JP2009519366A - Winding tape made of thermoplastic polyurethane (TPU) film - Google Patents

Abstract

【Task】
Combines the advantages of being halogen-free, flame retardant, heat resistant, and abrasion resistant with the mechanical properties of fiber-free non-flame retardant wound tape, halogen-free tensile strength and flexibility, and further Provision of a wound tape having excellent thermal aging resistance.
[Solution]
The problem is that, in a halogen-free flame retardant wound tape capable of high heat load, the film made of thermoplastic polyurethane is at least one flame retardant and at least one antioxidant and / or hydrolysis inhibitor as a stabilizer. It is solved by the above-mentioned winding tape characterized by containing an agent.

Description

  The present invention is a halogen-free, flame-retardant, preferably colored tape, more preferably having an adhesive coating and used for wrapping around air-conditioning ventilation tubes, wires or cables and for automobiles. It relates to said winding tape which is particularly suitable for field coils for cable looms and picture tubes. At this time, the wound tape serves for bundling, insulation, identification or protection.

  Cable winding tapes and insulating tapes are generally made of a plasticized PVC film having an adhesive coating on one side. It is increasingly desirable to eliminate the disadvantages of this product, such as evaporative release of plasticizers and high halogen content.

  The plasticizers of conventional insulating tapes and cable wrapping tapes gradually evaporate, which poses a health hazard, and the commonly used DOP is particularly undesirable. In addition, this vapor is deposited on the window glass in automobiles and degrades visibility (and hence considerably driving safety). This is referred to by those skilled in the art as clouding (fogging: DIN 75201). In the case of further evaporation due to high temperatures, for example high temperatures in the engine compartment of motor vehicles or in the case of insulating tapes in electrical systems, the wound tapes become brittle due to plasticizer loss and PVC-polymer degradation.

  Background of the controversy over the incineration of synthetic resin waste, such as crushed waste from the automobile regeneration stage, there is a trend to reduce the halogen content, i.e. reduce the generation of dioxins. Therefore, the thickness in the case of cable insulation and the thickness of the tape of the PVC film used for winding are reduced. The normal thickness of the PVC film for the wound tape is 85-150 μm. Below 85 μm, the calender method causes serious problems and as a result, such products with reduced PVC content can never be produced.

  Conventional wrapping tapes contain stabilizers based on harmful heavy metals such as lead, cadmium or barium.

  The prior art developed to bind a set of conductors includes a wound tape made of PVC support material with or without an adhesive coating, the PVC support material comprising a significant amount (30-40% by weight). ) To make it flexible. This support material is generally coated on one side with an adhesive based on SBR-rubber. JP-A-10-001,583A1, JP-A-5-250,947A1, JP-A-2000-198,895A1 and JP-A-200,515A1 disclose typical softness. A PVC adhesive tape is disclosed. In order to achieve the high flame resistance of the soft PVC material, for example, as described in JP-A-10-001,583A1, antimony oxide, which is a highly toxic compound, is generally used.

  Attempts have also been made to use woven or fleece instead of soft PVC film. However, the products obtained from these are relatively expensive and easy to handle (eg hand tearability, elastic restoring force) and wet (eg wet or durable to mechanical fluids) ) Is significantly different depending on the product obtained, and the thickness becomes particularly important as explained below, so it cannot be used in practice. This type of thick fleece is still thicker and less flexible than conventional PVC tape, even though it has a positive effect on sound insulation. However, the soundproofing effect is only advantageous in some areas of the cable room. However, the fleece cannot be stretched much and is virtually non-resilient. These properties are important because the narrow branch of the cable room must be wrapped tight enough so that it does not hang loose when assembled and can be easily positioned before the plug is clipped and attached. . Another disadvantage of fiber adhesive tape is that it has only a breakdown voltage of about 1 kV because only the adhesive layer is insulating. On the other hand, the film tape is located above 5 kV and has good voltage stability. Fiber wound tapes are not very flame retardant or contain halogen compounds (generally bromine compounds) as flame retardants. Examples are German Utility Model Registration No. 20,022,272U1, European Patent Application Publication No. 1,123,958A1, International Patent Application Publication No. 99 / 61,541A1 and US Pat. No. 992,331A1 can be known.

  Winding tapes and cable insulation made of thermoplastic polyester have been used experimentally to produce cable rooms. They have significant drawbacks in their flame retardancy, flexibility, processability, anti-aging properties, and compatibility with cable materials. However, the most serious drawback of polyester is that it is very sensitive to hydrolysis and as a result cannot be used in automobiles for safety reasons. Polyester-based wound tapes are not flame retardant or contain halogen compounds as flame retardants. Examples are German Patent Application No. 10,002,180A1, Japanese Patent Application Laid-Open No. 10-149,725, Japanese Patent Application Laid-Open No. 09-208,906A1, Japanese Patent Application Laid-Open No. 05-017,727A1, and Japanese Patent Application Laid-Open No. 07. -150, 126A1.

  These patent documents disclose winding tapes made of polyolefin. However, they can easily burn or contain halogen-containing flame retardants. In addition, materials made from ethylene copolymers have softening points that are too low (generally already melted in experiments testing heat aging stability), and when using conventional polypropylene polymers, this material is Usually not too flexible. In some cases, metal hydroxides are used, but the amount used of 40-100 phr is too low to be sufficiently flame retardant, i.e. not only self-extinguishing but also relatively high Indicates the burning rate (for example, 100 mm / min or more according to MVSS 302). Films containing more than 100 phr flame retardant are technically virtually unmanufacturable. Another factor is that such films have low tensile strength and are very stiff. That is, there is no substantial workability of a general PVC-based winding tape.

  WO 00/71634 A1 discloses a wound adhesive tape in which the base material of the film is an ethylene copolymer. This support film contains the halogen-containing flame retardant decabromo-diphenyl oxide. The film softens at temperatures below 95 ° C, but normal use temperatures are often above 100 ° C or even above 130 ° C in the short time. This is not uncommon when used in an internal combustion engine room.

  WO 97 / 05206A1 discloses a halogen-free wrapping adhesive tape in which the support film consists of a polymer blend of low density polyethylene and ethylene / vinyl acetate copolymer or ethylene / acrylate copolymer. . As the flame retardant, 40 to 90 phr of aluminum hydroxide or ammonium polyphosphate is used. A significant disadvantage of this support film is again that the softening temperature is low. To counter this, the use of silane crosslinking is described. However, this cross-linking method results only in a very non-uniform cross-linked material, and as a result, a stable manufacturing method or uniform product quality is not realized in the field.

  In the case of the electrical adhesive tapes described in WO 99 / 35,202 A1 and US Pat. No. 5,498,476 A1, similar problems of defective thermal shape stability are encountered. appear. A blend of EPDM and EVA as a support film material is described in combination with ethylenediamine phosphate as a flame retardant. This has high hydrolysis sensitivity like ammonium polyphosphate. Furthermore, it shows brittleness when aging in combination with EVA. When used in a conventional cable made of polyolefin and aluminum hydroxide or magnesium hydroxide, the compatibility is poor. Furthermore, since these metal hydroxides act as opposed to phosphorus compounds as will be described later, the combustion behavior of such cable rooms is poor. The described insulating tape is too thick and too stiff for cable room winding tape.

  Attempts to solve the dilemma that comes from the requirement of softening temperature, flexibility, flame retardancy and halogen freeness that are too low are described in the following patent documents.

  European Patent Application 0,953,599 A1 claims the use of a polymer mixture of LLDPE and EVA as cable insulation and as film material. As a flame retardant, a combination of magnesium hydroxide and red phosphorus having a special surface is described. However, this combination is accompanied by a relatively low temperature softening. The amount of magnesium hydroxide is 63 phr. In this way, red phosphorus is used because of its unsatisfactory combustion characteristics despite the high filler content.

  A very similar combination is described in EP 1,097,976 A1. Here, PP polymer having a relatively high softening temperature is used instead of LLDPE to improve thermal shape stability. However, the small flexibility obtained from this is a drawback. It is maintained that the film has sufficient flexibility to blend with EVA or EEA. However, from this document the person skilled in the art knows to blend these polymers with polypropylene in order to improve the flame retardancy. The above product has a film thickness of 0.2 mm, but in the case of a filler-containing polyolefin film, this thickness is not flexible. This is because the flexibility depends on the cube of the thickness. The described extrusion method is virtually impossible to carry out in the production line and is thin enough to fit the industry, as known to those skilled in the art, when the polyolefin used has a very low melt index. It is not possible to carry out the film. The very low melt index limits the amount of magnesium hydroxide used to 50-100 phr.

  Both solutions are based on the known synergistic flame retardant effect of red phosphorus and magnesium hydroxide. However, the use of elemental phosphorus poses significant drawbacks and dangers. During processing, a highly toxic phosphine with a strong self-extinguishing odor is generated. The finished wound tape also generates a garlic-like odor in a hot and humid application atmosphere. Another drawback is the generation of very dark white smoke in the event of a fire. Furthermore, only brown to black products can be produced. However, wound tape is used in a wide range of colors for color marking.

  JP 2001-049,208 A1 discloses an adhesive tape in which both layers are made of a mixture of EVA or EEA, a peroxide crosslinking agent, a silane crosslinking agent, a silane condensation catalyst and a flame retardant (100 phr magnesium hydroxide). An oil-resistant and heat-resistant film is disclosed. This film does not solve the problem that the polypropylene film containing a filler is poor in flexibility but also a high demand for anti-aging properties.

  WO 03 / 070,848 A1 describes a film made of reactive polypropylene and 40 phr magnesium hydroxide. The amount of this additive is not sufficient to essentially improve the combustion behavior.

  The above-mentioned patent documents of the prior art are deficient in the above-mentioned drawbacks, in particular flame retardancy, flexibility, tensile strength and / or heat resistance, so other requirements such as hand tearability, polyolefin cable insulation. It does not provide a film that eliminates compatibility with the material or sufficient unwinding power. In addition, problems remain in processing quality in the film manufacturing process, relatively high fogging value and breakdown voltage resistance. These major problems of the known invention based on flame retardant support films consisting of polyolefins and metal hydroxides are that they do not combine mechanical requirements with flame retardant requirements. With less than 60% by weight of flame retardant (metal hydroxide and possibly other flame retardant additives), self-extinguishing properties cannot be achieved, and from the 40% by weight level of flame retardant, flexibility and tear strength Is unacceptably low. The combination of polyolefin and metal hydroxide certainly delays the progress of combustion due to the mechanism of action (endothermic decomposition of metal hydroxide and cooling due to the generation of water vapor) but does not lead to self-extinguishing. This combination also has the disadvantage that when it is stretched in the winding process, in some cases it also turns white when the adhesive tape is unwound. These tapes are generally black and have a black-gray-spotted surface when fully wound. When the proportion of the filler is increased, the tensile strength can be reduced to such an extent that the tape is torn when unwinding.

  Also known are polyurethane (PU) adhesive tapes, some of which are flame retardant processed. In most cases, these are adhesive-processed PU foams and the film-based adhesive tapes described below.

  Japanese Patent Application Publication No. 2001-020,178A1 discloses a double-sided electromagnetic shielding tape comprising a polyester fabric and a halogen-containing PU-layer.

  Japanese Patent Application Laid-Open No. 2001-288,430A1 describes a flame retardant adhesive tape in which a support is produced from a polyurethane resin solution and dicyandiamide. The use of films cast from solution is not only uneconomical, but also meets the environmental protection objectives of the tapes of the present invention comprising films produced in a solvent free state by thermoplastic processing. Not. Attempts to incorporate dicyandiamide into thermoplastic polyurethane (TPU) have not been successful because TPU decomposes during compounding.

  JP 2003-013,026 A1 and JP 2004-115,608 A1 disclose (masking) adhesive tapes used with radioactive materials, in which the support is likewise produced from a solution. The support comprises a polyurethane resin solution and hydrazodicarbonamide. Hydrazodicarbonamide acts as a blowing agent by decomposing during thermoplastic processing and is not suitable for TPUs with high melting hard block portions (ie, relatively high processing temperatures).

  Japanese Unexamined Patent Publication No. 62-069,640A1 discloses a transparent adhesive tape for manufacturing a wafer chip. The PU support, which may optionally contain a flame retardant, for example 4,4'-dichloromethane diisocyanate, is produced from the solution.

  German Utility Model Registration No. 20,306,801 U1 discloses an adhesive tape made of a polyurethane film without describing a special composition of polyurethane. Adhesive tapes made of polyurethane film have been known in practice for several years. This document describes that the film may also contain additives and mentions UV and ozone stabilizers, fillers or flame retardants. Antioxidants or hydrolysis inhibitors are not described. Examples of flame retardants include ammonium polyphosphate, antimony trioxide and aluminum trihydrate (ATH), but are not specifically illustrated by the examples. Experiments have shown that ammonium polyphosphate (APP) degrades during the thermoplastic processing of polyurethanes, since this is because the APP is hygroscopic and therefore can cause hydrolysis. Not surprising to me. In addition, the acidity of APP additionally catalyzes hydrolysis. APP also acts as a strong ionogenic salt with poor electrical properties. This can be seen, for example, by using it in other materials for wire insulation elements. However, the wound tape of the present invention should also have good insulation. Furthermore, as those skilled in the art know, antimony trioxide only works in combination with halogens, and therefore has no meaning in the TPU alone. Those skilled in the art know that ATH is suitable only for PE and EVA as a flame retardant because it has a low decomposition temperature, but is not suitable for polypropylene and is therefore relatively high. It is certainly not suitable for high melting point TPUs with processing temperatures.

  European Patent Application No. 1,108,768 A1 discloses an exclusively colorless adhesive tape with a TPU-support that covers the joint of an airplane. However, the adhesive tape of the present invention is specified for winding, especially for winding wire bundles in automobiles. In practice, such a wound tape is black, rarely brightly colored, and not substantially colorless. Furthermore, although the adhesive tape described in this specification is limited to a transparent adhesive made of polyurethane, the wound tape of the present invention is sufficient to be applied in a slightly stretched state to an object to be wound. It must have a wrapping tape with a good unwinding force or adhesion to the back side. However, adhesives consisting essentially of polyacrylate, natural or synthetic rubber are suitable for this purpose. The claimed adhesive tape must have a thickness of at least 9 mils, that is, the film must have a minimum thickness of 8 mils (0.2 mm) to meet Boeing standard BSS 7230F2. I must. Furthermore, the adhesive tape described in this patent document contains a bromine-containing flame retardant. The described application does not require special heat resistance, and this document does not mention this requirement. This document therefore does not mention stabilizers such as antioxidants or hydrolysis inhibitors, and only mentions translucent dyes, antiblocking agents and lubricants (lubricants) as additives. The polyurethane film does not show any special composition.

  Japanese Patent Application Laid-Open No. 2005-264,112A describes an adhesive tape having a support made of copolyamide and subcomponents as main components. The latter includes polyurethane and nitrogen compounds. This document teaches that the addition of polyurethane improves the flexibility of a pure polyamide film, but that in large amounts, the scratch strength is significantly reduced, and therefore the proportion of polyamide should be 40-90 parts. Yes. As flame retardants, hydrazodicarbonamide, mono-, di-, tricyanoethyl cyanurate, melamine cyanurate and dicyandiamide are described. The combination of hydrazodicarbonamide and melamine cyanurate is particularly advantageous. The latter has been demonstrated as a flame retardant for polyamides (for example, JP 11-349,809 A1), whereas hydrazodicarbonamide is not inherently suitable for thermoplastic processing for the reasons described above. However, this document describes a processing temperature of 150-160 ° C., and such processing appears to be realized in the case of formulations with a low softening temperature. The reason is the low melting temperature of the selected raw material selected. That is, that of polyurethane is described as 60 to 120 ° C and that of polyamide is described as 100 to 180 ° C. In the examples, polyamides having a softening point of 133 ° C are used. However, the film for the wrapping tape of the present invention should have as high a heat resistance as possible, i.e. a short time heat resistance at 170 ° C and a heat resistance at 140 ° C. Therefore, a TPU having a significantly higher softening point than the TPU described in the above specification is necessary to modify the polyamide film. Also for the desired strength and module, the wound tape of the present invention must use a TPU material with a hard block component with a relatively high melting point, resulting in a processing temperature of 200 ° C. or higher. . It should be noted that the polyamide film described in the above specification can no longer be processed from 180 ° C. This film has a thickness of 0.2 mm. This patent document does not describe the requirement for heat resistance nor use of a stabilizer such as an antioxidant or a hydrolysis inhibitor. There is no description about a special composition about a polyurethane film. The film for the wrapping tape of the present invention has a high melting point hard block or a relatively high Shore hardness using the special combination of hydrazodicarbonamide and melamine cyanurate described in the above specification. It cannot be manufactured because it decomposes at the high temperatures required to process TPU.

  Furthermore, adhesive tapes having a support made of crosslinked non-thermoplastic polyurethane are also known. U.S. Pat. No. 5,807,637A discloses an adhesive tape having an adhesive layer and a sealing layer in which the underlying film contains calcium carbonate as a filler and is therefore not flame retardant. ing. US Pat. No. 6,129,983A also discloses a similar product, but with two sticky layers.

  European Patent Application No. 1,101,807 A1 discloses a marking adhesive tape having a composite support made of crosslinked polyurethane and polyester. The polyurethane layer may be modified with a filler, but no flame retardant is described.

  The above adhesive tape support is prepared by in-line metering and mixing of polyol, isocyanate and catalyst onto an auxiliary support. The advantage is that the raw material cost is lower than that of TPU, but the production is very difficult to implement in practice. Since the support is cross-linked, thermoplastic recycling is not possible. However, the essential disadvantage of the subject of the invention described in this document is that it is not compatible with wound tape because there is no flame retardancy nor sufficient tensile strength caused by physical crosslinking with hard blocks in the case of TPU. is there.

  European Patent Application Nos. 1,469,052A1 and 1,469,024A1 include an optional support, but a polyurethane crosslinked as a hard adhesive on what is not a TPU-film. An adhesive tape is disclosed.

  US Pat. No. 5,858,495 A1 discloses a very thick adhesive tape with afterglow produced by polymerizing a mixture of polyester acrylate or polyurethane acrylate and a pigment with afterglow. is doing. This material is a hard polymer containing urethane groups, although the chemical structure is different from TPU.

  The problem of the present invention is that it does not contain halogen, is flame retardant, has heat resistance and wear resistance, and the tensile strength of halogen-free PVC-wrapping tape of fibrous non-flame retardant winding tape and It is to provide a wound tape that combines the mechanical properties of flexibility and has better thermal aging durability, in which large-scale industrial productivity of the film should be guaranteed and certain applications The field requires a high level of dielectric breakdown voltage durability. As a result of the absence of heavy metal stabilizers and phthalate plasticizers, the wound tape should be environmentally and occupationally hygienic. In order to achieve high fogging values and to avoid plasticizer migration into the adhesive, such as telescopic deformation or edge sticking, the absence of plasticizers, especially DOP, completely or substantially Is desirable.

  It is a further object of the present invention to provide a winding tape of this kind which enables particularly reliable and quick winding, in particular winding on wires and cables, for marking, protection, insulation, sealing or bundling. In so doing, it does not cause the disadvantages of the prior art or at least not as much as in the prior art.

  It is also an object of the present invention to provide a thermoplastically produced film containing an additive combination that not only achieves the heat resistance of PVC, but is even better.

  This problem is solved by a wound tape as defined in detail in claim 1. The subject matter of the dependent claims describes advantageous embodiments of the subject of the invention as well as the use of the winding tape of the invention.

  Accordingly, the present invention provides a halogen-free flame-retardant wound tape capable of high heat load having a film made of thermoplastic polyurethane containing at least one flame retardant, wherein the film is at least one antioxidant as a stabilizer, and The present invention relates to the above wound tape, characterized by containing a hydrolysis inhibitor.

  In a particularly advantageous first embodiment of the invention, an adhesive, in particular a pressure-sensitive adhesive, is applied to at least one side of the support film.

  It is surprising and unexpected for a person skilled in the art that a support suitable for a wound tape comprising thermoplastic polyurethane, at least one halogen-free flame retardant and at least one stabilizer can be produced as follows: That is.

Polyurethane is
(A) at least one organic diisocyanate and (B) at least one polyol having a number average molecular weight M _n of at least 1.8 Tsuerubinofu active hydrogen atom and from 450 to 10,000 daltons up 3.0 on average (C) At least one low molecular weight polyol or polyamine having an average of at least 1.8 to up to 3.0 Zerbinov active hydrogen atoms and a number average molecular weight M _n of 60 to 400 Daltons as chain extenders and ( E) at least one halogen-free, non-reactive or incorporable flame retardant and stabilizer as (F) at least one antioxidant and / or (G) at least one hydrolysis inhibitor In some cases (H) it is prepared from other auxiliaries or additives.
The numerical value obtained by multiplying the quotient of the equivalent ratio between the isocyanate group from (A) and the total amount of Zerbinoff active hydrogen atoms of compounds (B) and (C) by 100 is 85 to 120, preferably 95 to 110. When using an incorporable phosphorus-containing flame retardant, this number is the quotient of the equivalent ratio between the isocyanate groups from (A) and the total amount of Zerbinoff active hydrogen atoms in compounds (B), (C) and (E). Calculated by multiplying by 100.

  In one particularly advantageous embodiment of the invention, components (B) and (C) are different.

  As the organic diisocyanate (A), aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates or any mixture of these diisocyanates can be used (HOUBEN-WEYL “Methoden der organischen Chemie (organic) Method of Chemistry) ”, Volume E 20,“ Makromolekulare Stoffe ”, Georg Thieme Publisher, Stuttgart, New York, 1987, pages 1587 to 1593 or Justus Liebigs Annalen der Chemie, 562, 75-136).

Illustrated in more detail below:
Aliphatic diisocyanates such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate; alicyclic 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'-dicyclohexyl Methane diisocyanate and corresponding isomer mixtures; further aromatic diisocyanates such as 2,4-toluylene diisocyanate, 2,4-toluylene Mixtures of isocyanates and 2,6-toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, mixtures of 2,4′-diphenylmethane diisocyanate and 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and 4,4 Mixtures of '-diphenylmethane diisocyanate, urethanephenic liquid 4,4'-diphenylmethane diisocyanate or 2,4'-diphenylmethane diisocyanate, 4,4'-diisocyanate diphenylethane- (1,2) and 1,5-naphthy Range isocyanate. 1,6-hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate content of more than 96% by weight of diphenylmethane diisocyanate isomer mixture and in particular 4,4'-diphenylmethane Preference is given to mixtures of diisocyanates and 1,5-naphthylene diisocyanates.

  The above diisocyanates can be used alone or in a mixture with each other. Together, they can be used up to 15 mol% of the polyisocyanate (calculated on the basis of total diisocyanate).

  The polyisocyanate should be used at most in such an amount that still produces a thermoplastically processable product.

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

  A particularly preferred isocyanate is 4,4'-diphenylmethane diisocyanate.

Polyols Tsuerubinofu activity which is used in the case of the products of the present invention (B) are those having a number average molecular weight M _n of at least 1.8 Tsuerubinofu active hydrogen atom and from 450 to 10,000 daltons up 3.0 on average is there. This often contains a small amount of non-linear compound depending on the production conditions. Therefore, the term “substantially linear polyol” is often used. Polyesters, polyethers, polycarbonate diols or mixtures thereof are particularly advantageous.

Amino groups, in addition to special one preferably having a number average molecular weight M _n of the compound is also 450 to 6000 Dalton with two to three, in particular two hydroxyl groups of a compound having a thiol group or a carboxyl group, and particularly preferably 600 to Those having a number average molecular weight _Mn of 4500 daltons, such as hydroxyl-containing polyesters, polyethers, polycarbonates and polyesteramides are included.

  Suitable polyether diols can be prepared by reacting one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene group with a starting molecule containing two active hydrogen atoms bonded.

  Examples of the alkylene oxide include the following: ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide and 2,3-butylene oxide. Ethylene oxide, propylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide are preferably used. Alkylene oxides can be used alone, alternately before or after each other, or as a mixture.

  Examples of suitable starting molecules are: water, amino alcohols such as N-alkyldiethanolamines such as N-methyldiethanolamine, and diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. In some cases, mixtures of starting molecules can also be used.

Suitable polyether diols further include hydroxyl-containing polymerization products of tetrahydrofuran. Trifunctional polyethers can also be used in proportions of 0 to 30% by weight, based on the difunctional polyether, but at most are those amounts that result in a thermoplastically processable product. The substantially linear polyether diols preferably have a number average molecular weight M _n of from 450 to 6000 daltons. These can be used individually or in a mixture 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. Dicarboxylic acids include, for example, 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 can be used alone or as a mixture, for example in the form of a mixture of succinic acid, glutaric acid and adipic acid. In order to produce polyester diols, corresponding dicarboxylic acid derivatives such as carboxylic acid diesters having 1 to 4 carbon atoms in the alcohol residue, carboxylic acid anhydrides or carboxylic acid chlorides are optionally used instead of dicarboxylic acids. be able to. Examples of polyhydric alcohols are glycols having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, such as 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 can be used alone or in a mixture with one another. Furthermore, esters of carboxylic acids with the above diols, in particular diols having 4 to 6 carbon atoms, such as 1,4-butanediol or 1,6-hexanediol, ω-hydroxycarboxylic acids such as ω-hydroxycaproic acid. Suitable are esters of condensation products or lactones, for example polymerization products of optionally substituted ω-caprolactones. Polyester diols include ethanediol-polyadipate, 1,4-butanediol polyadipate, ethanediol-1,4-butanediol polyadipate, 1,6-hexanediol-neopentylglycol polyadipate, 1,6-hexanediol Preference is given to using -1,4-butanediol polyadipate and polycaprolactone. Polyester - diols can also be used in the form of numbers has an average molecular weight M _n, alone or in mixtures with one another of from 450 to 10,000 daltons.

A particularly preferred diol is a hydroxyl group-containing polymerization product of tetrahydrofuran. This is because the TPU is 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.

  The Zelbinov-active polyol (C) is a so-called chain extender, has an average of 1.8 to 3.0 Zerubinov active hydrogen atoms, and has a molecular weight of 60 to 400 Daltons. These include compounds having 2 to 3, preferably 2 hydroxyl groups in addition to having an amino group, thiol group or carboxyl group.

  The chain extender is preferably an aliphatic diol having 2 to 14 carbon atoms, such as ethanediol, 1,2-propanediol, 1.3-propanediol, 2,3-butanediol, 1.4-butanediol, 1,5-pentanediol, 1,6 hexanediol, diethylene glycol and dipropylene glycol are used. However, diesters of terephthalic acid and glycols having 2 to 4 carbon atoms, such as terephthalic acid-bisethylene glycol or terephthalic acid-bis-1,4-butanediol, hydroquinone hydroxyalkylene ethers such as 1,4-di ( β-hydroxyethyl) -hydroquinone, ethoxylated bisphenols such as 1,4-di (β-hydroxyethyl) bisphenol A, (cyclo) aliphatic diamines such as isophorone diamine, ethylene diamine, 1,2-propylene diamine, 1, 3-propylenediamine, N-methyl-propylene-1,3-diamine, N, N′-dimethyl-ethylenediamine and aromatic diamines such as 2,4-toluylenediamine, 2,6-toluylenediamine, 3,5 -Diethyl-2,4-torr Irenamine or 3,5-diethyl-2,6-toluylenediamine or primary mono-, di-, tri- or tetraalkyl substituted 4,4'-diaminodiphenylmethane is suitable. Ethanediol, 1.4-butanediol, 1,6-hexanediol, 1,4-di (β-hydroxyethyl) -hydroquinone or 1,4-di (β-hydroxyethyl) bisphenol A is used as a chain extender. Is particularly advantageous. Mixtures of the above chain extenders can also be used. In addition, a small amount of triol may be added.

  A particularly preferred chain extender is 1,4-butanediol.

  The combination of 4,4'-diphenylmethane diisocyanate and 1,4-butanediol results in a hard block that is sufficiently durable to melt the specimen upon temperature loading.

  Monofunctional compounds with respect to isocyanates may also be used as so-called chain terminators in proportions up to 2% by weight, based on TPU. For example, monoamines such as butylamine, dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, piperidine or cyclohexylamine, monoalcohols such as butanol, 2-ethylhexanol, octanol, dodecanol, stearyl alcohol, various Amyl alcohol, cyclohexanol and ethylene glycol monomethyl ether are suitable.

  As the flame retardant (E), for example, an inorganic or preferably organic phosphorus-containing compound is selected. Examples are ammonium polyphosphate, ethylenediamine polyphosphate, polyphosphate ester and polyphosphonate ester such as triphenyl phosphate, tricresyl phosphate, alkylphenyl phosphate or diphenyl cresyl phosphate.

  Particularly advantageous is the general formula

[Wherein R is particularly preferably an aryl group (eg phenyl, cresyl group) and A is a linking group such as an arylene group (eg phenylene group), a biarylene group (eg biphenyl group), another group such as- Two arylene groups connected by CH2-, -C (CH3) 2-, -SO2- or -CO-, or an alkylene group (for example, neopentyl group), and n is 1-10. ]
It is hydroxycarbyl (dihydrocarbyl phosphate) represented by these. Such compounds are large-scale from phosphoric acid or phosphoxytrichloride and diphenylene such as resorcin or bisphenol A (which form group A) and monophenols such as phenol and cresol (which form group R). Manufactured industrially. Particular preference is given to phosphoric acid-1,3-phenylene-tetraphenyl ester and phosphoric acid-1,3-phenylene-tetraphenyl ester oligomers and bisphenol A bis (diphenyl phosphate) and oligomers thereof.

Of particular advantage are phosphate and phosphonate derivatives that do not release phenol or cresol upon hydrolysis, examples of which include trixylyl phosphate, butylated triphenyl phosphate (eg Fyrquel ^™ EHC-S), phosphorus There are acid-1,3-phenylene-tetraxylenyl esters and salts of phosphonic acids, such as sodium, magnesium, zinc or aluminum salts of propane- or phenylphosphonic acid (benzolphosphonic acid).

Examples of phosphorus-containing compounds that can be incorporated have an average of at least 1.5 and up to 3.0 Zerbinov active hydrogen atoms and a number average molecular weight M _n of 60-10000 Dalton and are represented by the following structural formula:

[Wherein R ¹ and R ² are branched or linear alkylene residues having 1 to 24 carbon atoms, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, and 6 to 6 carbon atoms. 30 substituted or unsubstituted aralkylene residues, substituted or unsubstituted alkylarylene residues having 6 to 30 carbon atoms, wherein R ¹ and R ² may be the same or different ,
R ³ is H, a branched or linear alkyl residue having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted group having 6 to 30 carbon atoms. Or an unsubstituted aralkyl residue, a substituted or unsubstituted alkylaryl residue having 6 to 30 carbon atoms,
x and y are 1-50. ]
A phosphonate represented by

[Wherein, R ¹ represents H, a branched or linear alkyl residue having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or 6 to 6 carbon atoms. 30 substituted or unsubstituted aralkyl residues, substituted or unsubstituted alkylaryl residues having 6 to 30 carbon atoms,
R ² and R ³ are branched or linear alkylene residues having 1 to 24 carbon atoms, substituted or unsubstituted arylene groups having 6 to 20 carbon atoms, and substituted groups having 6 to 30 carbon atoms. Or an unsubstituted aralkylene residue, a substituted or unsubstituted alkylarylene residue having 6 to 30 carbon atoms, wherein R ² and R ³ may be the same or different. ]
It is a phosphine oxide represented by.

  To avoid using the cumbersome IUPAC nomenclature, some of the following materials are denoted by their GAS-No.

  Halogen-free flame retardant (E) as melamine cyanurate, melamine, burette, tolulet, amelide, amelin, cyanuric acid, tris (2-hydroxyethyl) cyanurate, bis (2-hydroxyethyl) isocyanurate, 2-hydroxyethyl isocyanate Nurate, tris (carbomethyl) isocyanurate, tris (2-cyanoethyl) isocyanurate, bis (2-cyanoethyl) isocyanurate, 2-cyanoethyl isocyanurate, trimethylisocyanurate, HA (L) S, such as CAS-No. 40601-76-1 or 27676-62-6 or 34137-09-2 or 129757-67-1 or 191680-81-6, melam, melem, diisocyandiamide, granazine, biguanazine, triphenyl isocyanurate or tricresyl Also suitable are nitrogen-containing compounds such as isocyanurates. Flame retardants (E) include compounds containing both elements, such as melamine phosphate, melamine polyphosphate, urea phosphate, diethyl N, N-bis (2-hydroxyethyl) aminomethyl phosphate, N, N- Bis- (2-hydroxyalkyl) aminomethanephosphonic acid dimethyl ester, triethanolaminophosphate or oxytriamide phosphorus is suitable.

  Other halogen-free materials are also suitable as the flame retardant (E). Also suitable are, for example, aluminum hydroxide, magnesium hydroxide, expandable or expanded graphite.

  A particularly advantageous flame retardant (E) is melamine cyanurate.

  The thermoplastic polyurethanes used according to the invention may contain, as auxiliary and additive (H), which is not a flame retardant, preferably up to 20% by weight of customary auxiliary and additives, based on TPU. .

  Representative auxiliaries and additives include nucleating agents, lubricants such as fatty acid esters, metal salts thereof, fatty acid amides, fatty acid ester amides and silicone compounds, antiblocking agents, inhibitors, photoprotective agents, dyes, pigments, There are inorganic and / or organic fillers, plasticizers such as adipates, sebacates and alkyl sulfonates, fungistatic and bactericidal substances and fillers and mixtures and reinforcing agents such as textile substances.

  A detailed description of the above auxiliaries and additives can be found in the technical literature such as JH Saunders and KC Frisch's research paper “High Polymers”, Volume XVI, Polyurethane, 1st and 2nd. Part, Interscience Publishers publisher, 1962 or 1964; pocket version of synthetic resin additives from R. Gachter and H. Muller (Hanser publisher, Munich, 1990); or German Patent Application 2,901,774A1 Can know from.

The support film of the present invention is preferably substantially free of volatile plasticizers such as DOP or DINP and therefore has good combustion behavior and low emissions (plasticizer vapor, fogging material). The fogging value is preferably 90% or more. This film preferably contains up to 5 phr of phosphorus-free plasticizer,
More preferably, it does not contain any phosphorus-free plasticizer.

  When very high fogging values are required, phosphoric and phosphonic acid compounds which are incorporated and which do not evaporate very much due to their molecular weight of at least 300, preferably at least 400 daltons, are particularly advantageous. That is, phosphate plasticizers with a molecular weight of 300 Daltons or less or preferably 400 Daltons or less should be avoided.

  The film used according to the present invention contains at least one antioxidant (F). The amount is preferably at least 1 phr, particularly preferably at least 2 phr (the phr designation means the parts by weight of the relevant component based on 100 parts by weight of the total polymer component of the film). Examples are phenolic or amine based antioxidants and sulfur or phosphorous based second antioxidants. The wound tape of the present invention preferably contains a combination of first and second antioxidants. However, the functions of the first and second antioxidants may be present in different molecules or may be integrated in one molecule. In the stated quantities, any antioxidants such as metal deactivators or photoprotectants are not included.

  The amount of the second antioxidant is preferably at least 0.5 phr, particularly preferably at least 1 phr.

  PVC-product stabilizers cannot be diverted to TPU. The second antioxidant destroys the peroxide and is therefore used in the case of diene elastomers as part of the antioxidant package. Surprisingly, between a first antioxidant (eg a sterically hindered phenol or a C-radical scavenger such as CAS 181314-48-7) and a second antioxidant (eg a sulfur compound, a phosphite or a sterically hindered amine). We have found that the combination (both functions may be integrated in one molecule) also solves the desired problem in the case of a defined TPU. Among these, a first antioxidant, preferably a sterically hindered phenol with a molecular weight greater than 500 g / mol, in particular greater than 700 g / mol, and a phosphite-type antioxidant, preferably with a molecular weight greater than 600 g / mol. Combinations are particularly advantageous.

  In particular, a first phenolic antioxidant with low volatility and a sulfur compound type (preferably greater than 400 g / mol, particularly preferably greater than 500 g / mol) and a second antioxidant from the type of phosphite A combination is suitable. In this case, the functions of phenol, sulfur and phosphite do not need to exist in different molecules, and more than one function may be integrated in one molecule.

[Example]
Phenolic functions:
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, 10191-41-0, 1843-03-4.
Sulfur-containing function:
CAS 693-36-7, 123-28-4, 16545-54-3, 2500-88-1, 16545-34-3, 29598-76-3, 41484-34-9.
Phosfit system functions:
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, 145650-60-8, 26741-53-7, 119345-01-6.
Phenolic and sulfur-containing functions:
CAS 41484-35-9, 90-66-4, 110553-27-0, 96-96-5, 41484, 90-66-4.
Phenolic and amine functions:
CAS 991-84-4, 633843-89-0.
Amine-based functions:
CAS 52829-07-9, 411556-26-7, 129757-67-1, 71878-19-8, 65447-77-0, 65140-91-2.
A combination of CAS 6683-19-8 (eg Irganox 1010) and thiopropionic acid ester CAS 693-36-7 (Irganox PS 802) or 123-28-4 (Irganox PS 800) and CAS 31570-04-4 (Irgafos 168) is particularly advantageous. Furthermore, combinations in which the proportion of the second antioxidant is higher than that of the first antioxidant are particularly advantageous. In addition, metal deactivators for complexing trace amounts of heavy metals that can promote aging catalytically may also be added. Examples include CAS 32687-78-8, 70331-94-1, 6629-10-3, ethylenediaminetetraacetic acid, N, N'-disalicylidene-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 choice of anti-aging agent described above is particularly important for the wound tapes of the present invention, as phenolic antioxidants alone or in combination with sulfur-containing co-stabilizers may not necessarily result in a product that is actually compatible. is there. In the case of a calendering method in which it is inevitable that oxygen enters the roll for a relatively long time, it is necessary to use a phosphite stabilizer together to prevent the product from sufficiently heat aging. It has proven particularly suitable. In the case of extrusion processing, it has been found that adding phosphite still has a positive effect during the aging test of the product. For phosphite stabilizers an amount of at least 0.1 phr, preferably at least 0.3 phr, is advantageous.

  As the hydrolysis inhibitor (G), for example, a monomer or polymer carbodiimide, oxazoline or reactive polyurea can be used. Particular preference is given to polymeric carbodiimides based on aromatic isocyanates. The production and structure of this type of carbodiimide are described in US Pat. No. 2,941,956A, JP-A-4-733,279A, J. Org. Chem., 28, 2069-2075 (1963), Chemical Review. , Vol. 81, No. 4, pp. 619-621 (1981). The amount is advantageously at least 0.5, in particular at least 2 phr.

  It is particularly advantageous to use a combination of antioxidant (F) and hydrolysis inhibitor (G).

  Other polymer additives that can be incorporated into the TPU are thermoplastic resins such as polyethylene, ethylene / vinyl acetate copolymers, polypropylene homopolymers or copolymers. Synthetic elastomers such as hydrogenated styrene-diene copolymers or non-meltable polymers such as EVA-dispersion powders or impact modifiers (eg acrylate elastomer particles with shells made of PAN or PMMA) can also be used. It is advantageous to use a polymer additive which has an ester group or an amide group in the polymer main chain and is not sensitive to hydrolysis.

  Suitable catalysts (D) according to the invention are customary tertiary amines known from the prior art, for example triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N′-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diaza. -Bicyclo [2,2,2] octane and the like and in particular organometallic compounds such as titanates, iron or tin compounds such as tin diacetate, tin dioctoate, tin dilaurate or tin dialkyl salts of aliphatic carboxylic acids, For example, dibutyltin diacetate or dibutyltin dilaurate or the like.

  Particularly advantageous catalysts are organometallic compounds, in particular titanic acid esters, iron compounds and tin compounds. The total amount of catalyst in the TPU of the present invention is generally about 0-5% by weight, in particular 0-2% by weight, based on the total amount of TPU.

The TPU used in accordance with the present invention can be manufactured continuously or discontinuously. The most known production methods are the belt method (UK Patent Application No. 1,057,018) and the extrusion method (German Patent Application No. 1,964,834 A1). The synthesis of TPU is a stepwise process (reacting components (A) and (B) with (C) in the prepolymer metering method or all components (A), (B) and (C) in one step at the same time. (One-shot lightweight supply method) It is advantageous to use a prepolymer method.

  The addition of flame retardant (E), antioxidant (F), hydrolysis inhibitor (G) and / or auxiliary (H) can be carried out before, during or after the polyurethane reaction.

  The main object of the present invention is to contain no halogen under relatively high flame retardancy, tensile strength and flexibility. As mentioned above, the thermal demands in the application have increased, resulting in an additional increase compared to conventional PVC-wrapping tapes or PVC-free film-wrapping tapes based on polyolefins in the development stage. It is intended to achieve stability. Therefore, the features of the present invention will be described in more detail below.

  The product of the present invention is in a halogen-free state in the sense that the halogen content of the raw material is so small that it does not contribute to flame retardancy. Trace amounts of halogen that can be generated by impurities, processing additives (fluorinated elastomers) or catalyst residues are ignored.

  Discarding the halogen is generally accompanied by the property of easily burning. This does not meet safety requirements in electrical products such as home appliances, buildings or automobiles. The wound tape of the present invention is self-extinguishing and a particularly advantageous embodiment of the wound tape is under the test conditions described in the combustion test according to FMVSS 302 (horizontal test) and / or ASTM D 568 (vertical test). It is self-extinguishing.

  The thickness of the film of the present invention is preferably 30 to 180 μm, particularly preferably 50 to 150 μm, and more preferably 55 to 100 μm. Thus, sufficient suitability when wrapping, effective hand tearability and acceptable cost are achieved. The wound tape of the present invention is correspondingly increased in thickness by the thickness of the adhesive layer present in some cases. The surface may be structured or flat. Preferably the surface is slightly matte. This can be achieved by the use of sufficiently large particle size fillers or by rolls (eg embossing rolls in calendering or matte cooling rolls or embossing rolls in the case of extrusion).

  The wrapping tape used according to the invention is preferably colored (black, white or colored), the color of which is colored a support film and / or another layer, for example an adhesive. The pigments used are preferably free of toxic heavy metals such as those based on lead, cadmium or chromium.

  The wound tape according to the invention has a force of 2-20 N / cm, preferably 4-11 N / cm at 10% elongation in the longitudinal direction (machine direction), and 3-25 N / cm at 50% elongation. Preferably, it has a force of 6 to 17 N / cm.

  A force at 10% is a measure of the stiffness of the film and a force at 50% is a measure of suitability during winding when it deforms significantly due to high winding stress. However, the force at 50% should not be too low. This is because otherwise the tensile strength is generally too low.

  The tensile force (breaking load) of the support film is at least 10 N / cm, preferably at least 20 N / cm.

  Since TPU can be very tough, in some cases means to improve the hand tearability of the wound tape, such as incorporation of fillers, incompatible thermoplastics or non-meltable polymers, later There is a need for rough edges of the side edges where cracks have been formed in the film as viewed under a microscope, which obviously favors tear propagation, or side edges that are later notched, for example by partial punching. Rough cutting of the side edges can be done by cutting by pressing with a sharp knife or a regular saw blade rotating on a bowl-shaped product (giant roll, long roll) or by long fixed or rotating blades It can be manufactured by cutting and dividing a shaped product (manufacturing width and conventional sales length). The elongation at break can be adjusted with a suitable blade or knife. In particular, an embodiment in which a long product is manufactured by cutting and dividing using a fixed blade that is not sharp is advantageous. It is possible to further improve crack formation during the cutting operation by significantly cooling the long roll prior to the cutting operation.

  Sufficient thermal stability and short-term heat resistance requirements are a sufficient crystallite melting point of TPU (preferably at least 158 ° C., particularly preferably at least 170 ° C.) and durability against aging due to degradation is an antioxidant component and / or Or it can be reliably satisfied by hydrolysis inhibitors.

  The wound tape according to the invention has a high heat resistance, and in a particularly advantageous embodiment it exhibits an elongation at break of at least 100% after storage for 312 hours at 140 ° C. (heat resistance test) and / or at 170 ° C. Shows thermal load stability for a short time (no cracks or melting points after 30 minutes).

  In order to achieve this force value and thermal stability, the film of the wound tape contains a TPU having a sufficiently high hard block proportion, and therefore the Shore D hardness of the TPU raw material is preferably at least 35, particularly preferably. At least 50. This corresponds approximately to a Shore A hardness of at least 85, particularly preferably at least 100 Shore A hardness. The flame retardant adhesive tape described in the prior art uses a TPU (Shore A hardness 70 to 80) that is significantly softer than the flame retardant adhesive tape mixed with a flame retardant. When a phosphate ester as a plasticizer or a flame retardant is further added to such an adhesive tape made of soft TPU, it is far more inappropriate than the wound tape of the present invention.

  The film is produced by a calendar method or an extrusion method, for example, a blow molding method or a casting method. These methods are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, Wiley-VCH 2002. When solid or liquid additives are used in combination for TPU, the blend consisting of the main component or all components is used in a kneader (eg plunger kneader) or an extruder (eg twin screw or planetary roller extruder). And then converted to a solid state (eg granules). This is then further processed in a film extruder or extruder, kneader or calender roller.

  This polyurethane film is coated with an adhesive on at least one side.

The amount of adhesive layer which is preferably present is 10-40 g / cm ² , in particular 18-28 g / cm ² (this is the amount after removal treatment which is necessary in the case of water or solvent, the value being approximately 1 μm). Equivalent to thickness). In the case of having an adhesive layer, the figures given for the mechanical properties, which depend on the thickness exclusively related to the TPU-containing layer of the wound tape, take into account the adhesive layer or other beneficial layers related to the adhesive layer. Not. The covering need not be spread over the entire surface, and may be applied to a part of the surface. As an example, there may be mentioned those having adhesive stripes in the vicinity of each side edge of the wound tape. The tape can be cut so that an adhesive stripe sticks to the cable bundle and then another adhesive stripe forms a generally rectangular sheet that can be joined to the back side of the winding tape. This hose-like envelope, such as a sleeve-like package, has the advantage that the flexibility of the cable room is not substantially degraded by this package.

  Any conventional type of adhesive is suitable, and those based on rubber are particularly advantageous. Such rubbers are, for example, isobutene, l-butene, vinyl acetate, ethylene, acrylate esters, butadiene or isoprene homo- or copolymers. In particular, formulations based on polymers based on acrylic esters, vinyl acetate or isoprene are suitable.

In order to optimize properties, one or more additives in the adhesive used, such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, anti-aging An agent, a photoinitiator, a crosslinking agent or a crosslinking accelerator may be mixed. Examples of tackifiers include hydrocarbon resins (eg, polymers based on unsaturated C ₅ -C ₉ -monomers), terpene phenol resins, polyterpene resins such as polyterpenes made of raw materials such as α- or β-pinene. Resins, aromatic resins such as coumarone-indene resins or resins based on styrene or α-methylstyrene such as colophonium or derivatives thereof such as disproportionated, dimerized or esterified resins such as For example, reaction products with glycols, glycerin or pentaerythritol as well as other resins (for example those described in Ullmanns Enzyklopadie der technischen Chemie, Band 12, Seiten 525 bis 555 (4th edition), Weinheim). Can be mentioned. Resins that do not have easily oxidizable double bonds, such as terpene phenol resins, aromatic resins are preferred, especially resins produced by hydrolysis, such as hydrogenated aromatic resins, hydrogenated polycyclopentadiene resins Preference is given to using hydrogenated colophonium derivatives or hydrogenated terpene resins.

Suitable fillers and pigments are, for example, carbon black, titanium dioxide, calcium carbonate, zinc carbonate, zinc oxide, silicate or silicic acid. Suitable plasticizers that can be incorporated include, for example, aliphatic, cycloaliphatic and aromatic mineral oils; di- or polyesters of phthalic acid, trimellitic acid or adipic acid; liquid rubbers (eg low molecular weight nitrile or polyisoprene rubbers); butenes And / or liquid polymers composed of isobutene, acrylate esters, polyvinyl ethers; liquid and soft resins based on adhesive resin raw materials; lanolin and other waxes or liquid silicones. Examples of the crosslinking agent include isocyanate, phenol resin or halogenated phenol resin, melamine resin, and formaldehyde resin. Suitable crosslinking accelerators include, for example, melamine imides, allyl esters such as triallyl cyanurate, polyfunctional esters of acrylic acid and methacrylic acid. Anti-aging agents include, for example, sterically hindered phenols such as those known under the registered trade name Irganox ^™ .

  The cross-linking reaction is advantageous because it increases shear strength (eg, also expressed as holding force) and therefore reduces the tendency of the roll to deform (telescopic deformation or formation of cavities, also referred to as gaps) during storage. The bleeding of the adhesive is also reduced. This is confirmed at the non-sticky side edge of the roll and the non-sticky edge in the case of a spiral cable or a wound tape wrapped around a cable room. The holding force is preferably greater than 150 minutes.

  The adhesion strength to steel should be in the range of 1.5-3 N / cm.

  The winding tape of the present invention has an unwinding force of 1.2 to 6.0 N / cm, particularly 1.6 to 4.0 N / cm, particularly 1.8 to 2.5 N / cm at an unwinding speed of 300 mm / min. It is advantageous to have.

  In summary, a particularly advantageous embodiment has the solvent-free pressure sensitive adhesive obtained on one side by coextrusion, melting or dispersion application. Particularly preferred are dispersions based on polyacrylates or hot-melt adhesives.

  Using a primer layer between the backing film and the adhesive to improve the adhesion of the adhesive to the film and thereby preventing the adhesive from moving to the back of the film while unrolling the roll It is advantageous.

  Primers can be used with known dispersions and solvent systems such as those based on isoprene or butadiene containing rubber and / or cyclo rubber. Isocyanates or epoxy resins as additives improve adhesion and some increase the shear strength of the adhesive. Physical surface treatments such as flame treatment, corona or plasma treatment or coextruded layers are also suitable and improve adhesion. Such a method is particularly advantageous for use in solvent-free adhesive layers, especially those based on acrylates.

  The back side can be coated with a known release agent (optionally mixed with other polymers). Examples include stearyl compounds (eg polyvinyl stearyl carbamate, stearyl compounds of transition metals such as Cr or Zr), ureas formed from polyethyleneimine and stearyl isocyanate, polysiloxanes (eg copolymers with polyurethane or polyolefins) Grafted graft polymer) and thermoplastic fluoropolymer. Stearyl is synonymous with any linear or branched alkyl or alkenyl having at least 10 carbon atoms, such as octadecyl.

  Descriptions of customary adhesives and backside layers and primers are given, for example, in “Handbook of Pressure Sensitive Adhesive Technology”, D. Satas, (3rd edition).

  Long products may be stored in a heated state before cutting for increased unwinding force or stress relaxation of the film. Cutting of wound tape with woven, fleece and film supports (eg PVC) can be sheared (between two rotary knives), on a long roll with fixed or rotary knives rotating the product. Splitting (pressed), cutting with a blade (divided as the web passes through a sharp blade) or pressing (cutting between a rotating knife and roller).

  The winding tape of the present invention is excellently suitable for winding on long stretched products such as automotive field coils or cable harnesses. Flexibility must be wound in a flexed manner without any wrinkles at branches, inserts or stop clips, even if it is spirally moved to wrap the winding tape when used on wires and cables. It is further desirable that the wound tape be elastically pulled along with the cable strands. The wound tape of the present invention is equally suitable for sealing the exhaust pipe of an air conditioner, as the high flexibility is well suited to rivets, grooves and bent parts. These mechanical properties can only be achieved with a soft and flexible winding tape. The problem of achieving the necessary flexibility by avoiding the addition of large amounts of flame retardant is solved by the present invention.

  Today's occupational and environmental health requirements are met by not using halogen-containing raw materials. The absence of halogen is extremely important for recovering heat from waste containing such winding tape (eg incineration of synthetic resin from automobile recycling), but cable fires that do not produce toxic exhaust gas It is also important in the event of a building fire.

  In the process of increasing the complexity of electronic products and in the process of increasing the number of electricity consuming devices in the automotive field, the set of conductors and the like has always become more complex. As the cable room cross-sectional area decreases, induction heating increases more and more, while heat dissipation decreases. This has increased the demand for heat resistance of the materials used. PVC-materials typically used for wound adhesive tapes have reached their capacity limit. This problem is now considered to be resolved.

<Test method>
The measurement is carried out in a test environment of 23 ± 1 ° C. and 50 ± 5% relative humidity.

The crystallite melting point (T _cr ) is measured by DSC according to ISO 3146. Since the newly processed TPU has a very wide melting range, it cannot be measured in the final thermodynamic state of the crystal, so the specimen is conditioned at 140 ° C. for 24 hours before measuring the crystallite melting point.

  Shore A hardness and Shore D hardness are measured according to ISO 868.

  The hydrolysis resistance is measured by storing the specimen in warm distilled water. After 1000 hours at 80 ° C., the specimen is dried at 80 ° C. under reduced pressure, and then the amount of decrease in tensile strength compared to the fresh state is measured. The test passes when the tensile strength decreases by less than 50% and fails when it decreases by at least 50%.

  Elongation Behavior of Wound Tape Two types of specimens (rectangular specimen with a length of 150 mm and a width of 15 mm as much as possible) with a test speed of 300 mm / min, a clamping length of 100 mm and a pretension force of 0.3 N / cm taking measurement. In the case of specimens with rough cut edges, the edges are cleaned using a sharp blade before the tensile test. Tensile elongation behavior is tested in the machine direction (longitudinal direction, MD) unless otherwise indicated. The force is expressed in N / (strip width) and the elongation at break is expressed in%. As a result of the test, the elongation at break (elongation at break) was statistically determined by a sufficient number of measurements.

  Adhesion is measured according to AFERA 4001 (as much as possible) with a 15 mm wide test strip at a peel angle of 180 °. In this case, a steel plate according to the AFERA standard is used as a test substrate unless another bonding substrate is described.

  The film thickness is measured according to DIN 53370 (any adhesive layer is subtracted from the total thickness measured).

  Holding force is measured according to PSTC 107 (10/2001). However, the weight is 20 N and the dimensions of the bonded area are 20 mm high and 13 mm wide.

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

  Hand tearability cannot be expressed numerically, although the breaking force, breaking elongation and impact strength (all measured in the longitudinal direction) have an important influence.

Rating:
+++ = very easy
++ = good
+ = Still workable
= Difficult to process
-= The tear can only be done with a strong force and its edges are distorted.
--- = Cannot be processed.

  The combustion behavior is measured according to EMVSS 302 (specimen placed horizontally) and SATM D 568 (specimen placed vertically). In the case of EMVSS 302, the adhesive coating is on the top side. These methods make it possible to measure the burning rate of a combustible specimen. Only evaluate whether the specimen is burned (not passing) until it reaches the second mark (terminal mark) or self-extinguishes before passing. MVSS 302 (US Automotive Safety Standards) has evolved to ISO standards.

  Heat resistance is measured by two methods. The wrapping tape is first applied to a polyester film treated with sill cone and stored hot. After the test time has elapsed, the specimen is cooled at 23 ° C. for 30 minutes. In the case of the heat resistance test, it is checked whether the elongation at break is still at least 100% after storage at 140 ° C. for 312 hours. A short-term heat resistance test is performed by storing the specimen at 170 ° C. for 30 minutes, then winding it around a 10 mm diameter mandrel with at least 3 turns and 50% overlap, and then the specimen is damaged (eg, cracked, Check if it has a melting point).

  In the case of a low temperature test, the specimen is cooled at −40 ° C. according to ISO / DIS 6722 and the specimen is manually wrapped around a 5 mm diameter mandrel. Visually confirm defects (cracks) of the adhesive tape on the specimen.

  The breakdown voltage is measured according to ASTM D 1000. The maximum value that the specimen can withstand for 1 minute under this voltage is taken as a numerical value. This numerical value is converted to a test body thickness of 100 μm.

[Example]
A 200 μm thick specimen withstands a maximum voltage of 6 kV after 1 minute. The calculated breakdown voltage is 3 kV / 100 μm.

  The fogging value is measured according to DIN 75201 A.

  The following examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof.

[Description of PU raw material used in Examples:]
Terathane ^™ 1000: A polyether diol based on tetrahydrofuran with a molecular weight M _n = 1000 Dalton (manufacturer: DuPont).
Terathane ^™ 650: A polyether diol based on tetrahydrofuran with a molecular weight M _n = 650 daltons (manufacturer: DuPont).
MDI: 4,4′-diphenylmethane diisocyanate.
Exolit ^™ OP 560: a flame retardant based on diol phosphonates with Zelewitinoff active hydrogen atoms (manufacturer: Clariant).
NORD-MIN ^TM MC-25J: Melamine cyanurate (Manufacturer: Nordmann-Rassmann)
Fyrolflex ^TM RDP: Resorcinophosphate oligomer with the following formula (Manufacturer: Akzonobel):

BDO: 1,4-butanediol
Irganox ^™ 1010: Tetrakis (methylene- (3,5-ditert-butyl-4-hydroxycinnamate)) methane (manufacturer: Ciba Specialty Chemicals)
Irganox ^TM PS 800: Diarylthiodipropionate (Manufacturer: Ciba Specialty Chemicals)
Elastollan ^TM Konz 952: Starbatch Irganox ^TM 1010 in TPU (Manufacturer: Elastogran)
Licowax ^TM C: Release agent (Manufacturer: Clariant Wurtz)
Stabaxol ^TM KE 9463: Hydrolytic inhibitor based on aromatic carbodiimide (Manufacturer: Rheinchemie)
Carbodilite ^™ V-04B: Carbodiimide based hydrolysis inhibitor (manufacturer: Nisshinbo Industries).

A mixture consisting 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 stirred at 500 ° C. with stirring at 500 rpm. And then add 713 kg of MDI. After reaching maximum reaction temperature, stir for 30 seconds, after which 125 kg BDO and 100 kg Exolit ^™ OP 560 are added. The mixture is then stirred for 100 seconds, after which the TPU is cast. Finally, the material is post-treated at 80 ° C. for 30 minutes.

  The finished TPU is cut, ground and fed dry to the compounding equipment. This blend is fed into the nip of a "" inverted L "" type calender. The processing temperature is 220 ° C. It is formed into a smooth surface film with a thickness of 80 μm by a calender roll.

The film was stored for a week and smoothed at 60 ° C. in a coating apparatus with a roll and provided with a release layer on one side after corona treatment and an aqueous acrylate adhesive ( Rohm & Haas Primal PS 83 D and Clariant 5% Hostasinschwarz black preparation) are applied with a coating knife at a coating weight of 24 g / m ² . This finished winding tape is wound around a 1-inch core (25 mm) to form a roll having a length of 33 m. The cutting is performed using a fixed blade with a non-sharp angle (straight knife) and the long roll is divided into 29 mm wide rolls.

As in Example 1, the prepolymer was prepared in the presence of Irganox ^™ 1010, NORD-MIN ^™ MC-25J and Fyrolflex ^™ RDP at a molar ratio of MDI and Terathane ^™ 1000 to 2.5: 1. React with 95 mol% of BDO. The additive content is (based on 100 phr TPU polymer) 0.3 phr Irganox ^™ 1010, 23 phr NORD-MIN ^™ MC-25J and 4 phr Fyrolflex ^™ RDP.

The finished TPU is cut, crushed and processed into a 100 μm blown film at a temperature of 180-200 ° C. with the addition of 5% by weight white masterbatch and 5% Stabaxol ^™ KE 9463.

One side of this support film is subjected to a flame pretreatment and after storage for 10 days, it is coated with Acronis DS 3458 at 50 m / min with a roll coater. The temperature load on the support is reduced with a cooled backing roll. The coating amount is about 35 g / m ² . Appropriate crosslinking was achieved by in-line irradiation prior to winding with an ultraviolet device equipped with six medium pressure Hg lamps (120 W / cm each). The irradiated web is wound around a quarter inch core (31 mm) into a long 33 mm roll. For cutting, a long roll is divided using a fixed blade (straight knife) into a 25 mm wide roll.

As in Example 1, a prepolymer was prepared in the presence of Irganox ^™ 1010 and melamine polyphosphate (Dayang Chemicals) in a molar ratio of MDI and Terathane ^™ 650 to 2.2: 1 to give 95 equivalents of 1 equivalent of BDO. React with mol%. Carbodilite ^™ V-04B is added at the end of the reaction. The additive content is (based on 100 phr TPU polymer) 0.3 phr Irganox ^™ 1010, 27 phr melamine polyphosphate and 1 phr Carbodilite ^™ V-04B.

The finished TPU is cut, ground and cast with the addition of 5% by weight black batch and 5% anti-hydrolysis masterbatch (Rhein-Chemie KE 9463 = 20% Stabaxol ^™ P200 in TPU) A film with a thickness of 70 μm is formed with a (flat nozzle with cooling roll).

One side is coated with 0.6 g / m ^{2 with a} primer consisting of 5 parts MDI, 45 parts natural rubber and 50 parts cyclorubber and dried. The adhesive coating is applied directly on the adhesive layer at an application amount of 18 g / m ² (based on dry matter). The adhesive consists of a solution with a solid content of 30% by weight in which a natural rubber adhesive is dissolved in n-hexane. This consists of 50 parts natural rubber, 10 parts zinc oxide, 3 parts colophonium resin, 6 parts alkylphenol resin, 17 parts terpene phenol resin, 12 parts poly-β-pinene resin, 1 part antioxidant. (Irganox 1076) and 2 parts mineral oil. Drying after coating was performed in a drying tunnel at 100 ° C. Immediately downstream, this film is automatically cut and divided using a knife bar having sharp blades at intervals of 19 mm in a roll wound around a standard adhesive tape core (3 inches).

Manufactured in the same manner as Comparative Example 2, but antioxidant and hydrolysis inhibitor were added via a masterbatch during extrusion. These are 1.5% Elastollan ^™ Konz 952 and 11% Stabaxol ^™ KE 9463.

[Comparative Example 1]
A wound tape is produced in the same manner as in Example 1, but this TPU film is made of T-8375 (DIC Bayer Polymer's Shore A hardness 75 thermoplastic polyester polyurethane). At the same processing temperature, the melt was too sticky to the calender roll so that no film could be produced. After lowering to a temperature of 160 ° C., the film could be peeled off. This T-8375 was selected from those used in the examples of JP-A-2005-264112A (consisting of a copolyamide containing a mixed flame retardant based on TPU and a nitrogen-based substance).

[Comparative Example 2]
The winding tape was produced as in Comparative Example 1, except that the TPU was from 100 phr T-8375 and 10 phr Reofos 65 (Great Lakes isopropylated triaryl phosphate) as an unincorporated phosphorus-containing flame retardant. Become. However, due to the remarkable sticking to the calender roll, a film could not be obtained despite changing the processing conditions. The film could not be processed by the blow molding method as in Example 2 because the melt strength was insufficient. For the first time, a completely colorless film having a thickness of 80 μm could be obtained by the same casting method as in Example 3. Subsequently, an adhesive was applied in the same manner as in Example 1.

[Comparative Example 3]
The winding tape was manufactured in the same manner as in Example 1. The composition of the TPU film corresponds to Example 2 of JP-A-2005-264112A.
40 phr T-8375,
60 phr CM6541X3 (copolyamide of ω-aminocaproic acid and ω-aminolauric acid with a crystallite melting point of 133 ° C. from Toray Industries)
10 phr hydrazodicarbonamide
40 phr melamine cyanurate
1 phr Licowax ^TM OP,
・ 10 phr calcium carbonate.

  The melt adhered to the calender device at the same processing temperature as in Example 1. This had bubbles and pores (of course this was due to the decomposition of hydrazodicarbonamide) and the film could be produced after the temperature was lowered to 160-170 ° C. However, the thickness was 80 μm as in Example 1 instead of 0.2 mm as described in the above-mentioned Japanese Patent Laid-Open Publication.

[Comparative Example 4]
For coating, a conventional film for insulating tape from Singapore Plastic Products Pte. Under the name F2104S is used. This film, according to the manufacturer's specifications, is 100 phr (parts per hundred resin) suspension PVC with a K-value of 63-65, 43 parts DOP (di-2-ethylhexyl phthalate), 5 phr tribasic Lead sulfate (TLB, stabilizer), 25 phr ground chalk (Bukit Batu Murah Malaysia with fatty acid coating), 1 phr furnace black and 0.3 phr stearic acid (lubricant). The nominal thickness is 100 μm and the surface is smooth but matte.

One side is coated with Four Pillars Enterprise / Taiwan Primer Y01 (according to analysis, acrylate-modified SBR rubber in toluene) on which Four Pillars Enterprise / Taiwan 23 g / m ² adhesive IV9 (SBR as a main component measured by analysis and natural rubber, terpene resin and alkylphenol resin in toluene) are applied. Immediately after the dryer, this film is automatically cut and divided at intervals of 25 mm with a knife bar with a sharp blade to form a roll.

[Comparative Example 5]
TPU-polymers, films and wrapping tapes are produced in the same manner as the same, but the additives are changed as follows. Irganox ^™ 1010 and Fyrolflex ^™ RDP were omitted and the content of NORD-MIN ^™ MC-25J was increased to 27 phr.

<Consideration of results>
In the case of Comparative Example 2, the phosphate plasticizer deteriorated the fogging value and the adhesive strength. Comparative Example 3 shows similar behavior, of course, this very soft TPU (Shore A hardness = 75) contains a mobile plasticizer. The fogging value of Comparative Example 4 (containing DOP-plasticizer) is the worst.

  Tensile strength is acceptable in either case. Since the elongation at break of the comparative example is relatively high, the tearability by hand is poor in some cases.

  The two comparative examples are too soft to use as a wound tape.

  The heat resistance at 140 ° C. is poor in all comparative examples, of course they do not contain antioxidants and / or in some cases are also hydrolysable. Short-time heat resistance at 170 ° C. not described is insufficient for oxidizing components (partially causes cracking) and is too low in melting point (all specimens 1 to 3 are at least marginal) Melted in place). Comparative Example 4 does not serve for the evaporation of the plasticizer and Comparative Example 5 is similarly fragile.

  Hydrolytic stability is inadequate for all Comparative Examples 1-3, but this is not surprising to those skilled in the art for TPUs containing polyester polyols.

  Some of the comparative examples have only a slight flame retardancy (the specimen was completely burned). Comparative Example 5 was surprising because the test specimen contained a large amount of flame retardant, but burned completely even at a slow rate. In the case of Comparative Examples 1 to 3, the test body burned slowly in the same manner while dropping flammable molten droplets. Furthermore, comparative experiments not described here have shown that phosphorus content is absolutely necessary to pass the test. As the content of melamine or melamine cyanurate increases, the burning rate certainly decreases and at the same time the dripping of the melt decreases and the burning rate increases again rather than from about 30 phr, so that the specimen is completely removed from the critical concentration. It is accelerated until it burns out.

  Example 4 is produced in the same manner as Comparative Example 2, but demonstrates that it is well stabilized by the addition of antioxidants and hydrolysis inhibitors.

Claims (17)

In a halogen-free flame retardant wound tape capable of high heat load, the film made of thermoplastic polyurethane contains at least one flame retardant and at least one antioxidant and / or hydrolysis inhibitor as a stabilizer. The said wound tape characterized by the above-mentioned. The polyurethane film contains at least 0.5 phr, preferably at least 1 phr of at least one antioxidant and / or a combination of at least one first antioxidant and at least one second antioxidant. The wound tape according to 1. 3. Wrapping tape according to claim 1 or 2, wherein the polyurethane film contains at least 0.5 phr, preferably at least 2 phr hydrolysis inhibitor and / or the hydrolysis inhibitor is a polymeric aromatic carbodiimide. The winding tape according to any one of claims 1 to 3, wherein an adhesive, preferably an adhesive, is present on at least one side of the support film. The winding tape according to any one of claims 1 to 4, wherein the winding tape is colored. 6. A wound tape according to any one of claims 1 to 5 which exhibits self-extinguishing and / or exhibits a breakdown voltage of at least 4 kV under the test conditions of FMVSS 302 or ASTM D568. The thickness of the film is 30 to 180 μm, preferably 50 to 150 μm, particularly preferably 55 to 100 μm,
The force when stretching 10% in the machine direction is 2 to 20 N / cm, preferably 4 to 11 N / cm,
The force at 50% stretching is 3-25 N / cm, preferably 6-17 N / cm,
Tearing force greater than 10 N / cm, preferably greater than 20 N / cm,
The winding tape as described in any one of Claims 1-6. Elongation at break is at least 100% after 312 hours storage at 140 ° C. and / or damage is observed when wound at least 3 turns around a 10 mm diameter mandrel after 30 minutes storage at 170 ° C. The winding tape as described in any one of Claims 1-7 which is not carried out. Winding according to any one of claims 1 to 8, wherein the Shore D hardness of the polyurethane is at least 35, preferably at least 50 and / or the crystallite melting point of the polyurethane is at least 158 ° C, preferably at least 170 ° C. tape The adhesive is a solvent-free pressure-sensitive adhesive produced by coextrusion, melt coating or dispersion coating, in particular a hot-melt adhesive or dispersion pressure-sensitive adhesive based on polyacrylate. The winding tape as described in any one of. The amount of the adhesive layer is 10 to 40 g / m ² , preferably 18 to 28 g / m ² ;
The adhesive strength of the wound tape to steel is 1.5 to 3 N / cm,
The unwinding force of the winding tape is 1.2 to 6.0 N / cm, preferably 1.6 to 4.0 N / cm, particularly preferably 1.8 to 2.5 N / cm at an unwinding speed of 300 mm / min. Yes and / or the holding power of the wound tape is greater than 150 minutes,
The winding tape as described in any one of Claims 1-10. The wound tape according to any one of claims 1 to 11, wherein the tearability by hand is enhanced by additives in the film or by mechanically damaging the side edges of the film. Support polyurethane film A) at least one organic diisocyanate and B) at least one having a number average molecular weight M _n of at least Tsuerubinofu active hydrogen atoms of 1.8 up to 3.0 and from 450 to 10,000 daltons on average as polyol C) chain extender, at least one low molecular weight polyol has a number average molecular weight M _n of at least 1.8 up to 3.0 amino Tsuerubinofu active hydrogen atoms and 60 to 400 daltons on average or Polyamines and E) at least one halogen-free, reactive or non-incorporable flame retardant and stabilizer as F) at least one antioxidant and / or G) at least one hydrolysis inhibitor and Optionally H) consisting of another auxiliary or additive and optionally under the use of catalyst (D) The wound tape according to any one of claims 1 to 12, which is preferably manufactured by a prepolymer method. 14. The flame retardant is a phosphate ester or phosphonate ester, preferably hydrocarbyl (dihydrocarbyl phosphate) and / or does not release phenol or cresol when the phosphorus-containing flame retardant is hydrolyzed. The winding tape as described in one. The winding tape according to any one of claims 1 to 14, wherein the flame retardant is melamine cyanurate. The isocyanate (A) is 4,4'-diphenylmethane diisocyanate, the polyol (B) is a hydroxyl group-containing polymerization product of tetrahydrofuran and / or the chain extender (C) is 1,4-butanediol. The winding tape as described in any one of 1-15. The method of using the wound tape according to any one of claims 1 to 16, for binding an exhaust pipe, a wire or a cable, protection, marking, insulation or sealing, covering a field coil of an automobile cable harness or a picture tube .