DE102007027851A1 - Compound and wrapping tape made of TPU - Google Patents

Abstract

Halogen-free flame-retardant compound of thermoplastic polyurethane, which contains at least one boron compound as flame retardant, preferably in a proportion of 2 to 30 phr.

Description

The The present invention relates to a halogen-free, flame-retardant, preferably colored compound. The compound is halogen-free Insulation of wires and cables especially for Automotive applications suitable and for the production of a winding tape, which preferably has an adhesive coating and the for example for wrapping ventilation ducts in air conditioners, Wires or cables is used and that in particular for wiring harnesses in vehicles or field coils for Picture tube is suitable. The winding tape is used for Bundle, Isolate, Mark or Protect.

Wire insulation, Cable wrap and insulating tapes are usually made of plasticized PVC. There is an increasing desire to the disadvantages of these products, such as the evaporation of plasticizers and eliminate 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.

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. The usual PVC wrapping tapes contain stabilizers based on toxic heavy metals such as lead, cadmium or barium.

Efforts are being made to use woven or non-woven fabrics instead of soft PVC film. However, the resulting products are rarely used in practice, as they are relatively expensive and have very different handling characteristics (for example hand tearability, elastic recovery) and conditions of use (for example resistance to moisture or operating fluids) to conventional products. wherein - as explained below - the thickness has a special meaning. Such thick nonwovens make the wiring harnesses even thicker and less flexible than traditional PVC tapes, even if this has a positive effect on the sound insulation, but this is only advantageous in some areas of cable harnesses. However, nonwovens are not very stretchy and have virtually no resilience. This is important because thin branches of wiring harnesses must be wrapped so tightly that they do not hang slack down during installation and can be easily positioned before clipping and fitting 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 sensitivity to hydrolysis, so that use for 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 from 40 to 100 phr (in of this invention refers to phr parts by weight of a component to 100 parts by weight of the thermoplastic polymer such as Polypropylene or polyurethane) but are sufficient Flame protection too low, that is, they are not only not self-extinguishing, but even have a relatively high Fire speed (for example, over 100 mm / min after MVSS 302). Foils containing more than 100 phr of flame retardant are technically difficult to produce. In addition, such films have a low tear resistance and are very stiff, that is, the essential processing characteristics 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 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 polymer is used instead of the LLDPE, which has a higher softening temperature to improve the heat resistance. The disadvantage, however, is the resulting low flexibility. For blending with EVA or EEA it is said that the film has sufficient flexibility. However, it is known to the person skilled in the art from the literature that these polymers are blended with polypropylene to improve the flame retardancy. The products described have a film thickness of 0.2 mm, but this thickness excludes flexibility in filled polyolefin since it depends on the 3rd power of the thickness. The process of extrusion described is hardly feasible on a production line at the extremely low melt indices of the polyolefins used, as is known to the person skilled in the art, and certainly not for a practical thin film. The extremely low melt index limits the use to 50 to 100 phr of magnesium hydroxide.

Both solutions are based on the well-known synergistic flame retardancy of the red phos Phors with magnesium hydroxide. The use of elemental phosphorus, however, involves considerable disadvantages and dangers. The processing releases foul-smelling, self-igniting and highly toxic phosphine. Even the finished wrapping 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, only brown to black products can be produced, but wrapping tapes are used for color coding in a wide range of colors.

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

The WO 03/070848 A1 describes a film of reactive polypropylene and 40 phr of magnesium hydroxide. This 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 halogen-containing 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. It is described that the film may also contain additives, called UV and ozone stabilizers, fillers or flame retardants. For the latter, ammonium poly phosphate, antimony trioxide and aluminum trihydrate (ATH) are listed by name, but not substantiated by examples. Phosphoric acid esters, boron- or nitrogen-containing flame retardants are 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 EP 1 108 768 A1 describes an exclusively colorless adhesive tape with TPU carrier for the Überkiebung of joints in aircraft. However, the adhesive tape according to the invention is intended for winding applications, in particular wire bundles in vehicles. In practice, such winding tapes are black, colored less often and virtually never colorless. The adhesive tape claimed in the specification is additionally limited to a transparent polyurethane pressure-sensitive adhesive, but the winding tape according to the invention must have a penetrating unwinding force or adhesive force on the back in order to be applied in a slightly stretched state to the object to be wrapped. For this purpose, however, essentially adhesives of polyacrylate, natural or synthetic rubber are suitable. The claimed tape must have a thickness of at least 9 mils, that is, the film has a minimum thickness of 8 mils (0.2 mm) to meet the Boeing BSS 7230 F2 standard. The claimed in the publication adhesive tape also contains bromine-containing flame retardants, but the invention is halogen-free.

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

The Foil for the winding tape according to the invention would be with the preferred combination mentioned in the text from hydrazodicarbonamide and melamine cyanurate for decomposition at high temperatures, for the processing of TPU with the high-melting hard blocks or high Shore hardness is required, can not be 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.

There are numerous patents on compounds for halogen-free wire insulation. They describe mixtures of polypropylene homo- and copolymers and magnesium hydroxide or polyethylene or ethylene copolymers such as EEA or EVA with aluminum hydroxide, the latter are partially electron beam crosslinked. Such compounds are still relatively inexpensive, but the flame retardancy is moderate, although very high levels of flame retardants are used which reduce the abrasion resistance of the insulation. Therefore, other but relatively expensive materials such as polyphenylene oxide or polyurethane are proposed. The EP 0 505 072 describes a compound of TPU and melamine. This technical state was achieved by the invention of EP 0 617 079 A1 reconditioned by using a combination of phosphoric acid ester and melamine cyanurate as flame retardant. Due to the phosphoric acid ester, the burning melt tends to drip and improves the results of UL-94 fire testing. The WO 03/066723 A1 claims compounds made of TPU and melamine cyanurate without phosphoric acid ester, this should improve the results of the fire test in the Cone calorimeter because the burning melt does not drip off. The comparison of run number 13 with number 15 of WO 03/066723 A1 shows that omitting the phosphoric acid ester can (but does not have to, reduce the heat flow peak rate, see Run # 12), but it lowers the LOI and shortens the time to ignition.

The compound according to the invention also works without phosphoric acid ester, but has by dripping an improvement in the results of the fire test according to UL-94, FMVSS 302 and ASTM D 568 compared to the composition WO 03/066723 A1 on. Accordingly, the LOI value is higher.

aqueous Solutions of boric acid and borax (sodium tetraborate) are used for flame retardant finishing of wood or cellulose products like paper or tissue, as they use a glazing and charring the Effect surface. Zinc borate is used in polyamide and PVC formulations used as a smoke reducer, but it has no effect there as a flame retardant.

The The object of the invention is finding a solution for a wire insulation and a winding tape, which has the advantages of Flame retardancy, heat resistance, abrasion resistance and mechanical properties such as tensile strength and flexibility of soft PVC connects with the halogen-free and above In addition, a superior heat aging resistance having. Due to the absence of heavy metal stabilizers and phthalate plasticizers the wrapping tapes should be hygienic and ecological be beneficial. The complete or extensive waiver on plasticizers, especially on DOP, is desired to high fogging levels and the consequences of plasticizer migration to avoid.

task The invention furthermore relates to such compounds and wrapping tapes to provide a good insulation of Wires and fast wrapping, especially wires and cables for marking, protecting, isolating, sealing or bundles, with the disadvantages The prior art is not or at least not in the previous Scope occur.

Phosphoric acid esters act as flame retardants in polyurethane. One of the mechanisms is that phosphoric acid is formed during combustion, which cleaves the urethane groups of the polymer chain. Degradation decreases the viscosity and burning molten material drips off, removing heat from the burning point and burning or slowing down the flame. Meanwhile, there are already concerns about phosphorus compounds, especially against organic. Therefore, he is a solution wishes, which manages without phosphorus compounds.

Solved This task is accomplished by a compound as stated in the main claim is laid down. Subject of the dependent claims are advantageous Training of the subject invention and uses of the Compounds according to the invention.

Accordingly, the invention a halogen-free flame-retardant compound of thermoplastic Polyurethane (TPU) and a wound band made from it. Of the Compound contains at least one flame retardant Boron compound (E). For the expert surprising and unpredictable, boron compounds in thermoplastic can Polyurethanes, in particular in combination with nitrogen compounds act as a flame retardant. Preferably, boron compounds contained in an amount of 2 to 30 phr. Examples are zinc borate, Magnesium borate and sodium borate. Preferably, it is an organic boron compound such as melamine borate, triphenyl borate, Triethanolamine borate, triphenylborane and most preferably BDBA (1,4-benzenediboronic acid).

By the use of boron compounds are phosphorus based flame retardants dispensable, therefore, the subject invention preferably no phosphorus compounds, in particular no organic.

Prefers the compound of the invention is used as a carrier film used in a halogen-free flame-retardant winding tape, wherein in a further advantageous embodiment of the invention on at least one side of the carrier film an adhesive, in particular a pressure-sensitive adhesive is applied.

For the expert surprising and unpredictable is a Wrapping tape made of flame-retardant thermoplastic polyurethane as follows produced.

The polyurethane is out

• (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
• (E) at least one boron compound, preferably BDBA as a flame retardant and
• (F) optional other auxiliaries and additives
• (G) and optionally a nitrogen-containing flame retardant, if appropriate using a catalyst (D), preferably in the prepolymer process and preferably prepared without a phosphorus-based flame retardant.

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 reacting one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule containing two active hydrogen atoms bonded. 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 can also be trifunctional polyethers in proportions of 0 to 30 wt .-% based on the bifunctional Polyether can be used, but at most in such Amount that a still thermoplastic processable product is produced. The substantially linear polyether diols preferably have number average molecular weights M from 450 to 6000 daltons. she can be used individually as well as in the form of mixtures with each other come into use.

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

The preferred diol is a 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 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.

According to the invention have been found that thermoplastic polyurethanes with a Boron compound by adding nitrogen compounds improved Flame resistance may have. The subject invention therefore preferably contains a nitrogen compound as synergistic flame retardant. The amount of nitrogenous Flame retardant (G) is preferably between 5 and 40 phr. However, almost all nitrogen-containing flame retardants contain Amino groups such as melamine, melamine cyanurate, biuret, triuret, ammelide, Ammeline, cyanuric acid, melam, melem, dicyandiamide, guanadine or biguanadin. Preference is given to melamine cyanurate. Be thin Produced films (under 100 microns) at high temperatures, However, they can become inhomogeneous (the flame retardant is distributed unevenly, and the slide looks as if it contained many gel particles, thin ones Foils can also occur holes). It seems, that the urethane groups are thermally unstable and at high temperatures liberated isocyanate groups on the surface of such Nitrogen-based flame retardant react with the amino groups. The subject invention therefore preferably includes a nitrogen-containing flame retardant without amino groups such as Tris (2-cyanoethyl) isocyanurate, triphenyl isocyanurate, tricresyl isocyanurate or CAS no. 129757-67-1, even for thin layers to be suitable. 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.

Surprisingly is made by the solid nitrogen-containing flame retardant as well improves hand tearability.

The according to the invention related thermoplastic polyurethanes can as adjuvants and additives (F) up to preferably a maximum of 20 wt .-%, based on the total amount of TPU.

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 their mixtures and reinforcing agents such as fibrous materials. The additives include halogen, nitrogen and phosphorus-free flame retardants, examples of which are aluminum hydroxide, magnesium hydroxide, or expandable graphite. Further details about the auxiliaries and additives mentioned are the specialist literature or the DE 29 01 774 A1 refer to. The carrier film of the invention is preferably substantially free of volatile plasticizers such as DOP or DINP.

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 are antioxidants based on phenolic or aminic and secondary Sulfur or phosphorus based antioxidants. The invention Wrap bands preferably contain a combination of primary and secondary antioxidant, with the primary and secondary antioxidant function in different molecules may be present or combined in a molecule. at 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 used in diene elastomers as part of anti-aging 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 dienfreien TPU triggers. 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.

Especially is the combination of a little volatile primary phenolic antioxidant and one secondary each Antioxidants from the class of sulfur compounds (preferred having a molecular weight of more than 400 g / mol, in particular> 500 g / mol) and from the class of phosphites suitable, the phenolic, the sulfur-containing and the phosphitic functions not in three different molecules but also have more than one function in can be united to 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 sulfur-containing Function:

• CAS 41484-35-9, 90-66-4, 110553-27-0, 96-96-5, 41484

• Phenolic and aminic function:

• CAS 991-84-4, 633843-89-0

• Aminic function:

• CAS 52829-07-9, 411556-26-7, 129757-67-1, 71878-19-8, 65447-77-0

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 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.

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 in usually about 0 to 5 wt .-%, preferably 0 to 2 wt .-%, based on the total amount of TPU.

The TPU related to the invention may be produced continuously or discontinuously. The best known production methods are the strip method ( GB 1 057 018 A ) and the extruder process ( DE 19 64 834 A1 ). The structure of the TPU can 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 and / or excipients may be made before, during or after the polyurethane reaction.

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 wrapping tapes to be achieved. Therefore become the properties of the present invention in this regard described in detail below.

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 for the flame retardance does not matter. Halogens in Trace amounts, as caused by impurities, process additives (fluoroelastomer) or occur as residues of catalysts could be disregarded.

Of the Avoiding halogens usually pulls the property of light weight Flammability, which meets the safety requirements in electrical Applications like home appliances, buildings or Vehicles does not comply. The erfindungemäße Winding tape has self-extinguishing properties, wherein the preferred embodiments of the winding tape in fire tests according to FMVSS 302 (horizontal sample) and / or ASTM D 568 (vertical sample) test conditions of to extinguish yourself.

The thickness of the winding tape according to the invention is preferably in the range of 30 to 180 .mu.m, preferably 50 to 150 .mu.m, in particular 55 to 100 microns. If the wrapping tape has a pressure-sensitive adhesive coating, the stated thickness information relates only to the film. The relatively small thickness provides good conformability in winding, sufficient hand tearability and acceptable cost. The surface can be textured or smooth. Preferably, the surface is slightly dull. This can be done by using a filler with a sufficiently high particle size or by a roller (For example, embossing roll on the calender or frosted chill roll or embossing roll in the extrusion) can 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 blades. By strong cooling of the rods before cutting, cracking during the cutting process may still be 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 312 hours storage at 140 ° C (heat resistance test) or a short-term heat resistance of 170 ° C (no cracks or fused spots after 30 minutes).

to Achieving these force values as well as the heat resistance Contains the film of the winding tape a TPU with sufficient high hard block content, which is why the Shore D hardness of the TPU raw material preferably at least 35 and more preferably at least 50 is approximately equal to Shore A hardness of preferably at least 85, or more preferably at least 100. The flame resistant ones shown in the prior art Adhesive tapes use much softer TPU (Shore A 70 to 80) than the flame-resistant adhesive tapes sought here. If the tapes made of such soft TPUs are still plasticizers or phosphoric acid ester added as a flame retardant These are then much more inappropriate than the invention Wrapping tapes.

The Production of the film takes place on a calender or by extrusion as in the blowing or casting process. At the same time of solid or liquid additives for the TPU can be a compound of the main components or all components in a compounder such as kneader (for example, blender) or Extruder (for example twin-screw extruder, planetary roller extruder) prepared and then converted into a solid form (for example granules), which then in a film extrusion line or in an extruder, Kneader or rolling mill calendering be further processed.

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

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

When Adhesives are all common types in question, especially based on rubber. Such rubbers can, for example Homopolymers or copolymers of isobutylene, of 1-butene, of vinyl acetate, of ethylene, of acrylic esters, of butadiene or of isoprene. Especially suitable are formulations based on of polymers based on acrylic esters, vinyl acetate or isoprene.

To optimize the properties, the self-adhesive composition used can be 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 such as rosin and its derivatives, for example, disproportionated, dimerized or esterified resins, for example, which include reaction products with glycol, glycerol or pentaerythritol, to name a few, and include other resins. Preference is given to using resins without easily oxidizable double bonds, such as terpene-phenolic resins, aromatic resins and particularly preferably resins which are prepared by hydrogenation, for example hydrogenated aromatic resins, hydrogenated polycyclopentadiene resins, hydrogenated rosin derivatives or hydrogenated terpene resins.

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

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.

In summary, the preferred embodiment has on one side a solvent-free self-adhesive composition which has been produced by coextrusion, melt or dispersion coating. In particular, polyacrylate-based adhesives in the form of dispersions or hotmelts are preferred. An adhesive which has been found particularly suitable is a low molecular mass acrylate as under the name acResin UV or Acronal ^®, in particular Acronal DS 3458 by BASF ge leads. This adhesive obtains its application-oriented properties by radiation-induced crosslinking.

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.

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

A Coating the back can be done by known release agents (optionally blended with other polymers). 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.

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 is taken into account by the use of halogenated and if possible, even raw materials containing heavy metals are dispensed with becomes. The halogen-free is for thermal utilization of waste containing such wrapping tapes, of extraordinary importance (for example, waste incineration the plastic fraction from vehicle recycling) but also in cable or building fires, as there are no toxic flue gases arise.

in the The ever more complicated electronics and the rising Number of electrical consumers in automobiles will also the wiring harnesses become more complex. With rising cross sections of Wiring harnesses, inductive heating is getting bigger, while the heat dissipation decreases. Thereby rise the heat resistance requirements of used materials. The standard used Pvc materials for the winding tapes encounter here to its limits. This problem can now be solved as well be considered.

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 Hydrolysis resistance is determined by storage of the sample in determined warm distilled water. After 1000 hours at 80 ° C The sample is dried for 24 hours at 80 ° C in a vacuum and then the decrease in tear strength determined against the fresh state. When the tear strength less than 50%, the test passes (P, passed), and if it has decreased by at least 50%, the test is not passed (NP, not passed).

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 Bonding forces are reduced by a deduction angle of 180 ° AFERA 4001 on (if possible) 15 mm wide test strips certainly. Here, steel plates to AFERA standard as a test substrate used as far as no other primer is mentioned.

The thickness of the film will be after DIN 53370 determined (A possible pressure-sensitive adhesive layer is subtracted from the measured total thickness).

The Holding Power is determined according to the PSTC 107 (10/2001), where the Weight is 20 N and the dimensions 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 Hand tearability can not be counted express, even if breaking strength, breaking elongation and impact resistance (all measured lengthwise) are of significant influence.

Rating:

• - +++ = very easy,
• - ++ = good,
• - + = still processable,
• - 0 = difficult to process,
• - = can only be torn off with great effort, the ends are dirty,
• - --- = not processable

The fire behavior is measured according to FMVSS 302 (horizontal sample) or ASTM D 568 (vertical sample). 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 ).

The Cone calorimeter test is measured according to ASTM E-1354 with a heat flux of 35 kW / m ² (cf. WO 03/066 723 ).

Of the LOI value is determined according to ASTM D-2863.

The Temperature resistance is determined by two methods. The wrapping tape is first applied to a siliconized polyester film glued and stored in the heat. After expiry of the test time the sample is cooled at 23 ° C for 30 minutes. At the Heat resistance test becomes after 312 hours Storage at 140 ° C tested whether the elongation at break still at least 100%. The examination of Short-term heat resistance is achieved by storage for 30 minutes the sample at 170 ° C, followed by winding of at least 3 turns with 50% overlap by one Mandrel of 10 mm diameter and subsequent assessment, whether the pattern damages (for example, cracks, molten Places).

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

The breakdown voltage is measured according to ASTM D 1000. The number is taken to be the highest value that the sample withstands at this voltage for one minute. This number is converted to a sample thickness of 100 μm. Example:
A sample of 200 μm thickness withstands a maximum voltage of 6 kV after one minute, the calculated breakdown voltage is 3 kV / 100 μm.

The following examples are intended to illustrate the invention without limiting its scope. Explanation of the PU raw materials used in the examples Terathane ^TM 1000: Polyethers with a molecular weight of M _n = 1000 daltons (DuPont) Terathane ^TM 650: Polyethers with a molecular weight of M _n = 650 daltons (DuPont) MDI: 4,4'-diphenylmethane diisocyanate PPM Triazine ^TM : Poly- [2,4- (piperazin-1,4-y1) -6- (morpholin-4-yl) -1,3,5-triazine] (Degussa) NORD-MIN ^TM MC-25J: Melamine cyanurate (Nordmann-Rassmann) Melagard ^TM MB: Melamine borate (Italmatch) BDBA: 1,4-benzenediboric acid (University of South Carolina) Bisphenol A polysulfone: Poly (oxy-1,4-phenylenesulfonyl-1,4-phenyleneoxy-1,4- phenylene (1-methylethylidene) -1,4-phenylene) (udle) PX-200 ^TM : Tetrakis (2,6-dimethylphenyl) resorcinol diphosphate (Daihachi) BDO: 1,4-butanediol Irganox ^TM 1010: Tetrakis (methylene (3,5-di-tert-butyl-4-hydroxycinnamate)) methane (Ciba Specialty Chemicals) Licowax ^TM C: Release agent (Clariant Würtz GmbH) Shisuto 3H ^TM : Furnace black (Tokai Carbon)

example 1

From MDI and Terathane ^™ 1000, a prepolymer in the presence of Irganox ^™ 1010, Licowax ^™ C, PPM Triazine ^™ and BDBA was prepared at 2.5: 1 molar ratio and reacted with 95 mol% of the equivalent amount of BDO, after which the TPU was poured out , Finally, the material was post-treated at 80 ° C for 30 minutes. The contents of the additives were 0.3 phr Irganox ^™ 1010, 0.3 phr Licowax ^™ C, 23 phr PPM Triazine ^™ and 8 phr BDBA (based on 100 phr TPU polymer).

The finished TPU was cut, granulated and added with the addition of 5 % By weight Masterbatch white at a temperature of 180 to 200 ° C to a 100 micron blown film processed.

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

Example 2

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, Shisuto 3H ^™ and Melagard ^™ MB and reacted with 95 mol% of the equivalent amount of BDO. The levels of additives are 0.3 phr Irganox ^™ 1010 (based on 100 phr TPU polymer), 1 phr Shisuto 3H ^™ and 27 phr Melagard ^™ MB.

The finished TPU was cut, granulated and with the addition of 5 wt .-% of a black batch and 5 wt .-% of a Hydrolysschutzmittelmasterbatches (KE 9463 from Rhein-Chemie = 20 wt .-% Stabaxol ^TM P200 in TPU) in the cast process (flat die with Chillroll) formed into a 70 micron thick film.

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

Comparative Example 1

The Production of the winding tape was carried out analogously to Example 1, however the bisphenol A polysulfone was omitted.

Comparative Example 2

The Production of the winding tape was carried out analogously to Example 2, however the diphenylsulfone was omitted.

Comparative Example 3

• • 40 phr T-8375,
• • 60 phr CM6541X3 (Copolyamid aus ε-Aminocapronsäure und ω-Aminolaurinsäure mit Kristallitschmelzpunkt 133°C von Toray Industries),
• • 10 phr Hydrazodicarbonamid,
• • 40 phr NORD-MIN^TM MC-25J
• • 1 phr Licowax^TM OP,
• • 10 phr Calciumcarbonat.

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

• • 40 phr T-8375,
• 60 phr of CM6541X3 (copolyamide of ε-aminocaproic acid and ω-aminolauric acid having a crystallite melting point of 133 ° C. from Toray Industries),
• • 10 phr of hydrazodicarbonamide,
• • 40 phr NORD-MIN ^TM MC-25J
• • 1 phr Licowax ^TM OP,
• • 10 phr calcium carbonate.

at a processing temperature similar to Example 1 glued the melt on the calender rolls. She had blisters and holes (presumably by decomposition of the hydrazodicarbonamide), after lowering the temperature at 160 to 170 ° C, a film could be produced. However, the thickness was 80 μm instead of 0.2 as in Example 1 mm as in Japanese writing.

Comparative Example 4

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

• ND = not determined (nicht bestimmt), P = passed (erfüllt), NP = not passed (nicht erfüllt), Y = ja, N = nein
• * erfüllt, Probe ist jedoch weiß verfärbt

On the one hand, the primer Y01 was applied by Four Pillars Enterprise / Taiwan (analytically acrylate-modified SBR rubber in toluene) and thereon 23 g / m ^{2 of} the adhesive IV9 from Four Pillars Enterprise / Taiwan (analytically detectable major component: SBR and natural rubber, terpene resin and alkylphenol resin in toluene). The film was cut into rolls immediately after the dryer with a knife bar with sharp blades at a distance of 25 mm in an automatic machine. Properties of Examples and Comparative Examples example 1 Example 2 Comparative Example 1 Comparative example 2 Comparative example 3 Comparative example 4 Film thickness [μm] 100 70 100 70 80 100 Bond strength steel [N / cm] 3.0 2.9 3.1 3.0 2.2 1.8 Breaking force [N / cm] 32 31 35 35 30 15 Elongation at break [%] 380 450 470 400 400 150 Force at 10% strain [N / cm] 11 5 11 7 2 6 Force at 50% elongation [N / cm] 16 10 19 12 3 12 Heat resistance 168h @ 140 ° C P ND P ND NP NP Short term heat resistance 30 min @ 170 ° C P P P P NP NP hand tearability + + + 0 + +++ FMVSS 302 P P P P P NP ASTM D 568 NP P P P NP NP hydrolysis P P * P P NP P Breakdown voltage [kV / 100 μm] 6 6 7 7 ND 4

• ND = not determined, P = passed, NP = not passed, Y = yes, N = no
• * met, sample is white discolored

Example A1

There were test specimens according to Example 2 of EP 0 617 079 A1 prepared, but with BDBA instead of the phosphoric acid ester. The polyurethane used was Elastollan 11895 A and the melamine cyanurate NORD-MIN ^™ MC-25J.

Comparative Example C1

There were test specimens according to Example 2 of EP 0 617 079 A1 produced. The raw materials used were Elastollan 11895 A, NORD-MIN ^™ MC-25J and phosphoric acid ester PX-200 ^™ .

Comparative Example V2

This comparative example corresponds to the composition of WO 03/066723 A1 (without phosphoric acid ester), but according to the EP 0 617 079 A1 checked. The raw materials used were 75% by weight of Elastollan 11895 A and 25% by weight of NORD-MIN ^™ MC-25J. Test results A1, V1 and V2 attempt LOI UL94 phosphorus free Example A1 24 V0 Yes Comparative Example C1 25 V0 No Comparative Example V2 21.5 Sample burns Yes

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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Claims (16)

Halogen-free flame-retardant compound made of thermoplastic Polyurethane, as a flame retardant at least one boron compound contains, preferably in a proportion of 2 to 30 phr. Compound according to claim 1, characterized the boron compound is organic, preferably BDBA. Compound after at least one of the previous ones Claims, characterized in that it does not contain a flame retardant based on phosphorus. Use of a compound according to at least one of previous claims as wire insulation. Use of a compound according to at least one of preceding claims as a carrier film in one halogen-free flame-retardant wrapping tape. Use of a compound according to at least one of preceding claims as a carrier film in one halogen-free flame-retardant winding tape, characterized in that at least on one side of the carrier film an adhesive, preferably PSA is present. Use of a compound according to at least one of preceding claims as a carrier film in one halogen-free flame-retardant winding tape, characterized that the wrapping tape is colored. Use of a compound according to at least one of preceding claims as a carrier film in one halogen-free flame-retardant winding tape, characterized that the wrapping tape is under those mentioned in the FMVSS 302 or ASTM D 568 Test conditions is self-extinguishing. Use of a compound according to at least one of preceding claims as a carrier film in one halogen-free flame-retardant wrapping tape, characterized, that the thickness of the film 30 to 180 microns, preferably 50 to 150 μm, very particularly 55 to 100 μm is, the force in the machine direction at 10% elongation has a value of 2 to 20 N / cm, especially 4 to 11 N / cm, the Force at 50% elongation a value of 3 to 25 N / cm, especially 6 up to 17 N / cm and / or the tear strength bigger is 10 N / cm and preferably greater than 20 N / cm. Use of a compound according to at least one of the preceding claims as a carrier film in a halogen-free flame-retardant winding tape, characterized, that the breaking elongation after 312 hours storage at 140 ° C at least 100% and / or after 30 minutes storage at 170 ° C when winding with at least 3 turns and 50% overlap around a mandrel of 10 mm diameter no damage to be observed. Use of a compound according to at least one of the preceding claims as a carrier film in a halogen-free flame-retardant winding tape, characterized that the Shore D hardness of the polyurethane is at least 35, preferably at least 50 and / or the crystallite melting point of Polyurethane at least 158 ° C, preferably at least 170 ° C is. Use of a compound according to at least one of the preceding claims as a carrier film in a halogen-free flame-resistant winding tape, characterized in that the amount of the adhesive layer 10 to 40 g / m ² , preferably 18 to 28 g / m ² , the bond strength of the winding tape on steel. 1 , 5 to 3 N / cm, the unwind force of the winding belt 1.2 to 6.0 N / cm at 300 mm / min unwinding speed, preferably 1.6 to 4.0 N / cm, particularly preferably 1.8 to 2.5 N / cm and / or the holding power of the winding tape is more than 150 min. Use of a compound according to at least one of the preceding claims as a carrier film in a halogen-free flame-retardant winding tape, characterized in that the polyurethane of the carrier film of (A) at least one organic diisocyanate and (B) at least one polyol having an average of at least 1.8 and at most 3.0 Zerewitinoff-active hydrogen atoms and a number average molecular weight M _n of 450 to 10,000 daltons with (A) C) at least one low molecular weight polyol or polyamine having on average 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 (E) at least boron compound, preferably BDBA as flame retardant and (F) optionally further auxiliaries and additives (G) and optionally a nitrogen-containing flame retardant and optionally using a catalyst (D) is preferably prepared by the prepolymer process and preferably does not contain a flame retardant based on phosphorus. Use of a compound according to at least one of the preceding claims as a carrier film in a halogen-free flame-retardant winding tape, characterized, that the isocyanate (A) 4,4'-diphenylmethane diisocyanate, the Polyol (B) a hydroxyl-containing polymerization of the Tetrahydrofuran and / or the chain extender (C) is 1,4-butanediol. Use of a compound according to at least one of the preceding claims as a carrier film in a halogen-free flame-retardant winding tape, characterized the polyurethane film is at least 1, preferably at least 2 phr stabilizers against oxidation and / or hydrolysis. Use of a compound according to at least one of the preceding claims as a carrier film in a halogen-free flame-retardant wrapping tape for bundling, Protecting, marking, insulating or sealing ventilation pipes, Wires or cables or for sheathing cable harnesses in vehicles or field coils for picture tubes.