KR101482602B1

KR101482602B1 - A heating polymer manufacturing process, heating-yarn manufacturing process and that heating-yarn

Info

Publication number: KR101482602B1
Application number: KR1020140062445A
Authority: KR
Inventors: 조형진; 전영민; 전영준
Original assignee: 주식회사 에코원홀딩스
Priority date: 2014-05-23
Filing date: 2014-05-23
Publication date: 2015-01-14
Also published as: WO2015178569A1

Abstract

The present invention relates to a thermoplastic resin composition comprising a thermoplastic resin containing a thermoplastic rubber in which a physical property-compensating agent and an antioxidant are mixed, a conductive filler, an internal lubricant, and an external lubricant, mixing and stirring the thermoplastic resin, A method of producing a conductive / pyrogenic polymer for producing a heat generating yarn characterized by obtaining a resin that maintains a uniformly dispersed state, and a method of producing a conductive / heat generating polymer by a method in which a conductive / pyrogenic polymer is uniformly dispersed through an extruder And then the solidified pellets are melted by being fed into a shaping extruder and the conductive polymer which is melted and extruded from the mold extruder side is coated on the outer circumferential surface of the yarn supplied to the die side provided at the end of the shaping extruder, A method of manufacturing a heat generating yarn using a conductive / heat generating polymer, There is provided a heat generating yarn obtained by a method for producing a heat generating polymer and a method for producing a heat generating yarn,
The production of gas harmful to the human body and the environment can be suppressed in the production process, the conductivity of the product is uniform because there is no volatile dispersing medium, and there is no air gap phenomenon caused by volatilization. In the weaving process using the heat- It is possible to obtain a product having uniform conductivity, thereby improving not only the reliability of the product but also the physical properties and mass productivity of the resulting product, and the economic effect of remarkably reducing the production cost of the product The present invention also relates to a method for manufacturing a conductive / heat-generating polymer for manufacturing a heating yarn, a method for manufacturing a heating yarn using the same, and a heating yarn manufactured therefrom.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a conductive / heat-generating polymer for use in the production of a heating yarn, a method for manufacturing a heating yarn using the same, and a heating /

The present invention relates to the production of heat-generating yarns for use in heating elements used for bedding, fomentation and sauna facilities, various drying apparatuses, heating films and heating boards, heating apparatuses or thermal insulation garments, And a process for producing a heat generating yarn using the extruding apparatus and a method for manufacturing a heat generating yarn using the extruding apparatus, And to a heat generating yarn produced from the apparatus.

A large number of heating elements for use in facilities such as bedclothes, fomentation and sauna, various dryers or heating films, heating boards, heating devices,

As an example of such a heating element, a surface heating element may be prepared by coating an insulating coating on the surface of a current-carrying hot wire, or by coating a film of a conductive carbon and a thermoplastic or thermosetting resin dispersed in a solvent on the film, And the dried heat-treated yarn is applied to the weft or warp of the fiber.

Particularly, the heating element which is applied to the weft of the fiber is composed of a plane. Since the heating element is less likely to cause shearing due to the physical coupling between the heating wire and the metal wire for energization, the heating performance is excellent.

Generally, when a heat generating yarn is manufactured by an embodiment known to have excellent conductivity by using a liquid coating method like the above-described method, there is a problem that the thermal property is excellent but the physical properties and mass productivity are poor.

That is, an example of a method of manufacturing a heat-generating yarn using a conventional liquid-phase coating method will be described. A method of manufacturing a heat-generating yarn by passing through a yarn in a state in which a conductive material is dispersed in a solution of a polymer, .

And a method of coating the solution with a film of PET, PP, PETG, PE, NYLON, PBT or the like.

The film is adhered to a metal wire having a low resistance such as a copper wire and coated with a conductive coating solution or coated with a conductive solution and then electrically connected to the copper wire. In the course of conducting electricity through the copper wire, Or the conductive polymeric material has a difference in thermal linear expansion coefficient. The difference in the thermal linear expansion coefficient or the cracking phenomenon of the coating material due to the repeated impact at the time of use occurs, and a short circuit between the copper wire and the heating element is inevitably caused.

As described above, there is a problem that spark occurs due to a short circuit between the copper wire and the heating element, and the durability of the product is remarkably lowered.

In order to compensate for this, there is an attempt to lower the probability of short-circuiting by coating the copper wire with the Ag solution. In this case, the durability can be improved, but a short circuit between the copper wire and the heating element can not be avoided due to the difference in thermal linear expansion coefficient do.

It is also possible to dissolve a thermoplastic resin in an oligomer or solvent having a liquid form in the thermosetting stage and to conduct the conductive material such as conductive carbon, carbon nanotube (CNT), carbon fiber, silver nano, There is disclosed a method of improving conductivity by coating a solution on a yarn and passing holes of a predetermined size one or more times repeatedly through coating / drying.

There is a problem that the volatile solvent is dried in the process of drying the coated yarn when the heating yarn is manufactured through the above method and the environmental pollutant harmful to the human body is emitted.

In addition, it is necessary to install a drying line to achieve the drying process. In order to increase the mass productivity of the product, it is necessary to install a long drying line, which raises a problem of an increase in equipment cost, .

In order to solve the above problems, it is proposed to use a solvent having a higher volatility to shorten the drying line as one of the methods for reducing the drying line. In such a case, the viscosity of the solution There is a problem that the amount of solid content to be coated is changed to gradually change, and there is a problem that electric conductivity or calorific value is continuously changed, so that it is difficult to maintain a constant quality and the reliability of the product may be deteriorated.

In addition, there is a problem that voids are generated in the course of evaporation of the solvent, so that the strength of the coating for imparting conductivity is remarkably lowered, and the product is worn out during the weaving process, thereby diluting the value as a product.

In addition, CNT (carbon nanotube) may be added to the polypropylene to disperse the conductive polymer by extrusion kneading, and then the conductive polymer may be spun and spun to produce a conductive heating yarn. There are many limitations to follow.

Korean Patent Registration No. 10-0585504 Korean Patent Registration No. 10-1161102

SUMMARY OF THE INVENTION Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to solve the above-mentioned problems and to provide a method of manufacturing a heat- The present invention relates to a method for producing a conductive polymer for manufacturing a heat generating yarn, a method for manufacturing a heat generating yarn using the same, an apparatus therefor and a process for producing the same, which can improve tensile strength and mass productivity The object of the present invention is to provide such an excellent heating yarn.

According to an aspect of the present invention,

A thermoplastic rubber in which a physical property-improving agent composed of EPDM (Ethylene Propylene Terpolymers) and NBR (acrylonitrile-butadiene rubber) and a antioxidant composed of a primary antioxidant based on a phenolic antioxidant system and a primary antioxidant based on a phenolic antioxidant (Polypropylene), PE (polyethylene), PET (polyethylene terephthalate), PETG (polyethylene terephthalate glycol), ABS (acrylonitrile-butadiene-styrene copolymer) Nylon, PBT (polybutylene terephthalate), Teflon, silicone, urethane, PVC (polyvinyl chloride), SBS (styrene-butadiene-styrene block copolymer), MS-SAN (methyl methacrylate- Nitrile) -based thermoplastic resin and a thermoplastic resin selected from the group consisting of conductive carbon, conductive CF (carbon fiber), CNT (carbon nanotube), silver nano, copper nano, PTC and an external lubricant composed of Teflon wax (TEFLON), followed by kneading and stirring. Thereafter, the kneaded and agitated thermoplastic resin (B) To obtain a resin that maintains the resin uniformly dispersed through an extruder. A method for producing a conductive / heat-generating polymer for producing a heat yarn is disclosed.

The present invention also relates to a method for producing a thermoplastic resin composition, which comprises the steps of adding a conductive carbon and a thermosetting agent to a thermosetting resin of PRE-POLYMER type and extruding and dispersing the thermosetting resin through a first extruder at a temperature not hardening, And then subjecting the surface of the yarn passing through the dies provided in the secondary extruder to a coating treatment followed by a hot-air drying to obtain a heat generating yarn using the conductive / exothermic polymer .

In addition, the present invention provides a method for producing a pellet of the present invention, which comprises solidifying a conductive / pyrogenic polymer produced as described above in the form of pellets uniformly dispersed through an extruder, introducing the solidified pellet into a mold- And a conductive polymer which is melted and extruded from the side of the shaping extruder is coated on the outer circumferential surface of the yarn to be supplied, followed by hot air drying to obtain a heat generating yarn using the conductive / exothermic polymer.

In addition, the present invention discloses a method of manufacturing a heating yarn using the conductive / heat generating polymer, wherein the PTC (Positive Temperature Coefficient) is limited to barium metatitanate (BaTiO ₃ ).

In addition, the present invention includes a method for producing the conductive / pyrogenic polymer and a heating yarn manufactured in the method for manufacturing a heating yarn using the same.

The heat generating yarn disclosed by the conductive / exothermic polymer produced by the present invention and the method of manufacturing a heat generating yarn using the same can inhibit the generation of harmful gases to the human body and the environment during the manufacturing process thereof, So that there is no phenomenon of voids caused by volatilization, so that a phenomenon such as being broken during the weaving process using the heat-generating yarn according to the present invention is not generated, so that a product having uniform conductivity can be obtained, , The physical properties and the mass productivity of the product are excellent, and the economic effect of remarkably reducing the production cost of the product can also be expected.

Hereinafter, specific examples of the present invention will be described in detail by way of examples and comparative examples.

First, a method for producing a conductive / exothermic polymer should be disclosed in order to obtain a heating yarn as a final product of the present invention.

(Conduction / heat generation property Polymer Manufacturing method)

A conductive carbon, a conductive CF (carbon fiber), a carbon nanotube (CNT), a silver nano, a copper nano, a PTC (positive electrode), and a thermoplastic resin containing a thermoplastic rubber in which a physical property- (Teflon), which is a Teflon wax (Teflon) for the purpose of reducing shear force, is kneaded and agitated, and then the kneaded product is kneaded A resin that maintains the uniformly dispersed state of the thermoplastic resin in a stirred state through an extruder is obtained.

One of the conductive fillers, PTC (Positive Temperature Coefficient), is limited to barium metatitanate (BaTiO ₃ ).

On the other hand, the thermoplastic resin should be structurally fixed to the conductive filler.

Thermoplastic resins for this purpose include ABS (acrylonitrile-butadiene-styrene copolymer), HIPS (high-impact poly-styrene), PP (polypropylene), PE (polyethylene), PET (polyethylene terephthalate), PETG (polyethylene terephthalate Poly (methyl methacrylate), poly (ethylene glycol), nylon, PBT (polybutylene terephthalate), Teflon, silicone, urethane, PVC Lid-styrene-acrylonitrile) -based resin and extrusion-kneaded.

The thermoplastic resin is made to include a thermoplastic rubber.

Here, the thermoplastic resin formed by mixing the above-mentioned thermoplastic rubber with the above-mentioned kind is 1 to 20 wt%; 80 to 99 wt% of the entire thermoplastic resin mixture.

On the other hand, the conductive filler is added in an amount of 1 to 40 parts by weight, the internal lubricant for dispersing is 0.01 to 3 parts by weight, the amount of the internal lubricant for dispersing is 0.01 to 3 parts by weight based on 100 parts by weight of the thermoplastic resin mixture mixed in the liquid mixture, And 0.01 to 2 parts by weight of an external lubricant are mixed and kneaded / extruded to obtain a conductive / heat generating polymer.

In the meantime, the thermoplastic rubber mixed for the preparation of the conductive / exothermic polymer is mixed with a physical property-modifying agent and an antioxidant. The physical property-modifying agent is composed of EPDM (Ethylene Propylene Terpolymers) and NBR (acrylonitrile-butadiene rubber) The antioxidant is composed of a primary antioxidant of phenolic antioxidants and a secondary antioxidant of phosphite antioxidants.

As described above, the thermoplastic rubber and the thermoplastic resin contain 1 to 20 wt%; By weight based on 100 parts by weight of the whole thermoplastic resin mixture which is in a ratio of 80 to 99% by weight based on 100 parts by weight of the total amount of the conductive filler, 0.01 to 3 parts by weight of the internal lubricant for dispersion, And 0.01 to 2 parts by weight of the external lubricant for the external kneading agent. The kneaded mixture is mixed with a cross-linking agent suitable for the thermoplastic resin to form a solid component, and then the kneaded mixture is uniformly dispersed into pellets through an extruder.

The crosslinking agent is usually a known crosslinking agent.

In the present invention, the conductive / exothermic polymer obtained by using a thermoplastic resin is described. However, the present invention is not limited thereto. For example, a conductive / heat generating polymer having the same effect can be obtained by using a thermosetting resin.

That is, it can be obtained by adding a conductive carbon and a thermosetting agent to a thermosetting resin made of PRE-POLYMER type epoxy, melamine, phenol or the like having a low molecular weight.

(Conduction / heat generation property The polymer Used Fever Manufacturing method)

Using the conductive / exothermic polymer obtained by the above-mentioned method, first, a pellet as a solid component in a uniformly dispersed form is obtained through an extruder, and then the pellet is applied to a profile extruder and melt extruded at an appropriate temperature The liquid resin discharged through the mold extruder, that is, the conductive polymer in the present invention, is discharged onto the outer circumferential surface of the chamber separately supplied from the outside through the dies provided at the end of the mold extruder, Coating treatment is carried out to obtain a finished heat-treated yarn.

In the present invention, as described above, a thermally conductive yarn can be obtained by using a thermosetting resin as well as a thermoplastic resin as described above. For example, a PRE-POLYMER type thermosetting resin having a low molecular weight, The thermosetting resin liquid extruded and dispersed in the primary extruder is secondarily dispersed in a secondary extruder, and then the thermosetting resin liquid extruded and dispersed in the primary extruder is dispersed in the die And then heat-cured by hot air drying to obtain a heat-resistant yarn.

The yarn used in the present invention may be a material such as PET yarn, cotton yarn, and nylon yarn, and yarn added with conductivity, that is, a yarn-like material including carbon nanotube (CNT) for preventing electrification.

Thus, a conductive / thermolabile polymer is produced and then a heat-generating sheet is produced using the conductive / heat-generating polymer. As described above, the heat-generating sheet obtained by the above method can be used for bedding, It is possible to produce products by applying to a heating element or an area heating element which is used for a dryer, a drying machine, a heating film, a heating board, a heating device or a garment for thermal insulation.

Hereinafter, specific examples according to the production method of the present invention will be described.

Table 1 shows the composition ratios and the like according to each example and a comparative example which can be compared with them.

Kinds Example 1 Example 1-1 Examples 1-2 Comparative Example 1 Example 2 Example 2-1 Example 3 Example 4 Example 5 Example 6 Example 7 Example 7-1 Example 8 Example 9 Comparative Example 2 Suzy ABS 90 90 90 90 90 90 90 90 90 90 NBR 10 10 10 10 10 10 10 10 10 10 PA808 100 HIPS 80 SBS 20 PP 80 EPDM 20 10 PE 90 Filler Carbon 10 7 10 15 7 10 10 10 10 3 CNT 3 3 CF 5 2 CU One BaTiO ₃ 3 10 8 5 Lubricant EBA 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 TEFLON 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 1076 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 6260 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Cross-linking agent 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Average resistance value (k? / M) 12 15 17 15 8 14 10 19 11 10 15 14 18 13 10 Standard Deviation 0.3 0.4 0.6 1.02 0.35 0.5 0.28 0.42 0.5 0.45 0.2 0.35 0.8 0.11 1.03 Current Amp 40 ℃ 80 85 97 90 75 82 77 100 79 78 91 84 99 90 96 60 ° C 95 101 105 102 83 98 85 107 89 86 97 94 109 95 85 80 ℃ 100 101 107 110 92 101 95 112 98 99 102 99 113 100 99 100 ℃ 101 99 103 121 95 100 99 115 101 102 103 97 115 102 105

In the above table, the mixing ratio of each type of resin is wt%, and the ratio of the filler, the lubricant (which is referred to as an internal lubricant and the external lubricant) and the crosslinking agent is 100 wt% Means the weight per 100 parts by weight of the resin.

The above table is shown in the graph below.

( Example One)

First, 90 wt% of ABS and 10 wt% of NBR for improving impact resistance / chemical resistance are mixed and kneaded to form a matrix to obtain a conductive / exothermic polymer, and conducting conductive carbon, which can generate heat when energized, 10 parts by weight based on the total weight of NBR, 0.5 parts by weight of EBA (ethylbisamide) as an internal activator capable of improving dispersibility, 0.1 part by weight of Teflon wax as an external activator for improving workability, primary antioxidant 1076 0.3 parts by weight of 6260 (product name of Songwon Industrial Co., Ltd.) as a secondary antioxidant, and 0.2 parts by weight of dimethyrol phenol-based crosslinking agent were thoroughly mixed by a stirrer, and then extruded by using an extruder (twin extruder) At a temperature of about 230 < RTI ID = 0.0 > C, < / RTI >

Then, the conductive resin pellets prepared as described above were introduced into the conductive resin pellets by using a shaping extruder, and the conductive resin was fed through the dies designed to prevent the conductive resin from flowing back to the supply part where the yarn was fed. And the conductive resin was melted and supplied through a shape extruder having a temperature of 200 ° C to coat the periphery of the yarn, thereby obtaining a heat yarn.

The thickness of the product varies in accordance with the speed of the above-described drawing. In this embodiment, the thickness of the product is 0.6 mm.

Also, when the electrical resistance value was measured at a resistance value of 1 m, the resistance value was 12 KΩ / m, and 20 samples were taken every 500 m. When the uniformity of the electrical resistance value was measured using the sample, the standard deviation was 0.3.

The following equation was used to obtain the above standard deviation.

( Example For 1 Comparative Example One)

Comparative Example 1 of Example 1 was implemented as shown in Table 1.

Specifically, 0.5 part by weight of EBA (ethylbisamide) as an internal activator capable of improving dispersibility in Example 1, 0.1 part by weight of Teflon wax as an external activator for improving workability, 0.6 part by weight of an industrial product name SONGNOX 1076, 0.3 part by weight of a SONGNOX 6260 manufactured by Songwon Industrial Co., Ltd. as the secondary antioxidant, and 0.2 part by weight of a dimethyrol phenol based cross-linking agent. And the resistance value and the standard deviation were calculated by the same "Equation 1 ". The results are shown in Table 1.

( Example 1-1)

First, 90 wt% of ABS and 10 wt% of NBR for improving impact resistance / chemical resistance are mixed and kneaded to form a matrix to obtain a conductive / exothermic polymer, and conducting conductive carbon, which can generate heat when energized, 7 parts by weight based on the total weight of NBR, 3 parts by weight of PTC (Positive Temperature Coefficient) barium metatitanic acid (BaTiO ₃ ) based on the total weight of ABS and NBR, and EBA 0.1 part by weight of Teflon wax as an activator for improving workability, 0.6 part by weight of a primary antioxidant 1076 (product name of Songwon Industry Co., Ltd., Korea) and 6260 (a product of Songwon Industry Co., Ltd., Korea) ) And 0.2 parts by weight of dimethyrol phenol-based crosslinking agent were thoroughly mixed with a stirrer, and then pellets solidified with a workable conductive property at a cylinder temperature of about 230 DEG C were extruded using an extruder (twin extruder) Costs.

Also, when the electrical resistance value was measured at a resistance value of 1 m, the resistance value was 15 KΩ / m, and 20 samples were taken every 500 m. When the uniformity of the electrical resistance value was measured using the sample, the standard deviation was 0.4.

The equation for obtaining the standard deviation described above was used in the equation of the first embodiment.

( Example For 1-1 Comparative Example One)

Comparative Example 1 of Example 1-1 was implemented as shown in Table 1.

Specifically, 0.5 part by weight of EBA (ethylbisamide) as an internal activator capable of improving dispersibility in Example 1-1, 0.1 part by weight of Teflon wax as an external activator for improving workability, 0.6 part by weight of SONGNOX 1076, a product name of SONGNOX 1076, 0.3 part by weight of SONGNOX 6260 manufactured by Songwon Industrial Co., Ltd. as the second antioxidant, and 0.2 part by weight of dimethyrol phenol based crosslinking agent, And the resistance value and the standard deviation were obtained by the same "Equation 1 ". The results are shown in Table 1.

That is, in Example 1-1, conductive carbon, which is the conductive filler employed in Example 1, was added in an amount of 10 parts by weight based on the total weight of the ABS and the NBR, 7 parts by weight of the conductive carbon with respect to the total weight of the ABS and the NBR, And 3 parts by weight of barium metatitanate (BaTiO ₃ ) which is a positive temperature coefficient.

( Example 1-2)

First, to obtain a conductive / exothermic polymer, PTC (Positive Temperature Coefficient) capable of generating heat by mixing and kneading 90 wt% of ABS and 10 wt% of NBR for improving impact resistance / chemical resistance to form a matrix, 10 parts by weight of barium metatitanium oxide (BaTiO ₃ ) as a stabilizer for improving the dispersibility, 0.5 parts by weight of EBA (ethylbisamide) as an internal activator capable of improving dispersibility, , 0.1 part by weight of Teflon wax, 0.6 part by weight of a primary antioxidant 1076 (product name of Songwon Industrial Co., Ltd., Korea), 0.3 part by weight of 6260 (product name of Songwon Industrial Co., Ltd.) as a secondary antioxidant, and 0.2 part by weight of dimethylol phenol type crosslinking agent After mixing, an extruder (twin extruder) is used to make the processed pellets solid at a cylinder temperature of about 230 ° C.

Also, when the electrical resistance value was measured at a resistance value of 1 m, the resistance value was 17 KΩ / m, and 20 samples were taken every 500 m. When the uniformity of the electrical resistance value was measured using the sample, the standard deviation was 0.6.

( Example For 1-2 Comparative Example One)

Comparative Example 1 of Example 1-2 was implemented as shown in Table 1.

That is, 0.5 parts by weight of EBA (ethylbisamide) as an internal activator capable of improving dispersibility in Example 1-2, 0.1 part by weight of Teflon wax as an external activator for improving workability, 0.6 part by weight of SONGNOX 1076, a product name of SONGNOX 1076, 0.3 part by weight of SONGNOX 6260 manufactured by Songwon Industrial Co., Ltd. as the second antioxidant, and 0.2 part by weight of dimethyrol phenol based crosslinking agent, And the resistance value and the standard deviation were obtained by the same "Equation 1 ". The results are shown in Table 1.

That is, the conductive carbon used as the conductive filler employed in Example 1 is replaced with barium metatitanic acid (BaTiO ₃ ), which is a PTC (Positive Temperature Coefficient).

( Example 2)

In Example 2, the amount of conductive carbon was increased to 15 parts by weight in Example 1, and a heating yarn was produced under the same conditions. The resistance value and the standard deviation were calculated by the same "Equation 1".

( Example 2-1)

In Example 2-1, the amount of conductive carbon was adjusted to 7 parts by weight in Example 1, the amount of barium metatitanic acid (BaTiO ₃ ), which is PTC (Positive Temperature Coefficient), was increased to 8 parts by weight, And the resistance value and the standard deviation are obtained by the same "Equation 1 ". The results are shown in Table 1.

( Example 3 )

100 wt% of MS-SAN (manufactured by LG Chemical Co., Ltd .: methyl methacrylate-styrene-acrylonitrile, hereinafter referred to as PA808) was added instead of 90 wt% of ABS and 10 wt% of NBR in Example 1, % And 100% by weight, and the resistance value and the standard deviation of the produced heat-generating yarn were determined by the same "Equation 1 ". The results are shown in Table 1.

( Example 4)

In Example 1, instead of 90 wt% of ABS and 10 wt% of NBR, 80 wt% of HIPS and 20 wt% of SBS rubber (K-RESIN) were mixed to make 100 wt% , And a resistance value and a standard deviation of the produced heat-generating yarn were determined by the same "Equation 1", and the results are shown in Table 1.

( Example 5)

Instead of 90 wt% of ABS and 10 wt% of NBR in Example 1, 80 wt% of PP and 20 wt% of EPDM were mixed to make 100 wt%, and 100 wt parts of the mixed resin was used. And the resistance value and the standard deviation of the produced heat-generating yarn were determined by the same "Equation 1 ". The results are shown in Table 1.

( Example 6)

In Example 1, instead of 90 wt% of ABS and 10 wt% of NBR, 90 wt% of PE and 10 wt% of EPDM were mixed to make 100 wt%, and 100 wt. Parts of the mixed resin was used. The resistance value and the standard deviation of the heat-generating yarn were obtained by the same "Equation 1", and the results were as shown in Table 1.

( Example 7)

In Example 1, 90 wt.% Of ABS and 10 wt.% Of NBR were mixed to make 100 wt.%. The mixed resin was used in an amount of 100 wt. Parts, and CNT (carbon nanotube) was used instead of conductive carbon 10 wt. And the resistance value and the standard deviation of the heat-generating yarn were obtained by the same "Equation 1", and the results were as shown in Table 1.

( Example 7-1)

In Example 1, 90 wt.% Of ABS and 10 wt.% Of NBR were mixed to make 100 wt.%. The mixed resin was used in an amount of 100 wt. Parts, and CNT (carbon nanotube) was used instead of conductive carbon 10 wt. And 5 parts by weight of barium metatitanic acid (BaTiO ₃ ), which is a PTC (Positive Temperature Coefficient), were added to the mixture to prepare a heating yarn under the same conditions as in Example 1, The standard deviations were obtained by the same "Equation 1 ", and the results were as shown in Table 1.

( Example 8)

In Example 1, 90 wt.% Of ABS and 10 wt.% Of NBR were mixed to make 100 wt.%. The mixed resin was used in an amount of 100 parts by weight. Conductive CF (carbon fiber) was used instead of 10 wt. 5 parts by weight were added to prepare a heating yarn under the same conditions as in Example 1, and then the resistance value and the standard deviation of the produced heating yarn were calculated by the same "Equation 1".

( Example 9)

In Example 1, 90 wt.% Of ABS and 10 wt.% Of NBR were mixed to make 100 wt.%. The mixed resin was used in an amount of 100 parts by weight. In place of 10 wt. Parts of the conductive carbon in Example 1, 3 wt. , 2 parts by weight of conductive CF (carbon fiber) and 1 part by weight of copper nano were put into a heat generating yarn under the same conditions as in Example 1, and the resistance value and the standard deviation of the heat generating yarn were the same as those in Equation 1 The results are shown in Table 1.

( Example For 9 Comparative Example 2)

Unlike Example 9, the solution-deposited heat sinks distributed in the market were obtained, and sampling standard deviations of the same lengths were applied to the same "Equation 1". As a result, the average resistance values and standard deviations of the heat- I came with you.

Claims

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EPDM (Ethylene Propylene Terpolymers), NBR (acrylonitrile-butadiene rubber); (Acrylonitrile-butadiene-styrene copolymer), HIPS (high-polymer-polyurethane), a thermoplastic rubber in which a primary antioxidant based on phenolic antioxidants and an antioxidant composed of a secondary antioxidant based on phosphite antioxidants are mixed. Poly (ethylene terephthalate), PET (polyethylene terephthalate glycol), nylon, PBT (polybutylene terephthalate), Teflon, silicone, urethane, PVC (polyvinyl A thermoplastic resin selected from among SBS (styrene-butadiene-styrene block copolymer) and MS-SAN (methyl methacrylate-styrene-acrylonitrile) thermoplastic resin; A conductive filler selected from conductive carbon, conductive CF (carbon fiber), CNT (carbon nanotube), silver nano, copper nano, and PTC (Positive Temperature Coefficient); An internal lubricant consisting of EBA (ethyl bisamide); PREPOLYMER < / RTI > (PRE-POLYMER < (R) >) were mixed with an external lubricant composed of Teflon wax (TEFLON), and the resulting mixture was kneaded and stirred. The resulting thermoplastic resin in the kneaded and stirred state was dispersed through an extruder, Wherein the thermosetting resin is extruded and dispersed through a first extruder at a temperature at which the conductive carbon and the thermosetting agent are added to the thermosetting resin at a temperature at which the thermosetting resin is not hardened, and the thermosetting resin liquid extruded and dispersed in the first extruder is secondarily dispersed in the second extruder, Wherein the surface of the yarn passing through the dies provided in the secondary extruder is coated and then thermally cured by hot air drying to obtain a heat generating yarn using the conductive /
Wherein the PTC (Positive Temperature Coefficient) is limited to barium metatitanate (BaTiO ₃ ).

EPDM (Ethylene Propylene Terpolymers), NBR (acrylonitrile-butadiene rubber); (Acrylonitrile-butadiene-styrene copolymer), HIPS (high-polymer-polyurethane), a thermoplastic rubber in which a primary antioxidant based on phenolic antioxidants and an antioxidant composed of a secondary antioxidant based on phosphite antioxidants are mixed. Poly (ethylene terephthalate), PET (polyethylene terephthalate glycol), nylon, PBT (polybutylene terephthalate), Teflon, silicone, urethane, PVC (polyvinyl A thermoplastic resin selected from among SBS (styrene-butadiene-styrene block copolymer) and MS-SAN (methyl methacrylate-styrene-acrylonitrile) thermoplastic resin; A conductive filler selected from conductive carbon, conductive CF (carbon fiber), CNT (carbon nanotube), silver nano, copper nano, and PTC (Positive Temperature Coefficient); An internal lubricant consisting of EBA (ethyl bisamide); And an external lubricant composed of Teflon wax (TEFLON) is mixed and kneaded and stirred. Thereafter, the conductive / exothermic polymer which obtains a resin that maintains the uniformly dispersed state of the thermoplastic resin in the kneaded and stirred state through an extruder is fed through an extruder The solidified pellets are put into a mold extruder to be melted, and a conductive polymer which is melted and extruded from the side of the mold extruder, which is supplied to the die side provided at the end of the mold extruder, And then drying it by hot air to obtain a heating yarn using the conductive / heat generating polymer,
In order to form the matrix, 90 wt% of ABS and 10 wt% of NBR for improving impact resistance / chemical resistance were mixed and kneaded, and then barium metatitanic acid barium (BaTiO ₃ ), which is a positive temperature coefficient (PTC) 10 parts by weight based on the total weight of the ABS and NBR, 0.5 part by weight of EBA (ethylbisamide) as an internal activator capable of improving dispersibility, 0.1 part by weight of Teflon wax as an external activator for improving workability, 0.6 parts by weight of a polypropylene resin (trade name, available from Songwon Industrial Co., Ltd., Korea), 0.3 parts by weight of 6260 (a product name of Songwon Industrial Co., Ltd.) as a secondary antioxidant, and 0.2 parts by weight of dimethylol phenol type crosslinking agent were mixed thoroughly with a stirrer, The processed pellets solidified at about 230 DEG C were fed into a shaping extruder and fed / drawn to the feed site where the yarn was fed to have a thickness of 0.6 mm, Wherein the solidified pellet type conductive resin is melted and supplied through a shape extruder having a temperature of 0 占 폚 to be coated on the periphery of the yarn, thereby producing a heat generating yarn using the conductive / exothermic polymer.

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