WO1998004422A1 - Enjoliveurs - Google Patents

Enjoliveurs Download PDF

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Publication number
WO1998004422A1
WO1998004422A1 PCT/EP1997/004026 EP9704026W WO9804422A1 WO 1998004422 A1 WO1998004422 A1 WO 1998004422A1 EP 9704026 W EP9704026 W EP 9704026W WO 9804422 A1 WO9804422 A1 WO 9804422A1
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WO
WIPO (PCT)
Prior art keywords
weight
component
graft
use according
monomers
Prior art date
Application number
PCT/EP1997/004026
Other languages
German (de)
English (en)
Inventor
Herbert Naarmann
Graham Edmund Mc Kee
Alfred Pirker
Hans-Josef Sterzel
Franz Brandstetter
Bernd-Steffen Von Bernstorff
Bernhard Rosenau
Ulrich Endemann
Burkhard Straube
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP97940021A priority Critical patent/EP0912353A1/fr
Publication of WO1998004422A1 publication Critical patent/WO1998004422A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60B—VEHICLE WHEELS; CASTORS; AXLES FOR WHEELS OR CASTORS; INCREASING WHEEL ADHESION
    • B60B7/00—Wheel cover discs, rings, or the like, for ornamenting, protecting, venting, or obscuring, wholly or in part, the wheel body, rim, hub, or tyre sidewall, e.g. wheel cover discs, wheel cover discs with cooling fins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • 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
    • C08L51/04—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 rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the invention relates to hub caps.
  • the invention relates to wheel caps with good weather and aging resistance, good yellowing resistance and excellent surface properties.
  • a large number of materials are used for the manufacture of hubcaps, for example for passenger vehicles.
  • Wheel covers made of ABS generally have to be painted in order to maintain adequate weather and aging stability for all requirements.
  • Hub caps made of polyamides or polypropylene must be painted, which means a second step. In addition, they show anisotropic shrinkage behavior and warpage behavior.
  • ABS / polycarbonate blends do not always show sufficient weather and aging stability and usually also have to be painted.
  • the object of the present invention is to provide hub caps which can be produced in one operation without post-processing and which are good Have dimensional accuracy, no weld lines and excellent surface properties.
  • Another object of the invention is to provide hub caps that have high weather and aging resistance.
  • Another object of the invention is to provide hub caps that have a low density and thus a low weight, but are still stable.
  • Another object of the invention is to provide wheel caps that have good chemical resistance and high scratch resistance.
  • thermoplastic molding composition different from ABS comprising, based on the sum of the amounts of components A and B, and optionally C and / or D, which gives a total of 100% by weight,
  • a 1-99% by weight of a particulate emulsion polymer with a glass transition temperature below 0 ° C. and an average particle size of 50-1000 nm as component A
  • b 1-99% by weight of at least one amorphous or partially crystalline
  • the hubcaps described are weather and aging resistant, scratch-resistant, stable and chemical-resistant. They have very good dimensional stability combined with low density.
  • thermoplastic molding compositions used according to the invention for producing the wheel caps according to the invention are known per se.
  • DE-A-12 60 135, DE-C-19 11 882, DE-A-28 26 925, DE-A-31 49 358, DE-A-32 27 555 and DE-A-40 11 162 Molding compositions which can be used according to the invention are described.
  • the molding compositions other than ABS used to produce the wheel covers according to the invention contain components A and B and, if appropriate, C and / or D, as defined below. They contain, based on the sum of the amounts of components A and B, and if appropriate C and / or D, which gives a total of 100% by weight,
  • Component A is a particulate emulsion polymer with a glass transition temperature below 0 ° C and an average particle size of 50-1000 nm.
  • Component A is preferably a graft copolymer
  • a graft A2 composed of the monomers, based on A2, a21: 40-100% by weight, preferably 65-85% by weight, of units of a vinylaromatic monomer, preferably styrene, a substituted styrene or one (Meth) acrylic acid ester or mixtures thereof, in particular styrene and / or ⁇ -methylstyrene as component A21 and a22: up to 60% by weight, preferably 15-35% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile , in particular of acrylonitrile as component A22.
  • the graft pad A2 consists of at least one graft shell, the graft copolymer A overall having an average particle size of 50-1000 nm.
  • component AI consists of the monomers
  • C ⁇ _- 8- alkyl esters of acrylic acid preferably n-butyl acrylate and / or ethylhexyl acrylate as component All, al2: 0.01-20% by weight, preferably 0.1-5.0% by weight, of at least one polyfunctional crosslinking monomer , preferably diallyl phthalate and / or DCPA as component A12.
  • the average particle size of component A is 50-800 nm, preferably 50-600 nm.
  • the particle size distribution of component A is bimodal, 60-90% by weight having an average particle size of 50-200 nm and 10-40% by weight having an average particle size of 50-400 nm, based on the Total weight of component A.
  • the sizes determined from the integral mass distribution are given as the average particle size or particle size distribution.
  • the mean particle sizes according to the invention are in all cases the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972), pages 782-796.
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this you can see how much weight percent of the particles have a diameter equal to or smaller than a certain size.
  • the average particle diameter which is also referred to as the d 50 value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the d 50 value. Likewise, 50% by weight of the particles then have a larger diameter than the d 50 value.
  • d 10 - d ⁇ To characterize the breadth of the particle size distribution of the rubber particles, in addition to the d50 value (median particle diameter) resulting from the integral mass distribution are d 10 - d ⁇ and used values.
  • the d j0 or d ⁇ value of the integral mass distribution is defined in accordance with the d 50 value with the difference that they are based on 10 or 90% by weight of the particles. The quotient
  • Emulsion polymers A which can be used according to the invention as component A preferably have Q values less than 0.5, in particular less than 0.35.
  • the glass transition temperature of the emulsion polymer A and also of the other components used according to the invention is determined by means of DSC (Differential Scanning Calorimetry) according to ASTM 3418 (mid point temperature).
  • emulsion polymer A such as epichlorohydrin rubbers, ethylene-vinyl acetate rubbers, polyethylene chlorosulfone rubber according to one embodiment of the invention.
  • Chuke silicone rubbers, polyether rubbers, hydrogenated diene rubbers, polyalkenamer rubbers, acrylate rubbers, ethylene-propylene rubbers, ethylene-propylene-diene rubbers, butyl rubbers and fluororubbers.
  • Acrylate rubber, ethylene-propylene (EP) rubber, ethylene-propylene-diene (EPDM) rubber, in particular acrylate rubber, are preferably used.
  • the diene basic building block content in the emulsion polymer A is kept so low that as few unreacted double bonds remain in the polymer. According to one embodiment, there are no basic diene building blocks in the emulsion polymer A.
  • the acrylate rubbers are preferably alkyl acrylate rubbers made from one or more C 1-6 alkyl acrylates, preferably C. g - Alkyl acrylates, butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl and 2-ethylhexyl acrylate, preferably being used at least in part.
  • These AUcylacrylat rubbers can contain up to 30 wt .-% hard polymer-forming monomers such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate or vinyl ether in copolymerized form.
  • the acrylate rubbers further contain 0.01-20% by weight, preferably 0.1-5% by weight, of cross-linking polyfunctional monomers (cross-linking monomers).
  • cross-linking monomers examples of these are monomers which contain 2 or more double bonds capable of copolymerization, which are preferably not conjugated in the 1,3 positions.
  • Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, triallyl phosphate, allyl acrylate, allyl acrylate.
  • Dicyclopentadienyl acrylate (DCPA) has proven to be a particularly favorable crosslinking monomer (cf. DE-C 12 60 135).
  • Suitable silicone rubbers can be, for example, crosslinked silicone rubbers composed of units of the general formulas R 2 SiO, RSiO 3/2 , R 3 SiO 1/2 and SiO 2/4 , the radical R representing a monovalent radical.
  • the amount of the individual siloxane units is such that for 100 units of the formula R 2 SiO 0 to 10 mol units of the formula RSiO 3/2 , 0 to 1.5 mol units R 3 SiO 2 and 0 to 3 mol SiO 2 4 units are present.
  • R can be either a monovalent saturated hydrocarbon radical having 1 to 18 carbon atoms, the phenyl radical or the alkoxy radical or a radical which is easily attackable by free radicals, such as the vinyl or mercaptopropyl radical. It is preferred that at least 80% of all R groups are methyl groups; combinations of methyl and ethyl or phenyl radicals are particularly preferred.
  • Preferred silicone rubbers contain built-in units of groups which can be attacked by free radicals, in particular vinyl, allyl, halogen, mercapto groups, preferably in amounts of 2-10 mol%, based on all radicals R. They can be prepared, for example, as in EP-A -0 260 558.
  • an emulsion polymer A made from uncrosslinked polymer All of the monomers mentioned above can be used as monomers for the production of these polymers.
  • Preferred uncrosslinked emulsion polymers A are, for example, homopolymers and copolymers of acrylic acid esters, in particular n-butyl and ethylhexyl acrylate, and homopolymers and copolymers of ethylene, propylene, butyl lens, isobutylene, and poly (organosiloxanes), all with the proviso that they may be linear or branched.
  • the emulsion polymer A can also be a multi-stage polymer (so-called “core / shell structure", “core-shell morphology”).
  • core / shell structure a multi-stage polymer
  • core-shell morphology a rubber-elastic core (T g ⁇ 0 ° C) can be encased by a “hard” shell (polymers with T g > 0 ° C) or vice versa.
  • component A is a graft copolymer.
  • the graft copolymers A of the molding compositions according to the invention have an average particle size d 50 of 50-1000 nm, preferably 50-600 nm and particularly preferably 50-400 nm. These particle sizes can be achieved if A1 of this component A is used as the graft base Particle sizes of 50-350 nm, preferably 50-300 nm and particularly preferably 50-250 nm are used.
  • the graft copolymer A is generally one or more stages, i.e. a polymer composed of a core and one or more shells.
  • the polymer consists of a basic stage (graft core) Al and one or - preferably - several stages A2 grafted thereon, the so-called graft stages or graft shells.
  • One or more graft shells can be applied to the rubber particles by simple grafting or multiple step-wise grafting, each graft sheath having a different composition.
  • polyfunctional crosslinking or reductive Monomers containing active groups are grafted on (see, for example, EP-A-0 230 282, DE-A-36 01 419, EP-A-0 269 861).
  • component A consists of a multi-stage graft copolymer, the graft stages being generally made from resin-forming monomers and having a glass transition temperature T g above 30 ° C., preferably above 50 ° C.
  • the multi-stage structure serves, inter alia, to achieve (partial) compatibility of the rubber particles A with the thermoplastic B.
  • Graft copolymers A are prepared, for example, by grafting at least one of the monomers A2 listed below onto at least one of the graft bases or graft core materials AI listed above. All of the polymers described above under emulsion polymers A are suitable as the graft bases A1 of the molding compositions according to the invention.
  • the graft base AI is composed of 15-99% by weight of acrylate rubber, 0.1-5% by weight of crosslinking agent and 0-49.9% by weight of one of the further monomers or rubbers indicated.
  • Suitable monomers for forming the graft A2 can be selected, for example, from the monomers listed below and their mixtures:
  • Vinylaromatic monomers such as styrene and its substituted derivatives, such as ⁇ -methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, p-tert-butylstyrene, o- and p-divinylbenzene and p-methyl- ⁇ -methylstyrene or C r C 8- alkyl (meth) acrylates such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate; styrene, ⁇ -methylstyrene, methylme- thacrylate, in particular styrene and / or ⁇ -methylstyrene, and ethylenically unsaturated monomers, such as acrylic and methacrylic compounds, such as acrylonitrile, methacrylonit
  • Vinyl naphthalene, vinyl carbazole;; 12 -alkyl radicals, halogen atoms, halomethyl groups can continue as (co) monomers styrene, vinyl, acrylic or methacrylic compounds (eg, styrene, optionally substituted with C 1 j vinyl ether with C ⁇ - ether radicals;..
  • Vinylimidazole 3- (4-) vinylpyridine, dimethylaminoethyl (meth) acrylate, p-dimethylaminostyrene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, butyl acrylate, ethyl acrylate and methyl methacrylate as well as fumaric acid, maleic acid, itaconic acid or their anhydrides, amides, nitriles or esters with 1 to 22 carbon atoms, preferably alcohols containing 1 to 10 carbon atoms) can be used.
  • component A comprises 50-90% by weight of the above-described graft base AI and 10-50% by weight of the above-described graft base A2, based on the total weight of component A.
  • crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. serve as the graft base.
  • the crosslinked acrylic ester polymers should preferably have a glass transition temperature below -20 ° C., in particular below -30 ° C.
  • the graft A2 consists of at least one graft shell and the outermost graft shell thereof has a glass transition temperature of more than 30 ° C, a polymer formed from the monomers of the graft A2 would have a glass transition temperature of more than 80 ° C.
  • the graft copolymers A can also be prepared by grafting pre-formed polymers onto suitable graft homopolymers. Examples of this are the reaction products of copolymers containing maleic anhydride or acid groups with base-containing rubbers.
  • Suitable preparation processes for graft copolymers A are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers A are preferably prepared by free-radical emulsion polymerization, in particular in the presence of latices of component AI at temperatures from 20 ° C. to 90 ° C. using water-soluble or oil-soluble initiators such as peroxodisulfate or benzyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
  • Suitable emulsion polymerization processes are described in DE-A-28 26 925, 31 49 358 and in DE-C-12 60 135.
  • the graft casings are preferably built up in the emulsion polymerization process, as described in DE-A-32 27 555, 31 49 357, 31 49 358, 34 14 118.
  • the defined particle sizes of 50-1000 nm according to the invention are preferably carried out after the procedures that are described in DE-C-12 60 135 and DE-A-28 26 925, or Applied Polymer Science, Volume 9 (1965), page 2929.
  • the use of polymers with different particle sizes is known, for example, from DE-A- 28 26 925 and US 5,196,480.
  • the graft base A1 is first prepared by adding the acrylic acid ester (s) used according to one embodiment of the invention and the multifunctional monomers which bring about crosslinking, if appropriate together with the others Comonomers, in aqueous emulsion in a conventional manner at temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C, polymerized.
  • the usual emulsifiers such as alkali salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms or resin soaps can be used.
  • the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are preferably used.
  • the emulsifiers are used in amounts of 0.5-5% by weight, in particular 1-2% by weight, based on the monomers used in the preparation of the graft base AI.
  • the weight ratio of water to monomers is from 2: 1 to 0.7: 1.
  • the usual persulfates, such as potassium persulfate, are used in particular as polymerization initiators. However, redox systems can also be used.
  • the initiators are generally used in amounts of 0.1-1% by weight, based on the monomers used in the preparation of the graft base AI.
  • the usual buffer substances by means of which pH values of preferably 6-9, such as sodium bicarbonate and sodium pyrophosphate, and 0-3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric ⁇ -methylstyrene, can be added as further polymerization auxiliaries the polymerization can be used.
  • a molecular weight regulator such as mercaptans, terpinols or dimeric ⁇ -methylstyrene
  • the exact polymerization conditions in particular the type, dosage and amount of the emulsifier, are determined in detail within the ranges given above such that the latex of the crosslinked acrylic ester polymer obtained ad 50 value in the range of about 50-1000 nm, preferably 50- 150 nm, particularly preferably in the range of 80-100 nm.
  • the particle size distribution of the latex should preferably be narrow. The quotient
  • a monomer mixture of styrene and acrylonitrile is then polymerized in a next step in the presence of the latex of the crosslinked acrylic acid ester polymer obtained in accordance with one embodiment of the invention, the weight ratio of styrene to acrylonitrile in the monomer mixture according to one embodiment of the invention in the range from 100: 0 to 40:60, preferably in the range from 65: 35 to 85: 15. It is advantageous to carry out this graft copolymerization of styrene and acrylonitrile on the crosslinked polyacrylic ester polymer used as the graft base again in an aqueous emulsion under the customary conditions described above.
  • the graft copolymerization can expediently take place in the same system as the emulsion polymerization for the preparation of the graft base A1, it being possible, if necessary, to add further emulsifier and initiator.
  • the monomer mixture of styrene and acrylonitrile to be grafted on according to one embodiment of the invention can be added to the reaction mixture all at once, batchwise in several stages or preferably continuously during the polymerization.
  • the graft copolymerization the mixture of styrene and acrylonitrile in the presence of the crosslinking acrylic ester polymer is carried out in such a way that a degree of grafting of 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, based on the total weight of the Component A results in the graft copolymer A. Since the graft yield in the graft copolymerization is not 100%, a somewhat larger amount of the monomer mixture of styrene and acrylonitrile must be used in the graft copolymerization than corresponds to the desired degree of grafting.
  • the control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A is known to the person skilled in the art and can be carried out, for example, by the metering rate of the monomers or by adding a regulator (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 ff .).
  • the emulsion graft copolymerization generally gives rise to about 5 to 15% by weight, based on the graft copolymer, of free, non-grafted styrene / acrylonitrile copolymer.
  • the proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method given above.
  • graft copolymers A In the production of the graft copolymers A by the emulsion process, in addition to the process-related advantages which are given, reproducible changes in particle size are also possible, for example by at least partially agglomerating the particles into larger particles. This means that polymers with different particle sizes can also be present in the graft copolymers A.
  • Component A in particular, consisting of the graft base and graft shell (s) can be optimally adapted for the particular application, in particular with regard to the particle size.
  • the graft copolymers A generally contain 1-99% by weight, preferably 55-80 and particularly preferably 55-65% by weight of the graft base Al and 1-99% by weight, preferably 20-45%, particularly preferably 35-45% by weight, of the graft pad A2, in each case based on the entire graft copolymer.
  • Component B is an amorphous or partially crystalline polymer.
  • Component B is preferably a copolymer of
  • bl 40-100% by weight, preferably 60-70% by weight, units of a vinylaromatic monomer, preferably styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or ⁇ -methylstyrene as
  • Component B1, b2 up to 60% by weight, preferably 30-40% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, in particular acrylonitrile as component B2.
  • the viscosity number of component B is 50-90, preferably 60-80.
  • the amorphous or partially crystalline polymers of component B of the molding composition used according to the invention for producing the wheel caps according to the invention are preferably composed of at least one polymer made from partially crystalline polyamides, partially aromatic copolyamides, polyolefins, ionomers, polyesters, polyether ketones, polyoxyalkylenes, polyarylene sulfides and polymers made from vinyl aromatic monomers and / or ethylenically un- saturated monomers selected. Polymer mixtures can also be used.
  • Component B of the molding composition used according to the invention for the production of the wheel covers according to the invention are partially crystalline, preferably linear polyamides such as polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 6,12 and partially crystalline copolyamides based on these components.
  • Particrystalline polyamides can also be used, the acid component of which consists wholly or partly of adipic acid and / or terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / orginaic acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid, and their All or part of the diamine component consists in particular of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine and / or isophorone diamine, and their compositions in Principle are known from the prior art (cf. Encyclopedia of Polymers, Vol. 11, p. 315 ff.).
  • Polymers are partially crystalline polyolefins, preferably homo- and copolymers of olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1,
  • Suitable polyolefins are polyethylene, polypropylene, polybutene-1 or poly-4-methylpentene-1. In general, a distinction is made with polyethylene (PE) high
  • HDPE Density-PE
  • LDPE low-density-PE
  • component B is an ionomer.
  • these are generally polyolefins as described above, in particular polyethylene, the monomers with acid contain re-groups co-condensed, for example acrylic acid, methacrylic acid and possibly other copolymerizable monomers.
  • the acid groups are generally converted into ionic, optionally ionically crosslinked polyolefins with the aid of metal ions such as Na + , Ca 2+ , Mg 2+ and Al 3+ , but these can still be processed thermoplastically (see, for example, US Pat. No. 3,264,272; 3,404,134; 3,355,319 ; 4,321,337).
  • Component B according to the invention is also suitable for polyolefins containing free acid groups, which then generally have a rubber-like character and in some cases also contain further copolymerizable monomers, for example (meth) acrylates.
  • component B can also be polyester, preferably aromatic-aliphatic polyester.
  • polyester preferably aromatic-aliphatic polyester.
  • polyalkylene terephthalate e.g. based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis-hydroxymethyl-cyclohexane, as well as polyalkylene naphthalates.
  • Aromatic polyether ketones such as those e.g. are described in GB 1 078 234, US 4,010,147, EP-A-0 135 938, EP-A-0 292 211, EP-A-0 275 035, EP-A-0 270 998, EP 165 406, and in the publication by CK Sham et. al., Polymer 29/6, 1016-1020 (1988).
  • component B of the molding compositions used according to the invention for the production of the wheel covers according to the invention polyoxyalkyls, e.g. Polyoxymethylene, and oxymethylene polymers are used.
  • suitable components B are the polyarylene sulfides, in particular the polyphenylene sulfide. According to one embodiment of the invention, it is composed of 50-99% by weight of vinyl aromatic monomers and 1-50% by weight of at least one of the other specified monomers.
  • Component B is preferably an amorphous polymer, as described above as graft A2.
  • a copolymer of styrene and / or ⁇ -methylstyrene with acrylonitrile is used as component B.
  • the acrylonitrile content in these copolymers of component B is 0-60% by weight, preferably 30-40% by weight, based on the total weight of component B.
  • Component B also includes those in the graft copolymerization to prepare the component A free, non-grafted styrene / acrylonitrile copolymers formed.
  • component B has already been formed in the graft copolymerization. In general, however, it will be necessary to mix the products obtained in the graft copolymerization with additional, separately prepared component B.
  • This additional, separately produced component B can preferably be a styrene / acrylonitrile copolymer, an ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile terpolymer.
  • These copolymers can be used individually or as a mixture for component B, so that the additional, separately prepared component B of the molding compositions used according to the invention is, for example, a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile -Copolymer can act.
  • component B of the molding compositions used according to the invention consists of a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer
  • the acrylonitrile content of the two copolymers should preferably not more than 10% by weight, preferably not more than 5% by weight, based on the total weight of the copolymer, differ from one another.
  • Component B of the molding compositions used according to the invention can, however, also consist of only a single styrene / acrylonitrile copolymer if, in the graft copolymerizations for the production of component A and also in the production of the additional, separately produced component B, the same monomer mixture of styrene and acrylonitrile is assumed.
  • the additional, separately manufactured component B can be obtained by the conventional methods.
  • the copolymerization of the styrene and / or ⁇ -methylstyrene with the acrylonitrile can be carried out in bulk, solution, suspension or aqueous emulsion.
  • Component B preferably has a viscosity range of 40 to 100, preferably 50 to 90, in particular 60 to 80. The viscosity number is determined in accordance with DIN 53 726, 0.5 g of material being dissolved in 100 ml of dimethylformamide.
  • Components A and B and optionally C, D can be mixed in any desired manner by all known methods. If components A and B have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, to precipitate the polymers together thereupon and to work up the polymer mixture. However, components A and B are preferably mixed by extruding, kneading or rolling the components together, the components having, if necessary, been isolated beforehand from the solution or aqueous dispersion obtained in the polymerization.
  • the products of the graft copolymerization (component A) obtained in aqueous dispersion can also only be partially dewatered and mixed as a moist crumb with component B, the complete drying of the graft copolymers then taking place during the mixing.
  • the molding compositions used according to the invention for producing the wheel covers according to the invention contain, in addition to components A and B, additional components C and / or D and, if appropriate, further additives, as described below.
  • Suitable polycarbonates C are known per se. They preferably have a molecular weight (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range from 10,000 to 60,000 g / mol. They can be obtained, for example, in accordance with the processes of DE-B-1 300 266 by interfacial polycondensation or in accordance with the process of DE-A-1 495 730 by reacting diphenyl carbonate with bisphenols.
  • Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally - as also hereinafter - referred to as bisphenol A.
  • aromatic dihydroxy compounds can also be used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxy naphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4 , 4'-dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenylmethane, l, l-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkane, preferably dihydroxydiphenylcyclohexane or dihydroxylcyclopentane, especially l, l-bis (4- hydroxyphenyl) -3,3,5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.
  • Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the aromatic dihydroxy compounds mentioned above.
  • Copolycarbonates according to US Pat. No. 3,737,409 can also be used; Of particular interest are copolycarbonates based on bisphenol A and di (3,5-dimethyl-dihydroxyphenyl) sulfone, which are characterized by high heat resistance. It is also possible to use mixtures of different polycarbonates.
  • the average molecular weights (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates C are in the range from 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol. This means that the polycarbonates C have relative solution viscosities in the range from 1.1 to 1.3, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33. The relative solution viscosities of the polycarbonates used preferably differ by no more than 0.05, in particular no more than 0.04.
  • the polycarbonates C can be used both as regrind and in granular form. They are present as component C in amounts of 0 to 98% by weight, preferably 20 to 80% by weight, in particular 40 to 70% by weight, in each case based on the total molding composition.
  • the addition of polycarbonates leads, inter alia, to higher thermal stability and improved crack resistance of the molding compositions used to produce the wheel covers according to the invention.
  • Component D contains the preferred thermoplastic materials used according to the invention for the production of the wheel covers according to the invention Molding compositions 0 to 50% by weight, preferably 0 to 40% by weight, in particular 0 to 30% by weight of fibrous or particulate fillers or mixtures thereof, in each case based on the total molding composition. These are preferably commercially available products. Reinforcing agents such as carbon fibers and glass fibers are usually used in amounts of 5-50% by weight, based on the total molding composition.
  • the glass fibers used can be made of E, A or C glass and are preferably equipped with a size and an adhesion promoter. Their diameter is generally between. 6 and 20 ⁇ m. Both continuous fibers (rovings) and chopped glass fibers (staples) with a length of 1-10 ⁇ m, preferably 3-6 ⁇ m, can be used.
  • fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can be added.
  • metal flakes e.g. aluminum flakes from Transmet Corp.
  • metal powder e.g. aluminum flakes from Transmet Corp.
  • metal fibers e.g. nickel-coated glass fibers
  • metal-coated fillers e.g. nickel-coated glass fibers
  • other additives that shield electromagnetic waves are added to the molding compounds used in the manufacture of the wheel covers according to the invention.
  • Aluminum flakes K 102 from Transmet
  • EMI electro-magnetic interference
  • the compositions can be mixed with additional carbon fibers, carbon black, in particular conductivity carbon black, or nickel-coated carbon fibers.
  • the molding compositions used according to the invention for the production of the hubcaps according to the invention can also contain further additives which are suitable for polycarbonates, SAN polymers and graft copolymers or their mixtures. are typical and common.
  • additives are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve thermal stability, to increase light stability, to increase hydrolysis resistance and chemical resistance, agents against heat decomposition and in particular the lubricants / lubricants, which are expedient for the production of molded articles or molded parts.
  • These additional additives can be metered in at any stage of the production process, but preferably at an early point in time, in order to take advantage of the stabilizing effects (or other special effects) of the additive at an early stage.
  • Heat stabilizers or oxidation retardants are usually metal halides (chlorides, bromides, iodides) which are derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).
  • Suitable stabilizers are the usual hindered phenols, but also vitamin E or compounds with an analog structure.
  • HALS stabilizers hindered amine light stabilizers
  • benzophenones hindered amine light stabilizers
  • resorcinols salicylates
  • benzotriazoles and other compounds are also suitable (for example Irganox ", Tinuvin *, such as Tinuvin * 770 (HALS absorber, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebazate) or Tinuvin * P (UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol), topanol *).
  • Tinuvin * such as Tinuvin * 770 (HALS absorber, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebazate) or Tinuvin * P (UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol), topanol *.
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12-30 carbon atoms.
  • the amounts of these additives are in the range of 0.05-1% by weight.
  • Silicone oils, oligomeric isobutylene or similar substances are also suitable as additives, the usual amounts being 0.05-5% by weight.
  • Pigments, dyes, color brighteners, such as ultramarine blue, phthalocyanines, titanium Dioxide, cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used.
  • Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in quantities of 0.01 - 5% by weight, based on the total molding compound.
  • thermoplastic molding compositions used according to the invention for producing the wheel covers according to the invention can be produced by methods known per se by mixing the components. It can be advantageous to premix individual components. Mixing the components in solution and removing the solvents is also possible.
  • Suitable organic solvents are, for example, chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene or aromatic hydrocarbons, e.g. Toluene.
  • the solvent mixtures can be evaporated, for example, in evaporation extruders.
  • Mixing the e.g. dry components can be made by all known methods. However, the mixing is preferably carried out by extruding, kneading or rolling the components together, preferably at temperatures of 180-400 ° C., the components having, if necessary, been isolated beforehand from the solution obtained in the polymerization or from the aqueous dispersion.
  • the wheel caps and fastening parts according to the invention can be produced from the thermoplastic molding compositions used according to the known methods of thermoplastic processing.
  • the production can be carried out by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding.
  • the hubcaps according to the invention can have any shape that does not hinder the use as hubcaps.
  • the wheel covers are used for motor vehicles, in particular passenger vehicles.
  • the surface of the wheel covers is flat, i.e. the outside is flat.
  • the surface or outside of the wheel covers is structured.
  • the wheel caps have openings.
  • the wheel caps have openings which are preferably delimited by webs or struts.
  • the webs or struts run radially.
  • the hubcaps according to the invention can be produced by injection molding. Any desired shape is possible, even fine details can be reproduced well.
  • the wheel covers according to the invention can optionally be colored using pigments or dyes. A painting of the shaped hubcaps can thus be omitted.
  • the wheel covers according to the invention can be provided on all suitable wheels.
  • These can be wheels of land vehicles, such as motor vehicles, in particular passenger cars, but also wheels of aircraft.
  • the hubcaps produced from the molding compositions according to the invention show only a very low weld line visibility. The occurrence of optically disturbing visible weld lines can thus be largely suppressed.
  • hubcaps made of molding compounds which contain polycarbonates as component C are very heat-resistant and resistant to sustained heat. By adding the polycarbonate as component C, the heat resistance and impact resistance of the hubcaps is further improved.
  • These hubcaps also have a balanced ratio of toughness and rigidity and good dimensional stability, as well as excellent resistance to heat aging and high resistance to yellowing under thermal loads and exposure to UV radiation.
  • Hub caps made of molding compounds containing components A and B have excellent surface properties that can be obtained without further surface treatment.
  • the appearance of the finished surfaces of the hubcaps can be modified by suitable modification of the rubber morphology, for example in order to achieve glossy or matt surface designs.
  • the hubcaps show on exposure weather and UV radiation have a very low graying or yellowing effect, so that the surface properties are retained.
  • Further advantageous properties of the hubcaps are the high weather stability, good thermal resistance, high yellowing resistance under UV radiation and thermal stress, good stress crack resistance, especially when exposed to chemicals, and good anti-electrostatic behavior. In addition, they have high color stability, for example due to their excellent resistance to yellowing and embrittlement.
  • the hubcaps according to the invention made of the thermoplastic molding compositions used according to the invention do not show any significant loss of toughness or impact strength at low temperatures or after prolonged exposure to heat, which loss is retained even when exposed to UV rays. The tensile strength is also retained. They also show a balanced relationship between rigidity and toughness.
  • thermoplastic molding compositions already used to produce the wheel covers according to the invention are very suitable for reuse.
  • the proportion of reused (recycled) molding compound can be high.
  • the relevant material properties such as flowability, Vicat softening temperature and impact strength of the molding compounds and the wheel caps according to the invention produced therefrom did not change significantly. Similar results were obtained when the weather resistance was examined.
  • the latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40% by weight.
  • the mean particle size (weight average) was found to be 76 nm.
  • Butyl acrylate polymers had a solids content of 40%.
  • the mean particle size (weight average) of the latex was found to be 410 nm.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 80 ml / g.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 60 ml / g.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copoly obtained merisat had an acrylonitrile content of 27% by weight, based on the copolymer, and a viscosity number of 80 ml / g.
  • the graft rubber content was 29% by weight, based on the total weight of the finished polymer.
  • HIPS polymer high impact polystyrene: impact-resistant polystyrene
  • a HIPS polymer high impact polystyrene: impact-resistant polystyrene
  • MVR 200/5 ml / min
  • VST / B50 96.
  • a polymer blend was used which was based on a
  • Polybutadiene rubber based which was grafted with a styrene-acrylonitrile copolymer.
  • the rubber was in a styrene-acrylonitrile copolymer material trix before.
  • the polycarbonate content was 60% by weight.
  • Bayblend T65 MN from Byer can be used.
  • a conventional polycarbonate (PC) was used as component C, which had a viscosity number of 61.5 ml / g, determined in the solvent methylene chloride.
  • PC polycarbonate
  • Lexan 161 from General Electric can be used.
  • the molding compositions used for the weathering tests additionally contained 2% by weight of TiO 2 , based on the total amount of the molding composition.
  • test specimens were injection molded according to the spraying conditions specified in DIN 16777.
  • the plastic temperature was 250 ° C, the mold temperature 60 ° C, the injection time 1.5 seconds.
  • the test specimens for the weld line test 1) had a trapezoidal cross-section with edge lengths of the parallel edges of 60 and 40 mm, which were at a distance of 40 mm.
  • the test specimen had a length of 120 mm.
  • the sprue was arranged in the middle of the area formed by the short parallel edge, around which a portion of the test specimen had a kidney-shaped opening. This kidney-shaped breakthrough was used to assess the flow and weld line visibility.
  • a telephone housing 2) in dark colors was used as the second test specimen, which was colored, for example, with 0.5% by weight, based on the total weight of the molding composition, of black carbon pearls 880.
  • the weld lines on the keypad were examined.
  • the spray conditions were plastic temperature 260 ° C, mold temperature 60 ° C, injection time 2.5 seconds. The results are shown in Table 3 below.
  • the molding compositions according to the invention show no weld line in comparison to the comparison molding compositions.
  • Table 4 shows that the molding compositions according to the invention have a significantly better aging resistance than the comparative molding compositions.
  • the molding compositions according to the invention are therefore very well suited for the production of wheel caps.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation d'une matière moulable thermoplastique pour produire des enjoliveurs. Cette matière, différente de l'ABS, contient, toujours par rapport à la somme des quantités des composants A et B, et éventuellement C et/ou D totalisant 100 %, a) comme composant A, 1 à 99 % en poids, de préférence 5 à 70 % en poids, notamment 10 à 45 % en poids d'un polymère obtenu par émulsion, se présentant sous forme de particules et ayant une température de transition vitreuse inférieure à 0 °C et une taille moyenne de particules comprise entre 50 et 1000 nm, de préférence entre 50 et 500 nm, b) comme composant B, 1 à 99 % en poids, de préférence 10 à 70 % en poids, notamment 15 à 50 % en poids d'au moins un polymère amorphe ou semi-cristallin, c) comme composant C, 0 à 98 % en poids, de préférence 20 à 80 % en poids, notamment de 40 à 70 % en poids de polycarbonates et d) comme composant D, 0 à 50 % en poids de charges sous forme de fibres ou de particules, ou de leur mélange.
PCT/EP1997/004026 1996-07-25 1997-07-24 Enjoliveurs WO1998004422A1 (fr)

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EP97940021A EP0912353A1 (fr) 1996-07-25 1997-07-24 Enjoliveurs

Applications Claiming Priority (2)

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DE19630099.1 1996-07-25
DE19630099A DE19630099A1 (de) 1996-07-25 1996-07-25 Radkappen

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WO1998004422A1 true WO1998004422A1 (fr) 1998-02-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000020084A1 (fr) * 1998-10-07 2000-04-13 Basf Aktiengesellschaft Jouets d'exterieur

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277913B1 (en) * 1998-05-25 2001-08-21 Kaneka Corporation Thermoplastic resin composition and interior or exterior parts for vehicle thereof
DE19846209A1 (de) * 1998-10-07 2000-04-13 Basf Ag Sportartikel
DE19846246A1 (de) * 1998-10-07 2000-04-13 Basf Ag Karosserieteile für Kraftfahrzeuge

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0320836A2 (fr) * 1987-12-17 1989-06-21 BASF Aktiengesellschaft Matières à mouler exemptes d'halogènes et résistant au feu, procédé pour leur préparation et leur utilisation
EP0429957A2 (fr) * 1989-11-25 1991-06-05 BASF Aktiengesellschaft Masse à mouler thermoplastique ayant une résistance élevée aux chocs à froid
DE4342048A1 (de) * 1993-12-09 1995-06-14 Basf Ag Dreistufige Pfropfcopolymerisate und solche enthaltende thermoplastische Formmassen mit hoher Zähigkeit
EP0676449A2 (fr) * 1994-04-04 1995-10-11 Mitsubishi Gas Chemical Company, Inc. Composition de résine thermoplastique pour extrusion de profile
DE19536892A1 (de) * 1995-10-04 1997-04-10 Basf Ag Formteile aus thermoplastischen Formmassen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0320836A2 (fr) * 1987-12-17 1989-06-21 BASF Aktiengesellschaft Matières à mouler exemptes d'halogènes et résistant au feu, procédé pour leur préparation et leur utilisation
EP0429957A2 (fr) * 1989-11-25 1991-06-05 BASF Aktiengesellschaft Masse à mouler thermoplastique ayant une résistance élevée aux chocs à froid
DE4342048A1 (de) * 1993-12-09 1995-06-14 Basf Ag Dreistufige Pfropfcopolymerisate und solche enthaltende thermoplastische Formmassen mit hoher Zähigkeit
EP0676449A2 (fr) * 1994-04-04 1995-10-11 Mitsubishi Gas Chemical Company, Inc. Composition de résine thermoplastique pour extrusion de profile
DE19536892A1 (de) * 1995-10-04 1997-04-10 Basf Ag Formteile aus thermoplastischen Formmassen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000020084A1 (fr) * 1998-10-07 2000-04-13 Basf Aktiengesellschaft Jouets d'exterieur

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KR20000029505A (ko) 2000-05-25
EP0912353A1 (fr) 1999-05-06

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