EP0089584B1 - Cable covering - Google Patents
Cable covering Download PDFInfo
- Publication number
- EP0089584B1 EP0089584B1 EP83102444A EP83102444A EP0089584B1 EP 0089584 B1 EP0089584 B1 EP 0089584B1 EP 83102444 A EP83102444 A EP 83102444A EP 83102444 A EP83102444 A EP 83102444A EP 0089584 B1 EP0089584 B1 EP 0089584B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fire
- cables
- cable
- cable covering
- event
- 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.)
- Expired
Links
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 5
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 7
- 239000003063 flame retardant Substances 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
Definitions
- Cables for example electrical cables, are generally coated with a polymer.
- a polymer e.g. Thermoplastics, cross-linked thermoplastics or elastomers are used.
- a disadvantage of these cable jackets is that the polymers used tend to burn at high temperatures or when exposed to flame. As a result, the source of the fire can spread in a short time.
- polymers can be made flame-retardant by adding fire-retardant additives.
- fire retardant additives e.g. Combinations of halogenated hydrocarbons and antimony trioxide can be used.
- Another possibility is to use polymers with a high halogen content, e.g. PVC to use.
- these cables generate, among other things, harmful and highly corrosive gases. This can lead to temporary signs of poisoning and corrosion damage to materials near the fire site. As a rule, the damage caused by corrosion is much higher than the fire damage. Therefore, halogen-free, fire-retardant additives are increasingly being used to manufacture cable sheaths.
- aluminum hydroxide hydrate e.g. martinale
- calcium aluminate are used.
- Cable sheathing consisting of polymer mixtures which contain small amounts of (partially) saponified ethylene-vinyl acetate copolymers are known from DD-A-140 095.
- cables are sheathed using the extrusion process.
- Polymers with a very high molecular weight or very low melt index are used for the extrusion. This creates a pressure build-up in front of the nozzle and achieves a uniform wall thickness during extrusion.
- the invention relates to cable sheathing made from (partially) saponified ethylene-vinyl acetate copolymers.
- the ethylene-vinyl acetate copolymers which can be used according to the invention have a content of 10 to 35% by weight, preferably 15 to 30% by weight, of vinyl alcohol.
- copolymers which can be used according to the invention from 60% to 100% of the acetyl groups can be saponified to give the alcohol.
- the copolymers have a melt index according to DIN 53 735 (190 ° C / 21.18 N) of 90 to 1.0 g / 10 minutes, preferably 50 to 5 g / 10 minutes.
- cables are sheathed cables.
- Glass fiber cables and electrical line cables, particularly preferably electrical line cables, are preferably sheathed according to the invention.
- the cables can be used in the home, in the industrial sector and in the field of transport.
- Copolymers based on ethylene-vinyl alcohol are characterized by a very high ignition temperature (approx. 470 ° C). The softening range is 108-110 ° C. In the event of a fire, the surface temperature of the casing increases. At approx. 200 ° C the viscosity of the melt is reduced. As the temperature continues to rise, the material begins to drip. The polymer begins to burn at a temperature of over 400 ° C.
- the copolymer is used as cable sheathing, in the event of fire, a considerable proportion of the heat of combustion is dissipated as melting energy. As a result, the flame extinguishes itself after a very short time, so that the cable is self-extinguishing and therefore flame-retardant.
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Insulated Conductors (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Kabel, beispielsweise Elektrokabel, werden im allgemeinen mit einem Polymeren ummantelt. Dazu werden z.B. Thermoplaste, vernetzte Thermoplaste oder Elastomere verwendet.Cables, for example electrical cables, are generally coated with a polymer. For this, e.g. Thermoplastics, cross-linked thermoplastics or elastomers are used.
Ein Nachteil dieser Kabelummantelungen ist darin zu sehen, dass die verwendeten Polymeren bei hohen Temperaturen oder Flammeinwirkung zum Brennen neigen. Dadurch kann sich der Brandherd in kurzer Zeit ausbreiten.A disadvantage of these cable jackets is that the polymers used tend to burn at high temperatures or when exposed to flame. As a result, the source of the fire can spread in a short time.
Es ist bekannt, dass Polymere durch die Zugabe von feuerhemmenden Zusatzstoffen flammwidrig eingestellt werden können. Als feuerhemmende Zusatzstoffe können z.B. Kombinationen aus halogenierten Kohlenwasserstoffen und Antimontrioxid verwendet werden. Eine andere Möglichkeit besteht darin, Polymere mit hohem Halogengehalt, z.B. PVC, zu verwenden. Im Brandfall entstehen jedoch bei diesen Kabeln unter anderem gesundheitsschädliche und stark korrosive Gase. Diese kann zu vorübergehenden Vergiftungserscheinungen und Korrosionsschäden an Materialien in der Nähe der Brandstelle führen. In der Regel sind die Schäden durch Korrosion viel höher als die Feuerschäden. Daher werden im zunehmendem Masse halogenfreie, feuerhemmende Zusatzstoffe zur Herstellung von Kabelummantelungen verwendet.It is known that polymers can be made flame-retardant by adding fire-retardant additives. As fire retardant additives e.g. Combinations of halogenated hydrocarbons and antimony trioxide can be used. Another possibility is to use polymers with a high halogen content, e.g. PVC to use. In the event of fire, however, these cables generate, among other things, harmful and highly corrosive gases. This can lead to temporary signs of poisoning and corrosion damage to materials near the fire site. As a rule, the damage caused by corrosion is much higher than the fire damage. Therefore, halogen-free, fire-retardant additives are increasingly being used to manufacture cable sheaths.
Beispielsweise werden Aluminiumhydroxid-Hydrat (z.B. Martinale ) oder Calciumaluminat dazu verwendet.For example, aluminum hydroxide hydrate (e.g. martinale) or calcium aluminate are used.
Jedoch wird eine merkliche flammhemmende Wirkung erst bei einer Konzentration über 25 Gew.-% erzielt. Dadurch werden bei manchen Polymeren die mechanischen Eigenschaften stark beeinträchtigt. Ausserdem können im Brandfall Nebel entstehen, so dass der Brandherd nicht mehr rechtzeitig erkannt werden kann. So kann, beispielsweise bei Auftreten eines Kabelbrandes, in Schächten wie U-Bahnschächten, durch Nebelbildung das Auffinden von Fluchtwegen erschwert werden. Bis heute wurde kein Material zur Kabelummantelung gefunden, das halogenfrei ist und im Brandfall keine toxischen und korrosiven Gase abspaltet und darüber hinaus keine Rauchgase und Nebel bildet.However, a noticeable flame retardant effect is only achieved at a concentration above 25% by weight. As a result, the mechanical properties of some polymers are severely impaired. In addition, fog can form in the event of a fire so that the source of the fire can no longer be recognized in time. For example, if a cable fire occurs in shafts such as subway shafts, finding escape routes can be difficult due to the formation of fog. To date, no cable sheathing material has been found that is halogen-free and does not split off toxic and corrosive gases in the event of a fire and also does not form smoke and mist.
Kabelumrnantelungen, die aus Polymermischungen bestehen, die geringe Anteile an (teil) verseiften Ethylen-Vinylacetat-Copolymeren beinhalten, sind aus der DD-A-140 095 bekannt.Cable sheathing consisting of polymer mixtures which contain small amounts of (partially) saponified ethylene-vinyl acetate copolymers are known from DD-A-140 095.
Bekannt ist auch aus der EP-A-41 192 die Herstellung von Kabelummantelungen aus teilverseiften Ethylen-Vinylacetat-Copolymeren, die mit Polyisocyanaten vernetzt sind.It is also known from EP-A-41 192 to manufacture cable sheaths from partially saponified ethylene-vinyl acetate copolymers which are crosslinked with polyisocyanates.
In der Regel werden Kabel im Extrusionsverfahren ummantelt. Für die Extrusion werden Polymere mit sehr hohem Molekulargewicht bzw. sehr niedrigem Schmelzindex verwendet. Dadurch wird ein Druckaufbau vor der Düse erreicht und eine gleichmässige Wanddicke bei der Extrusion erzielt.As a rule, cables are sheathed using the extrusion process. Polymers with a very high molecular weight or very low melt index are used for the extrusion. This creates a pressure build-up in front of the nozzle and achieves a uniform wall thickness during extrusion.
Überraschenderweise wurde gefunden, dass (teil)-verseifte Ethylen-Vinylacetat-Copolymerisate mit einem Vinylalkoholgehalt zwischen 10 und 35 Gew.-% im Brandfall praktisch keine toxischen und korrosiven Gase abspalten. Ausserdem entstehen beim Brand sehr wenig Russ und Schwebeteile enthaltendes Rauchgas, d.h. die Rauchgasdichte ist sehr gering. Ausserdem verlöschen derartig ummantelte Kabel im Brandfall je nach Molekulargewicht des verwendeten Copolymerisats nach 0,2 bis 0,6 Minuten von selbst.Surprisingly, it has been found that (partially) saponified ethylene-vinyl acetate copolymers with a vinyl alcohol content of between 10 and 35% by weight in the event of fire release practically no toxic and corrosive gases. In addition, during the fire very little soot and floating parts contain flue gas, i.e. the smoke density is very low. In addition, cables coated in this way extinguish themselves in the event of a fire, depending on the molecular weight of the copolymer used, after 0.2 to 0.6 minutes.
Die Erfindung betrifft Kabelummantelungen aus (teil)-verseiften Ethylen-Vinylacetat-Copolymeren.The invention relates to cable sheathing made from (partially) saponified ethylene-vinyl acetate copolymers.
Die erfindungsgemäss verwendbaren Ethylen-Vinylacetat-Copolymeren haben einen Gehalt von 10 bis 35 Gew.-%, vorzugsweise 15 bis 30 Gew.-% Vinylalkohol.The ethylene-vinyl acetate copolymers which can be used according to the invention have a content of 10 to 35% by weight, preferably 15 to 30% by weight, of vinyl alcohol.
Bei den erfindungsgemäss einsetzbaren Copolymeren können von 60% bis zu 100% der Acetylgruppen zum Alkohol verseift sein.In the copolymers which can be used according to the invention, from 60% to 100% of the acetyl groups can be saponified to give the alcohol.
Die Copolymerisate haben einen Schmelzindex nach DIN 53 735 (190°C/21,18 N) von 90 bis 1,0g/10 Minuten, bevorzugt von 50 bis 5 g/10 Minuten.The copolymers have a melt index according to DIN 53 735 (190 ° C / 21.18 N) of 90 to 1.0 g / 10 minutes, preferably 50 to 5 g / 10 minutes.
Als ummantelnde Kabel werden Kabel im weitesten Sinne verstanden. Vorzugsweise werden Glasfaserkabel und elektrische Leitungskabel, besonders bevorzugt elektrische Leitungskabel erfindungsgemäss ummantelt.In the broadest sense, cables are sheathed cables. Glass fiber cables and electrical line cables, particularly preferably electrical line cables, are preferably sheathed according to the invention.
Die Kabel können im Haushalt, im industriellen Bereich und im Bereich des Transportwesens eingesetzt werden.The cables can be used in the home, in the industrial sector and in the field of transport.
Weiter wurde gefunden, dass durch eine Erniedrigung des Molekulargewichts bzw. durch Erhöhung des Schmelzindex des erfindungsgemäss zu verwendenden Copolymerisats der Kabelummantelung das Verhalten im Brandfall merklich verbessert -'.'ird, ohne dass die Verarbeitbarkeit des Produkte nd die mechanischen, chemischen, elektrische. Eigenschaften beeinträchtigt werden. Ein Schmeizindex nach DIN 53 735 bei 190°C und 21,18 N zwischen 90 und 1,0 g/10 Minuten erwies sich geeignet.It was further found that to be used copolymer of the cable jacket, the fire performance significantly improved by lowering the molecular weight or by increasing the melt index of the present invention - '. '' without the processability of the product and the mechanical, chemical, electrical. Properties are affected. A melt index according to DIN 53 735 at 190 ° C and 21.18 N between 90 and 1.0 g / 10 minutes proved to be suitable.
Obwohl solche Produkte als nicht geeignet für Extrusionsverfahren gelten, konnten sie ohne Schwierigkeiten verarbeitet werden. Um das Niveau der mechanischen Eigenschaften zu erhöhen, wurde gefunden, dass durch den Zusatz von Nukleierungsmittel, wie z.B. Talkum, die mechanischen Eigenschaften verbessert werden können. Copolymerisate auf Basis Ethylen-Vinylalkohol zeichnen sich durch eine sehr hohe Entzündungstemperatur (ca. 470°C) aus. Der Erweichungsbereich liegt bei 108-110°C. Im Brandfall steigt die Oberflächentemperatur der Ummantelung an. Bei ca. 200°C wird die Viskosität der Schmelze erniedrigt. Bei weiter steigender Temperatur fängt das Material zu tropfen an. Bei einer Temperatur von über 400°C fängt das Polymere an zu verbrennen. Im Falle der Verwendung des Copolymeren als Kabelummantelung wird im Brandfalle durch Abtropfen ein beträchtlicher Anteil der Verbrennungswärme als Schmelzenergie abgeführt. Dadurch erlöscht die Flamme nach sehr kurzer Zeit von selbst, so dass das Kabel selbstverlöschend und dadurch flammwidrig ist.Although such products are not considered suitable for extrusion processes, they could be processed without difficulty. In order to increase the level of mechanical properties, it has been found that by adding nucleating agents such as e.g. Talc, the mechanical properties can be improved. Copolymers based on ethylene-vinyl alcohol are characterized by a very high ignition temperature (approx. 470 ° C). The softening range is 108-110 ° C. In the event of a fire, the surface temperature of the casing increases. At approx. 200 ° C the viscosity of the melt is reduced. As the temperature continues to rise, the material begins to drip. The polymer begins to burn at a temperature of over 400 ° C. If the copolymer is used as cable sheathing, in the event of fire, a considerable proportion of the heat of combustion is dissipated as melting energy. As a result, the flame extinguishes itself after a very short time, so that the cable is self-extinguishing and therefore flame-retardant.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3210726 | 1982-03-24 | ||
| DE19823210726 DE3210726A1 (en) | 1982-03-24 | 1982-03-24 | CABLE SHEATHING |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0089584A1 EP0089584A1 (en) | 1983-09-28 |
| EP0089584B1 true EP0089584B1 (en) | 1986-02-19 |
Family
ID=6159117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83102444A Expired EP0089584B1 (en) | 1982-03-24 | 1983-03-12 | Cable covering |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0089584B1 (en) |
| JP (1) | JPS58175212A (en) |
| DE (2) | DE3210726A1 (en) |
| ES (1) | ES520886A0 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5727624B2 (en) * | 1972-03-10 | 1982-06-11 | ||
| CA1115044A (en) * | 1977-05-26 | 1981-12-29 | Michael J. Keogh | Polyethylene composition containing talc filler for electrical applications |
| WO1979000683A1 (en) * | 1978-03-02 | 1979-09-20 | Aeg Telefunken Kabelwerke | Non-inflammable polymer mixture free from halogen and use thereof |
| DD140095B1 (en) * | 1978-08-24 | 1980-10-29 | Heinz Hofmann | POLYETHYLENE FORMULAS FOR ISOLATION METALLIC HEAD |
| JPS5922411Y2 (en) * | 1979-08-29 | 1984-07-04 | 東芝テック株式会社 | roaster |
| DE3021044A1 (en) * | 1980-06-03 | 1981-12-24 | Siemens AG, 1000 Berlin und 8000 München | METHOD FOR THE PRODUCTION OF NETWORKED CABLE AND CABLE INSULATIONS AND FABRICS |
| JPS6140021Y2 (en) * | 1980-07-24 | 1986-11-15 |
-
1982
- 1982-03-24 DE DE19823210726 patent/DE3210726A1/en not_active Withdrawn
-
1983
- 1983-03-12 EP EP83102444A patent/EP0089584B1/en not_active Expired
- 1983-03-12 DE DE8383102444T patent/DE3362144D1/en not_active Expired
- 1983-03-18 JP JP58044549A patent/JPS58175212A/en active Granted
- 1983-03-23 ES ES520886A patent/ES520886A0/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3362144D1 (en) | 1986-03-27 |
| JPS58175212A (en) | 1983-10-14 |
| JPH0317167B2 (en) | 1991-03-07 |
| ES8403659A1 (en) | 1984-03-16 |
| EP0089584A1 (en) | 1983-09-28 |
| DE3210726A1 (en) | 1983-10-06 |
| ES520886A0 (en) | 1984-03-16 |
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