CN101987902A - Halogen-free thermoplastic elastomer and manufacturing method thereof and environment-friendly electric wires and cables using halogen-free thermoplastic elastomer - Google Patents
Halogen-free thermoplastic elastomer and manufacturing method thereof and environment-friendly electric wires and cables using halogen-free thermoplastic elastomer Download PDFInfo
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Abstract
The invention discloses a halogen-free thermoplastic elastomer composition, which is characterized by consisting of the following components in percentage by mass: 30 to 40 percent of elastomer, 15 to 30 percent of thermoplastic, 2 to 8 percent of EVA (ethylene-vinyl acetate) resin, 3 to 6 percent of compatilizer, 10 to 25 percent of plasticizer, 2 to 8 percent of inorganic filler and 5 to 10 percent of auxiliary agent. In the halogen-free thermoplastic elastomer composition and a manufacturing method thereof and environment-friendly electric wires and cables using the same, the composition does not contain harmful heavy metals, halogen and chemical substances harming human health and natural environment; and the environment-friendly new material is non-toxic and pollution-free, can be recycled, has the advantage of resisting water, cold, high temperature, oil, acid and alkali, and is widely applied in high-end cables of military industry, ships, nuclear power, wind energy, railway track traffic, magnetic suspension and the like and related fields.
Description
Technical field
The present invention relates to a kind of snappiness, high strength, and it is superior to have processing characteristics simultaneously, soft-touch, and the Halogen thermoplastic elastomer that can be recycled specifically, is a kind of Halogen thermoplastic elastomer and manufacture method thereof, and the environment-friendly electric wire cable that uses it.
Background technology
Cable structure mainly comprises insulation layer, restrictive coating, band, fill, braiding, metal armoring and conductor, cable material (insulation and sheath material) usually by polyvinyl chloride resin and Halogen rubber (as chloroprene rubber, chlorosulphonation rubber, chlorinated polyethylene rubber etc.) and various softening agent, stablizer, lubricant, fire retardant is formed, this type of cable is when presence of fire, can discharge a large amount of obnoxious flavoures such as hydrogenchloride, produce a large amount of toxic smogs simultaneously, escape unharmed to the scene of fire people brings very big difficulty, megastore particularly, the hotel, the supermarket, densely populated type place such as Office Area, developed countries such as present Japan have prohibited its use.The cable that has is in order to reach the good flame effect, can add a lot of halogen containing flame-retardants (as hexabromocyclododecane, decabromodiphynly oxide, tetrabromo-bisphenol etc.), in burning, produce a large amount of black smokes, can discharge obnoxious flavour and materials such as hydrogen halide, dioxin simultaneously, environment around polluting is returned human body and is brought injury; Some auxiliary agents of these materials employings mostly contain objectionable impuritiess such as lead, cadmium, mercury, sexavalent chrome, Polybrominated biphenyl, Poly Brominated Diphenyl Ethers in addition, and this is that all states of developed country such as European Union, Japan, the U.S. etc. prohibite the material that occurs in cable material.
In order to overcome the shortcoming of above-mentioned materials, people have invented some type materials, as thermoplastic elastomer (TPE), TPE (Thermoplastic elastomer) refers to have more than the twice that can be stretched to raw footage at ambient temperature repeatedly, behind stress relieving, almost completely return to its original length, the time flow deformation can take place in heating, can keep the mixture of high molecular polymer of the character of definite shape after the cooling.The thermoplasticity that had both had thermoplastics has the snappiness of rubber, high strength, high resilience again, environment-protecting asepsis safety, good tint permanence, soft-touch, and weathering resistance, fatigue resistance and temperature tolerance are all good, and processing characteristics is superior, need not vulcanize, and can recycle.TPE is the advantage combination of plastics and rubber, is called as " third generation rubber ".TPE is progressively capturing the manor that only belongs to vulcanized rubber originally.TPE has the physical and mechanical properties of vulcanized rubber and the processing characteristics of thermoplastics.Owing to need not pass through hot sulfurization, use general device of plastic processing can finish products production.These characteristics make the rubber industry Production Flow Chart shorten 1/4, and energy efficient 25～40% is raised the efficiency 10～20 times, can be rated as rubber industry material and Technology revolution again.TPE has good electric property, mechanical and physical performance and weathering resistance, and not halogen-containing and heavy metal is to substitute polyvinyl chloride (PVC), and part substitutes the environment-friendly type " green material " of traditional rubber insulation, sheath.The compression set of TPE is poor with rubber phase, on the price also a little more than similar rubber.But after making electric wire, because of manufacturing process simple, do not need special-purpose vulcanizing equipment, proportion is low (about coventional type 0.9, about flame retardant type 1.2), its price index and rubber cable are suitable, but its mechanical-physical and electrical property have more advantage, indivedual indexs such as tensile strength are greatly improved, and because of it is the high order network configuration, resistance toheat is better than General Purpose Rubber, temperature resistant grade reaches 125 ℃ even 150 ℃, add molecular structure stabilized, its current capacity when identical cross section can be promoted more than 40%, its superiority is self-evident.Be used for cable industry, both can economize on copper, can reduce the harm to environment and people again, also recyclable utilization again meets the target that country makes up " conservation-minded society ".
Therefore, be badly in need of a kind of alternative traditional rubber and plastics thermoplastic elastomer environmental protection cable and manufacture method thereof for the electric wire of insulation and sheath material.
Summary of the invention
Purpose of the present invention is to propose a kind of environmental friendliness, does not contain harmful heavy metal, the Halogen thermoplastic elastomer of halogen and serious harm human health and physical environment.
Another object of the present invention is to propose a kind of environmental friendliness, does not contain harmful heavy metal, the Halogen thermoplastic elastomer manufacture method of halogen and serious harm human health and physical environment.
Another purpose of the present invention, the environment-friendly electric wire cable of being to propose a kind of environmental friendliness, not containing harmful heavy metal, the Halogen thermoplastic elastic material of halogen and serious harm human health and physical environment being made.
For achieving the above object, technical solution of the present invention is:
A kind of Halogen composition for thermoplastic elastomer is characterized in that, by mass percentage, its component comprises:
Elastomerics 30-40%
Thermoplastics 15-30%
EVA resin 2-8%
Compatilizer 3-6%
Softening agent 10-25%
Mineral filler 2-8%
Auxiliary agent 5-10%
Halogen thermoplastic elastomer of the present invention can also be further achieved by the following technical measures.
Aforementioned compositions, wherein said elastomerics are hydrogenation of ethylene-butylene copolymer.
Aforementioned compositions, wherein said thermoplastics are polypropylene.
Aforementioned compositions, wherein said thermoplastics also comprises polyethylene.
Aforementioned compositions, wherein said EVA resin is a vinyl-vinyl acetate copolymer.
Aforementioned compositions, wherein said compatilizer are maleic anhydride graft S EBS.
Aforementioned compositions, wherein said softening agent are white oil.
Aforementioned compositions, wherein said mineral filler are lime carbonate or talcum powder, and described lime carbonate or talcous particle diameter surpass 1250 orders.
Aforementioned compositions, wherein said auxiliary agent are tackifying resin, and described tackifying resin is the solid coumarone resin.
Aforementioned compositions, wherein said auxiliary agent also comprises lubricant, described lubricant is a polyoxyethylene glycol.
Aforementioned compositions, wherein said auxiliary agent also comprises oxidation inhibitor, described oxidation inhibitor is antioxidant 1010.
Aforementioned compositions wherein also comprises fire retardant, and described fire retardant is inorganic hydrogen magnesium oxide, aluminium hydroxide or organophosphorus nitrogen efficient flame-retarding agent.
Aforementioned compositions wherein also comprises vulcanizing agent, and described vulcanizing agent is peroxide vulcanizing agent DCP, resol or silane.
A kind of Halogen composition for thermoplastic elastomer is characterized in that, by mass percentage, its component comprises::
Rubber 30-40%
Thermoplastics 15-30%
EVA resin 2-8%
Compatilizer 3-6%
Softening agent 10-20%
Mineral filler 2-8%
Auxiliary agent 5-10%
Aforementioned compositions, wherein said rubber are terpolymer EP rubber or paracril.
Aforementioned compositions, wherein said thermoplastics are polypropylene.
Aforementioned compositions, wherein said thermoplastics also comprises polyethylene.
Aforementioned compositions, wherein said EVA resin is a vinyl-vinyl acetate copolymer.
Aforementioned compositions, wherein said compatilizer are maleic anhydride graft EPDM or maleic anhydride graft PP.
Aforementioned compositions, wherein said softening agent are paraffin oil or dioctyl phthalate (DOP).
Aforementioned compositions, wherein said mineral filler are lime carbonate or talcum powder, and described lime carbonate or talcous particle diameter surpass 1250 orders.
Aforementioned compositions, wherein said auxiliary agent are tackifying resin, and described tackifying resin is the solid coumarone resin.
Aforementioned compositions, wherein said auxiliary agent also comprises lubricant, described lubricant is a polyoxyethylene glycol.
Aforementioned compositions, wherein said auxiliary agent also comprises oxidation inhibitor, described oxidation inhibitor is antioxidant 1010.
Aforementioned compositions wherein also comprises fire retardant, and described fire retardant is inorganic hydrogen magnesium oxide, aluminium hydroxide or organophosphorus nitrogen efficient flame-retarding agent.
Aforementioned compositions wherein also comprises vulcanizing agent, and described vulcanizing agent is peroxide vulcanizing agent DCP, resol or silane.
A kind of manufacture method of Halogen composition for thermoplastic elastomer is characterized in that may further comprise the steps:
First step: take by weighing raw material, by mass percentage, elastomerics or rubber 30-40%, thermoplastics 15-30%, EVA resin 2-8%, compatilizer 3-6%, softening agent 10-25%, mineral filler 2-8%, auxiliary agent 5-10%;
Second step: mix, all powderies and granular main and auxiliary batching are added in the high-speed mixer, Xian Hegai smashes, and prevents the batch mixing inequality, uncaps again to add described softening agent and auxiliary agent, and first stirring at low speed, high-speed stirring again, whole mixing process needs 3-8 minute;
Third step: granulation; open pneumatic transport and start the dual-screw pelletizer main frame, the fluxing zone temperature is set between the 170-190, and blanking section and head temperature are set between 140-160 ℃; rotating speed 200-500rpm adopts water-cooled tie rod pelletizing or air-cooled flour milling fervent.
A kind of environment-friendly electric wire cable is characterized in that, uses as each described Halogen composition for thermoplastic elastomer in the claim 1 to 26 in insulation or sheath.
After adopting technique scheme, its environment-friendly electric wire cable of Halogen composition for thermoplastic elastomer of the present invention and manufacture method thereof and use has the following advantages:
1. the chemical substance that does not contain harmful heavy metal, halogen and harm humans health and physical environment, nontoxic, pollution-free, recyclable utilization is environmentally friendly novel material.
2. water-fast, cold-resistant, high temperature resistant, oil resistant, acid and alkali-resistance can be used as the environmental protection cable of excellent combination property.
3. can be widely used in military project, boats and ships, nuclear power, wind energy, railroad track traffic, the contour end line cable of magnetic levitation field.
Description of drawings
Fig. 1 is for manufacturing the schema of the manufacture method of environment-friendly electric wire cable with Halogen composition for thermoplastic elastomer of the present invention.
Fig. 2 makes the structure iron of environmental protection cable for Halogen composition for thermoplastic elastomer of the present invention.
Fig. 3 makes the sectional view of environmental protection cable for Halogen composition for thermoplastic elastomer of the present invention.
Among the figure: 1 conductor, 2 insulation, 3 twining package tapes, 4 sheaths.
Embodiment
Below in conjunction with embodiment and accompanying drawing thereof the present invention is illustrated further.
In following table 1, SEBS among the embodiment 1 is got through hydrogenation hydrogenation by thermoplastic elastomer SBS's (styrene-butadiene-styrene block copolymer), structure becomes polystyrene-poly ethene-polybutene-polystyrene block copolymer after the SBS hydrogenation, and embodiment 1 composition is applicable to the manufacturing flexible cable.EPDM among the embodiment 2 is a terpolymer EP rubber, is the terpolymer of ethene, propylene and non-conjugated diene hydrocarbon, is applicable to make to substitute traditional PVC electric wire.Embodiment 3 compositions are products of dynamic vulcanization (relative static vulcanization is the process of carrying out synchronously with sulfuration of realizing in the melt blending process) TPE, are applicable to make to substitute the sulfide type Plastic-sheathed Cable.NBR among the embodiment 4 is a paracril, and embodiment 4 compositions are applicable to that manufacturing has the cable of strict demand to oil resistant, as place cables such as petroleum prospecting, oil-immersed pump, offshore drilling platform.
Table 1
Embodiment 1 is applicable to and makes the environmental protection flexible cable that embodiment 2 is applicable to and makes the environment-friendly cable that substitutes the PVC cable that embodiment 3 is applicable to make and substitutes the sulfide type Plastic-sheathed Cable that embodiment 4 is applicable to has the environment-friendly cable of strict demand to making oil resistant.The PP of thermoplastics described in the table 1 is a polypropylene, PE is a polyethylene, described EVA resin is a vinyl-vinyl acetate copolymer, described compatilizer is maleic anhydride graft SEBS (MSEBS-G-MAH), maleic anhydride graft EPDM (MEPDM-G-MAH) or maleic anhydride graft PP (MPP-G-MAH), described softening agent is a white oil, paraffin oil or dioctyl phthalate (DOP), described mineral filler is lime carbonate (precipitator method) or talcum powder, described lime carbonate or talcous particle diameter surpass 1250 orders, described fire retardant is an inorganic hydrogen magnesium oxide, aluminium hydroxide (German Martin, the refined treasured of the U.S.) or organophosphorus nitrogen efficient flame-retarding agent (China of the magnificent Hue industry science skill of breaking a seal development company is along HS-219), described vulcanizing agent is peroxide vulcanizing agent DCP, resol or silane, described tackifying resin is the solid coumarone resin, and described lubricant is PEG4000.
It is starting material that Halogen composition for thermoplastic elastomer TPE of the present invention selects elastomerics or rubber for use, with the thermoplastics is external phase, with rubber and elastomerics is disperse phase (the another kind of polymkeric substance of a kind of surrounded, besieged polymkeric substance is called disperse phase, and another kind of polymkeric substance is called external phase), be commonly called as " sea-island " structure, form and to show caoutchouc elasticity at normal temperatures, macromolecular material that again can plasticizing forming under the high temperature.In the compounding process, add compatilizer, softening agent, inorganic filler, dispersion agent, oxidation inhibitor etc., as the suitable fire retardant of the fire-retardant adding of need.
Except that above-mentioned component, can also add processing aid as required, the additive of flame retardant, linking agent, crosslinking coagent, inorganic filler, stablizer, tinting material etc., and guarantee all raw material Halogen, environmental protection.
The manufacture method of Halogen thermoplastic elastomer TPE of the present invention is characterized in that may further comprise the steps:
First step: take by weighing raw material, elastomerics or rubber 30-40%, thermoplastics 15-30%, EVA resin 2-8%, compatilizer 3-6%, softening agent 10-20%, mineral filler 2-8%, auxiliary agent 5-10%;
Second step: mix, all powderies and granular main and auxiliary batching are added in the high-speed mixer, Xian Hegai smashes, and prevents the batch mixing inequality, uncaps again to add described softening agent and auxiliary agent, and first stirring at low speed, high-speed stirring again, whole mixing process needs 3-8 minute;
Third step: granulation; open pneumatic transport and start the dual-screw pelletizer main frame, the fluxing zone temperature is set between 170-190 ℃, and blanking section and head temperature are set between 140-160 ℃; rotating speed 200-500rpm adopts water-cooled tie rod pelletizing or air-cooled flour milling fervent.
Adopt Halogen thermoplastic elastomer TPE of the present invention environmental friendliness, do not contain the electric wire and cable that the non-halogen thermoplastic elastic material of harmful heavy metal, halogen and serious harm human health and physical environment is made, its manufacture method following (referring to Fig. 1):
TPE expects pre-treatment: the TPE material after the granulation must be deposited more than 16 hours and could reprocess.The material oven dry particularly must have been opened the material of bag before extruding, can not influence its state in forcing machine to guarantee moisture content.70～90 ℃ of suggestion baking material temperature, the time is 2～8 hours;
Conductor is selected for use: press particular requirements such as the nominal section of cable and field of employment, and conductor structure reasonable in design, general single core cross section is at 1200mm
2Below, copper, aluminium conductor are twisted into thigh or directly select single cored structure for use through buncher, tube-type line strander, frame winch and other wire twisting equipments, the conductor of cable is divided into the core of the 1st kind, the 2nd kind, the 5th kind, the 6th kind and nonstandard particular requirement, filament diameter and structure can be according to the practical use adjustment, with 3 * 2.50mm
2The equipment line be example, select for use 7 filament diameter 0.675mm copper wire bundles to close and form.No matter how conductor structure to design, meet corresponding safety and require and the resistance appraisal standards, and copper, filling, band are the material by environmental protection test (RoHS);
Insulating exruded: the used TPE material of this patent can use common PVC screw rod to come extrusion moulding, the temperature setting range of each section of forcing machine is: 150～220 ℃, and raise successively, adopt plsitive mold production when extruding, the line that squeezes after insulating must be through hot water bath, temperature is about 90～95 ℃, and cooling is piecemeal adopted in suggestion.Conductor is through preheating, can squeeze insulation behind discharge smooth and easy and material inclusion-free and the bubble, and the speed that bursts at the seams is more than 40m/min, and each section tension force is wanted steadily, otherwise easily causes the line distortion and phenomenon such as come unstuck;
Stranding: general cable is a multicore, and structure is more stable behind the stranding, is convenient to following process and use.The pitch of electric wire is an important indicator of examination, directly influences the distortion and the flexibility of insulated wire cores.The lay ratio of cable (pitch and external diameter ratio) is generally 5-80, decides on the structure and the purposes of concrete cable.In the time of stranding, can fill and wrap band, technology controlling and process is convenient need select the gasket for packing of suitable size and the band of suitable width and thickness for use in order to make, and the linear rounding (fan-shaped, flat also need reach relevant criterion) behind the final stranding, level and smooth is filled closely full.Filling and band must be the qualified product by environmental protection test equally;
Sheath is extruded: use common PVC screw rod, the extrusion temperature scope is: 150～220 ℃, the temperature of flame retardant type is set low spot slightly.The employing plsitive mold is extruded, and goes out behind the head to eliminate internal stress through hot water bath, and temperature is about 90～95 ℃, and cooling is piecemeal adopted in suggestion.The speed that bursts at the seams more than 20m/min, visual particular case adjustment.
Fig. 2 and Fig. 3 are respectively structure iron and the sectional view that Halogen thermoplastic elastomer of the present invention is made cable, and 1 is conductor among the figure, and 2 are insulation, and 3 is twining package tape, and 4 is sheath.
Above embodiment is only for the usefulness that the present invention is described, but not limitation of the present invention, person skilled in the relevant technique under the situation that does not break away from the spirit and scope of the present invention, can also be made various conversion or variation.Therefore, all technical schemes that are equal to also should belong to category of the present invention, should be limited by each claim.
Claims (28)
1. a Halogen composition for thermoplastic elastomer is characterized in that, by mass percentage, its component comprises:
Elastomerics 30-40%
Thermoplastics 15-30%
EVA resin 2-8%
Compatilizer 3-6%
Softening agent 10-25%
Mineral filler 2-8%
Auxiliary agent 5-10%
2. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that, described elastomerics is hydrogenation of ethylene-butylene copolymer.
3. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that, described thermoplastics is a polypropylene.
4. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that described thermoplastics also comprises polyethylene.
5. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that, described EVA resin is a vinyl-vinyl acetate copolymer.
6. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that, described compatilizer is maleic anhydride graft SEBS.
7. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that, described softening agent is a white oil.
8. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that, described mineral filler is lime carbonate or talcum powder, and described lime carbonate or talcous particle diameter surpass 1250 orders.
9. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that, described auxiliary agent is a tackifying resin, and described tackifying resin is the solid coumarone resin.
10. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that described auxiliary agent also comprises lubricant, and described lubricant is a polyoxyethylene glycol.
11. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that described auxiliary agent also comprises oxidation inhibitor, described oxidation inhibitor is antioxidant 1010.
12. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that, also comprises fire retardant, described fire retardant is an inorganic hydrogen magnesium oxide, aluminium hydroxide or organophosphorus nitrogen efficient flame-retarding agent.
13. Halogen composition for thermoplastic elastomer according to claim 1 is characterized in that, also comprises vulcanizing agent, described vulcanizing agent is peroxide vulcanizing agent DCP, resol or silane.
14. a Halogen composition for thermoplastic elastomer is characterized in that, by mass percentage, its component comprises:
Rubber 30-40%
Thermoplastics 15-30%
EVA resin 2-8%
Compatilizer 3-6%
Softening agent 10-20%
Mineral filler 2-8%
Auxiliary agent 5-10%
15. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that, described rubber is terpolymer EP rubber or paracril.
16. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that, described thermoplastics is a polypropylene.
17. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that described thermoplastics also comprises polyethylene.
18. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that, described EVA resin is a vinyl-vinyl acetate copolymer.
19. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that, described compatilizer is maleic anhydride graft EPDM or maleic anhydride graft PP.
20. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that, described softening agent is paraffin oil or dioctyl phthalate (DOP).
21. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that, described mineral filler is lime carbonate or talcum powder, and described lime carbonate or talcous particle diameter surpass 1250 orders.
22. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that, described auxiliary agent is a tackifying resin, and described tackifying resin is the solid coumarone resin.
23. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that described auxiliary agent also comprises lubricant, described lubricant is a polyoxyethylene glycol.
24. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that described auxiliary agent also comprises oxidation inhibitor, described oxidation inhibitor is antioxidant 1010.
25. Halogen composition for thermoplastic elastomer according to claim 14 is characterized in that, also comprises fire retardant, described fire retardant is an inorganic hydrogen magnesium oxide, aluminium hydroxide or organophosphorus nitrogen efficient flame-retarding agent.
26., it is characterized in that also comprise vulcanizing agent, described vulcanizing agent is peroxide vulcanizing agent DCP, resol or silane according to claim 14 Halogen composition for thermoplastic elastomer according to claim 1.Described Halogen composition for thermoplastic elastomer is characterized in that, also comprises vulcanizing agent, and described vulcanizing agent is peroxide vulcanizing agent DCP, resol or silane.
27. the manufacture method of a Halogen composition for thermoplastic elastomer is characterized in that may further comprise the steps:
First step: take by weighing raw material, by mass percentage, elastomerics or rubber 30-40%, thermoplastics 15-30%, EVA resin 2-8%, compatilizer 3-6%, softening agent 10-20%, mineral filler 2-8%, auxiliary agent 5-10%;
Second step: mix, all powderies and granular main and auxiliary batching are added in the high-speed mixer, Xian Hegai smashes, and prevents the batch mixing inequality, uncaps again to add described softening agent and auxiliary agent, and first stirring at low speed, high-speed stirring again, whole mixing process needs 3-8 minute;
Third step: granulation; open pneumatic transport and start the dual-screw pelletizer main frame, the fluxing zone temperature is set between 170-190 ℃, and blanking section and head temperature are set between 140-160 ℃; rotating speed 200-500rpm adopts water-cooled tie rod pelletizing or air-cooled flour milling fervent.
28. an environment-friendly electric wire cable is characterized in that, uses as each described Halogen composition for thermoplastic elastomer in the claim 1 to 26 in insulation or sheath.
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