CN1115989A - 改进涂布塑料基质抗冲击性的方法 - Google Patents

改进涂布塑料基质抗冲击性的方法 Download PDF

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CN1115989A
CN1115989A CN94190853A CN94190853A CN1115989A CN 1115989 A CN1115989 A CN 1115989A CN 94190853 A CN94190853 A CN 94190853A CN 94190853 A CN94190853 A CN 94190853A CN 1115989 A CN1115989 A CN 1115989A
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布鲁斯·M·法珀尔
威廉·C·哈宾逊
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Abstract

一种改进涂布塑料基质,特别是具有高折射率的聚合物的抗冲击强度的方法,包括将含水聚氨酯分散体作为底漆层涂于塑料基质的至少一个表面,通过在室温下空干使含水聚氨酯至少部分固化,将涂料组合物涂于聚氨酯底漆层上,及固化涂料组合物形成耐磨硬质涂层,含水聚氨酯分散体优选在耐磨涂料组合物之前在室温下空干不超过1小时,本方法提供了具有强界面粘合力的抗冲击、耐磨涂层体系,此体系优选为透明的,可优选用于透明塑料制品,如镜片和防护眼罩。

Description

改进涂布塑料基质抗冲击性的方法
本发明涉及一种通过在塑料基质的至少一个表面涂布一底漆层,改进塑料其质(如用作眼镜片)的抗冲击性的方法,其中底漆层由热固性聚氨酯分散体组成,此分散体在另一层涂布上去之前可在室温下空干固化。
人们清楚,透明塑料材料因其独特的性能如重量轻、易于加工和制品易成型,在很多场合被广泛用作玻璃的替代品。然而,塑料材料不是没有缺点,如大多数塑料为软质的,容易出现刮痕。因而,通常塑料材料应用于某些领域之前,要用有机或硅氧烷涂布组合物对其进行涂布,以提供一耐磨的“硬质涂层”。这种硬质涂层优选为透明的无色涂料。有机涂料的例子包括可热固化的环氧树脂和聚氨酯树脂及可用紫外光固化的丙烯酸树脂。虽然这种有机涂料要比硅氧烷涂料便宜,其耐磨性也不如硅氧烷料好。
许多硅氧烷涂料组合物是已知的,当其涂于基质上并固化时,在塑料基质的表面上形成一高耐磨性的涂层。这些涂料组合物中有许多在Clark的美国专利3986997和4027073,Baney等人的美国专利4177175、4242416和4027073,Ubersax的美国专利4177375,Humphrey的美国专利4188451和4218508,Goosens的美国专利4207357、4242381和4242383,January的美国专利4355135,White等人的美国专利4390373和44442168,Ashlock等人的美国专利4500669、4540634、4571365和4702773,Yoldas的美国专利4753827及Guest等人的美国专利5013608和5102695中有描述。这些专利中描述的硬质涂层已广泛用于使包括用作眼镜和防护眼罩的塑料镜片、建筑物和汽车中的窗户、塑料表盘和其它对于表而涂层耐磨或抗刮痕重要的制品赋予耐磨性。然而,人们还知道,这种耐磨硬质涂层降低了在某些应用中的塑料基质的抗冲击性。
近年来,具有格外高折射率的塑料材料已用于制备眼镜片。随着镜片折射率的增加,需要达到相同校准水平的镜片的厚度减小,得到的镜片又薄又轻,因而更吸引用户。然而,这些折射率较高的材料,与玻璃相比仍趋于相对柔软并容易出现刮痕,已知的有机或硅氧烷涂料组合物可涂于这些塑料材料上以提供一防护耐磨涂层。然而,当这种硬质涂层涂于这些折射率较高的塑料材料上时,其抗冲击强度与未涂布的塑料材料相比,趋于降低。这是一个严重缺陷,特别是这种降低有可能足够大,使抗冲击强度减至政府规定标准的最低值。同时,另外的涂布层,如抗折射涂层涂于这些已涂布的塑料材料后,还有可能进一步降低其抗冲击强度性能。
解决此问题的一个方法是在塑料基质层和耐磨涂层之间,涂一层热塑性树脂如聚氨酯的弹性体底漆层。此弹性体层用作能量吸收以防止因冲击在硬质层中形成的裂纹扩散至塑料基质层中。然而,热塑性树脂缺少交联结构,会受到含溶剂或单体的上涂层的不利影响,所以,当涂有热塑性聚合物底漆层的塑料材料随后用有机或聚硅氧烷涂料溶液浸渍或涂布时,其中的溶剂或单体可溶解热塑性底漆层同时造成底漆层被洗脱入耐磨涂料溶液中。这对于耐磨涂布制品的透明造成不利影响。热塑性底漆层由于受到溶剂的浸蚀还可能失去其透明性或变白。
为避免这些问题,提出底漆层应由在至少一种有机溶剂中的热固性聚氨酯构成,其中聚氨酯由封端异氰酸酯形成,此封端异氰酸酯需要运用加热使封端剂解离,这样异氰酸酯基团可与多醇的活泼氢发生反应和交联。使用封端异氰酸酯可防止此反应在室温下发生。然而,在防护硬质涂层涂于其上之前,增加固化热固性聚氨酯底漆层的加热步骤很昂贵,并使方法过份复杂,通常也是不必要的。同时,溶剂还可能进一步浸蚀塑料基质。
因此,要求存在改进塑料基质抗冲击性的方法,此方法不需要涂布热塑性聚合物底漆层或在另一种涂料组合物涂于其上之前加热基于溶剂的热固性聚氨酯底漆层使其固化。
本发明提供一种通过直接在塑料基质的至少一个表面涂布由含水聚氨酯分散体构成的一层底漆层,以改进塑料基质抗冲击性的方法,其中底漆层在另一涂料层涂于其上之前可在室温下经空干而充分固化。令人预想不到和吃惊的是,含水聚氨酯分散体可在室温下充分固化,因而在另外的涂料,如耐磨涂料组合物涂于底漆层上之前不需要增加使底漆层固化的加热或其它辐射步骤,也不会溶解或浸渍聚氨酯底漆层。有机或硅氧烷耐磨涂料组合物优选可在一小时内直接涂于本发明的聚氨酯底漆层上。聚氨酯底漆层和防护硬质涂层的结合提供一具有强界面粘结力的增强抗冲击、耐磨涂层体系,此体系涂于塑料制品如眼镜片和安全眼罩上具有较好透明性。
优选的含水胶体状聚氨酯分散体为阴离子稳定的,具有的pH值为约7至约9,固含量为约5%至约40%,平均颗粒大小为约10至约100纳米。经室温下空干,含水聚氨酯分散体自交交联形成热固性,优选透明的薄膜,此薄膜提供一层对塑料基质具有强粘合力的柔韧弹性底漆层。
固化的底漆层对现有技术中众所熟知的可用作形成防护硬质涂层的各种有机或聚硅氧烷涂料组合物具有强粘合力。这类涂料组合物可热固化或辐射固化以提供一层优选透明的硬质层。特别优选的热固化涂料组合物包括硅胶的胶体分散体或其它在部分浓缩硅烷醇的水—醇溶液中的水不溶分散体。特别优选的可辐射固化的涂料组合物包括已知的丙烯酸酯和硅烷/基于丙烯酸酯的涂料。已知的抗反射金属氧化物涂料,如铟锡氧化物,也可以用作硬质外涂层。此外,可选择的防护硬质涂层如现有技术中已知的要具有快速和深染色能力。
塑料基质优选为透明的,包括(但并不限于)既能拉伸又能流延的聚碳酸酯和丙烯酸酯,特别是PPG Industry的CR-39R塑料和高折射率的聚合物。
本发明包括一种改进涂布塑料基质,特别是透明的涂布塑料基质抗冲击强度的方法,它通过在基质的至少一个表面涂布由含水聚氨酯分散体组成的底漆层,在室温下经空干固化含水聚氨酯分散体,在底漆层上涂布形成耐磨涂层的涂料组合物,固化涂料组合物形成防护硬质涂层。
塑料基质可选自任何适合用作眼镜或防护眼罩的塑料镜片,或用作建筑物或运输工具包括飞机和汽车中的窗户的塑料材料。这些材料通常包括透明塑料,包括但不限于既能拉伸又能流延的聚碳酸酯和丙烯酸。特别有用的塑料基质包括CR-39R塑料,即由PPG Industry生产聚(双烯丙基碳酸二甘醇酯)。两种具有高折射率的专用塑料材料,可从一日本公司Mitsui-Toatsu购到,即熟知的MR-6和MR-7塑料;聚酯;乙酸丁酸纤维;和丙烯腈一丁二烯一苯乙烯。特别优选的塑料镜片是由通过游离基聚合含N—取代的苯基马来酰亚胺衍生物的单体混合物而得的聚合物制备的。
由这些材料制备塑料镜片的方法在现有技术中是众所熟知的。总之,此方法包括(1)将单体浇铸入模(优选由玻璃模形成并具有由乙烯—乙酸乙烯酯共聚物制备的垫片)中,将模在预定的时间内加热至预定的温度,从模中脱出得到的塑料材料,然后在预定温度下在预定的时间段内将其固化即得塑料镜片,或(2)将聚合物如丙烯酸或聚碳酸酯聚合物挤出或模压成镜片形状。
由含水聚氨酯分散体组成的底漆层直接涂于塑料基质的至少一个表面上。通常,含水聚氨酯分散一般为聚氨酯-聚脲,即特征为在大分子链中同时出现氨基甲酸酯(-NH-CO-O)和脲(-NH-CO-NH-)基团的聚合物。这些基团是通过熟知的得到聚氨酯链段的多异氰酸酯和多醇之间,及得到聚脲链段的多异氰酸酯和多胺之间的加聚反应形成的。选择适合生产含水聚氨酯分散体的特定多异氰酸酯、多醇和多胺通常与常规的聚氨酯化学中已知的相同。然而,特殊地,在操作过程中异氰酸酯必须对水具有足够的稳定性。
优选地,本发明的氨基甲酸酯聚合物是通过多官能团的异氰酸酯与多醇和阴离子二醇,如二羟甲基丙醇的缩合反应形成的。当此高分子量预聚物在分散剂,特别是叔胺如三乙醇胺存在下分散在水中时,形成阴离子稳定的胶体状分散体。此外,此含水聚氨酯分散体可与阴离子稳定的丙烯酸乳液共混。此含水聚氨酯分散体、优选具有pH值为约7至约9,固含量为约5%至约40%,平均颗粒大小约10至约100nm。如此小的颗粒是优选的,因为固化的聚氨酯将是透明的,然而,为了形成和保持如此小的颗粒,此含水聚氨酯分散体必须是阴离子稳定的。特别优选的可市购的含水聚氨酯分散体包括WitcobandR W-240,可从Houston,Texas的Organics Division of Witco Corporation购买,和NeoRezR-9637,可从Wilmington,Massachusetts的ICI Resins US购买。因这些可市购的含水聚氨酯分散体在涂布的基质于水中煮沸三小时,不从塑料基质上分离,故当防护硬质涂层使用现有技术中已知的着色浴液在升高温下进行着色时,此含水聚氨酯分散体特别适合用作本发明方法中底漆层。
用于形成脂族聚氨酯的优选异氰酸酯包括异佛尔酮二异氰酸酯,二环己基甲烷二异氰酸酯,例如,从Pittsburgh,Pennsylvania的Miles Inc.购买的Desmodur WTM,1,6-己二异氰酸酯、和四甲基二甲苯二异氰酸酯。在某些不要求光稳定或必须是低成本的应用中,可使用通过采用甲苯二异氰酸酯或二苯基甲烷二异氰酸酯形成的芳香族氨基甲酸酯。
可市购的广泛的多醇,包括线性或轻度支化的聚醚、聚酯、和聚碳酸酯多醇可用于形成本发明的聚氨酯。特别优选的多醇包括聚醚二醇和聚酯二醇。短链二醇和三醇还可用于调节氨基甲酸酯基团的含量和聚合物的支化。其它类多醇,例如环氧树脂、羟基丙烯酸酯,或油改性的醇酸树脂可用于带来特殊性能。
当聚氨酯分散体在水介质中形成时,异氰酸酯也能与水发生反应。异氰酸酯基团水解产生各种胺并释放出二氧化碳。接着按此方式形成的氨基基团可与余下的异氰酸酯基团反应形成脲键,此脲键有助于大分子链的延长,也有助于含水聚氨酯分散体的典型性质。然而,这种异氰酸酯/水反应在生产高性能聚氨酯分散体过程中优选要减至最低,原因是释放的二氧化碳导致不需要的剧烈发泡。同时,主要通过这种“水链延长”建立起来的含水聚氨酯分散体在聚合物性能方面趋于比通过多胺进行链延长的那些聚氨酯差。
底漆层是这样形成的:首先用含水聚氨酯分散体涂布塑料基质,然后使含水聚氨酯分散体在室温下空干直至充分固化,以使另外涂料组合物涂于底漆层上而不溶解或浸蚀底漆层。所谓室温是指约70°至约80°F。固化时间将根据特定含水聚氨酯分散体和环境空气流速和湿度条件而变化,但优选不超过1小时,更优选不超过约15分钟,特别优选的含水聚氨酯分散体可通过空干在5分钟内充分固化。底漆层的厚度可为约0.05至约5μm,优选为约0.1至约2.0μm。当厚度小于约0.05μm,底漆层不能充分改进塑料基质的抗冲击性,而厚度大于约5μm时趋于增加不必要的干燥和固化时间。经固化的含水聚氨酯分散体形成优选的热固性聚氨酯薄膜。
本发明的方法包括在聚氨酯底漆层上涂布至少一种其它涂料组合物,这些涂料组合物优选经固化形成耐磨涂层,它们包括现有技术中已知的能热固化或辐射固化的有机和聚硅氧烷涂料。由含二氧化硅的混合物,如胶体状二氧化硅或硅胶;或其它水不溶分散体,包括金属和合金,它们的盐、氧化物和氢氧化物;及在水解介质,如乙醇或水中可水解的硅烷形成的可热固化的涂料是特别优选的。例如参见美国专利3986997、4027073、4177175、4177315、4188451、4207357、4218508、4242381、4242383、4242416、4275118、4390373、4442168、4500669、4540634、4571365、4702773和4753827,这些专利公开的内容这里作为参考引入本文。固化后形成可染色的耐磨涂层的涂料组合物对于本发明的方法特别适合。例如,参见美国专利4355135、5013608和5102695,这些专利公开的内容这里作为参考引入本文。优选的可通过紫外光固化的防护硬质涂料包括Chung的美国专利4348462、4478876和4486504及Revis等人的美国专利4973612、5075348和5126394,这些专利公开的内容这里作为参考引入本文。
虽然防护硬质涂层考虑到其较大的耐磨性,优选硅氧烷基的可固化树脂体系,对于不要求这样的耐磨性时由已知的有机涂料形成的硬质涂层也可以使用。特别是,优选通过暴露于辐射中固化的丙烯酸酯基涂料也可以使用,例如公开于Hodnett,III的美国专利5114783,Yoshimara等人的美国专利4499217和Bilkadi的美国专利5104929中的涂料,这里作为参考引入本文。
当聚氨酯底漆层被防护涂料组合物覆盖后,上面的涂层的固化或聚合可通过加热或辐射实现。当已涂布的基质放入固化烘箱中加热时,对于大多数塑料基质可使用的温度范围为约50℃至约150℃,条件是固化时间和固化温度相配合不至使塑料基质软化和变形。因此,温度为约80℃至约130℃对于固化上面的涂层是优选的。
当通过辐射固化时,聚合反应可由任何能生成游离基的离子照射源,包括红外、γ射线照射、微波,和由电子束或紫外线照射引发。当通过紫外线照射进行聚合反应时,涂料组合物通常将包括现有技术中已知的用于固化UV可固化组合物的光引发剂。紫外光因其成本相当低、操作容易和对用户危险性小,是最广泛使用的固化化学组合物的照射方式之一。采用紫外光的快速光引发聚合反应代替热能固化硬质涂层可获得显著的经济效益,并且消耗的热能与常规的热固化体系相比要低得多。许多对热特别敏感的塑料材料可通过紫外光安全涂布和固化,而不必使用会损害这些基质的热能。同时,辐射固化涂层可以使用较小量溶剂,因而减少了花费在消除污染过程中的必须的费用及时间。
已知的无机抗反射涂料也可采用现有技术中熟知沉积技术,如真空沉积、喷涂和离子电镀方法施于聚氨酯底漆层上,或施于覆盖底漆层的硬质涂层上。优选的无机涂料包括金属氧化物,如铟锡氧化物。
各个涂层分次涂于塑料基质上,同时下一层涂布之前上一层要至少部分固化。如果底漆层通过室温下空干还没有完全固化,但仅充分固化至使其不被涂于其上的涂料组合物溶解或浸蚀,然后通过加热或辐射固化上面的涂层时,也将使底漆层充分固化。
通常,本发明的涂布基质层,当其最外层防护硬质涂层的厚度为约1至约10μm,优选约3至约5μm,使涂层总厚度为约1.0至约15.0μm,优选约3.0至7.0μm时,性能最佳。在这些范围内的厚度使耐磨性改进最优,不会例如因裂纹损害涂布基质的光学清晰度。
在底漆层涂布之前,塑料基质优选用现有技术中已知的技术进行清洗。底漆层和涂于底漆层上的涂料组合物都可用公知的涂布方法如浸渍涂布、喷涂、刷涂、旋涂、辊涂、流涂或分级涂布(Cascading)法进行涂布。这些涂布方法都是惯用的,可根据基质的性质,所需的厚度和其它因素选用。浸渍涂布和其它同时涂布基质两面的工艺也可以使用,或需要时在基质每一面上重复使用单面涂布工艺。这些涂布方法可使在基质的至少一个表面上以各种厚度涂布,这样可得到用途广泛的特定涂布层。
为了更充分和清楚地描述本发明,以使本技术领域熟炼人员更好地掌握实施本发明的方法,提供下列实施例。这些实施例是用于说明本发明的,而不应以任何方式解释为对本发明公开的内容和权利要求的限制。
实施例1
为了证明本发明的优点,采用本发明的方法用一种含水聚氨酯分散体WitcobondRW-240和—基于甲基三甲氧基硅烷和γ—缩水丙氧基三甲氧基硅烷的以胶体状二氧化硅为填料的硅氧烷涂料SILVURR339(可从Anaheim,California的SDC Coatings Inc.购买到,并可根据January的美国专利4355135公开的方法制备)涂布几种不同的塑料基质。首先用浸渍涂布方法将含水聚氨酯分散体涂于各塑料基质上,然后使其在室温下空干15分钟使其固化,得到的底漆层厚度为约2.0微米。令人吃惊和预想不到的是,当用浸渍涂布方法将涂料组合物SILVUER339涂于底漆层上时,即便底漆层没有经加热或置于其它射线下固化之,而只是使底漆层仅通过在室温下空干15分钟固化后涂布SILVUER339,此涂料组合物也不溶解或浸蚀底漆层。SILVUER339涂料组合物通过将涂布基质置于温度为120℃的烘箱中1小时固化,然后冷却至室温。固化后的防护硬质层的厚度为约4.0微米。还可将一抗反射涂料涂于下面所示的某些涂布基质上,即使用周知的真空沉积方法沉积由Tokai Optical Company(一日本公司)制备的金属氧化物层,此氧化物层在SILVUE339R上为一具有超硬度,同时含二氧化硅和氟化镁的复层抗反射涂层。作为对比,测试了各种塑料材料的未涂布基质和按上述方法仅用SILVUER339硬质涂料涂布的基质。
涂布基质和对比基质的耐磨性通过利用10个向前和向后动作(strokes)的简单手动摩擦(hand—rub)的钢棉(用0000钢棉)试验方法测量。若与未涂布的CR-39R塑料基质相比,刮痕有显著降低,则此基质标记为“好”,若与未涂布CR-39塑料相比有较多刮痕,则标记为“差”。耐磨性的试验结果列于下表中。
            表1    耐磨性试验结果
                (0000钢棉)
                              塑料材料
底漆    涂料    抗反射    CR-39    MR-6    MR-7
 无      无       不      一般     差      差
 无    S-339      不       好      好      好
 无    S-339      是       好      好      好
W-240  S-339      不       好      好      好
W-240  S-339      是       好      好      好
涂布基质和对比基质的抗冲击性用美国专利389657中公开的American Optical Corporation的仪器测量。这种仪器使用一球形投掷物,它由一磁铁垂直支撑在平台(anvil)上面,平台上装设一镜片,此镜片与投掷物之间的距离固定。投掷物使用压缩空气加速。此仪器使投掷物能以各种冲击能量撞击测试镜片,而不改变投掷物的尺寸和重量。涂布前测试的每种塑料基质其中心厚度为2.0mm±0.1mm,但标记为MR-6和MR-7的基质除外,其中心厚度为1.1mm±0.1mm。能量可通过测量投掷物的重量和速度计算。投掷物的速度通过测量两个光敏器之间的时间间隔决定。这些抗冲击性的测试结果列入下表II中。
                表2    抗冲击强度(单位:焦尔)
                                       塑料材料
底漆    涂料    抗反射    CR-39    MR-6    MR-7
 无     无        不      2.15     74.64     -
 无    S-339      不      0.73     0.88      -
 无    S-339      是      0.13     0.63      -
W-240  S-339      不      1.23     1.361    1.591
W-240  S-339      是      1.20     3.431    2.441
11.1mm,±0.1mm,中心厚度。
如表I和II所示,用本发明的方法涂布的塑料基质较用SILVUER339涂布的无底漆层的涂布基质,其冲击强度改进了,并且具有良好的耐磨性。用本发明的方法制备的各种涂布基质的冲击强度大大超过了FDA要求的最低值0.2焦尔。涂布基质在基质与底漆层之间和底漆层与硬质涂层之间,也具有很好的粘合力。所以,用本发明的方法制备的涂布基质特别适用于眼镜和防护眼罩的塑料镜片,和建筑物及交通工具中的窗户。
根据上述公开的内容,有可能对本发明进行其它更替和变化。例如,添加剂和其它改性剂可加入底漆层或加到耐磨涂料组合物中,同时另外的涂料组合物可涂于本发明的涂布基质上。但是,应注意对前面描述的特定实施方案进行的变化,完全属于本发明所附的权利要求定义的保护范围。

Claims (11)

1.一种改进涂布塑料基质抗冲击性的方法,包括:
将pH值为7至9,固含量为5%至40%,颗粒大小为10至100纳米的含水聚氨酯分散体涂于塑料基质的至少一个表面上,其中聚氨酯由多官能异氰酸酯与阴离子二醇和选自聚醚二醇和聚酯二醇的多醇缩合而成;
通过室温下空干使含水聚氨酯部分固化形成底漆层;
将耐磨涂料组合物涂于聚氨酯底漆层上,其中耐磨涂料组合物由硅基树脂或丙烯酸基树脂组成;
使耐磨涂料组合物固化形成防护耐磨硬质涂层。
2.如权利要求1的方法,其中基质为聚碳酸酯塑料、丙烯酸塑料、或具有高折射率的塑料材料。
3.如权利要求2的方法,其中塑料基质由含N取代的苯基马来酰亚胺衍生物的单体混合物的游离基聚合获得的聚合物形成。
4.如权利要求2的方法,其中塑料基质为眼镜片。
5.如权利要求1的方法,其中使含水聚氨酯分散体至少部分固化的步骤包括在涂布耐磨涂料组合物之前,在室温下空干聚氨酯分散体不超过1小时。
6.如权利要求1的方法,其中阴离子二醇为二羟甲基丙酸。
7.如权利要求1的方法,其中含水聚氨酯分散体包括用三乙醇胺作为分散剂。
8.如权利要求1的方法,其中基质、底漆层和耐磨硬质涂层是透明的。
9.如权利要求1的方法,其中底漆层的厚度为0.1至2微米,上层耐磨涂层的厚为1至10微米,总涂层厚度为1微米至15微米。
10.如权利要求1的方法,其中塑料基质为包含聚碳酸酯塑料、丙烯酸塑料、或具有高折射率的塑料材料的眼镜片;
含水聚氨酯分散体由多官能异氰酸酯与二羟甲基丙酸和选自聚醚二醇和聚酯二醇的多醇缩合而成,并包括三乙醇胺作为分散剂;
使含水聚氨酯分散体至少部分固化的步骤包括在涂布耐磨涂料组合物之前,在室温下空干聚氨酯分散体不超过1小时;
底漆层的厚度为0.1至2微米,上层耐磨涂层的厚度为1至10微米,涂层总厚度为1微米至15微米。
11.如权利要求1或10的方法,进一步包括的步骤为:将无机抗反射涂料涂于耐磨硬质涂层上。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103226220A (zh) * 2012-01-31 2013-07-31 Hoya株式会社 偏光透镜
CN103226220B (zh) * 2012-01-31 2017-06-23 Hoya株式会社 偏光透镜
CN112574657A (zh) * 2020-11-30 2021-03-30 湖南中车弘辉科技有限公司 一种刚性风机叶片防护底面合一防腐涂料及其施工方法

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ATE151787T1 (de) 1997-05-15
CA2150237A1 (en) 1994-08-04
GR3024106T3 (en) 1997-10-31
TW274563B (zh) 1996-04-21
SG47408A1 (en) 1998-04-17
DE69402682T2 (de) 1997-10-16
EP0680492A1 (en) 1995-11-08
DE69402682D1 (de) 1997-05-22
CA2150237C (en) 2002-07-30
KR100301408B1 (ko) 2001-11-22
JP3269630B2 (ja) 2002-03-25
US5316791A (en) 1994-05-31
KR960700285A (ko) 1996-01-19
EP0680492B1 (en) 1997-04-16
HK1008033A1 (en) 1999-04-30
WO1994017116A1 (en) 1994-08-04
JPH08505896A (ja) 1996-06-25
AU674389B2 (en) 1996-12-19
DK0680492T3 (zh) 1997-05-26
CN1045972C (zh) 1999-10-27
AU6023294A (en) 1994-08-15
ES2104349T3 (es) 1997-10-01

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