:

At the component A that in IKA Duplex kneading machine, gets quantitative proportion described in the table 1 under 120-150 ℃ the temperature, portions adds equally in other component of quantitative proportion described in the table 1 and mixes (data unit is weight %, under every kind of situation based on the gross weight of all components).The moulding compound that obtained after kneading about 30 minutes is injection molding and produces the length of side is the dull and stereotyped experimental sample of 50 * 50mm.

Surface active:

Following surface active also suitably carries out on the sample of indication in table 1.

's 80 ℃ the 6 weight %KMnO that comprise with sample in temperature ₄With dipping in the aqueous solution of the 4.5 weight %NaOH gross weight of the aqueous solution (under every kind of situation based on) 2 minutes.Then sample was washed 30 seconds with running water stream.At last, sample is being comprised 2 weight %H ₂O ₂With 10 weight %H ₂SO ₄Dipping is 1 minute in the aqueous solution of the gross weight of the aqueous solution (under every kind of situation based on).

Metallization:

By in commercially available acidity from Atotech

HS copper sulfate is bathed (the 21 weight %CuSO that comprise aqueous solution form ₄, 5.5 weight %H ₂SO ₄, 0.2 weight % brightening agent, 0.5 weight %HS leveler and 0.02 weight %NaCl, under every kind of situation based on the solution gross weight) in dipping and apply 1V electromotive force and with sample metallization 30 minutes.If visual inspection has deposited uniform copper layer then has thought that this sample can metallize on whole sample after electroplating 30 minutes.

But table 1 has provided the metal voltinism of sample.

Table 1

Embodiment ＊	1	2	3	Contrast-1	Contrast-2
						The formation of moulding compound [weight % is based on the gross weight of moulding compound]
A-i	80	92	-	80	80
						A-ii	-	-	90	-	-
B-i	20	8	10	-	10
						Contrast-i	-	-	-	20	10
Surface active	Not	Be	Be	Not	Not
						But metal voltinism * *	Be	Be	Be	Not	Not

^*The embodiment that is shown as " contrast " is Comparative Examples,

^*If visual inspection has deposited uniform copper layer on whole sample after electroplating 30 minutes described in the specification sheets, but then is classified as "Yes" for this sample of metal voltinism.

Experimental section 2: use the dispersion coating substrate that comprises carbon nanotube:

Below as component A ':

2G66 is from the S-TPE of BASF Aktiengesellschaft.

Below as B component ':

C150P is from the multi-walled carbon nano-tubes of Bayer Material Science AG, carbon content〉95 weight %, median size is 13-16nm, length is 1-10 μ m.

Below as component C ':

C '-i n-butyl acetate.

Below as component E ':

E '-i:

XC 72R is from the graphitized carbon black of Cabot Corp.

The preparation of dispersion:

Get the component A ' of quantitative proportion described in the table 2, portions adds equally B component at quantitative proportion described in the table 2 ' and mix (data unit is weight %, under every kind of situation based on the gross weight of all components) down at 120 ℃ in IKA Duplex kneading machine.

If the gained mixture was mixed 1 hour with the component C ' of quantitative proportion described in the table 2 and suitable other component (data unit is weight %, under every kind of situation based on the gross weight of all components) in the presence of glass particle in Skandex DAS 200 mixing machines.Take out glass particle then.

Coating substrate:

Further process dispersions obtained by two kinds of optional methods (shown in the table 2):

α) dispersion is applied to the thin slice of forming by polyethylene terephthalate as matrix.This dispersion of 80 ℃ of dryings ten minutes, on matrix, form the layer that thickness is about 25 μ m subsequently; Perhaps

β) with the colored checking table printing of the Saueressig CP90/200 intaglio printing of dispersion by the RFID antenna form to the thin slice of forming by polyethylene terephthalate as matrix, dry then formation bed thickness is about the track of 3 μ m.

Surface active:

Also carry out following surface active on the coating substrate of in table 2, suitably indicating:

's 80 ℃ the 6 weight %KMnO that comprise with coating substrate in temperature ₄With dipping in the aqueous solution of the 4.5 weight %NaOH gross weight of the aqueous solution (under every kind of situation based on) 2 minutes.Then coating substrate was washed 30 seconds with running water stream.At last, coating substrate is being comprised 2 weight %H ₂O ₂With 10 weight %H ₂SO ₄Dipping is 1 minute in the aqueous solution of the gross weight of the aqueous solution (under every kind of situation based on).Metallization:

By in commercially available acidity from Atotech

HS copper sulfate is bathed (the 21 weight %CuSO that comprise aqueous solution form ₄, 5.5 weight %H ₂SO ₄, 0.2 weight % brightening agent, 0.5 weight %HS leveler and 0.02 weight %NaCl, under every kind of situation based on the solution gross weight) in dipping and apply 1V electromotive force and with coating substrate metallization 30 minutes.If visual inspection has deposited uniform copper layer then has thought that this coating substrate can metallize on whole matrix after electroplating 30 minutes.

But table 2 has provided substrate coated metal voltinism.

Table 2

Embodiment ＊	1	2
			The formation of dispersion [weight % is based on the gross weight of dispersion]
A′-i	22	12.2
			B′-i	3	1.7
C′-i	75	83.3
			E′-i	-	2.8
Further method for processing	α	β
			Surface active	Be	Be
But metal voltinism ＊	Be	Be

^*If visual inspection has deposited uniform copper layer on whole matrix after electroplating 30 minutes described in the specification sheets, but then is classified as "Yes" for this coating substrate of metal voltinism.

Claims (13)

1. one kind applies the method for metal level by deposition on matrix from the metal of metal salt solution, and it is included in stromal surface and has carbon nanotube.

2. according to the process of claim 1 wherein that used carbon nanotube comprises that length is 0.5-1000 μ m, diameter is single wall-or multi-walled carbon nano-tubes of 0.002-0.5 μ m.

3. according to the method for claim 1 or 2, wherein said matrix comprises thermoplastic composition, and wherein based on the gross weight of component A, B, C and D, it is 100 weight %, and described thermoplastic composition comprises following component:

The thermoplastic polymer of a20-99 weight % is as component A,

The carbon nanotube of b1-30 weight % is as B component,

The dispersion agent of c0-10 weight % as component C and

Fibrous or the granulated filler of d0-40 weight % or its mixture are as component D.

4. according to the method for claim 3, wherein used component A comprises that one or more are selected from the polymkeric substance of impact modification vinyl aromatic copolymers, polyolefine, polycarbonate, thermoplastic polyurethane and styrenic based thermoplastic elastomer.

5. according to the method for claim 1 or 2, wherein said matrix provides dispersion, described dispersion is by and/or at least partially hardened dry to small part, and dry to small part and/or at least after the described dispersion of partially hardened, carry out metal deposition by chemistry and/or electrochemical plating, wherein said dispersion comprises:

A ' is the organic binder bond component A ' of 0.1-99.9 weight % based on the gross weight of component A ', B ' and C ';

B ' based on the gross weight of component A ', B ' and C ' be 0.1-30 weight % carbon nanotube as B component ';

C ' is the solvent composition C ' of 0-99.8 weight % based on the gross weight of component A ', B ' and C '.

6. according to the method for claim 5, it is the dispersion agent component D ' of 0.1-50 weight % based on the gross weight of component A ', B ' and C ' that wherein said dispersion also comprises at least a following component: d '; And e ' is the filler component E ' of 0.1-50 weight % based on the gross weight of component A ', B ' and C '.

7. according to the method for claim 5 or 6, wherein said binder component A ' is made up of polymkeric substance or polymeric blends.

8. according to each method among the claim 5-7, wherein said dispersion is applied to described matrix with structurizing or non-structure form.

9. according to each method among the claim 1-8, wherein before by chemistry and/or electrochemical plating metal refining, will wherein exist the stromal surface of carbon nanotube to activate.

10. carbon nanotube is applying the purposes of metal level to the matrix.

11. have the stromal surface of conductive metal layer to small part according to what each method among the claim 1-9 obtained.

12. according to the stromal surface of claim 11 in conduction current or heat or as the purposes in decorative metals surface or electromagnetic radiation shielding or the magnetization.

13. purposes according to claim 12, as the conductor rail in printed circuit board (PCB), RFID antenna, transponder antenna or other antenna structure, seat heating system, flat cable, patch conductor, contactless chip card, the solar cell, perhaps be used for LCD display or plasma panel, perhaps be used to produce the product of any desired form that applies by chemistry and/or electrochemical plating.