WO2008151893A1 - Composé et bande à enrouler en film de polyuréthane thermoplastique - Google Patents

Composé et bande à enrouler en film de polyuréthane thermoplastique Download PDF

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Publication number
WO2008151893A1
WO2008151893A1 PCT/EP2008/055873 EP2008055873W WO2008151893A1 WO 2008151893 A1 WO2008151893 A1 WO 2008151893A1 EP 2008055873 W EP2008055873 W EP 2008055873W WO 2008151893 A1 WO2008151893 A1 WO 2008151893A1
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WIPO (PCT)
Prior art keywords
halogen
compound according
winding tape
carrier film
free flame
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PCT/EP2008/055873
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German (de)
English (en)
Inventor
Bernhard MÜSSIG
Original Assignee
Tesa Se
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Publication date
Priority claimed from DE102007028593A external-priority patent/DE102007028593A1/de
Application filed by Tesa Se filed Critical Tesa Se
Publication of WO2008151893A1 publication Critical patent/WO2008151893A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/302—Applications of adhesives in processes or use of adhesives in the form of films or foils for bundling cables
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C09J2475/006—Presence of polyurethane in the substrate

Definitions

  • the present invention relates to a halogen-free, flame-retardant, preferably colored compound.
  • the compound is suitable for halogen-free insulation of wires and cables, in particular for automotive applications and for the production of a winding tape, which preferably has an adhesive coating and which is used for example for wrapping ventilation ducts in air conditioners, wires or cables and in particular for harnesses in vehicles or cables Field coils suitable for picture tubes.
  • the wrapping tape serves for bundling, isolating, marking or protecting.
  • Wire insulation, cable wrapping tapes and insulating tapes are usually made of plasticized PVC.
  • plasticized PVC plasticized PVC.
  • disadvantages of these products such as the evaporation of plasticizers and the high halogen content.
  • the plasticizers of conventional wire insulation, insulating tapes and cable tapes are gradually evaporating, resulting in a health burden, in particular, the commonly used DOP is questionable. Furthermore, the vapors in vehicles impact on the windows down, which deteriorates the visibility (and thus considerably the driving safety) and is referred to by the expert as fogging (DIN 75201). 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.
  • wrap bands contain stabilizers based on toxic heavy metals such as lead, cadmium or barium.
  • textile adhesive tapes 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 can be taken from DE 200 22 272 U1, EP 1 123 958 A1, WO 99/61541 A1 and US Pat. No. 4,992,331 A1.
  • 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 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 can be found in DE 100 02 180 A1, JP 10 149 725 A1, JP 09 208 906 A1, JP 05 017 727 A1 and JP 07 150 126 A1.
  • phr means parts by weight of a component based on 100 parts by weight of the thermoplastic polymer such as polypropylene or polyurethane
  • phr means parts by weight of a component based on 100 parts by weight of the thermoplastic polymer such as polypropylene or polyurethane
  • phr means parts by weight of a component based on 100 parts by weight of the thermoplastic polymer such as polypropylene or polyurethane
  • Ethylene copolymer is 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 below briefly even over 130 0 C, which is not uncommon when used in the engine compartment.
  • WO 97/05206 A1 describes a halogen-free wound 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.
  • Analogous problems of lack of heat resistance occur in the electrical adhesive tapes described in WO 99/35202 A1 and US Pat. No. 5,498,476 A1.
  • 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.
  • 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.
  • EP 0 953 599 A1 claims a polymer blend of LLDPE and EVA for cable insulation applications and as a sheet material.
  • 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 is described in EP 1 097 976 A1.
  • a PP polymer is used instead of the LLDPE to improve the heat resistance, which has a higher softening temperature.
  • the disadvantage is the resulting low flexibility.
  • the film has sufficient flexibility.
  • EVA or EEA it is said that the film has sufficient flexibility.
  • 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 method of extrusion described is barely feasible on a production line at the extremely low melt indices of the poly-olefins 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.
  • JP 2001 049 208 A1 describes an oil and heat-resistant film for an adhesive tape, in which both layers comprise a mixture of EVA or EEA, peroxide crosslinker, silane crosslinker, catalyst for the silanol condensation and flame retardant (100 phr of magnesium hydroxide).
  • This film solves neither the problem of poor flexibility of a filled polypropylene film, nor the high demands on the aging resistance.
  • 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 cited prior art documents lead because of the disadvantages mentioned, in particular lack of flame retardancy, flexibility, tear resistance and / or heat resistance, no films that also solve the other requirements such as hand tearability, compatibility with Polyolefin mecanicisol ist or sufficient unwinding force. In addition, processability in film forming processes, high fogging value and breakdown voltage strength remain questionable.
  • the main problem of the known inventions based on flame-retardant carrier films of polyolefin and metal hydroxide is the incompatibility of the mechanical requirements with those of flame resistance.
  • Adhesive tapes made of polyurethane (PU) are known, some with flame retardant equipment. These are mostly tack-sensitively treated PU foams and also foil-based adhesive tapes explained below.
  • JP 2001 020 178 A1 describes a double-sided adhesive tape for electromagnetic shielding made of a polyester fabric and a halogen-containing PU layer.
  • JP 2001 288 430 A1 describes a flame-retardant adhesive tape whose support has been produced 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. Tries, Dicyandiamide incorporation into thermoplastic polyurethane (TPU) have failed due to decomposition of the TPU during compounding.
  • JP 2003 013 026 A1 and JP 2004 115 608 A1 describe (masking) adhesive tapes for handling radioactive substances, whose carrier is also produced 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).
  • 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.
  • APP as a strong ionic salt, also causes poor electrical properties, as is known from use in other materials, for example wire insulation compounds.
  • the winding tape according to the invention should also have good insulating properties.
  • antimony trioxide only works in combination with halogens and therefore makes no sense in TPU alone.
  • 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.
  • EP 1 108 768 A1 describes an exclusively colorless adhesive tape with TPU carrier for the gluing of joints in aircraft.
  • 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.
  • JP 2005 264 1 12 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.
  • 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 film for the winding tape according to the invention should have the highest possible temperature resistance, that is, a short-term heat resistance at 170 0 C and a heat resistance at 140 0 C, therefore, a TPU with significantly higher Softening point required than mentioned in the document TPUs to modify 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 0 C and more result.
  • the film has a thickness of 0.2 mm.
  • the adhesive tape described is phosphorus-free.
  • the film for the winding tape according to the invention would not be produced with the mentioned in the text preferred combination of hydrazodicarbonamide and melamine cyanurate because of the decomposition at high temperatures, which is required for the processing of TPU with high-melting hard blocks or high Shore hardness.
  • EP 1 101 807 A1 mentions a mask adhesive tape with a composite carrier of crosslinked polyurethane and polyester.
  • the PU layer may be modified with fillers, flame retardants are not mentioned.
  • the adhesive tape carriers mentioned are produced by in-line metering and mixing of polyol, isocyanate and catalyst on an auxiliary carrier.
  • the advantage lies in low raw material costs compared to TPU, however the process is very difficult to realize in practice. Since the carriers are crosslinked, is also a thermoplastic
  • Subject of the invention is the lack of suitability for winding tapes, since they have neither flame retardancy nor a sufficient tensile strength, which results in TPU from the physical crosslinking on the hard blocks.
  • EP 1 469 052 A1 and EP 1 469 024 A1 describe adhesive tapes with crosslinked polyurethanes as pressure-sensitive adhesives on any supports, but not TPU films.
  • US Pat. No. 5,858,495 A1 describes a very thick luminescent adhesive tape whose support is produced 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.
  • Comparing 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 degrades the LOI and time shortened to inflammation.
  • 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 according to WO 03/066723 A1. Accordingly, the LOI value is higher.
  • the object of the invention is to find a solution for a wire insulation and a winding tape, which has the advantages of halogen-free, flame retardant, heat resistance, abrasion resistance, and mechanical properties such Combines tensile strength and flexibility of PVC wrapping tapes and PVC wire insulations with the halogen freedom of textile non-flame resistant tapes, and moreover has superior heat aging resistance, to ensure large-scale manufacturability and high dielectric strength in some applications. Due to the absence of heavy metal stabilizers, antimony oxide as flame retardants and phthalate plasticizers, the wire insulation and wrapping tapes should be hygienic and ecologically beneficial. The complete or substantial abandonment of plasticizers, in particular DOP, is desirable in order to achieve high fogging values and to avoid the consequences of plasticizer migration in the adhesive, such as telescoping or edge tackiness.
  • the object of the invention is also to provide such compounds for wire insulation and winding tapes available, which allow a particularly safe and fast wrapping, especially of wires and cables for marking, protecting, insulating, sealing or bundling, and insulating copper wires with the disadvantages of the prior art do not occur or at least not in the previous extent.
  • thermoplastically prepared compounds for wire insulation and films with additive combinations that not only reach, but even surpass the heat resistance and flame resistance of PVC.
  • the invention relates to a halogen-free, flame-retardant compound and a wire insulation produced therefrom and a wound strip made therefrom with a thermoplastic polyurethane carrier film.
  • the compound contains as flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or a reaction product of DOPO and another compound in which the H of the PH bond is substituted by an organic radical.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • the compound of the invention is preferably used as a carrier film in a halogen-free flame-resistant winding tape, wherein in a further advantageous development of the invention on at least one side of the carrier film an adhesive, in particular a pressure-sensitive adhesive is applied.
  • a compound for a wire insulation and for a support made of thermoplastic polyurethane with at least one flame retardant suitable in a winding band can be produced as follows.
  • the polyurethane is out
  • the index (formed from the multiplied by 100 quotient of the equivalence ratios of the isocyanate groups from (A) and the sum of the Zerewitinoff-active hydrogen atoms of the compounds (B) and (C)) is 85 to 120, preferably 95 to 110. If a phosphorus-containing polyol (see below), this is to be added to the sum of the Zerewitinoff-active hydrogen atoms of the compounds (B) and (C).
  • the components (B) and (C) are different.
  • organic diisocyanates (A) it is possible to use aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates or any desired mixtures of these diisocyanates.
  • 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'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures; also aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2,4-tolylene diisocyanate and 2,6-
  • 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 - Naphthylene diisocyanate.
  • the diisocyanates mentioned can be used individually or in the form of mixtures with one another. They may also be used together with up to 15 mole% (calculated on total diisocyanate) of a polyisocyanate. However, it may be added at most as much polyisocyanate that a still thermoplastically processable product is formed.
  • polyisocyanates examples include triphenylmethane-4,4 ', 4 "-triisocyanate and polyphenyl polymethylene polyisocyanates.
  • the most preferred isocyanate is 4,4'-diphenylmethane diisocyanate.
  • Zerewitinoff-active polyols (B) which are used in the products of the invention are those having on average 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.
  • amino groups include 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.
  • 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:
  • amino alcohols such as N-alkyl-diethanolamine, for example N-methyl-diethanolamine and diols such as ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
  • diols such as ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
  • mixtures of starter molecules can be used.
  • Suitable polyetherols are also the hydroxyl-containing polymerization of tetrahydrofuran. It is also possible to use trifunctional polyethers in proportions of from 0 to 30% by weight, based on the bifunctional polyethers, but at most in such an amount that a still thermoplastically processable product is formed.
  • the substantially linear polyether diols preferably have number average molecular weights M n of 450 to 6000 daltons. They can be used both individually and in the form of mixtures with one another.
  • Suitable polyester diols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohols.
  • 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.
  • 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.
  • 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.
  • the polyhydric alcohols may be used alone or mixed with each other.
  • 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 caprolactones.
  • polyester diols Preferably used as polyester diols are 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.
  • 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 are so-called chain extenders and have an average of 1, 8 to 3.0 Zerewitinoff15 hydrogen atoms and have a molecular weight of 60 to 400 daltons. By these is meant, in addition to amino groups, thiol groups or carboxyl-containing compounds, those having two to three, preferably two hydroxyl groups.
  • chain extenders are preferably used aliphatic diols having 2 to 14 carbon atoms such as ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 2,3-butanediol, 1, 5-pentanediol, 1, 6 Hexanediol, diethylene glycol and dipropylene glycol.
  • diesters of terephthalic acid with glycols having 2 to 4 carbon atoms for example terephthalic acid bis-ethylene glycol or terephthalic acid bis-1,4-butanediol, hydroxyalkylene ethers of hydroquinone, for example 1,4-di (beta-hydroxyethyl) hydroquinone ethoxylated bisphenols for example 1,4-di (beta-hydroxyethyl) bisphenol A, (cyclo) aliphatic diamines such as isophoronediamine, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, N-methyl-propylene-1,3 -diamine, N, N'-dimethylethylenediamine and aromatic diamines such as 2,4-toluenediamine, 2,6-toluylenediamine, 3,5-diethyl-2,4-toluenediamine or 3,5-diethyl-2
  • Ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-di (beta-hydroxyethyl) hydroquinone or 1,4-di (beta-hydroxyethyl) bisphenol A are particularly preferably used as chain extenders. It is also possible to use mixtures of the abovementioned chain extenders. In addition, smaller amounts of triols 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 resistance to melting of the samples under temperature load.
  • Compounds which are monofunctional towards isocyanates can be used in proportions of up to 2% by weight, based on TPU, as so-called chain terminators.
  • Suitable examples are monoamines such as butyl and dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, piperidine or cyclohexylamine, monoalcohols such as butanol, 2-ethylhexanol, octanol, dodecanol, stearyl alcohol, the various amyl alcohols, cyclohexanol and ethylene glycol monomethyl ether.
  • the compound contains 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) or a reaction product of DOPO and another compound in which the H of the PH bond is substituted by an organic radical, the amount is preferably 5 to 40 phr.
  • catalysts such as boric acid or imidazole derivatives can be used.
  • the reaction can be carried out, for example, as an addition reaction (for example DOPO with acrylonitrile, quinone, itaconic acid or acrylic ester) or condensation reactions (for example with alkylated phenolic resins or formaldehyde resins such as dimethylolbenzoguanamine).
  • DOPO or its reaction products may be added to the polyurethane or incorporated into the polyurethane.
  • the phosphorus-containing flame retardant (G) is selected from inorganic or preferably organic compounds.
  • the amount of phosphorus-containing flame retardant is preferably between 5 and 40 phr. Examples are ammonium polyphosphate, ethylenediamine polyphosphate and phosphoric acid and phosphonic acid esters such as, for example, triphenyl phosphate, tricresyl phosphate, alkyphenyl phosphates, diphenyl cresyl phosphate.
  • R is preferably an aryl group (for example phenyl, cresyl)
  • A is a linking group such as arylene (for example phenylene), biarylene (for example
  • Biphenyl two arylene groups represented by another group such as -CH 2 -, -C (CH 3 ) 2 -,
  • diphenols such as resorcinol or bisphenol A (which then form the group A)
  • monophenols such as phenol and cresol (which then form the group R) produced.
  • Bisphenol A bis (diphenylphosphate) and its oligomers Bisphenol A bis (diphenylphosphate) and its oligomers.
  • phosphonic acid esters (G) are dimethyl methylphosphonate, diethyl-N, N-bis-
  • Antiblaze TM or Vircol TM available.
  • phosphonic acid groups such as diphosphonates, for example nitrilotris (methylene phosphonic acid) and its salts and amides.
  • the phosphonic acid esters can also be polymeric, for example reaction products of methanephosphonic dichloride, and bisphenol A.
  • phosphoric or phosphonic acid derivatives which on hydrolysis release neither phenol nor cresol, examples of which are trixylyl phosphate, butylated triphenyl phosphates (for example Fyrquel TM EHC-S), phosphoric acid-1, 3-phenylene tetraxylenyl ester.
  • the phosphor may also be incorporated in the polyurethane.
  • incorporable phosphorus-containing compounds are phosphonates or phosphine oxides having an average of at least 1, 5 and at most 3.0 Zerewitinoff-active hydrogen atoms and a number average molecular weight M n of 60 to 10,000 daltons have the following structural formula
  • R 1 , R 2 branched or unbranched alkylene radicals having 1 to 24 carbon atoms, substituted or unsubstituted arylene radicals having 6 to 20 carbon atoms, substituted or unsubstituted aralkylene radicals having 6 to 30 carbon atoms, substituted or unsubstituted Alkarylene radicals having 6 to 30 carbon atoms, where R 1 and R 2 may be identical or different, R 3 H, branched or unbranched alkyl radicals having 1 to 24 carbon atoms, substituted or unsubstituted aryl radicals having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl radicals having 6 to 30 carbon atoms, substituted or unsubstituted alkaryl radicals with 6 to 30 carbon atoms,
  • R 1 H branched or unbranched alkyl radicals having 1 to 24 carbon atoms, substituted or unsubstituted aryl radicals having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl radicals having 6 to 30 carbon atoms, substituted or unsubstituted alkaryl radicals with 6 to 30 carbon atoms,
  • R 2 , R 3 branched or unbranched alkylene radicals having 1 to 24 carbon atoms, substituted or unsubstituted arylene radicals having 6 to 20 carbon atoms, substituted or unsubstituted aralkylene radicals having 6 to 30 carbon atoms, substituted or unsubstituted Alkarylene radicals having 6 to 30 carbon atoms, wherein R 2 and R 3 may be the same or different
  • nitrogen-containing flame retardants (F) are, for example melamine cyanurate, melamine,
  • Biuret, triuret, ammelide, ammeline, cyanuric acid tris (2-hydroxyethyl) isocyanurate, bis (2-hydroxyethyl) isocyanurate, 2-hydroxyethyl isocyanurate, Tris (carbomethyl) isocyanurate, tris (2-cyanoethyl) isocyanurate, bis (2-cyanoethyl) isocyanurate, 2-cyanoethyl isocyanurate, trimethyl isocyanurate, HA (L) S such as CAS no.
  • nitrogen-containing flame retardant is melamine cyanurate.
  • nitrogen-containing flame retardants without amino groups such as tris (2-cyanoethyl) isocyanurate, triphenyl isocyanurate, tricresyl isocyanurate or CAS no. 129757-67-1 better suited.
  • the amount of nitrogen-containing flame retardant is preferably between 5 and 40 phr.
  • solid nitrogen-containing flame retardants also improve hand tearability.
  • Suitable combined phosphorus- and nitrogen-containing flame retardants (F) / (G) are compounds which contain both elements, for example melamine phosphate, melamine polyphosphate, urea phosphate, triethanolamine phosphate or phosphoroxytriamide.
  • thermoplastic polyurethanes used according to the invention may contain as auxiliary agents and additives (H) up to a maximum of preferably 20% by weight, based on the total amount of TPU.
  • 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 substances and fillers and their mixtures and reinforcing agents such as fibrous materials.
  • the additives include the halogen, nitrogen and phosphorus-free flame retardants, examples of which are aluminum hydroxide, magnesium hydroxide, expandable or exfoliated graphite. Furthermore you can multifunctional alcohols such as pentaerythritol, dipentaerythritol and cellulose further improve the flame resistance.
  • the compound according to the invention or the carrier film produced therefrom are preferably substantially free of volatile plasticizers such as DOP or DINP and therefore have an excellent fire behavior and low emission (plasticizer evaporation, fogging).
  • the fogging value is preferably over 90%.
  • the compound of the invention or the carrier film produced therefrom preferably contain at least 1 phr and in particular at least 2 phr of stabilizers against oxidation and / or hydrolysis (the data in phr mean parts by weight of the relevant component based on 100 parts by weight of all polymer components of the film).
  • stabilizers against oxidation and / or hydrolysis examples are phenolic or amine based antioxidants and sulfur or phosphorus based secondary antioxidants.
  • the compound according to the invention or the carrier film produced therefrom preferably contain a combination of primary and secondary antioxidant, wherein the primary and secondary antioxidant function may be present in different molecules or may be combined in one molecule.
  • the listed quantities do not include optional stabilizers such as metal deactivators or light stabilizers.
  • the amount of secondary antioxidant is preferably at least 0.5 phr, more preferably at least 1 phr.
  • Stabilizers for PVC products can not be transferred to TPU.
  • Secondary antioxidants break down peroxides and are therefore used in diene elastomers as part of anti-aging packages.
  • primary antioxidants for example sterically hindered phenols or C radical scavengers such as CAS 181314-48-7
  • secondary antioxidants for example sulfur compounds, phosphites or sterically hindered amines
  • a low-volatile primary phenolic antioxidant and in each case a secondary antioxidant from the class of sulfur compounds (preferably having a molecular weight of more than 400 g / mol, in particular> 500 g / mol) and from the class of phosphites is suitable in which the phenolic, sulfurous and phosphitic functions need not be present in three different molecules, but more than one function may be combined in one molecule.
  • Phosphitic function CAS 31570-04-4, 26741-53-7, 80693-00-1, 140221-14-3, 1 19345-01-6, 3806-34-6, 80410-33-9, 14650- 60-8, 161717-32-4
  • Phenolic and aminic function CAS 991-84-4, 633843-89-0
  • Examples are CAS 32687-78-8, 70331-94-1, 6629-10-3, ethylenediaminetetraacetic acid, N, N'-di-salicylidene-1,2-diaminopropane, 3- (N-salicylol) -amino-1, 2,4-triazole (Palmarole ADK STAB CDA-1), N, N'-bis [3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionyl] hydrazide (Palmarole MDA.P. 10) or 2,2'-oxamido-bis- [ethyl-3- (tert-butyl-4-hydroxyphenyl) propionate] (Palmarole MDA.P.11.).
  • phenolic antioxidants alone or even in combination with sulfur-containing costabilizers can not always be used to achieve practical products.
  • the concomitant use of phosphite stabilizers is found to be particularly suitable for sufficient heat aging stability of the product. Even in extrusion processing, the addition of phosphites in the aging test of the product is still positively noticeable.
  • an amount of at least 0.1, preferably at least 0.3, phr is preferred.
  • 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 carbodiimides, 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.
  • thermoplastics such as polyethylenes, ethylene / vinyl acetate copolymers, polypropylene homopolymers or copolymers. mers.
  • 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 having a shell of PAN or PMMA) can be used.
  • EVA dispersion powder or impact modifier for example acrylate elastomer particles having a shell of PAN or PMMA
  • no hydrolysis-sensitive polymeric additives having ester or amide groups in the polymer backbone are used.
  • Suitable catalysts (D) are the tertiary amines known and customary in the prior art, for example 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 the Zinndialkylsalze aliphatic carboxylic acids such as dibutyltin diacetate or dibutyltin dilaurate or the like.
  • Preferred catalysts are organic metal compounds, in particular titanic acid esters, iron and tin compounds.
  • the total amount of catalysts in the TPU according to the invention is generally about 0 to 5 wt .-%, preferably 0 to 2 wt .-%, based on the total amount of TPU.
  • the TPU related to the invention may be produced continuously or discontinuously.
  • the best known production methods are the belt process (GB 1 057 018 A) and the extruder process (DE 19 64 834 A1).
  • the structure of the TPU can be carried out either stepwise (prepolymer dosing method, reaction of components (A) and (B) and then with (C) or by the simultaneous reaction of all components (A), (B) and (C) in one step (one- Preferably, the prepolymer method is used.
  • the addition of the flame retardants (E), (F) and / or (G) and / or the auxiliaries (H) can be carried out before, during or after the polyurethane reaction.
  • the object of the present invention is primarily the absence of halogens with high flame retardancy, tear resistance and flexibility.
  • the rise thermal requirements of the application so that in addition an increased resistance to conventional PVC insulation and wrapping tapes or under development PVC-free insulation and film wrapping tapes is to be achieved polyolefin-based. Therefore, the characteristics of the present invention will be described below in detail.
  • the product according to the invention is halogen-free in the sense that the halogen content of the raw materials is so low that it plays no role in the flame retardance. Traces of trace halogens, such as impurities, process additives (fluoroelastomer) or catalyst residues, are not taken into consideration.
  • the compound according to the invention or the winding film produced using the compound have self-extinguishing properties, the preferred embodiments of the wire with TPU insulation and the winding band in fire tests according to FMVSS 302 (horizontal sample) and / or ASTM D 568 (vertical sample) test conditions to extinguish by itself.
  • the thickness of the film of the invention is preferably in the range of 30 to 180 .mu.m, preferably 50 to 150 .mu.m, in particular 55 to 100 microns.
  • the winding tape according to the invention has a corresponding thickness increased by the thickness of the optional pressure-sensitive adhesive coating.
  • the surface can be textured or smooth. Preferably, the surface is slightly dull. This can be achieved by using a filler with a sufficiently high particle size or by a roll (for example embossing roll on the calender or frosted chill roll or embossing roll on extrusion).
  • the winding tape used according to the invention is preferably colored (black, white or colored), wherein the carrier film and / or a further layer such as the adhesive are colored.
  • the pigments used are preferably free of toxic heavy metals such as lead, cadmium or chromium.
  • the winding tape according to the invention has a force at 10% elongation of 2 to 20 N / cm in the longitudinal direction, preferably from 4 to 11 N / cm, and at 50% elongation a force of 3 to 25 N / cm, preferably of 6 up to 17 N / cm.
  • the 10% force is a measure of the stiffness of the film
  • the 50% force is a measure of the conformability of winding in high deformation by high winding tension.
  • the 50% force must not be too low, because otherwise the tear strength is usually too low.
  • the tensile strength (breaking strength) of the carrier film is at least 10 N / cm, preferably at least 20 N / cm.
  • TPUs can be very tough, measures to improve the hand tearability of the wrapping tape may be necessary, such as blending with fillers, incompatible thermoplastic or non-meltable polymers, rough side edges, which on microscopic observation form cracks in the film, which then appear to be Favor tear further, or provided with subsequently attached, for example by punching notches provided side edges.
  • Rough cut edges can be produced, in particular, by using a squeeze cut with dull or jagged rotating knives on bale goods (jumbos, long rolls) or by cutting off with fixed blades or rotating knives of bar stock (rolls of production width and commercial length).
  • the elongation at break can be adjusted by a suitable grinding of the blades and blades. Preference is given to the execution of the production of bar stock with cut-away with blunt fixed blades. By strongly cooling the bars before cutting, the cracking during the cutting process can be improved.
  • Prerequisites for a sufficient heat resistance and short-term heat resistance are a sufficient crystallite melting point of the TPU (preferably at least 158 0 C and more preferably at least 170 0 C) and a resistance to aging by degradation which can be ensured by antioxidants and / or hydrolysis.
  • the winding tape according to the invention has a high temperature resistance, in preferred embodiments should have an elongation at break of at least 100% after 312 hours of storage at 140 0 C (heat resistance test) or a short-term heat resistance of 170 0 C (after 30 min no cracks or molten points).
  • the film of the winding tape contains a TPU with a sufficiently high proportion of hard blocks, which is why the Shore D hardness of the TPU raw material is preferably at least 35 and more preferably at least 50, which corresponds approximately to Shore A hardnesses of preferably at least 85, or more preferably at least 100.
  • the flame-resistant adhesive tapes shown in the prior art use significantly softer TPU (Shore A 70 to 80) than the flame-resistant adhesive tapes sought here. If plasticizers or phosphoric acid esters are added to the adhesive tapes of such soft TPU as flame retardants, then these are much more inappropriate than the winding tapes according to the invention.
  • the film is produced on a calender or by extrusion, for example in the blowing or casting process.
  • a compounder such as kneader (for example, pad kneader) or extruder (for example, twin-screw extruder, planetary roller extruder) and then into a solid form (for example, granules ), which are then further processed in a film extrusion line or in an extruder, kneader or rolling mill calendering.
  • the polyurethane film is preferably coated on at least one side with an adhesive.
  • the amount of preferably present adhesive layer is 10 to 40 g / m 2 , preferably 18 to 28 g / m 2 (which is the amount of any necessary
  • Such rubbers may be, for example, homopolymers or copolymers of isobutylene, of 1-butene, of vinyl acetate, of ethylene, of acrylic acid esters, of butadiene or of isoprene.
  • formulations based on polymers based on acrylic acid esters, vinyl acetate or isoprene are especially suitable.
  • 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.
  • 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 Cg monomers), terpene-phenolic resins, polyterpene resins from raw materials such as (- or ⁇ -pinene, aromatic resins such as coumarone-indene resins or styrene-based resins or ( Methyl styrene such as rosin and its derivatives, for example disproportionated, dimerized or esterified resins, for example including reaction products with glycol, glycerol or pentaerythritol, to name but a few, and other resins Preferred are resins without readily 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.
  • hydrocarbon resins for example polymers
  • Suitable fillers and pigments are, for example, carbon black, titanium dioxide, calcium carbonate, zinc carbonate, zinc oxide, silicates or silicic acid.
  • Suitable miscible plasticizers are, for example, aliphatic, cycloaliphatic and aromatic mineral oils, di- or poly-esters of phthalic acid, trimellitic acid or adipic acid, liquid rubbers (for example low molecular weight nitrile or polyisoprene rubbers), liquid polymers of butene and / or isobutene, acrylic esters, polyvinyl ethers, Liquid and soft resins based on the raw materials of adhesive resins, wool wax and other waxes or liquid silicones.
  • Crosslinking agents are, for example, isocyanates, phenolic resins or halogenated phenolic resins, melamine and formaldehyde resins.
  • Suitable crosslinking promoters are, for example, maleimides, allyl esters, such as triallyl cyanurate, polyfunctional esters of acrylic and methacrylic acid.
  • Anti-aging agents include, for example, hindered phenols, known, for example, under the trade name Irganox TM.
  • Crosslinking is advantageous because the shear strength (for example as lifting power) is increased and thus the propensity to deformation of the rolls during storage (telescoping or formation of voids, also called gaps) is reduced.
  • the squeezing of the PSA is also reduced. This is expressed in tack-free side edges of the rollers and tack-free edges of the wound strip guided in a spiral movement around cables or a cable harness.
  • the holding power is preferably above 150 min.
  • the bond strength to steel should be in the range of 1.5 to 3 N / cm.
  • the winding tape according to the invention preferably has an unwinding force of from 1.2 to 6.0 N / cm, very particularly preferably from 1.6 to 4.0 N / cm and in particular from 1.8 to 2.5 N / cm at 300 mm / min Unwinding speed.
  • the preferred embodiment has on one side a solvent-free self-adhesive composition which has been produced by coextrusion, melt or dispersion coating.
  • a solvent-free self-adhesive composition which has been produced by coextrusion, melt or dispersion coating.
  • polyacrylate-based adhesives in the form of dispersions or hotmelts are preferred.
  • An adhesive which is particularly suitable is a low molecular weight acrylate hot melt pressure-sensitive adhesive, such as that marketed under the name acResin UV or Acronal®, in particular Acronal DS 3458, by BASF.
  • acResin UV or Acronal® in particular Acronal DS 3458
  • the use of a primer layer between the carrier film and adhesive is advantageous for improving the adhesion of the adhesive to the film and thus avoiding the transfer of adhesive to the film back during the unwinding of the rolls.
  • the known dispersion and solvent systems can be used, for example, based on isoprene- or butadiene-containing rubber and / or cyclo-rubber.
  • Isocyanates or epoxy resins as additives improve the adhesion and in part also increase the shear strength of the pressure-sensitive adhesive.
  • Physical surface treatments such as flame treatment, corona or plasma or coextrusion layers are also suitable for improving adhesion. Particularly preferred is the use of such methods on solvent-free adhesive layers, especially those based on acrylate.
  • a coating of the back can be carried out by known release agents (optionally blended with other polymers).
  • release agents for example polyvinyl stearyl carbamate, stearyl compounds of transition metals such as Cr or Zr), ureas of polyethyleneimine and stearyl isocyanate, polysiloxanes (for example as a copolymer with polyurethanes or as a graft copolymer on polyolefin), thermoplastic fluoropolymers.
  • stearyl is synonymous with all straight or branched alkyls or alkenyls having a C number of at least 10 such as octadecyl.
  • the bar stock can be subjected to a heat storage to increase the unwind force or relaxation of the tensions of the films before cutting.
  • the cutting of wrapping tapes with fabric, non-woven and film carriers is carried out by shearing cut (between two rotating knives), cut-off cut (fixed or rotating knives are pressed into a rotating bar of the product), Blade cut (the web is split when passing through sharp blades) or crimp cut (between a rotating blade and a roller).
  • the compound according to the invention is outstandingly suitable for the insulation of electrical conductors and for the production of films for winding tapes or sealing tapes for the aircraft industry. It is preferably processed by extrusion into films and insulated wires.
  • 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 paramount importance, since, when used on wires and cables, it not only has to be wound in a spiral motion, but also has to be wound flexibly at bend points, plugs or fastening clips in a curve-flexible manner.
  • the winding tape elastically contracts the wire harness.
  • the wrapping tape according to the invention is also suitable for other applications such as for the sealing of ventilation pipes in climatic degradation, since the high flexibility ensures good conformability to rivets, beads and folds. These mechanical properties can only be achieved by a soft flexible wrapping tape.
  • the object to achieve the necessary flexibility by avoiding the addition of larger amounts of flame retardants is achieved according to the invention.
  • the measurements are made at test conditions of 23 ⁇ 1 0 C and 50 ⁇ 5% relative humidity. Humidity carried out.
  • T cr The crystallite melting point (T cr ) is determined by DSC according to ISO 3146. Since freshly processed TPUs have an extremely wide melting range because they are not already in thermodynamic final stage of crystallization, the samples are annealed for 24 hours at 140 0 C before determining the Kristallitschmelzddling.es.
  • the Shore A and Shore D hardness are determined according to ISO 868.
  • the hydrolysis resistance is determined by storage of the sample in warm distilled water. After 1000 hours at 80 0 C, the sample is dried for 24 hours at 80 0 C in a vacuum and then determines the decrease in tensile strength compared to the fresh state. If the tear strength is less than 50%, the test passes (P, passed) and if it has decreased by at least 50%, the test is failed (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) according to DIN EN ISO 527-
  • 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.
  • Adhesive forces are determined at a deduction angle of 180 ° according to AFERA 4001 on (if possible) 15 mm wide test strips. In this case, steel plates according to the AFERA standard are used as the test substrate unless another primer is mentioned.
  • the thickness of the film is determined according to DIN 53370 (a possible pressure-sensitive adhesive layer is subtracted from the measured total thickness).
  • the Holding Power is determined according to PSTC 107 (10/2001), whereby the weight is 20 N and the dimensions of the bonding surface are 20 mm in height and 13 mm in width.
  • the unwind force is measured at 300 mm / min according to DIN EN 1944.
  • the hand tearability can not be expressed in numbers even though breaking strength, elongation at break, and tensile toughness (all measured longitudinally) are of substantial influence.
  • the fire behavior is measured according to FMVSS 302 (horizontal sample) or ASTM D 568 (vertical sample).
  • 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 temperature resistance is determined by two methods. The wrapping tape is first glued to a siliconized polyester film and stored in the heat. After the test time, the sample is cooled for 30 min at 23 0 C.
  • the heat resistance test is after 312 hours of storage at 140 0 C tested whether the elongation at break is still at least 100%.
  • the short-time heat resistance is carried out by 30 minutes the sample was stored at 170 0 C, followed by winding of at least 3 turns at 50% overlap around a mandrel of 10 mm diameter and subsequent judgment of whether the pattern damage (for example cracks, melted spots ) having.
  • 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 ⁇ m.
  • the fogging value is determined according to DIN 75201 A.
  • DOPO 3 Reaction product of DOPO and Phenodur TM VPR 1785
  • NORD-MIN TM MC-25J melamine cyanurate (Nordmann-Rassmann)
  • Irganox TM 1010 tetrakis (methylene- (3,5-di-tert-butyl-4-hydroxycinnamate)) -methane (Ciba Specialty Chemicals)
  • Licowax TM C Release agent (Clariant Würtz GmbH) Step Example! 1
  • the finished TPU was cut, granulated and fed to a compounder in the dry state. This fed the nip of a calender of the type "inverted L", the processing temperatures were 220 to 0 C. With the aid of the calender rolls a film with a smooth surface and a thickness of 80 microns was formed.
  • the film was stored for one week, leveled on the coater with rolls at 60 ° C. to improve the flatness, and provided with a release layer after corona treatment on one side and on the other with an aqueous acrylate pressure-sensitive adhesive (Primal PS 83 D from Rohm and Haas and addition of 5% Hostasin Black [color preparation] from Clariant) using a doctor blade at a coating weight of 24 g / m 2 .
  • the finished wrapping tape was wound into bars of 33 m in length on a 1-inch core (25 mm). The cutting was done by cutting off the rods by means of fixed blade with not very acute angle (straight knife) in 29 mm wide rolls.
  • a prepolymer was prepared from MDI and Terathane TM 1000 in the molar ratio 2.5: 1 in the presence of Irganox TM 1010, NORD-MIN TM MC-25J and Sanko TM 220 and reacted with 95 mole% of the equivalent amount of BDO.
  • the contents of the additives were 0.3 phr Irganox TM 1010 (based on 100 phr of TPU polymer), 23 phr of NORD-MIN TM MC-25J and 10 phr of Sanko TM 220.
  • the finished TPU was cut, granulated and processed with the addition of 5% masterbatch white at a temperature of 180 to 200 0 C to a 100 micron blown film.
  • 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 .
  • a suitable cross-linking was achieved in-line before winding by irradiation with a UV system equipped with 6 medium-pressure Hg lamps at 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.
  • a prepolymer was prepared from MDI and Terathane TM 650 in a molar ratio of 2.2: 1 in the presence of Irganox TM 1010 and DOPO 3 and reacted with 95 mol% of the equivalent amount of BDO.
  • the contents of the additives are 0.3 phr Irganox TM 1010 and 40 phr DOPO 3 (based on 100 phr TPU polymer).
  • the adhesive coating was applied directly to the primer layer by means of a comma bar with a coating weight of 18 g / m 2 (based on dry matter).
  • the adhesive consisted of a solution of a natural rubber adhesive in n-hexane with a solids content of 30 percent by weight. This consisted of 50 parts of natural rubber, 10 parts of zinc oxide, 3 parts of rosin, 6 parts of alkylphenol resin, 17 parts of terpene phenolic resin, 12 parts of poly- ⁇ -pinene resin, 1 part of Irganox 1076 antioxidant and 2 parts of mineral oil.
  • the drying This subsequent in a drying tunnel at 100 0 C.
  • the film was immediately thereafter cut into a composite cutting machine with a knife bar with sharp blades at 19 mm distance from rolls on standard tape cores (3 inches).
  • the winding tape was produced analogously to Example 1, but the TPU film consisted of T-8375 (thermoplastic polyester polyurethane with Shore A hardness of 75 from DIC Bayer Polymer). At the same processing temperature, the melt stuck so strong on the calender rolls that no film could be produced. After lowering the temperature to 160 0 C, a film could be removed.
  • T-8375 was chosen because it was used for the examples of JP 2005 264 112 A (copolyamide-modified adhesive tape with TPU and a nitrogen-based compound flame retardant).
  • the preparation of the winding tape should be carried out analogously to Comparative Example 1, the TPU FoNe should, however, from 100 phr T-8375 and 10 phr Reofos 65 (isopropylated triaryl phosphate from Great Lakes) as a non-incorporated phosphorus-containing flame retardant. Because of very strong sticking to the calender rolls, however, it was not possible to obtain a film despite varying the processing conditions. The film could not be processed in the blowing process analogous to Example 2 because of lack of melt strength. Only with the casting process analogous to Example 3 was it possible to produce a colorless film 80 ⁇ m thick. These were then coated analogously to Example 1 with pressure-sensitive adhesive.
  • Example 2 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,
  • a conventional film for insulating tape of Singapore Plastic Products Pte. used under the name F2104S contained about 100 phr (parts per hundred resin) suspension PVC with a K value of 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 ⁇ m and the surface was smooth but dull.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)

Abstract

L'invention concerne un composé sans halogène, ininflammable, en polyuréthane thermoplastique, comportant du 9,10-dihydro-9-oxa-10- phosphaphénanthrène-10-oxyde (DOPO) ou un produit réactionnel du DOPO et d'un autre composé, dans lequel le H de la liaison P-H est substitué par un groupe organique.
PCT/EP2008/055873 2007-06-13 2008-05-14 Composé et bande à enrouler en film de polyuréthane thermoplastique WO2008151893A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102007027854 2007-06-13
DE102007027854.5 2007-06-13
DE102007028593.2 2007-06-19
DE102007028593A DE102007028593A1 (de) 2007-06-19 2007-06-19 Compound und Wickelband aus einer TPU-Folie

Publications (1)

Publication Number Publication Date
WO2008151893A1 true WO2008151893A1 (fr) 2008-12-18

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011080306A3 (fr) * 2009-12-31 2011-12-22 Chemische Fabrik Budenheim Kg Composition ignifuge pour matières à mouler thermoplastiques
CN103827223A (zh) * 2011-10-21 2014-05-28 东洋纺株式会社 阻燃性树脂组合物以及熔融成形体
CN103965432A (zh) * 2014-05-21 2014-08-06 厦门大学 一种无卤含磷阻燃硬质聚氨酯泡沫塑料及其制备方法
DE102013101487A1 (de) * 2013-02-14 2014-08-14 Chemische Fabrik Budenheim Kg Duromer, Herstellungsverfahren, Verwendung und Zusammensetzungen
CN104629086A (zh) * 2015-03-03 2015-05-20 北京奥格森新材料科技有限公司 一种含dopo基团的阻燃剂及其制备方法
JP2016041805A (ja) * 2014-08-15 2016-03-31 ランクセス・ドイチュランド・ゲーエムベーハー 低スコーチ性難燃化ポリウレタンフォーム
JP2016160437A (ja) * 2015-03-05 2016-09-05 ランクセス・ドイチュランド・ゲーエムベーハー 難燃性セルロースエステル調製物
DE102017108976A1 (de) * 2017-04-26 2018-10-31 Martin Elze Brandschutzmaterial zum Umhüllen eines Kabels oder einer Leitung und/oder zum Ausbilden eines Formteils mit wenigstens einer gekrümmten Oberfläche
CN111484530A (zh) * 2020-04-22 2020-08-04 中航复材（北京）科技有限公司 一种松香基反应型阻燃固化剂及其制备方法
CN112358804A (zh) * 2020-11-20 2021-02-12 兰州理工大学白银新材料研究院 一种高效阻燃聚氨酯材料的制备方法
CN114075409A (zh) * 2020-08-19 2022-02-22 德莎欧洲股份公司 具有聚氨酯载体的胶带
CN115260739A (zh) * 2022-08-08 2022-11-01 上海鑫亘环保科技有限公司 一种tpu阻燃母粒、tpu薄膜及其制备方法和应用
CN117417717A (zh) * 2023-12-18 2024-01-19 烟台隆达树脂有限公司 改性聚氨酯增韧环氧树脂电子胶的制备方法

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EP1108768A2 (fr) * 1999-12-13 2001-06-20 Tyco International (US) Inc. Ruban adhésif de polyuréthane thermiquement stable et transparent
WO2007031450A1 (fr) * 2005-09-16 2007-03-22 Ciba Specialty Chemicals Holding Inc. Compositions ignifuges a base de polyurethane

Patent Citations (2)

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EP1108768A2 (fr) * 1999-12-13 2001-06-20 Tyco International (US) Inc. Ruban adhésif de polyuréthane thermiquement stable et transparent
WO2007031450A1 (fr) * 2005-09-16 2007-03-22 Ciba Specialty Chemicals Holding Inc. Compositions ignifuges a base de polyurethane

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CN102741335A (zh) * 2009-12-31 2012-10-17 化学制造布敦海姆两合公司 用于热塑性模塑化合物的阻燃剂组合物
CN102741335B (zh) * 2009-12-31 2014-07-30 化学制造布敦海姆两合公司 用于热塑性模塑化合物的阻燃剂组合物
WO2011080306A3 (fr) * 2009-12-31 2011-12-22 Chemische Fabrik Budenheim Kg Composition ignifuge pour matières à mouler thermoplastiques
CN103827223A (zh) * 2011-10-21 2014-05-28 东洋纺株式会社 阻燃性树脂组合物以及熔融成形体
CN103827223B (zh) * 2011-10-21 2016-08-17 东洋纺株式会社 阻燃性树脂组合物以及熔融成形体
US9403952B2 (en) 2013-02-14 2016-08-02 Chemische Fabrik Budenheim Kg Duromer, production method, use and compositions
DE102013101487A1 (de) * 2013-02-14 2014-08-14 Chemische Fabrik Budenheim Kg Duromer, Herstellungsverfahren, Verwendung und Zusammensetzungen
CN103965432B (zh) * 2014-05-21 2016-08-24 厦门大学 一种无卤含磷阻燃硬质聚氨酯泡沫塑料及其制备方法
CN103965432A (zh) * 2014-05-21 2014-08-06 厦门大学 一种无卤含磷阻燃硬质聚氨酯泡沫塑料及其制备方法
JP2016041805A (ja) * 2014-08-15 2016-03-31 ランクセス・ドイチュランド・ゲーエムベーハー 低スコーチ性難燃化ポリウレタンフォーム
CN104629086A (zh) * 2015-03-03 2015-05-20 北京奥格森新材料科技有限公司 一种含dopo基团的阻燃剂及其制备方法
JP2016160437A (ja) * 2015-03-05 2016-09-05 ランクセス・ドイチュランド・ゲーエムベーハー 難燃性セルロースエステル調製物
DE102017108976A1 (de) * 2017-04-26 2018-10-31 Martin Elze Brandschutzmaterial zum Umhüllen eines Kabels oder einer Leitung und/oder zum Ausbilden eines Formteils mit wenigstens einer gekrümmten Oberfläche
DE102017108976B4 (de) 2017-04-26 2020-01-16 Martin Elze Brandschutzmaterial zum Umhüllen eines Kabels oder einer Leitung und/oder zum Ausbilden eines Formteils mit wenigstens einer gekrümmten Oberfläche, Verfahren zum Herstellen desselben, ein damit hergestelltes Brandschutzmaterial und eine Verwendung eines Primers in einem Brandschutzmaterial
CN111484530A (zh) * 2020-04-22 2020-08-04 中航复材（北京）科技有限公司 一种松香基反应型阻燃固化剂及其制备方法
CN111484530B (zh) * 2020-04-22 2022-07-26 中航复材（北京）科技有限公司 一种松香基反应型阻燃固化剂及其制备方法
CN114075409A (zh) * 2020-08-19 2022-02-22 德莎欧洲股份公司 具有聚氨酯载体的胶带
CN114075409B (zh) * 2020-08-19 2022-08-30 德莎欧洲股份公司 具有聚氨酯载体的胶带
CN112358804A (zh) * 2020-11-20 2021-02-12 兰州理工大学白银新材料研究院 一种高效阻燃聚氨酯材料的制备方法
CN115260739A (zh) * 2022-08-08 2022-11-01 上海鑫亘环保科技有限公司 一种tpu阻燃母粒、tpu薄膜及其制备方法和应用
CN115260739B (zh) * 2022-08-08 2023-08-15 上海鑫亘环保科技有限公司 一种tpu阻燃母粒、tpu薄膜及其制备方法和应用
CN117417717A (zh) * 2023-12-18 2024-01-19 烟台隆达树脂有限公司 改性聚氨酯增韧环氧树脂电子胶的制备方法
CN117417717B (zh) * 2023-12-18 2024-02-20 烟台隆达树脂有限公司 改性聚氨酯增韧环氧树脂电子胶的制备方法

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