WO2015167134A1 - Rubber heating element containing silver nanowire - Google Patents
Rubber heating element containing silver nanowire Download PDFInfo
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- WO2015167134A1 WO2015167134A1 PCT/KR2015/003208 KR2015003208W WO2015167134A1 WO 2015167134 A1 WO2015167134 A1 WO 2015167134A1 KR 2015003208 W KR2015003208 W KR 2015003208W WO 2015167134 A1 WO2015167134 A1 WO 2015167134A1
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- Prior art keywords
- heating element
- rubber
- rubber heating
- silver nanowires
- present
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 64
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000010438 heat treatment Methods 0.000 title claims abstract description 46
- 239000002042 Silver nanowire Substances 0.000 title claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 8
- -1 thiol compound Chemical class 0.000 claims description 7
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229920002379 silicone rubber Polymers 0.000 claims description 6
- 239000004945 silicone rubber Substances 0.000 claims description 6
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- VPIAKHNXCOTPAY-UHFFFAOYSA-N Heptane-1-thiol Chemical compound CCCCCCCS VPIAKHNXCOTPAY-UHFFFAOYSA-N 0.000 claims description 3
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229920006311 Urethane elastomer Polymers 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000003190 viscoelastic substance Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- WCZAXBXVDLKQGV-UHFFFAOYSA-N n,n-dimethyl-2-(7-oxobenzo[c]fluoren-5-yl)oxyethanamine oxide Chemical compound C12=CC=CC=C2C(OCC[N+](C)([O-])C)=CC2=C1C1=CC=CC=C1C2=O WCZAXBXVDLKQGV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/18—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor the conductor being embedded in an insulating material
Definitions
- the present invention relates to a rubber heating element containing silver nanowires. More specifically, the present invention relates to a rubber heating element comprising silver nanowires to which a lipophilic ligand is bound.
- the prior art related to the invention of the rubber heating element of the present invention is a rubber product sold by JSR Corporation as a product called JSR PCR Switch Grade.
- This product is a product in which well-known carbon black is uniformly dispersed in a rubbery material, which improves various physical properties of rubber.
- the electric resistance is too high, a very high voltage is required to generate heat by electric flow. It is hard to use it as a heating element.
- the present inventors uniformly disperse silver nanowires exhibiting lipophilic properties as filed by the inventors in Korean Patent Application No. 10-2014-0052995 among the silver nanowire products developed so far in a rubbery material
- the present invention can be made by noting that the rubber-like product having a much lower electric impedance than the product in which carbon black is dispersed in the rubber phase is suitable, and that the rubber having low electrical resistance is particularly suitable for use as a vehicle handle coating or seat heating element. It was completed.
- the basic object of the present invention is to provide a rubber heating element comprising silver nanowires.
- the C 6 -C 18 thiol compound covering the surface of the silver nanowire may be hexanethiol, heptanethiol, octanethiol or dodecanethiol.
- the silver nanowires may have a diameter of 20 nm to 200 nm and a length of 5 ⁇ m to 100 ⁇ m.
- the rubber may include a known natural or synthetic viscoelastic material such as SBS rubber, silicone rubber, nitrile rubber, SBR rubber, urethane rubber, urethane skin foam, and the like.
- the rubber may contain pores.
- the rubber may contain pores, the elasticity is improved, and therefore, the rubber is suitable for application to clothing, for example.
- Still another object of the present invention can be achieved by providing a vehicle seat made of a rubber heating element including silver nanowires.
- Silver nanowires included in the rubber heating element used in the vehicle seat of the present invention is a C 6 -C 18 alkyl amine which is a lipophilic ligand as a part of the polyvinylpyrrolidone in the silver nanowires coated with polyvinylpyrrolidone or Substituted with a C 6 -C 18 thiol compound.
- the surface modified silver nanowires are well dispersed in the organic material.
- the C 6 -C 18 alkyl amine covering the surface of the silver nanowire may be hexylamine, heptylamine, octylamine, dodecylamine or oleylamine.
- the silver nanowires may have a diameter of 20 nm to 200 nm and a length of 5 ⁇ m to 100 ⁇ m.
- the rubber may include a known natural or synthetic viscoelastic material such as SBS rubber, silicone rubber, nitrile rubber, SBR rubber, urethane rubber, urethane skin foam, and the like.
- the steering wheel for vehicles can also be manufactured using the rubber heating element of the present invention.
- garments can also be manufactured using the rubber heating element of the present invention.
- the rubber heating element preferably contains pores. This is because when the rubber heating element contains pores, the elasticity is improved.
- the rubber heating element according to the present invention contains silver nanowires, the rubber heating element does not require a high voltage as compared to the rubber heating element containing carbon black or carbon nanotubes, and thus is very suitable for application to seats or steering wheels of vehicles.
- Figure 2 is a micrograph of the silver nanowires synthesized in the embodiment of the present invention.
- Figure 3 shows the conductivity change according to the proportion of the polymer bound to the surface of the surface-modified silver nanowires of the present invention.
- FIG. 5 is a graph showing the temperature change according to the DC voltage according to the concentration of the surface-modified silver nanowires of the present invention.
- FIG. 6 is an infrared camera photograph showing a high temperature of a film having a high silver nanowire concentration when a 0.4V DC voltage is applied according to the concentration of the surface-modified silver nanowire.
- ethylen glycol 100 mL of ethylen glycol was placed in a 500 mL beaker and kept at 160 ° C. After 30 minutes, 30 mL of 0.147 M polyvinylpyrrolidone (PVP) solution was injected into the ethylene glycol. After 10 minutes, 800 ⁇ L of CuCl 2 solution (0.4 mM) serving as a seed was injected. After 10 minutes, 30 mL of silver precursor solution (AgNO 3 + ethylene glycol, 0.094 M) was injected using a syringe pump. The injection rate of the silver precursor solution was 20 ⁇ L / sec. After 1 hour 30 minutes, the reaction product solution was washed three times with acetone.
- PVP polyvinylpyrrolidone
- Silver nanowires of 50 nm in diameter and 10 ⁇ m in length were synthesized in the same manner as in Example 1, except that 800 ⁇ L of CuCl 2 solution (0.4 mM) was injected after 5 minutes. .
- Example 1 or Example 2 The silver nanowires synthesized in Example 1 or Example 2 were dispersed in a 0.01 M nitrosonium tetrafluoroborate (NOBF 4 ) solution dissolved in dimethylformamide (DMF) at a concentration of 5 mg / mL. The same amount of hexane was added and stirred, and then hexanoic acid corresponding to 1/5 of the volume of the hexane was added and shaken. Then, the same amount of hexyl amine was added thereto and maintained for 1 hour while shaking. The reaction product was washed twice with ethanol and then dispersed in toluene.
- NOBF 4 nitrosonium tetrafluoroborate
- DMF dimethylformamide
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a rubber heating element containing silver nanowires. More specifically, the present invention relates to a rubber heating element containing silver nanowires to which lipophilic ligands are bonded.
Description
본 발명은 은 나노와이어가 함유된 고무 발열체에 관한 것이다. 보다 상세하게는, 본 발명은 친유성 리간드가 결합된 은 나노와이어를 포함하는 고무 발열체에 대한 것이다.The present invention relates to a rubber heating element containing silver nanowires. More specifically, the present invention relates to a rubber heating element comprising silver nanowires to which a lipophilic ligand is bound.
본 발명의 고무 발열체 발명과 관련된 선행기술로는 일본합성고무주식회사(JSR Corporation)가 JSR PCR Switch Grade라는 상품으로 시판중인 고무제품이다. 이 제품에는 공지의 카본 블랙을 고무상 물질에 균일하게 분산시킨 제품으로서 고무의 여러가지 물성을 향상시키고는 있지만 전기 저항이 너무 커서 전기 흐름에 의한 발열을 위해서는 매우 높은 전압이 요구되기 때문에 자동차 내부 전원을 사용하여 발열체로 사용하기에 무리가 있다.The prior art related to the invention of the rubber heating element of the present invention is a rubber product sold by JSR Corporation as a product called JSR PCR Switch Grade. This product is a product in which well-known carbon black is uniformly dispersed in a rubbery material, which improves various physical properties of rubber. However, since the electric resistance is too high, a very high voltage is required to generate heat by electric flow. It is hard to use it as a heating element.
또한, 독일의 바커사(WACKER)가 ELASTOSIL R PLUS 573/50이라는 상품명으로 시판중인 고무제품 역시 카본 블랙을 균일하게 분산시킨 제품으로서 상기의 JSR사의 제품처럼 전기 전도도가 너무 낮아서 발열체로 사용하기 위해서는 매우 높은 전압이 가해져야 한다는 문제점이 있다.In addition, the rubber products sold under the brand name ELASTOSIL R PLUS 573/50 by WACKER of Germany are also products that uniformly disperse carbon black. There is a problem that a high voltage must be applied.
따라서 당업계에는 여러가지 고무 제품이 개발되어 있지만 자동차 핸들 피복용 또는 시트용 고무상 발열체로 사용하기에 적합한 소재는 아직까지 개발되지 아니하였다.Therefore, various rubber products have been developed in the art, but a material suitable for use as a rubber heating element for car handle coating or seat has not been developed yet.
이에 본 발명자들은 현재까지 개발된 은 나노 와이어 제품들중 본 발명자들이 대한민국 특허출원 제10-2014-0052995호로 출원한 친유성 특성을 나타내는 은 나노와이어를 고무상 물질에 균일하게 분산시켜서 카본 나노튜브나 카본 블랙을 고무상에 분산시킨 제품보다 전기 임피던스가 훨씬 낮은 고무상 제품을 만들 수 있고, 이러한 전기 저항이 낮은 고무를 자동차 핸들 피복이나 시트 발열체로 사용하기가 특히 적합하다는 사실에 주목하여 본 발명을 완성하기에 이르렀다.Therefore, the present inventors uniformly disperse silver nanowires exhibiting lipophilic properties as filed by the inventors in Korean Patent Application No. 10-2014-0052995 among the silver nanowire products developed so far in a rubbery material, The present invention can be made by noting that the rubber-like product having a much lower electric impedance than the product in which carbon black is dispersed in the rubber phase is suitable, and that the rubber having low electrical resistance is particularly suitable for use as a vehicle handle coating or seat heating element. It was completed.
본 발명의 기본적인 목적은 은 나노와이어를 포함하는 고무 발열체를 제공하는 것이다.The basic object of the present invention is to provide a rubber heating element comprising silver nanowires.
본 발명의 또 다른 목적은 은 나노와이어를 포함하는 고무 발열체로 제작된 차량용 시트, 차량용 운전대 또는 의복 등을 제공하는 것이다.Still another object of the present invention is to provide a vehicle seat, a vehicle steering wheel, or a garment made of a rubber heating element including silver nanowires.
전술한 본 발명의 기본적인 목적은 은 나노와이어를 포함하는 고무 발열체를 제공함으로써 달성될 수 있다.The basic object of the present invention described above can be achieved by providing a rubber heating element comprising silver nanowires.
본 발명의 고무 발열체에 전압을 인가함으로써 발열 기능을 발휘하게 된다. 특히, 본 발명의 고무 발열체는 높은 전압을 요하지 아니하기 때문에, 차량용 시트나 운전대에 적용하기에 적합하다.The heat generating function is exerted by applying a voltage to the rubber heating element of the present invention. In particular, since the rubber heating element of the present invention does not require a high voltage, it is suitable for application to a vehicle seat or a steering wheel.
본 발명의 고무 발열체에 포함되는 은 나노와이어는 폴리비닐피롤리돈으로 피복된 은 나노와이어에서 상기 폴리비닐피롤리돈의 일부분을 친유성 리간드인 C6-C18알킬 아민 또는 C6-C18 티올 화합물로 치환한 것이다. 이렇게 표면개질된 은 나노와이어는 유기계 물질에 잘 분산된다.Silver nanowires included in the rubber heating element of the present invention is a C 6 -C 18 alkyl amine or C 6 -C 18 lipophilic ligand to a part of the polyvinylpyrrolidone in the silver nanowires coated with polyvinylpyrrolidone It is substituted by the thiol compound. The surface modified silver nanowires are well dispersed in the organic material.
상기 은 나노와이어의 표면을 피복하는 상기 C6-C18알킬 아민은 헥실아민, 헵틸아민, 옥틸아민, 도데실아민 또는 올레일아민일 수 있다.The C 6 -C 18 alkyl amine covering the surface of the silver nanowire may be hexylamine, heptylamine, octylamine, dodecylamine or oleylamine.
또한, 상기 은 나노와이어의 표면을 피복하는 상기 C6-C18 티올 화합물은 헥산티올, 헵탄티올, 옥탄티올 또는 도데칸티올일 수 있다.In addition, the C 6 -C 18 thiol compound covering the surface of the silver nanowire may be hexanethiol, heptanethiol, octanethiol or dodecanethiol.
상기 은 나노와이어의 직경은 20 nm 내지 200 nm이고, 길이는 5 μm 내지 100μm일 수 있다.The silver nanowires may have a diameter of 20 nm to 200 nm and a length of 5 μm to 100 μm.
본 발명의 고무 발열체에서 상기 고무는 SBS 고무, 실리콘 고무, 니트릴 고무, SBR 고무, 우레탄 고무, 우레탄 스킨 폼 등 공지된 천연 또는 합성의 점탄성 물질이 포함될 수 있다.In the rubber heating element of the present invention, the rubber may include a known natural or synthetic viscoelastic material such as SBS rubber, silicone rubber, nitrile rubber, SBR rubber, urethane rubber, urethane skin foam, and the like.
더욱이, 상기 고무는 기공을 함유할 수도 있다. 상기 고무가 기공을 함유하는 경우에는 신축성이 향상되기 때문에, 예를 들면, 의복에 적용하기에 적합하다.Moreover, the rubber may contain pores. When the rubber contains pores, the elasticity is improved, and therefore, the rubber is suitable for application to clothing, for example.
전술한 본 발명의 또 다른 목적은 은 나노와이어를 포함하는 고무 발열체로 제작된 차량용 시트를 제공함으로써 달성될 수 있다.Still another object of the present invention can be achieved by providing a vehicle seat made of a rubber heating element including silver nanowires.
본 발명의 차량용 시트에 사용되는 고무 발열체에 포함되는 은 나노와이어는 폴리비닐피롤리돈으로 피복된 은 나노와이어에서 상기 폴리비닐피롤리돈의 일부분을 친유성 리간드인 C6-C18알킬 아민 또는 C6-C18 티올 화합물로 치환한 것이다. 이렇게 표면개질된 은 나노와이어는 유기계 물질에 잘 분산된다.Silver nanowires included in the rubber heating element used in the vehicle seat of the present invention is a C 6 -C 18 alkyl amine which is a lipophilic ligand as a part of the polyvinylpyrrolidone in the silver nanowires coated with polyvinylpyrrolidone or Substituted with a C 6 -C 18 thiol compound. The surface modified silver nanowires are well dispersed in the organic material.
상기 은 나노와이어의 표면을 피복하는 상기 C6-C18알킬 아민은 헥실아민, 헵틸아민, 옥틸아민, 도데실아민 또는 올레일아민일 수 있다.The C 6 -C 18 alkyl amine covering the surface of the silver nanowire may be hexylamine, heptylamine, octylamine, dodecylamine or oleylamine.
또한, 상기 은 나노와이어의 표면을 피복하는 상기 C6-C18 티올 화합물은 헥산티올, 헵탄티올, 옥탄티올 또는 도데칸티올일 수 있다.In addition, the C 6 -C 18 thiol compound covering the surface of the silver nanowire may be hexanethiol, heptanethiol, octanethiol or dodecanethiol.
상기 은 나노와이어의 직경은 20 nm 내지 200 nm이고, 길이는 5 μm 내지 100μm일 수 있다.The silver nanowires may have a diameter of 20 nm to 200 nm and a length of 5 μm to 100 μm.
본 발명의 차량용 시트에 사용되는 고무 발열체에서 상기 고무는 SBS 고무, 실리콘 고무, 니트릴 고무, SBR 고무, 우레탄 고무, 우레탄 스킨 폼 등 공지된 천연 또는 합성의 점탄성 물질이 포함될 수 있다.In the rubber heating element used in the vehicle seat of the present invention, the rubber may include a known natural or synthetic viscoelastic material such as SBS rubber, silicone rubber, nitrile rubber, SBR rubber, urethane rubber, urethane skin foam, and the like.
더욱이, 본 발명의 고무 발열체를 사용하여 차량용 운전대를 제조할 수도 있다. Moreover, the steering wheel for vehicles can also be manufactured using the rubber heating element of the present invention.
또한, 본 발명의 고무 발열체를 사용하여 의복을 제조할 수도 있다. 이 경우에는 상기 고무 발열체가 기공을 함유하는 것이 바람직하다. 상기 고무 발열체가 기공을 함유하는 경우에는 신축성이 향상되기 때문이다.Moreover, garments can also be manufactured using the rubber heating element of the present invention. In this case, the rubber heating element preferably contains pores. This is because when the rubber heating element contains pores, the elasticity is improved.
본 발명에 따른 고무 발열체는 은 나노와이어를 함유하기 때문에, 카본 블랙이나 탄소 나노튜브를 함유하는 고무 발열체와 대비하여, 높은 전압을 요하지 아니하기 때문에 차량의 시트나 운전대 등에 적용하기에 매우 적합하다.Since the rubber heating element according to the present invention contains silver nanowires, the rubber heating element does not require a high voltage as compared to the rubber heating element containing carbon black or carbon nanotubes, and thus is very suitable for application to seats or steering wheels of vehicles.
또한, 본 발명의 고무 발열체에 기공을 함유시키면 의복의 제작에도 응용할 수 있다.In addition, when the rubber heating element of the present invention contains pores, it can be applied to the production of clothing.
도 1은 본 발명의 하나의 실시 태양에 따른 표면개질된 은 나노와이어의 합성 과정을 보여 준다.1 shows a process for synthesizing surface modified silver nanowires according to one embodiment of the present invention.
도 2는 본 발명의 실시예에서 합성한 은 나노와이어에 대한 현미경 사진이다.Figure 2 is a micrograph of the silver nanowires synthesized in the embodiment of the present invention.
도 3은 본 발명의 표면개질된 은 나노와이어어의 표면에 결합되어 있는 고분자의 비율에 따른 전도도 변화를 보여 준다.Figure 3 shows the conductivity change according to the proportion of the polymer bound to the surface of the surface-modified silver nanowires of the present invention.
도 4는 본 발명의 실시예에 따라 리간드 치환을 통한 고분자와의 분산 균일도 증가를 비교한 결과이다.4 is a result of comparing the dispersion uniformity increase with the polymer through ligand substitution according to an embodiment of the present invention.
도 5는 본 발명의 표면개질된 은 나노와이어의 농도에 따른 직류전압별 온도변화를 나타내는 그래프이다.5 is a graph showing the temperature change according to the DC voltage according to the concentration of the surface-modified silver nanowires of the present invention.
도 6은 본 발명은 표면개질된 은 나노와이어의 농도에 따라 0.4V 직류전압을 가했을 때 높은 은나노와이어 농도를 가진 필름이 높은 온도를 보이는 적외선카메라 사진이다.6 is an infrared camera photograph showing a high temperature of a film having a high silver nanowire concentration when a 0.4V DC voltage is applied according to the concentration of the surface-modified silver nanowire.
이하, 다음의 실시예 또는 도면을 들어 본 발명을 보다 구체적으로 설명하고자 한다. 그러나 다음의 실시예 또는 도면에 대한 설명은 본 발명의 구체적인 실시 태양을 특정하여 설명하고자 하는 것일 뿐이며, 본 발명의 권리 범위를 이들에 기재된 내용으로 한정하거나 제한해석하고자 의도하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples or drawings. However, the following description of the embodiments or drawings is only intended to specifically describe the specific embodiments of the present invention, it is not intended to limit or limit the scope of the present invention to the contents described therein.
실시예 1. 직경 100 nm 및 길이 30 μm의 은 나노와이어의 합성Example 1 Synthesis of Silver Nanowires 100 nm in Diameter and 30 μm in Length
100 mL의 에틸린 글리콜을 500 mL 비커에 넣고 160℃로 유지시켰다. 30분 후, 상기 에틸렌글리콜에 30 mL의 0.147 M 폴리비닐피롤리돈(PVP) 용액을 주입하였다. 10분 후, 응집핵(seed) 역할을 하는 CuCl2 용액(0.4 mM) 800 μL를 주입하였다. 10분 후에, 30 mL의 은 전구체 용액(AgNO3 + 에틸렌글리콜, 0.094 M)을 주사기 펌프를 이용하여 주입하였다. 상기 은 전구체 용액의 주입 속도는 20 μL/sec이었다. 1시간 30분 후, 상기 반응 결과물 용액을 아세톤으로 3번 세척하였다.100 mL of ethylen glycol was placed in a 500 mL beaker and kept at 160 ° C. After 30 minutes, 30 mL of 0.147 M polyvinylpyrrolidone (PVP) solution was injected into the ethylene glycol. After 10 minutes, 800 μL of CuCl 2 solution (0.4 mM) serving as a seed was injected. After 10 minutes, 30 mL of silver precursor solution (AgNO 3 + ethylene glycol, 0.094 M) was injected using a syringe pump. The injection rate of the silver precursor solution was 20 μL / sec. After 1 hour 30 minutes, the reaction product solution was washed three times with acetone.
실시예 2. 직경 50 nm 및 길이 10 μm의 은 나노와이어의 합성Example 2 Synthesis of Silver Nanowires of 50 nm Diameter and 10 μm Length
CuCl2 용액(0.4 mM) 800 μL를 주입한 후 5분 후에 은 전구체 용액을 주입한 것을 제외하고는, 실시예 1의 방법과 동일한 방법으로 직경 50 nm 및 길이 10 μm의 은 나노와이어를 합성하였다.Silver nanowires of 50 nm in diameter and 10 μm in length were synthesized in the same manner as in Example 1, except that 800 μL of CuCl 2 solution (0.4 mM) was injected after 5 minutes. .
실시예 3. 표면개질된 은 나노와이어의 합성Example 3 Synthesis of Surface Modified Silver Nanowires
실시예 1 또는 실시예 2에서 합성한 은 나노와이어를, 다이메틸폼아마이드(DMF)에 녹인 0.01 M 니트로소니움 테트라플루오르보레이트(NOBF4) 용액에 5 mg/mL의 농도로 분산시켰다. 이와 동량의 헥산을 첨가하고 교반한 후 상기 헥산의 부피의 1/5에 해당하는 헥사노익산을 첨가하고 흔든 후, 같은 양의 헥실 아민을 넣고 흔들면서 1시간 동안 유지하였다. 반응 결과물을 에탄올을 사용하여 2회 세척한 후 톨루엔에 분산시켰다.The silver nanowires synthesized in Example 1 or Example 2 were dispersed in a 0.01 M nitrosonium tetrafluoroborate (NOBF 4 ) solution dissolved in dimethylformamide (DMF) at a concentration of 5 mg / mL. The same amount of hexane was added and stirred, and then hexanoic acid corresponding to 1/5 of the volume of the hexane was added and shaken. Then, the same amount of hexyl amine was added thereto and maintained for 1 hour while shaking. The reaction product was washed twice with ethanol and then dispersed in toluene.
실시예 4. 표면개질된 은 나노와이어의 합성Example 4 Synthesis of Surface Modified Silver Nanowires
헥사노익산 대신에 아세트산을 사용한 것을 제외하고, 실시예 3의 방법과 동일한 방법으로 표면개질된 은 나노와이어를 합성하였다.Surface-modified silver nanowires were synthesized in the same manner as in Example 3, except that acetic acid was used instead of hexanoic acid.
실시예 5. 고무 발열체 제조Example 5. Rubber Heating Element
실시예 4 또는 실시예 5에서 제조한 표면개질된 은 나노와이어와 SBS고무나 실리콘 고무 등이 분산된 용매를 약 10초간 bath type 초음파처리기에서 섞어주고 등과 유리 몰드에 컴파운딩하고 톨루엔을 날려 고무 발열체를 제조하였다. 컴파운드된 고무 발열체 양끝을 전도성 풀을 이용하여 구리선에 연결시킨다.The surface-modified silver nanowires prepared in Example 4 or Example 5 and a solvent in which SBS rubber or silicone rubber is dispersed are mixed in a bath-type sonicator for about 10 seconds, compounded in a back glass mold, and blown toluene into a rubber heating element. Was prepared. Both ends of the compound rubber heating element are connected to the copper wire using a conductive paste.
실시예 6. 전기를 이용한 발열Example 6 Heat Generation Using Electricity
실시예 5에서 만든 발열체의 구리선 양 끝에 0.4V, 0.5V, 0.6V, 0.8V, 1.0V, 2.0V 등의 직류전압을 가한다.DC voltages, such as 0.4V, 0.5V, 0.6V, 0.8V, 1.0V, 2.0V, are applied to both ends of the copper wire of the heating element made in Example 5.
실시예 7. 자동차 시트에 적용되는 고무발열체Example 7 Rubber Heating Element Applied to Automobile Seat
실시예 4에서 제조한 표면개질된 은 나노와이어를 실시예 5와 같이 자동차 시트의 크기에 맞게 SBS고무, 실리콘 고무등과 컴파운딩 하여 고무 발열체를 제조하였다. 자동차 시트에 부착 후 전압을 가하면 전원이 커지기 전 20~25도 였던 것이 전원이 켜진 후 30~37도로 상승하였으며, 전원이 계속 연결된 상태에서는 온도가 계속 유지되며, 반복적인 꺼짐과 켜짐에도 일정하게 온도가 상승하락을 반복한다.The surface-modified silver nanowires prepared in Example 4 were compounded with SBS rubber, silicone rubber, etc. to fit the size of the car seat as in Example 5 to prepare a rubber heating element. After attaching to the car seat and applying voltage, the temperature rose from 20 to 25 degrees before the power was turned on and rose to 30 to 37 degrees after the power was turned on. Repeats rising and falling.
실시예 8. 의복에 적용되는 고무발열체Example 8 Rubber Heating Element Applied to Garment
실시예 4에서 제조한 표면개질된 은 나노와이어를 실시예 5와 같이 옷의 크기에 맞게 SBS고무, 실리콘 고무등과 컴파운딩 하여 고무 발열체를 제조하였다. 옷의 안감에 부착 후 전압을 가하면 전원이 커지기 전 20~25도 였던 것이 전원이 켜진 후 30~37도로 상승하였으며, 전원이 계속 연결된 상태에서는 온도가 계속 유지되며, 반복적인 꺼짐과 켜짐에도 일정하게 온도가 상승하락을 반복한다.The surface-modified silver nanowires prepared in Example 4 were compounded with SBS rubber, silicone rubber, etc. according to the size of clothes as in Example 5 to prepare a rubber heating element. After attaching to the lining of clothes, the voltage increased from 20 to 25 degrees before the power was turned on, and rose to 30 to 37 degrees after the power was turned on.The temperature is maintained continuously while the power is still connected. The temperature rises and falls repeatedly.
Claims (12)
- 은 나노와이어를 포함하는 고무 발열체.Rubber heating element containing silver nanowires.
- 제1항에 있어서, 상기 은 나노와이어의 표면에 친유성 리간드가 결합되어 있는 것임을 특징으로 하는 고무 발열체.The rubber heating element according to claim 1, wherein a lipophilic ligand is bound to a surface of the silver nanowire.
- 제1항에 있어서, 상기 고무가 SBS 고무 또는 실리콘 고무인 것임을 특징으로 하는 고무 발열체.The rubber heating element according to claim 1, wherein the rubber is SBS rubber or silicone rubber.
- 제1항에 있어서, 상기 은 나노와이어의 직경이 20 nm 내지 200 nm이고, 길이가 5 μm 내지 100μm인 것임을 특징으로 하는 은 나노와이어.The silver nanowire of claim 1, wherein the silver nanowire has a diameter of 20 nm to 200 nm and a length of 5 μm to 100 μm.
- 제2항에 있어서, 상기 친유성 리간드가 C6-C18알킬 아민인 것임을 특징으로 하는 고무 발열체.The rubber heating element according to claim 2, wherein the lipophilic ligand is a C 6 -C 18 alkyl amine.
- 제5항에 있어서, 상기 C6-C18알킬 아민이 헥실아민, 헵틸아민, 옥틸아민, 도데실아민 및 올레일아민으로 이루어진 군으로부터 선택되는 것임을 특징으로 하는 고무 발열체.The rubber heating element according to claim 5, wherein the C 6 -C 18 alkyl amine is selected from the group consisting of hexylamine, heptylamine, octylamine, dodecylamine and oleylamine.
- 제2항에 있어서, 상기 친유성 리간드가 C6-C18 티올 화합물인 것임을 특징으로 하는 고무 발열체.The rubber heating element according to claim 2, wherein the lipophilic ligand is a C 6 -C 18 thiol compound.
- 제7항에 있어서,상기 C6-C18 티올 화합물이 헥산티올, 헵탄티올, 옥탄티올 및 도데칸티올로 이루어진 군으로부터 선택되는 것임을 특징으로 하는 고무 발열체.The rubber heating element according to claim 7, wherein the C 6 -C 18 thiol compound is selected from the group consisting of hexanethiol, heptanethiol, octanethiol and dodecanethiol.
- 제1항에 있어서, 상기 고무가 기공을 함유하는 것임을 특징으로 하는 고무 발열체.The rubber heating element according to claim 1, wherein the rubber contains pores.
- 은 나노와이어를 포함하는 고무 발열체로 제작된 차량용 시트.A vehicle seat made of a rubber heating element containing silver nanowires.
- 은 나노와이어를 포함하는 고무 발열체로 제작된 차량용 운전대.Vehicle steering wheel made of a rubber heating element containing silver nanowires.
- 은 나노와이어를 포함하는 고무 발열체로 제작된 의복.A garment made of a rubber heating element containing silver nanowires.
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| KR1020150038616A KR101751862B1 (en) | 2014-04-30 | 2015-03-20 | Elastomeric Heating Element Comprising Silver Nanowire |
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| KR20120129297A (en) * | 2011-05-19 | 2012-11-28 | 삼성전자주식회사 | Heating composite, and heating apparatus and fusing apparatus including the same |
| KR20140021470A (en) * | 2012-08-12 | 2014-02-20 | 주식회사 태건솔루텍 | Electrically conductive silicone rubber heater and the manufacturing method of the same |
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