TWI682084B - 無氟撥水劑的製造方法與撥水織物 - Google Patents

無氟撥水劑的製造方法與撥水織物 Download PDF

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TWI682084B
TWI682084B TW108100433A TW108100433A TWI682084B TW I682084 B TWI682084 B TW I682084B TW 108100433 A TW108100433 A TW 108100433A TW 108100433 A TW108100433 A TW 108100433A TW I682084 B TWI682084 B TW I682084B
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fluorine
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powder
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蔡翔秦
張怡萱
劉邦錦
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遠東新世紀股份有限公司
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Abstract

無氟撥水劑的製造方法包含將石蠟、無機奈米粉體及第一反應單體混合以形成第一混合物；將乳化劑、助溶劑及水混合，形成第二混合物；將第二混合物及第一混合物混合，形成預乳化液；以及加入引發劑及第二反應單體於預乳化液中，使第一反應單體與第二反應單體進行聚合反應，以形成撥水劑。

Description

無氟撥水劑的製造方法與撥水織 物
本發明係關於一種無氟撥水劑的製造方法，更詳細關於一種可塗布於織物表面的無氟撥水劑。
織界長期以來使用如杜邦公司開發的TEFLON等全氟化物作為織物的防水加工劑。但因相關研究發現，衣服中含有的全氟化物具有致癌毒性，且可能導致孕婦生出畸形兒；不僅如此，全氟化物具有難以分解的特性，導致其能持續存在並不斷累積於動、植物體內而在自然環境中長期循環；有鑑於全氟化物的危險性，，因此歐盟於西元2008年6月27日實施限制使用全氟辛烷磺醯基化合物的政策。為了解決上述問題，目前已有人提出將具有蓮花效應的奈米金屬粒子溶液塗佈織物表面使其形成一具備撥水效果的隔離層，然而奈米金屬粒子材料須經由複雜的合成步驟與嚴苛的反應條件，甚至需搭配特有的研磨分散技術才得以製作，因此前述方法的製造成本過高導致無法普及應用， 而且上述織物水洗後的撥水效果不佳，其有不耐水洗的缺點。有鑑於上述撥水劑存在技術缺陷，本創作之目的在於提供一種製備無氟撥水劑的方法，因利用所述方法製得的無氟撥水劑不含氟元素，而能符合環保訴求及法律規範並且有優異的耐水洗牢度。
本發明之一目的，係提供一種無氟撥水劑的製造方法，此方法包含將石蠟、無機奈米粉體及第一反應單體混合以形成第一混合物，第一反應單體具有式(A)、式(B)或其組合之結構， 其中式(A)為
Figure 108100433-A0101-12-0002-1
，X1為苯，式(B)為
Figure 108100433-A0101-12-0002-2
，X2為CH3或H，X3為碳數大於等於18的烷基；將乳化劑、助溶劑及水混合，形成第二混合物；將第二混合物及第一混合物混合，形成預乳化液；以及加入引發劑及第二反應單體於預乳化液中，使第二反應單體與第一反應單體進行聚合反應，以形成撥水劑，其中第二反應單體為偏二氯乙烯，且以無機奈米粉體、第一反應單體、第二反應單 體、石蠟及乳化劑的總重為100wt%計，無機奈米粉體為1-20wt%，第一反應單體及第二反應單體總和為10-40wt%，石蠟為20-60wt%，乳化劑為1-20wt%。
本發明之一目的，係提供一種織物，包含上述之無氟撥水劑的製造方法中的撥水劑。
本發明之一目的，係由上述製造方法所製得之無氟撥水劑。
以下揭露提供許多不同實施例，或示例，以建置所提供之標的物的不同特徵。以下敘述之成份和排列方式的特定示例是為了簡化本公開。這些當然僅是做為示例，其目的不在構成限制。舉例而言，元件的尺寸不被揭露之範圍或數值所限制，但可以取決於元件之製程條件與/或所需的特性。
本發明提供一種無氟撥水劑製造方法，使用該方法所製得的無氟撥水劑，在不含氟的情況下，具有良好的撥水性能，將其塗布於織物上時不僅具有良好的撥水效果，更具有優異的耐水洗牢度。
本發明之提供一種無氟撥水劑的製造方法，此方法包含將石蠟、無機奈米粉體及第一反應單體混合以形成第一混合物，第一反應單體具有式(A)、式(B)或其組合之結構， 其中式(A)為
Figure 108100433-A0101-12-0004-4
，X1為苯，式(B)為
Figure 108100433-A0101-12-0004-3
，X2為CH3或H，X3為碳數大於等於18的烷基；將乳化劑、助溶劑及水混合，形成第二混合物；將第二混合物及第一混合物混合，形成預乳化液；以及加入引發劑及第二反應單體於預乳化液中，使第二反應單體與第一反應單體聚合反應，以形成撥水劑。
在部分實施例中，無機奈米粉體例如可為二氧化矽(SiO2)。更佳地，該無機奈米粉體的粒徑可以為5nm至100nm，若無機奈米粉體的粒徑過大，例如大於100nm，無機奈米粉體的分散性不好。若無機奈米粉體的粒徑過小，例如小於5nm，無機奈米粉體對於無氟撥水劑的撥水性質提昇不顯著。無機奈米粉體可以增加無氟撥水劑成膜後的表面粗糙度，亦可以作為物理交聯點，以提高耐洗性。較佳地，該無機奈米粉體的粒徑可以為20nm至80nm，最佳地為50nm。
在部分實施例中，第一反應單體具有如式(A)、式(B)或其組合之結構：
Figure 108100433-A0101-12-0005-5
Figure 108100433-A0101-12-0005-6
 其中X1為苯，X2為CH3或H，X3為碳數大於等於18的烷基。值得注意的是，此處的式(A)與式(B)的組合意即第一反應單體同時具有式(A)及式(B)的結構。在部分實施例中，上述的第一反應單體包含丙烯酸山嵛基酯(Docosyl acrylate)、甲基丙烯酸山嵛基酯(Docosyl methyl acrylate)、苯乙烯、氯乙烯、丙烯醯胺或其組合。
在部分實施例中，第二反應單體包含甲基丙烯酸縮水甘油酯(glycidyl methacrylate)、甲基丙烯酸羥乙酯(2-hydroxyethyl methacrylate)、偏二氯乙烯、丙烯酸烴乙酯、甲基丙烯酸羥丙酯(2-hydroxypropyl methacrylate)、3-氯-2-烴基丙基-甲基丙烯酸酯(3-chloro-2-hydroxypropyl methacrylate)或其組合，較佳為偏二氯乙烯。
更進一步說明，以第一反應單體/第二反應單體的重量比為1.5-2較佳為1.75。
在部分實施例中，石蠟的熔點範圍為55℃-85℃。當石蠟的熔點越高，無氟撥水劑的撥水性越好，然而當 熔點超過85℃，會導致乳化困難，更會造成生產上的困難。
在部分實施例中，乳化劑係為乙氧基化季銨鹽(ethoxylated quaternary ammonium compounds)，舉例來說，例如AkzoNobel公司的Ethoquad HT/25。
在部分實施例中，引發劑可以為2,2'-偶氮二異丁基脒二鹽酸鹽(2,2'-Azobis(2-methylpropionamide)dihydrochloride)、偶氮二異丁腈或其組合。
在部分實施例中，以無機奈米粉體、石蠟、第一反應單體、第二反應單體以及乳化劑的總重為100wt%計，無機奈米粉體為1-20wt%、石蠟為20-60wt%以及乳化劑為1-20wt%。若無機奈米粉體含量過多或過少，例如大於20wt%或小於1wt%，無氟撥水劑的撥水性質較差。若石蠟含量過多，例如大於60wt%，則加工不易，若石蠟含量過少，例如小於20wt%，無氟撥水劑的撥水性質較差。若乳化劑含量過多，例如大於20wt%，會使無氟撥水劑的其他組分的含量降低，影響無氟撥水劑的撥水性質，若乳化劑含量過少，例如小於1wt%，則乳化劑作為介面活性劑的功效大幅降低。
以下更詳細說明本發明的無氟撥水劑的製造方法。首先，將石蠟、無機奈米粉體以及第一反應單體混合以形成第一混合物，其中第一反應單體可以為至少一種第一反應單體。
在另外的容器中，將乳化劑、助溶劑及水混合， 以形成第二混合物。在部分實施例中，上述形成第一混合物以及第二混合物的步驟可以使用高壓分散的方式進行，其中高壓分散係在200-800kgf/cm2的壓力以及50-85℃的溫度下執行。
在部分實施例中進一步可包含助溶劑及水，該助溶劑包含1,2-丙二醇、二丙二醇、三丙二醇、四丙二醇、丙酮、丁酮、丙二醇甲醚、二丙二醇甲醚或其組合。該助溶劑之用量無特別限制，該水的用量也無特別限制，較佳用量為大於第一混合物之重量。
之後，將第一混合物與第二混合物混合，形成預乳化液，此處形成預乳化液的方法亦可以使用上述的高壓分散的方式進行，其中係在200-800kgf/cm2的壓力以及50-85℃的溫度下執行。
在預乳化液形成之後，加入第二反應單體以及引發劑於預乳化液中，並混合均勻。第二反應單體為偏二氯乙烯。
將第二反應單體以及引發劑加入預乳化液之後，第二反應單體與第一反應單體進行聚合反應，以形成無氟撥水劑。在部分實施例中，此聚合反應係在55-70℃的溫度下進行。在部分實施例中，係在氮氣氣氛下回流反應。更詳細說明，反應單體快速捕捉引發劑所產生的自由基，舉例來說，偏二氯乙烯上的雙鍵與其他第一反應單體上的雙鍵進行聚合反應。
本揭露亦提供一種織物，係使用上述的製造方 法製作的無氟撥水劑進行織物塗布處理。因此，此織物包含使用上述製造方法製作的無氟撥水劑。上述塗布處理的方法並無限制，可用一般習知的織物塗佈方式，例如直接塗佈、轉移貼合塗佈及壓延塗布。
為了使本揭露更清楚說明，以下提供根據本揭露的一些實施例。
實施例1
取5克奈米二氧化矽、105克石蠟(熔程為68℃-74℃)、17.5克丙烯酸山嵛基酯、17.5克甲基丙烯酸山嵛基酯及10克苯乙烯混合，並且在250bar的壓力及85℃下高壓分散。在另外的容器中，將12克乙氧基化季銨鹽(Ethoquad HT/25)、30克二丙二醇及450克的水混合，並且在250bar的壓力及85℃下高壓分散。再將上述兩混合液混合，待混合均勻後，加入20克偏二氯乙烯及引發劑溶液，其中引發劑溶液係由2.5克的2,2'-偶氮二異丁基脒二鹽酸鹽(V50)及15克水混合而得。接著置於氮氣氣氛下於56℃回流反應8小時，形成無氟撥水劑。
實施例2
取10克奈米二氧化矽、105克石蠟(熔程為68℃-74℃)、17.5克丙烯酸山嵛基酯、17.5克甲基丙烯酸山嵛基酯及10克苯乙烯混合，並且在250bar的壓力及85℃下高壓分散。在另外的容器中，將12克乙氧基化季銨鹽(Ethoquad HT/25)、30克二丙二醇及450克的水混合，並且在250bar的壓力及85℃下高壓分散。再將上述兩混合液 混合，待混合均勻後，加入20克偏二氯乙烯及引發劑溶液，其中引發劑溶液係由2.5克的2,2'-偶氮二異丁基脒二鹽酸鹽(V50)及15克水混合而得。接著置於氮氣氣氛下於56℃回流反應8小時，形成無氟撥水劑。
比較例1(未添加無機奈米粉體)
取17.5克丙烯酸山嵛基酯、17.5克甲基丙烯酸山嵛基酯、10克苯乙烯、12克乙氧基化季銨鹽(Ethoquad HT/25)、30克二丙二醇及450克的水混合，並且在250bar的壓力及85℃下高壓分散。在另外的容器中，將105克石蠟(熔程為68℃-74℃)熔化。再將上述兩者混合，待混合均勻後，加入20克偏二氯乙烯及引發劑溶液，其中引發劑溶液係由2.5克的2,2'-偶氮二異丁基脒二鹽酸鹽(V50)及15克水混合而得。接著置於氮氣氣氛下於56℃回流反應8小時，形成無氟撥水劑。
比較例2(未添加石蠟)
取5克奈米二氧化矽、17.5克丙烯酸山嵛基酯、17.5克甲基丙烯酸山嵛基酯及10克苯乙烯混合，並且在250bar的壓力及85℃下高壓分散。在另外的容器中，將12克乙氧基化季銨鹽(Ethoquad HT/25)、30克二丙二醇及450克的水混合，並且在250bar的壓力及85℃下高壓分散。再將上述兩混合液混合，待混合均勻後，加入20克偏二氯乙烯及引發劑溶液，其中引發劑溶液係由2.5克的2,2'-偶氮二異丁基脒二鹽酸鹽(V50)及15克水混合而得。接著置於氮氣氣氛下於56℃回流反應8小時，形成無氟撥水劑。
比較例3(未添加無機奈米粉體與石蠟)
取17.5克丙烯酸山嵛基酯、17.5克甲基丙烯酸山嵛基酯及10克苯乙烯混合，並且在250bar的壓力及85℃下高壓分散。在另外的容器中，將12克乙氧基化季銨鹽(Ethoquad HT/25)、30克二丙二醇及450克的水混合，並且在250bar的壓力及85℃下高壓分散。再將上述兩混合液混合，待混合均勻後，加入20克偏二氯乙烯及引發劑溶液，其中引發劑溶液係由2.5克的2,2'-偶氮二異丁基脒二鹽酸鹽(V50)及15克水混合而得。接著置於氮氣氣氛下於56℃回流反應8小時，形成無氟撥水劑。
比較例4(僅有石蠟)
取105克石蠟，並將此石蠟熔融，其中石蠟的熔融溫度為68℃-74℃。在另外的容器中，將12克乙氧基化季銨鹽(Ethoquad HT/25)、30克二丙二醇及450克的水混合，之後加入上述熔融後的石蠟，並且在250bar的壓力及85℃下高壓分散混合均勻形成無氟撥水劑。
將上述實施例1-2及比較例1-4所製作的無氟撥水劑依照100克/升的比例以水稀釋，使用滌綸梭織布，以一浸一軋的方式浸漬，之後在120℃下烘乾，再在160℃下熱處理兩分鐘後作以下測試。
表1為實施例1-2及比較例1-4的測試結果，其中撥水效果的測試係採AATCC 22標準，而多次洗滌係根據ISO6330標準。儲存穩定性係將無氟撥水劑在室溫下儲存三個月後，檢查是否有分層的現象或固體析出物，若無分層 且無固體析出物，則代表為「穩定」。反之，則為「不穩定」。
Figure 108100433-A0101-12-0011-7
由表1的結果可以發現，實施例1-2在初始撥水效果皆優於比較例1-4，而在多次洗滌之後，實施例1-2依舊維持良好的撥水性質。反觀比較例1-4，在多次洗滌之後，撥水性質已大幅衰退。綜上，本揭露的無氟撥水劑製造方法所製得的無氟撥水劑確實具有優秀的撥水性質，更具有良好的耐洗性，可以在多次洗滌後，依然保持與初始撥水效果相當的撥水性質。
本發明實施方式提供的無氟撥水劑及其製作方法，可以大幅增加織物的撥水性質，並且同時具有良好的耐洗性，在多次洗滌後，依舊維持優秀的撥水性。此外，本揭露提供的無氟撥水劑亦具有良好的儲存穩定性，可以長時間存放而不分層或析出固體。
本發明實施方式已經詳細地描述某些實施方 式，但其他的實施方式也是可能的。因此，所附請求項的精神和範疇不應限於本文所描述的實施方式。
雖然本發明實施方式已以實施方式揭露如上，然其並非用以限定本揭露內容，任何熟習此技術者，在不脫離本揭露內容之精神與範圍內，當可作各種更動與潤飾，因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。

Claims (12)

  1. 一種無氟撥水劑的製造方法，包含：將一石蠟、一無機奈米粉體及一第一反應單體混合以形成一第一混合物，該第一反應單體具有式(A)、式(B)或其組合之結構，其中式(A)為
    Figure 108100433-A0305-02-0015-1
    ，X1為苯，式(B)為
    Figure 108100433-A0305-02-0015-2
    ，X2為CH3或H，X3為碳數大於等於18的烷基；將一乳化劑、一助溶劑及水混合，形成一第二混合物；將該第二混合物及該第一混合物混合，形成一預乳化液；以及加入一引發劑及一第二反應單體於該預乳化液中，使該第一反應單體與該第二反應單體聚合反應，以形成一撥水劑，其中該第二反應單體為偏二氯乙烯。
  2. 如請求項1所述之製造方法，其中以該石蠟、該無機奈米粉體、該第二反應單體、該乳化劑及該第一反應單體的總重為100wt%計，該無機奈米粉體為1-20wt%，該石蠟為20-60wt%，該第二反應單體與該第 一反應單體合計為10-40wt%，該乳化劑為1-20wt%。
  3. 如請求項2所述之製造方法，其中該第一反應單體對該第二反應單體的重量比為1.5-2。
  4. 如請求項1所述之製造方法，其中該第一反應單體包含丙烯酸山嵛基酯(Docosyl acrylate)、甲基丙烯酸山嵛基酯(Docosyl methyl acrylate)、苯乙烯、氯乙烯、丙烯醯胺或其組合。
  5. 如請求項1所述之製造方法，其中該無機奈米粉體的粒徑為5nm-100nm。
  6. 如請求項1所述之製造方法，其中該無機奈米粉體包含二氧化矽(SiO2)。
  7. 如請求項1所述之方法，其中將該石蠟、該無機奈米粉體及該第一反應單體混合，以及將該第二混合物及該第一混合物混合，係使用高壓分散方法。
  8. 如請求項7所述之製造方法，其中該高壓分散方法係在200-800kgf/cm2的壓力以及50-85℃的溫度下執行。
  9. 如請求項1所述之製造方法，其中使該預 乳化液反應形成該撥水劑係在55-70℃的溫度下執行。
  10. 如請求項1所述之製造方法，其中該引發劑包含2,2'-偶氮二異丁基脒二鹽酸鹽、偶氮二異丁腈或其組合。
  11. 一種織物，包含請求項1所述之無氟撥水劑的製造方法製作之該撥水劑。
  12. 一種無氟撥水劑，係以請求項1所述之無氟撥水劑的製造方法製作。
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