TWI716202B - 製備活性粒子鍵結系統之方法 - Google Patents

製備活性粒子鍵結系統之方法 Download PDF

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TWI716202B
TWI716202B TW108142357A TW108142357A TWI716202B TW I716202 B TWI716202 B TW I716202B TW 108142357 A TW108142357 A TW 108142357A TW 108142357 A TW108142357 A TW 108142357A TW I716202 B TWI716202 B TW I716202B
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葛哥利 哈格奎士特
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美商可可那公司
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Abstract

一種活性粒子連結系統，包含一活性粒子、化學鍵結至該活性粒子之一材料、及嵌置至該活性粒子及該材料中之至少一者的一基材。

Description

製備活性粒子鍵結系統之方法
本發明係有關於包含活性粒子之材料。更明確言之，但非限制性，本發明係有關於使用染色製程將活性粒子摻混入紡織品及聚合物內。
已有使用寬廣範圍之方法將活性粒子摻混入織物內。此等方法之範圍自印刷至膜上，至摻混活性粒子至紡織品本身上，以透過從製造紗的母批料而將活性粒子摻混入紗內。於所有此等方法中，當製造終產物時，為了實現自活性粒子的完整效益，須阻止該等活性粒子被去活化、被塗覆或被覆蓋。再者，為了實現添加活性粒子的完整效益，所有此等方法需要一種外部環境與活性粒子表面間之交互作用，以便該等活性粒子之效益存在於該終產物內。
為了形成包含尚未經去活化的活性粒子之織物終產物，發展出一種系統、織物及纖維。一個此種具體例包含一活性粒子連結系統。一種活性粒子連結系統包含一活性粒子、化學鍵結至該活性粒子之一材料(亦即聚合物錨點)、及嵌置至該活性粒子或該聚合物錨點的一基材。該活性粒子及/或該聚合物錨點的嵌置係發生於紡織品染色製程期間。
另一具體例包含偶合一或多個活性粒子至一纖維之方法，該纖維可為一紡織品之一部分。一個此種方法包含化學鍵結一材料(聚合物錨點)至該等一或多個活性粒子及溶脹該纖維。出現該等一或多個活性粒子中之至少一者擴散入該纖維內。此時，纖維體積縮小，而該等一或多個活性粒子係操作式偶合至或嵌置於該纖維內。
本發明之又另一具體例包含纖維。一個此種纖維包含操作式偶合至一活性粒子之一基材及化學鍵結至該活性粒子之一材料。於一個此種具體例中，該材料係與該基材可相溶混，且該活性粒子及該材料中之至少一者係經由化學擴散偶合至該基材。
100‧‧‧活性粒子連結系統
110‧‧‧活性粒子
110’‧‧‧活性粒子
120‧‧‧材料
125‧‧‧纖維粒子
130‧‧‧基材
135‧‧‧空間
140‧‧‧剖面
145‧‧‧粒徑
250‧‧‧方法
255‧‧‧步驟
260‧‧‧步驟
265‧‧‧步驟
270‧‧‧步驟
275‧‧‧步驟
285‧‧‧步驟
290‧‧‧步驟
305‧‧‧纖維
310‧‧‧活性粒子
310’‧‧‧活性粒子
320‧‧‧材料
330‧‧‧基材
藉參考如下詳細說明部分及參考隨附之申請專利範圍結合附圖將更為彰顯且更加明瞭本發明之各項目的及優點及更完整瞭解，附圖中：
圖1描繪依據本發明之一具體例之一活性粒子連結系統；
圖1A描繪依據本發明之一具體例於溶脹狀態下圖1之剖面140之特寫圖；
圖1B描繪依據本發明之一具體例於非溶脹狀態下圖1之剖面140之特寫圖；
圖2描繪一種以此處描述之具體例進行之方法；及
圖3描繪依據本發明之一具體例之纖維。
對下列各段的括號(「」)內之術語及片語下定義。除 非上下文中另行明白指示否則此等定義意圖適用於全文文件的術語及片語，包括申請專利範圍各項。又復，與字元或片語的情況獨立無關，當適用時，所陳述定義適用於該經界定之字元或片語的時態或任何單複數變化。
如用於本說明書及隨附之申請專利範圍各項，「或」一詞並非意圖為互斥；反而該術語為包含性，表示「任一者或兩者」。於本說明書中述及「一個具體例」、「具體例」、「較佳具體例」、「替代具體例」、「變化例」、「一個變化例」及類似片語表示連結該具體例描述之一特定特徵、結構、或特性係含括於至少一個本發明之具體例中。於說明書中各處出現「於一個具體例中」、「於一具體例中」、或「於一變化例中」等片語並非必要全部皆係指相同具體例或變化例。
現在轉向參考圖1，可見用以製造織物及紡織品等其它產品的活性粒子連結系統100之一個具體例。活性粒子連結系統100包含一活性粒子110、一材料120、及一基材130。活性粒子110為具有孔隙或陷阱的粒子，其有能力吸附及解吸附呈固相、液相及/或氣相及/或其組合的物質。取決於使用的活性粒子110之類型，此等孔隙的大小、形狀、及數量各異。舉例言之，某些活性粒子110天然地具有孔隙，諸如火山岩，而其它活性粒子110諸如碳可使用極端溫度及活化劑諸如氧氣處理以形成孔隙。
活性粒子110可對活性粒子含括於其中的品項提供效能增強性質。此等效能增強性質包括氣味吸附、水分管理、濕度捕集及釋放、紫外光防護、紅外線吸收、化學劑保護性質、生物危害保護性質、阻燃性、抗菌保護性質、抗病毒保護性質、抗真菌保護 性質、抗微生物保護性質、乾燥性質、及其組合。活性粒子110可包括，但非限制性，活性碳、碳奈米管、碳烯、石墨、氧化鋁(活性氧化鋁)、二氧化矽凝膠、蘇打灰、鋁三水合物、小蘇打、桂皮酸對-甲氧基-2-乙氧基乙基酯(cinoxate)、氧化鋅、沸石類、二氧化鈦、二氧化矽、分子過濾型材料、及其它合宜材料。
於一個具體例中，該材料120係化學鍵結至該活性粒子110。舉例言之，活性粒子100可使用材料120初步處理或反應以產生化學鍵。與活性粒子100產生化學鍵結的也與基材130可相溶混的任何材料120皆可使用。舉例言之，此種材料之一部分可鍵結至活性粒子，而該材料之另一部分可偶合至該基材130，顯示如下。材料120可包含一長鏈端官能基及於此處可稱作為長鏈基、官能基、反應基、胺基、錨點、或錨定基。其它材料120類型包含與下列中之一或多者有關的長鏈基：纖維素、聚醚、端官能胺基、聚酯、聚乙烯醇、聚苯乙烯、聚丙烯酸系、改性聚丙烯酸系、聚丙烯、聚胺基甲酸酯(脂肪族及芳香族)、芳香族聚醯胺類、及聚醯胺。
該基材130可包含聚合物、聚合摻合物、或天然纖維。再者，該基材130可於此處稱作聚合物、聚合纖維、天然纖維、或纖維。於一個具體例中，該基材130可包含一或多個聚酯或天然纖維群組。於此一具體例中，該材料120可包含具有一端官能胺基之聚醚。於此一具體例中的活性粒子110可首先與該端官能胺基之一第一部分反應。一個第一部分可包含該端官能胺基之一第一端。一第二部分(例如該端官能胺基之一第二端)可偶合至基材130，容後詳述。因此，各個端官能胺基可化學鍵結至活性粒子110且偶合至基材130。
舉例言之，當化學鍵結至活性粒子110時，該材料120(及/或該活性粒子110)摻混入該基材130內。於一個此種具體例中，長鏈基於染色製程期間用作為錨點，以將該活性粒子110附接至纖維。技藝界已知之各種染色製程溶脹了纖維(亦即基材130)，其許可此等錨點偶合至基材130。參考圖1A，可見於纖維溶脹期間自圖1之剖面140的特寫圖。如圖可知，於此種纖維130之溶脹期間，纖維粒子125間之空間135或體積係夠大以許可長鏈基120嵌合入該等纖維粒子125間。此種體積於此處可稱作為「自由體積」。纖維粒子125於此處也可稱作為纖維分子。雖然空間135可能夠大以容納該材料120，但即便於溶脹期間，該空間135可能不夠大以許可活性粒子110嵌合入該等纖維粒子125間。
現在轉向參考圖1B，可見於纖維溶脹停止之後自圖1之剖面140的特寫圖。如圖可知，圖1B中該等纖維粒子125間之空間135係小於該纖維之溶脹期間該等纖維粒子125間之空間135，如圖1A可見。由於此種基材130內體積之縮小，該長鏈基變成顯微上纏結在該纖維內部，鎖定該材料120，及如圖1可見，附接至該纖維的活性粒子110。材料120與基材130之纏結發生在該材料120與該基材130為可相溶混時，換言之，當該基材130與該材料120包含相似的溶解度或匹配的溶解度時。雖然未顯示於圖1A-1B，但也預期空間135可夠大使得圖1可見之該活性粒子變成纏結，及因而顯微上地鎖定或錨定於該基材130的聚合物鏈。
於溶脹期間，該空間135係具有許可包含約1奈米至約100奈米之粒徑145的長鏈粒子變成纏結於該基材130內之尺寸。藉由額外溶脹，該空間135可具有許可包含約100奈米至約1微米之粒 徑145的長鏈粒子變成纏結於該基材130內之尺寸；及藉由更進一步額外溶脹，該空間135可具有許可包含約1微米至約5微米之粒徑145的長鏈粒子變成纏結於該基材130內之尺寸。
基材130可包含用於織物、絲線、或任何其它產品的下列材料中之一或多者：聚酯、聚醯胺、芳香族聚醯胺類(Kevlar®及Nomex®)、棉類、毛類、聚胺基甲酸酯類、改性丙烯酸系、聚丙烯酸系、嫘縈類、聚丙烯類、技藝界已知之其它紡織纖維或任何其它材料。預期圖1所見的基材130可包含如圖1B可見之先前已經溶脹之基材130，其包含偶合至材料120之一基材。但該基材130也可或另可附接至活性粒子110。如圖1可見，藉使用該長鏈基作為一錨點以偶合該活性粒子110至該基材130，比起直接地偶合至纖維的活性粒子110’，前者活性粒子110有更大表面積暴露於周圍環境。該活性粒子110於此處可稱作第一活性粒子110，及該活性粒子110’於此處可稱作第二活性粒子110’。
現在轉向參考圖2，可見偶合一或多個活性粒子至纖維之方法250。舉例言之，該等一或多個活性粒子可包含圖1中所見之活性粒子110，及纖維可包含圖1中所見之基材130。一個此種方法始於255，及於260包括將一材料化學鍵結至一或多個活性粒子110。舉例言之，及如此處討論，圖1中所見之材料120可化學鍵結至活性粒子110。於265，方法250包含溶脹該纖維。舉例言之，該纖維可於技藝界已知之纖維著色或染色製程程序期間被溶脹。但也預期涵蓋技藝界已知之溶脹一纖維之其它製程程序。於270，方法250包含允許該等一或多個活性粒子110中之至少一者及該材料120擴散入該纖維內。舉例言之，及如前文參考圖1A及圖1B描述，於 纖維之溶脹期間，該空間135允許該等一或多個活性粒子110及該材料120擴散入該纖維內，且可能出現該等長鏈粒子120與該等纖維粒子125之顯微纏結。舉例言之，纏結可能發生在步驟275，該步驟包含縮小纖維體積。如參考圖1A及圖1B描述，纖維體積的縮小可能出現在當纖維粒子125間之該空間135係隨著該纖維自圖1A所見之溶脹態過渡至圖1B所見之非溶脹態之時。操作式偶合一或多個活性粒子110至該纖維的步驟285也如前文參考圖1A及圖1B描述，及其伴隨的長鏈材料120及/或活性粒子110(如圖1可見)與該等纖維粒子125之顯微纏結之揭示。
如同於265之溶脹纖維，於270允許該等一或多個活性粒子中之至少一者及該材料擴散入該纖維內，於275縮小纖維體積，及於285操作式偶合一或多個活性粒子至該纖維也可能出現在染色製程期間。纖維的染色可透過習知分散染色法或超臨界二氧化碳(CO2)染色法進行。因此，於一個具體例中，超臨界二氧化碳染色製程可用以協助方法250之步驟265、270、275及285之實現，及透過材料120之使用而摻混活性粒子100至纖維110內部。因此，使用超臨界二氧化碳的一項優點為此種製程無需除了二氧化碳以外之任何進一步化學品以實現活性粒子100之鍵結至纖維110。採用此種具體例，該二氧化碳可用作為此處描述的材料120。再者，透過只使用二氧化碳，活性粒子100更可能防止染色製程期間的去活化，原因在於該製程中不存在有任何其它化學品。
當一材料偶合至該等活性粒子之孔隙及/或其它表面積且封阻了該等活性粒子的吸收、吸附、及解吸附一物質的能力時，可能出現該等活性粒子之去活化。活性粒子乃包含孔隙或其它 表面積特性件的粒子，其能夠吸收、吸附、及解吸附一物質，或有潛力吸收、吸附、及解吸附一物質。當該等活性粒子之孔隙及/或表面積被封阻或遏止某個分子尺寸的一物質之吸附時，活性粒子可存在於去活化態。但如此並非經常性地表示此等孔隙/表面積被永久性地排除不能吸附物質。活性粒子之此等孔隙/表面積可透過再活化或再生而被解除封阻或解除遏止(亦即大致上或實質上回復其原先狀態)。再活化或再生去除了堵塞在活性粒子之此等孔隙內而阻擋其活性的物質。但若有害物質被該等活性粒子所吸附，則再活化或再生不可能回復該等活性粒子之吸附能力。
於一個具體例中，該等活性粒子可於織物染色製程期間施用至基材，有或無借助於一保護層以防止該等活性粒子之持久性去活化。一個此種保護層可包含密封劑。密封劑為一種可去除式物質，其藉防止該等活性粒子之過早去活化(例如防止有害物質或非期望物質被吸附或透過其它不良條件而被去活化)而保有活性粒子相聯結的性質。在一預定時間且當接受一或多個預期條件(例如加熱、時間等)或物質(例如，水、光、分散劑、溶劑等)之施用時，該密封劑可從該等活性粒子去除。該密封劑可包括，但非限制性，水溶性界面活性劑、其它類型之界面活性劑、鹽類(例如氯化鈉、氯化鈣)、聚合物鹽類、聚乙烯醇類、蠟類(例如，石蠟、巴西棕櫚蠟)、光反應性材料、可生物分解材料、可生物分解材料以外之可降解材料、乙氧基化炔屬二醛類、及任何其它合宜物質。但透過使用二氧化碳染色製程，由於製程期間不存在有有害物質，可能無需此等密封劑。
預期化學鍵結材料120至一或多個活性粒子110之步 驟260可包含於溶脹該纖維之前化學鍵結材料120至一或多個活性粒子110；於溶脹該纖維期間化學鍵結材料120至一或多個活性粒子110；或兩者。舉例言之，於溶脹該纖維之前(例如，於染色製程諸如，但非限制性，超臨界二氧化碳染色製程開始之前)，該等活性粒子110可透過一分開化學鍵結處理而化學鍵結至前文描述之該等材料120中之一或多者。於活性粒子110與材料120之鍵結出現之後，該活性粒子/材料組合可在該染色製程開始之前或在該製程的任何一點進入該染色製程。
如先前描述，材料120可包含一或多個長鏈基。於此一具體例中，允許該等一或多個活性粒子110中之至少一者及該材料120擴散入該纖維內之該步驟270可包含，藉該等一或多個活性粒子110及該等一或多個長鏈基的大小，自動地選擇該等一或多個活性粒子110及該等一或多個長鏈基用以擴散入該纖維內。舉例言之，及如前文參考圖1A及圖1B顯示及描述，根據纖維粒子125間之空間135及體積之大小可能出現擴散現象。若於纖維溶脹期間該空間/體積向外擴展而變夠大，則活性粒子110可擴散至基材130內部。但若活性粒子110係大於該體積/空間，則活性粒子110將不會擴散至基材130內部。因此，活性粒子愈大，則愈難以擴散。同理，於纖維溶脹期間，該空間/體積可夠大以許可出現該等長鏈基及基材130間之擴散。但若該纖維尚未溶脹，則不可能出現該等長鏈基及基材130間之擴散，原因在於該空間/體積可能不足以許可該等長鏈基變成與該等纖維粒子125纏結。因此該等長鏈基及活性粒子110之大小決定了活性粒子110及/或該等長鏈基是否偶合至基材130，而具有適當尺寸的長鏈基及活性粒子110(變成纏結者)被自動地選用作為錨 點。因此，藉該等一或多個活性粒子110及該等一或多個長鏈基的大小，自動地選擇該等一或多個活性粒子110及該等一或多個長鏈基用以擴散入該纖維內，包含根據該等一或多個活性粒子110及該等一或多個長鏈基的大小，接納選擇該等一或多個活性粒子110及該等一或多個長鏈基，該大小係適用以基於該基材130中之該空間135(亦即體積)而嵌合入該溶脹纖維中之一或多個區域者。縮小纖維體積包含縮小多個纖維粒子125間之空間。於一個此種具體例中，基材130可包含聚酯，及材料120可包含具有端官能胺基之聚醚，該端官能胺基係用以附接該聚醚至該纖維。
如圖1可知，透過材料120之擴散入纖維而偶合至纖維的該第一活性粒子110之暴露至周圍環境之一表面積(環繞系統100之該區)係大於透過第二活性粒子110’之擴散入纖維而偶合至纖維的該第二活性粒子110’之暴露至周圍環境之該表面積。方法250結束於290。
本發明之另一個具體例可為纖維。圖3所見之纖維305係類似前文就圖1描述的系統100，與系統100相關部分爰引於此並融入本說明書之揭示且應用至針對圖3之纖維305的全文描述。同理，後文有關纖維305之描述可適用至圖1所見系統100。
於一個具體例中，纖維305包含具有一基材330及至少一個活性粒子310之聚合材料。材料320可化學鍵結至活性粒子310。如前文描述，材料320須與基材330為可相溶混(可相容性地溶解)，包含一反應性基團以與活性粒子310化學鍵結，及該活性粒子310中之至少一者及該材料320係透過擴散而偶合至該基材。舉例言之，圖3所見活性粒子310’係偶合至該基材330。又復，該反應性基 團可包含具有端官能胺基之聚醚。如前文描述，於染色製程諸如，但非限制性，超臨界二氧化碳染色製程期間，當該基材330溶脹時，活性粒子310及/或材料320可透過擴散而偶合至該基材330。預期該端官能胺基可包含多個長鏈基，及預期該等長鏈基中之至少一者化學鍵結至該活性粒子。於此一具體例中，可能發生該等長鏈基中之至少一者擴散入該基材內。
一個錨定基可包含化學鍵結至活性粒子100之一個反應性部分或部位。此種錨定基可在染色製程之前含括，或長鏈基120可於染色製程期間附接至活性粒子100。一個長鏈基120與纖維110為可相容且可相溶混。又復，一染色方法可充分地溶脹該纖維110，因而許可活性粒子100或該錨定基之擴散入纖維110內。無需預先分類粒子大小。其製程本身即可對能夠擴散進入已溶脹之纖維的粒子做尺寸選擇。於該超臨界二氧化碳製程中，於染色之後，回收未使用的活性粒子。
熟諳技藝人士將方便瞭解可於本發明做出無數變化及取代，其使用及其組態可達成與藉如此處描述之該等具體例所達成的相同結果。據此，絕非意圖限制本發明於所揭示之範例形式。許多變化、修改及替代組成落入於如申請專利範圍各項表明的揭示本發明之範圍及精髓內。
100‧‧‧活性粒子連結系統
110‧‧‧活性粒子
110’‧‧‧活性粒子
120‧‧‧材料
130‧‧‧基材
140‧‧‧剖面

Claims (8)

  1. 一種製備活性粒子鍵結系統之方法，包含：溶脹一包含多個聚合物鏈之纖維；許可下列中之至少一者擴散入該纖維內：一或多個活性粒子，其具有包含一長鏈基化學鍵結至該活性粒子之錨點，及一或多個長鏈基；及縮小該纖維體積至一非溶脹的狀態；藉此該等活性粒子或該等長鏈基之至少一者成為顯微纏結至該纖維之該等多個聚合物鏈中之至少一部分中，以鎖定該等一或多個活性粒子或該等活性粒子之長鏈基之至少一者至該纖維。
  2. 如請求項1之方法，其中，該等活性粒子之粒徑約100奈米至約1微米。
  3. 如請求項1或2之方法，其進一步包含於溶脹該纖維之前，化學鍵結該錨點至該等一或多個活性粒子；或於溶脹該纖維期間，化學鍵結該錨定材料至該等一或多個活性粒子。
  4. 如請求項1或2之方法，其中，溶脹該纖維係發生在一超臨界二氧化碳製程期間以染色該纖維；或在一分散製程期間以染色該纖維。
  5. 如請求項1或2之方法，其中，許可該等一或多個活性粒子或該等長鏈基之至少一者擴散入該纖維內係包含藉該等一或多個活性粒子及該等一或多個長鏈基之大小，自動地選擇用以擴散入該纖維內之該等一或多個活性粒子及該等一或多個長鏈基。
  6. 如請求項5之方法，其中，藉該等一或多個活性粒子及該等一 或多個長鏈基之大小，自動地選擇用以擴散入該纖維內之該等一或多個活性粒子及該等一或多個長鏈基係包含下列中之一者：接納該等一或多個活性粒子及該等一或多個長鏈基之大小，該大小係適合用以嵌合入該經溶脹的纖維中之一或多個區域者；及接納該等一或多個活性粒子及該等一或多個長鏈基之大小，該大小係適合用以嵌合入該經溶脹的纖維中之一或多個區域者，且在該經溶脹的纖維中之該等一或多個區域係適用於接納該等一或多個活性粒子及該等一或多個長鏈基。
  7. 如請求項1或2之方法，其中，縮小纖維體積包含減少多個纖維粒子間之空間；該纖維包含聚酯、聚醯胺、芳香族聚醯胺類、棉類、毛類、聚胺基甲酸酯類、改性丙烯酸系、聚丙烯酸系、嫘縈類、及聚丙烯類之至少一者；及該長鏈基包含與下列中之一或多者有關的一端官能長鏈基中之至少一者：纖維素、聚醚、改性聚丙烯酸系、聚酯、聚乙烯醇、聚苯乙烯、聚丙烯酸系、聚丙烯、聚胺基甲酸酯(脂肪族及芳香族)、芳香族聚醯胺類、及聚醯胺。
  8. 如請求項7之方法，其中，該纖維係聚酯，及該長鏈基包含與聚醚有關的一端官能長鏈基中之至少一者。
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