WO2000020509A1

WO2000020509A1 - Sporting good made from polycarbonate mixtures

Info

Publication number: WO2000020509A1
Application number: PCT/EP1999/007444
Authority: WO
Inventors: Norbert Güntherberg; Heiner GÖRRISSEN; Graham Edmund Mc Kee; 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: DE19846209A1

Abstract

The invention relates to the utilization of a shaped thermoplastic material different from ABS for the production of sporting goods and semi-finished goods thereof, containing, 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 a single or multiphase particulate emulsion polymer with a glass transition temperature below 0° 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. The shaped materials are preferably mixtures of polycarbonate, a graft polymer of stryrol and acrylonitrile on a butyl acrylate rubber (ASA) with a bimodal particle size distribution and a styrol-acrylonitrile copolymer (SAN).

Description

SPORTS ARTICLES MADE OF POLYCARBONATE BLENDS

The invention relates to sports articles, such as sports equipment, transport containers for sports equipment and camping items, hereinafter referred to as

"Sports articles" are summarized.

In particular, the invention relates to such sports articles with good dimensional stability, great stability, good chemical resistance and good yellowing resistance.

So far, various materials have been used for the production of sporting goods. Metal castings are heavy and expensive and have to be painted. Sheet steel has a high density, is susceptible to corrosion and complex to process, since it can only be machined or reshaped.

ABS (acrylonitrile / butadiene / styrene) polymers do not always show sufficient resistance to yellowing and become brittle when used outdoors due to post-crosslinking of the butadiene double bonds. As a result, the mechanical properties deteriorate significantly. The swelling behavior towards alcohols and cleaning agents is not always good enough.

ASA (acrylonitrile / styrene / acrylate) polymers show good stress cracking behavior, but not always sufficient scratch resistance, color depth and not always sufficient toughness / rigidity ratio. Blends too Small amounts of polycarbonate do not always have sufficient stress crack resistance, chemical resistance or adequate toughness / stiffness ratio.

The object of the present invention is therefore to provide sports articles which are stable and resistant to chemicals and do not yellow. They are also said to be scratch-resistant. be 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 at

Manufacturing and application.

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, the total of 100

Wt% gives

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 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 conventional additives and / or fibrous or particulate fillers or mixtures thereof as component D.

for the production of sports articles or semi-finished products thereof. Specified glass transition temperatures of phases refer to a polymer with the composition corresponding to this phase.

The sporting goods described are scratch-resistant, stable and resistant to chemicals. They also have very good yellowing resistance and depth of color.

The components of the thermoplastic molding compositions used according to the invention for the production of the sports articles 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 compositions other than ABS used to produce the sporting articles according to the invention contain components A and B and C and, if appropriate, 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

Polycarbonates as component C, and d: 0 to 47% by weight, preferably 0 to 37% by weight, in particular 0 to 30% by weight of additive, and / or fibrous or particulate fillers or mixtures thereof as component D.

The invention is explained in more detail below.

The molding compositions used to produce the sports articles according to the invention and the components from which they are constructed are first described.

COMPONENT A

Component A is at least one single or multiphase particulate ^'rmiges emulsion polymer having a glass transition temperature below 0 ° C in at least one phase and an average particle size of 50 - nm 1000th

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% 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 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 wt .-% 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 gives 100 wt .-%.

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 greater 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 styrene, 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 weight .-%, preferably 95 to 99.9 wt .-%, of a Cι _-8 -alkyl acrylate, preferably n-butyl acrylate and / or ethylhexyl acrylate, as component space,

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 is

Component A 50-1000 nm, preferably 50-800 nm.

According to a further embodiment according to 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. The mean particle sizes according to the invention are in all cases 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 mean particle diameter, which is also referred to as the d ₀ 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 larger in diameter than the d ₅₀ value. To characterize the width of the particle size distribution of the rubber particles, in addition to the d ₅ o value (average particle diameter), the d ₀ and d ₉₀ values resulting from the integral mass distribution are used. The dio or d9 ₀ value of the integral mass distribution is defined in accordance with the d o value, with the difference that they are based on 10 or 90% by weight of the particles. The quotient.

1 90 ^' HO

= Q you 50

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. Preferably, the

Molding compounds free from butadiene rubbers.

According to one embodiment, the diene basic building block component in the emulsion polymer A 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 O-8 alkyl acrylates, preferably C _4-8 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 alkyl acrylate rubbers can contain up to 30% by weight of 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 which are capable of copolymerization and which are preferably not conjugated in the 1,3 positions.

Suitable crosslinking monomers are, for example, ethylene glycol di (meth) acrylate,

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

Suitable silicone rubbers may, for example, crosslinked silicone rubbers of units of the general formulas R ₂ SiO, RSiO / _2, R ₃ SiOι be / 2 and SiO _{_2/4,} where the radical R is a monovalent radical. The amounts of the individual siloxane units are dimensioned so that 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 / ₂ and 0 to 3 moles -Units SiO ₂ / 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.

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-0260 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 Polymensat A

The emulsion polymer A can also be a multi-stage polymer (so-called "core / shell structure", "core-shell morphology").

For example, a rubber-elastic core (T _g <0 ° C) can be encased by a "hard" shell (polymers with T _g > 0 ° C) or vice versa.

In a particularly preferred embodiment of the invention, component A is a graft copolymer. The graft copolymers A of the molding compositions according to the invention have an average particle size d ₀ of 50 1000 nm, preferably from 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 onto it, the so-called graft calls or graft shells.

One or more graft shells can be applied to the rubber particles by simple grafting or multiple stepwise grafting, each

Graft shell can have 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 from 15 -

99.9% by weight of acrylate rubber, 0.1-5% by weight of crosslinking agent and 0-49.9% by weight composed of one of the specified further monomers or rubbers.

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 α-. Methyl styrene, p-methyl styrene, 3,4-dimethyl styrene, p-tert-butyl styrene, o and p-methyl-α-methyl styrene or C ₈ -C ₈ alkyl (meth) acrylates such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n- Butyl acrylate, i-butyl acrylate; styrene, α-methylstyrene, methyl methacrylate, in particular styrene and / or α-methylstyrene, and ethylenically unsaturated monomers, such as acrylic and methacrylic compounds, such as acrylonitrile, methacrylonitrile, acrylic and methacrylic acid, methyl acrylate, ethyl acrylate, n- and isopropyl acrylate, n are preferred 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, isobornyl methacrylate,

Maleic anhydride and its derivatives such as maleic esters, maleic diesters and maleimides, e.g. Alkyl and aryl maleimides, such as methyl, cyclohexyl or phenyl maleimide. 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 12 alkyl radicals, halogen atoms, halogen methylene radicals; vinyl naphthalene, vinyl carbazole; vinyl ethers with C1-12 ethene radicals; vinyl imidazole, 3 - (4-) Vinylpyridine, 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 - Atoms, preferably alcohols containing 1 to 10 carbon 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 first phase described above (graft base) Al and 0 to 50% by weight, preferably 10 to 50% by weight the above-described second phase (graft) A2, based on the total weight of component A. In particular, the third phase is styrene

Copolymers into consideration.

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 be one

Glass transition temperature below -20 ° C, especially below -30 ° C, have.

In a preferred embodiment, the graft A2 consists of one or more graft shells, the outermost graft shell of which has a glass transition temperature of more than 30 ° C., one of which consists of the monomers

Polymer A2 formed graft 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 as well as the Q values, the same applies to the graft copolymers A.

Emulsion polymers A Said.

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 the emulsion,

Solution, bulk or suspension polymerization. The graft copolymers A are preferably prepared by radical emulsion polymerization, in particular in the presence of latices of component AI at temperatures of 20 ° C - 90 ° C using water-soluble or oil-soluble initiators such as peroxodisulfate or benzoyl peroxide, or with the help 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 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 according to the invention are defined

- 1000 nm is preferably carried out according to the methods 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 are 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 AI is first prepared by adding the acrylic acid ester (s) used according to one embodiment of the invention and the polyfunctional monomers which cause crosslinking, 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 with 10 to 18 are preferably used

Carbon atoms. 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, the weight ratio of water to monomers is from 2: 1 to 0.7: 1. The usual persulfates, such as potassium persulfate, in particular, serve as polymerization initiators. However, it can redox systems are also 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 are set, such as sodium bicarbonate and

Sodium pyrophosphate, and 0-3% by weight of a molecular weight regulator, such as mercaptans, terpmoles or dimeric α-methylstyrene, are used in the polymerization.

In a next step, the graft polymer A is then prepared in

In the presence of the latex of the crosslinked acrylic acid ester polymer thus obtained, according to one embodiment of the invention, a monomer mixture of styrene and acrylonitrile is polymerized, the weight ratio of styrene to acrylonitrile in the monomer mixture according to one embodiment of the invention being in the range from 100: 0 to 40:60, preferably should be 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 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 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 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 can be used as it 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 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 a few% by weight, based on the graft copolymer, of free, ungrafted 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 in the

Graft copolymers A can also be polymers with different particle sizes.

In a particular embodiment, bimodal 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 be different in their composition and shell structure (core / shell, core / shell / shell, etc.), or a bimodal particle size distribution can be generated by partial agglomeration , during or after the grafting.

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 to 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 layer) A2, in each case based 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 methacrylonitrile, in particular acrylonitrile as component B2,

b3: 0 to 60% by weight of a further ethylenically unsaturated copolymerisable

Monomers.

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

The amorphous or partially crystalline polymers of component B of the molding composition used according to the invention for the production of the sports articles according to the invention are composed of at least one polymer of partially crystalline polyamides, partially aromatic copolyamides, polyolefins, ionomers, polyesters, polyether ketones, polyoxyalkylenes, polyarylene sulfides and preferably

Polymers made from vinyl aromatic monomers and / or ethylenically unsaturated Monomers selected. Polymer mixtures can also be used.

Also 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 are suitable as component B of the molding composition used according to the invention for the production of the sports articles according to the invention. 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 acelaic acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid, and their

Diamine component wholly or partly in particular consists 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 are known from the prior art (cf. 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 the production of the sports articles 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, component B is an ionomer. 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, further copolymerizable monomers. The acid groups are generally crosslinked with the aid of metal ions such as Na ⁺ , Ca ⁺ , Mg ⁺ and Al ⁺ into ionic, possibly ionic Converted polyolefins that can still be processed thermoplastically (see, for example, US 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. 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 also known as. Component B according to the invention is suitable.

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.

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-A-0 165 406, and in the publication by CK Sham et . al., Polymer 29/6, 1016-1020 (1988).

Component B can also be used for the preparation of the invention

Molding materials used 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 / or α-methylstyrene with acrylonitrile is preferably used as component B. The acrylonitrile content in these copolymers of component B is 0-60% by weight, preferably 15-40% by weight, based on the total weight of component B. To the component

B also includes those in the graft copolymerization to produce the component A free, non-grafted styrene / acrylonitrile copolymers formed. 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 produced component B -.

This additional, separately produced component B can preferably be a styrene / acrylonitrile copolymer, an α-methylstyrene /

Trade acrylonitrile copolymer or a "-MethylstyroyStyro acyl nitrile terpolymer. These copolymers can be used individually or as a mixture for component B, so that the additional, separately produced component B of the molding compositions used according to the invention is, for example, a mixture of a styrene-acrylonitrile copolymer and an α-methylstyrene / acrylonitrile copolymer can act. 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 an α-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 be obtained by the conventional methods. Thus, according to one embodiment of the invention, the copolymerization of the styrene and / or α-methylstyrene with the acrylonitrile in Mass, solution, suspension or aqueous emulsion are carried out. 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 DTN 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 - as also hereinafter - referred to as bisphenol A.

Instead of bisphenol A, other aromatic dihydroxy compounds can also be used are 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, 1 -Di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxylcyclopentanes, in particular 1,1-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 a high

Characterize 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)

According to the invention, 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 relative

Solution viscosities in the range from 1.1 to 1.3, measured in 0.5 wt .-% 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 the entire molding compound.

According to one embodiment of the invention, the addition of polycarbonates leads, among other things, to higher thermal stability and improved crack resistance of those used to produce the sports articles according to the invention

Molding compounds.

COMPONENT D

As component D contain those for the production of the invention

Preferred thermoplastic molding compositions used according to the invention are 0 to 50% by weight, preferably 0 to 37% by weight, in particular 0 to 30% by weight of fibrous or particulate fillers and other additives 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 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 flour and wollastonite can be added.

In addition, metal flakes (e.g. aluminum flakes from Transmet Corp.), metal powder, metal fibers, metal coated fillers, e.g. nickel coated

Glass fibers and other additives that shield electromagnetic waves, are added to the molding compositions used in the manufacture of the sports equipment according to the invention. Aluminum flakes (K 102 from Transmet) are particularly suitable for EMI (electro-magnetic interference) purposes. Furthermore, the masses 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 sporting articles according to the invention may also contain other additives D which are typical and customary for polycarbonates, SAN polymers and graft copolymers or mixtures thereof. 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 to chemicals, buffer substances, drip inhibitors, transesterification inhibitors,

Flame retardants, agents against heat decomposition and in particular the lubricants / lubricants and waxes which are useful for the production of moldings or moldings. These additional additives can be metered in at any stage of the production process, but preferably at an early stage in order to achieve the stabilization effects (or other special effects) at an early stage

Effects) of the additive. 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 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 ^® ). 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 20% 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, in particular poly (tetrabromobisphenol-A-

(glycidyl) ether) with a molecular weight of 40,000 is 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 according to the invention for the production of the sports articles according to the invention can be produced by methods known per se by mixing the components. It can be advantageous to premix individual components. Even mixing the components in

Solvent and solvent removal is possible.

Suitable organic solvents are, for example, chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene or aromatic hydrocarbons, for example 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 sports articles according to the invention can be produced from the thermoplastic molding compositions used according to the invention by the known methods of thermoplastic processing. In particular, 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. Especially in calendering and deep drawing, plates and foils are produced or used as an intermediate stage.

The sporting goods can be sports equipment, transport containers or camping articles. These are preferably used outdoors.

The sports equipment or its housings or semi-finished products include, for example, parts of bicycles, skis, sleds, safety equipment for the sports sector such as bicycle helmets, components for bike trailers, table tennis tables, soccer goals, etc. The sports equipment also includes body-building equipment, such as those used in fitness -Studios and use with exercise bikes. Other sports equipment are

Leisure vehicles (fun cars and fun bikes), golf caddies, snowboards, snow bikes, Snowmobiling, as well as water sports articles. Sports equipment also includes boat fittings, especially for interior and exterior boat fitting. Solarium parts can also be constructed from the molding compositions according to the invention. The camping articles include, for example, tent poles, camping furniture, caravan parts, as well as beach chairs, screens, wind and sun protection devices.

Transport containers for sporting goods are, for example, roof racks and roof boxes, bicycle and ski holders, as well as transport boxes and other transport containers.

The list of the above sports articles is not exhaustive but serves to explain the term. In addition to the articles themselves, semi-finished products, profiles, plates, shells, etc. can also be constructed from the molding materials.

The combination of properties such as weather resistance, dimensional stability, resistance to stress cracking, scratch resistance and resistance to fuel components is particularly important for sports equipment with motor drive, snowmobiles, water motorcycles, golf caddies etc.

In addition, the sports articles 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 sporting goods are very heat-resistant and resistant to lasting heat. By adding the polycarbonate as component C, the heat resistance and impact resistance of the sporting goods are further improved. These sports articles 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 sporting goods have excellent surface textures that can be obtained without further surface treatment. The appearance of the finished surfaces of the sporting goods can be modified by suitable modification of the rubber morphology, for example in order to achieve glossy or matt surface designs. The sports articles 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 sporting goods 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 sports articles according to the invention made from 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. Furthermore, the molding compositions or sports articles according to the invention have high resistance to scratching, high resistance to swelling and low permeability to liquids and gases, as well as good fire resistance.

It is possible to recycle thermoplastic molding compositions already used to produce the sports articles 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, the relevant changes Material properties such as flowability, Vicat softening temperature and impact resistance of the molding compositions and the sporting goods 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.

The invention is illustrated by the following examples.

EXAMPLES

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 parts of water with the addition of part of the sodium salt of a C12 to C ₈ paraffmsulfonic acid, 0.3 part of potassium per-sulfate, 0.3 part of sodium hydrogen carbonate and 0.15 Parts of sodium pyrophosphate heated to 60 ° C with stirring. A mixture of 82 parts of butyl acrylate and 1.6 parts of tricyclodecenyl acrylate was added within 3 hours 10 minutes after the start of the polymerization reaction. After the monomer addition had ended, the mixture 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 found to be 76 nm. The particle size distribution was narrow (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 75:25) and 60 parts of water and with stirring after the addition of further _. 0.03 part of potassium persulfate and 0.05 part of lauroyl peroxide heated to 65 ° C for 4 hours. After the graft copolymerization had ended, the polymerization product was precipitated from the dispersion by means of 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, a mixture of 49 parts of butyl acrylate was added to a sample of 2.5 parts of the latex produced in step (a1) from Example 1 after the addition of 50 parts of water and 0.1 part of potassium persulfate over the course of 3 hours 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 paraffinsulfonic 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 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 of water and under

Stir after adding a further 0.03 part of potassium persulfate and 0.05 part Lauroyl peroxide heated to 65 ° C for 4 hours. The polymerization product obtained in the graft copolymerization 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 added to 150 parts of water with the addition of 0.5 part of the sodium salt of a C12 to cis paraffin sulfonic acid, 0.3 part of potassium persulfate, 0.3 part of sodium hydrogen carbonate and 0.15 part Sodium pyrophosphate heated to 60 ° C with stirring. 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. After the monomer addition had ended, the mixture 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 (a1) were mixed with 20 parts of styrene and 60 parts of water and heated with stirring after the addition of a further 0.03 part of potassium persulfate and 0.05 part of lauroyl peroxide to 65 ° C. for 3 hours. After the first stage of the graft copolymerization had ended, the graft polymer had a degree of grafting of 17%. This graft copolymer 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 end of the graft copolymerization, the Product 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 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) To a template from 2.5 parts of that prepared in Example 3 (component A)

Latex were, after addition of 50 parts of water and 0.1 part of potassium persulfate in the course of 3 hours, on the one hand a mixture of 49 parts of butyl acrylate and 1 part of tricyclodecenyl acrylate on the other hand a solution of 0.5 parts of the sodium salt of a C12 to ₈ Cι -paraffinsulfonic acid in Let 25 parts of 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 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 (al) were mixed with 20 parts

Styrene and 60 parts of water mixed and heated with stirring after the addition of a further 0.03 part of potassium persulfate and 0.05 part of lauroyl peroxide to 65 ° C for 3 hours. The dispersion obtained in this graft copolymerization was then polymerized with 20 parts of a mixture of styrene and acrylonitrile in the ratio 75:25 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 butyl acrylate 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 at 65 ° C. for 3 hours. An approximately 40% dispersion was obtained. The average particle size of the latex was approximately 100 nm.

A mixture of 49 parts of butyl acrylate, 1 part of tricyclodecenyl acrylate and 0.38 part of the emulsifier was added at 65 ° C. to an initial charge of 2.5 parts of this latex, 400 parts of water and 0.5 part of potassium persulfate within 1 hour. Over the course of a further hour, a mixture of 49 parts of butyl acrylate, 1 part, was added

Tricyclodecenyl acrylate and 0.76 parts 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

Divide the polymer latex according to (al) with the average particle size 0.1 or

Polymerized 0.3 or 0.5 microns, 2 parts of potassium sulfate, 1.33 parts of lauryl peroxide and 1005 parts of water with stirring at 60 ° C. A 40% was obtained

Dispersion from which the solid product by adding a 0.5% calcium chloride solution was precipitated, 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 18% by weight, based on the copolymer, and a viscosity number of 70 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

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

Example 9

Component C

A conventional polycarbonate (PC) was used as component C, the one

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 the comparative compositions are mixed in a screw extruder at a temperature of 250 ° C. to 280 ° C. Molded bodies were produced from the molding compositions formed in this way.

The composition of the molding compositions 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'Electromque et de Microtechmque 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 is 2.6 N, unless otherwise stated. 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 had 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. In b2 it became a common one

Household cleaner (Ajax Ultra Classic® from Colgate Palmolive Germany, a surfactant household cleaner). 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 π, cl shows the change in weight in methanol, in c2 in super petrol and in c3 the change in tensile modulus in super gasoline.

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 W Weertrtee iinn ((ccmm ³ 110000 Uμmm)) / (md bar) for gases or in (g 100 μm) / (md) for water are given (Table LT).

Molding compositions which 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 premium petrol.

The results are shown in Tables U and DI below.

Table III

In addition, the swelling at different exposure times was investigated on the molding compound HI and the comparative molding compound VE. 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 I, II and the comparative compound. Little fogging was observed for molding compound I, hardly any fogging for molding compound π, and noticeable fogging for the comparative molding compound.

The maximum service temperature was 110 ° C for molding compound and 115 ° C for molding compound H.

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 the manufacture of sports articles.

Claims

claims

1. Use of a thermoplastic molding composition other than 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- 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, 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

for the production of sporting goods and housings or semi-finished products thereof.

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

al: 1-99 wt .-% of a particulate first phase AI with a

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 of units of a vinyl aromatic 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 being 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 monomer 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, 1-99 % By weight o have an average particle size of 50-200 nm and 1-99% by weight have an average particle size 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 sports articles are sports equipment, camping items or transport containers for sports equipment.

7. Use according to one of claims 1 to 6, characterized in that the sports equipment is motor-operated.

8. Sports articles made of a thermoplastic molding composition as defined in one of claims 1 to 5.

9. Sports article according to claim 8, characterized in that it is sports equipment, transport containers or camping articles.

10. Use according to any one of claims 1-4 for the production of semi-finished products, profiles, tubes, foils and plates, which are processed for the production of sports equipment, camping items and transport containers.