CN115052943A - 以含氟聚合物作为有效成分的柔软性防水防油剂 - Google Patents
以含氟聚合物作为有效成分的柔软性防水防油剂 Download PDFInfo
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- CN115052943A CN115052943A CN202080095211.1A CN202080095211A CN115052943A CN 115052943 A CN115052943 A CN 115052943A CN 202080095211 A CN202080095211 A CN 202080095211A CN 115052943 A CN115052943 A CN 115052943A
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- Prior art keywords
- oil
- flexible water
- repellent agent
- meth
- acrylic acid
- Prior art date
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- 239000005871 repellent Substances 0.000 title claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 41
- 239000004480 active ingredient Substances 0.000 title claims abstract description 9
- 239000004811 fluoropolymer Substances 0.000 title description 4
- 229920002313 fluoropolymer Polymers 0.000 title description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- -1 alcohol (meth) acrylic acid derivative Chemical class 0.000 claims abstract description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 16
- 239000011737 fluorine Substances 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
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- 238000000576 coating method Methods 0.000 abstract description 9
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- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
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- 239000006185 dispersion Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
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- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 3
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- 238000010556 emulsion polymerization method Methods 0.000 description 3
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
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- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明提供一种柔软性防水防油剂,其以全氟聚醚醇(甲基)丙烯酸衍生物和(甲基)丙烯酸酯的共聚物作为有效成分,所述全氟聚醚醇(甲基)丙烯酸衍生物由通式CH2=CR1COOCH2CF(CF3)〔OCF2CF(CF3)〕nOC3F7〔I〕(此处,R1为氢原子或甲基,n为1~20的整数)表示,所述(甲基)丙烯酸酯由通式CH2=CR1COOR2〔II〕(此处,R1为氢原子或甲基,R2为烷基、烷氧基烷基、环烷基、芳基或芳烷基)表示、且玻璃化转变温度Tg为51~120℃。对于该柔软性防水防油剂,由涂布剂形成的被膜紧贴追随于橡胶、树脂的变形且显示防水防油性。
Description
技术领域
本发明涉及一种以含氟聚合物作为有效成分的柔软性防水防油剂。更详细而言,涉及以生物蓄积性低的含氟聚合物(其是含有碳原子数6以下的全氟烷基的(甲基)丙烯酸衍生物的共聚物)作为有效成分的柔软性防水防油剂。
背景技术
含全氟烷基的醇的丙烯酸衍生物、例如CF3(CF2)7CH2CH2OCOCH=CH2大量用作形成纤维用防水防油剂的含氟共聚物的合成单体。另外,作为其丙烯酸酯化前体的全氟烷基醇广泛用作表面活性剂等(参照专利文献1)。
在专利文献2中记载了如下内容:基材的表面处理剂中的含全氟烷基〔Rf〕的(甲基)丙烯酸酯的防水防油性的表现起因于处理膜中的Rf基的取向,而且为了使Rf基取向,需要使来自Rf基(碳原子数8以上)的微晶存在熔点,因此开始使用了具有碳原子数8以上的全氟烷基的含全氟烷基的(甲基)丙烯酸酯。另外,还指明:在使用具有碳原子数8以下的全氟烷基的含全氟烷基的(甲基)丙烯酸酯、且不含有异氰酸酯单体的情况下,在碳原子数8以上时观察到的对防水防油性能的贡献不充分。
然而,近年来,对于不存在于自然界的全氟辛酸(PFOA)或具有碳原子数8以上的全氟烷基的含全氟烷基的羧酸(PFCA),确认到其存在于大气中、河川等。对于这些化合物之中具有碳原子数8左右的全氟烷基的化合物,有报告指出其生物体蓄积性高、在环境方面出现问题,预测今后其制造、使用会变得困难。
此处,在目前用作防水防油剂等表面改性剂的原料的调聚物(telomer)化合物之中,具有碳原子数8以上的全氟烷基的化合物已被揭示可能在环境中成为PFCA,预测今后其制造、使用会变得困难。另一方面,关于全氟烷基的碳原子数为6以下的化合物,虽然生物体蓄积性低,但是具有碳原子数6以下的全氟烷基的化合物难以得到柔软性防水防油剂等产品所要求的性能。
除此之外,对于以往的防水防油涂布剂,由于由其形成的被膜没有柔软性,且因轻微的冲击、压力等便产生破裂,因此使用用途受到限制。
现有技术文献
专利文献
专利文献1:日本特公昭63-22237号公报
专利文献2:WO2004/035708A1
发明内容
发明所要解决的技术问题
本发明的目的在于提供一种柔软性防水防油剂,其由涂布剂形成的被膜紧贴追随于橡胶、树脂的变形且显示防水防油性。
用于解决技术问题的技术手段
上述本发明的目的通过下述柔软性防水防油剂来达成,该柔软性防水防油剂以全氟聚醚醇(甲基)丙烯酸衍生物和(甲基)丙烯酸酯的共聚物作为有效成分,所述全氟聚醚醇(甲基)丙烯酸衍生物由下述通式〔I〕表示,
CH2=CR1COOCH2CF(CF3)〔OCF2CF(CF3)〕nOC3F7 〔I〕
(在通式〔I〕中,R1为氢原子或甲基,n为1~20的整数)
所述(甲基)丙烯酸酯由下述通式〔II〕表示、且玻璃化转变温度Tg为51~120℃。
CH2=CR1COOR2 〔II〕
(在通式〔II〕中,R1为氢原子或甲基,R2为烷基、烷氧基烷基、环烷基、芳基或芳烷基)。
其中,(甲基)丙烯酸是指丙烯酸或甲基丙烯酸。
发明效果
对于本发明的柔软性防水防油剂,由涂布剂形成的被膜紧贴追随于橡胶、树脂的变形且显示防水防油性,在粘性试验中也无粘性。
对于本发明所使用的含氟共聚物,由于在共聚物形成时具有多个使玻璃化转变温度Tg降低的醚键,因此能够形成柔软的被膜,另外,由于其表面能非常小,因此能够充分发挥防水防油性、脱模性、防污性等对于防水防油剂而言必需的性能。
因此,能够有效地用作在使用时伴有变形的橡胶产品、柔软性树脂产品等的防水防油剂。
具体实施方式
本发明的防水防油剂以由下述式〔I〕所示的全氟聚醚醇(甲基)丙烯酸衍生物和由下述式〔II〕所示的(甲基)丙烯酸酯的共聚物作为有效成分。
CH2=CR1COOCH2CF(CF3)〔OCF2CF(CF3)〕nOC3F7 〔I〕
R1:氢原子或甲基,优选甲基
n:1~20的整数,优选1~4的整数
CH2=CR1COOR2 〔II〕
R1:氢原子或甲基,优选甲基
R2:烷基、烷氧基烷基、环烷基、芳基、芳烷基,优选烷基
全氟聚醚醇(甲基)丙烯酸衍生物〔I〕为公知的化合物,例如记载于专利文献1等。作为上述化合物,可以例示使来自六氟环氧丙烷的全氟聚醚醇C3F7O〔CF(CF3)CF2O〕nCF(CF3)CH2OH与(甲基)丙烯酰卤进行酯化反应而生成的如下的化合物:
CH2=CR1COOCH2CF(CF3)〔OCF2CF(CF3)〕OC3F7
CH2=CR1COOCH2CF(CF3)OCF2CF(CF3)〕2OC3F7
CH2=CR1COOCH2CF(CF3)〔OCF2CF(CF3)〕3OC3F7
CH2=CR1COOCH2CF(CF3)〔OCF2CF(CF3)〕4OC3F7
优选使用:
CH2=CHCOOCH2CF(CF3)〔OCF2CF(CF3)〕OC3F7
CH2=C(CH3)COOCH2CF(CF3)〔OCF2CF(CF3)〕OC3F7
另外,(甲基)丙烯酸酯〔II〕的玻璃化转变温度Tg(基于与ISO 3146对应的JISK7121基准来测定)必须为51~120℃,优选为65~105℃,例如可以使用甲基丙烯酸甲酯(Tg:105℃)、甲基丙烯酸乙酯(Tg:65℃)等。
当使用具有比其高的Tg的(甲基)丙烯酸酯〔II〕时,缺乏柔软性,另一方面,当使用具有比其低的Tg的(甲基)丙烯酸酯〔II〕时,流动性上升而无法维持涂膜。
在共聚物中以占约5~30重量%、优选约5~10重量%的比例使用这些(甲基)丙烯酸酯〔II〕。当(甲基)丙烯酸酯〔II〕的共聚物比例比其少时,则不发挥柔软性效果,另一方面,当以比其多的比例进行使用时,防水防油性变差。
共聚反应也通过乳液聚合法、悬浮聚合法来进行,优选通过溶液聚合法进行。作为溶液聚合法的反应溶剂,只要是供含氟共聚物溶解的溶剂就没有特别限定,可优选为具有氟原子的有机溶剂。例如,在1,4-双(三氟甲基)苯、1,1,1,2,2-五氟-3,3-二氯丙烷、1,1,2,2,3-五氟-1,3-二氯丙烷、1,1,1,2,3,4,4,5,5,5-十氟戊烷、全氟己烷等氢氟烃或其卤素取代物、3M公司的Novec 7200(C4F9OC2H5)、Novec7300〔C2F5CF(OCH3)C3F7)〕等的氢氟醚等含氟有机溶剂中,进行聚合反应。
此外,还可以使用以下的氢氟烃、氢氟醚等
氢氟烃:CF3(CF2)2CHF2、CF3(CF2)2CH2F、CF3CF2CH2CF3、F2CH(CF2)2CHF2、F2CHCH2CF2CF3、CF3CHFCH2CF3、CF3CH2CF2CHF2、F2CHCHFCF2CHF2、CF3CHFCF2CH3、F2CH(CHF)2CHF2、CF3CH2CF2CH3、CF3CF2CH2CH3、F2CHCH2CF2CH3、F2CH(CF2)3CF3、CF3(CF2)2CHFCF3、F2CH(CF2)3CHF2、CF3(CHF)2CF2CF3、CF3CHFCF2CH2CF3、CF3CF(CF3)CH2CHF2、CF3CH(CF3)CH2CF3、CF3CH2CF2CH2CF3、F2CHCHFCF2CHFCHF2、F2CH(CF2)2CHFCH3、CF3(CH2)3CF3、F2CHCH2CF2CH2CHF2、CF3(CF2)4CHF2、CF3(CF2)4CH2F、CF3(CF2)3CH2CF3、F2CH(CF2)4CHF2、CF3CH(CF3)CHFCF2CF3、CF3CF2CH2CH(CF3)2、CF3CH2(CF2)2CH2CF3、CF3CF2(CH2)2CF2CF3、CF3(CF2)3CH2CH3、CF3CH(CF3)(CH2)2CF3、F2CHCF2(CH2)2CF2CHF2、CF3(CF2)2(CH2)2CH3等
氢氟醚:CF3CF2CF20CH3、(CF3)2CFOCH3、CF3(CF2)20CH2CH3、CF3(CF2)30CH3、(CF3)2CFCF20CH3、C(CF3)30CH3、CF3(CF2)30CH2CH3、(CF3)2CFCF20CH2CH3、(CF3)3COCH2CH3、CF3CF(OCH3)CF(CF3)2、CF3CF(0CH2CH3)CF(CF3)2、C5F110CH2CH3、CF3(CF2)2CF(0CH2CH3)CF(CF3)2、CH30(CF2)40CH3、CH30(CF2)20CH2CH3、C3H70CF(CF3)CF20CH3等
在全氟聚醚醇(甲基)丙烯酸酯在含氟有机溶剂中的溶解性不良的情况下,优选使其与醇混合。醇没有特别限定,优选具有所得含氟共聚物的溶解性、且与含氟有机溶剂的相容性好、而且具有与全氟聚醚醇(甲基)丙烯酸衍生物的相容性。例如,作为上述醇,可以使用异丙醇等。混合比优选为含氟有机溶剂∶醇=95∶5~70∶30。
也可以与醇同样地使用脂肪族烃、脂环式烃、芳香族烃、酯、酮等。
脂肪族烃:正戊烷、2-甲基丁烷、正己烷、3-甲基戊烷、2,2-二甲基丁烷、2,3-二甲基丁烷、正庚烷、正辛烷、2,2,4-三甲基戊烷、正壬烷、2,2,3-三甲基己烷、正癸烷、正十一烷、正十二烷、2,2,4,6,6-五甲基庚烷、正十三烷、正十四烷、正十六烷等
脂环式烃:环戊烷、环己烷、甲基环己烷、乙基环己烷等
芳香族烃:苯、甲苯、二甲苯、1,4-双(三氟甲基)苯、1,3-双(三氟甲基)苯等
酯:乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯、乳酸甲酯、乳酸乙酯、乳酸戊酯等
酮:丙酮、甲乙酮、2-戊酮、3-戊酮、2-己酮、甲基异丁基酮等
共聚反应以聚合转化率为90%以上的方式进行,因此加入的各单体重量比大致为生成的共聚物的共聚组成重量比。
在得到的共聚物中,可以以不损害本发明共聚物的柔软性的比例进一步共聚其他能够共聚的烯键式不饱和单体,例如为苯乙烯、α-甲基苯乙烯、乙烯基甲苯、乙烯基萘、(甲基)丙烯腈、丙烯酰胺、醋酸乙烯酯、乙烯、丙烯、间戊二烯、丁二烯、异戊二烯、戊二烯等。
进而,根据需要,出于改善混炼加工性、挤压加工性等的目的,还可以将在侧链具有二醇残基的多官能性(甲基)丙烯酸酯或低聚物(例如为乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、1,9-壬二醇等亚烷基二醇的二(甲基)丙烯酸酯、新戊二醇、四乙二醇、三丙二醇、聚丙二醇等的二(甲基)丙烯酸酯、双酚A·环氧乙烷加成物二丙烯酸酯、二羟甲基三环癸烷二丙烯酸酯、甘油甲基丙烯酸酯丙烯酸酯、3-丙烯酰氧基甘油单甲基丙烯酸酯等)进一步共聚来使用,。
此外,也可以使用作为市售品的昭和电工产品karenz MOI-BP(甲基丙烯酸2-〔(3,5-二甲基吡唑基)羰基氨基〕乙酯等。
作为相对于共聚单体总量以约0.1~4重量%、优选约1~2重量%的比例使用的引发剂,可以使用二酰基过氧化物、过氧化碳酸酯、过氧化酯等,具体而言,可以使用过氧化异丁酰、过氧化月桂酰、过氧化硬脂酰、过氧化琥珀酸、双(七氟丁酰基)过氧化物、过氧化五氟丁酰、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸二正丙酯、过氧化二碳酸二异丙酯等有机过氧化物,根据聚合反应还可以使用偶氮化合物、无机过氧化物或其氧化还原系。虽然也存在因反应条件、组成比不同而难以进行聚合反应的情况,但是在该情况下,还可以在聚合反应的中途再次追加聚合引发剂。
另外,为了进行分子量的调整,还可以根据需要使用链转移剂,作为链转移剂,例如可以举出二甲醚、甲基叔丁基醚、碳原子数1~6的烷烃类、甲醇、乙醇、2-丙醇、环己烷、四氯化碳、氯仿、二氯甲烷、甲烷、乙酸乙酯、丙二酸乙酯、丙酮等。
共聚反应使用这些反应溶剂、反应引发剂等,优选在约60~80℃的反应温度下进行约10~24小时。在反应结束后,得到固体成分浓度为约5~40重量%的共聚物溶液,从该反应混合物去除溶剂,由此得到含氟共聚物。
关于共聚反应所使用的全氟聚醚醇(甲基)丙烯酸衍生物〔I〕,用气相色谱法分析了未反应的残留共聚单体,结果确认到几乎被完全共聚。
聚氟烷基醇(甲基)丙烯酸衍生物的共聚物的制造方法并不限定于上述的溶液聚合法,例如也可以使用将水作为分散介质、且包含非离子表面活性剂和/或阳离子表面活性剂的悬浮聚合法、乳液聚合法等。
对于如此得到的聚氟烷基醇(甲基)丙烯酸衍生物的共聚物,通过蒸发干固的方法、添加无机盐等凝聚剂使其凝聚的方法等进行分离,并通过用溶剂等清洗的方法进行纯化。所得到的共聚物的重均分子量Mw通过高效液相色谱法来表示,其值为约2,000~2,000,000。
通过溶液聚合法得到的聚合物溶液进一步通过1,4-双(三氟甲基)苯、1,3-双(三氟甲基)苯等含氟有机溶剂(优选与聚合反应所使用的含氟有机溶剂相同的含氟有机溶剂)稀释至固体成分浓度为约0.01~30重量%、优选约0.05~15重量%后,作为涂布剂来使用。
对于通过水系的乳液聚合法、悬浮聚合法等得到的聚合物,也可以直接或在用水稀释至固体成分浓度为约0.1~10重量%后以水性分散液的形式来制备涂布剂,或者也可以通过向聚合反应液中添加凝聚剂使聚合物凝聚、再将使用水或有机溶剂清洗并分离出的共聚物分散于水中或溶解于含氟有机溶剂,由此以其水性分散液或有机溶剂溶液的形式来制备涂布剂。作为水性分散液,优选使用含有20重量%以下的表面活性剂和水溶性有机溶剂的水性分散液。
在由该共聚物的水性分散液或它们的含氟有机溶剂溶液形成的聚合物溶液中,作为其他添加剂,还可以添加三聚氰胺树脂、尿素树脂、封端异氰酸酯等交联剂、聚合物延伸剂、有机硅树脂、或油、蜡等其他防水剂、防虫剂、抗静电剂、染料稳定剂、防皱剂、防污剂(stain blocker)等表面处理剂用途所需的添加剂。
如此得到的共聚物溶液作为防水防油剂有效地应用于各种橡胶产品、弹力性树脂产品等。作为应用方法,通常使用涂布、浸渍、喷涂、轧染(padding)、辊涂或它们的组合法,例如通过使浴的固体成分浓度为约0.1~10重量%,从而作为轧染浴使用。在该轧染浴中轧染被处理材料,根据需要用轧液辊除去过剩的液体并干燥,以对被处理材料的附着含氟共聚物量为约0.01~10重量%的比例的方式进行附着。之后,虽然也取决于被处理材料的种类,但是通常在约100~200℃的温度下进行约1分钟至约2小时左右的干燥,结束防水防油处理。
实施例
接下来,对实施例进行说明。
实施例1
在具备电容器和温度计的容量50ml的玻璃制反应容器中,加入以下成分,一边搅拌一边在70℃进行21小时共聚反应,得到固体成分浓度28.6重量%的聚合反应溶液。
在该聚合反应溶液中添加相同的溶剂,将其固体成分浓度调整为10重量%,并将其在15.0×30.0×2.0mm的EPDM制基板上以转速1000rpm旋涂10秒,并在120℃下在烘箱中进行10分钟烧结,制成试验样品。针对该试验样品,进行柔软性试验、防水防油试验和粘性试验,按照以下的评价等级进行评价。
柔软性试验方法:
用拉伸试验机将试验样品拉伸10~80%,使用显微镜观察其中途经过,进行被膜的龟裂等的观察,并进行了如下的等级评价。
◎:返回0%时,没有龟裂、褶皱
拉伸+40%时,没有龟裂
○:返回0%时,没有龟裂、褶皱
拉伸+20%时,没有龟裂
△:返回0%时,没有龟裂、褶皱
拉伸+10%时,没有龟裂
×:返回0%时,有龟裂、褶皱
防水防油试验方法:
对于试验样品,使用协和界面科学制Dropmaster DM500,用接触角测定法进行。试验液使用水或十六烷两种。等级评价如下所述。
防水试验(纯水)
◎:接触角110°以上
○:接触角105°~109°
△:接触角100°~104°
×:接触角99°以下
防油试验(十六烷)
◎:接触角70°以上
○:接触角65°~69°
△:接触角60°~64°
×:接触角59°以下
粘性试验方法:
按照以下的评价等级对用手指轻触试验样品时的被膜的状态进行了评价。
◎:无粘性
○:残留指纹的程度
△:有些许粘着感
×:拉丝的程度
实施例2
在实施例1中,代替PO-3-AC,使用8.25g的PO-3-MAC。另外,将溶剂量变更为18.15g,将聚合引发剂量变更为44.2mg,得到固体成分浓度为31.3重量%的聚合反应溶液。
CH2=C(CH3)COOCH2CF(CF3)〔OCF2CF(CF3)〕OC3F7 〔PO-3-MAC〕
实施例3
在实施例2中,代替甲基丙烯酸甲酯,使用0.73g的甲基丙烯酸乙酯(Tg:65℃)。另外,将溶剂量变更为18.35g,将聚合引发剂量变更为44.0mg,得到固体成分浓度为31.3重量%的聚合反应溶液。
实施例4
在实施例2中,将PO-3-MAC量变更为8.26g,进一步使用甲基丙烯酸2-〔(3,5-二甲基吡唑基)羰基氨基〕乙酯〔昭和电工产品karenz MOI-BP〕54.8mg作为交联性单体。另外,将溶剂量变更为18.26g,将聚合引发剂量变更为44.7mg,得到固体成分浓度为31.9重量%的聚合反应溶液。
比较例1
在实施例1中,代替PO-3-AC,使用10.73g的下述含氟系单体A,没有使用甲基丙烯酸甲酯。另外,将溶剂量变更为21.83g,将聚合引发剂量变更为37.1mg,得到固体成分浓度为33.0重量%的聚合反应溶液。
CH2=CH(CH3)COOC5F10CH2C6F13 〔含氟系单体A〕
比较例2
在实施例1中,代替PO-3-AC,使用8.26g的FAMAC-6,没有使用甲基丙烯酸甲酯。另外,将溶剂量变更为26.45g,将聚合引发剂量变更为61.9mg,得到固体成分浓度为34.6重量%的聚合反应溶液。
CH2=CHCOOCH2CH2C6F13 〔FAMAC-6〕
比较例3
在实施例2中,进一步追加使用丙烯酸2-羟基乙酯〔2HEA〕28.1mg作为交联性单体。另外,将溶剂量变更为18.21g,将聚合引发剂量变更为44.6mg,但是2HEA与溶剂Novec 7300的相容性低,因此生成物白浊固化,无法进行各特性的测定。
比较例4
在实施例1中,代替甲基丙烯酸甲酯,使用0.82g的丙烯酸正丁酯(Tg:-49℃)。另外,将溶剂量变更为18.09g,但是生成物为不具有固体成分的液状物,无法进行各特性的测定。
比较例5
在实施例2中,代替甲基丙烯酸甲酯,使用0.91g的甲基丙烯酸正丁酯(Tg:20℃)。另外,将溶剂量变更为17.91g,得到固体成分浓度为27.6重量%的聚合反应溶液。
以上的实施例1~4和比较例1~2、5中所得到的结果如下表所示。
表
权利要求书(按照条约第19条的修改)
1.一种柔软性防水防油剂,其以CH2=CHCOOCH2CF(CF3)〔OCF2CF(CF3)〕OC3F7和(甲基)丙烯酸酯的共聚物作为有效成分,
所述(甲基)丙烯酸酯由下述通式〔II〕表示、且玻璃化转变温度Tg为51~120℃,
CH2=CR1COOR2〔II〕
在通式〔II〕中,R1为氢原子或甲基,R2为烷基、烷氧基烷基、环烷基、芳基或芳烷基。
2.根据权利要求1所述的柔软性防水防油剂,其中,玻璃化转变温度51~120℃的(甲基)丙烯酸酯为甲基丙烯酸甲酯或甲基丙烯酸乙酯。
3.根据权利要求1所述的柔软性防水防油剂,其中,在共聚物中以5~30重量%的比例共聚有(甲基)丙烯酸酯。
4.根据权利要求1所述的柔软性防水防油剂,其中,所述柔软性防水防油剂被调制为有机溶剂溶液。
5.根据权利要求4所述的柔软性防水防油剂,其中,所述柔软性防水防油剂被调制为含氟有机溶剂溶液。
6.一种适用于橡胶制品的柔软性,其是全氟聚醚醇(甲基)丙烯酸衍生物和(甲基)丙烯酸酯的共聚物的有机溶剂溶液,
所述全氟聚醚醇(甲基)丙烯酸衍生物由下述通式〔I〕表示,
CH2=CR1COOCH2CF(CF3)〔OCF2CF(CF3)〕nOC3F7〔I〕
在通式〔I〕中,R1为氢原子或甲基,n为1~20的整数,
所述(甲基)丙烯酸酯由下述通式〔II〕表示、且玻璃化转变温度Tg为51~120℃,
CH2=CR1COOR2〔II〕
在通式〔II〕中,R1为氢原子或甲基,R2为烷基、烷氧基烷基、环烷基、芳基或芳烷基。
7.根据权利要求6所述的柔软性防水防油剂,其中,橡胶产品为弹力性树脂产品。
8.一种橡胶产品,其用权利要求6所述的柔软性防水防油剂进行了表面涂布。
9.一种弹力性树脂产品,其用权利要求7所述的柔软性防水防油剂进行了表面涂布。
Claims (10)
1.一种柔软性防水防油剂,其以全氟聚醚醇(甲基)丙烯酸衍生物和(甲基)丙烯酸酯的共聚物作为有效成分,
所述全氟聚醚醇(甲基)丙烯酸衍生物由下述通式〔I〕表示,
CH2=CR1COOCH2CF(CF3)〔OCF2CF(CF3)〕nOC3F7〔I〕
在通式〔I〕中,R1为氢原子或甲基,n为1~20的整数,
所述(甲基)丙烯酸酯由下述通式〔II〕表示、且玻璃化转变温度Tg为51~120℃,
CH2=CR1COOR2〔II〕
在通式〔II〕中,R1为氢原子或甲基,R2为烷基、烷氧基烷基、环烷基、芳基或芳烷基。
2.根据权利要求1所述的柔软性防水防油剂,其中,全氟聚醚醇(甲基)丙烯酸衍生物〔I〕为CH2=CHCOOCH2CF(CF3)〔OCF2CF(CF3)〕OC3F7或者CH2=C(CH3)COOCH2CF(CF3)〔OCF2CF(CF3)〕OC3F7。
3.根据权利要求1所述的柔软性防水防油剂,其中,玻璃化转变温度51~120℃的(甲基)丙烯酸酯为甲基丙烯酸甲酯或甲基丙烯酸乙酯。
4.根据权利要求1所述的柔软性防水防油剂,其中,在共聚物中以5~30重量%的比例共聚有(甲基)丙烯酸酯。
5.根据权利要求1所述的柔软性防水防油剂,其中,所述柔软性防水防油剂被调制为有机溶剂溶液。
6.根据权利要求5所述的柔软性防水防油剂,其中,所述柔软性防水防油剂被调制为含氟有机溶剂溶液。
7.根据权利要求5或6所述的柔软性防水防油剂,其中,所述柔软性防水防油剂被应用于橡胶产品。
8.根据权利要求5或6所述的柔软性防水防油剂,其中,所述柔软性防水防油剂被应用于弹力性橡胶制品。
9.一种橡胶产品,其用权利要求7所述的柔软性防水防油剂进行了表面涂布。
10.一种弹力性树脂产品,其用权利要求8所述的柔软性防水防油剂进行了表面涂布。
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PCT/JP2020/041315 WO2021161593A1 (ja) | 2020-02-10 | 2020-11-05 | 含フッ素重合体を有効成分とする柔軟性撥水撥油剤 |
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US (1) | US20230084014A1 (zh) |
EP (1) | EP4105249A4 (zh) |
JP (1) | JP7269430B2 (zh) |
KR (1) | KR20220125309A (zh) |
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US4587165A (en) * | 1981-11-12 | 1986-05-06 | Daikin Kogyo Co., Ltd. | Films of a copolymer of an ester derived from a fluorine-containing alcohol |
JP2003012588A (ja) * | 2001-07-02 | 2003-01-15 | Asahi Glass Co Ltd | 含フッ素化合物、その製造方法、含フッ素重合体および撥水撥油剤組成物 |
JP2003025512A (ja) * | 2001-07-23 | 2003-01-29 | Dainippon Ink & Chem Inc | 柔軟性物品 |
JP2005336234A (ja) * | 2004-05-24 | 2005-12-08 | Asahi Glass Co Ltd | 溶剤型撥水撥油剤組成物 |
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JPS5883011A (ja) * | 1981-11-12 | 1983-05-18 | Daikin Ind Ltd | フツ素含有アクリレ−トまたはメタクリレ−トの重合体およびその用途 |
JPS5890524A (ja) * | 1981-11-24 | 1983-05-30 | Daikin Ind Ltd | フツ素含有アルコ−ルおよびその誘導体 |
JPS58164672A (ja) * | 1982-03-24 | 1983-09-29 | Nippon Mektron Ltd | 撥水撥油剤 |
JPS59108081A (ja) | 1982-12-13 | 1984-06-22 | Nippon Mektron Ltd | 撥水撥油剤 |
JPS6322237A (ja) | 1986-07-14 | 1988-01-29 | Mazda Motor Corp | コイルスプリング組付け装置 |
JP2003221406A (ja) | 2002-01-31 | 2003-08-05 | Asahi Glass Co Ltd | 水性分散液 |
CA2502421A1 (en) | 2002-10-15 | 2004-04-29 | Asahi Glass Company, Limited | Water-and-oil repellant composition |
JP4930058B2 (ja) * | 2004-10-06 | 2012-05-09 | ダイキン工業株式会社 | 含フッ素撥水撥油剤組成物 |
WO2012049158A1 (de) | 2010-10-14 | 2012-04-19 | Basf Se | Verfahren zur herstellung von isocyanaten |
US9045450B2 (en) | 2011-08-10 | 2015-06-02 | Zhen Yang | Method for chemical synthesis of antrocin and use thereof for suppressing non-small cell lung cancer |
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2020
- 2020-11-05 KR KR1020227027201A patent/KR20220125309A/ko active Search and Examination
- 2020-11-05 CN CN202080095211.1A patent/CN115052943A/zh active Pending
- 2020-11-05 EP EP20918241.9A patent/EP4105249A4/en active Pending
- 2020-11-05 WO PCT/JP2020/041315 patent/WO2021161593A1/ja unknown
- 2020-11-05 JP JP2022500227A patent/JP7269430B2/ja active Active
- 2020-11-05 US US17/798,338 patent/US20230084014A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4587165A (en) * | 1981-11-12 | 1986-05-06 | Daikin Kogyo Co., Ltd. | Films of a copolymer of an ester derived from a fluorine-containing alcohol |
JP2003012588A (ja) * | 2001-07-02 | 2003-01-15 | Asahi Glass Co Ltd | 含フッ素化合物、その製造方法、含フッ素重合体および撥水撥油剤組成物 |
JP2003025512A (ja) * | 2001-07-23 | 2003-01-29 | Dainippon Ink & Chem Inc | 柔軟性物品 |
JP2005336234A (ja) * | 2004-05-24 | 2005-12-08 | Asahi Glass Co Ltd | 溶剤型撥水撥油剤組成物 |
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JP7269430B2 (ja) | 2023-05-08 |
EP4105249A4 (en) | 2024-03-13 |
EP4105249A1 (en) | 2022-12-21 |
WO2021161593A1 (ja) | 2021-08-19 |
KR20220125309A (ko) | 2022-09-14 |
JPWO2021161593A1 (zh) | 2021-08-19 |
US20230084014A1 (en) | 2023-03-16 |
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