CN106715565B - 硫化橡胶用表面处理剂 - Google Patents

硫化橡胶用表面处理剂 Download PDF

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CN106715565B
CN106715565B CN201580051219.7A CN201580051219A CN106715565B CN 106715565 B CN106715565 B CN 106715565B CN 201580051219 A CN201580051219 A CN 201580051219A CN 106715565 B CN106715565 B CN 106715565B
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polybutadiene
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vulcanized rubber
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木村奈津美
阿部克己
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Abstract

本发明涉及硫化橡胶用表面处理剂，其中，相对于总量为100重量份的含有异氰酸酯基的1,2‑聚丁二烯和以下组合物，所述组合物含有(A)(甲基)丙烯酸全氟烷基烷基酯和(B)含有羟基的(甲基)丙烯酸酯的共聚物[I]、丙烯酸烷基酯的聚合物[II]、氟代烯烃的聚合物[III]和固化剂[IV]，分别以10~160重量份的比例含有软化点为40~160℃的蜡和氟树脂粒子，含有异氰酸酯基的1,2‑聚丁二烯与含有OH基的氟树脂组合物的比例按重量比计，以50:50~95:5的比例使用。

Description

硫化橡胶用表面处理剂
技术领域
本发明涉及硫化橡胶用表面处理剂。更详细而言，涉及进一步提高涂层被膜整体的低摩擦化和耐磨损性的硫化橡胶用表面处理剂。
背景技术
一直以来，在被覆橡胶的金属制垫圈的橡胶层或轴承密封、油封等橡胶制弹性体滑动部的表面，为了防止粘着、防止粘连和提高耐磨损性，形成石墨的涂层膜，或脂肪酸的金属盐或酰胺、石蜡等蜡、硅油等的涂层膜，或含有乙基纤维素、酚醛树脂等作为粘结剂的涂层膜。发动机垫圈等在高面压、高温度条件下使用，若在此基础上进一步加上发动机的振动，则垫圈表面的橡胶被覆层磨损，有时会发生漏气。另外，轴承密封或油封等橡胶制弹性体滑动部的橡胶被覆层因反复滑动而磨损，有时会发生漏油。
因此，本申请人之前提出了以下硫化橡胶用表面处理剂，其是在作为发动机汽缸盖垫圈的使用环境的高面压、高温度下，甚至在如加上振动之类的苛刻的使用条件下，也几乎看不到在垫圈表面的橡胶被覆层产生磨损或破坏的现象，能够形成对气体密封有效的垫圈等的橡胶层的硫化橡胶用表面处理剂，其中，在液态1,2-聚丁二烯的含羟基成分及作为其固化剂的1,2-聚丁二烯含异氰酸酯基成分中添加聚烯烃树脂的水性分散液(专利文献1)。
在这里，提出的硫化橡胶用表面处理剂虽然达成提高橡胶被覆层的耐磨损性的所期望的目的，但由于使用水性分散液，所以水促进1,2-聚丁二烯的羟基与异氰酸酯基之间的反应，另外水与异氰酸酯基本身也起反应，因此引起表面处理分散液的粘度上升和胶凝，发现有涂布加工时的操作性差的问题。另外，水与异氰酸酯基的反应会妨碍1,2-聚丁二烯的高分子量化，还发现有表面处理层的耐磨损性、耐剥离性和滑动性差的缺点。
为了解决上述问题，本申请人进一步提出了将聚烯烃树脂的水性分散液变更为聚烯烃树脂的有机溶剂分散液的硫化橡胶用表面处理剂(专利文献2)。但是，由于在该方法中不含有聚四氟乙烯等氟树脂，所以会有因高温压缩时的粘着或高面压下的摩擦磨损而发生涂膜剥落的问题。
本申请人进一步提出了以下硫化橡胶用表面处理剂，其是不损害以往的防止粘着、防止粘连和提高耐磨损性的硫化橡胶用表面处理剂所要求的性能，且不因高温压缩时的粘着或高面压下的摩擦磨损而发生涂膜剥落的硫化橡胶用表面处理剂，其包含以下有机溶剂溶液，所述有机溶剂溶液相对于100重量份的含有异氰酸酯基的1,2-聚丁二烯或在其中共混含有羟基的1,2-聚丁二烯的1,2-聚丁二烯混合物，分别以10~160重量份的比例含有软化点为40~160℃的蜡和氟树脂(专利文献3)。
现有技术文献
专利文献
专利文献1：日本特开平3-252442号公报
专利文献2：日本特开平7-165953号公报
专利文献3：日本特开2003-213122号公报
专利文献4：日本特许第3449014号公报。
发明内容
发明所要解决的课题
本发明的目的在于，提供硫化橡胶用表面处理剂，其是以含有异氰酸酯基的1,2-聚丁二烯、软化点为40~160℃的蜡和氟树脂粒子为必要成分的硫化橡胶用表面处理剂，其可进一步提高由其形成的涂层被膜整体的低摩擦化和与之相伴的滑动面的耐磨损化。
解决课题的手段
上述本发明的目的可通过以下硫化橡胶用表面处理剂达成，其中，相对于总量为100重量份的含有异氰酸酯基的1,2-聚丁二烯和具有以下组成的含有OH基的氟树脂组合物，所述组合物含有以下(A)和(B)的共聚物[I]、丙烯酸烷基酯的聚合物[II]、氟代烯烃的聚合物[III]和固化剂[IV]，
(A) (甲基)丙烯酸全氟烷基烷基酯，
(B) 含有羟基的(甲基)丙烯酸酯，
分别以10~160重量份的比例含有软化点为40~160℃的蜡和氟树脂粒子，含有异氰酸酯基的1,2-聚丁二烯与含有OH基的氟树脂组合物的比例按重量比计，以50:50~95:5的比例使用。
发明的效果
在以往的技术中，通过掺混氟树脂粒子作为涂层剂的填充剂成分，提高低摩擦化和耐磨损性，但由于在作为粘结剂成分的含有异氰酸酯基的1,2-聚丁二烯树脂中不含有低摩擦化成分，所以难以实现进一步低摩擦化。
在本发明中，通过在上述现有实例的粘结剂成分中作为有机溶剂溶液加入具有低摩擦化效果的含有OH基的氟树脂组合物，可实现填充剂成分和粘结剂成分的低摩擦化，达成涂层被膜整体的进一步低摩擦化和与之相伴的滑动面的耐磨损性的提高。
本发明所涉及的硫化橡胶用表面处理剂不仅可有效地应用于油封的密封唇口部等密封部件，而且对复印机用的橡胶辊、橡胶带，工业用的橡胶软管、橡胶带，汽车用的刮水器、密封条、门玻璃导槽等橡胶部件的防止粘着、低摩擦化、提高耐磨损性也有效。
具体实施方式
作为含有异氰酸酯基的1,2-聚丁二烯，使用加成异氰酸酯基作为端基的分子量为1,000~3,000左右的材料，其可直接使用固体成分浓度约为3~70重量%的市售品、例如日本曹达制品日曹TP-1001 (固体成分浓度为50重量%的醋酸丁酯溶液)等。该聚丁二烯树脂可与硫化橡胶表面的官能团或含有羟基的成分反应，进行粘接、固化，与同样用异氰酸酯基进行反应而高分子化的聚氨基甲酸酯树脂相比，与橡胶的亲和性(相性)、相容性好，因此有与橡胶的粘附性好、特别是耐摩擦磨损特性好的特征。
另外，由于该含有异氰酸酯基的1,2-聚丁二烯在端基加成异氰酸酯基，所以通过与硫化橡胶表面的官能团反应来高分子化。
作为有机溶剂溶液使用的含有OH基的氟树脂组合物包含以下组合物，所述组合物的固体成分浓度约为10~50重量%，含有以下(A)和(B)的共聚物[I]、丙烯酸烷基酯的聚合物[II]、氟代烯烃的聚合物[III]和固化剂[IV]，
(A) (甲基)丙烯酸全氟烷基烷基酯，
(B) 含有羟基的(甲基)丙烯酸酯，
且共聚物[I]、聚合物[II]和聚合物[III]为2~15:35~70:20~50的重量比(总和为100)等。由于该含有OH基的氟树脂组合物溶液具有OH改性基，所以可与作为粘结剂成分的含有异氰酸酯基的1,2-聚丁二烯有效地反应，形成稳定的耐久性高的被膜。上述含有OH基的氟树脂组合物的详细内容例如记载在专利文献4中。另外，作为有机溶剂，例如使用甲基异丁基酮-醋酸乙酯-甲乙酮混合溶剂等。
作为共聚物[I]的(B)成分的含有羟基的(甲基)丙烯酸酯，例如使用(甲基)丙烯酸2-羟基乙基酯等。聚合物[II]是在与基材的粘附性、与其它成分的相容性、形成与需求一致的皮膜的方面重要的成分。作为聚合物[III]，例如使用偏氟乙烯系聚合物等，在皮膜的断面方向位于作为表面成分的共聚物[I]与作为粘附成分的聚合物[II]的中间，担负防止基材树脂中含有的颜料、染料、增塑剂等添加剂向涂布层转移的屏障层的作用。作为固化剂[IV]，相对于聚合物[I]、[II]、[III]的总量，以约0.001~100重量%的比例使用具有与OH基反应的反应性官能团(例如异氰酸酯基、环氧基等)的有机化合物。
作为含有OH基的氟树脂组合物溶液，实际上使用市售品，例如DIC制品DefensaTR-101 (OH值：6.0mgKOH/g溶液)、102 (OH值：2.7mgKOH/g溶液)、103 (OH值：4.1mgKOH/g溶液)等。
含有异氰酸酯基的1,2-聚丁二烯和含有OH基的氟树脂组合物按重量比计，以50:50~95:5、优选60:40~90:10的比例使用。若使用比该范围少的含有OH基的氟树脂组合物，则无法改善低摩擦化、耐磨损性，另一方面即使比上述范围多地使用，也无法改善耐磨损性。
作为蜡，使用软化点为40~160℃、优选为60~120℃的植物系蜡、石油系蜡、合成蜡等。作为植物系蜡可列举出巴西棕榈蜡、小烛树蜡、米糠蜡等，作为石油系蜡可列举出石蜡、微晶蜡等，另外作为合成蜡可列举出聚乙烯蜡、费托蜡、脂肪酰胺、各种改性蜡等，通常可直接使用市售的蜡。若使用软化点比上述软化点高的蜡，则滑动性、非粘着性能会降低。另一方面，若使用软化点比上述软化点低的蜡，则橡胶与表面处理剂的粘附性或耐摩擦磨损性会降低。
作为氟树脂粒子，可列举出粒子状的聚四氟乙烯[PTFE]、四氟乙烯/六氟丙烯共聚物、四氟乙烯/全氟(烷基乙烯基醚)共聚物、聚偏氟乙烯、聚氟乙烯、乙烯/四氟乙烯共聚物等。
作为这些的氟树脂粒子，使用将通过本体聚合、悬浮聚合、溶液聚合、乳液聚合等得到的氟树脂分级为粒径约为0.1~5μm左右的粒子，或将通过悬浮聚合、溶液聚合、乳液聚合等得到的分散液通过剪切搅拌等来微粒分散为约0.1~5μm左右的粒子，将通过上述聚合得到的树脂进行凝结·干燥后，通过干式粉碎或冷却粉碎来微粒化为约10μm以下的粒子。对于设定为约0.1~10μm的粒径，在粒径更小的情况下，有形成小的涂布厚度的优点，但接触面积因涂布表面的凹凸变小而变小，因此在低面压下摩擦系数有变大的倾向，另一方面在粒径更大的情况下，涂布厚度变大，涂布时的成本增加，但凹凸变大，在低面压下与对象材料的接触面积变小，因此摩擦系数会降低。因此，根据使用要求适宜调整粒径，例如在密封部件等中考虑上述优点、缺点来确定，优选使用约0.5~2μm左右的粒子。
蜡和氟树脂粒子相对于总量为100重量份的含有异氰酸酯基的1,2-聚丁二烯和含有OH基的氟树脂组合物，以10~160重量份的比例使用植物系蜡、石油系蜡、合成蜡中的任意1种以上，另外以10~160重量份的比例使用氟树脂粒子。若蜡的比例比上述比例多，则与橡胶的粘附性、耐摩擦磨损特性变差，另一方面若比该范围少，则皮膜的柔软性、滑动性、非粘着性会变差。另外，若氟树脂粒子的比例比上述比例多，则与橡胶的粘附性、耐摩擦磨损特性变差，损害皮膜的柔软性，结果在固化涂膜上产生裂缝，另一方面若比该范围少，则滑动性、非粘着性会变差。上述各成分作为固体成分浓度约为1~40重量%的有机溶剂的溶液或分散液使用。需说明的是，在将本发明所涉及的硫化橡胶表面处理剂用于密封部件等的情况下，蜡、氟树脂粒子分别优选25~120重量份。
作为有机溶剂，单独或作为混合溶剂使用甲苯、二甲苯、醋酸乙酯、醋酸丁酯、甲乙酮、甲基异丁基酮等。使用有机溶剂的稀释量根据涂布厚度(膜厚)、涂布方法适宜选择，通常设定使得所有固体成分浓度约为5~20重量%。需说明的是，膜厚通常为1~10μm，优选为2~5μm，在膜厚比上述厚度小的情况下，无法完全地被覆橡胶表面，有时会损害滑动性、非粘着性。另一方面，若膜厚比上述厚度大，则涂布表面的刚性变高，有时会损害密封性、柔软性。在密封部件等使用用途中，优选1~5μm左右。
作为可通过上述表面处理剂处理的橡胶，可列举出氟橡胶、丁腈橡胶、氢化丁腈橡胶、乙烯-丙烯橡胶、苯乙烯-丁二烯橡胶、丙烯酸橡胶、氯丁二烯橡胶、丁基橡胶、天然橡胶等一般的橡胶材料，其中优选使用在橡胶中掺混的防老化剂、油等向橡胶表面层的起霜少的橡胶材料。需说明的是，根据橡胶材质或目的，适宜选择上述各种成分的掺混比例和有机溶剂的种类、有机溶剂量、有机溶剂混合比例。
作为硫化橡胶表面处理剂向橡胶表面的涂布方法，可列举出浸渍、喷雾、辊式涂布、流动涂布等涂布方法，但并不限定于上述方法。此时，优选预先在涂布表面处理剂前通过清洗等除去橡胶表面的污垢等。特别是在起霜物、渗出物从硫化橡胶中析出至表面的情况下，进行使用水、洗剂、溶剂等的清洗和干燥。
在向橡胶表面涂布硫化橡胶表面处理剂后，在约150~250℃下进行约10分钟~24小时左右的热处理来进行煅烧。在加热温度比上述温度低，且加热时间比上述时间短的情况下，皮膜的固化和与橡胶的粘附性不充分，非粘着性、滑动性变差。另一方面，在加热温度比上述温度高，且加热时间比上述时间长的情况下，会引起橡胶的热老化。因此，需要根据各种橡胶的耐热性，适宜设定加热温度、加热时间。
另外，在要求降低排气量的硫化橡胶的情况下，可单独或组合进行热处理、减压处理、提取处理等，但热处理在经济上最好，为了减少排气量，优选在约150~250℃下进行1~24小时左右的热处理来进行煅烧，为了将橡胶中的低分子成分和皮膜中的蜡、聚丁二烯中含有的低分子成分气化，温度越高或时间越长越有效。
实施例
以下针对实施例说明本发明。
实施例1
氟树脂粒子溶液(粒径为0.2μm，　　　　　 　　467重量份
固体成分浓度为5重量%的醋酸丁酯溶液)
PE蜡溶液(固体成分浓度为5重量%的醋酸丁酯溶液) 467 〃
含有NCO的1,2-聚丁二烯溶液(日本曹达制品　　　　　55 〃
日曹TP-1001，固体成分浓度为50重量%的醋酸丁酯溶液)
含有OH基的氟树脂组合物溶液(DIC制品Defensa　　 　11 〃
TR-103，OH值为4.1mgKOH/g的溶液，
固体成分浓度为30重量%的MIBK-醋酸丁酯-MEK溶液)
使用包含以上各种成分的表面处理剂(含有NCO的聚丁二烯/含有OH基的氟树脂组合物=90/10)，进行以下各种测定、评价。
粘结剂硬度：在金属板上，只涂布涂层剂的粘结剂成分(除去氟树脂粒子成分)使得成为50μm的膜厚，在200℃下煅烧10小时，制备样品，使用岛津制作所制动态超微硬度计，在负荷速度为14.1mN/秒下压入三棱锥压头(棱间角为115°)，测定压入深度为10μm时的动态硬度。
摩擦系数：在厚度为2mm的硫化压缩成形的氟橡胶表面涂布涂层剂使得膜厚为10μm，在200℃下煅烧10小时，制备样品，使用新东科学制HEIDON TYPE 14DR，在涂层被膜表面按压加载50g负荷的直径为10mm的钢球(網球)，在往复移动距离为50mm、速度为50mm/分钟的速度下移动，测定动摩擦系数。
(评价)　　○：低于0.13
　　　　　△：0.13以上且低于0.17
　　　　　×：0.17以上
耐磨损性试验：在厚度为2mm的硫化压缩成形的氟橡胶表面涂布涂层剂使得膜厚为10μm，在200℃下煅烧10小时，制备样品，使用Rhesca制Friction Player FPR-2000，在涂层被膜表面按压加载2kg负荷的直径为3mm的压头球，在平均面压为3.9MPa、线速度为20.9cm/秒的速度下旋转，测定至涂层被膜剥落、露出橡胶为止的转数。
(评价)　　◎：15万次以上
　　　　　○：5万次以上且低于15万次
　　　　　△：1万次以上且低于5万次
　　　　　×：低于1万次
实施例2
氟树脂粒子溶液(与实施例1相同)　　　　　　　　460重量份
PE蜡溶液(与实施例1相同)　　　　　　　　　　　460　〃
含有NCO的聚丁二烯溶液(日曹TP-1001)　　　 　　30 　〃
含有OH基的氟树脂组合物溶液(Defensa TR-103) 　50 　〃
使用包含以上各种成分的表面处理剂(含有NCO的聚丁二烯/含有OH基的氟树脂组合物=50/50)，进行与实施例1相同的各种测定、评价。
比较例1
氟树脂粒子溶液(与实施例1相同)　　　　　　　 　458重量份
PE蜡溶液(与实施例1相同)　　　　　　　　　 　458　〃
含有NCO的聚丁二烯溶液(日曹TP-1001)　　　 　24　 〃
含有OH基的氟树脂组合物溶液(Defensa TR-103) 　60　　〃
使用包含以上各种成分的表面处理剂(含有NCO的聚丁二烯/含有OH基的氟树脂组合物=40/60)，进行与实施例1相同的各种测定、评价。
比较例2
使用在实施例1中分别将氟树脂粒子溶液量变更为469重量份，将PE蜡溶液量变更为469重量份，将含有NCO的聚丁二烯溶液量变更为62重量份，且不使用含有OH基的氟树脂组合物溶液的表面处理剂(含有NCO的聚丁二烯/含有OH基的氟树脂组合物=100/0)，进行与实施例1相同的各种测定、评价。
比较例3
氟树脂粒子溶液(与实施例1相同)　　　　　　　　365重量份
PE蜡溶液(与实施例1相同)　　　　　　　　　　　365　　〃
含有OH基的氟树脂组合物溶液(Defensa TR-103) 　40　 　〃
氨基甲酸酯树脂溶液(DIC制品16-416，　　　　　　40　 　〃
固体成分浓度为30重量%的MEK-IPA溶液)
甲乙酮[MEK]　　　　　　　　　　　　　　　　　95　 　〃
异丙醇[IP]　　　　　　　　　　　　　　　　 　95　 　〃
使用包含以上各种成分的表面处理剂(氨基甲酸酯树脂/含有OH基的氟树脂组合物=50/50)，进行与实施例1相同的各种测定、评价。
将在以上各个实施例和比较例中得到的测定、评价结果示出于以下的表中。
表

Claims (4)

1.硫化橡胶用表面处理剂，其中，
相对于总量为100重量份的含有异氰酸酯基的1,2-聚丁二烯和具有以下组成的含有OH基的氟树脂组合物，所述组合物含有以下(A)和(B)的共聚物[I]、丙烯酸烷基酯的聚合物[II]、氟代烯烃的聚合物[III]和固化剂[IV]，
(A) (甲基)丙烯酸全氟烷基烷基酯，
(B) 含有羟基的(甲基)丙烯酸酯，
分别以10~160重量份的比例含有软化点为40~160℃的蜡和氟树脂粒子，含有异氰酸酯基的1,2-聚丁二烯与含有OH基的氟树脂组合物的比例按重量比计，以50:50~95:5的比例使用，其中共聚物[I]、聚合物[II]和聚合物[III]为2~15:35~70:20~50的重量比。
2.权利要求1的硫化橡胶用表面处理剂，其中，含有异氰酸酯基的1,2-聚丁二烯和含有OH基的氟树脂组合物均作为有机溶剂溶液使用。
3.权利要求1的硫化橡胶用表面处理剂，其用于油封的密封唇口部的涂层。
4.油封，其具有用权利要求3的硫化橡胶用表面处理剂形成涂层被膜的密封唇口部。
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