CN1163535C - 热塑性树脂用抗冲击性改性剂 - Google Patents

热塑性树脂用抗冲击性改性剂 Download PDF

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CN1163535C
CN1163535C CNB008023654A CN00802365A CN1163535C CN 1163535 C CN1163535 C CN 1163535C CN B008023654 A CNB008023654 A CN B008023654A CN 00802365 A CN00802365 A CN 00802365A CN 1163535 C CN1163535 C CN 1163535C
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高木彰
水田利雄
桥本友道
森稔幸
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Abstract

提供氯乙烯系树脂用的优良的抗冲击性改性剂。在玻璃化转变温度Tg为0℃以下，胶乳状态下的空隙率为3～90体积%，相对合计100重量份的橡胶成分单体，含有0.1～5重量份的交联剂的中空橡胶粒子30～90重量%存在下，选自丙烯酸酯化合物、芳香族乙烯基化合物、氰化乙烯基化合物、氯乙烯组成的组中的至少1种的乙烯单体60～100重量%和其他的可以共聚的单体0～40重量%组成的单体10～70重量%聚合而成，形成的共聚物作为氯乙烯系树脂用抗冲击性改性剂使用。

Description

热塑性树脂用抗冲击性改性剂
                      技术领域
本发明涉及用于氯乙烯系树脂的抗冲击性改性剂。
                      背景技术
为了改进热塑性树脂的抗冲击性，已有各种提案。例如已知在氯乙烯系树脂的情况下，配合二烯系橡胶或丙烯酸酯系橡胶的共聚物(特公昭39-19035号)。而且，提出用于提高抗冲击性的橡胶成分的粒子直径的方法(特公昭42-22541号)及降低橡胶成分的Tg的方法(特开平2-1763号公报、特开平8-100095号公报)。但是，利用这些方法要么难于进一步大幅度地提高抗冲击性，要么原料费大幅度地提高，存在着问题。
为了提高氯乙烯系树脂等的热塑性树脂组合物的抗冲击性，成形体的应力集中及产生·扩大橡胶中的空隙具有重要的作用。为了测定应力集中需要引入弹性模量大大低于热塑性树脂组合物的橡胶成分。实际上引入了各种各样的橡胶，并且进行了橡胶成分的大小、形状的最优化。橡胶中的空隙的产生及扩大有助于冲击试验时的能量吸收量大的剪切屈服的成长，可以预计与含有橡胶热塑性树脂的抗冲击性的提高有关。
所以在成形体冲击时(应力下)如何促进橡胶成分中的空隙的产生及扩大非常重要，该橡胶成分中的空隙的产生·扩大对橡胶的交联状态具有很大的影响。另外，预先将橡胶成分设定为中空的情况，在应力下可以容易地进行空隙的扩大。
因此，在改变支配橡胶成分的交联状态的交联剂量的同时，考察在胶乳状态下的橡胶成分的空隙(中空)状态、配合有含有橡胶成分的抗冲击性改性剂的热塑性树脂成形体的中空状态、以及成形体的冲击强度的关系。结果发现，Tg在0℃以下交联剂使用量为0～5重量％，成形结束时为非中空，胶乳状态下的空隙率为3～9体积％的中空橡胶30～90重量％、和10～70重量％的单体——所述单体由选自(甲基)丙烯酸酯化合物、芳香族乙烯基化合物、氰化乙烯基化合物、氯乙烯组成的组中至少一种的乙烯基单体60～100重量％和可以与之共聚合的单体0～40重量％组成——组成的抗冲击性改性剂对热塑性树脂的抗冲击性改善具有非常大的改进效果。即，首要的是引入比形成成形体的连续相的氯乙烯系树脂等的热塑性树脂弹性模量低得多的橡胶成分(Tg为0℃以下)，使应力集中，但是，减少该软橡胶成分的交联剂，冲击时(应力下)橡胶粒子空隙化也很重要。但是，交联剂量过少为0％时，橡胶粒子在成形时分裂微分散，从而有难于作为应力集中点的倾向。
而且，交联剂少的中空橡胶在胶乳状态下具有用水填充的空隙，在接枝共聚的过程中进行的凝固、热处理、干燥、共混、成形的工序中，橡胶粒子中的水被赶出，干燥后或成形后橡胶中的空隙消失，可以形成非中空，可以通过TEM观察或比重测定进行确认。
一方面，含有胶乳状态下在橡胶中具有空隙的中空橡胶的抗冲击性改性剂在冲击时(应力下)容易发生橡胶粒子中的空隙及扩大，冲击强度大幅度地提高。尽管橡胶中的交联剂量增多可以保持强固的中空，但是，从总的空隙的扩展容易度判断，最好将橡胶中的交联剂量控制在少量，利用胶乳状态下中空橡胶，在干燥时以及成形后为非中空的抗冲击性改性剂显示最大的改良效果。
                      发明的概述
即本发明涉及氯乙烯系树脂用抗冲击性改性剂，是在玻璃化转变温度Tg为0℃以下，胶乳状态下的空隙率为3～90体积％，相对橡胶成分单体合计100重量份，含有0.1～5重量份的交联剂的中空橡胶粒子以相对于改性剂总重量30～90重量％存在下，由选自(甲基)丙烯酸酯化合物、芳香族乙烯基化合物、氰化乙烯基化合物、氯乙烯组成的组中的至少1种的乙烯基单体以相对于单体总重量60～100重量％和其他的可以共聚的单体以相对于单体总重量0～40重量％组成的单体以相对于改性剂总重量10～70重量％聚合而成的。
所述改性剂中优选交联剂的使用量为0.1～1.5重量份。
所述改性剂中更优选交联剂的使用量为0.2～0.7重量份。
所述改性剂中胶乳状态下的中空橡胶的平均粒径优选50～300nm。
另外，本发明涉及由含有50重量％以上的氯乙烯的氯乙烯系树脂以及所述抗冲击性改性剂组成的氯乙烯系树脂组合物。
                  发明的最佳实施例
合成中空橡胶粒子有各种方法。例如如下的方法(《合成胶乳的应用》、杉村孝明等、p285)。本发明的胶乳状态下具有中空的橡胶粒子也可以利用几种方法进行制造。
(a)制成W/O/W乳液，使O层的单体聚合的方法(O：亲油性、W：亲水性)
(b)使具有溶胀性的核的核·壳粒子在外壳层的玻璃化转变温度以上的温度下溶胀，而中空化的方法。
(c)溶解度参数的不同的聚合物的二段聚合的方法
(d)使含有交联性单体和亲水性单体的聚合性单体和油性物质在水中微分散，形成O/W乳液，聚合单体，除去油性物质的方法
(e)利用在粒子中共聚合的羧酸在酸或碱性条件下在粒子中的移动的方法
本发明使用的中空橡胶成分只要是玻璃化转移温度为0℃以下的橡胶弹体都可以，玻璃化转变温度优选低。玻璃化转变温度需要0℃以下，优选-20～-130℃。玻璃化温度超过0℃，抗冲击性改性效果明显降低。
满足这样的条件的具体的例子为二烯系橡胶、丙烯酸系橡胶、硅系橡胶、烯烃系橡胶，不限于此。作为二烯系橡胶例如有：丁二烯橡胶、苯乙烯-丁二烯橡胶、丙烯腈-丁二烯橡胶，作为丙烯酸系橡胶例如有：丙烯酸丁酯橡胶、丁二烯-丙烯酸丁酯橡胶、丙烯酸2-乙基己酯-丙烯酸丁酯橡胶等，硅系橡胶例如有：聚二甲基硅氧烷橡胶等，另外烯烃系橡胶例如有：乙烯-丙烯橡胶，乙烯-丙烯-二烯橡胶等。
橡胶聚合中使用的交联剂具有防止橡胶粒子成形时崩裂而分散的功能。使用量过多时，虽然在成形时完全没有崩裂，但是冲击时(应力下)空隙难于扩大，最终成形体的冲击强度小。作为交联性单体例如有：甲基丙烯酸烯丙基酯、二乙烯基苯、邻苯二甲酸二烯丙基酯、聚乙二醇二甲基丙烯酸酯、1，3-丁二醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯等。这些可以单独使用也可以2种以上混合使用。交联剂的使用量相对橡胶成分单体100重量份为0.1～5重量份，优选0.1～1.5重量份，更优选0.2～0.7重量份。交联剂的使用量超过5重量份，冲击时(应力下)橡胶中难于扩展空隙，所以最终成形体的抗冲击性改良效果差。另外，在不足0.1重量份时，橡胶粒子成形时崩裂而分散，减小最终成形体的抗冲击性改良效果。
在中空橡胶粒子存在下聚合单体时，可以在中空橡胶粒子上直接进行单体聚合，得到接枝聚合物，利用橡胶粒子的酸膨胀及盐膨胀等膨胀技术制成大的接枝聚合物也可以。
在胶乳状态下中空橡胶的空隙，通过环氧树脂等包附橡胶胶乳，之后，可以利用4氧化钌等染色进行TEM观察，确认。另外利用微轨道UPA等正确求得胶乳的粒子直径，之后通过测定相同的粒子直径的橡胶胶乳的光散射强度，可以计算空隙率。胶乳状态下的中空橡胶的空隙率从最终成形体的抗冲击性改善效果考虑为3～90体积％，优选10～60体积％。空隙率超过90体积％，橡胶粒子成形时有时崩裂，不能稳定地改善冲击强度。空隙率不足3％时，最终成形体在冲击时橡胶中的空隙难于产生扩大，抗冲击性的改良效果变小。
为了最大限度地发挥最终成形体的抗冲击性改良效果，本发明的接枝共聚物的粒子直径根据热塑性树脂的种类合适的值多少不同，优选0.05～2.0μm。超过该范围，则倾向于抗冲击性的改良效果变小。
中空橡胶的合成法没有特别限定，只要使用乳液聚合，就可以有效的合成。
本发明的接枝共聚物在中空橡胶成分为30～90重量％、优选60～88重量％存在下，可以聚合10～70重量％、优选12～40重量％的单体而形成。中空橡胶成分不足30重量％时，抗冲击性的改良效果小，另外超过90重量％，配合而成的成形体成形时，抗冲击性改良剂的粒子崩裂，成形体的抗冲击性的改良效果小。
中空橡胶粒子存在下聚合的单体为含有60重量％以上的(甲基)丙烯酸酯化合物、芳香族乙烯基化合物、氰化乙烯基化合物、氯乙烯中的至少一种的单体或单体混合物。
(甲基)丙烯酸酯例如有：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸2-乙基己基酯等的甲基丙烯酸酯，丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己基酯等的丙烯酸酯。
芳香族乙烯基化合物例如有苯乙烯、α-甲基苯乙烯、氯苯乙烯等，氰化乙烯基化合物例如有丙烯腈、甲基丙烯腈等。
作为其他的可以共聚的单体，有(甲基)丙烯酸缩水甘油酯等的所述以外的(甲基)丙烯酸酯、马来酰亚胺、N-苯基马来酰亚胺等的马来酸酐缩亚胺化合物。
本发明使用的氯乙烯系树脂例如有：聚氯乙烯、含有50重量％以上的氯乙烯并且和醋酸乙烯酯及乙烯等可与氯乙烯共聚合的单体的共聚物及氯化氯乙烯树脂等。
相对氯乙烯系树脂100重量份，抗冲击性改性剂通常配合使用1～30重量份。不足1重量份，抗冲击性改良效果几乎没有，超过30重量份，有最终成形体的拉伸强度的降低的倾向。
下面根据实施例对本发明进行更详细地说明，但本发明不限于此。
实施例1
将200重量份的水、3.5重量份的油酸钠、0.4重量份的磷酸三钾、0.2重量份的β-萘磺酸甲醛缩合物的Na盐混合之后，混合10重量份的丙烯酸丁酯、3重量份的叔十二烷基硫醇、0.1重量份的p-methane氢过氧化物，之后升温至50℃。添加0.002重量份的硫酸亚铁(FeSO4·7H2O)、0.005重量份的乙二胺4乙酸·2Na盐、0.2重量份的甲醛次硫酸钠，聚合1小时。其后利用3小时连续添加90重量份的丙烯酸丁酯、27重量份的叔十二烷基硫醇、0.9重量份的p-methane氢过氧化物。进行2小时的后聚合，得到平均粒子直径为0.04μm的原种胶乳(S-1)。
将2重量份的原种胶乳(S-1)(固体部分)和50重量份的水混合。利用均化器使98重量份的丙烯酸丁酯、0.3重量份的甲基丙烯酸烯丙基酯、0.75重量份的5％十二烷基硫酸Na(固体部分)、400重量份的水的混合物微分散添加于其中，室温下搅拌1小时。添加0.002重量份的硫酸亚铁(FeSO4·7H2O)、0.005重量份的乙二胺4乙酸·2Na盐、0.2重量份的甲醛次硫酸钠，1份的p-methane氢过氧化物，在40℃下聚合4小时，得到空隙率为30体积％、粒径为0.15μm的中空橡胶胶乳(R-1)。
将85重量份的中空橡胶胶乳(R-1)(固体部分)升温至45℃，之后加入0.15重量份(固体部分)的5％十二烷基硫酸Na水溶液、0.016重量份的硫酸亚铁(FeSO4·7H2O)、0.004重量份的乙二胺4乙酸·2Na盐、0.2重量份的甲醛次硫酸钠。利用1小时连续添加15重量份的甲基丙烯酸甲酯及0.01重量份的氢过氧化异丙苯的混合液，进行1小时的后聚合，得到平均粒径为0.18μm的中空接枝共聚物胶乳(G-1)。
利用氯化钙使该中空接枝共聚物胶乳(G-1)凝固，热处理、脱水、干燥，得到粉末状的中空接枝共聚物(A-1)。
在100重量份的聚合度400的氯乙烯树脂(钟渊化学工业株式会社制、KANE VINYL S400)中将10重量份的中空接枝共聚物(A-1)、3.0重量份的辛基锡硫醇盐、1.0重量份的硬脂醇、0.5重量份的硬脂酰胺、0.5重量份的褐煤酸二醇酯、1.0重量份的加工助剂(钟渊化学工业株式会社制、PA20)共混，使用田边塑料机械株式会社制50mm单螺杆挤出机(VS50-26型)在旋转数：30rpm、C1：140℃、C2：160℃、C3：160℃、C4：165℃、D：160℃的条件下挤出加工，得到树脂颗粒。然后使用三菱重工制注塑成形机IS-170G，进行注塑成形(C1：150℃、C2：160℃、C3：170℃、喷嘴175℃、模具温度：40℃)，得到哑铃型、艾佐德试验用试件。根据JIS-K7110，测定艾佐德强度。结果示于表1。
实施例2～4
除了改变橡胶成分甲基丙烯酸烯丙酯的量分别为0.5重量份、1.0重量份、5.0重量份之外，其他和实施例1一样进行合成·凝固·热处理·脱水干燥粉末化·配合·成形·评价。结果示于表1。
实施例5
除了将种聚合时的叔十二烷基硫醇的量改变为10重量份之外，其他和实施例1一样进行合成·凝固·热处理·脱水干燥粉末化·配合·成形·评价。结果示于表1。
比较例1
将100重量份的甲基丙烯酸丁酯、0.5重量份的甲基丙烯酸烯丙基酯、1.2重量份的5％十二烷基硫酸Na(固体部分)、450重量份水的混合物利用匀化器微分散加入，室温下搅拌1小时。添加0.002重量份的硫酸亚铁(FeSO4·7H2O)、0.005重量份的乙二胺4乙酸·2Na盐、0.2重量份的甲醛次硫酸钠，1.0重量份的p-methane氢过氧化物，在40℃下聚合4小时，得到空隙率为0体积％、粒子直径为0.15μm的通常的橡胶胶乳(R-2)。
将85重量份的中空橡胶胶乳(R-2)(固体部分)升温至45℃，之后加入0.15重量份(固体部分)的5％十二烷基硫酸Na水溶液、0.001重量份的硫酸亚铁(FeSO4·7H2O)、0.004重量份的乙二胺4乙酸·2Na盐、0.2重量份的甲醛次硫酸钠。利用1小时连续添加15重量份的甲基丙烯酸甲酯及0.01重量份的氢过氧化异丙苯的混合液，进行1小时的后聚合，得到平均粒子直径为0.18μm的通常的接枝共聚物胶乳(G-2)，和实施例1同样进行后处理·成形·评价。
比较例2
除了将橡胶成分的甲基丙烯酸烯丙基酯的量改变为7重量份之外，其他和比较例1一样进行聚合·凝固·热处理·脱水干燥粉末化·配合·成形·评价。结果示于表1。
比较例3～4
除了将橡胶成分的甲基丙烯酸烯丙基酯的量分别改变为7重量份、10重量份之外，其他和实施例1一样进行聚合·凝固·热处理·脱水干燥粉末化·配合·成形·评价。结果示于表1。
比较例5
除了将接枝聚合时的中空橡胶量改变为5重量份，甲基丙烯酸甲酯的量改变为95重量份之外，其他和比较例1一样进行聚合·凝固·热处理·脱水干燥粉末化·配合·成形·评价。结果示于表1。
表1
实施例号 成形体中的接枝共聚物 氯乙烯系成形体
橡胶种类 橡胶中的交联剂量 橡胶粒子空隙率(体积％) 橡胶量(份) 艾佐德冲击强度(kgf-cm/cm2)
12345 中空橡胶中空橡胶中空橡胶中空橡胶中空橡胶  0.30.51.05.00.5  3030303010  8585858585  5165443140
比较例12345 普通橡胶普通橡胶中空橡胶中空橡胶中空橡胶 0.57.07.010.00.5 00303030 858585855 211422168
                      工业实用性
本发明的抗冲击性改性剂是使用适当的交联剂，而且使用合适的空隙率的橡胶粒子的抗冲击性改性剂，所以相对氯乙烯系树脂具有优良的抗冲击性改良的效果。

Claims (3)

1、一种氯乙烯系树脂用抗冲击性改性剂，其中，是在玻璃化转变温度Tg为0℃以下，胶乳状态下的空隙率为3～90体积％，相对合计100重量份的交联的橡胶成分的单体，含有0.2～0.7重量份的交联剂的中空橡胶粒子以相对于改性剂总重量30～90重量％存在下，
由选自(甲基)丙烯酸酯化合物、芳香族乙烯基化合物、氰化乙烯基化合物、氯乙烯组成的组中的至少1种的乙烯基单体以相对于单体总重量60～100重量％和其他的可以共聚的单体以相对于单体总重量0～40重量％组成的单体以相对于改性剂总重量10～70重量％聚合而成的。
2、如权利要求1所述的氯乙烯系树脂用抗冲击性改性剂，其中，其中胶乳状态下的中空橡胶的平均粒径为50～300nm。
3、一种含有50重量％以上氯乙烯的氯乙烯系树脂以及如权利要求1所述的抗冲击性改性剂组成的氯乙烯系树脂组合物。
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