EP1567231A1 - Fire extinction and fire prevention method - Google Patents
Fire extinction and fire prevention methodInfo
- Publication number
- EP1567231A1 EP1567231A1 EP03784087A EP03784087A EP1567231A1 EP 1567231 A1 EP1567231 A1 EP 1567231A1 EP 03784087 A EP03784087 A EP 03784087A EP 03784087 A EP03784087 A EP 03784087A EP 1567231 A1 EP1567231 A1 EP 1567231A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fire
- agent
- hydrate
- extinguishing agent
- hexafluoroacetone
- 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- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims description 15
- 230000002265 prevention Effects 0.000 title claims description 10
- 230000008033 biological extinction Effects 0.000 title abstract 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical class FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003380 propellant Substances 0.000 claims abstract description 8
- 150000004677 hydrates Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 16
- 239000004604 Blowing Agent Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- SNZAEUWCEHDROX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-one;trihydrate Chemical compound O.O.O.FC(F)(F)C(=O)C(F)(F)F SNZAEUWCEHDROX-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- HEBNOKIGWWEWCN-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-one;hydrate Chemical compound O.FC(F)(F)C(=O)C(F)(F)F HEBNOKIGWWEWCN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 3
- 239000010702 perfluoropolyether Substances 0.000 claims description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 claims description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 150000002576 ketones Chemical class 0.000 description 21
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- -1 ketone hydrates Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- QZBHDPVTAHIYBF-UHFFFAOYSA-N carbonyl difluoride;hydrate Chemical compound O.FC(F)=O QZBHDPVTAHIYBF-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DCEPGADSNJKOJK-UHFFFAOYSA-N 2,2,2-trifluoroacetyl fluoride Chemical compound FC(=O)C(F)(F)F DCEPGADSNJKOJK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical class [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical class F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
- A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0028—Liquid extinguishing substances
- A62D1/0057—Polyhaloalkanes
Definitions
- the invention relates to a method for extinguishing fire or preventing the occurrence of fire (fire prevention) using hydrates of perfluorinated ketones, in particular hexafluoroacetone, of CF 3 C (0) CF 5 or CF 3 C (0) nC 3 F 7 / and their aqueous preparations.
- the latter two compounds can be obtained by adding trifluoroacetyl fluoride to tetrafluoroethylene or perfluoropropylene.
- brominated (fluorine) carbon compounds appear to have a negative impact on the ozone layer above the earth
- fire extinguishing agents have been developed which are based on the use of compounds which are less ozone depleting or harmless.
- fluorocarbon compounds have proven useful.
- the usability of fluorinated ketones is disclosed in WO 01/05468.
- the ketones indicated there as usable have at least four carbon atoms.
- the object of the present invention is to specify further methods for extinguishing a fire or for preventing the occurrence of a fire, and compositions which can be used for this purpose. This object is achieved by the method according to the invention and the fire-extinguishing or fire-preventing compositions according to the invention. drive and solved the fire-extinguishing or fire-preventing compositions of the invention.
- the method according to the invention for extinguishing a fire or for preventing the occurrence of a fire provides that perfluoroketones with 3 to C atoms, preferably hexafluoracetone, CF 3 C (0) C 2 F 5 or CF 3 C (0) nC 3 F 7 in the form of their hydrates or aqueous preparations, as an extinguishing agent, part of an extinguishing agent, as a means of fire prevention or as part of such an agent. Mixtures of two or more ketones can be included.
- hydrates of perfluoroketones means compounds defined in the context of the present invention. Hexafluoroacetone trihydrate is such a defined compound.
- hexafluoroacetone hydrate means a defined compound of hexafluoroacetone and water in the context of the present invention.
- these defined compounds can be used as such or together with blowing agents, other extinguishing agents or with auxiliaries such as surfactants or foaming agents.
- the perfluoroketones with 3 to 7 carbon atoms can also be used as aqueous preparations.
- the preparations consist of ketone and water.
- the water content is in the range from 1 to 70% by weight of the total content of ketone and water, the ketone represents the rest to 100% by weight.
- the aqueous preparation contains one or more ketones, water and other constituents, such as one or more propellants, one or more other fire extinguishing agents, or auxiliaries such as surfactants or foaming agents.
- the ketone content is between 1 and 98% by weight, the water content between 1 and 70% by weight, the remainder to 100% by weight is caused by one or more propellants, other fire extinguishing agents and / or Auxiliaries such as surfactants or foaming agents are formed.
- the blowing agent is contained in an amount of 0 to 70% by weight, the other fire extinguishing agent or agents in an amount of 0 to 70% by weight, the auxiliary agent or additives in an amount of 0 to 10% by weight. At least one of the above-mentioned agents must therefore be contained in the preparation, advantageously in an amount of at least 1% by weight.
- the ketone hydrates are preferably used to extinguish a fire, if desired combined with propellant, other fire extinguishing agent and / or auxiliary agent.
- the invention is further illustrated by the preferred embodiment, the use of hexafluoroacetone trihydrate.
- the hexafluoroacetone trihydrate can be used alone, in conjunction with other known fire extinguishing agents, in conjunction with blowing agents or auxiliaries such as surfactants. It can also contain additional water if a defined ketone hydrate compound is used. If another fire extinguishing agent is used, it is preferred to use one with a boiling point of up to 100 ° C. Instead of another fire extinguishing agent or additionally contain a blowing agent, nitrogen and trifluoromethane being suitable blowing agents. Other inert gases or low-boiling substances such as argon or carbon dioxide can also be used. Trifluoromethane has the advantage that it also has good fire extinguishing / fire prevention properties.
- a fire extinguishing agent is preferably selected from the group consisting of fluorocarbon compounds, fluorocarbon compounds, chlorofluorocarbon compounds, perfluoropolyether compounds and hydrofluoroether compounds. Fluorocarbons in particular are well suited as a further fire extinguishing agent.
- the preferred compounds from this group include trifluoromethane, tetrafluoroethane, pentafluoroethane, hexafluoropropane and heptafluoropropane.
- the process according to the invention is preferably carried out in such a way that the ketone hydrate, the aqueous ketone preparation or corresponding mixtures is applied in liquid or gaseous form to the fire to be extinguished.
- a base can be used together with or separately from the fire extinguishing agent, simultaneously with its use or before or later, e.g. B. an alkali or a carbonate or hydrogen carbonate.
- the fire extinguishing agent is used in a known manner. It can be sprayed into the fire in the form of a jet using a fire extinguisher, for example a portable fire extinguisher. It can be nebulized or brought into the room in which a fire is to be extinguished.
- a blowing agent is expediently contained, for example nitrogen, argon, carbon dioxide or trifluoromethane. The same procedure is followed to prevent a fire from occurring.
- the amount of fire extinguishing agent to be used one proceeds, for example, by using the fire extinguishing agent until the fire has gone out.
- the ketone e.g. Hexafluoroacetone trihydrate, or the preparation with it, also in the form of a foam, for example water-based, can be used to extinguish fire. Extinguishing with such foams is described, for example, in U.S. Patent 4,459,213.
- the method according to the invention can be used to extinguish burning materials such as paper, wood, flammable liquids, plastics or electrical devices. It can also be used in vehicles such as cars, ships and airplanes. Fire prevention is carried out analogously.
- Hydrates of perfluoroketones and their aqueous preparations, especially of hexafluoroacetone hydrate, have the advantage that they have a good extinguishing effect and the ozone layer is not endangered.
- the invention further relates to a fire-extinguishing or fire-preventing composition which comprises a hydrate or an aqueous preparation of a perfluoroketone having 3 to 7 C atoms, preferably hexafluoroacetone hydrate, CF 3 C (0) C 2 F 5 or CF 3 C (0) nC 3 F 7 and at least one further blowing agent which is gaseous under normal conditions and / or at least one further fire extinguishing agent and / or at least one auxiliary substance which is advantageous in terms of application technology or consists thereof.
- the auxiliary can be a surfactant, for example.
- ketone hydrate again denotes defined compounds, for example the hemihydrate or the trihydrate of hexafluoroacetone.
- Aqueous preparation is again a mixture which comprises 1 to 99% by weight of the ketone and the remainder to 100% by weight of water if ketone and water are the only ingredients. If other components such as propellants, other fire extinguishing agents or surfactants are contained, the content information given above applies.
- Preferred blowing agents are nitrogen, argon, carbon dioxide and trifluoromethane. If desired, you can of course use mixtures.
- the fire extinguishing agents specified above are used as further fire extinguishing agents.
- the ketone is contained in the composition in an amount of at least 1% by weight, preferably in an amount of at least 5% by weight and at most in an amount of 99% by weight , The remainder to 100% by weight is water.
- the composition also contains a blowing agent, this is contained in the fire-extinguishing composition in an amount of up to 70% by weight. If a further fire extinguishing agent is contained, this is contained in the fire extinguishing composition in an amount of up to 70% by weight.
- the perfluoroketone preferably hexafluoroacetone (it is preferably in the form of hexafluoroacetone trihydrate), or CF 3 C (0) C 2 F 5 or CF 3 C (0) nC 3 F 7 is present in the composition in an amount of 1 to 98% by weight.
- composition can also contain a base as an auxiliary in addition to the hexafluoroacetone hydrate.
- a base as an auxiliary in addition to the hexafluoroacetone hydrate.
- Alkali is preferably sodium, alkaline earth, calcium or magnesium.
- compositions can be prepared by simply mixing the substances, if necessary under pressure or at low temperatures.
- a perfluoroketone hydrate can be mixed with a blowing agent, other fire extinguishing agent and / or auxiliary agent.
- the perfluoroketone hydrate can also be prepared in situ by mixing ketone and the appropriate amount of water.
- Aqueous preparations of the ketone can be prepared by using a ketone hydrate and the desired amount of water or by using the (more or less water-containing or dry) ketone and the desired amount of water and optionally adding the propellant, other fire extinguishing agents and / or auxiliaries ,
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
The invention relates to hydrates of perfluoroketones or aqueous preparations thereof, which can be used as fire extinction agents. Said compounds can, if desired, be combined with propellants and/or other known fire extinction agents or bases.
Description
Verfahren zum Feuerlöschen und Feuerverhüten Fire extinguishing and fire prevention procedures
Beschreibungdescription
Die Erfindung bezieht sich auf ein Verfahren zum Feuerlöschen oder dem Verhindern des Entstehen eines Feuers (Feuerverhütung) unter Verwendung von Hydraten von perfluorierten Ketonen, insbesondere des Hexafluoracetons, von CF3C(0)C F5 oder CF3C (0)n-C3F7/ und deren wässrigen Zubereitungen. Die beiden letztgenannten Verbindungen sind durch Anlagerung von Trifluoracetylfluorid an Tetrafluorethylen bzw. Perfluorpro- pylen erhältlich.The invention relates to a method for extinguishing fire or preventing the occurrence of fire (fire prevention) using hydrates of perfluorinated ketones, in particular hexafluoroacetone, of CF 3 C (0) CF 5 or CF 3 C (0) nC 3 F 7 / and their aqueous preparations. The latter two compounds can be obtained by adding trifluoroacetyl fluoride to tetrafluoroethylene or perfluoropropylene.
Da bromierte (Fluor) Kohlenstoffverbindungen einen negativen Einfluß auf die Ozonschicht über der Erde zu haben scheinen, sind Feuerlöschmittel entwickelt worden, die auf der Verwendung von weniger ozonschädlichen oder ozonunschädlichen Verbindungen basieren. Als brauchbar haben sich beispielsweise FluorkohlenwasserstoffVerbindungen erwiesen. Die Verwendbarkeit von fluorierten Ketonen wird in der WO 01/05468 offenbart. Die dort als verwendbar angegebenen Ketone haben mindestens vier Kohlenstoffatome.Since brominated (fluorine) carbon compounds appear to have a negative impact on the ozone layer above the earth, fire extinguishing agents have been developed which are based on the use of compounds which are less ozone depleting or harmless. For example, fluorocarbon compounds have proven useful. The usability of fluorinated ketones is disclosed in WO 01/05468. The ketones indicated there as usable have at least four carbon atoms.
Aufgabe der vorliegenden Erfindung ist es, weitere Verfahren zum Löschen eines Feuers oder zum Verhindern des Entstehen eines Feuers sowie dafür brauchbare Zusammensetzungen anzugeben. Diese Aufgabe wird durch das erfindungsgemäße Verfahren und die erfindungsgemäßen feuerlöschenden bzw. feuerverhütenden Zusammensetzungen gelöst.
fahren und die erfindungsgemäßen feuerlöschenden bzw. feuerverhütenden Zusammensetzungen gelöst.The object of the present invention is to specify further methods for extinguishing a fire or for preventing the occurrence of a fire, and compositions which can be used for this purpose. This object is achieved by the method according to the invention and the fire-extinguishing or fire-preventing compositions according to the invention. drive and solved the fire-extinguishing or fire-preventing compositions of the invention.
Das erfindungsgemäße Verfahren zum Löschen eines Feuers bzw. zum Verhindern des Entstehen eines Feuers sieht vor, daß man Perfluorketone mit 3 bis C-Atomen, vorzugsweise Hexafluo- raceton, CF3C(0)C2F5 oder CF3C (0)n-C3F7 in Form ihrer Hydrate oder wässrigen Zubereitungen, als Löschmittel, Bestandteil eines Löschmittels, als Mittel zur Feuerverhütung oder als Bestandteil eines solchen Mittels einsetzt. Es können Gemische von zwei oder mehr Ketonen enthalten sein. Der Begriff „Hydrate von Perfluorketonen" bedeutet im Rahmen der vorliegenden Erfindung definierte Verbindungen. Hexafluoraceton- Trihydrat ist eine solche definierte Verbindung. Der Begriff "Hexafluoraceton-Hydrat" bedeutet im Rahmen der vorliegenden Erfindung eine definierte Verbindung aus Hexafluoraceton und Wasser.The method according to the invention for extinguishing a fire or for preventing the occurrence of a fire provides that perfluoroketones with 3 to C atoms, preferably hexafluoracetone, CF 3 C (0) C 2 F 5 or CF 3 C (0) nC 3 F 7 in the form of their hydrates or aqueous preparations, as an extinguishing agent, part of an extinguishing agent, as a means of fire prevention or as part of such an agent. Mixtures of two or more ketones can be included. The term “hydrates of perfluoroketones” means compounds defined in the context of the present invention. Hexafluoroacetone trihydrate is such a defined compound. The term “hexafluoroacetone hydrate” means a defined compound of hexafluoroacetone and water in the context of the present invention.
Diese definierten Verbindungen können, wie weiter unten noch erläutert wird, als solche oder zusammen mit Treibmitteln, anderen löschwirksamen Mitteln oder mit Hilfsmitteln wie Tensiden oder Schaumbildnern eingesetzt werden.As will be explained further below, these defined compounds can be used as such or together with blowing agents, other extinguishing agents or with auxiliaries such as surfactants or foaming agents.
Die Perfluorketone mit 3 bis 7 C-Atomen können auch als wässrige Zubereitungen eingesetzt werden. Gemäß einer Ausführungsform bestehen die Zubereitungen aus Keton und Wasser. In diesem Fall liegt der Gehalt an Wasser im Bereich von 1 bis 70 Gew.-% des Gesamtgehaltes an Keton und Wasser, das Keton stellt den Rest auf 100 Gew.-% dar.
Gemäß einer weiteren Ausführungsform enthält die wäßrige Zubereitung ein oder mehrere Ketone, Wasser und weitere Bestandteile, wie ein oder mehrere Treibmittel, ein oder mehrere andere Feuerlöschmittel, oder Hilfsstoffe wie Tenside oder Schaumbildner. In dieser Ausführungsform liegt der Gehalt an Keton zwischen 1 und 98 Gew.-%, der Gehalt an Wasser zwischen 1 und 70 Gew.-%, der Rest auf 100 Gew.-% wird durch ein oder mehrere Treibmittel, andere Feuerlöschmittel und/oder Hilfsstoffe wie Tenside oder Schaumbildner gebildet. Dabei ist das Treibmittel in einer Menge von 0 bis 70 Gew.-%, das oder die anderen Feuerlöschmittel in einer Menge von 0 bis 70 Gew.-%, das oder die Hilfsmittel in einer Menge von 0 bis 10 Gew.-% enthalten. Mindestens eines der vorstehend genannten Mittel muss also in der Zubereitung enthalten sein, zweckmäßig in einer Menge von mindestens 1 Gew.-%.The perfluoroketones with 3 to 7 carbon atoms can also be used as aqueous preparations. According to one embodiment, the preparations consist of ketone and water. In this case, the water content is in the range from 1 to 70% by weight of the total content of ketone and water, the ketone represents the rest to 100% by weight. According to a further embodiment, the aqueous preparation contains one or more ketones, water and other constituents, such as one or more propellants, one or more other fire extinguishing agents, or auxiliaries such as surfactants or foaming agents. In this embodiment, the ketone content is between 1 and 98% by weight, the water content between 1 and 70% by weight, the remainder to 100% by weight is caused by one or more propellants, other fire extinguishing agents and / or Auxiliaries such as surfactants or foaming agents are formed. The blowing agent is contained in an amount of 0 to 70% by weight, the other fire extinguishing agent or agents in an amount of 0 to 70% by weight, the auxiliary agent or additives in an amount of 0 to 10% by weight. At least one of the above-mentioned agents must therefore be contained in the preparation, advantageously in an amount of at least 1% by weight.
Bevorzugt werden die Ketonhydrate zum Löschen eines Feuers eingesetzt, gewünschtenfalls kombiniert mit Treibmittel, anderem Feuerlöschmittel und /oder Hilfsmittel.The ketone hydrates are preferably used to extinguish a fire, if desired combined with propellant, other fire extinguishing agent and / or auxiliary agent.
Die Erfindung wird anhand der bevorzugten Ausführungsform, der Verwendung von Hexafluoraceton-Trihydrat, weiter erläutert.The invention is further illustrated by the preferred embodiment, the use of hexafluoroacetone trihydrate.
Das Hexafluoraceton-Trihydrat kann allein, in Verbindung mit anderen bekannten Feuerlöschmitteln, in Verbindung mit Treibmitteln oder Hilfsmitteln wie z.B. Tensiden eingesetzt werden. Es kann auch zusätzliches Wasser enthalten, wenn eine definierte Keton-Hydrat-Verbindung eingesetzt wird. Setzt man ein weiteres Feuerlöschmittel ein, dann verwendet man bevorzugt ein solches mit einem Siedepunkt von bis zu 100 °C. Anstelle eines weiteren Feuerlöschmittels oder zusätzlich kann
ein Treibmittel enthalten sein, wobei Stickstoff und Triflu- ormethan gut geeignete Treibmittel sind. Gut brauchbar sind auch andere inerte Gase oder niedrigsiedende Substanzen wie Argon oder Kohlendioxid. Trifluormethan hat den Vorteil, dass es auch gute feuerlöschende/feuerverhütende Eigenschaften hat.The hexafluoroacetone trihydrate can be used alone, in conjunction with other known fire extinguishing agents, in conjunction with blowing agents or auxiliaries such as surfactants. It can also contain additional water if a defined ketone hydrate compound is used. If another fire extinguishing agent is used, it is preferred to use one with a boiling point of up to 100 ° C. Instead of another fire extinguishing agent or additionally contain a blowing agent, nitrogen and trifluoromethane being suitable blowing agents. Other inert gases or low-boiling substances such as argon or carbon dioxide can also be used. Trifluoromethane has the advantage that it also has good fire extinguishing / fire prevention properties.
Sofern man das Hexafluoraceton-Trihydrat mit einem weiteren Feuerlöschmittel einsetzt, so wählt man vorzugsweise ein Feuerlöschmittel ausgewählt aus der Gruppe bestehend aus FluorkohlenstoffVerbindungen, FluorkohlenwasserstoffVerbindungen, Chlorfluorkohlenwasserstoffverbindungen, Perfluorpo- lyetherverbindungen und Hydrofluoroetherverbindungen. Besonders Fluorkohlenwasserstoffe sind als weiteres Feuerlöschmittel gut geeignet. Zu den bevorzugten Verbindungen aus dieser Gruppe gehören Trifluormethan, Tetrafluorethan, Pentafluor- ethan, Hexafluorpropan und Heptafluorpropan.If the hexafluoroacetone trihydrate is used with a further fire extinguishing agent, a fire extinguishing agent is preferably selected from the group consisting of fluorocarbon compounds, fluorocarbon compounds, chlorofluorocarbon compounds, perfluoropolyether compounds and hydrofluoroether compounds. Fluorocarbons in particular are well suited as a further fire extinguishing agent. The preferred compounds from this group include trifluoromethane, tetrafluoroethane, pentafluoroethane, hexafluoropropane and heptafluoropropane.
Das erfindungsgemäße Verfahren wird bevorzugt so durchgeführt, daß das Keton-Hydrat, die wässrige Keton-Zubereitung oder entsprechende Gemische, flüssig oder gasförmig auf das zu löschende Feuer aufgebracht wird. Zusammen mit dem Feuerlöschmittel oder getrennt davon, gleichzeitig mit seinem Einsatz oder vorher oder später, kann eine Base eingesetzt werden, z. B. eine Alkalilauge oder ein Carbonat oder Hydrogen- carbonat .The process according to the invention is preferably carried out in such a way that the ketone hydrate, the aqueous ketone preparation or corresponding mixtures is applied in liquid or gaseous form to the fire to be extinguished. A base can be used together with or separately from the fire extinguishing agent, simultaneously with its use or before or later, e.g. B. an alkali or a carbonate or hydrogen carbonate.
Das Feuerlöschmittel wird in bekannter Weise eingesetzt . Es kann in Form eines Strahles mittels eines Feuerlöschers, beispielsweise eines tragbaren Feuerlöschers, in das Feuer gesprüht werden. Es kann vernebelt oder in den Raum eingebracht werden, in welchem ein Feuer zu löschen ist. Damit
möglichst schnell möglichst viel Feuerlöschmittel eingesetzt werden kann, ist zweckmäßig ein Treibmittel enthalten, beispielsweise Stickstoff, Argon, Kohlendioxid oder Trifluormethan. Analog geht man vor, um das Entstehen eines Feuers zu verhüten.The fire extinguishing agent is used in a known manner. It can be sprayed into the fire in the form of a jet using a fire extinguisher, for example a portable fire extinguisher. It can be nebulized or brought into the room in which a fire is to be extinguished. In order to As much fire extinguishing agent as possible can be used as quickly as possible, a blowing agent is expediently contained, for example nitrogen, argon, carbon dioxide or trifluoromethane. The same procedure is followed to prevent a fire from occurring.
Im Hinblick auf die einzusetzende Menge an Feuerlöschmittel geht man beispielsweise so vor, daß man das Feuerlöschmittel solange einsetzt, bis das Feuer erloschen ist. Gemäß einer anderen Ausführungsform kann das Keton, z.B. Hexafluoraceton-Trihydrat, oder die Zubereitung damit, auch in Form eines Schaums, beispielsweise auf Wasserbasis, zum Feuerlöschen eingesetzt werden. Das Löschen mit solchen Schäumen wird beispielsweise im US-Patent 4 459 213 beschrieben.With regard to the amount of fire extinguishing agent to be used, one proceeds, for example, by using the fire extinguishing agent until the fire has gone out. According to another embodiment, the ketone, e.g. Hexafluoroacetone trihydrate, or the preparation with it, also in the form of a foam, for example water-based, can be used to extinguish fire. Extinguishing with such foams is described, for example, in U.S. Patent 4,459,213.
Das erfindungsgemäße Verfahren kann zum Löschen von brennenden Materialien wie Papier, Holz, brennbaren Flüssigkeiten, Kunststoffen oder elektrischen Geräten verwendet werden. Es läßt sich auch in Fahrzeugen wie Autos, Schiffen und Flugzeugen einsetzen. Die Feuerverhütung wird analog durchgeführt .The method according to the invention can be used to extinguish burning materials such as paper, wood, flammable liquids, plastics or electrical devices. It can also be used in vehicles such as cars, ships and airplanes. Fire prevention is carried out analogously.
Hydrate von Perfluorketonen und ihre wässrigen Zubereitungen, besonders von Hexafluoraceton-Hydrat, haben den Vorteil, daß eine gute Löschwirkung vorliegt und die Ozonschicht nicht gefährdet wird.Hydrates of perfluoroketones and their aqueous preparations, especially of hexafluoroacetone hydrate, have the advantage that they have a good extinguishing effect and the ozone layer is not endangered.
Ein weiterer Gegenstand der Erfindung ist eine feuerlöschende bzw. feuerverhütende Zusammensetzung, die ein Hydrat oder eine wässrige Zubereitung eines Perfluorketons mit 3 bis 7 C-Atomen, vorzugsweise Hexafluoraceton-Hydrat, CF3C(0)C2F5
oder CF3C (0)n-C3F7 und mindestens ein weiteres bei Normalbedingungen gasförmiges Treibmittel und/oder mindestens ein weiteres Feuerlöschmittel und/oder mindestens einen anwendungstechnisch vorteilhaften Hilfsstoff enthält oder daraus besteht. Der Hilfsstoff kann beispielsweise ein Tensid sein. Der Begriff „Keton-Hydrat" bezeichnet wieder definierte Verbindungen, z.B. das Halbhydrat oder das Trihydrat des Hexafluoracetons . „Wässrige Zubereitung" ist wieder eine Mischung, die 1 bis 99 Gew.-% des Ketons und Rest auf 100 Gew.- % Wasser umfasst, wenn Keton und Wasser die einzigen Bestandteile sind. Sind weitere Bestandteile wie Treibmittel, andere Feuerlöschmittel bzw. Tenside enthalten, gelten die oben angegebenen Gehaltsangaben. Bevorzugte Treibmittel sind Stickstoff, Argon, Kohlendioxid und Trifluormethan. Gewünschten- falls kann man natürlich Gemische einsetzen. Als weitere Feuerlöschmittel verwendet man die weiter oben angegebenen Feuerlöschmittel .The invention further relates to a fire-extinguishing or fire-preventing composition which comprises a hydrate or an aqueous preparation of a perfluoroketone having 3 to 7 C atoms, preferably hexafluoroacetone hydrate, CF 3 C (0) C 2 F 5 or CF 3 C (0) nC 3 F 7 and at least one further blowing agent which is gaseous under normal conditions and / or at least one further fire extinguishing agent and / or at least one auxiliary substance which is advantageous in terms of application technology or consists thereof. The auxiliary can be a surfactant, for example. The term “ketone hydrate” again denotes defined compounds, for example the hemihydrate or the trihydrate of hexafluoroacetone. “Aqueous preparation” is again a mixture which comprises 1 to 99% by weight of the ketone and the remainder to 100% by weight of water if ketone and water are the only ingredients. If other components such as propellants, other fire extinguishing agents or surfactants are contained, the content information given above applies. Preferred blowing agents are nitrogen, argon, carbon dioxide and trifluoromethane. If desired, you can of course use mixtures. The fire extinguishing agents specified above are used as further fire extinguishing agents.
Sofern die Zusammensetzung nur aus Perfluorketon und Wasser besteht, ist das Keton in einer Menge von mindestens 1 Gew.-%, vorzugsweise in einer Menge von mindestens 5 Gew.-%, maximal in einer Menge von 99 Gew.-% in der Zusammensetzung enthalten. Rest auf 100 Gew.-% ist Wasser.If the composition consists only of perfluoroketone and water, the ketone is contained in the composition in an amount of at least 1% by weight, preferably in an amount of at least 5% by weight and at most in an amount of 99% by weight , The remainder to 100% by weight is water.
Sofern die Zusammensetzung auch ein Treibmittel enthält, ist dieses in einer Menge von bis zu 70 Gew.-% in der feuerlöschenden Zusammensetzung enthalten. Sofern ein weiteres Feuerlöschmittel enthalten ist, ist dies in einer Menge von bis zu 70 Gew.-% in der feuerlöschenden Zusammensetzung enthalten. Das Perfluorketon, vorzugsweise Hexafluoraceton (es liegt vorzugsweise als Hexafluoraceton-Trihydrat vor) , oder
CF3C(0)C2F5 oder CF3C (0)n-C3F7 ist in einer Menge von 1 bis 98 Gew.-% in der Zusammensetzung vorhanden.If the composition also contains a blowing agent, this is contained in the fire-extinguishing composition in an amount of up to 70% by weight. If a further fire extinguishing agent is contained, this is contained in the fire extinguishing composition in an amount of up to 70% by weight. The perfluoroketone, preferably hexafluoroacetone (it is preferably in the form of hexafluoroacetone trihydrate), or CF 3 C (0) C 2 F 5 or CF 3 C (0) nC 3 F 7 is present in the composition in an amount of 1 to 98% by weight.
Die Zusammensetzung kann auch zusätzlich zum Hexafluor- aceton-Hydrat eine Base als Hilfsmittel enthalten. Gut geeignet sind z. B. Alkalihydroxide, Erdalkalihydroxide, Alkalioder Erdalkalicarbonate oder deren Zubereitungen mit Wasser wie Lösungen oder Aufschlämmungen. Alkali ist bevorzugt Natrium, Erdalkali, Calcium oder Magnesium.The composition can also contain a base as an auxiliary in addition to the hexafluoroacetone hydrate. Z. B. alkali metal hydroxides, alkaline earth metal hydroxides, alkali or alkaline earth metal carbonates or their preparations with water such as solutions or slurries. Alkali is preferably sodium, alkaline earth, calcium or magnesium.
Die Zusammensetzungen lassen sich durch einfaches Vermischen der Substanzen, wenn notwendig unter Druck oder tiefen Temperaturen herstellen. Dabei kann man ein Perfluorketon- Hydrat mit Treibmittel, anderem Feuerlöschmittel und/oder Hilfsmittel vermischen. Das Perfluorketon-Hydrat kann auch durch Vermischen von Keton und der entsprechenden Menge an Wasser in situ hergestellt werden. Wässrige Zubereitungen des Ketons können durch Verwendung eines Keton-Hydrats und der gewünschten Menge an Wasser oder durch Verwendung des (mehr oder weniger wasserhaltigen oder trockenen) Ketons und der gewünschten Menge Wasser sowie ggf. Zusatz des Treibmittels, anderen Feuerlöschmittels und/oder Hilfsmittels hergestellt werden.
The compositions can be prepared by simply mixing the substances, if necessary under pressure or at low temperatures. A perfluoroketone hydrate can be mixed with a blowing agent, other fire extinguishing agent and / or auxiliary agent. The perfluoroketone hydrate can also be prepared in situ by mixing ketone and the appropriate amount of water. Aqueous preparations of the ketone can be prepared by using a ketone hydrate and the desired amount of water or by using the (more or less water-containing or dry) ketone and the desired amount of water and optionally adding the propellant, other fire extinguishing agents and / or auxiliaries ,
Claims
1. Verfahren zum Löschen eines Feuers oder zum Verhindern des Entstehen eines Feuers, wobei man Hydrate oder wässrige Zubereitungen von Perfluorketonen mit 3 bis 7 C-Atomen, bevorzugt von Hexafluoraceton als Löschmittel, als Mittel zur Feuerverhütung oder als Bestandteil eines Mittels zum Feuerlöschen oder Feuerverhüten verwendet.1. A method of extinguishing a fire or preventing the occurrence of a fire, using hydrates or aqueous preparations of perfluoroketones having 3 to 7 carbon atoms, preferably of hexafluoroacetone as an extinguishing agent, as an agent for fire prevention or as part of an agent for fire extinguishing or fire prevention used.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Hexafluoraceton-Trihydrat , eine wässrige Zubereitung von Hexafluoraceton oder das Hydrat oder eine wässrige Zubereitung von CF3C(0)C2F5 oder CF3C (0) n-C3F7 einsetzt.2. The method according to claim 1, characterized in that hexafluoroacetone trihydrate, an aqueous preparation of hexafluoroacetone or the hydrate or an aqueous preparation of CF 3 C (0) C 2 F 5 or CF 3 C (0) nC 3 F 7 starts.
3. Verfahren nach Anspruch 1 oder 2 , dadurch gekennzeichnet, daß das Hydrat des Perfluorketons oder seine wässrige Zubereitung Löschmittelbestandteil oder Bestandteil eines Mittels zur Feuerverhütung ist und das Löschmittel oder Mittel zur Feuerverhütung mindestens ein Treibmittel und/oder mindestens ein weiteres Feuerlöschmittel mit einem Siedepunkt von bis zu 100 °C enthält.3. The method according to claim 1 or 2, characterized in that the hydrate of the perfluorocetone or its aqueous preparation is an extinguishing agent component or part of an agent for fire prevention and the extinguishing agent or agent for fire prevention at least one propellant and / or at least one other fire extinguishing agent with a boiling point of contains up to 100 ° C.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man als Treibmittel Stickstoff, Argon, Kohlendioxid oder Trifluormethan einsetzt.4. The method according to claim 3, characterized in that the blowing agent used is nitrogen, argon, carbon dioxide or trifluoromethane.
5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man mindestens ein weiteres Feuerlöschmittel aus der Gruppe bestehend aus FluorkohlenstoffVerbindungen, Fluorkohlenwasserstoffen, Chlorfluorkohlenwasserstoffen, Perfluorpo- lyethern oder Hydrofluoroethern einsetzt. 5. The method according to claim 3, characterized in that one uses at least one further fire extinguishing agent from the group consisting of fluorocarbon compounds, fluorocarbons, chlorofluorocarbons, perfluoropolyethers or hydrofluoroethers.
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man zusätzlich eine Base, vorzugsweise eine Alkalilauge oder ein Carbonat, einsetzt.6. The method according to claim 1, characterized in that one additionally uses a base, preferably an alkali metal hydroxide solution or a carbonate.
7. Feuerlöschende oder feuerverhütende Zusammensetzung, enthaltend ein Hydrat eines Perfluorketons mit 3 bis 7 C- Ato en, vorzugsweise ein Hexafluoraceton-Hydrat, oder eine wässrige Zubereitung des Perfluorketons, oder ein Hydrat oder eine wässrige Zusammensetzung von CF3C(0)C2F5 oder CF3C(0)n- C3F7 und ein bei Normalbedingungen gasförmiges Treibmittel und/oder mindestens ein weiteres Feuerlöschmittel.7. Fire-extinguishing or fire-preventive composition, containing a hydrate of a perfluorocetone with 3 to 7 carbon atoms, preferably a hexafluoroacetone hydrate, or an aqueous preparation of the perfluorocetone, or a hydrate or an aqueous composition of CF 3 C (0) C 2 F 5 or CF 3 C (0) n - C 3 F 7 and a blowing agent which is gaseous under normal conditions and / or at least one further fire extinguishing agent.
8. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß sie als Treibmittel Stickstoff, Argon, Kohlendioxid oder Trifluormethan enthält.8. The composition according to claim 1, characterized in that it contains nitrogen, argon, carbon dioxide or trifluoromethane as blowing agent.
9. Zusammensetzung nach Anspruch 8, dadurch gekennzeichnet, daß sie mindestens ein weiteres Feuerlöschmittel ausgewählt aus der Gruppe bestehend aus Fluorkohlenstoffverbindungen, Fluorkohlenwasserstoffen, Fluorchlorkohlenwasserstoffen, Perfluorpolyethern, Hydrofluorpolyethern und Hydrofluorethern enthält.9. The composition according to claim 8, characterized in that it contains at least one further fire extinguishing agent selected from the group consisting of fluorocarbon compounds, fluorocarbons, chlorofluorocarbons, perfluoropolyethers, hydrofluoropolyethers and hydrofluoroethers.
10. Zusammensetzung nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß sie mindestens ein weiteres Feuerlöschmittel ausgewählt aus der Gruppe bestehend aus Trifluormethan, Tetrafluorethan, Pentafluorethan, Pentafluorpropan, Hexaflu- orpropan und Heptafluorpropan enthält.10. The composition according to claim 8 or 9, characterized in that it contains at least one further fire extinguishing agent selected from the group consisting of trifluoromethane, tetrafluoroethane, pentafluoroethane, pentafluoropropane, hexafluoropropane and heptafluoropropane.
11. Zusammensetzung nach Anspruch 7, dadurch gekennzeichnet, daß sie 1 bis 99 Gew.-% eines Perfluorketons mit 3 bis 7 C-Atomen, vorzugsweise Hexafluoraceton-Hydrat, CF3C(0)C2F5 oder CF3C (0)n-C3F7, 0 bis 70 Gew.-% eines Treib- mittels, 0 bis 70 Gew.-% eines weiteren Feuerlöschmittels, 1 bis 70 Gew.-% Wasser und 0 bis 10 Gew.-% Hilfsstoffe wie Tenside enthält oder daraus besteht, wobei die Bestandteile sich zu 100 Gew.-% addieren.11. The composition according to claim 7, characterized in that it contains 1 to 99 wt .-% of a perfluorocetone with 3 to 7 carbon atoms, preferably hexafluoroacetone hydrate, CF 3 C (0) C 2 F 5 or CF 3 C (0 ) nC 3 F 7, 0 to 70 wt .-% of a propellant contains, or consists of, 0 to 70% by weight of a further fire extinguishing agent, 1 to 70% by weight of water and 0 to 10% by weight of auxiliaries such as surfactants, the components adding up to 100% by weight.
12. Zusammensetzung nach Anspruch 7 , dadurch gekennzeichnet, daß sie eine Base enthält.12. The composition according to claim 7, characterized in that it contains a base.
13. Zusammensetzung nach Anspruch 12 , dadurch gekennzeichnet, daß sie NaOH als Base enthält. 13. The composition according to claim 12, characterized in that it contains NaOH as the base.
Applications Claiming Priority (3)
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DE2002136087 DE10236087A1 (en) | 2002-08-07 | 2002-08-07 | Extinguishing or preventing fires involves use of hydrates or aqueous compositions of 3-7C perfluoroketones, especially hexafluoroacetone |
DE10236087 | 2002-08-07 | ||
PCT/EP2003/008288 WO2004014490A1 (en) | 2002-08-07 | 2003-07-28 | Fire extinction and fire prevention method |
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EP1567231A1 true EP1567231A1 (en) | 2005-08-31 |
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EP03784087A Withdrawn EP1567231A1 (en) | 2002-08-07 | 2003-07-28 | Fire extinction and fire prevention method |
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AU (1) | AU2003257756A1 (en) |
DE (1) | DE10236087A1 (en) |
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DE102004040149A1 (en) * | 2004-08-19 | 2006-05-11 | Boris Schubert | Method and container with a liquid medium for cooling |
US7189106B2 (en) | 2005-05-17 | 2007-03-13 | Young Eric D | Electric adapter organizer |
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US4459213A (en) * | 1982-12-30 | 1984-07-10 | Secom Co., Ltd. | Fire-extinguisher composition |
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JP2893038B1 (en) * | 1998-03-31 | 1999-05-17 | 工業技術院長 | Fire extinguisher |
EP1169376B1 (en) * | 1998-10-26 | 2004-09-15 | 3M Innovative Properties Company | Process for preparation of polymeric foam using fluorinated ketones as blowing agents |
DE60014443T3 (en) * | 1999-07-20 | 2016-09-01 | 3M Innovative Properties Co. | USE OF FLUORINATED KETONES IN FIRE EXTINGUISHING COMPOSITIONS |
-
2002
- 2002-08-07 DE DE2002136087 patent/DE10236087A1/en not_active Withdrawn
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2003
- 2003-07-28 EP EP03784087A patent/EP1567231A1/en not_active Withdrawn
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US4459213A (en) * | 1982-12-30 | 1984-07-10 | Secom Co., Ltd. | Fire-extinguisher composition |
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