CN1311011C - 树脂成型品及其加工品 - Google Patents
树脂成型品及其加工品 Download PDFInfo
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- CN1311011C CN1311011C CNB200480000973XA CN200480000973A CN1311011C CN 1311011 C CN1311011 C CN 1311011C CN B200480000973X A CNB200480000973X A CN B200480000973XA CN 200480000973 A CN200480000973 A CN 200480000973A CN 1311011 C CN1311011 C CN 1311011C
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- Prior art keywords
- synthetic resin
- irradiation
- electron rays
- resin according
- polyhutadiene
- Prior art date
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- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
本发明提供一种树脂成型品,是用电子射线照射含有(A)晶化度为等于5%或大于5%的间规1,2-聚丁二烯100~60重量份、及(B)其他的热塑性聚合物0~40重量份的树脂成型品而得到的成型品,电子射线照射后的成型品的50%应力(50%M:M2)是电子射线照射前的50%应力(50%M:M1)的1.01~2.5倍,且具有耐蒸汽灭菌性。本发明的树脂成型品在柔软性和硬度优异的同时,耐蒸汽灭菌性优异,在输液管、输液用容器、及导尿管等的医疗用途方面是有用的。
Description
技术领域
本发明涉及电子射线照射由含有间规1,2-聚丁二烯的组合物构成的树脂成型品而得到的成型品。更详细地讲,涉及柔软性和硬度优异、且具有耐蒸汽灭菌性的含有间规1,2-聚丁二烯的成型品。
背景技术
间规1,2-聚丁二烯是同时具有塑料(硬度)和橡胶(弹性、柔软性)的性质的热塑性弹性体,具有一定的结晶性,同时能够利用通用的聚合物加工机容易地成型,因此被用于各种工业用品。
特别是与耐气体透过性、透明性优异、大量地需要增塑剂的氯乙烯系树脂等比较,不添加增塑剂就能成型加工,适度地具有柔软且自粘合性,因此在输液管、及导尿管等的医疗用途上的应用不断扩大。
可是,间规1,2-聚丁二烯在晶化度低的情况,熔点低为70~95℃,当将它用于输液管或输液容器、以及导尿管等的医疗用具,并蒸汽灭菌时,缺乏耐热性,实用上往往成为问题。
作为保持间规1,2-聚丁二烯的同时具有塑料(硬度)和橡胶(弹性、柔软性)的性质的热塑性弹性体这一特性,同时消除性能平衡的不足的方法,提出了通过照射所限定的波长的紫外线,仅使成型物的表层交联、固化的方法(特开2000-129017号公报)。该方法在提高作为医疗用部件的柔软性、透明性及耐热生(耐高压蒸汽灭菌性)的性能平衡方面发挥出相应的效果。
另外,为了得到更硬质的表面,也提出了种种照射电子射线的方法。这些方法在关于耐划伤性方面发挥出一定的效果。
可是,采用上述公报所公开的方法得到的成型物,由于是通过照射所限定的区域的波长的紫外线来仅交联表层的,因此例如关于医疗用管的内部的耐热性,未必能得到充分满足。另外,过去的使用电子射线的方法将成型物的内部也过分地硬质化,存在几乎丧失了间规1,2-聚丁二烯具有的一个性质即柔软性的问题。
本发明的目的是提供在输液管、输液用容器、及导尿管等的医疗用途等中有用的、柔软性和硬度优异、同时耐蒸汽灭菌性优异的含有间规1,2-聚丁二烯的成型品。
发明内容
本发明涉及一种树脂成型品,其特征在于,是电子射线照射含有(A)晶化度为等于5%或大于5%的间规1,2-聚丁二烯100~60重量份、及(B)从聚丙烯、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)、它们的氢化物(SEBS、或SEPS)、上述间规1,2-聚丁二烯以外的聚丁二烯(BR)、ABS树脂、聚异戊二烯、聚乙烯(LLDPE、ULDPE、或LDPE)、乙烯-乙酸乙烯酯共聚物(copolymer)、乙烯-丙烯酸酯共聚物、以及乙烯-甲基丙烯酸共聚物中选择的至少1种热塑性聚合物0~40重量份[其中,(A)+(B)=100重量份]的树脂成型品而得到的成型品,电子射线照射后的成型品的50%应力(50%M:M2)是电子射线照射前的50%应力(50%M:M1)的1.01~2.5倍,且具有耐蒸汽灭菌性。
在此,优选具有树脂成型品的浊度值为等于50或小于50的透明性。
另外,电子射线照射后的树脂成型品的对甲苯不溶的成分通常是50~99重量%。
而且,电子射线照射量用电子射线加速电压(kV)和照射射线量(Mrad)的积表示是2~1000000(kV·Mrad)。
作为树脂成型品的具体例子,列举出选自管(tube)、片、膜、袋(bag)及插接件(connector)的至少1种。
这些树脂成型品优选卤素原子的含量是等于50ppm或小于50ppm。
本发明的树脂成型品尤其适用于医疗用途方面。
而且,本发明涉及加工上述树脂成型品而得到的食品用途、鞋类用途、车辆用途、电线包覆用途等方面的加工品。
具体实施方式
(A)间规1,2-聚丁二烯
本发明所用的(A)间规1,2-聚丁二烯是具有晶化度为等于5%或大于5%、优选为10~40%的结晶性的间规1,2-聚丁二烯,其熔点优选在50~130℃、进一步优选在60~120℃的范围。通过使晶化度·熔点在该范围,可以得到拉伸强度、撕裂强度等力学强度和柔软性优异的结果。
本发明所用的(A)间规1,2-聚丁二烯例如是1,2-键含有量为等于70%或大于70%的,例如是在含有钴化合物及铝烷的催化剂存在下,将丁二烯聚合而得到的,但不限定于这个制造方法。
本发明所用的(A)间规1,2-聚丁二烯的丁二烯键单元中的1,2-键含有量,通常是等于70%或大于70%、优选是等于80%或大于80%、进一步优选是等于90%或大于90%。通过1,2-键含有量为等于70重量%或大于70重量%,该1,2-聚丁二烯发挥出良好的作为热塑性弹性体的性质。
本发明所用的(A)间规1,2-聚丁二烯,也可以少量共聚丁二烯以外的共轭二烯。作为丁二烯以外的共轭二烯,可列举出1,3-戊二烯、用高级烷基取代的1,3-丁二烯衍生物、2-烷基取代-1,3-丁二烯等。其中,作为用高级烷基取代的1,3-丁二烯衍生物,可列举出1-戊基-1,3-丁二烯、1-己基-1,3-丁二烯、1-庚基-1,3-丁二烯、1-辛基-1,3-丁二烯等。
在此,2-烷基取代-1,3-丁二烯的代表性的物质可列举出2-甲基-1,3-丁二烯(异戊二烯)、2-乙基-1,3-丁二烯、2-丙基-1,3-丁二烯、2-异丙基-1,3-丁二烯、2-丁基-1,3-丁二烯、2-异丁基-1,3-丁二烯、2-戊基-1,3-丁二烯、2-异戊基-1,3-丁二烯、2-己基-1,3-丁二烯、2-环己基-1,3-丁二烯、2-异己基-1,3-丁二烯、2-庚基-1,3-丁二烯、2-异庚基-1,3-丁二烯、2-辛基-1,3-丁二烯、2-异辛基-1,3-丁二烯等。在这些共轭二烯之中,作为与丁二烯共聚的优选的共轭二烯,可列举出异戊二烯、1,3-戊二烯。供聚合用的单体成分中的丁二烯的含量优选为等于50摩尔%或大于50摩尔%,特别优选为等于70摩尔%或大于70摩尔%。
在本发明中使用的(A)间规1,2-聚丁二烯,如上述,例如在含有钴化合物及铝烷的催化剂存在下,将丁二烯聚合而得到。作为上述钴化合物,可优选列举出碳数4或大于4的钴的有机酸盐。作为该钴的有机酸盐的具体例子,可列举出酪酸盐;己酸盐;庚酸盐;2-乙基-己酸盐等的辛酸盐;癸酸盐;硬脂酸盐、油酸盐、芥子酸盐等的高级脂肪酸盐;苯甲酸盐;二甲苯基乙醇酸盐、甲苄基(xylyl)酸盐、乙基苯甲酸盐等的烷基、芳烷基、烯丙基取代苯甲酸盐;萘甲酸盐;以及烷基、芳烷基或烯丙基取代萘甲酸盐。这些盐之中,2-乙基己酸盐的所谓的辛酸盐、和硬脂酸盐、苯甲酸盐由于对烃溶剂的优异的溶解性,故优选。
作为上述铝烷,例如可列举出用下述通式(I)或通式(II)表示的物质。
在用该通式(I)或(II)表示的铝烷中,R是甲基、乙基、丙基、丁基等的烃基,优选是甲基、乙基,特别优选是甲基。另外,m是2或大于2、优选是5或大于5、进一步优选是10~100的整数。作为铝烷的具体例子,可举出甲基铝烷、乙基铝烷、丙基铝烷、丁基铝烷等,特别优选甲基铝烷。
聚合催化剂更优选在上述钴化合物和铝烷以外还含有膦化合物。膦化合物是对聚合催化剂的活性化、乙烯基键结构及结晶性的控制有效的成分,可优选举出用下述通式(III)表示的有机磷化合物。
P(Ar)n(R’)3-n……(III)
通式(III)中,Ar表示下面所示的基。
在上述基中,R1、R2、R3相同或不同,表示氢原子、碳数优选为1~6的烷基、卤素原子、碳数优选为1~6的烷氧基或碳数优选为6~12的芳基。
另外,通式(III)中,R’表示环烷基、烷基取代环烷基,n是0~3的整数。
作为用通式(III)表示的膦化合物,可具体举出三-(3-甲基苯基)膦、三-(3-乙基苯基)膦、三-(3,5-二甲基苯基)膦、三-(3,4-二甲基苯基)膦、三-(3-异丙基苯基)膦、三-(3-叔丁基苯基)膦、三-(3,5-二乙基苯基)膦、三-(3-甲基-5-乙基苯基)膦、三-(3-苯基苯基)膦、三-(3,4,5-三甲基苯基)膦、三-(4-甲氧基-3,5-二甲基苯基)膦、三-(4-乙氧基-3,5-二乙基苯基)膦、三-(4-丁氧基-3,5-二丁基苯基)膦、三(对甲氧基苯基膦)、三环己基膦、二环己基苯基膦、三苄基膦、三(4-甲基苯基膦)、三(4-乙基苯基膦)等。这些化合物之中,特别优选的化合物列举出三苯基膦、三-(3-甲基苯基)膦、三-(4-甲氧基-3,5-二甲基苯基)膦等。
另外,作为钴化合物,可使用用下述通式(IV)表示的化合物。
用上述通式(IV)表示的化合物,是对于氯化钴在配位基上具有在上述通式(III)中n为3的膦化合物的配位化合物。在使用该钴化合物时,可以使用预先合成的,或者可以采用在聚合体系中使氯化钴和膦化合物接触的方法使用。通过选择种种的配位化合物中的膦化合物,能够进行所得到的间规1,2-聚丁二烯的1,2-键的量、晶化度的控制。
作为用上述通式(IV)表示的钴化合物的具体例子,能够使用钴双(三苯基膦)二氯化物、钴双[三(3-甲基苯基膦)]二氯化物、钴双[三(3-乙基苯基膦)]二氯化物、钴双[三(4-甲基苯基膦)]二氯化物、钴双[三(3,5-二甲基苯基膦)]二氯化物、钴双[三(3,4-二甲基苯基膦)]二氯化物、钴双[三(3-异丙基苯基膦)]二氯化物、钴双[三(3-叔丁基苯基膦)]二氯化物、钴双[三(3,5-二乙基苯基膦)]二氯化物、钴双[三(3-甲基-5-乙基苯基膦)]二氯化物、钴双[三(3-苯基苯基膦)]二氯化物、钴双[三(3,4,5-三甲基苯基膦)]二氯化物、钴双[三(4-甲氧基-3,5-二甲基苯基膦)]二氯化物、钴双[三(4-乙氧基-3,5-二乙基苯基膦)]二氯化物、钴双[三(4-丁氧基-3,5-二丁基苯基膦)]二氯化物、钴双[三(4-甲氧基苯基膦)]二氯化物、钴双[三(3-甲氧基苯基膦)]二氯化物、钴双[三(4-十二烷基苯基膦)]二氯化物、钴双[三(4-乙基苯基膦)]二氯化物等。
这些钴化合物之中,特别优选的列举出钴双(三苯基膦)二氯化物、钴双[三(3-甲基苯基膦)]二氯化物、钴双[三(3,5-二甲基苯基膦)]二氯化物、钴双[三(4-甲氧基-3,5-二甲基苯基膦)]二氯化物等。
催化剂的用量,经钴原子换算,丁二烯均聚的情况每1摩尔丁二烯,丁二烯共聚的情况每1摩尔的丁二烯和丁二烯以外的共轭二烯的合计量,使用0.001~1毫摩尔、优选0.01~0.5毫摩尔左右。另外,膦化合物的用量,作为磷原子对钴原子的比(P/Co)通常是0.1~50,优选是0.5~20,进一步优选是1~20。此外,铝烷的用量,作为铝原子对钴化合物的钴原子的比(Al/Co)通常是4~107,优选是10~106。使用用通式(IV)表示的配位化合物的情况,膦化合物的用量定为磷原子对钴原子的比(P/Co)为2,铝烷的用量按照上述记载。
作为聚合溶剂使用的惰性有机溶剂,例如举出苯、甲苯、二甲苯、异丙苯等的芳香族烃溶剂,正戊烷、正己烷、正丁烷等的脂肪族烃溶剂,环戊烷、甲基环戊烷、环己烷等的脂环族烃溶剂以及它们的混合物。
聚合温度通常是-50℃至120℃,优选是-20℃至100℃。
聚合反应可以是间歇式,也可以是连续式。溶剂中的单体浓度通常是5~50重量%,优选是10~35重量%。
另外,为了制造聚合物,为了不使本发明的催化剂和聚合物失活,必须考虑极力消除在聚合体系内混入氧、水或二氧化碳等的有失活作用的化合物。聚合反应一进行到所要求的阶段就向反应混合物中添加醇、其他的停止聚合剂、抗老化剂、抗氧化剂、紫外线吸收剂等,接着按照通常的方法将生成聚合物分离、洗涤、干燥,从而能够得到用于本发明的间规1,2-聚丁二烯。
用于本发明的(A)间规1,2-聚丁二烯的重均分子量,优选是1万~500万,进一步优选是1万~150万,特别优选是5万~100万。当重均分子量小于1万时,流动性极端地高,加工非常困难,另外,成型品发粘,故不优选,而超过500万时,流动性极端地低,加工非常困难,故不优选。
(B)热塑性聚合物
作为(B)热塑性聚合物,是上述(A)成分以外的热塑性树脂和/或热塑性弹性体,具体讲,是从聚丙烯、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)、它们的氢化物(SEBS、SEPS)、上述间规1,2-聚丁二烯以外的聚丁二烯(BR)、ABS树脂、聚异戊二烯、各种聚乙烯(LLDPE、ULDPE、LDPE)、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸酯共聚物、以及乙烯-甲基丙烯酸共聚物中选择的至少1种。
(B)成分的配合量,在(A)~(B)成分的合计量100重量份中为等于40重量份或小于40重量份,优选是0~35重量份。当超过40重量份时,(A)成分的使用比例变少,柔软性或硬度和透明性丧失。
在本发明所用的组合物中,也可以在上述(A)~(B)成分以外根据需要含有润滑剂、填料、油或发泡剂等添加剂。作为上述添加剂的具体例子,可举出芥酸酰胺、硬脂酰胺、油酰胺等润滑剂、滑石、二氧化硅、氢氧化镁、碳酸钙、玻璃、碳纤维、玻璃球等填料、石蜡、硅油、エクスパンセル发泡剂(日本フイライト公司制造的珠型发泡剂マイクロスフエア-:在成型加工时珠膨胀至40倍或大于40倍)、ADCA(偶氮二碳酰胺;Azodicarbonamide)、OBSH(p,p’-羟基联苯基磺酰肼;p,p’-oxybisbenzen sulfonyl hydrazine)、碳酸氢钠、AIBN(偶氮双异丁腈)等的发泡剂。
另外,为了提高电子射线照射的耐热性和柔软性,也可以相对于间规1,2-聚丁二烯100重量份含有5重量份或小于5重量份的三甲基丙烷三甲基丙烯酸酯等的多官能单体、羟基环己基苯基酮等的光聚合引发剂,二苯甲酮等的光增敏剂等。
组合物的制备和成型
本发明所用的组合物,使上述(A)~(B)成分加热软化,混炼成型,或向它们之中进一步根据需要添加上述添加剂等,加热软化,混炼成型。混炼和成型在间规1,2-聚丁二烯的软化温度乃至熔融温度或大于熔融温度的成型性良好的温度范围进行,形成均质的成型品。
为此,成型温度优选90~170℃左右。为了得到成型品,利用挤压成型、挤出成型、射出成型、吹塑成型、异型挤出成型、T模膜成型、吹胀成型、粉末搪塑、旋转模塑等。
电子射线照射
本发明的树脂成型品接着照射电子射线而得到。当照射电子射线时,通过间规1,2-聚丁二烯的乙烯基的自由基反应变成三维交联结构,使成型品固化的同时,付与耐热性。
电子射线对合成树脂有透射性,其透射的程度依赖于成型品厚度、和电子射线的动能。
若按照其照射厚度在厚度方向可均匀透射地调节电子射线的能量,则能够制成在厚度方向使交联度均一的成型品。
电子射线的能量,对于上述成型品,优选为20~5000kV,进一步优选为50~3000kV,最优选为100~2000kV。当小于20kV时,在表层部捕获吸收的电子的比例相对地多,透过成型品的电子射线变少,内部的交联比表层部慢,交联度发生差别,因此不优选。另一方面当大于5000kV时,交联度过大,变成硬质,因此弹力性和延伸率变小,故不优选。
另外,此时的电子射线的照射量,优选在0.1~200Mrad(在SI单位体系中相当于1~2000kGy)、进一步优选在0.5~100Mrad的范围照射使之交联固化。当少于0.1Mrad时,间规1,2-聚丁二烯的交联度小,另一方面,当超过200Mrad时,交联度过大,变成硬质,因此弹力性和延伸率变小,故不优选。
电子射线照射的交联度可用电子射线能量与照射量的积表示。在本发明中,电子射线加速电压(kV)与照射射线量(Mrad)的积优选为2~1000000(kV·Mrad),进一步优选为25~300000(kV·Mrad),最优选为50~100000(kV·Mrad)。当小于2(kV·Mrad)时,在表层部捕获吸收的电子的比例相对地多,透过成型品的电子射线变少,内部的交联比表层部慢,交联度发生差别,因此不优选。另一方面当大于1000000(kV·Mrad)时,交联度过大,变成硬质,因此弹力性和延伸率变小,故不优选。
通过对本发明的成型品实施上述那样的电子射线照射,能够使M2/M1比优选为1.01~2.5倍、进一步优选为1.02~2.0倍。在此,M2、M1意指电子射线照射后的成型品的50%应力(50%M:M2)、电子射线照射前的50%应力(50%M:M1)。当小于1.01时,电子射线交联未进行,耐蒸汽灭菌性差。另一方面,当超过2.5时,交联成型品过硬,柔软性丧失,故不优选。M2/M1,通过使上述电子射线加速电压(kV)与照射射线量(Mrad)的积优选为2~1000000(kV·Mrad)、进一步优选为25~300000(kV·Mrad)、最优选为50~100000(kV·Mrad)而能够容易地调整。
另外,这样得到的电子射线照射后的交联成型品,具有耐蒸汽灭菌性,例如使用作为本发明的交联成型品一种的输液管,在90~140℃蒸汽灭菌10~20分钟左右也不会变形。
在此,所谓耐蒸汽灭菌性意指:例如将输液管等树脂成型品(一例:内径Φ3mm、外径Φ4.4mm、壁厚0.7mm的管、管长20cm)放入到高压蒸汽灭菌器中,在121℃蒸汽灭菌20分钟的情况,保持灭菌前的形状,观察不到变形。
而且,本发明的照射了电子射线的树脂成型品的浊度值是等于50或小于50,优选是等于30或小于30。浊度值是透明性的尺度,其值越小,透明性越好。该浊度值是依据ASTMD-1003测定的值。
另外,电子射线照射后的本发明的树脂成型品,对甲苯不溶的成分通常是50~99重量%,优选是80~95重量%。对甲苯不溶的成分,是表示通过电子射线照射树脂成型品,(A)间规1,2-聚丁二烯中的双键交联到如何程度的参数。
在此,对甲苯不溶的成分,使本发明的树脂成型品[(a)g]浸渍在100ml的甲苯中,在30℃振荡48小时后,使用100目金属网过滤,采集过滤液的一部分[(c)ml]后,使之蒸发干燥固化,称量所得到的残存固体成分[对甲苯不溶的成分:(b)g],通过下式算出凝胶含量。
凝胶含量(重量%)=[(a-b×(100/c)}/a]×100
对甲苯不溶的成分小于50重量%时,电子射线照射的交联不充分,耐热性差,耐蒸汽灭菌性差。另一方面,当超过99重量%时,电子射线照射的交联过于进行,树脂成型品过硬,柔软性丧失,故不优选。
上述对甲苯不溶的成分,通过使上述电子射线加速电压(kV)与照射射线量(Mrad)的积优选为2~1000000(kV·Mrad)、进一步优选为25~300000(kV·Mrad)、最优选为50~100000(kV·Mrad)而能够容易地调整。
而且,本发明的树脂成型品,卤素原子的含量等于50ppm或小于50ppm、优选等于20ppm或小于20ppm。该卤素原子的含量,例如如上述那样通过使用非卤素系的惰性有机溶剂作为聚合溶剂,能够使所得到的1,2-聚丁二烯中的卤素原子的含量等于50ppm或小于50ppm、优选等于20ppm或小于20ppm。另外,在催化剂体系中,只使用非卤素系的化合物能够进一步降低树脂成型品中的卤素原子的含量,故优选。
本发明的树脂成型品是柔软性和硬度优异、且具有耐蒸汽灭菌性的含有间规1,2-聚丁二烯的成型品,在输液管、输液用容器、以及导尿管等的医疗用途中是有用的。
实施例
以下举出实施例进一步具体说明本发明,但本发明并不限定于以下的实施例。实施例中,只要不特别声明,份及%是以重量为基准。另外,实施例中的各种测定按照以下进行。
耐蒸汽灭菌性:在本文中记载
透明性(浊度值):在本文中记载
拉伸强度、拉伸断裂延伸率、拉伸弹性模量:
依据JIS K6301在试验速度200mm/分、夹具间距离50mm下测定。
凝胶分率:在本文中记载
硬度:将电子射线照射后的成型品的50%应力(50%M:M2)为等于5MPa或小于5MPa记为硬度不高,视为良好。
柔软性:将电子射线照射后的拉伸断裂延伸率为等于100%或大于100%己为良好。
实施例1
将1,2-聚丁二烯(JSR公司制,商品名:JSR RB810,晶化度=18%)100重量份经挤出成型成型为内径Φ3mm、外径Φ4.4mm、壁厚0.7mm的管,使用电子射线照射装置(日新ハイボルテ-ジ公司制,商品名:EPS800-35)在加速电压300kV、照射射线量20Mrad下对该管进行电子射线照射处理。表1中示出评价结果。
实施例2
在实施例1中,将电子射线的加速电压变成800kV,除此以外与实施例1同样。表1中示出评价结果。
实施例3
在实施例2中,将电子射线的照射射线量变成5Mrad,除此以外与实施例2同样。表1中示出评价结果。
实施例4
在实施例3中,使用了在1,2-聚丁二烯中掺和了30重量份的SIS(苯乙烯-异戊二烯-苯乙烯嵌段共聚物,JSR公司制,JSR SIS 5229P)的混合物,除此以外与实施例3同样。表1中示出评价结果。
比较例1
在实施例1中,将挤出成型1,2-聚丁二烯100重量份的管不进行电子射线照射就进行评价。表1中示出评价结果。
比较例2
在实施例1中,将电子射线的加速电压变成30kV,将照射射线量变成0.05Mrad,除此以外与实施例1同样。表1中示出评价结果。
比较例3
在实施例2中,将电子射线的加速电压变成5000kV,将照射射线量变成300Mrad,除此以外与实施例1同样。表1中示出评价结果。
表1
实施例 | 比较例 | ||||||||
1 | 2 | 3 | 4 | 1 | 2 | 3 | |||
材料 | (*1)RB | 100 | 100 | 100 | 70 | 100 | 100 | 100 | |
(*2)SIS | 30 | ||||||||
照射条件 | ①加速电压 | (kV) | 300 | 800 | 800 | 800 | 无 | 30 | 5000 |
②照射射线量 | (Mrad) | 20 | 20 | 5 | 5 | 无 | 0.05 | 300 | |
①×②的积 | 6000 | 1600 | 4000 | 4000 | 1.5 | 1500000 | |||
耐蒸汽灭菌性 | 形状保持 | ○ | ○ | ○ | ○ | × | × | ○ | |
透明性 | 浊度 | 15 | 14 | 16 | 20 | 18 | 17 | 9 | |
拉伸强度 | (MPa) | 12 | 16 | 20 | 22 | 14 | 15 | 14 | |
拉伸断裂延伸率 | (%) | 410 | 210 | 720 | 790 | 910 | 870 | 10 | |
照射前拉伸50%应力(M1) | M1(MPa) | 3.4 | 3.4 | 3.4 | 3.2 | 3.4 | 3.4 | 3.4 | |
照射后拉伸50%应力(M2) | M2(MPa) | 3.6 | 4.0 | 3.5 | 3.3 | - | 3.4 | 10.0 | |
M2/M1 | (-) | 1.06 | 1.18 | 1.03 | 1.03 | - | 1.00 | 2.94 | |
凝胶分率 | (%) | 57 | 99 | 91 | 87 | 0 | 30 | 100 |
(*1)RB;1,2-聚丁二烯(JSR公司制,商品名:JSR RB810,晶化度=18%)
(*2)SIS;(苯乙烯-异戊二烯-苯乙烯嵌段共聚物,JSR公司制,JSR SIS 5229P)
如表1所示可知,满足本发明的电子射线照射条件,即电子射线加速电压(kV)与照射射线量(Mrad)的积2~1000000(kV·Mrad)的实施例1,与不满足照射条件的比较例1(没有照射)及比较例2(加速电压:30kV、照射射线量:0.05Mrad)比,耐热性提高,另外柔软性优异。
另外不可知,将实施例1中的加速电压300kV提高至800kV的实施例2也提高耐热性(蒸汽灭菌性)。
而且,实施例3是将实施例2中的照射射线量20Mrad降至5Mrad的实施例,但得到耐热性(蒸汽灭菌性)提高、而且柔软性优异的结果。
实施例4是在实施例3的照射条件下使用了在1,2-聚丁二烯中掺和了30重量份的SIS(苯乙烯-异戊二烯-苯乙烯嵌段共聚物,JSR公司制,JSR SIS 5229P)的实施例,但也得到了耐热性(蒸汽灭菌性)提高和柔软性优异的结果。
另一方面,比较例1是未实施电子射线照射的管,耐热性(蒸汽灭菌性)差。
比较例2其电子射线照射条件用电子射线加速电压(kV)与照射射线量(Mrad)的积表示,在小于2~1000000(kV·Mrad),耐热性(蒸汽灭菌性)差。
比较例3其电子射线照射条件用电子射线加速电压(kV)与照射射线量(Mrad)的积表示,在大于2~1000000(kV·Mrad),柔软性差。
产业上的利用可能性
本发明的树脂成型品,由于柔软性和硬度优异,还具有耐蒸汽灭菌性,因此在管、片、膜、袋、插接件等的用途方面是有用的。特别是在输液管、输液用容器、以及导尿管等的医疗用途中是有用的。
另外,通过同样的电子射线照射加工本发明的树脂成型品而得到的加工品,在食品用途、鞋类用途、车辆用途、电线包覆用途等方面也是有用的。
Claims (17)
1.一种树脂成型品,其特征在于,是用电子射线照射含有(A)熔点为50~130℃、晶化度为10~40%、1,2-键含有量为等于70%或大于70%的间规1,2-聚丁二烯100~60重量份、以及(B)从聚丙烯、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、它们的氢化物、上述间规1,2-聚丁二烯以外的聚丁二烯、丙烯腈-丁二烯-苯乙烯树脂、聚异戊二烯、聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸酯共聚物、以及乙烯-甲基丙烯酸共聚物中选择的至少1种热塑性聚合物0~40重量份的树脂成型品而得到的成型品,其中,(A)+(B)=100重量份,
电子射线照射量用电子射线加速电压和照射射线量的积表示是2~1000000kV·Mrad,其中加速加压的单位是kV,照射射线量的单位是Mrad,
电子射线照射后的成型品的50%应力的50%M:M2是电子射线照射前的50%应力的50%M:M1的1.01~2.5倍,且具有耐蒸汽灭菌性。
2.根据权利要求1所述的树脂成型品,具有2mm片的浊度值为等于50或小于50的透明性。
3.根据权利要求2所述的树脂成型品,电子射线照射后的对甲苯不溶的成分是50~99重量%。
4.根据权利要求3所述的树脂成型品,成型品形态是选自管、片、膜、袋及插接件的至少1种。
5.根据权利要求4所述的树脂成型品,为医疗用途。
6.根据权利要求5所述的树脂成型品,卤素原子的含量等于50ppm或小于50ppm。
7.根据权利要求1所述的树脂成型品,电子射线照射后的对甲苯不溶的成分是50~99重量%。
8.根据权利要求7所述的树脂成型品,具有2mm片的浊度值为等于50或小于50的透明性。
9.根据权利要求8所述的树脂成型品,为医疗用途。
10.根据权利要求9所述的树脂成型品,卤素原子的含量等于50ppm或小于50ppm。
11.根据权利要求1所述的树脂成型品,成型品形态是选自管、片、膜、袋及插接件的至少1种。
12.根据权利要求11所述的树脂成型品,为医疗用途。
13.根据权利要求12所述的树脂成型品,卤素原子的含量等于50ppm或小于50ppm。
14.根据权利要求1所述的树脂成型品,卤素原子的含量等于50ppm或小于50ppm。
15.根据权利要求1所述的树脂成型品,为医疗用途。
16.一种加工品,是加工树脂成型品而得到的;
其中所述的树脂成型品,是用电子射线照射含有(A)熔点为50~130℃、晶化度为10~40%、1,2-键含有量为等于70%或大于70%的间规1,2-聚丁二烯100~60重量份、以及(B)从聚丙烯、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、它们的氢化物、上述间规1,2-聚丁二烯以外的聚丁二烯、丙烯腈-丁二烯-苯乙烯树脂、聚异戊二烯、聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸酯共聚物、以及乙烯-甲基丙烯酸共聚物中选择的至少1种热塑性聚合物0~40重量份的树脂成型品而得到的成型品,其中,(A)+(B)=100重量份,
电子射线照射量用电子射线加速电压和照射射线量的积表示是2~1000000kV·Mrad,其中加速加压的单位是kV,照射射线量的单位是Mrad,
电子射线照射后的成型品的50%应力的50%M:M2是电子射线照射前的50%应力的50%M:M1的1.01~2.5倍,且具有耐蒸汽灭菌性。
17.根据权利要求16所述的加工品,为食品用途、鞋类用途、车辆用途、电线包覆用途、或者医疗用途。
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CN101365726B (zh) * | 2005-12-09 | 2011-08-10 | Jsr株式会社 | 可紫外固化聚合物组合物、树脂模塑制品和它们的制备方法 |
US20080136064A1 (en) * | 2006-12-12 | 2008-06-12 | Husky Injection Molding Systems Ltd. | Molding apparatus and a molding method |
DE102007050582B4 (de) * | 2007-10-23 | 2018-09-06 | Khs Corpoplast Gmbh | Verfahren und Vorrichtung zum Sterilisieren sowie Vorrichtung zur Blasformung von Behältern |
CN102187114A (zh) | 2008-08-14 | 2011-09-14 | 凡士通工业产品公司 | 进行重复变形的橡胶制品和制造其的组合物 |
CN101735402B (zh) * | 2008-11-07 | 2011-06-22 | 中国石油天然气股份有限公司 | 一种间规聚1,2-丁二烯热塑性弹性体的制备方法 |
KR101425208B1 (ko) * | 2011-03-14 | 2014-08-01 | 주식회사 나다이노베이션 | 플라스틱 사출 성형물의 표면 개질 방법 |
US8679607B2 (en) * | 2012-07-12 | 2014-03-25 | 3M Innovative Properties Company | Foamable article |
KR101931585B1 (ko) * | 2016-03-18 | 2019-02-26 | 주식회사 엘지화학 | 열가소성 수지 조성물 및 이로부터 제조된 성형품 |
CA3069155A1 (en) | 2017-07-11 | 2019-01-17 | Sustained Nano Systems Llc | Radiation sterilization of hypercompressed polymer dosage forms |
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US6187400B1 (en) * | 1996-05-03 | 2001-02-13 | Baxter International Inc. | Medical tubing and pump performance enhancement by ionizing radiation during sterilization |
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US7011872B2 (en) * | 2001-08-24 | 2006-03-14 | Baxter International Inc. | Method and process for enhancing properties and medical tubing performance in a polybutadiene material |
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