CN1003791B - 防水和防油剂 - Google Patents
防水和防油剂 Download PDFInfo
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Abstract
一种防水和防油剂,包括含有由(a)单体和(b)单体构成的重复单元的共聚物,(a)是至少有一个全氟烷基或全氟亚烷基和一种丙烯酸酯或甲基丙烯酸酯基团的单体化合物,而(b)是甲基丙烯酸酯,其均聚物的玻璃化温度不低于115℃。该防水和防油剂的耐干洗性和耐滑移性良好。
Description
本发明关于一种防水和防油剂,特别是关于含一种共聚物的防水和防油剂,该共聚物包括一种至少含有一个全氟烷基或全氟亚烷基和一种丙烯酸酯或甲基丙烯酸酯基团的单体化合物。
众所周知,含有至少一个全氟烷基或全氟亚烷基和一种丙烯酸酯或甲基丙烯酸酯基团的单体化合物的聚合物,可以用作织物防水和防油剂(参看美国专利4,296.224)。
为了改进耐洗涤和/或耐干洗性,已经提出过一些改进的办法,但是任何办法均不能改进耐滑移性,例如织物移位:用普通防水和防油剂处理过的纺织品的耐滑移性比未处理过的更差。在本说明书中,“滑移”是指织物的丝线受外力作用而移动或移位。
本发明的一个目的是提供一种耐久性好,即耐干洗的防水和防油剂。
本发明的另一个目的是提供一种能使织物,特别是机织物具有良好的耐滑移性的防水和防油剂。
这些目的和其它目的均通过使用含有一种共聚物的防水和防油剂而达到。这种共聚物由(a)单体和(b)单体构成的重复单元连接而成;(a)单体是至少含有一种全氟烷基或全氟亚烷基和一种丙烯酸酯或甲基丙烯酸酯基团的化合物;(b)单体是甲基丙烯酸酯化合物,其均聚物的玻璃化温度(Tg)不低于115℃。
尽管本发明的防水和防油剂可以是溶液或气溶液形式。但最好是水分散液形式。甲基丙烯酸酯均聚物的玻璃化温度(Tg)不低于115℃,最好不低于130℃,实例有甲基丙烯酸异冰片酯(均聚物的Tg为180℃)和甲基丙烯酸4-氰基苯基酯(均聚物的Tg为155℃)。最好,这种共聚物含有1-50%(重量)的甲基丙烯酸酯(b)(按共聚物总重计),当甲基丙烯酸酯(b)的含量低于5%(重量)时,防水和防油剂不能使织物有足够的耐滑移性。甲基丙烯酸酯(b)的含量超过50%(重量)则不经济。因为耐滑移性并不随甲基丙烯酸酯(b)含量的增加成比例提高。
单体化合物(a)具有一个全氟烷基或全氟亚烷基和一种丙烯酸酯或甲基丙烯酸酯基团。例如日本专利公开47041/1980和日本特许公开(未审查的)45756/1980和71779/1980中都介绍了这种单体化合物(a)的一些实例。
单体化合物(a)最好的实例,其分子式如下:
(1)
Rf-(CH2)OCOCR3=CH2 (2)
(3)
Rf-O-Ar-CH2OCOCR3=CH2 (6)
式中,Rf为C3-C21全氟烷基或全氟亚烷基,R1为氢原子或者C1-C10烷基;R2为C1-C10亚烷基;R3为氢原子或甲基;Ar为取代的或未取代的芳基;和n为1-10的整数。
这种单体化合物(a)的特定实例有:
CF3(CF2)7(CH2)OCOCH=CH2,
CF3(CF2)6(CH2)OCOC(CH3)=CH2,
(CF3)2CF(CF2)6(CH2)2OCOCH=CH2,
CF3(CF2)7(CH2)2OCOC(CH3)=CH2,
CF3(CF2)7(CH2)2OCOCH=CH2,
CF3(CF2)7SO2N(CH3)(CH2)2OCOCH=CH2,
CF3(CF2)7SO2N(C2H5)(CH2)OCOC(CH3)=CH2,
(CF3)2CF(CF2)6CH2CH(OCOCH3)CH2OCOC(CH3)=CH2,
(CF3)2CF(CF2)6CH2CH(OH)CH2OCOCH*CH2,
C9F17O--CH2OCOCH=CH2和
单体化合物(a)在共聚物中的含量至少为25%(重量),最好至少为40%(重量)。最好至少为40%(重量)。
除了单体化合物(a)和甲基丙烯酸酯(b)外,本发明所用的共聚物还可以进一步包括至少一种其它可以共聚的单体。这些可以共聚的单体的实例为:
(1)丙烯酸和甲基丙烯酸;甲基、乙基、*基、异丁基、丙基、2-乙基己基、己基、癸基、十二烷基、十八烷基、β-羟乙基,氢-或烷基-聚氧化乙烯、缩水甘油和苄酯类;和甲基丙烯酸乙基、丁基、己基、癸基、十二烷基、十八烷基、β-羟乙基、氯代羟丙基、氢-或烷基-聚氧化乙烯和缩水甘油酯类;
(2)一种脂肪酸,例如乙酸、丙酸、辛酸、月桂酸和硬脂酸的乙烯基酯类;
(3)苯乙烯及其衍生物,例如,α-甲基苯乙烯和对-甲基苯乙烯;
(4)乙烯基卤化物和亚乙烯基卤化物,例如氟乙烯、氯乙烯、溴乙烯、1,1-二氟乙烯和*1-二氯乙烯;
(5)烯丙酯,例如庚酸烯丙酯、辛酸烯丙酯和己酸烯丙酯;
(6)乙烯基烷基酮,例如,乙烯基甲乙酮和乙烯基乙酮;(7)丙烯酰胺,例如N-甲基丙烯酰胺和N-羟甲基丙烯酰胺,和
(8)二烯,例如2,3-二氯-1,3-丁二烯和异戊二烯。
本发明采用的共聚物可用普通的乙烯基化合物的聚合方法制得,单体化合物(a)、甲基丙烯酸酯(b)和任选择至少一种其它可以共聚的单体的聚合,可以使用任何聚合方法,如本体聚合、溶液聚合、悬浮聚合、乳液聚合和辐射聚合。因为本发明的防水和防油剂通常以水分散液形式使用,所以最好采用乳液聚合法。
例如,在一个装有搅拌器和温度控制装置的反应器中进行乳液聚合。在含大约5-50%(重量)表面活性剂的水溶液中,使单体混合物乳化。在一种用于引发烯键不饱和化合物的引发剂存在下,于大约40-70℃下进行反应。引发剂特定例为2,2′-偶氮二异丁脒二氢氯化物、2,2′-偶氮二异丁腈、2,2′-偶氮二(2,4-二甲基-4-甲氧基戊腈)、过氧化纳、过氧化钡、过氧化氢、过硫酸钠和类似的化合物,引发剂的用量以单体总重计算通常为0.1~2%(重)。为了控制共聚物的分子量,可以在聚合系统中加入少量一种通用链转移剂,如含有1-12个碳原子的链烷基硫醇。
表面活性剂可以是任何一种阳离子、阴离子或非离子型乳化剂,最好是一种阳离子乳化剂和一种非离子乳化剂,或其混合物。阳离子表面活性剂特定实例为十二烷基三甲基醋酸铵、三甲基十四烷基氯化铵、十六烷基三甲基溴化铵、三甲基十八烷基氯化铵、(十二烷基甲基苄基)三甲基氯化铵、苄基十二烷基二甲基氯化铵、甲基十二烷基(氢化聚氧化乙烯),氯化铵、甲基十二烷基(氢化聚乙烯)氯化铵、N-〔2-(二乙氨基)乙基〕油酰胺氢氯化物和类似的化合物。非离子表面活性剂特定实例是环氧乙烷,其带有已基苯酚、异辛基苯酚、十六醇、油酸、C12-C16链烷基硫醇、脱水山梨醇单(C7-C19)脂肪酸酯或C12-C18烷基胺的缩合产物。
本发明的防水和防油剂适用于由天然聚合物、改性天然聚合物或合成聚合材料制得的薄膜、纤维、纱和线、织物或无纺布,以及由长丝、纤维或纱生产的制品。
本发明的防水和防油剂最好使用涂复、浸渍、喷涂、浸涂或滚涂、或者其中的两种或多种相结合的方法涂于基质上。例如,用乳液聚合制得的高浓度分散液用水和任意的表面活性剂稀释到固体物含量达0.1-10(重量)。以这种稀释的乳液用作浸涂浴。基质在此浴中浸涂,过量的液体用挤压辊除去,以便使干燥的基质上约含0.01-1%(重量)的共聚物。然后在100-200℃下将处理过的基质进行干燥。
本发明将用下列实施例进一步详细说明。
在实施例中,防水性用按JIS(日本工业标准)L-1005所述喷涂法测定的防水性编号(见表1)表示,防油性用防油编号表示,这是按AATCC-118-1975方法在用防水和防油剂处理过的布面的两处各滴几滴试验溶剂,在30秒之后观察渗透情况(见表2)而定。
耐干洗性是于30℃下,将用防水和防油剂处理过的布放在含洗涤剂(1.0克)(Ripal P,日本Lion公司的牌号,一种阴离子表面活性剂和一种非离子表面活性剂的混合物)的四氯乙烯(100毫升)中洗涤1小时,经干燥测定。在干洗一个周期和五个周期之后,用不同的防水性和防油性编号来评价耐干洗性。
耐滑移性是按ASTM D1336-64(1970)方法用一个织物移位测试器测定的,并用织物移位(毫米)来表示。移位越少,则耐滑移性越好。
实施例1
在一个装有温度计、搅拌器和回流冷凝器的300毫升玻璃烧瓶中,装入CF3(CF2)nCH2CH2OCOCH=CH2(式中n为5,7,9,11和13,重量比为1∶65∶25∶6∶2)混合物(65克)、甲基丙烯酸异冰片酯(33克)、甲基丙烯酸1-氯-2-羟丙酯(2克)、十八烷酰三甲基氯化铵(2克)、聚氧化乙烯(20)辛基苯基醚(5克)、丙酮(20克)、乙二醇(10克)、纯水(120克)、正一十二烷基硫醇(0.1克)和偶氮二异丁脒二氢氯化物(0.2克),并在氮气存在下进行搅拌使之分散。搅拌一个小时之后,内部温度升至60℃开始聚合,在同样温度下聚合三小时,得到含35.5%(重量)共聚物的乳化胶乳。
用生成的这种胶乳,试验耐干洗性和耐滑移性。为了进行这些性能测定,将聚酯纤维和棉花混纺(65/35)织物(测醋干洗性)或尼龙塔夫绸(测耐滑移性)浸渍在胶乳中,并用轧布机挤压至吸湿65%,在80℃下干燥3分钟,再于150℃加热3分钟。
结果见表3。
实施例2
以与实施例1相同的方法,只是用甲基丙烯酸4-氰基苯基酯代替甲基丙烯酸异冰片酯,进行聚合制取胶乳。耐干洗性和耐滑移性均见表3。
对比例1
以与实施例1相同的方法,只是用甲基丙烯酸十二烷基酯(均聚物的Tg为-65℃)代替甲基丙烯酸异冰片酯,进行聚合得到含35.0%(重量)共聚物的胶乳,耐干洗性和耐滑移性见表3。
对比例2
以与实施例1相同的方法,只是用丙烯酸十分烷酰酯(均聚物的Tg为-80℃)代替甲基丙烯酸异冰片酯,进行聚合得到含35.3%(重量)共聚物的胶乳。耐干洗性和耐滑移性见表3。
表1
防水性编号 状态
100 表面不湿
90 表面稍湿
80 表面部分湿
70 表面湿
50 整个表面湿
0 整个表面全湿 直浸到背面
表2
防油性编号 试验溶剂
8 正庚烷
7 正辛烷
6 正癸烷
5 正十二烷
4 正十四烷
3 正十六烷
2 正十六烷*液体〈&&〉
(重量比为〈&&〉)
1 液体石蜡
0 比1更差
表3
实施 耐干洗性 耐滑移性
防水性编号 防油性编号
例号 1周期 5周期 1周期 5周期 (空白值=1.2毫米)
1 100 90 6 5 0.2-0.4
2 100 90 6 5 0.2-0.4
对比1 90 50 6 3 1.2-1.4
对比2 80 50 5 3 1.6
Claims (9)
1、一种防水和防油剂,其特征在于,它包括由(a)单体的重复单元和占共聚物5~50%(重量)的甲基丙烯酸酯(b)的重复单元构成的一种共聚物,其中(a)单体化合物具有至少一种全氟烷基或全氟亚烷基,以及一种丙烯酸酯或甲基丙烯酸酯基团;(b)是一种甲基丙烯酸酯,它选自甲基丙烯酸异冰片酯和甲基丙烯酸4-氰基苯基酯。
2、按照权利要求1的防水和防油剂,其中单体化合物(a)至少是由下列化合物中选择的一种化合物:
Rf-(CH2)nOCOCR3=CH2 (2)
(3)
(4)
式中Rf是C3-C21全氟烷基或全氟亚烷基,R是氢原子或C1-C10烷基;R2是C1-C10亚烷基;R3是氢原子或甲基;n为1-10的整数。
3、按权利要求1的防水和防油剂,其中共聚物包括至少40%(重量)的(a)单体化合物重复单元,5-50%(重量)的(b)甲基丙烯酸酸重复单元,而余量〔或55~10%(重量)〕为至少一种其它可聚合单体的重复单元。
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JP5526285 | 1985-03-18 | ||
JP55262/1985 | 1985-03-18 |
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CN86101691A CN86101691A (zh) | 1986-09-17 |
CN1003791B true CN1003791B (zh) | 1989-04-05 |
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US (1) | US4728707A (zh) |
EP (1) | EP0198252B1 (zh) |
JP (1) | JPS62577A (zh) |
KR (1) | KR860007412A (zh) |
CN (1) | CN1003791B (zh) |
DE (1) | DE3683523D1 (zh) |
Families Citing this family (28)
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US4795793A (en) * | 1986-12-05 | 1989-01-03 | Daikin Industries Ltd. | Fluorine-containing copolymer and oil and water repellent composition containing the same |
DE3708032A1 (de) * | 1987-03-12 | 1988-09-22 | Agfa Gevaert Ag | Fluorhaltige perlpolymerisate |
JPH01153784A (ja) * | 1987-12-11 | 1989-06-15 | Daikin Ind Ltd | 撥水撥油剤組成物 |
US4791166A (en) * | 1988-03-23 | 1988-12-13 | Hoechst Celanese Corporation | Fluorocarbon polymer compositions and methods |
US4791167A (en) * | 1988-03-23 | 1988-12-13 | Hoechst Celanese Corporation | Autoxidizable fluorocarbon polymer compositions and methods |
JP2869071B2 (ja) * | 1988-08-01 | 1999-03-10 | 東レ株式会社 | フッ素含有被覆組成物 |
CA2008379C (en) * | 1989-01-24 | 1993-08-31 | Hajime Sakiyama | Semiconductor lasers |
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DE2609462C3 (de) * | 1976-03-08 | 1979-11-29 | Hoechst Ag, 6000 Frankfurt | Perfluoralkyläthylacrylat-Copolymere |
JPS54132694A (en) * | 1978-04-07 | 1979-10-15 | Asahi Glass Co Ltd | Preparation of high-performance water- and oil-repellent |
JPS559619A (en) * | 1978-07-04 | 1980-01-23 | Daikin Ind Ltd | Water and oil repellant composition |
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JPS5871977A (ja) * | 1981-10-23 | 1983-04-28 | Asahi Glass Co Ltd | 低温キユア型撥水撥油剤 |
JPS59108081A (ja) * | 1982-12-13 | 1984-06-22 | Nippon Mektron Ltd | 撥水撥油剤 |
-
1986
- 1986-03-12 US US06/838,945 patent/US4728707A/en not_active Expired - Lifetime
- 1986-03-14 KR KR1019860001861A patent/KR860007412A/ko not_active Application Discontinuation
- 1986-03-15 JP JP61057396A patent/JPS62577A/ja active Pending
- 1986-03-18 EP EP86103630A patent/EP0198252B1/en not_active Expired - Lifetime
- 1986-03-18 CN CN86101691.2A patent/CN1003791B/zh not_active Expired
- 1986-03-18 DE DE8686103630T patent/DE3683523D1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
CN86101691A (zh) | 1986-09-17 |
DE3683523D1 (de) | 1992-03-05 |
JPS62577A (ja) | 1987-01-06 |
KR860007412A (ko) | 1986-10-13 |
EP0198252A2 (en) | 1986-10-22 |
US4728707A (en) | 1988-03-01 |
EP0198252B1 (en) | 1992-01-22 |
EP0198252A3 (en) | 1987-07-22 |
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