CN109715738B - 具有改善的粘附性的tac底漆涂层 - Google Patents

具有改善的粘附性的tac底漆涂层 Download PDF

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CN109715738B
CN109715738B CN201680089383.1A CN201680089383A CN109715738B CN 109715738 B CN109715738 B CN 109715738B CN 201680089383 A CN201680089383 A CN 201680089383A CN 109715738 B CN109715738 B CN 109715738B
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tac
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P·江
C·泰
M·庞德尔斯
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EssilorLuxottica SA
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Abstract

本文披露了一种增强的底漆配制品,所述增强的底漆配制品可以用于各种镜片和膜层压体应用中。所述增强的底漆配制品可以用于增强膜或层压体与可聚合或聚合材料之间的粘附性。

Description

具有改善的粘附性的TAC底漆涂层
技术领域
本发明涉及眼科镜片领域,包括用于眼镜和太阳镜的偏振和/或光致变色眼科镜片。
背景技术
TAC偏振膜由于其优异的光学和机械特性而广泛用于太阳镜镜片应用中。在一个具体应用,TAC偏振膜用于聚碳酸烯丙基二甘醇酯(CR-39)镜片浇铸中。将TAC偏振层压体放置在聚碳酸烯丙基二甘醇酯单体中,然后使单体聚合,以提供具有嵌入在镜片内部的偏振层压体的固体偏振镜片。嵌入的偏振层压体提供偏振功能并且受周围聚合材料的保护。
尽管层压体嵌入在聚合材料中,但仍存在脱层的可能性。采用最佳镜片实践(包括镜片生成、细磨和抛光)的Rx实验室加工条件可能导致嵌入的层压体脱层。极端温度和高湿度条件也可能导致嵌入的镜片脱层。
为了增加嵌入的层压体的粘附性,可以在镜片浇铸之前将底漆涂层预先施加到层压体表面上。底漆增加了层压体与周围材料之间的粘合强度,然而,在次优的底漆条件下,层压体仍然会发生脱层。如果底漆太软,则可能发生脱层,这可能是由于聚合物网络中的低交联所致。如果底漆太硬或者如果底漆厚度太大,也可能发生脱层。尽管在偏振膜粘性底漆领域取得了进步,但仍存在脱层的可能性。需要增强的底漆配制品以增加层压体与可聚合材料之间的粘附性,从而减少或消除脱层的可能性。
发明内容
本文披露了一种底漆组合物,所述底漆组合物具有比传统的市售底漆高很多的粘合强度。申请人已经发现在底漆组合物中包含交联剂致使底漆配制品具有显著改善的粘合强度。本文所披露的底漆配制品可以用于膜层压体中各层之间的粘附或层压体与可聚合材料的粘附。在一些方面,底漆用于增加层压体在浇铸聚合组合物中的粘附性。不希望受理论束缚,认为交联剂增加了底漆组分的内聚力,从而产生改善的膜层粘附性。交联剂还可以将底漆组分与可聚合材料连接,从而增加膜与聚合材料的粘附性。可聚合材料可以是浇铸树脂单体或反应性粘合剂。
在一些实施例中,采用底漆组合物将TAC膜粘附到聚合材料上。在其他实施例中,采用底漆组合物将TAC膜粘附到可聚合材料上。在进一步实施例中,采用底漆组合物将TAC层压体粘附到聚合材料上。在其他实施例中,采用底漆组合物将TAC层压体粘附到可聚合材料上。在一些实施例中,所述TAC膜是透明光学膜或光学功能膜。
光学功能膜的实例包括偏振膜和光致变色膜。在一些实施例中,所述TAC层压体是TAC-PVA-TAC偏振层压体。在一些实施例中,所述TAC层压体是光致变色层压体。在一些实施例中,光学功能膜是光致变色膜。
在一些实施例中,采用底漆组合物将膜粘附到聚合材料表面上或在浇铸材料内提供嵌入粘附。在一些方面,所述聚合材料是聚醚嵌段酰胺膜(Pebax膜)、聚碳酸酯膜、聚甲基丙烯酸甲酯膜、聚酰胺膜(尼龙膜)、聚酯膜(PET)、醋酸丁酸纤维素(CAB)膜、或包含前述任意组合的复合膜。在一些实施例中,所述可聚合材料是浇铸树脂单体,比如聚碳酸烯丙基二甘醇酯;中间折射率丙烯酸、胺或苯乙烯单体;或环硫氨基甲酸乙酯单体。在一些实施例中,可聚合材料是选自由以下各项组成的组的反应性粘合剂:UV丙烯酸粘合剂、聚氨酯粘合剂、环氧粘合剂、胺粘合剂或双组分聚氨酯或环氧粘合剂。
在一些方面,底漆组合物包含至少一种丙烯酸聚合物树脂、至少一种反应性丙烯酸低聚物、至少一种UV引发剂或热引发剂、至少一种交联剂、以及溶剂。在一些方面,所述至少一种丙烯酸聚合物树脂以范围从底漆组合物的按重量计10%至按重量计30%的量存在。在一些实施例中,至少一种反应性丙烯酸低聚物以范围从底漆组合物的按重量计10%至按重量计30%的量存在。在一些方面,至少一种UV引发剂或热引发剂以范围从底漆组合物的按重量计1%至按重量计5%的量存在。在一些实施例中,至少一种交联剂以范围从底漆组合物的按重量计1%至按重量计25%的量存在。在一些实施例中,所述溶剂以范围从底漆组合物的按重量计50%至按重量计90%的量存在。在一些实施例中,丙烯酸聚合物的分子量在约10,000g/mol与100,000g/mol之间。在一些实施例中,反应性丙烯酸低聚物的分子量在约1,000g/mol至50,000g/mol之间。
在一些方面,所述交联剂每分子包含至少两个反应性官能团。所述至少两个反应性官能团可以独立地选自由以下各项组成的组:丙烯酸、丙烯酸酯、烯丙基、乙烯基、炔丙基、异氰酸酯、胺、以及环氧基。在进一步实施例中,所述交联剂是多官能丙烯酸酯。在具体方面,所述多官能丙烯酸酯是季戊四醇三丙烯酸酯。在一些实施例中,所述丙烯酸聚合物树脂是甲基丙烯酸酯共聚物。在一些方面,甲基丙烯酸聚合物在共聚物中含有10至80的酸值。“酸值”是中和1克化学物质所需的氢氧化钾(KOH)质量(以毫克计)。
在一些实施例中,所述底漆组合物溶剂是酮溶剂、乙酸酯溶剂、二氯甲烷或其组合。所述酮溶剂可以选自由以下各项组成的组:丙酮、甲基乙基酮环戊酮环己酮或其任何组合。在一些方面,所述乙酸酯溶剂是乙酸乙酯。在一些实施例中,通过铅笔硬度测试,底漆硬度在9B与6B之间。在一些方面,底漆的厚度在约1μm与约4μm之间。
任何所披露的组合物和/或方法的任何实施例可以由任何所描述的要素和/或特征和/或步骤组成或基本上由其组成—而不是包含/包括/含有/具有任何所描述的要素和/或特征和/或步骤。因此,在任何权利要求中,术语“由...组成”或“基本上由...组成”可以代替以上所述的任何开放式连系动词,以便从使用开放式连系动词否则将是的范围改变给定权利要求的范围。
术语“基本上”及其变化被定义为在很大程度上但不一定完全是如本领域普通技术人员所理解的指定的内容,并且在一个非限制性实施例中基本上是指在10%以内、在5%以内、在1%以内、或在0.5%以内的范围。
“类似物(Analogue和analog)”,当是指化合物时,指的是改性的化合物,其中一个或多个原子已经被其他原子取代,或其中一个或多个原子已经从所述化合物中删除,或其中一个或多个原子已经被添加到所述化合物中,或者此类改性的任何组合。此类原子的添加、删除或取代可以沿着包含所述化合物的初级结构在任何点、或多个点处发生。
涉及母体化合物的“衍生物”指的是以化学方式改性的母体化合物或其类似物,其中至少一个取代基不存在于所述母体化合物或其类似物中。一个此类非限制性实例是已经共价地改性的母体化合物。典型的改性是胺类、碳水化合物类、烷基基团、酰基基团、酯类、聚乙二醇化(pegylation)等。
术语“约”或“近似”或“基本上不变”定义为接近于本领域普通技术人员所理解的,并且在一个非限制性实施例中,这些术语被定义为在10%以内、优选在5%以内、更优选在1%以内、并且最优选在0.5%以内。
当与权利要求和/或说明书中的术语“包含”结合使用时,使用词语“一(a或an)”可以是指“一个”,但也符合“一个或多个”、“至少一个”以及“一个或多于一个”的含义。
如在本说明书和一项或多项权利要求中使用的,词语“包含(comprising)”(以及包含的任何形式,如“包含(comprise)”和“包含(comprises)”)、“具有(having)”(以及具有的任何形式,如“具有(have)”和“具有(has)”)、“包括(including)”(以及包括的任何形式,如“包括(includes)”和“包括(include)”)或“含有(containing)”(以及含有的任何形式,如“含有(contains)”和“含有(contain)”)是包含性的或开放式的并且不排除额外的、未被描述的要素或方法步骤。
用于其用途的组合物和方法可以“包含”、“基本上由...组成”或“由...组成”贯穿说明书披露的任何成分或步骤。
本发明的其他目的、特征和优点将从下面的详细描述中变得明显。然而,应当理解,详细描述和实例,虽然指示本发明的具体实施例,但仅通过说明的方式给出。此外,预期本发明的精神和范围内的变化和修改对于本领域技术人员将从此发明内容中变得明显。
附图说明
图1是浇铸的偏振镜片100的侧视图,其中110是TAC膜,120是偏振PVA膜,130是含有交联剂的底漆,140是CR-39树脂。
图2是偏振光致变色层压体200的侧视图,其中110是TAC膜,120是偏振光致变色Pebax膜,130是含有交联剂的底漆,150是反应性粘合剂。
具体实施方式
参考附图中所示并在下面的描述中详述的非限制性实施例,更全面地解释了各个特征和有利的细节。然而,应当理解,详细描述和具体实例,虽然指示实施例,但仅通过说明的方式而不是限制的方式给出。根据本披露,各种替代、修改、添加和/或重排对于本领域普通技术人员将是明显的。
在下面的描述中,提供了许多具体细节以提供对所披露的实施例的透彻理解。然而,相关领域的普通技术人员将认识到,可以在没有一个或多个具体细节的情况下或者用其他方法、组分、材料等实施本发明。在其他情况下,未示出或详细描述众所周知的结构、材料或操作以避免模糊本发明的多个方面。
生产了几种底漆实例(溶液)和对比底漆实例(溶液)。实例变量包括存在和不存在交联单体、以及不同的底漆厚度。以下描述了实例和结果。
针对浇铸脱层的表面处理和磨边测试(SET)
在以下描述的实验中,采用表面处理和磨边测试以在各种镜片样品中引起可能导致脱层的应力。
表面处理和磨边测试适用于所有具有嵌入的或表面安装的膜的眼科镜片。镜片可以是有涂层的或没有涂层的,并且可以包括或可以不包括硬涂层、减反射组分、精加工真空涂层和表涂层中的至少一种。观察失效率提供了在镜片处理期间失效的风险的指示。
生成具有焦度偏移的镜片。然后用增加的压力在镜片边缘上施加机械力对镜片进行细磨,在界面处产生高应力,可能削弱粘附性。以本领域技术人员已知的典型方式进行抛光。在典型的磨边机上用最具侵蚀性的设置进行磨边。
以下概述的测试结果在偏振CR39单光镜片上进行。将镜片加工至+0.50焦度,目标厚度为2.8mm。在发生器与细磨后曲线之间偏移0.1屈光度用金属合金封阻镜片。将细磨压力升高至设备的安全最大极限(25PSI,格柏柯本公司(Gerber-Coburn))。根据标准操作程序进行抛光。在快速循环磨边机上进行磨边,所述磨边机被选择为尤其具有侵蚀性的(Triumph磨边机)。
检查
对每个镜片进行由前述步骤中的任一步骤产生的任何异常的目视检查。目视检查镜片是否脱层。任何脱层都被解释为镜片失效。
层压体粘附性的剥离力测量
通过Mark-10设备测量TAC与另一功能膜之间的剥离力值。在无水环境中测试25mm的膜宽度。首先TAC膜与TAC-Pebax-TAC层压体界面分离,然后以1.5mm/min的剥离速度在180°T-剥离下剥离。当剥离力值(牛顿)达到某一稳定水平时,通常在剥离20mm以上后记录剥离力值。本领域技术人员将考虑的是剥离力的值是足够的,即,当值高于10N/英寸时,膜在进一步的表面处理和磨边过程中不会脱层。
实例1
底漆配制品和浇铸
步骤一:底漆配制品和在TAC极性层压体上涂布
对比底漆溶液由基底漆或与交联剂相结合的基底漆组成,基底漆溶液用作对照。基底漆配制品包含丙烯酸聚合物树脂(MW~10,000至~100,000)、反应性丙烯酸低聚物、以及UV引发剂或热引发剂。实例中采用的一种示例性、非限制性交联剂是季戊四醇三丙烯酸酯。然而,起到交联基底漆组分作用的其他化合物也是有效的。使用溶剂来降低基底漆和改性的底漆的固体含量。
使用以可聚合材料浇铸的TAC偏振层压体检查底漆配制品的粘合强度。用于以下实验的层压体是TAC-PVA-TAC偏振层压体。
通过具有不同棒尺寸(数量)的迈耶棒(Meyer Rod)涂布机以约4mm/秒的涂布速度将基底漆和改性的底漆涂布在TAC层压体的两侧面上。然后使用具有600mJ/cm2的平均UV强度的融合输送机UV系统固化涂层,以得到一系列TAC偏振层压体膜。每个TAC偏振层压体膜包括固化的基底漆涂层(对照)或固化的改性底漆涂层(对比底漆实例)。
步骤二:偏振层压体成形和使用可聚合材料浇铸
使用LEMA成形设备使涂布有底漆的TAC偏振层压体热成形,以获得用于偏振镜片浇铸的4或6基弯。然后将弯曲的TAC偏振层压体薄片放入玻璃模具组件中,以使用可聚合材料进行浇铸。以下实例采用聚碳酸烯丙基二甘醇酯(CR-39)作为可聚合材料。在浇铸和模具拆卸之后,获得一系列TAC极性CR-39半成品(SF)镜片。
步骤三:浇铸TAC偏振CR-39-Leus SET评估
SET结果汇总于以下表1中。基底漆对照镜片(底漆#1,由Onbitt公司提供)在SET测试期间脱层。两个基底漆+交联剂实例(底漆#3和底漆#4)也脱层。这些实例分别包括30%和10%的交联剂。底漆#2(10%交联剂)没有脱层,并且使用不同于底漆#4的棒号涂布。底漆#5和底漆#6分别包含5%和3%的交联剂,并且没有脱层。这些结果表明交联剂改善了底漆的粘合强度。高交联浓度(30%)产生刚性底漆,降低了TAC与浇铸树脂之间的粘附性水平。当底漆的施加厚度大于5μm时,粘附性水平是次优的。结果证明交联剂浓度与粘合强度之间存在负相关,因为较低的交联剂浓度产生改善的粘附性,并且底漆厚度应该保持低于某个值。
表1:SET结果
Figure BDA0001998006120000081
CA=交联剂(季戊四醇三丙烯酸酯);所有实例均经过棒涂;额外的溶剂=乙酸乙酯。
实例2
用于TAC膜层压体的底漆配制品
通过涂布有底漆的TAC膜带有聚醚嵌段酰胺膜的TAC层压体
使用底漆#5底漆配制品涂布透明TAC膜(Lofo 916)。然后将有涂层的TAC膜UV固化以获得涂布有底漆的TAC膜。使用双组分聚氨酯粘合剂(U09FL,由Loctite公司提供),通过在15psi下辊层压,将有涂层的TAC膜与聚醚嵌段酰胺(Pebax)光致变色膜(由Transition公司提供)层压。然后将层压体在室温下固化24小时。所得光致变色层压体在TAC与聚醚嵌段酰胺界面之间显示出优异的粘附性。通过Mark 10设备测量剥离力,其中值大于18N/英寸。因此,认为TAC膜表现出与Pebax膜非常好的粘附性。
在对比对照实例中,在相同的层压条件下使用相同的双组分聚氨酯粘合剂层压上述TAC和聚醚嵌段酰胺膜。在本对照实例中不使用底漆。所得层压体显示出差的粘附性,剥离力为约5N/英寸。不同TAC膜类型的粘合强度也不一致。此实验证明,可以将交联组分添加到底漆上以增加膜层压体内的层内粘合强度。
权利要求不应被解释为包括装置加功能的或步骤加功能的限定,除非这样的限定在给定权利要求中分别使用短语“用于...的装置”或“用于...的步骤”明确地被叙述。

Claims (15)

1.底漆的用途,用于将TAC膜或TAC层压体粘附到聚合或可聚合材料上,所述底漆由底漆组合物得到,所述底漆组合物包含:
按重量计10%-30%的至少一种丙烯酸聚合物树脂,其为甲基丙烯酸酯共聚物,
按重量计10%-30%的至少一种反应性丙烯酸低聚物,其为官能氨基甲酸乙酯丙烯酸低聚物,
按重量计1%-25%的至少一种交联剂,
按重量计1%-5%的至少一种UV引发剂或热引发剂,和
溶剂;
其中所有组分之和为100%;
并且
其中,所述底漆的厚度在从1μm至4μm的范围内。
2.如权利要求1所述的用途,其中,所述底漆组合物中的所述交联剂包含至少两种反应性官能团,其独立地选自由以下各项组成的组:丙烯酸、丙烯酸酯、烯丙基、乙烯基、炔丙基、异氰酸酯、胺、以及环氧基。
3.如权利要求1或2中任一项所述的用途,其中,所述底漆组合物中的所述交联剂是多官能丙烯酸酯。
4.如权利要求3所述的用途,其中,所述多官能丙烯酸酯是季戊四醇三丙烯酸酯。
5.如权利要求1所述的用途,其中,所述底漆组合物中的所述丙烯酸聚合物树脂是甲基丙烯酸酯共聚物,分子量在从10,000g/mol至100,000g/mol的范围内,并且在所述共聚物中含有10至80的酸值。
6.如权利要求1所述的用途,其中,所述反应性丙烯酸低聚物是官能氨基甲酸乙酯丙烯酸低聚物,分子量在从1,000g/mol至50,000g/mol的范围内。
7.如权利要求1所述的用途,其中,所述聚合材料是聚醚嵌段酰胺膜、聚甲基丙烯酸甲酯膜、聚酰胺膜、聚酯膜、醋酸丁酸纤维素膜、或包含前述任意组合的复合膜。
8.如权利要求7所述的用途,其中,所述聚酯膜是聚碳酸酯膜。
9.如权利要求1所述的用途,其中,所述可聚合材料选自由以下各项组成的组:聚碳酸烯丙基二甘醇酯;中间折射率丙烯酸、胺或苯乙烯单体;环硫氨基甲酸乙酯单体;或选自由以下各项组成的- 反应性粘合剂:UV丙烯酸粘合剂、聚氨酯粘合剂、环氧粘合剂、胺粘合剂和双组分聚氨酯。
10.如权利要求1所述的用途,其中,所述TAC膜是透明光学膜或光学功能膜。
11.如权利要求1所述的用途,其中,所述TAC层压体是TAC-PVA-TAC偏振层压体。
12.如权利要求1所述的用途,其中,所述粘附是膜到聚合材料表面上的粘附或在浇铸材料内的嵌入粘附。
13.如权利要求1所述的用途,其中,所述底漆组合物中的所述溶剂是酮溶剂、乙酸酯溶剂、二氯甲烷溶剂、或以上的组合中的至少一种。
14.如权利要求1所述的用途,其中,通过铅笔硬度测试,底漆硬度在9B与6B之间。
15.一种用于将TAC膜或TAC层压体粘附到聚合或可聚合材料上的方法,包括使用底漆,所述底漆由底漆组合物得到,所述底漆组合物包含:
按重量计10%-30%的至少一种丙烯酸聚合物树脂,其为甲基丙烯酸酯共聚物,
按重量计10%-30%的至少一种反应性丙烯酸低聚物,其为官能氨基甲酸乙酯丙烯酸低聚物,
按重量计1%-25%的至少一种交联剂,
按重量计1%-5%的至少一种UV引发剂或热引发剂,和
溶剂;
其中所有组分之和为100%;
并且
其中,所述底漆的厚度在从1μm至4μm的范围内。
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US20200376804A1 (en) 2020-12-03

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