CN101611124A - 疏水且疏油的超薄涂层、其制造方法及其作为基膜在钟表制造业中的应用 - Google Patents
疏水且疏油的超薄涂层、其制造方法及其作为基膜在钟表制造业中的应用 Download PDFInfo
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- CN101611124A CN101611124A CNA2007800439661A CN200780043966A CN101611124A CN 101611124 A CN101611124 A CN 101611124A CN A2007800439661 A CNA2007800439661 A CN A2007800439661A CN 200780043966 A CN200780043966 A CN 200780043966A CN 101611124 A CN101611124 A CN 101611124A
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- gold
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/68—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/20—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
- C10M105/54—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen, halogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary amines
- C10M105/60—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom
- C10M105/62—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及疏水且疏油的超薄涂层，其通过使通式为A－B的化合物自组装到固体基底表面上而形成，其中A为式(I)所示基团，其中Z表示C或N+；X表示C－H或C－L，L是选自F、Cl、Br、I、CF3、NO2和N(CH3)3 +的吸电基团；Y表示H或CH3，或Y和X共同构成5或6原子杂环；T表示NH、CO、CONH或NH2 +U－，U－是可溶的阴离子例如F－、Cl－、Br－、I－、OH－、NO3 －、HSO4 －、SO4 2－、CO3 2－、HCO3 －或SCN－，B表示部分或全部被F取代的C1－C20脂肪族直链烷基。本发明还涉及制备该涂层的方法以及其作为基膜的应用。
Description
本发明涉及一种疏水且疏油的新型超薄涂层，其通过将具有儿茶酚基的化合物自组装到固体基底的表面上而形成，还涉及制备该超薄涂层的方法及将其用作基膜。
钟表的良好运转尤其取决于润滑作用。润滑油的耐久性特别依赖于其在运转区间的保持状况：然而，所有钟表业者业已发现，一滴润滑油即会在清洁部件上迅速铺展。基膜沉积层通常以不被看到的疏水且疏油的分子涂层形式存在，能够避免润滑油及其组份的铺展。
液体的铺展取决于液体、表面和环境空气间的相互作用力(参见J.C.Berg，“Wettability”，Marcel Dekker，纽约，1993以及A.W.Adamson，“PhysicalChemistry of Surface”，Wiley)。表征液体和气体间相互作用力的参数是表面张力γLV。以类似方式将固体和环境空气之间的相互作用力表征为表面能γSV，并将固体和液体之间的相互作用力表征为参数γLS。针对在某表面上达到平衡的液滴，杨氏方程明确指出γSV-γLS＝γLVcosθ，这里θ是液滴相对于表面的接触角。杨氏方程还表明，如果液体表面张力比表面能低，则接触角为零且液体将润湿表面。此现象同样发生在涂敷在清洁金属表面上的润滑油：事实上，润滑油具有35-40mN/m的表面张力，而常用金属的表面具有更高的表面能。
表面能取决于多种因素(J.P.Renaud和P.Dinichert，1956，“Etats desurface et étalement des huiles d’horlogerie(表面状态及钟表用润滑油的铺展)”，Bulletin SSC III，681页)：
表面的几何参数及其粗糙度(其上的缺陷和/或抛光状况)；
表面能常常由最末一层原子或分子层决定。与表面状态及其上覆盖的污染物相比，固体本身的化学属性并不重要。在清洁的金属表面上且排除有机污染物的影响，水滴的前进接触角小于10°。用具有-OH官能团的分子(例如HOC11H22SH)形成自组装单分子膜(SAM：Self-Assembled Monolayers)，此时该接触角约为30°，如使用具有-CH3官能团的分子(例如C12H25SH)，则其约为110°，如使用具有-CF3官能团的分子(例如C10F17H4SH)则约为118°。
直至1930年代，钟表制造业仍旧保留采用的技术是利用可降低表面能的膜使表面的状态能够最小化润滑油在其上的铺展(M.Osowiecki，1957，“Unnouvel épilame resistant aux lavages(一种新型耐洗涤基膜)”，Bulletin SSC III，735页)。随着清洗技术的改进，该膜的消除导致润滑油或多或少以更快的速率铺展开。在1930年，Raffinage法国公司的P.Woog开发了一种基于硬脂酸的抗迁移产品，将其命名为“基膜(épilame)”。至60年代末，该产品已被应用于各个工业分支。该名称被延用并被设计用于钟表业以确保润滑油在所有产品表面上的性能。
将化合物沉积到功能表面以降低表面能并控制润湿性及附着性是相当普遍的方法。然而，将其用作屏蔽或抗迁移膜的应用仅限于钟表业(M.Massin，“et lubrifiants associés àhaute stabilité：propiétés，technologied’application et résultats en horlogerie(用于钟表制造业的在性能、涂敷工艺和效果方面具有高稳定性的基膜和润滑油)”，Actes du congrès de ChronométrieFranco-Allemand(法-德计时学年会会刊)，第85页，1970；以及“Conception dela lubrification en micromécanique：réalisations nouvelles par préparation dessurfaces associées àdes fluides silicones(微型机械用润滑油的设计理念：通过制备与硅酮流体结合的表面而实现润滑的新方法)”，Actes du congrès desSociétés Allemand et
Chronométrie (法国和德国微型机械协会年会会刊)，第95页，1971)、空间工业(M.Marchetti，“Aspects globaux et locaux de lamise en oeuvre de la lubrication fluide en ambiance spatiale(在宇宙空间环境中对流体润滑油进行处理时的整体和局部情况研究)”，INSA博士论文，里昂，2000)以及电子学。前两个领域具有共同的难点，即难以替换用过的或耗尽的润滑油。
直至1970年代，仍旧使用的是稀释于甲苯中的硬脂酸基产品(M.Osowiecki，前述文献及P.Ducommun，1956，“Les huiles d’horlogeriesynthétiques(钟表用润滑油的合成)”，J.Suisse Horl.Bij.9-10，117)。60年代末，企业的研究实现两项重要进展。一方面，基于硅酮的产品被开发出来(P.MAssin，前述文献)但是仅获得有限的成功。另一方面，基于含氟聚合物的产品被引入成为70年代的主流产品，并且至今仍在使用。
实际上，市场上提供的大部分基膜由溶解在全氟化溶剂中的含氟聚合物组成，例如Moebius公司的Fixodrop FK-BS或者3M公司的Fluorad产品系列(FC-722及其他)。
化合物在基底上的沉积通过将该基底浸泡在全氟化溶剂中充满聚合物溶质的溶液中。所用的溶剂通常为十四氟己烷(C6F14)，其在空气中可稳定保留3200年，因而，一旦挥发，即成为导致温室效应的气体，且具有7400CO2当量的温室效应潜能。
本发明目的在于提供可用作基膜的化合物，该基膜无需采用对环境有害的含氟溶剂即可结合到固体基底的表面上。
这些目的通过由所附权利要求的内容所定义的本发明而实现。
本发明实际上提供一种疏水且疏油的新型超薄涂层，其通过使具有儿茶酚基的化合物自组装到固体基底的表面上而形成，还提供一种制备该超薄涂层的方法，其使用环保的无氟溶剂，例如使用水和2-丙醇的混合物。由于所用化合物具有儿茶酚基，该超薄涂层能够牢固地结合到固体基底的表面上。与由商品FixoDrop FK-BS制备的涂层全面比较，使用该超薄涂层作为基膜具有令人满意的性能，尤其是水的前进接触角和油滴的铺展性方面。
因而本发明对基膜的环保制备做出了巨大贡献。
这些具有儿茶酚基的化合物具有如下通式：
A-B
其中
A表示下式所示基团
其中，
Z表示C或N+，
X表示C-H或C-L，L是选自F、Cl、Br、I、CF3、NO2和N(CH3)3 +的吸电基团，
Y表示H或CH3，或Y和X共同构成5或6原子杂环，
T表示NH、NH-CO、NH-CO-NH或NH2 +U-，U-是可溶的阴离子，如F-、Cl-、Br-、I-、OH-、NO3 -、HSO4 -、SO4 2-、CO3 2-、HCO3 -或SCN-，以及
B表示部分或全部被F取代的C1-C20的脂肪族直链烷基。
基团A特别适于将化合物结合到固体基底的表面上，这要归因于儿茶酚基团的存在和浸泡溶液中两亲分子A-B的溶解性。
基团B赋予超薄涂层以疏水和疏油的特性。
优选地，基团B是末端全氟化的脂肪族直链烷基，如式
(CH2)n-(CF2)mCF3。
其中n为1-5，特别是1-3，且m为4-11，特别是5-9。
A基团优选自以下任一基团：
特别优选的化合物是N-(3，4-二羟基苯乙基)-4，4，5，5，6，6，7，7，8，8，9，9，10，10，11，11，11-十七氟十一烷酰胺
A-B型化合物可由已知化合物通过有机化学工作者熟知的工艺和反应制得。
例如N-(3，4-二羟基苯乙基)-4，4，5，5，6，6，7，7，8，8，9，9，10，10，11，11，11-十七氟十一烷酰胺可由2H，2H，3H，3H-全氟十一烷酸-N-琥珀酰亚胺酯和盐酸化3-羟基-酪氨酸在N-甲基吗啡啉存在下于DMF溶液中反应制得。
3-(4，4，5，5，6，6，7，7，8，8，9，9，10，10，11，11，11，-十七氟十一烷酰胺基)-6，7-二羟基-1，1-二甲基-1，2，3，4-四氢喹啉鎓
可由ANACAT和2H，2H，3H，3H-全氟十一烷酸-N-琥珀酰亚胺通过类似于Y.Bethuel.K.Gademann，J.Org.Chem 2005，70，6258.；Zürcher，S.；
D.；Bethuel，Y.；Malisova，B.；Textor，M.；Tosatti，S.；Gademann，K.Journal ofAmerican chemistry Soceity，2006，128，1064-1065.所描述的方法制得。
1-(2-(4，4，5，5，6，6，7，7，8，8，9，9，10，10，11，11，11-十七氟十一烷酰胺基)乙基)-3，4-二羟基吡啶鎓
也可通过与前述方法类似的方法由1-(2-氨乙基)-3，4-二羟基吡啶鎓和2H，2H，3H，3H-全氟十一烷酸-N-琥珀酰亚胺制备。
N-(3，4-二羟基苯乙基)-3，3，4，4，5，5，6，6，7，7，8，8，9，9，10，10，10-十七氟癸烷-1-铵盐
也可通过与前述提到的类似方法，由盐酸化3-羟基酪氨酸和1，1，2，2，3，3，4，4，5，5，6，6，7，7，8，8-十七氟-10-碘癸烷制备。
N-(4，5-二羟基-2-硝基苯乙基)-4，4，5，5，6，6，7，7，8，8，9，9，10，10，11，11，11-十七氟十一烷酰胺
也可通过与前述提及的类似方法，由4-(2-氨乙基)-5-硝基-1，2-苯酚和2H，2H，3H，3H-全氟十一烷酸-N-琥珀酰亚胺制备。
表面上发生自组装的固体基底可以是机械运动运行时所牵涉到的任何固体基底，特别是由选自金、银、钢——特别是20AP型钢、铝、黄铜、青铜、铍铜合金、二氧化钛、红宝石、蓝宝石、硅、镍和磷-镍的材料构成，其也可以具有其他的金属表面，如铁、铬、钽、钇、硅、锗、铜、铂、和金属氧化物或陶瓷，例如氧化锆、铌酐(氧化铌)，该列举是非限定性的。作为基底，也可以采用聚合物，例如聚乙烯、聚苯乙烯、聚酰胺、聚二甲基硅氧烷、聚氯乙烯、环氧树脂，该列举也是非限定性的。该基底也可以是由上述材料之一或者另一种材料构成的表面被覆盖或装饰的基底，例如通过电镀在其上沉积金、金-铜-镉和金、镍、铑、锡-镍，或通过阳极氧化进行处理，例如针对铝或钛的合金制件，或通过表面处理进行改性，例如通过氧化、碳化或氮化。
椭圆光度法测得该超薄涂层的厚度约为0.5-10nm，该值高于已有的对超薄涂层的定义，优选为1-4nm。
为了有效地作为基膜，即以满意的方式防止油滴铺展，水的前进接触角通常至少为100°。
优选地，式A-B构成的超薄涂层经过两次钟表洗涤后仍然具有作为基膜的功能。
本发明还涉及钟表部件，特征在于其包括前述定义的超薄涂层。
本发明还涉及前述定义的超薄涂层的制备方法，特征在于其包括将基底浸入到式A-B化合物在例如水或水和质子溶剂的混合物中的溶液，如在2-丙醇的混合物中。该方法未使用含氟溶剂，因而是环保的。
借助下述典型且非限定性的实施例可更好地理解本发明。
实施例1：N-(3，4-二羟基苯乙基)-4，4，5，5，6，6，7，7，8，8，9，9，10，10，11，11，11-十七氟十一烷酰胺(SuSoS2)的合成
2H，2H，3H，3H-全氟十一烷酸-N-琥珀酰亚胺酯的合成
将2H，2H，3H，3H-全氟十一烷酸(1.354g，2.75mmol)、N-羟基琥珀酰亚胺(348mg，3.02mmol)、二环己基碳二酰亚胺(622mg，3.02mmol)溶于乙酸乙酯(120ml)中，环境温度温下混合18小时。过滤掉生成的白色沉淀(二环己基脲，DCU)，将剩余溶液蒸馏至干。将残渣用乙酸乙酯重结晶二次。产量为1.00g(62％)，其中含有微量DCU。
1H-NMR(CDCl3，300MHz，ppm)：3.0(m，2H CH2)，2.88(s，4H CH2NHS)，2.6(m，2H CH2)。
N-(3，4-二羟基苯乙基)-4，4，5，5，6，6，7，7，8，8，9，9，10，10，11，11，11-十七氟十一
烷酰胺的合成
将盐酸化3-羟基酪氨酸(257.5mg，1.35mmol)和N-甲基吗啡啉(241μl)溶于DMF(8ml)中。加入全氟-NHS-酯(800mg)，于氮气氛下搅拌该混合物过夜。加水(40ml)，过滤掉生成的沉淀，用水洗涤。将该固体溶于乙酸乙酯，用硫酸镁干燥有机相。蒸除溶剂，残渣用氯仿(30ml，4℃)重结晶。产量752mg(88％)。
分子量：627.29
重量百分数：C 36.38；H 2.25；F 51.49；N 2.23；O 7.65
不计H时：C 47.5；F 42.5；N 2.5；O 7.5
1H-NMR(CDCl3，300MHz，ppm)：8.7(s，宽，2H OH)，8.08(t，1HNH)，6.7-6.4(m，3H多巴胺)，3.2(q，2H CH2)，2.7-2.3(m，6H CH2)。
对应N-(3，4-二羟基苯乙基)-4，4，5，5，6，6，7，7，8，8，9，9，10，10，11，11，11-十七氟十一烷酰胺
实施例2：浸泡溶液的制备和将各基底浸泡在其中
SuSoS2浸泡溶液的制备
在100ml容量瓶中将33mg的SuSoS2(0.052mmol)溶于35ml的2-丙醇中，振荡直至完全溶解。加入超纯水至刻度线并剧烈振荡，以上操作将增加溶液温度。待溶液恢复到环境温度后，加数滴水调整容量至100ml。将该溶液置于超声波下10秒钟，以赶出气体，使水和2-丙醇完全混合。
金、抛光钢、铝、钛的氧化物和红宝石的基底在浸泡溶液中浸泡
将金、抛光钢、铝、钛的氧化物和红宝石的样品在UV/臭氧舱中清洗30分钟，浸入SuSoS2溶液中过夜。然后将这些样品浸入2-丙醇10秒，用2-丙醇漂洗并用氮气流干燥。针对钢，使用浸透2-丙醇的布条对其轻微抛光，另外用2-丙醇漂洗，用氮气流干燥。
实施例3：对在各个基底上通过自组装形成的超薄涂层进行分析
对在各个基底上通过自组装形成的单层涂层进行以下分析：
所用各基底为：
通过VASE和CA测得的主要参数集中列于下表1中。
表1：利用椭圆光度法测得的厚度和与水的前进接触角
利用X射线光电子能谱(XPS)进行分析，通过检测元素N和F以证明SuSoS2分子存在于所有表面上。
该结果表明在所有被测基底上都制得了SuSoS2超薄涂层。
水的前进接触角的数值(大于100°)能够满足其用作为基膜的要求。
实施例4：比较SuSoS2和Fixodrop FK-BS在金、抛光钢和红宝石表面上通过自组装形成的超薄涂层
1)制备各基底表面上的SuSoS2和Fixofrop超薄涂层
如实施例2所述，在金、抛光钢和红宝石基底表面上涂覆SuSoS2超薄涂层。该表面的外观很好，看不出沉积留下的痕迹。
按照制造商的指示将基底浸入到十四氟环己烷溶液中，使Fixodrop FK-BS超薄涂层覆盖在金、抛光钢和红宝石基底表面上。
椭圆光度法测得金上SuSoS2涂层的厚度为0.7nm，Fixodrop涂层为1.7nm。
2)测量使用不同溶剂时的接触角并确定表面能
采用与实施例3中所应用的类似的测角技术，通过测量动态接触角以确定水、十六烷、二碘甲烷和乙二醇的前进接触角。
利用由Owens-Wendt模型得到的测量结果推算出表面能的色散和极性分量(Owens D.K.和Wendt R.C.，1969，Journal of Applied Polymer Science，13，8，第1741页)。
所得主要结果集中列于下表2中。
表2：各溶剂的接触角和表面能
| 液体 | 钢SuSoS2 | 红宝石SuSoS2 | 余SuSoS2 | 金Fixodrop |
| 接触角[°] | ||||
| 十六烷 | 64.1 | 56.8 | 47.3 | 56.8 |
| 二碘甲烷 | 90.4 | 84.4 | 77.8 | 78.0 |
| 乙二醇 | 93.2 | 87.2 | 84.9 | 88.4 |
| 水 | 103.0 | 113.8 | 104.8 | 104.2 |
| 表面能[mJ/m2] | ||||
| 色散分量 | 12.5 | 16.3 | 18.6 | 16.8 |
| 极性分量 | 2.2 | 0.2 | 0.8 | 0.4 |
| 总计 | 14.6 | 16.6 | 19.4 | 17.3 |
对于金、钢和红宝石，水、十六烷、二碘甲烷和乙二醇的接触角对于将其用作基膜是可以接受的，且与对Fixodrop测量获得的值相似。
对于金、钢和红宝石，由SuSoS2形成的涂层表现出卓越的色散性，正如对该类分子所期望的那样。表面能看上去因材料而改变，然而所有情况下其变化都小于20mJ/m2。最低表面能(且从而具有最优异的性能)在使用钢的情况下获得的，其次是红宝石和金。
3)润滑油铺展性测试
测量直径基本为0.5mm的液滴在表面上刚刚沉积后以及沉积20分钟后的平均直径以表征润滑油在表面上的铺展性。铺展性对应于20分钟后平均直径的相对改变。润滑油的良好性能对应于2％或更小的铺展率。超过10％的铺展率将被检测到并不被接受。用于测试的油是钟表用润滑油“941”(Moebius和Fils公司销售的烷芳基单油酸酯和两种C10-C13二酯组成的混合物，20℃时粘度为110cSt，表面张力为32.8mN/m)和CESNIII测试润滑油(瑞士钟表研究实验室，硅酮油，表面张力为23.1mN/m，“La Suisse Horlogèe(瑞士钟表)”No43，7.11.1974)。
在钢、红宝石和金上涂布SuSoS2分子，根据制造商的指示在金上涂布Moebius和Fils公司销售的商品Fixodrop FK-BS，比较在这些表面上测得的铺展率。对于使用SuSoS2分子的情况，其铺展率在所有情况下都低于1％，与对Fixodrop测得的结果相似，如下表所示。
表3：润滑油的铺展率
| 表面 | 超薄涂层 | Moebius941润滑油 | CESNIII润滑油 |
| 钢 | SuSoS2 | 0.11％ | 0.92％ |
| 红宝石 | SuSoS2 | 0.37％ | 0.46％ |
| 金 | SuSoS2 | 0.30％ | 0.14％ |
| 金 | Fixodrop FK-BS | -0.90％ | 0.86％ |
4)结论
对于所有被研究的表面，在由SuSoS2分子形成的超薄涂层上测得的接触角大于100°，表面能小于20mJ·m-2，铺展率低于1％。
SuSoS2超薄涂层的性能至少与利用商品Fixodrop所得涂层的性能同样优异，且用于浸泡的溶剂是环保的。
Claims (12)
1.疏水且疏油的超薄涂层，其通过使通式为A-B的化合物自组装到固体基底表面上而形成，其中，
A表示下式基团
其中，
Z表示C或N+，
X表示C-H或C-L，L是选自F、Cl、Br、I、CF3、NO2和N(CH3)3 +的吸电基团，
Y表示H或CH3，或者Y和X共同构成5或6原子杂环，
T表示NH、CO、CONH或NH2 +U-，其中U-是可溶的阴离子，例如F-、Cl-、Br-、I-、OH-、NO3 -、HSO4 -、SO4 2-、CO3 2-、HCO3 -或SCN-，以及
B表示部分或全部被F取代的C1-C20脂肪族直链烷基。
2.根据权利要求1所述的超薄涂层，特征在于：B是末端全氟化的脂肪族直链烷基，如式(CH2)n-(CF2)mCF3所示，其中n为1-5，且m为4-11。
3.根据权利要求2所述的超薄涂层，特征在于：n为1-3，且m为5-9。
4.根据前述任一权利要求所述的超薄涂层，其特征在于：A选自如下基团之一：
5.根据前述任一权利要求所述的超薄涂层，特征在于：其由N-(3，4-二羟基苯乙基)-4，4，5，5，6，6，7，7，8，8，9，9，10，10，11，11，11-十七氟十一烷酰胺制得。
6.根据前述任一权利要求所述的超薄涂层，特征在于：所述固体基底由选自金、银、钢、铝、黄铜、青铜、铍铜合金、二氧化钛、红宝石、蓝宝石、硅、镍和镍-磷的材料构成，也可具有其他的金属表面如铁、铬、钽、钇、锗、铜、铂以及金属氧化物或陶瓷如氧化锆或铌酐(氧化铌)，或者由聚合物如聚乙烯、聚苯乙烯、聚酰胺、聚二甲基硅氧烷、聚氯乙烯、环氧树脂构成，或者该固体基底也可以是一种由上述这些材料中一种或另外一种材料构成且表面被覆盖或装饰的基底，例如通过电镀在其上沉积金、金-铜-镉、镍、铑、锡-镍，或通过阳极氧化法对其进行处理，例如针对使用铝或钛合金制件的情况，或通过表面处理进行改性，如通过氧化、碳化或氮化。
7.根据前述任一权利要求所述的超薄涂层，特征在于：其与水的前进接触角至少为100°。
8.根据前述任一权利要求所述的超薄涂层，特征在于：其在椭圆光度法中测得的厚度为0.5-10nm。
9.钟表部件，特征在于：其包括前述任一权利要求所述的超薄涂层。
10.制备权利要求1-9任一项所述超薄涂层的方法，特征在于：其包括将基底浸入式A-B化合物在水或水与质子溶剂的混合物中的溶液。
11.根据权利要求10所述的方法，特征在于：该质子溶剂是2-丙醇。
12.根据权利要求1-9中任一项所述的超薄涂层作为基膜的应用。
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| PCT/CH2007/000601 WO2008064510A1 (fr) | 2006-12-01 | 2007-11-29 | Couche ultra-mince hydrophobe et oleophobe, procede de fabrication et utilisation en horlogerie comme epilame |
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| CN107974680A (zh) * | 2016-10-21 | 2018-05-01 | 苏州汉力新材料有限公司 | 一种铝基底表面制备超疏油表面的方法 |
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| EP1927648A1 (fr) * | 2006-12-01 | 2008-06-04 | Rolex Sa | Couche ultra-mince hydrophobe et oléophobe, procédé de fabrication et utilisation en horlogerie comme épilame |
| US8951630B2 (en) | 2006-12-01 | 2015-02-10 | Rolex S.A. | Ultra-thin hydrophobic and oleophobic layer, method of manufacture and use in watchmaking as an epilame and in mechanical engineering as a barrier film |
| JP5537745B2 (ja) * | 2010-12-23 | 2014-07-02 | ロレックス・ソシエテ・アノニム | 腕時計製造用構成部品の疎油性を高めるための組成物 |
| DE102011088232A1 (de) * | 2011-12-12 | 2013-06-13 | Aktiebolaget Skf | Lagerkäfig und Lagerkäfigsegment |
| FR2990433A1 (fr) * | 2012-05-10 | 2013-11-15 | Surfactis Technologies | Compositions catanioniques de recouvrement de surface par des molecules phosphoniques et amines |
| DE212013000152U1 (de) * | 2012-07-10 | 2015-04-01 | The Swatch Group Research And Development Ltd. | Mittel für die Oberflächenschmierung eines Gegenstands |
| EP3315214B1 (fr) | 2016-10-25 | 2020-07-15 | The Swatch Group Research and Development Ltd | Procédé d'épilamage d'un élement d'une pièce d'horlogerie ou de bijouterie |
| EP3398978B1 (fr) * | 2017-05-05 | 2020-03-11 | The Swatch Group Research and Development Ltd | Agent d'épilamage et procédé d'épilamage utilisant un tel agent d'épilamage |
| EP4075205A1 (fr) * | 2021-04-16 | 2022-10-19 | ETA SA Manufacture Horlogère Suisse | Procédé de fabrication d'un mobile d'horlogerie et mobile d'horlogerie obtenu par sa mise en oeuvre |
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| WO2008064058A2 (en) * | 2006-11-21 | 2008-05-29 | Abbott Laboratories | Use of a terpolymer of tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride in drug eluting coatings |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104553140A (zh) * | 2013-10-28 | 2015-04-29 | 斯沃奇集团研究和开发有限公司 | 防扩散剂涂覆的贵重产品 |
| CN109968760A (zh) * | 2013-10-28 | 2019-07-05 | 斯沃奇集团研究和开发有限公司 | 防扩散剂涂覆的贵重产品 |
| CN107974680A (zh) * | 2016-10-21 | 2018-05-01 | 苏州汉力新材料有限公司 | 一种铝基底表面制备超疏油表面的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1927648A1 (fr) | 2008-06-04 |
| EP2084253B1 (fr) | 2017-03-29 |
| JP2010511099A (ja) | 2010-04-08 |
| WO2008064510A1 (fr) | 2008-06-05 |
| EP2084253A1 (fr) | 2009-08-05 |
| EP2084252A1 (fr) | 2009-08-05 |
| US20100075138A1 (en) | 2010-03-25 |
| EP2084252B1 (fr) | 2017-03-29 |
| US20100068553A1 (en) | 2010-03-18 |
| JP5385788B2 (ja) | 2014-01-08 |
| WO2008064511A1 (fr) | 2008-06-05 |
| CN101611124B (zh) | 2013-11-06 |
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