DE2703052A1 - STABILIZED, FLAME-RESISTANT, THERMOPLASTIC MOLDING COMPOUNDS - Google Patents
STABILIZED, FLAME-RESISTANT, THERMOPLASTIC MOLDING COMPOUNDSInfo
- Publication number
- DE2703052A1 DE2703052A1 DE19772703052 DE2703052A DE2703052A1 DE 2703052 A1 DE2703052 A1 DE 2703052A1 DE 19772703052 DE19772703052 DE 19772703052 DE 2703052 A DE2703052 A DE 2703052A DE 2703052 A1 DE2703052 A1 DE 2703052A1
- Authority
- DE
- Germany
- Prior art keywords
- compositions according
- molding compositions
- acid
- phosphorus
- contain
- 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.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims description 10
- 238000009757 thermoplastic moulding Methods 0.000 title description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 33
- 239000003381 stabilizer Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- -1 aluminum compound Chemical class 0.000 claims description 5
- 229960002449 glycine Drugs 0.000 claims description 5
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- KBSDGEWBAHRIBK-UHFFFAOYSA-N acetic acid;2-aminoethanol Chemical compound CC(O)=O.CC(O)=O.NCCO KBSDGEWBAHRIBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000012815 thermoplastic material Substances 0.000 claims 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 16
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- FYGFTTWEWBXNMP-UHFFFAOYSA-N 10-amino-10-oxodecanoic acid Chemical compound NC(=O)CCCCCCCCC(O)=O FYGFTTWEWBXNMP-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
Landscapes
- 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)
Description
BASF AktiengesellschaftBASF Aktiengesellschaft
Unser Zeichen: O.Z. J2 39^ Dd/DKOur reference: O.Z. J2 39 ^ Dd / DK
6700 Ludwigshafen, 21.01.19776700 Ludwigshafen, January 21, 1977
Die Erfindung betrifft mit rotem Phosphor flammfest ausgerüstete thermoplastische Formmassen, die als Stabilisatoren gegen thermooxidative Zersetzung des roten Phosphors Metallsalze einer chelatbildenden Aminoessigsäure enthalten.The invention relates to thermoplastic molding compositions which are made flame-resistant with red phosphorus and which act as stabilizers against thermo-oxidative Decomposition of red phosphorus contain metal salts of a chelating aminoacetic acid.
Es ist bekannt, daß der Zusatz von rotem Phosphor "zu thermoplastischen Kunststoffen, vor allem zu verstärkten oder gefüllten Polyamiden, zu einem wirksamen Brandschutz führt (DT-AS 19 31 387). Roter Phosphor neigt jedoch unter ungünstigen Bedingungen, wie z.B. erhöhte Temperatur, Feuchtigkeit, Gegenwart von Alkali oder Sauerstoff, zur Bildung von Zersetzungsprodukten, wie Phosphin und Säuren des 1- bis 5-wertigen Phosphors. Die Bildung dieser Zerset£ungsprodukte wird schon durch geringe Mengen an Schwermetallspuren katalytisch gefördert. In thermoplastische Kunststoffe, z.B. Polyamide, eingearbeiteter roter Phosphor ist zwar infolge der Einbettung in das Polymere gegen Thermooxidation weitgehend geschützt, es kann jedoch auch hier längerfristig zur Bildung von Zersetzungsprodukten kommen. Dies ist insofern von Nachteil, als das z.B. bei der Verarbeitung von Granulaten im Spritzgußverfahren sich bildende Phosphin zu Geruchsbelästigungen führen kann und zudem toxisch ist; die gleichzeitig entstehenden Säuren des Phosphors können sich an der Oberfläche von Spritzgußteilen ausscheiden, wodurch vor allem die Kriechstromfestigkeit der Formteile herabgesetzt wird.It is known that the addition of red phosphorus "to thermoplastic Plastics, especially reinforced or filled polyamides, lead to effective fire protection (DT-AS 19 31 387). However, red phosphorus tends to occur under unfavorable conditions, such as elevated temperature, humidity, presence of alkali or Oxygen, for the formation of decomposition products such as phosphine and acids of 1- to 5-valent phosphorus. The formation of these decomposition products is catalytically promoted even by small amounts of heavy metal traces. In thermoplastics, e.g. polyamides, incorporated red phosphorus is largely against thermal oxidation due to the embedding in the polymer protected, but here, too, decomposition products can form in the long term. This is disadvantageous in that the phosphine, which is formed during the processing of granulates in the injection molding process, for example, can lead to unpleasant odors and is also toxic; the acids of phosphorus that are formed at the same time can precipitate on the surface of injection molded parts, whereby, above all, the tracking resistance of the molded parts is reduced.
Es hat daher nicht an Versuchen gefehlt, die Stabilität des als Flammschutzmittel für Kunststoffe eingesetzten roten Phosphors zu verbessern. So kann eine gewisse stabilisierende Wirkung durch Zugabe von Metalloxiden oder -hydroxiden des Zinks, Magnesiums oder Aluminiums erreicht werden. In der US-PS 3 8O6 1*88 ist die stabilisierende Wirkung von Komplexbildnern, wie z.B. Äthylendiamintetraessigsäure bzw. deren Ester oder Alkalisalze beschrieben.There has therefore been no lack of attempts to improve the stability of the red phosphorus used as a flame retardant for plastics to enhance. So can a certain stabilizing effect by adding metal oxides or hydroxides of zinc, magnesium or Aluminum can be achieved. In US-PS 3 8O6 1 * 88 is the stabilizing Effect of complexing agents such as ethylenediaminetetraacetic acid or their esters or alkali salts.
522/76 809830/0468 " 2 " 522/76 809830/0468 " 2 "
- *- M ο.ζ. 32- * - M ο.ζ. 32
Die stabilisierende Wirkung dieser Komplexbildner ist jedoch nicht in allen Fällen befriedigend, außerdem können stark alkalische Salze der Komplexbildner den roten Phosphor schädigen. Der Erfindung lag daher die Aufgabe zugrunde, wirksame Stabilisatoren für roten Phosphor bereitzustellen, die sich durch gute Beständigkeit bei den Verarbeitungstemperaturen der Formmassen und durch eine homogene Verteilbarkeit in der Kunststoffschmelze auszeichnen.However, the stabilizing effect of these complexing agents is not always satisfactory; in addition, strongly alkaline salts of the complexing agents can damage the red phosphorus. The invention was therefore based on the object of providing effective stabilizers for red phosphorus which are distinguished by good stability at the processing temperatures of the molding compositions and by homogeneous distributability in the plastic melt.
Diese Aufgabe wird gelöst, wenn man als Stabilisator ein Salz des Aluminiums oder Magnesiums mit einer chelatbildenden Aminoessigsäure verwendet.This object is achieved if a salt of aluminum or magnesium with a chelating aminoacetic acid is used as a stabilizer used.
Gegenstand der Erfindung sind demzufolge Formmassen aus thermoplastischen Kunststoffen, die roten Phosphor als Flammschutzmittel sowie 0,1 bis 20 Qew.%, bezogen auf Phosphor, eines Salzes von Magnesium oder Aluminium mit einer chelatbildenden Aminoessigsäure als Stabilisator enthalten.The invention accordingly relates to thermoplastic molding compositions Plastics containing red phosphorus as a flame retardant and 0.1 to 20 Qew.%, Based on phosphorus, of a salt of Contains magnesium or aluminum with a chelating aminoacetic acid as a stabilizer.
Die flamsnfest auszurüstenden thermoplastischen Kunststoffe sind vorzugsweise Polykondensate oder Polyaddukte, Dabei kommen insbesondere in Frage:The thermoplastics to be made flame-proof are preferably polycondensates or polyadducts, in particular in question:
1. Polyamide, vorzugsweise gesättigte lineare Horoopolyamide, wie z.B. Polycaprolactam (Polyamid-6), Polyhexamethylenadipinsäureamid (Polyaraid-6#6)t Polyhexymethylensebazinsäureamid, Polylaurinlactam, Polyundecanamid; ferner Homo- und Copolyamide, die unter Verwendung von Adipinsäure, Acelainsäure, Sebazinsäure, Dodecandisäure, Terephthalsäure einerseits und Hexamethylendiamin, Trimethylhexainethylendiamin, Bis-ί ^-aminocyclohexyD-methan, 2,2-Bis-(i*l-aminocyclohexyl)-propan andererseits hergestellt werden; sowie Copolyamide, die durch Polykondensation von Lactamen zusammen mit den oben genannten Dicarbonsäuren und Diaminen erhalten werden.1. Polyamides, preferably saturated linear horopolyamides, such as, for example, polycaprolactam (polyamide-6), polyhexamethylene adipamide (polyaraid-6 # 6) t polyhexymethylene sebacic acid amide, polylaurolactam, polyundecanamide; also homo- and copolyamides made using adipic acid, acelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid on the one hand and hexamethylenediamine, trimethylhexainethylenediamine, bis-ί ^ -aminocyclohexyD-methane, 2,2-bis- ( i * l -aminocyclohexyl) propane on the other getting produced; and copolyamides obtained by polycondensation of lactams together with the above -mentioned dicarboxylic acids and diamines.
2, Polyester, insbesondere lineare thermoplastische Polyester aus aromatischen oder aliphatischen Carbonsäuren, wie Tere-2, polyester, especially linear thermoplastic polyester from aromatic or aliphatic carboxylic acids, such as tertiary
809830/0468809830/0468
- ^i O.Z. 32 39*- ^ i O.Z. 32 39 *
phthal-, Isophthal-, Phthal- oder Adipinsäure einerseits und Glykolen, wie Äthylen-, Propylen-, Butylen- oder Neopentylglykol andererseits, wobei Polybutylenterephthalat und PoIyäthylenterephthalat bevorzugt sind.phthalic, isophthalic, phthalic or adipic acid on the one hand and Glycols such as ethylene, propylene, butylene or neopentyl glycol on the other hand, with polybutylene terephthalate and polyethyleneterephthalate are preferred.
3. Polyurethane, insbesondere lineare thermoplastische Polyurethane aus aromatischen oder aliphatischen Diisocyanaten, wie Diphenylmethandiisocyanat oder Hexamethylendiisocyanat und hydroxylgruppenhaltigen Polyestern oder Polyäthern, sowie gegebenenfalls Diolen, wie Butandiol, als Kettenverlängerungsmittel. 3. Polyurethanes, especially linear thermoplastic polyurethanes from aromatic or aliphatic diisocyanates, such as diphenylmethane diisocyanate or hexamethylene diisocyanate and hydroxyl-containing polyesters or polyethers, and optionally diols, such as butanediol, as chain extenders.
4. Polycarbonate aus Phosgen und Dioxydiphenylalkanen, vorzugsweise Dioxydiphenylpropan.4. Polycarbonates made from phosgene and dioxydiphenylalkanes, preferably Dioxydiphenylpropane.
Die erfindungsgemäß verwendeten Stabilisatoren sind z.B. Salze aus:The stabilizers used in the present invention are, for example, salts the end:
(1) 1 Mol Mg2+ und(1) 1 mole of Mg 2+ and
1 Mol Xthanolamindiessigsäure1 mole of xthanolamine diacetic acid
(2) 2 Molen Mg2+ und(2) 2 moles of Mg 2+ and
1 Mol Äthylendiamintetraessigsäure1 mole of ethylenediaminetetraacetic acid
(3) 3 Molen Mg2+ und(3) 3 moles of Mg 2+ and
2 Molen Nitrilotriessigsäure2 moles of nitrilotriacetic acid
(Ό 1 Mol Al3+ und(Ό 1 mol Al 3+ and
1 Mol Äthanolamindiessigsäure1 mole of ethanolamine diacetic acid
(5) 2 Molen Al3+ und(5) 2 moles of Al 3+ and
1 Mol Äthylendiamintetraessigsäure1 mole of ethylenediaminetetraacetic acid
(6) 1 Mol Al3+ und 1 Mol NH4+ mit
1 Mol Nitrilotriessigsäure.(6) 1 mole of Al 3+ and 1 mole of NH 4+ with
1 mole of nitrilotriacetic acid.
809830/0468809830/0468
- > - U ο.ζ. 32-> - U ο.ζ. 32
Besonders bevorzugt ist ein Stabilisator, der erhalten wird durch Umsetzung von Nitrilotriessigsäure mit Aluminiumverbindungen, z.B. Aluminiumchlorid oder -sulfat, in Gegenwart von Ammoniak.Particularly preferred is a stabilizer obtained by reacting nitrilotriacetic acid with aluminum compounds, e.g. Aluminum chloride or sulfate, in the presence of ammonia.
Die eingesetzten Mengen an Stabilisator, bezogen auf roten Phosphor, betragen 0,5 bis 20 Gew„#, vorzugsweise 1 bis 5 Gew.%. Die Stabilisatoren können sowohl mit dem roten Phosphor mechanisch abgemischt werden, als auch bei ihrer Herstellung in Gegenwart einer Phosphoraufschlämmung auf die Phosphorteilchen aufgefällt werden. Natürlich ist es auch möglich, die Stabilisatoren während der Einarbeitung des Phosphors in den Kunststoff direkt in die Schmelze zuzugeben.The amounts of stabilizer used, based on red phosphorus, are 0.5 to 20% by weight, preferably 1 to 5% by weight. The stabilizers can either be mixed mechanically with the red phosphorus or else they can be precipitated onto the phosphor particles during their preparation in the presence of a phosphorus slurry. It is of course also possible to add the stabilizers directly to the melt during the incorporation of the phosphorus into the plastic.
Zur Brandschutzausrüstung wird der rote Phosphor vorzugsweise in Mengen von 1 bis 12 Gew.*, insbesondere von 3 bis 7 Gew.SS, bezogen auf die gesamte Formmasse, eingesetzt. Er kann in handelsüblichen, auch bereits anderweitig vorstabilisierten Qualitäten verwendet werden; aber auch Phosphorkonzentrate z.B. in Caprolactam, Paraffin-Öl, Dioctylphthalat oder Polyamid mit 20 - 90 % rotem Phosphor, können zum Einsatz gelangen. Die mittlere Größe der im Kunststoff verteilten Phosphorpartikel soll bevorzugt zwischen 0,0001 und 0,5 mm, insbesondere zwischen 0,001 und 0,2 mm Durchmesser liegen.For fire protection, the red phosphorus is preferably used in amounts of 1 to 12 wt. *, In particular 3 to 7 wt. SS, based on the total molding compound. It can be used in commercially available qualities that have already been pre-stabilized in some other way; However, phosphorus concentrates, for example in caprolactam, paraffin oil, dioctyl phthalate or polyamide with 20 - 90 % red phosphorus, can also be used. The mean size of the phosphor particles distributed in the plastic should preferably be between 0.0001 and 0.5 mm, in particular between 0.001 and 0.2 mm, in diameter.
Als Füllstoffe kommen Glasfasern, vorzugsweise solche aus E-Glas, die mit einer Schlichte und einem Haftvermittler ausgerüstet sein können, in Mengen von 10 bis 60 Gew.%, bezogen auf die gesamte Formmasse, in Frage. Die Fasern können einen Durchmesser zwischen 8 und 20 /Um aufweisen, die mittlere Glasfaserlänge im Spritzgußteil liegt vorzugsweise zwischen 0,1 und 0,5 nun. Als weitere Füllstoffe kommen Schichtsilikate, wie Talkum und Glimmer in Betracht, wobei der mittlere Plättchendurchmesser 5 - 200 /Um, die mittlere Plättchendicke 0,01 - 10 /Um betragen kann. Weitere geeignete Füllstoffe sind Glaskugeln, Wollastonit, Asbest, Kaolin, Quarz und Kreide.Glass fibers, preferably those made of E-glass, which can be equipped with a size and an adhesion promoter, in amounts of 10 to 60% by weight, based on the total molding composition, are suitable as fillers. The fibers can have a diameter between 8 and 20 μm, the mean glass fiber length in the injection molded part is preferably between 0.1 and 0.5. As other fillers phyllosilicates such as talc and mica into consideration, the average platelet diameter 5-200 / To, the average platelet thickness from 0.01 to 10 / may be in order. Further suitable fillers are glass balls, wollastonite, asbestos, kaolin, quartz and chalk.
Die erfindungsgemäßen Formmassen können ferner die üblichen Zusätze,
wie Farbstoffe, Stabilisatoren, Gleitmittel und Verarbeitungshilfsmittel enthalten.
s 809830/0468 . 5 .The molding compositions according to the invention can also contain the usual additives, such as dyes, stabilizers, lubricants and processing aids.
s 809830/0468. 5 .
- S-- ^. O.Z. 32- S-- ^. O.Z. 32
Zur Herstellung der erfindungsgemäßen Mischungen werden roter Phosphor und gegebenenfalls Füllstoffe nach bekannten Methoden auf Extrudern oder anderen geeigneten Knet- und Mischvorrichtungen in die Kunststoff-Schmelze eingearbeitet, wie es z.B. in der US-Patentschrift 3 304 282 beschrieben ist. Die Phosphorstabilisatoren können hierbei direkt in die Schmelze zugegeben werden, sie können mit rotem Phosphor zuvor abgemischt oder aufgefällt zum Einsatz gelangen, sie können aber auch vor der Einarbeitung auf Kunststoffgranulat aufgebracht werden.To produce the mixtures according to the invention, they are redder Phosphorus and optionally fillers according to known methods on extruders or other suitable kneading and mixing devices in the plastic melt is incorporated, as described, for example, in U.S. Patent 3,304,282. The phosphorus stabilizers can be added directly to the melt, they can be mixed with red phosphorus beforehand or added to the Use, but they can also be applied to plastic granulate before incorporation.
Um die Wirksamkeit der Phosphorstabilisatoren zu prüfen, wurden aus den gewonnenen Granulaten Formkörper mit definierter Oberfläche spritzgegossen, an denen die Phosphinentwicklung über einen längeren Zeitraum gemessen wurde.In order to test the effectiveness of the phosphorus stabilizers, moldings with a defined surface were made from the granules obtained Injection molded, where the phosphine development over a longer period Period was measured.
Polyamid-6,6 mit einem K-Wert von 72 wurde auf einem Zweiwellenextruder bei Temperaturen von 280 C aufgeschmolzen. Glasfasern in Form von 6 mm langen Schnittglasfasern, Phosphorstabilisator und roter Phosphor in Form eines 20 gew.tigen Konzentrates in Polyamid-6,6 wurden über eine öffnung, die sich stromabwärts befindet, zugegeben. Die Menge der eingearbeiteten Glasfasern betrug 35 Gew.?, die des eingesetzten roten Phosphors 6 Gew.JS, jeweils bezogen auf die Gesamtmenge. Die in Tabelle 1 aufgeführten Stabilisatoren wurden in solcher Menge zugegeben, daß die Konzentration im Endprodukt 0,2 Gew.% betrug. Die Mischung wurde durch Düsen ausgepreßt, als Stränge abgezogen und nach dem Abkühlen granuliert.Polyamide-6.6 with a K value of 72 was melted in a twin-screw extruder at temperatures of 280.degree. Glass fibers in the form of 6 mm long chopped glass fibers, phosphorus stabilizer and red phosphorus in the form of a 20% by weight concentrate in polyamide-6,6 were added via an opening located downstream. The amount of the incorporated glass fibers was 35% by weight, that of the red phosphorus used was 6% by weight, based in each case on the total amount. The stabilizers listed in Table 1 was added in such an amount that the concentration was 0.2 wt.% In the final product. The mixture was pressed out through nozzles, drawn off as strands and, after cooling, granulated.
Aus den Granulaten wurden Normkleinstäbe in den Abmessungen 4 χ 6 χ 50 mm spritzgegossen. Jeweils 100 dieser Normkleinstäbe wurden im spritzfrischen Zustand in einen gasdichten Glaskolben gegeben und 5 Gew.% destilliertes Wasser, bezogen auf die Gesamtmasse der Formkörper hinzugefügt, der Kolben mit Sauerstoff gespült und dann auf 0,6 bar evakuiert. Die sich im Kolben bildende Menge an Phosphin wurde nach jeweils 20, 10 und 60 Tagen mittels Trägerröhrchen (Typ Phosphorwasserstoff 50/a der Firma Trägerwerk AG,Standard small rods measuring 4 × 6 × 50 mm were injection molded from the granules. 100 of these standard small bars were placed in a gas-tight glass flask in the freshly sprayed state and 5% by weight of distilled water, based on the total mass the molded body was added, the flask was flushed with oxygen and then evacuated to 0.6 bar. The amount that forms in the flask of phosphine was measured after 20, 10 and 60 days by means of carrier tubes (type phosphorus hydrogen 50 / a from the company Trägerwerk AG,
809830/0468 - 6 -809830/0468 - 6 -
- 4r - ft O. Z . 52- 4r - ft O. Z. 52
Lübeck) bestimmt. Nach jeder Messung wurde der Kolben zuerst mit Stickstoff, dann mit Sauerstoff gespült und wieder auf 0,6 bar evakuiert. Die Summe der nach 20, 'IO und 60 Tagen gemessenen Phosphingehalte diente als Richtwert für die Beurteilung der Wirksamkeit des verwendeten Phosphorstabilisators (Tabelle 2),Lübeck) definitely. After each measurement, the flask was flushed first with nitrogen, then with oxygen and again to 0.6 bar evacuated. The sum of the phosphine contents measured after 20, 10 and 60 days Served as a guide value for assessing the effectiveness of the phosphorus stabilizer used (Table 2),
Tabelle i Verwendete StabilisatorenTable i Stabilizers used
1. Keine (Vergleichsversuch)1. None (comparison test)
2. Hagne s iumoχ id2. Hagne s iumoχ id
3. Aluminiumoxid3. alumina
H. Ma-SaIz der Nitrilotriessigsäure r 5» Ha-SaIz der Sthylendlamintetraessigsäure H. Ma salt of nitrilotriacetic acid r 5 Ha salt of ethylenedlamine tetraacetic acid
6. Verbindung aus 1 Mol TIg und 1 Mol Kthanolamindiessigsätare6. Compound of 1 mol of TIg and 1 mol of Kthanolamindiessigsätare
7. Verbindung aus 2 Molen Mg1" und 1 MoI Sthylendiamintetraessigsäure 7. Compound of 2 moles of Mg 1 "and 1 mole of ethylenediaminetetraacetic acid
3, Verbindung aus 3 Molen Mg und 2 Molen Nitrilotriessigsäure 9. Verbindung aus 1 Mol Al mit einem Mol Äthanolamindiessigsäure 3, compound of 3 moles of Mg and 2 moles of nitrilotriacetic acid 9. Compound of 1 mole of Al with one mole of ethanolamine diacetic acid
VerbiVerbi
essigsäureacetic acid
Verbindunglink
triessigsäuretriacetic acid
Tabelle 2 Gemessene PhosphinmengenTable 2 Measured amounts of phosphine
Versuch Stabilisator Entstandene Phosphinmengen in ppm nachStabilizer experiment Amounts of phosphine produced in ppm
20 '40 60 Tagen20 '40 60 days
10. Verbindung aus 2 Molen Al mit einem Mol A"thylendiamintetrail. Verbindung aus 1 Mol Al und 1 Mol MH1. und einem Mol Hitrilo-10. Compound of 2 moles of Al with one mole of A "thylenediamine tetrail. Compound of 1 mole of Al and 1 mole of MH 1. And one mole of Hitrilo-
809830/0468 _ 7_809830/0468 _ 7 _
ORiGiNAL JNSPECTEDORiGiNAL JNSPECTED
Wie sich aus Tabelle 2 bei den Versuchen f - k im Vergleich zu den Versuchen a - e ergibt, ist die gemessene Menge an Phosphin in Gegenwart der erfindungsgemäßen Phosphorstabilisatoren wesentlich geringer.As can be seen from Table 2 in the tests f - k in comparison to the Tests a - e shows, the measured amount of phosphine in the presence of the phosphorus stabilizers according to the invention is essential less.
809830/0468 - δ -809830/0468 - δ -
Claims (9)
Phosphor als Flammschutzmittel, sowie 0,1 bis 20 Gew.%, bezogen auf Phosphor, eines Metallsalzes einer chelatbildenden Aminoessigsäure als Stabilisator enthalten, dadurch gekennzeichnet, daß der Stabilisator ein Salz des Magnesiums oder Aluminiums ist.1. Molding compounds made from thermoplastics, the red ones
Contain phosphorus as a flame retardant and 0.1 to 20% by weight , based on phosphorus, of a metal salt of a chelating aminoacetic acid as stabilizer, characterized in that the stabilizer is a salt of magnesium or aluminum.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2703052A DE2703052C2 (en) | 1977-01-26 | 1977-01-26 | Stabilized, flame-retardant, thermoplastic molding compounds |
| IT47693/78A IT1103259B (en) | 1977-01-26 | 1978-01-18 | STABILIZED FIREPROOF THERMOPLASTIC MOLDS |
| GB2958/78A GB1592813A (en) | 1977-01-26 | 1978-01-25 | Stabilised flameproofed thermoplastic moulding compositions |
| FR7802155A FR2378817A1 (en) | 1977-01-26 | 1978-01-26 | FIRE-RESISTANT AND STABILIZED THERMOPLASTIC MOLDING MATERIALS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2703052A DE2703052C2 (en) | 1977-01-26 | 1977-01-26 | Stabilized, flame-retardant, thermoplastic molding compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2703052A1 true DE2703052A1 (en) | 1978-07-27 |
| DE2703052C2 DE2703052C2 (en) | 1985-09-12 |
Family
ID=5999535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2703052A Expired DE2703052C2 (en) | 1977-01-26 | 1977-01-26 | Stabilized, flame-retardant, thermoplastic molding compounds |
Country Status (4)
| Country | Link |
|---|---|
| DE (1) | DE2703052C2 (en) |
| FR (1) | FR2378817A1 (en) |
| GB (1) | GB1592813A (en) |
| IT (1) | IT1103259B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0006549A1 (en) * | 1978-06-24 | 1980-01-09 | BASF Aktiengesellschaft | Stabilized, flame-resistant, thermoplastic moulding compositions |
| EP0278559A2 (en) * | 1987-02-11 | 1988-08-17 | Bip Chemicals Limited | Polyamide compositions |
| US5049599A (en) * | 1989-02-18 | 1991-09-17 | Basf Aktiengesellschaft | Flameproofed thermoplastic molding compositions based on phlegmatized red phosphorus |
| US5135971A (en) * | 1989-02-18 | 1992-08-04 | Basf Aktiengesellschaft | Flameproofed thermoplastic molding compositions based on phlegmatized red phosphorus |
| WO2012146624A1 (en) | 2011-04-28 | 2012-11-01 | Basf Se | Flame-retardant molding materials |
| EP2641939A1 (en) | 2012-03-21 | 2013-09-25 | Basf Se | Brightly coloured flame-retardant polyamides |
| US8629206B2 (en) | 2011-01-20 | 2014-01-14 | Basf Se | Flame-retardant thermoplastic molding composition |
| US8653168B2 (en) | 2011-05-10 | 2014-02-18 | Basf Se | Flame-retardant thermoplastic molding composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3215750A1 (en) * | 1982-04-28 | 1983-11-03 | Basf Ag, 6700 Ludwigshafen | FLAME RESISTANT POLYAMIDE OR POLYURETHANE MOLDS |
| DE3317822A1 (en) * | 1983-05-17 | 1984-11-22 | Bayer Ag, 5090 Leverkusen | STABILIZED, RED PHOSPHORUS AND THE USE THEREOF FOR FLAME RESISTANT, THERMOPLASTIC POLYAMIDE MOLDS |
| DE19648503A1 (en) * | 1996-11-22 | 1998-05-28 | Basf Ag | Flame retardant thermoplastic molding compounds |
-
1977
- 1977-01-26 DE DE2703052A patent/DE2703052C2/en not_active Expired
-
1978
- 1978-01-18 IT IT47693/78A patent/IT1103259B/en active
- 1978-01-25 GB GB2958/78A patent/GB1592813A/en not_active Expired
- 1978-01-26 FR FR7802155A patent/FR2378817A1/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| NICHTS-ERMITTELT * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0006549A1 (en) * | 1978-06-24 | 1980-01-09 | BASF Aktiengesellschaft | Stabilized, flame-resistant, thermoplastic moulding compositions |
| EP0278559A2 (en) * | 1987-02-11 | 1988-08-17 | Bip Chemicals Limited | Polyamide compositions |
| EP0278559A3 (en) * | 1987-02-11 | 1989-02-08 | Bip Chemicals Limited | Polyamide compositions |
| US5049599A (en) * | 1989-02-18 | 1991-09-17 | Basf Aktiengesellschaft | Flameproofed thermoplastic molding compositions based on phlegmatized red phosphorus |
| US5135971A (en) * | 1989-02-18 | 1992-08-04 | Basf Aktiengesellschaft | Flameproofed thermoplastic molding compositions based on phlegmatized red phosphorus |
| US8629206B2 (en) | 2011-01-20 | 2014-01-14 | Basf Se | Flame-retardant thermoplastic molding composition |
| WO2012146624A1 (en) | 2011-04-28 | 2012-11-01 | Basf Se | Flame-retardant molding materials |
| US8653168B2 (en) | 2011-05-10 | 2014-02-18 | Basf Se | Flame-retardant thermoplastic molding composition |
| EP2641939A1 (en) | 2012-03-21 | 2013-09-25 | Basf Se | Brightly coloured flame-retardant polyamides |
| WO2013139827A1 (en) | 2012-03-21 | 2013-09-26 | Basf Se | Pale-coloured flame-retardant polyamides |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2703052C2 (en) | 1985-09-12 |
| FR2378817A1 (en) | 1978-08-25 |
| IT1103259B (en) | 1985-10-14 |
| IT7847693A0 (en) | 1978-01-18 |
| FR2378817B3 (en) | 1980-10-17 |
| GB1592813A (en) | 1981-07-08 |
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| 8110 | Request for examination paragraph 44 | ||
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