CN101497703A - 提高ptfe疏油性的方法及所得疏油制品 - Google Patents
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Abstract
本发明涉及提高PTFE疏油性的方法及所得疏油制品。公开了在含氟聚合物(例如聚四氟乙烯(PTFE))上制备疏油性层的方法。疏油性层包括氟代烷基丙烯酸酯共聚物。含氟聚合物可以是在多孔膜中形成的发泡PTFE。根据AATCC测试方法118疏油性可以足以排斥#8油(正庚烷)。还公开了包括含氟聚合物及由氟代烷基丙烯酸酯共聚物制备的疏油性层的涂布制品。
Description
技术领域
[0001]本发明的某些实施方案涉及采用疏油处理的组合物涂布含氟聚合物(例如PTFE膜)的方法,所述组合物包含可以赋予出众的疏油特性的氟代烷基丙烯酸酯共聚物。
背景技术
[0002]包括聚四氟乙烯(PTFE)的材料是本领域众所周知的。PTFE具有多种已确定的用途,包括例如要求光滑性的应用(例如轴承、轴衬等)和要求多孔膜的应用。这些与膜相关的应用可以包括例如过滤、通风和/或扩散/阻挡应用。过滤可以使用盘或板。通风可以特别用于要求通风的与汽车相关的应用,例如前灯、电动马达(例如用于风档刮水器等)、刹车、内燃机等。另外,与健康护理相关的应用也可能要求通风,包括例如导尿管、与抽气相关的设备、仪器等。多孔膜的其它通风应用也是公知的。
[0003]至少在一些情况下改进PTFE的疏油性可能有利的,使得水、油和其它污染物可以更有效地被膜排斥。参见例如U.S.P.5,462,586;5,554,414;和6,196,708。
发明内容
[0004]在某些实施方案中,提供提高含氟聚合物疏油性的方法。该方法包括以下步骤:通过混合溶剂、水和氟代烷基丙烯酸酯共聚物形成含水疏油性处理组合物;在含氟聚合物上铸塑该含水疏油性处理组合物;以及干燥和固化该含水疏油性处理组合物。
[0005]在某些实施方案中,提供从包含聚四氟乙烯的多孔膜的表面排斥液体污染物的方法。该方法包括以下步骤:通过混合溶剂、水和氟代烷基丙烯酸酯共聚物形成含水疏油性处理组合物;通过喷涂该含水疏油性处理组合物在多孔膜上铸塑该含水疏油性处理组合物并且从多孔膜中除去过量液体;以及干燥和固化该含水疏油性处理组合物;并且将液体施涂到经过固化疏油性处理的多孔膜上。所述液体包括正庚烷、柴油或汽油,并且多孔膜显示对液体的疏油性。
[0006]在某些实施方案中,提供具有高疏油性的涂布制品,其包括:包含聚四氟乙烯的含氟聚合物;以及直接在含氟聚合物上和接触含氟聚合物的疏油层;其中疏油层包含氟代烷基丙烯酸酯共聚物。涂布制品排斥正庚烷。
附图说明
[0007]图1是根据本发明实施方案采用疏油表面处理涂布的含氟聚合物基材的横断面视图。
具体实施方式
[0008]在某些方面,本发明可以涉及向含氟聚合物如PTFE施涂表面处理。合适的含氟聚合物可以包括四氟乙烯/(全氟烷基)乙烯基醚共聚物(PFA)、四氟乙烯/六氟丙烯共聚物(PEA)、聚四氟乙烯(PTFE)等。根据具体应用,含氟聚合物可以用于要求光滑性的应用(例如轴承、轴衬等)或要求多孔膜的应用。例如,本发明的某些方面涉及包含PTFE,例如发泡PTFE(ePTFE)的多孔材料。
[0009]在某些方面,多孔材料例如膜可以是有益的基材,其表面可以接受疏油性处理。合适的多孔材料可以基本上是均匀的含氟聚合物或可以采用含氟聚合物层压。层压的材料可以是多孔和透气的,并且可以包括天然或合成材料,例如但不限于织造织物、针织织物、非织造织物、网、毡等,或合成聚合物、纤维素纸或玻璃纤维纸的多孔片材等。材料可以单独或组合使用,例如用于层压复合材料制品,并且可以为片材、管子或塞子形式。多种添加剂,例如紫外辐射稳定剂、着色剂、增塑剂、抗静电剂、抗菌剂等可以存在于含氟聚合物中作为加工助剂或赋予特殊性能。在这方面,术语“含氟聚合物”包括不纯和/或掺杂的含氟聚合物。根据最终用途要求,例如(在多孔膜的情况下)过滤要求、所要求的物理、化学和机械性能、应用环境、材料和制造成本等选择适当的材料和形式。
[0010]适用于某些实施方案的多孔聚四氟乙烯(和其它含氟聚合物)片材、棒或管材可以通过本领域已知的方法制备,例如通过拉伸或牵伸方法、造纸方法、其中填料材料与PTFE树脂一起掺入并且随后除去而留下多孔结构的方法、粉末烧结方法。在一些实施方案中,多孔聚四氟乙烯材料是具有互连结点和原纤的多孔发泡聚四氟乙烯片材、棒或管材。含氟聚合物的精确加工及其精确结构和构造在某些实施方案中可能是较不重要的并且可以广泛变化。
[0011]在一些实施方案中,含氟聚合物可以是促进或允许流体(例如空气和/其它气体物质)流入或流过膜的微孔聚合物薄膜。用作膜的可能的聚合物薄膜包括发泡聚四氟乙烯(PTFE)薄膜,例如U.S.P.3,953,566;4,187,390;4,945,125;5,066,683;5,157,058;和5,362,553所述的那些。
[0012]在一些实施方案中,可以提供未层压的过滤器用作疏油性处理的基材。这种过滤器可以与强酸、侵蚀性溶剂和高温相容。这些过滤器可以特别用于要求苛刻温度或化学品而不能向过滤器中添加微粒的应用。合适的膜过滤器可以具有一定的疏水性能并且可以用于气溶胶取样、空气通风和气体过滤,例如在包含水蒸汽的环境中。
[0013]在一些实施方案中,可以提供层压的过滤器用作疏油性处理的基材。这种过滤器可以由层压到聚丙烯载体上的纯PTFE组成,例如用于改进的耐久性和易于处理性。这些层压过滤器可以与强酸和极侵蚀性溶剂如醇化学相容。
[0014]合适的含氟聚合物基材包括例如BHA-TEX ePTFE膜,获自GE Energy。可能的基材包括例如QMO11和QMO12(其可以用于与服装有关的应用)及QMO901(其可以用于与微通风有关的应用),所有这些均获自GE Energy。
[0015]在一些实施方案中,提供改进ePTFE膜的疏油性的方法。已知的方法可能不足以排斥至少一些油,例如燃料(例如汽油、柴油、煤油、庚烷等)。在一些实施方案中,疏油性处理通过采用包括氟代烷基丙烯酸酯共聚物的疏油性涂饰剂处理膜来改进微孔ePTFE膜的疏油性。疏油性处理可以提供抵抗吸收油(例如庚烷、柴油和汽油)的透气的、透射湿蒸汽的及抗风和液体穿透的复合材料膜。与未处理的ePTFE膜相比,这种在ePTFE膜上的疏油性处理也可以改进水和油排斥性、抗污性、和/或去污性。
[0016]可以使用AATCC测试方法118-2002(其在技术上等同于ISO14419)测定疏油性。测试方法118-2002用于通过评价表面抵抗被一组规定的具有变化的表面张力的液体烃润湿的性能来检测具有低能表面的表面的存在。测试液体在下表中给出:
表1:用于AATCC测试方法118-2002的油
AATCC油排斥级数 | 组成 |
0 | 无(无Kaydol) |
1 | Kaydol(来自在测试方法中确定的来源) |
2 | 65:35Kaydol:正十六烷(体积) |
3 | 正十六烷 |
4 | 正十四烷 |
5 | 正十二烷 |
6 | 正癸烷 |
7 | 正辛烷 |
8 | 正庚烷 |
[0017]在测试方法中,将这些标准测试液体的液滴施涂在待测试表面。油排斥级数对应于最高标号的测试液体,其不润湿表面。如果液体不润湿测试表面,则观察到珠。该珠本身显示出测试液体边缘与测试表面之间的高接触角,表明测试表面的疏油性程度。
[0018]在一些实施方案中,可以提供排斥等级为8的疏油性膜或层压材料(即正庚烷可以有效地被排斥)。这种高排斥等级可以特别用于各种应用,包括例如保护性覆盖层、防护服、空气污染控制、真空介质等。例如,引入到微通风口中的过滤介质可以具有各种要求油排斥性、透气性、和/或湿蒸汽透射率(MVTR)的应用。可能的应用可以包括例如:汽车前灯通风口;风档刮水器马达通风口;医学上相关的通风口等。当然,处理过的含氟聚合物的所有可能的用途均在本发明的各种实施方案的考虑之列。
[0019]在一些实施方案中,疏油性处理使用包括至少一种包含氟代烷基丙烯酸酯共聚物的排斥剂的组合物,例如以Unidyne商品名购自Daikin America,Inc.的那些。这种合适的氟代烷基丙烯酸酯共聚物可以记载于U.S.P.4,365,049和4,686,168中。
[0020]疏油性处理组合物也可以包括至少一种溶剂和/或水。可能的醇基溶剂包括例如异丙醇、甲醇、乙醇、丙醇、异丁醇、丁醇、丙二醇、乙二醇等。在其它实施方案中非醇溶剂也是可能的。其它组分,例如表面活性剂、润湿剂、流变改性剂等也可以存在于某些实施方案中。
[0021]下表(表2)归纳了根据本发明的某些实施方案的可能的疏油性处理组合物。在某些实施方案中溶剂和水可以互换;即,某些实施方案包含0.1-10wt%(及所有其间的次范围)、1-5wt%(及所有其间的次范围)或2-3wt%(及所有其间的次范围)的氟代烷基丙烯酸酯共聚物,其余为水和溶剂的任何组合。
成分 | Wt% | Wt% | Wt% |
溶剂 | 0-99.9 | 30-70 | 40-60 |
水 | 0-99.9 | 20-80 | 30-70 |
氟代烷基丙烯酸酯共聚物 | 0.1-10 | 1-5 | 2-3 |
[0022]疏油性处理组合物可以以任何合适的方式铸塑在,例如施涂在基材上,包括例如喷涂、旋涂、辊涂、浸涂和将未固化组合物沉积或铸塑在基材上的任何其它方法。另外,过量的液体可以从基材擦去,尽管其在某些实施方案中不进行。
[0023]干燥可以在足以蒸发溶剂和/或水的温度进行,例如在100-350℃进行至多10分钟。固化可以在任何足以固化氟代烷基丙烯酸酯共聚物的温度进行(例如通过将氟代烷基丙烯酸酯共聚物粘附到含氟聚合物基材上来改进涂层的物理稳定性),例如在350-550℃进行至多5分钟。干燥和/或固化可以进行任何合适的时间长度,并且较短和较长的时间以及较高和较低的温度均在本发明示例性实施方案的考虑之列。
[0024]另外,真空和/或热空气烘箱可以用于影响干燥和/或固化的温度和时间。实际上,在某些实施方案中,在不施加热量的情况下干燥和/或固化疏油性处理组合物是可能的;这可以减小对含氟聚合物结构和/或性能的任何与热相关的影响。
[0025]图1举例说明了根据本发明的实施方案的涂布制品。基材10包含含氟聚合物,例如ePTFE膜。在基材10上是固化层20,其包括包含氟代烷基丙烯酸酯共聚物的疏油性表面处理。层20可以为足以赋予疏油性性能的任何合适的厚度,包括可以小至仅几微米的厚度。
[0026]根据本发明的示例性实施方案制备了几个非限制性的实施例。
[0027]实施例1
[0028]使用实验室混合器在室温混合50wt%异丙醇、40wt%水和10wt% Unidyne TG-581(获自Daikin America,Inc.)5分钟。通过喷涂将该混合物施涂到基材上,然后通过擦拭除去过量液体。在施涂混合物期间通过金属钩束缚基材。所用的基材是黄色通风口层压材料(自动通风GE产品码QVB657-ePTFE膜层压在70旦尼尔尼龙织造塔夫绸纯饰层上,黄色(Pantone #108)),然后在实验室烘箱中干燥和固化。干燥在250℉进行5分钟,而固化在400℉进行2分钟。
[0029]根据AATCC测试方法118测试处理过的层压材料的油排斥性。发现该处理非常有效地排斥100% IPA和油#8(庚烷)。还发现处理过的织物排斥发动机油、柴油和汽油。
[0030]实施例2
[0031]使用实验室混合器在室温混合50wt%异丙醇、30wt%水和20wt% Unidyne TG-470B(获自Daikin America,Inc.)5分钟。类似于实施例1,通过喷涂将该混合物施涂到基材上,然后通过擦拭除去过量液体。在实验室烘箱中干燥和固化涂布的基材。干燥在250℉进行5分钟,而固化在400℉进行2分钟。
[0032]根据AATCC测试方法118测试处理过的层压材料的油排斥性。发现该处理非常有效地排斥油#8(庚烷)。
[0033]在疏油性处理之前黄色通风口层压材料的透气性为0.43立方英尺每分钟。在疏油性处理之后透气性为0.53立方英尺每分钟。据认为透气性的提高是由于在处理的干燥/固化步骤期间暴露于热。加热时ePTFE膜微结构和孔隙率的变化是众所周知的。
[0034]如所述和要求保护的,所有的数字和数字范围均是近似的(无论是否立即同样指出),并且必然地包括至少一些偏差。
[0035]虽然本发明已经就目前认为最实用和优选的实施方案进行了描述,但应该理解,本发明不限于所公开的实施方案,并且相反,拟覆盖包括在所附权利要求的主旨和范围内的各种变化和等同安排。
Claims (10)
1.提高含氟聚合物(10)的疏油性的方法,该方法包括以下步骤:
通过混合溶剂、水和氟代烷基丙烯酸酯共聚物形成含水疏油性处理组合物;
在含氟聚合物(10)上铸塑该含水疏油性处理组合物;和
干燥和固化该含水疏油性处理组合物。
2.权利要求1的方法,其中含氟聚合物(10)包括多孔膜,该膜包括发泡的聚四氟乙烯膜。
3.权利要求1的方法,其中溶剂包括至少一种选自异丙醇、甲醇、乙醇、丙醇、异丁醇、丁醇、丙二醇和乙二醇的醇基溶剂。
4.权利要求1的方法,其中含水疏油性处理组合物包含0.1-10wt%的氟代烷基丙烯酸酯共聚物。
5.权利要求1的方法,其中含水疏油性处理组合物包含2-3wt%的氟代烷基丙烯酸酯共聚物。
6.权利要求1的方法,其中干燥和固化步骤包括(i)暴露于100-350℃至多10分钟和(ii)暴露于350-550℃至多5分钟。
7.从包含聚四氟乙烯的多孔膜(10)的表面排斥液体污染物的方法,该方法包括以下步骤:
通过混合溶剂、水和氟代烷基丙烯酸酯共聚物形成含水疏油性处理组合物;
通过喷涂该含水疏油性处理组合物在多孔膜上铸塑该含水疏油性处理组合物并且从多孔膜中除去过量液体;和
干燥和固化该含水疏油性处理组合物;和
将液体污染物施涂到经过固化疏油性处理的多孔膜上,其中液体污染物包括正庚烷、发动机油、柴油或汽油,并且其中多孔膜显示对液体污染物的疏油性。
8.权利要求7的方法,其中含水疏油性处理组合物包含2-3wt%的氟代烷基丙烯酸酯共聚物。
9.具有高疏油性的涂布制品,包括:包含聚四氟乙烯的含氟聚合物(10);及直接在含氟聚合物上和接触含氟聚合物的疏油层(20);其中疏油层包含氟代烷基丙烯酸酯共聚物;并且其中涂布制品排斥正庚烷。
10.权利要求9的涂布制品,其中含氟聚合物(10)包括多孔膜。
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CN102294181A (zh) * | 2010-06-23 | 2011-12-28 | 上海灵氟隆膜技术有限公司 | 双拒聚四氟乙烯微孔膜 |
TWI507291B (zh) * | 2011-07-21 | 2015-11-11 | Columbia Sportswear Na Inc | 製造撥油微孔膜之方法 |
CN105307851A (zh) * | 2013-06-15 | 2016-02-03 | 大众汽车有限公司 | 基于硅酮的具有疏油-疏水表面的层状结构、其制备方法以及具有该层状结构的电气机器 |
CN107922658A (zh) * | 2015-08-24 | 2018-04-17 | 旭硝子株式会社 | 拒液性成形体的制造方法及拒液剂组合物 |
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CN102294181A (zh) * | 2010-06-23 | 2011-12-28 | 上海灵氟隆膜技术有限公司 | 双拒聚四氟乙烯微孔膜 |
TWI507291B (zh) * | 2011-07-21 | 2015-11-11 | Columbia Sportswear Na Inc | 製造撥油微孔膜之方法 |
CN105307851A (zh) * | 2013-06-15 | 2016-02-03 | 大众汽车有限公司 | 基于硅酮的具有疏油-疏水表面的层状结构、其制备方法以及具有该层状结构的电气机器 |
CN105307851B (zh) * | 2013-06-15 | 2018-05-08 | 大众汽车有限公司 | 基于硅酮的具有疏油-疏水表面的层状结构、其制备方法以及具有该层状结构的电气机器 |
CN107922658A (zh) * | 2015-08-24 | 2018-04-17 | 旭硝子株式会社 | 拒液性成形体的制造方法及拒液剂组合物 |
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