WO2000020505A1 - Corps moules pour le secteur du batiment, utilises a l'interieur - Google Patents

Corps moules pour le secteur du batiment, utilises a l'interieur Download PDF

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Publication number
WO2000020505A1
WO2000020505A1 PCT/EP1999/007433 EP9907433W WO0020505A1 WO 2000020505 A1 WO2000020505 A1 WO 2000020505A1 EP 9907433 W EP9907433 W EP 9907433W WO 0020505 A1 WO0020505 A1 WO 0020505A1
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WIPO (PCT)
Prior art keywords
weight
component
phase
graft
particle size
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PCT/EP1999/007433
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German (de)
English (en)
Inventor
Norbert Niessner
Norbert Güntherberg
Heiner GÖRRISSEN
Graham Edmund Mc Kee
Martin Weber
Original Assignee
Basf Aktiengesellschaft
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Publication of WO2000020505A1 publication Critical patent/WO2000020505A1/fr

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/10—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products
    • E04C2/20—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products of plastics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the invention relates to moldings for the building sector in the interior.
  • the invention relates to such shaped articles with good dimensional stability, great stability, good chemical resistance and good yellowing resistance.
  • UV and heat aging resistance In addition to good UV and heat aging resistance, high scratch resistance, good chemical resistance, good recyclability and a high surface gloss after aging are necessary for the production of weather-stable molding compounds in the construction sector. Even indoors, the UV and heat aging resistance play a role, since the combination of both influences, even if they are weak - as in the case of UV exposure - lead to significant damage to the material within several years, so that the material yellows or can fade. The dimensional accuracy of the molded parts under thermal stress is also necessary, both in manufacture and in use, e.g. in intense sunlight. In addition, for indoor applications, it is required that the so-called "fogging", i.e. outgassing of volatile compounds over time is low.
  • ABS acrylonitrile / butadiene / styrene
  • Blends from ABS are also used.
  • a disadvantage of ABS is that it is not always sufficiently resistant to yellowing and the tendency to become brittle. Yellowing and embrittlement also occur when used indoors.
  • ABS is not always sufficiently resistant to cleaning agents and disinfectants.
  • ABS molded parts can in some cases show insufficient stress cracking behavior towards cleaning agents and alcohols. The surface may swell and become discolored when in contact with petrol.
  • the permeability to water and gases can be too high.
  • ASA acrylonitrile / styrene / acrylate
  • ASA acrylonitrile / styrene / acrylate
  • the use of ASA molding compounds in safety devices is, for example, in the PCT. EP97 / 04029.
  • the object of the present invention is therefore to provide moldings for the interior construction sector which are stable and resistant to chemicals and do not yellow. They should also be scratch-resistant and have good dimensional stability.
  • the UV and heat aging resistance should be high, so that the surface gloss is retained. Further requirements are good recyclability and poor fire behavior as well as good dimensional stability under thermal stress during manufacture and use.
  • 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
  • Specified glass transition temperatures of phases refer to a polymer with the composition corresponding to this phase.
  • the moldings described for the interior construction sector are scratch-resistant, stable and resistant to chemicals. They also have very good yellowing resistance and depth of color.
  • thermoplastic molding compositions used according to the invention for producing the moldings according to the invention for the building sector in the interior are known per se.
  • DE-A-12 60 135, DE-C-19 11 882, DE-A-28 26 925, DE-A-31 49 358, DE-A-32 27 555 and DE-A-40 11 162 Components and molding compositions which can be used according to the invention are described.
  • the molding compositions used according to the invention for the manufacture of the moldings according to the invention for the building sector in the interior contain ABS components A, 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,
  • b 1-48% by weight, preferably 5-40% by weight, in particular 5-35% by weight, of at least one amorphous or partially crystalline polymer as component B,
  • c 51-98% by weight, preferably 55-90% by weight, in particular 60-85% by weight, of polycarbonates as component C, and
  • component D 0 to 47% by weight, preferably 0 to 37% by weight, in particular 0 to 30% by weight, of customary additives and / or fibrous or particulate fillers or mixtures thereof as component D.
  • COMPONENT A Component A is at least one single-phase or multi-phase particulate emulsion polymer with a glass transition temperature below 0 ° C. in at least one phase and an average particle size of 50-1000 ⁇ m.
  • Component A is preferably a multi-phase polymer
  • 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 a component
  • a3 0 to 50% by weight of a third phase with a glass transition temperature of more than 0 ° C. as component A3, the total amount of components AI, A2 and A3 being 100% by weight.
  • the phases can be linked together in the manner of a graft copolymerization.
  • 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.
  • 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, 1-50% by weight, in particular 5-40% by weight. , based on component A, are present.
  • 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.
  • component AI consists of the monomers
  • al l 80-99.99% by weight, preferably 95-99.9% by weight, of a C 1-8 alkyl ester of acrylic acid, preferably n-butyl acrylate and / or ethylhexyl acrylate as component Al l, al2: 0.01-20% by weight, preferably 0.1-1.0% by weight, of at least one polyfunctional crosslinking monomer, component A12.
  • the average particle size of component A is 50-1000 nm, preferably 50-800 nm.
  • the particle size distribution of component A is bimodal, with 1-99, preferably 20-10, 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 they are using an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange,
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
  • the average particle diameter also known as the d 50 value
  • 25 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 ⁇ value. Likewise, 50% by weight of the particles then have a larger diameter than the djo value.
  • 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).
  • emulsion polymer A can be used as emulsion polymer A, such as, according to one embodiment of the invention, epichlorohydrin rubbers, ethylene vinyl acetate rubbers, poly ethylene chlorosulfone rubbers, silicone rubbers, polyether rubbers, hydrogenated diene rubbers, ethylene alkylene rubber rubbers.
  • Acrylate rubber, ethylene-propylene (EP) rubber, ethylene-propylene-diene (EPDM) rubber, in particular acrylate rubber, are preferably used.
  • the molding compositions are preferably free of butadiene rubbers.
  • the diene basic building block content in the emulsion polymer A is kept so low that as few unreacted double bonds remain in the polymer. According to one embodiment, there are no basic diene building blocks in the emulsion polymer A.
  • the acrylate rubbers are preferably alkyl acrylate rubbers made from one or more C 1-8 alkyl acrylates, preferably C ⁇ . 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.
  • the acrylate rubbers further contain 0.01-20% by weight, preferably 0.1-5% by weight, of cross-linking polyfunctional monomers (cross-linking monomers).
  • cross-linking monomers examples of these are monomers which contain 2 or more double bonds 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 di (meth) acrylate, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, dihydrodicyclopate, tradienyl acrylate,
  • Suitable silicone rubbers can be, for example, crosslinked silicone rubbers composed of units of the general formulas R 2 SiO, RSiO 3/2 , R 3 SiO 1/2 and SiO 2/4 , the radical R representing a monovalent radical.
  • the amounts of the individual siloxane units are such that for 100 units of the formula R 2 SiO 0 to 10 mol units of the formula RSiO ⁇ , 0 to 1.5 mol units R 3 SiO 1 2 and 0 to 3 mol units SiO 2 4 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; 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 2-10 mol%, based on all radicals R. They can be prepared, for example, as described in EP-A-0 260 558.
  • an emulsion polymer A made from uncrosslinked polymer All of the monomers mentioned above can be used as monomers for the production of these polymers.
  • Preferred uncrosslinked emulsion polymers A are 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.
  • the emulsion polymer A can also be a multi-stage polymer (so-called “core / shell structure”, “core-shell mor- phology ").
  • core / shell structure core-shell mor- phology
  • a rubber-elastic core T ⁇ ⁇ 0 ° C
  • a hard "shell polymers with T g > 0 ° C or vice versa.
  • component 5 is a graft copolymer.
  • the graft copolymers A of the molding compositions according to the invention have an average particle size d 50 of 50-1000 nm, preferably 50-800 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 grafted thereon (graft pad), the so-called graft stages or graft shells.
  • One or more graft shells can be applied to the rubber particles by single grafting or multiple stepwise grafting, each graft sheath having a different composition.
  • polyfunctional crosslinking or reactive group-containing monomers can also be grafted on (see e.g. EP-A-0 230
  • component A consists of a multi-stage graft copolymer, the graft calls generally being made from resin-forming monomers and having a glass 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 30 of at least one of the monomers A2 listed below to at least one one of the graft bases or graft core materials listed above AI. All polymers described above under emulsion polymers A are suitable as graft bases AI of the molding compositions according to the invention.
  • the graft base AI is composed of 15-99.9% by weight of acrylate rubber, 0.1-5% by weight of crosslinking agent and 0-49.9% by weight of one of the further monomers or rubbers indicated.
  • Suitable monomers for forming the graft A2 can be selected, for example, from the monomers listed below and their mixtures:
  • Vinylaromatic monomers such as styrene and its substituted derivatives, such as ⁇ -methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, p-tert-butylstyrene, o- and p-methyl- ⁇ -methylstyrene or CC 8 -alkyl (meth) acrylates such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate; styrene, ⁇ -methylstyrene, methyl methacrylate, in particular styrene and / or ⁇ -methylstyrene, and ethylenically unsaturated monomers, such as acrylic and methacrylic compounds, such as acrylonitrile, methacrylonitrile, acrylic and methacrylic acid, methyl acryl
  • monomers styrene, vinyl, acrylic or methacrylic compounds for example styrene, optionally substituted with C 1-12 alkyl radicals, halogen atoms, halogen methylene radicals; vinyl naphthalene, vinyl carbazole; vinyl ethers with C 1-12 ether radicals ; Vinylimidazole, 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 or amides, nitrides Esters with 1 to 22 carbon atoms,
  • component A comprises 50 to 100% by weight, preferably 50-90% by weight of the first phase described above (graft base) Al and 0 to 50% by weight, preferably 10-50% by weight the above-described second phase (graft) A2, based on the total weight of component A.
  • graft base graft base
  • graft graft base
  • graft graft-A2
  • styrene copolymers are suitable as the third phase.
  • crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. serve as the graft base.
  • the crosslinked acrylic ester polymers should preferably have a glass transition temperature below -20 ° C., in particular below -30 ° C.
  • the graft A2 consists of one or more graft shells, the outermost graft shell of which has a glass transition temperature of more than 30 ° C, a polymer formed from the monomers of the graft A2 would have a glass transition temperature of more than 80 ° C.
  • the emulsion polymers A applies to the graft copolymers A.
  • the graft copolymers A can also be prepared by grafting pre-formed polymers onto suitable graft homopolymers. Examples of this are the reaction products of copolymers containing maleic anhydride or acid groups with base-containing rubbers.
  • Suitable preparation processes for graft copolymers A are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers A are preferably prepared by free-radical emulsion polymerization, in particular in the presence of latices of component AI at temperatures from 20 ° C. to 90 ° C. using water-soluble or oil-soluble initiators such as peroxodisulfate or benzoyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
  • Suitable emulsion polymerization processes are described in DE-A-28 26 925, 31 49 358 and in DE-C-12 60 135.
  • the graft casings are preferably built up in the emulsion polymerization process, as described in DE-A-32 27 555, 31 49 357, 31 49 358, 34 14 118.
  • the defined particle sizes of 50-1000 nm according to the invention are preferably carried out after the processes 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 known.
  • the graft base AI is first prepared by adding the acrylic acid ester (s) used according to one embodiment of the invention and the multifunctional monomers which bring about crosslinking, if appropriate together with the others Comonomers, in aqueous emulsion in a conventional manner at temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C, polymerized.
  • the usual emulsifiers such as alkali salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms or resin soaps can be used.
  • the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are preferably used.
  • the emulsifiers are used in amounts of 0.5-5% by weight, in particular 1-2% by weight, based on the monomers used in the preparation of the graft base AI.
  • the weight ratio of water to monomers is from 2: 1 to 0.7: 1.
  • the 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.
  • buffer substances by means of which pH values are preferably set to 6-9, such as sodium bicarbonate and sodium pyrophosphate, and 0-3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric ⁇ -methyl, can be used as further polymerization auxiliaries - styrene, used in the polymerization.
  • a molecular weight regulator such as mercaptans, terpinols or dimeric ⁇ -methyl
  • Polymer according to an embodiment of the invention polymerizes a monomer mixture of styrene and acrylonitrile
  • 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 acrylonitrile to be grafted on according to an 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, is obtained on the total weight of component A, resulting in 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, non-grafted styrene / acrylonitrile copolymer.
  • the proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method given above.
  • reproducible particle size changes are also possible, for example by at least partially agglomeration of the particles into larger particles. This means that polymers with different particle sizes can also be present in the graft copolymers A.
  • 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 1-99% 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 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 vinylaromatic monomer, preferably styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or ⁇ -methylstyrene as component Bl,
  • b2 0 to 60% by weight, preferably 15-40% by weight, of units of an ethylenically unsaturated monomer, preferably of acrylonitrile or
  • Methacrylonitrile in particular acrylonitrile as component B2,
  • b3 0 to 60% by weight of a further ethylenically unsaturated copolymerizable monomer.
  • 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 in the interior for producing the moldings according to the invention for the building sector are made from at least one polymer from partially crystalline polyamides, partially aromatic copolyamides, polyolefms, ionomers, polyesters, polyether ketones, polyoxyalkylenes, polyarylene sulfides and preferably polymers vinyl aromatic monomers and / or ethylenically unsaturated monomers selected. Polymer mixtures can also be used.
  • component B are the molding compound used according to the invention for producing the moldings according to the invention for the building sector in the interior semi-crystalline, preferably linear polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 and semi-crystalline copolyamides based on these components are also suitable.
  • linear polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 and semi-crystalline copolyamides based on these components are also suitable.
  • 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 / orginaic 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 hexamethylene diamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine and / or isophoronediamine, and their compositions in principle are known from the prior art (cf. Encyclopedia of Polymers, Vol. 11, p. 315 ff.).
  • polymers which are furthermore suitable as component B of the polymers which are furthermore used according to the invention for the production of the moldings according to the invention for the building sector in the interior are partially crystalline polyolefins, preferably homo- and copolymers of olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, Hepten-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.
  • PE polyethylene
  • HDPE high-density PE
  • LDPE low-density PE
  • LLDPE linear low-density PE
  • 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 converted into ionic, possibly ionically crosslinked polyolefins with the aid of metal ions such as Na + , Ca 2+ , Mg 2+ and Al 3+ , but these still change can be processed thermoplastic (see e.g. US 3,264,272; 3,404,134; 3,355,319; 4,321,337).
  • Component B according to the invention is also suitable for polyolefins containing free acid groups, which then generally have a rubber-like character and in some cases also contain further copolymerizable monomers, for example (meth) acrylates.
  • component B can also be polyester, preferably aromatic-aliphatic polyester.
  • polyester preferably aromatic-aliphatic polyester.
  • polyalkylene terephthalate e.g. based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis-hydroxymethyl-cyclohexane, as well as polyalkylene naphthalates.
  • Aromatic polyether ketones such as those e.g. are described in GB 1 078 234, US 4,010,147, EP-A-0 135 938, EP-A-0 292 211, EP-A-0 275 035, EP-A-0 270 998, EP-A-0 165 406, and in the publication by CK Sham et. al., Polymer 29/6, 1016-1020 (1988).
  • component B the molding compositions used according to the invention for the production of the moldings according to the invention for the building sector in the interior area, e.g. Polyoxymethylene, and
  • Oxymethylene polymers are used.
  • suitable components B are the polyarylene sulfides, in particular the polyphenylene sulfide.
  • An amorphous copolymer of styrene and / or ⁇ -methylstyrene with acrylonitrile is preferably used as component B.
  • the acrylonitrile content in these copolymers of component B are 0 to 60% by weight, preferably 15 to 40% by weight, based on the total weight of component B.
  • Component B also does not include the free ones formed in the graft copolymerization to prepare component A. grafted styrene / acrylonitrile copolymers.
  • grafted styrene / acrylonitrile copolymers it may be possible that a sufficient proportion of component B has already been formed in the graft copolymerization. In general, however, it will be necessary to mix the products obtained in the graft copolymerization with additional, separately prepared component B.
  • This additional, separately produced component B can preferably be a styrene / acrylonitrile copolymer, an ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile terpolymer.
  • These copolymers can be used individually or as a mixture for component B, so that the additional, separately produced component B of the molding compositions used according to the invention is, for example, a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile Copolymer can act.
  • component B of the molding compositions used according to the invention consists of a mixture of a styrene / acrylonitrile copolymer and an .alpha.-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 production of component A and also in the production of the additional, separately produced component B, the same monomer mixture of styrene and acrylonitrile is assumed.
  • the additional, separately manufactured component B can be obtained by the conventional methods.
  • the copolymerization of the styrene and / or ⁇ -methylstyrene with the acrylonitrile can be carried out in bulk, solution, suspension or aqueous emulsion.
  • Component B preferably has a viscosity number of 40 to 120, preferably 50 to 120, in particular 55 to 100.
  • the viscosity number is determined in accordance with DIN 53 726, 0.5 g of material being dissolved in 100 ml of dimethylformamide.
  • Components A and B can be mixed in any desired manner by all known methods. If components A and B have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, to precipitate the polymers together thereupon and to work up the polymer mixture. However, components A and B are preferably mixed by extruding, kneading or rolling the components together, the components having, if necessary, been isolated beforehand from the solution or aqueous dispersion obtained in the polymerization.
  • the products of the graft copolymerization (component A) obtained in aqueous dispersion can also only be partially dewatered and mixed as a moist crumb with component B, the graft copolymers then being completely dried during the mixing.
  • Suitable polycarbonates C are known per se. You preferably have one
  • Molecular weight (weight average M w , determined by means of gel penetration 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. in general - as in the following - referred to as bisphenol A.
  • aromatic dihydroxy compounds can also be used, in particular 2,2-di (4-hydroxyphenyl) pentane.
  • Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the aromatic dihydroxy compounds mentioned above.
  • Copolycarbonates according to US Pat. No. 3,737,409 can also be used; Of particular interest are copolycarbonates based on bisphenol A and di (3,5-dimethyl-dihydroxyphenyl) sulfone, which are characterized by high heat resistance. It is also possible to use mixtures of different polycarbonates.
  • the average molecular weights (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates C are in the range from 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol.
  • the Polycarbonate C have relative solution viscosities in the range from 1.1 to 1.3, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33.
  • the relative solution viscosities of the polycarbonates used preferably differ by no more than 0.05, in particular no more than 0.04.
  • the polycarbonates C can be used both as regrind and in granular form. They are present as component C in amounts of 51-98% by weight, preferably 55-90% by weight, in particular 60-85% by weight, based in each case on the total molding composition.
  • the addition of polycarbonates leads, inter alia, to higher thermal stability and improved crack resistance of the molding compositions used for the production of the inventive foils for the building sector in the interior area.
  • the preferred thermoplastic molding compositions used according to the invention for the production of the moldings according to the invention for the building sector in the interior contain 0-50% by weight, preferably 0-37% by weight, in particular 0-30% by weight, of fibrous or particle-shaped fillers and other additives or their mixtures, in each case based on the total molding composition. These are preferably commercially available products.
  • Reinforcing agents such as carbon fibers and glass fibers are usually used in amounts of 5-50% by weight, based on the total molding composition.
  • the glass fibers used can be made of E, A or C glass and are preferably equipped with a size and an adhesion promoter. Their diameter is generally between 6 and 20 ⁇ m. Both continuous fibers (rovings) and chopped glass fibers (staple) can be used.
  • Filling or reinforcing materials such as glass balls, can also be used.
  • Mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can be added.
  • metal flakes e.g. aluminum flakes from Transmet Corp.
  • metal powder e.g. aluminum flakes from Transmet Corp.
  • metal fibers e.g. aluminum flakes from Transmet Corp.
  • metal coated fillers e.g. nickel-coated glass fibers and other additives that shield electromagnetic waves
  • Aluminum flakes K 102 from Transmet
  • EMI electromagnetic interference
  • 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 molded articles according to the invention for the building sector in the interior may also contain further additives D which are typical and customary for polycarbonates, SAN polymers and graft copolymers or mixtures thereof.
  • additives D are typical and customary for polycarbonates, SAN polymers and graft copolymers or mixtures thereof.
  • additives are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers for improving the thermostability, for increasing the light stability, for increasing the resistance to hydrolysis and the resistance to chemicals, buffer substances, drip inhibitors, transesterification inhibitors, agents against the
  • Heat decomposition, flame retardants and especially the lubricants / waxes and waxes that are used for the production of moldings or molded parts. are moderate.
  • These additional additives can be metered in at any stage of the production process, but preferably at an early point in time, in order to take advantage of the stabilizing effects (or other special effects) of the additive at an early stage.
  • Heat stabilizers or oxidation retardants are usually metal halides (chlorides, bromides, iodides) which are derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).
  • Other suitable stabilizers are the usual hindered phenols, but also vitamin E or compounds of an analog structure.
  • HALS stabilizers hindered amine light stabilizers
  • benzophenones hindered amine light stabilizers
  • resorcinols salicylates
  • benzotriazoles and other compounds are also suitable (for example Irganox, Tinuvin, such as Tinuvin 770 (HALS absorber, bis (2,2,6,6-tetramethyl-4 -piperidyl) sebazate) or Tinuvin P (UV absorber - (2H-Be__zotriazol-2-yl) -4-methylphenol), topanol).
  • Tinuvin 770 HALS absorber, bis (2,2,6,6-tetramethyl-4 -piperidyl) sebazate
  • Tinuvin P UV absorber - (2H-Be__zotriazol-2-yl) -4-methylphenol
  • 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.
  • Flame retardants are used in customary amounts, for example up to 20% by weight.
  • Examples of halogen-free flame retardants are 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
  • 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.
  • thermoplastic molding compositions used according to the invention for producing the moldings according to the invention for the building sector in the interior can be produced by methods known per se by mixing the components. It can be advantageous to premix individual components. Mixing the components in solution and removing the solvents is also possible.
  • Suitable organic solvents are, for example, chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene or aromatic hydrocarbons, e.g. Toluene.
  • the solvent mixtures can be evaporated, for example, in evaporation extruders.
  • the dry components can be mixed 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.
  • the moldings according to the invention for the interior construction sector can be produced from the thermoplastic molding compositions used according to the known methods of thermoplastic processing.
  • the production can be carried out by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding.
  • calendering and deep drawing plates and foils are produced and used as an intermediate stage.
  • the molding compositions are used for the production of moldings for the interior construction sector.
  • "Indoor area” means interiors of buildings including, for example, winter gardens and other interiors that have a large number of window surfaces and are therefore exposed to high levels of sunlight.
  • suitable molded bodies for the construction sector in the interior are profiles such as window and door profiles, cladding such as interior cladding. Roller shutter cladding, facings, supply and disposal lines such as pipes, tubes, cable sheathing, cable ducts, double-wall panels, hoses. Partitions, paneling, doors, floor coverings such as tiles and large-scale floor coverings can also be constructed from the molding compositions described.
  • All molded bodies connected with the air and water supply can also be constructed from the molding compositions used according to the invention. These are, for example, ventilation pipes, supply and waste water pipes, manholes, etc. Also laminating foils, pipe coatings, shims, protective caps, Sleeves, clips, slip closures etc. can be constructed from the molding compositions used according to the invention.
  • the moldings for the building sector in the interior can also be combined with other molding compounds.
  • window and door profiles from the molding compositions used according to the invention can be joined by coextrusion or lamination with ASA, ABS / PC, PYC, PVC / ABS or PMMA molding compositions.
  • foamed parts made of ASA, ABS / PC, PVC, PVC / ABS or PMMA molding compounds can be introduced.
  • the molding composition used according to the invention should preferably be on the outside, i.e. the side facing the light.
  • the molding compositions used according to the invention can be produced, for example, by gluing, welding or multi-component injection molding.
  • the molded articles for the building sector in the interior often come into contact with cleaning agents and disinfectants.
  • the molded bodies have a very good chemical resistance.
  • they are scratch-resistant, which is particularly advantageous when cleaning.
  • they show only very small amounts of condensate in the quick fogging test.
  • the molded articles according to the invention 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 building sector are very heat-resistant in the interior and resistant to lasting heat. By adding the polycarbonate as component C, the heat resistance and impact resistance of the molded articles for the construction sector in the interior are further improved. These molded articles for the interior construction sector also have good dimensional stability as well as excellent resistance to heat aging and high resistance to yellowing under thermal stress and exposure to UV radiation.
  • the molded bodies for the interior construction sector have excellent surface properties, which can be obtained without further surface treatment.
  • the appearance of the finished surfaces of the molded bodies for the construction sector can be modified by suitable modification of the rubber morphology, for example in order to achieve glossy or matt surface designs.
  • the moldings for the interior construction sector 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 molded body for the construction sector in the interior 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 molded articles according to the invention for the interior construction sector made of 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. Also the The tensile strength is retained. Furthermore, the molding compositions or molded articles according to the invention for the construction sector in the interior display high resistance to scratching, high resistance to swelling and low permeability to liquids and gases, as well as good fire resistance.
  • thermoplastic molding compositions already used for the production of the molded articles according to the invention for the interior construction sector according to 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.
  • the relevant material properties such as flowability, Vicat softening temperature and impact resistance of the molding compounds and the molding bodies according to the invention for the construction sector produced therefrom changed in the Interior not significant. Similar results were obtained when the weather resistance was examined.
  • Graft polymer was 35%.
  • the average particle size (weight average of the latex) was found to be 288 nm.
  • the degree of grafting of the graft copolymer was determined to be 27%.
  • 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 found to be 216 nm.
  • 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.
  • the product was terminated by means of graft copolymerization
  • Latex particles were found to be 238 nm.
  • 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.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 80 ml / g.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 60 ml / g.
  • 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.
  • the graft rubber content was 30% by weight, based on the total weight of the finished polymer.
  • a conventional polycarbonate (PC) was used as component C, which had a viscosity number of 61.5 ml / g, determined in the solvent methylene chloride. According to the information in Table 1 below, the stated amounts of the corresponding polymers (A), (B) and (C) or 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 scratch resistance is determined using a CSEM Automatic Scratch Tester model AMI (manufacturer: Center Canal d'Electronique et de Microtechnique S.A.).
  • the scratch tester has a diamond tip with a 120 ° tip angle and 0.2 mm radius. With this diamond tip, scratches of 5 mm length are introduced into injection molded test specimens from the material to be tested. The contact pressure of the diamond 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.
  • 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.
  • the test specimens were clamped in a template, bent and wetted with the test medium for 24 hours. Then the impact work at break is determined with a pendulum. Bl isopropanol was used as the test medium.
  • a common household cleaner (Ajax Ultra Classic ® from Colgate Palmolive Germany, a surfactant household cleaner) was used.
  • c swelling
  • injection-molded shoulder bars (tensile bars according to ISO 3167 with a thickness of 4 mm) are stored in the medium to be tested for 96 h. Then they are superficially dried, and the change in weight and, if necessary, the change in tensile modulus (determined according to ISO 527) are determined in comparison with the initial value.
  • Table II, cl shows the change in weight in methanol, in c2 in super gasoline and in c3 the change in tensile modulus in super gasoline.
  • foils are pressed from the material to be tested (thickness approx. 120 to 250 ⁇ m), the permeability of which to the specified gases or liquids is determined at 23 ° C. The values are given in (cm 3 100 ⁇ m) / (m 2 d bar) for gases or in (g 100 ⁇ m) / (m 2 d) for water (Table III).
  • Molding compositions that can be used advantageously should meet the following conditions: scratch depth of less than 6 ⁇ m, change in impact energy compared to the initial value of less than 10%, swelling in methanol of less than 1% or swelling and change in the modulus of elasticity of less than 6 % in super gasoline.
  • the proportion of volatile constituents was determined in accordance with PV 3341.
  • the molding compound HI had values of 22 mg / kg and 56 mg / kg, respectively.
  • the molding composition VI and the comparison composition VHI were examined in a rapid fogging test according to VW-PV 3015, method B (100 ° C., 16 h).
  • For the Molding compositions IV showed small amounts of condensate, while comparative compositions VIII showed significantly higher amounts of condensate.
  • the molding compositions with a polycarbonate content of more than 50% by weight had an excellent combination of properties. This advantageous range of properties makes them particularly suitable for use in molded articles for the interior construction sector.

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Abstract

L'invention concerne l'utilisation d'une matière moulable thermoplastique, différente de l'ABS, pour la production de corps moulés pour le secteur du bâtiment, utilisés à l'intérieur. Cette matière moulable contient, par rapport à la somme des proportions de constituants A, B et C, et éventuellement D, égale à 100 % en poids : a) 1 à 48 % en poids d'au moins un polymère en émulsion particulaire à une ou plusieurs phases, présentant une température de transition vitreuse inférieure à 0 °C, au moins une phase et une dimension moyenne de particules comprise entre 50 et 1000 nm, de préférence entre 50 et 500 nm, comme constituant A ; b) 1 à 48 % en poids d'au moins un polymère amorphe ou partiellement cristallin comme constituant B ; c) 51 à 98 % en poids de polycarbonates comme constituant C, et d) 0 à 47 % en poids d'additifs usuels, et/ou de charges fibreuses ou particulaires ou de leurs mélanges comme constituant D.
PCT/EP1999/007433 1998-10-07 1999-10-05 Corps moules pour le secteur du batiment, utilises a l'interieur WO2000020505A1 (fr)

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DE10058133A1 (de) * 2000-11-22 2002-05-23 Basf Ag Verfahren zur Herstellung kautschukhaltiger thermoplastischer Formmassen
DE10159316A1 (de) * 2001-12-04 2003-06-12 Basf Ag Polycarbonat-Styrolcopolymer-Blends mit verminderter Delaminationsneigung
KR100694456B1 (ko) * 2004-10-20 2007-03-12 주식회사 엘지화학 열가소성 수지 조성물 및 그의 제조방법
CN105820539A (zh) * 2016-05-26 2016-08-03 青岛海信电器股份有限公司 一种电子电器设备外壳及共挤出工艺方法
DE202016007085U1 (de) * 2016-10-28 2017-02-08 DEFLEX-Fugensysteme GmbH Fugen-Profilanordnungen mit dauerhafter Abriebfestigkeit zur Abdeckung von Fugen und betriebssichere überwachungsarme Vorrichtungen zur Abdeckung derselben

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