TW201831540A - 用於紡織物後處理的無氟水性分散液 - Google Patents
用於紡織物後處理的無氟水性分散液 Download PDFInfo
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Abstract
一種不含氟化物之水性分散液,其包含(A)至少一種共聚物,其由以下單體的聚合作用所得到:a)至少一種C16-C18醇的無氟(甲基)丙烯酸酯;b)至少一種C18-C22醇的無氟(甲基)丙烯酸酯;c)至少一種單體,其選自氯乙烯及二氯亞乙烯之群;且,視情況的d)至少一種單體,其選自2-羥基乙基(甲基)丙烯酸酯及3-氯-2-羥基乙基(甲基)丙烯酸酯之群;(B)至少一種組分,其選自具有55℃至75℃的熔融範圍的石蠟及具有25℃至55℃的熔融範圍的矽蠟之群;(C)至少一種界面活性劑;及(D)水,其中共聚物(A)之單體a)及b)是不同的,且不含任何苯乙烯或α-甲基苯乙烯聚合單元之共聚物(A)可用於天然及合成紡織物的後處理,以賦予所述織物優異 的撥水性質。
Description
本發明關於一種水性分散液,其包含基於兩種不同長烴鏈(甲基)丙烯酸酯的共聚物、蠟組分及界面活性劑;共聚物的製備;及用於使用所述共聚物的水性分散液處理紡織物之方法。根據本發明之水性分散液不含氟化物,且賦予天然及合成紡織物撥水性質。
過去幾年來,許多國家致力於通過節約自然資源和減少對氣候有害物質的排放以提高環境品質。政府提供資金以支持產業實現這些目標。消費者要求根據最高生態標準生產的對環境友善的紡織產品。品牌商和零售商將這些需求轉化為實際要件,而紡織廠藉由投資現代化設備和選擇環保化學物質不斷提高優化生產。
已知藉由以含有特定化學成分的水性分散液處理織物來後處理紡織物,諸如梭織物、針織物或非織物,其具有某些性質,例如撥水性。紡織品上的撥水性質藉由使用含氟產品這種化學成分來達成。然而,含氟產品成本高,且由於制定了化學品的法規架構,含氟產品之使用已被限制。或者,已經提出了包含石蠟及丙烯酸聚合物的水性系統以得到紡織品上的撥水性質。這些系統經描述於例如EP1424433A2及WO2010115496A1 中。WO2010115496A1揭示的水性分散液包含石蠟及一種共聚物,其由(甲基)丙烯酸酯、及苯乙烯或α-甲基苯乙烯得到。
先前技術的組成物不能滿足目前預期的所有要求,舉例而言,不同織物上(特別是合成纖維製成的織物)的優異防水性質。
本發明的一個目的係提供多種組成物,其即使在長時間儲存後也具有高穩定性、不含任何氟化物或苯乙烯,且其在包括含聚酯織物的所有紡織物上提供優異撥水性。本發明亦提供一種用於在該織物上得到優異撥水性質的方法。
因此,本發明關於一種不含氟化物之水性分散液,其包含(A)至少一種共聚物,其由以下單體的聚合作用所得到:a)至少一種C16-C18醇的無氟(甲基)丙烯酸酯;b)至少一種C18-C22醇的無氟(甲基)丙烯酸酯;c)至少一種單體,其選自氯乙烯及二氯亞乙烯之群;且,視情況的d)至少一種單體,其選自2-羥基乙基(甲基)丙烯酸酯及3-氯-2-羥基乙基(甲基)丙烯酸酯之群;(B)至少一種蠟,其選自具有55℃至75℃的熔融範圍的石蠟及具有25℃至55℃的熔融範圍的矽蠟之群;(C)至少一種界面活性劑;及(D)水,其中共聚物(A)之該單體a)及b)不同,且該共聚物(A)不含任何苯乙烯或α-甲基苯乙烯之聚合單元。
在本發明上下文中,用語「無氟(fluorine-free)」表示各化合 物不含有任何的氟烷基團。
根據本發明之水性分散液既不含任何氟化物,也不含任何苯乙烯。它們也不含任何N-羥甲基化合物。N-羥甲基化合物可以用非所欲的量將甲醛釋放到環境氛圍中。因此,本發明進一步限制了對健康及環境有潛在危害的、用於製備紡織應用的水性分散液中使用的成分數量。
至少一種共聚物(A)之單體a)係直鏈或分支鏈C16-C18醇的至少一種(例如:一種、兩種或三種)(甲基)丙烯酸酯。可以考慮這種直鏈或分支鏈C16-C18醇的(甲基)丙烯酸酯,舉例而言,甲基丙烯酸十六烷基酯、甲基丙烯酸十七烷基酯、甲基丙烯酸十八烷基酯、丙烯酸十六烷基酯、丙烯酸十七烷基酯及丙烯酸十八烷基酯,或C16-C18醇的至少兩種不同(甲基)丙烯酸酯的混合物,例如甲基丙烯酸十六烷基酯及甲基丙烯酸十八烷基酯的混合物,其作為工業級甲基丙烯酸硬脂酸酯(Stearylmethacrylate)市售可得(CAS:90551-83-0)。
至少一種共聚物(A)之單體b)係直鏈或分支鏈C18-C22醇的至少一種(例如:一種、兩種或三種)(甲基)丙烯酸酯。可以考慮這種直鏈或分支鏈C18-C22醇的(甲基)丙烯酸酯,舉例而言,甲基丙烯酸十八烷基酯、甲基丙烯酸二十烷基酯、甲基丙烯酸二十二烷基酯、丙烯酸十八烷基酯、丙烯酸二十烷基酯、丙烯酸二十二烷基酯、或C18-C22醇的至少兩種不同(甲基)丙烯酸酯的混合物,例如甲基丙烯酸十八烷基酯、甲基丙烯酸二十烷基酯及丙烯酸二十二烷基酯的混合物,其作為工業級甲基丙烯酸二十二烷基酯(behenylmethacrylate)市售可得(CAS:90551-86-3)。
共聚物(A)之單體a)及b)是不同的,即單體a)和單體b)在醇 的鏈長方面不同,例如單體a)和單體b)各自不能是相同C18醇的(甲基)丙烯酸酯。然而,各單體a)和b)可含有相同醇(例如C18醇)的(甲基)丙烯酸酯;如果單體a)或單體b)、或單體a)和b)是至少兩種(甲基)丙烯酸酯的混合物,其中該至少兩種(甲基)丙烯酸酯只有一者是相同的醇(例如C18醇)的酯。因此,單體a)可為甲基丙烯酸十六烷基酯及甲基丙烯酸十八烷基酯的混合物,而單體b)可為甲基丙烯酸十八烷基酯、甲基丙烯酸二十烷基酯及丙烯酸二十二烷基酯的混合物。
單體a)或單體b)各為丙烯酸酯或甲基丙烯酸酯、或丙烯酸酯及甲基丙烯酸酯之混合物,其莫耳比係例如1:1、1.5:1或1:1.5。
共聚物(A)的單體a)及單體b)市售可得,或可藉由一般已知方法製備。
在一個具體實例中,用於製備至少一種共聚物(A)的該至少一種(甲基)丙烯酸酯a)及b)含有飽合醇,即該至少一種(甲基)丙烯酸酯a)及b)不含帶有碳-碳多鍵的不飽和醇。
選自氯乙烯及二氯亞乙烯二氯亞乙烯之群的該至少一種單體c)係市售可得。
選自2-羥基乙基(甲基)丙烯酸酯及3-氯-2-羥基乙基(甲基)丙烯酸酯之群的該至少一種單體d)在該至少一種共聚物(A)的製備中不是強烈需要的,但可用於提高合成紡織物的效果程度。
至少一種共聚物(A)係藉由聚合作用得到:a)至少一種C16-C18醇的(甲基)丙烯酸酯、b)至少一種C18-C22醇的(甲基)丙烯酸酯、c)至少一種選自氯乙烯及二氯亞乙烯之群的單體,及視情況的d)至少一種選自2-羥基乙基(甲基)丙烯酸酯及3-氯-2-羥基乙基(甲基)丙烯酸酯之群的單體。除了單體a)、b)、c)及視情況的d)以外,可以在聚合反應中使用其他適合的單體,只要這些單體不劣化本發明所達到的有利效果。出人意料地,於該至少一種共聚物(A)的製備中不需要苯乙烯或α-甲基苯乙烯來達成有利效果,故其因此被省略。較佳地,至少一種共聚物(A)係藉由單體a)、b)、c)及視情況的d)的聚合作用得到,而未使用任何其他單體,即至少一種共聚物(A)有利地係由單體a)、b)、c)及視情況的d)組成。
藉由以下一般在本技術領域已知的方法、由單體a)、b)、c)及視情況的d)製備該至少一種共聚物(A)。共聚作用通常藉由使用自由基聚合起始劑、以自由基聚合來進行。於本發明目的有用的自由基聚合起始劑包括偶氮化合物,例如:分別來自Dupont或WAKO Pure Chemical Industries的Vazo 56或Wako V-50(CAS:2997-92-4)。自由基聚合起始劑以習慣的已知量被施用,舉例而言,該量係基於單體a)、b)、c)及視情況的d)的總重量計,在2.5重量%至5重量%範圍內。
至少一種共聚物(A)係得自於以下的彼此聚合:基於聚合反應中使用的單體a)、b)、c)及d)的總重量計,20重量%至50重量%、較佳30重量%至40重量%之單體a);20重量%至50重量%、較佳30重量%至40重量%之單體b);10重量%至40重量%、較佳20重量%至30重量%之單體c);及 0重量%至10重量%、較佳0重量%至5重量%之單體d),在聚合反應中使用的單體a)、b)、c)及d)的總量為100重量%。
共聚物(A)係新穎的。因此,本發明亦關於一種得自於以下的彼此聚合之共聚物(A):a)至少一種C16-C18醇的無氟(甲基)丙烯酸酯;b)至少一種C18-C22醇的無氟(甲基)丙烯酸酯;c)至少一種選自氯乙烯及二氯亞乙烯之群的單體;及視情況的d)至少一種選自2-羥基乙基(甲基)丙烯酸酯及3-氯-2-羥基乙基(甲基)丙烯酸酯之群的單體,其中上文中說明的意義和偏好仍適用。
至少一種蠟組分(B)係選自具有55℃至75℃熔融範圍的石蠟、及具有25℃至55℃熔融範圍的矽蠟之群。具有在這些限制以外的熔融範圍的石蠟和矽蠟不是非常適合於根據本發明的分散液。具有低於前述熔融範圍的石蠟和矽蠟不能提供經水性分散液處理的紡織品所需的撥水性效果程度。它們還造成經處理紡織品部分的洗滌耐久性降低。具有高於上述熔融範圍的石蠟和矽蠟可能致使紡織品的可接受撥水性和洗滌耐久性,但導致這些水性分散液具有增加的黏度,因此這些分散液的可加工性變得不足。此外,分散液的成本更高且更不便於製造。適合的石蠟係已知的且經敘述於例如「Römpp Chemie-Lexikon,9th edition,Georg-Thieme-Verlag,Stuttgart-New York,chapters headed "Paraffin" and "Wachse"」中。舉例而言,適合的矽蠟係含有烷基側鏈的聚矽氧烷。於本發明之分散液有用的至少一種蠟(B)係市售可得,舉例而言,適合的石蠟Sasol Wax GmbH的Sasolwax 7040、及適合的矽蠟Siltech Corporation的Silwax D222。
若使用石蠟作為該至少一種組分(B),根據本發明之水性分散液適合地包含例如:基於水性分散液中組分(A)與組分(B)的總重量計,20重量%至60重量%、較佳30重量至50重量%、尤其35重量%至45重量%之組分(A);及40重量%至80重量%、較佳50重量%至70重量%、尤其55重量%至65重量之作為組分(B)的石蠟,其具有55℃至75℃的熔融範圍,組分(A)及(B)的總量係100重量%。
若使用矽蠟作為該至少一種組分(B),根據本發明之水性分散液適合地包含例如:基於水性分散液中組分(A)與組分(B)的總重量計,60重量%至95重量%、較佳70重量至90重量%、尤其75重量%至85重量%之組分(A);及5重量%至40重量%、較佳10重量%至30重量%、尤其15重量%至25重量之作為組分(B)的矽蠟,其具有25℃至55℃的熔融範圍,組分(A)及(B)的總量係100重量%。
至少一種界面活性劑(C)係分散劑或分散劑的混合物,以確保分散液的穩定性。有用的分散劑包括已知的市售可得表面活性化合物,諸如:非離子乙氧基化化合物,例如乙氧基化醇或乙氧基化羧酸;陽離子界面活性劑,諸如四級銨鹽;或脂肪胺。適當地,脂肪胺與適合的酸被組合施用,例如有機酸,諸如醋酸。
較佳地,至少一種界面活性劑(C)係脂肪胺、或脂肪醇乙氧 基化物、或脂肪胺及脂肪醇乙氧基化物之界面活性劑混合物。舉例而言,適合的脂肪胺係C12-C22烷基二甲胺,諸如:月桂基二甲胺、十四基二甲胺、十六基二甲胺、二甲基椰油胺(dimethylcoconut amine)、十八基二甲胺、二十二基二甲胺、尤其十八基二甲胺。適合的脂肪胺係市售可得。適合的脂肪醇乙氧基化物係分支或不分支的。舉例而言,適合的分支二級醇乙氧化物係聚乙二醇三甲基壬基醚,諸如來自Dow的Tergitol TMN-10。
本發明之分散液含有基於分散液之總重量計,0.5重量%至3重量%之該至少一種界面活性劑(C)。較佳地,脂肪胺係以基於分散液之總重量計,0.5重量%至2重量%之量被施用。本發明之水性分散液具有非常高的穩定性。
根據本發明之水性分散液可在一步法或二步法中被製備。
在本發明的一個具體實例中,若蠟(B)為石蠟,則使用二步法。因此,石蠟(B)的水性分散液係藉由在容器中加熱蠟至約略高於其熔點20℃來製備。適當地,添加入少量適合的溶劑,例如二丙烯甘醇。單獨製備該至少一種界面活性劑(C)的熱水性混合物,並使用Turrax、在攪拌下將其添加至熔融蠟中,其後在例如250巴及85至90℃下高壓分散。在單獨的容器中,藉由混合以下來製備共聚物(A)的水性分散液:至少一種界面活性劑(C);單體a)、b)及視情況的d);以及溫水。舉例而言,藉由在250巴及50至60℃下高壓分散該混合物得到分散液。冷卻分散液至室溫,添加聚合起始劑及單體c),且聚合作用在一定溫度(例如55至65℃)下數個小時後達到。組合石蠟(B)的水性分散液及共聚物(A)的水性分散液,以產生穩定的水性分散液。
在本發明另一個具體實例中,若蠟(B)為矽蠟,則使用一步法。因此,水性分散液係藉由使用Turrax、在攪拌下添加以下至容器中來製備:該至少一種界面活性劑(C)、適當地少量適合的溶劑,例如二丙烯甘醇、矽蠟(B)、單體a)、b)及視情況的d)、及溫水。舉例而言,藉由在250巴及50至60℃下高壓分散該混合物得到分散液。冷卻分散液至室溫,添加聚合起始劑及單體c),且聚合作用在一定溫度(例如55至65℃)下進行數個小時,以產生穩定的水性分散液。
若需要,可以將已知可用作紡織品處理組合物的組分的進一步成分添加至所得到的本發明的水性分散液中。
紡織物的處理可以藉由以下一般習慣的方法進行,例如:藉由通過壓染(padding);隨後的乾燥;以及適當時,在例如90至190℃、較佳100至180℃的溫度下固化。在某些具體實例中,在100℃下進行低溫固化。在另一個具體實例中,在150℃下進行固化。待處理(以根據本發明之水性分散液)之紡織物係例如:棉、聚酯、或棉-聚酯混紡。通常,此等織物係梭織物、針織物或非織物。
根據本發明之分散液特別可用於賦予天然及合成紡織物上的撥水性質。出人意料地,即使在合成紡織物(諸如:聚酯織物、或棉與聚酯的混合織物)上亦達到所需的撥水性效果程度。藉由組合使用本發明的水性分散液與用於撥油產品或撥水產品的增效劑〔例如PHOBOL® XAN增效劑(Huntsman Corp)〕,可以增強效果程度。以根據本發明之水性分散液處理之紡織物尤其適用於外衣。
以下實施例用於說明本發明。除非另有說明,溫度以攝氏度 提供、份數為重量份、且百分比係關於重量百分比。重量份係關於公斤與公升比的體積份。
化學品:
‧十八基二甲胺(CAS:124-28-7)
‧Tergitol TMN-10:87%聚乙二醇三甲基壬基醚(CAS:60828-78-6)
‧二丙烯甘醇(CAS:25265-71-8)
‧醋酸(CAS:64-19-7)
‧在約70℃熔化之Paraffin 2222或Sasolwax 7040(CAS:8002-74-2;64742-51-4)
‧Silwax D222,34℃至42℃之熔融範圍(CAS:73891-93-7)
‧甲基丙烯酸二十二烷基酯1822(BEMA 1822)(CAS:90551-86-3)
‧甲基丙烯酸硬脂酸酯(MA 16-18)(CAS:90551-83-0)
‧2-羥基乙基甲基丙烯酸酯(CAS:868-77-9)
‧二氯亞乙烯(CAS:75-35-4)
‧Wako V 50:2,2'-偶氮雙(2-甲基丙脒)二鹽酸鹽(CAS:2997-92-4)
‧用於撥油及撥水產品的PHOBOL® XAN增效劑
實施例1:
a)向一個容器填充2.2份的十八基二甲胺、1.1份的Tergitol TMN-10、6.6份的二丙烯甘醇及2.0份的醋酸(60%)。添加15.0份的甲基丙烯酸二十二烷基酯、15.0份的甲基丙烯酸硬脂酸酯、及0.7份的2-羥基乙基甲基丙烯酸酯、以及最後110份的溫水至此混合物中。將混合物用Turrax攪拌約1分鐘,然後在250巴的壓力及50至60℃的溫度下進行高壓分散以 產生穩定乳液。冷卻所得到的乳液至溫度約20℃。在4.6份的水及12.0份的二氯亞乙烯中添加0.4份的Wako V 50後,在65℃的氮氣氛圍中進行聚合作用約8小時。得到152份的水性共聚物分散液(在120℃下乾燥90分鐘後,得到40.6份的產物)。
b)在一個容器中,在溫度約90℃下熔化60.0份的Paraffin 2222或Sasolwax 7040。將10.0份的二丙烯甘醇添加至所得到的石蠟熱熔體中。在攪拌下,向單獨的容器填充3.4份的十八基二甲胺、1.6份Tergitol TMN-10、及4.0份的醋酸(60%)、以及最後200份的熱水。在攪拌下將所得到的混合物添加至熔融蠟。隨後,將所得到的混合物用Turrax攪拌約1分鐘,然後在250巴的壓力及85至90℃的溫度下進行高壓分散,以產升265份的穩定分散液。
藉由混合以下得到根據本發明之水性分散液:56.3份藉由步驟a)得到的分散液、以及155.8份藉由步驟b)得到的分散液。
實施例2:
向一個容器填充2.2份的十八基二甲胺、1.1份的Tergitol TMN-10、6.6份的二丙烯甘醇及2.0份的醋酸(60%)。添加8.5份的矽蠟、15.0份的甲基丙烯酸二十二烷基酯、15.0份的甲基丙烯酸硬脂酸酯、及0.7份的2-羥基乙基甲基丙烯酸酯、以及最後110份的溫水至此混合物中。將混合物用Turrax攪拌約1分鐘,然後在250巴的壓力及50至60℃的溫度下進行高壓分散以產生穩定乳液。冷卻所得到的乳液至溫度約20℃。在4.5份的水及12.0份的二氯亞乙烯中添加0.5份的Wako V 50後,在65℃的氮氣氛圍中進行聚合作用約8小時。得到155份的根據本發明的水性分散液(在120℃下乾 燥90分鐘後,得到47.3份的產物)。
以下實施例描述了以根據實施例1及實施例2製備的分散液處理不同的紡織物。
應用實施例(後處理):
聚酯:用含有以下之液體來壓染100%聚酯的織物:1g/l的60%醋酸、5g/l的潤濕劑(INVADINE® PBN)、及40g/l(80g/l)的實施例1之分散液或實施例2之分散液(液體壓吸率59%)。
棉-聚酯混紡:在壓染機中用含有以下之液體來處理梭織物:1g/l的60%醋酸、5g/l的潤濕劑(INVADINE® PBN)、及40g/l(80g/l)的實施例1之分散液或實施例2之分散液(液體壓吸率51%)。
棉:在壓染機中用含有以下之液體來處理棉梭織物:1g/l的60%醋酸、5g/l的潤濕劑(INVADINE® PBN)、及40g/l(80g/l)的實施例1之分散液或實施例2之分散液(液體壓吸率69%)。
藉由使用水性處理組合物重複上述應用實施例,除了上述成分外,該組合物還含有5g/l(10g/l)的PHOBOL® XAN增效劑。
壓染後,織物(棉、聚酯及棉-聚酯混紡)在110℃下經乾燥10分鐘,然後在150℃下經固化5分鐘。
使根據應用實施例得到的經後處理織物經受以下試驗:
(I)根據AATCC 22-2005,ISO 4920(EN 24 920)的噴灑試驗(Spray test)
(II)根據DIN EN 29865,ISO 9865的Bundesmann試驗
測試結果總結於以下表1至表3中。
a)40g/l的實施例1(Ex1)之分散液或實施例2(Ex2)之分散液。
b)80g/l的實施例1(Ex1)之分散液或實施例2(Ex2)之分散液。
c)5g/l的PHOBOL® XAN增效劑。
d)10g/l的PHOBOL® XAN增效劑。
e)織物後處理後的初始等級。
f)經後處理織物在20次清洗和洗滌後的等級,20 x 7A LTD(洗衣翻轉乾燥)
a)至f)定義如表1下方所示
a)至f)定義如表1下方所示
Claims (8)
- 一種不含氟化物之水性分散液,其包含(A)至少一種共聚物,其由以下單體的聚合作用所得到:a)至少一種C 16-C 18醇的無氟(甲基)丙烯酸酯;b)至少一種C 18-C 22醇的無氟(甲基)丙烯酸酯;c)至少一種單體,其選自氯乙烯及二氯亞乙烯之群;且,視情況地d)至少一種單體,其選自2-羥基乙基(甲基)丙烯酸酯及2-氯-3-羥基乙基(甲基)丙烯酸酯之群;(B)至少一種組分,其選自具有55℃至75℃的熔融範圍的石蠟及具有25℃至55℃的熔融範圍的矽蠟之群;(C)至少一種界面活性劑;及(D)水,其中共聚物(A)之該單體a)及b)是不同的,且該共聚物(A)不含任何苯乙烯或α-甲基苯乙烯之聚合單元。
- 根據申請專利範圍第1項之水性分散液,其包含基於該水性分散液中組分(A)與組分(B)的總重量計,20至60重量%的組分(A);及40至80重量%之作為組分(B)的石蠟,其具有55℃至75℃的熔融範圍。
- 根據申請專利範圍第1項之水性分散液,其包含,基於該水性分散液中組分(A)與組分(B)的總重量計,60至95重量%的組分(A),及5至40重量%之作為組分(B)的矽蠟;其具有25℃至55℃的熔融範圍。
- 根據申請專利範圍第1項至第3項中任一項之水性分散液,其中該至少一種共聚物(A)係得自於以下的彼此聚合: 基於聚合反應中使用的單體a)、b)、c)及d)的總重量計,20重量%至50重量%、較佳30重量%至40重量%之單體a);20重量%至50重量%、較佳30重量%至40重量%之單體b);10重量%至40重量%、較佳20重量%至30重量%之單體c);及0重量%至10重量%、較佳0重量%至5重量%之單體d)。
- 根據申請專利範圍第1項至第4項中任一項之水性分散液,其中,該至少一種界面活性劑為脂肪胺、或脂肪醇乙氧基化物、或脂肪胺及脂肪醇乙氧基化物之界面活性劑混合物。
- 一種用於處理紡織物之方法,其包含施用根據申請專利範圍第1項至第5項中任一項之水性分散液至該紡織物。
- 根據申請專利範圍第6項之方法,其中該紡織物為棉、聚酯、或棉-聚酯混紡織物。
- 一種共聚物,其由以下單體的聚合作用所得到:a)至少一種C 16-C 18醇的無氟(甲基)丙烯酸酯;b)至少一種C 18-C 22醇的無氟(甲基)丙烯酸酯,c)至少一種單體,其選自氯乙烯及二氯亞乙烯之群;且,視情況的d)至少一種單體,其選自2-羥基乙基(甲基)丙烯酸酯及2-氯-3-羥基乙基(甲基)丙烯酸酯之群。
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