CN107530917B - 硫化橡胶成型用脱模剂 - Google Patents

硫化橡胶成型用脱模剂 Download PDF

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CN107530917B
CN107530917B CN201680028130.3A CN201680028130A CN107530917B CN 107530917 B CN107530917 B CN 107530917B CN 201680028130 A CN201680028130 A CN 201680028130A CN 107530917 B CN107530917 B CN 107530917B
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release agent
vulcanized rubber
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polyoxyalkylene
molding
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CN107530917A (zh
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气贺泽繁
锅岛敏一
堀江拓也
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DKS Co Ltd
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Abstract

本发明提供硫化后的橡胶与模具的脱模性优异且制造后容易将脱模剂除去的硫化橡胶成型用脱模剂。一种硫化橡胶成型用脱模剂，其含有聚氧亚烷基甘油醚(A)，上述聚氧亚烷基甘油醚(A)在氧亚烷基100质量份中含有50～95质量份氧亚乙基。上述聚氧亚烷基甘油醚(A)的数均分子量优选为2000～20000。

Description

硫化橡胶成型用脱模剂
技术领域
本发明涉及一种硫化橡胶成型用脱模剂。
背景技术
硫化橡胶使用于汽车部件、铁路部件、工程机械等。这些硫化橡胶通过将橡胶组合物投入模具等进行硫化成型并将其脱附而得到，但是为了容易进行脱附，在模具中涂布脱模剂。
作为上述脱模剂，使用了有机硅，但是为了除去附着于硫化后的橡胶软管的脱模剂，需要使用洗涤剂等，要求对其进行改善。因此，作为能够容易除去的脱模剂，专利文献1公开了甘油脂肪酸酯的环氧烷加成物。
现有技术文献
专利文献
专利文献1:日本特开2008－201010号公报
发明内容
但是，专利文献1记载的脱模剂如果不使用大量的脱模剂，则存在不能得到充分的脱模性的问题。另外，伴随脱模剂的使用量变多，用于除去脱模剂的清洗水也变为大量，因此也存在排水负荷大的问题。
因此，本发明提供一种硫化后的橡胶与模具的脱模性优异且用比较少量的清洗水能够除去的脱模剂。
本发明涉及的硫化橡胶成型用脱模剂含有聚氧亚烷基甘油醚(A)，上述聚氧亚烷基甘油醚(A)在将氧亚烷基整体设为100质量％时含有50～95质量％的氧亚乙基。
本发明涉及的硫化橡胶成型用脱模剂除了上述聚氧亚烷基甘油醚(A)外，优选还含有聚氧亚烷基二醇(B)。
如果为上述硫化橡胶成型用脱模剂，则硫化后的橡胶与模具的脱模性优异，且能够利用比较少量的清洗水将其从硫化橡胶表面除去，因此清洗性优异。
具体实施方式
本发明中的硫化橡胶成型用脱模剂含有聚氧亚烷基甘油醚(A)，上述聚氧亚烷基甘油醚(A)在将氧亚烷基整体设为100质量％时含有50～95质量％的氧亚乙基。
通过使用氧亚乙基的含量高的聚氧亚烷基甘油醚，能够提高硫化成型后的清洗性。另外，通过该含量为50～95质量％，能够提高模具与硫化后的橡胶的脱模性。将氧亚烷基整体设为100质量％时，上述氧亚乙基的含量优选为60～90质量％，更优选为70～85质量％。
本实施方式使用的聚氧亚烷基甘油醚(A)中的聚氧亚烷基，除了上述氧亚乙基以外，还可含有氧亚丙基、氧亚丁基等。氧亚乙基以外的氧亚烷基的含量在将氧亚烷基整体设为100质量％时，优选为5～50质量％，更优选为10～40质量％，进一步优选为15～30质量％。另外，由于清洗性更优异，因此氧亚乙基以外的氧亚烷基优选为氧亚丙基。
本实施方式使用的聚氧亚烷基甘油醚(A)的数均分子量(Mn)优选为2000～20000。通过使用上述数均分子量的聚氧亚烷基甘油醚，脱模剂的粘度变得更低，能够提高操作性。聚氧亚烷基甘油醚(A)的数均分子量更优选为3000～10000。
上述聚氧亚烷基甘油醚(A)的制造方法没有特别限制，可利用公知的聚氧亚烷基甘油醚的合成方法制造。例如，利用环氧烷加聚进行制造时，通过向甘油添加碱催化剂或酸催化剂，在80～150℃使环氧烷反应而得到。另外，环氧烷为2种以上时的加成方式，可以是嵌段加成也可以是无规加成，可以将它们组合。它们中，由于脱模剂的粘度变得更低，能够提高操作性，因此加成方式优选包括无规加成。
本实施方式涉及的硫化橡胶软管成型用脱模剂，除了上述聚氧亚烷基甘油醚(A)，优选还含有聚氧亚烷基二醇(B)。通过含有聚氧亚烷基二醇(B)，脱模性和清洗性更加优异。
本实施方式使用的聚氧亚烷基二醇(B)，在将该聚氧亚烷基二醇(B)所含有的氧亚烷基的总量设为100质量％时，优选含有20～80质量％的氧亚乙基。通过将氧亚乙基的含量设为上述范围内，脱模性和清洗性更加优异。上述氧亚乙基的含量优选为30～75质量％，更优选为40～70质量％。
上述聚氧亚烷基二醇(B)的数均分子量(Mn)优选为2000～20000。通过使用上述数均分子量的聚氧亚烷基二醇，脱模剂的粘度变得更低，能够提高操作性。聚氧亚烷基二醇(B)的数均分子量更优选为3000～10000。
上述聚氧亚烷基二醇(B)的制造方法没有特别限制，可利用公知的聚氧亚烷基二醇(B)的合成方法制造。例如，利用环氧烷加聚进行制造时，通过向二元醇添加碱催化剂或酸催化剂，在80～150℃使环氧烷反应而得到。另外，环氧烷为2种以上时的加成方式可以是嵌段加成也可以是无规加成，也可以将它们组合。它们中，由于脱模性和清洗性更加优异，因此加成方式优选包括无规加成。
作为能够用于上述聚氧亚烷基二醇(B)的制造的二元醇，没有特别限制，例如，可举出乙二醇、1，2－丙二醇、1，3－丙二醇、1，2－丁二醇、1，3－丁二醇、1，4－丁二醇、1，5－戊二醇、1，6－己二醇、3－甲基－1，5－戊二醇等。
上述聚氧亚烷基二醇(B)的含量，相对于上述聚氧亚烷基甘油醚(A)100质量份，优选为20～500质量份。通过设为上述范围内，脱模性和清洗性变得更加优异。聚氧亚烷基二醇(B)的含量，相对于上述聚氧亚烷基甘油醚(A)100质量份，更优选为30～300质量份，进一步优选为40～250质量份。
本发明的硫化橡胶成型用脱模剂可以用水稀释。例如，可举出以上述聚氧亚烷基甘油醚(A)、或上述聚氧亚烷基甘油醚(A)与上述聚氧亚烷基二醇(B)的混合物的浓度成为10～60质量％、更优选20～40质量％的方式用水稀释。
本发明的硫化橡胶成型用脱模剂，在不损害其效果的范围内，可以含有非离子系或阴离子系的表面活性剂、有机硅类等公知的脱模剂成分。
本发明的硫化橡胶成型用脱模剂能够用于丙烯腈－丁二烯共聚橡胶(NBR)、乙烯-丙烯-二烯共聚橡胶(EPDM)、将NBR与聚氯乙烯(PVC)混合的橡胶(NBR/PVC)、丙烯酸橡胶(ACM)、氟橡胶(FKM)等公知的橡胶。应予说明，上述橡胶可含有硫化剂、硫化助剂、加工助剂、增塑剂、加工用油、炭黑、白色填充材料、抗老化剂等公知的添加剂。
上述橡胶的硫化成型可按照常规方法进行，例如，在模具中涂布本发明的脱模剂，装填橡胶后，进行加热和硫化即可。硫化后，从模具取出橡胶，通过利用水或温水等将附着于橡胶表面的脱模剂进行清洗，得到硫化橡胶。
实施例
以下，利用实施例对本发明做更详细地说明，但本发明不局限于这些实施例。
数均分子量、相对于氧亚烷基的氧亚乙基的含量，利用以下方法测定。
(数均分子量的测定方法)
数均分子量利用GPC法求出。GPC装置和分析条件如以下所示，使用利用作为标准样品的分子量327、2000、8250、19700的聚乙二醇校正了的数均分子量。
GPC装置：系统控制器：SCL－10A(岛津制作所公司制)
检测器：RID－10A(岛津制作所公司制)
色谱柱：连接Shodex GPC KF－G、KF－803、KF802.5、KF－802、KF－801而成的柱(均是昭和电工公司生产)
洗脱液：四氢呋喃
样品注入：0.5重量％溶液，80μL
流速：0.8mL/min
温度：25℃
(相对于氧亚烷基的氧亚乙基的含量)
利用1H－NMR(溶剂：CDCl3)算出。
本实施例使用的原料如下述所示。
＜聚氧亚烷基甘油醚(A)＞
使用对甘油1摩尔加成表1记载的环氧烷而得的聚氧亚烷基甘油醚。应予说明，表中，环氧烷的种类和使用量中的EO表示环氧乙烷的使用量，PO表示环氧丙烷的使用量，均是相对于甘油1摩尔的使用量(mol)。另外，环氧烷含量中的EO表示氧亚乙基的含量，PO表示氧亚丙基的含量，均是将氧亚烷基整体设为100质量％时的含量。
[表1]
Figure BDA0001468854880000051
＜聚氧亚烷基多元醇(B)＞
使用以表2记载的种类和比例对二元醇1摩尔加成环氧烷而得的聚氧亚烷基多元醇。应予说明，表中，环氧烷的种类中的EO表示环氧乙烷，PO表示环氧丙烷。另外，环氧烷含量中的EO表示氧亚乙基含量，PO表示氧亚丙基含量，均是将氧亚烷基整体设为100质量％时的含量。
[表2]
Figure BDA0001468854880000052
＜其他原料＞
(c－1)甘油
(c－2)聚乙二醇(数均分子量：4000)
(c－3)二甲基聚硅氧烷(商品名：KF－96－20CS，信越化学工业公司生产)
(c－4)甘油脂肪酸酯的环氧烷加成物
聚氧亚烷基甘油醚(A－5)中，代替甘油使用甘油单月桂酸酯1摩尔，除此以外，进行同样的操作，得到甘油脂肪酸酯的环氧烷加成物(c－4)。
(实施例1～9、比较例1～6)
通过以下述表3记载的比例(质量比)将各原料混合，得到脱模剂。使用该脱模剂，进行下述的评价。应予说明，“二甲基聚硅氧烷”是信越化学工业公司生产的KF－96－20CS(商品名)。
(脱模性)
将涂布有脱模剂的未硫化橡胶(丙烯腈－丁二烯共聚橡胶(NBR)或氯丁橡胶(CR))装填于模具(120×120×2mm)。接下来，在150℃进行1小时硫化处理，从模具中取出硫化橡胶。将此时的操作性作为脱模性，按照下述标准进行评价。将结果示于表3。
○：与使用二甲基聚硅氧烷的情形相比，操作性为相同程度，
×：与使用二甲基聚硅氧烷的情形相比，操作性差。
(清洗性)
将在上述脱模性的评价中得到的硫化橡胶浸渍于2L的水(温度：80℃)，从浸渍开始1分钟后和2分钟后，确认硫化橡胶表面的粘液，按照下述标准进行评价。应予说明，硫化橡胶表面有粘液的情形表示脱模剂残留，没有粘液的情形表示脱模剂没有残留。将结果示于表1。
◎：浸渍1分钟后在硫化橡胶的表面没有粘液，
○：浸渍2分钟后在硫化橡胶的表面没有粘液，
×：浸渍2分钟后在硫化橡胶的表面还有粘液。
[表3]
Figure BDA0001468854880000071
根据表3可知，本发明的硫化橡胶成型用脱模剂的清洗性和脱模性优异。另外，可知通过并用聚氧亚烷基甘油醚(A)和聚氧亚烷基二醇(B)，即使是少量的脱模剂也能够得到充分的脱模性。另一方面，如比较例1所示，可知氧亚乙基的含量少时，清洗性差，如比较例2、3所示，可知使用甘油、聚氧乙烯二醇时，脱模性差，如比较例4所示，可知使用二甲基聚硅氧烷时，清洗性差。另外，如比较例5所示，使用甘油脂肪酸酯的环氧烷加成物时，脱模性差，清洗性也有改善的余地。另外，如比较例6所示，可知为了提高脱模性使用大量的甘油脂肪酸酯的环氧烷加成物时，清洗性大大降低。

Claims (4)

1.一种硫化橡胶成型用脱模剂，其特征在于，含有聚氧亚烷基甘油醚(A)，所述聚氧亚烷基甘油醚(A)在将氧亚烷基整体设为100质量％时含有50～95质量％的氧亚乙基。
2.根据权利要求1所述的硫化橡胶成型用脱模剂，其中，所述聚氧亚烷基甘油醚(A)的数均分子量为2000～20000。
3.根据权利要求1或2所述的硫化橡胶成型用脱模剂，其中，还含有聚氧亚烷基二醇(B)。
4.根据权利要求3所述的硫化橡胶成型用脱模剂，其中，所述聚氧亚烷基二醇(B)的含量相对于所述聚氧亚烷基甘油醚(A)100质量份为20～500质量份。
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