CN103930483A - 氯乙烯树脂组合物 - Google Patents

氯乙烯树脂组合物 Download PDF

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CN103930483A
CN103930483A CN201280042505.3A CN201280042505A CN103930483A CN 103930483 A CN103930483 A CN 103930483A CN 201280042505 A CN201280042505 A CN 201280042505A CN 103930483 A CN103930483 A CN 103930483A
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vinyl chloride
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坂井昂次
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Abstract

提供热稳定性和加工性优异并且溶出性小的氯乙烯树脂组合物。氯乙烯树脂组合物，其含有氯乙烯树脂100重量份、二（2-乙基己基）对苯二甲酸酯10～120重量份、和过氧化物值为5以下的环氧化植物油0.5～20重量份。

Description

氯乙烯树脂组合物
技术领域
本发明涉及氯乙烯树脂组合物。更详细地，涉及热稳定性和加工性优异，并且溶出性小，因而适于医疗用管或医疗用袋等医疗用器具的氯乙烯树脂组合物。
背景技术
在氯乙烯树脂中添加了增塑剂的氯乙烯树脂组合物可以根据上述增塑剂的量的多少来进行柔软性的大范围调整，由于成形性、粘接性、加工性、耐热性和耐结块性也良好，而且价格低廉，因而被广泛用作医疗用器具，例如，导管等医疗用管、或血液袋、药液袋和废液袋等医疗用袋等的材料。但是，若使由含有增塑剂的氯乙烯树脂组合物形成的成形品预先与血液等体液、或各种水溶液等接触，则增塑剂和其它添加剂会被溶出。
通常，对供于医疗用器具的树脂组合物，期望增塑剂等添加剂不溶出。另外，医疗用器具必须进行灭菌处理，所以期望供于医疗用器具的树脂组合物是热稳定性的。
为了减少溶出物的量，提出了各种方案。例如，已知在含有二（2-乙基己基）邻苯二甲酸酯（DOP）作为增塑剂的氯乙烯树脂组合物中添加特定的硅油（专利文献1）。另外，还提出了在含有上述DOP作为增塑剂的氯乙烯树脂组合物中添加过氧化物值为10以下的环氧化植物油的方案（专利文献2）。但是，实质上仅记载了过氧化物值大于5的环氧化植物油，溶出物的量的降低并不能说是充分的。
另外，作为添加于氯乙烯系树脂中的增塑剂，提出了代替以往的DOP而使用对苯二甲酸双（2-乙基己基）酯（DOTP）的方案（专利文献3～5）。这些文献对于将氯乙烯系树脂组合物适用于医疗用器具和使溶出性减小的内容均未提及。另外，这些氯乙烯系树脂组合物的热稳定性和加工性差。
现有技术文献
专利文献
专利文献1 : 日本特开昭59-33343号公报
专利文献2 : 日本特开平8-24329号公报
专利文献3 : 日本特开2003-226788号公报
专利文献4 : 日本特开2003-253072号公报
专利文献5 : 日本特开昭63-75050号公报。
发明内容
发明要解决的技术问题
本发明是鉴于上述情况而完成的发明，其目的在于提供热稳定性和加工性优异并且溶出性小的氯乙烯树脂组合物。
用于解决技术问题的方法
本发明人发现，若在氯乙烯树脂中配合作为增塑剂的二（2-乙基己基）对苯二甲酸酯、并且配合过氧化物值为5以下的环氧化植物油，可实现上述目的。
即，本发明为氯乙烯树脂组合物，其含有氯乙烯树脂100重量份、二（2-乙基己基）对苯二甲酸酯10～120重量份、和过氧化物值为5以下的环氧化植物油0.5～20重量份。另外，本发明还提供由上述氯乙烯树脂组合物形成的医疗用器具。
发明效果
本发明的氯乙烯树脂组合物的热稳定性和加工性优异并且溶出性小，所以适宜用于医疗用管或医疗用袋等医疗用器具。
具体实施方式
以下，对本发明的氯乙烯树脂组合物进行详细说明。本发明的氯乙烯树脂组合物含有氯乙烯树脂、作为增塑剂的二（2-乙基己基）对苯二甲酸酯和过氧化物值为5以下的环氧化植物油。
氯乙烯树脂是指具有-CH2-CHCl-所示基团的所有聚合物，包括氯乙烯的均聚物和乙烯-氯乙烯共聚物等氯乙烯与除乙酸乙烯酯之外的其它聚合性单体的共聚物、以及后氯化乙烯基共聚物等将均聚物和共聚物改性的产物、进而氯化聚乙烯等在结构上与氯乙烯树脂类似的氯化聚烯烃。
氯乙烯树脂优选数均聚合度为300以上且7000以下，进一步期望具有500以上且3000以下的聚合度。可将这些氯乙烯树脂单独使用或二种以上并用，来作为本发明的氯乙烯树脂组合物中的氯乙烯树脂成分。
本发明中可用作增塑剂的二（2-乙基己基）对苯二甲酸酯是下式所示的化合物。该化合物的2-乙基己基氧基羰基处于对位，与2-乙基己基氧基羰基处于邻位的二（2-乙基己基）邻苯二甲酸酯（DOP）不同。
[化1]
上述二（2-乙基己基）对苯二甲酸酯可以商业性地获得。
上述二（2-乙基己基）对苯二甲酸酯的添加量相对于氯乙烯树脂100重量份为10～120重量份，优选为10～100重量份，更优选为20～80重量份，进一步优选为20～65重量份。若不足上述下限，则有时组合物的柔软性不充分，若超过上述上限，则有时组合物的强度显著降低或发生漏出（bleed）。
本发明的树脂组合物通过含有作为增塑剂的二（2-乙基己基）对苯二甲酸酯，可获得降低的溶出性。特别地，如后述的pH试验所述，将由本发明的树脂组合物形成的片材浸于蒸馏水中时，可实现蒸馏水的pH变化非常小的效果。这意味着对pH造成影响的溶出物的量少。上述pH变化小的事实意味着将该树脂组合物用作医疗用器具的材料时，也可适用于易受pH影响的药剂。
本发明的氯乙烯树脂组合物进一步含有环氧化植物油。本发明中使用的环氧化植物油是通过将天然产生的植物油用过氧化氢或过乙酸等有机过酸进行环氧化的公知方法来制造的，过氧化物值为5以下、优选为4以下、更优选为3以下。过氧化物值若大于5，则使溶出物量降低的效果不充分。
上述环氧化植物油可商业性地获得，或者可以以例如如下所述方式制造。将植物油用作为氧化剂的有机过酸进行氧化处理，得到过氧化物值为20～40的环氧化植物油。通过将其在减压下进行加热处理，可制造过氧化物值为5以下的环氧化植物油。加热处理条件通常优选为120℃～250℃，优选130℃～200℃。处理时间为数分钟～数小时。该处理时间越长，则越可得到过氧化物值小的环氧化植物油。优选为1小时以上。处理温度不足120℃的情形中，处理变得需要长时间，在超过250℃时，可能产生环氧基聚合等副反应。
作为用于上述环氧化植物油的植物油，可举出大豆油、亚麻籽油、菜籽油等，特别优选大豆油。
应予说明，上述过氧化物值是指表示在试样中加入碘化钾时游离出的碘相对于试样1kg的毫当量数的值，是按照日本油化学协会编《基准油脂分析试验法》（朝仓书店发行，1966年）中记载的方法确定的值。上述过氧化物值越大，则表示试样中含有越多过氧化物基团。
上述环氧化植物油的配合量相对于氯乙烯树脂100重量份为0.5～20重量份，优选为1～12重量份，更优选为1～7重量份。不足上述下限时，则在组合物的热稳定性不充分的同时，还存在观察不到溶出物量的降低效果的情形。若超过上述上限，则有时发生漏出，另外，即使超过上述上限添加也观察不到增量效果。
进而，本发明的氯乙烯树脂组合物还可以含有硅油。硅油的配合量相对于氯乙烯树脂100重量份为0.05～10重量份，优选为0.1～10重量份。不足上述下限时，有时观察不到溶出物量的降低效果。即使超过上述上限添加也观察不到增量效果。
作为硅油，可举出：聚甲基苯基硅氧烷、聚二甲基硅氧烷和聚甲基氢硅氧烷、以及将它们用氨基或羧基改性而成的物质。
另外，本发明的氯乙烯树脂组合物在面向食品用途或医疗用途时可进一步配合通常可用于软质氯乙烯树脂的稳定剂。作为上述稳定剂，可举出例如：钡-锌系和钙-锌系的稳定剂，例如，钙与锌的复合硬脂酸盐等。稳定剂的添加量相对于氯乙烯系树脂100重量份优选为0.1～10重量份。稳定剂的添加量不足0.1重量份时，得不到作为稳定剂的效果，即使超过10重量份添加也观察不到增量效果。
进而，本发明的氯乙烯树脂组合物中可以根据需要配合其它增塑剂、颜料或染料、热稳定剂、抗氧化剂和润滑剂等添加剂。
本发明的氯乙烯树脂组合物可通过将氯乙烯树脂、二（2-乙基己基）对苯二甲酸酯和环氧化植物油与根据需要的任意成分一起投入加压捏合机中，在树脂温度150～160℃下熔融混炼5～10分钟而得到。
本发明的氯乙烯树脂组合物的热稳定性优异并且溶出性小，因而可适宜地用于医疗用管、医疗用袋和呼吸面罩等各种医疗用器具。作为医疗用管，可举出例如：管饲管、血液透析管、呼吸道管、导管、压力监测管和肝素管等。作为医疗用袋，可举出血液袋、药液袋和废液袋等。
以下，通过实施例更详细地说明本发明，但本发明并不受这些实施例所限定。
实施例
实施例1～7和比较例1～14
将表1所示量（重量份）的成分用加压捏合机在约160℃下进行熔融混炼而制造氯乙烯树脂组合物，使其通过辊，制为片材状。接着，以加压装置成形为规定大小的片材而制为试验片，进行以下的试验（1）和（2）。另外，使用上述氯乙烯树脂组合物，进行以下试验（3）。结果示于表1。
应予说明，表中的缩写表示如下含义：
?PVC：氯乙烯树脂（平均聚合度＝1300）
?DOTP：二（2-乙基己基）对苯二甲酸酯
?DOP　：二（2-乙基己基）邻苯二甲酸酯
?TOTM：三（2-乙基己基）偏苯三酸酯
?DINCH：二异壬基环己烷-1，2-二甲酸酯
?DOA：二（2-乙基己基）己二酸酯。
试验
（1）溶出物试验
按照“日本药典”进行以下的试验。将厚度1mm的试验片15.00g用水清洗，在室温下干燥。将该试验片放入内容量500ml的三角烧瓶，加入蒸馏水300ml，以硅橡胶栓密封，并使用高压蒸汽灭菌器在121℃下对其进行60分钟加热。减压后，将放入有试验片的三角烧瓶从高压蒸汽灭菌器中取出，放置直到变为室温。将试验片与蒸馏水一起转移至300ml容量的量瓶中，追加蒸馏水准确定容至300ml，将其作为试验液。另外，作为空白试验液，以上述方法制备不含试验片的试验液。对试验液和空白试验液进行下述试验（i）～（v）。
（i）pH试验
将试验液和空白试验液分别取20ml，向其中分别加入将氯化钾1.0g溶于水定容至1000ml而得的溶液1ml，测定两溶液的pH，计算其差值。该值越大，则意指对pH造成影响的物质的溶出量越多。
（ii）锡试验
锡试验用检查液的制备
将试验液10.0ml放入25ml的量瓶，滴加高锰酸钾试液直至溶液的颜色稍微呈微红色，然后加入少量L-抗坏血酸直至脱色。接着，依次加入1N盐酸1.5ml、用水稀释10倍的柠檬酸溶液5.0ml、聚合度2000的聚乙烯醇2.5ml，进而加入苯基荧光酮的乙醇溶液5.0ml和水，定容至25.0ml，充分摇混，静置约20分钟，将其作为锡试验用检查液。
稀硝酸水溶液的制备
按照“日本药典第16版（日本薬局方第16改正）”来制备稀硝酸。即，在硝酸10.5ml中加入水定容至100ml，将其作为10%的稀硝酸。进而将其稀释3倍来作为稀硝酸水溶液（A）。
锡试验用基准液
将关东化学制的锡标准液（1000ppm）稀释，使得浓度为1.0μg/ml，将其5.0ml加入20ml的带有塞子的量瓶中，滴加高锰酸钾试液，直至溶液颜色稍微呈现微红色后，进行与上述检查液的制备相同的处理，然后加入上述制备的稀硝酸水溶液（A）定容至20ml，将其作为锡试验用基准液（0.25μg/ml）。同样地，制备0.01μg/ml、0.05μg/ml和0.1μg/ml的锡试验用基准液。
锡的定量
以水作为对照，对上述锡试验用基准液测定波长510nm下的吸光度，制作校准曲线。对于上述锡试验用检查液，也同样地以水作为对照在相同波长下测定吸光度，与校准曲线对照，进行锡的定量。应予说明，氯乙烯系树脂组合物可以以氯乙烯的制造步骤中的催化剂或混入物的形式含有锡。
（iii）高锰酸钾还原性物质试验
将试验液20.0ml取至带塞子的三角烧瓶中，加入0.002mol/L的高锰酸钾液20.0ml和稀硝酸1ml，煮沸3分钟，进行冷却。向其中加入碘化钾0.1g，盖上塞子，摇混并放置10分钟后，加入作为指示剂的淀粉试液5滴，用0.01mol/L硫代硫酸钠溶液进行滴定，求出高锰酸钾液消耗量（X）。对于空白试验液20.0ml也进行同样的操作，求出高锰酸钾液消耗量（Y）。将X-Y的值表示为ΔKMnO4。该值越大，则表示高锰酸钾还原性物质（主要为有机物）的溶出量越多。
（iv）蒸发残留物试验
将试验液20ml在水浴上蒸发凝固，将残留物在105℃干燥1小时，测量其质量。
（v）紫外线吸收光谱试验
将上述制备的空白试验液取至液厚10mm的石英池中，进行紫外可见分光光度计（日立制作所制、U-3010）的校正后，将上述制备的试验液同样地取至石英池中，以相同试验仪器测定220～350nm的波长下的吸光度，将其最大值示于表1。
（2）热稳定性试验
按照JIS　K6723进行热稳定性试验，在170±3℃的条件下测定试验片保持稳定状态的时间（分）。上述试验如下进行：将试验片与试验纸（刚果红试纸）一起放入试验管并进行密闭，将该试验管放入170±3℃的油浴中，测定试验片发生变化为止的时间。应予说明，将刚果红试纸的颜色发生变化的时刻作为试验片发生变化的时刻。
（3）加工性试验
将氯乙烯系树脂组合物使用Labo Plasto Mill（东洋精机制作所制，30C150型）以试样量30g、池温度160℃、旋转数50rpm、预热5分钟的条件进行混炼，测定达到最高扭矩值的时间，将其表示为凝胶化时间。凝胶化时间越短则表示加工性越好。
[表1]
由表1可知，含有作为增塑剂的二（2-乙基己基）对苯二甲酸酯（DOTP）、并且含有作为环氧化大豆油的过氧化物值为5以下的环氧化大豆油的本发明的氯乙烯树脂组合物的热稳定性和加工性优异、溶出性小、pH的变化也小。另一方面，环氧化大豆油的量不足本发明的范围的比较例1的组合物的热稳定性和加工性差。另外，环氧化大豆油的过氧化物值大于5的比较例3～6的组合物分别与实施例1、3、5和6相比，蒸发残留物和紫外线吸收光谱的试验中的值大。这表明溶出性高。另外，在这些实施例和比较例的比较中，将蒸发残留物和紫外线吸收光谱的试验结果为相同水平的例如实施例3与比较例3进行比较时，实施例3的组合物也较比较例3的热稳定性优异。含有DOTP以外的增塑剂的比较例7～14的组合物在pH试验中的pH的变化大。
实施例8和比较例15～23
将表2所示量（重量份）的成分用加压捏合机在约160℃下进行熔融混炼而制造氯乙烯树脂组合物，使其通过辊，制为片材状。接着，以加压装置成形为规定大小的片材而制为试验片，进行以下的GS-MS试验。结果示于表2。
GS-MS试验
（i）利用蒸馏水的提取试验
将65mm×65mm大小的试验片（厚度2mm）约10.00g用蒸馏水清洗，在室温下干燥。将该试验片放入内容量500ml的玻璃（硝子）制密闭容器中，加入蒸馏水300ml，在37℃下振动浸渍5小时。将该蒸馏水转移至300ml容量的量瓶中，追加新的蒸馏水准确定容至300ml，将其作为试验液。另外，除了不使用试验片以外，以与上述试验液相同的方法制备空白试验液。
将所得试验液和空白试验液用蒸发器浓缩干燥固化，得到干燥固体。一边将干燥固体溶解于丙酮，一边定容至10ml。将该溶液用气相色谱-质量分析装置（GC-MS装置）分析，求出提取至蒸馏水中的增塑剂的量（mg/ml）。测定条件如下所述。应予说明，校准曲线的制作中，对于DOTP、DOP、TOTM和DOA是使用关东化学社制的标准物质，对于DINCH是使用BASF社制的产品来进行。
测定条件：
装置：GCMS-QP2010Plus（岛津制作所社制）
柱：DB-1　MS（アジレント?テクノロジー社制）φ0.25mm×30m×膜厚0.25μm
注入口温度：280℃
界面温度：280℃
载气：氦（2mL/分）
试验液注入量：1μL（使用自动取样器）
柱温：100℃（1分）～20℃/分～230℃（0分）～10℃/分～300℃（15分）。
（ii）利用40vol/vol%乙醇水溶液的提取试验：
在上述试验（i）中，除了将蒸馏水改变为40vol/vol%乙醇水溶液以外，与试验（i）相同地进行，求出提取至40vol/vol%乙醇水溶液中的增塑剂的量（mg/ml）。应予说明，上述乙醇水溶液是使用关东化学社制的特级乙醇和蒸馏水来制备的。
[表2]
由表2可知，增塑剂为DOTP并且环氧化大豆油的过氧化物值为5以下的实施例8的组合物，与不满足上述两个要件的一者或两者的比较例15～23的组合物相比，在蒸馏水和乙醇水溶液中的增塑剂的溶出量少。

Claims (4)

1. 氯乙烯树脂组合物，其含有氯乙烯树脂100重量份、二（2-乙基己基）对苯二甲酸酯10～120重量份、和过氧化物值为5以下的环氧化植物油0.5～20重量份。
2. 权利要求1所述的氯乙烯树脂组合物，其中，进一步含有硅油0.05～10重量份。
3. 医疗用器具，其包含权利要求1或2所述的氯乙烯树脂组合物。
4. 权利要求3所述的医疗用器具，其为医疗用管或医疗用袋。
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