NO160930B - POLYMER MIXTURE BASED ON VINYL OR VINYLIDENE POLYMERS SUITABLE AS A FORM MATERIAL WITH IMPROVED FIRE PROPERTIES, AND USE OF THE POLYMER MIXTURE FOR MANUFACTURING GOODS. - Google Patents
POLYMER MIXTURE BASED ON VINYL OR VINYLIDENE POLYMERS SUITABLE AS A FORM MATERIAL WITH IMPROVED FIRE PROPERTIES, AND USE OF THE POLYMER MIXTURE FOR MANUFACTURING GOODS. Download PDFInfo
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- NO160930B NO160930B NO792734A NO792734A NO160930B NO 160930 B NO160930 B NO 160930B NO 792734 A NO792734 A NO 792734A NO 792734 A NO792734 A NO 792734A NO 160930 B NO160930 B NO 160930B
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- Prior art keywords
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- polymer mixture
- magnesium hydroxide
- parts
- oxides
- Prior art date
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- 229920002959 polymer blend Polymers 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920002554 vinyl polymer Polymers 0.000 title claims description 4
- 239000000463 material Substances 0.000 title description 5
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 title 1
- 229920001959 vinylidene polymer Polymers 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 34
- 239000000654 additive Substances 0.000 claims description 16
- RJZNFXWQRHAVBP-UHFFFAOYSA-I aluminum;magnesium;pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Al+3] RJZNFXWQRHAVBP-UHFFFAOYSA-I 0.000 claims description 13
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 13
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000004014 plasticizer Substances 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000012778 molding material Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000779 smoke Substances 0.000 description 16
- 239000010455 vermiculite Substances 0.000 description 7
- 229910052902 vermiculite Inorganic materials 0.000 description 7
- 235000019354 vermiculite Nutrition 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- -1 magnesium hydroxide aluminum silicates Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229960000892 attapulgite Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 229910052625 palygorskite Inorganic materials 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 101000929885 Bacillus subtilis (strain 168) Isochorismatase Proteins 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102100026891 Cystatin-B Human genes 0.000 description 1
- 101000912191 Homo sapiens Cystatin-B Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 239000004411 aluminium Substances 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
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical group OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229910001647 dawsonite Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 229910052631 glauconite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- SJOCPYUKFOTDAN-ZSOIEALJSA-N methyl (4z)-4-hydroxyimino-6,6-dimethyl-3-methylsulfanyl-5,7-dihydro-2-benzothiophene-1-carboxylate Chemical compound C1C(C)(C)C\C(=N\O)C=2C1=C(C(=O)OC)SC=2SC SJOCPYUKFOTDAN-ZSOIEALJSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 150000003751 zinc Chemical class 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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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)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Description
■Foreliggende oppfinnelse vedrører en polymerblanding på ■The present invention relates to a polymer mixture of
basis av vinyl- eller vinylidenkloridpolymer egnet som formmaterial med forbedrede egenskaper ved brann inneholdende pr. 100 vektdeler polymer, 0,5 til 100 vektdeler magnesiumhydroksyd-aluminiumsilikat med et ..innhold regnet som oksyder, av henholdsvis magnesium mellom 3 og 30 vekt%, aluminium mellom 10 og 20 vekt%, silisium mellom 30 og 60 vekt%, krystallvanninnhold mellom 2 og 10 vekt%, såvel som eventuelt oksyder av jern og/eller sink som er kjemisk bundet i mengder på under 15 vekt%, idet magnesiumhydroksyd-aluminiumsilikatet anvendes i form av et fint pulver med midlere par-tikkelstørrelse høyst 200 ^um, foretrukket under 10 ^urn, basis of vinyl or vinylidene chloride polymer suitable as molding material with improved fire properties containing per 100 parts by weight polymer, 0.5 to 100 parts by weight magnesium hydroxide-aluminium silicate with a ..content calculated as oxides, respectively of magnesium between 3 and 30% by weight, aluminum between 10 and 20% by weight, silicon between 30 and 60% by weight, crystal water content between 2 and 10% by weight, as well as possibly oxides of iron and/or zinc which are chemically bound in amounts of less than 15% by weight, the magnesium hydroxide aluminum silicate being used in the form of a fine powder with an average particle size of no more than 200 µm, preferably under 10 ^urn,
og det særegne ved blandingen i henhold til oppfinnelsen er at blandingen ytterligere inneholder ett eller flere tilsetningsmidler valgt fra kobbersulfat og kobberoksyder i en mengde mellom 0,1 og 50 vekt% i forhold til mengden magnesiumhydroksyd-aluminiumsilikat. and the peculiarity of the mixture according to the invention is that the mixture further contains one or more additives selected from copper sulphate and copper oxides in an amount between 0.1 and 50% by weight in relation to the amount of magnesium hydroxide-aluminium silicate.
Oppfinnelsen vedrører også anvendelse av polymerblandingen for fremstilling av formede gjenstander med brannhemmende egenskaper. The invention also relates to the use of the polymer mixture for the production of shaped objects with fire-retardant properties.
Disse og andre trekk ved oppfinnelsen fremgår av patentkravene. These and other features of the invention appear in the patent claims.
Man vet at de halogenerte polymerer, og spesielt polyvinylklorid har gode selvslukkende egenskaper på grunn av nærvær av saltsyre i gassene fra den termiske spalting. I et branntil-felle vil imidlertid den tette røk og utsendelse av giftige gasser bli betraktet som minst, like farlig som flammespred-ningen. Den relative brennbarhet og utsendelse av røk kan forklares ved nærvær av flyktige organiske forbindelser i materialene på basis av halogenerte polymerer og ved dannelse av aromatiske og/eller alifatiske forbindelser ved pyrolysen. Studium av den termiske spaltningskinetikk for industrielle blandinger på basis av polyvinylklorid viser at det ikke fore-går samtidig dannelse av brennbare flyktige bestanddeler og saltsyre. It is known that the halogenated polymers, and especially polyvinyl chloride, have good self-extinguishing properties due to the presence of hydrochloric acid in the gases from the thermal decomposition. In the event of a fire, however, the dense smoke and release of toxic gases will be considered at least as dangerous as the spread of flames. The relative flammability and emission of smoke can be explained by the presence of volatile organic compounds in the materials based on halogenated polymers and by the formation of aromatic and/or aliphatic compounds during the pyrolysis. Study of the thermal decomposition kinetics for industrial mixtures based on polyvinyl chloride shows that there is no simultaneous formation of flammable volatile components and hydrochloric acid.
For å oppnå en forbedring for disse materialer i forholdet ved brann er det på den ene side nødvendig å styre nærværet av saltsyre i spaltraingsgassen under hele varigheten av den termiske påvirknlmg og på den annen side samtidig å modifisere pyrolyseprosessera, slik at det oppnås et minimum av flyktige brennbare gasser som kan danne røk. Denne modifikasjon med-fører en samtidig; nedsettelse av selvantenneligheten, tettheten og hastigheten for røkavgivelsen. In order to achieve an improvement for these materials in relation to fire, it is necessary on the one hand to control the presence of hydrochloric acid in the fission gas during the entire duration of the thermal effect and on the other hand to simultaneously modify the pyrolysis processes, so that a minimum of volatile flammable gases that can form smoke. This modification entails a simultaneous; reduction of self-ignition, density and speed of smoke release.
For å løse problemet med røken er det foreslått å blande inn oksydet eller salter av sink i blandingene på basis av halogenerte polymerer og man har understreket synergismen for sink i forhold til vanlige fyllstoffmaterialer, som oksyder eller karbonater av kalsium, magnesium eller aluminiumoksyd som kan danne klorider eller oksyklorider under pyrolysen. In order to solve the problem with the smoke, it has been proposed to mix in the oxide or salts of zinc in the mixtures based on halogenated polymers and the synergism of zinc in relation to common filler materials, such as oxides or carbonates of calcium, magnesium or aluminum oxide, which can form chlorides or oxychlorides during the pyrolysis.
Disse fyllstoffmaterialer kan innvirke på varigheten av selv-slukkingen og øker ofte hastigheten for røkavgivelsen, og følgelig tettheten av denne i et gitt tidsrom. Sinksaltene har som vesentlig ulempe en kraftig destabiliserende virkning, slik at de ikke kan anvendes i tilstrekkelig mengde i faste blandinger hvor diet er nødvendig med anvendelsestemperaturer som kan gå opp i 250°C. These filler materials can affect the duration of self-extinguishing and often increase the rate of smoke release, and consequently the density of this in a given period of time. As a significant disadvantage, the zinc salts have a strong destabilizing effect, so that they cannot be used in sufficient quantity in solid mixtures where diet is necessary with application temperatures that can rise to 250°C.
I henhold til US patentskrift 3.869-420 kjenner man myknings-middelholdige blandinger som samtidig fremviser en reduksjon av brennbarheten og utsendelsen av røk ved tilsetning av et "reaktivt modifiseringsmiddel", f. eks. hydratisert aluminiumoksyd, oksyder, hydroksyder eller karbonater av magnesium eller Dawsonitt. Ved den nevnte tidligere kjente teknikk er det nødvendig å anvende et fosfatmykningsmiddel. According to US patent 3,869-420, plasticizer-containing mixtures are known which simultaneously exhibit a reduction in flammability and the emission of smoke by adding a "reactive modifier", e.g. hydrated alumina, oxides, hydroxides or carbonates of magnesium or Dawsonite. In the aforementioned prior art, it is necessary to use a phosphate softener.
Den foreliggende oppfinnelse tar sikte på å unngå de nevnte ulemper og omfatter som nevnt blandinger på basis av vinyl-eller vinylidenkloridpolymerer, som samtidig frembyr en reduksjon av brennbarheten, dannelsen og avgivelseshastigheten for røk og som kan anvendes ved alle vanlige omdannelsesprosesser hvor temperaturene kan gå opp til 250°C. The present invention aims to avoid the aforementioned disadvantages and, as mentioned, comprises mixtures based on vinyl or vinylidene chloride polymers, which at the same time reduce the flammability, the formation and emission rate of smoke and which can be used in all normal conversion processes where temperatures can rise to 250°C.
Magnesiumhydroksyd-aluminiumsilikat kan • defineres ved hjelp av den generelle bruttoformel (angitt i form av oksydene) med x MgO - y hl^ O^ - z Si02 - n H^ O hvori x, y og z representerer antall mol oksyder og n antallet mol krystallvann. I de magnesiumhydroksyd-aluminiumsilikater som anvendes ved den foreliggende oppfinnelse har x, y, z og n verdier slik at mengden MgO, A^O^., Si02 og krystallvann er som nevnt over. Magnesium hydroxide-aluminium silicate can • be defined using the general gross formula (expressed in terms of the oxides) with x MgO - y hl^ O^ - z SiO2 - n H^ O where x, y and z represent the number of moles of oxides and n the number of moles crystal water. In the magnesium hydroxide aluminum silicates used in the present invention, x, y, z and n have values such that the amount of MgO, A^O^, SiO 2 and crystal water is as mentioned above.
De magnesiumhydroksyd-aluminiumsilikater som svarer til den ovennevnte definisjon forekommer i naturlig tilstand og man kan anvende leirederiverte fyllitter av micastrukturtypen eller av klorittstrukturtypen. Blant micatypene med den angitte sammensetning kan det f. eks. nevnes vermikulitt (aluminiumholdig talkum), montmorillonittene og bentonittene (pyrofyllittene) og mangesiummicatyper som glaukonitt, flogo-pitt, biotitt såvel som attapulgitt. The magnesium hydroxide aluminum silicates that correspond to the above definition occur in their natural state and one can use clay-derived phyllites of the mica structure type or of the chlorite structure type. Among the mica types with the specified composition, there can be e.g. mention is made of vermiculite (aluminium-containing talc), the montmorillonites and bentonites (pyrophyllites) and manganese mica types such as glauconite, phlogo-pitte, biotite as well as attapulgite.
Tilsetningsstoffene anvendes i form av et fint pulver med midlere partikkelstørrelse som nevnt over. De kommersielle produkter i mikronisert form anvendes mer spesielt. The additives are used in the form of a fine powder with average particle size as mentioned above. The commercial products in micronized form are used more specifically.
Polymerene som anvendes i henhold til den foreliggende oppfinnelse omfatter spesielt alle typer av homopolymerer av vinylklorid eller vinylidenklorid, kopolymerer eller deres blandinger, uansett deres fremstillingsmåte (polymerisering i smelte, emulsjon, suspensjon, mikrosuspensjon) og molekylvekt. Kopolymerene kan spesielt være kopolymerer av vinylklorid og vinylacetat, vinylklorid og akrylsyre eller metakrylsyre eller deres estere, vinylklorid og monomeren av typen monoallyl-eller difunksjonelle typer. Kopolymerene inneholder vanligvis minst 50 vekt% vinylklorid. The polymers used according to the present invention include in particular all types of homopolymers of vinyl chloride or vinylidene chloride, copolymers or their mixtures, regardless of their manufacturing method (melt polymerization, emulsion, suspension, microsuspension) and molecular weight. The copolymers can in particular be copolymers of vinyl chloride and vinyl acetate, vinyl chloride and acrylic acid or methacrylic acid or their esters, vinyl chloride and the monomer of the monoallyl or difunctional type. The copolymers usually contain at least 50% by weight of vinyl chloride.
Blandingene kan være av fast, halvfast eller fleksibel type og kan inneholde vanlige bestanddeler som er kjent for fagfolk, spesielt vanlige fyllstoffer, stabiliseringsmidler, opasifi-serende og/eller smørende midler, og vanlige tilsetningsmidler som mykniargsmidler, antioksydasjonsmidler og andre. The mixtures may be of a solid, semi-solid or flexible type and may contain common ingredients known to those skilled in the art, in particular common fillers, stabilizers, opacifying and/or lubricating agents, and common additives such as plasticizers, antioxidants and others.
De nøyaktige mengder av magnesiumhydroksyd-aluminiumsilikat kan variere for oppnåelse av et optimalt resultat, alt etter den nøyaktige natur av blandingen, spesielt naturen og mengden av mykningsmidler,. såvel som det ønskede nivå for beskyt-telsen. Disse faktorer vil kunne bestemmes av fagfolk i hvert enkelt tilfelle. Generelt kan man innføre inntil omtrent 10 vektdeler magnesiumhydroksyd-aluminiumsilikat i faste blandinger og inntil omtrent 100 vektdeler i mykningsmiddel-holdige plastblanidinger. The exact amounts of magnesium hydroxide-aluminosilicate may vary to achieve an optimum result, depending on the exact nature of the mixture, particularly the nature and amount of plasticizers. as well as the desired level of protection. These factors can be determined by professionals in each individual case. In general, up to approximately 10 parts by weight of magnesium hydroxide-aluminosilicate can be introduced in solid mixtures and up to approximately 100 parts by weight in plasticizer-containing plastic mixes.
Reduksjon av røk og tendens til flammespredning reduseres ved ytterligere tilsetning av metallholdige tilsetningsmidler som kobbersulfat og kobberoksyder. Disse tilsetningsmidler kan innblandes samtidig med de andre tilsetningsmidler og de kan også blandes med magnesiumhydroksyd-aluminiumsilikater eller med visse andre tilsetningsmidler i blandingen, f.eks. i form av en tilsetningsmiddelblanding som til slutt innblandes i polymeren. Reduction of smoke and tendency to flame spread is reduced by further addition of metal-containing additives such as copper sulphate and copper oxides. These additives can be mixed in at the same time as the other additives and they can also be mixed with magnesium hydroxide aluminum silicates or with certain other additives in the mixture, e.g. in the form of an additive mixture which is finally mixed into the polymer.
En spesielt interessant utførelsesform består i å avsette sekundære brannhemmende tilsetningsmidler ved impregnering på magnesiumhydroksyd-aluminiumsilikatet som tjener som bærer. Det er således mulig å oppnå interessante egenskaper med mengder av tilsetningsmidler merkbart mindre enn dem som anvendes i form av blandingen av pulveret. For impregnering er det praktisk å dispergere magnesiumhydroksyd-aluminiumsilikatet ved mekanisk omrøring i en oppløsning av det valgte metallsalt, for deretter å fjerne løsningsmiddelet ved av-damping. Mengden, av metallsalt som avsettes eller anvendes i blandingen kan variere innenfor vide grenser og kan være inntil 50 vekt% i forhold til vekten av magnesiumhydroksyd-aluminiumsilikatet. A particularly interesting embodiment consists in depositing secondary fire-retardant additives by impregnation on the magnesium hydroxide aluminum silicate which serves as a carrier. It is thus possible to achieve interesting properties with quantities of additives noticeably smaller than those used in the form of the mixture of the powder. For impregnation, it is practical to disperse the magnesium hydroxide-aluminosilicate by mechanical stirring in a solution of the selected metal salt, to then remove the solvent by evaporation. The amount of metal salt that is deposited or used in the mixture can vary within wide limits and can be up to 50% by weight in relation to the weight of the magnesium hydroxide aluminum silicate.
Blandingene i henhold til oppfinnelsen kan anvendes innenfor all vanlig teknologi for formgivning, henholdsvis sprøyte-støpning, ekstrudering, kalandrering, pressing, etc. for fremstilling av støpte gjenstander, rør og andre ^gjenstander med forbedrede egenskaper ved. brann. The mixtures according to the invention can be used within all common technology for shaping, respectively injection molding, extrusion, calendering, pressing, etc. for the production of molded objects, pipes and other objects with improved properties by. fire.
Følgende eksempler illustrerer oppfinnelsen. The following examples illustrate the invention.
EKSEMPLER 1- 4: (sammenligningseksempler ) EXAMPLES 1-4: (comparison examples)
Følgende blanding fremstilles: The following mixture is prepared:
100 vektdeler homopolymer av vinylklorid med viskositets-indeks 100 (LYCOVYL GB 1150), 100 parts by weight homopolymer of vinyl chloride with viscosity index 100 (LYCOVYL GB 1150),
0,5 vektdeler tobasisk blystearat, 0.5 parts by weight dibasic lead stearate,
0,5 vektdeler trebasisk blysulfat, 0.5 parts by weight tribasic lead sulphate,
0,5 vektdeler kalsiumstearat, 0.5 parts by weight calcium stearate,
0,5 vektdeler voks av type "PA 520", 0.5 parts by weight of wax of type "PA 520",
0,2 vektdeler titandioksyd. 0.2 parts by weight titanium dioxide.
I denne utgangsblanding, som tjener som blindprøve, tilsettes x vektdeler magnesiumhydroksyd-aluminiumsilikat. In this starting mixture, which serves as a blank test, x parts by weight of magnesium hydroxide-aluminum silicate are added.
I hvert forsøk blandes alle produktene i pulverform i en hurtigblander av typen "Papenmeier" ved en temperatur opp til 90 til 100°C. Etter at blandingene er fremstilt formes plater med tykkelse 5 mm. In each experiment, all the products are mixed in powder form in a rapid mixer of the "Papenmeier" type at a temperature of up to 90 to 100°C. After the mixtures have been prepared, plates with a thickness of 5 mm are formed.
Med prøvestykker avkuttet fra disse plater gjennomføres følgende tester: The following tests are carried out with test pieces cut from these plates:
- Termisk stabilitet: DHC. - Thermal stability: DHC.
Nødvendig tid for tilsynekomst av HC1 ved 200°C alt etter metoden i henhold til CSTB. Time required for the appearance of HC1 at 200°C according to the method according to CSTB.
Oksygengrenseindeks: L 01. Oxygen limit index: L 01.
Opasitet av røken. Opacity of the smoke.
- Etter fransk standard NF 51073 - prøvetemperatur: 450°C og 650°C. Man angir som resultat (middel av tre prøve-stykker) den totale mengde av røk avgitt som konvensjonell enhet UFfc.- According to French standard NF 51073 - test temperature: 450°C and 650°C. The result (average of three test pieces) is given as the total quantity of smoke emitted as a conventional unit UFfc.
I henhold til røkkammermetoden i National Bureau of According to the smoke chamber method of the National Bureau of
Standards: NBS. Standards: NBS.
Testene gjennomføres med og uten flamme for prøvestykkene 76,2 x 76,2 x 5 mm. Man oppnår følgende resultat: The tests are carried out with and without flame for the test pieces 76.2 x 76.2 x 5 mm. The following result is obtained:
SOI1+: Røfeuklarhetsindeks etter fire minutter. SOI1+: Cloud opacity index after four minutes.
Do 90: Opifcisk densitet etter 90 sekunder. Do 90: Official density after 90 seconds.
DMC: Maksimal korrigert tetthet av røken. DMC: Maximum corrected density of the smoke.
Resultatene er gjengitt i den etterfølgende tabell I. I forhold til blindprøven iakttas en økning av den termiske stabilitet og en bedre: opptreden ved brann, både hva angår brennbarheten som utsendelse av røk med hensyn til mengde og hastighet. The results are reproduced in the following table I. In relation to the blank test, an increase in thermal stability and a better: behavior in case of fire are observed, both in terms of flammability as emission of smoke with regard to quantity and speed.
EKSEMPLER 5- 9- EXAMPLES 5- 9-
Disse eksempler viser innvirkningen av et sekundært tilset-ningsmiddel i kombinasjon med magnesiumhydroksyd-aluminiumsilikat. These examples show the effect of a secondary additive in combination with magnesium hydroxide-aluminosilicate.
Man anvender utgangsblandingen fra de foregående eksempler hvortil det tilsettes x vektdeler av tilsetningsmiddelet i henhold til oppfinnelsen og y vekt% sekundært tilsetnings-middel. Vermikulitten impregneres på forhånd med en vandig løsning av kobbersulfat i mengde på 10 vekt% kobbersulfat (tørr vekt) for 100 vektdeler vermikulitt. Vermikulitten har etter tørking en midlere kornstørrelse på 5 mikrometer. The starting mixture from the preceding examples is used to which x parts by weight of the additive according to the invention and y% by weight secondary additive are added. The vermiculite is impregnated in advance with an aqueous solution of copper sulphate in an amount of 10% by weight of copper sulphate (dry weight) for 100 parts by weight of vermiculite. After drying, the vermiculite has an average grain size of 5 micrometres.
Resultatene er gjengitt i den etterfølgende tabell II. Man konstaterer i fo-rhold til kontrollprøven en vesentlig for-bedret opptreden under brann for alle verdiene. Impregnering av bæreren tillater å nedsette mengden kobbersulfat til forholdet 5/1 og umngåelse av en ellers forventet destabilisering ved anvendelse av blandingen. The results are reproduced in the subsequent table II. Compared to the control test, a significantly improved performance under fire is observed for all values. Impregnation of the support allows the amount of copper sulphate to be reduced to a ratio of 5/1 and avoidance of an otherwise expected destabilization when using the mixture.
EKSEMPLER 10 og 11: EXAMPLES 10 and 11:
Man anvender blandingen fra de foregående eksempler som utgangsblanding, men tilsetter 1,5 vektdeler kalsiumkarbonat idet denne nye blanding tjener som sammenligning. Ved et første forsøk tilsettes to deler vermikulitt. I et annet forsøk tilsettes to deler vermikulitt impregnert med 10 vekt% kobbersulfat med en midlere kornstørrelse på 5 mikrometer. Resultatene er uttrykt i tabell III. Sammenligning av prøve-blandingen med prøveblandingen i tabell I viser at kalsium-karbonatet øker utsendelseshastigheten for røk (NBS). For-søkene 10 og 11 viser forbedringen i egenskapene ved brann for alle verdier. The mixture from the previous examples is used as the starting mixture, but 1.5 parts by weight of calcium carbonate are added, this new mixture serving as a comparison. In a first attempt, two parts of vermiculite are added. In another experiment, two parts of vermiculite impregnated with 10% by weight of copper sulphate with an average grain size of 5 micrometres are added. The results are expressed in Table III. Comparison of the sample mixture with the sample mixture in Table I shows that the calcium carbonate increases the emission rate of smoke (NBS). Tests 10 and 11 show the improvement in fire properties for all values.
EKSEMPLER 12 og 13: EXAMPLES 12 and 13:
Det fremstilles en blanding med følgende sammensetning: A mixture with the following composition is prepared:
Til denne blanding tilsettes: To this mixture is added:
I eksempel 12: 1,5 vektdeler vermikulitt impregnert med In example 12: 1.5 parts by weight vermiculite impregnated with
10 vekt% kobbersulfat. 10% by weight of copper sulphate.
I eksempel 13: 3 vektdeler attapulgitt impregnert med In example 13: 3 parts by weight of attapulgite impregnated with
30 vekt% kobbersultat. 30% by weight of copper sulfate.
Produktene homogeniseres og blandingen anvendes for fremstilling av et rør med tykkelse 2,5 mm ved ekstrudering på en maskin av typen "Kesterman K 86-16-D". Arbeidsbetingelsene er følgende: The products are homogenized and the mixture is used to produce a tube with a thickness of 2.5 mm by extrusion on a "Kesterman K 86-16-D" type machine. The working conditions are as follows:
På et prøvestykke kuttet ut fra røret gjennomføres tester på brennbarhet- og tetthet av røk i kammer NBS og resultatene sammenlignes (i tabell IV) med et rør fremstilt under de samme betingelser ved hjelp av samme blanding men uten magnesiumhydroksyd-aluminiumsilikat. On a test piece cut from the pipe, tests are carried out on flammability and density of smoke in chamber NBS and the results are compared (in table IV) with a pipe produced under the same conditions using the same mixture but without magnesium hydroxide-aluminium silicate.
EKSEMPEL 14: EXAMPLE 14:
Man fremstiller en blanding av mykningsmiddelholdig type ved følgende sammensetning som tjener som sammenligning. A mixture of the plasticizer-containing type is prepared with the following composition, which serves as a comparison.
Polyvinylklorid i emulsjon (IV:130) 100 vektdeler Oktyltrimellitat '45 vektdeler Blystabilisator 12 vektdeler Antioksydasjonsmiddel 2 vektdeler Polyvinyl chloride in emulsion (IV:130) 100 parts by weight Octyltrimellitate '45 parts by weight Lead stabilizer 12 parts by weight Antioxidant 2 parts by weight
Det tilsettes 5 vektdeler attapulgitt impregnert med 10 vekt% kobbersulfat. 5 parts by weight of attapulgite impregnated with 10% by weight of copper sulphate are added.
Man oppnår følgende resultater: The following results are achieved:
EKSEMPEL 15: EXAMPLE 15:
Man erstatter oktyltrimellitatet fra sammensetningen i henhold til eksempel 14 med 37 vektdeler polypropylenglykoladipat og oppnår følgende resultat: The octyl trimellitate from the composition according to example 14 is replaced with 37 parts by weight of polypropylene glycol adipate and the following result is obtained:
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7824534A FR2434188A1 (en) | 1978-08-24 | 1978-08-24 | HALOGENATED POLYMER COMPOSITIONS HAVING IMPROVED FIRE BEHAVIOR |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO792734L NO792734L (en) | 1980-02-26 |
| NO160930B true NO160930B (en) | 1989-03-06 |
| NO160930C NO160930C (en) | 1989-06-14 |
Family
ID=9212042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO792734A NO160930C (en) | 1978-08-24 | 1979-08-23 | POLYMER MIXTURE BASED ON VINYL OR VINYLIDENE POLYMERS SUITABLE AS A FORM MATERIAL WITH IMPROVED FIRE PROPERTIES, AND USE OF THE POLYMER MIXTURE FOR MANUFACTURING GOODS. |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5548237A (en) |
| BE (1) | BE878402A (en) |
| CH (1) | CH642090A5 (en) |
| DE (1) | DE2933806A1 (en) |
| FR (1) | FR2434188A1 (en) |
| GB (1) | GB2028833B (en) |
| GR (1) | GR67233B (en) |
| IT (1) | IT1123530B (en) |
| NL (1) | NL7906366A (en) |
| NO (1) | NO160930C (en) |
| SE (1) | SE445354B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK169628B1 (en) * | 1979-11-03 | 1994-12-27 | Raychem Ltd | Water-stabilized polymeric material and electrical equipment |
| GB8312992D0 (en) * | 1983-05-11 | 1983-06-15 | Ici Plc | Poly(aryl ethers) |
| JPS6084342A (en) * | 1983-06-29 | 1985-05-13 | Dainichi Nippon Cables Ltd | Low-smoking polyvinyl chloride composition |
| JPS6011548A (en) * | 1983-06-29 | 1985-01-21 | Dainichi Nippon Cables Ltd | Low smoking polyvinyl chloride composition |
| JPS60152547A (en) * | 1984-01-19 | 1985-08-10 | Toyo Soda Mfg Co Ltd | Prevention against smoking of polymer material |
| JPS6261201A (en) * | 1985-09-09 | 1987-03-17 | 日立電線株式会社 | Flame resisting electric insulation composition |
| US4965309A (en) * | 1987-11-04 | 1990-10-23 | H. B. Fuller Company | Smoke suppressant compositions for halogen-containing plastics and methods of using |
| JPH0618916B2 (en) * | 1988-05-28 | 1994-03-16 | サンスター技研株式会社 | Polyvinyl chloride resin soft foam |
| DE3943450A1 (en) * | 1988-06-16 | 1991-01-24 | Vickers Shipbuilding & Eng | IMPROVED THERMAL OR HEAT RESISTANT MATERIALS |
| JP2766926B2 (en) * | 1988-10-13 | 1998-06-18 | 丸菱油化工業株式会社 | Flameproof, moisture-permeable water-resistant coating material |
| CN1103649A (en) * | 1993-04-22 | 1995-06-14 | 苏马吕株式会社 | Laser beam absorbing resin composition, coloring material therefor and laser beam marking method |
| CN102408713A (en) * | 2011-09-21 | 2012-04-11 | 镇江忆诺唯记忆合金有限公司 | Preparation method for PANI-TiO2-ATP composite material |
| CN102504433B (en) * | 2011-10-09 | 2014-03-19 | 南京大学 | Nano attapulgite composite PVC (Poly Vinyl Chloride) flame retardant and PVC flame retardant material and preparation methods of nano attapulgite composite PVC flame retardant and PVC flame retardant material |
| CN104262820A (en) * | 2014-09-04 | 2015-01-07 | 苏州市景荣科技有限公司 | High-fracture-strength PVC foamed sole material and preparation method thereof |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1054700A (en) * | 1964-12-23 | |||
| FR1566193A (en) * | 1967-12-18 | 1969-05-09 | ||
| DE2137271B2 (en) * | 1971-07-26 | 1973-06-07 | Metallgesellschaft AG, 6000 Frank fürt | FLAME RETARDANT ADDITIVE IN PLASTICS |
| US3845001A (en) * | 1971-11-08 | 1974-10-29 | Ethyl Corp | Smoke retardant compositions |
| JPS5142628B2 (en) * | 1972-03-01 | 1976-11-17 | ||
| JPS4920248A (en) * | 1972-06-17 | 1974-02-22 | ||
| JPS4918615A (en) * | 1972-06-21 | 1974-02-19 | ||
| IN139125B (en) * | 1973-04-25 | 1976-05-08 | Ishikawa T | |
| JPS5531849B2 (en) * | 1973-07-19 | 1980-08-21 | ||
| JPS5033915A (en) * | 1973-07-31 | 1975-04-02 | ||
| JPS5147737B2 (en) * | 1973-10-22 | 1976-12-16 | ||
| JPS5120263A (en) * | 1974-01-31 | 1976-02-18 | Dainippon Toryo Kk | Ototsu moyo o jusuru goseijushishiito no seizohoho |
| US3883480A (en) * | 1974-02-01 | 1975-05-13 | Goodrich Co B F | Flame and smoke retardant vinyl chloride and vinylidene chloride polymer compositions |
| US3883482A (en) * | 1974-02-01 | 1975-05-13 | Goodrich Co B F | Flame and smoke retardant vinyl chloride and vinylidene chloride polymer compositions |
| JPS5637255B2 (en) * | 1974-05-28 | 1981-08-29 | ||
| JPS5123538A (en) * | 1974-08-21 | 1976-02-25 | Canon Kk | JUSHI SEIBUTSU |
| JPS51106147A (en) * | 1975-03-14 | 1976-09-20 | Unitika Ltd | Purasuchitsukusuno taidenboshososeibutsu |
| US4098748A (en) * | 1976-08-16 | 1978-07-04 | Amax Inc. | Plasticized polyvinyl chloride resin composition containing molybdenum flame retardant and antimony compound smoke suppressant agent |
| US4098753A (en) * | 1976-08-16 | 1978-07-04 | Amax Inc. | Ester-plasticized polyvinyl chloride resin composition containing molybdenum flame retardant and smoke suppressant agent |
| JPS5337735A (en) * | 1976-09-18 | 1978-04-07 | Hideo Iio | Compounding composition especially suitable for floor material |
| DE2655038A1 (en) * | 1976-12-04 | 1978-06-08 | Kalk Chemische Fabrik Gmbh | Process for the production of flame-retardant, corrugated bitumen sheets |
| JPS5487748A (en) * | 1977-12-26 | 1979-07-12 | Shin Etsu Chem Co Ltd | Flame-retardant vinyl chloride resin composition |
| JPH06127004A (en) * | 1992-10-15 | 1994-05-10 | Sony Corp | Thermal head |
-
1978
- 1978-08-24 FR FR7824534A patent/FR2434188A1/en active Granted
-
1979
- 1979-08-20 IT IT25169/79A patent/IT1123530B/en active
- 1979-08-21 DE DE19792933806 patent/DE2933806A1/en not_active Withdrawn
- 1979-08-22 GB GB7929188A patent/GB2028833B/en not_active Expired
- 1979-08-22 GR GR59887A patent/GR67233B/el unknown
- 1979-08-23 BE BE0/196859A patent/BE878402A/en not_active IP Right Cessation
- 1979-08-23 NL NL7906366A patent/NL7906366A/en not_active Application Discontinuation
- 1979-08-23 SE SE7907052A patent/SE445354B/en not_active IP Right Cessation
- 1979-08-23 NO NO792734A patent/NO160930C/en unknown
- 1979-08-23 JP JP10669979A patent/JPS5548237A/en active Granted
- 1979-08-23 CH CH769179A patent/CH642090A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CH642090A5 (en) | 1984-03-30 |
| BE878402A (en) | 1980-02-25 |
| GB2028833B (en) | 1982-12-01 |
| JPS638137B2 (en) | 1988-02-20 |
| IT1123530B (en) | 1986-04-30 |
| NO160930C (en) | 1989-06-14 |
| FR2434188B1 (en) | 1981-01-09 |
| SE445354B (en) | 1986-06-16 |
| DE2933806A1 (en) | 1980-03-06 |
| GR67233B (en) | 1981-06-25 |
| SE7907052L (en) | 1980-02-25 |
| FR2434188A1 (en) | 1980-03-21 |
| IT7925169A0 (en) | 1979-08-20 |
| NO792734L (en) | 1980-02-26 |
| GB2028833A (en) | 1980-03-12 |
| JPS5548237A (en) | 1980-04-05 |
| NL7906366A (en) | 1980-02-26 |
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