200800793 •九、發明說明·· 【發明所屬之技術領域】 本發明涉及-種電熱材料及—種加熱裝置，尤盆涉及 、-種以高分子材料爲基底之奈米柔性電熱材料，以及使用 声奈米柔性電熱材料之加熱裝置。 【先前技術】 電熱材料係指藉由自纟電阻能夠把電能轉化爲熱能之 材料。通常電熱材料係由金屬（例如鎢絲、鉬片等等）或 ⑩半導體（如石夕碳棒等）製成。由於金屬具有良好文電導参， 電阻通常很小，因此可以產生很高功率和溫度。 但同時由金屬或半導體組成之電熱材料也具有明顯之 缺點，如這些材料在常溫下不可隨意變形；且電阻通常很 低，功率過大，發熱量過高，不適合在常溫範圍使用。金 屬對人體之親和性差，甚至某些金屬如銅會對人體産生危 害。因此這些電熱材料不適合使用於與人體緊密接觸之加 _熱保溫裝置中，如電熱毯、電熱墊等。 由此研發出在咼分子材料基底中添加導電顆粒如金屬 物’石墨粉等之電熱材料，此種電熱材料具有柔性，且其 電阻可相對較高，可用於低溫加熱，但由於要達到合適之 導電率，其中之導電顆粒之含量需要較高，因此造成基底 材料強度下降。 有#於此’有必要提供一種具有柔性可隨意變形、機 械強度1% ’人體親和性高，可在低溫範圍下使用之電熱材 料〇 6 200800793 •【發明内容】 以下將以實施例說明一種奈米柔性電熱材料，及一種 包括該奈米柔性電熱材料之加熱裝置。 •該奈米柔性電熱材料包括基底及分散在該基底中之複 數奈米碳管，該奈米碳管於基底内形成導電網路，該基底 爲柔性高分子材料。 種加熱裝置’其包括奈米柔性電熱材料、兩根導線 _及開關，該兩根導線用於將該奈米柔性電熱材料接入電 源，該開關安裝在該兩根導線中任意一根上，該奈米柔性 電熱材料包括柔性高分子材料組成之基底及分散在該基底 中複數奈米碳管，該奈米碳管在基底内形成導電網路。 由於柔性高分子基底材料之採用，該奈米柔性電熱材 料y隨意彎曲且具有良好之人體親和性；根據奈米碳管之 含量不同，其電阻可調，奈米碳管含量低時，其電阻可調丨 至較高值，從而其適合用於低溫加熱；且由於奈米碳管之 _加入且在柔性高分子基底材料内部形成可導電之網路，除 了可用於導電，使該奈米柔性電熱材科整個材料上均勻發 熱外’還可提高該奈米柔性電熱材料之強度。 【實施方式】 參閱圖1，第一實施例之奈米柔性電熱材料1包括柔性 高分子基底材料10及分散在柔性高分子基底材料1〇中'之 複數奈米碳管12。奈米碳管12互相搭接而在柔性高分子臬 底材料10中形成導電網路，從而奈米柔性電熱材::可二 7 200800793 導電，通電以後便可發熱。 柔性高分子基底材料10可選自石夕橡膠彈性體 :二環氧樹脂其中之一或其组合物。奈米碳管12可爲多： =管或單壁綱管。其長度可爲_微米，優選二 ;;里百:分比含量爲整個電熱材料之〇1%〜4%。奈米碳这 之含量不㈣電熱材料之電阻率亦不同。 ' 中太二:二參見圖2’其爲奈米柔性電熱材料1 中不未石反官含置與電阻率之關係曲線。可以看出， 性電熱材料1隨奈米碳管重量辦不/、一 降，含景Ε + 里白刀比含里增加電阻率下 ::為0.4糾，電阻率近似爲1〇歐姆米㈣ 二…小於1%時電阻率下降之速度較快，隨後下降速产 =近當奈米碳管含量達到4%時，其電a率下降至較低： 个近似爲0.1歐姆·米（Ω·πι)。 材料2柔性電熱材料1中還可添加有各種添加劑以提高 :物，化學性能’，抗氧化劑、阻燃劑。抗氧化劑品 :二爷見的如虱’虱-二召萘基-對苯二胺。阻燃劑可選 人：石蠟、氯化脂環烴、四氯鄰笨二甲酸酐、磷酸酯、 =碟酸酯、函化鱗、磷多元醇及南代酸肝等，阻燃劑之 3里可爲1%〜10% 〇 本實施例之奈米柔性電熱材料i具有以下特點： 形上由於採用柔性回分子基底材料，因此其可以任意變 且高分子材料比金屬或半導體更具人體親和性。 一由於加人了奈米碳官’其機械勤性得到加強，強度 曰向’不易損壞’且同時具有合適之導熱性，可迅速將内 8 200800793 部產生之熱量傳導出來。 3、其電阻可在一定範圍内可調，且整個電熱材料面上 同時均勻發熱，溫度可控制在較低水平，如低於·。C，因 -此本實施例之奈米柔性電熱材料不會因過熱産生危害。對 於用於給人體進行保溫之電熱材料其溫度可控制之更低， 例如在361到鐵之間。例如，一塊3〇χ3〇χ〇仍⑽之這 種奈米柔性電熱材料，奈米碳管含量爲2.5%，用36V之電 _源沿膜面導電，消耗之功率不到i瓦特。 基於以上特性，可將本實施例之奈米柔性電熱材料i 應用於各種需求低溫加熱之領域’如汽車電熱座椅、電熱 地毯、理療電熱帶、減肥腰帶、保溫服等。 本實施例之奈米柔性電熱材料i可以採用如下方法 備： 〜步驟1，提供一種分散均勻之預聚物溶液或預聚物單體 /谷液。預聚物材料經進一步聚合後可得到柔性高分子基底 料，例如矽橡膠彈性體、聚氨脂、環氧樹脂之預聚物: 單體或者其組合。以聚氨酯爲例，將聚氨酯之預聚物用溶 劑如乙酸乙酯等溶解稀釋，降低其粘度，然後用超聲波清 洗一段時間，得到分散均勻之聚氨酯預聚物溶液。 步驟2,將奈米碳管加入上述溶液，並且用超聲波分散 一段時間。其中，奈米碳管之重量百分比含量爲〇1〜4%。 超聲波分散之作用係使奈米碳管能夠在聚氨酯預聚物溶液 中初步分散。奈米碳管可爲多壁奈米碳管或者單壁奈米碳 管，奈米碳管之製備方法可採用先前技術中之化學氣相沈 9 200800793 積法、電錢電法、雷射燒㈣等。奈米碳管 1〜10微米。 两 另外，由於奈米碳管易於聚集和纏結，可以進一步藉 .由超聲波破碎儀破碎—段時間，將聚鮮㈣之奈米碳^ *分開，然後再藉由超聲波分散-段時間，從而能夠使奈米 石反管分散比較均勻。 步驟3,加入引發劑，使預聚物溶液或預聚物單體溶液 發生反應或發生交聯而聚合並固化成所需求之形狀，以便 於實際應用。引發劑之選擇根據預聚物材料之不同而不 同對於♦氨知其可爲去離子水。適當之超聲清洗一段時 間，收集溶液中生成之膏狀物質，即得到複合材料之預加 工物。 優選的，固化前可在兩端埋上電極311、312，則可得 以如圖3所示之奈米柔性電熱材料，電極311、312之材料 可採用高導電率之金屬如銅或鋁。 參閱圖4,本實施例之電加熱裝置包括奈米柔性電熱材 料41、導線421、422及開關43，奈米柔性電熱材料41兩 端埋有兩電極411、412，導線421、422分別用於將電極 411、412接入電源44。開關43可設置在導線421及422 當中任意一根上。 結上所述，本發明確已符合發明專利之要件，遂依法 提出專利申請。惟，以上所述者僅為本發明之較佳實施方 式，自不能以此限制本案之申請專利範圍。舉凡熟悉本案 技藝之人士援依本發明之精神所作之等效修飾或變化，皆 200800793 •應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 •圖1係^一實施例之奈米柔性電熱材料剖面示意圖。 •圖2係第一實施例之奈米柔性電熱材料中奈米碳管含 量-電阻率關係曲線。 圖3係第二實施例之奈米柔性電熱材料之剖面示意圖 圖4係加熱裝置第一實施例之示意圖。 i 【主要元件符號說明】 基底 10 奈米碳管 12 電極 311，312，411，412 導線 421，422 開關 43 電源44 11200800793 • Nine, invention descriptions··Technical field of the invention The present invention relates to an electrothermal material and a heating device, and relates to a nano-material flexible electrothermal material based on a polymer material, and the use of sound A heating device for nano flexible electrothermal materials. [Prior Art] Electrothermal material refers to a material that can convert electrical energy into thermal energy by self-twisting resistance. Usually, the electrothermal material is made of metal (e.g., tungsten wire, molybdenum sheet, etc.) or 10 semiconductor (e.g., Shixi carbon rod, etc.). Since metals have good electrical conductance, the resistance is usually small, so high power and temperature can be produced. However, electrothermal materials composed of metals or semiconductors also have obvious disadvantages, such as the fact that these materials are not freely deformable at normal temperature; and the resistance is usually low, the power is too large, and the amount of heat is too high, which is not suitable for use in a normal temperature range. Metals have poor affinity for the human body, and even certain metals such as copper can be harmful to the human body. Therefore, these electrothermal materials are not suitable for use in a heat-insulating device that is in close contact with the human body, such as an electric blanket, a heating pad, and the like. Therefore, an electrothermal material in which a conductive particle such as a metal material 'graphite powder or the like is added to a base of a ruthenium molecular material is developed, and the electrothermal material has flexibility, and the electric resistance thereof can be relatively high, and can be used for low-temperature heating, but since it is suitable The electrical conductivity, in which the content of the conductive particles is required to be high, causes a decrease in the strength of the base material. It is necessary to provide a thermoelectric material which is flexible and freely deformable, has a mechanical strength of 1% and has high human affinity and can be used in a low temperature range. 20086 200800793 • [Description of the Invention] A meter of flexible electrothermal material, and a heating device comprising the nano flexible electrothermal material. • The nano-flexible electrocaloric material comprises a substrate and a plurality of carbon nanotubes dispersed in the substrate, the carbon nanotubes forming a conductive network in the substrate, the substrate being a flexible polymer material. Heating device comprising: a nano-flexible electrothermal material, two wires _ and a switch for connecting the nano-flexible electrothermal material to a power source, the switch being mounted on any one of the two wires, the switch The nano flexible electrothermal material comprises a substrate composed of a flexible polymer material and a plurality of carbon nanotubes dispersed in the substrate, the carbon nanotubes forming a conductive network in the substrate. Due to the adoption of the flexible polymer base material, the nano flexible electrothermal material y is bent at will and has good human affinity; according to the content of the carbon nanotubes, the electric resistance is adjustable, and when the carbon nanotube content is low, the electric resistance is low. Adjustable to a higher value, so that it is suitable for low temperature heating; and because the carbon nanotubes are added and form an electrically conductive network inside the flexible polymer substrate material, in addition to being used for electrical conduction, the nanometer is flexible The electric heating material can uniformly heat the whole material to improve the strength of the nano flexible electric heating material. [Embodiment] Referring to Fig. 1, a nano-flexible electrothermal material 1 of the first embodiment comprises a flexible polymer base material 10 and a plurality of carbon nanotubes 12 dispersed in a flexible polymer base material. The carbon nanotubes 12 are overlapped with each other to form a conductive network in the flexible polymer base material 10, so that the nanometer flexible electric heating material: can be electrically conductive, and can be heated after being energized. The flexible polymer base material 10 may be selected from the group consisting of a Lithium rubber elastomer: one of the two epoxy resins or a combination thereof. The carbon nanotubes 12 can be many: = tube or single wall tube. The length may be _micron, preferably two;; rib: the fractional content is 〇 1% to 4% of the entire electrothermal material. The content of nanocarbon is not the same. (4) The electrical resistivity of the electrothermal material is also different. 'Zhong Tai 2: 2 See Figure 2' which is the relationship between the resistivity and the resistivity of the nano-flexible electrothermal material 1. It can be seen that the electric heating material 1 does not have a weight with the weight of the carbon nanotubes, including the Jingjing + the white knife increases the resistivity under the ratio:: 0.4, the resistivity is approximately 1 〇 ohm meters (4) Second, when the temperature is less than 1%, the resistivity decreases rapidly, and then the yield decreases. When the carbon nanotube content reaches 4%, the electric a rate drops to a lower value: approximately 0.1 ohm·m (Ω· Πι). Various additives may be added to the material 2 flexible electrothermal material 1 to improve: chemical properties, antioxidants, and flame retardants. Antioxidant products: such as 虱 虱 二 二 二 二 萘 naphthyl-p-phenylenediamine. Flame retardant optional: paraffin, chlorinated alicyclic hydrocarbon, tetrachloro-o-dicarboxylic acid anhydride, phosphate ester, = dish acid ester, functionalized scale, phosphorus polyol and southern acid liver, etc. The nano flexible electrothermal material i of the present embodiment has the following characteristics: The shape is arbitrarily changed due to the use of a flexible molecular backing material, and the polymer material is more human-friendly than metal or semiconductor. Sex. As a result of the addition of the Nano Carbon official's mechanical flexibility, the strength of the 不易 to 'not easy to damage' and at the same time the appropriate thermal conductivity, can quickly transfer the heat generated by the inner 8 200800793. 3. The resistance can be adjusted within a certain range, and the entire surface of the electrothermal material is uniformly heated at the same time, and the temperature can be controlled at a low level, such as below. C, because the nano flexible electrothermal material of this embodiment does not cause damage due to overheating. The electrothermal material used to insulate the human body can be controlled to a lower temperature, for example between 361 and iron. For example, a piece of 3 〇χ 3 〇χ〇 still (10) of this nano-flexible electrothermal material, the carbon nanotube content of 2.5%, with a 36V electric source along the membrane surface conduction, the power consumption is less than i watts. Based on the above characteristics, the nanometer flexible electrothermal material i of the present embodiment can be applied to various fields of low temperature heating such as automobile electric heating seats, electric heating carpets, physiotherapy electric heating belts, slimming belts, and thermal insulation clothes. The nano flexible electrothermal material i of the present embodiment can be prepared by the following method: ~ Step 1, providing a uniformly dispersed prepolymer solution or prepolymer monomer / gluten solution. The prepolymer material is further polymerized to obtain a flexible polymeric substrate such as a ruthenium rubber elastomer, a polyurethane, an epoxy resin prepolymer: a monomer or a combination thereof. Taking polyurethane as an example, the prepolymer of polyurethane is dissolved and diluted with a solvent such as ethyl acetate to reduce its viscosity, and then ultrasonically washed for a while to obtain a uniformly dispersed polyurethane prepolymer solution. In step 2, a carbon nanotube was added to the above solution and dispersed by ultrasonic waves for a while. Wherein, the content of the carbon nanotubes is 〇1 to 4% by weight. The effect of ultrasonic dispersion is to enable the carbon nanotubes to be initially dispersed in the polyurethane prepolymer solution. The carbon nanotubes can be multi-walled carbon nanotubes or single-walled carbon nanotubes. The preparation method of the carbon nanotubes can be carried out by using the chemical vapor deposition method of the prior art 9 200800793, electric charge method, and laser burning. (4) Wait. Nano carbon tube 1~10 microns. In addition, since the carbon nanotubes are easy to aggregate and entangle, it can be further broken by a sonicator for a period of time, and the nano-carbons of the fresh (four) carbon are separated, and then dispersed by ultrasonic waves for a period of time. It can make the nano stone reverse tube dispersion more uniform. In step 3, an initiator is added to cause the prepolymer solution or the prepolymer monomer solution to react or crosslink to polymerize and solidify into a desired shape for practical use. The choice of initiator can vary from prepolymer material to deionized water. Proper ultrasonic cleaning is used for a period of time to collect the creamy substance formed in the solution to obtain a pre-processed composite. Preferably, the electrodes 311, 312 can be buried at both ends before curing, so that a nano-flexible electrothermal material as shown in Fig. 3 can be obtained, and the materials of the electrodes 311, 312 can be made of a metal having high conductivity such as copper or aluminum. Referring to FIG. 4, the electric heating device of the embodiment includes a nano-flexible electrothermal material 41, wires 421 and 422, and a switch 43. Two electrodes 411 and 412 are buried at both ends of the nano-flexible electrothermal material 41, and wires 421 and 422 are respectively used for The electrodes 411, 412 are connected to the power source 44. The switch 43 can be disposed on any of the wires 421 and 422. In conclusion, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the present invention are intended to be included in the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a nanometer flexible electrothermal material according to an embodiment. • Fig. 2 is a graph showing the relationship between the carbon nanotube content and the resistivity in the nano-flexible electrothermal material of the first embodiment. Figure 3 is a schematic cross-sectional view showing a nano-flexible electrothermal material of the second embodiment. Figure 4 is a schematic view showing a first embodiment of the heating device. i [Description of main component symbols] Substrate 10 Carbon nanotubes 12 Electrode 311, 312, 411, 412 Conductor 421, 422 Switch 43 Power supply 44 11