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TWI671453B - 石墨烯導電織物之製造方法 - Google Patents

石墨烯導電織物之製造方法 Download PDF

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Publication number
TWI671453B
TWI671453B TW107132555A TW107132555A TWI671453B TW I671453 B TWI671453 B TW I671453B TW 107132555 A TW107132555 A TW 107132555A TW 107132555 A TW107132555 A TW 107132555A TW I671453 B TWI671453 B TW I671453B
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Taiwan
Prior art keywords
graphene
graphene conductive
layer
solvent
hot
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TW107132555A
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TW202010898A (zh
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吳以舜
謝承佑
陳靜茹
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安炬科技股份有限公司
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Priority to TW107132555A priority Critical patent/TWI671453B/zh
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Publication of TWI671453B publication Critical patent/TWI671453B/zh
Priority to US16/569,131 priority patent/US11313073B2/en
Publication of TW202010898A publication Critical patent/TW202010898A/zh

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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
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Abstract

一種石墨烯導電織物，包含：纖維組織、熱熔膠層、石墨烯導電層以及疏水性保護層。纖維組織具有空隙。熱熔膠層附著於纖維組織上。石墨烯導電層附著於熱熔膠層且未滲入纖維組織的空隙，包含：至少一可固化樹脂及分散於可固化樹脂之奈米石墨烯片。疏水性保護層設置於石墨烯導電層上。本發明復提供石墨烯導電織物之製造方法。

Description

石墨烯導電織物之製造方法
本發明係關於一種具有導電功能的織物，特別係關於一種石墨烯導電織物及其製造方法。
隨著經濟成長與生活水平的提升，人們對紡織品除了過去基本的保暖與美觀的需求之外，強調機能性的紡織品逐漸受到歡迎，且隨著健康意識的抬頭，希望能進一步藉由隨身的穿戴裝置來主動監測生理狀態，以提早因應生理異常狀況。因此，現有技術開發出智慧衣、恆溫衣等機能織物，智慧衣是將可隨時監控生理狀態的生理監測感應器嵌入織物，恆溫衣是將可調節身體溫度的電力裝置嵌入織物。
機能衣要達到前述功能，首要條件是使織物具有導電能力，以傳遞生理監測系統的電子訊號，或在通電時能夠發熱保暖。現有技術如美國專利案US 6957525B2揭露使用金屬線與傳統紗線以梭織、針織或不織方式一體加工形成的導電布料。雖然金屬線具有優異的導電性能，但是機械性能較為脆弱，在穿著時容易因為衣物之間或衣物與身體之間的摩擦，或是汗水的侵蝕而造成金屬線斷裂，且人體長時間接觸金屬是否對健康有影響也存有疑慮。
為改善金屬線的問題，美國專利案US 7767298B2揭露製備複合導電紗的方法，係添加碳黑於聚酯形成複合導電紗。然而，受限於碳黑在聚酯中的添加量，此方法製得的複合導電紗的電阻值在6次方以上，遠高於智慧衣所需求的2次方以下電阻值，僅能作為抗靜電用途，無法作為智慧衣使用。
為改善前述將導電物質一同抽紗導致紗線導電度不足的問題，美國專利案US 20130090030A1揭露使用奈米碳管製造導電纖維的技術，包含：將奈米碳管分散於懸浮液中並加入可固化樹脂，並將懸浮液塗布於纖維表面形成導電纖維，所得導電纖維的最低電阻值可達到6次方以下；美國專利案US 20180080171A1揭露使用金屬粒子製造導電纖維的技術，包含：將金屬粒子塗布於紗線表面形成導電纖維，所得導電纖維的導電度可達到1次方甚至更低。塗布導電物質的製造方法雖可有效提升纖維的導電度，但是耐水洗次數是紡織品應用評估上非常重要的測試，商業用紡織品的耐水洗次數最低標準為25次，雖然塗佈金屬粒子可讓織物的電阻值降到0.9歐姆，前述專利揭露的導電纖維水洗4次之後，電阻值即已經大幅上升到73.8歐姆，明顯無法通過水洗測試。
因此，如何使織物達到機能衣所需的導電度，符合業界水洗測試的標準，且無影響健康疑慮，即為發展本發明的主要目的。
為達上述目的，本發明提供一種石墨烯導電織物，包含：纖維組織、熱熔膠層、石墨烯導電層以及疏水保護層。纖維組織具有空隙。熱熔膠層附著於纖維組織。石墨烯導電層附著於熱熔膠層且未滲入空隙，包含：至少一可固化樹脂及分散於可固化樹脂之奈米石墨烯片。疏水性保護層設置於石墨烯導電層上。
為達上述目的，本發明復提供一種石墨烯導電織物之製造方法，包含：混合第一溶劑、第二溶劑及奈米石墨烯片，以機械力分散奈米石墨烯片形成石墨烯懸浮溶液，其中第一溶劑之沸點不大於80 oC，且第二溶劑之沸點不小於120 oC；將至少一可固化樹脂加入石墨烯懸浮溶液，以機械力分散奈米石墨烯片及可固化樹脂形成石墨烯樹脂溶液；塗佈石墨烯樹脂溶液於疏水性保護層上，固化石墨烯樹脂溶液形成附著於疏水性保護層上之石墨烯導電層；塗佈或印刷熱熔膠於石墨烯導電層上；平貼纖維組織層於熱熔膠層，熱壓纖維組織使熱熔膠層分別接著石墨烯導電層及纖維組織，從而形成石墨烯導電織物。
纖維組織包含大量的空隙，直接塗佈導電物質於纖維組織表面會使得導電物質滲入纖維組織的空隙，以致導電度下降，本發明製作具有高導電性的石墨烯樹脂，將石墨烯樹脂塗佈於疏水性保護層，固化石墨烯樹脂形成石墨烯導電層，以熱熔膠覆蓋石墨烯導電層，藉由熱熔膠接著石墨烯導電層及纖維組織，可防止石墨烯導電層滲入纖維組織空隙而保持其導電度，疏水性保護層可保護石墨烯導電層免於因水洗而剝離或脫落。本發明之石墨烯導電織物之製造方法相容於現有紡織製程，可有效降低製造成本，深具產業應用性。
以下配合圖式及元件符號對本發明的實施方式做更詳細的說明，俾使本技術領域具有通常知識者在研讀本說明書後能據以實施。值得注意的是，為清楚展現本發明的主要特點，各圖僅以示意方式顯示主要元件之間的相對關係或運作方式，並非依據實際大小而繪製，所以圖中主要元件的厚度、大小、形狀、排列、配置等等都只是參考，並非用以限定本發明的範圍。
石墨烯的電阻率比銅或銀更低，是目前世界上最薄、最堅硬且電阻率最小的材料。因此，本發明利用石墨烯的高導電性，結合可固化樹脂及奈米石墨烯片形成之石墨烯導電層，可作為生理感測器或通電發熱元件的導電線路，有效增加機能衣的設計彈性且大幅降低製造成本。
第1圖為本發明之石墨烯恆溫織物的剖面示意圖。如第1圖所示，石墨烯導電織物1包含：纖維組織10、熱熔膠層11、石墨烯導電層12以及疏水性保護層13。纖維組織10具有第一組織面101、第二組織面102及位於第一組織面101與第二組織面102之間的空隙103。熱熔膠層11附著於纖維組織第一組織面101。石墨烯導電層12附著於熱熔膠層11上且不滲入纖維組織10的空隙103，包含：至少一可固化樹脂121及分散於可固化樹脂121之奈米石墨烯片122。疏水性保護層13設置於石墨烯導電層12上，可保護石墨烯導電層12於水洗時不剝離或脫落。
纖維組織10例如是但不限於尼龍、聚酯、壓克力等纖維的針織布或平織布，其厚度通常介於50-500微米。若石墨烯導電織物作為衣著材料，第一組織面101是朝向外界環境的外側面；第二組織面102是人體皮膚的內側面；空隙103的孔徑大小大致上反比於單位面積的纖維數量（即組織密度）及織法，組織密度越高，則空隙103的孔徑越小。熱熔膠層11的厚度不大於石墨烯導電層12，例如是1-20微米，熱熔膠層11的材料係選自乙烯 - 醋酸乙烯共聚物及聚醯胺之任一者。石墨烯導電層12的厚度不大於纖維組織10的厚度，例如是10-50微米，可固化樹脂121選自聚氨酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯、矽酮樹脂及其組合；奈米石墨烯片122呈片狀，具有0.005-0.05 g/cm 3的堆積密度、0.68-10 nm的厚度、及1-100 μm的平面橫向尺寸。疏水性保護層13的厚度介於10-100微米，可選自聚氨酯及矽酮樹脂任一者。
值得說明的是，可固化樹脂通常為電絕緣物質，為了提高含石墨烯的附著性，現有石墨烯導電塗層所含的可固化樹脂的比例高於50 wt%，然而此石墨烯導電塗層的實測體積電阻值介於10 5-10 12ohm*cm，僅能達到抗靜電效果。本發明的石墨烯導電織物1係以熱熔膠層11與疏水性保護層13夾合石墨烯導電層12形成類三明治的結構，可大幅提高石墨烯導電層12與纖維組織10的附著性及保持石墨烯導電網絡的完整性，藉此石墨烯導電層12所含奈米石墨烯片122的比例可提高至60-95 wt%，使石墨烯導電層12的體積電阻降至10 -2-10 3ohm*cm，符合機能衣所需的導電度。
由於奈米石墨烯片122具有0.005-0.05 g/cm 3的堆積密度，其體積遠大於可固化樹脂121，較高比例的奈米石墨烯片122與較低比例的可固化樹脂121不易均勻混合，可添加碳黑或石墨，降低奈米石墨烯片122的填充體積，以均勻分散奈米石墨烯片122形成石墨烯導電網絡。
本發明提供石墨烯導電織物的製造方法，包含: 製備石墨烯懸浮溶液步驟，混合溶劑及奈米石墨烯片，以機械力分散奈米石墨烯片形成石墨烯懸浮溶液，其中溶劑包含第一溶劑及第二溶劑，第一溶劑之沸點不大於80 oC，且第二溶劑之沸點不小於120 oC；製備石墨烯樹脂步驟，將至少一可固化樹脂加入石墨烯懸浮溶液，以機械力分散奈米石墨烯片及可固化樹脂形成石墨烯樹脂溶液；形成石墨烯導電層步驟，塗佈或印刷石墨烯樹脂溶液於疏水性保護層，加熱去除溶劑，固化石墨烯樹脂形成石墨烯導電層；形成熱熔膠層步驟，塗佈熱熔膠於石墨烯導電層表面；貼合步驟，平貼纖維組織於熱熔膠層，熱壓纖維組織使熱熔膠層分別接著石墨烯導電層及纖維組織，從而形成石墨烯導電織物。
於製備石墨烯懸浮溶液步驟，由於石墨烯的表面張力約為45-50 mJ/m 2，若石墨烯與溶劑表面張力差異過大，奈米石墨烯片容易在溶劑中團聚沉澱，不易分散；選擇表面張力接近的溶劑有助於石墨烯的分散，但沸點過高的溶劑不易去除；因此組合沸點較低的第一溶劑與表面張力接近石墨烯的第二溶劑作為製備石墨烯懸浮溶液的溶劑。由於第二溶劑的表面張力與石墨烯相匹配，一般分散設備的機械力即可有效將奈米石墨烯片分散於溶劑，且溶劑易於去除。分散設備的機械力例如是超音波、均質攪拌、球磨或高壓剪切。
第一溶劑可選自丙酮、丁酮、乙酸乙酯、乙酸丁酯及其組合，第二溶劑可選自N,N-二甲基乙醯胺(N,N-Dimethylacetamide)、二甲基亞碸(dimethyl sulfoxide)、二甲基甲醯胺(Dimethyformamide)、二甲基乙醯胺(Dimethylacetamide)及其組合。
於製備石墨烯樹脂步驟，由於第一溶劑及第二溶劑的組合可保持奈米石墨烯片的分散狀態，即使可固化樹脂的黏度較高，使用前述分散設備的機械力足以將奈米石墨烯片均勻分散在石墨烯樹脂溶液。可固化樹脂可選自聚氨酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯、矽酮樹脂及其組合。
於形成石墨烯導電層步驟，以刮刀塗佈或網版印刷石墨烯樹脂溶液，使石墨烯樹脂溶液完全或部分覆蓋疏水性保護層的表面；加熱去除溶劑，形成完全或部分覆蓋疏水性保護層的石墨烯導電層。為便於形成石墨烯導電層及後續加工步驟，可使用形成於離形膜上的疏水性保護層。若石墨烯導電織物有特定導電線路的設計，亦可使用雷射圖案化石墨烯導電層。
於形成熱熔膠層步驟，以刮刀塗布或網版印刷方式在石墨烯導電層上覆蓋熱熔膠層，熱熔膠層的材料選自聚氨酯及矽酮樹脂任一者。
於貼合步驟，平貼纖維組織於熱熔膠層，熱壓纖維組織使熱熔膠層分別接著於石墨烯導電層及纖維組織，即可形成石墨烯導電織物；於疏水性保護層形成於離型膜的實施方式，移除離型膜露出疏水性保護層，即可進行石墨烯導電織物的後續加工製程，例如：染色、裁切、連接電子元件等。
為進一步顯示本發明之石墨烯導電織物的具體功效使相關技術領域的通常知識者能更加清楚了解，下文中將以示範性實例詳細說明本發明的實施方式。
實驗示例1 丁酮作為第一溶劑，二甲基乙醯胺作為第二溶劑，以8：2的體積比例混合丁酮及二甲基乙醯胺，形成混合溶劑。以10：90的重量比將奈米石墨烯片加入混合溶劑，以均質機將奈米石墨烯片均勻分散於混合溶劑，形成石墨烯懸浮溶液，奈米石墨烯片佔石墨烯懸浮溶液10 wt%。將300克固含量為20 wt%的聚氨酯樹脂加入1000克的石墨烯懸浮溶液，以均質機分散奈米石墨烯片與聚氨酯樹脂，形成石墨烯樹脂溶液。以網版印刷石墨烯樹脂溶液於疏水性矽膠層上，加熱至100 oC去除石墨烯樹脂溶液中的混合溶劑，得到固化之石墨烯導電層 ; 塗佈材質為乙烯/醋酸乙烯酯共聚物的熱熔膠層於石墨烯導電層之表面；平貼纖維組織於熱熔膠層，加熱至95 oC並壓合使熱熔膠層分別接著於石墨烯導電層及纖維組織，形成石墨烯導電織物。疏水性矽膠層可有效保護石墨烯導電層，提高石墨烯導電織物的耐水洗次數。
實驗示例2 丁酮作為第一溶劑，二甲基亞碸作為第二溶劑，以9：1的體積比例混 合丁酮及二甲基亞碸，形成混合溶劑。以15：85的重量比將奈米石墨烯片加入混合溶劑，以均質機將奈米石墨烯片均勻分散於混合溶劑，形成石墨烯懸浮溶液，奈米石墨烯片佔石墨烯懸浮溶液15 wt%。將100克固含量為35 wt%的聚氨酯樹脂加入400克的石墨烯懸浮溶液，以公自轉攪拌機於自轉轉速1000 rpm及公轉轉速400 rpm分散奈米石墨烯片與聚氨酯樹脂，形成石墨烯樹脂溶液。以網版印刷石墨烯樹脂溶液於疏水性矽膠層上，加熱至100 oC去除石墨烯樹脂溶液中的混合溶劑，得到固化之石墨烯導電層 ; 塗佈材質為熱塑性聚氨酯的熱熔膠層於石墨烯導電層之表面；平貼纖維組織於熱熔膠層，加熱至105 oC並壓合使熱熔膠層分別接著於石墨烯導電層及纖維組織，形成石墨烯導電織物。
實驗示例3 丁酮作為第一溶劑，二甲基亞碸作為第二溶劑，以9：1的體積比例混合丁酮及二甲基亞碸，形成混合溶劑。以15：85的重量比將奈米石墨烯片加入混合溶劑，以均質機將奈米石墨烯片均勻分散於混合溶劑，形成石墨烯懸浮溶液，奈米石墨烯片佔石墨烯懸浮溶液15 wt%。將100克固含量為35 wt%的聚氨酯樹脂加入400克的石墨烯懸浮溶液，以公自轉攪拌機於自轉轉速1000 rpm及公轉轉速400 rpm分散奈米石墨烯片與聚氨酯樹脂，形成石墨烯樹脂溶液。以刮刀將石墨烯樹脂溶液塗佈於可剝離聚酯膜的一側表面，加熱至100 oC去除石墨烯樹脂溶液中的混合溶劑，形成石墨烯導電層，塗佈材質為聚氨酯的熱熔膠層於石墨烯導電層之表面；平貼纖維組織於熱熔膠層，加熱至90 oC並壓合使熱熔膠層分別接著於石墨烯導電層及纖維組織，移除聚酯離型膜，形成表面電阻為2*10 -2ohm/sq的石墨烯導電織物。
實驗示例4 丁酮作為第一溶劑，異氟爾酮作為第二溶劑，以1：1的體積比例混合丁酮及異氟爾酮，形成混合溶劑。以均質機均勻混合40克的奈米石墨烯片、40克碳黑及400克的混合溶劑，形成奈米石墨烯片懸浮溶液；以公轉自轉攪拌機於自轉轉速1000 rpm及公轉轉速混合400 rpm 1200克的石墨烯懸浮溶液與230克固含量為55 wt%的聚酯樹酯，形成黏度大於20,000 cps的石墨烯樹脂溶液；將石墨烯樹脂溶液放入分散裝置，第一次分散加工設定20 bar的壓力及150 μm的狹縫，石墨烯樹脂溶液於1 L/min的流速通過狹縫，第二次分散加工設定 24bar的壓力及30 μm的狹縫，石墨烯樹脂溶液於2.0 L/min的流速通過狹縫，將奈米石墨烯片及碳黑均勻分散在聚酯樹酯；以200目的網版將石墨烯樹脂溶液印刷於聚酯離型膜上之疏水性聚氨酯層，加熱至130 oC去除石墨烯樹脂溶液中的混合溶劑，得到固化之石墨烯導電層 ; 塗佈材質為聚氨酯的熱熔膠層於石墨烯導電層之表面；平貼纖維組織於熱熔膠層，加熱至90 oC並壓合使熱熔膠層分別接著於石墨烯導電層及纖維組織，移除聚酯離型膜露出疏水性聚氨酯層，形成石墨烯導電織物。本實驗示例的石墨烯導電織物的表面電阻為150 ohm/sq，可符合生理感測器導電線路的要求。
實驗示例5 正丁醇作為第一溶劑，異氟爾酮作為第二溶劑，以8：2的體積比例混合正丁醇及異氟爾酮，形成混合溶劑。以均質機均勻混合120克的奈米石墨烯片、130克碳黑及680克的混合溶劑，形成奈米石墨烯片懸浮溶液；以研磨機轉速2000 rpm轉速混合930克的石墨烯懸浮溶液與300克固含量為55 wt%的醇酸樹酯，將奈米石墨烯片及碳黑均勻分散在醇酸樹酯；以刮刀將石墨烯樹脂溶液印刷於聚酯離型膜上之疏水性聚氨酯層，加熱至100 oC去除石墨烯樹脂溶液中的混合溶劑，得到固化之石墨烯導電層 ; 塗佈材質為聚氨酯的熱熔膠層於石墨烯導電層之表面；平貼纖維組織於熱熔膠層，加熱至90 oC並壓合使熱熔膠層分別接著於石墨烯導電層及纖維組織，移除聚酯離型膜露出疏水性聚氨酯層，形成石墨烯導電織物。實驗示例5的石墨烯導電織物的表面電阻為130 ohm/sq，可符合生理感測器導電線路的要求。
實驗示例6 醋酸正丁酯作為第一溶劑，異氟爾酮作為第二溶劑，以9：1的體積比例混合醋酸正丁酯及異氟爾酮，形成混合溶劑。以均質機均勻混合40克的奈米石墨烯片、50克碳黑及360克的混合溶劑，形成石墨烯懸浮溶液；以公轉自轉攪拌機於自轉轉速1000 rpm及公轉轉速混合400 rpm 450克的石墨烯懸浮溶液與23克的矽酮樹酯，形成黏度大於20,000 cps的石墨烯樹脂溶液；將石墨烯樹脂溶液以200目的網版將石墨烯樹脂溶液印刷於聚酯離型膜上之疏水性聚氨酯層上，加熱至130 oC去除石墨烯樹脂溶液中的混合溶劑，得到固化之石墨烯導電層 ; 塗佈材質為聚氨酯的熱熔膠層於石墨烯導電層之表面；平貼纖維組織於熱熔膠層，加熱至90 oC並壓合使熱熔膠層分別接著於石墨烯導電層及纖維組織，移除聚酯離型膜露出疏水性聚氨酯層，形成石墨烯導電織物。本實驗示例的石墨烯導電織物的表面電阻為300 ohm/sq且具有拉伸特性，可符合生理感測器導電線路的要求，維持導電線路不斷裂且增加人體穿戴之舒適性。
水洗測試 以AATCC 135測試標準水洗實驗示例4至6的石墨烯恆溫織物20次，測量水洗前後石墨烯恆溫織物的表面電阻，以測試石墨烯導電層的附著牢度，測量結果如表1所示。 表1
測試樣品 表面電阻(ohm/sq)測量結果
水洗前 水洗後
實驗示例4 150 153
實驗示例5 130 148
實驗示例6 300 310
如表1所示，即使石墨烯導電織物添加天然石墨或導電碳黑，水洗前後的表面電阻值並無太大差異，尤其是實驗示例6的石墨烯導電層的表面電阻值經過水洗測試後仍然符合導電線路的電阻值規範，可證明本發明之石墨烯導電織物具有良好的導電性及耐水洗次數。
綜上所述，本發明利用石墨烯具有特殊的熱學特性及優異的導電性，以低沸點及高表面張力的溶劑組合製備石墨烯懸浮溶液，混合石墨烯懸浮溶液及疏水性樹脂製備石墨烯樹脂溶液，固化石墨烯樹脂形成石墨烯導電層，以熱熔膠覆蓋石墨烯導電層，藉由熱熔膠將石墨烯導電層轉貼於纖維組織，同時可防止石墨烯導電層滲入纖維組織空隙，疏水性保護層可保護石墨烯導電層免於因水洗而剝離或脫落相較於現有製造功能性纖維的技術，本發明之石墨烯導電織物具有優異的導電性、附著度及耐水洗性，且本發明之石墨烯導電織物的製造方法不會影響纖維及織造的良率及效率，有效降低製造成本，深具產業應用性。
上述實施例僅例示性說明本發明之原理及其功效，而非用於限制本發明。任何熟習此項專業之人士均可在不違背本發明之精神及範疇下，對上述實施例進行修飾與改變。因此，舉凡所屬技術領域中具有此項專業知識者，在未脫離本發明所揭示之精神與技術原理下所完成之一切等效修飾或改變，仍應由本發明之申請專利範圍所涵蓋。
1‧‧‧石墨烯導電織物
10‧‧‧纖維組織
11‧‧‧熱熔膠層
12‧‧‧石墨烯導電層
13‧‧‧疏水性保護層
101‧‧‧第一組織面
102‧‧‧第二組織面
103‧‧‧空隙
121‧‧‧可固化樹脂
122‧‧‧奈米石墨烯片
第1圖為本發明之石墨烯導電織物的剖面示意圖。

Claims (9)

  1. 一種石墨烯導電織物之製造方法，包含：混合第一溶劑、第二溶劑及奈米石墨烯片，以機械力分散該奈米石墨烯片形成石墨烯懸浮溶液，其中該第一溶劑之沸點不大於80℃，且該第二溶劑之沸點不小於120℃；將至少一可固化樹脂加入該石墨烯懸浮溶液，以機械力分散該奈米石墨烯片及該可固化樹脂形成石墨烯樹脂溶液；塗佈或印刷該石墨烯樹脂溶液於疏水性保護層，固化該石墨烯樹脂溶液形成附著於該疏水性保護層上之石墨烯導電層；塗佈熱熔膠層於該石墨烯導電層上；以及平貼纖維組織於該熱熔膠層上，熱壓該纖維組織使該熱熔膠層分別接著該石墨烯導電層及該纖維組織，形成石墨烯導電織物。
  2. 如申請專利範圍第1項所述石墨烯導電織物之製造方法，其中該第一溶劑係選自丙酮、丁酮、正丁醇、乙酸乙酯、乙酸丁酯及其組合。
  3. 如申請專利範圍第1項所述石墨烯導電織物之製造方法，其中該第二溶劑之表面張力介於30-60mJ/m2。
  4. 如申請專利範圍第1項所述石墨烯導電織物之製造方法，其中該第二溶劑係選自N,N-二甲基乙醯胺(N,N-Dimethylacetamide)、二甲基亞碸(dimethyl sulfoxide)、二甲基甲醯胺(Dimethyformamide)、二甲基乙醯胺(Dimethylacetamide)及其組合。
  5. 如申請專利範圍第1項所述石墨烯導電織物之製造方法，其中該機械力係選自超音波、均質攪拌、球磨及高壓剪切。
  6. 如申請專利範圍第1項所述石墨烯導電織物之製造方法，其中該可固化樹脂係選自聚氨酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯、環氧樹脂、矽酮樹脂及其組合，且該奈米石墨烯片佔該石墨烯導電層60-95wt%。
  7. 如申請專利範圍第1項所述石墨烯導電織物之製造方法，其中該疏水性保護層形成於離型膜上，該熱熔膠層分別接著該石墨烯導電層及該纖維組織後，移除該離型膜露出該疏水性保護層。
  8. 如申請專利範圍第1項所述石墨烯導電織物之製造方法，其中該疏水性保護層係選自矽酮樹脂及聚氨酯樹脂之任一者。
  9. 如申請專利範圍第1項所述石墨烯導電織物之製造方法，復包含：使用雷射圖案化該石墨烯導電層，再塗佈該熱熔膠層於圖案化之該石墨烯導電層上。
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