DE102008037223A1 - Wrap tape made of a TPU film with coextruded release - Google Patents

Abstract

Halogen-free flame-retardant winding tape made from a co-extruded at least two-layer film with a first layer of thermoplastic polyurethane, on which a second layer of polar modified polyolefin is, preferably on the first layer, the second layer of polar modified polyolefin thermoplastic polyurethane opposite a layer made of an aging-resistant polar pressure-sensitive adhesive.

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 used in air conditioners, wires or cables and especially for wire harnesses in vehicles or field coils suitable for picture tubes. The Wrapping tape serves for bundling, isolating, marking or shooter.

Cable wrapping tapes and insulating tapes are usually made of plasticized PVC film with a one-sided pressure-sensitive adhesive coating. It exists the desire to overcome the disadvantages of these products like the To eliminate evaporation of plasticizers and the high halogen content.

The plasticizers of conventional insulating tapes and cable wrapping tap gradually, resulting in a health burden, in particular, the commonly used DOP is questionable. Furthermore, the vapors hit in vehicles on the windows down, which deteriorates the view (and thus significantly the driving safety) and by the expert as fogging ( DIN 75201 ) referred to as. With even greater evaporation by higher temperatures, for example in the engine compartment of vehicles or insulating tapes in electrical equipment, the winding band embrittled by the resulting plasticizer loss and the decomposition of the PVC polymer.

In front the background of the discussion about the incineration of plastic waste, For example, shredder waste from vehicle recycling, consists of Trend towards the reduction of the halogen content and thus the dioxin formation. Therefore, the wall thicknesses in the cable insulation and the thicknesses of the tapes used for wrapping PVC film reduced. The usual thickness of PVC films for Winding tapes is 85 to 150 microns. Below of 85 μm, considerable problems occur in the calendering process so that such products with reduced PVC content barely available are.

The usual Wrap straps 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 soft PVC foil fabric or nonwovens to use. The resulting products are however in The practice used only a little, since they are relatively expensive and themselves in handling (for example, hand tearability, elastic Resilience) and under conditions of use (for Example resistance to moisture or operating fluids) strongly different from the usual products, whereby - like executed below - the thickness of a special Meaning. Such thick webs make the wiring harnesses even thicker and inflexible than classic PVC tapes, though This has a positive effect on the sound insulation, but what only in some areas of harnesses is beneficial. However, nonwovens are less extensible and have virtually no resilience on. This is significant because thin branches of Wiring harnesses must be wrapped so tightly that they do not sag slack when installing and light before clipping on and attaching 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 , of the 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 Literature is also made of wrapping tapes made of polyolefins described. However, these are easily flammable or contain halogen-containing flame retardants. In addition, point the materials made from ethylene copolymers too low Softening point (they usually melt already when trying to to check heat aging resistance), and in the case of using conventional polypropylene polymers the material is usually too inflexible. Metal hydroxides are Although sometimes used, the amounts used are from 40 to 100 phr but too low for adequate flame retardancy, that is, Not only are they not self-extinguishing, they are wise even a relatively high fire speed (for example, over 100 mm / min according to MVSS 302). Slides over 100 phr to flame retardants are technically difficult to produce. in addition comes that such films have a low tensile strength and are very rigid, that is, the essential processing properties of a typical PVC wrap band is missed.

In the WO 00/71634 A1 is a winding adhesive tape described, the film consists of an ethylene copolymer as a base material. The carrier film contains the halogen-containing flame retardant decabromodiphenyl oxide. The film softens below a temperature of 95 ° C, but the normal use temperature is often above 100 ° C or even briefly above 130 ° C, which is not uncommon when used in the engine compartment.

In the WO 97/05206 A1 describes a halogen-free winding adhesive tape whose carrier film consists of a polymer blend of low-density polyethylene and an ethylene / vinyl acetate or ethylene / acrylate copolymer. As flame retardants, 40 to 90 phr of aluminum hydroxide or ammonium polyphosphate are used. A significant disadvantage of the carrier film is again the low softening temperature. To counteract this, the use of a silane crosslinking is described. However, this crosslinking method only leads to very non-uniformly crosslinked material, so that in practice no stable production process or uniform quality of the product can be realized.

Similar problems of lack of heat resistance occur in the 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 halogen-free to solve describe subsequent 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. However, this thickness excludes flexibility in filled polyolefin films, since this depends on the thickness in the third power. 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 Solutions build on the well-known synergistic Flame retardancy of red phosphorus with magnesium hydroxide. The However, use of elemental phosphorus involves significant disadvantages and Hazards. When processing is smelly, selbstentzündliches and released highly toxic phosphine. Also the finished winding tape smells like garlic in a hot and humid environment. Another disadvantage arises from the formation of very dense, white smoke in case of fire. In addition, are only brown to black products can be produced, wrapping tapes However, for the purpose of color coding, they are available in a wide range of colors used.

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 additional amount is not sufficient for a significant improvement of the fire behavior.

The mentioned writings lead to the prior art because the mentioned disadvantages, in particular 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 adequate Release unwind force. In addition, the stay Processability in film production processes, 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) can not achieve self extinguishing be and from just 40 wt .-% flame retardants are flexibility and tear strength at hardly acceptable low level. The combination polyolefin and metal hydroxide results due 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 Tape, comes to Weißbruch. 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.

tapes made of polyurethane (PU) are known, some with flame retardant Equipment. It is mostly tacky-finished PU foams as well as adhesive tapes explained below 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. It 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. Organic phosphorus or nitrogen based flame retardants were not mentioned. 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 Foil is not coextruded. The PSA is not polar or age-stable types.

at Coating with polar adhesive anchors this very well the polyurethane, when stored the liability increases with the back so strong that the roll of adhesive tape can not be unwound again. The patent does not describe the possibility of Application of a release layer (non-stick layer) on the back of the tape. Such a measure could be unwinding be enabled. Separate the known release layers however, so strong that the adhesion of the tape on the back is low. When wrapping objects, for example Wire bundles, however, a high adhesion is necessary so the end of the tape does not peel off again or as the expert says off-flag.

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 adhesive tape must have a thickness of at least 9 mils, that is, the foil has a minimum thickness of 8 mils (0.2 mm) around the Boeing standard BSS 7230 F2 to fulfill. The claimed in the publication adhesive tape also contains bromine-containing flame retardants, but the invention should be 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 ° C to 160 ° C, so that processing for compounds with low softening temperature appears realistic. The reason for this lies in the low melting temperatures of the selected raw materials, for the polyurethane are mentioned 60 ° C to 120 ° C and for the polyamide 100 ° C to 180 ° C, 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 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 film for the winding tape according to the invention would be with the mentioned in the document preferred combination of hydrazodicarbonamide and melamine cyanurate because of the decomposition at high temperatures, the processing of TPU is required with the high-melting hard blocks or high Shore hardness, not produced.

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 by in-line metering and mixing the polyol, isocyanate and catalyst onto 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. Since the carriers are networked, is also one thermoplastic recycling not possible. The essential Disadvantage of the invention mentioned in the publications however, is the lack of suitability for wrapping tapes, as they have neither flame resistance nor sufficient tensile strength, Which in TPU from the physical networking over the hard blocks results show.

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 finding a solution for a winding tape, which has the advantages of halogen-free, flame-retardant, Heat resistance, abrasion resistance, unwindability and mechanical properties such as tensile strength and flexibility of PVC wrapping tapes with the halogen-free of textile non-flame-resistant wrap bands connects and above In addition, a superior heat aging resistance , wherein a large - scale producibility of the Film should be ensured and a high breakdown voltage necessary in some applications. Due to the absence of heavy metal stabilizers and Phthalatweichmachern the wrapping tapes are hygienic work and be ecologically beneficial. The complete or largely dispensing with plasticizers, in particular DOP, is desirable to achieve high fogging levels and the Consequences of plasticizer migration in the adhesive like telescoping or edge tackiness. The object of the invention is Furthermore, such winding tapes available which is a particularly safe and fast wrapping, in particular of wires and cables for marking, protecting, Insulate, seal or bundle, the disadvantages of the prior art do not or at least not occur in the previous extent. It then exists the Task, thermoplastically produced films with additive combinations to find out the heat resistance and flame resistance not only achieve, but even surpass PVC. in particular the simultaneous demand for unwindability (medium high Unwind force) and high back adhesion are polar Pressure-sensitive adhesives can not be fulfilled on a polyurethane film. Although natural rubber adhesives achieve this requirement, but have a low aging stability. The due to the Heat and aging stability and flame resistance predestined applications of the winding tape as a cable wrapping tape for the automotive engine room require pressure-sensitive adhesive with high Aging stability of the pressure-sensitive adhesive. Natural rubber adhesive are for wrapping tapes made of polyurethane at low Application temperatures suitable. Because of the high cost and the high performance of the backing film should However, the winding tape for thermally highly loaded applications used for example 3000 hours at 105 ° C. In this case, however, can not age-resistant adhesive For example, based on natural rubber to embrittlement lead the carrier film and the wire insulation.

Solved This task is performed by a winding tape, as in the main claim is laid down. Subject of the dependent claims are advantageous Training of the subject invention and uses of the winding tape according to the invention.

Accordingly, the invention relates to a halogen-free flame-retardant winding tape of a co-extruded at least two-layer film with a first layer of thermoplastic polyurethane, on which a second layer of polar modified polyolefin is located, preferably located on the first layer, the second layer of polar modified thermoplastic polyolefin polyolefin opposite a layer of an aging-stable polar pressure sensitive adhesive.

Of the Pressure-sensitive adhesive contains no oxidatively sensitive double bonds such as natural rubber, styrene-butadiene rubber or block copolymers of styrene with butadiene or isoprene.

In In a preferred embodiment, the PSA is composed polyacrylate or ethylene-vinyl acetate copolymer, which are preferred solvent-free as from dispersion, from the melt or by coextrusion.

For the expert surprising and unpredictable is a for the winding tape suitable carrier made of thermoplastic Polyurethane with at least one flame retardant as follows.

• (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
• (F) optional einem stickstoffhaltigen Flammschutzmittel und
• (G) optional einem phosphorhaltigen Flammschutzmittel gegebenenfalls unter Verwendung
• (D) eines Katalysators und/oder
• (H) weiteren Hilfs- und Zusatzstoffen

hergestellt, wobei auf der einen Seite eine polar modifizierte Polyolefinschicht vorzugsweise durch Coextrusion aufgebracht ist und die andere Seite mit einem alterungsstabilen polaren Haftkleber versehen wird.The polyurethane carrier is off

• (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 extender and
• (F) optionally a nitrogen-containing flame retardant and
• (G) optionally a phosphorus-containing flame retardant optionally using
• (D) a catalyst and / or
• (H) other auxiliaries and additives

prepared, on the one hand a polar modified polyolefin layer is preferably applied by coextrusion and the other side is provided with an aging-stable polar pressure-sensitive adhesive.

The Key figure (formed from the multiplied by 100 quotient of the equivalence ratios the isocyanate groups from (A) and the sum of the Zerewitinoffaktiv Hydrogen atoms of the compounds (B) and (C)) is 85 to 120, preferably 95 to 110. Will be a phosphorus-containing polyol (see below), this is the sum of the Zerewitinoff-active Add hydrogen atoms of the compounds (B) and (C).

In a preferred embodiment of the invention are the Components (B) and (C) different.

When Organic diisocyanates (A) can be aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates or Any mixtures of these diisocyanates are used.

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 diisocyanates mentioned can be used individually or in the form of mixtures with one another. They can also be used together with up to 15 mol% (calculated on total diisocyanate) of a Polyisocyanates are used. However, it may be added at most as much polyisocyanate that a still thermoplastically processable product is formed.

Examples for polyisocyanates are triphenylmethane-4,4 ', 4' '- triisocyanate and polyphenyl polymethylene 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 be prepared by: one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule, the two active Contains hydrogen atoms bound, reacted.

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-methyldiethanolamine 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-dexanediol, 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 each other are used.

The preferred diol is a hydroxylated polymerization product of tetrahydrofuran, as these are relatively stable to hydrolysis, microbial degradation and oxidation. The molecular weight M _n is in the range of 450 to 10,000 daltons, preferably in the range of 600 to 1500 daltons.

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

When Chain extenders (C) are preferably aliphatic Diols with 2 to 14 carbon atoms are used, for example 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 ether of the 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-toluylenediamine or 3,5-diethyl-2,6-toluylenediamine or primary mono-, di-, tri- or tetraalkyl-substituted 4,4'-diaminodiphenylmethanes. Particularly preferred are chain extenders Ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-di (beta-hydroxyethyl) -hydroquinone or 1,4-di (beta-hydroxyethyl) bisphenol A. It can also used mixtures of the above chain extender become. In addition, smaller amounts of triplet can be added.

The preferred chain extender is 1,4-butanediol.

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

Across from Isocyanates monofunctional compounds may be present in proportions 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 Film preferably contains a phosphorus-based flame retardant (G), preferably an organic and most preferably one Esters of phosphoric acid, a phosphonic acid or a salt of a phosphinic acid is used, wherein the Amount is preferably 5 to 40 phr. examples are Ammonium polyphosphate, ethylenediamine polyphosphate and phosphoric acid and phosphonic acid esters such as triphenyl phosphate, Tricresyl phosphate, alkyphenyl phosphates, diphenyl cresyl phosphate.

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(CH₂)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 is hydrocarbyl (dihydrocarbylphosphate) of the general formula

where R preferably represents an aryl group (for example phenyl, cresyl), A a linking group such as arylene (for example phenylene), biarylene (for example biphenyl), two arylene groups which can be replaced by another group such as -CH ₂ -, -C (CH ₃ ) ₂ ) ₂ -, -SO ₂ - 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.

Examples of phosphonic acid esters are dimethyl methylphosphonate, diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, dimethylpropane phosphonate, 3- (hydroxy-phenylphosphinyl) propanoic acid (Hi retar ^TM -205) and their derivatives. Other phosphonates are under the tradename Exolit OP ^™ . Fyrol ^™ , Levagard ^™ , Antiblaze ^™ or Vircol ^™ . There may also be several phosphonic acid groups such as diphosphonates, for example nitrilotris (methylene phosphonic acid) and its salts and amides. The phosphonic acid esters can also be polymeric, for example reaction products of methanephosphonic dichloride and bisphenol A.

Very particular preference is given to flame retardants which release neither phenol nor cresol upon hydrolysis, examples of which are trixylyl phosphate, butylated triphenyl phosphates (for example Fyrquel ^™ EHC-S), phosphoric acid 1,3-phenylentetraxylenyl ester.

The Wrap tape may be 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) or a reaction product of DOPO and another compound, in which the H of the P-H bond is substituted by an organic radical is included. The reaction may be, for example, as an addition reaction (For example, DOPO with acrylonitrile, quinone, itaconic acid or acrylic acid esters) or condensation reactions (for Example with alkylated phenolic resins or formaldehyde resins such Dimethylolbenzoguanamine).

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

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
auf.Instead of or in addition to the added phosphorus-based flame retardants, the phosphor may also be incorporated in the polyurethane. Examples of incorporable phosphorus-containing compounds are phosphonates or phosphine oxides 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 have the following structural formula

With
R ¹ , R ² branched or unbranched alkylene radicals having 1 to 24 carbon 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 Alkarylenreste having 6 to 30 carbon atoms, wherein
R ¹ and R ^{2 may be the} same or different,
R ³ H, branched or unbranched alkyl radicals having 1 to 24 C atoms,
substituted or unsubstituted aryl radicals having 6 to 20 C atoms,
substituted or unsubstituted aralkyl radicals having 6 to 30 C atoms,
substituted or unsubstituted alkaryl radicals having 6 to 30 carbon atoms,
x, y = 1 to 50
or

With
R ¹ H, branched or unbranched alkyl radicals having 1 to 24 C atoms,
substituted or unsubstituted aryl radicals having 6 to 20 C atoms,
substituted or unsubstituted aralkyl radicals having 6 to 30 C 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 C atoms,
substituted or unsubstituted aralkylene radicals having 6 to 30 C atoms,
substituted or unsubstituted alkarylene radicals having from 6 to 30 carbon atoms,
where R ² and R ^{3 may be the} same or different
on.

to Avoiding the use of cumbersome IUPAC designations Below are some substances with their CAS no. characterized.

The film according to the invention preferably contains a nitrogen-containing flame retardant (F) for Example melamine cyanurate, melamine, biuret, triuret, ammelide, ammeline, cyanuric acid, tris (2-hydroxyethyl) isocyanurate, bis (2-hydroxyethyl) isocyanurate, 2-hydroxyethyl isocyanurate, tris (carbomethyl) isocyanurate, tris (2-cyanoethyl) isocyanurate, bis (2-cyanoethyl) isocyanurate, 2-cyanoethyl isocyanurate, trimethyl isocyanurate, HA (L) S as CAS no. 40601-76-1 or 27676-62-6 or 34137-09-2 or 129757-67-1 or 191680-81-6, melam, melem, dicyandiamide, guanadine, biguanadine, triphenyl isocyanurate or tricresyl isocyanurate. Preferred nitrogen-containing flame retardant is melamine cyanurate. For thin films are nitrogen-containing flame retardants without amino groups such as tris (2-cyanoethyl) isocyanurate, triphenyl isocyanurate, tricresyl isocyanurate or CAS no. 129757-67-1 better suited. Particularly preferred is poly [2,4- (piperazin-1,4-yl) -6- (morpholin-4-yl) -1,3,5-triazine] according to CAS no. 93058-67-4 is. The amount of nitrogen-containing flame retardant is preferably between 5 and 40 phr.

Surprisingly Solid nitrogen-containing flame retardants also make hand tearability improved.

When combined phosphorus- and nitrogen-containing flame retardant (F) / (G) Connections that contain both elements, such as Example melamine phosphate, melamine polyphosphate, urea phosphate, Triethanolamine phosphate or phosphoroxytriamide.

The according to the invention related thermoplastic polyurethanes can as adjuvants and additives (H) up to preferably a maximum of 20 wt .-%, based on the total amount of TPU, the usual Auxiliaries and additives. Typical auxiliaries and additives are nucleating agents, lubricants such as fatty acid esters, 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 acting substances and fillers and mixtures thereof and reinforcing agents such as fibrous materials. The Additives are halogen, nitrogen and phosphorus free Flammschutzmittel attributed, examples of which are aluminum hydroxide, Magnesium hydroxide, expandable or exfoliated graphite. Farther may be multifunctional alcohols such as pentaerythritol, dipentaerythritol and cellulose further improve the flame resistance.

The Carrier film according to the invention is preferably essentially free of volatile plasticizers such as Example DOP or DINP and therefore has an excellent fire behavior and low emission (plasticizer evaporation, fogging). The fogging value is preferably over 90%.

The Contains film used in the invention preferably at least 1 phr and in particular at least 2 phr Stabilizers against oxidation and / or hydrolysis (the information in phr mean parts by weight of the relevant component based on 100 parts by weight of all polymer components of the film). Examples Antioxidants are phenolic or aminic Base and secondary antioxidants based on sulfur or phosphorus. The wrapping tapes according to the invention contain preferably a combination of primary and secondary Antioxidant, with the primary and secondary antioxidant function exist in different molecules or in a molecule can be united. In 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, especially at least 1 phr.

stabilizers for PVC products can not be transferred to TPU. Secondary antioxidants break down peroxides and therefore become in diene elastomers as part of. Used aging protection packages. Surprised was found to be a combination of primary antioxidants (For example, hindered phenols or C radical scavengers like CAS 181314-48-7) and secondary antioxidants (for For example, sulfur compounds, phosphites or sterically hindered Amines), where the two functions are also in one molecule can be united, the task even with dienstfreien TPU solves. 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 Phosphitic secondary antioxidant (preferably with a molecular weight> 600 g / mol) is preferred. Combinations of primary and secondary Anti-aging agents have not been used in wrapping foils made of TPU used.

In particular, the combination of a low-volatile primary phenolic antioxidant and a secondary antioxidant from the class of sulfur compounds (preferably having a molecular weight of more than 400 g / mol, in particular> 500 g / mol) and from the class of phosphites is suitable, wherein the phenolic, sulfur and phosphite functions need not be in three different molecules, but more than one function may be combined in a molecule.

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 sulphurous 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. Prefers is further a combination in which the proportion of secondary Antioxidant exceeds that of the primary. Zusätzich can still metal deactivators for the complexation of Heavy metal traces that catalytically accelerate aging can be added. 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 winding 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 calender processing, at the on the rollers a relatively long lasting access of atmospheric oxygen unavoidable, is the concomitant use of phosphite stabilizers as particularly suitable for a sufficient heat aging stability of the product. Even in extrusion processing is going on the addition of phosphites in the aging test of Product still positively noticeable. For the phosphite stabilizer is an amount of at least 0.1, preferably at least 0.3 phr preferred.

As hydrolysis protective agents it is possible, for example, to use monomeric or polymeric carbodiimides, oxazolines or reactive polyureas. 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 phr to 3 phr.

Further Additives that 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 non-fusible polymers such as EVA dispersion powder or impact modifier (for example acrylate elastomer particles with a shell of PAN or PMMA) can be used become. Preferably, no hydrolysis-sensitive polymers Additions with ester or amide groups in the polymer backbone mitverwandt.

suitable Inventive catalysts (D) are according to the prior art known and customary tertiary Amines such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo [2,2,2] octane and similar 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 Zinndialkylsalze aliphatic carboxylic acids such as 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 generally 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 be carried out either stepwise (prepolymer dosing method, reaction of components (A) and (B) and then with (C) or by the simultaneous reaction of all components (A), (B) and (C) in one step (one- Preferably, the prepolymer method is used.

The Addition of the flame retardants (F) and / or (G) and / or the excipients (H) may be before, during or after the polyurethane reaction respectively.

The Polyurethane layer is on the pressure-sensitive adhesive facing away by covered a polar modified polyolefin layer. coextruded Allow foils of polyurethane and polyethylene or polypropylene easily separate into two films from the respective layers. The polar modification of the article of the invention the aim is sufficient adhesion between polyurethane and polyolefin.

The polar modified polyolefin layer can with another polyolefin layer such as polyethylene or polypropylene (including and terpolymers) to the outside. The amount all polyolefin layers including the polar modified Polyolefin layers should not exceed 20%, preferably at most 10%, in particular not exceed 5% of the total film thickness, otherwise the flame resistance of the winding band suffers.

The Polyolefin layer (s) may contain additives such as pigments, fillers, Flame retardants, processing aids, polymers, etc. included.

Polar modified polyolefin is understood as meaning polymers of olefin monomers and polar comonomers. These are preferably copolymers or terpolymers of ethylene, propylene, 1-butene with polar monomers such as acrylic acid, methacrylic acid, itaconic acid and salts thereof and vinyl esters such as vinyl acetate or butyrate, acrylic and methacrylic esters such as methyl methacrylate, ethyl acrylate or butyl acrylate. Particular preference is given to copolymers or terpolymers of ethylene with (meth) acrylic acid or salts thereof, (meth) acrylic esters or vinyl acetate having a comonomer content of preferably at least 5% by weight, particularly preferably at least 10% by weight. If no (meth) acrylic acid or its salt is present but only (meth) acrylic esters or vinyl acetate, the comonomer content is preferably at least 15% by weight, particularly preferably at least 25% by weight. The comonomers may be random or built in blocks or grafted. For example, acrylic acid or maleic anhydride can be grafted onto polyethylene in the presence of peroxides by reactive extrusion. The person skilled in the art is not surprised that the polar modification brings about an improvement in the adhesion between the polyurethane and polyolefin layers. The adhesion between the polyolefin layer and polar pressure-sensitive adhesive, for example in terms of adhesion on the back or unwind force, surprisingly does not increase or only slightly increases with the polar modification of the polyolefin layer. Therefore, in practice, it is even appropriate to increase the polyolefin layer by physical processes such as corona treatment in surface tension, so that the adhesion on the back is high enough to avoid flagging. The dose of corona discharge is preferably 5 to 80 Wmin / m ² and more preferably 10 to 30 Wmin / m ² and the surface tension of the back of the winding tape is preferably 30 to 55 mN / m, more preferably 32 to 45 mN / m. However, the comonomer content should not be too high, because then the adhesion between the polyolefin layer and polar pressure sensitive adhesive may become too high. The comonomer content is therefore at most 60 wt .-%, preferably at most 45 wt .-% and particularly preferably at most 35 wt .-%.

The The present invention mainly has the absence of halogens with high flame resistance, tear resistance and flexibility to the goal. As stated, rise the thermal requirements of the application, so in addition an increased resistance to conventional PVC winding tapes or in development present PVC-free polyolefin-based film winding tapes should be achieved. Therefore, the properties of the present Invention in this regard in detail below described.

The product according to the invention is halogen-free in the sense that the halogen content of the raw materials is so low that it plays no role in the flame retardance. Traces of trace halogens, such as impurities, process additives (fluoroelastomer), or catalyst residues, stay 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, with the preferred embodiments of the winding tape in fire tests according to FMVSS 302 (horizontal sample) and / or ASTM D 568 (vertical sample) mentioned test conditions extinguish by itself.

The Thickness of the film according to the invention is preferably in the range of 30 to 180 μm, preferably 50 to 150 μm, in particular 55 to 100 microns. Thus, a sufficient Slip flexibility, good hand tearability and achievable costs.

The winding tape according to the invention has a corresponding Thickness increased by the thickness of any existing Pressure-sensitive adhesive coating on. The surface can be structured or be 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 roll during extrusion) be achieved.

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

The winding tape according to the invention has 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% force is a measure of the stiffness of the Foil, and the 50% power is a measure of conformability when winding with strong deformation due to high winding tension. The 50% power must not be too low, because otherwise usually the tear strength is too low.

The Tensile strength (breaking strength) of the carrier film is included at least 10 N / cm, preferably at least 20 N / cm.

There TPUs can be very tough, if necessary Measures to improve hand tearability the winding band required such as blending with fillers, incompatible thermoplastic or non-meltable Polymers, by rough-cut side edges, at microscopic Consider forming cracks in the foil, which then appears to be a Favor further tearing, or by with subsequently For example, provided by punching notches provided Side edges. Rough cutting edges can in particular by the application of a squeezing with blunt or defined jagged rotating knives on bales (jumbos, rolls in large Length) or by a cut-off with fixed Blades or rotating knives of rod products (rolls in production width and customary length). The Elongation at break can be determined by a suitable cut of the blades and Be adjusted. The embodiment is preferred the production of bar products with cut-off with blunt fixed Sound. By strongly cooling the rods before cutting the cracking during the cutting process can be improved.

requirements for a sufficient heat resistance and short term heat resistance are a sufficient crystallite melting point of the TPU (preferably at least 158 ° C and more preferably at least 170 ° C) and resistance to aging by degradation by antioxidants and / or hydrolysis protectants can be ensured.

The winding tape according to the invention has a high temperature resistance in, in preferred embodiments, an elongation at break of at least 100% after 3000 hours of storage at 105 ° C, respectively 312 hours storage at 140 ° C (heat resistance test) and a short term heat resistance of 170 ° C (no cracks or fused spots after 30 minutes).

To achieve these strength values as well as the heat resistance, the film of the winding tape contains a TPU with a sufficiently high proportion of hard block, which is why the Shore D hardness of the TPU raw material is preferably at least 35 and more preferably at least 50, which corresponds approximately to Shore A hardnesses of preferably at least 85 or more preferably at least 100. The flame-resistant adhesive tapes shown in the prior art use significantly softer TPU (Shore A 70 to 80) than the flame-resistant adhesive tapes sought here. If plasticizers or phosphoric acid esters are added to the adhesive tapes of such soft TPU as flame retardants, then these are much more inappropriate than the winding tapes according to the invention.

The Production of the film is carried out by extrusion such as in Blowing or casting process. With the concomitant use of solid or liquid Additives for the TPU will be a compound of the main components or all components in a compounder like Kneader (for example Die kneader) or extruder (for example twin-screw extruder, Planetary roller extruder) and then into a solid form (for example Granules), which are then processed in a further become.

The Polyurethane film is preferably made with a non-aging polar 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 age-resistant polar Adhesive in question. Such pressure-sensitive adhesives can be, for example Homopolymers or copolymers of isobutylene, of 1-butene, of vinyl acetate, of ethylene, of acrylic acid esters or of methacrylic acid esters be. Particularly suitable are pressure-sensitive adhesives based on acrylic acid esters or vinyl acetate.

To optimize the properties, the self-adhesive composition used can be mixed with one or more additives, such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, aging inhibitors, 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, hydrogenated aromatic resins, hydrogenated Polycyclopentadienharze, hydrogenated rosin derivatives or hydrogenated terpene resins used.

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, di- or poly-esters of phthalic acid, trimellitic acid or adipic acid, liquid polymers of butene, isobutene, acrylic esters and / or polyvinyl ethers, liquid and soft resins based on the raw materials of adhesive resins or wool wax. Crosslinking agents are, for example, isocyanates, 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 include, for example, 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 tendency to deformation of the rollers during storage (Telescoping or formation of voids, also called gaps) reduced. The squeezing of the PSA is also reduced. This Expresses itself in tack-free side edges of the rollers and tack-free Edges of in a spiral movement around cables respectively a harness guided winding tape. The holding Power is preferably above 150 min.

The Adhesion to steel should be in the range of 1.5 to 3 N / cm and on Back in the range of 0.5 to 3 N / cm are.

The The winding tape according to the invention preferably has one Unwind force of 1.2 to 6.0 N / cm, most preferably of 1.6 to 4.0 N / cm and especially 1.8 to 2.5 N / cm at 300 mm / min unwinding speed on. Unwind force and adhesion on the back are for the applications of great importance.

In summary For example, the preferred embodiment is solvent-free on one side Aging stable polar pressure-sensitive adhesive layer, which by coextrusion, Melt or dispersion coating has come about. Especially are adhesives based on ethylene-vinyl acetate and in particular Polyacrylate 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 film back during unwinding the Roll.

For the application of age-resistant polar pressure sensitive adhesives to a (Polar) polyurethane layer is a primer due to the good adhesion usually dispensable. As primers, the known dispersion and solvent systems. Isocyanates or epoxy resins as additives improve the adhesion and increase in part also the shear strength of the pressure-sensitive adhesive. Physical surface treatments like flames, corona or plasma or coextrusion layers also suitable for improving adhesion.

to easy unwinding needs no release agent on the back be applied because the adhesion of the polar pressure sensitive adhesive on the Polyolefin outer layer is high enough, flagging to avoid, but nevertheless ensures easy rolling. In exceptional cases, the back by known release agents (optionally blended with other polymers) modified. Examples are stearyl compounds (for example polyvinyl stearyl carbamate, Stearyl compounds of transition metals such as Cr or Zr), Polyethyleneimine 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 alkyls or alkenyls with a C-number of at least 10 such as Octadecyl. If the adhesive force on the back or the Unwind force can be raised, the polyolefinic back be treated with physical methods, preferably the Foil back treated with a weak corona discharge.

The Rod goods can increase the unwind force or relaxation the tensions of the films before cutting a heat storage be subjected. The cutting of winding tapes with Tissue, non-woven and film carrier (for example PVC) takes place by cutting paper (between two rotating knives), cut-off (fixed or rotating knives become rotating Rod of the product pressed), 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. The flexibility is of outstanding Meaning, as when using on wires and cables not just wrapped in a spiraling motion, but at branching points, plugs or fixing clips also wrinkle-free bend flexible must be wound. In addition, it is desired that the winding band elastic the cable harness contracts. The winding tape according to the invention is also suitable for other applications such as for the sealing of ventilation pipes in the Klimabau, since the high Flexibility a good conformability to rivets, beads and folding secures. These mechanical properties can can only be achieved by a soft flexible wrapping tape. The Task, the necessary flexibility through avoidance the addition of larger amounts of flame retardants to achieve, is achieved according to the invention.

The today's occupational hygiene and environmental requirements will be taken into account by focusing on the use of halogenated raw materials is waived. The halogen-free is for the thermal Recycling of waste, such winding tapes contain, of extraordinary importance (for example Waste incineration of the plastic fraction from vehicle recycling) but also in cable or building fires, as no toxic fumes arise.

In the course of increasingly complicated electronics and the increasing number of electrical consumers in automobiles, the wiring harnesses are becoming ever more complex. With increasing cross sections of the harnesses, the inductive heating is getting larger, while the heat dissipation decreases. This increases the requirements for the heat resistance of the materials used. The standard ver used PVC materials for the tapes tap their limits here. This problem can now be considered solved.

Test Methods

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

The crystallite melting point (T _cr ) is _detected by DSC ISO 3146 determined. 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 will decrease ISO 868 determined.

The surface tension of the back of the winding tape is after DIN ISO 8296 measured.

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

The bond strengths are reduced by a deduction angle of 180 ° AFERA 4001 on (if possible) 15 mm wide test strips determined. In this case, steel plates according to the AFERA standard are used as the test substrate unless another primer is mentioned.

The thickness of the film will be after DIN 53370 determined (the pressure-sensitive adhesive layer of the finished winding tape is deducted 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 of the bond area 20 mm in height and 13 mm in width.

The unwinding force is at 300 mm / min after DIN EN 1944 measured.

The fire behavior is according to FMVSS 302 (horizontal sample) respectively ASTM D 568 (vertical sample) measured. For FMVSS 302, the pressure-sensitive adhesive coating is up. These methods also allow determination of the burning rate of flammable samples. It is only judged whether the sample burns (not passed) until the second mark (end mark) is reached, or passes by itself before it (passed). The MVSS 302 (Engine Vecile Safety Standard, US) has also been further developed into an ISO standard ( ISO 3795 ).

to Testing the temperature resistance of the winding band is glued to a siliconized polyester film and 3000 hours stored at 105 ° C in a convection oven, then withdrawn and the elongation at break determined.

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

Explanation of the examples used PU raw materials

• Terathane ^™ 1000: polyethers having a molecular weight of M _n = 1000 daltons (DuPont) Terathane ^™ 650: polyethers having a molecular weight of M _n = 650 daltons (DuPont)
• MDI: 4,4'-diphenylmethane diisocyanate
• BDO: 1,4-butanediol
• Exolit ^TM OP 560: flame retardant based on diol phosphonate with Zerewitinoff-active hydrogen atoms (Clariant)
• Lucalen ^™ A2910M: polyethylene with 4% by weight of acrylic acid and 7% by weight of tert-butyl acrylate (Basell)
• Escorene ^TM Ultra UL 00728: EVA with 28% by weight vinyl acetate (Exxonmobil)
• LL 1002YB: LLDPE from ethylene and butene (Exxonmobil)
• Novex ^TM M21G764: polyethylene ionomer with zinc cations (BP)
• Levapren ^TM 600 HV: EVA with 60% by weight vinyl acetate (Lanxess)
• NORD-MIN ^TM MC-25J: melamine cyanurate (Nordmann-Rassmann)
• Fyrolflex ^™ RDP: resorcinol phosphate oligomer (Akzonobel) of the formula
  
• Melamine polyphosphate: (Dayang Chemicals)
• Irganox ^™ 1010: Tetrakis (methylene (3,5-di-tert-butyl-4-hydroxycinnamate)) methane (Ciba Specialty Chemicals)
• Licowax ^TM C: release agent (Clariant Würtz GmbH)

example 1

A mixture of 1045 kg of Terathane ^™ 1000, 6.3 kg of Irganox ^™ 1010, 1000 kg of NORD-MIN ^™ MC-25J and 10 kg of Licowax ^™ C was heated to 160 ° C. while stirring with a paddle stirrer at a speed of 500 rpm, then 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 dried.

A film was produced therefrom on a flat film coextrusion line. The polyurethane layer has a thickness of 90 microns. The coextrusion layer is 10 μm thick and consists of Lucalen ^™ A2910M. The film was stored for one week, leveled on the coater with rollers at 60 ° C to improve the flatness and on the polyurethane side with a dispersion of acrylic adhesive (Primal PS 83 D from Rohm and Haas and addition of 5 wt .-% hostasin black [color preparation] of Clariant) by means of a wire doctor 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 1a

The procedure was as in Example 1, wherein the polyolefin layer was provided with a corona treatment with a power of 12 Wmin / m ² .

Example 2

Analogously to Example 1, a prepolymer was prepared from MDI and Terathane ^™ 1000 in the molar ratio 2.5: 1 in the presence of Irganox ^™ 1010, NORD-MIN ^™ MC-25J and Fyrolflex ^™ RDP and reacted with 95 mol% of the equivalent amount of BDO. The contents of the additives are 0.3 phr Irganox ^™ 1010 (based on 100 phr TPU polymer), 23 phr NORD-MIN ^™ MC-25J and 4 phr Fyrolflex ^™ RDP.

The finished TPU was cut, granulated, dried and processed black with the addition of 5 wt .-% masterbatch to a 100 micron thick blown film. The thickness of the polyurethane layer is 95 microns and that of the coextrusion of Escorene ^TM Ultra UL 00728 5 microns.

The carrier film was after 10 days of storage on the polyolefin layer with a corona treatment with a power of 18 Wmin / m ² . and then on the polyurethane side with Acronal DS 3458 coated by 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

Analogously to Example 1, a prepolymer was prepared from MDI and Terathane ^™ 650 in a molar ratio of 2.2: 1 in the presence of Irganox ^™ 1010 and melamine polyphosphate (Dayang Chemicals) and reacted with 95 mol% of the equivalent amount of BDO. The contents of the additives are 0.3 phr of Irganox ^™ 1010 and 27 phr of melamine polyphosphate (based on 100 phr of TPU polymer).

• – 20 µm Levapren^TM 600 HV
• – 95 µm obiges Polyurethan
• – 5 µm Novex^TM M21G764

The finished TPU was cut, granulated, dried and with the addition of 5% by weight of a black batch and 5% by weight of a hydrolysis protective masterbatch (KE 9463 from Rhein-Chemie = 20% by weight Stabaxol ^™ P200 in TPU) in the casting Process (flat die with chill roll) formed into a wrapping film. The layer sequence (calculated from Chillroll) is as follows:

• - 20 μm Levapren ^TM 600 HV
• - 95 microns above polyurethane
• - 5 μm Novex ^TM M21G764

The Pressure-sensitive adhesive film was wound into rods roll and 19 mm wide cut.

Comparative Example 1

The procedure was as in Example 1 but without the layer of Lucalen ^TM A2910M.

Comparative Example 2

The procedure was as in Comparative Example 1 but without Irganox 1010 in the film and a modified coating. The film was coated with a primer of 5 parts of MDI, 45 parts of 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 of natural rubber, 10 parts of zinc oxide, 3 parts of rosin, 6 parts of alkylphenol resin, 17 parts of terpene phenolic resin, 12 parts of poly-β-pinene resin and 2 parts of mineral oil. The drying of the coat was carried out in a drying tunnel at 100 ° C. The finishing took place analogously to Example 1.

Comparative Example 3

The procedure was as in Comparative Example 1 but with LL 1002YB instead of Lucalen ^TM A2910M.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Cited non-patent literature

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• - ISO 3795 [0130]
• DS 3458 [0138]

Claims (14)

Halogen-free flame-retardant winding tape from a at least two-layer coextruded film with a first Layer of thermoplastic polyurethane, on which a second Layer of polar modified polyolefin is, preferably on the first layer, the second layer of polar modified Polyolefin of thermoplastic polyurethane opposite a layer of an aging-stable polar pressure sensitive adhesive is located. Winding belt according to claim 1, characterized that the polar modified polyolefin of olefin monomers and polar Comonomers, with copolymers or terpolymers of ethylene, Propylene, 1-butene with polar monomers such as acrylic acid, Methacrylic acid, itaconic acid and salts thereof as well Vinyl esters such as vinyl acetate or butyrate, acrylic and methacrylic esters such as methyl methacrylate, ethyl acrylate or butyl acrylate and especially copolymers or terpolymers of ethylene with (meth) acrylic acid or their salts, (meth) acrylic esters or vinyl acetate to be favoured. Winding tape according to claim 2, characterized the comonomer content is 5 to 60% by weight, preferably 10 to 35 Wt .-% is. Winding tape according to at least one of claims 1 to 3, characterized in that the open back of the second layer of polar modified polyolefin treated with a corona discharge preferably at a dose of 5 to 80 Wmin / m ² and particularly preferably from 10 to 30 Wmin / m ² becomes, so that the surface tension of the back of the winding tape is preferably 30 to 55 mN / m, more preferably 32 to 45 mN / m. Wrap band according to at least one of the preceding Claims, characterized in that the polar pressure-sensitive adhesive a polyacrylate or an ethylene-vinyl acetate copolymer. Wrap band according to at least one of the preceding Claims, characterized in that the polar pressure-sensitive adhesive as a hotmelt PSA, as a dispersion or by coextrusion the first layer of thermoplastic polyurethane applied becomes. Wrapping tape according to at least one of the preceding claims, characterized in that the adhesive is applied in an amount of 10 to 40 g / m ² , preferably 18 to 28 g / m ² . Wrap band according to at least one of the preceding Claims, characterized in that the winding band a phosphorus-based flame retardant, preferably an organic one and particularly preferably an ester of phosphoric acid, a phosphonic acid or a salt of a phosphinic acid contains, wherein the amount is preferably 5 to 40 phr. Wrap band according to at least one of the preceding Claims, characterized in that the winding band a nitrogen-based flame retardant, preferably melamine cyanurate or an amino group-free flame retardant such as poly- [2,4- (piperazin-1,4-yl) -6- (morpholin-4-yl) -1,3,5-triazine], contains, wherein the amount is preferably 5 to 40 phr. Wrap band according to at least one of the preceding Claims, characterized in that the winding band under the test conditions specified in FMVSS 302 or ASTM D 568 self-extinguishing. Wrap band according to at least one of the preceding Claims, characterized in that the elongation at break of the wrapping tape after 3000 hours of storage at 105 ° C at least 100%, the bond strength of the wrapping tape on steel 1.5 to 3 N / cm and on the back in 0.5 to 3 N / cm, the unwind force of the winding band 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 of the winding tape is more than 150 min. Wrapping tape according to at least one of the preceding claims, characterized in that the isocyanate (A) 4,4'-diphenylmethane diisocyanate, the polyol (B) is a hydroxyl-containing polymerization of tetrahydrofuran and / or the chain extender (C) is 1,4-butanediol. Wrap band according to at least one of the preceding Claims, characterized in that the film at least 1 phr, preferably at least 2 phr stabilizers against oxidation and / or hydrolysis. Use of a winding band after at least one of the preceding claims for bundling, shooting, Marking, insulating or sealing ventilation pipes, Wires or cables or for sheathing cable harnesses in vehicles or field coils for picture tubes.