CN1898304A - 聚丁二烯成型品的粘接方法、用该法制得的聚丁二烯复合成型品、医疗用构件与输液装置 - Google Patents
聚丁二烯成型品的粘接方法、用该法制得的聚丁二烯复合成型品、医疗用构件与输液装置 Download PDFInfo
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- CN1898304A CN1898304A CNA2004800389669A CN200480038966A CN1898304A CN 1898304 A CN1898304 A CN 1898304A CN A2004800389669 A CNA2004800389669 A CN A2004800389669A CN 200480038966 A CN200480038966 A CN 200480038966A CN 1898304 A CN1898304 A CN 1898304A
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- molded article
- polybutadiene
- resin
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- water contact
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Abstract
提高聚丁二烯成型品与极性树脂成型品的接合(粘接)力,而且通过选择(组合)这些成型品的溶剂进一步提高接合力。聚丁二烯成型品的粘接方法,其包含:(1)对聚丁二烯成型品进行臭氧处理、电子射线处理、电晕放电处理、等离子体放电处理、紫外线激光处理、或化学处理从而减小该成型品表面的水接触角的工序,和(2)将水接触角被减小的聚丁二烯成型品与极性树脂成型品进行粘接的工序。
Description
技术领域
本发明涉及聚丁二烯成型品的粘接方法、用该法制得的聚丁二烯复合成型品、医疗用构件与输液装置。
技术背景
近年来,间同立构1,2-聚丁二烯(RB)所代表的聚丁二烯作为不使用增塑剂的PVC(氯乙烯系树脂)替代材料引人注目,本发明者们提出了将RB管与RB管接头粘接的医疗用构件(专利文献1:特开2004-321788号公报)等。
输液装置将管与管接头进行溶剂接合(粘接)已商品化。迄今,作为上述输液装置,使用PVC管/溶剂(极性溶剂)/极性树脂管接头已商品化。但是,近年来脱PVC的趋势显著,如上所述研究RB代替PVC管在增长。但是,RB缺乏极性,根据用途有时使用极性溶剂/极性树脂的接合不充分。
特别是在日本、美国,使用输液装置给患者点滴时,有时使用泵,这种场合由于对输液装置施加压力,因此有可能从例如管与管接头的接合部产生漏液。
专利文献1:特开2004-321788号公报
发明内容
本发明的目的在于提高聚丁二烯成型品与极性树脂成型品的接合(粘接)力,而且通过选择(组合)这些成型品的溶剂,进一步提高接合力。
本发明涉及聚丁二烯成型品的粘接方法,其包含:
(1)使聚丁二烯成型品表面的水接触角减小的工序(以下也称为“(1)工序”),和
(2)将上述水接触角被减小的聚丁二烯成型品与极性树脂成型品粘接的工序(以下也称为“(2)工序”)。
其中,作为上述聚丁二烯,优选结晶度大于等于5%的间同立构1,2-聚丁二烯。
另外,作为上述(1)工序,可举出选自臭氧处理、电子射线处理、电晕放电处理、等离子体放电处理、放射线(X射线、γ射线、β射线)处理、紫外线处理、紫外线激光处理和化学处理的至少1种。
由上述(1)工序得到的水接触角被减小的聚丁二烯成型品的水接触角(CABR)小于等于80度。
作为上述极性树脂,可举出选自聚碳酸酯树脂、聚酯树脂、ABS树脂、聚苯乙烯树脂、聚氨酯树脂、聚酰胺树脂、聚丙烯酸烷基酯树脂、聚甲基丙烯酸烷基酯树脂、聚醋酸乙烯酯树脂、聚氯乙烯和聚偏氯乙烯树脂的至少1种。
由上述(1)工序得到的水接触角被减小的聚丁二烯成型品的水接触角(CABR)与极性树脂成型品的水接触角(CAPR)之差(ΔCA)是+60度~-15度。
作为上述(2)工序中的粘接,优选使用有机溶剂的粘接。
作为上述有机溶剂,可优选举出选自环己酮、四氢呋喃、环己烷、甲基乙基酮、丙酮和醋酸乙酯的至少1种。
(2)工序中的粘接时,优选预先使用上述有机溶剂对由(1)工序得到的水接触角被减小的聚丁二烯成型品和极性树脂成型品进行处理。
其次,本发明涉及采用上述聚丁二烯成型品的粘接方法得到的聚丁二烯复合成型品。
另外,本发明还涉及至少包含上述聚丁二烯复合成型品的医疗用构件。
此外,本发明还涉及以上述医疗用构件为构成要素的输液装置。
根据本发明,通过在上述聚丁二烯成型品的表面移植极性基团,或进行粗面化,通过减小聚丁二烯成型品表面的水接触角从而提高与极性树脂成型品的接合(粘接)力,另外,通过选择(组合)这些成型品的溶剂,可进一步提高接合力。
附图说明
图1是以本发明的聚丁二烯复合成型品(医疗用构件)为构成要素的输液装置的平面图。
图2(a)是管接头的简略图,(b)是管的简略图。
符号说明
10-输液装置,11-点滴筒,12-输液袋,13-穿刺针,14-输液排出用管,15-连接构件(管接头),16-帽,17-滚珠,18-夹子,19-接合构件,T1、T2-管。
具体实施方式
聚丁二烯成型品
作为构成本发明的管等聚丁二烯成型品的聚丁二烯,优选单独使用(A)间同立构1,2-聚丁二烯,或使用(A)间同立构1,2-聚丁二烯与(B)其他热塑性聚合物的组合物。该(A)间同立构1,2-聚丁二烯是具有结晶度大于等于5%、优选10~40%的结晶性的间同立构1,2-聚丁二烯,其熔点优选在50~150℃,更优选在60~140℃的范围。由于结晶度、熔点在该范围,故成为拉伸强度、撕裂强度等力学强度与柔软性的平衡性优异的结果。
应予说明,结晶度在5~25质量%左右的间同立构1,2-聚丁二烯(以下也称为“低结晶RB”)由于柔软性优异,故可作为管主体使用。然而这种低结晶度RB由于熔点低(熔点=约70~95℃),故耐蒸汽灭菌性差。因此,如后所述,优选使用电子射线照射使之交联从而赋予耐热性。
另一方面,结晶度在25~40质量%左右的间同立构1,2-聚丁二烯(以下也称为“高结晶RB”),虽然熔点比较高(熔点=约105~140℃),而另一方面由于硬度高且柔软性差,故可优选作为管接头使用。
本发明使用的(A)间同立构1,2-聚丁二烯,例如是1,2-结合含量大于等于70%的聚丁二烯,例如是在含有钴化合物与铝氧烷的催化剂存在下,将丁二烯聚合得到的聚丁二烯,但并不限定于该制造方法。
本发明使用的(A)间同立构1,2-聚丁二烯的丁二烯结合单元中的1,2-结合含量通常是大于等于70%,优选大于等于80%,更优选是大于等于90%。由于1,2-结合含量为大于等于70%,可发挥该1,2-聚丁二烯作为良好的热塑性弹性体的性质。
本发明使用的(A)间同立构1,2-聚丁二烯,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,可举出1,3-戊二烯、被高级烷基取代的1,3-丁二烯衍生物、2-烷基取代-1,3-丁二烯等。
其中,作为被高级烷基取代的1,3-丁二烯衍生物,可举出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。
其中,2-烷基取代-1,3-丁二烯的代表例,可举出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。这些共轭二烯中,作为与丁二烯共聚的优选的共轭二烯,可举出异戊二烯、1,3-戊二烯。供于聚合的单体成分中的丁二烯含量优选大于等于50摩尔%,特别优选大于等于70摩尔%。
本发明中使用的(A)间同立构1,2-聚丁二烯,如上所述,例如可在含有钴化合物与铝氧烷的催化剂存在下,将丁二烯聚合制得。作为上述钴化合物,可优选举出大于等于C4的钴的有机酸盐。作为这种钴的有机酸盐的具体例,可举出丁酸盐、己酸盐、庚酸盐、2-乙基己酸盐等辛酸盐、癸酸盐,硬脂酸、油酸、芥酸等的高级脂肪酸盐,苯甲酸盐、甲基苯甲酸盐、二甲基苯甲酸盐、乙基苯甲酸盐等烷基、芳烷基、烯丙基取代苯甲酸盐,萘甲酸盐、烷基、芳烷基或烯丙烯取代萘甲酸盐。其中,2-乙基己酸盐的所谓辛酸盐、硬脂酸盐、苯甲酸盐由于在烃溶剂中的优异溶解性而优选。
作为上述铝氧烷,可举出例如下述通式(I)或通式(II)表示的铝氧烷。
该通式(I)或(II)表示的铝氧烷中,R是甲基、乙基、丙基、丁基等烃基,优选是甲基、乙基,特别优选是甲基。另外,m是大于等于2,优选大于等于5,更优选是10~100的整数。作为铝氧烷的具体例,可举出甲基铝氧烷、乙基铝氧烷、丙基铝氧烷、丁基铝氧烷等,特别优选甲基铝氧烷。
聚合催化剂,除了上述钴化合物与铝氧烷以外,特别优选含有膦化合物。膦化合物是对聚合催化剂的活化、乙烯基结合结构与结晶性的控制有效的成分,可优选举出下述通式(III)表示的有机磷化合物。
P(Ar)n(R′)3-n (III)
通式(III)中,Ar表示下述所示的基团。
(上述基团中,R1、R2、R3相同或不同,表示氢原子、碳数优选1~6的烷基、卤素原子、碳数优选1~6的烷氧基或碳数优选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。
作为通式(III)表示的膦化合物,具体地可举出三(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。其中,作为特别优选例,可举出三苯基膦、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,可以使用下述通式(IV)表示的化合物。
上述通式(IV)表示的化合物是氯化钴的配体具有上述通式(III)中n为3的膦化合物的络合物。使用这种钴化合物时可以使用预先合成的络合物,或者采用在聚合体系中使氯化钴与膦化合物接触的方法而使用。通过种种地选择络合物中的膦化合物,可以控制制得的间同立构1,2-聚丁二烯的1,2-结合的量、结晶度。
作为上述通式(IV)表示的钴化合物的具体例,可举出双(三苯基膦)二氯化钴、双[三(3-甲基苯基膦)]二氯化钴、双[三(3-乙基苯基膦)]二氯化钴、双[三(4-甲基苯基膦)]二氯化钴、双[三(3,5-二甲基苯基膦)]二氯化钴、双[三(3,4-二甲基苯基膦)]二氯化钴、双[三(3-异丙基苯基膦)]二氯化钴、双[三(3-叔丁基苯基膦)]二氯化钴、双[三(3,5-二乙基苯基膦)]二氯化钴、双[三(3-甲基-5-乙基苯基膦)]二氯化钴、双[三(3-苯基苯基膦)]二氯化钴、双[三(3,4,5-三甲基苯基膦)]二氯化钴、双[三(4-甲氧基-3,5-二甲基苯基膦)]二氯化钴、双[三(4-乙氧基-3,5-二乙基苯基膦)]二氯化钴、双[三(4-丁氧基-3,5-二丁基苯基膦)]二氯化钴、双[三(4-甲氧基苯基膦)]二氯化钴、双[三(3-甲氧基苯基膦)]二氯化钴、双[三(4-十二烷基苯基膦)]二氯化钴、双[三(4-乙基苯基膦)二氯化钴等。
其中,作为特别优选的例,可举出双(三苯基膦)二氯化钴、双[三(3-甲基苯基膦)]二氯化钴、双[三(3,5-二甲基苯基膦)]二氯化钴、双[三(4-甲氧基-3,5-二甲基苯基膦)]二氯化钴等。
催化剂的使用量,在丁二烯均聚时每1摩尔丁二烯,在进行共聚时每1摩尔丁二烯与丁二烯以外的共轭二烯的合计量,按钴原子换算使用钴化合物0.001~1毫摩尔,优选使用0.01~0.5毫摩尔左右。另外,膦化合物的使用量,作为磷原子与钴原子的比(P/Co),通常是0.1~50,优选0.5~20,更优选是1~20。此外,铝氧烷的使用量,作为铝原子与钴化合物的钴原子的比(Al/Co),通常是4~107,优选是10~106。使用通式(IV)表示的络合物时,膦化合物的使用量使磷原子与钴原子的比(P/Co)为2,铝氧烷的使用量按照上述的记载。
作为聚合溶剂使用的惰性有机溶剂,可举出例如苯、甲苯、二甲苯、异丙苯等芳香族烃溶剂,正戊烷、正己烷、正丁烷等脂肪族烃溶剂,环戊烷、甲基环戊烷、环己烷等脂环族烃溶剂与这些的混合物。
聚合温度通常是-50~120℃,优选是-20~100℃。
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质量%,优选是10~35质量%。
另外,为了制造聚合物,为了不使本发明的催化剂与聚合物失去活性,必须考虑极力设法不使聚合体系内混入氧、水或二氧化碳等具有失活作用的化合物。如果聚合反应进行到了所期望的阶段,可以对反应混合物添加醇、其他聚合终止剂、防老剂、抗氧剂、紫外线吸收剂等,然后按照通常的方法将生成聚合物进行分离、洗涤、干燥,制得本发明使用的间同立构1,2-聚丁二烯。
本发明使用的(A)间同立构1,2-聚丁二烯的重均分子量优选是1万~500万,更优选1万~150万,特别优选是5万~100万。重均分子量低于1万时流动性极高,加工变得非常困难,并且由于成型品(医疗用构件)发粘而不优选,另一方面,超过500万时流动性极低,加工变得非常困难而不优选。
另一方面,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,具体地是选自聚乙烯、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)、这些的氢化物(SEBS、SEPS)、上述间同立构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-醋酸乙烯酯共聚物、乙烯-丙烯酸酯共聚物、和乙烯-甲基丙烯酸共聚物的至少1种。
(B)成分的混配量,在(A)~(B)成分的合计量100质量份中是小于等于40质量份,优选是0~35质量份。超过40质量份时,(A)成分的使用比例变少,失去(A)成分本来的柔软性。
在本发明使用的组合物中,除了上述(A)~(B)成分以外,根据需要可以含有润滑剂、填充剂或发泡剂等添加剂。作为上述添加剂的具体例,可举出石蜡油、硅油、液体聚异戊二烯、液体聚丁二烯、芥酸酰胺、硬脂酰胺等润滑剂,滑石、二氧化硅、氢氧化镁、碳酸钙、玻璃、碳纤维、玻璃中空小球等填充剂,和松本油脂公司制的微球体、ADCA、OBSH、碳酸氢钠、AIBN等发泡剂。
润滑剂的使用量,相对于树脂成分即(A)~(B)成分的合计100质量份是小于等于10质量份,优选是0.01~8质量份。超过10质量份时,润滑剂从制品中析出,由于溶解于使用药剂中而不优选。
另外,为了提高电子射线照射产生的耐热性与柔软性的平衡性,可以相对于间同立构1,2-聚丁二烯100质量份含有小于等于5质量份的其他添加剂,例如三甲基丙烷三甲基丙烯酸酯等多官能单体、羟基环己基苯基酮等光聚合引发剂、二苯甲酮等光增感剂等。
组合物的制备与成型
用于本发明聚丁二烯成型品的组合物,将上述(A)成分单独或(A)~(B)成分,根据需要再向其添加上述添加剂等,加热软化,混炼成型。混炼与成型在间同立构1,2-聚丁二烯的软化温度乃至熔融温度以上的成型性良好的温度范围进行,加工成均质的成型品(管等医疗用构件)。因此成型温度优选90~170℃左右。为了制得管、管接头等成型品,采用加压成型、挤出成型、注射成型、吹塑成型、异型挤出成型、T形模头薄膜成型、吹塑薄膜成型、粉末搪塑成型、旋转成型等,成型加工成管等、具有管连接部的管接头。
电子射线照射
本发明的聚丁二烯成型品中,因为管必须具有柔软性,故使用低结晶RB,但因为熔点低,为了体现耐蒸汽灭菌性,可以接着照射电子射线进行交联。照射电子射线时通过间同立构1,2-聚丁二烯的乙烯基的自由基聚合而成为三维交联结构,对成型品(管)赋予耐热性。电子射线对合成树脂具有透过性,其透过的程度依赖于成型品的厚度和电子射线的动能。
按照其照射厚度调节电子射线的能量使之沿厚度方向能均匀地透过,可成为厚度方向均匀地形成交联度的成型品(管)。
对管接头也可以进行电子射线照射。
另外,电子射线照射可以在管与管接头的粘接前,也可以在粘接后。
电子射线能量对于上述管等聚丁二烯成型品(医疗用构件),优选使电子射线加速电压为50~3000kV,更优选为300~2000kV,小于50kV时,在表层部捕获吸收的电子的比例相对增多,透过成型品的电子射线减少,内部的交联比表层部慢,由于交联度产生差别而不优选。另一方面,大于3000kV时,交联度过大,成为硬质的同时弹性、伸长率变小而不优选。
另外,此时的电子射线的照射量优选1~100Mrad(SI单位系,相当于10~1000kGy),更优选在1~50Mrad的范围进行照射使之交联固化。小于1Mrad时,1,2-聚丁二烯的交联度小,而大于100Mrad时,交联度过大而成为硬质,因此弹性、伸长率小而不优选。
电子射线照射产生的交联可以用电子射线加速电压和照射量的积表示,在本发明中,优选使电子射线加速电压(kV)和照射量(Mrad)的积为2000~20000(kV·Mrad),更优选为5000~16000(kV·Mrad)。如果比2000(kV·Mrad)小,在表层部捕获吸收的电子的比例相对增多,透过聚丁二烯成型品(医疗用构件)的电子射线减少,内部的交联比表层部慢,交联度产生差异,因此不优选。另一方面,如果大于20000(kV·Mrad),交联度过大而成为硬质,所以弹性、伸长率小,因此不优选。
通过对本发明的聚丁二烯成型品(管等医疗用构件)实施上述的电子射线照射,可优选使电子射线照射后的医疗用构件在50%伸长率下的弹性模量(M250)为电子射线照射前在50%伸长率下的弹性模量(M150)的1.1~2.5倍,更优选可成为1.1~2.0倍。M250/M150低于1.1时,不进行电子射线交联,耐蒸汽灭菌性差,而超过2.5时,交联的聚丁二烯成型品(管等医疗用构件)过硬,失去柔软性而不优选。通过使上述电子射线加速电压(kV)与照射量(Mrad)之积为2000~20000(kV·Mrad),可以容易地调节M250/M150。
另外,这样制得的电子射线照射后的交联的管等聚丁二烯成型品(医疗用构件)具有耐蒸汽灭菌性,例如,使用本发明的交联的输液管,即使是在100~121℃下蒸汽灭菌10~20分钟左右也不会变形。
其中,所谓耐蒸汽灭菌性,具体地讲意味着:把输液管等树脂成型品(例如,内径φ3mm、外径φ4.4mm、壁厚0.7mm的管,管长20cm)放入高压蒸汽灭菌器中,在121℃下进行蒸汽灭菌20分钟时,仍保持灭菌前的圆形,没有观察到变形。
此外,本发明的照射了电子射线的聚丁二烯成型品(管等医疗用构件)的雾度值优选小于等于30,更优选小于等于25。雾度值是透明性的尺度,雾度值愈小则透明性愈好。该雾度值按照ASTM D-1003进行测定。
另外,电子射线照射后的本发明的聚丁二烯成型品(管等医疗用构件),甲苯不溶成分通常是50~99质量%,优选是80~95质量%。甲苯不溶成分是表示通过对该聚丁二烯成型品进行电子射线照射,(A)间同立构1,2-聚丁二烯中的双键进行何种程度交联的晴雨表。
其中,甲苯不溶成分是使本发明的聚丁二烯成型品(医疗用构件)[(a)g]浸渍在100ml的甲苯中,在30℃下放置48小时后,使用100目金属网过滤,取过滤液的一部分[(c)ml]后,使之蒸发干燥固化,称量所得的残留固体成分[甲苯可溶成分:(b)g],按下式算出凝胶含量。
凝胶含量(质量%)=[{a-b×(100/c)}/a]×100
甲苯不溶成分低于50质量%时,电子射线照射产生的交联不充分,耐热性差,耐蒸汽灭菌性差。而超过99质量%时,电子射线照射产生的交联过多,医疗用构件过硬,失去柔软性而不优选。
上述甲苯不溶成分,通过使上述电子射线加速电压(kV)与照射量(Mrad)之积为2000~20000(kV·Mrad)可容易地进行调节。
此外,本发明的聚丁二烯成型品(管等医疗用构件),卤素原子的含量优选小于等于200ppm,更优选小于等于100ppm。该卤素原子的含量,例如,如上所述通过使用非卤素系的惰性有机溶剂作为聚合溶剂,可使所得1,2-聚丁二烯中的卤素原子的含量优选小于等于200ppm,更优选小于等于100ppm。另外,在催化剂体系中只使用非卤素系的化合物可进一步降低聚丁二烯成型品(医疗用构件)中的卤素原子的含量,因此优选。
这样进行了电子射线照射的聚丁二烯成型品柔软性与硬度优异,而且具有耐蒸汽灭菌性,故除管外也用于管接头。
本发明使用的所谓聚丁二烯成型品,是指上述的1,2-聚丁二烯制成的管、1,2-聚丁二烯与苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)的共混物制成的管、1,2-聚丁二烯与橡胶的共混物制成的管、1,2-聚丁二烯与烯烃树脂的共混物制成的管。其中,对于与苯乙烯-异戊二烯-苯乙烯嵌段共聚物的组合,可以是氢化的苯乙烯-乙烯-丙烯-苯乙烯,也可以是部分氢化品。对于与橡胶的组合可以使用各种橡胶,但优选异戊二烯橡胶与天然橡胶。对于与烯烃树脂的组合,可举出LDPE、L-LDPE、EVA作为优选的树脂。
极性树脂
其次,用于本发明极性树脂成型品的极性树脂,作为热塑性塑料,可举出ABS树脂、聚苯乙烯树脂、丙烯酸类树脂、聚丙烯酰胺、聚丙烯酸、聚丙烯酸甲酯、聚丙烯酸乙酯等聚丙烯酸烷基酯、聚丙烯腈、丙烯腈-苯乙烯共聚物、聚甲基丙烯酰胺、聚甲基丙烯酸、聚甲基丙烯酸甲酯树脂、聚甲基丙烯酸乙酯树脂等聚甲基丙烯酸烷基酯、聚氨酯树脂、聚甲基丙烯腈、缩醛树脂、聚甲醛、离子键聚合物、氯化聚乙烯、香豆酮-茚树脂、再生纤维素、石油树脂、纤维素衍生物、碱纤维素、纤维素酯、醋酸纤维素、醋酸丁酸纤维素、黄原酸纤维素、硝酸纤维素、纤维素醚、羧甲基纤维素、纤维素醚酯、氟树脂、FEP、聚三氟氯乙烯、聚四氟乙烯、聚偏氟乙烯、聚氟乙烯、尼龙11、尼龙12、尼龙6、尼龙6,10、尼龙6,12、尼龙6,6、尼龙4,6等聚酰胺树脂、聚间苯二甲酰间苯二胺、聚对苯二甲酰对苯二胺、间苯二甲胺等芳香族聚酰胺、聚酰亚胺、聚苯硫醚、聚醚醚酮、聚酰胺酰亚胺、聚芳酯、聚对苯二甲酸乙二醇酯等聚酯树脂、聚氯乙烯、聚偏氯乙烯树脂、氯化聚乙烯、氯磺化聚乙烯、聚碳酸酯、CR-39、聚磺、聚醚砜、聚磺酰胺、聚乙烯醇、聚乙烯基酯、聚肉桂酸乙烯酯、聚醋酸乙烯酯、聚乙烯基醚、聚异丁基乙烯基醚、聚甲基乙烯基醚、聚苯醚、聚对苯二甲酸丁二醇酯等,而作为热固性塑料,可举出氨基树脂、苯胺树脂、尿素树脂、三聚氰胺树脂、烯丙基树脂、邻苯二甲酸二烯丙酯树脂、醇酸树脂、环氧树脂、硅树脂、乙烯基酯树脂、酚醛树脂、酚醛清漆树脂、间苯二酚树脂、不饱和聚酯树脂、低收缩不饱和聚酯、呋喃树脂等。
其中,优选的极性树脂可举出聚碳酸酯树脂、聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯等聚酯树脂、ABS树脂、聚苯乙烯树脂、聚丙烯酸树脂、聚氨酯树脂、聚酰胺树脂、聚醋酸乙烯酯树脂、聚氯乙烯树脂和聚偏氯乙烯树脂。
极性树脂的溶解度参数(SP值)优选9~13,更优选是9.5~12。
其中,溶解度参数是采用John Wiley & Son公司出版的“聚合物手册”1999年、第4版、部分VII第682~685页所述的基团贡献法,使用Small的基团参数算出的值。例如,聚甲基丙烯酸甲酯(重复单元分子量100g/摩尔,密度=1.19g/cm3(以下省略单位))是9.25(cal/cm3)1/2,聚丙烯酸丁酯(重复单元分子量128,密度1.06)是8.97(cal/cm3)1/2,聚甲基丙烯酸丁酯(重复单元分子量142,密度1.06)是9.47(cal/cm3)1/2,聚苯乙烯(重复单元分子量104,密度1.05)是9.03(cal/cm3)1/2,聚丙烯腈(重复单元分子量53,密度1.18)是12.71(cal/cm3)1/2。各聚合物的密度使用VCH公司出版的“ULLMANN’S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY”1992年、第A21卷、第169页所述的值。另外,共聚物的溶解度参数δc,质量分率低于5%时使用主成分的值,质量分率大于等于5%时,加成性按质量分率成立。即,可由构成由m种类单体构成的共聚物的各个单体的均聚物的溶解度参数δn及其质量分率Wn,采用下式(1)算出。
例如,由75质量%苯乙烯与25质量%丙烯腈构成的共聚物的溶解度参数,使用聚苯乙烯的溶解度参数9.03(cal/cm3)1/2和聚丙烯腈的溶解度参数12.71(cal/cm3)1/2,代入式(1)中得到9.95(cal/cm3)1/2的值。
另外,采用大于等于2阶段并且在各阶段改变乙烯基系单体的种类将乙烯基系单体聚合得到的乙烯基系聚合物的溶解度参数δs,加成性按用各阶段得到的乙烯基系聚合物的质量除以最终得到的乙烯基系聚合物的总质量得到的值,即质量分率成立。即,采用q阶段进行聚合,可由各阶段得到的聚合物的溶解度参数δi及其质量分率Wi,采用下式(2)算出。
例如,采用2阶段进行聚合,第1阶段得到由75质量%苯乙烯与25质量%丙烯腈构成的共聚物50质量份,第2阶段得到甲基丙烯酸甲酯的聚合物50质量份时,这2阶段聚合得到的聚合物的溶解度参数,使用苯乙烯(75质量%)-丙烯腈(25质量%)共聚物的溶解度参数9.95和聚甲基丙烯酸甲酯的溶解度参数9.25(cal/cm3)1/2,代入式(2)中得到9.60(cal/cm3)1/2的值。
使溶解度参数在上述范围内时,接近臭氧处理、电子射线处理、电晕放电处理、等离子体放电处理、紫外线处理、紫外线激光处理和化学处理使水接触角减小的聚丁二烯复合成型品的水接触角,使用极性溶剂进行溶剂粘接时,产生获得高粘接强度的效果。
溶解度参数低于9时,极性溶剂产生的粘接力变得不充分而不优选。而超过13时药物吸附增强,不适于管接头用途。
作为满足这样的溶解度参数的极性树脂,可举出上述优选的极性树脂。
作为本发明使用的极性树脂成型品,可举出由上述各种极性树脂制成的管接头、输液装置辅助器具等。
本发明的聚丁二烯成型品的粘接方法包含:(1)通过首先对聚丁二烯成型品进行臭氧处理,在聚丁二烯成型品的表面引入后述所述的极性基团,接着(2)将经臭氧处理的聚丁二烯成型品与极性树脂成型品进行粘接的工序。
(1)工序(水接触角减小工序)
作为(1)工序,只要是使聚丁二烯成型品表面的水接触角减小的方法则可以采用任何方法,可举出例如臭氧处理、电晕放电处理、等离子体放电处理、受激准分子激光处理、电子射线处理、紫外线处理、或化学处理。
臭氧处理:
臭氧处理通过将聚丁二烯成型品暴露在臭氧中进行。暴露方法可采用在臭氧存在的气氛中将聚丁二烯成型品保持设定时间的方法、在臭氧气流中暴露设定时间的方法等适宜的方法进行。
其中,可以通过将空气、氧气、或添加氧的空气等含有氧的气体供给到臭氧发生装置(紫外线照射装置等)产生臭氧。把制得的含有臭氧的气体导入装有聚丁二烯成型品的容器、槽等中进行臭氧处理。含有臭氧的气体中的臭氧浓度、暴露时间、暴露温度的诸条件可根据极性树脂成型品种类和表面改性的目的适当地决定。
臭氧处理的条件因聚丁二烯成型品的形状等而不同。可使用氧或空气的气流,以流量20~2000ml/分产生浓度1~200mg/l的臭氧,在温度0~80℃处理1分钟~24小时。例如,以臭氧浓度10~80mg/l、室温下、20~30分钟左右的处理是适当的。此外,膜形状的场合,以臭氧浓度1~20mg/l左右、室温下、30分钟~6小时左右的处理是适当的。使用了空气时的产生臭氧浓度为使用了氧时的约50%。
经臭氧处理,推定在聚丁二烯成型品表面通过以氧化为主的反应引入过碳酸基(-C-O-OH),其一部分变成羟基(-OH)、羰基(C=O)等官能团。
电子射线处理:
电子射线处理使用具有电子射线加速器的电子射线照射装置代替上述臭氧发生装置,通过对拟处理的聚丁二烯成型品的表面照射电子射线加速器发生的电子射线实施处理。作为上述电子射线照射装置,例如,可以使用能由线状的灯丝呈帘状照射均匀的电子射线的装置(例如电幕型的装置)等。此时的电子射线照射量通常是大于等于0.5Mrad,优选大于等于1.5Mrad,更优选大于等于3Mrad。电子射线照射量针对电子射线照射装置入口侧的处理膜的线速度设定,其上限没有特殊限定,但通常是20Mrad左右。
电晕放电处理:
电晕处理,通过使用例如公知的电晕放电处理器,使拟处理的聚丁二烯成型品在惰性气体中产生的电晕气氛中通过而进行。此时的电晕放电密度通常是大于等于10(W·分/m2),优选是30~300(W·分/m2)。作为上述惰性气体,可举出氩、氦、氪、氖、氙、或氮的单独或这些的2种或多种的混合气体,工业上特别优选氮。上述惰性气体,可在气体中的氧浓度小于等于1容量%、优选小于等于0.1容量%、更优选小于等于0.01容量%的范围内含有氧。
等离子体处理:
等离子体处理包括低压等离子体处理和大气压等离子体处理。低压等离子体处理,可通过在0.1~5托的低压状态下以200~1000W的输出功率采用等离子喷射使上述惰性气体电子激发后,除去带电粒子,使成为电中性的激发惰性气体与拟处理的聚丁二烯成型品接触而实施。此时的处理时间是10~60秒,优选是20~40秒。
此外,大气压等离子体处理,可通过在上述惰性气体中在电极间外加3~5kHz、2~3000V的交流电流,发生与低压等离子体处理同样的激发惰性气体后,使该激发惰性气体与拟处理的聚丁二烯成型品接触而实施。此时的处理时间是10~60秒,优选20~40秒。
紫外线激光处理:
作为紫外线激光,有具有180~360nm、优选190~250nm振荡波长的激光,优选是受激准分子激光。受激准分子激光使用的气体有KrF、KrCl、ArF、ArCl、F2等,各自具有固有的振荡波长。例如,ArF激光有192nm的振荡波长,光子能量是148Kcal。因此,可以切断键能为100~110Kcal的C-H键,通过受激准分子激光照射而激发的氢容易被引发,通过取而代之共存的空气中的氧等,可以引入例如羰基、羧基、羟基等。
受激准分子激光的照射量,作为能量密度是15~25mJ/cm2,优选是18~22mJ/cm2。即,能量密度低于15mJ/cm2时,难得到所期望的亲水性,而即使超过25mJ/cm2,不仅亲水性不相应地提高,反而作为基材的聚丁二烯成型品的表面粗糙。
化学处理:
所谓化学处理,是对聚丁二烯成型品进行蚀刻或劣化处理或者在表面引入官能团的处理,作为化学处理的具体例,可举出对该成型品采用过氧化氢等的过氧化物处理,采用硝酸、盐酸、硫酸、铬酸、高锰酸钾溶液等无机酸的处理,采用氯化铝、氯化铁的甲苯等的溶液的处理等。
作为化学处理的条件,在酸性、中性、碱性溶剂(包含水)下使聚丁二烯成型品与2~50质量%浓度的硝酸、盐酸、硫酸、铬酸、高锰酸钾的任何一种浸渍5分钟~48小时进行氧化。根据需要也可以采用加热到30~50℃的方法。
以上的(1)工序,可以单独地或组合使用上述臭氧处理、电子射线处理、电晕放电处理、等离子体放电处理、紫外线激光处理或化学处理。
例如,(1)工序,从减小聚丁二烯成型品的水接触角的方面考虑,优选在臭氧的存在下进行紫外线激光处理。
采用上述(1)工序可减小聚丁二烯成型品表面的水接触角。
其理由如上所述,推测是通过这些处理在聚丁二烯成型品的表面上引入例如羰基、羧基、羟基、醛基等极性基团,或通过使该表面粗面化从而减小水接触角。
其中,水接触角可以使用市售的自动接触角计,例如协和界面科学公司制的自动接触角计测定在处理过的板状的聚丁二烯成型品上静静地放置一滴水时的接触角。
经(1)工序处理的聚丁二烯成型品的水接触角通常是小于等于80度,优选小于等于75度,更优选是10度~70度。超过80度时,与极性树脂成型品的粘接差,而且发生不能使用极性溶剂的问题。
上述极性树脂的水接触角通常是80度~20度,优选78度~30度,更优选是75度~40度。
因此,经(1)工序得到的水接触角被减小的聚丁二烯成型品的水接触角(CABR)与极性树脂成型品的水接触角(CAPR)之差(ΔCA)通常是+60度~-15度,优选+60度~-10度,更优选+60度~-5度,特别优选是+50度~0度。
聚丁二烯本身的溶解度参数通常是8.3~8.5,优选是8.4,而采用(1)工序处理后的聚丁二烯成型品的溶解度参数通常上升为9.0~12.0,优选上升为9.3~11.0,与上述极性树脂的溶解度参数接近。因此,(1)工序,通过使聚丁二烯与极性树脂的溶解度参数近似,也可以提高粘接性。
以上的(1)工序,使聚丁二烯成型品与极性树脂成型品粘接时适用于该聚丁二烯成型品,除此之外也可适用于极性树脂成型品。
在这种情况下,对极性树脂成型品的上述各处理的条件与聚丁二烯成型品相同。
(2)工序(粘接工序)
本发明中,接着把经(1)工序的处理,水接触角被减小的聚丁二烯成型品与极性树脂成型品进行粘接。
作为粘接方法,可举出粘接时不破坏透明性的溶剂粘接、超声波粘接、或高频粘接、使用了粘接剂的粘接(包括紫外线固化丙烯酸型瞬间粘接剂、氰基丙烯酸酯型瞬间粘接剂)等,优选是溶剂粘接。
其中,溶剂粘接是使用对聚丁二烯成型品和/或极性树脂成型品可溶解的有机溶剂粘接两者的方法。
溶剂粘接可以使用聚丁二烯成型品与极性树脂成型品通用的有机溶剂,也可以个别地使用对各个分别可溶的有机溶剂。
作为上述粘接用的有机溶剂,可举出四氢呋喃、环己烷、甲苯、环己酮、甲基乙基酮,丙酮、醋酸乙酯等。
作为该粘接的条件,可采用把聚丁二烯成型品与极性树脂成型品的粘接部位浸渍在粘接用溶剂中,或喷涂粘接溶剂,或使用毛刷、布端等涂布粘接溶剂等方法实施。
上述的各粘接时,优选使用上述粘接的通用的有机溶剂或将个别的有机溶剂组合使用,分别对聚丁二烯成型品和极性树脂成型品预先进行处理。
采用本发明,通过将(1)工序中采用臭氧处理等处理的管等聚丁二烯成型品与管接头等极性树脂成型品进行粘接,可制得粘接部位牢固地粘接的聚丁二烯复合成型品。
以下,利用图1对使用了本发明的聚丁二烯复合成型品(医疗用构件:管及具有管连接部的管接头)的输液装置更具体地进行说明。
该输液装置10具有与输液袋12内的输液排出用管14结合用的连接构件(管接头)15、将连接构件15与点滴筒11连接的第1管T1、连接点滴筒11与穿刺针13的第2管T2、调节输液速度用的夹子18、包盖穿刺针13的帽16。符号19是连接第2管T2与穿刺针13用的接合构件。
其中,作为穿刺针13,使用顶端具有穿刺用刀尖的中空不锈钢等制的金属针、合成树脂制针。另外,作为夹子18可使用滚珠夹,该滚珠夹具有设置成能移动的滚珠17,通过该滚珠17向穿刺针13侧的移动,第2管T2的流路变窄,可调节输液速度。点滴筒11内收容过滤器(未图示)以备万一输液剂等中含异物的场合。作为穿刺针13可以使用以往使用的穿刺针。
另外,本发明中,接合构件15、点滴筒11、接合构件19均相当于“具有管连接部的管接头”,均可使用聚碳酸酯、聚酯、透明ABS、聚氯乙烯等极性树脂。
另外,作为管T1、T2,优选具有透明性的软质管,具体地可以使用以往使用的软质氯乙烯树脂、结晶度5~25%左右的低结晶度的间同立构1,2-聚丁二烯,还可以使用对本发明的结晶度大于等于5%、优选结晶度5~25%左右的低结晶度的间同立构1,2-聚丁二烯进行了臭氧处理的间同立构1,2-聚丁二烯。
其中,管T1、T2的各顶端与结合构件15、点滴筒11、接合构件19(均相当于本发明中的管接头)的管连接部,采用溶剂粘接、超声波粘接或高频粘接紧密牢固地固定。
本发明中,由臭氧处理过的间同立构1,2-聚丁二烯制成的管,由于与聚碳酸酯制成的管接头粘接,故两者能紧密牢固地固定而不漏液。
其中,作为溶剂粘接的溶剂,如上所述可举出四氢呋喃、环己烷、环己酮、甲基乙基酮、丙酮、醋酸乙酯、甲苯等。
本发明中,由管与具有管接合部的管接头构成的医疗用构件,也适合作为上述的输液装置的构成要素、给药用导管等医疗用器具的构成要素使用。
实施例
以下,举出实施例更具体地说明本发明,但本发明不限定于以下的实施例。实施例中,份和%只要没有特殊说明则是质量基准。另外,
实施例中的各种测定如下。
片材的透明性
成型温度150℃
模具温度20℃
利用2mm厚注射成型片材的雾度判定。
雾度使用ガ一ドナ一公司制HAZE仪进行测定。
判定
小于3:○良好(有商品价值)
大于等于3小于5:△
大于等于5:×不良(无商品价值)
300%拉伸应力(柔软性评价)
按JIS3号哑铃形冲裁在成型温度150℃下制作的2mm厚加压成型片材,使用岛津制万能拉伸试验机AG10kNE测定应力,判定柔软性。
判定
小于5MPa:○良好(柔软性吸收振动,具有商品价值)
大于等于5MPa小于10MPa:△
大于等于10MPa:×不良(缺乏柔软性,传导振动,无商品价值)
臭氧处理和粘接试验用试验片的制作
使用日本制钢所公司制的注射成型机N-100,1,2-聚丁二烯[JSR公司制RB810(1,2-乙烯基结合含量=90%,密度=0.901×103kg/m3)]在成型温度130℃/模具温度20℃,聚酯树脂(伊士曼化学公司制Easter DN010)在成型温度270℃/模具温度30℃,聚碳酸酯树脂(三菱工程塑料公司制ュ一ピロンS-3000R)在成型温度270℃/模具温度30℃,ABS树脂(テクノ聚合物公司制テクノABS810)在成型温度240℃/模具温度30℃下分别成型宽20mm×长为100mm×厚2mm成型品,供给粘接试验用试验片。
臭氧处理
使用岩崎电气公司制的低压水银灯型OC2507(25W7灯),对预先实施了脱脂处理的JSR公司制的RB810试验片(宽20mm×长100mm×厚2mm)进行臭氧处理。臭氧处理使从水银灯到试验片表面的距离为20cm,照射时间为3分钟。此时,波长254nm的紫外线的强度是18mW/cm2,积分光量是7J/cm2。
接触角测定
使用ェルマ公司制的测角计式接触角测定器G1型,测定滴在试验片上的蒸馏水1μl的接触角。
粘接试验
在刚臭氧处理后与未处理试验片(JSR公司制的RB810,宽20mm×长100mm×厚2mm)上由1ml注射器滴加设定溶剂,与预先实施了脱脂处理的各种管接头片(宽20mm×长100mm×厚2mm)重合进行溶剂粘接。溶剂粘接部分使各试验片的端部为25mm×12.5mm的矩形,将2片成型片重合。溶剂粘接的试验片实施50℃×24小时热处理后,恢复到室温静置2小时后,使用岛津制作所公司制的万能拉伸试验机AG10kNE测定剪切强度。
判定
大于等于8kgf/cm2:○良好(有商品价值)
大于等于7~小于8kgf/cm2:△
小于7kgf/cm2:×不良(无商品价值)
药物吸附试验
药剂选用硝化甘油(浓度6μg/ml),测定以流速70ml/hr通过输液管内时经过1小时后的药剂残存率。
判定
残存率大于等于95%:○良好(有商品价值)
大于等于80%~小于95%:△
小于80%:×不良(无商品价值)
供于试验的管
将RB810(JSR公司制)、PVC(日本瑞翁公司制101EP/邻苯二甲酸二辛酯/环氧辅助增塑剂/有机锡稳定剂/硬脂酸锌=100/46/8/2/1)使用JSR研究所实验挤出机(池贝FS40(单螺杆40mm挤出机(L/D=28)))制造管(外径/内径/厚=3.7mm/3mm/0.7mm)。
实施例1、比较例1
把实施例1、比较例1示于表1。实施例1是对RB的试验片实施了臭氧处理的例。可知在1720cm-1存在羰基的吸收。可知由于赋予了极性基团故接触角得到改善成为32度,容易与作为极性溶剂的环己酮亲合,能与作为极性树脂的聚碳酸酯粘接,粘接力充分体现。
比较例1由于RB的试验片没有实施臭氧处理,故可知与极性溶剂、极性树脂的相容不令人满意,结果粘接力不足。
实施例2、比较例2
把实施例2、比较例2示于表1。实施例2是对RB的试验片实施了臭氧处理的例。可知在1720cm-1存在羰基的吸收。可知由于赋予了极性基团故接触角得到改善成为32度,容易与作为极性溶剂的环己酮亲合,能与作为极性树脂的透明ABS粘接,粘接力充分体现。
比较例2由于RB的试验片没有实施臭氧处理,故可知与极性溶剂、极性树脂的相容不令人满意,结果粘接力不足。
实施例3、比较例3
把实施例3、比较例3示于表1。实施例3是对RB的试验片实施了臭氧处理的例。可知在1720cm-1存在羰基的吸收。可知由于赋予了极性基团故接触角得到改善成为32度,容易与作为极性溶剂的环己酮亲合,能与作为极性树脂的聚酯粘接,粘接力充分体现。
比较例3由于对RB的试验片没有实施臭氧处理,故可知与极性溶剂、极性树脂的相容不令人满意,结果粘接力不足。
实施例1、比较例4
把实施例1、比较例4示于表1。实施例1是对RB的试验片实施了臭氧处理的例。可知在1720cm-1存在羰基的吸收。可知由于赋予了极性基团故接触角得到改善成为32度,容易与作为极性溶剂的环己酮亲合,能与作为极性树脂的聚碳酸酯粘接,粘接力充分体现。此外可知作为输液管用途重要的药物吸附性无,没有药剂的损失。
比较例4是使用了PVC的例,因此即使不实施臭氧处理,与极性溶剂、极性树脂的相容好,粘接强度优异。但作为输液管重要的药物吸附性高,药剂的残存量减少(有损失)而不优选。另外,PVC含有的增塑剂有可能对人体引起各种伤害,因此不优选。
实施例1、比较例5
把实施例1、比较例5示于表1。实施例1是对RB的试验片实施了臭氧处理的例。可知在1720cm-1存在羰基的吸收。可知由于赋予了极性基团故接触角得到改善成为32度,容易与作为极性溶剂的环己酮亲合,能与作为极性树脂的聚碳酸酯粘接,粘接力充分体现。此外,具有作为输液管用途重要的透明性(可确认药液的适当流动)、柔软性(300%拉伸应力:由于具有柔软性故与管接触的冲击不会传播到与人体相连的针上而优选),具有优异的特性。
比较例5是使用了PE的例,由于没有极性故与极性溶剂、极性树脂的相容差且缺乏粘接强度。另外,作为输液管重要的透明性、柔软性缺乏,不是优选的例。
表1
实施例1 | 比较例1 | 实施例2 | 比较例2 | 实施例3 | 比较例3 | 比较例4 | 比较例5 | |
1.管成型体2.管接头3.粘接溶剂 | RB处理品聚碳酸酯环己酮 | RB未处理品聚碳酸酯环己酮 | RB处理品透明ABS环己酮 | RB未处理品透明ABS环己酮 | RB处理品聚酯环己酮/THF混合溶剂 | RB未处理品聚酯环己酮/THF混合溶剂 | PVC聚碳酸酯环己酮 | PE聚碳酸酯环己酮 |
[评价结果](RB)成型体与水的接触角(度)粘接强度(kgf/cm2)刚经过药物吸附后的残存率(%)透明性雾度(%)300%拉伸应力(MPa) | 3212.21002.63.9 | 936.8 | 328.4 | 934.8 | 3215.3 | 9 37.4 | 661270 | 962.28.770 |
根据本发明,可提供在医疗用途中有用,接合部无液漏,而且柔软性和硬度优异,同时耐蒸汽灭菌性优异,可再循环利用,又不含氯乙烯系树脂从而对环境问题有利的以间同立构1,2-聚丁二烯为主体的医疗用构件和使用这种构件的医疗用器具。
Claims (12)
1.聚丁二烯成型品的粘接方法,其包含:(1)使聚丁二烯成型品表面的水接触角减小的工序、和(2)将上述水接触角被减小的聚丁二烯成型品与极性树脂成型品粘接的工序。
2.权利要求1所述的聚丁二烯成型品的粘接方法,其中聚丁二烯是结晶度大于等于5%的间同立构1,2-聚丁二烯。
3.权利要求1或2所述的聚丁二烯成型品的粘接方法,其中上述(1)工序是选自臭氧处理、电子射线处理、电晕放电处理、等离子体放电处理、紫外线激光处理和化学处理的至少1种。
4.权利要求1~3任何一项所述的聚丁二烯成型品的粘接方法,其中由上述(1)工序制得的水接触角被减小的聚丁二烯成型品的水接触角(CABR)小于等于80度。
5.权利要求1~4任何一项所述的聚丁二烯成型品的粘接方法,其中极性树脂是选自聚碳酸酯树脂、聚酯树脂、ABS树脂、聚苯乙烯树脂、聚氨酯树脂、聚酰胺树脂、聚丙烯酸烷基酯树脂、聚甲基丙烯酸烷基酯树脂、聚醋酸乙烯酯树脂、聚氯乙烯树脂和聚偏氯乙烯树脂的至少1种。
6.权利要求1~5任何一项所述的聚丁二烯成型品的粘接方法,其中由(1)工序制得的水接触角被减小的聚丁二烯成型品的水接触角(CABR)与极性树脂成型品的水接触角(CAPR)之差(ΔCA)是+60度~-15度。
7.权利要求1~6任何一项所述的聚丁二烯成型品的粘接方法,其中(2)工序中的粘接是使用有机溶剂的粘接。
8.权利要求1~7任何一项所述的聚丁二烯成型品的粘接方法,其中有机溶剂是选自环己酮、四氢呋喃、环己烷、甲基乙基酮、丙酮和醋酸乙酯的至少一种。
9.权利要求1~8任何一项所述的聚丁二烯成型品的粘接方法,其中预先使用权利要求8所述的有机溶剂对由(1)工序制得的水接触角被减小的聚丁二烯成型品和极性树脂成型品进行处理。
10.采用权利要求1~9任何一项所述的聚丁二烯成型品的粘接方法制得的聚丁二烯复合成型品。
11.至少包含权利要求10所述的聚丁二烯复合成型品的医疗用构件。
12.以权利要求11所述的医疗用构件为构成要素的输液装置。
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US (1) | US20080226930A1 (zh) |
EP (1) | EP1698654A4 (zh) |
KR (1) | KR20060123391A (zh) |
CN (1) | CN1898304A (zh) |
WO (1) | WO2005063859A1 (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101357552B (zh) * | 2007-07-30 | 2011-06-15 | 比亚迪股份有限公司 | 一种用于光固化涂层表面的印刷方法 |
CN102958989A (zh) * | 2010-06-29 | 2013-03-06 | 伊士曼化工公司 | 纤维素酯组合物和纤维素酯/弹性体组合物以及它们的制造方法 |
CN103189085A (zh) * | 2010-10-01 | 2013-07-03 | 莫门蒂夫性能材料股份有限公司 | 自润滑的药品注射器栓 |
CN104619757A (zh) * | 2012-05-07 | 2015-05-13 | 托马斯·尼克特压力处理有限责任公司 | 具有高表面能的聚合物表面及其制备方法 |
CN112156266A (zh) * | 2020-10-13 | 2021-01-01 | 湖南平安医械科技有限公司 | 一次性使用静脉留置针导管 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5391772B2 (ja) * | 2009-03-26 | 2014-01-15 | 富士ゼロックス株式会社 | 記録装置 |
US9782542B2 (en) * | 2009-10-01 | 2017-10-10 | Momentive Performance Materials Inc. | Self-lubricating pharmaceutical syringe stoppers |
US9708472B2 (en) | 2011-12-07 | 2017-07-18 | Eastman Chemical Company | Cellulose esters in highly-filled elastomeric systems |
WO2015124236A1 (en) * | 2014-02-20 | 2015-08-27 | Fresenius Hemocare Netherlands B.V. | Medical containers and system components with non-dehp plasticizers for storing red blood cell products, plasma and platelets |
US10077342B2 (en) | 2016-01-21 | 2018-09-18 | Eastman Chemical Company | Elastomeric compositions comprising cellulose ester additives |
Family Cites Families (13)
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BE524672A (zh) * | 1952-11-29 | 1900-01-01 | ||
US3333634A (en) * | 1965-06-29 | 1967-08-01 | Mobil Oil Corp | Secondary recovery method achieving high macroscopic and microscopic sweep efficiency |
US3928664A (en) * | 1973-01-17 | 1975-12-23 | Du Pont | Ozone treatment of elastomers |
US4144153A (en) * | 1975-10-03 | 1979-03-13 | Takiron Co., Ltd. | Radiation process for producing 1,2-polybutadiene foamed products |
US4422907A (en) * | 1981-12-30 | 1983-12-27 | Allied Corporation | Pretreatment of plastic materials for metal plating |
JPH02305834A (ja) * | 1989-03-15 | 1990-12-19 | Terumo Corp | 耐放射線性ポリブタジエン組成物 |
US5254390B1 (en) * | 1990-11-15 | 1999-05-18 | Minnesota Mining & Mfg | Plano-convex base sheet for retroreflective articles |
JP2000129017A (ja) * | 1998-10-22 | 2000-05-09 | Terumo Corp | 医療用部材およびその製造方法 |
JP3884588B2 (ja) * | 1999-03-03 | 2007-02-21 | テルモ株式会社 | 医療用コネクターおよび医療用コネクターを備えた医療用具 |
JP2001162723A (ja) * | 1999-12-08 | 2001-06-19 | Tokai Rubber Ind Ltd | ゴム・ポリアミド複合体及びその製造方法 |
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 |
JP2003190274A (ja) * | 2001-12-28 | 2003-07-08 | Nippon Zeon Co Ltd | 医療用チューブの製造方法 |
US20050069716A1 (en) * | 2003-09-11 | 2005-03-31 | Sun Sasongko | Composition of coextruded adhesive film to bond non-polar to polar surfaces |
-
2004
- 2004-12-24 WO PCT/JP2004/019296 patent/WO2005063859A1/ja not_active Application Discontinuation
- 2004-12-24 US US10/583,865 patent/US20080226930A1/en not_active Abandoned
- 2004-12-24 CN CNA2004800389669A patent/CN1898304A/zh active Pending
- 2004-12-24 EP EP20040807653 patent/EP1698654A4/en not_active Withdrawn
- 2004-12-24 KR KR1020067012660A patent/KR20060123391A/ko not_active Application Discontinuation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101357552B (zh) * | 2007-07-30 | 2011-06-15 | 比亚迪股份有限公司 | 一种用于光固化涂层表面的印刷方法 |
CN102958989A (zh) * | 2010-06-29 | 2013-03-06 | 伊士曼化工公司 | 纤维素酯组合物和纤维素酯/弹性体组合物以及它们的制造方法 |
CN103189085A (zh) * | 2010-10-01 | 2013-07-03 | 莫门蒂夫性能材料股份有限公司 | 自润滑的药品注射器栓 |
CN104619757A (zh) * | 2012-05-07 | 2015-05-13 | 托马斯·尼克特压力处理有限责任公司 | 具有高表面能的聚合物表面及其制备方法 |
CN112156266A (zh) * | 2020-10-13 | 2021-01-01 | 湖南平安医械科技有限公司 | 一次性使用静脉留置针导管 |
Also Published As
Publication number | Publication date |
---|---|
WO2005063859A1 (ja) | 2005-07-14 |
KR20060123391A (ko) | 2006-12-01 |
US20080226930A1 (en) | 2008-09-18 |
EP1698654A4 (en) | 2007-05-30 |
EP1698654A1 (en) | 2006-09-06 |
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