EP1123351A1

EP1123351A1 - Moulded forms for use in gardening and animal husbandry

Info

Publication number: EP1123351A1
Application number: EP99948964A
Authority: EP
Inventors: Norbert Güntherberg; Heiner GÖRRISSEN; Graham Edmund Mc Kee; Norbert Niessner; Martin Weber
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1998-10-07
Filing date: 1999-10-06
Publication date: 2001-08-16
Also published as: WO2000020510A1; DE19846244A1; US6566436B1

Abstract

The invention relates to the use of a thermoplastic moulding material which is different from ABS for producing moulded forms and semi-finished products for use in the areas of gardening and animal husbandry, containing the following in relation to the sum of the quantities of the components A, B and C and optionally, D, which is 100 wt. % overall: a) 1 to 48 wt. % of at least one single or multiphase particulate emulsion polymer with a glass transition temperature of less than 0 °C in at least one phase and an average particle size of 50 to 1000 nm, preferably 50 to 800 nm as component A; b) 1 to 48 wt. %, of at least one amorphous or partially crystalline polymer as component B; c) 51 to 98 wt. % polycarbonates as component C; and: 0 to 47 wt. % usual additives and/or fibrous or particulate fillers or their mixtures as components D.

Description

Shaped body for the garden and animal husbandry area

The invention relates to moldings for the garden and animal husbandry sector: In particular, the invention relates to moldings of this type with good properties

Dimensional stability, great stability, good chemical resistance and good yellowing resistance. Previously used materials have a number of disadvantages. Wood has a poor stability against weather influences and is susceptible to mold, rotting, small animal bites and insect damage. A high maintenance effort is necessary.

Sheet steel has a high density and thus a high weight, is susceptible to corrosion and can only be processed with great effort.

ABS (acrylonitrile / butadiene / styrene) polymers do not always show sufficient results

Scratch resistance and rapid embrittlement in outdoor applications through cross-linking of the butadiene double bonds. This is associated with a deterioration in the mechanical properties, in particular the toughness. The moldings show discolouration and fading. The swelling behavior towards alcohols and cleaning agents is inadequate, and it also occurs when in contact with petrol

Discoloration.

ASA (Acrylnitri Styrol / Acrylat) molding compounds show good stress cracking behavior, but the scratch resistance, color depth and the toughness / stiffness ratio are not sufficient for all applications. Even adding small amounts of polycarbonate to produce a blend does not lead to a sufficient improvement.

The object of the present invention is therefore to provide moldings for the garden and To provide animal husbandry areas that 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 to 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 to 1000 nm as component A,

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

Polymer as component B,

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

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

Additives or mixtures thereof as component D.

for the production of moldings and semi-finished products for the garden and animal husbandry area.

Specified glass transition temperatures of phases refer to a polymer with the composition corresponding to this phase. The moldings described for gardening and animal husbandry are scratch-resistant, stable and resistant to chemicals. They also have very good yellowing resistance and depth of color.

The components of the for the production of the shaped body according to the invention for the

Garden and animal husbandry areas thermoplastic molding compositions used 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 moldings according to the invention for gardening and animal husbandry 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 to 48% by weight, preferably 3 to 35% by weight, in particular 5 to 30% by weight, of a particulate emulsion polymer with a glass transition temperature below 0 ° C. and an average particle size of 50 to 1000 nm , preferably 50 to 800 nm, as component A,

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

c: 51 to 98% by weight, preferably 55 to 90% by weight, in particular 60 to 85% by weight, of 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 additives or mixtures thereof as component D. The invention is explained in more detail below.

The molding compositions used for the production of the shaped articles according to the invention for the garden and animal husbandry area 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 to 1000 nm.

Component A is preferably a multi-phase polymer

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

Wt .-%, a particle-shaped first phase AI with a glass transition temperature below 0 ° C,

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

a21: 40 to 100% by weight, preferably 65 to 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-methyl _s tyrols as component A21 and

a22: 0 to 60% by weight, preferably 15 to 35% by weight, 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 giving 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 of more than 60 ° C. This third phase can be, for example, 1 to 50% by weight, in particular 5 to 40% by weight, based on the

Component A, are present.

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 to 99.99% by weight, preferably 95 to 99.9% by weight, of a Ci-β-

Alkyl esters of acrylic acid, preferably n-butyl acrylate and / or ethylhexyl acrylate as component All, al2 0.01 to 20% by weight, preferably 0.1 to 5.0% by weight, of at least one polyfunctional crosslinking monomer as component AI 2

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

According to a further embodiment according to the invention, the particle size distribution of component A is bimodal, 1 to 99, preferably 20 to 95, in particular 45 to 90% by weight an average particle size of 50 to 200 nm and 1 to 99, preferably 5 to 80, in particular 10 to 55% by weight an average

Have particle sizes of 200 to 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 average particle sizes according to the invention are in all cases the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W Scholtan and H Lange, Kolloid-Z and Z -Polymer 250 (1972), pages 782-796, were determined. The ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen how many percent by weight of the particles have a diameter equal to or smaller than a certain size The dso 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 dso value. 50% by weight then also has

Particles larger in diameter than the dso value In order to characterize the width of the particle size distribution of the rubber particles, in addition to the dso value (average particle diameter), the dio and d9o values resulting from the integral mass distribution are used, the dio and dw values of the integrals Mass distribution is defined according to the dso value with the difference that they are based on 10 or 90% by weight of the particles quotient

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

The glass transition temperature of the emulsion polymer A and of the other components used according to the invention is determined by means of DSC (differential scanning calorimetry) in accordance with ASTM 3418 (mid-point temperature).

Relevant customary rubbers can be used as emulsion polymer A. According to one embodiment of the invention, epichlorohydrin rubbers, ethylene-vinyl acetate rubbers, polyethylene chlorosulfone rubbers, silicone rubbers, polyether rubbers, hydrogenated diene rubbers, polyalkenamer rubbers, acrylate rubbers, ethylene-propylene rubbers and fluoro-rubbers, ethylene-propylene rubbers, ethylene-propylene rubbers used. 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 diene basic building block content in the emulsion polymer A is kept so low that as few unreacted double bonds remain in the polymer. According to one embodiment, there are no basic diene building blocks in the emulsion polymer A.

The acrylate rubbers are preferably alkyl acrylate rubbers from one or more Gs-alkyl acrylates, preferably C 1 -s-alkyl acrylates, preferably at least partially butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl and 2-ethylhexyl acrylate, is used. This alkyl acrylate rubber 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 to 20% by weight, preferably 0.1 to 5% by weight, of crosslinking, polyfunctional monomers (crosslinking monomers). Examples of these are monomers which have 2 or more double bonds capable of copolymerization included, which are preferably not conjugated in the 1,3 positions

Suitable crosslinking monomers are, for example, ethylene glycol diacrylate or - methacrylate, butanediol diacrylate or hexanediol diacrylate or methacrylate, divinylbenzene, di allyl maleate, diallyl fumarate, diallyl isocyanurate, diethyl phthalate, triallyl cyanurate, triallyl, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, Triallylphos- phosphate, allyl acrylate, allyl methacrylate and dicyclopentadienyl acrylate (DCPA ) (see DE-C-12 60 135)

Suitable silicone rubbers can be, for example, crosslinked silicone rubbers composed of units of the general formulas PvzSiO, RSiO-Λ, R3S-O1Ω and SiO ^, where the radical R represents a monovalent radical. The amounts of the individual siloxane units are such that 0 to 10 mol units of the formula RSiO-β, 0 to 1.5 mol units 3S.O1Ω and 0 to 3 mol units SiO per 100 units of the formula R-SiO -v ₄ are present, R can either be 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 radicals R are methyl radicals, particularly preferred are 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 to 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 expedient 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 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 dso of 50 to 1000 nm, preferably from 50 to 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.

By simple grafting or multiple gradual grafting one or multiple graft shells are applied to the rubber particles, 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, for example, 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 a (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 grafting materials A1 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 an embodiment of the invention, the graft base AI from 15 to

99.9% by weight of acrylate rubber, 0.1 to 5% by weight of crosslinking agent and 0 to 49.9% by weight 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:

Nmyl aromatic monomers, such as styrene and its substituted derivatives, such as α-methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, p-tert-butylstyrene, p-methyl-α-methylstyrene or C ₈ -C ₈ alkyl (meth) acrylates such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate; are preferred

Styrene, α-methylstyrene, methyl methacrylate, especially styrene and / or α-me- thylstyrene, 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- and isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate , n- and isopropyl methacrylate, n- and isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, maleic anhydride and its derivatives, such as maleic acid esters, maleic acid diesters and maleimides, for example alkyl and aryl maleimides, such as methyl or phenyl hexyl imide, such as methyl or phenyl hexyl imide 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 1 -C ₂ alkyl radicals, halogen atoms, halogen methylene radicals, vinyl naphthalene, vinyl carbazole, vinyl ether with C 1 -C 1) ₂ -ether esters, vinylimidazole, 3- (4-) vinylpyridine, dimethylaminoethyl (meth) acrylate, p-dimethylaminostyrene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid,

Acrylic acid butyl ester, acrylic acid ethyl hexyl ester and methyl methacrylate and fumaric acid, maleic acid, itaconic acid or their anhydrides, amides, nitriles or esters with alcohols containing 1 to 22 carbon atoms, preferably 1 to 10 carbon atoms)

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 of the second described above Phase (graft) A2, based on the total weight of component A The third phase comes in particular from 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 AI. The crosslinked acrylic acid ester polymers should preferably have a glass transition temperature below -20 ° C., in particular below -30 ° C. 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 having 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, 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. Graft copolymers A are preferably prepared by free-radical emulsion polymerization, in particular in the presence of latices of component AI at temperatures from 20 ° C. to 90 ° C. using water-soluble or less soluble ones 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 49358 and in DE-C-1260 135

The graft shells are preferably built up in the emulsion polymerization process, as described in DE-A-32 27 555, 31 49 357, 31 49 358, 34 14 118. The particle sizes of 50 to 1000 nm according to the invention are preferably set according to Methods that are described in DE-C-12 60 135 and DE-A-28 26 925, or Applied Polymer Science, Volume 9 (1965), page 2929. The use of polymers with different particle sizes is known, for example, from DE-A-28 26 925 and US 5,196,480

According to the process described in DE-C-12 60 135, the

Graft base AI prepared by the or the used according to an embodiment of the invention and the multi-functional, the 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, can be polymerized The usual emulsifiers, such as alkali metal salts of alkyl or alkylarylsulphonic acid alkyl sulphates, fatty alcohol sulphonates, salts of higher fatty acids with 10 to 30 carbon atoms or resin soaps can be used. Preferably, the sodium salts of alkyl sulphonates or fatty acids with 10 to 18 carbon atoms In one embodiment, the emulsifiers are used in amounts of 0.5 to 5

% By weight, in particular from 1 to 2% by weight, based on the monomers used in the preparation of the graft base AI, is generally used with a weight ratio of water to monomers of 2 1 to 0.7 1. The polymerization initiators used are in particular the Usable persulfates, such as potassium persulfate. However, redox systems can also be used. The initiators are generally used in amounts of 0.1 to 1% by weight, based on the monomers used in the preparation of the graft base AI. The customary polymerization auxiliaries can be conventional Buffer substances, by means of which pH values of preferably 6 to 9, such as sodium bicarbonate and sodium pyrophosphate, and 0 to 3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric α-methylstyrene, are used in the polymerization

To produce the graft polymer A, in a next step, 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 polymerizes, the weight ratio of styrene to acrylonitrile in the monomer mixture according to one embodiment of the invention should be in the range from 100.0 to 40:60, preferably in the range from 65:35 to 85:15. It is advantageous to carry out this graft copolymerization of styrene and acrylonitrile on the crosslinked polyacrylic ester polymer used as the graft base again in an aqueous emulsion under the customary conditions described above. The graft copolymerization can expediently take place in the same system as the emulsion polymerization for the preparation of the graft base AI, it being possible, if necessary, to add further emulsifier and initiator. The monomer mixture of styrene and. To be grafted on according to an embodiment of the invention

Acrylonitrile 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 to 99% by weight, preferably 20 to 85% by weight, in particular 35 to 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 than corresponds to the desired degree of grafting. The control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A is known to the person skilled in the art and can be carried out, for example, by the metering rate of the monomers or by adding a regulator (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 ff) . The emulsion graft copolymerization generally gives rise to a few% by weight, based on the graft copolymer, of free, un-grafted

Styrene / acrylonitrile copolymer. The proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method given above.

In the production of the graft copolymers A by the emulsion process, in addition to the given process engineering advantages, reproducible particle Size changes possible, for example by at least partially agglomerating the particles into larger particles. This means that polymers with different particle sizes can also be present in the graft copolymers A.

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 one can be produced

Particle size distribution by partial agglomeration before, 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 to 80 and particularly preferably 40 to 65% by weight of the first phase (graft base) Al and 1 to 99% by weight, preferably 20 to 85, particularly preferably 35 to 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 to 100% by weight, preferably 60 to 85% by weight, units of a vinyl aromatic monomer, preferably styrene, of a substituted one 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 to 40% by weight, of 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 copolymerizable monomer

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

The amorphous or partially crystalline polymers of component B of the molding composition used according to the invention for producing the shaped articles for gardening and animal husbandry are made from at least one polymer made 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 component crystalline, preferably linear polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 and partially crystalline copolyamides are also used as component B of the molding compound used for the production of the shaped articles according to the invention for the garden and animal husbandry area Suitable on the basis of these components. Partially crystalline polyamides can also be used, the acid component of which consists wholly or partly of adipic acid and / or terephthalic acid and / or isophthalic acid and / or cork 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 from m- and / or p-xylylenediamine and / or hex-imethylenediainine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine and / or isophoronediamine, and the compositions of which are known in principle from the prior art (see Encyclopedia of Polymers, Vol 11, p 315 ff)

Examples of as component B for the preparation of the inventive

Shaped bodies for the molding compositions used in the garden and animal husbandry area according to the invention are also suitable polymers are partially crystalline polyolefins, preferably homo- and copolymers of olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 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-l. In general, a distinction is made with 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 Acid groups are generally identified with the help of

Metal ions such as Na ⁺ , Ca ⁺ , Mg ⁺ and Al ^{+ are converted} into ionic, optionally ionically crosslinked polyolefins, which, however, 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, e.g. B (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, for example based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis- hydroxymethyl-cyclohexane, and polyalkylene naphthalates Aromatic polyether ketones can also be used as component B, as described, for example, in documents GB 1,078,234, US Pat. No. 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, the molding compositions used according to the invention for the production of the moldings according to the invention for gardening and animal husbandry can be used polyoxyalkylenes, for example polyoxymethylene, and oxymethylene polymers

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 to 60% by weight, preferably 15 to 40% by weight, based on the total weight of the Component B Component B also includes the free, non-grafted styrene / acrylonitrile copolymers formed in the graft copolymerization for the production of component A. Depending on the conditions selected in the graft copolymerization for the production of the graft copolymer A, it may be possible that in the graft copolymerization A sufficient proportion of component B has been formed. In general, however, it will be necessary to mix the products obtained in the graft copolymerization with additional, component B prepared separately

This additional, separately prepared component B can preferably be a styrene / acrylonitrile copolymer, an α-methylstyrene / 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 invention can, for example, be a mixture of a styrene / acrylonitrile copolymer and an α-methylstyrene / acrylonitrile copolymer according to the molding compositions used. 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 should preferably

The acrylonitrile content of the two copolymers does not differ by more than 10% by weight, preferably not more than 5% by weight, based on the total weight of the copolymer. Component B of the molding compositions used according to the invention can, however, also consist of only a single styrene / acrylonitrile copolymer if the graft copolymers used to prepare the

Component A as well as in the production of the additional, separately produced component B is based on the same monomer mixture of styrene and acrylonitrile.

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 graft products obtained in aqueous dispersion Copolymerization (component A) can also only be partially dewatered and mixed with component B as a moist crumb, the complete drying of the graft copolymers then taking place 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 are, for example, according to the methods of DE-B-1 300 266 by

Interfacial polycondensation or according to the process of DE-A-1 495 730 obtainable 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, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4 '-Dihydroxy-diphenylsulfite, 4,4'-dihydroxydiphenylmethane, l, 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 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, copolycarbonates based on bisphenol A and are of particular interest

Di- (3,5-dimethyl-dihydroxyphenyl) sulfone, which is characterized by a high thermoforming Characterizing durability 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 have relative solution viscosities 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, preferably the relative solution viscosities of the polycarbonates used differ by no more than 0.05, especially not 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 to 98% by weight, preferably 55 to 90% by weight, in particular 60 to 85% by weight, based in each case on the total Molding compound, before

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 the production of the molding materials according to the invention for the garden and animal husbandry sector

COMPONENT D

Component D contains the preferred thermoplastic molding compositions used according to the invention for the production of the molded articles according to the invention for the garden and animal husbandry sector from 0 to 50% by weight, preferably from 0 to 37% by weight, in particular from 0 to 30% 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 to 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 H-ift mediator.Your diameter is generally between 6 and 20 μm. Both continuous fibers (rovings) and commercially available chopped glass fibers (staple ) are 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 (e.g. aluminum flakes from Transmet Coφ), metal powder, metal fibers, metal-coated fillers, e.g. nickel-coated glass fibers and other additives that shield electromagnetic waves, can be added to the molding materials used according to the invention for the production of the shaped body according to the invention. In particular, aluminum flakes (K 102 from Transmet) for EMI (electro-magnetic interference) purposes. The masses can also be mixed with additional carbon fibers, carbon black, in particular conductivity black, or nickel-coated carbon fibers

The molding compositions used according to the invention for the production of the molding materials according to the invention for the garden and animal husbandry area may also contain further 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 the thermal stability, to increase the light stability, to increase the hydrolysis resistance and the chemical resistance, buffer substances, flame retardants, drip inhibitors, transesterification inhibitors, agents against heat decomposition and in particular those Lubricants / lubricants and waxes which are expedient for the production of moldings or moldings. The metering in of these additional additives can take place at any stage of the production process, but preferably at an early stage in order to achieve the stabilizing effects (or other special effects) of the additive at an early stage Heat stabilizers or oxidation retarders are usually metal halides (chlorides, bromides, iodides) which are derived from metals from 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 with 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) used

Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding ones

Fatty acid mixtures with 12 to 30 carbon atoms The amounts of these additives are in the range from 0.05 to 1% by weight.

Silicones, oligomeric isobutylene or similar substances are also suitable as additives; the usual amounts are 0.05 to 5% by weight of pigments, dyes,

Color brighteners such as ultramarine blue, phthalocyanine, titanium dioxide, cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used

Commercially available 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-01 49 813 DE-A-34 36 815, wherein poly (tetrabromobisphenol A (glycidil / ether) with a molecular weight of 40,000 is particularly preferred

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

The thermoplastic molding materials used for the production of the moldings according to the invention for gardening and animal husbandry 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 solvent is also an option 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

The mixing of, for example, dry components can be carried out by all known methods. However, the mixing is preferably carried out by extruding, kneading or rolling the components together, preferably at temperatures of 180 to 400 ° C., the components if necessary beforehand from the solution obtained in the polymerization or have been isolated from the aqueous dispersion

The components can be metered in together or separately / one after the other

The mold body according to the invention for the garden and animal husbandry area can be according to an embodiment of the invention according to the known methods of Thermoplastic processing can be produced from the thermoplastic molding compositions used in accordance with the invention. In particular, production can be carried out by thermoforming, extrusion, injection molding, calendering, hollow-body blowing, pressing, press sintering, deep-drawing or sintering, preferably by injection molding. Specifically in calendering and deep-drawing, plates and foils are used as an intermediate stage generated or used

The shaped elements for the garden and animal husbandry area can be garden buildings, garden tools, garden furniture and garden equipment. Garden buildings are, for example, garden houses, tool sheds, carports,

Greenhouses, trellis elements, pergolas Examples of garden tools or housings thereof are lawn mowers, quick composters, shredders, rainwater collection systems and weather stations. Examples of garden equipment include garden lamps, candelabras, lighting systems, party lights, decorative elements, decorative grilles, flower boxes and planters, hose cars and irrigation systems, as well as irrigation systems , for example garden gnomes, nesting boxes, etc. For garden furniture, for example, benches, tables, chairs, loungers, parasols, etc. are considered. Body parts from the animal husbandry area are, for example, pasture fences, for example for paddocks, small animal cages and small animal transport containers, play equipment for small animals, for example cat trees, chicken houses and other houses, rabbits Buildings that are suitable for animal husbandry

All of the above-mentioned areas of application have in common that they are exposed to the weather, ie rain, cold, heat, sunlight, etc. They are also "free-standing", ie they have a certain inherent stability and rigidity

The invention also relates to semifinished products from the molding compositions and to plates, profiles, foils, etc

Can increase stiffness and improve thermal insulation For example, hollow profiles suitable for garden buildings can also be foamed using suitable foam systems (e.g. PUR) by adding a foaming system into the cavity of the component later or already during profile extrusion and foaming there. Such profile / plate systems are suitable, for example, for the garden houses mentioned above , Fences,

Caφorts, trellis elements and garden furniture Such profiles can also be closed, for example, in the open spaces formed by mineral glass, acrylic glass, PC plates and other partially or fully transparent materials. The molding compositions according to the invention can be stiff, scratch-resistant, weather-resistant, resistant to mold and bacteria and resistant to biting can also be used for transport and holding cages for small animals. They are easy to clean, since animal excrements adhere poorly and cleaning agents generally do not lead to corrosion

Because of the high heat resistance and dimensional stability, the molding compositions according to the invention can also be used for parts of solar systems, for example in the field of photovoltaics and hot water preparation

In addition, the moldings according to the invention for gardening and animal husbandry or 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 moldings for the garden and animal husbandry area are very heat resistant and resistant to persistent heat. The addition of the polycarbonate as component C further improves the heat resistance and impact resistance of the molded articles for the garden and animal husbandry area These molded parts for gardening and animal husbandry also have good dimensional stability, excellent resistance to heat aging and high resistance to yellowing under thermal stress and exposure to UV radiation The molded bodies for the garden and animal husbandry sector have excellent surface properties, which can also be obtained without further surface treatment. The appearance of the finished surfaces of the molded bodies for the garden and animal husbandry area can be modified by suitable modification of the rubber morphology, for example with glossy or matt surface designs to achieve The moldings for the garden and animal husbandry 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 moldings for the gardening and keeping area 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. They also have high color stability, for example also due to the excellent resistance to yellowing and embrittlement. The shaped bodies according to the invention for the garden - and

Animal husbandry areas made from the thermoplastic molding compositions used according to the invention show no 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. The molding compositions or molding bodies according to the invention also show the Garden and animal husbandry areas 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 for the production of the molded articles according to the invention for the garden and animal husbandry area according to the present invention. Because of the high color stability, weathering resistance and aging resistance, the molding materials used according to the invention are very suitable for reuse reused (recycled) molding compound should be high when using, for example, 30% by weight of molding compound already used, which is in ground form When the molding compositions used according to the invention were admixed, the relevant material properties such as flowability, Vicat softening temperature and impact strength of the molding compositions and the molding bodies according to the invention produced therefrom for the garden and animal husbandry area were not significantly similar. Results were obtained when the weather resistance was examined

Impact resistance was constant over a long time even when recycled thermoplastic molding compositions were used, 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 yellowing resistance was also retained

The invention is explained in more detail with reference to the following examples

EXAMPLES

example 1

Production of Clamped Graft Copolymer (A)

(al) 16 parts of butyl acrylate and 0.4 part of tricyclodecenyl acrylate were mixed in 150 parts

Water with the addition of one part of the sodium salt of a Cπ- to cis-paraffin sulfonic acid, 0.3 part of potassium per-sulfate, 0.3 part of sodium hydrogen carbonate and 0.15 part of sodium pyrophosphate, heated to 60 ° C. with stirring 10 minutes after the start of the The polymerization reaction became a mixture of 82 parts of butyl acrylate and 1.6 parts within 3 hours

Tricyclodecenyl acrylate added 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 mean 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 (a1) 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 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 Pfropfgra ^'d 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 ₁₂ - to cis-P-t-taffinsulfonic 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 with stirring after the addition of a further 0.03 part of potassium persulfate and 0.05 part of lauroyl peroxide to 65 for 4 hours ° C heated. The polymerization product obtained in the graft polymerization 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 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 to cis paraffinsulfonic acid, 0.3 part of potassium persulfate, 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 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 completion of the first stage of the graft copolymerization, the graft copolymer 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 graft polymerization was complete

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 copolymer was 35%, 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 was after the 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 and on the other hand a solution of 0.5 part of the sodium salt of a C ₂ - to cis-paraffin sulfonic 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 polymerization was then polymerized with 20 parts of a mixture of styrene and acrylonitrile in a ratio of 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 copolymer 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 mixed in 154

Parts of water with the addition of 2 parts of dioctylsulfosuccinate sodium (70%) as Emulsifier and 0.5 part of potassium persulfate polymerized 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, 400 parts of water and 0.5

Parts of potassium persulfate were added at 65 ° C. to a mixture of 49 parts of butyl acrylate, 1 part of tricyclodecenyl acrylate and 0.38 part of the emulsifier within 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 was added Share emulsifier after adding 1

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

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

Tabenel

Investigation results

a scratch resistance

The scratch resistance is determined using a CSEM Automatic Scratch Tester model AMI (manufacturer Center Suisse dΕlectronique et de Microtechnique SA). The scratch tester has a diamond tip with a 120 ° tip angle and 0.2 mm radius. This diamond tip is used to injection-molded test specimens from the material to be tested Scratches of 5 mm in length, unless otherwise stated, the contact pressure of the diamond is 2.6 N. After an hour of waiting, the scratches created are scanned in the transverse direction and displayed as a high / low profile. The scratch depth can then be read off

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 bent with a bending radius of 50 mm. The test specimens were clamped in a template. bent and wetted with the test medium for 24 hours. The impact energy at break is then determined with a pendulum. The test medium was used in bl isopropanol. In b2, a common household cleaner (Ajax Ultra Classic® from Colgate Palmolive Germany, a surfactant household cleaner) was used

c swelling

To measure the 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 hours, then they are superficially dried, and the change in weight and, if necessary, the change in tensile modulus (determined according to ISO 527) are in Comparison to the initial value determined. Table π, column 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 about 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) / (m ² d bar) for gases or in (g 100 μm) / (m ² d) for water. (Table HI)

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 of the modulus of elasticity in premium gasoline of less than 6%.

The results are shown in Tables II and HI below.

<u p

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 VI Swelling (change in weight) 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, π and the comparative compound HI. Little fogging was observed for molding compound I, hardly any fogging for molding compound II, and noticeable fogging for the comparative molding compound HI.

The maximum service temperature was 110 ° C for molding compound and π il5 ° C for molding compound.

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 molded articles for the garden and animal husbandry sector.

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, if appropriate, D, which gives a total of 100% by weight,

a: 1 to 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 a medium phase

Particle size from 50 to 1000 nm, as component A,

b: 1 to 48 wt .-% of at least one amorphous or partially crystalline

Polymer as component B,

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

d: 0 to 47% by weight of customary additives and / or fibrous or particulate fillers or mixtures thereof as component D.

for the production of molded articles and semi-finished products for the garden and animal husbandry area.

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

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

Glass transition temperature below 0 ° C,

a2: 1 to 99% by weight> of a second phase A2 from the monomers, based on A2, a21: 40 to 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 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 to 99.99% by weight of a C ₈ alkyl ester of acrylic acid as component All,

al2: 0.01 to 20 wt .-% of at least one polyfunctional crosslinking

Monomers as component AI 2.

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

6. Use according to any one of claims 1 to 5, characterized in that the shaped bodies for the garden area are garden buildings, garden tools, garden furniture or garden equipment.

7. Use according to one of claims 1 to 5, characterized in that the molded bodies for animal husbandry are pasture fences, cages or transport containers.

8. Use according to one of claims 1 to 5, characterized in that the molding compositions for the production of profiles, plates, tubes or films for the

Use in the garden and animal husbandry area.

9. molded body for the garden and animal husbandry area or housing thereof made of a thermoplastic molding composition as defined in one of claims 1 to 5.

10. Form body according to Anspmch 8, characterized in that it is garden buildings, garden tools, garden equipment, garden furniture, pasture fences, small animal cages or small animal transport containers.