WO2000020503A1

WO2000020503A1 - Massage apparatus and corresponding housing

Info

Publication number: WO2000020503A1
Application number: PCT/EP1999/007431
Authority: WO
Inventors: Graham Edmund Mc Kee; Heiner GÖRRISSEN; Norbert Güntherberg; Norbert Niessner; Martin Weber
Original assignee: Basf Aktiengesellschaft
Priority date: 1998-10-07
Filing date: 1999-10-05
Publication date: 2000-04-13
Also published as: DE19846201A1

Abstract

The invention relates to the utilization of a shaped material different from ABS for the production of massage apparatus and housings for said apparatus. Said shaped material contains, in relation to the sum of the portions of components A, B and C and optionally D, a total of 100 % by weight of a) 1-48 % by weight of at least one single or multiphase particulate emulsion polymer with a glass transition temperature below 0 DEG C in at least one phase and a mean particle size of 50-1000 nm, preferably 50-800 nm as component A; b) 1-48 % by weight of at least one amorphous or semi-crystalline polymer as component B; c: 51-98 % by weight of a polycarbonate as component c), and d) 0-47 % by weight of usual additives and/or fibrous or particulate filling materials or the mixtures thereof as component D.

Description

Massagers and housings therefor

The invention relates to massage devices or housings therefor and parts of massage devices which come into contact with the human body. _, In particular, the invention relates to massage devices with good dimensional stability, great stability, good chemical resistance and good yellowing resistance.

Various materials have so far been used for the manufacture of massage devices. For example, ABS (acrylonitrile / butadiene styrene) polymers are used. A disadvantage of ABS is that it is not always sufficiently resistant to yellowing, so that yellowing also occurs in part when used indoors. In addition, ABS is not always sufficiently resistant to cleaning agents and disinfectants, as well as skin creams and massage oils. In addition, ABS molded parts can in some cases show insufficient stress cracking behavior towards cleaning agents and alcohols. The surface may swell and become discolored when in contact with petrol. In addition, the permeability to water and gases can be too high.

The use of PMMA (polymethyl methacrylate) is often disadvantageous due to the low impact strength of the material and the poor resistance to stress corrosion cracking when it comes into contact with cleaning agents or alcohols.

WO 98/04232 describes massage devices and housings therefor, which are preferably constructed from an ASA (actylate styrene / acrylonitrile) molding composition with a polycarbonate content of up to 50% by weight. However, the scratch resistance, the swelling behavior, especially when in contact with petrol and the color depth are not sufficient for all applications Eliminating polycarbonate does not always provide long-term heat resistance. There may be problems with the fire protection equipment.

The object of the present invention is therefore to provide massage devices which are stable and resistant to chemicals and do not yellow. They should also be scratch-resistant and have good dimensional stability. The UV and heat aging resistance should be high, so that the surface gloss is retained. Further requirements are good recyclability and poor fire behavior as well as good dimensional stability under thermal stress during manufacture and use.

According to the invention, these objects are achieved by using a thermoplastic molding composition different from ABS, comprising, based on the sum of the amounts of components A, B, C and optionally D, which gives a total of 100% by weight,

a: 1-48% by weight of at least one single-phase or multi-phase particulate emulsion polymer having a glass transition temperature below 0 ° C. in at least one phase and an average particle size of 50-1000 nm as component A,

b: 1-48% by weight of at least one amorphous or partially crystalline

Polymer as component B,

c: 51-98% by weight of polycarbonates as component C, and

d: 0-47% by weight of additives and / or fibrous or particulate

Additives or mixtures thereof as component D.

for the manufacture of massage devices and housings thereof. Specified glass transition temperatures of phases refer to a polymer with the composition corresponding to this phase.

The massage devices described are scratch-resistant, stable and resistant to chemicals. They also have very good yellowing resistance and color animals.

The components of the thermoplastic molding compositions used according to the invention for producing the massage devices according to the invention are known per se. For example, 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 Components and molding compositions which can be used according to the invention are described.

According to one embodiment, the molding devices other than ABS used to manufacture the massage devices or housings thereof according to the invention contain components A and B and C and optionally D, as defined below. They contain, based on the sum of the amounts of components A, B, C and optionally D, which gives a total of 100% by weight,

a: 1-48% by weight, preferably 3-35% by weight, in particular 5-30% by weight, of a particulate emulsion polymer with a glass transition temperature below 0 ° C. and an average particle size of 50-1000 nm , preferably 50-800 nm, as component A,

b: 1-48% by weight, preferably 5-40% by weight, in particular 5-35% by weight, of at least one amorphous or partially crystalline polymer as component B,

c: 51-98% by weight, preferably 55-90% by weight, in particular 60-85% by weight, of polycarbonates as component C, and d: 0-47% by weight, preferably 0-37% by weight, in particular 0-30% by weight of additives, and / or fibrous or particulate additives or mixtures thereof as component D.

The invention is explained in more detail below.

The molding compositions used to manufacture the massage devices according to the invention and the components from which they are constructed are first described.

COMPONENT A

Component A is at least one single-phase or multi-phase particulate emulsion polymer with a glass transition temperature below 0 ° C. in at least one phase and an average particle size of 50-1000 nm.

Component A is preferably a multi-phase polymer

al: 1-99% by weight, preferably 15-80% by weight, in particular 40-65% by weight

%, a particulate first phase AI with a glass transition temperature below 0 ° C,

a2: 1-99% by weight, preferably 20-85% by weight, in particular 35-60% by weight, of a second phase A2 from the monomers, based on A2,

a21: 40-100% by weight, preferably 65-85

Units of a vinyl aromatic monomer, preferably styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or α-methylstyrene as component A21 and a22: 0 to 60% by weight, preferably 15-35% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, in particular acrylonitrile as component A22.

a3: 0 to 50% by weight of a third phase with a glass transition temperature of more than 0 ° C. as component A3,

the total amount of components AI, A2 and A3 being 100% by weight.

The phases can be linked together in the manner of a graft copolymerization. Here, for example, the first phase AI can form the graft base and the second phase A2 a graft pad. Several phases can be provided, corresponding to a graft copolymer with one graft base and several graft pads. However, the graft pad need not necessarily be in the form of a sheath around the graft core. Different geometries are possible, for example part of the first phase AI can be covered with the second phase A2, interpenetrating networks can form etc. The first phase AI particularly preferably has a glass transition temperature below -10 ° C., in particular below - 15 ° C. The third phase preferably has a glass transition temperature of more than 60 ° C. This third phase can be present, for example, at 1-50% by weight, in particular 5-40% by weight, based on component A.

In the following, instead of "first phase" it can also be understood to mean "graft base", corresponding to "graft base" instead of "second phase".

The third phase can preferably be constructed from more than 50% by weight of styrene, in particular from more than 80% by weight of syrene, based on the total number of monomers of the third phase. According to one embodiment of the invention, component AI consists of the monomers

all: 80-99.99% by weight, preferably 95-99.9% by weight, of a Ci-β-alkyl ester of acrylic acid, preferably n-butyl acrylate and / or

Ethyl hexyl acrylate as component All,

al2: 0.01-20% by weight, preferably 0.1-5.0% by weight, of at least one polyfunctional crosslinking monomer as component A12.

According to one embodiment of the invention, the average particle size of component A is 50-1000 nm, preferably 50-800 nm.

According to a further embodiment of the invention, the particle size distribution of the component is Abimodal, 1-99, preferably 20-95, in particular 45-90% by weight, an average particle size of 50-200 nm and 1-99, preferably 5-80, in particular 10-55% by weight have an average particle size of 200-1000 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. In all cases, the mean particle sizes according to the invention are the weight-average 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 it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size. The average particle diameter, which is also referred to as d ₅ o of the cumulative mass distribution, is defined as the particle, in which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the dso value. Likewise, 50% by weight of the particles then have a larger diameter than the dso value. To characterize the breadth of the particle size distribution of rubber particles are in addition to the DSO value (median particle diameter) resulting from the integral mass distribution are used DIO and d ₉ o values. The do or d o value of the integral mass distribution is defined in accordance with the dso value with the difference that they are based on 10 or 90% by weight of the particles. The quotient

dw - d 10 = 0 d. <

represents a measure of the distribution width of the particle size.

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).

Relevant common rubbers can be used as emulsion polymer A, such as epichlorohydrin rubber, ethylene-vinyl acetate rubbers, polyethylene chlorosulfone rubbers, silicone rubbers, polyether rubbers, hydrogenated diene rubbers, according to one embodiment of the invention.

Polyalkename 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.

Pure butadiene rubbers, such as those used in ABS, cannot be used as exclusive component A. The molding compositions are preferably free of butadiene rubbers. According to one embodiment, the proportion of diene building blocks in the emulsion polymer A is kept so low that as few unreacted double bonds remain in the polymer as possible. According to one embodiment, there are no basic diene building blocks in the emulsion polymer A.

The acrylate is preferably alkyl acrylate rubbers of one or more Cι _-8 -alkyl, preferably C --- ₅ - alkyl acrylates, preferably wherein at least some butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n Butyl and 2-ethylhexyl acrylate is used. These alkyl acrylate rubbers can contain up to 30% by weight copolymerizable monomers, such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate or vinyl ether, in copolymerized form.

According to one embodiment of the invention, the acrylate rubbers further contain 0.01-20% by weight, preferably 0.1-5% by weight, of cross-linking polyfunctional 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

Butanediol or hexanediol di (meth) acrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanate, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, diallyl phosphylate, allylphosphate, allylphosphate, diallyl acrylate, allylphosphate, allylphosphate, allylphosphate, allylphosphate, allylphosphate, allylphosphate, allylphosphate, allylphosphate, allylphosphate, allylphosphate, allylphosphate, allylphosphate ).

Suitable silicone rubbers can be, for example, crosslinked silicone rubbers composed of units of the general formulas R ₂ SiO, RSiO ₃ /, R ₃ SiOι / ₂ and SiOτ / 4, the rest

R represents a monovalent radical. The quantities of the individual siloxane units are dimensioned such that for each 100 units of the formula R ₂ SiO 0 to 10 mole units of the formula RSiO _{_3/2,} 0 to 1.5 moles of units R ₃ SiOι / and 0 to 3 moles of units SiO _2. available. R can be either a einwerti ^g he sesättister hydrocarbon radical having 1 to 18 carbon atoms, the phenyl or alkoxy, or a free-radical attack group such as vinyl or mercaptopropyl be. 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.

In some cases it may be appropriate to use 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 e.g. Homopolymers and copolymers of acrylic acid esters, especially n-butyl and ethylhexyl acrylate, and homopolymers and copolymers of ethylene, propylene, butylene, isobutylene and poly (organosiloxanes), all with the proviso that they are linear or branched allowed to.

Core / shell - emulsion polymer A

The emulsion polymer A can also be a multi-stage structure

Act polymer (so-called "core / shell structure", "core-shell morphology").

For example, a rubber-elastic core (T _g <0 ° C) of a "hard"

Shell (polymers with T _g > 0 ° C) or vice versa.

In a particularly preferred embodiment of the invention, the Component A is a graft copolymer. The graft copolymers A of the molding compositions according to the invention have an average particle size d _f of 50-1000 nm, preferably 50-800 nm.

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) AI and one or more stages A2 (graft layer) 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. In addition to the grafting monomers, polyfunctional crosslinking or reactive group-containing monomers can also be grafted on (see e.g. EP-A-0 230 282, DE-A-36 01 419, EP-A-0 269 861).

In a preferred embodiment, 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 outer graft shell serves, among other things, 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 polymers described above under emulsion polymers A are suitable as graft bases AI of the molding compositions according to the invention. According to one embodiment of the invention, the graft base AI is composed of 15-99.9% 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:

Vinyl aromatic monomers, such as styrene and its substituted derivatives, such as c ..

Methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, p-tert-butylstyrene and p-methyl- «-methylstyrene or -CC ₈ -alkyl (meth) acrylates such as methyl methacrylate,

Ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate. Butyl acrylate; styrene, α-methylstyrene, methyl methacrylate, in particular styrene and / or α-methylstyrene, and ethylenically unsaturated monomers are preferred. like acrylic and

Methacrylic compounds, such as acrylonitrile, methacrylonitrile, acrylic and methacrylic acid, methyl acrylate, ethyl acrylate, n- and isopropyl acrylate, n- and

Isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate,

Ethyl methacrylate, n- and isopropyl methacrylate, n- and isobutyl methacrylate, tert.-

Butyl methacrylate, cyclohexyl methacrylate, isobomyl methacrylate,

Maleic anhydride and its derivatives such as maleic acid esters, λlaleic acid diesters and maleimides, e.g. Alkyl and aryl maleimides, such as methylcyclohexyl or

Phenylmaleimide. Methacrylates, acrylonitrile and methacrylonitrile, in particular acrylonitrile, are preferred.

Furthermore, as (co) monomers styrene, vinyl, acrylic or methacrylic compounds (for example styrene, optionally substituted with C.-ι: -alkyl radicals, halogen atoms, halogen-methylene radicals; vinylnaphthalene, nrnylcarbazole; vinyl ether with Cι-. ₂ - Ether residues; vinylimidazole,

Dimethylaminoethyl (meth) acrylate, p-dimethylaminostyrene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, butyl acrylate, ethylhexyl 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 1 to 10 Alcohols containing C atoms) can be used.

According to one embodiment of the invention, component A comprises 50 to 100% by weight, preferably 50 to 90% by weight of the above-described first phase (graft base) Al and 0 to 50% by weight, preferably 10 to 50% by weight the second phase (graft) A2 described above. based on the total weight of component A. In particular, styrene copolymers can be considered as the third phase.

According to one embodiment of the invention, 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. have.

In a preferred embodiment, the graft A2 consists of at least one or more graft shells, the outermost graft shell of which 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. .

With regard to the measurement of the glass transition temperature and the average particle size and the Q values, what has been said for the emulsion polymers A applies to the graft copolymers A.

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 are preferred Graft copolymers A prepared by 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 benzoyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ^C 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 shells are preferably constructed 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 processes 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.

According to the process described in DE-C-12 60 135, 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 crosslinking monomers, optionally together with the other 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. According to one embodiment, 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. In general, in a weight ratio of W ater ^τ to monomers of from 2: 1 to 0.7: 1 worked. The usual persulfates, such as potassium persulfate, in particular, serve 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. Further polymerization auxiliaries which can be used are the customary 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 α-methylstyrene, during the polymerization be used.

To produce the graft polymer A, a monomer mixture of styrene and acrylonitrile is then polymerized in a next step in the presence of the latex of the crosslinked acrylic ester polymer thus obtained, 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 acid 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 AI, 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 of the mixture of styrene and acrylonitrile in the presence of the crosslinking acrylic acid ester polymer is carried out in such a way that a degree of grafting of 1-99% by weight, preferably 20-85% by weight, in particular 35-60% by weight, based on the Total weight of component A, resulting in graft copolymer A. There the graft yield in the graft copolymerization is not 100%, a somewhat larger amount of the monomer mixture of styrene and acrylonitrile is 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 familiar to the facrn --- m and can be carried out, for example, by the metering speed of the sLo orers or by adding a regulator (Chauvel, Daniel, ACS Polymer Prεrrints 15 (1974 ), Page 329 ff). The emulsion graft copolymerization generally gives rise to about 5-15% by weight, based on the graft copolymer, of free, non-grafted styrene / acrylonitrile copolymer. The share of

Graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method given above.

In the production of the graft copolymers A by the emulsion process, in addition to the given process engineering advantages, reproducible particle size changes are also possible, for example by at least partially agglomeration of 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 intended use, in particular with regard to the particle size.

In a particular embodiment, bimcdale particle size distributions of component A have proven to be particularly advantageous. These can be generated by mixing separately produced particles of different sizes, which can also have different compositions and shells (core / shell, core / shell / shell etc.) or a bimodal particle size distribution by partial agglomeration before, during or after the grafting. The graft copolymers A generally contain 1-99% by weight, preferably 15-80 and particularly preferably 40-65% by weight of the first phase (graft base) Al and 1-99% by weight, preferably 20-85, particularly preferably 35-60% by weight of the second phase (graft) A2, based in each case on the entire graft copolymer.

COMPONENT B

Component B is an amorphous or partially crystalline polymer.

Component B is preferably a copolymer of

bl: 40-100% by weight, preferably 60-85% by weight, units of a vinyl aromatic monomer, preferably styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or α Methylstyrene as component B1,

b2: 0 to 60% by weight, preferably 15-40% by weight, units of an ethylenically unsaturated monomer, preferably acrylonitrile or λlemacrylonitrile, in particular acrylonitrile as component B2.

b3: 0 to 60% by weight of a further ethylenically unsaturated copolymerizable monomer.

According to a preferred embodiment of the invention, the \ isosity number of component B is 50-120, preferably 55-100.

The amoφhen or partially crystalline polymers of component B for

Manufacture of the massage devices according to the invention, molding compositions used according to the invention, are made of at least one polymer from partially crystalline polyamides, partially aromatic copolyamides, polyolefins, ionomers, polyesters, Polyether ketones, polyoxyalkylenes, polyarylene sulfides and preferably polymers selected from vinyl aromatic monomers and / or ethylenically unsaturated monomers. Polymer mixtures can also be used.

Also suitable as component B of the molding composition used according to the invention for the production of the massage devices 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. Furthermore, partially crystalline polyamides can 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 / or azelaic acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid, and whose diamine component consists entirely or partially 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 isophoronediamine, and their compositions in principle from the prior art Technology are known (see Encyclopedia of Polymers, Vol. 11, p. 315 ff).

Examples of polymers which are furthermore suitable as component B of the molding compositions used according to the invention for producing the massage devices according to the invention are partially crystalline polyolefins, preferably homo- and copolymers of olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1 and heptene-1 , 3-methylbutene-1, 4-methylbutene-1, 4-methylpentene-1 and octene-1. Suitable polyolefins are polyethylene, polypropylene, polybutene-1 or poly-4-methylpentene-1. In general, a distinction is made between polyethylene (PE) high-density PE (HDPE), low-density PE (LDPE) and linear low-density -PE (LLDPE).

In another embodiment of the invention, the

Component B around ionomers. These are generally polyolefins as described above, in particular polyethylene, which contain monomers copolymerized with acid groups, for example acrylic acid, methacrylic acid and, if appropriate, others copolymerizable monomers. The acid groups are generally converted into ionic, possibly ionically crosslinked polyolefins with the aid of metal ions such as Na, ^Caτ , Mg ^" and Af ^{^} , 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). However, it is not absolutely necessary to convert the polyolefins containing acid groups by means of metal ions, and 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, are suitable as component B according to the invention.

In addition, component B can also be polyester, preferably aromatic-aliphatic polyester. Examples are polyalkylene terephthalates, 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.

As component B aromatic polyether ketones can be used, such as z. B. are described in publications GB 1 078 264, 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-A -0 165 406, and in the publication by CK Sham et. al., Polymer 29/6, 1016-1020 (1988).

Furthermore, as component B of the molding compositions used according to the invention for the production of the massage devices according to the invention, polyoxyalkylenes, e.g. Polyoxymethylene, and oxymethylene polymers are used.

Other suitable components B are the polyarylene sulfides, in particular the polyphenylene sulfide.

An amorphous copolymer of styrene and α-methyl styrene with acrylonitrile is preferably used as component B. The acrylonitrile content in these

Copolymers of component B are 0-60% by weight, preferably 15 40% by weight, based on the total weight of component B. Component B also includes the free, non-grafted styrene / acrylonitrile copolymers formed in the graft copolymerization for the preparation of component A. Depending on the conditions chosen for the production of the graft copolymer A in the graft copolymerization, it may be possible that a sufficient proportion of 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 prepared component B can preferably be a styrene / acrylonitrile copolymer, an α-ethylstyrene / acrylonitrile copolymer or an α-methylstyrene / styrene / acrylonitrile polymer. 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 StyroVAcryl itril copolymer and a c-methylstyτoyacrylonitrile copolymer can. In the event that component B of the molding compositions used according to the invention consists of a mixture of a styrene / acrylonitrile copolymer and a c .. methylstyrene / acrylonitrile copolymer, the acrylonitrile content of the two copolymers should preferably not be 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 preparation of component A and also in the preparation of the additional, separately prepared component B, the same monomer mixture of styrene and Acrylonitrile is assumed.

The additional, separately manufactured component B can according to the conventional Procedure can be obtained. Thus, according to one embodiment of the invention, the copolymerization of the styrene and / or α-methylstyrene with the acrylonitrile can be carried out in bulk, solution, suspension or aqueous emulsion. Component B preferably has a viscosity number of 40 to 120, preferably 50 to 120, in particular 55 to 100. 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 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 graft copolymers then being completely dried during the mixing.

COMPONENT C

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 - like also referred to below - as bisphenol A.

Instead of bisphenol A, other aromatic dihydroxy compounds can be used, in particular 2,2-di (4-hydroxyphenyl) pentane. 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl sulfane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenyl methane. 1, l-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxylcyclopentanes, in particular l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane as well as 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.

According to the invention, the average molecular weights (weight average M, 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 51-98% by weight, preferably 55-90% by weight, in particular 60-85% by weight, based in each case on the total molding composition.

According to one embodiment of the invention, the addition of polycarbonates leads, inter alia, to higher thermal stability and improved crack resistance of the molding compositions used according to the invention for producing the massage devices according to the invention.

COMPONENT D

As component D, the preferred thermoplastic molding compositions used according to the invention for producing the massage devices according to the invention contain 0 to 37% by weight, preferably 0 to 30% by weight, in particular 0 to 10% by weight of fibrous or particulate fillers and other additives or their mixtures, 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 µm. Both continuous fibers (rovings) and chopped glass fibers (staple) can be used.

Furthermore, fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can be added. In addition, metal flakes (for example aluminum flakes from Transmet Coφ.), Metal powder, metal fibers, metal-coated fillers, for example nickel-coated glass fibers and other additives which shield electromagnetic waves, can be added to the molding compositions used in accordance with the invention for the production of the flat wall elements according to the invention. Aluminum flakes (K 102 from Transmet) are particularly suitable for EMI (electromagnetic interference) purposes. The compositions can also 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 massage devices according to the invention can furthermore contain further additives D which are typical and customary for polycarbonates, SAN polymers and graft copolymers or their mixtures. Examples of such additives are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve thermal stability, to increase light stability, to increase resistance to hydrolysis and chemicals, buffer substances, flame retardants, drip inhibitors, transesterification inhibitors against heat decomposition and in particular the lubricants / lubricants and waxes 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). Other suitable stabilizers are the usual hindered phenols, but also vitamin E or compounds of an analog structure. HALS stabilizers (hindered amine light stabilizers), benzophenones, resorcinols, salicylates, benzotriazoles and other compounds are also suitable (for example Irganox, Tinuvin, such as Tmuvm 770 (HALS absorber, Bis (2,2,6, 6-tetramethyl-4-piperidyl) sebazate) or TinuvinT ³ (UN absorber - (2H-benzotriazol-2-yl) -4-methylphenol), topanol). These are usually used in amounts of up to 2% by weight (based on the total mixture).

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.

Commercial halogen-free or halogen-containing flame retardants can also be used in customary amounts, for example up to 50% by weight. Examples of halogen-free flame retardants are described in EP-A-0 149 813. Otherwise, reference is made to DE-A-34 36 815, poly (tetrabromobisphenol A (glycidyl) ether) having a molecular weight of 40,000 being particularly preferred.

Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01-5% by weight, based on the total molding composition.

The thermoplastic molding compositions used for the production of the massage devices 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, such as 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 components can be metered in together or separately / one after the other.

According to one embodiment of the invention, the massage devices and housings thereof (massage device housings) can be produced from the thermoplastic molding compositions used according to the known methods of thermoplastic processing. In particular, the production can be carried out by thermoforming, extruding, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding. Especially in calendering and deep drawing, plates and foils are produced or used as intermediate stages.

According to one embodiment of the invention, the massage devices are operated electrically. However, they can also be operated in other suitable ways, for example pneumatically.

The massagers are used in the medical or therapeutic as well as in the cosmetic massage of the human body. she support the activity of the masseur. According to one embodiment of the invention, the massage devices perform rotary or vibratory movements or a combination thereof, in particular on the part of the massage device that comes into contact with human skin.

In particular, the parts that come into contact with the human body consist of the thermoplastic molding composition according to the invention.

All suitable massage devices known to the person skilled in the art can be considered as massage devices. The massagers can be installed mobile or stationary.

Since massage devices or their housings come into contact with skin creams and massage oils or other substances used in the massage as well as with cleaning agents and disinfectants, they have to be very resistant to chemicals. The massage devices according to the invention produced from the thermoplastic molding compositions described have very good chemical resistance. In addition, they are scratch-resistant, which is particularly advantageous when cleaning.

In addition, the massage devices according to the invention and their housings are resistant to yellowing and very stable. They have a balanced ratio of toughness and bending stiffness.

Due to the high content of polycarbonates in the molding compounds, the massage devices and housings are very heat-resistant and resistant to lasting heat. By adding the polycarbonate as component C, the heat resistance and impact resistance of the massage devices are further improved. These massagers also have good dimensional stability as well as excellent resistance to heat aging and high resistance to yellowing under thermal stress and exposure to UV radiation. The massagers or housings for this have excellent surface properties that can be obtained without further surface treatment. The appearance of the finished surfaces of the massage devices can be modified by suitable modification of the rubber morphology, for example in order to achieve glossy or matt surface designs. The massagers. show very little graying or yellowing effect when exposed to weather and UV radiation, so that the surface properties are retained. Further advantageous properties of the massage devices are the high weather stability, good thermal resistance, high yellowing resistance under UV radiation and thermal stress, good stress crack resistance, in particular 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 massage devices according to the invention made of the thermoplastic molding compositions used according to the invention show no significant loss of toughness or impact resistance, even 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. Furthermore, the molding compositions or massage devices according to the invention have a high resistance to scratching, a high resistance to swelling and a low permeability to liquids and gases, as well as good fire resistance.

It is possible to recycle thermoplastic molding compositions already used to manufacture the massage devices according to the invention in accordance with the present invention. Because of the high color stability, weather resistance and aging resistance, the molding compositions used according to the invention are very suitable for reuse. The proportion of reused (recycled) molding compound can be high. When using, for example, 30% by weight of molding compound already used, which was mixed in the ground form with the molding compounds used according to the invention, changed the relevant material properties such as flowability, Vicat softening temperature and impact resistance of the molding compositions and the massage devices according to the invention produced therefrom are not significant. Similar results were obtained when the weather resistance was examined. The impact strength was constant over a long time even when using recycled thermoplastic molding compositions, see Lindenschmidt, Ruppmich, Hoven-Nievelstein, International Body Engineering Conference, September 21-23, 1993, Detroit, Michigan, USA, Interior and Exterior Systems, pages 61 to 64. The resistance to yellowing was also retained. 10

The invention is illustrated by the following examples.

EXAMPLES

15 Example 1

Production of small-part graft copolymer (A)

(al) 16 parts of butyl acrylate and 0.4 part of tricyclodecenyl acrylate were in 150 0 parts of water with the addition of part of the sodium salt of a C ₂ - bis

Cι ₈ -paraffinsulfonic acid, 0.3 parts Kaliumper-sulfate, 0.3 parts of sodium bicarbonate is heated and 0.15 part of sodium pyrophosphate with stirring to 60 ° C. A mixture of 82 parts of 5-butyl acrylate and 1.6 parts of tricyclodecenyl acrylate was added within 3 hours 10 minutes after the start of the polymerization reaction. To

The completion of the monomer addition was left to react for an hour. 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. The particle size distribution was narrow

30 (quotient Q = 0.29). (a2) 150 parts of the polybutyl acrylate latex obtained according to (al) were mixed with 40 parts of a mixture of styrene and acrylonitrile (weight ratio ~ 5:25) and 60 parts of water and with stirring after the addition of a further 0.03 part of potassium persulfate and 0 , 05 parts of lauroyl peroxide heated to 65 ° C for 4 hours. After the end of the graft copolymerization, the polymerization product was precipitated from the dispersion using calcium chloride solution at 95 ° C., washed with water and dried in a warm air stream. The degree of grafting of the graft copolymer was 35%.

Example 2

Production of large-scale graft copolymer (A)

(al) On the one hand, after adding 50 parts of water and 0.1 part of potassium persulfate, a mixture of 49 parts of butyl acrylate and 1 Part of tricyclodecenyl acrylate and on the other hand a solution of 0.5 part of the sodium salt of a C. to cis paraffin sulfonic acid in 25 parts

Let water run in at 60 ° C. After the end of the feed, polymerization was continued for 2 hours. The latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40%. The average particle size (weight average of the latex) was found to be 288 nm. The particle size distribution was narrow (Q = 0.1).

(a2) 150 parts of this latex were mixed with 40 parts of a mixture of styrene and

Acrylonitrile (ratio 75:25) and 110 parts water mixed and under

Stirring after addition of a further 0.03 part of potassium persulfate and 0.05 part of lauroyl peroxide is heated to 65 ° C. for 4 hours. That at the

Graft copolymerization polymerization product obtained was then precipitated from the dispersion using a calcium chloride solution at 95 ° C., separated off, washed with water and dried in a warm air stream. The degree of grafting of the graft copolymer was determined to be 27%.

Example 3

Production of large-scale graft copolymer (A)

(al) 16 parts of butyl acrylate and 0.4 part of tricyclodecenyl acrylate were in 150 parts of water with the addition of 0.5 part of the sodium salt of a C12 bis

Ci8 paraffin sulfonic acid, 0.3 part potassium persulfate. 0.3 parts

Sodium bicarbonate and 0.15 parts of sodium pyrophosphate under

Stirring heated to 60 ° C. 10 minutes after the start of the

A reaction mixture of 82 parts of butyl acrylate and 1.6 parts of tricyclodecenyl acrylate was added over the course of 3 hours. To

The completion of the monomer addition was left to react for an hour. The latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40% by weight. The average particle size

(Weight average) was determined to be 216 nm. The particle size distribution was narrow (Q = 0.29).

(a2) 150 parts of the polybutyl acrylate latex obtained according to (al) were mixed with 20 parts of styrene and 60 parts of water and heated to 65 ° C. for 3 hours with stirring after the addition of a further 0.03 part of potassium persulfate and 0.05 part of lauroyl peroxide. After completing the first stage of

The graft polymer had a degree of grafting of 17%. This graft polymer dispersion was polymerized without further additives with 20 parts of a mixture of styrene and acrylonitrile (ratio 75:25) for a further 3 hours. After the graft polymerization had ended, the product was precipitated from the dispersion using calcium chloride solution at 95 ° C., washed with water and in the warm Airflow dried. The degree of grafting of the graft polymer was 35%, and the average particle size of the latex particles was found to be 238 nm.

Example 4

Production of large-scale graft copolymer (A)

(al) On the one hand, a mixture of 49 was added to a template from 2.5 parts of the latex produced in Example 3 (component A) after the addition of 50 parts of water and 0.1 part of potassium persulfate over the course of 3 hours

Parts of butyl acrylate and 1 part of tricyclodecenyl acrylate and, on the other hand, a solution of 0.5 part of the sodium salt of a C12- to cis-paraffin sulfonic acid in 25 parts of water at 60 ° C. After the end of the feed, polymerization was continued for 2 hours. The latex of the crosslinked butyl acrylate polymer obtained had a solids content of 40%. The mean particle size (weight average) of the latex was found to be 410 nm. The particle size distribution was narrow (Q = 0.1).

(a2) 150 parts of the polybutyl acrylate latex obtained according to (a1) were mixed with 20 parts of styrene and 60 parts of water and with stirring after the addition of a further 0.03 part of potassium persulfate and 0.05 part of lauroyl peroxide 3

Heated to 65 ° C for hours. The one obtained from this graft polymerization

The dispersion was then mixed with 20 parts of a mixture of styrene and

Acrylonitrile in the ratio 75:25 polymerized for a further 4 hours. The reaction product was then precipitated from the dispersion using a calcium chloride solution at 95 ° C., separated off, washed with water and dried in a warm air stream. The degree of grafting of the graft polymer was determined to be 35%, and the average particle size of the latex particles was

490 nm. Example 5

Production of large-scale graft copolymer (A)

(al) 98 parts of acrylic acid butviester and 2 parts of tricyclodecenyl acrylate were polymerized in 154 parts of water with the addition of 2 parts of dioctylsulfosuccinate sodium (70%) as emulsifier and 0.5 parts of potassium persulfate with stirring for 3 hours at 65 ° C. An approximately 40% dispersion was obtained. The average particle size of the latex was approximately 100 nm.

To a template from 2.5 parts of this latex. A mixture of 49 parts of butyl acrylate, 1 part of tricyclodecenyl acrylate and 0.38 part of the emulsifier was added to 400 parts of water and 0.5 part of potassium persulfate at 65 ° C. in the course of 1 hour. In the course of a further hour, a mixture of 49 parts of butyl acrylate, 1

Part of tricyclodecenyl acrylate and 0.76 part of emulsifier. After adding 1 part of potassium persulfate in 40 parts of water, a mixture of 196 parts of butyl acrylate, 4 parts of tricyclodecenyl acrylate and 1.52 parts of the emulsifier was finally added dropwise over the course of 2 hours. The polymer mixture was then polymerized at 65 ° C. for a further 2 hours. An approximately 40% dispersion with an average particle diameter of approximately 500 nm was obtained.

If only 100 parts were added instead of a total of 300 parts of monomers, a latex with an average particle diameter of about 300 nm was obtained.

(a2) 465 parts of styrene and 200 parts of acrylonitrile were in the presence of 2500

Parts of the polymer latex according to (al) with the mean particle size 0.1 or 0.3 or 0.5 μm, 2 parts of potassium sulfate, 1.33 parts of lauryl peroxide and 1005

Parts of water polymerized with stirring at 60 ° C. A 40% was obtained Dispersion from which the solid product was precipitated by adding a 0.5% calcium chloride solution, washed with water and dried.

Example 6

Production of copolymer (B)

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.

Example 7

Production of copolymer (B)

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.

Example 8

Production of copolymer (B)

A monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions. The styrene-acrylonitrile copolymer obtained had an acrylonitrile content of 27% by weight, based on the copolymer, and a viscosity number of 80 ml / g. Comparative Example 1

ABS polymer

5 As a comparative polymer, a polybutadiene rubber was used which was grafted with a styrene-acrylonitrile copolymer as component (A), which was present in a styrene-acrylonitrile copolymer matrix as component (B). The graft rubber content was 30% by weight, based on the total weight of the finished polymer. 10

Example 9

Component C

15 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. According to the information in Table 1 below, the stated amounts of the corresponding polymers (A), (B) and (C) or of the comparative materials are in a screw extruder at a temperature of 250 ° C.

20 280 ° C mixed. Molded bodies were produced from the molding compositions formed in this way.

The composition of the molding compounds is shown in the table below:

Table I

Test results:

a: scratch resistance

The scratch resistance is determined using a CSEM Automatic Scratch Tester model AMI (manufacturer: Center Suisse d'Electronique et de Microtechnique S.A.). The scratch tester has a diamond tip with a 120 ° tip angle and 0.2 mm radius. With this diamond tip, scratches of 5 mm length are introduced into injection molded test specimens from the material to be tested. The contact pressure of the diamond, unless otherwise stated, is 2.6 N. After an hour of waiting, the scratches that are created are scanned in the transverse direction and displayed as a height / depth profile. The scratch depth can then be read from this.

b: Stress crack resistance

The resistance to stress cracking is determined using the bending strip method in accordance with ISO 4599. The test specimens used are injection molded. They have the dimensions 80 x 15 x 2 mm. Unless otherwise stated, the test specimen was machined with a bending radius of 50 mm. For this purpose, the test specimens were clamped in a template, bent and wetted with the test medium for 24 hours. Then the impact work at break is determined with a pendulum. Bl isopropanol was used as the test medium. A common household cleaner (Ajax Ultra Classic® from Colgate Palmohve Germany, a surfactant household cleaner) was used in b2. c: swelling

To measure swelling, injection-molded shoulder bars (tensile bars according to ISO 3167 with a thickness of 4 mm) are stored in the medium to be tested for 96 h. Then they are superficially dried, and the change in weight and, if necessary, the change in tensile modulus (determined according to ISO 527) are determined in comparison with the initial value. Table II, cl shows the change in weight in methanol, in c2 in super gasoline and in c3 the change in tensile modulus in super gasoline.

d: permeability

To test the permeability, foils are pressed from the material to be tested (thickness approx. 120 to 250 μm), the permeability of which to the specified gases or liquids is determined at 23 ° C. The values are given in (cm ³ 100 μm) / (md bar) for gases or in (g 100 μm) / (md) for water (Table IT).

Molding compositions that can be used advantageously should meet the following conditions: scratch depth of less than 6 μm, change in impact energy compared to the initial value of less than 10%, swelling in methanol of less than 1% or swelling and change in the modulus of elasticity of less than 6 % in super gasoline.

The results are shown in Tables II and HI below. -O

E5

In addition, the swelling at different exposure times was investigated on the molding compound LT and the comparative molding compound VTI. The results are shown in Table IV below:

Table IV Swelling (weight change) in methanol and premium gasoline

Furthermore, the fogging behavior according to VW-PV 3015, method B (100 ° C., 16 h) was investigated for the molding compound DJ and the comparative molding compound Nu. No noteworthy quantities could be analyzed.

The molding compositions with a polycarbonate content of more than 50% by weight had an excellent combination of properties. This advantageous property spectrum makes them particularly suitable for use in massage devices and housings thereof.

Claims

claims

1. Use of a thermoplastic form other than ABS. containing, based on the sum of the amounts of components A, B, C and optionally D, which gives a total of 100% by weight,

a: 1-48% by weight of at least one single-phase or multi-phase particulate emulsion polymer with a glass transition temperature below 0 ° C. in at least one phase and rather average particle size of 50-1000 nm, as component A,

b: 1-48% by weight) of at least one amorphous or partially crystalline

Polymer as component B,

c: 51-98% by weight> polycarbonates as component C, and

d: 0 - 47% by weight of conventional additives and / or fibrous or particulate

Fillers or their mixtures as component D

for the manufacture of massage devices and housings thereof.

2. Use according to claim 1, characterized in that component A is a multi-phase polymer from

al: 1 - 99 wt .-% of a teilchenfb ^'shaped first phase with an AI

Glass transition temperature below 0 ° C,

a2: 1-99% by weight of a second phase A2 from the monomers, based on A2, a21: 40-100% by weight> units of a vinylaromatic monomer as component A21 and

a22: 0 to 60% by weight of units of an ethylenically unsaturated monomer as component A22,

a3: 0 to 50% by weight of a third phase with a glass transition temperature of more than 0 ° C. as component A3, the total amount of components AI, A2 and A3 giving 100% by weight.

3. Use according to claim 2, characterized in that the molding composition contains as a particulate first phase AI an acrylate, EP, EPDM or silicone rubber.

4. Use according to claim 3, characterized in that component AI consists of the monomers

all: 80-99.99% by weight of a C 8 _-8- alkyl ester of acrylic acid as component All,

al2: 0.01-20% by weight of at least one polyfunctional crosslinking agent

Monomers as component AI 2.

5. Use according to one of claims 1 to 4, characterized in that the particle size distribution of component A is bimodal, with 1-99% by weight an average particle size of 50-200 nm and 1-99% by weight »an average Have particle sizes of 200-1000 nm, based on the total weight of component A.

6. Use according to one of claims 1 to 5, characterized in that the massagers are operated electrically.

7. Use according to one of claims 1 to 6, characterized in that the massagers perform a rotational or vibratory movement or a combination thereof.

8. Use according to any one of claims 1 to 7, characterized in that the parts which come into contact with the human body, or whose sheathing are made from the thermoplastic molding compositions.

9. massagers or housings thereof made of a thermoplastic molding composition as defined in one of claims 1 to 5.

10. Massager or housing thereof according to claim 9, characterized in that the parts which come into contact with the human body, or the sheathing of a thermoplastic molding composition, as defined in one of claims 1 to 5, exist.

11. Use according to one of claims 1 to 5 for the production of semi-finished products, profiles, tubes, films and plates which are used for the production of

Housing are processed.