TWI529183B - 含氟聚合物之製造方法 - Google Patents
含氟聚合物之製造方法 Download PDFInfo
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- TWI529183B TWI529183B TW102124142A TW102124142A TWI529183B TW I529183 B TWI529183 B TW I529183B TW 102124142 A TW102124142 A TW 102124142A TW 102124142 A TW102124142 A TW 102124142A TW I529183 B TWI529183 B TW I529183B
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- fluorine
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- 125000001153 fluoro group Chemical group F* 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 5
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- 239000011737 fluorine Substances 0.000 claims description 78
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- 239000003795 chemical substances by application Substances 0.000 claims description 21
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Description
本發明係關於對纖維製品(例如,地毯)、紙、不織布、石材、靜電過濾網、防塵罩、燃料電池之物品賦予優異的撥水性、撥油性、防污性之含氟聚合物及包含此聚合物之處理劑組成物,特別是關於表面處理劑組成物。
以往,已提案各種含氟化合物。含氟化合物之優點係具有優異的耐熱性、抗氧化性、耐候性等特性。含氟化合物之自由能低,即,利用其難以附著之特性,含氟化合物可作為,例如,撥水撥油劑及防污劑使用。例如,美國專利第5247008號說明書中記載丙烯酸或甲基丙烯酸之全氟烷基酯、與丙烯酸或甲基丙烯酸之烷基酯、與丙烯酸或甲基丙烯酸之胺基烷基酯之共聚物之水性分散物作為纖維製品、皮革、紙及礦物基材用之加工處理劑(finishing agent)。
再者,以往以提升對水洗、乾洗等之撥水撥油性之耐久性為目的,已嘗試使含有氟烷基之聚合性單體與具有接著性基之單體共聚合,或混合含有氟烷基之聚合物與皮膜強度高之聚合物。於塗料(塗佈劑)領域中,藉由使用具有多層結構之粒子聚合物維持氟之特性,已成功賦予加工性之新穎特性(例如,日本特
開平06-56944號公報)。
再者,為了帶有耐久性、低溫固化等特性,已提倡多層結構粒子聚合物之組成物(例如,日本特開平02-001795號公報、日本特開平07-278422號公報、日本特開平11-172126號公報、日本特開平2007-291373號公報)。
再者,以往在稀釋一般的水性分散液而調配撥水撥油劑之加工浴中,當放入欲處理布料時,因受到機械性衝擊而損壞分散液並引起乳液粒子凝集、沉降,撥輥上附著聚合物而汙染布料的輥汙染等之問題時常發生。雖已提案幾個優異的汙染物之安定性之方法(例如,日本特開平9-118877號公報、WO2004/069924號公報),但伴隨近年來之撥水撥油加工之多樣性,不一定能達到提供充分滿足的安定性。再者,關於輥上附著聚合物之問題,易引起聚合物之高黏著性等的問題。再者,在氟烷基之碳數為6以下之含有氟烷基之聚合物方面,因聚合物之熔點降低,而有黏著性高於氟烷基之碳數為8以上者之傾向。
[專利文獻1]美國專利第5247008號說明書
[專利文獻2]日本特開平06-56944號公報
[專利文獻3]日本特開平02-001795號公報
[專利文獻4]日本特開平07-278422號公報
[專利文獻5]日本特開平11-172126號公報
[專利文獻6]日本特開平2007-291373號公報
[專利文獻7]日本特開平9-118877號公報
[專利文獻8]WO2004/069924號公報
本發明之目的係提供一種撥水撥油劑組成物,其賦予纖維製品等之基材優異的撥水撥油性,且於基材之加工處理中,可有效地防止聚合物對輥之附著。
本發明者等人為了解決上述問題,以提供抑制高黏著性之聚合物部分之生成、發揮高的撥水撥油性、且耐久性(特別是撥水撥油性之耐洗性)亦優異之撥水撥油劑組成物為目的而進行密集研究。其結果係發現,藉由改變帶有具有特定化學結構之聚合單元之聚合物與具有含有氟烷基之單體之聚合單元之聚合物的聚合起始時刻,達成上述目的而完成本發明。
本發明係提供一種含氟聚合物,該含氟聚合物包含由第1單體所形成之第1聚合物與由第2單體所形成之第2聚合物,其中,在第1聚合物之存在下聚合第2單體,第1單體及第2單體之至少一者包含含氟單體(a),且第1單體及第2單體兩者皆包含鹵化烯烴(b)。
又,本發明係提供一種含氟聚合物之製法,係包含由第1單體所形成之第1聚合物與由第2單體所形成之第2聚合物之含氟聚合物的製法,且該製法包含:
(I)聚合第1單體而得到第1聚合物之步驟,及(II)在第1聚合物之存在下,藉由將第2單體饋入並聚合而得到第2聚合物之步驟,其中,第1單體及第2單體之至少一者包含含氟單體(a),且第1單體及第2單體兩者皆包含鹵化烯烴(b)。
此外,本發明亦提供以上述含氟聚合物為必須成分之撥水撥油劑。
含氟聚合物具有由含氟單體衍生之重複單元及由鹵化烯烴等的非氟單體衍生之重複單元。
含氟聚合物可藉由分別饋入而製造。藉由分別饋入而進行單體之二段式聚合。分別饋入意指延緩1種以上單體之饋入(開始聚合),而進行其它之1種以上單體之饋入(開始聚合)。二段式聚合意指在聚合包含1種以上單體之第1單體而得之第1聚合物存在下,進行包含其它之1種以上單體之第2單體之聚合。
藉由使用本發明,可得到一種賦予纖維製品等之基材優異的撥水撥油性,且於基材之加工處理中,可有效地防止聚合物對輥之附著之撥水撥油劑組成物。此外,撥水撥油劑組成物之撥水撥油性的耐久性高。
本發明之含氟聚合物具有由第1單體衍生之重複單元及由第2單體衍生之重複單元。第1聚合物與第2聚合物可共
聚合。即,第1聚合物與第2聚合物亦可化學性鍵結。或者,第1聚合物與第2聚合物不形成化學鍵結,而可為物理性鍵結。物理性鍵結之例為第1聚合物形成核而第2聚合物形成殼之核/殼結構。在核/殼結構中,第1聚合物與第2聚合物會有無化學性鍵結之情形,但可為化學性鍵結。
在本發明中,單體係使用含氟單體(a)及鹵化烯烴單體(b)。可視需要而使用非氟非交聯性單體(c)、及/或非氟交聯性單體(d)。
第1單體及第2單體之至少一者包含含氟單體。較佳為第1單體包含含氟單體,而第2單體不含含氟單體。
第1單體及第2單體兩者皆包含鹵化烯烴單體。
第1單體可包含非氟非交聯性單體。較佳為第2單體不含非氟非交聯性單體。因第2單體不含非氟非交聯性單體,在包含含氟聚合物之處理劑之加工處理中,對於因輥上附著聚合物之輥汙染之防止性能優異。
第1單體及第2單體之至少一者亦可包含非氟交聯性單體。在含氟聚合物包含非氟交聯性單體時,可為第1單體不含非氟交聯性單體,而第2單體包含非氟交聯性單體,或者亦可為第1單體包含非氟交聯性單體,而第2單體不含非氟交聯性單體。
第1單體與第2單體之單體的較佳種類係如下述之態樣。
含氟單體及非氟交聯性單體亦可各自存在於第1單體與第2單體兩者。即,可使用除了含氟單體存在於第1單體與第2單體兩者中以外,與態樣1至7相同之態樣、除了非氟交聯性單體存在於第1單體與第2單體兩者中以外,與態樣1至7相同之態樣。
(a)含氟單體
含氟單體為下式所示之含氟單體。
CH2=C(-X)-C(=O)-Y-Z-Rf[式中,X為氫原子、一價有機基或鹵素原子,Y為-O-或-NH-,Z為直接鍵結或二價有機基,Rf為碳數1至20之氟烷基。]
Z可為例如碳數1至20之直鏈伸烷基或支鏈伸烷基,例如,式
-(CH2)X-所示之基(式中,X為1至10),或者式-SO2N(R1)R2-或式-CON(R1)R2所示之基(式中,R1為碳數1至10之烷基,R2為碳數1至10之直鏈伸烷基或支鏈伸烷基)、或者式-CH2CH(OR3)CH2-所示之基(式中,R3表示氫原子、或碳數1至10之醯基(例如,甲醯基或乙醯基等))、或者式-Ar-CH2-(式中,Ar為視需要具有取代基之伸芳基)所示之基、-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(但是,m為1至10,n為0至10)。X之具體例為H、Me(甲基)、Cl、Br、I、F、CN、CF3。
含氟單體(a)較佳為通式(I)所示之丙烯酸酯或丙烯醯胺。
CH2=C(-X)-C(=O)-Y-Z-Rf (I)[式中,X為氫原子、碳數1至21之直鏈狀或支鏈狀之烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(但是,X1及X2為氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21之直鏈狀或支鏈狀之氟烷基、經取代或未經取代之苯甲基、經取代或未經取代之苯基;Y為-O-或-NH-;Z為碳數1至10之脂肪族基、碳數6至18之芳香族基或環狀脂肪族基、-CH2CH2N(R1)SO2-基(但是,R1為碳數1至4之烷基)、或-CH2CH(OZ1)CH2-基(但是,Z1為氫原子或乙醯基)、或-(CH2)m-SO2-(CH2)n-基、或-(CH2)m-S-(CH2)n-基(但是,m為1至10,n為0至10);Rf為碳數1至20之直鏈狀或支鏈狀之氟烷基。]
含氟單體(a)之(丙烯酸酯或甲基丙烯酸酯之)α位置
有經鹵素原子等取代之情形。因此,式(1)中,X可為碳數2至21之直鏈狀或支鏈狀之烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(但是,X1及X2為氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21之直鏈狀或支鏈狀之氟烷基、經取代或未經取代之苯甲基、經取代或未經取代之苯基。
上記式(1)中,Rf基較佳為全氟烷基。Rf基之碳數較佳為1至12,例如1至6,特佳為4至6。Rf基之例為-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3、-(CF2)4CF3、-(CF2)2CF(CF3)2、-CF2C(CF3)3、-CF(CF3)CF2CF2CF3、-(CF2)5CF3、-(CF2)3CF(CF3)2、-(CF2)4CF(CF3)2、-C8F17等。
Z較佳為碳數1至10之脂肪族基、碳數6至18之芳香族基或環狀脂肪族基、-CH2CH2N(R1)SO2-基(但是,R1為碳數1至4之烷基)、或-CH2CH(OZ1)CH2-基(但是,Z1為氫原子或乙醯基)、或-(CH2)m-SO2-(CH2)n-基、或-(CH2)m-S-(CH2)n-基(但是,m為1至10,n為0至10)。脂肪族基較佳為伸烷基(特別是碳數1至4,例如1或2)。芳香族基或環狀脂肪族基可經取代或未經取代。S基或SO2基可直接鍵結於Rf基。
含氟單體(a)之具體例可例如以下例示者,但並不限定於此等者。
CH2=C(-H)-C(=O)-O-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-C6H4-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-CH3)SO2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2N(-C2H5)SO2-Rf
CH2=C(-H)-C(=O)-O-CH2CH(-OH)CH2-Rf
CH2=C(-H)-C(=O)-O-CH2CH(-OCOCH3)CH2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-H)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-H)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CH3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CH3)-C(=O)-NH-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-F)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-F)-C(=O)-NH-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CN)-C(=O)-NH-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-S-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-NH-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-F)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-F)-C(=O)-NH-(CH2)3-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-Cl)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CF3)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CF2H)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CN)-C(=O)-O-(CH2)3-SO2-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-S-(CH2)2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)3-SO2-Rf
CH2=C(-CF2CF3)-C(=O)-O-(CH2)2-SO2-(CH2)2-Rf[上述式中,Rf為碳數1至20之氟烷基。]
(b)鹵化烯烴單體
鹵化烯烴單體(b)較佳為經1至10個氯原子、溴原子或碘原子取代之碳數2至20之烯烴。鹵化烯烴單體(b)較佳為碳數2至20之氯化烯烴,特佳為具有1至5個氯原子之碳數2至5之烯烴。鹵化烯烴單體(b)之較佳具體例為鹵化乙烯,例如氯化乙烯、溴化乙烯、碘化乙烯,鹵化亞乙烯,例如氯化亞乙烯、溴化亞乙烯、碘化亞乙烯。因撥水撥油性(特別是撥水撥油性之耐久性)提高,較佳為氯化乙烯。
(c)非氟非交聯性單體
非氟非交聯性單體(c)為不含氟原子之單體。非氟非交聯性單體(c)不具有交聯性官能基。非氟非交聯性單體(c)與交聯性單體(d)不同,係非交聯性。非氟非交聯性單體(c)較佳為具有碳-碳雙鍵之非氟單體。非氟非交聯性單體(c)較佳為不含氟之乙烯基單體。非氟非交聯性單體(c)一般為具有1個碳-碳雙鍵之化合物。
較佳之非氟非交聯性單體(c)可為下式所示之化合物。
CH2=CA-T[式中,A為氫原子、甲基、或氟原子以外之鹵素原子(例如,氯原子、溴原子及碘原子),T為氫原子、碳數1至30(例如,1至20)之鏈狀或環狀烴基、或具有酯鍵之鏈狀或環狀之碳數1至31(例如,1至20)之有機基。]
碳數1至30之鏈狀或環狀烴基之例為碳數1至30之直鏈或支鏈之脂肪族烴基、碳數4至30之環狀脂肪族基、碳數
6至30之芳香族烴基、碳數7至30之芳香脂肪族烴基。
具有酯鍵之鏈狀或環狀之碳數1至31之有機基之例為-C(=O)-O-Q及-O-C(=O)-Q(於此,Q為碳數1至30之直鏈或支鏈之脂肪族烴基、碳數4至30之環狀脂肪族基、碳數6至30之芳香族烴基、碳數7至30之芳香脂肪族烴基)。較佳為碳數12至30(特別是18至30)之直鏈或支鏈之脂肪族烴基、碳數4至30之環狀脂肪族基、碳數6至30之芳香族烴基、碳數7至30之芳香脂肪族烴基,更佳為碳數12至30(特別是18至30)之直鏈或支鏈之脂肪族烴基、碳數4至30之環狀脂肪族基。
非氟非交聯性單體(c)之較佳例中,包含例如,乙烯、乙酸乙烯酯、丙烯腈、苯乙烯、聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、及乙烯基烷基醚。非氟非交聯性單體(c)不限定於此等例。
非氟非交聯性單體(c)可為具有烷基之(甲基)丙烯酸酯。烷基之碳原子數可為1至30,例如,6至30(例如,10至30,特別是18至30)。例如,非氟非交聯性單體(c)可為下述通式所示之丙烯酸酯。
CH2=CA1COOA2[式中,A1為氫原子、甲基、或氟原子以外之鹵素原子(例如,氯原子、溴原子及碘原子),A2為CnH2n+1(n=1至30)所示之烷基。]
因輥上附著聚合物之防止性提高,含氟聚合物較佳為具有由丙烯酸酯(CH2=CA1COOA2)衍生之重複單元,其中,A2為碳數12
至30,特別是18至30之烷基。
非氟非交聯性單體(c)可為具有環狀烴基之(甲基)丙烯酸酯單體。具有環狀烴基之(甲基)丙烯酸酯單體(B)為具有(較佳為一價之)環狀烴基及一價之(甲基)丙烯酸酯基之化合物。一價之環狀烴基與一價之(甲基)丙烯酸酯基為直接鍵結。環狀烴基可列舉飽和或不飽和之單環基、多環基、交聯環基等。環狀烴基較佳為飽和。環狀烴基之碳數較佳為4至20。環狀烴基可列舉碳數4至20,特別是5至12之環狀脂肪族基、碳數6至20之芳香族基、碳數7至20之芳香脂肪族基。環狀烴基之碳數特佳為15以下,例如10以下。較佳為環狀烴基之環中之碳原子直接鍵結於(甲基)丙烯酸酯基中之酯基。環狀烴基較佳為飽和環狀脂肪族基。環狀烴基之具體例為環己基、第三丁基環己基、異莰基、二環戊烷基、二環戊烯基。(甲基)丙烯酸酯基為丙烯酸酯基或甲基丙烯酸酯基,但較佳為甲基丙烯酸酯基。具有環狀烴基之單體之具體例可列舉甲基丙烯酸環己酯、甲基丙烯酸第三丁基環己酯、甲基丙烯酸苯甲酯、甲基丙烯酸異莰酯、丙烯酸異莰酯、甲基丙烯酸二環戊酯、丙烯酸二環戊酯、丙烯酸二環戊烯酯等。
(d)非氟交聯性單體
本發明之含氟聚合物可具有由非氟交聯性單體(d)衍生之重複單元。非氟交聯性單體(d)為不含氟原子之單體。非氟交聯性單體(d)可為具有至少2個反應性基及/或碳-碳雙鍵,且不含氟原子之化合物。非氟交聯性單體(d)可為具有至少2個碳-碳雙鍵之化合物、或者具有至少1個碳-碳雙鍵及至少1個反應性基之化合物。反應性基之例為羥基、環氧基、氯甲基、嵌段異氰酸酯基、胺基、
羧基等。非氟交聯性單體(d)可為具有反應性基之單(甲基)丙烯酸酯、(甲基)二丙烯酸酯或單(甲基)丙烯醯胺。或者,非氟交聯性單體(d)可為二(甲基)丙烯酸酯。
非氟交聯性單體(d)例示為,例如,二丙酮(甲基)丙烯醯胺、(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、(甲基)丙烯酸羥甲酯、(甲基)丙烯酸羥乙酯、(甲基)丙烯酸3-氯-2-羥丙酯、(甲基)丙烯酸2-乙醯基乙醯氧基乙酯、丁二烯、異戊二烯、氯丁二烯、(甲基)丙烯酸環氧丙酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等,但並不限定於此等者。
在本說明書中,「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯,「(甲基)丙烯醯胺」則意指丙烯醯胺或甲基丙烯醯胺。
藉由使非氟非交聯性單體(c)及/或非氟交聯性單體(d)共聚合,視需要可改善撥水撥油性、防污性及此等性能之清潔性、耐洗濯性、對溶劑之溶解性、硬度、觸感等各種性質。
含氟聚合物中,相對於含氟單體(a)100重量份,鹵化烯烴(b)之量可為2至500重量份,例如5至200重量份,特別是20至150重量份,非氟非交聯性單體(c)之量可為1000重量份以下,例如0.1至300重量份,特別是1至200重量份,非氟交聯性單體(d)之量可為50重量份以下,例如30重量份以下,特別是0.1至20重量份。
關於鹵化烯烴單體之量,第1單體之鹵化烯烴單體與第2單體之鹵化烯烴單體之重量比可為3至97:97至3,例如5至50:95至50,特別是8至40:92至60。或者,相對於第1
單體及第2單體之鹵化烯烴單體總量,第1單體之鹵化烯烴單體之比例為0.1至49重量%,更佳為5至40重量%,再更佳為8至35重量%,特佳為15至30重量%。
在鹵化烯烴單體以外之同種類單體(例如,含氟單體)皆包含於第1單體與第2單體兩者時,第1單體之同種單體與第2單體之同種單體之重量比可為3至97:97至3,例如5至95:95至5,特別是10至90:90至10。
本發明之含氟聚合物亦可以通常之聚合方法製造,或可任意選擇聚合反應之條件。此等聚合方法可列舉溶液聚合、懸浮液聚合、乳化聚合。
溶液聚合係採用在聚合起始劑之存在下,使單體溶解於有機溶劑,以氮氣置換後,在30至120℃之範圍內加熱攪拌1至10小時之方法。聚合起始劑可舉例,例如偶氮二異丁腈、過氧化苯甲醯、二第三丁基過氧化物、月桂醯基過氧化物、異丙苯過氧化氫、過氧化新戊酸第三丁酯、過氧化二碳酸二異丙酯等。相對於單體100重量份,使用0.01至20重量份,例如0.01至10重量份之範圍之聚合起始劑。
有機溶劑為對單體無活性而溶解此等單體者,例如,可為酯(例如,碳數2至30之酯,具體而言為乙酸乙酯、乙酸丁酯)、酮(例如,碳數2至30之酮,具體而言為甲基乙基酮、二異丁基酮)、醇(例如,碳數1至30之醇,具體而言為異丙醇)。有機溶劑之具體例可列舉丙酮、氯仿、HCHC225、異丙醇、戊烷、己烷、庚烷、辛烷、環己烷、苯、甲苯、二甲苯、石油醚、四氫呋喃、1,4-二噁烷、甲基乙基酮、甲基異丁基酮、二異丁基酮、乙酸
乙酯、乙酸丁酯、1,1,2,2-四氯乙烷、1,1,1-三氯乙烷、三氯乙烯、全氯乙烯、四氯二氟乙烷、三氯三氟乙烷等。相對於單體總量為100重量份,使用10至2000重量份,例如,50至1000重量份之範圍之有機溶劑。
乳化聚合係採用在聚合起始劑及乳化劑之存在下,使單體於水中乳化,以氮氣置換後,在50至80℃之範圍內攪拌1至10小時,使之共聚合之方法。聚合起始劑係使用過氧化苯甲醯、月桂醯基過氧化物、過氧化苯甲酸第三丁酯、1-羥基環己基過氧化氫、3-羧基丙醯基過氧化物、過氧化乙醯、偶氮二異丁基脒-二鹽酸鹽、偶氮二異丁腈、過氧化鈉、過硫酸鉀、過硫酸銨等水溶性者、或偶氮二異丁腈、過氧化苯甲醯、二第三丁基過氧化物、月桂醯基過氧化物、異丙苯過氧化氫、過氧化新戊酸第三丁酯、過氧化二碳酸二異丙酯等油溶性者。相對於單體100重量份,使用0.01至10重量份之範圍之聚合起始劑。
為了得到放置安定性優異的共聚合物水分散液,期望使用如高壓均質機、超音波均質機之可賦予強力破碎能之乳化裝置,單體於水中微粒子化,使用油溶性聚合起始劑聚合。再者,乳化劑可使用陰離子性、陽離子性或非離子性之各種乳化劑,相對於單體100重量份,使用0.5至20重量份之範圍之乳化劑。較佳為使用陰離子性及/或非離子性及/或陽離子性之乳化劑。單體未完全相溶時,較佳為添加使此等單體充分相溶之相溶化劑,例如,添加水溶性有機溶劑或低分子量之單體。藉由添加相溶化劑,可使乳化性及共聚合性提高。
水溶性有機溶劑可列舉丙酮、甲基乙基酮、乙酸乙酯、丙二
醇、二丙二醇單甲基醚、二丙二醇、三丙二醇、乙醇等,相對於水100重量份,可使用1至50重量份,例如10至40重量份之範圍之水溶性有機溶劑。再者,低分子量之單體可列舉甲基丙烯酸甲酯、甲基丙烯酸環氧丙酯、甲基丙烯酸2,2,2-三氟乙酯等,相對於單體之總量為100重量份,可使用1至50重量份、例如10至40重量份之範圍之低分子量之單體。
聚合中亦可使用鏈轉移劑。依鏈轉移劑之使用量可使共聚合物之分子量變化。鏈轉移劑之例為月桂硫醇(lauryl mercaptan)、巰基乙酸、硫甘油等含有巰基之化合物(特別是(例如碳數1至30之)烷基硫醇)、次磷酸鈉、亞硫酸氫鈉等無機鹽等。鏈轉移劑之使用量,相對於單體之總量為100重量份,可使用0.01至10重量份,例如0.1至5重量份之範圍之鏈轉移劑。
一般而言,在包含第1單體之液體中進行聚合反應而製造第1聚合物,接著,在包含第1聚合物及第2單體之液體中進行聚合反應而製造第2聚合物,得到由第1聚合物與第2聚合物構成之含氟聚合物。可在第1聚合物之聚合中使第2聚合物開始聚合,或者在第1聚合物之聚合結束後使第2聚合物開始聚合。可在第1聚合物之聚合反應(即,第1單體之聚合反應)10%以上(即,10至100%),例如40%以上(即,40至100%),特別是70%以上(即,70至100%)結束後,使第2聚合物開始聚合。聚合反應結束比例%(即,聚合反應進行比例%)意指反應完成之單體(經聚合之單體)之莫耳%。例如,聚合反應10%結束時,聚合完成之單體為10莫耳%,未反應(未聚合)之單體為90莫耳%。第1單體為至少2種單體之組合時,第1單體之莫耳%係以第1單體之至
少2種單體之總莫耳為基準。
第1聚合物之聚合中意指第1聚合物之聚合反應(即,第1單體之聚合反應)未完全結束。例如,第1聚合物之聚合為10%以上至未滿40%、40%以上至未滿70%、或70%以上至未滿100%(特別是80%至99%,又特別是85%至98%)結束後,可使第2聚合物開始聚合。
第1聚合物之聚合結束後意指第1聚合物之聚合反應(即,第1單體之聚合反應)約100%結束。
使第2聚合物在第1聚合物之聚合中開始聚合時,第2聚合物具有由第1單體及第2單體衍生之重複單元。第1聚合物之聚合結束後使第2聚合物開始聚合時,第2聚合物具有僅由第2單體衍生之重複單元。
第1單體之饋入可一次性(一次)進行,或者亦可連續進行。第1單體之饋入較佳為一次進行。
第2單體之饋入可一次性進行,或者亦可連續進行。第2單體之連續饋入較佳為在第2單體之聚合中單體之氣體(特別是氯化乙烯等鹵化烯烴)之壓力為定值而進行。
本發明之含氟聚合物中,第1聚合物與第2聚合物有化學鍵或無化學鍵。
在使第2單體開始聚合時,較佳為聚合系統中實質上不存在未反應之非氟非交聯性單體。實質上不存在意指,在使第2單體開始聚合時,相對於饋入之非氟非交聯性單體,未反應之非氟非交聯性單體量為10莫耳%以下,較佳為8莫耳%以下,更佳為5莫耳%,再更佳為3莫耳%以下,特佳為1莫耳%以下。
因實質上不存在非氟非交聯性單體,在包含含氟聚合物之處理劑之加工處理中,其對輥上附著聚合物之輥汙染之防止性能優異。
本發明之含氟聚合物較佳為藉由乳化聚合製造。在以第1聚合物及第2聚合物形成之水性分散物之粒子中,第2聚合物可包圍第1聚合物,含氟聚合物可具有由第2聚合物之殼包圍第1聚合物之核的核/殼結構。
含氟聚合物可適用於藉由為了以液體處理纖維製品之已知方法之任一者處理之纖維狀基材(例如,纖維製品等)。纖維製品所適用之溶液中之含氟聚合物的濃度可為例如,0.5重量%至20重量%,或者1重量%至5重量%。纖維製品為布時,可將布浸於溶液中,或者可將溶液附著或噴霧於布上。經處理之纖維製品為表現撥油性而乾燥,較佳為例如,以100℃至200℃加熱。
或者,含氟聚合物可適用於經清淨法之纖維製品,例如,可適用於洗濯適用或乾洗法等之纖維製品。
經處理之纖維製品典型為布,此雖包含織物、編物及不織布、衣料品形態之布及地毯,但亦可為纖維或線或中間纖維製品(例如,纖維束(sliver)或粗線等)。纖維製品材料可為天然纖維(例如,棉或羊毛等)、化學纖維(例如,黏液纖維、嫘縈或新溶媒再生纖維(lyocell)等)、或合成纖維(例如,聚酯、聚醯胺或丙烯酸纖維等)、或者纖維之混合物(例如,天然纖維及合成纖維之混合物等)。本發明之製造聚合物在使纖維素纖維(例如,棉或嫘縈等)具有疏油性及撥油性的方面特別有效。再者,本發明之方法一般係使纖維製品具有疏水性及撥水性。
或者,纖維狀基材可為皮革。為了使皮革具有疏水
性及疏油性,在皮革加工之各種階段中,例如,在皮革之潤濕加工期間、或在皮革之最終處理期間中,來自水溶液或水性乳化物之製造聚合物可適用於皮革。
或者,纖維狀基材亦可為紙。製造聚合物可適用於預先形成之紙,或亦可適用於製紙之各種階段,例如,紙之乾燥期間中。
本發明之表面處理劑較佳為溶液、乳液或氣霧劑之形態。表面處理劑包含含氟聚合物(表面處理劑之活性成分)及介質(特別是液狀介質,例如,有機溶劑及/或水)。表面處理劑中,含氟聚合物之濃度可為例如,0.01至50重量%。
本發明之表面處理劑較佳為包含含氟聚合物及水性介質。在本說明書中,「水性介質」意指僅包含水之介質、及除了水之外,亦含有有機溶劑(有機溶劑之量,相對於水100重量份,為80重量份以下,例如0.1至50重量份,特別是5至30重量份。)之介質。含氟聚合物較佳為藉由乳化聚合製造含氟聚合物之分散液。表面處理劑較佳為含氟聚合物之粒子分散於水性介質之水性分散液。分散液中,含氟聚合物之平均粒徑較佳為0.01至200微米,例如0.1至5微米,特佳為0.05至0.2微米。平均粒徑可以動態光散射裝置、電子顯微鏡等測定。
本發明之表面處理劑可適用於經習知方法處理之被處理物。通常,採用將該表面處理劑分散於有機溶劑或水而稀釋,藉由浸塗法、噴塗法、泡塗法等這樣的已知方法,使該表面處理劑附著於被處理物表面,並乾燥之方法。再者,若有需要,亦可同時使用適當的交聯劑,進行固化。此外,亦可於本發明之表面處理劑中添加防蟲劑、柔軟劑、抗菌劑、難燃劑、抗靜電劑、塗
料固定劑、防皺劑等加以併用。在與基材接觸之處理液中之含氟化合物之濃度可為0.01至10重量%(特別是浸塗法時),例如0.05至10重量%。
以本發明之表面處理劑(例如,撥水撥油劑)處理之被處理物較佳為纖維製品。纖維製品可列舉各種例。例如,棉、麻、羊毛、絹等動植物性天然纖維、聚醯胺、聚酯、聚乙烯醇、聚丙烯腈、聚氯化乙烯、聚丙烯等合成纖維、嫘縈、乙酸酯等半合成纖維、玻璃纖維、碳纖維、石棉纖維等無機纖維、或者此等者之混合纖維。
纖維製品亦可為纖維、線、布等形態之任一者。
「處理」意指將處理劑使用於經浸漬、噴霧、塗佈等之被處理物。藉由處理,處理劑之有效成分之含氟聚合物浸透至被處理物內部及/或附著於被處理物表面。
接下來,列舉實施例、比較例及試驗例具體說明本發明。但是,此等說明並未限定本發明。
後文中,若無特別記載,份或%表示重量份或重量%。
特性係如後述測定。
聚合物分散液之安定性
聚合物分散液之安定性為目視觀察聚合後高壓釜內附著之反應鍋垢,如下述評價之。
◎:無反應鍋垢
○:僅有少許反應鍋垢附著
△:有少量反應鍋垢附著
×:有大量反應鍋垢附著
聚合物之黏著性
將聚合物之水性分散液10g分散於甲醇20g中者使用離心機以10000rpm,60分鐘將聚合物與乳化劑分離,得到測定用樣本聚合物。以黏著性(tacking)試驗機TAC-2((株)RHESCA社製造)測定此聚合物之黏著性。測定樣本聚合物0.1g,測定溫度40℃,荷重500gf之黏著性。
撥水性
使聚合物之水性分散液之固體成分濃度變為1重量%之方式而以水稀釋,並調整處理液。將耐綸布浸漬於處理液,以軋輥(mangle)4kg/cm2、4m/分鐘擰乾,以170℃熱處理1分鐘後,評價該處理布之撥水性。
撥水性係評價洗濯前(HL0)與以AATCC 88B(1)(III)進行5次或10次重複洗濯後(HL5或HL10)(撥水性之耐久性)。撥水性係以JIS-L-1092之噴霧法表示撥水性NO.(參照下表I)。
實施例1
將C6F13CH2CH2OCOC(CH3)=CH2(C6SFMA)179g、丙烯酸硬脂
酯(StA)25g、三丙二醇75.8g、純水446g、聚氧乙烯月桂基醚10.2g、聚氧乙烯油基醚2.47g、聚氧乙烯異十三基醚7.6g加入1L高壓釜,於60℃加溫後,以高壓均質機乳化分散之。乳化後,將氯化乙烯6g壓入充填。此外,添加2,2-偶氮雙(2-脒基丙烷)二鹽酸鹽1.72g,於61℃反應1小時後(聚合反應C6SFMA99%結束,StA 97%結束),為了使高壓釜之內壓維持在0.3MPa,一邊繼續壓入氯化乙烯54g,此外一邊於61℃反應4小時,得到聚合物之水性分散液。使其固形分濃度成為30重量%之方式以純水調整濃度,測定經調整之水性分散液之特性。結果顯示於表A。
實施例2
乳化後,除了將氯化乙烯15g壓入充填,於61℃反應1小時後(聚合反應C6SFMA99%結束,StA 98%結束),為了使高壓釜之內壓維持在0.3MPa,一邊繼續壓入氯化乙烯45g,此外一邊於61℃反應4小時以外,以與實施例1相同方法得到聚合物之分散液。
實施例3
乳化後,除了將氯化乙烯15g壓入充填,於61℃反應1小時後(聚合反應C6SFMA99%結束,StA 97%結束),為了使高壓釜之內壓維持在0.3MPa,一邊繼續壓入氯化乙烯60g,此外一邊於61℃反應5小時以外,以與實施例1相同方法得到聚合物之分散液。
實施例4
乳化後,除了將氯化乙烯15g壓入充填,於61℃反應1小時後(聚合反應C6SFMA99%結束,StA 96%結束),為了使高壓釜之內壓維持在0.3MPa,一邊繼續壓入氯化乙烯75g,此外一邊於61℃
反應6小時以外,以與實施例1相同方法得到聚合物之分散液。
實施例5
乳化後,除了將氯化乙烯15g壓入充填,於61℃反應1小時後(聚合反應C6SFMA99%結束,StA 95%結束),壓入辛硫醇0.075g,為了使高壓釜之內壓維持在0.3MPa,一邊繼續壓入氯化乙烯45g,此外一邊於61℃反應4.5小時以外,以與實施例1相同方法得到聚合物之分散液。
比較例1
將C6F13CH2CH2OCOC(CH3)=CH2 179g、丙烯酸硬脂酯25g、三丙二醇75.8g、純水446g、聚氧乙烯月桂基醚10.2g、聚氧乙烯油基醚2.47g、聚氧乙烯異十三基醚7.6g加入1L高壓釜,於60℃加溫後,以高壓均質機乳化分散之。乳化分散後,添加2,2-偶氮雙(2-脒基丙烷)二鹽酸鹽1.72g,於60℃反應1小時後(聚合反應C6SFMA99%結束,StA 95%結束),壓入氯化乙烯60g,此外反應2小時,得到聚合物之水性分散液。使其固形分濃度成為30重量%之方式以純水調整濃度,測定經調整之水性分散液之特性。結果顯示於表A。
比較例2
將C6F13CH2CH2OCOC(CH3)=CH2 179g、丙烯酸硬脂酯25g、三丙二醇75.8g、純水446g、聚氧乙烯月桂基醚10.2g、聚氧乙烯油基醚2.47g、聚氧乙烯異十三基醚7.6g加入1L高壓釜,於60℃加溫後,以高壓均質機乳化分散之。乳化後,將氯化乙烯6g壓入充填。此外,添加2,2-偶氮雙(2-脒基丙烷)二鹽酸鹽1.72g,於60℃反應3小時,得到聚合物之水性分散液。使其固形分濃度成為30
重量%之方式以純水調整濃度,測定經調整之水性分散液之特性。
各例之特性顯示於表A。
包含本發明之含氟聚合物之處理劑組成物可使用對纖維製品(例如,地毯)、紙、不織布、石材、靜電過濾網、防塵罩、燃料電池之物品賦予優異的撥水性、撥油性、防污性之撥水撥油劑及防污劑等。
Claims (31)
- 一種含氟聚合物,係包含由第1單體所形成之第1聚合物與由第2單體所形成之第2聚合物,其中,在第1聚合物之存在下聚合第2單體,第1單體及第2單體之至少一者包含含氟單體(a),第1單體及第2單體兩者皆包含鹵化烯烴(b),第1單體包含非氟非交聯性單體(c),含氟單體(a)為下式所示者:CH2=C(-X)-C(=O)-Y-Z-Rf[式中,X為氫原子、一價有機基或鹵素原子,Y為-O-或-NH-,Z為直接鍵結或二價有機基,Rf為碳數4至6之氟烷基],鹵化烯烴(b)為經氯原子、溴原子或碘原子取代之碳數2至20之烯烴,非氟非交聯性單體(c)為下式所示者:CH2=CA-T[式中,A為氫原子、甲基、或氟原子以外之鹵素原子,T為氫原子、碳數1至30之鏈狀或環狀之烴基、或具有酯鍵之鏈狀或環狀之碳數1至31的有機基]。
- 如申請專利範圍第1項所述之含氟聚合物,係連續饋入第2單體。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,相對於第1單體及第2單體之鹵化烯烴單體總量,第1單體之鹵化烯 烴單體之比例係0.1至49重量%。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,第1單體包含含氟單體(a)。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,第2單體包含含氟單體(a)。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,第2單體不含非氟非交聯性單體(c)。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,第2單體包含非氟交聯性單體(d)。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,第1聚合物除了包含含氟單體(a)之外,復包含非氟非交聯性單體(c),及視需要而存在之非氟交聯性單體(d)。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,第2聚合物僅包含鹵化烯烴。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,第2聚合物除了包含鹵化烯烴之外,亦包含含氟單體(a)及/或非氟交聯性單體(d)之至少一者。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,含氟單體(a)為(I)式所示者:CH2=C(-X)-C(=O)-Y-Z-Rf (I)[式中,X為氫原子、碳數1至21之直鏈狀或支鏈狀之烷基、氟原子、氯原子、溴原子、碘原子、CFX1X2基(但是,X1及X2為氫原子、氟原子、氯原子、溴原子或碘原子)、氰基、碳數1至21之直鏈狀或支鏈狀之氟烷基、經取代或未經取代之苯甲 基、經取代或未經取代之苯基;Y為-O-或-NH-;Z為碳數1至10之脂肪族基、碳數6至18之芳香族基或環狀脂肪族基、-CH2CH2N(R1)SO2-基(但是,R1為碳數1至4之烷基)或-CH2CH(OZ1)CH2-基(但是,Z1為氫原子或乙醯基)或-(CH2)m-SO2-(CH2)n-基或-(CH2)m-S-(CH2)n-基(但是,m為1至10,n為0至10),Rf為碳數4至6之直鏈狀或支鏈狀之氟烷基]。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,該鹵化烯烴(b)為氯化乙烯、溴化乙烯、碘化乙烯、氯化亞乙烯、溴化亞乙烯或碘化亞乙烯。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,鹵化烯烴(b)為氯化乙烯。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,非氟非交聯性單體(c)為不含氟原子,不具有交聯性官能基,而具有1個碳-碳雙鍵之單體。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,非氟非交聯性單體(c)中,T為碳數12至30之長鏈烴基及飽和環狀烴基。
- 如申請專利範圍第1或2項所述之含氟聚合物,其中,非氟非交聯性單體(c)為下列通式所示之丙烯酸酯:CH2=CA1COOA2[式中,A1為氫原子、甲基、或氟原子以外之鹵素原子, A2為CnH2n+1(n=1至30)所示之烷基]。
- 如申請專利範圍第16項所述之含氟聚合物,其中,A2為碳數12至30之烷基。
- 如申請專利範圍第7項所述之含氟聚合物,其中,該非氟交聯性單體(d)為具有至少2個反應性基及/或碳-碳雙鍵,且不含氟之化合物。
- 一種含氟聚合物之製法,係包含由第1單體所形成之第1聚合物與由第2單體所形成之第2聚合物的含氟聚合物之製法;且該製法包含:(I)聚合第1單體而得到第1聚合物之步驟,及(II)在第1聚合物之存在下,藉由將第2單體饋入並聚合而得到第2聚合物之步驟;其中,第1單體及第2單體之至少一者包含含氟單體(a),第1單體及第2單體兩者皆包含鹵化烯烴(b),第1單體包含非氟非交聯性單體(c),含氟單體(a)為下式所示者:CH2=C(-X)-C(=O)-Y-Z-Rf[式中,X為氫原子、一價有機基或鹵素原子,Y為-O-或-NH-,Z為直接鍵結或二價有機基,Rf為碳數4至6之氟烷基],鹵化烯烴(b)為經氯原子、溴原子或碘原子取代之碳數2至20之烯烴,非氟非交聯性單體(c)為下式所示者: CH2=CA-T[式中,A為氫原子、甲基、或氟原子以外之鹵素原子,T為氫原子、碳數1至30之鏈狀或環狀之烴基、或具有酯鍵之鏈狀或環狀之碳數1至31的有機基]。
- 如申請專利範圍第19項所述之製法,其中,連續饋入第2單體。
- 如申請專利範圍第19或20項所述之製法,其中,第1單體之鹵化烯烴(b)與第2單體之鹵化烯烴(b)之重量比為3:97至97:3。
- 如申請專利範圍第19或20項所述之製法,其在第1聚合物之聚合中,使第2聚合物開始聚合。
- 如申請專利範圍第19或20項所述之製法,其在第1聚合物之聚合結束後,使第2聚合物開始聚合。
- 如申請專利範圍第19或20項所述之製法,其在第1單體之聚合反應至10%以上反應結束後,使第2聚合物開始聚合。
- 如申請專利範圍第19或20項所述之製法,其在第1單體之聚合反應至40%以上反應結束後,使第2聚合物開始聚合。
- 如申請專利範圍第19或20項所述之製法,其在第1單體之聚合反應至70%以上反應結束後,使第2聚合物開始聚合。
- 一種撥水撥油劑,係以申請專利範圍第1至18項中任一項所述之含氟聚合物為必須成分。
- 如申請專利範圍第27項所述之撥水撥油劑,其亦含有水性介質。
- 如申請專利範圍第27項所述之撥水撥油劑,其係水性分散液。
- 一種處理基材之方法,係包含以申請專利範圍第27至29項中任一項所述之撥水撥油劑處理者。
- 一種纖維製品,係經申請專利範圍第27至29項中任一項所述之撥水撥油劑所處理者。
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US20150191869A1 (en) | 2015-07-09 |
US9416486B2 (en) | 2016-08-16 |
JPWO2014007344A1 (ja) | 2016-06-02 |
TW201406796A (zh) | 2014-02-16 |
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CN104428327B (zh) | 2017-03-22 |
CN104428327A (zh) | 2015-03-18 |
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