CN110337351A - 成型加工机洗涤用的热塑性树脂组合物 - Google Patents
成型加工机洗涤用的热塑性树脂组合物 Download PDFInfo
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- CN110337351A CN110337351A CN201880014335.5A CN201880014335A CN110337351A CN 110337351 A CN110337351 A CN 110337351A CN 201880014335 A CN201880014335 A CN 201880014335A CN 110337351 A CN110337351 A CN 110337351A
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Abstract
本发明提供洗涤性能得到了进一步提高的成型加工机洗涤用的热塑性树脂组合物。本发明的成型加工机洗涤用的热塑性树脂组合物含有:(A)烯烃类树脂、和(B)(B1)HLB为13~20的非离子表面活性剂,且相对于(A)成分100质量份,含有0.5~10质量份的(B)成分。
Description
技术领域
本发明涉及成型加工机洗涤用的热塑性树脂组合物,其用于洗涤挤出机、注塑成型机等成型加工机。
背景技术
作为热塑性树脂的成型加工机用的洗涤剂,已知有将基体树脂和其他成分组合而成的物质。
在日本特开2014-77049号公报、日本特开2013-154484号公报、日本特开2012-140481号公报以及日本特开2011-46808号公报中,公开了在作为基体树脂的聚烯烃树脂中组合其他成分而成的成型加工机洗涤用的热塑性树脂组合物。
发明内容
本发明的目的在于提供洗涤性能得到了进一步提高的成型加工机洗涤用的热塑性树脂组合物。
本发明提供一种成型加工机洗涤用的热塑性树脂组合物,其含有:(A)烯烃类树脂、和(B)(B1)HLB为13~20的非离子表面活性剂,且相对于(A)成分100质量份,含有0.5~10质量份的(B)成分。
根据本发明的洗涤用的热塑性树脂组合物,对成型加工机的内部进行洗涤时的洗涤性和操作性良好。
具体实施方式
[洗涤用的热塑性树脂组合物]
<(A)成分>
(A)成分是烯烃类树脂。(A)成分的烯烃类树脂可举出:HDPE(高密度聚乙烯)、LDPE(低密度聚乙烯)、LLDPE(直链状低密度聚乙烯)、聚丙烯均聚物、乙烯和丙烯的共聚物、以及乙烯和/或丙烯与能够与它们共聚的单体的共聚物等,它们可以使用一种或两种以上。从提高洗涤性能的观点出发,(A)成分优选为选自HDPE、LDPE、LLDPE及聚丙烯均聚物中的一种以上,更优选为选自HDPE和聚丙烯均聚物中的一种以上。
就(A)成分的基于ISO1133的熔体流动速率(下文中称为MFR)(在10分钟内流出的树脂的重量(g/10min))而言,在190℃、负载2.16kg的情况下,优选为0.01~6,更优选为0.01~3。此外,就所述(A)成分的MFR(g/10min)而言,在230℃、负载2.16kg的情况下,优选为0.5~15,更优选为0.5~10。
<(B)成分>
(B)成分是非离子表面活性剂。
(B1)成分是HLB为13~20的非离子表面活性剂。从提高洗涤性能的观点出发,(B1)成分的HLB优选为14~20,更优选为16~20。
需要说明的是,在本发明中,HLB是亲水亲油平衡值(Hydrophile LipophileBalance)的缩写,是获知化合物是亲水性还是亲油性的指标,取0~20的值。HLB值越小,则表示亲油性越强。在本发明中,HLB值由如下所示的格里芬(Griffin)式所定义。
HLB值=20×Mw/M
(式中,M是非离子表面活性剂的分子量,Mw是该非离子表面活性剂的亲水性部分的分子量)。
就(B1)成分的非离子表面活性剂而言,在上述HLB的范围内,可举出:聚氧化烯型非离子表面活性剂、脱水山梨糖醇型非离子表面活性剂、甘油酯型非离子表面活性剂(甘油(单、二)脂肪酸酯类)、丙二醇脂肪酸酯、蔗糖脂肪酸酯、糖苷型非离子表面活性剂(烷基多糖苷、烷基葡糖苷)、脂肪族烷醇酰胺等,它们可以使用一种或两种以上。
其中,从提高洗涤性能的观点出发,(B1)成分在上述HLB的范围内优选为聚氧乙烯(单、二)脂肪酸酯,更优选为聚氧乙烯二脂肪酸酯。此外,当(B1)成分是聚氧乙烯(单、二)脂肪酸酯的情况下,上述化合物的一个脂肪酸部分的碳原子数优选为8~22,更优选为12~18。
从提高洗涤性能的观点出发,本发明的成型加工机洗涤用的热塑性树脂组合物优选还含有作为(B2)成分的HLB为1~12的非离子表面活性剂。即,本发明的洗涤用的热塑性树脂组合物优选含有(B1)成分和(B2)成分这两者作为(B)成分。
从提高洗涤性能的观点出发,(B2)成分的HLB优选为1~10,更优选为1~8,进一步优选为1~5。
就(B2)成分的非离子表面活性剂而言,在上述HLB的范围内,可举出:聚氧化烯型非离子表面活性剂、脱水山梨糖醇型非离子表面活性剂、甘油酯型非离子表面活性剂(甘油(单、二)脂肪酸酯类)、丙二醇脂肪酸酯、蔗糖脂肪酸酯、糖苷型非离子表面活性剂(烷基多糖苷、烷基葡糖苷)、脂肪族烷醇酰胺等,它们可以使用一种或两种以上。
其中,从提高洗涤性能的观点出发,(B2)成分在上述HLB的范围内优选为选自甘油(单、二)脂肪酸酯及脱水山梨糖醇(单、二、三)脂肪酸酯中的一种以上,更优选为选自甘油单脂肪酸酯和脱水山梨糖醇三脂肪酸酯中的一种以上,进一步优选为甘油单脂肪酸酯。此外,当(B2)成分是甘油(单、二)脂肪酸酯的情况下,上述化合物的一个脂肪酸部分的碳原子数优选为8~22,更优选为16~22。此外,当(B2)成分是脱水山梨糖醇(单、二、三)脂肪酸酯时,所述化合物的一个脂肪酸部分的碳原子数优选为8~22,更优选为12~22。
从提高洗涤性能的观点出发,本发明的成型加工机洗涤用的热塑性树脂组合物中(B)成分的含有比例相对于(A)成分的总量100质量份,优选为0.5~10质量份,更优选为1~10质量份,进一步优选为1~8质量份,更进一步优选为3~7质量份。
从提高洗涤性能的观点出发,本发明的成型加工机洗涤用的热塑性树脂组合物中(B1)成分的含有比例相对于(A)成分的总量100质量份,优选为0.25~5质量份,更优选为0.5~5质量份,进一步优选为0.5~4质量份,更进一步优选为1.5~3.5质量份。
从提高洗涤性能的观点出发,本发明的成型加工机洗涤用的热塑性树脂组合物中(B2)成分的含有比例相对于(A)成分的总量100质量份,优选为0.25~5质量份,更优选为0.5~5质量份,进一步优选为0.5~4质量份,更进一步优选为1.5~3.5质量份。
从提高洗涤性能的观点出发,在本发明的成型加工机洗涤用的热塑性树脂组合物中,(B1)成分在(B1)成分和(B2)成分的总量中的含有比例优选为10~90质量%,更优选为20~80质量%,进一步优选为30~70质量%,更进一步优选为40~60质量%,从提高洗涤性能的观点出发,(B2)成分的含有比例优选为90~10质量%,更优选为80~20质量%,进一步优选为70~30质量%,更进一步优选为60~40质量%。
从提高洗涤性能的观点出发,本发明的成型加工机洗涤用的热塑性树脂组合物优选还含有作为(C)成分的热塑性弹性体。
就(C)成分的热塑性弹性体而言,可举出:氨基甲酸酯弹性体、聚酯弹性体、烯烃类弹性体、聚酰胺弹性体、苯乙烯类弹性体等,它们可以使用一种或两种以上。
作为具体的(C)成分,可举出选自苯乙烯-丁二烯-苯乙烯嵌段聚合物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段聚合物(SIS)、氢化苯乙烯-乙烯-丁烯-苯乙烯嵌段聚合物(SEBS)、氢化苯乙烯-乙烯-丙烯-苯乙烯嵌段聚合物(SEPS)、乙烯-α烯烃类聚合物、乙烯-α烯烃-多烯聚合物、有机硅橡胶、丙烯酸橡胶、及丁二烯-(甲基)丙烯酸酯聚合物中的一种以上,从提高洗涤性能的观点出发,优选为选自苯乙烯-丁二烯-苯乙烯嵌段聚合物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段聚合物(SIS)、氢化苯乙烯-乙烯-丁烯-苯乙烯嵌段聚合物(SEBS)及氢化苯乙烯-乙烯-丙烯-苯乙烯嵌段聚合物(SEPS)中的一种以上,更优选为选自苯乙烯-丁二烯-苯乙烯嵌段聚合物(SBS)、氢化苯乙烯-乙烯-丁烯-苯乙烯嵌段聚合物(SEBS)及氢化苯乙烯-乙烯-丙烯-苯乙烯嵌段聚合物(SEPS)中的一种以上,进一步优选为选自苯乙烯-丁二烯-苯乙烯嵌段聚合物及氢化苯乙烯-乙烯-丁烯-苯乙烯嵌段聚合物(SEBS)中的一种以上,更进一步优选为氢化苯乙烯-乙烯-丁烯-苯乙烯嵌段聚合物(SEBS)。
从提高洗涤性能的观点出发,本发明的成型加工机洗涤用的热塑性树脂组合物中(C)成分的含有比例相对于(A)成分的总量100质量份,优选为0.5~20质量份,更优选为1~15质量份,进一步优选为1~12质量份,更进一步优选为2~7质量份。
从提高洗涤性能的观点出发,本发明的成型加工机洗涤用的热塑性树脂组合物优选还含有作为(D)成分的无机填充剂。
作为(D)成分的无机填充材料,可以使用粒状或粉状的填充材料、纤维状的填充材料。
作为粒状或粉状的填充材料,可举出:滑石、二氧化钛、二氧化硅、云母、硫酸钙、碳酸钙(重质碳酸钙、沉淀碳酸钙)、碳酸钡、碳酸镁、硫酸镁、硫酸钡、含氧硫酸盐、氧化锡、氧化铝、高岭土、碳化硅、金属粉末、玻璃粉、玻璃片、玻璃珠等,它们可以使用一种或两种以上。
粒状或粉状的填充材料的平均粒径优选为100μm以下,更优选为50μm以下,进一步优选为10μm以下,特别优选为5μm以下。平均粒径通过沉降天平法进行测定,以50%粒度中值表示。
作为纤维状的填充材料,可举出:硅灰石、玻璃纤维、玻璃纤维的磨碎纤维、钛酸钾晶须、硼酸铝晶须、氧化锌晶须、硅镁土等,它们可以使用一种或两种以上。
从提高洗涤性能的观点出发,(D)成分优选为选自滑石和玻璃纤维中的一种以上,更优选为滑石。
从提高洗涤性能的观点出发,本发明的成型加工机洗涤用的热塑性树脂组合物中(D)成分的含有比例相对于(A)成分的总量100质量份,优选为0.1~10质量份,更优选为0.1~5质量份,进一步优选为0.1~3质量份,更进一步优选为0.5~2质量份。
本发明的成型加工机洗涤用的热塑性树脂组合物可以通过将上述各成分利用亨舍尔混合机、转鼓混合机、捏合机等混合机进行预混,然后利用挤出机进行混炼,或利用加热辊、班伯里混合机进行熔融混炼而制造。
本发明的成型加工机洗涤用的热塑性树脂组合物优选作为挤出成型加工机或注塑成型加工机洗涤用的热塑性树脂组合物,更优选作为挤出成型加工机洗涤用的热塑性树脂组合物。
实施例
实施例和比较例
利用转鼓混合机将表1、2所示组成的各成分混合后,利用挤出机进行熔融混炼,得到颗粒状的树脂组合物。使用这些组合物,通过下述方法进行了洗涤试验。结果示于表1、2中。
[挤出成型加工机的洗涤性的评价]
在挤出成型机(GT-25A,株式会社塑料工学研究所制造)中,在螺杆转速100rpm、树脂温度210℃的条件下,进行了作为先前使用树脂的HIPS(耐冲击性聚苯乙烯)的黑色着色品(黑色着色剂浓度1质量%)1kg的挤出成型。
然后,将表1的各组合物投入挤出成型机的料斗中进行挤出,将先前使用树脂的黑色消失的时间点作为洗涤终点,根据至此为止的上述组合物的使用量(kg)对洗涤性进行了评价。可认为,洗涤中使用的树脂组合物的使用量越少,则洗涤性越优异。
[注塑成型加工机的洗涤性的评价]
在注塑成型机(α-S150iA,FANUC株式会社制)中,在机筒温度230℃的条件下,进行了作为先前使用树脂的聚丙烯的黑色着色品(黑色着色剂浓度3质量%)1kg的注塑成型。
然后,将表2的各组合物投入注塑成型机中进行注射成型,将先前使用树脂的黑色消失的时间点作为洗涤终点,根据至此为止的上述组合物的使用量(kg)对洗涤性进行了评价。可认为,洗涤中使用的树脂组合物的使用量越少,则洗涤性越优异。
此外,在洗涤结束后,将HDPE树脂(HI-ZEX 5300B,PRIME POLYMER株式会社制造)投入注塑成型机中进行注塑成型,根据此时能否确认到先前使用树脂(聚丙烯的黑色着色品)的黑色而对洗涤性(先前使用树脂有无残留)进行了评价。在未能确认到先前使用树脂的黑色的情况下,可认为洗涤中使用的树脂组合物的洗涤性优异。
(A)成分
A-1:HDPE(NIPOLONE HARD 6900B,TOSOH株式会社制造,MFR0.07)
A-2:HDPE(NIPOLONE HARD 6000,TOSOH株式会社制造,MFR0.15)
A-3:聚丙烯(SUN AROMA PM472W,SUNAROMA株式会社制造,MFR2.7)
A-4:LLDPE(NIPOLONE-L T240F,TOSOH株式会社制造,MFR1.6)
A-5:聚丙烯(SUN AROMA PL400A,SUNAROMA株式会社制造,MFR2.0)
需要说明的是,A-1、A-2以及A-4的MFR(g/10min)是基于ISO1133,在温度190℃及负载2.16kg的条件下测得的值;A-3和A-5的MFR(g/10min)是基于ISO1133、在温度230℃及负载2.16kg的条件下测得的值。
(B)成分
B1-1:聚氧乙烯二硬脂酸酯(花王株式会社制造,HLB 18.9)
B2-1:羟基硬脂酸单甘油酯(RIKEN VITAMIN株式会社制造,HLB 3.4)
B2-2:脱水山梨糖醇三山萮酸酯(RIKEN VITAMIN株式会社制造,HLB 2.5)
B2-3:硬脂酸二甘油酯(RIKEN VITAMIN株式会社制造,HLB 5.7)
(B’)成分((B)成分的比较成分)
B’-1:α烯烃磺酸钠(DAIICHI KOGYO SEIYAKU株式会社制造)
B’-2:硬脂酸钠(株式会社ADEKA制造)
B’-3:酸式磷酸硬脂酯锌盐(zinc stearyl acid phosphate)(LBT-1830,SAKAICHEMICAL INDUSTRY株式会社制造)
(C)成分
C-1:SEBS(TOUGH TECH 1043,ASAHI KASEI CHEMICALS株式会社制造,苯乙烯/乙烯-丁烯(摩尔比)=67/33)
C-2:SEBS(TOUGH TECH 1221,ASAHI KASEI CHEMICALS株式会社制造,苯乙烯/乙烯-丁烯(摩尔比)=12/88)
C-3:SBS(ASAPRENE T-437,ASAHI KASEI株式会社制造,苯乙烯/丁二烯(摩尔比)=30/70)
(D)成分
D-1:滑石(PHSH Talc,TAKEHARA KAGAKU KOGYO株式会社制造)
(E)成分(其他成分)
E-1:MS(CEVIAN MAS30,DAICEL POLYMER株式会社制造)
E-2:EMA(ELVALOY AC 1820,MITSUI DUPONT POLYCHEMICAL株式会社制造)
[表1]
在表1中,在洗涤性的评价中,组合物的使用量(kg)记载为“0.4<”的比较例,表示洗涤用的热塑性树脂组合物的使用量为超过0.4kg的量。
[表2]
Claims (12)
1.一种成型加工机洗涤用的热塑性树脂组合物,其含有:
(A)烯烃类树脂、和
(B)(B1)HLB为13~20的非离子表面活性剂,
相对于(A)成分100质量份,(B)成分的含量为0.5~10质量份。
2.根据权利要求1所述的成型加工机洗涤用的热塑性树脂组合物,其还含有(B2)HLB为1~12的非离子表面活性剂作为(B)成分。
3.根据权利要求1或2所述的成型加工机洗涤用的热塑性树脂组合物,其中,(B1)成分为聚氧乙烯脂肪酸酯。
4.根据权利要求2所述的成型加工机洗涤用的热塑性树脂组合物,其中,(B2)成分为选自甘油脂肪酸酯及脱水山梨糖醇脂肪酸酯中的一种以上。
5.根据权利要求2所述的成型加工机洗涤用的热塑性树脂组合物,其中,在(B1)成分和(B2)成分的总量中,(B1)成分的含有比例为10~90质量%。
6.根据权利要求1~4中任一项所述的成型加工机洗涤用的热塑性树脂组合物,其还含有(C)热塑性弹性体。
7.根据权利要求6所述的成型加工机洗涤用的热塑性树脂组合物,其中,(C)成分是选自下组中的一种以上:苯乙烯-丁二烯-苯乙烯嵌段聚合物(SBS)、苯乙烯-异戊二烯-苯乙烯嵌段聚合物(SIS)、氢化苯乙烯-乙烯-丁烯-苯乙烯嵌段聚合物(SEBS)、氢化苯乙烯-乙烯-丙烯-苯乙烯嵌段聚合物(SEPS)、乙烯-α烯烃聚合物、乙烯-α烯烃-多烯聚合物、有机硅橡胶、丙烯酸橡胶、及丁二烯-(甲基)丙烯酸酯聚合物。
8.根据权利要求6或7所述的成型加工机洗涤用的热塑性树脂组合物,其中,相对于(A)成分的总量100质量份,(C)成分的含量为0.5~20质量份。
9.根据权利要求1~6中任一项所述的成型加工机洗涤用的热塑性树脂组合物,其还含有(D)无机填充剂。
10.根据权利要求9所述的成型加工机洗涤用的热塑性树脂组合物,其中,(D)成分是选自滑石及玻璃纤维中的一种以上。
11.根据权利要求9或10所述的成型加工机洗涤用的热塑性树脂组合物,其中,相对于(A)成分的总量100质量份,(D)成分的含量为0.1~10质量份。
12.根据权利要求1~11中任一项所述的成型加工机洗涤用的热塑性树脂组合物,其是挤出成型加工机或注塑成型加工机洗涤用的热塑性树脂组合物。
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