KR101864413B1 - Anti-oxidant semi-conductive polymer compound self-regulating heating cable therein and a manufacturing method - Google Patents

Abstract

The present invention relates to a polymer semi-conductive compound having anti-oxidant properties and a method of manufacturing a self-regulating heating cable using the same. A silane-grafted adhesive resin production step of producing an adhesive resin which has been subjected to a heat treatment; A melt kneading step of producing a polymer semiconductive composition; A pelletizing step of making a semi-conductive composition pellet; A conductive heat treatment step of removing a foreign substance and a fresh oil adhering to the surface of the conductor to produce a heat-treated conductor; An adhesive layer formation step of forming an adhesive layer having a thickness of 0.1 to 10 mu m on the outer periphery of the conductor; A semi-conductive heating element manufacturing step of producing a semi-conductive heating element by extrusion molding the semi-conductive composition pellet produced in the pelletizing step; A stabilization step of stabilizing the semi-conductive heating element manufactured in the semi-conductive heating element manufacturing step; 100 to 200 parts by weight of a copolymer resin is added to a conductor composed of a metal wire such as a copper wire, a silver wire and a nickel wire, or a metal plating copper wire or an alloy wire composed of a tin-plated copper wire, a nickel plated copper wire, 1 to 5.0 parts by weight of an initiator, 10 to 25 parts by weight of vinylsilane, 1 to 20 parts by weight of a metal-coated carbon nanotube, 40 to 250 parts by weight of a conductive carbon black, 200 to 700 parts by weight of a polymer resin, , 1 to 5 parts by weight of a dispersing agent, 5 to 100 parts by weight of a metal oxide, and 1 to 10 parts by weight of a porous silica carrying an irradiation crosslinking agent are coated on the surface, A self-controlling heating cable is manufactured using the polymer semiconductive composition having the oxidation resistance characteristic.

Description

[0001] The present invention relates to an autocontrolled heating cable using a polymer semiconductive composition having oxidation resistance and an oxidation resistance, and a self-regulating heating cable and a manufacturing method thereof,

TECHNICAL FIELD The present invention relates to a polymer semi-conductive compound having anti-oxidant properties and a method of manufacturing a self-regulating heating cable using the semi-conductive compound. The heating elements and the conductors suppress the slip phenomenon due to the difference in thermal expansion and the bending at the time of construction due to the repetition of the heat cycle during use, Solves the problem of falling. A polymeric semiconductive composition having an oxidation resistance characteristic that significantly improves the lifetime of a product by suppressing a tendency of a conductive filler causing nonuniform resistivity to move in a polymer matrix and an autonomous controlled heating And a method of manufacturing a cable.

TECHNICAL FIELD The present invention relates to a polymer semi-conductive compound having anti-oxidant properties and a method of manufacturing a self-regulating heating cable using the semi-conductive compound. The heating elements and the conductors suppress the slip phenomenon due to the difference in thermal expansion and the bending at the time of construction due to the repetition of the heat cycle during use, Solves the problem of falling. A polymeric semiconductive composition having an oxidation resistance characteristic that significantly improves the lifetime of a product by suppressing a tendency of a conductive filler causing nonuniform resistivity to move in a polymer matrix and an autonomous controlled heating And a method of manufacturing a cable.

Korean Patent No. 100902402 discloses a cable in which a pair of electric wires are arranged at the center and a semiconductive polymer, an insulating film, a braided ground wire and an outer insulating film are sequentially stacked on the outer surface, And the copper wire is characterized in that the copper thin film is formed in a tape form and wound on the surface of the aluminum wire and welded and then drawn to a predetermined thickness. Provide a heating cable. Korean Patent No. 101548983 provides a positive temperature coefficient heating cable and a method of manufacturing the same. A first electrode string formed by extruding a conductive composition around a conductor bundled into a plurality of strands for this purpose; a second electrode string having the same structure as the first electrode string, the first electrode string having a constant pitch, A two-electrode string, and a coating surrounding the first electrode string and the second electrode string. According to the present invention, since the conductive composition is coated only on the periphery of the conductor, the conductive composition is extruded in a concentric circular form for each conductor because of excellent flexibility and easy bending, The control of the thickness of the conductive composition surrounding the electrode is easy, and the output uniformity is improved. Korean Patent No. 101445264 discloses that three heater electrodes surrounded by a semiconductive polymer composition having a constant temperature coefficient property in an insulating covering member form a three-phase electrode, and the distance between the electrodes is larger than that of the heating cable And the balance between the phases is maintained by positioning the electrodes in the same manner. According to the above-described invention, since the three-phase 380V is applied while maintaining the constant-temperature characteristic of the single-phase heater, the current load is reduced to 67% as compared with the conventional single-phase 220V, A constant temperature coefficient heating cable with a reduced inrush current which can be operated with a high temperature can be obtained. In addition, there is an advantage that the three-way heater having 1/3 output advances side by side along the longitudinal direction of the heating cable, and the phase load balance is not broken by the ambient temperature or the temperature change of the object. Korean Patent No. 10-0196298 discloses a polymeric heating element using a polymer composite material having a positive temperature coefficient characteristic, and particularly, an autonomous controlled polymeric heating element having improved static temperature coefficient characteristics. 5 to 40 parts by weight of carbon black, 2 to 30 parts by weight of a heat stabilizer, and 0.1 to 10 parts by weight of a phenol type antioxidant are added to the autonomic controlled polymer heat generating material polyolefin type or fluorine type crystalline resin of the present invention, And an outer heating element made of a polymer composite material composed of a polymeric composite material. Korean Registered No. 200137043 discloses an autonomously controlled polymer heater used as a heating element that uses an electrically conductive polymer as an exothermic body whose electrical resistance increases as the ambient temperature rises, and is used for prevention of frost, heat insulation, and snow melting of pipes and tanks. The idea is to form a conductive coating layer between the conductor and the heating element so as to maintain a definite adhesive force so that the increase in interfacial resistance during use between the conductor and the heating element is minimized, Wherein the conductive coating layer is formed between the conductor and the heating element. The self-controlling type polymer heater according to claim 1, wherein the conductive coating layer is formed between the conductor and the heating element.

However, according to the construction of the conventional autonomous control heating cable described above, as the heat cycle is repeated during use, the polymeric heating element and the conductor exhibit a difference in thermal expansion, or an interface by bending in the bent- There is a problem that slipping occurs and the interface resistance is increased and the output is lowered.

Also, due to the tendency of the conductive filler to move to a portion with less pressure in the polymer matrix, the non-uniformity of the resistivity in the polymer matrix is caused, thereby promoting oxidation of the semi-conductive composition and shortening the life of the product.

In order to solve the above problems, the present invention provides an adhesive layer for improving adhesion between a conductor and a heating element, thereby minimizing an increase in surface resistance due to oxidation of the semi-conductive composition during use between the conductor and the heating element A first object of the present invention is to provide a method for surface treatment of a conductor with a low process cost which improves long-term output stability.

It is a second object of the present invention to provide a semiconductive polymer composition which improves the lifetime and output stability of a product by controlling the tendency of carbon black to move in the polymer matrix to suppress non-uniformity in resistivity.

Another object of the present invention is to provide a manufacturing method of an autonomously controlled heating cable that can reduce the loss of electric wires during work and improve workability.

In order to accomplish the above object, the present invention provides a method for producing a polyimide precursor solution by adding trichlorobenzene or dichlorobenzene to a reactor equipped with a temperature controller, a stirrer and an evaporator, 600 to 1000 parts by weight of an organic solvent such as toluene, xylene, cyclohexane or tetrahydrofuran, and an ethylene-vinyl acetate copolymer, 100 to 200 parts by weight of a copolymer resin such as ethylene-propylene diene copolymer or styrene-butadiene copolymer is added, and then the temperature of the reactor is raised to 80 to 150 DEG C and 500 1 to 5.0 wt% of an initiator such as dicumyl peroxide or azobisisobutyronitrile was added to the polymer solution dissolved with stirring at a speed of 1000 rpm. Vinyltrimethoxy silane, vinyltriethoxy silane, vinyl-tris (2-methoxy-ethoxy-) silane], vinyltrimethoxysilane, , 3-methacryloxypropyltrimethoxy silane, 3-methacryloxypropyltriethoxy silane, vinyldimethylethoxy silane, vinyl methyl dibutoxysilane, and 10 to 25 parts by weight of vinyl silane such as vinylmethyldibutoxy silane were successively added to the mixture, and the mixture was stirred at 80 to 150 ° C for 120 minutes at 500 to 1500 rpm for grafting reaction. A silane-grafted adhesive resin manufacturing step of removing an organic solvent by using a solvent such as methyl alcohol or hexane, followed by washing and drying to produce a silane-grafted adhesive resin;

111 to 230 parts by weight of the silane-grafted adhesive resin prepared in the step of preparing the silane-grafted adhesive resin in a mixed mixer such as a Kneader mixer or a Banbury mixer, 1 to 20 parts by weight of carbon-coated carbon nanotubes such as copper, antimony, silver and copper; conductive carbon black such as ketjenblack and acetylene black; 40 to 250 parts by weight of a polyolefin resin such as polyethylene or polypropylene or polymethyl pentene or a polyvinyl fluoride or a poly (ethylene-co- 200 to 1500 parts by weight of a polymer resin which is a fluororesin such as poly (ethylene-co-tetrafluoroethylene), 1 to 10 parts by weight of an antioxidant, 1 to 5 parts by weight of a dispersant, oxide, indium oxide, tin oxide, and the like. 5 to 100 parts by weight of a metal oxide, a porous silica 1 carrying an irradiation crosslinking agent such as triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, To 10 parts by weight, and melt-kneading the mixture at 120 to 300 ° C. for 10 to 30 minutes to produce a polymer semiconductive composition;

The semi-conductive polymer composition prepared in the above melt-kneading step was melt-extruded using a single screw extruder or a twin screw extruder to form a semi-conductive composition pellet having a size of 2 to 3 mm A pelletizing step of making;

A conductor made of a metal wire such as copper wire, silver wire or nickel wire, or a metal plating copper wire or alloy wire composed of tin-plated copper wire, nickel-plated copper wire or silver-plated copper wire is passed through a gas touch or gas oven A conductor heat treatment step of heating the conductor to a temperature of 400 to 1000 ° C to remove a foreign substance and a fresh oil adhering to the surface of the conductor to produce a heat-treated conductor;

The heat-treated conductor manufactured in the conductor heat treatment step is impregnated into a coating dye containing a reactive adhesive and is passed through a heating oven or a heater box maintained at 80 to 200 ° C. An adhesive layer forming step of forming an adhesive layer having a thickness of 0.1 to 10 mu m on the outer periphery of the conductor by curing and drying the reactive adhesive;

The pellets of the semi-conductive composition prepared in the pelletizing step were introduced into a single-screw extruder hopper. The pellets were fed into a single-screw extruder hopper under the following conditions: cylinder 1 at 100 to 200 ° C, cylinder 2 at 170 to 270 ° C, cylinder 3 at 180 to 300 ° C, ° C in the order of 10 to 40 kg / hour; and a semi-conductive heating element production step of producing a semi-conductive heating element by extrusion molding the die at an extrusion rate of 10 to 40 kg /

A stabilization step of stabilizing the semi-conductive heating element manufactured in the semi-conductive heating element by passing it through a water bath maintained at 60 to 100 ° C at a rate of 5 m / min to 50 m / min;

A step of irradiating the semi-conductive heating body manufactured in the step of manufacturing the semi-conductive heating body by irradiating the semi-conductive heating body with 100 to 1200 kGy using a radiation irradiation equipment such as an electron beam or a gamma ray to crosslink the semi-conductive heating body 100 to 200 parts by weight of a copolymerized resin and 1 to 5.0 parts by weight of a initiator in a conductor composed of a metal wire such as a copper wire, a silver wire and a nickel wire, or a metal plating copper wire or an alloy wire composed of a tin-plated copper wire, a nickel- 10 to 25 parts by weight of vinyl silane, 1 to 20 parts by weight of metal-coated carbon nanotubes, 40 to 250 parts by weight of conductive carbon black, 200 to 700 parts by weight of a polymer resin, 1 to 10 parts by weight of an antioxidant, By weight of a polymeric semiconductive composition having an oxidation resistance property, which is composed of 5 to 100 parts by weight of a metal oxide, 1 to 10 parts by weight of a porous silica having supported thereon an irradiation crosslinking agent, To prepare a self-regulating heating cable with a semi-conductive polymer compositions having oxidation properties, it characterized in that the configured semi-conductive heating element is made of four.

As described above, the present invention resists the problem that the thermal expansion difference between the polymer heat generating material and the conductor and the interfacial slipping phenomenon due to the bending during the construction are suppressed and the output is lowered as the heat cycle is repeated during use. The present invention has the effect of easily manufacturing an autonomously controlled heating cable having anti-oxidizing properties that significantly suppresses the tendency of the conductive filler causing the non-resistivity non-uniformity to move in the polymer matrix and greatly improves the life of the product.

1 is an exemplary diagram of a conventional autonomously controlled heating cable;
Fig. 2 is a cross-sectional view of the autonomic control semi-
3 is a process flow diagram illustrating an embodiment of the present invention;

The embodiments of the present invention, which can best match the above objects and features, will now be described in detail with reference to the process flowchart of FIG.

Temperature regulator. A reactor equipped with a stirrer and an evaporator is charged with 600 to 1000 parts by weight of an organic solvent such as trichlorobenzene, dichlorobenzene, toluene, xylene, cyclohexane or tetrahydrofuran, an ethylene vinyl acetate copolymer or ethylene-propylene diene And 100 to 200 parts by weight of a copolymer resin such as styrene-butadiene copolymer, and then the temperature of the reactor is raised to 80 to 150 DEG C and the solution is stirred and stirred at a speed of 500 to 1000 rpm. Dicumyl peroxide or azobis 1 to 5.0 parts by weight of an initiator such as isobutylonitrile and 1 to 5 parts by weight of vinyltrimethoxysilane or vinyltriethoxysilane, vinyltris (2-methoxy-ethoxy-) silane, 3-methacryloxypropyltrimethoxy 10 to 25 parts by weight of vinylsilane such as silane, 3-methacryloxypropyltriethoxysilane, vinyldimethylethoxysilane, and vinylmethyldibutoxysilane are sequentially administered, and then 120 minutes The grafting reaction is carried out at 80 to 150 ° C with stirring at a rate of 500 to 1500 rpm and the organic solvent is removed using an evaporator, followed by washing with a solvent such as methyl alcohol or hexane and drying to produce a silane-grafted adhesive resin Silane-grafted adhesive resin;

A mixed mixer such as a kneader mixer or a Banbury mixer is coated with 111 to 230 parts by weight of the silane-grafted adhesive resin produced in the silane-grafted adhesive resin preparation step, and a metal- 1 to 20 parts by weight of carbon nanotubes, 40 to 250 parts by weight of conductive carbon black such as Ketjenblack and acetylene black, polyolefin resin such as polyethylene, polypropylene, polymethylpentene, polyvinyl fluoride, poly (ethylene- tetrafluoroethylene), 1 to 10 parts by weight of an antioxidant, 1 to 5 parts by weight of a dispersant, and 5 to 100 parts by weight of a metal oxide such as zinc oxide, indium oxide and tin oxide And 1 to 10 parts by weight of porous silica supporting irradiation crosslinking agent such as triallyl cyanurate, triallyl isocyanurate and trimethylolpropane trimethacrylate are sequentially added, In the melt-kneading temperature 10-30 minutes during the melt-kneading step for producing the polymer semi-conductive composition;

Pelletizing the semiconducting polymer composition prepared in the melt-kneading step into a semi-conductive composition pellet having a size of about 2 to 3 mm through a melt extrusion molding process using a single-screw extruder or a twin-screw extruder;

Conductors made of metal wires such as copper wires, silver wires and nickel wires, or metal conductor copper wire or alloy wire composed of tin-plated copper wire, nickel-plated copper wire and silver-plated copper wire are passed through a gas torch or gas oven and heated to a temperature of 400 to 1000 ° C. A conductor heat treatment step of heating the conductor to remove heat and foreign matter adhering to the surface of the conductor to produce a heat-treated conductor;

The heat-treated conductor produced in the conductor heat-treating step is impregnated into a coating bath containing a reactive adhesive, and is passed through a heating oven or a heater box maintained at 80 to 200 ° C to cure and dry the reactive adhesive so that 0.1 to 10 μm An adhesive layer forming step of forming an adhesive layer having a predetermined thickness;

The pellets of the semi-conductive composition prepared in the pelletizing step were introduced into a single-screw extruder hopper. The pellets were fed into a single-screw extruder hopper under the following conditions: cylinder 1 at 100 to 200 ° C, cylinder 2 at 170 to 270 ° C, cylinder 3 at 180 to 300 ° C, Deg.] C per minute at an extrusion rate of 10 to 40 kg / hour to produce a semi-conductive heating element;

A stabilization step of stabilizing the semi-conductive heating element manufactured in the semi-conductive heating element by passing it through a water bath maintained at 60 to 100 ° C at a rate of 5 m / min to 50 m / min;

The semi-conductive heating body manufactured in the semi-conductive heating body is irradiated with 100 to 1200 kGy using a radiation irradiation apparatus such as an electron beam or a gamma ray to cross-bond the semi-conductive heating body,

100 to 200 parts by weight of a copolymerized resin, 1 to 5.0 parts by weight of an initiator, 100 to 200 parts by weight of an initiator, and 100 to 200 parts by weight of a copolymer resin, which are composed of a metal wire such as copper wire, silver wire and nickel wire, or a metal wire copper wire or alloy wire composed of tin- 10 to 25 parts by weight of vinyl silane, 1 to 20 parts by weight of carbon-coated carbon nanotubes, 40 to 250 parts by weight of conductive carbon black, 200 to 700 parts by weight of a polymer resin, 1 to 10 parts by weight of an antioxidant, Wherein the polymeric semiconductive composition is coated with a radiation-curable polymeric composition having an oxidation-resistant property, wherein the radiation-sensitive resin composition comprises 5 to 100 parts by weight of a metal oxide, 1 to 10 parts by weight of porous silica having a radiation crosslinking agent, The self-controlling heating cable using the polymer semiconductive composition having the oxidation resistance characteristic is manufactured.

The vinylsilane used in the adhesive resin production step may be vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxy-ethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyldimethylethoxysilane, vinylmethyldibutoxysilane, etc. may be used singly or in combination of two or more thereof in an amount of 10 to 25 parts by weight, and the present invention is not limited thereto.

If the vinyl silane is less than 10 parts by weight, adhesion between the conductor and the semi-conductive composition is deteriorated. If the vinyl silane is added by 25 parts by weight or more, economical efficiency is low.

The initiator used to chemically graft the copolymer resin and the vinyl silane is used in an amount of 1 to 5 parts by weight. The initiator may be selected from the group consisting of benzoyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t- T-butyl peroxyisobutyrate, cyclohexanone peroxide, or a mixture thereof may be used, but the present invention is not limited thereto.

If the amount of the initiator is less than 1 part by weight, the grafting reaction efficiency is lowered. If the amount of the initiator is more than 5 parts by weight, it acts as an impurity and adversely affects the conductivity.

Examples of the antioxidant used in the melt-kneading step include poly (1,2-dihydro-2,2,4-trimethyl quinoline), 2 Methyl-phenol, 2,6-di-tert-butyl-4-methyl phenol, tetrakis [ Tetrakis [methylene-3- (3 '' hydroxyphenyl-propionate)] methane] or tris (2,4-di-tert-butylphenyl) phosphite [tris -di-tert-butyl-phenyl) phosphite], tetrakis methylene (3,5-di-t-butyl-4-hydroxy hydrocinamate)] is used in an amount of 1 to 10 parts by weight.

If the amount of the antioxidant is less than 1 part by weight, the polymer resin is oxidized to deteriorate the durability. If the amount of the antioxidant is more than 10 parts by weight, impurities may adversely affect the conductivity.

The dispersing agent used in the melt-kneading step is preferably a metal salt stearate of calcium stearate, zinc stearate and magnesium stearate, but also lauric acid, Myristic acid, palmitic acid, and the like may be used, and the present invention is not limited thereto.

In this case, 1 to 5 parts by weight of the dispersing agent is used. When the amount is less than 1 part by weight, workability is poor. When 5.0 parts by weight or more is added, the melt-kneading property is deteriorated.

The irradiation cross-linking agent used in the melt-kneading step may be used alone or in combination of two or more thereof, such as triallyl cyanurate, triallyl isocyanurate and trimethylolpropane trimethacrylate, The present invention is not limited thereto.

In this case, the irradiated crosslinking agent is used in an amount of 1 to 10 parts by weight, and when the amount is less than 1 part by weight, irradiation crosslinking is lowered, and when 10 parts by weight or more is added, mechanical properties are poor.

The adhesive reactive adhesive in a layer-forming step kemrok's load ^(Lord)? (Chemlok ^? ) 200 or 220X, 6100 and 6108 products are preferred, but the present invention is not limited thereto.

In this case, the thickness of the adhesive layer is 0.1 to 10 μm, and when it is coated to a thickness of 0.1 μm or less, compatibility with a conductor is poor.

A polymer semiconductive composition having oxidation resistance characteristics according to the present invention and a method of manufacturing an autonomously controlled heating cable using the same will be described in detail below.

Hereinafter, the present invention will be described in more detail with reference to examples.

However, the scope of the present invention is not limited to the illustrated embodiments.

The components listed in Table 1 were mixed at the respective blending ratios using a mixer in the following manufacturing process to produce a polymer semiconductive composition having oxidation resistance characteristics and an autonomously controlled heating cable using the same.

<Polymeric Semiconductive Composition with Oxidizing Properties and Examples and Comparative Examples of Manufacturing Method of Autonomously Controlled Heating Cable Using the Same

Raw material (parts by weight) Example 1 Example 2 Example 3 Comparative Example Adhesive resin Vinyltrimethoxysilane Grafted ethylene vinyl acetate 172 - - Vinyltrimethoxysilane Grafted polyvinylidene fluoride - 172 - Vinyltrimethoxysilane Grafting poly (ethylene-co-tetrafluoroethylene) - - 172 Ethylene vinyl acetate - - - 172 Metal-coated carbon nanotubes Nickel-coated carbon nanotubes 5 5 5 - Conductive carbon black Acetylene black 180 180 180 180 Antioxidant Tetrakis [methylene-3- (3 '' ditert-butyl-4-hydroxyphenyl-propionate) methane 2 2 2 2 Dispersant Calcium stearate 5 5 2 5 Metal oxide Zinc oxide 50 50 50 50 Irradiation cross-linking agent Triallyl isocyanurate-supported silica 5 5 5 - Triallyl isocyanurate - - - 5 Polymer resin Polyethylene 1000 - - 600 Polyvinylidene fluoride - 800 - - Poly (ethylene-co-tetrafluoroethylene) - - 800 - Semi-conductive composition Total 1,419 1,219 1,216 1,014 Polymer flame retardant resin Polyethylene ○ - - ○ Polyvinylidene fluoride - ○ - - Poly (ethylene-co-tetrafluoroethylene) - - ○ - Metal braiding Tinned copper wire ○ ○ ○ ○ Coated polymer flame retardant resin Polyethylene ○ - - ○ Polyvinylidene fluoride - ○ - - Poly (ethylene-co-tetrafluoroethylene) - - ○ -

Method for producing flame retardant silane cross-linking compositions of Examples and Comparative Examples

Temperature regulator. 750 parts by weight of xylene and 150 parts by weight of an ethylene vinyl acetate copolymer resin were added to a reactor equipped with a stirrer and an evaporator, and then the reactor was heated to 80 DEG C and stirred at 800 rpm while stirring. To the polymer solution, 2 parts by weight of dicumyl peroxide And 20 parts by weight of vinyltrimethoxysilane were sequentially added, and then the grafting reaction was carried out while stirring at 1000 rpm at 100 DEG C for 120 minutes to prepare a silane-grafted polyolefin resin solution. The vinyltrimethoxysilane grafting 172 parts by weight of an ethylene vinyl acetate adhesive resin.

Metal-coated carbon nanotubes, conductive carbon black, an antioxidant, a dispersant, a metal oxide, a polymer resin and an irradiation crosslinking agent were sequentially charged into a 20 L kneader mixer in accordance with the blending ratios of Table 1 in order, Kneaded at 165 ° C for Example 2, 210 ° C for Example 2, 295 ° C for Example 3 and 165 ° C for Comparative Example for 20 minutes, using a twin-screw extruder to a size of 2 to 3 mm A semi-conductive composition was prepared.

Example 1 and Comparative Example

The semi-conductive composition thus prepared and the high-density polyethylene resin were mixed and injected into a hopper. The temperature of the cylinder 1 was 160 ° C, the temperature of the cylinder 2 was 170 ° C, The cylinder 3 and the die were extruded at a rate of 20 kg / hr under a temperature condition of 180 캜 and a die of 175 캜 at a rate of 20 m / min by extruding a self-regulating semi-conductive heating element having a width of 8.1 mm and a thickness of 2.1 mm, Air was sprayed to produce moisture on the surface, and then an electron beam of 500 kGy was irradiated to complete the semi-conductive heating element.

A flame retardant high density polyethylene resin was extruded and insulated to a thickness of 0.7 mm on the semi-conductive heating element, braided to 0.16 mm diameter tin-plated copper wire, and then coated with a flame retardant high density polyethylene resin to complete an autocontrolled heating cable.

Example 2

The semi-conductive composition and the polyvinylidene fluoride resin were mixed and injected into the hopper. Then, in a uniaxial extruder (skew: 100Φ) equipped with a die for 40 mm extrusion molding, cylinder 1 was heated to 180 ° C, cylinder 2 was heated to 200 ° C, cylinder 3 And the die was 215 ° C, extruded at a rate of 20 kg / hr and a thickness of 2.1 mm and a thickness of 2.1 mm was passed through a water tank maintained at 95 ° C. at a rate of 20 m / After spraying the water on the surface, an electron beam of 600 kGy was irradiated to mold the semi-conductive heating element.

Polyvinylidene fluoride resin was extruded and insulated to a thickness of 0.7 mm on the semi-conductive heating element, braided with 0.16 mm diameter tin-plated copper wire, and then coated with polyvinylidene fluoride resin to complete autonomous control heating cable production Respectively.

Example 3

The prepared semi-conductive composition and a poly (ethylene-co-tetrafluoroethylene) resin were mixed and injected into a hopper. Then, in a uniaxial extruder (skew: 100Φ) equipped with a die for 40 mm extrusion molding, The autocontrolled semi-conductive heating element having a width of 8.1 mm and a thickness of 2.1 mm was extruded at a rate of 20 kg / hr under a temperature condition of 270 캜 for cylinder 2, 300 캜 for cylinder 3, and 295 캜, And the air was sprayed at 20 m / min to form water on the surface. Then, an electron beam of 600 kGy was irradiated to mold the semi-conductive heating element.

A poly (ethylene-co-tetrafluoroethylene) resin was extruded and insulated to a thickness of 0.7 mm on the semi-conductive heating element, braided with 0.16 mm diameter tin-plated copper wire, and then coated with a flame retardant high density polyethylene resin. .

 Table 2 shows the results of evaluating the adhesive strength and the power drop between the antistatic and the semi-conductive heating body by fabricating the specimen with the semi-conductive heating body thus manufactured.

<Table 2> Measurement results of each experiment according to the embodiment

Test Items Example 1 Example 2 Example 3 Comparative Example 1 Adhesive strength (MPa) 15 20 20 9 Output degradation (after 50,000 cycles 200 V power on-off test) 0% 0% 0% 15%

As shown in Table 2, the eco-friendly non-toxic flame retardant compound for extrusion coating of the ultra-high voltage electric wire according to the example of the present invention has excellent deep part cracking, mechanical properties, oxygen index and flame retardancy.

The polymeric semiconductive composition having the oxidation resistance characteristic of the present invention and the method of manufacturing an autonomously controlled heating cable using the same can suppress the thermal expansion difference between the polymeric heating element and the conductor and the interfacial slip phenomenon due to bending during the application, Solves the problem that the output drops. The present invention has the effect of easily manufacturing an autonomously controlled heating cable having anti-oxidizing properties that significantly suppresses the tendency of the conductive filler causing the non-resistivity non-uniformity to move in the polymer matrix and greatly improves the life of the product. In addition, it will reduce the loss of airflow by improving the workability of the site by blocking the loss of air at the time of construction, facilitating the production cost reduction and production, and finally having a long-term service life.

1 (1a, 1b, 1c): conductor 2; Semi-conductive heating body 3; Isolation
4; Metal braiding 5; Cloth 10: Adhesive layer

Claims (4)

Temperature regulator. A reactor equipped with a stirrer and an evaporator is charged with an organic solvent such as trichlorobenzene, dichlorobenzene, toluene, xylene, cyclohexane or tetrahydrofuran, an ethylene vinyl acetate copolymer, an ethylene-propylene diene copolymer, a styrene- Butadiene copolymer, and then the temperature of the reactor is raised to 80 to 150 DEG C and the solution is stirred and stirred at a speed of 500 to 1000 rpm. To the polymer solution is added an initiator such as dicumyl peroxide or azobisisobutyronitrile Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxy-ethoxy-) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, Vinyl dimethyl ethoxy silane, and vinyl silane such as vinyl methyl dibutoxysilane are sequentially administered, followed by stirring at 80 to 150 ° C for 120 minutes at 500 to 1500 rpm, Proceed to Ting reaction, and by using an evaporator to remove the organic solvent methyl silane grafting the adhesive resin manufacturing step of washing and drying produce a silane-grafting the adhesive resin in a solvent such as alcohol or hexane, and;
A mixed mixer such as a kneader mixer or a Banbury mixer is coated with 111 to 230 parts by weight of the silane-grafted adhesive resin produced in the silane-grafted adhesive resin preparation step, and a metal- Conductive carbon blacks such as carbon nanotubes, Ketjen black and acetylene black, polyolefins such as polyethylene, polypropylene and polymethylpentene, polyvinyl fluoride such as polyvinyl fluoride and poly (ethylene-co-tetrafluoroethylene) A resin such as a polymer resin, an antioxidant, a dispersing agent, a metal oxide such as zinc oxide or indium oxide or tin oxide, a porous material having a crosslinking agent such as triallyl cyanurate, triallyl isocyanurate or trimethylolpropane trimethacrylate Silica is sequentially added thereto and melted and kneaded at a temperature of 120 to 300 ° C for 10 to 30 minutes to produce a polymer semiconductive composition A kneading step;
Pelletizing the semiconducting polymer composition prepared in the melt-kneading step into a semi-conductive composition pellet having a size of about 2 to 3 mm through a melt extrusion molding process using a single-screw extruder or a twin-screw extruder;
A conductor made of a metal wire such as copper wire, silver wire or nickel wire, or a metal-plated copper wire or alloy wire composed of tin-plated copper wire, nickel-plated copper wire or silver-plated copper wire is passed through a gas torch or gas oven at a temperature of 400 to 1000 ° C A conductor heat treatment step of heating the conductor to remove heat and foreign matter adhering to the surface of the conductor to produce a heat-treated conductor;
The heat-treated conductor produced in the conductor heat-treating step is impregnated into a coating bath containing a reactive adhesive, and is passed through a heating oven or a heater box maintained at 80 to 200 ° C to cure and dry the reactive adhesive so that 0.1 to 10 μm An adhesive layer forming step of forming an adhesive layer having a predetermined thickness;
The pellets of the semi-conductive composition prepared in the pelletizing step were introduced into a single-screw extruder hopper. The pellets were fed into a single-screw extruder hopper under the following conditions: cylinder 1 at 100 to 200 ° C, cylinder 2 at 170 to 270 ° C, cylinder 3 at 180 to 300 ° C, Deg.] C per minute at an extrusion rate of 10 to 40 kg / hour to produce a semi-conductive heating element;
A stabilization step of stabilizing the semi-conductive heating element manufactured in the semi-conductive heating element by passing it through a water bath maintained at 60 to 100 ° C at a rate of 5 m / min to 50 m / min;
The semi-conductive heating element manufactured in the semi-conductive heating element is irradiated with 100 to 1200 kGy using a radiation irradiation apparatus such as an electron beam or a gamma ray to irradiate the semi-conductive heating element to crosslink the semi-conductive heating element, In the method of manufacturing the self-controlling heating cable,
The adhesive resin is prepared by mixing 100 to 200 parts by weight of a copolymer resin with 600 to 1000 parts by weight of an organic solvent such as trichlorobenzene, dichlorobenzene, toluene, xylene, cyclohexane or tetrahydrofuran, And 10 to 25 parts by weight of a vinyl silane. The method of manufacturing an autonomously controlled heating cable using the polymer semiconductive composition according to claim 1, delete The method according to claim 1,
The polymer semiconductive composition is prepared by mixing 1 to 20 parts by weight of metal-coated carbon nanotubes, 40 to 250 parts by weight of conductive carbon black, 200 to 700 parts by weight of a polymer resin as a fluororesin, 1 to 10 parts by weight of an antioxidant, 1 to 5 parts by weight of a dispersant, 5 to 100 parts by weight of a metal oxide, and 1 to 10 parts by weight of a porous silica carrying a crosslinking agent. (EN) METHOD FOR MANUFACTURING AUTOMATIC CONTROLLED HEATING CABLE USING COMPOSITION. A semiconductive composition is coated on a conductor made of a metal wire such as copper wire, silver wire, nickel wire, or a wire made of a metal plating copper wire or an alloy wire composed of a tin-plated copper wire, a nickel plated copper wire and a silver plated copper wire, Wherein the semi-conductive heating body is formed by irradiating the heat-
The semi-conductive composition is an adhesive resin comprising 100 to 200 parts by weight of a copolymer resin, 600 to 1,000 parts by weight of an organic solvent such as trichlorobenzene, dichlorobenzene, toluene, xylene, cyclohexane or tetrahydrofuran, And 10 to 25 parts by weight of vinyl silane were added to 1 to 20 parts by weight of metal-coated carbon nanotubes, 40 to 250 parts by weight of conductive carbon black, 200 to 200 parts by weight of polymeric resin, 1 to 10 parts by weight of an antioxidant, 1 to 5 parts by weight of a dispersant, 5 to 100 parts by weight of a metal oxide, and 1 to 10 parts by weight of a porous silica carrying an irradiated crosslinking agent. Controlled heating cable using polymeric semiconductive composition.

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