CN104114364A - 橡胶层叠树脂复合体 - Google Patents
橡胶层叠树脂复合体 Download PDFInfo
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- CN104114364A CN104114364A CN201380010959.7A CN201380010959A CN104114364A CN 104114364 A CN104114364 A CN 104114364A CN 201380010959 A CN201380010959 A CN 201380010959A CN 104114364 A CN104114364 A CN 104114364A
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Abstract
使橡胶与由聚酰胺系树脂成型而得到的聚酰胺系树脂成型物进行硫化粘接而成的橡胶层叠树脂复合体,所述聚酰胺系树脂是以相对于每1g聚酰胺系树脂达到0.045毫摩尔以上、优选0.050~2.0毫摩尔、进一步优选0.065~1.5毫摩尔的比例添加胺当量为950以下的脂肪族胺化合物而成的,所述聚酰胺系树脂中,填充剂以其与聚酰胺系树脂的合计量中的0~70重量%进行配混。该橡胶层叠树脂复合体通过在配混或未配混填充剂的聚酰胺系树脂中添加脂肪族胺化合物并成型,然后使所得聚酰胺系树脂成型物与氟橡胶或丙烯酸类橡胶进行硫化粘接,从而制造。
Description
技术领域
本发明涉及橡胶层叠树脂复合体。更详细而言,涉及将橡胶与聚酰胺系树脂成型物硫化粘接而不使用粘接剂的橡胶层叠树脂复合体。
背景技术
作为将聚酰胺系树脂成型物与丙烯酸类橡胶或氟橡胶进行复合一体化的方法,已知有使用粘接剂将树脂成型物与橡胶进行硫化粘接的方法。然而,使用粘接剂的方法由于工序复杂,因此工序管理繁杂,从而不仅成本变高,而且存在不一定能够获得充分的粘接性的问题。
针对所述问题,例如专利文献1中提出了在对树脂的表面实施使平均表面粗糙度为0.1以上的表面处理后,在其处理面涂布粘接剂而将橡胶进行硫化粘接这一将树脂粘接于橡胶的粘接方法。但是,该方法中除了使用粘接剂的工序之外,还需要树脂表面的表面处理这一新的工序。
现有技术文献
专利文献
专利文献1:日本特开2006-89565号公报。
发明内容
发明要解决的问题
本发明的目的在于,提供不使用粘接剂而通过简单化的工序使聚酰胺系树脂成型物与丙烯酸类橡胶或氟橡胶等橡胶以充分的粘接强度粘接而成的橡胶层叠树脂复合体。
用于解决问题的手段
所述本发明的目的可通过使橡胶与由聚酰胺系树脂成型而得到的聚酰胺系树脂成型物进行硫化粘接而成的橡胶层叠树脂复合体来达成,所述聚酰胺系树脂是以相对于每1g聚酰胺系树脂达到0.045毫摩尔以上、优选0.050~2.0毫摩尔、进一步优选0.065~1.5毫摩尔的比例添加胺当量为950以下的脂肪族胺化合物而成的,所述聚酰胺系树脂中,填充剂以其与聚酰胺系树脂的合计量的0~70重量%进行配混。
发明的效果
本发明所述的橡胶层叠树脂复合体通过在聚酰胺系树脂中以相对于每1g聚酰胺系树脂达到0.045毫摩尔以上的比例添加胺当量为950以下的脂肪族胺化合物,所述聚酰胺系树脂中,填充剂以其与聚酰胺系树脂的合计量的0~70重量%、优选为0~50重量%进行配混,从而发挥不使用粘接剂而仅通过将橡胶与多胺系树脂成型物进行硫化粘接就显示出充分的粘接性这一优异的效果。
具体实施方式
作为聚酰胺系树脂,可以使用聚酰胺66(熔点260℃)、聚酰胺6(熔点220℃)、聚酰胺610(熔点215℃)、聚酰胺612(熔点220℃)、聚酰胺11(熔点187℃)、聚酰胺12(熔点176℃)、聚酰胺46(熔点290℃)、聚酰胺6T/6I(熔点310℃)、6T/66(熔点260~340℃)、6T/6(熔点230~340℃)、9T(熔点306℃)等中的至少一种以及它们的熔合(アロイ)或共混树脂等,只要是聚酰胺系则可以任意使用。
另外,为了确保强度、加工性等树脂物性而配混有填充剂例如玻璃纤维、碳纤维、芳纶纤维、金属纤维等,优选配混有玻璃纤维、碳纤维。其配混量为其与聚酰胺系树脂的合计量的70重量%以下、优选为15~50重量%。
作为玻璃纤维,通常使用将直径约为1~50μm、优选约为5~20μm且长度约为1~50mm、优选约为1~10mm的短切原丝(チョップドストランド)或原丝粉碎并制成微粉的磨碎纤维等。这些玻璃纤维可以是利用作为高分子乳胶的结捆剂(結束剤)或硅烷系偶联剂进行表面处理而得到的纤维。另外,也可以是将E玻璃、T玻璃等玻璃纤维用环氧树脂、乙烯基酯等进行复合化而得到的单方向材料复合材料。作为碳纤维,通常使用PAN系碳纤维,其直径约为1~50μm、长度约为1~50mm。另外,也可以使用沥青系碳纤维。
在聚酰胺系树脂中添加脂肪族胺化合物。作为脂肪族胺化合物,可以使用胺当量为950以下、优选为250以下的脂肪族胺化合物。使用胺当量为其以上的化合物时,缺乏反应性,无法期待粘接性的改善效果。另外,即使胺当量在所规定的范围内,若使用芳香族胺化合物,则如后述比较例4~5所示那样地观察不到粘接性的改善效果。
需要说明的是,胺化合物的沸点比聚酰胺系树脂的熔点低太多时,将其添加至聚酰胺中时胺化合物会挥发,因此虽然因所使用的聚酰胺的种类而异,但作为向例如熔点为260℃的聚酰胺66中添加的胺化合物,期望是沸点为120℃以上、优选为150℃以上的胺化合物。
所述脂肪族胺化合物以相对于每1g聚酰胺系树脂达到0.045毫摩尔以上、优选0.050~2.0毫摩尔、进一步优选0.065~1.5毫摩尔的比例进行使用,所述聚酰胺系树脂中,填充剂以其与聚酰胺系树脂的合计量的0~70重量%进行配混。脂肪族胺化合物以少于其的比例使用时,观察不到粘接性的改善效果。作为脂肪族胺化合物,可以使用例如四亚乙基五胺(沸点330℃)、降冰片烷二胺(熔点226℃)、六亚甲基二胺二氨基甲酸酯(熔点325.3℃)、α,ω-二氨基十二烷(熔点304℃)、胺当量为50~950的聚醚胺(熔点260℃以上)等多胺化合物。此处,聚醚胺是指聚醚醇与氨、脂肪族胺或脂环式胺的反应产物。
聚酰胺系树脂和脂肪族胺化合物在配混填充剂时与填充剂一起使用双螺杆挤出机、单螺杆挤出机等以190~330℃进行熔融混合,从而进行混炼,接着使用注射成型机、挤出机、吹塑成型机、真空成型机等进行聚酰胺系树脂的成型。
使氟橡胶复合物、丙烯酸类橡胶复合物等橡胶复合物与已成型的聚酰胺系树脂成型物接合,根据需要以其有机溶剂溶液的形式进行接合,在所使用的橡胶复合物的硫化条件下、例如以约100~250℃进行约1~120分钟的加压硫化,从而可以得到聚酰胺树脂与形成为厚度约0.01~10mm左右的橡胶层以充分的强度粘接而成的橡胶层叠树脂复合体。
作为氟橡胶复合物,可以使用多元醇硫化性或过氧化物交联性氟橡胶复合物。多元醇硫化性氟橡胶复合物是在利用多元醇硫化剂进行硫化了的氟橡胶中配混各种配混剂而成的复合物。过氧化物交联性氟橡胶复合物是在氟橡胶中、通常是在导入了作为末端基团的碘基和/或溴基的氟橡胶中配混各种配混剂而成的复合物,此时,优选的是,与有机过氧化物交联剂一同配混使用以三烯丙基异氰脲酸酯为代表的多官能性不饱和化合物共交联剂。
作为丙烯酸类橡胶复合物,是在丙烯酸类橡胶中配混各种配混剂而成的复合物,所述丙烯酸类橡胶是使具有碳原子数1~8的烷基的丙烯酸烷基酯和/或具有碳原子数2~8的亚烷基的丙烯酸烷氧基烷基酯少量共聚具有各种交联性基团的乙烯基单体、例如含反应性卤素的乙烯基单体、含羧基的乙烯基单体、含环氧基的单体、含羟基的单体等而成的。此时,根据交联性基团的种类而使用各种交联剂。
作为含有交联性基团的乙烯基单体而共聚有含不饱和基团的乙烯基单体的丙烯酸类橡胶或乙烯-丙烯酸烷基酯共聚橡胶等的情况下,作为交联剂而使用有机过氧化物,此时,优选组合使用多官能性不饱和化合物共交联剂。这些丙烯酸类橡胶中,除了交联剂、共交联剂之外,还配混各种配混剂来形成丙烯酸类橡胶复合物。
实施例
接着,针对实施例来说明本发明。
实施例1
使用螺杆直径Φ25mm、L/D=41的双螺杆挤出机,相对于聚酰胺66(东丽株式会社制品CM3006;熔点260℃)80重量份,从侧进料口投入玻璃纤维(日东纺制品CSX-3J-451S;直径11μm、长度3mm)20重量份,另外,从其排出口部投入聚醚胺(huntsman制品JEFFAMINE T403;理论分子量440、官能团数3、理论胺当量147g/mol、沸点260℃以上)5重量份,使用注射成型机,将料筒(シリンダー)温度设定为280℃、模具温度设定为80℃,将以270℃熔融混合而成的聚酰胺树脂组成物制作成25×60×2mm的酰胺树脂成型平板。需要说明的是,理论胺当量通过理论分子量/理论官能团数而算出,纯度以100%进行计算(以下相同)。
接着,使下述配混的未硫化氟橡胶复合物或未硫化丙烯酸类橡胶复合物与酰胺树脂成型平板进行接合,在180℃、6分钟(氟橡胶复合物)或8分钟(丙烯酸类橡胶复合物)的条件下进行加压硫化,从而得到形成有厚度6mm的橡胶层的橡胶层叠树脂复合体。
〔氟橡胶复合物;配混例I〕
氟橡胶(杜邦公司制品Viton E45) 100重量份
硅酸钙 40 〃
MT炭黑 20 〃
氧化镁(协和化学株式会社制品マグネシア#150) 6 〃
氢氧化钙 3 〃
硫化剂(杜邦公司制品キュラティブ#30) 2 〃
硫化促进剂(杜邦公司制品キュラティブ#20) 1 〃
〔丙烯酸类橡胶复合物;配混例II〕
丙烯酸类橡胶(UNIMATEC CO.LTD.制品PA-522HF) 100重量份
HAF炭黑 55 〃
硬脂酸 1 〃
防老剂(SHIRAISHI CALCIUM Corporation制品
NAUGARD 445) 2 〃
加工助剂(Schil&Seilacher(GmbH&Co)Struktol WB212) 2 〃
加工助剂(东邦化学工业株式会社制品PHOSPHANOL RL210) 0.5 〃
胺硫化剂(UNIMATEC CO.LTD.制品CHEMINOX AC-6) 0.6 〃
硫化促进剂(大内新兴化学株式会社制品NOCCELER DT) 2 〃。
实施例2
在实施例1中,使用了相同量的四亚乙基五胺(理论分子量189.3、官能团数5、理论胺当量38g/mol、沸点330℃)来代替聚醚胺。
实施例3
在实施例1中,使用了相同量的降冰片烷二胺(理论分子量154、官能团数2、理论胺当量77g/mol、沸点227℃)来代替聚醚胺。
实施例4
在实施例1中,使用了相同量的六亚甲基二胺二氨基甲酸酯(理论分子量160、官能团数2、理论胺当量80g/mol、沸点325.3℃)来代替聚醚胺。
实施例5
在实施例1中,使用了相同量的α,ω-二氨基十二烷(理论分子量200.37、官能团数2、理论胺当量100g/mol、沸点304℃)来代替聚醚胺。
实施例6
在实施例1中,作为聚醚胺,使用了相同量的同公司制品JEFFAMINE D400(理论分子量400、官能团数2、理论胺当量200g/mol、沸点260℃)。
实施例7
在实施例1中,将聚醚胺量变更为10重量份而使用。
实施例8
在实施例1中,将聚醚胺量变更为1重量份而使用。
实施例9
在实施例1中,将聚醚胺量变更为0.75重量份而使用。
实施例10
在使用了5重量份聚醚胺的实施例1中,不使用玻璃纤维,使用了100重量份聚酰胺66。
实施例11
在使用了1重量份聚醚胺的实施例8中,不使用玻璃纤维,使用了100重量份聚酰胺66。
比较例1
在实施例1中,不使用聚醚胺。
比较例2
在实施例1中,作为聚醚胺,使用了相同量的同公司制品JEFFAMINE D2000(理论分子量2000、官能团数2、理论胺当量1000g/mol、沸点260℃以上)。
比较例3
在实施例1中,作为聚醚胺,使用了相同量的同公司制品JEFFAMINE T5000(理论分子量5000、官能团数3、理论胺当量1667g/mol、沸点260℃以上)。
比较例4
在实施例1中,使用了相同量的4,4′-二氨基二苯砜(理论分子量154.1、官能团数2、理论胺当量77g/mol)来代替聚醚胺。
比较例5
在实施例1中,使用了相同量的1,3-双(3-氨基苯氧基)苯(理论分子量292.1、官能团数2、理论胺当量146g/mol)来代替聚醚胺。
比较例6
在实施例1中,将聚醚胺量变更为0.6重量份而使用。
比较例7
在使用了0.6重量份聚醚胺的比较例6中,不使用玻璃纤维,使用了100重量份聚酰胺66。
针对以上的各实施例和比较例中得到的橡胶层叠树脂复合体,通过90°剥离试验(按照对应于ISO 813的JIS K6256)进行粘接强度和橡胶残留面积率的测定。测定结果与相对于每1g配混有填充剂的聚酰胺系树脂的胺化合物重量以及胺毫摩尔数一同示于以下的表1~2。此处,1g配混有填充剂的聚酰胺系树脂中的胺毫摩尔数(理论值)通过1g配混有填充剂的聚酰胺系树脂中的胺化合物重量(g)×1000/胺当量(g/mol)而算出。
Claims (10)
1.橡胶层叠树脂复合体,其使橡胶与由聚酰胺系树脂成型而得到的聚酰胺系树脂成型物进行硫化粘接而得到,所述聚酰胺系树脂是以相对于每1g聚酰胺系树脂达到0.045毫摩尔以上的比例添加胺当量为950以下的脂肪族胺化合物而成的,所述聚酰胺系树脂中,填充剂以其与聚酰胺系树脂的合计量的0~70重量%进行配混。
2.根据权利要求1所述的橡胶层叠树脂复合体,其中,聚酰胺系树脂是聚酰胺66、聚酰胺6、聚酰胺610、聚酰胺612、聚酰胺11、聚酰胺12、聚酰胺46、聚酰胺6T/6I、6T/66、6T/6以及9T中的至少一种或者它们的熔合或共混树脂。
3.根据权利要求1所述的橡胶层叠树脂复合体,其中,填充剂是玻璃纤维或碳纤维。
4.根据权利要求1所述的橡胶层叠树脂复合体,其中,脂肪族胺化合物以相对于每1g聚酰胺系树脂为0.050~2.0毫摩尔的比例进行使用,所述聚酰胺系树脂中,填充剂以其与聚酰胺系树脂的合计量的0~70重量%进行配混。
5.根据权利要求1所述的橡胶层叠树脂复合体,其使用胺当量为250以下的脂肪族胺化合物。
6.根据权利要求1或5所述的橡胶层叠树脂复合体,其使用沸点为120℃以上的脂肪族胺化合物。
7.根据权利要求1所述的橡胶层叠树脂复合体,其中,配混有填充剂的聚酰胺系树脂具有由聚酰胺系树脂100~50重量%和填充剂0~50重量%构成的组成。
8.根据权利要求1所述的橡胶层叠树脂复合体,其中,橡胶为氟橡胶或丙烯酸类橡胶。
9.橡胶层叠树脂复合体的制造方法,其特征在于,将在聚酰胺系树脂中以相对于每1g聚酰胺系树脂达到0.045毫摩尔以上的比例配混胺当量为950以下的脂肪族胺化合物而成的聚酰胺系树脂成型后,使橡胶与所得聚酰胺系树脂成型物硫化粘接,所述聚酰胺系树脂中,填充剂以其与聚酰胺系树脂的合计量的0~70重量%进行配混。
10.根据权利要求9所述的橡胶层叠树脂复合体的制造方法,其使用配混有填充剂的聚酰胺系树脂,所述配混有填充剂的聚酰胺系树脂具有由聚酰胺系树脂100~50重量%和填充剂0~50重量%构成的组成。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09239905A (ja) * | 1996-03-12 | 1997-09-16 | Yokohama Rubber Co Ltd:The | ゴム/ポリアミド系樹脂積層体 |
JP2005067189A (ja) * | 2003-08-05 | 2005-03-17 | Bridgestone Corp | ゴムと樹脂部材との加硫接着体及びその製造方法 |
JP2007270877A (ja) * | 2006-03-30 | 2007-10-18 | Tokai Rubber Ind Ltd | コネクター一体型燃料用ホースおよびその製法 |
WO2010047315A1 (ja) * | 2008-10-21 | 2010-04-29 | 宇部興産株式会社 | ゴム組成物及びポリアミド積層体 |
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-
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09239905A (ja) * | 1996-03-12 | 1997-09-16 | Yokohama Rubber Co Ltd:The | ゴム/ポリアミド系樹脂積層体 |
JP2005067189A (ja) * | 2003-08-05 | 2005-03-17 | Bridgestone Corp | ゴムと樹脂部材との加硫接着体及びその製造方法 |
JP2007270877A (ja) * | 2006-03-30 | 2007-10-18 | Tokai Rubber Ind Ltd | コネクター一体型燃料用ホースおよびその製法 |
WO2010047315A1 (ja) * | 2008-10-21 | 2010-04-29 | 宇部興産株式会社 | ゴム組成物及びポリアミド積層体 |
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EP2781348A4 (en) | 2015-07-08 |
CN104114364B (zh) | 2016-01-27 |
US9586383B2 (en) | 2017-03-07 |
US20150017453A1 (en) | 2015-01-15 |
EP2781348A1 (en) | 2014-09-24 |
JPWO2013129293A1 (ja) | 2015-07-30 |
EP2781348B1 (en) | 2019-03-13 |
JP5594447B2 (ja) | 2014-09-24 |
WO2013129293A1 (ja) | 2013-09-06 |
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