CN100354370C - Impact-strength-modified polymer compositions - Google Patents

Impact-strength-modified polymer compositions Download PDF

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CN100354370C
CN100354370C CNB2003801091648A CN200380109164A CN100354370C CN 100354370 C CN100354370 C CN 100354370C CN B2003801091648 A CNB2003801091648 A CN B2003801091648A CN 200380109164 A CN200380109164 A CN 200380109164A CN 100354370 C CN100354370 C CN 100354370C
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composition
rubber
component
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acid
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CN1742054A (en
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M·瓦特豪尔
G·夸斯
T·布雷
D·约阿西米
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Lanxess Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences

Abstract

Polyamide composition contains 0.1-8 wt.% electrically conductive carbon particles and 0.5-50 wt.% of a graft copolymer. An Independent claim is also included for shaped products produced from the composition.

Description

The improved polymer composition of shock strength
Technical field
The mo(u)lded item that the present invention relates to the improved daiamid composition of shock strength and produce by it, it is fit to, particularly direct-on-line sprays paint (Online-Lackierung) and need mo(u)lded item not anticipated with the conductive primer system, also relates to this online mo(u)lded item that sprays paint.
Background technology
DE-A 101 019 225 has usually described the fine mineral particulate polymer composition that contains polymeric amide, graftomer, vinyl (being total to) polymkeric substance, compatible promotor and have the anisotropic particle geometric parameter.Composition of the present invention is a kind of selection relevant with the disclosure.In DE-A 101 019 225, the composition of not mentioning described in its literary composition can onlinely spray paint.
Can learn from EP 0 202 214 A by the blend polymer that polymeric amide, styrene/acrylonitrile copolymer and compatible promotor are formed.A kind of by vi-ny l aromatic monomers and vinyl cyanide, methacrylonitrile, methacrylic acid C 1～C 4Alkyl ester or vinylformic acid C 1～C 4Alkyl ester is used as the use of compatible promotor by the multipolymer of weight ratio generation in 85: 15～15: 85.By the use of this compatible promotor, be intended to reach the raising of shock strength.A shortcoming of the blend polymer of describing in the publication of this printing is that they show deflection and cross low too high with the coefficient of expansion for the thin-walled purposes.
Learn a kind of polyamide moulding composition from JP 112 410 16.A2, it comprises, and except polymeric amide, also has the styrene polymer of modified rubber, based on the graftomer of ethylene/propylene rubber and the particle diameter talcum powder between 1 μ m～4 μ m.
EP-A 0 718 350 describes a kind of blend polymer, by crystallization and amorphous or semi-crystalline polymer, also has 2～7wt% conductive carbon (carbon black) to form, and is used for producing molding, the thermoplastic article of carrying out electrostatic convergence painting at further step.In the document, there is not to describe the extra high polymer blend of thermostability with conduction finishing composition.
At US-A 4,974, in 307, a kind of method of the body of a motor car that can be sprayed paint subsequently by metal and plastics-production has been described.For this reason, the mo(u)lded item of having described a kind of moulding compound of forming by fluoropolymer resin and electro-conductive material and having produced by its, its surface resistivity is between 5 * 10 2Ω * cm and 1 * 10 5Ω * cm.In order to obtain this kind high conductivity, require to add a large amount of conductivity additive, this flowability and toughness to corresponding polymer molding compositions has negative impact.
In addition, the fine particulate inorganic material is at some polymer composition, and particularly the application in polycarbonate compositions is well-known.This inorganic materials is used as in this kind composition, for example, strongthener uses, and is intended to improve deflection and tensile strength, so that improve the dimensional stability under the temperature fluctuation situation, with improve surface property or---in fire retardant material---also as the synergist of anti-the flame.Inorganic materials and material for preparing with synthetic method and usefulness.For example, at US-A5, in 714,537, describe a kind of polycarbonate Alloys, it comprises certain mineral filler and is used to improve deflection and suppresses linear thermal expansion.
Learn a kind of rubber modified polymers composition from EP 0 785 234 A1, it comprises, as compatible promotor, and a kind of terpolymer that generates by vinylbenzene, vinyl cyanide and maleic anhydride.The adding of this compatible promotor causes the shock strength under the improvement of mechanical property, particularly low temperature.Yet shortcoming is that the over-all properties of polymkeric substance, the particularly processing in injection moulding show, and worsen along with the adding of compatible promotor.
Be fit to onlinely to spray paint, the improved polyethylene terephthalate/polycarbonate Alloys of shock strength is disclosed among the WO 01/34703.Polyamide blend is not described.
But spray paint to be suitable for certain direct-on-line/(inline) application scenario is celebrated on the line is the Noryl that is produced by General Electric's Plastics Company GTX (referring to EP-A 685 527).In such cases, it is a kind of problem that contains polymeric amide and polyphenylene ether blend (PA/PPO blend).
Generally speaking, the body exterior part that is made of plastics must spray paint.Under the situation of the plastics of being dyed vehicle color, the common quilt cover of being produced by it of vehicle body add-on parts is coated with one or more layers transparent varnish.Under the situation of the plastics of not dying vehicle color as yet, which floor lacquer the vehicle body add-on parts of being produced by it is coated with, and wherein one deck is (the applying lacquer) of contribution color at least.Thermostability on plastics is decided, and is installed between the whole bag of tricks of the asynchronism(-nization) on the body exterior part at the plastics add-on parts here, must be distinguished.If the whole process of plastics add-on parts through spraying paint just generally is called " online " and sprays paint, this thermostability for plastics proposes the highest requirement.Under the situation that so-called " on the line (inline) " sprays paint, the plastics add-on parts just is installed on the body exterior part after so-called negative electrode dip-coating (KTL) and is incorporated in the painting line.Under the situation that so-called " off-line " sprays paint, whole plastics add-on parts sprays paint with external low temperature at the line that sprays paint, and just just is installed to the body exterior part after this and gets on.
" online " method is that automotive industry is preferred, because it has simplified algorithm to greatest extent, in addition, also can obtain optimal colors coupling between plastics and the metal sheet.Adopt this kind method, temperature reaches as high as 205 ℃, and therefore the thermostability to mo(u)lded item proposes very high request.
If can modified plastics, so that make it become so low, so that can be used in the electrostatic convergence painting and need not anticipate with the conductive primer system than resistivity, then will save a production stage.
For the additional requirement of the vehicle body add-on parts that is made of plastics is good deflection, low-thermal-expansion, excellent surface quality, well japanning property and good resistance to chemical attack.In addition, the moulding compound that is used to produce the body exterior part must show good fluidity in molten state.
Summary of the invention
The purpose of this invention is to provide the electrically conductive polyamide moulding compound that shows superior heat-stability and low-thermal-expansion.The present composition also show in addition the enhanced tensile strength and, meanwhile, well processed performance.
Therefore, the invention provides a kind of polymeric amide and 0.1～8 weight part conductive carbon particle of comprising, also have the composition of 0.5～50 weight part graftomer.
Preferred polymeric compositions comprises:
(A) 40～90, preferred 45～85, especially preferred 50～80,55～70 weight parts of polyamide particularly;
(B) 0.5～50, preferred 1～35, especially preferred 1～30,5～25 weight part graftomer particularly;
(C) 0.1～30, preferred 1～20, especially preferred 1.5～15,2.5～13 weight part mineral grains particularly;
(D) 0.1～8, preferred 1～5, especially preferred 1.5～4.5 weight part conductive carbon particles.
Said composition can comprise, as further component, and compatible promotor (component E) and/or vinyl (being total to) polymkeric substance (component F), polymeric additive such as stablizer, and resol (H).
In addition, the present invention also provides the online Painting mould plastic that can be obtained by above-mentioned composition.
Have now found that, the plastics with above composition show superior heat-stability and, Just because of this, be particularly suitable in " online " method for paint spraying.Have, the present composition shows high elastic coefficient again, and A-level surface, high-stiffness and remarkable resistance to chemical attack.
Illustrate all components of the polymer composition that is fit to the present invention's use below.
Component A
Be applicable to that polymeric amide of the present invention (component A) is known or can adopts known method preparation in the document.
Being fit to polymeric amide of the present invention is the mixture of known homopolyamide, copolyamide and these polymeric amide.They can be partial crystallization and/or amorphous polyamide.Be suitable as partial crystallization polymeric amide be polyamide 6, polyamide 66, mixture and the corresponding multipolymer made by these components.In addition, the partial crystallization polymeric amide is at the row of consideration, its acid constituents completely or partially is made up of terephthalic acid and/or m-phthalic acid and/or suberic acid and/or sebacic acid and/or nonane diacid and/or hexanodioic acid and/or cyclohexane dicarboxylic acid, and its diamine components completely or partially by-and/or right-dimethylphenylene diamine and/or hexamethylene-diamine and/or 2,2,4-trimethylhexamethylenediamine and/or 2,4,4-trimethylhexamethylenediamine and/or isophorone diamine are formed, and are known on its composing principle.
In addition, should mention such polymeric amide, it completely or partially by the lactan preparation that has 7～12 carbon atoms in the ring, is randomly followed and uses one or more feed composition above-mentioned.
Particularly preferred partial crystallization polymeric amide is polyamide 6 and polyamide 66 and composition thereof.Known product can be used as amorphous polyamides and uses.They can be by diamines such as quadrol, hexamethylene-diamine, decamethylene diamine, 2,2,4-and/or 2,4, the 4-trimethylhexamethylenediamine, between-and/or the p-Xylol diamines, two (4-aminocyclohexyl) methane, two (4-aminocyclohexyl) propane, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane, 3-aminomethyl-3,5,5-trimethylcyclohexyl amine, 2,5-and/or 2, two (aminomethyl) norbornanes and/or 1 of 6-, 4-diaminomethyl hexanaphthene, with dicarboxylic acid such as oxalic acid, hexanodioic acid, nonane diacid, decane dicarboxylic acid, heptadecane dicarboxylic acid, 2,2,4-and/or 2,4, the 4-trimethyladipic acid, the polycondensation of m-phthalic acid and terephthalic acid is produced.
The suitable multipolymer of producing by several monomeric polycondensations in addition; Also has multipolymer by the addition reaction preparation of aminocarboxylic acid such as epsilon-amino caproic acid, omega-amino-undecanoic acid or omega-amino-lauric acid or its lactan.
Specially suitable amorphous polyamides be by m-phthalic acid, hexamethylene-diamine and other diamines as 4,4-diamino-dicyclohexyl methane, isophorone diamine, 2,2,4-and/or 2,4,4-trimethylhexamethylenediamine, 2,5-and/or 2, two (aminomethyl) norbornylenes of 6-; Perhaps by m-phthalic acid, 4 and ε-Ji Neixianan; Or m-phthalic acid, 3,3 '-dimethyl-4,4 '-diamino-dicyclohexyl methane and laurolactam; Perhaps by terephthalic acid and 2,2,4-and/or 2,4, the heterogeneous mixture of 4-trimethylhexamethylenediamine, prepared polymeric amide.
The instead of pure 4 also can adopt the mixture of various diamino-dicyclohexyl methane positional isomerss, is made up of following:
70～99mol% 4,4 '-diamino isomer,
1～30mol% 2,4 '-diamino isomer and
0～2mol% 2,2 '-diamino isomer,
The corresponding diamines of the height condensed of producing by the hydrogenation of technical grade diaminodiphenylmethane randomly.M-phthalic acid can change terephthalic acid into according to the quantity of the highest 30% ratio.
This polymeric amide preferably shows 2.0～5.0, especially preferred 2.5～4.0 relative viscosity (with respect to the solution of 1wt% in meta-cresol 25 ℃ of mensuration).
Polymeric amide can be separately or is present among the component A with each other any mixture form.
B component
B component comprises one or more modified rubber graftomer.By vinyl monomer B.1 modified rubber graftomer B comprises, B.1.1 and B.1.2 preferably according to, what generate has rule (statistisches) (a being total to) polymkeric substance, and vinyl monomer in the grafting, preferably according to B.1.1 and the rubber of vinyl monomer B.1.2 B.2.The preparation of B, for example, is implemented according to emulsion, body or solution or body-suspension polymerization by radical polymerization according to known mode, for example, is described in US-A 3,243,481, US-A 3,509, and 237, US-A3,660,535, US-A 4,221, and 833 and U S-A 4,239,863.Specially suitable graft rubber also has abs polymer, can pass through the redox initiation with the initiator system of being made up of organic hydroperoxide and xitix, and according to US-A 4,937,285 obtain.
Preferred one or more such graftomer, they are by 5～95, B.1, at least a vinyl monomer of preferred 20～90wt% is grafted on 95～5, and one or more second-order transition temperatures of preferred 80～10wt% are lower than 10 ℃, and composition is gone up in the grafting basis that preferably is lower than-10 ℃ B.2.
Preferred monomers B .1.1 be that vinylbenzene, alpha-methyl styrene, halogen replace or alkyl-ring on-vinylbenzene of replacement, for example, p-methylstyrene, to chloro-styrene, (methyl) vinylformic acid C 1～C 8Alkyl ester, for example, methyl methacrylate, n-butyl acrylate and tert-butyl acrylate.Preferred monomers B .1.2 is a unsaturated nitrile, for example, and vinyl cyanide, methacrylonitrile, (methyl) vinylformic acid C 1～C 8Alkyl ester, for example, the derivative of methyl methacrylate, vinylformic acid normal-butyl, tert-butyl acrylate, unsaturated carboxylic acid (for example, acid anhydrides and imide), for example, maleic anhydride and N-phenylmaleimide or its mixture.
Especially preferred monomers B .1.1 is vinylbenzene, alpha-methyl styrene and/or methyl methacrylate; Especially preferred monomers B .1.2 is vinyl cyanide, maleic anhydride and/or methyl methacrylate.
Especially preferred monomer is B.1.1 vinylbenzene and B.1.2 vinyl cyanide.
B.2, the rubber that is suitable for modified rubber graftomer B is, for example, and elastoprene, acrylic elastomer, urethanes, silicon rubber, chloroprene rubber and ethylene/vinyl acetate rubber.The matrix material of being made by various described rubber also is suitable as the grafting basis.
Preferred rubber B.2 be elastoprene (for example, based on divinyl, isoprene etc.) but or the multipolymer of the mixture of elastoprene or elastoprene or itself and other copolyethylene monomer (for example, B.1.1 and B.1.2 according to) mixture, condition is, the second-order transition temperature of B component .2 is lower than 10 ℃, preferably is lower than-10 ℃.Especially preferred pure polybutadiene rubber.Other copolymerisable monomer can be included in the rubber basis, the highest 50wt% of its ratio, preferably the highest 30wt%, particularly the highest 20wt% (with respect to the rubber basis B.2 for).
The acrylic elastomer that is fit to polymer B is B.2 preferably by the polymkeric substance of alkyl acrylate generation, and it randomly has the highest 40wt%, for B.2, and other polymerizable ethylenically unsaturated monomer.Preferred polymerizable acrylic ester comprises C 1～C 8Alkyl ester, for example, the ester of methyl, ethyl, butyl, n-octyl and 2～ethylhexyl; The haloalkyl ester, preferred halo C 1～C 8Alkyl ester, for example, vinylformic acid chloroethene ester also has these monomeric mixtures.
Especially preferred be, graftomer of the present invention does not have based on ethylene-propylene rubber(EPR) (EPR) or based on the grafting basis of ethylene/propene and non-conjugated diene (EPDM) rubber, for example, and as what in JP 1,124 1016 A2, describe.
Preferred " other " polymerizable ethylenically unsaturated monomer promptly, also can randomly be used to prepare B.2 diene of grafting basis except acrylate, for example be vinyl cyanide, vinylbenzene, alpha-methyl styrene, acrylamide, vinyl C 1～C 6Alkyl oxide, methyl methacrylate, divinyl.Preferred is that gel content is the emulsion polymer of 60wt% at least as grafting basis acrylic elastomer B.2.
B.2, another kind of suitable grafting basis is the silicon rubber with grafting active site, as is described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3 631539.
Grafting basis gel content B.2 25 ℃, in appropriate solvent, measure (M.Hoffmann, H.Kr  mer, R.Kuhn, " polymer analysis I and II ", Georg Thieme press, Stuttgart 1977).
Mean particle size d 50Be such diameter, the above and following 50wt% particle that respectively distributing of this numerical value.It can determine (W.Scholtan, H.Lange, " colloid and polymkeric substance magazine " 250 (1972), 782～1796) by super centrifugal assay method.
B component, if require, if can and the therefore not affected words of rubber performance of B component .2, comprise on a small quantity in addition, generally be lower than 5wt%, preferably be lower than 2wt%, for B.2, have the ethylenically unsaturated monomer of crosslinked action.The monomeric example that this kind has crosslinked action is the ester of 3～8 carbon atom unsaturated monocarboxylics and 3～12 unsaturated monohydroxy-alcohols of carbon atom, or the ester of the saturated polyol of 2～4 OH groups and 2～20 carbon atoms, many unsaturated heterocyclic compounds, the polyfunctional vinyl compound, for example, two of alkanediol (methyl) acrylate, polyester two (methyl) acrylate, Vinylstyrene, trivinylbenzene, cyanogen urea triethylenetetraminehexaacetic acid alkene ester, triallyl cyanurate, (methyl) allyl acrylate, diallyl maleate, diallyl fumarate, triallyl phosphate and Phthalic acid, diallyl ester.
Preferred cross-linking monomer is dimethacrylate, the Phthalic acid, diallyl ester of allyl methacrylate(AMA), ethylene glycol and the heterogeneous ring compound with at least 3 ethylenically unsaturated groups.
Under the situation that adopts body or solution or body-suspension polymerization, modified rubber graftomer B is by 50～99, preferred 65～98, especially preferred 75～97 weight parts are by 50～99, the mixture that preferred 60～95 weight parts monomer and 1～50 B.1.1, preferred 5～40 weight parts monomer is B.1.2 formed, 1～50, preferred 2～35, especially preferred 2～15, carry out under the existence of 2～13 parts by weight of rubber B component .2 particularly that graft polymerization reaction produces.
The average particulate diameter d of grafted rubber particles 50Generally show as between 0.05 μ m～10 μ m preferred 0.1 μ m～5 μ m, the numerical value of especially preferred 0.2 μ m～1 μ m.
The average particulate diameter d of the grafted rubber particles that obtains that can produce by body or solution or body-suspension polymerization 50(by to electromicroscopic photograph making an inventory of to determine) generally between 0.5 μ m～5 μ m, the scope of preferred 0.8 μ m～2.5 μ m.
Graft copolymer can be separately or with each other arbitrarily form of mixtures be comprised in the B component.
The content of B component in polymer composition of the present invention is preferably between 0.5～50 weight part, especially preferred 1～35 weight part, preferred especially 5～25 weight parts.
Component C
Being fit to mineral grain of the present invention is the inorganic materials with flakey or stratiform feature, for example, talcum, mica/clay-row (Tonschicht) mineral, montmorillonite, the latter also can be the organic form of the parent of the modification by ion-exchange, and kaolin and vermiculite are arranged again.
Talcum is preferred especially.Term " talcum " refers to the talcum of natural existence or synthetic preparation.Pure talc has chemical constitution 3MgO4SiO 2H 2O, and therefore MgO content is 31.9wt%, SiO 2Content is 63.4wt%, and the content of chemically-bonded water is 4.8wt%.What it related to is the silicate with laminate structure.
Preferred especially high-purity talc type.The latter is contained, for example, and 28～35wt%, preferred 30～33wt%, especially preferred 30.5～32wt%MgO content and 55～65wt%, preferred 58～64wt%, especially preferred 60～62.5wt%SiO 2Content.Preferred talcum type is in addition also with Al 2O 3Content＜5wt%, especially preferably＜1wt%, particularly＜0.7wt% is a feature.
Preferred mineral grain also has in addition, has those of anisotropic particle geometric parameter.This is interpreted as such particle, and its so-called in length and breadth (Aspekt) ratio---ratio of minimum and maximum particle diameter---is preferably greater than 2 greater than 1, especially is preferably greater than about 5.This kind particle is stratiform or microfilament (faser) form at least in a broad sense.This kind material comprises for example, having some talcum and some (aluminium) silicate of stratiform or fiber geometries, for example, and wilkinite, wollastonite, mica, kaolin, hydrotalcite, hectorite or montmorillonite.
Also particularly favourable, the talcum of employing fine grinding type form, its mean particle size d 50＜10 μ m, preferred＜5 μ m, especially preferred＜2.5 μ m especially preferably are less than or equal to 1.5 μ m.Especially preferably use mean particle size d 50Talcum between 350nm-1.5 μ m.
On meaning of the present invention, granularity and particle diameter are meant average particulate diameter d 50, determine by super centrifugal assay method, according to people such as W.Scholtan " colloid and polymkeric substance magazine " 250 (1972), pp.782～796.
Have, mineral grain can carry out surface modification with organic molecule again, and for example, silanization is to reach and the better consistency of polymkeric substance.In this way, can produce hydrophobic or water-wetted surface.
The fine mineral particle with anisotropic particle geometrical shape that is specially adapted to the present composition is described in US-A 5,714 in addition, 537 and US-A 5,091,461 in inorganic materials.
With regard to this respect, it is the number average particle size ratio that is less than or equal to 10 μ m and mean diameter/thickness (D/T) between the material of 4～30 talcum powder, clay or similar type.Several talcum powder and clay filler material are specially suitable.
As at US-A 5,091, described in 461, particularly have the short grained long and narrow or flaky material of regulation and be more suitable for than microfilament shape or Ball-type packing.Highly preferably contain mean diameter/thickness than (D/T), according to US-A 5,714, the method for describing in 537 is measured, and is 4 at least, preferably is 6 at least, more preferably is those compositions of particulate of 7 at least.About the maximum value of ratio D/T, have now found that satisfying to be to have the highest and comprise 30, preferably the highest and comprise 24, more preferably the highest and comprise 18, further preferably the highest and comprise 13, most preferably the highest and comprise 10 numerical value.
Mineral grain can powder, the form of lotion, colloidal sol, dispersion or suspensoid exists.Powder can be obtained through precipitation by dispersion, colloidal sol or suspensoid.
Material also can be processed into thermoplastic composition according to traditional method, for example, and by the direct kneading or the extrusion molding of moulding compound and ultra-fine-particle inorganic powder.Preferable methods comprises the production of masterbatch, for example, the form of component in monomer or solvent that is additive of anti-flame the and at least a moulding compound of the present invention, the co-precipitation of perhaps a kind of thermoplastic component and ultra-fine grain inorganic powder, for example, by the co-precipitation of a kind of water miscible liquid and ultra-fine grain inorganic powder, randomly with the form of dispersion, suspensoid, lotion or the colloidal sol of ultra-fine grain inorganic materials.
Preferably being used for examples of substances of the present invention as mineral grain is Tremin  939-300EST, by (the Frechen of Quarzwerke company, Germany) supply (wollastonite of aminosilane-dressing, average spicule diameter 3 μ m), Finntalc  M30SL, produce (uncoated talcum, granularity d by Omya company (K  ln, Germany) 50=8.5 μ m), Wicroll  40PA produces (silanization wollastonite, granularity d by Omya company (K  ln, Germany) 50=1.3 μ m), and also have Burgess  2211, produce (pure aluminium silicate of aminosilane-dressing, granularity d by Omya company (K  ln, Germany) 50=1.3 μ m), Naintsch A3 (referring to example, component C), Nyglos  4-10013 (silanization wollastonite, granularity d 50=4.8 μ m), (Willboro, NY USA) produce by NYCO mineral company.
The content of the mineral grain of component C in the present composition can preferably the highest 30 weight parts, and especially preferred the highest 20 weight parts are and if comprise preferred 1.5～15 weight parts.
Component D
As component D), said composition comprises, according to kryptol compound of the present invention, for example, and carbon black, it is suitable for preparing electroconductibility, and those skilled in the art also are called conductive carbon black, Graphite Powder 99 and/or carbon nanometer microfilament.
According to the present invention, under the situation of Graphite Powder 99, what it related to is ground graphite.Those skilled in the art understand that graphite is a kind of mutation of carbon, as, for example be described in A.F.Hollemann, E.Wieberg, N.Wieberg, " inorganic chemistry study course " the 91st～100 edition, pp.701～702.Graphite is made up of plane parallel to each other, overlapping arrangement up and down carbon-coating.
According to the present invention, graphite for example can grind by grinding.Granularity is between the highest 0.1 μ m～1mm, preferably between 1 μ m～300 mu m ranges, most preferably between the scope of 2 μ m～20 μ m.
Under the situation according to conductive carbon black of the present invention, primary particle size is between 0.005 μ m～0.2 μ m, preferably between 0.01 μ m～0.1 μ m.The absorption of the dibutyl phthalate of conductive carbon black is between the every 100g carbon black of 40mL～1000mL, preferably between the every 100g carbon black of 90mL～600mL.A large amount of band oxygen groups, for example, carboxyl, lactoyl, phenolic groups, quinoid carbonyl group and/or pyrone structure can be positioned on the black carbon surface.
Conductive carbon black for example can perhaps be produced by oil, carrier gas and air according to oven process by acetylene, by synthetic gas production.Production method is described in, for example, R.G.Gilg, " Ru β f ü rleitf  hige Kunststoffe " in:Elektrisch leitende Kunststoffe, Hrsg.:H.J.Mair, S.Roth, 2. Aufl.Carl Hanser Verlag, 1989, M ü nchen, Wien is S.21-36 and in the document of wherein being quoted.
According to the present invention, the adding of carbon black and/or graphite can generate component A at monomer polymerization) thermoplastics before, during or implement later on.If the polymerization that is added in according to carbon black of the present invention and/or graphite is implemented later on, then preferably implement by joining in the thermoplastic melt in extruding machine or the kneader.According to the present invention, carbon black and/or graphite also can add with the high density master batch form in thermoplastics of metered amounts, and wherein thermoplastics preferably is selected from as component A) thermoplastics that uses.Carbon black and/or the graphite concentration in masterbatch is between 5～70, and is preferred 8～50, in especially preferred 12～30wt% scope, for masterbatch.Carbon black and/or graphite, the purpose in order to measure better also can join binding agent, for example, in wax, fatty acid ester or the polyolefine.They also can be cut into slices or granulation, can add or not add additional binding agent, and for example, by the method for compression moulding or compacting, this equally also can play the purpose of metering better.
Generally have the form of pipe according to carbon nanometer microfilament of the present invention, constitute by graphite linings.Graphite linings disposes round the axis of cylinder with one heart.
The length-to-diameter ratio of carbon nanometer microfilament is 5 at least, preferably is 100 at least, especially preferably is 1000 at least.The diameter of nanometer microfilament is usually between the scope of 0.003 μ m～0.5 μ m, preferably at 0.005 μ m～0.08 mu m range, especially preferably in 0.006 μ m～0.05 mu m range.The length of carbon nanometer microfilament is generally at 0.5 μ m～1000 μ m, preferred 0.8 μ m～100 μ m, especially preferred 1 μ m～10 μ m.Carbon nanometer microfilament has hollow cylindrical wick, is twining graphite linings around it in form.This kind hollow space generally has the diameter of 0.001 μ m～0.1 μ m, the diameter of preferred 0.008 μ m～0.015 μ m.In the embodiment of typical carbon nanometer microfilament, around the microfilament wall of hollow space by, for example, 8 graphite linings are formed.Carbon nanometer microfilament, in such cases, can be with the highest 1000 μ m of diameter, the aggregate form of the preferred the highest 500 μ m of diameter exists, and is made up of some nanometer microfilaments.This aggregate can have the form of Bird's Nest, heckling yarn or lax web frame.
The adding of carbon nanometer microfilament can generate component A at monomer polymerization) thermoplastics before, during or implement later on.If the polymerization that is added in of carbon nanometer microfilament is implemented later on, then preferably implement by joining in the thermoplastic melt in extruding machine or kneader.Because the result of mixing processing in kneader or extruding machine, aggregate particularly described above will be pulverized basically or fully equably, so carbon nanometer microfilament can be dispersed in the thermoplastic matrix.
In preferred embodiments, carbon nanometer microfilament adds with the high density master batch form in thermoplastics of metered amounts, and wherein thermoplastics preferably is selected from as component A) thermoplastics that uses.The concentration of carbon nanometer microfilament in masterbatch is between 5～50, and is preferred 8～30, in especially preferred 12～22wt% scope, for masterbatch.The production of masterbatch for example, at US-A 5,643, is described in 502.Pulverizing by the employing of masterbatch, particularly aggregate can improve.Owing to will be processed into moulding compound or moulded parts, carbon nanometer microfilament can show as the shorter length distribution in moulding compound or the original employing of ratio in moulded parts.
In preferred embodiments, also can adopt the mixture of each component.
According to conductive carbon black of the present invention, for example, can be according to trade(brand)name Ketjenblack  from FaA KZO Nobel, with trade(brand)name Vulcan  from Fa Cabot, perhaps with trade(brand)name Printex Buy from Fa Degussa.
Can form of powder buy according to graphite of the present invention, for example, from Fa Vogel﹠amp; Prenner Nachf., Wiesbaden, Germany buys.
Carbon nanometer microfilament can from, for example, Fa Hyperion Catalysis or buy from FaApplied Sciences company.The synthesis example of carbon nanometer microfilament as, can be in the reactor that carbonaceous gas and metal catalyst are housed according to, for example, US-A 5,643, those that describe in 502 are implemented.
Component E
Thermoplastic polymer with polar group is preferably as according to component E) compatible promotor use.
According to the present invention, can adopt the polymkeric substance that comprises following ingredients:
E.1 vi-ny l aromatic monomers,
E.2 at least a monomer is selected from methacrylic acid C 2～C 12Alkyl ester, vinylformic acid C 2～C 12Alkyl ester, methacrylonitrile and vinyl cyanide, and
E.3 the α that contains dicarboxylic anhydride, β-unsaturated component.
Vinylbenzene especially preferably as vi-ny l aromatic monomers E.1; Vinyl cyanide especially preferably as component E.2; Maleic anhydride is preferred especially as the α that contains dicarboxylic anhydride, and β-unsaturated component E.3.
E.1, E.2 and E.3 described monomeric terpolymer preferably is used as component.So, preferably use the terpolymer of vinylbenzene, vinyl cyanide and maleic anhydride.These terpolymers especially contribute for improving mechanical property such as tensile strength and extension at break.The content of the maleic anhydride in the terpolymer can fluctuate in wide region.This content is preferably between 0.2～5mol%.Especially preferred content between 0.5～1.5mol%.In this scope, will obtain in mechanical property good especially aspect tensile strength and the extension at break.
Terpolymer can prepare according to known mode itself.A kind of suitable method is that with the monomer component of terpolymer, for example, vinylbenzene, maleic anhydride or vinyl cyanide are dissolved in appropriate solvent such as the butanone (MEK).In this solution, add a kind of or, randomly, the number of chemical initiator.Suitable initiator for example is a superoxide.Subsequently, mixture is at the high temperature polymerization several hrs.Shift out solvent and unreacted monomer according to known mode own subsequently.
Component E.1 (vi-ny l aromatic monomers) and component E.2, for example, acrylonitrile monemer, the ratio in terpolymer is preferably between 80: 20～50: 50.In order to improve the compatibility of terpolymer and graft copolymer B, vi-ny l aromatic monomers consumption E.1 preferably is chosen as corresponding to the consumption B.1 of the vinyl monomer among the graft copolymer B.
The example that can be used for compatible promotor E of the present invention is described among EP-A 785 234 and the EP-A202 214.According to the polymkeric substance of enumerating among the especially preferred EP-A 785 234 of the present invention.
Compatible promotor can also can any mixture form each other exist separately in component E.
Another kind of is vinylbenzene and vinyl cyanide according to 2.1: 1 weight ratio as the material of compatible promotor especially preferably, contains the terpolymer of 1mol% maleic anhydride in addition.
The content of component E is preferably between 0.5～30 weight part in the polymer composition of the present invention, 1～20 weight part particularly, especially preferred 2～10 weight parts.Most preferred content is between 3～7 weight parts.
Component F
Component F comprises one or more thermoplastic ethylene's base (being total to) polymkeric substance.
Suitable vinyl (being total to) polymkeric substance is at least a following polymer of monomers that is selected from: vinyl-arene, vinyl cyanide (unsaturated nitrile), (methyl) vinylformic acid (C 1～C 8) derivative (for example, acid anhydrides and imide) of alkyl ester, unsaturated carboxylic acid and unsaturated carboxylic acid.Specially suitable by following monomer generation (being total to) polymkeric substance:
F.1 50～99, preferred 60～80 parts by weight of ethylene base aromatic hydrocarbons and/or nuclear substituted vinyl-arene (for example, vinylbenzene, alpha-methyl styrene, p-methylstyrene, to chloro-styrene) and/or methacrylic acid (C 1～C 8) alkyl ester (for example, methyl methacrylate, Jia Jibingxisuanyizhi), and
F.2 1～50, preferred 20～40 parts by weight of ethylene base cyanogen (unsaturated nitrile) for example, vinyl cyanide and methacrylonitrile and/or (methyl) vinylformic acid (C 1～C 8) imide (for example, N-phenylmaleimide) of alkyl ester (for example, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and/or unsaturated carboxylic acid.
(being total to) polymkeric substance F is arborescens, thermoplasticity and does not contain rubber.
Especially preferably by F.1 vinylbenzene and the F.2 multipolymer of vinyl cyanide generation.
(being total to) polymkeric substance F is known and can prepares according to radical polymerization, particularly by emulsion, suspension, solution or mass polymerization.(being total to) polymkeric substance preferably has 15,000～200,000 average molecular weight Mw (weight average adopts scattering of light or settling process to measure).
Vinyl (being total to) polymkeric substance can separately or can any mixture form each other be present among the component F.
The content of component F in polymer composition is preferably between 0～30 weight part, 0～25 weight part particularly, especially preferred 0～20 weight part, particularly 0～10 weight part.
Component G
Can contain conventional additive according to polymer composition of the present invention, for example, flame-proofness, dripping inhibitor, lubricant, releasing agent, nucleator, static inhibitor, stablizer, filler and be different from the strongthener of component C, and dyestuff and pigment, and hydrophobizing agent, for example, resol.
The present composition generally can also have 0.01～20 weight part, for whole composition, and flame-proofness.The fire retardant that can enumerate is an organohalogen compound as an example, for example, decabromodiphynly oxide, tetrabromobisphenol, inorganic halogen compounds such as brometo de amonio, nitrogen compound such as trimeric cyanamide, melamino-formaldehyde resin, inorganic hydroxide such as hydroxide Mg-Al, mineral compound such as aluminum oxide, titanium dioxide, weisspiessglanz, barium metaborate, six hydrogen stibnates (Hydroxoantimonat), zirconium white, zirconium hydroxide, molybdenum oxide, ammonium molybdate, boric acid tin, ammonium borate and stannic oxide and silicone compounds.
As flame-retardant compound, also can adopt phosphorus compound, as be described in EP-A 363 608, EP-A 345 522 and/or EP-A 640 655.
As further filler and strongthener, can consider to be different from component C) those.Suitable, for example, be glass fibre, randomly cut off or ground granulated glass sphere, glass envelope, silicate, quartz and titanium dioxide or its mixture.Cut-out or ground glass fibre preferably are used as strongthener.
Suitable hydrophobizing agent for example is a resol, they are by phenols and aldehydes, the condensation reaction of preferred formaldehyde, the deriving or prepare by phenols is added on unsaturated compound such as acetylene, the terpenes etc. of the condenses by generation like this.In this kind situation, condensation can be implemented in acidity or alkaline range, and aldehyde can be between 1: 0.4～1: 2.0 to the mol ratio of phenol.In this method, generate oligopolymer or the polymkeric substance of molar mass between 150～5000g/mol.This moulding compound preferably contains resol, and its add-on is generally the highest by 15, and is preferred 1～12, particularly 2～8 weight parts.
In this application, all weight part sums that relate to that the data of weight part all should be normalized to whole components are 100 weight parts.
The present composition is to mix to be incorporated in conventional apparatus such as Banbury mixer, extruding machine and the Bitruder at 200～300 ℃ temperature melting mixing and to melt extrude according to known mode by each component to make, and wherein adopts the releasing agent of congealed mixt form.
The mixing of each component can or side by side be implemented in about 20 ℃ (room temperatures) with at comparatively high temps according to known mode order.
Polymer composition of the present invention can be used for producing any kind mo(u)lded item.Specifically, mo(u)lded item can adopt injection moulding production.The example of mo(u)lded item is: the casing part of any kind, for example, household electrical appliance such as electric shaver, flat screens, indicating meter, printer, duplicating machine, the perhaps panel used of building industry, and motor vehicle and rail vehicle part.In addition, they can be used for the electric works field, because they have extraordinary electric property.
Moreover polymer composition of the present invention for example can be used for producing the purpose of following mo(u)lded item:
The interior finish part of rail vehicle, boats and ships, motorbus, other motor vehicle and aircraft, lid wheel, the electric installation shell of small transformers is housed, the shell with instrument is propagated and transmitted to information, dull and stereotyped wall-element, security device shell, afterbody interceptor and other body of a motor car part, thermal isolation transport container, keep and feed the device, ventilation opening double-edged fine-toothed comb, villa of animalcule and instrument shed with mo(u)lded item and, the gardening instrument outer shell.
Another kind of form processing is to produce mo(u)lded item by sheet material or the film produced in advance by thermoforming.
Therefore, the present invention also provides the present composition producing any kind mo(u)lded item, the application of preferred those aspects above-mentioned, and the mo(u)lded item that is made of the present composition.
Because excellent online spraying paint property, the present invention also provides the online mo(u)lded item that sprays paint, the preferred online automobile external part that sprays paint, for example, wheel cover cap, the wing, rear vision mirror shell etc.
Following example is used to further specify the present invention.
Embodiment
Example
According to the data of table 1, produce composition, and further be processed into sample and test.
Component A1
Polyamide 66 (Ultramid A3, BASF, Ludwigshafen, Germany).
Component A2
Noryl GTX974, General Electric's Plastics Company, Bergen op Zoomen, Holland.
B component
Graftomer, by 40 weight parts by vinylbenzene and vinyl cyanide according to the multipolymer of 73: 27 ratios, be grafted on granular, the crosslinked polybutadiene rubber of 60 weight parts (average particulate diameter d 50=0.28 μ m) goes up composition, adopt letex polymerization production.
Component C
Naintsch A3 (Naintsch Mineralwerke company, Graz, Austria).
Talcum powder, average particulate diameter (d 50), according to manufacturers's data, 1.2 μ m.
Component D
Ketjenblack EC 600 (Akzo Nobel, Verkaufsb ü ro D ü ren, 52349D ü ren, Germany) (conductive carbon black).
Component E
Terpolymer contains the 1mol% maleic anhydride by vinylbenzene and vinyl cyanide in addition according to 2.1: 1 weight ratio and forms.
Component F
Styrene/acrylonitrile copolymer, wherein the styrene/acrylonitrile weight ratio is 72: 28, limiting viscosity 0.55d1/g (in dimethyl formamide 20 ℃ of mensuration).
Component G
About additive G.1 and G.2, referring to table 1.
G.3:Rhenosin RB (resol), Rhein chemistry Rheinau company, Mannheim.
The production of moulding compound of the present invention and test
The mixing of all components of composition adopts the 3L Banbury mixer to implement.Moulded parts at the injection moulding machine of model Arburg 280E 260 ℃ of productions.
The mensuration of HDT thermostability is implemented according to ISO R 75.
The mensuration (10 of the coefficient of expansion along its length -4* K -1) implement according to ASTM E 831.
Be to determine range estimation (optical) shrinkage determination value, injection moulding the sheet material of a kind of 60 * 60 * 2mm, temperature of charge is 280 ℃ during the injection moulding, pressure 500bar, 80 ℃ of die temperatures.Subsequently, measure sheet material vertical and horizontal size immediately,, and then measure then at 80 ℃ of annealing 1h.The difference of this length measurment is shunk with length and the percentage of shrinkage in width is represented.Repeat this program 5 times, and record mean value.
The result of each test sums up in table 1.
Table 1
Example/component Comparative Examples 1 2
A1 Polyamide 66 60.09
A2 Noryl GTX 974 100
B Graftomer 18.28
C Talcum powder 3.93
D Carbon black 3.93
E Compatible promotor 4.71
F Styrene/acrylonitrile copolymer 2.59
G1 Releasing agent 0.24
G2 Stablizer 1.29
H Resol 4.91
Performance
Young's modulus [MPa] 2200 3100
HDT B [℃] 167 170
Shrink [％] 1.3 1.16
Thermal expansivity 1) 10 -4/K 0.99/ 0.88/0.96
The surface i.O. 2) i.O
Surface resistivity 3) [Ω] 2.5 E+8 3.8 E+7
1)Vertically/laterally
2)I.O.=OK (A level)
3)According to DIN IEC 60 167
Varnish coating quality in ESTA (static) spray-painting plant is assessed to example 1 of the present invention and Comparative Examples 1, wherein limit of error in 11 μ m the person because equally matched with steel plate, so i.O. (OK).
Under same varnish coating quality situation, moulding compound of the present invention shows obviously higher deflection (Young's modulus), better shrinks performance and better thermal expansivity.

Claims (14)

1. improved daiamid composition of shock strength, it comprises:
(A) 40～90 weight parts of polyamide;
(B) 0.5～50 weight part graftomer; Described graftomer is at least a following monomeric graftomer that is selected from:
B.1.1 vinylbenzene, alpha-methyl styrene, halogen replace or alkyl-nuclear substituted vinylbenzene, (methyl) vinylformic acid C 1～C 8Alkyl ester and
B.1.2 unsaturated nitrile, (methyl) vinylformic acid C 1～C 8The derivative of alkyl ester and unsaturated carboxylic acid is grafted on
Second-order transition temperature is less than or equal on 10 ℃ the grafting basis;
(C) 0.1～30 weight part mineral grain;
(D) 0.1～8 weight part conductive carbon particle.
2. the composition of claim 1 contains another kind of at least component, and it is selected from compatible promotor, vinyl (being total to) polymkeric substance, polymeric additive and resol.
3. the composition of claim 1, it contains one or more graftomer, is less than or equal at least a second-order transition temperature by at least a vinyl monomer on 10 ℃ the grafting basis to form.
4. the composition of claim 3, wherein the grafting basis is selected from least a rubber, and the latter belongs to a kind of in the middle of multipolymer, acrylic elastomer, urethane/silicon rubber, chloroprene rubber and the ethylene/vinyl acetate rubber of elastoprene, elastoprene.
5. the composition of claim 3, wherein the grafting basis is selected from least a rubber of being made up of the multipolymer and the acrylic elastomer of elastoprene, elastoprene, and except the ethylene/propylene rubber.
6. the composition of claim 4, wherein the grafting basis is a polyhutadiene.
7. the composition of claim 1, wherein conductive carbon particle is selected from the middle of carbon black, graphite and the carbon nanometer microfilament at least a.
8. the composition of claim 1, wherein mineral grain is selected from talcum powder, mica, clay-ore discharge thing, montmorillonite, at least a in the middle of kaolin, vermiculite, the wollastonite.
9. the composition of claim 8, it contains talcum powder.
10. the composition of claim 1, it contains 1～12 weight part resol.
11. the composition of claim 1 contains the multipolymer that is made of following monomer:
E.1 vi-ny l aromatic monomers,
E.2 at least a methacrylic acid C that is selected from 2～C 12Alkyl ester, vinylformic acid C 2～C 12The monomer of alkyl ester, vinyl cyanide and methacrylonitrile, and
E.3 at least a α that contains dicarboxylic anhydride, β-unsaturated component.
12. the composition of claim 1 is used to produce the application of mo(u)lded item.
13. the mo(u)lded item that can produce by the composition of claim 1.
14. the online Painting mould plastic that can produce by the composition of claim 1.
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