CN106715610A - 涂布剂水性分散液 - Google Patents

涂布剂水性分散液 Download PDF

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CN106715610A
CN106715610A CN201580053547.0A CN201580053547A CN106715610A CN 106715610 A CN106715610 A CN 106715610A CN 201580053547 A CN201580053547 A CN 201580053547A CN 106715610 A CN106715610 A CN 106715610A
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aqueous liquid
weight
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东良敏弘
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Nok Corp
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Abstract

涂布剂水性分散液，其中，作为固体成分，含有：PTFE 20~80重量%、优选为29~70重量%；丙烯酸树脂10~50重量%、优选为14~36重量%；以及乙烯‑乙酸乙烯酯共聚物树脂10~50重量%、优选为20~45重量%。本发明所述的涂布剂水性分散液用作橡胶制密封材料等的表面处理剂时，可以发现对密封对象材料的粘附降低、由橡胶材料表面出现的起霜受到抑制，加上柔软性，从而橡胶材料与涂布剂的粘接性的平衡优异。

Description

涂布剂水性分散液
技术领域
本发明涉及涂布剂水性分散液。进一步详细而言，涉及能有效用作橡胶制密封材料的表面处理剂等的涂布剂水性分散液。
背景技术
作为用作橡胶制密封材料的表面处理剂的涂布剂水性分散液，可以使用许多种类。例如，专利文献1中记载了PTFE水性分散液组合物，其包含PTFE(聚四氟乙烯树脂)颗粒和聚氧亚烷基烷基醚系化合物，其还能够包含作为成膜改良剂的丙烯酸树脂、表面活性剂等。该组合物的开裂临界膜厚极大，通过一次浸渗或者涂布就可以制成厚膜，然而，尽管满足了后述各种试验当中的柔软性评价、粘接性评价等，但不能满足通过加湿试验进行的粘接性降低评价。
专利文献2中记载了涂布组合物，其包含微粒状的全氟碳聚合物、云母或金属片、(甲基)丙烯酸系聚合物、以及液体状载体。其主要用于PTFE包覆的炊具，尽管满足后述各种试验当中的粘接性评价，但不能满足柔软性评价、通过加湿试验进行的粘接性降低评价。
专利文献3中记载了水性涂布剂组合物，其包含乙烯-乙酸乙烯酯共聚物树脂乳液、以及两种以上的粒径不同的PTFE粉末。该组合物的涂膜密合性、作业性、耐热性、耐药品性优异，尽管满足后述各种试验当中的柔软性评价、通过加湿试验进行的粘接性降低评价，但不能满足粘接性评价。
专利文献4中记载了非粘附性涂料，其具有氟聚合物、丙烯酸类聚合物、以及多元醇或二醇。此外，专利文献5中记载了氟树脂涂布用水性分散组合物，其包含氟树脂颗粒分散液、以及解聚性丙烯酸树脂颗粒乳液。
然而，由于将这些组合物在300℃以上的温度下进行烧制，因此在氟橡胶、硅酮橡胶中发现了橡胶的劣化，在NBR等耐热性低的橡胶材料中出现了显著的劣化，从而不能应用于密封部件。
现有技术文献
专利文献
专利文献1：日本特开2006-117900号公报
专利文献2：日本特开昭48-68559号公报
专利文献3：日本特开2010-106222号公报
专利文献4：日本特表2006-511674号公报
专利文献5：日本特开2007-191709号公报
专利文献6：日本特开昭61-171776号公报
专利文献7：日本特开平02-138380号公报
专利文献8：日本特开昭60-226509号公报
专利文献9：日本特开昭61-69880号公报
非专利文献1：J. Applied Polymer Science 第17卷 第3253~7页 (1973)。
发明内容
发明要解决的课题
本发明的目的在于，提供在用于橡胶制密封材料等时满足其所要求的各种特性的涂布剂水性分散液。
解决课题的手段
所述本发明的目的通过下述涂布剂水性分散液实现，所述涂布剂水性分散液含有PTFE20~80重量%、丙烯酸树脂10~50重量%、以及乙烯-乙酸乙烯酯共聚物树脂10~50重量%作为固体成分。
发明的效果
通过添加丙烯酸树脂以及乙烯-乙酸乙烯酯共聚物树脂两者作为PTFE颗粒的粘接剂，能够通过加热处理而得到基于丙烯酸树脂的热固化、和基于乙烯-乙酸乙烯酯共聚物树脂的熔化的对橡胶熔合的效果，此外，加热处理可以在约180℃以下的温度下以短时间的处理来进行，因此不会使橡胶劣化。
通过添加这两者，可以发现对密封对象材料的粘附降低、由橡胶材料表面出现的起霜受到抑制，加上柔软性，从而橡胶材料与涂布剂的粘接性的平衡优异。添加表面活性剂、油的情况下也能够降低粘附性，但无法避免地会导致与橡胶材料的粘接性降低，另一方面，在本发明中，由于不添加所述低分子成分，因此与橡胶的粘接性也良好。
本发明的涂布剂水性分散液可以有效地应用于O型圈、油封、垫片、隔膜(diaphragm)、阀等的各种橡胶制密封材料，除此之外，还可以应用于各种橡胶部件的防粘附、降低摩擦、防止磨耗等。
具体实施方式
本发明的涂布剂水性分散液中，作为固体成分，含有：PTFE 20~80重量%、优选为29~70重量%；丙烯酸树脂10~50重量%、优选为15~40重量%；乙烯-乙酸乙烯酯共聚物树脂10~50重量%、优选为14~36重量%，其总计量为100重量%。对于该涂布剂水性分散液，可以使这3种成分同时分散而制成水性分散液，优选以均为市售品的PTFE水性分散液、丙烯酸树脂水性分散液、以及乙烯-乙酸乙烯酯共聚物树脂水性分散液的混合物的形式进行制备。
PTFE水性分散液以下述目的而使用：降低摩擦、降低对密封对象材料的粘附性、降低柔软性、抑制由橡胶材料表面出现的起霜、使得因涂布中的接触而导致的粘附变得困难等。这些是由于PTFE为微粒状、且由于PTFE的非粘附性、低摩擦特性而表现出的性质，此外，PTFE的分子量大、且粒径小，因此实现了对来自橡胶材料表面的起霜进行遮蔽、使其延迟。
作为PTFE，不仅包括四氟乙烯的均聚物，还包括使其与少量的全氟乙烯基醚、六氟丙烯、乙烯等共聚而得到的聚合物，其数均分子量Mn优选为2×104~1×107、特别优选为2×105~8×106。如果Mn比其小，则存在涂布膜变脆的倾向，如果Mn比其大，则熔融粘度过高，可发现颗粒彼此的变得难以融合的倾向。Mn可以通过非专利文献1所记载的方法求得。
此外，PTFE水性分散液的平均粒径优选为约200~500nm。特别优选为约200~400nm，如果小于约200nm，则颗粒彼此容易凝集，从而在涂布面上产生粗糙不平，如果大于约500nm，则颗粒容易沉降，水性分散液组合物的稳定性下降。如果全部固体成分中的PTFE的比例少于约20重量%，则摩擦系数会变高，变得容易粘附。此外，无法遮蔽来自橡胶材料表面的起霜。另一方面，如果多于约80重量%，则会使得与橡胶的粘接性、柔软性会下降。进一步，会在涂布膜表面产生PTFE颗粒的凝集块，表面粗糙度增大，不仅密封性恶化，而且该凝集块会脱落而形成污染物。
丙烯酸树脂水性分散液以下述目的而使用：降低摩擦、降低对密封对象材料的粘附性、降低柔软性、抑制由橡胶材料表面出现的起霜等，其通过热而固化。
作为丙烯酸树脂，使用通式CH2=CRCOOR'(R：氢原子或甲基、优选为甲基，R'：C1~C16、优选为C2~C12的直链状或支链状的烷基)所示的(甲基)丙烯酸烷基酯的均聚物或共聚物，该均聚物的玻璃化转变温度Tg为-20℃以下。该Tg越低，则越会失去粘附性、***、达到低摩擦。相反的是，如果Tg高，则强度会下降，存在粘附，摩擦系数变高。
作为前述通式所示的(甲基)丙烯酸烷基酯、优选的甲基丙烯酸烷基酯，通常使用具有甲基、乙基、丙基、丁基、异丁基、戊基、二甲基丙基、正己基、正辛基、异辛基、2-乙基己基、异壬基、正癸基、正十二烷基等碳原子数为1~16、优选碳原子数为2~12的烷基的酯。
作为丙烯酸树脂水性分散液，例如可以使用如专利文献6~7所记载的物质，但不限定于此。如果全部固体成分中的丙烯酸树脂的比例少于约10重量%，则摩擦系数变高，此外变得容易粘附。另一方面，如果以多于50重量%来使用，则与橡胶的粘接性、柔软性会恶化。
如上文所述，如果PTFE的比例高，则在涂布膜表面产生PTFE颗粒的凝集块，表面粗糙度增大，不仅密封性恶化，而且该凝集块会脱落而形成污染物，如果减少PTFE，则会损害非粘附特性、低摩擦特性，但通过替代PTFE的一部分而配合丙烯酸树脂，能够克服这样的PTFE的问题。
作为乙烯-乙酸乙烯酯共聚物树脂水性分散液，例如可以使用如专利文献8~9所记载的物质，但不限定于此。乙烯-乙酸乙烯酯共聚物树脂具有粘附性且柔软，因此使摩擦系数升高、使对密封对象材料的粘附性增大，但会提高柔软性、提高与橡胶的粘接性。
如果乙烯-乙酸乙烯酯共聚物树脂以在全部固体成分中少于10重量%来使用，则柔软性、与橡胶的粘接性会降低。另一方面，如果以大于50重量%使用，则摩擦系数变高，不仅容易粘附，而且涂布时在基材彼此接触的情况中也容易粘附。
包含以上3种水性分散液的混合物的涂布剂的涂布方法没有特别的限定，可以通过浸涂法、喷雾法、辊涂法、刮刀涂布法、爪涂(クローコート)法等来进行。涂布后的干燥可以在室温至约100℃下进行约5~20分钟左右，其烧制根据所使用的橡胶的种类，在比PTFE的熔融温度低的约120~230℃、优选约180℃以下的温度下进行约5~120分钟左右，由此形成约5~10μm厚的涂布覆膜。
作为构成密封材料的橡胶，不仅可以使用耐热性低的NBR，还可以使用氢化NBR、丙烯酸橡胶、氟橡胶等，本发明的涂布剂水性分散液可以有效地应用于这些橡胶制密封材料。
实施例
接着，针对实施例来说明本发明。
实施例1
将下述配比的NBR组合物在180℃下进行6分钟的加压硫化，
成型为厚度为2mm的片材或O型圈后，用无尘纸浸蘸甲乙酮并擦拭表面，此时，使用喷雾器以5~10μm的厚度将涂布剂进行涂布，在140℃下进行30分钟加热处理。
作为涂布剂，使用PTFE水性分散液(ダイキン制品ポリフロンディスパージョンD-1E，固体成分浓度为61重量%，平均粒径为220nm)52重量份(以固体成分计为59重量%)、丙烯酸树脂水性分散液(日本カーバイド制品ニカゾールFX-329，固体成分浓度为45重量%)23重量份(以固体成分计为19.5重量%)、以及乙烯-乙酸乙烯酯共聚物树脂水性分散液(同公司制品ニカゾールRX-66E，固体成分浓度为46重量%)25重量份(以固体成分计为21.7重量%)的混合物。
针对加热处理片材或O型圈，进行以下各项目的测定或评价。
摩擦系数：
按照ASTM D-1894、JIS K7125、JIS P8147、ISO 8295，使用新东科学制造的表面性试验机HEIDON-TriboGear，测定经涂布的橡胶片材表面的动摩擦系数。
(试验条件)
对象材料：直径为10mm的SUS304钢球
移动速度：50mm/分钟
载重：0.49N
振幅：50mm。
通过弯曲试验进行的涂布剂的柔软性评价：
在直径为6mm的芯棒上使经涂布的橡胶片材弯曲，使粘附胶带粘附于其弯曲部上，评价涂布剂是否剥离。
(评价)
○：不存在弯曲部分的涂布剂的剥离、不存在向胶带的转印
×：存在弯曲部分的涂布剂的剥离、存在向胶带的转印。
通过粘附试验进行的粘接性评价：
将经涂布的橡胶片材冲裁成直径为13mm的圆盘状，以下述条件：
对象材料：SUS430
压缩率：33.3%
用2片对象材料夹持，在80℃下加热60分钟，其后，在室温条件下静置1小时后，从压缩模具中释出，评价因涂布剂对SUS430对象材料的粘附而引起的涂布剂的转印状态。
(评价)
○：涂布剂没有转印
△：一部分涂布剂发生转印
×：脱模后涂布剂转印至对象材料的整个压缩面上。
通过加湿试验进行的因来自橡胶的起霜而引起的与橡胶的粘接性降低的评价：
针对经涂布的橡胶片材，在50℃、90%RH下进行15小时的加热试验，反复进行5次胶带剥离试验，通过加湿试验评价是否发生因来自橡胶的起霜而引起的涂布剂的剥离。
(评价)
○：没有剥离
△：5次胶带剥离试验为止，每次剥离试验会逐渐出现些许剥离
×：以1次胶带剥离试验就剥离。
渗出评价：
针对经涂布的橡胶片材，在70℃下进行30天的加热试验，评价在涂布剂表面是否析出来自橡胶的起霜成分。
(评价)
○：通过目视无法判断出固体物质在表面上析出
×：通过目视可见固体物质在表面上析出。
通过整列送料机进行的O型圈的输送特性评价：
将经涂布的O型圈(内径7.8mm，线径1.9mm，型号JIS B2401-4种DP8)用于通过整列送料机(parts feeder)进行的输送特性评价。
(评价)
○：输送速度大于涂覆硅酮油而未进行涂布处理的情况
×：输送速度与涂覆硅酮油而未进行涂布处理的情况相同
注) 对未进行涂布处理的橡胶涂覆硅酮油从而进行输送时，由于硅酮油的发粘而导致输送变慢，此外，堵塞的O型圈残留在整列送料机上。
未粘附、摩擦系数越低，则输送速度变得越大。
O型圈的泄露试验：
将经涂布的O型圈(内径119.6mm，线径7mm，型号P120)压缩5%，使用氦气泄露检测仪，测定投入氦气3分钟后的氦气泄漏量。
(评价)
○：泄露少
×：泄露多。
实施例2
在实施例1中，分别将PTFE水性分散液量变更为24重量份(以固体成分计为29.7重量%)、丙烯酸树脂水性分散液量变更为38重量份(以固体成分计为34.8重量%)、乙烯-乙酸乙烯酯共聚物树脂水性分散液量变更为38重量份(以固体成分计为35.6重量%)。
实施例3
在实施例1中，分别将PTFE水性分散液量变更为38重量份(以固体成分计为45.25重量%)、丙烯酸树脂水性分散液量变更为45重量份(以固体成分计为39.5重量%)、乙烯-乙酸乙烯酯共聚物树脂水性分散液量变更为17重量份(以固体成分计为15.25重量%)。
比较例1
在实施例1中，不使用PTFE水性分散液，分别将丙烯酸树脂水性分散液量变更为51重量份(以固体成分计为50重量%)、乙烯-乙酸乙烯酯共聚物树脂水性分散液量变更为49重量份(以固体成分计为50重量%)。
比较例2
在实施例1中，不使用丙烯酸树脂水性分散液，分别将PTFE水性分散液量变更为43重量份(以固体成分计为50重量%)、乙烯-乙酸乙烯酯共聚物树脂水性分散液量变更为57重量份(以固体成分计为50重量%)。
比较例3
在实施例1中，不使用乙烯-乙酸乙烯酯共聚物树脂水性分散液，分别将PTFE水性分散液量变更为42重量份(以固体成分计为49.5重量%)、丙烯酸树脂水性分散液量变更为58重量份(以固体成分计为50.5重量%)。
比较例4
在实施例1中，分别将PTFE水性分散液量变更为8重量份(以固体成分计为10.4重量%)、丙烯酸树脂水性分散液量变更为41重量份(以固体成分计为39.4重量%)、乙烯-乙酸乙烯酯共聚物树脂水性分散液量变更为51重量份(以固体成分计为50.1重量%)。
比较例5
在实施例1中，分别将PTFE水性分散液量变更为87重量份(以固体成分计为90重量%)、丙烯酸树脂水性分散液量变更为7重量份(以固体成分计为5.3重量%)、乙烯-乙酸乙烯酯共聚物树脂水性分散液量变更为6重量份(以固体成分计为4.6重量%)。
上述各实施例和比较例中得到的测定或评价结果如下表所示。
[表]

Claims (7)

1.涂布剂水性分散液，其含有PTFE 20~80重量%、丙烯酸树脂10~50重量%、以及乙烯-乙酸乙烯酯共聚物树脂10~50重量%作为固体成分。
2.根据权利要求1所述的涂布剂水性分散液，其含有PTFE 29~70重量%、丙烯酸树脂15~40重量%、以及乙烯-乙酸乙烯酯共聚物树脂14~36重量%作为固体成分。
3.根据权利要求1或2所述的涂布剂水性分散液，其包含PTFE水性分散液、丙烯酸树脂水性分散液、以及乙烯-乙酸乙烯酯共聚物树脂水性分散液的混合物。
4.根据权利要求3所述的涂布剂水性分散液，其中，使用平均粒径为200nm~500nm的PTFE水性分散液。
5.根据权利要求1或2所述的涂布剂水性分散液，其用作橡胶制密封材料的表面处理剂。
6.橡胶制密封材料，其用权利要求5所述的涂布剂水性分散液进行表面处理。
7.根据权利要求6所述橡胶制密封材料，其为NBR制密封材料。
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