CN113924523A - 用于眼用镜片的防污涂层 - Google Patents
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Abstract
一种用于具有增加的有效厚度和水接触角的眼用镜片的疏水性和/或疏油性涂层系统。在一个实施方案中，所述疏水性和/或疏油性涂层系统包括被施加到眼用镜片上的抗反射涂层，所述抗反射涂层包括高指数材料和低指数材料的交替层，带有具有暴露的羟基的二氧化硅的外层。将疏水性涂层施加到所述抗反射涂层上，所述疏水性涂层包括具有疏水基团和少于三个能够与所述抗反射涂层的所述暴露的羟基键合的反应性基团的硅烷。
Description
相关申请的交叉引用
本申请要求于2019年3月19日提交的美国临时专利申请第62/820,364号的权益，其通过引用整体被并入本文。
背景技术
本发明涉及用于眼用镜片的光学涂层，并且特别地涉及用于眼用镜片的疏水性和/或疏油性涂层系统。
眼用镜片通常具有一个或多个光学涂层，这些涂层可改善镜片性能，诸如防刮性、抗反射性、抗静电性和其他性质。最后的防污涂层通常被施加在这些其他涂层的顶部，该涂层具有疏水和/或疏油性质，以保护内部涂层免受湿气影响，并改善清洁镜片表面的简易性。疏水性和/或疏油性涂层还通过提供光滑的表面使异物滑落并避免损坏镜片表面来提高镜片涂层系统的耐用性。
可通过涂层表面的水接触角来衡量涂层的疏水性——即在水滴的外表面接触涂层表面的点处绘制的切线之间形成的角度。例如，表面上一滴完美球形的水滴会停留在表面上的单个点处，并且具有180°的接触角。疏水性涂层通常具有超过90°的水接触角。施加于光滑表面的疏水性涂层通常可实现高达约120°的水接触角。利用具有微/纳米结构的粗糙表面可实现水接触角大于150°的超疏水性表面。
用于眼用镜片的常规疏水性涂层通常具有约112°至113°的最大水接触角，这远低于光滑表面已实现的约120°的潜在最大水接触角。因此，期望提供更接近120°的最大水接触角的疏水性涂层。疏水性的增加会显著改善涂层的防污性质以及眼用镜片内部涂层的防护性和耐用性。
发明内容
公开了用于眼用镜片的防污涂层系统，包括：光学镜片；被施加到所述镜片上的第一涂层，所述第一涂层包括具有暴露的羟基的二氧化硅的外层；以及被施加到所述第一涂层的所述外层上的疏水性第二涂层。所述第二涂层包括带有氟化烃基团并具有1个或2个官能团的硅烷，所述官能团具有反应性以与所述第一涂层的所述暴露的羟基形成键。在一个实施方案中，所述第一涂层是包括高指数材料和低指数材料的交替层的抗反射涂层。在优选的实施方案中，所述高指数材料层选自由以下组成的组：TiO2、ZrO2和HfO2，并且所述低指数材料层选自由以下组成的组：SiO2、MgF2和Al2O3。在另一个实施方案中，所述官能团是甲氧基，并且所述硅烷优选地包括乙氧基。在另一个实施方案中，所述疏水性第二涂层具有大于113°、优选地在113°至114°之间、并且更优选地在115°至117°之间的水接触角。在另一个实施方案中，所述疏水性第二涂层形成具有大于20nm、优选地至少约30nm、并且更优选地至少约40nm的最大有效厚度的层。
附图说明
图1示出了被施加到二氧化硅层上的包括常规氟化硅烷的防污涂层系统的化学结构。
图2示出了被施加到二氧化硅层上的包括具有两个甲氧基和一个乙氧基的氟化硅烷的防污涂层系统的实施方案的化学结构。
具体实施方式
描述了用于眼用镜片的防污涂层系统。眼用镜片通常被生产为具有多个光学涂层。例如，可对镜片的表面施加硬涂层以提高防刮性和耐用性。可在防刮涂层上施加抗反射涂层以减少镜片表面的反射和眩光。可在抗反射涂层上施加疏水性和/或疏油性涂层以排斥水和油，从而有助于清洁和保护抗反射涂层。
典型的疏水性涂层包括氟化化合物，诸如氟化硅氧烷、氟化硅烷、氟化硅烷醇和/或碳氟化合物。除了疏水之外，此类氟化化合物还可以是疏油的。可通过本领域已知的多种方式(包括真空沉积)将疏水性涂层施加到镜片的表面。疏水性涂层与潜在的基材结合或以其他方式牢固地粘附至潜在的基材并且抵抗机械去除，使得通常不能通过用溶剂擦拭或以类似的机械方式去除疏水性涂层。
不希望受任何特定理论的束缚，认为疏水性涂层通过化学键粘附至基材。图1示出了疏水性涂层系统的实例，包括被施加到抗反射涂层基材10上的疏水性化合物。疏水性涂层分子12是具有疏水基团的硅烷，诸如氟化烃(X)。常规的抗反射涂层通常包括高指数材料和低指数材料的交替层。常见的高指数材料包括金属氧化物，诸如TiO2、ZrO2、HfO2，而常见的低指数材料包括SiO2、MgF2、Al2O3。在图1的实施方案中，抗反射涂层带有具有暴露的羟基(OH)基团的二氧化硅(SiO2)的外层。疏水性涂层通过氟化硅烷的硅烷醇基团与二氧化硅层的OH基团之间的氢键和/或共价键粘附至抗反射涂层。本领域技术人员将理解，不同的基材和疏水性涂层可能涉及不同的化学键合相互作用。
疏水性涂层的水接触角通常随着涂层厚度的增加而增加。然而，尽管涂层的厚度增加，但涂层的疏水性在某一点达到峰值并保持基本恒定。常规的疏水性涂层通常在约20nm的涂层厚度下实现约112°至113°的最大水接触角。在该厚度下，认为基材上可用于与疏水性涂层反应并形成化学键的位点被有效地饱和，并且附加的疏水性涂层仅轻微地粘附并且可被机械地去除。因此，常规的疏水性涂层具有约20nm的最大有效厚度，并且以大于20nm的厚度施加疏水性材料不会明显地增加疏水性涂层的水接触角。
疏水性化合物的改性可允许增加结合到基材上的疏水性化合物分子的密度并增加疏水性涂层的最大有效厚度。常规的疏水性化合物具有多个官能团，这些官能团能够与基材上的多个位点反应并结合。例如，氟化硅烷疏水性化合物可具有通式CF3(CF2)n(CH2)mSi(OR)3，其中m≥0,n≥1且优选为2、4或6，并且R优选为氢或烷基，诸如甲基。在R为氢基团的情况下，氟化硅烷具有三个能够与基材的OH基团键合的反应性基团，如图1所示。
为了增加结合到基材表面上的疏水性化合物分子的密度，可用反应性较低的基团取代一个或多个反应性官能团。图2示出了改性的疏水性化合物14的实施方案，其在基材10上占据较少的结合位点，这允许额外的疏水性化合物分子结合至基材。甲氧基硅烷可在高温无水条件下与基材的OH基团键合，而乙氧基硅烷的反应性较低并且可能需要催化。包括甲氧基和乙氧基的组合的氟化硅烷具有较少数量的官能团(即少于三个，1个或2个)，这些官能团能够容易地与二氧化硅基材的OH基团反应并与其键合，这允许更多的氟化硅烷分子结合至基材。
认为基材上疏水性化合物分子密度的增加容许具有增加的水接触角的较厚的有效疏水性涂层。具有增加的最大有效厚度的改性的疏水性化合物是可商购获得的(日本Kisan Kinzoku Chemicals Co.Ltd.)，其包括具有能够与二氧化硅层的OH基团键合的反应性基团的碳氟化合物。表1示出了改性的疏水性化合物的涂层厚度和所得的水接触角。
表1
改性的疏水性化合物在最大有效厚度为40nm时具有117°的峰值水接触角。因此，可有效地以至少两倍于常规疏水性化合物的厚度施加改性的疏水性化合物，这引致水接触角和疏水性显著增加而更接近120°的潜在最大水接触角。
本领域技术人员将理解疏水性涂层的有效厚度和最大水接触角将根据疏水性化合物的配方和结构而变化。此外，本发明不限于应用于任何特定类型或形式的镜片，并且可包括由本领域已知的各种材料中的任何材料制成的成品或半成品镜片。尽管已经说明和描述了本公开的特定实施方案，但是对于本领域技术人员来说将显而易见的是，在不脱离本公开的精神和范围的情况下可以做出各种其他改变和修改。因此，意图在所附权利要求中涵盖在本公开范围内的所有此类改变和修改。
Claims (11)
1.一种用于眼用镜片的防污涂层系统，包括：
光学镜片；
被施加到所述镜片上的第一涂层，所述第一涂层包括具有暴露的羟基的二氧化硅的外层；
被施加到所述第一涂层的所述外层上的疏水性第二涂层，所述第二涂层包括带有氟化烃基团并具有1个或2个官能团的硅烷，所述官能团具有反应性以与所述第一涂层的所述暴露的羟基形成键。
2.根据权利要求1所述的防污涂层系统，其中，所述第一涂层是包括高指数材料和低指数材料的交替层的抗反射涂层。
3.根据权利要求2所述的防污涂层系统，其中，所述高指数材料层选自由以下组成的组：TiO2、ZrO2和HfO2，并且所述低指数材料层选自由以下组成的组：SiO2、MgF2和Al2O3。
4.根据权利要求1所述的防污涂层系统，其中，所述官能团是甲氧基。
5.根据权利要求4所述的防污涂层系统，其中，所述硅烷还具有乙氧基。
6.根据权利要求1所述的防污涂层系统，其中，所述疏水性第二涂层具有大于113°的水接触角。
7.根据权利要求1所述的防污涂层系统，其中，所述疏水性第二涂层具有在113°至114°之间的水接触角。
8.根据权利要求1所述的防污涂层系统，其中，所述疏水性第二涂层具有在115°至117°之间的水接触角。
9.根据权利要求1所述的防污涂层系统，其中，所述疏水性第二涂层形成具有大于20nm的最大有效厚度的层。
10.根据权利要求1所述的防污涂层系统，其中，所述疏水性第二涂层形成具有至少约30nm的最大有效厚度的层。
11.根据权利要求1所述的防污涂层系统，其中，所述疏水性第二涂层形成具有至少约40nm的最大有效厚度的层。
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| US201962820364P | 2019-03-19 | 2019-03-19 | |
| US62/820,364 | 2019-03-19 | ||
| PCT/US2020/023558 WO2020191157A1 (en) | 2019-03-19 | 2020-03-19 | Anti-soiling coating for an ophthalmic lens |
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| US20230393308A1 (en) | 2023-12-07 |
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| EP3942357A1 (en) | 2022-01-26 |
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