EP0914385A1 - Pieces moulees pour equipements sanitaires et de salles de bains - Google Patents

Pieces moulees pour equipements sanitaires et de salles de bains

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Publication number
EP0914385A1
EP0914385A1 EP97940022A EP97940022A EP0914385A1 EP 0914385 A1 EP0914385 A1 EP 0914385A1 EP 97940022 A EP97940022 A EP 97940022A EP 97940022 A EP97940022 A EP 97940022A EP 0914385 A1 EP0914385 A1 EP 0914385A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
graft
parts
particle size
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97940022A
Other languages
German (de)
English (en)
Inventor
Herbert Naarmann
Graham Edmund Mc Kee
Alfred Pirker
Hans-Josef Sterzel
Franz Brandstetter
Bernd-Steffen Von Bernstorff
Bernhard Rosenau
Ulrich Endemann
Burkhard Straube
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0914385A1 publication Critical patent/EP0914385A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds

Definitions

  • the invention relates to molded parts for sanitary and bathroom equipment, and fastening parts therefor.
  • the invention relates to film parts with good dimensional stability, good chemical resistance and high scratch resistance.
  • ABS acrylonitrile / butadiene / styrene copolymer
  • HIPS high impact polystyrene: impact-resistant polystyrene
  • Polypropylene (PP) shows an insufficient toughness / stiffness ratio and a low hardness.
  • PMMA polymethyl methacrylate
  • Another object of the invention is to provide molded parts for sanitary and bathroom equipment that are largely free of weld lines.
  • thermoplastic molding composition different from ABS comprising, based on the sum of the amounts of components A and B, and optionally C and / or D, which gives a total of 100% by weight,
  • a 1-99% by weight of a particulate emulsion polymer with a glass transition temperature below 0 ° C. and an average particle size of 50-1000 nm as component A
  • b 1-99% by weight of at least one amorphous or partially crystalline
  • the described fo ⁇ ne parts for sanitary and bathroom equipment are scratch-resistant, stable and resistant to chemicals and have a very good dimensional stability.
  • thermoplastic molding compositions used according to the invention for producing the film parts according to the invention are known per se.
  • DE-OS 12 60 135, DE-PS 19 11 882, DE-OS 28 26 925, DE-OS 31 49 358, DE-OS 32 27 555 and DE-OS 40 11 162 described molding compositions usable according to the invention.
  • the molding compositions other than ABS used to produce the molded parts according to the invention contain components A and B and, where appropriate, C and / or D, as defined below. They contain, based on the sum of the amounts of components A and B, and if appropriate C and / or D, which gives a total of 100% by weight,
  • d 0 to 50% by weight of fibrous or particulate fillers or mixtures thereof as component D.
  • Component A is a particulate emulsion polymer with a glass transition temperature below 0 ° C and an average particle size of 50-1000 nm.
  • Component A is preferably a graft copolymer
  • a21 40-100% by weight, preferably 65-85% by weight, of units of a vinylaromatic monomer, preferably styrene, a substituted styrene or one (Meth) acrylic acid ester or mixtures thereof, in particular styrene and / or methylstyrene as component A21 and a22: up to 60% by weight, preferably 15-35% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, especially acrylonitrile as component A22.
  • a vinylaromatic monomer preferably styrene, a substituted styrene or one (Meth) acrylic acid ester or mixtures thereof, in particular styrene and / or methylstyrene as component A21 and a22: up to 60% by weight, preferably 15-35% by weight, of units of an ethylenically unsaturated monomer, preferably
  • the graft pad A2 consists of at least one graft shell, the graft copolymer A overall having an average particle size of 50-1000 nm.
  • component AI consists of the monomers
  • C 1-6 alkyl ester of acrylic acid preferably n-butyl acrylate and / or ethylhexyl acrylate as component All, al2: 0.01-20% by weight, preferably 0.1-5.0% by weight, of at least one poly-crosslinking Monomers, preferably diallyl phthalate and / or DCPA as component A12.
  • the average particle size of component A is 50-800 nm, preferably 50-600 nm.
  • the particle size distribution of component A is bimodal, 60-90% by weight having an average particle size of 50-200 nm and 10-40% by weight having an average particle size of 50-400 nm on the total weight of component A.
  • the sizes determined from the integral mass distribution are given as the average particle size or particle size distribution.
  • the mean particle sizes according to the invention are in all cases the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972), pages 782-796.
  • the ultracentrirage measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
  • the mean particle diameter which is also referred to as the d ⁇ value of the integral mass distribution, is the Che diameter defined in which 50 wt .-% of the particles have a smaller diameter than the diameter that corresponds to the d ⁇ value. Likewise, 50% by weight of the particles then have a larger diameter than the d 50 value.
  • the d 10 and d 90 values resulting from the integral mass distribution are used to characterize the width of the particle size distribution of the rubber particles.
  • the d 10 or d 90 value of the integral mass distribution is defined in accordance with the d 50 value with the difference that they are based on 10 or 90% by weight of the particles. The quotient
  • Emulsion polymers A which can be used according to the invention as component A preferably have Q values less than 0.5, in particular less than 0.35.
  • the glass transition temperature of the emulsion polymer A and also of the other components used according to the invention is determined by means of DSC (differential scanning calorimetry) according to ASTM 3418 (mid point temperature).
  • emulsion polymer A such as epichlorohydrin rubbers, ethylene-vinyl acetate rubbers, polyethylene chlorosulfone rubbers, silicone rubbers, polyether rubbers, hydrogenated diene rubbers, polyalkylene rubber rubbers, polyalkylene rubber rubbers, polyalkylene rubber rubbers, according to one embodiment of the invention.
  • Ethylene propylene diene rubbers, butyl rubbers and fluororubbers Acrylate rubber, ethylene propylene (EP) rubber, ethyl len-propylene-diene (EPDM) rubber, especially acrylate rubber.
  • EP ethylene propylene
  • EPDM ethyl len-propylene-diene
  • 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 is preferably alkyl acrylate rubbers of one or more C j .g-alkyl acrylates, preferably C. g - alkyl acrylates, butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl and 2-ethylhexyl acrylate, preferably being used at least in part.
  • These alkyl acrylate rubbers can contain up to 30 wt .-% hard polymer-forming monomers such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate or vinyl ether copolymerized.
  • the acrylate rubbers further contain 0.01-20% by weight, preferably 0.1-5% by weight, of crosslinking, poly-ionic monomers (crosslinking monomers).
  • crosslinking monomers examples of these are monomers which contain 2 or more double bonds capable of copolymerization, which are preferably not conjugated in the 1,3-positions.
  • Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, triallyl phosphate, allyl acrylate, allyl methacrylate.
  • Dicyclopentadienyl acrylate (DCPA) has proven to be a particularly favorable crosslinking monomer (cf. DE-C 12 60 135).
  • Suitable silicone rubbers can be, for example, crosslinked silicone rubbers composed of units of the general formulas R 2 SiO, RSiO 3/2 , R 3 SiO 1/2 and SiO 2/4 , the radical R representing a monovalent radical.
  • the amount of the individual siloxane units is such that 0 to 10 mol units of the formula RSiO 3/2 , 0 to 1.5 mol units R 3 SiO 1/2 and 0 to 3 per 100 units of the formula R 2 SiO Mol units of 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; combinations of methyl and ethyl or phenyl radicals are particularly preferred.
  • Preferred silicone rubbers contain built-in units of groups which can be attacked by free radicals, in particular vinyl, allyl, halogen, mercapto groups, preferably in amounts of 2-10 mol%, based on all radicals R. They can be prepared, for example, as in EP-A-0 260 558.
  • an emulsion polymer A made from uncrosslinked polymer All of the monomers mentioned above can be used as monomers for the production of these polymers.
  • Preferred uncrosslinked emulsion polymers A are, for example, homopolymers and copolymers of acrylic esters, in particular n-butyl and ethylhexyl acrylate, and homopolymers and copolymers of ethylene, propylene, butylene, isobutylene, and also poly (organosiloxanes), all with provided that they can be linear or branched.
  • the emulsion polymer A can also be a multi-stage polymer (so-called “core / shell structure", “core-shell morphology”).
  • core / shell structure a multi-stage polymer
  • core-shell morphology a rubber-elastic core (T g ⁇ 0 ° C) can be encased by a “hard” shell (polymers with T g > 0 ° C) or vice versa.
  • component A is a graft copolymer.
  • the graft copolymers A of the molding compositions according to the invention have an average particle size d 50 of 50-1000 nm, preferably 50-600 nm and particularly preferably 50-400 nm. These particle sizes can be achieved if, as the graft base AI of this component A, particle sizes of 50-350 nm, preferably from 50-300 nm and particularly preferably from 50-250 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) Al and one or - preferably - several stages A2 grafted thereon, the so-called graft stages or graft shells.
  • One or more graft shells can be applied to the rubber particles by simple grafting or multiple step-wise grafting, each graft sheath having a different composition.
  • polyfunctional crosslinking or 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).
  • component A consists of a multi-stage graft copolymer, the graft stages being generally made from resin-forming monomers and having a glass transition temperature T g above 30 ° C., preferably above 50 ° C.
  • the multi-stage structure serves, inter alia, to achieve (partial) compatibility of the rubber particles A with the thermoplastic B.
  • Graft copolymers A are prepared, for example, by grafting at least one of the monomers A2 listed below onto at least one of the graft bases or graft core materials AI listed above. All 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% by weight of acrylate rubber, 0.1-5% by weight of crosslinking agent and 0-49.9% by weight of one of the further monomers or rubbers indicated.
  • Suitable monomers for forming the graft A2 can be selected, for example, from the monomers listed below and their mixtures:
  • Vinyl aromatic monomers such as styrene and its substituted derivatives, such as ⁇ -methylstyrene, p-methylstyrene, 3,4-dimethylstyrene, p-tert-butylstyrene, o- and p-divinylbenzene and p-methyl- ⁇ -methylstyrene or C Cg- Alkyl acrylates such as methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, s-butyl acrylate; styrene, ⁇ -methylstyrene, methyl methacrylate, in particular styrene and / or ⁇ -methylstyrene, and ethylenically unsaturated monomers such as acrylic and methacrylic compounds such as acrylic nitrile, methacrylonitrile, acrylic and methacrylic acid, methyl
  • styrene vinyl, acrylic or methacrylic compounds (for example styrene, optionally substituted with C 1 -C 12 -alkyl radicals, halogen atoms, halogen-methylene radicals; vinyl naphthalene, vinyl carbazole; vinyl ethers with C ⁇ 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, nitriles with 1 to 22 carbon atoms, preferably alcohols containing 1 to 10 carbon atoms) can be used.
  • styrene vinyl, acrylic or methacrylic compounds
  • component A comprises 50-90% by weight of the above-described graft base AI and 10-50% by weight of the above-described graft base A2, based on the total weight of component A.
  • crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. serve as the graft base.
  • the crosslinked acrylic ester polymers should preferably have a glass transition temperature below -20 ° C., in particular below -30 ° C.
  • the graft A2 consists of at least one graft shell and the outermost graft shell thereof has a glass transition temperature of more than 30 ° C, a polymer formed from the monomers of the graft A2 would have a glass transition temperature of more than 80 ° C.
  • the graft copolymers A can also be prepared by grafting pre-formed polymers onto suitable graft homopolymers. Examples of this are the reaction products of copolymers containing maleic anhydride or acid groups with base-containing rubbers.
  • Suitable production processes for graft copolymers A are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers A are preferably prepared by free-radical emulsion polymerization, in particular in the presence of latices of component AI at temperatures from 20 ° C. to 90 ° C. using water-soluble or oil-soluble initiators such as peroxodisulfate or benzyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
  • Suitable emulsion polymerization processes are described in DE-A-28 26 925, 31 49 358 and in DE-PS 12 60 135.
  • the graft casings are preferably built up using the emulsion polymerization process, as described in DE-A 32 27 555, 31 49 357, 31 49 358, 34 14 118.
  • Surface sizes of 50-1000 nm are preferably carried out according to the processes described in DE-C-12 60 135 and DE-A-28 26 925, or Applied Polymer Science, Volume 9 (1965), page 2929.
  • the use of polymers with different particle sizes is known for example from DE-A-28 26 925 and US 5,196,480.
  • the graft base AI is first prepared by adding the acrylic acid ester (s) used according to one embodiment of the invention and the polyfunctional monomers which cause crosslinking, if appropriate together with the other comonomers, in an aqueous emulsion in a conventional manner at temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C, polymerized.
  • the usual emulsifiers such as alkali salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms or resin soaps can be used.
  • the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are preferably used.
  • the emulsifiers are used in amounts of 0.5-5% by weight, in particular 1-2% by weight, based on the monomers used in the preparation of the graft base AI.
  • the weight ratio of water to monomers is from 2: 1 to 0.7: 1.
  • the usual persulfates, such as potassium persulfate, are used in particular as polymerization initiators. However, redox systems can also be used.
  • the initiators are generally used in amounts of 0.1-1% by weight, based on the monomers used in the preparation of the graft base AI.
  • buffer substances by means of which pH values of preferably 6-9, such as sodium bicarbonate and sodium pyrophosphate, and 0-3% by weight of a molecular weight weight regulators, such as mercaptans, terpinols or dimeric ⁇ -methylstyrene, are used in the polymerization.
  • pH values of preferably 6-9 such as sodium bicarbonate and sodium pyrophosphate
  • a molecular weight weight regulators such as mercaptans, terpinols or dimeric ⁇ -methylstyrene
  • the precise polymerization conditions in particular the type, dosage and amount of the emulsifier, are determined in detail within the ranges given above such that the latex of the crosslinked acrylic ester polymer obtained ad 50 value in the range from about 50-1000 nm, preferably 50- 150 nm, particularly preferably in the range of 80-100 nm.
  • the particle size distribution of the latex should preferably be narrow. The quotient
  • the weight ratio of styrene to acrylonitrile in the monomer mixture according to one embodiment - Form 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 acid ester polymer used as the graft base again in aqueous emulsion under the customary conditions described above.
  • the graft copolymerization can advantageously be carried out in the same system as the emulsion polymerization for producing the graft base AI, where , if necessary, further emulsifier and initiator can be added. That to be grafted on according to an embodiment of the invention Monomer mixture of styrene and 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 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, based 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 about 5 to 15% by weight, based on the graft copolymer, of free, non-grafted styrene / acrylonitrile copolymer.
  • the proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method given above.
  • graft copolymers A In the production of the graft copolymers A by the emulsion process, in addition to the given process engineering advantages, reproducible particle size changes are also possible, for example by at least partially agglomerating the particles into larger particles. This means that polymers with different particle sizes can also be present in the graft copolymers A.
  • Component A in particular, consisting of the graft base and graft shell (s) can be optimally adapted for the particular application, in particular with regard to the particle size.
  • the graft copolymers A generally contain 1-99% by weight, preferably 55-80 and particularly preferably 55-65% by weight of graft base AI and 1-99% by weight, preferably 20-45, particularly preferably 35-45% by weight .-% of the graft A2, each based on the entire graft copolymer.
  • Component B is an amorphous or partially crystalline polymer.
  • Component B is preferably a copolymer of
  • bl 40-100% by weight, preferably 60-70% by weight, of units of a vinyl aromatic monomer, preferably styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or ⁇ -methylstyrene as
  • Component B1, b2 up to 60% by weight, preferably 30-40% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile, in particular acrylonitrile as component B2.
  • the viscosity number of component B is 50-90, preferably 60-80.
  • the amorphous or partially crystalline polymers of component B of the molding composition used according to the invention for the production of the moldings according to the invention are preferably composed of at least one polymer made from partially crystalline polyamides, partially aromatic copolyamides, polyolefins, ionomers, polyesters, polyether ketones, polyoxyalkylenes, polyarylene sulfides and polymers made from vinyl aromatic monomers and / or ethylenically unsaturated monomers selected. Polymer mixtures can also be used.
  • Part B crystalline, preferably linear polyamides such as polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 6,12 and partially crystalline copolyamides based on these components are suitable as component B of the molding composition used according to the invention for the production of the molded parts according to the invention.
  • partially crystalline polyamides can be used, the acid component of which consists wholly or partly of adipic acid and / or terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or glacial acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid, and whose diamine component wholly or partly consists in particular of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine and / or isophoronediamine, and their compositions in principle 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 molding compositions used according to the invention for the production of the moldings according to the invention are partially crystalline polyolefins, preferably homo- and copolymers of olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1 and He ⁇ ten-1 , 3-methylbutene-1, 4-methylbutene-1, 4-methylpentene-1 and octene-1.
  • Suitable polyolefins are polyethylene, polypropylene, polybutene-1 or poly-4-methylpentene-1. In general, a distinction is made with polyethylene (PE) high Density-PE (HDPE), low-density-PE (LDPE) and linear-low-density-PE (LLDPE).
  • component B is an ionomer.
  • polyolefins as described above, in particular polyethylene, which contain monomers co-condensed with acid groups, for example acrylic acid, methacrylic acid and optionally further copolymerizable monomers.
  • the acid groups are generally converted with the aid of metal ions such as Na + , Ca 2+ , Mg 2+ and Al 3 + into ionic, optionally ionically crosslinked polyolefins, which, however, can still be processed thermoplastically (see, for example, US Pat. No. 3,264,272; 3,404,134; 3,355,319 ; 4,321,337).
  • Component B according to the invention is also suitable for polyolefins containing free acid groups, which then generally have a rubber-like character and in some cases also contain further copolymerizable monomers, for example (meth) acrylates.
  • component B can also be polyester, preferably aromatic-aliphatic polyester.
  • polyester preferably aromatic-aliphatic polyester.
  • polyalkylene terephthalate e.g. based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis-hydroxymethyl-cyclohexane, as well as polyalkylene naphthalates.
  • Aromatic polyether ketones can also be used as component B, as described, for example, in 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).
  • component B of the molding compositions used according to the invention for the production of the moldings according to the invention can be polyoxyalkylenes, for example polyoxymethylene, and oxymemylene polymers.
  • suitable components B are the polyarylene sulfides, in particular the polyphenylene sulfide.
  • it is composed of 50-99% by weight of vinyl aromatic monomers and 1-50% by weight of at least one of the other specified monomers.
  • Component B is preferably an amorphous polymer, as described above as graft A2.
  • a copolymer of styrene and / or ⁇ -methylstyrene with acrylonitrile is used as component B.
  • the acrylonitrile content in these copolymers of component B is 0-60% by weight, preferably 30-40% by weight, based on the total weight of component B.
  • Component B also includes those formed in the graft copolymerization to produce component A. free, non-grafted styrene / acrylonitrile copolymers.
  • 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 are used for component B, so that the additional, separately produced component B of the molding compositions used according to the invention can be, for example, a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer.
  • component B of the molding compositions used according to the invention consists of a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer
  • the acrylonitrile content of the two copolymers should preferably not 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 100, preferably 50 to 90, in particular 60 to 80. The viscosity number is determined in accordance with DIN 53 726, 0.5 g of material being dissolved in 100 ml of dimethylformamide.
  • Components A and B and optionally C, D can be mixed in any desired manner by all known methods. If components A and B have been produced, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, to precipitate the polymers together thereon and work up the polymer mixture. However, components A and B are preferably mixed by extruding, kneading or rolling the components together, the components having, if necessary, been isolated beforehand from the solution or aqueous dispersion obtained in the polymerization.
  • the products of the graft copolymerization (component A) obtained in aqueous dispersion can also only be partially dewatered and mixed as a moist crumb with component B, the complete drying of the graft copolymers then taking place during the mixing.
  • the molding compositions used according to the invention for producing the moldings according to the invention contain, in addition to components A and B, additional components C and / or D, and, if appropriate, further additives, as described below.
  • Suitable polycarbonates C are known per se. They preferably have a molecular weight (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range from 10,000 to 60,000 g / mol. They can be obtained, for example, in accordance with the processes of DE-B-1 300 266 by interfacial polycondensation or in accordance with the process of DE-A-1 495 730 by reacting diphenyl carbonate with bisphenols.
  • Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally - as also hereinafter - referred to as bisphenol A.
  • bisphenol A may also be other aromatic dihydroxy compounds are used compounds, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4, -Dihydroxydiphenylsulfan, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfite, 4,4'-dil ⁇ ydroxydiphenylmethane, l, l-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkane, preferably dihydroxydiphenylcyclohexane or dihydroxylcyclopentane, especially l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.
  • 2,2-di (4-hydroxyphenyl) pentane 2,6-dihydroxynaphthalene
  • Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the aromatic dihydroxy compounds mentioned above.
  • Copolycarbonates according to US Pat. No. 3,737,409 can also be used; Of particular interest are copolycarbonates based on bisphenol A and di (3,5-dimethyl-dihydroxyphenyl) sulfone, which are characterized by high heat resistance. It is also possible to use mixtures of different polycarbonates.
  • the average molecular weights (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates C are in the range from 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol. This means that the polycarbonates C have relative solution viscosities in the range from 1.1 to 1.3, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33. The relative solution viscosities of the polycarbonates used preferably differ by no more than 0.05, in particular no more than 0.04.
  • the polycarbonates C can be used both as regrind and in granular form. They are present as component C in amounts from 0 - 50% by weight, preferably from 10 to 40% by weight, in each case based on the total molding composition.
  • the addition of polycarbonates leads, inter alia, to higher thermal stability and improved crack resistance of the molding compositions used according to the invention for producing the moldings according to the invention.
  • the preferred thermoplastic molding compositions used according to the invention for the production of the moldings according to the invention contain 0 to 50% by weight, preferably 0 to 40% by weight, in particular 0 to 30% by weight of fibrous or particulate fillers or mixtures thereof, each - Weil based on the entire molding compound. These are preferably commercially available products.
  • Reinforcing agents such as carbon fibers and glass fibers are usually used in amounts of 5-50% by weight, based on the total molding composition.
  • the glass fibers used can be made of E, A or C glass and are preferably equipped with a size and an adhesion promoter. Their diameter is generally between 6 and 20 ⁇ m. Both continuous fibers (rovings) and chopped glass fibers (staples) with a length of 1-10 ⁇ m, preferably 3-6 ⁇ m, can be used.
  • fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can be added.
  • metal flakes for example aluminum flakes from Transmet Corp.
  • metal powder, metal fibers, metal-coated fillers, for example nickel-coated glass fibers and other additives which shield electromagnetic waves, can be admixed with the molding compositions used according to the invention for the production of the moldings according to the invention.
  • Aluminum flakes K 102 from Transmet
  • 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 moldings according to the invention may also contain further additives which are typical and customary for polycarbonates, SAN polymers and graft copolymers or mixtures thereof.
  • additives are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers to improve thermal stability, to increase light stability, to increase resistance to hydrolysis and chemicals, to prevent heat decomposition and in particular to lubricants / Lubricants that are useful for the production of molded bodies or molded parts.
  • These additional additives can be metered in at any stage of the production process, but preferably at an early point in time, in order to take advantage of the stabilizing effects (or other special effects) of the additive at an early stage.
  • Heat stabilizers or oxidation retardants are usually metal halides (chlorides, bromides, iodides) which are derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).
  • Suitable stabilizers are the usual hindered phenols, but also
  • Vitamin E or analogue compounds are also HALS stabilizers (hindered amine light stabilizers), benzophenones, resorcinols, salicylates, Benzotriazoles and other compounds are suitable (for example Irganox *, Tinuvin *, such as Tinuvin * 770 (HALS absorber, bis (2,2,6,6-tetramethyl-4-piperidyl) sebazate) or Tinuvin * P (UV Absorber - (2H-benzotriazol-2-yl) -4-methylphenol), topanol). These are usually used in amounts of up to 2% by weight (based on the total mixture).
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12-30 carbon atoms.
  • the amounts of these additives are in the range of 0.05-1% by weight.
  • Silicone oils, oligomeric isobutylene or similar substances are also suitable as additives, the usual amounts being 0.05-5% by weight.
  • Pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used.
  • 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 compound.
  • thermoplastic molding compositions used according to the invention for the production of the molded parts according to the invention can be produced by methods known per se by mixing the components. It can be advantageous to premix individual components. Mixing the components in solution and removing the solvents is also possible.
  • Suitable organic solvents are, for example, chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene or aromatic hydrocarbons, for example toluene.
  • the solvent mixtures can be evaporated, for example, in evaporation extruders.
  • Mixing the e.g. dry components can be made by all known methods. However, the mixing is preferably carried out by extruding, kneading or rolling the components together, preferably at temperatures of 180-400 ° C., the components having, if necessary, been isolated beforehand from the solution obtained in the polymerization or from the aqueous dispersion.
  • the components can be metered in together or separately / one after the other.
  • the moldings and fastening parts according to the invention can be produced from the thermoplastic molding compositions used according to the known methods of thermoplastic processing.
  • the production can be carried out by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding or extrusion blowing.
  • the molded parts according to the invention for sanitary and bathroom equipment can be used for a large number of applications in the sanitary and bathroom sector.
  • the molded parts can be used for a wide range of equipment.
  • basins and tubs are produced from the molding compositions according to the invention.
  • pools and tubs are sinks and sinks, bidets and toilet bowls, as well as shower trays and bathtubs.
  • the molding compositions according to the invention can also be used for all other basins and tubs used in the sanitary area.
  • the molding compositions according to the invention are used to produce covers, trays and handles.
  • Covers are, for example, covers for toilets, cisterns, hot water devices, boilers, tanks and vessels for water absorption, etc.
  • Tables are, for example, towel racks, racks for soap and personal care products, as well as racks for dental care products and electrical devices as used in the bathroom. Examples of such electrical devices are hair dryers, electric shavers, electric toothbrushes, electric oral irrigators and other electrical devices.
  • the handles can be provided in showers, shower trays, bathtubs, etc. in order to provide support when using these devices.
  • the handles can also be towel racks and other holder devices.
  • the molded parts are taps or fittings.
  • This includes sink fittings, bidet fittings, shower fittings, bath fittings, etc.
  • the fittings also include closures for the basins and baths, as well as holders for shower heads and other supply and disposal lines in the sanitary area.
  • molded parts for sanitary and bathroom equipment are known to the person skilled in the art. They can also be smaller molded parts, such as mirror holders, toothbrush holders, toothbrush holders, soap dishes, etc.
  • the moldings according to the invention are scratch-resistant, stable and resistant to chemicals and have very good dimensional stability. In addition, they do not yellow and are free of weld lines. Even when exposed to moisture and chemicals, they have very good dimensional stability and chemical resistance.
  • molded parts made from molding compositions which contain polycarbonates as component C are very heat-resistant and resistant to lasting heat. By adding the polycarbonate as component C, the heat resistance and impact strength of the molded parts are further improved. These molded parts also have a balanced ratio of toughness and rigidity and good dimensional stability as well as excellent resistance to heat aging and high resistance to yellowing under thermal loads and exposure to UV radiation.
  • Molded parts made of molding compounds containing components A and B have excellent surface properties that can be obtained without further surface treatment.
  • the appearance of the finished surfaces of the molded parts can be modified by suitable modification of the rubber morphology, for example in order to achieve glossy or matt surface designs.
  • the moldings 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 parts are the high weather stability, good thermal resistance, high yellowing resistance under UV radiation and thermal stress, good stress crack resistance, in particular when exposed to chemicals, and good anti-electrostatic behavior. In addition, they have high color stability, for example due to the excellent resistance to yellowing and embrittlement. the.
  • the film parts according to the invention made of the thermoplastic molding compositions used according to the invention show no significant loss of toughness or impact strength, even at low temperatures or after prolonged exposure to heat, which loss is retained even when exposed to UV rays.
  • the tensile strength is also retained. They also show a balanced relationship between rigidity and toughness.
  • thermoplastic molding compositions already used to produce the molded parts according to the invention are very suitable for reuse.
  • the proportion of reused (recycled) molding compound can be high.
  • Butyl acrylate polymers had a solids content of 40%.
  • the mean particle size (weight average) of the latex was found to be 410 nm.
  • Allocate emulsifier After adding 1 part of potassium persulfate in 40 parts of water, a mixture of 196 parts of butyl acrylate, 4 parts of tricyclodecenyl acrylate and 1.52 parts of the emulsifier was finally added dropwise over the course of 2 hours. The polymer mixture was then polymerized at 65 ° C. for a further 2 hours. An approximately 40% dispersion with an average particle diameter of approximately 500 nm was obtained. If only 100 parts were added instead of a total of 300 parts of monomers, a latex with an average particle diameter of about 300 nm was obtained.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 80 ml / g.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile copolymer obtained had an acrylonitrile content of 35% by weight, based on the copolymer, and a viscosity number of 60 ml / g.
  • a monomer mixture of styrene and acrylonitrile was polymerized in solution under customary conditions.
  • the styrene / acrylonitrile 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 29% by weight, based on the total weight of the finished polymer.
  • a HIPS polymer high impact polystyrene: impact-resistant polystyrene
  • the damping maximum of the mechanical damping is -75 ° C.
  • the MVI 200/5 is 4 ml / 10 min. Comparative Example 3
  • test specimens were injection molded according to the spraying conditions specified in DIN 16777.
  • the plastic temperature was 250 ° C, the mold temperature 60 ° C, the injection time 1.5 seconds.
  • the test specimens for the weld line test 1) had a trapezoidal cross section with edge lengths of the parallel edges of 60 and 40 mm, which were at a distance of 40 mm.
  • the test specimen had a length of 120 mm.
  • the sprue was arranged in the middle of the area formed by the short parallel edge, around which a portion of the test specimen had a kidney-shaped opening. This kidney-shaped breakthrough was used to assess the flow and weld line visibility.
  • a telephone housing 2) in dark colors was used as the second test specimen, for example with 0.5% by weight, based on the total weight of the molding compound, was colored on black carbon pearls 880.
  • the weld lines on the keypad were examined.
  • the spray conditions were plastic temperature 260 ° C, mold temperature 60 ° C, injection time 2.5 seconds. The results are shown in Table 3 below.
  • the results from Table 1 show that the molding compositions according to the invention have no visible weld line, in contrast to the comparative molding compositions.
  • the ball indentation hardness determined according to ISO 2039-1, is greater or similar to the ball indentation hardness of the comparative masses.
  • the ASA molding composition according to the invention is clearly superior to ABS.
  • Lysoformin ® contains in 100 g: 16.8 g formaldehyde DAB 8
  • the molding composition I according to the invention has better resistance to disinfectants and chemicals than comparison molding composition I.

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

Abstract

L'invention concerne l'utilisation d'une matière moulable thermoplastique pour produire des pièces moulées destinées aux équipements sanitaires et de salles de bains. Cette matière, différente de l'ABS, contient, par rapport à la somme des quantités des composants A et B, et éventuellement C et/ou D, représentant 100 % en poids, a) comme composant A, 1 à 99 % en poids, de préférence 15 à 60 % en poids, notamment 25 à 50 % en poids d'un polymère obtenu par émulsion, se présentant sous forme de particules et ayant une température de transition vitreuse inférieure à 0 °C et une taille moyenne de particules comprise entre 50 et 1000 nm, de préférence entre 50 et 500 nm, b) comme composant B, 1 à 99 % en poids, de préférence 40 à 85 % en poids, notamment 50 à 75 % en poids d'au moins un polymère amorphe ou semi-cristallin, c) comme composant C, 0 à 50 % en poids de polycarbonates et d) comme composant D, 0 à 50 % en poids de charges sous forme de fibres ou de particules, ou de mélange de ces charges.
EP97940022A 1996-07-25 1997-07-24 Pieces moulees pour equipements sanitaires et de salles de bains Withdrawn EP0914385A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19630098 1996-07-25
DE19630098A DE19630098A1 (de) 1996-07-25 1996-07-25 Formteile für Sanitär- und Badausrüstungen
PCT/EP1997/004027 WO1998004631A1 (fr) 1996-07-25 1997-07-24 Pieces moulees pour equipements sanitaires et de salles de bains

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EP0914385A1 true EP0914385A1 (fr) 1999-05-12

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DE19846202A1 (de) * 1998-10-07 2000-04-13 Basf Ag Formkörper für den Bausektor im Innenbereich
US20050165148A1 (en) * 2004-01-28 2005-07-28 Bogerd Jos V.D. Infra-red radiation absorption articles and method of manufacture thereof
US8900693B2 (en) * 2005-07-13 2014-12-02 Sabic Global Technologies B.V. Polycarbonate compositions having infrared absorbance, method of manufacture, and articles prepared therefrom
US20080057808A1 (en) * 2006-07-12 2008-03-06 Bwxt Y-12, L.L.C. Cleaning wipe for removing contamination from an article and method of making

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DE3742768A1 (de) * 1987-12-17 1989-06-29 Basf Ag Halogenfreie flammfeste formmassen, verfahren zur herstellung und ihre verwendung
DE4100978A1 (de) * 1991-01-15 1992-07-16 Basf Ag Thermoplastische formmassen auf der basis von polyphenylenethern und schlagzaeh modifizierten vinylaromatischen polymerisaten
DE4342048A1 (de) * 1993-12-09 1995-06-14 Basf Ag Dreistufige Pfropfcopolymerisate und solche enthaltende thermoplastische Formmassen mit hoher Zähigkeit
EP0676449B1 (fr) * 1994-04-04 1998-08-19 Mitsubishi Gas Chemical Company, Inc. Composition de résine thermoplastique pour extrusion de profile

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WO1998004631A1 (fr) 1998-02-05

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