EP1525263A1

EP1525263A1 - Polymer blend based on polyamide

Info

Publication number: EP1525263A1
Application number: EP03740451A
Authority: EP
Inventors: Marc Vathauer; Detlev Joachimi
Original assignee: Lanxess Deutschland GmbH
Current assignee: Lanxess Deutschland GmbH
Priority date: 2002-07-22
Filing date: 2003-07-10
Publication date: 2005-04-27
Also published as: CN100537664C; CN1685012A; AU2003281478A1; KR20060052645A; KR100958477B1; DE10233170A1; US20040063857A1; WO2004009706A1; CA2493266A1; TW200413470A; JP2005533886A; MXPA05000934A

Abstract

The invention relates to compositions containing: A) 40 to 90 parts by weight of polyamide; B) 0.5 to 50 parts by weight of impact-resistance modifiers; C) 0 to 50 parts by weight of fillers and reinforcing substances, and; D) 0.1 to 15 parts by weight of phenol-formaldehyde resin or of an oligomeric or polymeric compound, which is different from phenol-formaldehyde resins and which has at least two phenolic hydroxyl groups, whereby the sum of the parts by weight of all constituents equals 100.

Description

Polymer balls based on polyamide

The present invention relates to compositions based on impact-modified polyamide compositions and moldings produced therefrom.

A great advantage of impact-modified polyamide molding compounds is their excellent chemical resistance and high heat resistance. These molding compositions, in particular those based on aliphatic polyamides such as e.g. PA 66 and PA 6 are therefore suitable, among other things. for use in exterior parts of the body.

Another important property is the dimensional stability of the molded part. The water absorption of the polyamide, which leads to a change in the properties of the plastic, in particular the dimensional stability, is perceived as disturbing here. There are polyamides that absorb little or no water (PAH, PA12, partially aromatic copolyamides), but these have too low a heat resistance, are sometimes too brittle and in any case more expensive than PA 6 and PA 66.

In order to reduce the moisture absorption of aliphatic polyamides such as polyamide 6 and 66 or corresponding copolyamides in thermoplastic molding compositions, a hydrophobicizing agent is often added.

US Pat. No. 5,670,576 describes a blend of polyphenylene ether (PPE) and polyamide, which is equipped with a phenol novolak resin in order to reduce water absorption. In addition, the good flame retardancy of the claimed molding composition is mentioned in this document, no statement is made about thermal expansion coefficients. US Pat. No. 4,970,272 describes a polyamide-PPE blend to which a phenolic hydrophobicizing agent is added. Low water absorption is described with consistently good mechanical properties.

No. 4,849,474 describes a polyamide which is provided with a phenolic additive and has a lower water absorption. Phenol-formaldehyde resins are not mentioned.

EP-A 0 240 887 describes molding compositions made of polyamide, a rubber and a bisphenol, which show an improved flowability caused by the additive.

DE-A 32 48 329 describes the addition of phenolic compounds to polyamide to reduce water absorption. Phenol-formaldehyde resins are not mentioned.

The object of the present invention was to provide polyamide molding compositions which have low water absorption, low thermal expansion and low processing shrinkage. In addition, the reduction in the modulus of elasticity when absorbing water should be as small as possible. The invention

Compositions have the desired properties.

The invention therefore relates to polymer compositions comprising

(A) 40 to 90, preferably 45 to 85, particularly preferably 45 to 75 parts by weight

polyamide

(B) 0.5 to 50, preferably 1 to 30, particularly preferably 1 to 25, in particular 4 to 25 parts by weight of impact modifier (C) 0 to 50 parts by weight, preferably 7 to 40, in particular 10 to 35 parts by weight of fillers and reinforcing materials and

(D) 0.1 to 15, preferably 1 to 12, particularly preferably 2 to 8 parts by weight of phenol-formaldehyde resin or an oligomeric or polymeric compound other than phenol-formaldehyde resins with at least 2 phenolic OH groups.

The compositions according to the invention can furthermore

(E) compatibility agent and / or

(F) vinyl (co) polymer

contain.

It was found that a plastic with the above composition shows a lower water absorption than a composition without component (D) and, compared to other hydrophobizing agents, has a significantly lower coefficient of thermal expansion, a lower processing shrinkage and a higher modulus in the conditioned state.

Component A

Polyamides suitable according to the invention are known homopolyamides, copolyamides and mixtures of these polyamides. These can be partially crystalline and / or amorphous polyamides. Polyamide-6, polyamide-6,6, mixtures and corresponding copolymers of these components are suitable as partially crystalline polyamides. Also suitable are partially crystalline polyamides, the acid components of which are wholly or partly composed of terephthalic acid and / or isophthalic acid and / or

Suberic acid and / or sebacic acid and / or azelaic acid and / or adipic acid and / or cyclohexanedicarboxylic acid, the diamine component of which consists wholly or partly of m- and / or p-xylylene diamine and / or hexamethylene diamine and / or 2,2,4-trimethylhexamethylene diamine and or 2,4,4-trimethylhexamethylene diamine and / or isophorone diamine and whose composition is known in principle.

Also to be mentioned are polyamides which are wholly or partly prepared from lactams with 7 to 12 carbon atoms in the ring, optionally with the use of one or more of the above-mentioned starting components.

Particularly preferred partially crystalline polyamides are polyamide 6 and polyamide 6,6 and their mixtures. Known products can be used as amorphous polyamides. They are obtained by polycondensation of diamines such as ethylene diamine, hexamethylene diamine, decamethylene diamine, 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine, m- and / or p-xylylene diamine, bis- (4th -aminocyclo-hexyij-methane, bis- (4-aminocyclohexyl) propane, 3,3'-dimethyl-4,4'-diamino-di-cyclohexyl-methane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 2 , 5- and or 2,6-bis (aminomethyl) norbornane and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid, decanedicarboxylic acid, hepta-decanedicarboxylic acid, 2,2,4- and / or 2,4,4-trimethyladipic acid, isophthalic acid and

Terephthalic acid.

Copolymers which are obtained by polycondensation of several monomers are also suitable, as are copolymers which are prepared with the addition of ammocarboxylic acids such as ε-aminocaproic acid, ω-ammoundecanoic acid or ω-aminolauric acid or their lactams.

Particularly suitable amorphous polyamides are the polyamides prepared from isophthalic acid, hexamethylene diamine and other diamines such as 4,4-diaminodicyclohexyl methane, isophorone diamine, 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine, 2,5- and / or 2,6-bis (aminomethyl) norbornene; or from isophthalic acid, 4,4'- Diamino-dicyclohexylmethane and caprolactam; or from isophthalic acid, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane and laurolactam; or from terephthalic acid and the mixture of isomers of 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine.

Instead of the pure 4,4'-diaminodicyclohexylmethane, it is also possible to use mixtures of the positional isomers diamine dicyclohexalmethane, which are composed of

70 to 99 mol% of the 4,4'-diamino isomer

1 to 30 mol% of the 2,4'-diamino isomer

0 to 2 mol% of the 2,2'-diamino isomer

if appropriate, correspondingly more highly condensed diamines obtained by hydrogenating technical-grade diaminodiphenylmethane. Up to 30% of the isophthalic acid can be replaced by terephthalic acid.

The polyamides can be used alone or in any mixture.

The polyamides preferably have a relative viscosity (measured on a 1% strength by weight solution in m-cresol at 25 ° C.) from 2.0 to 5.0, particularly preferably from 2.5 to 4.0.

Component B

As component B one or more components e.g. Copolymers and / or graft polymers are used. In the case of graft polymers, these are preferably graft polymers of

Bl 5 to 95, preferably 30 to 90 wt .-%, of at least one vinyl monomer B.2 95 to 5, preferably 70 to 10% by weight of one or more graft bases with glass transition temperatures <10 ° C, preferably <0 ° C, particularly preferably <-20 ° C.

The graft base B.2 (d ₅ o value) microns generally have an average particle size of 0.05 to 5, preferably from 0.10 to 2 microns, particularly preferably 0.20 to 1 micron, especially 0.2 to 0 5 μm.

Monomers B.l are preferably mixtures of

Bll 50 to 99 wt .-% vinyl aromatics and / or core-substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters (such as eg methyl methacrylate, ethyl methacrylate) and

Bl2 1 to 50 wt .-% vinyl cyanide (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters (such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate) and / or Derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (e.g. maleic anhydride and N-phenyl-maleimide).

Preferred monomers B.l.l are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, preferred monomers B.l.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.

Particularly preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile.

Examples of graft bases B.2 suitable for the graft polymers B are

Diene rubbers, EP (D) M rubbers, i.e. those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.

Preferred graft bases B.2 are diene rubbers. Diene rubbers for the purposes of the present invention include diene rubbers, e.g. based on butadiene, isoprene etc., or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to B1 and B1), preferably butadiene-styrene copolymers, with the proviso that the glass transition temperature of component B. 2 is below <10 ° C, preferably <0 ° C, particularly preferably <-10 ° C.

Pure polybutadiene rubber is particularly preferred.

Particularly preferred polymers B are e.g. ABS polymers (emulsion, bulk and suspension ABS), such as z. B. in DE-OS 2 035 390 (= US-PS

3 644 574) or in DE-OS 2 248 242 (= GB-PS 1 409 275) or in Ulimann, Encyclopedia of Technical Chemistry, Vol. 19 (1980), p. 280 ff. The gel fraction of the graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).

The graft copolymers B are obtained by radical polymerization, e.g. prepared by emulsion, suspension, solution or bulk polymerization, preferably by emulsion polymerization or bulk polymerization.

Particularly suitable graft rubbers are also ABS polymers that pass through

Redox initiation with an initiator system made of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.

Since, as is known, in the graft reaction the graft monomers are not necessarily grafted completely onto the graft base, according to the invention,

Graft polymers B also understood those products which are (co) polymer tion of the graft monomers can be obtained in the presence of the graft base and are obtained during the workup.

Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers made from acrylic acid alkyl esters, optionally with up to 40% by weight, based on B.2, of other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include -CC ₈ alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably Haiogen C 1 -C ₈ alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.

Monomers with more than one polymerizable double bond can be copolymerized for crosslinking. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH

Groups and 2 to 20 carbon atoms, e.g. Ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, e.g. Trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes. The amount of the crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight, based on the graft base B.2. In the case of cyclic crosslinking monomers with at least 3 ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base B.2.

Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to prepare the graft base B.2 are, for. B. acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl-C C _o -alkyl ether, methyl methacrylate, butadiene. Preferred acrylate rubbers as graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.

Further suitable graft bases according to B.2 are silicone rubbers with graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.

The gel content of the graft base B.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and π, Georg Thieme-Verlag, Stuttgart 1977).

The average particle size d ₅₀ is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).

Further rubber-elastic polymers that are suitable for B are presented below.

Such polymers are described, for example, in Houben-Weyl, Methods of Organic Chemistry, Vol. 14/1 (Georg-Thime-Verlag, Stuttgart, 1961). Pages 392 to 406 and in the monograph by CB Bucknall, "Toughened Plastics" (Applied Science Publishers, London, 1977). Preferred elastomers are the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers.

EPM rubbers generally have practically no more double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.

Examples of diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-l, 4-diene, hexa-l, 4-diene, hexa- 1,5 -diene, 2,5-dimethylhexa-l, 5-diene and -octa-

1,4-dienes, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and alkenylnorbornenes such as 5-ethylened-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5 -norbornene and tricyclo-dienes such as 3-methyl-tricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof. Hexa-l, 5-diene, 5-ethylidene norbornene and dicyclopentadiene are preferred. The diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8,% by weight, based on the total weight of the rubber.

EPM or EPDM rubber pads can preferably also be grafted with reactive carboxylic acids or their derivatives. Here are e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as maleic anhydride.

Component C

As filler and reinforcing materials, for example glass fibers, optionally cut or ground, can contain glass beads, glass balls, flake-like reinforcing materials such as kaolin, talc, mica, silicates, quartz, talc, titanium dioxide, wool astonite, mica, carbon fibers or a mixture thereof. Cut or ground glass fibers are preferably used as the reinforcing material. Preferred fillers, which can also have a reinforcing effect, are glass balls, mica, Silicates, quartz, talc, titanium dioxide, wollastonite and kaolin. Kaolin, talc and wollastonite are particularly preferred.

Component D

Resins suitable according to the invention are known or can be prepared by processes known from the literature.

Resins according to the invention are obtained by condensation reaction from phenols with aldehydes, preferably formaldehyde, by derivatization of the resultant

Condensates or by adding phenols to unsaturated compounds, e.g. Acetylene, terpenes etc. produced.

The condensation can be acidic or basic and the molar ratio of aldehyde to phenol can be from 1: 0.4 to 1: 2.0. Here, oligomers or

Polymers with a molecular weight of generally 150-5000 g / mol.

Component E

Thermoplastic polymers with polar groups are preferably suitable as compatibilizers E).

According to the invention, preference is given to using polymers which

E.l a vinyl aromatic monomer,

E.2 at least one monomer selected from the group C2 to C ₁₂ alkyl methacrylates, C ₂ to C ^ alkyl acrylates, methacrylonitriles and acrylonitriles and

E.3 α-, β-unsaturated components containing dicarboxylic anhydrides

contain. Styrene is particularly preferred as vinyl aromatic monomers E.1.

Acrylonitrile is particularly preferred for component E.2.

Maleic anhydride is particularly preferred for α-, β-unsaturated components containing dicarboxylic anhydrides E.3.

Terpolymers of the monomers mentioned are preferably used as component E.l, E.2 and E.3. Accordingly, terpolymers of styrene preferably

Acrylonitrile and maleic anhydride are used. These terpolymers contribute in particular to improving the mechanical properties, such as tensile strength and weather stability. The amount of maleic anhydride in the terpolymer can vary within wide limits. The amount is preferably 0.2-5 mol%. Amounts between 0.5 and 1.5 mol% in the component are particularly preferred

E.l included. Particularly good mechanical properties with regard to tensile strength and weather stability are achieved in this area.

The terpolymer can be prepared in a conventional manner. A suitable method is to dissolve the monomer components of the terpolymer, e.g. of styrene,

Maleic anhydride or acrylonitrile in a suitable solvent, e.g. Mefethyl ethyl ketone (MEK). One or optionally several chemical initiators are added to this solution. Suitable initiators are e.g. Peroxides. The mixture is then polymerized at elevated temperature for several hours. The solvent and the unreacted monomers are then removed in a manner known per se.

The ratio between the component E.l (vinyl aromatic monomer) and the

Component E.2, e.g. the acrylonitrile monomer in the terpolymer is preferably between 80:20 and 50:50. To determine the miscibility of the terpolymer with

To improve graft copolymer B is preferably a lot of vinyl flavor table monomer El selected, which corresponds to the amount of the vinyl monomer Bl in the graft copolymer B.

The amount of component E in the polymer blends according to the invention is between 0.5 and 50 parts by weight, preferably between 1 and 30 parts by weight, particularly preferably between 2 and 10 parts by weight. Amounts between 3 and 7 parts by weight are most preferred.

Such polymers are described for example in EP-A-785 234 and EP-A-202 214. According to the invention, particular preference is given to the polymers mentioned in EP-A-202 214.

Component F

Component F comprises one or more thermoplastic vinyl (co) polymers.

Suitable as vinyl (co) polymers are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles) and (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters. (Co) polymers of are particularly suitable

Fl 50 to 99, preferably 60 to 80 wt .-% vinyl aromatics and / or nucleus-substituted vinyl aromatics such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C ₁ -C ₈ ) alkyl esters such as eg methyl methacrylate, ethyl methacrylate), and

F.2 1 to 50, preferably 20 to 40 wt .-% of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile, and / or (meth) acrylic acid _{_(Cι-C8).} - alkyl esters (such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate). The (co) polymers F are resin-like, thermoplastic and rubber-free.

The copolymer of F.l styrene and F.2 acrylonitrile is particularly preferred.

The (co) polymers according to F are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) polymers preferably have molecular weights M _w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.

The amount of (co) polymers according to component F in the polymer blend according to the invention is generally up to 30 parts by weight, preferably up to 20 parts by weight, in particular up to 10 parts by weight.

Component G

The polymer blends according to the invention can contain conventional additives, such as flame retardants, anti-dripping agents, very finely divided inorganic compounds other than component C), lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers, dyes and pigments.

The polymer blends according to the invention can generally contain 0.01 to 20% by weight, based on the total molding composition, of flame retardants. Examples of flame retardants are organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds such as Mg-alhydroxide, inorganic compounds such as aluminum oxides, titanium dioxide, antimony oxides, barium metaborate, hydroxoantimonate , Zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, tin borate, ammonium borate, barium metaborate and tin oxide as well as siloxane compounds. Furthermore, phosphorus compounds as described in EP-A-363 608, EP-A-345 522 or EP-A-640 655 can be used as flame retardant compounds.

All parts by weight in this application are standardized so that the sum of the parts by weight of all components in the composition is 100.

The molding compositions according to the invention containing components A) to F) and optionally other known additives such as stabilizers, dyes,

Pigments, lubricants and mold release agents, nucleating agents and antistatic agents are produced by mixing the respective components in a known manner and melt compounding and melt extruding at temperatures of 200 ° C to 300 ° C in conventional units such as internal kneaders, extruders and twin-screw screws.

The individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.

The polymer blends of the present invention can be used to produce moldings or moldings of any type. In particular, moldings can be produced by injection molding. Examples of moldings that can be produced are: Housing parts of all types, e.g. for household appliances, such as juicers, coffee machines, mixers, for office machines, such as computers, printers, monitors or cover plates for the construction sector and parts for the motor vehicle sector.

The polymer blends are particularly suitable for the production of molded parts to which particularly high demands are made with regard to heat resistance, tensile strength and stress crack resistance. The use of the polymer blends for the production of moldings and the moldings obtainable therefrom are also the subject of the present invention.

The invention is explained in more detail below with the aid of a few examples:

Examples

Components used:

AI: polyamide 6.6 (Ultramid® A3, BASF AG, Ludwigshafen, Germany)

A2: copolyamide from caprolactam and AH salt with a resulting total content of PA-66 units of 4 to 6% by weight, ηrel of 2.8 to 3.1, measured on a 1% by weight solution in ml Cresol at 25 ° C

A3: polyamide 6: Durethan B35F, Bayer AG ηrel from 3.5 to 3.7, measured on a 1% strength by weight solution in m-cresol at 25 ° C.

Bl: Pfiropφolymerisat of 40 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 73:27 to 60 parts by weight of particulate crosslinked polybutadiene rubber (average particle diameter d50 = 0.3 μm), produced by emulsion polymerization

B2: Exxelor® VA 1803, ExxonMobil (ethylene propylene / maleic anhydride rubber)

CI: Naintsch A3 (Naintsch Mineralwerke GmbH, Graz, Austria), talc with an average particle diameter (d ₅₀ ) according to the manufacturer's specification of 1.2 μ

C2: kaolin (Polarite 102A, Imerys Minerals Ltd., England, calcined and silanized kaolinite)

DI: Rhenosine RB (phenol-formaldehyde resin), Rhein Chemie Rheinau GmbH, Mannheim

D2: Bisphenol A, Bayer AG Contracting agent: terpolymer of styrene and acrylonitrile (weight ratio 2.1: 1) containing 1 mol% of maleic anhydride

Styrene / acrylonitrile copolymer with a styrene / acrylonitrile weight ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g (measurement in dimethylformamide at 20 ° C)

Gl: mold release agent

G2: Irganox® 1076, Ciba Specialties, Basel, Switzerland

G3: Irganox® P 5802, Ciba Specialties

G4: Montan ester wax (Licowax® E Fl, Clariant GmbH)

G5: Irganox 1098 (12.5% in PA 66), Ciba Specialties

G6: Irganox 1098 (10% in PA 6), Ciba Specialties

G7: Soot masterbatch UN 2014 (50% masterbatch in Poiyolefm) from Colloids

The polymer blends according to the invention are produced by mixing the respective constituents in a known manner and melt-compounding or melt-extruding them at temperatures of 200 to 300 ° C. in conventional units, such as kneaders, extruders and twin-screw screws.

The individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at an elevated temperature. The specified modulus of elasticity was determined in a three-point bending test on 80x10x4 mm ³ test specimens. The shrinkage measurement was carried out on rectangular plates with the dimensions 150x105x3 mm ³ , which were sprayed with a holding pressure of 500 bar at a mold temperature of 80 ° C.

Table 1

* measured at: 23 ° C-55 ° C

It is clear from the data in Table 1 that the use of the hydrophobicizing reagent D1 has advantages over a formulation with the same constituents (% by weight) of D2 in relation to the modulus of elasticity in a conditioned state as well as in the linear thermal expansion coefficient.

Compared to a molding compound without a hydrophobicizing reagent, the water absorption during conditioning according to ISO 1110 is reduced. Furthermore, test 1 also shows a higher modulus of elasticity in the conditioned state compared to test V2. Furthermore, both experiment 1 and experiment VI show an improved expansion coefficient compared to experiment V2. Table 2

# measured at: -20 ° C - 23 ° C

The data in Table 2 demonstrate that the composition 2 according to the invention, containing hydrophobicizing agent D1, has clear advantages in terms of modulus of elasticity in the conditioned state, expansion coefficient and processing shrinkage compared to V3, containing hydrophobicizing agent D2. Table 3

# measured at: -20 ° C - 23 ° C

The data in Table 3 show that the composition 3 according to the invention, containing hydrophobicizing agent D1, has clear advantages in terms of modulus of elasticity in the conditioned state, expansion coefficient and processing shrinkage compared to V3, containing hydrophobicizing agent D2. Table 4

# measured at: -20 ° C - 23 ° C V = comparison

The data in Table 4 show that the composition 4 according to the invention, containing hydrophobicizing agent D1, has clear advantages in terms of expansion coefficient and processing shrinkage compared to V5, containing hydrophobicizing agent D2.

Claims

Patentansprttche

1. Containing compositions

A) 40 to 90 parts by weight of polyamide

B) 0.5 to 50 parts by weight of impact modifier

C) 0 to 50 parts by weight of fillers and reinforcing materials and

D) 0.1 to 15 parts by weight of phenol-formaldehyde resin or an oligomeric or polymeric compound other than phenol-formaldehyde resins with at least 2 phenolic hydroxyl groups,

where the sum of the parts by weight of all components is 100.

2. Composition according to claim 1 containing at least one further component selected from

E) compatibility mediators and

F) vinyl (co) polymer.

3. Composition according spoke 1 containing at least one polyamide selected from polyamide-6, polyamide-6,6, their copolyamides, polyamides whose acid component wholly or partly from at least one acid from the group terephthalic acid, isophthalic acid, suberic acid, sebacic acid, azelaic acid, adipic acid and Cyclohexanedicarboxylic acid and its diamine component are wholly or partly selected from m-methyl-diamino-dicyclohexylmethane and laurolactam or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine.

4. Composition according to claim 3 containing polyamide-6, polyamide-6,6 or their copolyamides or mixtures thereof.

5. Composition according to claim 1 containing as component B) graft polymers from B.l 5 to 95 wt .-% of at least one vinyl monomer to B.2 95 to 5 wt .-% one or more graft bases with a glass transition temperature <10 ° C.

6. The composition according to claim 5 containing as component B) graft polymers, obtained by polymerization of

B. 1.1 50 to 99 wt .-% of at least one monomer selected from vinyl aromatics, core-substituted vinyl aromatics and (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters and

B1 2 to 50% by weight of at least one monomer selected from vinyl cyanides, (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters and derivatives of unsaturated carboxylic acids

B.2 graft bases selected from at least one from the group consisting of diene rubbers, EP (D) M rubbers, acrylate rubbers, polyurethane rubbers, silicone, chloroprene and ethylene / vinyl acetate rubbers.

7. The composition according to claim 6, wherein the graft base is selected from polybutadiene or butadiene copolymers with styrene and / or methyl (meth) acrylate as comonomers.

8. The composition according to claim 1 containing as component B) ethylene-propylene or ethylene-propylene-diene rubbers.

9. The composition according to claim 1 containing as component C) at least one filler and reinforcing material selected from glass fibers, glass balls, mica, silicates, kaolin, talc, wollastonite.

10. Composition according spoke 1 containing as component E) containing thermoplastic polymers

E.1 a vinyl aromatic monomer,

E.2 at least one monomer selected from the group C to C ₁ alkyl methacrylates, C ₂ to C ₁₂ alkyl acrylates, methacrylonitriles and acrylonitriles and

E.3 α-, β-unsaturated components containing dicarboxylic anhydrides.

11. Composition according spoke 10 containing as component E) a thermoplastic polymer of styrene, acrylonitrile and maleic anhydride.

12. Composition according spoke 1 containing as component F) vinyl (co) polymers

Fl 50 to 99 wt .-% vinyl aromatics and / or core-substituted vinyl aromatics and or methacrylic acid (C ₁ -C ₈ ) alkyl esters, and

F.2 1 to 50 wt .-% vinyl cyanide and / or (meth) acrylic acid (-C-C ₈ ) - alkyl ester.

13. Composition according to spoke 1 containing additives selected from at least one from the group of flame retardants, anti-dripping

Agents, very finely divided inorganic compounds, lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers, dyes and pigments.

14. A process for the preparation of the composition according to spoke 1, in which the individual components are mixed and compounded at elevated temperature.

15. Use of the composition according spoke 1, for the production of moldings.

16. Molded parts obtainable from a composition according to spoke 1.