CN100349999C - 含有含氟聚合物的溶胶凝胶涂料 - Google Patents

含有含氟聚合物的溶胶凝胶涂料 Download PDF

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CN100349999C
CN100349999C CNB200480005178XA CN200480005178A CN100349999C CN 100349999 C CN100349999 C CN 100349999C CN B200480005178X A CNB200480005178X A CN B200480005178XA CN 200480005178 A CN200480005178 A CN 200480005178A CN 100349999 C CN100349999 C CN 100349999C
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G·斯诺森
M·R·博伊梅
M·苏里亚特马贾
D·D·克哈斯尼斯
W·A·J·斯托克斯
R·尤斯乔德
L·G·P·J·德哈恩恩斯
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EIDP Inc
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Abstract

公开了一种含有含氟聚合物颗粒的溶胶凝胶涂料组合物。含氟聚合物颗粒均匀分布在涂料中，导致抗刮抗粘结和低摩擦涂层，其适用于例如家用电器和家用非电驱动器具。

Description

含有含氟聚合物的溶胶凝胶涂料
本发明涉及基于溶胶凝胶前体并包含基本均匀分布的含氟聚合物颗粒的溶胶凝胶涂料。
在中到高温用途如蒸汽熨斗或煎锅中能够提供抗粘结和低摩擦性能的含氟聚合物涂料通常含有一定含量的用作粘合剂的耐热聚合物(如聚酰胺酰亚胺)。这些涂料的机械性能(如抗刮性和耐磨性)劣于含有溶胶凝胶粘合剂材料的那些涂料。
尽管涂料的耐磨性和抗刮性通过使用溶胶凝胶粘合剂得以改善，在溶胶凝胶制剂中的含氟聚合物的抗粘结性能仍不能达到期望值。对抗粘结性能的适宜量度是与水的接触角。该接触角依赖于含氟聚合物颗粒的体积分数和它们在涂料中的颗粒分布。如果颗粒絮凝，那么在界面发现它们的概率很低。因此粘合剂将很大程度上决定接触角。已知与含氟聚合物混合的溶胶凝胶制剂趋于包括相当可观程度的含氟聚合物颗粒的絮凝。因此，仅能取得最大为约85°的接触角。为获得更大的接触角而增加含氟聚合物颗粒的体积分数将对由粘合剂提供的耐磨性具有消极影响。
本发明的目的在于提供第一段中所述的溶胶凝胶涂料，该涂料提供相对较高的抗粘结性能。
为了该目的，本发明提供了基于含有至少一种溶胶凝胶前体和含氟聚合物颗粒的涂料组合物的溶胶凝胶涂料，该涂料具有憎水性使得在其表面的水接触角至少为88°，优选至少为90°，并更优选至少为94°。这样大的接触角导致涂料的高抗粘结性能。所述抗粘结性能较已知的由溶胶凝胶粘合剂和含氧聚合物颗粒组成的涂料显著增高，在该已知涂料中，含氟聚合物颗粒发生絮凝。
在优选实施方案中，溶胶凝胶涂料组合物包含至少一种溶胶凝胶前体和含氟聚合物颗粒的稳定化水分散体。在本发明的一个特定实施方案中，含氟聚合物颗粒用聚硅氧烷聚氧化烯共聚物稳定化。
稳定剂的聚硅氧烷部分提供稳定剂的憎水部分，其被吸引到分散的含氟聚合物颗粒，而稳定剂的氧化烯部分提供稳定剂的亲水部分，使得稳定剂可以分散于水性介质中，这两种部分的存在使得稳定剂本身在分散体中起作用。用于本发明的该聚硅氧烷聚氧化烯共聚物是非离子性的(即不带电荷)，由稳定剂的憎水部分和亲水部分的存在获得稳定化效果。
优选地，根据本发明的溶胶凝胶涂料还包含填料颗粒，特别是二氧化硅颗粒。这种颗粒可以来源于水性硅溶胶。
溶胶凝胶材料在固化时显著收缩，因此它们有利地被其他颗粒(通常为二氧化硅颗粒)填充，以取得对于施涂而言足够的层厚。
在一个特定实施方案中，溶胶凝胶涂料中的含氟聚合物颗粒的体积分数低于50％。
颗粒的体积分数大于50％时，存在的粘合剂不足，导致多孔涂层。因此，在颗粒的体积分数大于50％时可以预期非常差的耐磨性。
优选地，溶胶凝胶涂料中的含氟聚合物颗粒的体积分数在15-30％范围内。
在本发明的优选实施方案中，涂料中的含氟聚合物颗粒包括在380℃时具有至少为1×108Pa·s的熔体粘度的聚四氟乙烯(PTFE)颗粒，其在含氟聚合物中具有最高的热稳定性。这种PTFE也可以含有少量的用于在烘烤(熔融)时提高成膜能力的共聚单体改性剂，例如全氟烯烃(尤其是六氟丙烯(HFP))，或尤其是其中烷基基团含有1-5个碳原子的全氟(烷基乙烯基)醚，并优选全氟(乙基或丙基乙烯基醚)(PEVE或PPVE)。这样的改性剂的量将不足以赋予PTFE熔体可加工成型性，通常是不超过0.5摩尔％。所述PTFE也可以是超细粉末型，其中链转移剂存在于水性聚合介质中以产生低分子量的PTFE，其特征在于在372℃时熔体粘度为0.1-100×103Pa·s。这种PTFE是熔体可流动的，但不是熔体可加工成型的，即当从熔体加工成型时，由这种PTFE加工成型的制品缺乏完整性并会自发地或者在经受轻微应力的情况下发生断裂。
尽管PTFE是优选的含氟聚合物，含氟聚合物组分也可以是熔体可加工成型的含氟聚合物。这样的熔体可加工成型的含氟聚合物的实例包括四氟乙烯(TFE)和至少一种氟化的可共聚单体(共聚单体)的共聚物，其以足够的量存在于聚合物中使得将共聚物的熔点降低到显著低于PTFE均聚物的熔点，例如降低至不高于315℃的熔融温度。优选和TFE一起的共聚单体包括全氟化的单体例如含3-6个碳原子的全氟烯烃和其中烷基基团含有1-5个碳原子，特别是1-3个碳原子的全氟(烷基乙烯基醚)(PAVE)。特别优选的共聚单体包括六氟丙烯(HFP)、全氟(乙基乙烯基醚)(PEVE)、全氟(丙基乙烯基醚)(PPVE)和全氟(甲基乙烯基醚)(PMVE)。优选的TFE共聚物包括FEP(TFE/HFP共聚物)、PFA(TFE/PAVE共聚物)、其中PAVE是PEVE和/或PPVE的TFE/HFP/PAVE，和MFA(其中PAVE的烷基基团具有至少两个碳原子的TFE/PMVE/PAVE)。熔体可加工成型的四氟乙烯共聚物的分子量是不重要的，只要其对于成膜是足够的并能够保持成型形状以具备完整性，即是熔体可加工成型的。典型地，按照ASTM D-1238在372℃时测定，熔体粘度为至少1×102Pa·s并可高达约60-100×103Pa·s的范围。
含有含氟聚合物颗粒的溶胶凝胶制剂优选由包括有机硅烷化合物的混杂溶胶凝胶前体制备。优选的溶胶凝胶前体包括甲基三甲氧基硅烷或甲基三乙氧基硅烷、苯基三甲氧基硅烷或苯基三乙氧基硅烷、二苯基二甲氧基硅烷或二苯基二乙氧基硅烷、环氧丙氧丙基三甲氧基硅烷或环氧丙氧丙基三乙氧基硅烷、或它们的组合物。也可以添加少量的非混杂溶胶凝胶前体材料例如四甲氧基硅烷或四乙氧基硅烷。
特别地，依据本发明的溶胶凝胶涂料具有高达400℃的耐温性。
依据本发明获得了混有含氟聚合物颗粒的水分散体的不发生含氟聚合物颗粒絮凝的溶胶凝胶制剂。由这些制剂制得的涂层由于含氟聚合物颗粒的更好分布而具有改善的憎水性。优选地，涂料中至少80％的含氟颗粒以基本上游离的非聚集颗粒存在。
依据本发明的溶胶凝胶涂料有利地沉积在基材上。基材可以是可以承受高烘烤温度的任何材料，例如金属和陶瓷，它们的实例包括铝或铝合金、冷轧钢、不锈钢、瓷釉、玻璃和高温陶瓷材料。
(蒸汽)熨斗的铝底板可以作为实例提及。这些底板用根据本发明的溶胶凝胶涂料涂覆之前被阳极化和用溶剂凝胶基涂料涂覆。
优选地，依据本发明的溶胶凝胶涂料用于家用用途中以形成被涂覆的制品如蒸汽熨斗、烘炉、三明治机、壶和咖啡机、真空吸尘器、电扇和家用空气处理装置、搅拌器和食品加工机，冰激凌机、油炸锅(deep fatfrayer)、烤架和电烹饪套具(electric gourmet sets)和炒锅。
此外，所述溶胶凝胶涂料还应用于制品如烹调用具、煎锅和其他蒸煮罐和器具，烤盘、炉的衬里、饭锅和它们的衬垫。此外，本发明的溶胶凝胶涂料具有很多工业用途，用于例如切割刀片、阀门、线、鞋业模具、雪铲和雪犁、船底、滑槽、传送带、辊表面、模具、工具、工业容器、模具、衬里反应容器、自动仪表盘、热交换器、管材等制品。
本发明还涉及获得其中含氟聚合物颗粒不絮凝而是绝大部分以单独颗粒存在的溶胶凝胶涂料的方法。
为了该目的，本发明提供了一种制备含有含氟聚合物颗粒的溶胶凝胶涂料的方法，所述方法包括下列步骤：
-将硅溶胶酸化到pH值大约3；
-添加足以稳定二氧化硅颗粒的部分溶胶凝胶前体总量；
-水解和稳定化混合物；
-添加余量的溶胶凝胶前体总量；
-水解混合物；和
-添加含氟聚合物分散体。
通过实施根据本发明的方法可以配制出其中含氟聚合物颗粒不絮凝并以单独的独立颗粒存在的涂料液体。在这种情况下含氟聚合物颗粒在涂料中可以均匀分布和对涂料的憎水性将具有更加显著的贡献。通过这种方法，具有溶胶凝胶母料的涂料中具有仅为20体积％的含氟聚合物颗粒可以取得94°或更高的水接触角。
如上所述，这些含有含氯聚合物颗粒的溶胶凝胶制剂可以由例如甲基三甲氧基硅烷或甲基三乙氧基硅烷(MTMS、MTES)的溶胶凝胶前体制备，其通常用于抗刮性和耐温性涂料，例如用在熨衣熨斗的底板上。这些前体在施加前必须被水解。在水解反应中需要水，并且酸通常用作催化剂。溶胶凝胶前体不溶于水，因此在通常实践中经常添加醇类以从水解反应开始就获得单相体系。
制备溶胶凝胶涂料液体的要求包括低pH值、醇和水的存在和添加其他颗粒，这些要求对溶胶凝胶涂料液体制剂构成了限制。当添加了含氟聚合物分散体时，容易发生絮凝，导致含氟聚合物颗粒聚集体的涂料液体，并因此导致含氟聚合物颗粒在涂料中的分布不均匀。
为提高涂料制剂的胶态稳定性，含氟聚合物分散体可以被改性以赋予与溶胶凝胶涂料液体改善的相容性，或者可以调节溶胶凝胶清漆制剂以获得与碳氟化合物分散体更好的相容性。在实践中这两种方法的组合被证明更为有效。
由于含氟聚合物颗粒的憎水性，在水分散体中稳定化氟碳化合物颗粒是困难的。已经研发出能取得经良好稳定化的水分散体的特定表面活性剂，其必须在狭窄的浓度范围内使用的。有益地，含氟聚合物颗粒用聚硅氧烷聚氧化烯共聚物稳定化。添加醇到这种分散体中可易于导致被吸附的表面活性剂的层在吸附量和表面活性剂分子取向上的改变，这可能导致胶体稳定性的丧失。
因此，溶胶凝胶配方的改进的第一目标在于需要使醇的使用量最小化。醇在溶胶凝胶前体的水解和醇缩合反应中形成。这在溶胶凝胶工艺中是不可避免的。然而如前体与水完全混合，为保证从水解反应开始即为单一相而添加醇是不必要的。
在水解过程中，将形成足够的醇以溶解未反应的溶胶凝胶前体，其在视觉上易于继以非分散单相的形成。因为氟碳化合物分散体将含有足够量的表面活性剂以在干燥过程中在涂料中降低表面表面张力和有效地抑制非均匀态的形成，通过添加醇来降低涂料的表面张力和提高涂料的干燥性能是没有必要的。
不含颗粒的溶胶凝胶层的最大层厚通常是受限制的，经常加入颗粒以减少在干燥阶段和固化阶段的收缩，这导致最大无开裂层层厚的增加。
水性硅溶胶通常用于该目的。为保持最终制剂中的高固含量，用水性溶胶中的水来水解溶胶凝胶前体是有利的。在溶胶凝胶前体的水解过程中，通过调节其pH值到大约3，优选是通过溶解固体酸如马来酸，然后添加极少量的溶胶凝胶前体，例如甲基三甲氧基硅烷，硅溶胶的絮凝可得以避免。实际上，溶胶凝胶前体的量将为最终添加的溶胶凝胶前体的总量的约0.01-1％。这种少量在溶胶中水解并将被吸附在二氧化硅颗粒的表面上。
这种处理使得二氧化硅的胶态稳定性较少地依赖于在大量硅烷水解中产生的醇的量，而醇可以导致絮凝。文献中经常记载，添加溶胶凝胶前体时硅溶胶先表现出浊度的增加，显示发生絮凝，然后接着是浊度的降低，显示发生重新稳定。因为重新稳定可能是不完全的和可能需要额外的过滤步骤，这是不理想的。逐步添加溶胶凝胶前体可以避免这种情况。
上述方法与Handbook of Advanced Electronic and PhotonicMaterials 5，219-262页，2000，Academic Press中描述的方法不同，在后者的方法中溶胶凝胶前体被预水解并导致更稀的制剂。预水解步骤也导致部分缩合产物的形成，其对二氧化硅表面具有低得多的亲和力，并可能导致二氧化硅颗粒对经受MTMS的第二次添加而不发生絮凝的稳定性不够。
在第二次添加的溶胶凝胶前体水解完全后，可以添加含氟聚合物分散体并不会发生絮凝。得到的制剂然后可以以喷涂来施加。固化后可以得到其中含氟聚合物颗粒均匀分布而导致与水的大接触角的10μm厚的涂层。
本发明通过参照附图得到进一步的阐述，其中：
图1示意性地表示接触角的定义；
图2为扫描电子显微镜照片，示出了配备了依据实施例1的溶胶凝胶/PTFE面漆层的溶胶凝胶底涂层的横截面；
图3为扫描电子显微镜照片，示出了配备了依据对比实施例1的溶胶凝胶/PTFE面漆层的溶胶凝胶底涂层的横截面；和
图4示意性地示出了一个底板配备了含有均匀分布的含氟聚合物颗粒的溶胶凝胶涂层的熨斗。
部分插图是示意性的且不是按照比例作图。为了清楚起见，相似组分用同样的标记数字提到。
图1示意性地表示接触角的定义。标记数1表示涂层表面。在所述涂层表面1上的水滴用标记数3表示。线4是液滴3的外表面在表面1相交处的切线。接触角定义为线4和表面1的夹角。接触角用美国Rame-Hart Inc生产的Surface Contact Angle Goniometer测定。下面的实施例阐述了依据本发明的含氟聚合物溶胶凝胶涂料和其制备方法，与依据现有技术的溶胶凝胶涂料及其制备方法进行比较。
实施例1
在反应容器中将5.5g马来酸溶于380g Ludox AS40中。酸化的硅溶胶的pH值测得为2.5-2.9。然后加入0.95g MTMS并将混合物搅拌45分钟。随后将391g MTMS在搅拌下加入到酸化和表面改性的硅溶胶中。60分钟后该混合物用196g水稀释，随后逐步加入用聚硅氧烷聚氧化烯共聚物(SILWET L77)与合适的消泡剂一起稳定化的315g 30％的聚四氟乙烯(PTFE)在水中的分散体中。PTFE添加完成后，加入30g的云母基颜料。
将涂料喷涂到位于阳极化铝板上的之前经过干燥的溶胶凝胶层上并在300℃下固化。在经固化的涂层中PTFE颗粒的量大约为18体积％。经固化的涂层的水接触角经测定为94±2°。
PTFE颗粒均匀分布在涂料中，在扫描电子显微镜获得的横截面图片中没有观察到絮凝的迹象。作为实例，典型的横截面照片在图2中给出。
被喷涂的涂层的光泽度、抗刮性和水接触角性质对于在制备后立即进行喷涂的涂料和在涂料液体制剂完成8小时后进行喷涂的涂料是一样的。涂料清漆的粘度在所述时间段保持不变。
实施例2
本实施例与实施例1相当，区别在于调节二氧化硅颗粒与聚四氟乙烯(PTFE)颗粒的比率以增加PTFE在最终涂料中的体积分数。
在反应容器中将2.2g马来酸溶于124g Ludox AS40和110g水中。酸化的硅溶胶测得的pH值为2.5-2.9。然后加入0.31g MTMS并将混合物搅拌45分钟。随后将308g MTMS在搅拌下加入到酸化和表面改性的硅溶胶中。60分钟后混合物用154g水稀释，然后逐步加入用聚硅氧烷聚氧化烯共聚物(SILWET L77)与合适的消泡剂一起稳定化的460g30％的PTFE在水中的分散体中。PTFE添加完成后，加入35g的云母基颜料。
将涂料喷涂到之前经过干燥的位于阳极化铝板上的溶胶凝胶层上并在300℃下固化。在经固化的涂层中PTFE颗粒的量为大约30体积％。经固化的涂层的水接触角经测定为98±2°。
实施例3
本实施例与实施例1相当，区别在于调节二氧化硅颗粒对聚四氟乙烯(PTFE)颗粒的比率以增加PTFE在最终涂料中的体积分数。
在反应容器中将7.5g马来酸溶于425g Ludox AS40中。酸化的硅溶胶测得的pH值为2.5-2.9。然后加入1.1g MTMS并将混合物搅拌45分钟。随后将385g MTMS在搅拌下加入到酸化和表面改性的硅溶胶中。60分钟后混合物用193g水稀释，之后逐步加入用聚硅氧烷聚氧化烯共聚物(SILWET L77)与合适的消泡剂一起稳定化的194g 30％的PTFE在水中的分散体中。PTFE添加完成后，加入37g云母基颜料。涂料被喷涂到之前经过干燥的阳极化铝板上的溶胶凝胶层上并在300℃下固化。在经固化的涂层中PTFE颗粒的量为大约10体积％。经固化的涂层的水接触角经测定为89±3°。
对比实施例1
在本实施例中使用用烷基苯酚乙氧基化物表面活性剂稳定化的聚四氟乙烯(PTFE)分散体。
348g MTMS与18g云母基颜料、5g马来酸和174g乙醇混合。水解在加入345g Ludox AS40后开始。在连续搅拌1小时后添加合适的消泡剂，然后添加107g商业可获得的用烷基苯酚乙氧基化物表面活性剂和3.5g全氟烷基亚磺酰氨基氧乙烯基表面活性剂稳定化的由62重量％PTFE颗粒组成的PTFE分散体。PTFE初始粒径为大约250nm。混合至少15分钟后，涂料液体喷涂到之前经过干燥的阳极化铝板上的溶胶凝胶层上并在300℃下固化。
在图3中给出了涂层横截面的扫描电子显微镜照片。该照片表明由于PTFE颗粒的絮凝导致的涂层的非均质性。能量分散X-射线分析显示出非均质性是富含氟，意味着絮凝的PTFE颗粒。
PTFE颗粒的絮凝降低了表面上的PTFE的量并导致水接触角仅为84±2°。
对比实施例2
向100g MTMS、50g乙醇和1.4g马来酸的混合物中缓慢加入100gLudox AS40。60分钟后缓慢添加用聚硅氧烷聚氧化烯共聚物稳定化的75g 30重量％聚四氟乙烯(PTFE)在水中的悬浮液，然后添加30g云母基颜料。
涂料喷涂到阳极化铝板上的之前经过干燥的溶胶凝胶层上并在300℃下固化。第一次喷涂的涂层的光泽度大大高于涂料液体制备完成两小时后喷涂的涂层的光泽度。在不足2小时后粘度升高到无法接受的高值。在经固化的涂层中PTFE颗粒的量为约18体积％，然而经固化的涂层的水接触角经测得仅为82±3°。
图4是依据本发明的熨斗的示意性的侧视图。所述熨斗包括可以由合成树脂材料制备的外壳5。外壳的底面配备有金属底板6。在本实施方案中底板用将铝薄板8紧固于其上的铝压铸块7制备。所述薄板8也称为熨平板。如前所述，铝板可以含有铝和铝合金。溶胶凝胶涂层10含有均匀分布的含氟聚合物颗粒，依据本发明施加在薄板8的表层。所述溶胶凝胶涂层提供非常好的耐磨性和抗刮性以及高抗粘结性能，这对于底板的滑动性能是极为有利的。

Claims (18)

1、一种基于含有含氟聚合物颗粒的溶胶凝胶前体的溶胶凝胶涂料，所述涂料具有使得在其表面的水接触角至少为88°的憎水性质，特征在于含氟聚合物颗粒用聚硅氧烷聚氧化烯共聚物稳定化。
2、权利要求1的溶胶凝胶涂料，特征在于涂料中包含填料颗粒。
3、权利要求2的溶胶凝胶涂料，特征在于所述填料颗粒包括源于水性硅溶胶的二氧化硅颗粒。
4、权利要求1-3的溶胶凝胶涂料，特征在于所述含氟聚合物颗粒的体积分数低于50％。
5、权利要求4的溶胶凝胶涂料，特征在于所述含氟聚合物颗粒的体积分数在15-30％的范围。
6、权利要求1-3的溶胶凝胶涂料，特征在于所述含氟聚合物颗粒包括聚四氟乙烯颗粒。
7、权利要求1的溶胶凝胶涂料，特征在于所述涂料基于含有有机硅烷化合物的混杂溶胶凝胶前体。
8、权利要求1的溶胶凝胶涂料，特征在于所述溶胶凝胶前体包括甲基三甲氧基硅烷或甲基三乙氧基硅烷、苯基三甲氧基硅烷或苯基三乙氧基硅烷、二苯基二甲氧基硅烷或二苯基二乙氧基硅烷、环氧丙氧丙基三甲氧基硅烷或环氧丙氧丙基三乙氧基硅烷，或它们的组合物。
9、权利要求1-3中任一项的溶胶凝胶涂料，特征在于所述涂料具有高达400℃的耐温性。
10、权利要求1-3中任一项的溶胶凝胶涂料，特征在于所述涂料沉积在金属基材上。
11、权利要求10的溶胶凝胶涂料，特征在于其沉积在铝或铝合金上。
12、包含用根据权利要求1-11中任一项的溶胶凝胶涂料涂覆的基材的涂覆制品。
13、权利要求12的涂覆制品，特征在于所述涂覆制品包括家用器具。
14、权利要求13的涂覆制品，特征在于所述涂覆制品选自蒸汽熨斗、真空吸尘器、电扇和家用空气处理装置、壶和咖啡机、搅拌器和食品加工机，烘炉和三明治机、冰激凌机、油炸锅、烤架和电烹饪套具和炒锅、饭锅、罐和煎锅以及烹饪器具。
15、制备根据权利要求1-11中任一项的溶胶凝胶涂料的方法，特征在于其包括以下步骤：
-将硅溶胶酸化到pH值大约3；
-添加足以稳定二氧化硅颗粒的部分溶胶凝胶前体；
-水解和稳定混合物；
-添加余量的溶胶凝胶前体；
-水解混合物；和
-添加含氟聚合物分散体。
16、权利要求15的方法，特征在于含氟聚合物颗粒用聚硅氧烷聚氧化烯共聚物稳定化。
17、含有溶胶凝胶前体和稳定化的含氟聚合物颗粒水分散体的溶胶凝胶涂料组合物，其中含氟聚合物颗粒用聚硅氧烷聚氧化烯共聚物稳定化。
18、用基于含有溶胶凝胶前体和含氟聚合物颗粒的稳定化水分散体的涂料组合物的溶胶凝胶涂料涂覆的基材，其中含氟聚合物颗粒用聚硅氧烷聚氧化烯共聚物稳定化。
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