EP1675906A1 - Pellicule de gainage composee de copolymere de polypropylene et d'un polymere incompatible avec le polypropylene - Google Patents

Pellicule de gainage composee de copolymere de polypropylene et d'un polymere incompatible avec le polypropylene

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Publication number
EP1675906A1
EP1675906A1 EP04787154A EP04787154A EP1675906A1 EP 1675906 A1 EP1675906 A1 EP 1675906A1 EP 04787154 A EP04787154 A EP 04787154A EP 04787154 A EP04787154 A EP 04787154A EP 1675906 A1 EP1675906 A1 EP 1675906A1
Authority
EP
European Patent Office
Prior art keywords
wrapping film
phr
film
adhesive
wrapping
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
EP04787154A
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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
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Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Publication of EP1675906A1 publication Critical patent/EP1675906A1/fr
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C08L23/0861—Saponified vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • Y10T428/14—Layer or component removable to expose adhesive
    • 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
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y10T428/1476—Release layer

Definitions

  • the present invention relates to a filled, soft, halogen-free, flame-retardant wrapping film made from at least one polypropylene copolymer and a polymer incompatible with polypropylene for wrapping, for example, ventilation lines in air conditioning systems or wires or cables, and in particular cable harnesses in vehicles or field coils for picture tubes, which are optionally equipped with a pressure-sensitive adhesive coating is.
  • 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.
  • Cable wrapping tapes and insulating tapes usually consist of plasticized PVC film with a one-sided adhesive coating.
  • plasticized PVC film with a one-sided adhesive coating.
  • Corresponding disadvantages include evaporation of plasticizer, high halogen content and low thermal stability.
  • plasticizers of conventional PVC insulating tapes and PVC cable winding tapes gradually evaporate, which leads to a health burden, in particular the commonly used DOP is of concern. Furthermore, 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. In the event of even greater evaporation due to higher temperatures, for example in the interior of vehicles or in the case of insulating tapes in electrical devices, 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.
  • Typical soft PVC adhesive tapes are described in JP 10 001 583 A1, JP 05 250 947 A1, JP 2000 198 895 A1 and JP 2000 200 515 A1.
  • the highly toxic compound antimony oxide is usually used, as described for example in JP 10 001 583 A1.
  • EP 1 123 958 A1 and WO 99/61541 A1 describe 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.
  • Thermoplastic polyester is also used experimentally for the production of wrapping foils and cable insulation. These have considerable shortcomings with regard to their flexibility, processability, hand tearability, aging resistance or compatibility with the cable materials.
  • the most serious disadvantage of polyester is its considerable sensitivity to hydrolysis, so that it cannot be used in automobiles for safety reasons.
  • DE 100 02 180 A1, 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.
  • 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.
  • WO 97/05206 A1 describes a halogen-free winding adhesive tape, the backing film of which consists of a polymer blend of low-density polyethylene and an ethylene / vinyl acetate or ethylene / acrylate copolymer. 48 to 90 phr aluminum hydroxide are used as flame retardants.
  • a significant disadvantage of the carrier film is the low softening temperature due to the polymer blend of polyethylene and ethylene / vinyl acetate copolymer.
  • silane crosslinking is described. This networking method is complex and in practice only leads to very unevenly networked material, so that no stable production process or uniform product quality can be achieved in production.
  • 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 has not been resolved.
  • EP 1 097 976 A1 A combination of polyolefin and EVA is described in EP 1 097 976 A1.
  • a PP polymer is used instead of LLDPE.
  • the main idea is the achievement of certain mechanical properties at 100 ° C by the PP polymer, which means in concrete terms that the problem of poor heat resistance of mixtures of polyethylene homopolymer and polyethylene copolymer should be solved. This results in little flexibility.
  • This disadvantage of the invention can also be confirmed by measurements on the reworked examples.
  • the third component of the mixture (in addition to PP copolymer and flame retardant) are EVA or EEA; what serves to improve the flame retardancy of combinations of polyethylene or polypropylene and filler, as is known to the person skilled in the art from the literature, and what can be seen from the LOI values of the examples. Due to their composition, these foils are hard and inflexible. A review of the force in the running direction at 1% elongation reveals values of over 10 N / cm when the examples are reworked. In practice, PVC wrapping films with a value of around 1 N / cm have become established. This underlines that these foils are too inflexible for practical use. In the reworked example, tearing by hand is only possible with great effort.
  • the object of the invention remains to find a solution for a wrapping film which combines the advantages of flame retardancy, 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, moreover, a superior one Resistance to heat aging, the large-scale producibility of the film must be ensured and a high dielectric strength and a high fogging value are necessary in some applications. It is also an object of the invention to provide soft, halogen-free, flame-retardant wrapping films 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 not or at least not to the extent.
  • the subclaims relate to advantageous developments of the wrapping film according to the invention, the use of the wrapping film in a soft, flame-retardant adhesive tape, further uses of the same and methods for producing the wrapping film.
  • the invention relates to a flame-retardant, halogen-free wrapping film
  • At least one polypropylene copolymer is At least one polypropylene copolymer
  • the thickness of the film according to the invention is advantageously 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 during 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.
  • a wrapping film according to the invention can be produced from a polypropylene copolymer, from flame-retardant fillers and from a polymer incompatible with polypropylene copolymer.
  • the thermal aging resistance is not worse compared to PVC as a high-performance material, but rather comparable or even better.
  • the wrapping film according to the invention has a force in the longitudinal direction at 1% elongation of 1 to 4 N / cm and at 100% elongation a force of 2 to 20 N / cm, preferably from 3 to 15 N / cm.
  • the force at 1% elongation is greater than or equal to 1 N / cm and the force at 100
  • the 1% force is a measure of the stiffness 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 a soft polypropylene copolymer with a flexural modulus of less than 500 MPa, particularly preferably 80 MPa or less and in particular 30 MPa or less.
  • a homopolymer mixed with a soft polyolefin can also be used.
  • 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 100 ° 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 (e.g. grafting, reactor blend), the melt lowering of the point 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, 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.
  • Ethylene is particularly preferred as the monomer for the polypropylene copolymer.
  • the polymer can also be modified by grafting, for example with maleic anhydride or acrylate monomers, for example to improve the processing behavior or the mechanical properties.
  • a polypropylene copolymer is 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 that 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 wrapping 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, the force at 1% elongation and in particular the shape of the force-elongation curve of the wrapping film in the optimal range bring.
  • a further ethylene- or propylene-containing copolymer is used in addition to the polypropylene polymer according to the invention, it preferably has a specified melt index in the range of ⁇ 50% of the melt index of the polypropylene polymer. 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.
  • the problem of poor tearability of the carrier film and the associated more complex winding process is achieved in the underlying invention by adding at least one polymer which is incompatible with the polypropylene copolymer.
  • This incompatible polymer creates predetermined breaking points in the micrometer range within the carrier film, which enables the wrapping film to be easily torn by hand without the usual formation of a very long frayed tear-off edge.
  • the mechanical properties such as flexibility and tensile strength are surprisingly not adversely affected by the incompatible polymer.
  • Highly polar polymers are considered by those skilled in the art to be incompatible with polypropylene.
  • Incompatible polymers are understood to mean that the polymers form two polymer phases. This second phase is, for example, by electron micrographs, DSC (differential scanning calorimetry / differential thermal analysis) or dynamic mechanical measurements recognizable. An externally visible, apparently homogeneous miscibility should not be used as a measure of the tolerance. An incompatibility or immiscibility of polymers also results from the difference in the solubility parameters (Hildebrand parameters). If the solubility parameter ⁇ of a polymer is at least 19 J y 7cm 32 , this polymer is incompatible with the polypropylene (co) polymer. Solubility parameters and their description can be found, inter alia, in the "Polymer Handbook", 4th edition, Wiley & Son or “Properties of Polymers", van Krevelen; Elsevier Scientific Publishing Co., 1976.
  • the incompatible polymers according to the invention contain olefinic comonomers such as ethylene, the content must be low enough to ensure incompatibility; polymers without olefinic comonomers are therefore preferred.
  • these strongly polar polymers such as oxygen- and nitrogen-containing polymers
  • these strongly polar polymers have proven to be particularly suitable for positively influencing the hand tearability of the wrapping film without at the same time impairing the mechanical properties such as flexibility and elongation at break of the film.
  • these oxygen- and nitrogen-containing polymers have a flame-retardant effect when blended with polyolefins and magnesium hydroxide.
  • 1 to 30 phr and particularly preferably 5 to 15 phr of at least one polymer incompatible with the polypropylene polymer such as, for example, polyamides and polyesters with a sufficiently low softening point (suitable for the processing temperature of polypropylene), polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, vinyl acetate vinyl alcohol copolymer , Poly (meth) acrylates, polyethylene vinyl alcohol, ethylene vinyl acetate or polyurethanes, which can also be crosslinked.
  • These can also have a core-shell structure, for example a core made of polyacrylates with alcohols having 2 to 8 carbon atoms and a shell made of polymethyl methacrylate.
  • acrylate impact modifiers which are produced for the modification of PVC, have proven to be particularly suitable.
  • Poly (meth) acrylates and in particular polyvinyl acetate are preferred.
  • improved wetting of the flame retardant magnesium hydroxide is achieved by using polyvinyl acetate, and the processing time is therefore reduced in order to achieve a homogeneous mixture.
  • the tendency to form small holes and specks in the manufacturing process is significantly lower a higher breakdown voltage of these film materials was observed.
  • vinyl acetate-based dispersion powders for example with a polyvinyl alcohol shell, such as are used as modifiers for plaster and cement products
  • a polyvinyl alcohol shell such as are used as modifiers for plaster and cement products
  • Synthetic or natural magnesium hydroxide is used as a flame retardant.
  • the magnesium hydroxide is preferably provided with a surface coating for better compatibility with the polymer. Examples are coatings with fatty acids or aminosifanes. Additional flame retardants or fillers can be combined with the magnesium hydroxide. The combination of the special magnesium hydroxide and nitrogen-containing flame retardants is preferred. Examples of this are dicyandiamide, melamine cyanurate and sterically hindered amines such as from the class of HA (L) S.
  • Red phosphorus works synergistically with magnesium hydroxide and can therefore be used. However, it has disadvantages: only colored and only black and brown products can be produced, phosphine is produced during compounding, which requires protective measures to avoid health risks, and strong white smoke is produced in the event of a fire. Red phosphorus is therefore preferred and the proportion of filler is increased or an oxygen-containing polymer is used or added.
  • the amount of magnesium hydroxide is preferably in the range from 70 to 200 phr and particularly preferably in the range from 110 to 150 phr.
  • the amount of magnesium hydroxide is therefore chosen so high that the wrapping film is flame-retardant, i.e. slowly burning or self-extinguishing.
  • the fire The speed of the wrapping film coated with adhesive according to FMVSS 302 for a horizontal sample is preferably below 300 mm / min, preferably below 200 mm / min and particularly preferably below 70 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 19%, in particular above 21% and particularly preferably above 23%.
  • 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”, Hanser Verlag, ed. H. Saechtling, 28th edition or "Plastic Additives Handbook”, Hanser-Verlag, ed. H. Doubt, 5th edition " - ..
  • the main object of the present invention is the absence of halogens and volatile plasticizers.
  • the thermal requirements increase, so that an additional resistance to conventional PVC wrapping films or the PVC-free film wrapping tapes currently being tested is to be achieved. Therefore, the present invention in this regard will be described in detail below.
  • the wrapping film according to the invention advantageously 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 10%. 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, high-performance products based on polymer plasticizers reach 105 ° C.
  • the combination of an unsuitable polypropylene wrapping film is a negative example a copper-stabilized polyamide corrugated pipe, in this case both the corrugated pipe and the wrapping film are brittle after 3,000 hours at 105 ° C.
  • the use of the right anti-aging agents plays a special role in achieving good aging stability and tolerance.
  • the total amount of stabilizer must also be taken into account, since previous attempts to manufacture such wrapping tapes used no or only less than 0.3 phr anti-aging agents, as is also common in the production of other films.
  • the winding tapes according to the invention contain more than 0.3 and in particular more than 1 phr of antioxidant (which does not include an optional metal deactivator).
  • the proportion of secondary antioxidant is more than 0.3 phr.
  • Stabilizers for PVC products cannot be transferred to polypropylene. Secondary antioxidants break down peroxides and are therefore used in diene elastomers as part of anti-aging packages.
  • a combination of primary antioxidants for example sterically hindered phenols or C-radical scavengers
  • secondary antioxidants for example sulfur compounds, phosphites or sterically hindered amines
  • the task also dissolves with diene-free polyolefins such as polypropylene.
  • a primary antioxidant preferably sterically hindered phenols with a molecular weight of more than 500 g / mol (especially> 700 g / mol), with a phosphitic secondary antioxidant (especially with a molecular weight> 600 g / mol) is preferred.
  • Phosphites or a combination of primary and several secondary anti-aging agents have so far not been used in wrapping films made of polypropylene copolymers.
  • the combination of 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) and from the class of the phosphites is suitable, wherein the phenolic, the sulfur-containing and the phosphoric functions do not have to be present in three different molecules, but more than one function can be combined in one molecule.
  • the wrapping film according to the invention is preferably pigmented, in particular black.
  • the coloring can be carried out in the base film, in the adhesive layer or in another layer.
  • the use of organic pigments or dyes in the Wrapping film is possible, soot 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. 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 though furnace black is customary for coloring films. For optimum aging, 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 stamp kneader) or extruder (for example 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.
  • 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%, • tensile strength in md in the range from 4 to 15, particularly preferably from 5 to 8 N / cm, the film being cut with sharp blades to determine the data.
  • 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 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).
  • the information given here on 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 acid 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.
  • additives such as tackifiers (resins), plasticizers, fillers, flame retardants, pigments, UV absorbers, light stabilizers, anti-aging agents, photoinitiators, crosslinking agents or crosslinking promoters.
  • Tackifiers are, for example, hydrocarbon resins (for example polymers based on unsaturated C 5 or C 9 monomers), terpene phenol resins, polyterpene resins made from raw materials such as ⁇ - or ⁇ -pinene, aromatic resins such as coumarone Inden 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 (such as, for example listed in Ulimann's Encyclopedia of Technical 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 ⁇ -pinene
  • aromatic resins
  • 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 (e.g. 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 on one side, which can be produced by coextrusion, melting or dispersion. coating has come about.
  • Dispersion adhesives are particularly preferably those based on polyacrylate.
  • the known dispersion and solvent systems can be used as primers, for example based on rubber containing isoprene or butadiene 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, steary 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, for example octadecyl.
  • the design of the back of the film can also serve to increase the adhesion of the adhesive on the back of the film (for example to control the unwinding force).
  • polar adhesives such as those based on acrylate polymers
  • the back adhesion on a film based on polypropylene polymers is often not sufficient.
  • polar rear surfaces are achieved by corona treatment, flame pretreatment or coating / coextrusion with polar raw materials.
  • a wrapping film is claimed 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 wrapping tapes, since the adhesives usually used have a sufficiently high adhesion to the polar PVC surface.
  • the importance of back 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 back adhesion or unwinding force is necessary compared to PVC film in order to achieve sufficient stretch to be provided for the application when unrolling.
  • the preferred embodiment of the wrapping film is therefore produced by tempering or physical surface treatment in order to achieve an outstanding unwinding force and elongation during unwinding, the unwinding force at 300 mm / min preferably being at least 50% higher than without such a measure.
  • the wrapping film according to the invention is excellent for wrapping elongated goods such as ventilation pipes in air conditioning, field coils or cable sets in vehicles Suitable because the high flexibility ensures good conformability on wires, cables, rivets, beads and folds.
  • halogen-containing raw materials 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 retardancy. Halogens in trace amounts, such as those that could occur due to impurities or as residues of catalysts (for example from the polymerisation of polymers) or as process aids, for example fluorine elastomers, 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 lack of flexibility and poor flame retardancy when using conventional PVC substitute materials such as polypropylene, polyethylene, polyester, polystyrene, polyamide or polyimide for the wrapping film is preferred by using a mixture of a soft polypropylene copolymer (with a low flexural modulus) and a flame retardant Magnesium hydroxide reached.
  • the flexibility of a wrapping film is, however, of paramount importance, since when used on wires and cables, not only is the winding wound spirally, but it is also necessary to wind it in a crease-free, flexible manner at branching points, plugs or fastening clips.
  • the processability of the winding tapes also plays a major role. Since the winding tapes are mainly processed by hand, the processor requires, for economic reasons, a wrapping film with a high degree of flexibility, which can easily be torn by hand without the aid of aids such as scissors or knives.
  • the term hand tearability includes both a tear from the side with two hands between the thumb and index finger as well as jerky tear in the longitudinal direction.
  • the simultaneous requirement for easy stretchability and easy tearing by hand is incompatible with films or adhesive tapes produced therefrom. Put simply, foils are usually either soft and stretchy or brittle and tearable by hand.
  • the measurements are carried out in a test climate of 23 ⁇ 1 ° C and 50 ⁇ 5% rel. Humidity carried out.
  • 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.
  • the force or tension at 1% elongation deviates from this a test speed of 10 mm / min and a preload setting of 0.5 N / cm measured 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 a different adhesive surface 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.
  • 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 from 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. After 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.
  • the 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 failed. In the 125 ° C test, samples were sometimes also checked at other times. The test time is 300 hours unless otherwise expressly described in individual cases.
  • the short-term heat resistance is measured on cable bundles made of 19 wires of type TW with a cross section of 0.5 mm 2 , 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). To determine the heat resistance, the wrapping film is stored at 170 ° C. for 30 minutes, cooled to room temperature for 30 minutes and wrapped with at least 3 turns with a 50% overlap around a mandrel with a diameter of 10 mm. Then the sample is 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.
  • a sample with a thickness of 200 ⁇ m withstands a maximum voltage of 6 kV after one minute, the calculated breakdown voltage is 3 kV / 100 ⁇ m.
  • the fogging value is determined in accordance with DIN 75201 A.
  • the carrier film 90 phr polymer A, 10 phr Vinnapas B 100 160 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 an "inverted L" type calender.
  • a film with a smooth surface with a 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 e Also in the following examples in the cut-off section, an automatic machine is used for the reasons stated in the description of the invention.
  • this self-adhesive wrapping film shows good flexibility.
  • the wrapping film is characterized by very good workability and hand tearability.
  • the aging resistance and compatibility with PP and PA cables and polyamide corrugated pipe are outstanding.
  • the compound is produced using a stick extruder (Buss) without soot and with underwater pelletizing. After drying, the compound is mixed in a mixer with the soot masterbatch.
  • the carrier film is produced on a blown film extrusion system with the following recipe: 75 phr polymer B, 15 phr Pacrel 637, 160 phr Magnifin H 5 GV, 20 phr of a masterbatch made from 50% flame black 101 and 50% polyethylene. 0.8 phr Irganox 1076, 0.8 phr Irganox PS 800, 0.2 phr Ultranox 626.
  • 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 using pressure-sensitive adhesive analogous to Example 1, but which additionally contains 10% by weight of Melapur MC 25, the rods are heat-treated 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).
  • Faxing can be prevented by storing the film for 1 week before coating and by winding the coated film on foam-coated cores.
  • the film is characterized by excellent processability including hand tearability and very good aging resistance.
  • the preparation takes place analogously to Example 1 with the following changes:
  • the compound consists of 90 phr polymer A, 10 phr PEG 6000, 120 phr brucite 15 ⁇ , 15 phr flame black 101, 0.8 phr Irganox 1010, 0.8 phr Irganox PS 802.0 , 3 phr Irgafos 168 and 1 phr Irganox MD 1024.
  • the brucite is added in% in zones 1 and 5.
  • the carrier film produced from this is subjected to a one-sided flame pretreatment and, after 10 days of storage, 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 1 1/4 inch core (31 mm).
  • the bars are annealed in an oven at 60 ° C for 5 hours to increase the unwinding force.
  • This wrapping film is characterized by an even greater flexibility than that from example 1.
  • the rate of fire is sufficient for the application.
  • the film has a slightly matt surface. During the application, the wrapping tape can be processed very easily by hand and torn off.
  • the preparation is carried out analogously to Example 2 with the following changes:
  • the compound consists of 80 phr polymer B, 10 phr Evaflex A 702, 10 phr EVAI 105 B, 160 phr Kisuma 5A, 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 (with the addition of 1% by weight Desmodur Z 4470 MPA / X to 100 parts by weight of adhesive to dry content) at 23 g / m 2 .
  • the adhesive is dried in a warming channel and chemically cross-linked, wrapped in jumbos at the end of the dryer, after 1 week on the uncoated one Slightly corona-treated side and thereby wound into rods with a 25 m barrel length. These are stored in an oven at 100 ° C for 1 hour and then cut into rolls.
  • This wrapping film has balanced properties in terms of flexibility, processability and hand tearability.
  • the compound consists of 72 phr Polymer A, 10 phr RPT 200, 120 phr Magnifin H 5
  • 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 side of the wrapping film is subjected to a weak corona treatment in a cutting machine to increase the unwinding force and processed into 33 m long rolls with a width of 19 mm on a 1 inch core (37 mm inside diameter).
  • the production takes place analogously to Example 1 with the following changes:
  • the film contains 75 phr polymer C, 20 phr Escorene UL 00119, 5 phr RPT 1800, 150 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 minutes, the total kneading time to discharge into the granulating extruder is 4 minutes.
  • 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 casting process (die width 1400 mm, melt temperature at the die head 190 ° C., chilli roll temperature 30 ° C., speed 30 m / min).
  • the carrier film has the following recipe structure: Layer 1:
  • the film is heat set.
  • 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 wrapping film Due to the colored layer 1, which contains little flame retardant, the wrapping film shows almost no whitening when stretched.
  • the fogging value is 97%.
  • 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 well bound to the polar polymer , The fire behavior is nevertheless excellent due to the polar polymer content and the polypropylene-containing layers prevent the film from melting. Although the incompatible polymer is only contained in the middle layers, the wrapping tape shows good 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 components 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 ,
  • melt index of the compound increased by 30% after 4 minutes of mixing (which may be due to the lack of a phosphite stabilizer or due to the greater mechanical degradation due to the extremely low melt index of the polypropylene polymer).
  • the filler has been pre-dried and there is an exhaust air device above the kneading compounder, a penetrating smell of phosphine arises on the system during kneading.
  • 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 film is produced at 10 m / min, the mechanical data in the longitudinal and transverse directions indicated a strong longitudinal orientation, which is confirmed by a shrinkage of 20% in the running direction during coating. Therefore, the test is repeated at a still slow speed, which led 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 is known to be from the thickness and the force at 1% elongation
  • the breakdown voltage of 2 kV / 100 ⁇ m of comparative example 2 is too low for use as an insulating tape in order to achieve a sufficient absolute breakdown voltage at thicknesses which allow acceptable flexibility.
  • the low elongation at break indicates inhomogeneities which, although positive in terms of hand tear, have a negative impact on the breakdown voltage.
  • the compound is mixed more intensively.
  • the breakdown voltage is improved to 4 kV / 100 ⁇ m, but this is accompanied by a deterioration in the ability to be torn by hand and an increase in the elongation at break to 570%.
  • EP 1 097 976 A1 have an elongation at break of the order of magnitude of 300%, which generally indicates poor mixing and thus low elongation at break and low breakdown stresses.
  • Example 4 of EP 1 097 976 A1 is inadequate in terms of mechanical properties
  • the formulation from experiment 1 is processed: 80 phr Cataloy KS-353 P, 20 phr Evaflex A 702, 100 phr Magshizu N-3, 8 phr Norbaexcell F5, 2 phr Seast 3H.
  • 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.
  • 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 because of the low melting point.
  • a UV-crosslinkable acrylic hot melt adhesive of the Acronal DS 3458 type is added to a textile carrier of the type Maliwatt (80 g / m 2 , fineness 22, black, thickness approx. 0.3 mm) by means of 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 into rolls on standard 3-inch cores in a silhouette (between a set of rotating knives slightly offset in pairs).
  • 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.
  • 100 phr polymer A, 150 phr Magnifin H 5 GV, 10 phr flame black 101, 0.8 phr Irganox 1010, 0.8 phr Irganox PS 802 and 0.3 phr Irgafos 168 are compounded in a co-rotating twin-screw extruder.
  • 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 an "inverted L" type calender.
  • the film is stored for one week, on the coating system with rollers at 60 ° C. to improve the flatness. siert and applied after a corona treatment with an aqueous acrylic pressure sensitive adhesive Primal PS 83 D using 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 is wound into bars with a length of 33 m on 1-inch core (25 mm).
  • the cutting is done by parting the rods using a fixed blade with a not very acute angle (straight knife) in 29 mm wide rolls. As in the examples below, an automatic cut-off is used for the reasons given in the description of the invention.
  • This self-adhesive wrapping film shows good flexibility despite the high proportion of filler.
  • the aging resistance and compatibility with PP and PA cables and polyamide corrugated pipe are outstanding. In the case of application tests, inadequate hand tearability has become noticeable in manual processing.
  • 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 Petrothene 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 pre-treated, 20 g / m 2 JB 720 coated, wound on bars with a 3-inch core and cut by parting off 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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Adhesive Tapes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une pellicule de gainage ignifuge exempte d'halogènes composée d'au moins un copolymère de polypropylène, d'au moins un agent ignifuge anorganique, et de 1 à 30 phr, de préférence de 5 à 15 phr d'au moins un polymère incompatible avec le copolymère de polypropylène.
EP04787154A 2003-10-14 2004-09-16 Pellicule de gainage composee de copolymere de polypropylene et d'un polymere incompatible avec le polypropylene Ceased EP1675906A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10348479A DE10348479A1 (de) 2003-10-14 2003-10-14 Wickelfolie aus Polypropylencopolymer und einem mit Polypropylen unverträglichen Polymer
PCT/EP2004/052210 WO2005037918A1 (fr) 2003-10-14 2004-09-16 Pellicule de gainage composee de copolymere de polypropylene et d'un polymere incompatible avec le polypropylene

Publications (1)

Publication Number Publication Date
EP1675906A1 true EP1675906A1 (fr) 2006-07-05

Family

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Application Number Title Priority Date Filing Date
EP04787154A Ceased EP1675906A1 (fr) 2003-10-14 2004-09-16 Pellicule de gainage composee de copolymere de polypropylene et d'un polymere incompatible avec le polypropylene

Country Status (6)

Country Link
US (1) US20070190279A1 (fr)
EP (1) EP1675906A1 (fr)
JP (1) JP2007508431A (fr)
DE (1) DE10348479A1 (fr)
MX (1) MXPA06004110A (fr)
WO (1) WO2005037918A1 (fr)

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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
US8885139B2 (en) * 2005-01-21 2014-11-11 Johnson & Johnson Vision Care Adaptive electro-active lens with variable focal length
EP2209842A1 (fr) * 2007-10-19 2010-07-28 Saint-Gobain Ceramics & Plastics, Inc. Applications de nanohydrate d'alumine mis en forme en tant qu'amplificateur de la propriété barrière des polymères
US8460768B2 (en) * 2008-12-17 2013-06-11 Saint-Gobain Ceramics & Plastics, Inc. Applications of shaped nano alumina hydrate in inkjet paper
EP3026523B1 (fr) 2014-11-28 2019-08-28 Nokia Technologies OY Procédé et appareil pour la mise en contact de la peau avec un équipement de capteur
AT517060B1 (de) * 2015-03-25 2017-03-15 Bategu Gummitechnologie Gmbh & Co Kg Flammgeschützte polymere Zusammensetzung
DE102016203911A1 (de) * 2016-03-10 2017-09-14 Clariant Plastics & Coatings Ltd Halogenfreie, dämmschichtbildende Brandschutzbeschichtung sowie deren Verwendung
CN107722439A (zh) * 2017-09-29 2018-02-23 南京创贝高速传动机械有限公司 一种环保型电缆绝缘层及其制备工艺
CN109111645A (zh) * 2018-08-29 2019-01-01 三斯达（江苏）环保科技有限公司 一种阻燃橡胶组合物及复合阻燃剂
CN109867867A (zh) * 2019-03-21 2019-06-11 杨春生 一种新能源汽车阻燃环保胶管及其制备方法
EP3974471A1 (fr) * 2020-09-29 2022-03-30 Sika Technology Ag Composition thermoplastique présentant des propriétés mécaniques améliorées
CN112477296B (zh) * 2020-12-14 2023-05-23 爱喏工业科技（苏州）有限公司 一种环保阻燃保温ppr管材及其制备方法
CN116396610B (zh) * 2023-05-22 2024-03-08 江苏发安建设工程有限公司 一种阻燃电缆电线材料及其制备方法

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EP1491314A1 (fr) * 2003-06-26 2004-12-29 Nitto Denko Corporation Support pour ruban adhésif sensible à la pression, ruban adhésif sensible à la pression comprenant ce support et son procédé de fabrication

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DE3620273A1 (de) * 1986-05-17 1987-11-19 Kalk Chemische Fabrik Gmbh Schwerbrennbare thermoplastische formmassen auf der basis von polymerblends aus polypropylen-polyethylen-epdm und eva-copolymer und magnesiumhydroxid
US5498476A (en) * 1993-10-08 1996-03-12 Minnesota Mining And Manufacturing Company Electrically insulating film backing
JP3303477B2 (ja) * 1993-11-16 2002-07-22 住友化学工業株式会社 難燃剤および難燃性熱可塑性樹脂組成物
GB9515827D0 (en) * 1995-08-02 1995-10-04 Scapa Group Plc Pressure sensitive adhesive tape
JP3495629B2 (ja) * 1998-04-28 2004-02-09 協和化学工業株式会社 難燃性樹脂組成物及びその使用
JP3404368B2 (ja) * 1999-11-04 2003-05-06 日東電工株式会社 粘着テープ
DE10216078A1 (de) * 2002-04-11 2003-10-23 Tesa Ag Weiche flammwidrige Wickelfolie

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EP1491314A1 (fr) * 2003-06-26 2004-12-29 Nitto Denko Corporation Support pour ruban adhésif sensible à la pression, ruban adhésif sensible à la pression comprenant ce support et son procédé de fabrication

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See also references of WO2005037918A1 *

Also Published As

Publication number Publication date
DE10348479A1 (de) 2005-06-02
JP2007508431A (ja) 2007-04-05
WO2005037918A1 (fr) 2005-04-28
US20070190279A1 (en) 2007-08-16
MXPA06004110A (es) 2006-06-27

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