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WO2007068596A1 - Bande de matiere a enrouler, faite d'un film de polyurethane thermoplastique - Google Patents

Bande de matiere a enrouler, faite d'un film de polyurethane thermoplastique Download PDF

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Publication number
WO2007068596A1
WO2007068596A1 PCT/EP2006/069111 EP2006069111W WO2007068596A1 WO 2007068596 A1 WO2007068596 A1 WO 2007068596A1 EP 2006069111 W EP2006069111 W EP 2006069111W WO 2007068596 A1 WO2007068596 A1 WO 2007068596A1
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Prior art keywords
carbon atoms
film
winding tape
tape according
radicals
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PCT/EP2006/069111
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German (de)
English (en)
Inventor
Bernhard MÜSSIG
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Tesa SE
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Tesa SE
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Priority to JP2008544940A priority Critical patent/JP2009519365A/ja
Publication of WO2007068596A1 publication Critical patent/WO2007068596A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • 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
    • 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
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • 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
    • C08K5/5397—Phosphine oxides
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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 winding tape, which further preferably has an adhesive coating and which is used for example for wrapping ventilation ducts in air conditioners, wires or cables and which is particularly suitable for wiring harnesses in vehicles or field coils for picture tubes.
  • the wrapping tape serves for bundling, isolating, marking or protecting.
  • Cable wrapping tapes and insulating tapes are usually made of plasticized PVC film with a one-sided pressure-sensitive adhesive coating.
  • plasticized PVC film with a one-sided pressure-sensitive adhesive coating.
  • disadvantages of these products such as the evaporation of plasticizers and the high halogen content.
  • the plasticizers of conventional insulating tapes and cable wrapping tap gradually, resulting in a health burden, in particular, the commonly used DOP is questionable. Furthermore, the vapors in vehicles impact on the windows, 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.
  • the incineration of plastic waste for example shredder waste from vehicle recycling, there is a trend towards the reduction of the halogen content and thus the dioxin formation.
  • the wall thicknesses of the cable insulation and the thicknesses of the tapes of the PVC film used for wrapping are reduced.
  • the usual thickness of the PVC films for winding tapes is 85 to 150 microns. Below 85 ⁇ m, considerable problems occur in the calendering process, so that such products with reduced PVC content are scarcely available.
  • 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.
  • WO 00/71634 A1 describes a wound adhesive tape whose film consists of an ethylene copolymer as the 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 service temperature is often above 100 ° C or even over 130 ° C for a short time, 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.
  • 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.
  • 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.
  • 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 used 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.
  • 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 flame retardants (D) have on average at least 1, 5 and at most 3.0, preferably 1, 8 to 2.5, particularly preferably 2 Zerewitinoff-active hydrogen atoms. These Zerewitinoff-active hydrogen atoms are preferably based on alcohol or amine.
  • the flame retardants (D) have a number average molecular weight M n of 60 to 10,000 daltons, preferably 100 to 5000 daltons, particularly preferably 100 to 1000 daltons.
  • the flame retardants (D) are based on phosphonate and / or phosphine oxide.
  • the phosphonate used is compounds of the general formula 1 (see above).
  • the phosphine oxide used are compounds of the general formula 2 (see above).
  • the flame retardants (D) are preferably used in an amount of 1 to 15, particularly preferably 1 to 10 wt .-% based on the total amount of TPU.
  • R preferably an aryl group (for example, phenyl, cresyl), A is a connecting
  • 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.
  • 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
  • auxiliaries and additives can be found in the specialist literature, for example the monograph by J. H. Saunders and K.C. Frisch “High Polymers”, Volume XVI, polyurethanes, Part 1 and 2, published by Interscience Publishers 1962 and 1964, the paperback for plastic additives by R. Gumbleter and H. Müller (Hanser Verlag Kunststoff 1990) or DE 29 01 774 A1 remove.
  • the amount of secondary antioxidant is preferably at least 0.5 phr, more preferably at least 1 phr.
  • a low-volatile primary phenolic antioxidant and a secondary antioxidant from the class of sulfur compounds preferably having a molecular weight of more than 400 g / mol, in particular> 500 g / mol
  • 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
  • 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.
  • 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
  • Phenolic and sulphurous function CAS 41484-35-9, 90-66-4, 110553-27-0, 96-96-5, 41484
  • Phenolic and aminic function CAS 991-84-4, 633843-89-0
  • CAS 6683-19-8 for example Irganox 1010
  • thiopropionic acid ester CAS 693-36-7 Irganox PS 802
  • 123-28-4 Irganox PS 800
  • CAS 31570-04-4 Irgafos 168
  • metal deactivators can be added to complex heavy metal traces, which can accelerate aging catalytically.
  • Examples are CAS 32687-78-8, 70331-94-1, 6629-10-3, ethylenediaminetetraacetic acid, N, N'-di-salicylidene-1,2-diaminopropane, 3- (N-salicylol) -amino-1, 2,4-triazole (Palmarole ADK STAB CDA-1), N, N'-bis [3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionyl] hydrazide (Palmarole MDA.P. 10) or 2,2'-oxamido-bis- [ethyl-3- (tert-butyl-4-hydroxyphenyl) propionate] (Palmarole MDA.P.11.).
  • the selection of the mentioned anti-aging agents is of particular importance for the winding film according to the invention, since phenolic antioxidants alone or even in combination with sulfur-containing costabilizers can not always be used to achieve practical products.
  • 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 protection agent (G) for example, monomeric or polymeric
  • Carbodiimides, oxazolines or reactive polyureas are used. Preference is given to a polymeric carbodiimide based on aromatic isocyanates. For the production 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.
  • Suitable catalysts (E) according to the invention are the tertiary amines known and customary in the prior art, for example triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2-
  • 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 either step by step (Prepolymerdosiervon) or by the simultaneous reaction of all components in one step (one-shot dosing) take place.
  • Preferably The incorporable phosphorus-containing compounds are incorporated in the prepolymer process in the TPU.
  • the addition of the flame retardant (F) and / or the auxiliaries (G) 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 thermal requirements of the application increase, so that in addition an increased resistance to conventional PVC winding tapes or under development PVC-free film winding tapes is to be achieved polyolefin-based. Therefore, the characteristics of the present invention will be described below in detail.
  • the winding tape according to the invention has self-extinguishing properties, the preferred embodiments of the winding tape automatically extinguishing in fire tests according to FMVSS 302 (horizontal sample) and / or ASTM D 568 (vertical sample).
  • the thickness of the film of the invention is preferably in the range of 30 to 180 .mu.m, preferably 50 to 150 .mu.m, in particular 55 to 100 microns. Thus, sufficient conformability in winding, good hand tearability and acceptable cost are achieved.
  • 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 done by using a filler with a sufficiently high particle size or be achieved by a roller (for example, embossing roll on the calender or frosted chili ro 11 or embossing roll in the extrusion).
  • the carrier film of the invention is substantially free of volatile plasticizers such as DOP or DINP and therefore has excellent fire behavior and low emission (plasticizer evaporation, fogging).
  • the fogging value is preferably over 90%.
  • the film preferably contains 0 to 5 phr of phosphorus-free
  • Plasticizers especially no phosphorus-free plasticizers. It preferably contains 0 to 10 phr of phosphorus-containing plasticizers as flame retardants and in particular no phosphorus-containing plasticizers at all.
  • 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 1 1 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 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 may be required to improve the hand tearability of the wrapping tape, such as blending with
  • Fillers incompatible thermoplastic or non-meltable polymers, by rough-cut side edges, which when examined microscopically cracks in the
  • Form film which then apparently favor a tearing, or by later provided with, for example, by punching notches provided side edges.
  • Rough cutting edges can be achieved in particular by the application of a Crush cut with blunt or defined jagged rotating knives on bales (jumbos, rolls in long lengths) or by a cut-off with fixed blades or rotating knives of bar stock (rolls in production width and commercial length) are produced.
  • 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 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 a resistance to aging by degradation, which can be ensured by antioxidants and / or hydrolysis protection.
  • the winding tape according to the invention has a high temperature resistance, 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 (after 30 min no cracks or molten points) have.
  • 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 particularly 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 with built-in flame retardant. 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 such as
  • Example in the blowing or casting process are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Wiley-VCH 2002.
  • a compounder such as kneader (for example, pad kneader) or extruder (for example, twin-screw extruder, planetary roller extruder) and then converted 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 (that is the amount after any necessary removal of water or solvent, the numerical values also correspond approximately to the thickness in microns).
  • 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.
  • a wrapping tape, each with a pressure-sensitive adhesive strip on the side edges is called.
  • 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 may be combined with one or more additives, such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, anti-aging agents, mittein, photoinitiators, crosslinking agents or crosslinking promoters be blended.
  • additives such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, anti-aging agents, mittein, photoinitiators, crosslinking agents or crosslinking promoters be blended.
  • 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 or ⁇ -styrene resins Methyl styrene such as rosin and its derivatives, for example disproportionated, dimerized or esterified resins, for example reaction products with glycol, glycerol or pentaerythritol, to name but a few, and also other resins (such as listed in Ullmanns Enzyklopadie der ischen Chemie, Volume 12) , Pages 525 to 555 (4th edition), Weinheim).
  • hydrocarbon resins for example polymers based on unsaturated C 5 or Cg monomers
  • terpene-phenolic resins polyterpene resins from raw materials such
  • resins without easily oxidizable double bonds such as terpene-phenolic resins, aromatic resins and particularly preferably resins which are prepared by hydrogenation, for example hydrogenated aromatic resins, hydrogenated polycyclopentadiene resins, hydrogenated rosin derivatives or hydrogenated terpene resins.
  • Suitable fillers and pigments are, for example, carbon black, titanium dioxide, calcium carbonate, zinc carbonate, zinc oxide, silicates or silicic acid.
  • Suitable miscible plasticizers are, for example, aliphatic, cycloaliphatic and aromatic mineral oils, di- or poly-esters of phthalic acid, trimellitic acid or adipic acid, liquid rubbers (for example low molecular weight nitrile or polyisoprene rubbers), liquid polymers of butene and / or isobutene, acrylic esters, polyvinyl ethers, Liquid and soft resins based on the raw materials of adhesive resins, wool wax and other waxes or liquid silicones.
  • Crosslinking agents are, for example, isocyanates, phenolic resins or halogenated phenolic resins, melamine and formaldehyde resins.
  • Suitable crosslinking promoters are, for example, maleimides, allyl esters, such as triallyl cyanurate, polyfunctional esters of acrylic and methacrylic acid.
  • Anti-aging agents 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.
  • 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 ones 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.
  • Blade cut the web is split when passing through sharp blades
  • crimp cut between a rotating blade 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 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 the Klimabau, since the high flexibility ensures good conformability to rivets, beads and folds.
  • the measurements are carried out at a test climate of 23 ⁇ 1 ° C and 50 ⁇ 5% rel. Humidity carried out.
  • the hydrolysis resistance is determined by storage of the sample in warm distilled water. After 1000 hours at 80 ° C, the sample is dried for 24 hours at 80 ° 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).
  • Adhesive forces are determined at a deduction angle of 180 ° according to AFERA 4001 on (if possible) 15 mm wide test strips.
  • 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 is the Pressure-sensitive adhesive coating upwards. 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 ° C.
  • the heat resistance test after 312 hours storage at 140 ° C is tested whether the elongation at break is still at least 100%.
  • the test of short-term heat resistance is carried out by 30 minutes storage of the sample at 170 ° C, then winding at least 3 turns with 50% overlap around a mandrel of 10 mm diameter and then judging whether the pattern damages (for example, cracks, molten areas ) having.
  • test specimen described above is cooled for 4 hours to -40 ° C. in accordance with ISO / DIS 6722 and the sample is hand-wound onto a 5 mm diameter mandrel.
  • the samples are checked visually for defects (cracks) in the adhesive tape.
  • the breakdown voltage is measured according to ASTM D 1000. 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.
  • a sample of 200 ⁇ m thickness withstands a maximum voltage of 6 kV after one minute, the calculated breakdown voltage is 3 kV / 100 ⁇ m.
  • the fogging value is determined according to DIN 75201 A.
  • Exolit TM OP 560 flame retardant based on diol phosphonate with Zerewitinoff-active hydrogen atoms (Clariant GmbH)
  • Levagard TM 4090 N Flame retardant (Bayer AG) OP (OC25) 2CH2N (C2H4OH) 2
  • Irganox TM 1010 tetrakis (methylene (3,5-di-tert-butyl-4-hydroxycinnamate)) -methane (Ciba
  • Disflamoll TM DPK Flame Retardant Diphenyl Cresyl Phosphate (Lanxess)
  • KE 9463 Masterbatch of 20% Stabaxol TM P100 and 80% TPU (Rhein-Chemie)
  • Example 4 At a processing temperature similar to Example 1, the melt adhered to the calender rolls. It had bubbles and holes (presumably by decomposition of the hydrazodicarbonamide), after lowering the temperature to 160 to 170 ° C, a film could be produced. However, the thickness was similar to Example 1 80 microns instead of 0.2 mm as in Japanese writing. Comparative Example 4
  • 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.
  • Hydrolysis resistance is inadequate in all of the comparative examples except for the PVC tape, which is not surprising to those skilled in the TPU with polyester polyol.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention concerne une bande à enrouler ignifuge exempte d'halogène, comprenant un film de polyuréthane thermoplastique, se caractérisant par l'intégration chimique d'un agent ignifugeant à base de phosphore.
PCT/EP2006/069111 2005-12-14 2006-11-30 Bande de matiere a enrouler, faite d'un film de polyurethane thermoplastique Ceased WO2007068596A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008544940A JP2009519365A (ja) 2005-12-14 2006-11-30 熱可塑性ポリウレタン（ｔｐｕ）フィルムよりなる巻きテープ

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005060232A DE102005060232A1 (de) 2005-12-14 2005-12-14 Wickelband aus einer TPU-Folie
DE102005060232.0 2005-12-14

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WO2007068596A1 true WO2007068596A1 (fr) 2007-06-21

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WO2008151894A1 (fr) * 2007-06-13 2008-12-18 Tesa Se Bande à enrouler dotée d'un film de polyuréthane thermoplastique
WO2008151892A1 (fr) * 2007-06-13 2008-12-18 Tesa Se Bande à enrouler dotée d'un film de polyuréthane thermoplastique
WO2010018061A1 (fr) * 2008-08-11 2010-02-18 Tesa Se Ruban d’enroulement à base d’un film de tpu avec antiadhésif coextrudé
CN102977585A (zh) * 2012-11-05 2013-03-20 安徽金桥电缆有限公司 一种聚氨酯阻燃环保电缆料及其制备方法
CN103525075A (zh) * 2013-09-30 2014-01-22 芜湖航天特种电缆厂 一种高阻燃高耐热无卤阻燃热塑性电缆料
EP2922114A4 (fr) * 2012-11-16 2016-07-06 Lg Chemical Ltd Bande de gonflement servant à remplir un espace
CN109666126A (zh) * 2018-12-24 2019-04-23 山东诺威聚氨酯股份有限公司 本质阻燃热塑性聚氨酯弹性体材料及其制备方法
CN109880568A (zh) * 2019-03-04 2019-06-14 闽江学院 阻燃压敏胶及其应用
EP3623400A1 (fr) * 2018-09-14 2020-03-18 tesa SE Mousse de polyuréthane ignifuge élastique, bande adhésive dotée d'un support de mousse de polyuréthane ignifuge élastique ainsi que procédé de fabrication correspondant
CN111019322A (zh) * 2019-12-06 2020-04-17 上海皆利新材料科技有限公司 一种高性能高阻燃无卤tpu材料及其制备方法
US12404427B2 (en) 2019-08-19 2025-09-02 3M Innovative Properties Company Adhesive tapes and methods of use in construction

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DE102007029100A1 (de) * 2007-06-21 2008-12-24 Tesa Ag Verfahren zum Fügen zweier Metallteile mittels Schweißens
CN105161173B (zh) * 2014-05-28 2018-01-05 安徽天星电缆科技有限公司 一种高性能通讯电缆
CN105088806A (zh) * 2015-09-05 2015-11-25 四川大学 利用tpu增塑pvc及减量使用增塑剂的人造革制造方法
DE102020210503B4 (de) 2020-08-19 2023-10-26 Tesa Se Klebeband mit Polyurethanträger, Verfahren zur Herstellung und Verwendung

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JPH11241070A (ja) * 1998-02-25 1999-09-07 Daihachi Chemical Industry Co Ltd 難燃剤および難燃性樹脂組成物
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US20040039147A1 (en) * 2002-08-21 2004-02-26 Henricus Peerlings Thermoplastically processable polyurethanes (TPU) with self-extinguishing properties, a process for their preparation and their use
DE20306801U1 (de) * 2003-04-30 2003-07-17 Certoplast Vorwerk & Sohn GmbH, 42285 Wuppertal Folienklebeband

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008151892A1 (fr) * 2007-06-13 2008-12-18 Tesa Se Bande à enrouler dotée d'un film de polyuréthane thermoplastique
WO2008151894A1 (fr) * 2007-06-13 2008-12-18 Tesa Se Bande à enrouler dotée d'un film de polyuréthane thermoplastique
WO2010018061A1 (fr) * 2008-08-11 2010-02-18 Tesa Se Ruban d’enroulement à base d’un film de tpu avec antiadhésif coextrudé
CN102977585A (zh) * 2012-11-05 2013-03-20 安徽金桥电缆有限公司 一种聚氨酯阻燃环保电缆料及其制备方法
CN102977585B (zh) * 2012-11-05 2016-03-30 安徽金桥电缆有限公司 一种聚氨酯阻燃环保电缆料及其制备方法
EP2922114A4 (fr) * 2012-11-16 2016-07-06 Lg Chemical Ltd Bande de gonflement servant à remplir un espace
US10243233B2 (en) 2012-11-16 2019-03-26 Lg Chem, Ltd. Swelling tape for filling gap
CN103525075B (zh) * 2013-09-30 2016-05-04 芜湖航天特种电缆厂 一种高阻燃高耐热无卤阻燃热塑性电缆料
CN103525075A (zh) * 2013-09-30 2014-01-22 芜湖航天特种电缆厂 一种高阻燃高耐热无卤阻燃热塑性电缆料
EP3623400A1 (fr) * 2018-09-14 2020-03-18 tesa SE Mousse de polyuréthane ignifuge élastique, bande adhésive dotée d'un support de mousse de polyuréthane ignifuge élastique ainsi que procédé de fabrication correspondant
CN109666126A (zh) * 2018-12-24 2019-04-23 山东诺威聚氨酯股份有限公司 本质阻燃热塑性聚氨酯弹性体材料及其制备方法
CN109880568A (zh) * 2019-03-04 2019-06-14 闽江学院 阻燃压敏胶及其应用
CN109880568B (zh) * 2019-03-04 2021-05-25 闽江学院 阻燃压敏胶及其应用
US12404427B2 (en) 2019-08-19 2025-09-02 3M Innovative Properties Company Adhesive tapes and methods of use in construction
CN111019322A (zh) * 2019-12-06 2020-04-17 上海皆利新材料科技有限公司 一种高性能高阻燃无卤tpu材料及其制备方法

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JP2009519365A (ja) 2009-05-14

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