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WO2008155175A1 - Feuille coextrudée, ignifugée, constituée d'au moins deux couches, exempte d'halogène, adhésive en surface - Google Patents

Feuille coextrudée, ignifugée, constituée d'au moins deux couches, exempte d'halogène, adhésive en surface Download PDF

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Publication number
WO2008155175A1
WO2008155175A1 PCT/EP2008/055919 EP2008055919W WO2008155175A1 WO 2008155175 A1 WO2008155175 A1 WO 2008155175A1 EP 2008055919 W EP2008055919 W EP 2008055919W WO 2008155175 A1 WO2008155175 A1 WO 2008155175A1
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WO
WIPO (PCT)
Prior art keywords
film
film according
core layer
layer
outer layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2008/055919
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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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Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Publication of WO2008155175A1 publication Critical patent/WO2008155175A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • 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
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl 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
    • C08G2290/00—Compositions for creating anti-fogging
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids

Definitions

  • the present invention relates to a surface-tacky, at least two-layer, halogen-free, flame-retardant, coextruded polyurethane film which preferably has no additional pressure-sensitive adhesive coating and which is intended for winding applications.
  • the foil is suitable, for example, for wrapping ventilation ducts in air conditioners, wires or cables and in particular for wiring harnesses in vehicles or picture tubes for picture tubes.
  • the foil 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.
  • adhesive tapes to reduce costs and avoid negative influences of the adhesive on the aging stability of the film and the wire insulation, there are adhesive tapes (so-called dry tapes) made of PVC with a high content (about 60 to 70 phr) of DOP plasticizer (Di-2). ethylhexyl phthalate).
  • DOP plasticizer DOP plasticizer
  • ethylhexyl phthalate ethylhexyl phthalate
  • the usual wrap bands also contain stabilizers based on toxic heavy metals such as lead, cadmium or barium. Dry tapes can not be made with heat-stable plasticizers such as polymer plasticizers, which limits the aging resistance, for higher demands, films made of PVC, polymer plasticizers and stabilizers are coated with pressure-sensitive adhesive.
  • plasticizers of conventional insulating tapes and cable winding tapes gradually leach out, which leads to a health burden, in particular, this is common used DOP questionably. Furthermore, the vapors in motor vehicles beat down on the windows, which deteriorates the visibility (and thus considerably the driving safety) and is referred to by the skilled person as fogging. With even greater evaporation by higher temperatures, for example in the engine compartment of vehicles or insulating tapes in electrical equipment, the adhesive tape or the dry tape embrittle due to the resulting loss of plasticizer and the decomposition of the PVC polymer.
  • the object of the invention is to provide winding films available which allow a particularly safe and fast wrapping, especially of wires and cables for marking, protecting, insulating, sealing or bundling, the disadvantages of the prior art not or at least not in the previous Scope occur.
  • thermoplastically produced films with additive combinations which not only the heat resistance of PVC reach, but even surpass.
  • the film should not require a pressure-sensitive adhesive coating.
  • the invention relates to a surface-adhesive at least two-layer, halogen-free, flame-retardant, coextruded film of a core layer with a top and a bottom, wherein at least on the underside an outer layer is present,
  • the core layer consists of a thermoplastic polyurethane with a Shore D
  • Hardness preferably at least 35, more preferably at least 50 and from a flame retardant based on phosphorus and optionally other additives.
  • the outer layer consists of a thermoplastic polyurethane having a Shore A hardness of not more than 97, preferably not more than 90 and optionally further additives.
  • a second outer layer is present on the upper side of the core layer, which preferably consists of a thermoplastic polyurethane having a Shore A hardness of not more than 97, preferably not more than 90 and optionally further additives.
  • the core layer and the outer layers have a different composition.
  • the film has no additionally applied outside adhesive or other adhesive coating.
  • Adhesive tapes of polyurethane foams or foils are - as stated above - known. Flameproof halogen-free polyurethane films which have a sticky surface without adhesive coating, however, are unknown.
  • the article according to the invention preferably contains no coating with
  • Pressure-sensitive adhesive thereby reducing the cost, the risk of aging of the film by migration of constituents of the adhesive decreases, and the flame resistance is significant improved. Especially the latter is of great importance, since pressure-sensitive adhesives are not halogen-free flame-resistant and thus the flame resistance of an adhesive tape is considerably worse than that of the carrier film.
  • the polyurethane of the core layer is preferably made of 4,4'-diphenylmethane diisocyanate, 1, 4-butanediol and a hydroxyl-containing polymerization of tetrahydrofuran to achieve hard blocks with sufficiently high resistance to melting of the samples under temperature load and soft blocks with resistance to oxidation and hydrolysis.
  • phosphorus-containing flame retardant for the core layer or the outer layers of inorganic or preferably organic compounds are selected.
  • ammonium polyphosphate ethylenediamine polyphosphate and phosphoric acid and phosphonic acid esters such as triphenyl phosphate, tricresyl phosphate, alkyphenyl phosphate, 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 which are represented by another group such as -CH 2 -, -C (CH 3) 2 -, -SO 2 - or - CO- are joined, or alkylene (for example, neopentyl) and n is between 1 and 10.
  • arylene for example phenylene
  • biarylene for example biphenyl
  • two arylene groups which are represented by another group such as -CH 2 -, -C (CH 3) 2 -, -SO 2 - or - CO- are joined, or alkylene (for example, neopentyl) and n is between 1 and 10.
  • alkylene for example, neopentyl
  • Such compounds are industrially prepared from phosphoric acid or phosphorus oxytrichloride
  • phosphoric acid and phosphonic acid derivatives which on hydrolysis release neither phenol nor cresol.
  • examples are trixylyl phosphate, butylated triphenyl phosphates (for example Fyrquel TM EHC-S), phosphoric acid-1, 3-phenylene tetraxylenyl esters and salts of phosphonic acids such as sodium, magnesium, zinc or aluminum salts of propane or phenylphosphonic acid (benzenephosphonic acid).
  • the phosphorus-containing flame retardant can also be incorporated.
  • These are, for example, 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.
  • the core layer preferably additionally contains nitrogen-containing flame retardants such as melamine cyanurate, melamine, biuret, triuret, ammelide, ammeline, cyanuric acid, tris (2-hydroxyethyl) isocyanurate, bis (2-hydroxyethyl) isocyanurate, 2-hydroxyethyl isocyanurate, tris (carbomethyl) isocyanurate, tris ( 2-cyanoethyl) isocyanurate, bis (2-cyanoethyl) isocyanurate, 2-cyanoethyl isocyanurate, trimethyl isocyanurate, HA (L) S as CAS no.
  • nitrogen-containing flame retardants such as melamine cyanurate, melamine, biuret, triuret, ammelide, ammeline, cyanuric acid, tris (2-hydroxyethyl) isocyanurate, bis (2-hydroxyethyl) isocyanurate, 2-hydroxyethyl iso
  • melam meiern, dicyandiamide, guanadine, biguanadine, triphenyl isocyanurate or tricresyl isocyanurate.
  • Preferred nitrogen-containing flame retardants have filler character to improve hand tearability since thermoplastic polyurethanes are very tough, most preferred is melamine cyanurate.
  • phosphorus and nitrogen-containing flame retardants for the core layer are also compounds which contain both elements such as melamine phosphate, melamine polyphosphate, urea phosphate, diethyl N, N-bis (2-hydroxyethyl) aminomethyl phosphonate, N, N-bis (2 -hydroxyalkyl) - aminomethanphosphon Acidimethylester, triethanolamine or phosphorus oxytriamid.
  • the outer layer (s) preferably contain a phosphorus-containing flame retardant, which particularly preferably has a plasticizing character and not a filler character, in order to achieve the most sticky surface possible.
  • the outer layers therefore preferably contain much less filler or flame retardant having Greetus var ⁇ но ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • the surfaces of the outer layer (s) have such a low tack that adhesive forces on AFERA 4001 steel are barely measurable. However, the surfaces are so sticky that the turns of the film do not slip against each other on spirally wrapped objects. If the film is wound into a roll and stored in particular above room temperature, then an unwind force can be determined. The latter is adjustable by the storage time and above all the storage temperature. So that the outer layers adhere well to one another, the surfaces are preferably smooth, in particular high-gloss.
  • the surface tackiness of the subject invention corresponds to the properties of a dry tape of highly plasticized PVC.
  • thermoplastic polyurethanes used according to the invention may contain as auxiliary agents and additives up to and including, preferably, not more than 20 phr of the customary auxiliaries and additives.
  • the outer layer (s) may contain as auxiliaries and additives up to preferably including at most 5 phr, in particular including at most 1 phr of the customary auxiliaries and additives.
  • 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 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.
  • Stabilizers for PVC products can not be transferred to TPU.
  • the film used according to the invention preferably contains 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). Examples include phenolic or amine based antioxidants and sulfur or phosphorus based secondary antioxidants. The listed quantities do not include other stabilizers such as metal deactivators or light stabilizers.
  • Preferred antioxidants are on a phenolic basis, particularly preferred are tetrakis (methylene (3,5-di-tert-butyl-4-hydroxycinnamates)) methane (for example Irganox TM 1010) or octadecyl-3- [3,5- di-tert-butyl-4-hydroxyphenyl] propionate] (for example, Irganox TM 1076).
  • 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.
  • the polyurethane for the core layer is made of
  • the polyurethanes used according to the invention may have been prepared continuously or batchwise.
  • 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 stepwise (Prepolymerdosier boulder, implementation of components (A) and (B) and then with (C)) or by the simultaneous reaction of all components (A), (B) and (C) in one stage (one -shot dosing) carried out.
  • the prepolymer method is used.
  • the addition of the flame retardants and / or the auxiliaries can be carried out before, during or after the polyurethane reaction.
  • 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 elimination of halogens usually entails the property of flammability, which does not meet the safety requirements in electrical applications such as household appliances, buildings or vehicles.
  • the film according to the invention has self-extinguishing properties, with the preferred embodiments automatically extinguishing in fire tests according to FMVSS 302 (horizontal sample) and / or ASTM D 568 (vertical sample).
  • the thickness of the film according to the invention is preferably in the range from 30 to 180 .mu.m, particularly preferably 50 to 150 .mu.m and in particular 55 to 100 .mu.m. Thus, sufficient conformability in winding, good hand tearability and acceptable cost are achieved.
  • the film used according to the invention is preferably colored (black, white or colored).
  • the pigments used are preferably free of toxic heavy metals such as lead, cadmium or chromium.
  • the film of 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 film is at least 10 N / cm, preferably at least 20 N / cm.
  • thermoplastic polyurethanes can be very tough, measures may be required to improve the hand tearability of the film, for example, such as blending with fillers preferably in the core layer, incompatible thermoplastic or non-meltable polymers, such as rough side edges, which will crack when viewed microscopically form the film, which then favor a tearing, or as provided by subsequently provided with, 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.
  • the rollers can be punched laterally.
  • Prerequisites for sufficient heat resistance and short-term heat resistance are a sufficient crystallite melting point of the thermoplastic polyurethane core layer (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 film 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 storage at 140 0 C (heat resistance test) or a short-time heat resistance of 170 0 C (after 30 min no cracks or molten points).
  • the core layer of the film contains a thermoplastic polyurethane with a sufficiently high proportion of hard blocks, which is why the Shore D hardness of the polyurethane raw material is preferably at least 35 and more preferably at least 50.
  • the film is produced by co-extrusion, for example in the blown or cast process.
  • the resulting film is wound into rods, these are preferably treated with heat.
  • the two outer layers coming into contact with each other due to rolling-up adhere to one another, and by selecting the temperatures and times, the unwinding force can be set to the desired value.
  • This should preferably be at least 1 N / cm, preferably at least 2 N / cm, so that the product does not roll too easily during winding.
  • a film which has no significant forces during unwinding does not stretch on unwinding. Elongation is a prerequisite for a wrinkle-free, tight winding.
  • the film according to the invention is excellently suited for wrapping elongated material such as field coils or cable harnesses 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. In addition, it is desirable that the film contract the cable harness elastically.
  • the film of 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 current occupational hygiene and ecological requirements are taken into account by dispensing with the use of halogen-containing raw materials. The absence of halogen is of utmost importance for the thermal utilization of waste containing such wrapping tapes (for example, waste incineration of the plastic fraction of Vehicle recycling) but also in cable or building fires, since no toxic flue gases.
  • the measurements are made at test conditions of 23 ⁇ 1 0 C and 50 ⁇ 5% relative humidity. Humidity carried out.
  • 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 of the hard block. If several melting peaks of the hard block occur despite tempering, then the peak with the highest temperature is determined as the crystallite melting point. The melting peak of polytetrahydrofuran at about 50 0 C is disregarded.
  • 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
  • the sample is dried for 24 hours at 80 0 C in a vacuum and then the decrease in tensile strength over the Fresh state determined. 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 film is determined on test specimens of type 2 (rectangular 150 mm long and, if possible, 15 mm wide test strips) according to DIN EN ISO 527-3 / 2/300 with a test speed of 300 mm / min, a clamping length of 100 mm and a pre-load of 0.3 N / cm determined. In the case of patterns with rough cut edges, the edges should be trimmed with a sharp blade before the tensile test.
  • the tensile elongation behavior is checked 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.
  • steel plates according to the AFERA standard are used as the test substrate.
  • the thickness of the film is determined according to DIN 53370.
  • 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 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 film 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.
  • Elastollan TM 1154 FHF (supplier: Elastogran): thermoplastic polyurethane composed of 4,4'-diphenylmethane diisocyanate, 1,4-butanediol and a polytetrahydrofuran-based diol. An additive has been identified:
  • Elastollan TM 1154 D (supplier: Elastogran): thermoplastic polyurethane from 4,4'-diphenylmethane diisocyanate, 1, 4-butanediol and a diol based on polytetrahydrofuran. An additive has been identified:
  • Elastollan TM 1175 A W (supplier: Elastogran): thermoplastic polyurethane consisting of 4,4'-diphenylmethane diisocyanate, 1,4-butanediol and a diol based on polytetrahydrofuran. An additive has been identified:
  • Elastollan TM 1180 A (supplier: Elastogran): thermoplastic polyurethane composed of 4,4'-diphenylmethane diisocyanate, 1,4-butanediol and a polytetrahydrofuran-based diol. An additive has been identified:
  • KE 9463 (supplier: Rhein-Chemie): Hydrolysing agent masterbatch with 20% Stabaxol TM P200 in TPU
  • Irganox TM 1010 (supplier: Ciba Specialty Chemicals): tetrakis (methylene (3,5-di-tert-butyl-4-hydroxycinnamate)) methane example 1
  • a three-layer film was produced in the flat film process with a glossy cooling roller. All components were well dried.
  • the 80 ⁇ m thick core layer consisted of 95% by weight of Elastollan TM 1 154 FHF and 5% by weight of KE 9463 and the two 10 ⁇ m outer layers of Elastollan TM 1175 A W.
  • the film became bars with a running length of 25 m wound.
  • the rods were stored for 12 hours at 70 0 C.
  • the cutting was done by cutting off the rods by means of fixed blade with not very acute angle (straight knife) in 19 mm wide rolls.
  • the preparation was similar to Example 1.
  • the core layer was 70 microns thick and consisted of a compound A, the two outer layers were each 15 microns thick and consisted of a compound B.
  • the film was produced analogously to Example 1, the film consisting of only one layer of Elastollan TM 1 154 FHF.
  • the thickness of the film was 100 ⁇ m.
  • the preparation of the film was carried out analogously to Comparative Example 1, wherein the film had a thickness of 70 microns and was equipped on one side with a primer and 30 microns Acrylathaftklebemasse.
  • the unwind force was determined in the fresh state, since the roll could no longer roll after heat storage.
  • the film was produced analogously to Example 1, the film consisting of only one layer of Elastollan TM 1175 AW.
  • the thickness of the film was 100 ⁇ m. Age or hydrolysis protectants were not added.

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Abstract

La présente invention a pour objet une feuille coextrudée, ignifugée, constituée d'au moins deux couches, exempte d'halogène, adhésive en surface, qui est composée d'une couche centrale dotée d'une face supérieure et d'une face inférieure, une couche extérieure étant présente au moins sur la face inférieure. La couche centrale se compose d'un polyuréthane thermoplastique d'une dureté d'au moins 35 Shore D de préférence, mieux encore d'au moins 50 Shore D, ainsi que d'un agent ignifuge à base de phosphore et, le cas échéant, d'autres additifs. La couche extérieure se compose d'un polyuréthane thermoplastique d'une dureté de 97 Shore A au maximum, de préférence de 90 Shore A au maximum et, le cas échéant, d'autres additifs.
PCT/EP2008/055919 2007-06-19 2008-05-14 Feuille coextrudée, ignifugée, constituée d'au moins deux couches, exempte d'halogène, adhésive en surface Ceased WO2008155175A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007028592.4 2007-06-19
DE102007028592A DE102007028592A1 (de) 2007-06-19 2007-06-19 Oberflächenklebrige, zumindest zweischichtige halogenfreie, flammwidrige, coextrudierte Folie

Publications (1)

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WO2008155175A1 true WO2008155175A1 (fr) 2008-12-24

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PCT/EP2008/055919 Ceased WO2008155175A1 (fr) 2007-06-19 2008-05-14 Feuille coextrudée, ignifugée, constituée d'au moins deux couches, exempte d'halogène, adhésive en surface

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DE (1) DE102007028592A1 (fr)
WO (1) WO2008155175A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011153048A1 (fr) 2010-05-31 2011-12-08 Corning Incorporated Dispositif microréacteur ayant une partie supérieure essentiellement verticale ou inclinée comprenant des moyens pour la collecte et l'élimination de gaz formé in situ pendant une réaction en milieu liquide et procédé correspondant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4022741A1 (de) * 1990-07-18 1992-01-23 Basf Ag Mehrschichtige polyurethanfolien und ihre verwendung zur herstellung von deckschichten
DE9422283U1 (de) * 1993-03-22 2000-03-09 Elastogran GmbH, 49448 Lemförde Selbstverlöschende thermoplastische Polyurethane
EP1394189A1 (fr) * 2002-08-21 2004-03-03 Bayer MaterialScience AG Polyuréthanes thermoplastiques ayant des proprietés auto-extinctrices, un procédé pour leur préparation et utilisation
WO2008087087A1 (fr) * 2007-01-17 2008-07-24 Basf Se Stratifié contenant une feuille et un non-tissé à base de polyuréthane thermoplastique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2941956A (en) 1956-08-15 1960-06-21 Socony Mobil Oil Co Inc Regeneration of contact material
BE673744A (fr) 1964-12-14
DE1964834A1 (de) 1969-12-24 1971-07-01 Bayer Ag Verfahren zur Herstellung von Polyurethan-Elastomeren

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4022741A1 (de) * 1990-07-18 1992-01-23 Basf Ag Mehrschichtige polyurethanfolien und ihre verwendung zur herstellung von deckschichten
DE9422283U1 (de) * 1993-03-22 2000-03-09 Elastogran GmbH, 49448 Lemförde Selbstverlöschende thermoplastische Polyurethane
EP1394189A1 (fr) * 2002-08-21 2004-03-03 Bayer MaterialScience AG Polyuréthanes thermoplastiques ayant des proprietés auto-extinctrices, un procédé pour leur préparation et utilisation
WO2008087087A1 (fr) * 2007-01-17 2008-07-24 Basf Se Stratifié contenant une feuille et un non-tissé à base de polyuréthane thermoplastique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011153048A1 (fr) 2010-05-31 2011-12-08 Corning Incorporated Dispositif microréacteur ayant une partie supérieure essentiellement verticale ou inclinée comprenant des moyens pour la collecte et l'élimination de gaz formé in situ pendant une réaction en milieu liquide et procédé correspondant

Also Published As

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