DE102005060232A1 - Wrap tape made of a TPU film - Google Patents

Abstract

Halogen-free, flame-retardant wrapping tape with a film made of thermoplastic polyurethane, characterized in that a flame retardant based on phosphorus is chemically incorporated.

Description

The The present invention preferably relates to a halogen-free flame retardant colored wrapping tape, more preferably a pressure-sensitive adhesive coating and that for example for wrapping ventilation ducts in air conditioners, wires or cables is used and in particular for wiring harnesses in vehicles or field coils for kinescopes suitable is. The wrapping tape serves for bundling, isolating, marking or shooter.

Cable wrapping tapes and Tapes usually exist made of plasticized PVC film with a one-sided pressure-sensitive adhesive coating. It is increasingly the Desire the disadvantages of these products such as the evaporation of plasticizers and eliminate the high halogen content.

The Softeners of conventional insulating tapes and cable wrapping tapes gradually which leads to a health burden, in particular, this is common used DOP questionably. Furthermore, the vapors beat in Vehicles on the windows down, what the view (and thus significantly the driving safety) and deteriorated by the professional as Fogging (DIN 75201) is called. With even greater evaporation by higher temperatures, For example, in the engine compartment of vehicles or insulating tape in electrical appliances, brittle the winding tape by the resulting plasticizer loss and the Decomposition of the PVC polymer.

In front the background of the discussion about incineration of plastic waste, for For example, shredder waste from vehicle recycling is the trend for the reduction of the halogen content and thus the dioxin formation. Therefore, the wall thicknesses at the cable insulation and the thicknesses used for wrapping bands the PVC film is reduced. The usual Thickness of PVC films for wrapping tapes is 85 to 150 μm. Below 85 μm Significant problems occur in the calendering process, so that such Products with reduced PVC content are hardly available.

The usual wrapping tapes contain stabilizers based on toxic heavy metals like lead, Cadmium or barium.

State of development for the bandaging of cable sets are wrapping tapes with and without adhesive coating, which consist of a PVC carrier material which is flexibly adjusted by incorporation of considerable amounts (30 to 40 wt .-%) of plasticizer. The carrier material is usually coated on one side with a self-adhesive composition based on SBR rubber. In JP 10 001 583 A1 . JP 05 250 947 A1 . JP 2000 198 895 A1 and JP 2000 200 515 A1 typical soft PVC adhesive tapes are described. In order to achieve a higher flame resistance of the soft PVC materials is usually, such as in JP 10 001 583 A1 described using the highly toxic compound antimony oxide.

It there are efforts instead of using soft PVC film fabric or nonwovens. The result However, the resulting products are rarely used in practice, because they are relatively expensive and in handling (for example hand tearability, elastic recovery) and under conditions of use (for example resistance to moisture or moisture) Operating fluids) strongly different from the usual products, whereby - as in the Following executed - the thickness a special meaning. Such thick webs make the harnesses even thicker and inflexible than classic PVC tapes, though This has a positive effect on the sound insulation, but only in some areas of wiring harnesses is beneficial. However, nonwovens are not very elastic and practical no resilience. This is significant because thin branches of harnesses so tightly wrapped that they do not fall asleep during installation and slightly before the Clip on and position to attach the connectors. Another disadvantage of textile adhesive tapes is the low breakdown voltage of about 1 kV, because only the adhesive layer isolated.

On the other hand, foil tapes are over 5 kV, they are good voltage resistant. Textile wrapping tapes are either not flameproof or contain halogen compounds (usually bromine compounds) as flame retardants. Examples are from the DE 200 22 272 U1 , of the EP 1 123 958 A1 , WO 99/61541 A1 and the US 4,992,331 A1 refer to.

Thermo-polyester wrap tapes and cable insulation are being used tentatively to make wiring harnesses. These have significant deficiencies in terms of their flame resistance, flexibility, processability, aging resistance or compatibility with the cable materials. The most serious disadvantage of polyester, however, is the considerable susceptibility to hydrolysis, so that an safety reasons in automobiles is no longer an option. Polyester-based wrapping tapes are either non-flame resistant or contain halogen compounds as flame retardants. Examples are in the DE 100 02 180 A1 , of the JP 10 149 725 A1 , of the JP 09 208 906 A1 , of the JP 05 017 727 A1 and the JP 07 150 126 A1 to find.

In The literature also describes wrapping tapes made of polyolefins. However, these are easily flammable or contain halogenated Flame retardants. About that In addition, the materials made from ethylene copolymers have too low a softening point (they usually melt already in the attempt, a heat aging resistance to consider), and in the case of the use of usual Polypropylene polymers, the material is usually too inflexible. metal hydroxides are sometimes used, the amounts used from 40 to 100 but are for adequate flame retardancy too low, that is, they are not only not self-extinguishing, but even have a relatively high fire speed (for Example over 100 mm / min according to MVSS 302). Foils containing more than 100 phr of flame retardant are technically difficult to produce. In addition, such films a low tear resistance and are very rigid, that is, the essential processing properties of a typical PVC wrap band is missed.

In WO 00/71634 A1 describes a wound adhesive tape whose Film consists of an ethylene copolymer as a base material. The support film contains the halogen-containing flame retardant decabromodiphenyl oxide. The foil softens below a temperature of 95 ° C, the normal use temperature but often lies above 100 ° C or even over for a short time 130 ° C, which is not uncommon when used in the engine compartment.

In WO 97/05206 A1 describes a halogen-free wound adhesive tape, its carrier film from a polymer blend of low density polyethylene and a Ethylene / vinyl acetate or ethylene / acrylate copolymer. When Flame retardants are 40 to 90 phr aluminum hydroxide or ammonium polyphosphate used. A significant disadvantage of the carrier film is again the low Softening temperature. To counteract this, the use becomes described by silane crosslinking. But this crosslinking method leads only too unevenly networked Material, so that in practice no stable production process or uniform quality of the product can be realized.

Analogous problems of lack of heat resistance occur in WO 99/35202 A1 and US 5,498,476 A1 described electrical adhesive tapes on. The carrier film material described is a blend of EPDM and EVA in combination with ethylenediamine phosphate as flame retardant. This has a high sensitivity to hydrolysis, as does ammonium polyphosphate. In combination with EVA embrittlement on aging also occurs. The application on conventional cables made of polyolefin and aluminum or magnesium hydroxide leads to poor compatibility. In addition, the fire behavior of such wiring harnesses is poor because these metal hydroxides are antagonistic with phosphorus compounds as set forth below. The insulating tapes described are too thick and too stiff for wiring harnesses.

Tries, the dilemma of too low softening temperature, flexibility, flame resistance and to release halogen-free, describe following writings.

The EP 0 953 599 A1 claims a polymer blend of LLDPE and EVA for cable insulation applications and as sheet material. As a flame retardant, a combination of magnesium hydroxide with a special surface and red phosphorus described, the softening at a relatively low temperature is, however, accepted. The amount of magnesium hydroxide is 63 phr. Because of the despite high filler content unsatisfactory fire properties red phosphorus is used.

A very similar combination will be in EP 1 097 976 A1 described. Here, however, a PP-poly is used to improve the heat resistance in place of the LLDPEs, which has a higher softening temperature. The disadvantage, however, is the resulting low flexibility. For blending with EVA or EEA it is said that the film has sufficient flexibility. However, it is known to the person skilled in the art from the literature that these polymers are blended with polypropylene to improve the flame retardancy. The products described have a film thickness of 0.2 mm, but this thickness excludes flexibility in filled polyolefin since it depends on the 3rd power of the thickness. The process of extrusion described is hardly feasible on a production line at the extremely low melt indices of the polyolefins used, as is known to the person skilled in the art, and certainly not for a practical thin film. The extremely low melt index limits the use to 50 to 100 phr of magnesium hydroxide.

Both Build solutions to the well-known synergistic flame retardancy of red phosphorus with magnesium hydroxide. The use of elemental phosphorus harbors However, significant disadvantages and dangers. When processing evil-smelling, pyrophoric and released highly toxic phosphine. Also the finished winding tape smells hotter and moist application environment garlic-like. Another disadvantage results from the formation of very dense, white smoke in case of fire. About that In addition, only brown to black products can be produced, wrapping tapes however, used for color coding in a wide range of colors.

The JP 2001 049 208 A1 describes an oil- and heat-resistant film for an adhesive tape in which both layers consist of a mixture of EVA or EEA, peroxide crosslinker, silane crosslinker, silanol condensation catalyst and flame retardant (100 phr magnesium hydroxide). This film solves neither the problem of poor flexibility of a filled polypropylene film, nor the high demands on the aging resistance.

The WO 03/070848 A1 describes a film of reactive polypropylene and 40 phr of magnesium hydroxide. This addition is enough to one significant improvement in fire performance is not enough.

The mentioned prior art because of the disadvantages mentioned, especially lack of flame resistance, flexibility, tear resistance and / or heat resistance, no transparencies that also meet other requirements such as hand tearability, compatibility with polyolefin cable insulation or sufficient unwind force. Furthermore remain the processability in Folienherstellprozessen, high Fogging value and the breakdown voltage strength is questionable. The main issue the well-known inventions based on flame-retardant carrier films made of polyolefin and metal hydroxide is the incompatibility of the mechanical Requirements with those of the flame resistance. With less than 60 Wt .-% flame retardant (metal hydroxide and optionally further Flame retardant additives), no self-extinguishing can be achieved and already from 40 wt .-% flame retardants are flexibility and tear resistance at barely acceptable low levels. The combination polyolefin and metal hydroxide leads due to the mechanism of action (cooling by endothermic decomposition of the metal hydroxide and generation of water vapor) to a Slowing down the combustion process but not to self-extinguishing. This system also has the disadvantage that it is in the Elongation in the winding process, sometimes even when unrolling the Adhesive tape, whitening comes. These ribbons are usually black and the finished wrap then has one black-gray piebald surface on. At high filler content The tensile strength can be so low that the tape when unrolling tears.

Adhesive tapes off Polyurethane (PU) are known, some with flame retardant equipment. It deals mostly adhesive-sensitized PU foams as well explained below Adhesive tapes on Film-based.

JP 2001 020 178 A1 describes a double-sided tape for electromagnetic shielding of a polyester fabric and a halogen-containing PU layer.

The JP 2001 288 430 A1 describes a flame-retardant adhesive tape whose support has been prepared from a polyurethane resin solution and dicyandiamide. The use of a solution cast film is not only expensive, but also does not meet the ecological goals of the tape of the invention from a film which is to be prepared solvent-free by thermoplastic processing. Attempts to incorporate dicyandiamide in thermoplastic polyurethane (TPU) have failed due to decomposition of the TPU during compounding.

The JP 2003 013 026 A1 and the JP 2004 115 608 A1 describe (cover) adhesive tapes for handling radioactive substances whose carrier is also prepared from solution. It consists of a polyurethane resin solution and hydrazodicarbonamide. Hydrazodicarbonamide acts as a foaming agent upon thermoplastic processing by decomposition and would be unsuitable for high melting point hard block TPU (ie, high processing temperature).

The JP 62 069 640 A1 describes a transparent adhesive tape for the production of wafer chips. The PU carrier, which may optionally contain a flame retardant such as 4,4'-dichlorohexylmethane diisocyanate, is prepared from solution.

The DE 203 06 801 U1 describes an adhesive tape made of a polyurethane film without specifying the polyurethane composition. But polyurethane tapes have been around for many years Practice known. In this utility model is described that the film may also contain additives, called UV and ozone stabilizers, fillers or flame retardants. For the latter, ammonium polyphosphate, antimony trioxide and aluminum trihydrate (ATH) are listed by name, but not substantiated by way of examples. Experiments have shown that ammonium polyphosphate (APP) degrades polyurethanes during thermoplastic processing, which is not surprising to the person skilled in the art, since APP is hygroscopic and therefore can cause hydrolytic degradation. In addition, due to the acidity of the APP, the hydrolysis is additionally catalyzed. APP, as a strong ionic salt, also causes poor electrical properties, as is known from use in other materials, for example wire insulation compounds. However, the winding tape according to the invention should also have good insulating properties. As is further known to those skilled in the art, antimony trioxide only works in combination with halogens and therefore makes no sense in TPU alone. It is also known to the person skilled in the art that ATH is suitable as flame retardant only for PE and EVA, since it has a low decomposition temperature, but not for polypropylene and therefore certainly not for TPU with even higher processing temperature.

The EP 1 108 768 A1 describes an exclusively colorless adhesive tape with TPU carrier for the gluing of joints in aircraft. However, the adhesive tape according to the invention is intended for winding applications, in particular wire bundles in vehicles. In practice, such winding tapes are black, colored less often and virtually never colorless. The adhesive tape claimed in the specification is additionally limited to a transparent polyurethane pressure-sensitive adhesive, but the winding tape according to the invention must have a penetrating unwinding force or adhesive force on the back in order to be applied in a slightly stretched state to the object to be wrapped. For this purpose, however, essentially adhesives of polyacrylate, natural or synthetic rubber are suitable. The claimed tape must have a thickness of at least 9 mils, that is, the film has a minimum thickness of 8 mils (0.2 mm) to meet the Boeing BSS 7230 F2 standard. The claimed in the publication adhesive tape also contains bromine-containing flame retardants, but the invention is halogen-free.

The JP 2005 264 112 A describes an adhesive tape with a carrier consisting of copolyamide as the main component and secondary components. The latter are polyurethane and nitrogen compounds. The document teaches that the addition of polyurethane improves the flexibility of a pure polyamide film, but greatly reduces the scratch resistance in larger quantities, therefore, the proportion of polyamide should be 40 to 90 parts. As flame retardants hydrazodicarbonamide, mono-, di-, tricyanoethyl cyanurate, melamine cyanurate and dicyandiamide are mentioned. Preference is given to a combination of hydrazodicarbonamide and melamine cyanurate. The latter has proven itself as a flame retardant for polyamides (see, for example JP 11 349 809 A1 Hydrazodicarbonamide, on the other hand, is unsuitable for thermoplastic processing, for the reasons stated above. However, the document describes a processing temperature of only 150 to 160 ° C, so that processing for compounds with low softening temperature appears realistic. The reason for this is the low melting temperatures of the selected raw materials, for the polyurethane 60 to 120 ° C and for the polyamide 100 to 180 ° C mentioned in the examples, a polyamide with 133 ° C softening point is used. However, the film for the winding tape according to the invention should have the highest possible temperature resistance, ie a short-time heat resistance at 170 ° C and a heat resistance at 140 ° C, therefore, a TPU with significantly higher softening point is required than the mentioned in the document TPUs for modifying the polyamide film. Also due to the desired strength and Moduli TPU raw materials should be used with a relatively high melting Hartblockanteil for the winding tape according to the invention, resulting in processing temperatures of 200 ° C and more. It is mentioned in relation to the polyamide film mentioned in the specification that it can no longer be processed from 180 ° C. The film has a thickness of 0.2 mm. The adhesive tape described is phosphorus-free.

The Foil for the winding tape according to the invention would be with the preferred combination of hydrazodicarbonamide mentioned in the document and melamine cyanurate because of decomposition at high temperatures, the for the Processing of TPU with the high-melting hard blocks respectively large Shore hardness required is not producible.

Furthermore, adhesive tapes have been known with supports of crosslinked non-thermoplastic polyurethane. The US 5,807,637 A describes an adhesive tape with a pressure-sensitive adhesive and a sealing layer, the underlying film contains as a filler calcium carbonate and is therefore not flame-resistant. The US 6,129,983 A describes an analogous product but with two pressure sensitive adhesive layers.

The EP 1 101 807 A1 mentions a masking tape having a cross-linked polyurethane and polyester composite backing. The PU layer may be modified with fillers, flame retardants are not mentioned.

The mentioned tape carrier are made by in-line dosing and mixing of polyol, isocyanate and Catalyst on a subcarrier produced. The advantage lies in low raw material costs in comparison to TPU, however, the process is very difficult in practice too realize. Because the carriers are crosslinked, a thermoplastic recycling is not possible. Of the essential disadvantage of the invention mentioned in the publications is however, the lack of aptitude for Wrapping tapes, as they have neither flame resistance nor sufficient tensile strength, which in the case of TPU results from physical networking via the hard blocks results.

The EP 1 469 052 A1 and the EP 1 469 024 A1 describe adhesive tapes with cross-linked polyurethanes as pressure-sensitive adhesives on any carriers, but not TPU films.

The US 5,858,495 A1 describes a very thick luminescent adhesive tape, the support of which is prepared by polymerization of a mixture of a polyester or polyurethane acrylate and a luminescent pigment. This material is not a TPU from the chemical structure but a very hard urethane group-containing hard polymer.

The The object of the invention is to find a solution for a winding tape, which the Advantages of halogen-free, flame retardant, heat resistance, abrasion resistance, and mechanical properties such as tensile strength and flexibility of PVC wrapping tapes the halogen-free of textile non-flame-resistant winding tapes connects and above a superior one Heat aging resistance having a large-scale Producibility of the film should be ensured and a high Breakdown voltage strength necessary in some applications is. Due to the absence of heavy metal stabilizers and phthalate plasticizers should the wrapping tapes hygienic and ecological be beneficial. The complete or largely dispensing with plasticizers, in particular DOP, is desired to achieve high fogging values and the consequences of plasticizer migration into the adhesive, such as telescoping or edge tackiness.

task The invention further, such winding tapes for disposal which is a particularly safe and fast wrapping, in particular of wires and cables for marking, shooters, Insulating, sealing or bundling enable, the disadvantages of the prior art do not or at least not occur in the previous extent.

It then there is the task thermoplastically produced films to find with additive combinations that not only the heat resistance of PVC reach, but even surpass.

Is solved this task by a winding tape, as laid down in the main claim is. Subject of the dependent claims are advantageous developments of the subject invention as well Uses of the winding tape according to the invention.

Accordingly, the invention a halogen-free flame-retardant winding tape with a Foil made of thermoplastic polyurethane, in which a flame retardant is phosphorus-based chemically incorporated.

In A first particularly preferred embodiment is at least on one side of the carrier film a Adhesive, in particular applied a pressure-sensitive adhesive.

For the expert surprising and unpredictable is the thermoplastic polyurethane with built-in Phosphorus-based flame retardant, which forms the carrier for the tape, as follows produced.

• A) wenigstens einem organischen Diisocyanat und
• B) wenigstens einem Polyol mit im Mittel mindestens 1,8 und höchstens 3,0 zerewitinoffaktiven Wasserstoffatomen und einem zahlenmittleren Molekulargewicht M_n von 450 bis 10000 Dalton mit
• C) wenigstens einem niedermolekularen Polyol oder Polyamin mit im Mittel mindestens 1,8 und höchstens 3,0 zerewitinoffaktiven Wasserstoffatomen und einem zahlenmittleren Molekulargewicht M_n von 60 bis 400 Dalton als Kettenverlängerer und
• D) mindestens einer organischen phosphorhaltigen Verbindung auf Basis Phosphonat und/oder Phosphinoxid mit im Mittel mindestens 1,5 und höchstens 3,0 zerewitinoffaktiven Wasserstoffatomen und einem zahlenmittleren Molekulargewicht M_n von 60 bis 10000 Dalton in einer Menge von 1 bis 15 Gew.-%, bezogen auf das TPU, welches die folgende Strukturformel aufweist
  
  (Formel 1) mit R¹, R² verzweigte oder unverzweigte Alkylenreste mit 1 bis 24 C-Atomen, substituierte oder nicht-substituierte Arylenreste mit 6 bis 20 C-Atomen, substituierte oder nicht-substituierte Aralkylenreste mit 6 bis 30 C-Atomen, substituierte oder nicht-substituierte Alkarylenreste mit 6 bis 30 C-Atomen, wobei R¹ und R² gleich oder verschieden sein können, R³ H, verzweigte oder unverzweigte Alkylreste mit 1 bis 24 C-Atomen, substituierte oder nicht-substituierte Arylreste mit 6 bis 20 C-Atomen, substituierte oder nicht-substituierte Aralkylreste mit 6 bis 30 C-Atomen, substituierte oder nicht-substituierte Alkarylreste mit 6 bis 30 C-Atomen, x, y = 1 bis 50 oder welches die folgende Strukturformel aufweist
  
  (Formel 2) mit R¹ H, verzweigte oder unverzweigte Alkylreste mit 1 bis 24 C-Atomen, substituierte oder nicht-substituierte Arylreste mit 6 bis 20 C-Atomen, substituierte oder nicht-substituierte Aralkylreste mit 6 bis 30 C-Atomen, substituierte oder nicht-substituierte Alkarylreste mit 6 bis 30 C-Atomen, R², R³ verzweigte oder unverzweigte Alkylenreste mit 1 bis 24 C-Atomen, substituierte oder nicht-substituierte Arylenreste mit 6 bis 20 C-Atomen, substituierte oder nicht-substituierte Aralkylenreste mit 6 bis 30 C-Atomen, substituierte oder nicht-substituierte Alkarylenreste mit 6 bis 30 C-Atomen, wobei R² und R³ gleich oder verschieden sein können, gegebenenfalls unter Verwendung von
• F) mindestens einem weiteren halogenfreien Flammschutzmittel, welches keine zerewitinoffaktiven Wasserstoffatome enthält und ein zahlenmittleres Molekulargewicht M_n von 60 bis 10000 aufweist, in einer Menge von 0 bis 70 Gew.-%, bezogen auf das TPU, und/oder
• G) 0 bis 20 Gew.-%, bezogen auf die Gesamtmenge TPU, weiterer Hilfs- und Zusatzstoffe, wobei die Kennzahl (gebildet aus dem mit 100 multiplizierten Quotienten der Äquivalenzverhältnisse der Isocyanatgruppen aus (A) und der Summe der zerewitinoffaktiven Wasserstoffatome der Verbindungen (B), (C) und (D)) 85 bis 120 beträgt,

hergestellt.The polyurethane is optionally in the presence of catalysts (E) by reacting an NCO-containing prepolymer

• A) at least one organic diisocyanate and
• B) at least one polyol having an average of at least 1.8 and at most 3.0 Zerewitinoff-active hydrogen atoms and a number average molecular weight M _n of 450 to 10,000 daltons with
• C) at least one low molecular weight polyol or polyamine having an average of at least 1.8 and at most 3.0 Zerewitinoff-active hydrogen atoms and a number average molecular weight M _n of 60 to 400 daltons as a chain extender and
• D) at least one organic phosphorus-containing compound based on phosphonate and / or phosphine oxide having an average of at least 1.5 and at most 3.0 Zerewitinoff-active hydrogen atoms and a number average molecular weight M _n of 60 to 10,000 daltons in an amount of 1 to 15 wt .-% , based on the TPU, which has the following structural formula
  
  (Formula 1) where R ¹ , R ^{2 are} branched or unbranched alkylene radicals having 1 to 24 C atoms, substituted or unsubstituted arylene radicals having 6 to 20 C atoms, substituted or unsubstituted aralkylene radicals having 6 to 30 C atoms, substituted or unsubstituted alkarylene radicals having 6 to 30 carbon atoms, wherein R ¹ and R ^{2 may be the} same or different, R ^{3 is} H, branched or unbranched alkyl radicals having 1 to 24 carbon atoms, substituted or unsubstituted aryl radicals with 6 to 20 carbon atoms, substituted or unsubstituted aralkyl radicals having 6 to 30 carbon atoms, substituted or unsubstituted alkaryl radicals having 6 to 30 carbon atoms, x, y = 1 to 50 or which has the following structural formula
  
  (Formula 2) with R ¹ H, branched or unbranched alkyl radicals having 1 to 24 carbon atoms, substituted or unsubstituted aryl radicals having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl radicals having 6 to 30 carbon atoms, substituted or unsubstituted alkaryl radicals having 6 to 30 carbon atoms, R ² , R ³ branched or unbranched alkylene radicals having 1 to 24 carbon atoms, substituted or unsubstituted arylene radicals having 6 to 20 carbon atoms, substituted or unsubstituted aralkylene radicals having 6 to 30 carbon atoms, substituted or unsubstituted alkarylene having 6 to 30 carbon atoms, wherein R ² and R ^{3 may be the} same or different, optionally using
• F) at least one further halogen-free flame retardant, which contains no Zerewitinoff-active hydrogen atoms and a number average molecular weight M _n of 60 to 10,000, in an amount of 0 to 70 wt .-%, based on the TPU, and / or
• G) 0 to 20 wt .-%, based on the total amount of TPU, other auxiliaries and additives, wherein the index (formed from the multiplied by 100 quotient of the equivalence ratios of the isocyanate groups of (A) and the sum of the Zerewitinoff-active hydrogen atoms of the compounds ( B), (C) and (D)) is 85 to 120,

produced.

The Polyurethane is formed into the film, and preferably at least coated on one side with an adhesive.

In a preferred embodiment of the invention are components (B) and (C) of component (D) different.

When organic diisocyanates (A) can aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates or any mixtures of these diisocyanates (see HOUBEN-WEYL "Methods of Organic Chemistry", Volume E 20 "Macromolecular Materials", Georg Thieme Verlag, Stuttgart, New York 1987, pages 1587 to 1593 or Justus Liebigs Annalen der Chemie, 562, pages 75 to 136).

Specifically, by way of example:
aliphatic diisocyanates such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate; cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and 2 , 2'-Dicyclohexylmethandiisocyanat and the corresponding isomer mixtures; also aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, mixtures of 2,4 'Diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, urethane-modified liquid 4,4'-diphenylmethane diisocyanates or 2,4'-diphenylmethane diisocyanates, 4,4'-diisocyanatodiphenylethane (1,2) and 1,5-naphthylene diisocyanate. Preference is given to 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate isomer mixtures having a 4,4'-diphenylmethane diisocyanate content of more than 96% by weight and in particular 4,4'-diphenylmethane diisocyanate and 1.5 -Naphthylendiisocyanat.

The mentioned diisocyanates individually or in the form of mixtures with each other for use come. You can also together with up to 15 mol% (calculated on total diisocyanate) a polyisocyanate can be used.

It but may at most so much polyisocyanate are added that a still thermoplastic processable product is created.

Examples for polyisocyanates are triphenylmethane-4,4 ', 4 "-triisocyanate and polyphenylpolymethylene polyisocyanates.

The Particularly preferred isocyanate is 4,4'-diphenylmethane diisocyanate.

Zerewitinoff-active polyols (B) which are used in the products according to the invention are those having an average of at least 1.8 to at most 3.0 Zerewitinoff-active hydrogen atoms and a number average molecular weight M _n of 450 to 10,000 daltons. Due to production, these often contain small amounts of nonlinear compounds. Therefore, one often speaks of "substantially linear polyols." Preference is given to polyester, polyether, polycarbonate diols or mixtures of these.

Included are in addition to amino groups, thiol groups or carboxyl-containing compounds in particular two to three, preferably two hydroxyl-containing compounds, especially those with number average molecular weights M _n from 450 to 6000 daltons, particularly preferably those having a number average molecular weight M _n of 600 to 4500 daltons, for example Hydroxyl-containing polyesters, polyethers, polycarbonates and polyesteramides.

suitable Polyether diols can produced thereby; that one or more alkylene oxides with 2 to 4 carbon atoms in the alkylene radical with one starter molecule, the two contains bound active hydrogen atoms.

As alkylene oxides may be mentioned, for example:
Ethylene oxide, 1,2-propylene oxide, epichlorohydrin and 1,2-butylene oxide and 2,3-butylene oxide. Preferably used are ethylene oxide, propylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide. The alkylene oxides can be used individually, alternately in succession or as mixtures.

Suitable starter molecules are, for example:
Water, amino alcohols such as N-alkyl-diethanolamine, for example N-methyl-diethanolamine and diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. Optionally, mixtures of starter molecules can be used.

Suitable polyetherols are also the hydroxyl-containing polymerization of tetrahydrofuran. It is also possible to use trifunctional polyethers in proportions of from 0 to 30% by weight, based on the bifunctional polyethers, but at most in such an amount that a still thermoplastically processable product is formed. The substantially linear polyether diols preferably have number average molecular weights M _n of 450 to 6000 daltons. They can be used both individually and in the form of mixtures with one another.

Suitable polyester diols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohols. Examples of suitable dicarboxylic acids are aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid or aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids may be used singly or as mixtures, for example in the form of an amber, glutaric and adipic acid mixture. For the preparation of the polyester diols, it may be advantageous to use, instead of the dicarboxylic acids, the corresponding dicarboxylic acid derivatives such as carbonic diesters having 1 to 4 carbon atoms in the alcohol radical, carboxylic anhydrides or carboxylic acid chlorides. Examples of polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6 carbon atoms, for example ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2 Dimethyl 1,3-propanediol, 1,3-propanediol or dipropylene glycol. Depending on the desired properties, the polyhydric alcohols may be used alone or mixed with each other. Also suitable are esters of carbonic acid with the abovementioned diols, in particular those having 4 to 6 carbon atoms, such as 1,4-butanediol or 1,6-hexanediol, condensation products of omega-hydroxycarboxylic acids such as omega-hydroxycaproic acid or polymerization products of lactones, for example optionally substituted omega-hydroxycarboxylic acids. caprolactones. Ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-1,4-butanediol polyadipates, 1,6-hexanediol neopentyl glycol polyadipates, 1,6-hexanediol-1,4-butanediol polyadipates and polycaprolactones are preferably used as polyester diols. The polyester diols have number average molecular weights M _n of 450 to 10,000 daltons and can be used individually or in the form of mixtures with one another.

The preferred diol is a hydroxyl-containing polymerization product of tetrahydrofuran, since such TPUs are relatively stable to hydrolysis, microbial degradation and oxidation.

Zerewitinoff active Polyols (C) are so-called chain extenders and possess an average of 1.8 to 3.0 Zerewitinoff-active hydrogen atoms and have a molecular weight of 60 to 400 daltons. By this one understands in addition to amino groups, thiol groups or carboxyl groups Compounds having two to three, preferably two hydroxyl groups.

When Chain extender It is preferred to use aliphatic diols having 2 to 14 carbon atoms such as ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol. Are suitable but also diesters of terephthalic acid with glycols with 2 to 4 carbon atoms, for example terephthalic acid bis-ethylene glycol or Terephthalic acid bis-1,4-butanediol, Hydroxyalkylene ethers of hydroquinone, for example 1,4-di (beta-hydroxyethyl) hydroquinone, ethoxylated bisphenols, for example 1,4-di (beta-hydroxyethyl) bisphenol A, (cyclo) aliphatic Diamines such as isophoronediamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methyl-propylene-1,3-diamine, N, N'-dimethylethylenediamine and aromatic diamines such as 2,4-toluenediamine, 2,6-toluenediamine, 3,5-diethyl-2,4-toluenediamine or 3,5-diethyl-2,6-toluylenediamine or primary mono-, di-, tri- or tetraalkyl-substituted 4,4'-diaminodiphenylmethanes. Particularly preferred chain extenders are ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-di (beta-hydroxyethyl) hydroquinone or 1,4-di (beta-hydroxyethyl) bisphenol A used. It can also mixtures of the above chain extender can be used. Besides can also smaller amounts of triols can be added.

The preferred chain extenders is 1,4-butanediol.

The Combination of 4,4'-diphenylmethane diisocyanate with 1,4-butanediol provides hard blocks with sufficiently high resistance against melting of the samples under temperature load.

Compared to isocyanates monofunctional compounds can in proportions of up to 2% by weight, based on TPU, as so-called chain terminators be used. Suitable examples are monoamines such as butyl and dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, Piperidine or cyclohexylamine, monoalcohols such as butanol, 2-ethylhexanol, Octanol, dodecanol, stearyl alcohol, the various amyl alcohols, Cyclohexanol and ethylene glycol monomethyl ether.

The flame retardants (D) have on average at least 1.5 and at most 3.0, preferably 1.8 to 2.5, particularly preferably 2 Zerewitinoff-active hydrogen atoms. These Zerewitinoff-active hydrogen atoms are preferably based on alcohol or amine. The flame retardants (D) have a number average molecular weight M _n of 60 to 10,000 daltons, preferably 100 to 5000 daltons, particularly preferably 100 to 1000 daltons. The flame retardants (D) are based on phosphonate and / or phosphine oxide. The phosphonate used is compounds of the general formula 1 (see above). As phosphine oxide compounds of general used my formula 2 (see above). The flame retardants (D) are preferably used in an amount of 1 to 15, particularly preferably 1 to 10 wt .-% based on the total amount of TPU.

When optional additional halogen-free flame retardants (F), the from the prior Technology known halogen-free flame retardants are used. Of these, only a few are known because polyurethanes in practice as far as possible with bromine or chlorine-containing Flame retardants equipped become. The halogen-free belong special graphites, ammonium polyphosphate, aluminum hydroxide, melamine cyanurate, Melamine, phosphoric acid and phosphonic acid esters such as diphenyl cresyl phosphate. Because of the resulting mechanical and electrical data and aging stability organic phosphorus and nitrogen compounds are preferred. Some can Transparency such as inorganic flame retardants deteriorate. It Although not the primary goal is to transparent wrapping tapes Generate the opportunity However, a colorless film has the advantage that the winding tape in different colors by colored primer (respectively Printing) or colored PSAs with high flexibility in the process can be produced. Phosphoric and phosphonic acid esters behave in this regard Cheap and are therefore preferred. As the sole flame retardant but quite high amounts needed to achieve the flame retardancy needed can reduce the force at and 50 stretch too far and / or by plasticizer migration and / or exudation adhesive Create problems or fogging. By having an organic phosphorus compound in the film of the winding tape according to the invention is built in can these problems are avoided. Organic phosphorus compounds like phosphoric acid ester, which melt in thermoplastic processing, can in Unlike flame retardants in the form of fillers no holes in produce the films that lower the breakdown voltage.

wobei R bevorzugt eine Arylgruppe (zum Beispiel Phenyl, Kresyl), A eine verbindende Gruppe wie Arylen (zum Beispiel Phenylen), Biarylen (zum Beispiel Biphenyl), zwei Arylengruppen welche durch eine weitere Gruppe wie -CH2-, -C(CH3)2-, -SO2- oder -CO- verbunden sind, oder Alkylen (zum Beispiel Neopentyl) ist und n zwischen 1 und 10 liegt. Derartige Verbindungen werden großtechnisch aus Phosphorsäure oder Phosphoroxytrichlorid und Diphenolen wie Resorcin oder Bisphenol A (welche dann die Gruppe A bilden) und Monophenolen wie Phenol und Kresol (welche dann die Gruppe R bilden) hergestellt. Bevorzugt werden Phosphorsäure-1,3-phenylen-tetraphenylester und Phosphorsäure-1,3-Phenylen-tetraphenylester-Oligomere sowie Bisphenol A bis-(diphenylphosphate) und dessen Oligomere.Particularly preferred are hydrocarbyl (dihydrocarbylphosphate) of the general formula

wherein R preferably an aryl group (for example, phenyl, cresyl), A is a linking group such as arylene (for example phenylene), biaryls (for example biphenyl), two arylene groups which by another group such as -CH2-, -C (CH3) 2 -, -SO2- or -CO- are joined, or alkylene (for example, neopentyl) and n is between 1 and 10. Such compounds are industrially prepared from phosphoric acid or phosphorus oxytrichloride and diphenols such as resorcinol or bisphenol A (which then form group A) and monophenols such as phenol and cresol (which then form the group R). Preference is given to phosphoric acid 1,3-phenylene tetraphenyl esters and phosphoric acid 1,3-phenylene tetraphenyl ester oligomers and bisphenol A bis (diphenyl phosphates) and its oligomers.

Very particular preference is given to phosphoric acid and phosphonic acid derivatives which on hydrolysis release neither phenol nor cresol, examples of which are trixylyl phosphate, butylated triphenyl phosphates (for example Fyrquel ^™ EHC-S), phosphoric acid 1,3-phenylene tetraxylenyl esters and salts of phosphonic acids such as sodium , Magnesium, zinc or aluminum salts of propane or phenylphosphonic acid (benzenephosphonic acid).

The relative amounts of the compounds (B), (C) and (D) are preferred chosen so that the ratio the sum of the isocyanate groups in (A) to the sum of the Zerewitinoff-active Hydrogen atoms in (B), (C) and (D) is 0.85: 1 to 1.2: 1, preferably 0.95: 1 to 1.1: 1.

The used in the invention thermoplastic polyurethanes can as auxiliaries and additives (G) preferably up to a maximum of 20% by weight, based on the total amount of TPU, the usual auxiliaries and additives contain.

typical Auxiliaries and additives are nucleating agents, lubricants such as fatty acid ester, their metal soaps, fatty acid amides, fatty acid ester amides and silicone compounds, antiblocking agents, inhibitors, hydrolysis stabilizers, Light stabilizers, antioxidants, dyes, pigments, inorganic and / or organic fillers, Plasticizers such as adipates, sebacates and alkylsulfonic acid esters, fungistatic and bacteriostatic substances and fillers and their mixtures and reinforcing agents like fibrous materials.

Further details of the auxiliaries and additives mentioned are the specialist literature, such as Monograph by JH Saunders and KC Frisch "High Polymers", Volume XVI, polyurethanes, part 1 and 2, published by Interscience Publishers 1962 and 1964, the paperback for plastic additives by R. Gächter and H. Müller (Hanser Verlag Munich 1990) or the DE 29 01 774 A1 refer to.

The in the following statements in phr mean parts by weight of relevant component based on 100 parts by weight of all polymer components the foil.

The used according to the invention Contains foil preferably at least 1 phr and in particular at least 2 phr Stabilizers against oxidation and / or hydrolysis. Examples are antioxidants phenolic or aminic based and secondary antioxidants based on sulfur or phosphorus. The wrapping tapes according to the invention contain preferably a combination of primary and secondary antioxidant, where the primary and secondary Antioxidant function in different molecules or in one molecule can be united. The listed quantities are optional Stabilizers such as metal deactivators or light stabilizers not included.

The Amount of secondary Antioxidant is preferably at least 0.5 phr, in particular at least 1 phr.

to Avoiding the use of more complicated IUPAC terms will subsequently become a few substances with theirs CAS-No. characterized.

stabilizers for PVC products can not be transferred to TPU. secondary Antioxidants break down peroxides and therefore become diene elastomers used as part of anti-aging packages. Surprisingly it was found that a combination of primary Antioxidants (for example sterically hindered phenols or C radical scavengers like CAS 181314-48-7) and secondary Antioxidants (for example, sulfur compounds, phosphites or sterically hindered amines), whereby the two functions also in one molecule can be united the task is solved even with non-serving TPU. Above all, the combination of primary Antioxidant, preferably sterically hindered phenols with a Molecular weight of more than 500 g / mol (preferably> 700 g / mol), with a phosphite secondary Antioxidant (preferably with a molecular weight> 600 g / mol) is preferred.

Especially is the combination of a low-volatile primary phenolic Antioxidants and a secondary antioxidant from the class the sulfur compounds (preferably having a molecular weight of more than 400 g / mol, in particular> 500 g / mol) and from the class of phosphites, where the phenolic, the sulphurous and the phosphitic functions are not in three different molecules must be present but also more than one function united in one molecule can be.

Examples:

• • Phenolic Function: CAS 6683-19-8, 2082-79-3, 1709-70-2, 36443-68-2, 1709-70-2, 34137-09-2, 27676-62-6, 40601-76-1, 31851-03-3, 991-84-4
• • Sulfur-containing Function: CAS 693-36-7, 123-28-4, 16545-54-3, 2500-88-1, 16545-34-3, 29598-76-3
• • Phosphitic Function: CAS 31570-04-4, 26741-53-7, 80693-00-1, 140221-14-3, 119345-01-6, 3806-34-6, 80410-33-9, 14650-60-8, 161717-32-4
• • Phenolic and sulfur-containing function: CAS 41484-35-9, 90-66-4, 110553-27-0, 96-96-5, 41484
• • Phenolic and aminic function: CAS 991-84-4, 633843-89-0
• • Aminic Function: CAS 52829-07-9, 411556-26-7, 129757-67-1, 71878-19-8, 65447-77-0

The combination of CAS 6683-19-8 (for example Irganox 1010) with thiopropionic acid ester CAS 693-36-7 (Irganox PS 802) or 123-28-4 (Irganox PS 800) with CAS 31570-04-4 (Irgafos 168) is particularly preferred. Further preferred is a combination in which the level of secondary antioxidant exceeds that of the primary. In addition, metal deactivators can be added to complex heavy metal traces which can catalytically accelerate aging. Examples are CAS 32687-78-8, 70331-94-1, 6629-10-3, ethylenediaminetetraacetic acid, N, N'-di-salicylidene-1,2-diaminopropane, 3- (N-salicylol) amino-1,2,4-triazole (Palmarole ADK STAB CDA-1), N, N'-bis [3- (3 ', 5'-di-tert-butyl-4' -hydroxyphenyl) propionyl] hydrazide (Palmarole MDA.P.10) or 2,2'-oxamido-bis- [ethyl-3- (tert-butyl-4-hydroxyphenyl) propionate] (Palmarole MDA.P.11.).

The Selection of the mentioned anti-aging agents is of particular importance for the wrapping film according to the invention, because with phenolic antioxidants alone or even in combination with sulfur-containing costabilizers not always practical Products can be achieved. In the calender processing, in which on the rollers a relative long-term access of atmospheric oxygen is unavoidable the concomitant use of phosphite stabilizers as special suitable for sufficient heat aging stability of the product out. Even with extrusion processing makes the addition of phosphites in the aging test of the product is still positive noticeable. For the phosphite stabilizer is an amount of at least 0.1, preferably at least 0.3 phr preferred.

For example, monomeric or polymeric carbodiimides, oxazolines or reactive polyureas can be used as hydrolysis stabilizers (G). Preference is given to a polymeric carbodiimide based on aromatic isocyanates. For the preparation and structure of such carbodimides see US 2,941,956 A . JP 04 733 279 A , J. Org. Chem., 28, 2069-2075 (1963); Chemical Review, Vol. 81, No. 4, pp. 619 to 621 (1981). The preferred amount is 0.5 to 3 phr.

Further polymeric additives, which can be incorporated into the TPU are thermoplastics such as Polyethylenes, ethylene / vinyl acetate copolymers, polypropylene homopolymers or copolymers. Also, synthetic elastomers such as hydrogenated styrene-diene copolymers or thermoplastic polyurethanes without incorporated flame retardant or non-meltable polymers such as EVA dispersion powder or Impact Modifier (for example acrylate elastomer particles with a shell of PAN or PMMA) be used. Preferably, no hydrolysis-sensitive polymeric additives associated with ester or amide groups in the polymer backbone.

suitable inventive catalysts (E) are the known and customary in the art tertiary Amines such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, Diazabicyclo [2,2,2] octane and the like and in particular organic metal compounds such as titanic acid esters, Iron compounds or tin compounds such as tin diacetate, tin dioctoate, Tin dilaurate or the Zinndialkylsalze aliphatic carboxylic acids such Dibutyltin diacetate or dibutyltin dilaurate or the like.

preferred Catalysts are organic metal compounds, in particular titanic acid esters, Iron and tin compounds. The total amount of catalysts in the TPU according to the invention is usually about 0 to 5 wt .-%, preferably 0 to 2 wt .-%, based on the total amount of TPU.

The TPU related to the invention may be produced continuously or discontinuously. The best known production methods are the strip method ( GB 1 057 018 A ) and the extruder process ( DE 19 64 834 A1 ). The structure of the TPU can either step by step (Prepolymerdosierverfahren) or by the simultaneous reaction of all components in one step (one-shot dosing) take place. Preferably, the incorporable phosphorus-containing compounds are incorporated in the prepolymer process in the TPU.

The Addition of the flame retardant (F) and / or the excipients (G) can each before, during or after the polyurethane reaction.

The the present invention has mainly the absence of halogens with high flame resistance, tear resistance and flexibility to the goal. As stated increase the thermal requirements of the application, so that in addition one increased resistance across from conventional PVC wrapping tapes or developing PVC-free film wrapping tapes Polyolefinbasis is to be achieved. Therefore, the properties of the present invention will be described below in detail.

The product according to the invention is halogen-free in the sense that the halogen content of the raw materials so low is he for the flame retardance does not matter. Halogens in trace amounts, as caused by impurities, process additives (fluoroelastomer) or as residues from Catalysts could remain, remain unconsidered.

The elimination of halogens usually entails the property of flammability, which does not meet the safety requirements in electrical applications such as household appliances, buildings or vehicles. The winding tape according to the invention has self-extinguishing properties, the preferred embodiments of the winding tape automatically extinguishing in fire tests according to FMVSS 302 (horizontal sample) and / or ASTM D 568 (vertical sample).

The Thickness of the film of the invention is preferably in the range of 30 to 180 .mu.m, preferably 50 to 150 .mu.m, in particular 55 to 100 μm. Thus, a sufficient conformability when winding, a good hand tearability and achievable costs.

The winding tape according to the invention has a corresponding thickness increased by the thickness of the optionally existing pressure-sensitive adhesive coating on. The surface can be structured or smooth. Preferably, the surface is light dull. This can be done by using a filler with a sufficiently high particle size or by a roller (for Example embossing roller on the calender or frosted chill roll or embossing roller during extrusion) be achieved.

The Carrier film according to the invention is essentially free of volatile Plasticizers such as DOP or DINP and therefore has an excellent Fire behavior and low emission (plasticizer evaporation, fogging). The fogging value is preferably over 90%. The film preferably contains 0 to 5 phr phosphorus-free plasticizers, especially at all no phosphorus-free plasticizers. It preferably contains 0 to 10 phr phosphorus-containing plasticizers as flame retardants and in particular at all no phosphorus-containing plasticizers.

The used according to the invention Winding tape is preferably colored (black, white or colorful), wherein the carrier film and / or another layer such as the adhesive are colored. The pigments used are preferably free of toxic heavy metals such as lead, cadmium or chromium.

The winding tape according to the invention points in the longitudinal direction a force at 10% elongation of 2 to 20 N / cm, preferably from 4 to 11 N / cm, and at 50% elongation a force of 3 to 25 N / cm, preferably from 6 to 17 N / cm.

The 10% strength is a measure of stiffness the film, and the 50% power is a measure of the conformability during Winding in strong deformation due to high winding tension. The 50th % Power may not be too low, because otherwise in the Usually the tear strength is too low.

The tensile force (Breaking strength) of the carrier film is at least 10 N / cm, preferably at least 20 N / cm.

There TPUs very tough could be, are measures if necessary to improve hand tearability the winding band required such as blending with fillers, incompatible thermoplastic or non-meltable polymers, by rough cut Side edges, which under microscopic observation cracks in the film Training, which then apparently favor a tearing, or by with retrospectively to Example by punching attached notched side edges. Rough cut edges can in particular by the use of a squish cut with blunt or defines serrated rotating knives on bales (jumbos, Roll in big Length) or by a cut-off with fixed blades or rotating Knives of bar products (rolls in production width and on sale Length) be generated. The elongation at break can be determined by a suitable cut the blades and knives are adjusted. Preferably, the embodiment of the Production of bar products with cut-off with blunt fixed ones Sound. By strong cooling The bars before cutting can crack during the cutting process to be improved.

requirements for one sufficient heat resistance and short-term heat resistance are a sufficient crystalline melting point of the TPU (preferably at least 158 ° C and more preferably at least 170 ° C) and a resistance against aging by degradation, resulting in antioxidants and / or hydrolysis protection agents can be ensured.

The winding tape according to the invention has a high temperature resistance on, in preferred embodiments should have an elongation at break of at least 100% after 312 hours of storage at 140 ° C (heat resistance test) or a short-term heat resistance of 170 ° C (after 30 min. no cracks or fused spots).

to Achieving these force values as well as the heat resistance contains the film the winding tape is a TPU with a sufficiently high proportion of hard blocks, why the Shore D hardness of TPU raw material preferably at least 35 and more preferably is at least 50, this roughly equates to Shore A hardnesses of preferably at least 85 or more preferably at least 100. The flame resistant ones shown in the prior art tapes use much softer TPU (Shore A 70 to 80) than the one we are aiming for flame-resistant adhesive tapes with built-in flame retardant. If the tapes are made of such Soft TPU still plasticizer or phosphoric acid ester as a flame retardant are added, then these are much more inappropriate than the winding tapes according to the invention.

The Production of the film takes place on a calender or by extrusion as in the blowing or casting process. These procedures are for example in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Wiley-VCH 2002 described. With the concomitant use of solid or liquid additives for the TPU becomes a compound of the main components or all components in a compounder such as kneader (for example, blender) or Extruder (for example twin-screw extruder, planetary roller extruder) prepared and then converted into a solid form (for example, granules), which then in a film extrusion line or in an extruder, kneader or rolling mill of a calendering be further processed.

The Polyurethane film is preferably at least one side with a Adhesive coated.

The amount of preferably present adhesive layer is 10 to 40 g / m ² , preferably 18 to 28 g / m ² (that is the amount after any necessary removal of water or solvent, the numerical values also correspond approximately to the thickness in microns). In a case with adhesive coating, the information given here on the thickness and thickness-dependent mechanical properties relate exclusively to the TPU-containing layer of the winding tape without consideration of adhesive layer or other layers that are advantageous in connection with adhesive layers. The coating does not have to be full-surface, but may also be part-surface. As an example, a wrapping tape, each with a pressure-sensitive adhesive strip on the side edges is called. This can be cut into approximately rectangular sheets, which are glued with the one adhesive strip on the cable bundle and then wound until the other adhesive strip on the Wickelbanddrückseite can be glued. Such a tube-like envelope, similar to a sleeve packaging, has the advantage that the flexibility of the cable harness is practically not deteriorated by the wrapping.

When Adhesive come all common Types in question, especially based on rubber. Such rubbers can for example homopolymers or copolymers of isobutylene, of 1-butene, of vinyl acetate, ethylene, of acrylic acid esters, of butadiene or of isoprene. Especially suitable are formulations based on of polymers based on acrylic esters, vinyl acetate or Isoprene.

To optimize the properties, the self-adhesive composition used can be blended with one or more additives such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, anti-aging agents, photoinitiators, crosslinking agents or crosslinking promoters. Tackifiers are, for example, hydrocarbon resins (for example polymers based on unsaturated C ₅ or C ₉ monomers), terpene-phenolic resins, polyterpene resins from raw materials such as α- or β-pinene, aromatic resins such as cumarone-indene resins or styrene-based resins α-methylstyrene such as rosin and its derivatives, for example disproportionated, dimerized or esterified resins, for example reaction products with glycol, glycerol or pentaerythritol, to name but a few, as well as other resins (such as listed in Ullmanns Enzyklopadie der technischen Chemie, Vol 12, pages 525 to 555 (4th edition), Weinheim). Preference is given to using resins without easily oxidizable double bonds, such as terpene-phenolic resins, aromatic resins and particularly preferably resins which are prepared by hydrogenation, for example hydrogenated aromatic resins, hydrogenated polycyclopentadiene resins, hydrogenated rosin derivatives or hydrogenated terpene resins.

Suitable fillers and pigments are, for example, carbon black, titanium dioxide, calcium carbonate, zinc carbonate, zinc oxide, silicates or silicic acid. Suitable miscible plasticizers are, for example, aliphatic, cycloaliphatic and aromatic mineral oils, di- or poly-esters of phthalic acid, trimellitic acid or adipic acid, liquid rubbers (for example low molecular weight nitrile or polyisoprene rubbers), liquid polymers of butene and / or isobutene, acrylic esters, polyvinyl ethers, Liquid and soft resins based on the raw materials of adhesive resins, wool wax and other waxes or liquid silicones. Crosslinking agents are, for example, isocyanates, phenolic resins or halogenated phenolic resins, melamine and formaldehyde resins. Suitable crosslinking promoters are, for example, maleimides, allyl esters, such as triallyl cyanurate, polyfunctional esters of acrylic and methacrylic acid. Anti-aging agents are for example sterically hindered Phenols known, for example, under the trade name Irganox ^™ .

A Crosslinking is advantageous because the shear strength (for example expressed as holding power) and thus the inclination to deformations of the roles Storage (telescoping or formation of voids, also gaps called) reduced. The squeezing of the PSA is also reduced. This expresses in tack-free side edges of the rolls and tack-free edges of in a spiral Movement around cable or a wiring harness guided winding tape out. The holding power is preferably above 150 min.

The Adhesion to steel should be in the range of 1.5 to 3 N / cm.

The winding tape according to the invention preferably has an unwinding force of 1.2 to 6.0 N / cm, especially preferably from 1.6 to 4.0 N / cm and in particular from 1.8 to 2.5 N / cm at 300 mm / min unwinding speed.

In summary shows the preferred embodiment one-sided a solvent-free Self-adhesive composition, which by coextrusion, melt or dispersion coating has come about. In particular, adhesives are based on polyacrylate in the form of dispersions or hotmelts preferred.

Advantageous is the use of a primer layer between the carrier film and adhesive for improving the adhesion of the adhesive on the Film and thus avoiding the transfer of adhesive the back of the film while unwinding of rolls.

When Primers are the known dispersion and solvent systems usable for example based on isoprene- or butadiene-containing rubber and / or cyclo rubber. Isocyanates or epoxy resins as additives improve liability and increase in part also the shear strength of the pressure-sensitive adhesive. physical surface treatments Like flaming, corona or plasma or coextrusion layers are also suitable to improve the adhesion. Particularly preferred is the Application of such methods to solvent-free adhesive layers, especially those based on acrylate.

A Coating the back can by known release agents (optionally with other polymers mixed). Examples are stearyl compounds (for example Polyvinyl stearyl carbamate, stearyl compounds of transition metals such as Cr or Zr), polyethylenimine and stearyl isocyanate ureas, Polysiloxanes (for example as a copolymer with polyurethanes or as a graft copolymer on polyolefin), thermoplastic fluoropolymers. The term stearyl is synonymous with all straight or branched Alkyle or Alkenyle with a C-number of at least 10 such as Example octadecyl.

descriptions the usual Adhesives and backside coatings and primers can be found, for example, in "Handbook of Pressure Sensitive Adhesive Technology ", D. Satas, (3rd edition).

The Poles can be used to increase the unwind force or relaxation of the tensions of the films before Cutting a heat storage be subjected. The cutting of wrapping tapes with fabric, fleece and film backing (for example, PVC) is made by shear cutting (between two rotating Knives), cutting off (fixed or rotating knives pressed into a rotating rod of the product), blade cut (the web is divided by sharp blades when passing) or squish (between a rotating knife and a roller).

The winding tape according to the invention is excellent for wrapping elongated material such as field coils or cable harnesses suitable in vehicles. Flexibility is of paramount importance there when using on wires and cables not just wrapped in a spiraling motion, but at branching points, plugs or mounting clips also wrinkle-free bend flexible must be wound. Furthermore is desired that the winding tape pulls the wire harness together elastically. The winding tape according to the invention is also for other applications suitable such as for sealing ventilation pipes in the climatic construction, since the high flexibility a good conformability at rivets, beads and folds secures. These mechanical properties can can only be achieved by a soft flexible wrapping tape. The Task, the necessary flexibility by avoiding the addition of larger quantities to achieve flame retardants is achieved according to the invention.

The current occupational hygiene and ecological requirements are taken into account by dispensing with the use of halogen-containing raw materials. The halogen-free is for thermal utilization Of waste containing such winding tapes of extraordinary importance (for example, waste incineration of the plastic fraction from vehicle recycling) but also in cable or building fires, since no toxic flue gases.

in the The ever more complicated electronics and the rising Number of electrical consumers in automobiles will also the wiring harnesses more and more complex. When rising cross sections of the harnesses is the inductive heating getting bigger while the heat dissipation decreases. This increases the requirements for heat resistance the materials used. The standard PVC materials used for the winding tapes bump here to its limits. Also this problem can now be considered solved become.

Test Methods

The Measurements are taken at a test climate of 23 ± 1 ° C and 50 ± 5% rel. Humidity carried out.

The crystallite melting point (T _cr ) is determined by DSC according to ISO 3146. Since freshly processed TPUs have an extremely wide melting range because they are not yet in the thermodynamic final state of the crystallization, the samples are tempered for 24 hours at 140 ° C. before the crystallite melting point is determined.

The Shore A and Shore D hardness are determined according to ISO 868.

The hydrolysis is determined by storing the sample in warm distilled water. To 1000 hours at 80 ° C the sample is kept at 80 ° C for 24 hours dried in vacuo and then the decrease in tensile strength across from the fresh state. If the tear strength is less than 50 % has decreased, the test is passed (P, passed), and if they are at least 50%, the test is failed (NP, not passed).

The Tensile expansion behavior of the winding band is measured on type 2 test specimens (rectangular 150 mm long and if possible 15 mm wide test strips) according to DIN EN ISO 527-3 / 2/300 at a test speed of 300 mm / min, one clamping length 100 mm and a pre-load of 0.3 N / cm determined. In the case of patterns with rough cut edges are the edges with a sharp blade to trim before the tensile test. The tensile elongation behavior is in the machine direction unless otherwise specified (MD, direction of travel) tested. The Force is expressed in N / stripe width and the breaking strain in. The test results in particular the elongation at break (elongation at break), are by a ensure a sufficient number of measurements statistically.

The adhesive forces become at a deduction angle of 180 ° AFERA 4001 (if possible) 15 mm wide test strips determined. Here are steel plates according to AFERA standard as test substrate used as far as no other primer is mentioned.

The Thickness of the film is determined according to DIN 53370 (A possible pressure-sensitive adhesive layer is subtracted from the measured total thickness).

The Holding Power is determined according to the PSTC 107 (10/2001), where the Weight is 20 N and the dimensions the bond area 20 mm in height and 13 mm in width.

The Unwind force is measured at 300 mm / min according to DIN EN 1944.

The hand tearability let yourself do not express in numbers, even if breaking strength, breaking elongation and impact toughness (all along measured) are of significant influence.

Rating:

+++

= very easy,

++

= good,

+

= still workable,

=

difficult to process,

-

= only with great effort torn off, the ends are dirty,

---

= not processable

The Fire behavior is determined by FMVSS 302 (horizontal sample) respectively ASTM D 568 (vertical sample) measured. For FMVSS 302, the pressure-sensitive adhesive coating is located up. These methods also allow determination of the rate of fire combustible samples. It is only judged whether the sample is up to reach the 2nd mark (end mark) burns (not passed) or before by itself extinguished (passed). The MVSS 302 (Engine Vecile Safety Standard, US) also became one ISO standard further developed (ISO 3795).

The temperature resistance is determined by two methods. The wrap band will open first glued a siliconized polyester film and stored in the heat. After expiry of the test time the sample is kept at 23 ° C for 30 min cooled. In the heat resistance test is tested after 312 hours of storage at 140 ° C if the elongation at break is still at least 100%. The exam the short-term heat resistance carried out by 30 minutes storage of the sample at 170 ° C, followed by winding of at least 3 turns with 50% overlap around a thorn of 10 mm diameter and subsequent Assess whether the pattern damages (for example, cracks, molten spots).

At the cold test the test specimen described above is based on ISO / DIS 6722 cooled to -40 ° C for 4 hours and The sample is wrapped by hand on a 5 mm diameter mandrel. The samples are checked visually for defects (cracks) in the adhesive tape.

The Breakdown voltage is measured according to ASTM D 1000. As a number becomes the highest Value that the sample withstands this tension for one minute. These Number is converted to a sample thickness of 100 μm.

Example:

A Sample of 200 μm Thickness holds After one minute, a maximum voltage of 6 kV was calculated Breakdown voltage is 3 kV / 100 μm.

Of the Fogging value is determined according to DIN 75201 A.

The following Examples are intended to illustrate the invention without its scope restrict.

explanation the PU raw materials used in the examples

• Terathane ^TM 1000: polyethers having a molecular weight of M _n = 1000 daltons (DuPont)
• MDI: 4,4'-diphenylmethane diisocyanate
• Exolit ^TM OP 560: Flame retardant based on diol phosphonate with Zerewitinoffaktiv
• Hydrogen atoms (Clariant GmbH)
• Levagard ^TM 4090 N: flame retardant (Bayer AG) OP (OC25) 2CH2N (C2H4OH) 2
• Cyagard ^™ RF-1243 Diol Phosphine Oxide based flame retardant (Cytec Inc.) BDO: 1,4-butanediol
• Irganox ^™ 1010: Tetrakis (methylene (3,5-di-tert-butyl-4-hydroxycinnamate)) methane (Ciba Specialty Chemicals)
• Licowax ^TM C: release agent (Clariant Würtz GmbH)
• Disflamoll ^TM DPK: flame retardant diphenyl cresyl phosphate (Lanxess)
• KE 9463: Masterbatch made of 20% Stabaxol ^TM P100 and 80% TPU (Rhein-Chemie)

example 1

A mixture of 1045 kg of Terathane ^™ 1000, 6.3 kg of Irganox ^™ 1010 and 10 kg of Licowax ^™ C was heated to 160 ° C. while stirring with a paddle stirrer at a speed of 500 rpm, after which 713 kg of MDI were added. After reaching the maximum reaction temperature was stirred for 30 s, after which 125 kg of BDO and 100 kg of Exolit ^™ OP 560 were added. The mixture was then stirred for 100 s, after which the TPU was poured out. Finally, the material was post-treated at 80 ° C for 30 minutes.

The finished TPU was cut, granulated and in a dry state supplied to a compounder. This fed the gap of an inverted type calender L ", the processing temperatures lay around 220 ° C. With the help of calender rolls, a film with a smooth surface of a Thickness of 80 μm formed.

The film was stored for one week, leveled on the coater with rollers at 60 ° C to improve the flatness and after a corona treatment on one side with a release layer and provided on the other with an aqueous acrylic adhesive (Primal PS 83 D from Rohm and Haas and addition of 5% Hostasin Black [color preparation] from Clariant) using a doctor blade with a coating weight of 24 g / m ² . The finished wrapping tape was wound into bars of 33 m in length on a 1-inch core (25 mm). The cutting was done by cutting off the rods by means of fixed blade with not very acute angle (straight knife) in 29 mm wide rolls.

Example 2

A mixture of 1045 kg of Terathane ^™ 1000, 6.3 kg of Irganox ^™ 1010 and 10 kg of Licowax ^™ C was heated to 160 ° C. while stirring with a paddle stirrer at a speed of 500 rpm, after which 686 kg of MDI were added. After reaching the maximum reaction temperature, stirring was continued for 30 seconds, after which 125 kg of BDO and 80 kg of Cyagard ^™ RF-1243 were added. The mixture was then stirred for 100 s, after which the TPU was poured out. Finally, the material was post-treated at 80 ° C for 30 minutes.

The finished TPU was cut, granulated and added with the addition of 5 % Masterbatch black with a temperature of 180 to 200 ° C to one 100 μm blown film processed.

The carrier film was subjected to a one-sided flame treatment and, after 10 days of storage, coated with Acronal DS 3458 by means of a roll applicator at 50 m / min. The temperature load on the carrier was reduced by a cooled counterpressure roller. The application was about 35 g / m ² . Suitable crosslinking was achieved in-line prior to wind-up by irradiation with a UV system equipped with 6 medium-pressure Hg lamps of 120 W / cm. The irradiated web was wound into bars of 33 m in length on a 1 1/4 inch core (31 mm). The cutting was done by cutting off the rods by means of a fixed blade (straight knife) in 25 mm wide rolls.

Example 3

A mixture of 1000 kg of Terathane ^™ 1000, 119 kg of BDO, 23 kg of Levagard ^™ 4090N, 6 kg of Irganox ^™ 1010, 9 kg of Licowax ^™ C and 30 kg of Disflamoll ^™ DPK was heated to 160 with a paddle at a speed of 500 rpm ° C heated, after which 615 g of MDI was added. The mixture was then stirred for 110 s, after which the TPU was poured out. Finally, the material was post-treated at 80 ° C for 30 minutes.

The finished TPU was cut, granulated and added with the addition of 5 Wt% of a blackbatch and 5 wt% of a hydrolysis masterbatch KE 9463 in the cast process (flat die with chill roll) to a 70 μm thick Molded film.

One side was coated with a primer of 5 parts MDI, 45 parts natural rubber and 50 parts of cyclo rubber at 0.6 g / m ² and dried. The adhesive coating was applied directly to the primer layer by means of a comma bar with a coating weight of 18 g / m ² (based on dry matter). The adhesive consisted of a solution of a natural rubber adhesive in n-hexane with a solids content of 30 percent by weight. This consisted of 50 parts natural rubber, 10 parts zinc oxide, 3 parts rosin, 6 parts alkylphenol resin, 17 parts terpene phenolic resin, 12 parts poly-β-pinene resin, 1 part antioxidant Irganox 1076 and 2 parts mineral oil. The drying of the coat was carried out in a drying tunnel at 100 ° C. The film was cut directly behind it in a compound cutting machine with a knife bar with sharp blades 19 mm apart from rolls on standard 3 inch (3 inch) adhesive tape cores. A part of the rolls was then punched on both sides about 0.2 mm deep, the resulting cuts were radial (perpendicular to the film webs), which significantly improves the hand tearability (these roles are Example 3a).

Comparative Example 1

The winding tape was produced analogously to Example 1, but the TPU film consisted of T-8375 (thermoplastic polyester polyurethane with Shore A hardness of 75 from DIC Bayer Polymer). At the same processing temperature, the melt adhered so strongly to the calender rolls that no film could be produced. After lowering the temperature to 160 ° C, a film could be removed. The T-8375 was chosen as it is for the examples of JP 2005 264 112 A (Adhesive tape of copolyamide modified with TPU and an admixed flame retardant based on nitrogen) was used.

Comparative Example 2

The Preparation of the winding tape should be analogous to Comparative Example 1 done, the TPU film should, however, consist of 100 phr T-8375 and 10 phr Reofos 65 (isopropylated Triaryl phosphate from Great Lakes) as unincorporated phosphorus Flame retardants. Because of very strong sticking to the calender rolls failed, however, despite variation in processing conditions to get a foil. The film could not be blown process analogously to Example 2 because of lack of melt strength. Only with the casting process analogous to Example 3 could a 80 micron thick colorless film are produced. These were then analogous example 1 coated with pressure-sensitive adhesive.

Comparative Example 3

• • 40 phr T-8375,
• • 60 phr CM6541X3 (Copolyamid aus ε-Aminocapronsäure und ω-Aminolaurinsäure mit Kristallitschmelzpunkt 133 °C von Toray Industries),
• • 10 phr Hydrazodicarbonamid,
• • 40 phr Melamincyanurat,
• • 1 phr Licowax^TM OP,
• • 10 phr Calciumcarbonat.

The production of the winding tape was carried out analogously to Example 1, the TPU film corresponded in its composition but the example 2 of JP 2005 264 112 A :

• • 40 phr T-8375,
• 60 phr of CM6541X3 (copolyamide of ε-aminocaproic acid and ω-aminolauric acid having a crystallite melting point of 133 ° C. from Toray Industries),
• • 10 phr of hydrazodicarbonamide,
• • 40 phr melamine cyanurate,
• • 1 phr Licowax ^TM OP,
• • 10 phr calcium carbonate.

at a processing temperature similar to Example 1 glued the melt on the calender rolls. She showed bubbles and holes (probably through Decay of the hydrazodicarbonamide), after lowering the temperature 160 to 170 ° C a film could be produced. The thickness, however, was analog Example 1 80 μm instead 0.2 mm as in Japanese writing.

Comparative Example 4

to Coating became a conventional film for insulating tape from Singapore Plastic Products Pte. used under the name F2104S. The According to the manufacturer, the film contained approx. 100 phr (parts per hundred Resin) suspension PVC with K value 63 to 65, 43 phr DOP (di-2-ethylhexyl phthalate), 5 phr tribasic lead sulphate (TLB, stabilizer), 25 phr ground Chalk (Bukit Batu Murah Malaysia with fatty acid coating), 1 phr Furnaceruß and 0.3 phr stearic acid (Lubricant). The nominal thickness was 100 μm and the surface was smooth but dull.

On one side was the primer Y01 from Four Pillars Enterprise / Taiwan applied (analytically acrylate-modified SBR rubber in toluene) and thereupon 23 g / m2 of IV9 adhesive from Four Pillars Enterprise / Taiwan (analytically detectable main component: SBR and natural rubber, Terpene resin and alkylphenol resin in toluene). The film became instant after the dryer with a knife bar with sharp blades in 25 mm distance cut into rolls in a machine.

Summary the Results

at Comparative Example 2, the phosphate plasticizer deteriorates the Fogging values and bond strengths. Comparative Example 3 behaves similar, probably contains the very soft TPU (Shore A = 75) is a plasticizer.

The tensile strengths are in all cases acceptable. The elongations at break of the comparative examples are relative high, so that the hand tearability in two cases is worsened.

The Comparative examples are in two cases for applications as wrapping tape too soft.

The heat resistance at 140 ° C is bad in all comparative examples, probably it is lacking antioxidant and possibly also the susceptibility to hydrolysis. The non-given short-term heat resistance at 170 ° C is in addition lack of oxidative resistance (partly cracking) at too low a melting point (all samples are at least melted at the edges). Comparative example 4 fails because of plasticizer evaporation.

The hydrolysis is inadequate in all the comparative examples except the PVC tape, which is not surprising to those skilled in a TPU with polyester polyol.

The Comparative examples have in part low flame resistance (Samples completely burned).

The Color is consistently fine, only produce in Comparative Example 3 the fillers a cloudiness (the is called Gray color).

Claims (18)

Halogen-free flame-retardant winding tape with a film of thermoplastic polyurethane, characterized in that a flame retardant based on phosphorus is chemically incorporated. Winding belt according to claim 1, characterized that at least on one side of the carrier film, an adhesive, preferably Pressure-sensitive adhesive is present. Winding belt according to claim 1 or 2, characterized that the wrap is colored. Winding tape according to at least one of claims 1 to 3, characterized in that among those in the FMVSS 302 or ASTM D 568 test conditions self-extinguishing and or has a breakdown voltage of at least 4 kV. Wrap band according to at least one of the preceding Claims, characterized in that the thickness of the film 30 to 180 microns, preferably 50 to 150 μm, in particular 55 to 100 microns is, the Force in the machine direction at 10% stretch a value of 2 to 20 N / cm, especially 4 to 11 N / cm, the force at 50 % Elongation is 3 to 25 N / cm, especially 6 to 17 N / cm and / or the breaking strength greater than 10 N / cm and preferably greater than 20 N / cm. Wrap band according to at least one of the preceding Claims, characterized in that the breaking elongation after 312 hours Storage at 140 ° C at least 100% and or after 30 minutes storage at 170 ° C during winding with at least 3 turns and 50-degree overlap around a mandrel of 10 mm diameter no damage can be observed. Wrap band according to at least one of the preceding Claims, characterized in that the Shore D hardness of the polyurethane at least Preferably at least 50 and / or the crystallite melting point of the polyurethane is at least 158, preferably at least 170 ° C. Wrap band according to at least one of the preceding Claims, characterized in that the adhesive is a solvent-free PSA is that which by coextrusion, melt coating or Dispersion coating is produced, preferably a pressure-sensitive adhesive or dispersion adhesive based on polyacrylate. Wrapping tape according to at least one of the preceding claims, characterized in that the amount of the adhesive layer 10 to 40 g / m ² , preferably 18 to 28 g / m ² , the bond strength of the winding tape on steel 1.5 to 3 N / cm, the Unwinding force of the winding belt 1.2 to 6.0 N / cm at 300 mm / min unwinding speed, preferably 1.6 to 4.0 N / cm, more preferably 1.8 to 2.5 N / cm and / or the holding power the winding band is more than 150 min. Winding tape according to at least one of the preceding claims, characterized characterized in that the hand tearability through additives in the film or by mechanical damage to the side edge (s) of the Slide increased becomes. Wrapping tape according to at least one of the preceding claims, characterized in that the polyurethane of the carrier film of A) at least one organic diisocyanate and B) at least one polyol having an average of at least 1.8 and at most 3.0 Zerewitinoff-active hydrogen atoms and a number average molecular weight M _n of 450 to 10,000 daltons with C) at least one low molecular weight polyol or polyamine having an average of at least 1.8 and at most 3.0 Zerewitinoff-active hydrogen atoms and a number average molecular weight M _n of 60 to 400 daltons as chain extenders and D) at least one organic phosphorus-containing compound Phosphonate and / or phosphine oxide with an average of at least 1.5 and at most 3.0 Zerewitinoff-active hydrogen atoms and a number average molecular weight M _n of 60 to 10,000 daltons in an amount of 1 to 15 wt .-%, based on the TPU, which has the following structural formula

R ¹ , R ^{2 are} branched or unbranched alkylene radicals having 1 to 24 C atoms, substituted or unsubstituted arylene radicals having 6 to 20 C atoms, substituted or unsubstituted aralkylene radicals having 6 to 30 C atoms, substituted or non-substituted substituted alkarylene radicals having 6 to 30 C atoms, where R ¹ and R ^{2 may be} identical or different, R ^{3 is} H, branched or unbranched alkyl radicals having 1 to 24 C atoms, substituted or unsubstituted aryl radicals having 6 to 20 C atoms Atoms, substituted or unsubstituted aralkyl radicals having 6 to 30 carbon atoms, substituted or unsubstituted alkaryl radicals having 6 to 30 carbon atoms, x, y = 1 to 50 or which has the following structural formula

with R ¹ H, branched or unbranched alkyl radicals having 1 to 24 carbon atoms, substituted or unsubstituted aryl radicals having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl radicals having 6 to 30 carbon atoms, substituted or unsubstituted Alkaryl radicals having 6 to 30 carbon atoms, R ² , R ³ branched or unbranched alkylene radicals having 1 to 24 carbon atoms, substituted or unsubstituted arylene radicals having 6 to 20 carbon atoms, substituted or unsubstituted aralkylene radicals having 6 to 30 C atoms, substituted or unsubstituted alkarylene radicals having 6 to 30 carbon atoms, where R ² and R ^{3 may be} identical or different, optionally using F) at least one further halogen-free flame retardant which contains no Zerewitinoff-active hydrogen atoms and a number average Molecular weight M _n of 60 to 10,000, in an amount of 0 to 70 wt .-%, based on the TPU, and / or G) 0 to 20 wt .-%, based on the total amount of T PU, other auxiliaries and additives, wherein the index (formed from the multiplied by 100 quotient of the equivalence ratios of the isocyanate groups of (A) and the sum of the Zerewitinoff-active hydrogen atoms of the compounds (B), (C) and (D) is 85 to 120 , optionally using a catalyst (E) is preferably prepared by the prepolymer process. Wrap band according to at least one of the preceding Claims, characterized in that the components (B) and (C) of component (D) are different. Wrap band according to at least one of the preceding Claims, characterized in that the relative amounts of the compounds (B), (C) and (D) are selected are that the ratio the sum of the isocyanate groups in (A) to the sum of the Zerewitinoff-active Hydrogen atoms in (B), (C) and (D) is 0.85: 1 to 1.2: 1, preferably 0.95: 1 to 1.1: 1. Wrap band according to at least one of the preceding Claims, characterized in that the isocyanate (A) 4,4'-diphenylmethane diisocyanate, the Polyol (B) a hydroxyl-containing polymerization of the Tetrahydrofuran and / or the chain extender (C) 1,4-butanediol is. Wrapping tape according to at least one of the preceding claims, characterized in that the polyurethane film at least 1, preferably at least 2 phr stabilizers against oxidation and / or Hy contains drolysis. Wrap band according to at least one of the preceding Claims, characterized in that as stabilizers a combination from primary Antioxidants such as sterically hindered phenols or C-radical scavengers and secondary Antioxidants such as sulfur compounds, phosphites or steric hindered amines are used, the two functions also in a molecule can be united. Wrap band according to at least one of the preceding Claims, characterized in that the content of phosphorus-free plasticizer in the film at 0 to 5 phr, preferably 0 phr, the salary of phosphorus-containing plasticizer in the film at 0 to 10 phr, preferably 0 phr is and / or the fogging value more than 90%. is. Use of a winding band after at least one the previous claims for bundling, protecting, marking, Insulating or sealing ventilation pipes, wires or cables or for sheathing cable harnesses in vehicles or field coils for picture tubes.