CN1328075A - 采用含氧化锌的耐磨多层稳定的塑料 - Google Patents

采用含氧化锌的耐磨多层稳定的塑料 Download PDF

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CN1328075A
CN1328075A CN01116594A CN01116594A CN1328075A CN 1328075 A CN1328075 A CN 1328075A CN 01116594 A CN01116594 A CN 01116594A CN 01116594 A CN01116594 A CN 01116594A CN 1328075 A CN1328075 A CN 1328075A
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S·霍法克尔
M·马格尔
H·J·沃梅尔斯多夫
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Abstract

本发明涉及具有涂层的塑料制品,所述涂层含有至少一层含氧化锌的层和至少一层耐磨外层。

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采用含氧化锌的耐磨多层稳定的塑料
本发明涉及采用含氧化锌的耐磨多层稳定的塑料。
许多塑料为了在户外使用必须采用适宜的紫外线(UV)吸收剂进行防护以防降解。实施该项措施的方法，可以采用，例如，将UV吸收剂加到整个塑料材料中。还能够采用含UV吸收剂的涂层来防护塑料，该涂层例如可以借助于共挤出或者采用湿化学方法来涂布。
一般说，塑料可以通过使用有机UV吸收剂有效地来防护。但是，在经受很长时间的UV幅射(如阳光)时，有机UV吸收剂本身会缓慢降解，因此失去其防护作用。另外，气候的作用(受潮，高温)可以使UV吸收剂受到损失，这是因为渗移和浸出而引起的。
另一方面，无机UV吸收剂，例如氧化锌，没有上述有机UV吸收剂的缺点。而且，如果所用的氧化锌(纳米ZnO)的粒度足够小，那末可以自此产生高透明层。这种氧化锌钠米粒子的制造叙述在，例如，德国专利申请DE19907704.5。
如果塑料材料除了需要UV辐射方面的防护之外，还需要抗机械磨损方面的防护，那末这可通过施涂抗磨涂层来实现。特别是在用诸如聚碳酸酯之类的塑料代替玻璃时，就需要极其耐磨。以前叙述过一些涂层，它们能够满足这些严格的技术要求。其实例可见述于US-A5677410、DE-A 19603241、WO98/52992、EP-A947520、DE-A4538361和EP-A0263428。然而，将氧化锌加入这些涂层之中常常会引起一些问题，因为这会使耐磨性下降。另外，相容性不适当也会引起涂层中的氧化锌纳米粒子发生聚集或附聚，这样会引起塑料发生混浊。如果涂料溶液含有酸性催化剂(在采用溶胶-凝胶溶液的情况下)，氧化锌就会溶解，不再起UV防护作用。
本发明的目的是提供一种具有耐久UV辐射防护性能和耐磨表面的塑料，其中不发生在生产涂层中所遇到的上述缺点。
现在令人惊异地发现，采用一种多层结构，其含有至少一层含ZnO的层和至少一层耐磨层，能够制造出具有上述性能的塑料。
本发明涉及一种具有涂层的塑料制品，所述涂层含有至少一层含氧化锌的层，和至少一层耐磨外层。
采用粒度＜30nm的ZnO纳米粒子作氧化锌原料。所优选的ZnO纳米粒子制剂是可以与涂覆溶液和/或涂覆溶液的至少一种组分直接混合的、而且不发生絮凝或其它分离现象的制剂。特别优选使用德国专利申请DE-A19907704.5所叙述的ZnO纳米粒子。
在本发明范围内，耐磨涂层是达到下述标准的涂层，在采用泰伯尔氏耐磨试验机(ISO3537，1000周期，每轮负荷5009，CS-10-F磨蚀介质)划痕之后，在划痕痕迹上的散射光(按ASTM D 1003)显示为20％以下，优选10％以下，更优选5％以下。相比之下，市售聚碳酸酯(Makrolon，由Bayer公司出品)。在泰伯尔氏耐磨试验机试验仅100周期之后，在划痕痕迹上的散射光大于30％。
耐磨涂层的例子是，特别应提及，热或辐射固化溶胶-凝胶材料。该溶胶-凝胶材料一般以低分子量有机烷氧基硅烷和/或有机硅烷醇的缩合物为基础，这些缩合物在基材上可以通过进一步缩合和/或聚合(在不饱和或环氧官能有机甲硅烷基残余物的情况下)而固化，从而产生高耐磨涂层。这些溶胶-凝胶材料反复见述于文献中，例如US-A5677410、DE-A19603241、WO98/52992、EP-A947520、DE-A4538361和EP-A0263428。
在本发明范围之中，含有氧化锌的涂料，除了适宜的基料之外，优选含有粒径主要为1-30nm的氧化锌粒子，这样在可见光范围中观察涂层就没有值得注意的散射或吸收。特别适于氧化锌的基料是仅仅稍微呈现或者没有光氧化分解趋势者。涂料含有1-50wt％氧化锌。
按照本发明的在塑料上的最简单的多层结构含有含氧化锌的层和耐磨外层。然而，也可以施涂另外的层。
在本发明的一个实施方案中，含有氧化锌的和耐磨的表面是这样得到的，先将含氧化锌的层涂布在基材上，快速挥发成分如溶剂等任选蒸发除去。然后涂布耐磨涂料，进行或不进行进一步固化，最后进行热或辐射固化。
在本发明的另一个实施方案中，基材表面先采用偶联剂进行化学处理或者进行物理处理(等离子体、电晕)，然后再涂布含氧化锌的层，以便改善粘合性。然而，也能够使用偶联剂本身作氧化锌粒子的粘合剂，如此不再需要另外的涂层步骤。
另外还能够以纯无机层或者主要是无机层的形式，以气相沉积按照本发明的多层结构的耐磨层。无机层可以含有诸如SiO2、TiO2、Al2O3或者其混合物。以这种方式，可以进一步增加耐磨性，和/或，可以改善减反射作用。
能够采用各种有机硅烷实现水分散体中的纳米结晶氧化锌的表面改性。有机硅烷必须含有至少一种缩合交联残基。这些残基的例子是烷氧基残基，特别是甲氧基或乙氧基残基，硅烷醇或乙酰氧基残基。有机硅烷的有机残基可以是脂族的，芳族的或任选脂族或芳族取代的。这些有机硅烷的例子包括甲基三乙氧基硅烷或3-环氧丙氧基丙基三甲氧基硅烷。
在本发明的一个实施方案中，水分散体中的纳米氧化锌的表面改性，通过加入有机硅烷(纯的或者溶于适宜溶剂中)以及在15℃和100℃之间的温度下搅拌反应混合物来进行。为了防止附聚，优选也可以在超声波存在下进行反应。
在固化涂层中有机硅烷和纳米氧化锌的比通常以达到这种程度为准，即，在涂布到诸如塑料、玻璃、陶瓷材料、金属等基材上，经干燥/固化之后，能够得到透明涂层。上述比例为纳米氧化锌1-50wt％，有机硅烷为5-90wt％。
特别优选的基材是透明基材。
含有氧化锌的、耐磨层可以通过所有常用方法进行涂布，包括离心涂布、喷涂、浸涂、流涂、刮涂或刷涂。
可以施加按照本发明的多层结构的基材的例子是塑料，例如聚酰胺、聚乙烯、聚丙烯、聚甲基丙烯酸甲酯、聚苯乙烯、聚乙烯基环己烷及其共聚物、丙类腈/丁二烯/苯乙烯共聚物(ABS)、聚氯乙烯、聚碳酸酯或其共混物。
按照本发明的具有耐UV和耐磨涂层的透明塑料可以用作，例如玻璃的替代品，用于玻璃镶嵌建筑或车辆(小汽车、公共汽车、卡车、火车)。
耐划痕涂料1：
耐划痕涂料由溶胶-凝胶溶液制造，其组成为6.8％环-{SiOCH3〔(CH2)2Si(CH3)2OH〕}4’32.1％原硅酸四乙酯，9.6％2-丁醇铝，5.1％乙酰乙酸酯，12.6％水，32.8％1-甲氧基-2-丙醇和1％光稳定剂(Tinuvin 384，ciba公司出品)。制造方法见述于EP-A947520。环-{SiOCH3〔(CH2)2Si(CH3)2OH〕}4的制备如US-A5880305所述。下文称环-{SiOCH3〔(CH2)2Si(CH3)2OH〕}4为D4-硅烷醇。
耐划痕涂料2：
将10g四乙氧基硅烷(TEOS)溶于5.5g1-甲氧基-2-丙醇中，与1.0g 0.1N对甲苯磺酸混合，同时搅拌，再搅拌另外30min。然后再加入另外1.0g 0.1N对甲苯磺酸，再搅拌另外60min(预水解)。3.0g仲丁醇铝溶解在1.0g 1-甲氧基-2-丙醇中，与1.6g乙酰乙酸酯混合，同时用冰冷却，在5℃下加入到预水解物中。一旦加完，加入另外2.0g0.1N对甲苯磺酸和2.4g D4-硅烷醇溶解在3.8g 1-甲氧基-2-丙醇中的溶液，再搅拌60min。
借助于离心涂布各层，其中在各种情况下，总指出最高转速(单位：rpm)和最高转速下的保持时间(以秒为单位)。
采用泰伯尔氏耐磨试验机试验检测耐磨性(ISO3537，1000周期，每轮500g，CS-10-F磨蚀介质)和随后测定散射光(ASTMD1003)。涂层的Makrolon3103的耐受性通过按照ASTM G154-97(周期4)的QUV-A和按照DIN53384的QUV-B天然老化进行测定。如同聚碳酸酯的泛黄测定一样，泛黄指数b*通过DIN6174反射进行测定。离心步骤用实验室离心机(Heraeus制造，Variofuge RE)，采用半径20.4cm的转筒。
多层涂层的一个实施方案如下：
耐划痕层
含ZnO层
偶联剂(底层)
聚碳酸酯
在获得含ZnO层与聚碳酸酯的足够的粘合性时，可以免除偶联剂(底层)。另外，也能够应用偶联剂作ZnO粒子的基料，从而有如下层结构：
耐划痕层
偶联剂+ZnO
聚碳酸酯
图1显示HFC528-1至-5的QUV-A天然老化的结果。
实例1
非表面改性的纳米氧化锌的制备
将590g醋酸锌脱水物在6L烧瓶中室温下搅拌入2000g分析级MeOH中。醋酸锌没有完全溶解。与此同时，在冷却下制备296.1g分析级KOH(86.6％)在1000g分析级MeOH中的KOH溶液。然后将100ml KOH溶液加入到醋酸锌溶液中。在以前未溶解的醋酸锌接着被溶解。然后加入其余KOH溶液。立即出现松散白色沉淀，在搅拌约70min之后成为半透明状。然后加热所得溶胶25min至沸点，此后切断热源。在静置过夜之后，形成白色沉淀物。搅拌之后，离心分离出该沉淀物(30min，5000rpm)。得到295.9g凝胶状残渣，X-射线衍射作为唯一结晶相的所得氧化锌。使凝胶状残渣与439.3g二氯甲烷混合，进行振荡直至沉淀完全分散。所得分散体是半透明的，沉降稳定几个月。
实例2
非表面改性纳米氧化锌的制备，适用于采用有机硅烷在水分散体中进行表面改性。
将590g醋酸锌脱水物在6L烧瓶中悬浮在2000g分析级MeOH中，并加热至60℃。醋酸锌被溶解。与此同时，在冷却下制备302g分析级KOH(84.7％)在1000g分析级MeOH中的KOH溶液。然后在60℃下将KOH溶液加入醋酸锌溶液中。立即出现松散白色沉淀，在约5min之后成为半透明的。在60℃下搅拌另外80min，在搅拌时间结束时，该批料为乳白色。除去热源之后，进行搅拌另外210min。静置过夜之后，排出3243g，并用1000g分析级MeOH补充。然后搅拌溶胶20min。沉降时间达45min后，排出768g上层清液，补充入500g分析级MeOH。再搅拌30min溶胶，沉降40min之后，再排出745g上层清液，补充入500g分析级MeOH。接着最后搅拌溶胶30min，然后离心分离(30min，5000rpm)，得到滗析出的253.15g凝胶状残渣，X-射线衍射研究显示为作为唯一结晶相的所得氧化锌。
实例3
采用自实例1的非表面改性的纳米氧化锌的双层结构
将29.5g仲丁醇铝溶解在5.9g 1-甲氧基-2-丙醇中，在室温下加入15.5g乙酰乙酸酯，该溶液加热至60℃。向所得溶液中滴加17.3gD4-硅烷醇和31.8g 1-甲氧基-2-丙醇，同时进行搅拌。在加完之后，将所得溶液在60℃下再搅拌1hr(铝/D4硅烷前体)。与此同时，将58.0g四乙氧基硅烷(TEOS)溶于50.3g正丁醇中，并与5.0g 0.1N对甲苯磺酸混合，在室温下搅拌1hr(预水解)。随后，预水解物在搅拌下与冷却到室温的铝/D4-硅烷醇前体混合，再搅拌所得溶液1hr。然后，加入94.8g按照实例1制造的纳米氧化锌分散体(25wt％ZnO)、5.0g去离子水和另外20.7g在38.1g 1-甲氧基-2-丙醇中的D4-硅烷醇，在室温下搅拌反应混合物另外1hr。
为改善粘合性，通过旋转涂布(1000rpm，20sec)，采用羟甲基三乙氧基硅烷(HMTS，在乙醇中含50wt％)，涂布5块聚碳酸酯板(Makrolon Bayer公司出品)。并在130℃下加热处理1hr。然后，把含有氧化锌的涂料溶液喷涂到以上述方法预处理过的板上；在固化(1hr，130℃)之后，所得板进行OUV-A天然老化试验。
表1汇总了OUV-A天然老化结果，并以图示出。表1：
样品No.   0h  250h 500h 750h 1000h
HFC528-1  2.9  × × × ×
HFC528-2  2.8  1.8 × × ×
HFC528-3  3.2  × 2.1 × ×
HFC528-4  2.5  × × 1.9 ×
HFC528-5  2.9  × × × 2.7
实例4
采用3-环氧丙氧基丙基三甲氧基硅烷在水分散体中进行自实例2的纳米氧化锌的表面改性
将10g按照实例2制造的纳米氧化锌凝胶(含有约55wt％氧化锌和约40wt％MeOH，蒸馏水，无机盐)与90g蒸馏水混合，剧烈搅拌，直至得到半透明的分散体。然后，10g 3-环氧丙氧基丙基三甲氧基硅烷加入其中，在70℃下于超声波浴中进行；然后再加热反应混合物经30min至70℃同时用超声波处理(反应容器不密封，使生成的甲醇逸出)。在冷却之后，得到无色/乳状的分散体/乳状液。
实例5
具有表面改性纳米氧化锌的三层结构(采用泰伯尔氏耐磨试验测定耐磨性)
为改善粘合性，在每种情况下，第一Makrolon板(10×10cm)先用3-氨基丙基三甲氧基硅烷(AMMO，200rpm，20sec)涂布，第二块板用羟基甲基三乙氧基硅烷(HMTS，在乙醇中含50wt％，1000rpm，20sec)涂布，均在130℃下热处理30min。然后，采用薄膜流延机(隙高30μm)向两块Makrolon板上涂布按照实例4制造的纳米氧化锌分散体，并在130℃下固化30min。最后再涂布耐划痕涂层2(500rpm，20sec)，在80℃下固化1hr，然后在130℃下固化1hr。在泰伯尔氏耐磨机划痕之后，发现散射光增量4.0％(AMMO)和3.5％(HMTS)。
与其比较，市售具有划痕涂层的聚碳酸酯(如Margard MR 10)散射光增量约12％。
实例6
具有表面改性纳米氧化锌的双层结构(采用QUV-B天然老化测定耐UV性)
为改善粘合性，先采用羟基甲基三乙氧基硅烷(在乙醇中含50wt％，1000rpm，20sec)涂布Makrolon板(7.5×15cm)，然后在130℃下加热处理1hr。然后，采用旋转涂布(400rpm，20sec)涂布按照实例4制造的纳米氧化锌分散体，在130℃下固化1hr之后，最后还涂布耐划痕涂层2，在80℃下固化1hr，在130℃下1hr。然后采用QUV-B天然老化试验测定耐UV性和耐天然老化性。象测定聚碳酸酯泛黄那样，测定泛黄指数b*。
与其比较，未涂层聚碳酸酯(Makrolon 3103，Bayer公司出品)泛黄指数b*在500hr之后为18.5。
在表2中汇总了QUV-B天然老化结果。表2：
样品  0h  250h  500h
Makrolon3103采用纳米ZnO  1.3  1.4  2.5
Makrolon3103  11.2  18.5
实例7
具有实例1的未表面改性的纳米氧化锌的三层结构(采用泰伯尔氏耐磨试验测定耐划痕性)
首先，将29.5g仲丁醇铝溶解在5.9g 1-甲氧基-2-丙醇中，与15.5g乙酰乙酸酯混合，并加热。向所得溶解中滴加17.3g在31.8g1-甲氧基-2-丙醇中的D4-硅烷醇，同时搅拌。在加完之后，在60℃下再进行搅拌1hr(铝/D4-硅烷醇前体)。
与此同时，将58.0gTEOS溶解在50.3g 1-丁醇中，与5.0g0.1N对甲苯磺酸混合，同时进行搅拌，再搅拌60min(预水解)。然后将铝/D4-硅烷醇前体和预水解物混合，并再搅拌60min。最后，加入94.8g ZnO溶胶(31wt％，在二氯甲烷中，自实例1制得)和5.0g去离子水，然后再加入20.7g在38.1g 1-甲氧基-2-丙醇的D4-硅烷醇。接着，再搅拌所得溶液60min，然后进行涂布。
为改善所得氧化锌涂料溶液对聚碳酸酯的粘合性，通过旋转涂布(1000rpm，20sec)，采用羟基甲基三乙氧基硅烷(HMTS，在乙醇中含50wt％)涂布5块Makrolon板(100mm×100mm)，在130℃下热处理1hr。
然而，可以采用其它化合物作偶联剂，如丙烯酸酯、丙烯酸酯烷氧基硅烷、甲基丙烯酸酯、甲基丙烯酸酯烷氧基硅烷、氧基硅烷或甚至聚氨酯。
在涂布偶联剂(底层)之后，通过旋转涂布(2000rpm，20sec)将氧化锌涂料溶液涂布到Makrolon板上，然后在130℃下热固化30min。
然后通过旋转涂布(800rpm，20sec)涂布耐划痕涂料1，并在130℃下固化60min。
在泰伯尔氏耐磨机划痕试验之后，散射光增量为4.6％。
虽然前文中为了说明的目的详述了本发明，能够理解，所进行的详述仅仅为了说明，本领域技术人员在不偏离本发明精神和范围的条件下，只要如权利要求所限定的，可以进行种种变更。

Claims (14)

1.一种具有涂层的塑料制品，所述涂层含有至少一层含氧化锌的层和至少一层耐磨的外层。
2.权利要求1的塑料制品，其中耐磨涂层含溶胶-凝胶材料。
3.权利要求2的塑料制品，其中含氧化锌的层含粒度主要为1-30nm的氧化锌粒子。
4.权利要求2的塑料制品，其中氧化锌粒子采用3-环氧丙氧基丙基三甲氧基硅烷进行表面改性。
5.权利要求1的塑料制品，其中含氧化锌的层含粒度主要为1-30nm的氧化锌粒子。
6.权利要求5的塑料制品，其中氧化锌粒子采用3-环氧丙氧基丙基三甲氧基硅烷进行表面改性。
7.权利要求1的塑料制品，其中氧化锌粒子采用3-环氧丙氧基丙基三甲氧基硅烷进行表面改性。
8.一种含有透明塑料和涂层的制品，所述塑料选自聚酰胺、聚乙烯、聚丙烯、聚甲基丙烯酸甲酯、聚苯乙烯、聚乙烯基环己烷及其共聚物、丙烯腈/丁二烯/苯乙烯共聚物(ABS)、聚氯乙烯、聚碳酸酯及其共混物，所述涂层含有至少一层含氧化锌的层和至少一层耐磨外层。
9.权利要求8的制品，其中耐磨涂层含溶胶-凝胶物料。
10.权利要求9的塑料制品，其中含氧化锌的层含有粒度主要为1-30nm的氧化锌粒子。
11.权利要求9的塑料制品，其中氧化锌粒子采用3-环氧丙氧基丙基三甲氧基硅烷进行表面改性。
12.权利要求8的塑料制品，其中含氧化锌的层含有粒度主要为1-30nm的氧化锌粒子。
13.权利要求12的塑料制品，其中氧化锌粒子采用3-环氧丙氧基丙基三甲氧基硅烷进行表面改性。
14.权利要求8的塑料制品，其中氧化锌粒子采用3-环氧丙氧基丙基三甲氧基硅烷进行表面改性。
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EP1146069B1 (de) 2007-09-12
US20010044020A1 (en) 2001-11-22
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ATE373038T1 (de) 2007-09-15
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US6884501B2 (en) 2005-04-26
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