EP1678248A1 - Pellicule de gainage souple en polyolefines resistant au vieillissement - Google Patents

Pellicule de gainage souple en polyolefines resistant au vieillissement

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Publication number
EP1678248A1
EP1678248A1 EP04766811A EP04766811A EP1678248A1 EP 1678248 A1 EP1678248 A1 EP 1678248A1 EP 04766811 A EP04766811 A EP 04766811A EP 04766811 A EP04766811 A EP 04766811A EP 1678248 A1 EP1678248 A1 EP 1678248A1
Authority
EP
European Patent Office
Prior art keywords
wrapping film
phr
wrapping
film
film according
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
EP04766811A
Other languages
German (de)
English (en)
Inventor
Bernhard MÜSSIG
Ingo Neubert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tesa SE
Original Assignee
Tesa SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Publication of EP1678248A1 publication Critical patent/EP1678248A1/fr
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the present invention relates to an aging-resistant wrapping film made of polyolefin, in particular a halogen-free and flame-retardant embodiment made of polypropylene copolymer, which is optionally provided with a pressure-sensitive coating which is used, for example, for wrapping ventilation ducts in air conditioning systems, wires or cables, and in particular for cable harnesses is suitable for picture tubes in vehicles or field coils.
  • the wrapping film is used for bundling, isolating, marking, sealing or protecting.
  • the invention further comprises methods for producing the film according to the invention.
  • the wrapping film is characterized by the use of special combinations of anti-aging agents such as antioxidants and metal deactivators in sufficient quantities.
  • Cable wrapping tapes and insulating tapes usually consist of plasticized PVC film with a one-sided adhesive coating.
  • Corresponding disadvantages include evaporation of plasticizer and high halogen content.
  • Alternative products made of polyolefin have a limited aging stability. They also soften at low temperatures. This does not apply to polypropylene and its copolymers, unfortunately they have a particularly poor aging stability compared to the easily melting polyolefins such as PE or EVA. If you want to make such a wrapping tape flame-retardant with appropriate additives, the aging stability decreases further.
  • plasticizers of conventional insulating tapes and cable winding tapes gradually evaporate, which leads to a health burden, in particular this is usually the case used DOP questionable.
  • the vapors in motor vehicles are deposited on the windows, which worsens visibility (and therefore considerably driving safety) and is referred to as fogging (DIN 75201) by a specialist.
  • fogging DIN 75201
  • the wrapping film becomes brittle as a result of the loss of plasticizer.
  • Plasticizers worsen the fire behavior of pure PVC, which is partially compensated for by the addition of antimony compounds, which are very toxic, or by the use of plasticizers containing chlorine or phosphorus.
  • the usual winding tapes contain stabilizers based on toxic heavy metals, mostly lead, less often cadmium or barium.
  • the highly toxic compound antimony oxide is usually used, as described for example in JP 10 001 583 A1.
  • Efforts have been made to use woven or non-woven fabrics instead of soft PVC film, but the resulting products are used only little in practice because they are relatively expensive and can be handled (for example by hand tearability, elastic resilience) and under conditions of use (for example resistance to operating fluids, electrical properties) differ greatly from the usual products, whereby in the following the thickness is of particular importance.
  • EP 1 123 958 A1 and WO 99/61541 A1 describe winding adhesive tapes made of a woven or non-woven backing material. These materials are characterized by a very high tear resistance. However, this has the disadvantage that these adhesive tapes cannot be torn off by hand without the use of scissors or knives. Elasticity and flexibility are two of the main requirements for winding tapes in order to be able to produce wrinkle-free and flexible cable harnesses. Furthermore, these materials do not meet the relevant fire protection standards such as FMVSS 302. Improved fire properties can only be achieved using halogen-containing flame retardants or polymers, as described in US Pat. No. 4,992,331 A1.
  • the wiring harnesses are becoming thicker and stiffer due to the large number of electrical consumers and the increased information transfer within the vehicles, while the installation space is being reduced more and more, making assembly (when installing in the body) more problematic.
  • the cable winding tapes are expected to be easy and quick to process for efficient and inexpensive cable harness production.
  • Wrapping tapes based on soft PVC films are used in automobiles for bandaging electrical cables to cable harnesses.
  • the focus was on improving the electrical insulation when using these winding tapes, which were originally developed as insulating tapes, such cable harness tapes must now perform other functions such as bundling and permanently fixing a large number of individual cables to form a stable cable harness and the protection of the individual cables and the entire cable harness against mechanical, thermal and chemical damage.
  • DE 199 10 730 A1 describes a laminate carrier which consists of velor or foam and a fleece which is adhesively bonded by means of a double-sided adhesive tape or with a hot melt adhesive.
  • EP 0 886 357 A2 describes a three-layer protective covering made of a spunbond nonwoven, a PET knitted fabric and a foam or felt strip which are laminated together, the protective covering additionally being provided at least partially with adhesive strips and Velcro fastening systems.
  • EP 1 000 992 A1 describes a perforated cotton fleece with a 10 to 45 ⁇ m thick polyethylene coating and an additional release coating.
  • DE-G 94 01 037 describes an adhesive tape with a band-shaped, textile carrier, which consists of a sewing fleece, which in turn is formed from a plurality of sewn seams running parallel to one another.
  • the fleece proposed here should have a thickness of 150 to 400 ⁇ m with a basis weight of 50 to 200 g / m 2 .
  • DE 44 42 092 C1 describes an adhesive tape based on sewing fleece, which is coated on the back of the carrier.
  • DE 44 42 093 C1 is based on the use of a nonwoven as a carrier for an adhesive tape which is produced by the formation of stitches from the fibers of the nonwoven reinforced cross-fiber nonwoven, ie a nonwoven known to the person skilled in the art under the name Malivlies.
  • DE 44 42 507 C1 discloses an adhesive tape for cable bandaging, but it is based on so-called Kunit or Multiknit fleeces. Nonwovens are used in all three documents, which have a basis weight of approximately 100 g / m 2 , as can be seen from the examples.
  • DE 195 23 494 C1 discloses the use of an adhesive tape with a carrier made of nonwoven material with a thickness of 400 to 600 ⁇ m for bandaging cable harnesses, which is coated on one side with an adhesive.
  • DE 199 23 399 A1 discloses an adhesive tape with a tape-shaped carrier made of nonwoven material, which is coated on at least one side with an adhesive, the nonwoven having a thickness of 100 ⁇ m to 3000 ⁇ m, in particular 500 to 1000 ⁇ m.
  • Nonwovens make the cable harnesses even thicker and less flexible than classic PVC tapes, even if this has a positive effect on sound insulation, which is only an advantage in some areas of cable harnesses.
  • Nonwovens are not very stretchy and have practically no resilience. This is important because thin branches of cable harnesses must be wound tightly so that they do not hang limply during installation and can be easily positioned in front of the clips and the connectors.
  • JP 10 149 725 A1 JP 09 208 906 A1 and JP 05 017 727 A1 describe the use of halogen-free thermoplastic polyester carrier films.
  • JP 07 150 126 A1 describes a flame-retardant wrapping film made of a polyester carrier film which contains a brominated flame retardant.
  • WO 00/71634 A1 describes a winding 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 usage temperature is often above 100 ° C or briefly even above 130 ° C, which is not uncommon when used inside the engine. Antioxidants are not mentioned.
  • Carrier film consists of a polymer blend of low-density polyethylene and an ethylene / vinyl acetate or ethylene / acrylate copolymer. As a flame retardant
  • a major disadvantage of the carrier film is again the low softening temperature.
  • EP 0 953 599 A1 claims a polymer mixture of LLDPE and EVA for applications as cable insulation and as a film material.
  • a combination of magnesium hydroxide with a special surface and red phosphorus is described as a flame retardant, but softening at a relatively low temperature is accepted.
  • Only the primary antioxidant Irganox 1010 with 0.2 phr is mentioned as an antioxidant.
  • EP 1 097 976 A1 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.
  • EVA or EEA it is claimed that the film has sufficient flexibility.
  • these polymers are blended with polypropylene to improve flame retardancy.
  • the products described have a film thickness of 0.2 mm; this thickness alone rules out flexibility in the case of filled polyolefin films, since the third power depends on the thickness.
  • WO 03/070848 A1 describes a reactive polypropylene and 40 phr magnesium hydroxide. This additional amount is not sufficient to significantly improve the fire behavior.
  • a possible use of anti-aging agents is mentioned but not described in detail (also not in the example and comparative example). The use of carbon black or spherical magnesium hydroxide has not been described.
  • DE 203 06 801 U describes a winding tape made of polyurethane, such a product is far too expensive for the usual applications described above. There is no evidence of the use of anti-aging agents or magnesium hydroxide.
  • the task therefore remains to find a solution for an aging-stable wrapping film which combines the advantages of aging resistance, flame resistance, abrasion resistance, tension resistance and the mechanical properties (such as elasticity, flexibility, hand tearability) of PVC wrapping tapes with the halogen-free nature of textile wrapping tapes, and in particular has a superior heat aging resistance, it must be ensured that the film can be produced on an industrial scale and a high dielectric strength and a high fogging value are required in some applications.
  • the object of the invention is also to provide soft, aging-stable wrapping films, in particular in a halogen-free, flame-retardant version, which enable particularly safe and rapid wrapping, in particular of wires and cables, for marking, protecting, isolating, sealing or bundling, the disadvantages of the prior art does not occur or at least not to the extent.
  • Another object of the invention is to achieve the necessary flexibility of the wrapping film in spite of large amounts of flame retardants.
  • the task with a wrapping tape made of polyolefin is much more difficult to solve than with PVC, since PVC requires little or no flame retardants and the flexibility can be easily achieved with conventional plasticizers.
  • the subclaims relate to advantageous developments of the wrapping film according to the invention and the use of the wrapping film in an aging-resistant soft adhesive tape, further uses of the same and methods for producing the wrapping film.
  • the invention relates to an aging-resistant soft wrapping film made of polyolefin, in particular a halogen-free and flame-retardant embodiment made of polypropylene copolymer, which is preferably provided with a pressure-sensitive adhesive coating.
  • the information given in phr below means parts by weight of the component in question based on 100 parts by weight of all polymer components of the film.
  • a wrapping film with a coating for example with adhesive
  • only the parts by weight of all polymer components of the polyolefin-containing layer are taken into account.
  • the total amount of anti-aging agent must also be taken into account, since no anti-aging agent or only less than 0.3 phr (x phr means x parts per 100 parts of polymer or polymer blend) have been used to produce such wrapping tapes, as is customary in the production of other films , In particular, no secondary antioxidants were used.
  • the winding tapes according to the invention contain at least 4 phr of a primary antioxidant or at least 0.3 phr of a combination of primary and secondary antioxidant, the primary and secondary antioxidant function being present in different molecules or being combined in one molecule.
  • Optional stabilizers such as metal deactivators or light stabilizers are not included in the stated quantities.
  • the amount of secondary antioxidant is preferably at least 0.5 phr, in particular at least 1 phr.
  • Stabilizers for PVC products cannot be transferred to polyolefins.
  • 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 primary antioxidant preferably sterically hindered phenols with a molecular weight of more than 500 g / mol (preferably> 700 g / mol)
  • a phosphitic secondary antioxidant preferably with a molecular weight> 600 g / mol
  • Phosphites or a combination of primary and several secondary anti-aging agents have so far not been used in wrapping films made of polyolefins such as polypropylene polymers.
  • a low-volatile primary phenolic antioxidant and a secondary antioxidant from the class of the sulfur compounds preferably with a molecular weight of more than 400 g / mol, in particular> 500 g / mol
  • a secondary antioxidant from the class of the sulfur compounds preferably with a molecular weight of more than 400 g / mol, in particular> 500 g / mol
  • the phenolic, the sulfur-containing and the phosphitic functions need not be present in three different molecules, but more than one function can be combined in one molecule.
  • Phenolic and amine 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
  • a combination is also preferred in which the proportion of secondary antioxidant exceeds that of the primary.
  • metal deactivators for complexing heavy metal traces which can catalytically accelerate aging, can also be added.
  • 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.).
  • a thiopropionic acid ester If more than approx. 0.5 phr of a thiopropionic acid ester is used, it can migrate to the surface, which is particularly unpleasant for black films.
  • the problem can surprisingly be solved by combining different thiopropionic acid esters in such a way that the solubility limit for each thiopropionic acid ester is not exceeded. A combination of several thiopropionic acid esters is therefore preferred. The easiest way to do this is to vary the alkyl chains.
  • the selection of the anti-aging agents mentioned is of particular importance for the wrapping film according to the invention, since phenolic antioxidants alone or even in combination with sulfur-containing costabilizers generally do not make it possible to achieve practical products.
  • an amount of at least 0.1, preferably at least 0.3 phr is preferred for the phosphite stabilizer.
  • migratable metal contaminants such as iron, manganese, chromium or copper can cause aging problems which can only be avoided by the above-mentioned knowledge of the correct combination and amount of anti-aging agents.
  • ground brucite has a number of technical advantages over precipitated magnesium hydroxide, so that the combination with antioxidants as described is particularly useful.
  • an embodiment is preferred which, in addition to the antioxidants, also contains a metal deactivator.
  • the thickness of the film according to the invention is in the range from 30 to 180 ⁇ m, preferably 50 to 150 ⁇ m, in particular 55 to 100 ⁇ m.
  • the surface can be textured or smooth.
  • the surface is preferably set slightly matt. This can be achieved by using a filler with a sufficiently large particle size or by a roller (for example embossing roller on the calender or matted chilli roll or embossing roller in the extrusion).
  • the film is provided on one or both sides with a pressure-sensitive adhesive layer in order to make the application simple, so that there is no need to fix the winding film at the end of the winding process.
  • the wrapping film according to the invention is essentially free of volatile plasticizers such as DOP or TOTM and therefore has excellent fire behavior and low emissions (plasticizer evaporation, fogging).
  • such a wrapping film can be produced from polyolefin and suitable combinations of anti-aging agents, in particular also with flame-retardant fillers such as magnesium hydroxide.
  • flame-retardant fillers such as magnesium hydroxide.
  • the wrapping film according to the invention advantageously has a force in the longitudinal direction at 1% elongation from 0.6 to 4 N / cm, preferably from 1 to 3 N / cm, and at 100% elongation a force from 2 to 20 N / cm, preferably from 3 to 10 N / cm.
  • the force at 1% elongation is greater than or equal to 1 N / cm and the force at 100% elongation is less than or equal to 15 N / cm.
  • the 1% force is a measure of the rigidity of the film
  • the 100% force is a measure of the suppleness when winding with strong deformation due to high winding tension.
  • the 100% force must not be too low, because otherwise the tear strength is too low.
  • the wrapping film preferably contains at least one polyolefin with a flexural modulus of less than 900 MPa, preferably 500 MPa or less and in particular 80 MPa or less.
  • the polyolefin can be a soft ethylene homopolymer or ethylene or propylene copolymer. A propylene copolymer is preferred.
  • the preferred melt index for calender processing is below 5 g / 10 min, preferably below 1 g / 10 min and in particular below 0.7 g / 10 min.
  • the preferred melt index for extrusion processing is between 1 and 20 g / 10 min, in particular between 5 and 15 g / 10 min.
  • the crystallite melting point of the polyolefin is advantageously between 120 ° C and 166 ° C, preferably below 148 ° C, particularly preferably below 145 ° C.
  • the crystalline region of the copolymer is preferably a polypropylene with a random structure, in particular with a content of 6 to 10 mol% of ethylene.
  • a polypropylene random copolymer (for example with ethylene) has a crystallite melting point between 120 ° C. and 145 ° C. (this is the range for commercial products).
  • a polypropylene homopolymer is between 163 ° C and 166 ° C depending on the molecular weight and tacticity. If the homopolymer has a low molecular weight and is modified with EP rubber (for example grafting, reactor blend), the lowering of the melting point leads to a crystallite melting point in the range from approximately 148 ° C. to 163 ° C.
  • the preferred crystallite melting point for the polypropylene copolymer according to the invention is therefore below 145 ° C. and is best achieved with a comonomer-modified polypropylene with a random structure in the crystalline phase and copolymeric amorphous phase.
  • Such copolymers have a relationship between the comonomer content both in the crystalline and in the amorphous phase, the flexural modulus and the 1% tension value of the winding film produced therefrom.
  • a high comonomer content in the amorphous phase enables a particularly low 1% force value.
  • a comonomer content in the hard crystalline phase has a positive influence on the flexibility of the filled film.
  • the crystallite melting point should not be below 120 ° C, as is the case with EPM and EPDM, because there is a risk of melting in applications on ventilation pipes, display coils or vehicle cables.
  • Wrapping films made from ethylene-propylene copolymers from the classes of the EPM and EPDM are therefore not according to the invention, but this does not rule out the possibility that such polymers are used in addition to the polypropylene copolymer according to the invention to adjust the mechanical properties.
  • ⁇ -olefins such as ethylene, propylene, butylene (1), isobutylene, 4-methyl-1-pentene, hexene or octene are preferably used.
  • Copolymers with three or more comonomers are included in the sense of this invention. It is particularly preferred as monomers for the polypropylene copolymer propylene and ethylene.
  • the polymer can continue be modified by grafting, for example with maleic anhydride or acrylate monomers, for example to improve the processing behavior or the mechanical properties.
  • Polypropylene copolymers are not only understood to mean copolymers in the strict sense of polymer physics such as block copolymers, but also commercially available thermoplastic PP elastomers with a wide variety of structures or properties. Such materials can be produced, for example, from PP homo- or random copolymers as a precursor by further reaction with ethylene and propylene in the gas phase in the same reactor or in subsequent reactors. If random copolymer is used as the starting material, the monomer distribution of ethylene and propylene in the EP rubber phase which forms is more uniform, which leads to better mechanical properties. This is another reason why a polymer with a crystalline random copolymer phase is preferred for the winding film according to the invention. Common processes can be used for the production, examples being the gas phase, Cataloy, Spheripol, Novolen and Hypol processes, which are described in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, Wiley-VCH 2002 are.
  • Suitable blending components are, for example, soft ethylene copolymers such as LDPE, LLDPE, Metallocen-PE, EPM or EPDM with a density of 0.86 to 0.92 g / cm 3, preferably 0.86 to 0.88 g / cm 3 .
  • Soft hydrogenated random or block copolymers of ethylene or (optionally substituted) styrene and butadiene or isoprene are also suitable, the flexibility to bring the force at 1% elongation and in particular the shape of the force-elongation curve of the wrapping film into the optimal range.
  • a further copolymer containing ethylene or propylene is used, it preferably has a specified melt index in the range of ⁇ 50% of the melt index of the polypropylene copolymer. This does not take into account that the melt index of ethylene-containing copolymers is usually specified for 190 ° C and not for 230 ° C as is the case with polypropylene.
  • ethylene copolymers with monomers containing carbonyl groups such as ethylene acrylate (for example EMA, EBA, EEA, EAA) or ethylene vinyl acetate, as is known to the person skilled in the art, can improve the fire behavior of PP polymers.
  • ethylene acrylate for example EMA, EBA, EEA, EAA
  • ethylene vinyl acetate as is known to the person skilled in the art, can improve the fire behavior of PP polymers.
  • This also applies to the wrapping film according to the invention with a polymer with the properties specifically required here.
  • polyethylene vinyl alcohol and olefin-free nitrogen- or oxygen-containing poly- mers are suitable as synergists, for example in the form of polyvinyl alcohol; Polyamides and polyesters with a sufficiently low softening point (suitable for the processing temperature of polypropylene), polyvinyl acetate, polyvinyl butyral, vinyl acetate-vinyl alcohol copolymer and poly (meth) acrylates.
  • the person skilled in the art considers these strongly polar materials to be incompatible with polypropylene, since the solubility parameter is at least 19 J 1/2 / cm 3/2 .
  • Polyvinyl acetate and poly (meth) acrylates which can also be crosslinked, are preferred.
  • This can also have a core-shell structure, for example a core made from polyacrylates of alcohols with 2 to 8 carbon atoms and a shell made from polymethyl methacrylate.
  • acrylate impact modifiers which are produced for the modification of PVC, have proven to be particularly suitable, since even in small quantities they bring about a significant improvement in fire behavior, without significantly impairing the flexibility of the wrapping film and despite their polarity do not increase the adhesion of the melt to calender or chill rolls.
  • polyolefins in which the oxygen is introduced by grafting (for example with maleic anhydride or a (meth) acrylate monomer).
  • the proportion of oxygen based on the total weight of all polymers is between 0.5 and 5 phr (also corresponds to% by weight), in particular 0.8 to 3 phr.
  • a thermoplastic polymer containing oxygen or nitrogen it preferably has a specified melt index in the range of + 50% of the melt index of the polypropylene copolymer.
  • a special embodiment is a wrapping film with at least one coextrusion layer made of a nitrogen- or oxygen-containing polymer, which can be provided with the flame retardants and anti-aging agents or carbon blacks disclosed here, in addition to a layer made of polypropylene copolymer.
  • halogen-free materials are suitable as flame retardants, for example fillers such as polyphosphates, carbonates and hydroxides of aluminum or magnesium, borates, stannates and organic nitrogen-based flame retardants.
  • fillers such as polyphosphates, carbonates and hydroxides of aluminum or magnesium, borates, stannates and organic nitrogen-based flame retardants.
  • Preferred are a) combinations of phosphates (for example ammonium polyphosphate or ethylenediamine polyphosphate) and nitrogen compounds and especially b) hydroxides of magnesium.
  • Polyphosphates and nitrogen compounds are suitable, but some are sensitive to water. This can lead to corrosion or deterioration in electrical properties such as breakdown voltage. Influence of water is not important for a wrapping film in the passenger compartment. In the engine compartment, however, the wrapping film can get warm and wet.
  • nitrogen-containing flame retardants are dicyandiamide, melamine cyanurate and sterically hindered amines such as the class of HA (L) S. Red phosphorus can also be used, preferably it is not used (i.e.
  • the amount is zero or not flame-retardant) because the processing is dangerous (self-ignition of released phosphine when mixed into the polymer, even with coated phosphorus, however much phosphine can be formed that there is a health risk for the operating personnel).
  • red phosphorus only colored and only black and brown products can be produced.
  • the preferred filler as a flame retardant is magnesium hydroxide, especially in combination with nitrogen-containing flame retardants.
  • nitrogen-containing flame retardants are melamine, ammeiin, melam, melamine cyanurate.
  • red phosphorus also acts synergistically when magnesium hydroxide is used. However, it is preferred to delay the use for the reasons mentioned above.
  • Organic and inorganic phosphorus compounds in the form of the known flame retardants for example based on triaryl phosphate or polyphosphate salts, have an antagonistic effect. In the preferred embodiments, bound phosphorus is therefore dispensed with, unless it is phosphites with an anti-aging effect. These should not exceed the chemically bound phosphorus content of 0.5 phr.
  • the flame retardant can be provided with a coating, which can also be applied subsequently during the compounding process.
  • Suitable coatings are silanes such as vinylsilane or such as free fatty acids (or their derivatives) such as stearic acid, Silicates, borates, aluminum compounds, phosphates, titanates but also chelating agents.
  • the content of free fatty acid or its derivative is preferably between 0.3 and 1% by weight.
  • Ground magnesium hydroxides are particularly preferred, examples being brucite (magnesium hydroxide), Kovdorskite (magnesium hydroxide phosphate), hydromagnesite (magnesium hydroxide carbon) and hydrotalcite (magnesium hydroxide with aluminum and carbonate in the crystal lattice), the use of brucite being particularly preferred.
  • Mixtures of magnesium carbonates such as dolomite [CaC0 3 ⁇ MgCO 3 , M r 184.41], magnesite (MgCO 3 ), huntite [CaCO 3 ⁇ 3 MgC0 3 , M r 353.05] are permissible.
  • a content of calcium carbonate (as a compound or in the form of a mixed crystal of calcium and magnesium and carbonate) even turns out to be advantageous for aging, with a proportion of 1 to 4% by weight calcium carbonate being considered favorable (the analytical calcium content becomes converted to pure calcium carbonate).
  • the calcium and carbonate content of brucite is present in many deposits as an impurity in the form of chalk, dolomite, huntite or hydrotalcite, but can also be specifically mixed with the magnesium hydroxide.
  • the positive effect may be due to the neutralization of acids. These arise, for example, from magnesium chloride, which is usually found as a catalyst residue in polyolefins (for example from the spheripole process).
  • Acidic components from the adhesive coating can also migrate into the film and thus deteriorate the aging.
  • the admixture of calcium stearate can have a similar effect to that of calcium carbonate, but the addition of larger amounts reduces the adhesive strength of the adhesive coating and, in particular, the adhesion of such an adhesive layer to the back of the wrapping film in the case of such wrapping tapes.
  • Magnesium hydroxide with an average particle size of more than 2 ⁇ m is particularly suitable, whereby the median value is meant (d 50 determined by laser light scattering according to Cilas) and in particular greater than or equal to 4 ⁇ m.
  • the specific surface area (BET) is preferably less than 4 m 2 / g (DIN 66131/66132). Usual wet-precipitated magnesium hydroxides are finely divided, as a rule the average particle size is 1 ⁇ m and below, the specific surface area is 5 m 2 / g and more.
  • the upper limit of the particle size distribution d 97 is preferably not more than 20 ⁇ m for the occurrence to avoid holes in the film and embrittlement. Therefore, the magnesium hydroxide is preferably sieved. A content of particles with a diameter of 10 to 20 ⁇ m gives the film a pleasant looking matt effect.
  • the preferred particle shape is irregularly spherical, similar to that of river pebbles. It is preferably obtained by grinding.
  • Magnesium hydroxide which was prepared by dry grinding in the presence of a free fatty acid, in particular stearic acid, is particularly preferred.
  • the resulting fatty acid coating improves the mechanical properties of mixtures of magnesium hydroxide and polyolefins and reduces the efflorescence of magnesium carbonate.
  • a fatty acid salt for example sodium stearate
  • the wrapping film produced therefrom has an increased conductivity when exposed to moisture, which is disadvantageous in applications in which the wrapping film also takes on the function of an insulating tape.
  • synthetically precipitated magnesium hydroxide the fatty acid is always added in salt form because of its water solubility. This is another reason why a ground magnesium hydroxide is preferred over a precipitated one for the wrapping film according to the invention.
  • FIGS. 1 to 3 Various particle shapes are shown in FIGS. 1 to 3.
  • Figure 1 shows regularly shaped, platelet-shaped ponds
  • Figure 2 shows irregularly shaped, platelet-shaped ponds
  • Figure 3 shows irregularly shaped, spherical ponds.
  • Magnesium hydroxide in platelet form is less suitable. This applies to regular (e.g. hexahedron) and irregular platelets.
  • the film on the calender can be removed more easily from the rollers or the tube is better in the case of blown extrusion (no breaks in the melt tube), but the flame resistance is somewhat worse than in the case of synthetic magnesium hydroxide, as is preferred by the person skilled in the art.
  • This can be countered by increasing the filler content, but this requires a particularly soft polymer.
  • This can be a soft ethylene homopolymer or ethylene copolymer, the film produced therefrom preferably being crosslinked in order to increase the heat resistance.
  • the specific problem solving of this invention is a particularly soft polypropylene copolymer as set out above.
  • This special polymer enables the use of large amounts of filler and even higher in the case of ground magnesium hydroxide with a higher d 50 value without the wrapping film becoming too stiff and inflexible for the application and requires no crosslinking.
  • the heavy metal traces of synthetic magnesium hydroxide can adversely affect aging, which is prevented by using the special aging protection combinations mentioned below.
  • the amount of flame retardant (s) is chosen so high that the wrapping film is flame-retardant, that is, slowly burning.
  • the fire speed according to FMVSS 302 for a horizontal sample is preferably below 200 mm / min, particularly preferably below 100 mm / min, in an outstanding embodiment of the wrapping film, it is self-extinguishing under these test conditions.
  • the oxygen index (LOI) is preferably above 20%, in particular above 23% and particularly preferably above 27%.
  • the proportion is preferably 70 to 200 phr and in particular 110 to 180 phr.
  • the following methods are preferred and claimed: - Mixing of polymer and filler in a kneader in batch mode or continuously (for example from Banbury), part of the filler is preferably added, if another part already was homogenized with the polymer.
  • additives customary in films such as fillers, pigments, anti-aging agents, nucleating agents, impact modifiers or lubricants, and others can be used to produce the wrapping film.
  • These additives are described, for example, in the "Kunststoff Taschenbuch” by Hanser Verlag, ed. H. Saechtling, 28th edition or "Plastic Additives Handbook", Hanser-Verlag, ed. H. Doubt, 5th edition. In the following explanations, the respective CAS Reg.No. used.
  • the present invention aims primarily at high aging stability and also the absence of halogens and volatile plasticizers. As stated, the thermal requirements increase, so that an additional resistance to conventional PVC wrapping foils or the PVC-free foil wrapping tapes being tested is to be achieved.
  • the high aging stability is achieved by using an adequately dosed and cleverly selected combination of anti-aging agents (antioxidants and metal deactivators, if applicable). Therefore, the present invention in this regard will be described in detail below.
  • the wrapping film according to the invention has a thermal stability of at least 105 ° C. after 3000 hours, which means that after this storage there is still an elongation at break of at least 100%. It should also have an elongation at break of at least 100% after 20 days of storage at 136 ° C (rapid test) or a heat resistance of 170 ° C (30 min.). In an excellent embodiment with the described antioxidants and optionally also with a metal deactivator, 125 ° C is reached after 2000 hours or even 125 ° C after 3000 hours.
  • Classic PVC wrapping films based on DOP have a thermal stability of 85 ° C (passenger compartment), high-performance products based on polymer plasticizers reach 105 ° C (engine compartment).
  • the wrapping film must be compatible with a polyolefin-based cable sheathing, that is, after storage of the cable / wrapping film assembly, neither embrittlement of the wrapping film or the cable insulation occurs.
  • compatibility at 105 ° C., preferably 125 ° C. (2000 hours, in particular 3000 hours) and short-term heat resistance of 140 ° C. (168 hours) can be achieved.
  • a further prerequisite for adequate short-term heat resistance and heat resistance is an adequate melting point of the polyolefin (at least 120 ° C.) and an adequate mechanical stability of the melt somewhat above the crystallite melting point.
  • the latter is guaranteed by a melt index of at most 20 g / 10 min with a filler content of at least 80 phr or of at most 5 g / 10 min with a filler content of at least 40 phr.
  • aging stabilization is crucial to achieve oxidative resistance from 140 ° C, which is achieved in particular by secondary antioxidants such as phosphites.
  • a negative example is the combination of an unsuitable polypropylene wrapping film with a copper-stabilized polyamide corrugated pipe, in which case both the corrugated pipe and the wrapping film become brittle after 3,000 hours at 105 ° C.
  • the wrapping film according to the invention is preferably pigmented, in particular black.
  • the coloring can be done in the base film, in the adhesive or another layer.
  • the use of organic pigments or dyes in the wrapping film is possible; the use of carbon black is preferred.
  • the proportion of carbon black is preferably at least 5 phr, in particular at least 10 phr, since it surprisingly shows a significant influence on the fire behavior.
  • the thermal aging stability is surprisingly higher if the carbon black (for example in the form of a masterbatch) is only added after the polypropylene polymer has been mixed with the anti-aging agents (antioxidants).
  • This advantage can be used by first compounding the polymer, anti-aging agent and filler and adding the carbon black as a masterbatch to an extruder in the film production system (calender or extruder).
  • An additional benefit is that when changing the product on the compounder (stamp kneader or extruder such as twin-screw extruder or planetary roller extruder) there is no time-consuming cleaning of soot residues is required.
  • soot masterbatch can also be added to the film line without any problems, that is to say not only 1 to 2, but even 15 to 30 phr.
  • All types such as, for example, gas black, acetylene black, thermal black, furnace black and flame black can be used, carbon black being preferred, even if fuma blacks are customary for coloring films.
  • carbon black types with a pH in the range from 6 to 8 are preferred, in particular flame black.
  • the wrapping film is produced on a calender or by extrusion, for example in the blowing or casting process.
  • a compounder such as a kneader (for example a stamp kneader) or an extruder (for example a twin-screw extruder, planetary roller extruder) and then converted into a solid form (for example granules), which is then in a film extrusion system or melted and processed in an extruder, kneader or rolling mill in a calender system.
  • the mixing process must therefore be carried out so thoroughly that the film made from the compound reaches a breakdown voltage of at least 3 kV / 100 ⁇ m, preferably at least 5 kV / 100 ⁇ m.
  • the compound and film are preferably produced in one operation.
  • the melt is fed from the compounder directly to an extrusion system or a calender, the melt possibly passing through auxiliary devices such as filters, metal detectors or rolling mills.
  • the film is oriented as little as possible in the manufacturing process in order to achieve good hand tearability, low force value at 1% elongation and low shrinkage. For this reason, the calendering process is particularly preferred.
  • the shrinkage of the wrapping film in the longitudinal direction after heat storage (30 minutes in an oven at 125 ° C. on a talc layer) is less than 5%, preferably less than 3%.
  • the mechanical properties of the wrapping film according to the invention are preferably in the following areas: Elongation at break in md (machine direction) from 300 to 1000, particularly preferably from 500 to 800%,
  • the wrapping film is provided on one or both sides, preferably on one side, with a sealing or pressure-sensitive adhesive coating in order to avoid the need to fix the winding end by means of an adhesive tape, wire or knotting.
  • the amount of the adhesive layer is in each case 10 to 40 g / m 2, preferably 18 to 28 g / m 2 (this is the amount after a possible removal of water or solvent; the numerical values also correspond approximately to the thickness in ⁇ m).
  • adhesive coating the information given here about the thickness and the thickness-dependent mechanical properties relate exclusively to the polypropylene-containing layer of the wrapping film without taking into account the adhesive layer or other layers which are advantageous in connection with adhesive layers.
  • the coating does not have to be over the entire surface, but can also be carried out over part of the surface.
  • An example is a wrapping film with a pressure-sensitive adhesive strip on the side edges. This can be cut off to form approximately rectangular sheets, which are glued to the cable bundle with one adhesive strip and then wound until the other adhesive strip can be glued to the back of the wrapping film.
  • Such a hose-like wrapping similar to a sleeve packaging, has the advantage that the flexibility of the wiring harness is practically not impaired by the wrapping.
  • Rubbers can be, for example, homo- or copolymers of isobutylene, 1-butene, vinyl acetate, ethylene, acrylic esters, butadiene or isoprene. Formulations based on polymers based on acrylic acid esters, vinyl acetate or isoprene are particularly suitable.
  • the self-adhesive used can be mixed with one or more additives such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, anti-aging agents, photoinitiators, crosslinking agents or crosslinking promoters his.
  • additives such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, anti-aging agents, photoinitiators, crosslinking agents or crosslinking promoters his.
  • Tackifiers are, for example, hydrocarbon resins (for example polymers based on unsaturated C 5 or C 9 monomers), terpene phenol resins, polyterpene resins made from raw materials such as ⁇ - or ⁇ -pinene, aromatic resins such as coumarone-indene resins or resins based on styrene or ⁇ -methylstyrene, such as rosin and its secondary products, for example disproportionated, dimerized or esterified resins, for example reaction products with glycol, glycerol or pentaerythritol, to name just a few, and further resins (as listed, for example, in Ulimann's encyclopedia of industrial chemistry, Volume 12, pages 525 to 555 (4th edition), Weinheim).
  • hydrocarbon resins for example polymers based on unsaturated C 5 or C 9 monomers
  • terpene phenol resins polyterpene resins made from raw materials such as ⁇ - or ⁇ -pin
  • Resins without easily oxidizable double bonds such as terpene-phenolic resins, aromatic resins and particularly preferably resins which are produced by hydrogenation, such as, for example, hydrogenated aromatic resins, hydrogenated hydrogenated polycyclopentadiene resins, hydrogenated rosin derivatives or hydrogenated terpene resins are preferred.
  • Suitable fillers and pigments are, for example, carbon black, titanium dioxide, calcium carbonate, zinc carbonate, zinc oxide, silicates or silica.
  • Suitable admixable 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 acid esters, Polyvinyl ether, 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 are, for example, sterically hindered phenols, which are known, for example, under the trade name Irganox TM.
  • Networking is advantageous because the shear strength (expressed, for example, as holding power) is increased and thus the tendency to deform the rolls during storage (telescoping or formation of cavities, also called gaps) is reduced. The squeezing out of the adhesive mass is also reduced. This is expressed in the non-sticky side edges of the rolls and non-sticky edges in the wrapping film which is spirally guided around the cable.
  • the holding power is preferably above 150 minutes.
  • the adhesive strength on steel should be in the range of 1.5 to 3 N / cm.
  • the preferred embodiment has a solvent-free self-adhesive composition on one side, which has been brought about by coextrusion, melt or dispersion coating. Dispersion adhesives are preferred, particularly those based on polyacrylate.
  • the known dispersion and solvent systems can be used as primers, for example based on isoprene or butadiene-containing rubber and / or cyclo-rubber.
  • Isocyanates or epoxy resins as additives improve the adhesion and in some cases 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 the adhesion.
  • the rear side can be coated using known release agents (optionally mixed with other polymers).
  • stearyl compounds for example polyvinyl stearyl carbamate, stearyl compounds of transition metals such as Cr or Zr, ureas from 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 with a C number of at least 10, such as octadecyl.
  • a wrapping film in which the logs have been tempered (stored in the heat) before cutting. Both methods can also be used in combination.
  • the wrapping film according to the invention preferably has a rolling force of 1.2 to 6.0 N / cm, very particularly preferably 1.6 to 4.0 N / cm and in particular 1.8 to 2.5 N / cm at 300 mm / min Unwind speed. Tempering is known for PVC winding tapes, but for a different reason. In contrast to semi-crystalline polypropylene copolymer films, soft PVC films have a wide softening range and, because the adhesive has little shear strength due to the emigrated plasticizer, PVC wrapping tapes tend to telescope.
  • the method according to the invention involves tempering to increase the unwinding force of material with a non-polar polypropylene back and polar adhesive, such as polyacrylate or EVA, since these adhesives have an extremely low back adhesion on polypropylene compared to PVC.
  • a non-polar polypropylene back and polar adhesive such as polyacrylate or EVA
  • An increase in the unwinding force due to tempering or physical surface treatment is not necessary with soft PVC winding tapes, since the adhesives usually used have a sufficiently high adhesion to the polar PVC surface.
  • the importance of rear adhesion is particularly pronounced, since, due to the higher force at 1% elongation (due to the flame retardant and the lack of conventional plasticizers), a significantly higher rear adhesion or unwinding force is necessary compared to PVC film, in order to achieve sufficient Provide stretching when unrolling for the application.
  • the preferred embodiment of the wrapping film is therefore produced by tempering or physical surface treatment in order to provide excellent unrolling force and stretch to achieve during unwinding, the unwinding force at 300 mm / min preferably being at least 50% higher than without such a measure.
  • the wrapping film is preferably stored beforehand at least 3 days, particularly preferably at least 7 days before the coating in order to achieve recrystallization so that the rolls are not inclined to telescope.
  • the film is preferably guided on the coating system over heated rollers for leveling (improving flatness), which is not common for PVC wrapping films.
  • Films made of polyethylene and polypropylene cannot usually be torn or torn off by hand. As semi-crystalline materials, they can be stretched easily and therefore have a high elongation at break, which is usually well above 500%. When trying to tear such films, an elongation occurs instead of a tear. Even high forces cannot necessarily overcome the typically high breaking forces. Even if this succeeds, a good-looking and glue-off tear is not produced, since a thin, narrow tail is formed at both ends. This problem can hardly be solved by additives, even if fillers reduce the elongation at break in large quantities. If polyolefin films are stretched biaxially, the elongation at break is reduced by more than 50%, which promotes tearability.
  • the elongation at break of the specially cut wrapping film is at least 30% lower than when cutting with sharp blades.
  • the elongation at break is 500 to 800%, in the embodiment of the foil whose side edges are damaged in a defined manner during cutting, between 200 and 500%.
  • the logs can be subjected to heat storage beforehand to increase the unwinding force.
  • the cutting of conventional wrapping tapes with fabric, fleece and film backing e.g. PVC
  • the cutting of conventional wrapping tapes with fabric, fleece and film backing is done by scissors cut (between two rotating knives), parting cut (fixed or rotating knives are pressed into a rotating rod of the product), blade cutting (the web is at Pass divided by sharp blades) or crush cut (between a rotating knife and a roller).
  • the aim of cutting is to produce rolls that are ready for sale from jumbos or bars, but not to produce rough cut edges for easier hand tearing.
  • the parting cut is quite common, since the process is economical with soft foils.
  • the material can be torn by hand because PVC is amorphous in contrast to polypropylene and therefore does not stretch when torn, but is only stretched a little.
  • care must be taken to ensure sufficient gelling during film production, which is an obstacle to optimal production speed.
  • material with a higher molecular weight is often used instead of standard PVC with a K value of 63 to 65 Corresponds to K values of 70 and more.
  • the cut-off cut has a different reason for the wrapping films according to the invention made of polypropylene than for those made of PVC.
  • the wrapping film according to the invention is excellently suitable for wrapping elongated material such as ventilation pipes, field coils or cable sets in vehicles.
  • the wrapping film according to the invention is also suitable for other applications, for example for ventilation pipes in air conditioning, since the high flexibility ensures rivets, beads and folds.
  • Today's occupational hygiene and ecological requirements are taken into account by not using halogen-containing raw materials. This also applies to volatile plasticizers, unless the quantities are so small that the fogging value is over 90%.
  • the absence of halogen is extremely important for the thermal recycling of waste containing such winding tapes (for example, waste incineration of the plastic fraction from vehicle recycling).
  • 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 resistance.
  • Halogens in trace amounts such as those that could occur due to impurities, process additives (fluoroelastomer) or as residues of catalysts (for example from the polymerisation of polymers) are not taken into account.
  • the absence of halogens entails the property of easy flammability, which does not meet the safety requirements in electrical applications such as household appliances or vehicles.
  • the measurements are carried out at a test climate of 23 + 1 ° C and 50 ⁇ 5% rel. Humidity carried out.
  • the density of the polymers is determined according to ISO 1183 and the flexural modulus according to ISO 178 and expressed in g / cm 3 or MPa. (The bending module according to ASTM D790 is based on different dimensions of the test specimens, but the result is comparable as a number.)
  • the melt index is tested according to ISO 1133 and expressed in g / 10 min. As usual in the market, the test conditions are 230 ° C and 2.16 kg for polymers with crystalline polypropylene and 190 ° C and 2.16 kg for polymers with crystalline polyethylene.
  • the crystallite melting point (Tcr) is determined with DSC according to MTM 15902 (Basell method) or ISO 3146.
  • the average particle size of the filler is determined by laser light scattering according to Cilas; the median value d 50 is decisive.
  • the specific surface area (BET) of the filler is determined according to DIN 66131/66132.
  • the tensile elongation behavior of the wrapping 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 preload of 0.3 N / cm determined. In the case of samples with rough cut edges, the edges must be trimmed with a sharp blade before the tensile test. To determine the force or tension at 1% elongation, a test speed of 10 mm / min and a preload setting of 0.5 N / cm are used to measure on a tensile testing machine model Z 010 (manufacturer Zwick).
  • the testing machine is specified because the 1% value can be influenced somewhat by the evaluation program. Unless otherwise stated, the tensile elongation behavior is checked in the machine direction (MD, running direction). The force is expressed in N / strip width and the tension in N / strip cross-section, the elongation at break in%. The test results, in particular the elongation at break (elongation at break), must be statistically verified by a sufficient number of measurements.
  • the adhesive forces are determined at a peel 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 surface, unless another primer is mentioned.
  • the thickness of the wrapping film is determined according to DIN 53370. A possible layer of pressure sensitive adhesive 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 rolling force is measured at 300 mm / min according to DIN EN 1944.
  • the hand tearability cannot be expressed in numbers, even if breaking strength, elongation at break and impact strength (all measured lengthways) are of major influence.
  • the fire behavior is measured according to MVSS 302 with a horizontal sample. In the case of a one-sided pressure-sensitive adhesive coating, this is on top. Another method is to check the Oxygen Index (LOI). For this, testing is carried out under the conditions of JIS K 7201.
  • LOI Oxygen Index
  • the heat stability is determined based on ISO / DIN 6722.
  • the furnace is operated according to ASTM D 2436-1985 with 175 air changes per hour.
  • the test time is 3000 hours.
  • the test temperatures selected are 85 ° C (class A), 105 ° C (similar to class B but not 100 ° C) and 125 ° C (class C).
  • the rapid aging takes place at 136 ° C, the test is passed if the elongation at break is still at least 100% after 20 days of aging.
  • test specimens are made of 5 conductors with a cross-section of 3 to 6 mm 2 and a length of 350 mm with wrapping foil by wrapping with 50% overlap pung manufactured.
  • the test specimens had been aged for 3,000 hours in a forced-air oven (conditions as in the heat stability test)
  • the samples were conditioned at 23 ° C and wound around a mandrel by hand in accordance with ISO / DIN 6722, the mandrel a diameter of 5 mm, the weight has a mass of 5 kg and the winding speed is 1 revolution per second.
  • the samples are then examined visually for defects in the wrapping film and in the wire insulation under the wrapping film.
  • test is unsuccessful if there are cracks in the wire insulation, in particular if this can be seen on the mandrel before bending. If the wrapping film shows cracks or has melted in the oven, the test is also considered to have failed 10. In the 125 "C test, samples were also sometimes tested at other times. The test time is 3000 hours unless expressly stated otherwise in individual cases.
  • the short-term heat resistance is measured on cable bundles made of 19 wires of type TW with 15 0.5 mm 2 cross-section, which are described in ISO 6722.
  • the wrapping film is wound with 50% overlap on the cable bundle, the cable bundle is bent around a mandrel with a diameter of 80 mm and stored in a convection oven at 140 ° C. After 168 hours, the sample is removed from the oven and checked for damage (cracks).
  • the wrapping film is 30 min. stored at 170 ° C, 30 min. cooled to room temperature and wound with at least 3 turns with a 50% overlap around a mandrel of 10 mm diameter. The pattern is then checked for damage (cracks).
  • test specimen described above is cooled to -40 ° C based on ISO / DIS 67224 hours and the specimen is wound by hand on a mandrel with a diameter of 5 mm. The samples are visually checked for defects (tears) in the adhesive tape.
  • the breakdown voltage is measured according to ASTM D 1000. The number taken is the highest value that the pattern can withstand for one minute at this tension. This number is converted to a sample thickness of 100 ⁇ m.
  • the fogging value is determined in accordance with DIN 75201 A.
  • 100 phr polymer A, 10 phr Vinnapas B 10, 150 phr Magnifin H 5 GV, 10 phr flame black 101, 0.8 phr Irganox 1010, 0.8 phr Irganox PS 802 and 0, are first used in a co-rotating twin-screw extruder. 3 phr Irgafos 168 compounded. The Magnifin is added to 1/3 in zones 1, 3 and 5.
  • the compound melt is fed from the die of the extruder to a rolling mill, from there through a strainer and then fed via a conveyor belt into the nip of a "inverted L" type calender.
  • a film with a smooth surface is produced in a Formed width of 1500 mm and a thickness of 0.08 mm (80 ⁇ m) and recrystallized on heat setting rollers, the film is stored for one week, leveled on the coating system with rollers at 60 ° C. to improve the flatness and after corona treatment with an aqueous solution
  • Acrylic pressure sensitive adhesive Primal PS 83 D applied with a doctor blade with an application weight of 24 g / m 2.
  • the adhesive layer is dried in the drying tunnel at 70 ° C, the finished wrapping film becomes bars with a length of 33 m on a 1 inch core (25 mm).
  • the cutting is done by parting the rods with a fixed blade with a not very acute angle (straight knife) in 29 mm wide rolls.
  • This self-adhesive wrapping film shows good flexibility despite the high proportion of filler. Furthermore, very good fire properties are achieved even without the addition of an oxygen-containing polymer. The aging resistance and compatibility with PP and PA cables and polyamide corrugated pipe are outstanding.
  • the preparation is carried out analogously to Example 1 with the following changes:
  • the compound consists of 100 phr polymer A, 120 phr brucite 15 ⁇ , 15 phr flame black 101, 0.8 phr Irganox 1010, 0.1 phr Irganox PS 802, 0.1 phr Sumilizer TPM , 0.1 phr Sumilizer TPL-R, 0.1 phr Sumilizer TP-D, 0.3 phr Irgafos 168 and 1 phr Irganox MD 1024.
  • the brucite is added to zones 1 and 5 each.
  • the carrier film produced therefrom is subjected to a one-sided flame pretreatment and, after 10 days of storage, is coated with Acronal DS 3458 using a roller applicator at 50 m / min.
  • the temperature load on the carrier is reduced by a cooled counter-pressure roller.
  • the mass application is approx. 35 g / m 2 .
  • a suitable cross-linking is achieved in-line prior to winding up by irradiation with a UV system which is equipped with 6 medium-pressure mercury lamps of 120 W / cm.
  • the irradiated web is wound into rods with a 33 m run length on a 1 1/4 inch core (31 mm).
  • the bars are tempered for 5 hours in an oven at 60 ° C to increase the unwinding force.
  • the cutting is done by parting the rods with a fixed blade (straight knife) into 25 mm wide rolls.
  • the film from Example 1 After 3 months of storage at 23 ° C, no anti-aging agent has exuded from the film. In comparison, the film from Example 1 has a light coating, which after analytical testing consists of Irganox PS 802.
  • This wrapping film is characterized by an even greater flexibility than that from example 1.
  • the rate of fire is more than sufficient for the application.
  • the film has a slightly matt surface. During the application, two fingers have to be placed in the core, which makes the application easier than in Example 1.
  • the preparation is carried out analogously to Example 1 with the following changes:
  • the compound consists of 80 phr polymer A, 20 phr Evaflex A 702, 120 phr Securoc B 10, 0.2 phr calcium carbonate, 10 phr flame black 101, 0.8 phr Irganox 1010, 0 , 8 phr Irganox PS 802 and 0.3 phr Irgafos 168.
  • the film is corona-treated in front of the winding station of the calender and applied to this side of the Rikidyne BDF 505 adhesive (calculated with the addition of 1% by weight of Desmodur Z 4470 MPA X per 100 parts by weight of adhesive to dry content) at 23 g / m 2 .
  • the glue is dried in a heating channel and chemically cross-linked, wrapped in jumbos at the end of the dryer, lightly corona-treated after 1 week on the non-coated side and wrapped in rods with a 25 m length. These are stored in an oven at 100 ° C for 1 hour.
  • the cutting is done by Parting off the rods using rotating, slightly blunt knives (round blades) in rolls of 15 mm width.
  • This wrapping film has balanced properties and a slightly matt surface.
  • the holding power is over 2000 min (measurement then stopped).
  • the elongation at break is 36% lower than for samples with a blade cut.
  • the rolling force is 25% higher than for samples without tempering.
  • the preparation takes place analogously to Example 1 with the following changes:
  • the compound consists of 100 phr polymer A, 120 phr Magnifin H 5 GV, 10 phr flame black 101, 2 phr irganox 1010, 1.0 phr Irganox PS 802, 0.4 phr Irgafos 168 ,
  • the film is flame-treated on one side and coated with 30 g / m 2 (dry application) of Airflex EAF 60.
  • the web is pre-dried with an IR lamp and finally dried in a channel at 100 ° C.
  • the tape is then wound into jumbos (large rolls).
  • the jumbos are unwound and the uncoated wrapping film side is subjected to a weak corona treatment in a cutting machine to increase the unwinding force and by means of a blunt squeeze cut (crush cutting, debris cut) to 33 m long rolls in 19 mm width on 1 Va inch Core (37 mm inner diameter) processed.
  • the elongation at break is 48% lower than for samples with a blade cut.
  • the rolling force is 60% higher than for samples without corona treatment.
  • two fingers have to be placed in the core, which facilitates the winding compared to example 1.
  • the compound is produced using a stick extruder (Buss) without soot and with underwater pelletizing. After drying, the compound is mixed with the soot masterbatch in a concrete mixer.
  • Buss stick extruder
  • the carrier film is produced on a blown film extrusion system with the following recipe: 100 phr polymer B, 100 phr brucite 15 ⁇ , 20 phr of a masterbatch from 50% Lamp black 101 and 50% polyethylene, 0.8 phr Irganox 1076, 0.8 phr Irganox PS 800, 0.2 phr Ultranox 626, 0.6 phr Naugard XL-1.
  • the film tube is slit and opened with a triangle to form a flat web and passed over a heat setting station, corona-treated on one side and stored for one week for recrystallization.
  • the film is fed to the coating system via 5 preheating rollers for leveling (improving the flatness), otherwise the coating is carried out with pressure sensitive adhesive analogous to Example 1, the rods are annealed at 65 C for 5 hours and cut analogously to Example 1.
  • the film Without heat-setting, the film shows significant shrinkage (5% in width, not measured lengthways) during the drying process.
  • the flatness of the freshly produced film is good, it is coated immediately after extrusion, unfortunately the rolls are already clearly telescoped after three weeks of storage at 23 ° C. This problem cannot be eliminated by tempering the bars (10 hours at 70 ° C).
  • the film is then stored for a week before coating, the rolls are only partially telecopied, but the flatness during coating is so bad and the adhesive application is so uneven that preheating rollers have been installed in the system.
  • the films are characterized by good heat resistance, i.e. without melting and embrittlement, with an additional storage period of 30 minutes at 170 ° C.
  • the production takes place analogously to Example 1 with the following changes:
  • the film contains 80 phr polymer C, 20 phr Escorene UL 00119, 130 phr Kisuma 5 A, 15 phr flame black 101, 0.8 phr Irganox 1010, 0.8 phr Irganox PS 802, 0.3 phr Irgafos 168.
  • This carrier film is corona treated on one side and stored for one week.
  • the pretreated side is coated with an adhesion promoter layer made of natural rubber, cyclo-rubber and 4,4'-diisocyanatodiphenylmethane (solvent toluene) of 0.6 g / m 2 and dried.
  • the adhesive coating is applied directly to the adhesive middle layer applied with a comma knife with an application weight of 18 g / m 2 (based on dry matter).
  • the adhesive consists of a solution of a natural rubber adhesive in n-hexane with a solids content of 30 percent by weight.
  • This consists of 50 parts of natural rubber, 10 parts of zinc oxide, 3 parts of rosin, 6 parts of alkylphenol resin, 17 parts of terpene-phenol resin, 12 parts of poly-ß-pinene resin, 1 part of Irganox 1076 antioxidant and 2 parts of mineral oil.
  • the coating is dried in the drying tunnel at 100 ° C.
  • the film is cut immediately behind in a compound cutting machine with a knife bar with sharp blades at a distance of 19 mm to rolls on standard adhesive tape cores (3 inches).
  • this wrapping film is characterized by very high flexibility, which is reflected in a low force value at 1% elongation.
  • This wrapping film has mechanical properties similar to those of soft PVC wrapping tapes, although it is even superior in terms of flame resistance and heat resistance.
  • the holding power is 1500 min and the rolling force at 30 m / min (not 300 mm / min) is 5.0 N / cm.
  • the fogging value is 62% (presumably due to the mineral oil of the adhesive). Due to the large roll diameter, the roll can only be pulled through diagonally between the winding board and the wiring harness, which creates folds in the winding.
  • the compounds for the individual layers of the film are produced without soot in a kneader with an extruder and underwater granulation.
  • the mixing time to homogenization is 2 min
  • the total kneading time to discharge into the granulating extruder is 4 min.
  • one half of the filler is added at the beginning and the other half after 1 minute.
  • the compound granules are mixed in a concrete mixer with the soot masterbatch and fed to a 3-layer coextrusion system using the cast process (die width 1400 mm, melt temperature at the die head 190 ° C., chill roll temperature 30 ° C., speed 30 m / min).
  • the carrier film has the following recipe structure:
  • Layer 1 15 ⁇ m 100 phr Evaflex P 1905, 40 phr Magnifin H 5 GV, 20 phr of a masterbatch made of 50% flame black 101 and 50% polyethylene, 0.4 phr Irganox 1076, 0.2 phr Irgafos 168
  • Layer 2 40 ⁇ m: 100 phr polymer B, 120 phr Magnifin H 5 GV, 20 phr 20 phr of a masterbatch made of 50% flame black 101 and 50% polyethylene, 0.8 phr Irganox 1076, 0.8 phr Irganox PS 800, 0 , 2 phr Irgafos 168
  • the film is heat set. After one week of intermediate storage at 23 ° C., the film is coated as in Example 1, but using the leveling rollers.
  • the wrapping film obtained in this way is wound into bars with a run length of 20 m, which are annealed at 40 ° C. for one week.
  • the cutting is done by parting the rods with a fixed blade (straight knife).
  • the film distinguishes itself from the other examples and the comparative examples based on polyolefin and magnesium hydroxide in that at an elongation of more than 20% no whitening is discernible, since the outermost layer has only a small proportion of filler, which is also good for the polar polymer is connected.
  • the fire behavior is nevertheless excellent due to the polar polymer content and the polypropylene-containing layers prevent the film from melting.
  • Example 2 The preparation is carried out analogously to Example 1 with the following changes:
  • the compound consists of 30 phr polymer D, 70 phr Exact 8201, 50 phr Exolit AP 750, 0.3 phr Flamestab NOR 116, 10 phr of a masterbatch made of 50% flame black and 50% polyethylene and 4.5 phr Irganox 1010.
  • the further processing takes place as in Example 1, the cutting takes place as in Example 6.
  • This film is characterized by improved hand tearability.
  • the nominal thickness is 100 ⁇ m and the surface is smooth but matt.
  • the primer Y01 from Four Pillars Enterprise / Taiwan is applied (analytically acrylate-modified SBR rubber in toluene) and then 23 g / m 2 of the adhesive IV9 from Four Pillars Enterprise / Taiwan (main component that can be determined analytically: SBR and natural rubber , Terpene resin and alkylphenol resin in toluene).
  • the film is cut into rolls with a knife bar with sharp blades at a distance of 25 mm in a compound cutting machine.
  • the following raw materials are compounded in a kneader: 80 phr Cataloy KS-021 P, 20 phr Evaflex P 1905, 100 phr Magshizu N-3, 8 phr Norvaexcel F-5, 2 phr Seast 3H and granulated, but the mixing time is 2 min ,
  • the carrier film is then produced by extrusion as described in Example 7 (all three extruders being fed with the same compound) via a slot nozzle and cooling roll in a thickness of 0.20 mm, the extruder speed being reduced until the film has a speed of Reached 2 m / min.
  • the speed of 30 m / min cannot be reached, as in Example 7, since the system switches off due to excessive pressure (too high viscosity).
  • the film is produced at 10 m / min, the mechanical data in the longitudinal and transverse directions indicate a strong longitudinal orientation, which is confirmed by a 20% shrinkage in the direction of travel when coating. Therefore, the test is repeated at a still slow speed, which leads to a technically perfect (including speck-free), but economically unsustainable film.
  • the coating is carried out analogously to Example 3, but with an adhesive application of 30 g / m 2 (this adhesive has a composition similar to that of the original adhesive of the reworked patent example).
  • this adhesive has a composition similar to that of the original adhesive of the reworked patent example.
  • the film is cut into 25 mm wide strips with a knife bar with sharp blades and wound together in rolls.
  • the self-adhesive wrapping tape is characterized by a lack of flexibility. Compared to Examples 5 and 6, the stiffness of Comparative Example 2 is 4030% and 19000% higher, respectively.
  • the stiffness can easily be calculated from the thickness and the force at 1% elongation (proportional to the modulus of elasticity).
  • the sample shows very good fire behavior due to the content of red phosphorus and the relatively high thickness (note: the LOI value is measured on the 0.2 mm thick sample with adhesive, but the LOI of 30% in the cited patent document comes from from a 3 mm thick specimen without adhesive). Comparative Example 3
  • the manufacture of the compound is not described.
  • the compound is granulated, dried and blown into a tubular film on a laboratory system and slit on both sides.
  • An attempt is made to coat the film after corona pretreatment with adhesive in the same way as in Example 1, but it has excessive shrinkage in the transverse and longitudinal directions, and the rolls can hardly be unwound after 4 weeks due to the excessive unwinding force.
  • Example 6 An attempt is therefore made to coat with a non-polar rubber adhesive as in Example 6, but this fails because of the solvent sensitivity of the film. Since the specified font does not describe an adhesive coating, but the adhesive properties are desirable, the foil is cut and wrapped in a silhouette between a set of pairs of two rotating knives into 25 mm wide strips.
  • the self-adhesive wrapping tape is characterized by good flexibility and flame resistance.
  • the hand tearability is not sufficient.
  • the low heat resistance which leads to the melting of the adhesive tape when the aging tests are carried out, is particularly disadvantageous.
  • the winding tape leads to a considerable shortening of the life of the cable insulation due to embrittlement.
  • the high tendency to shrink is due to the low melt index of the compound. Problems can also be expected with a higher melt index of the raw materials, although this will significantly reduce the shrinkage, because heat setting is not provided in the document mentioned, despite the low softening point of the film. Since the product has no significant unwinding force, it can hardly be applied to wire bundles. The fogging value is 73% (presumably due to the paraffin wax). Comparative Example 4
  • the preparation of the compound is mixed as described on a single-screw laboratory extruder: 85 phr Lupolex 18 E FA, 6 phr Escorene UL 00112, 9 phr Tuftec M-1943, 63 phr Magnifin H 5, 1, 5 phr magnesium stearate, 11 phr Novaexcel F 5, 4 phr carbon black FEF, 0.2 phr Irganox 1010, 0.2 phr Tinuvin 622 LD, whereby a clear release of phosphine can be smelled.
  • the film is produced as in Comparative Example 3.
  • the film has a large number of filler spots and small holes and the bubble tears off several times during the experiment.
  • the breakdown voltage varies widely from 0 to 3 kV / 100 ⁇ .
  • the granulate is therefore melted and granulated again in the extruder for further homogenization.
  • the compound now obtained has only a small number of specks. Coating and cutting is carried out analogously to example 1.
  • the self-adhesive wrapping tape is characterized by very good flame resistance due to the use of red phosphorus. Since the product has no rolling force, it can hardly be applied to wire bundles. The heat resistance is insufficient due to the low melting point.
  • a UV-crosslinkable acrylic hot-melt adhesive of the Acronal DS 3458 type is applied to a textile carrier of the Maliwatt nonwoven thread type (80 g / m 2 , fineness 22, black, thickness approx. 0.3 mm) using a nozzle coating 50 m / min applied.
  • the temperature load on the carrier is reduced by means of a cooled counter-pressure roller.
  • the mass application is approx. 65 g / m 2 .
  • a suitable crosslinking is achieved in-line prior to winding up by irradiation with a UV system which is equipped with 6 medium-pressure mercury lamps of 120 W / cm.
  • the bales are cut in a silhouette (between a set of rotating knives slightly offset in pairs) assembled into rolls on standard 3-inch cores.
  • This wrapping tape is characterized by good adhesive properties as well as very good compatibility with various cable insulation materials (PVC, PE, PP) and corrugated pipes. From a technical point of view, however, the high thickness and the lack of hand tearability are very disadvantageous.
  • the following mixture is produced in a Brabender plastograph (mixing time 5 minutes): 80 phr Elvax 470, 20 phr Epsyn 7506, 50 phr EDAP, 0.15 phr A 0750, 0.15 phr Irganox 1010.
  • test specimens 0.2 mm thick which are cut into 25 mm wide and 25 cm long strips and wound up into a small roll on a core. According to the writing, there is no coating with adhesive.
  • This wrapping film has neither acceptable flexibility nor resistance to melting. Since the product has no rolling force, it can hardly be applied to wire bundles. It is difficult to tear by hand.
  • the breakdown voltage is relatively high, since the mixture is obviously very homogeneous, the Brabender mixer mixes very intensively and the aminosilane could also make a positive contribution, for which the force-strain curves of the cited patent document speak.
  • the following mixture is produced in a kneader: 80.8 phr ESI DE 200, 19.2 phr Adflex KS 359 P, 30.4 phr calcium carbonate masterbatch SH3, 4.9 phr Petrothen PM 92049, 8.8 phr antimony oxide TMS and 17 , 6 phr DE 83-R.
  • the compound is processed into flat film on a cast laboratory system, corona treated, 20 g / m 2 JB 720 coated, wound on rods with a 3-inch core and cut by parting with a fixed blade (manual feed).
  • This wrapping tape is characterized by PVC-like mechanical behavior, which means high flexibility and good hand tearability.
  • the use of brominated flame retardants is disadvantageous.
  • the heat resistance at temperatures above 95 ° C is low, so that the film melts during the aging and compatibility tests.

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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)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Insulating Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une pellicule de gainage en polyoléfines notamment exempte d'halogènes, résistant au vieillissement, caractérisée en ce qu'elle contient au moins 4 phr d'un antioxydant primaire ou au moins 0,3 phr d'une combinaison d'antioxydants primaires et secondaires, les fonctions antioxydantes primaires et secondaires étant présentes dans différentes molécules ou pouvant être réunies dans une molécule.
EP04766811A 2003-10-14 2004-09-16 Pellicule de gainage souple en polyolefines resistant au vieillissement Ceased EP1678248A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2003148483 DE10348483A1 (de) 2003-10-14 2003-10-14 Alterungsbeständige weiche Wickelfolie aus Polyolefin
PCT/EP2004/052208 WO2005037908A1 (fr) 2003-10-14 2004-09-16 Pellicule de gainage souple en polyolefines resistant au vieillissement

Publications (1)

Publication Number Publication Date
EP1678248A1 true EP1678248A1 (fr) 2006-07-12

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US (1) US20070071966A1 (fr)
EP (1) EP1678248A1 (fr)
JP (1) JP2007510011A (fr)
DE (1) DE10348483A1 (fr)
MX (1) MXPA06004105A (fr)
WO (1) WO2005037908A1 (fr)

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DE10348482A1 (de) * 2003-10-14 2005-06-02 Tesa Ag Flammwidrige rußgefüllte Wickelfolie aus Polyolefin
DE10348484A1 (de) * 2003-10-14 2005-06-02 Tesa Ag Hochgefüllte halogenfreie flammwidrige Wickelfolie
DE10348477A1 (de) * 2003-10-14 2005-05-25 Tesa Ag Rußgefüllte alterungsbeständige Wickelfolie aus Polyolefin
DE10348478A1 (de) * 2003-10-14 2005-06-02 Tesa Ag Flammwidrige halogenfreie Wickelfolie
JP4689256B2 (ja) 2004-12-10 2011-05-25 矢崎総業株式会社 ハロゲンフリー粘着テープ
DE102005060215A1 (de) * 2005-12-14 2007-06-21 Tesa Ag Wickelband aus einer TPU-Folie
US9388329B2 (en) * 2007-12-18 2016-07-12 3M Innovative Properties Company Stretchable, hand-tearable, conformable, and cinchable reinforced adhesive tape articles
KR20100134800A (ko) * 2008-04-30 2010-12-23 테사 소시에타스 유로파에아 접착 테이프
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Also Published As

Publication number Publication date
MXPA06004105A (es) 2006-06-27
US20070071966A1 (en) 2007-03-29
DE10348483A1 (de) 2005-06-02
WO2005037908A1 (fr) 2005-04-28
JP2007510011A (ja) 2007-04-19

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