CN1090232C - 表面活性剂组合物 - Google Patents
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Abstract
提供一种表面活性剂组合物,即使较高浓度地配合表面活性剂,对洗涤对象也会显示出高的润湿浸透性,显示高的洗净性。该表面活性剂组合物含有平均分子量低于1200的化合物(1)和水,化合物(1)对水与化合物(1)合计量的配比为5重量%~50重量%:RO-(EO)x-(PO)y-(EO)x′-H(1)[式中,R为碳原子数12~15的烷基等,EO为氧化亚乙基,PO为氧化亚丙基。x、x′为1以上的数,y为0.5~6的数。另外,(EO)x、(PO)y、(EO)x′按顺序依次嵌段结合。]。
Description
技术领域
本发明涉及一种表面活性剂组合物。更详细地说,涉及这样一种表面活性剂组合物,该组合物可用作家庭用和产业用洗涤剂,含有特定的非离子表面活性剂,其浸透性高,洗净力优良。
背景技术
众所周知,聚氧乙烯型非离子活性剂从很早就用作表面活性剂和洗涤剂,对于其物性和合成方法、所谓乳化/增溶/洗涤的特性已有相当详细的研究报告(NONIONIC SURFACTANTS PHYSICAL CHEMISTRY:Martin J.Schick,1987等)。
这种聚氧乙烯型非离子活性剂由于其高洗净力,以及容易与其他例子性活性剂组合使用,曾提出各种组合。
另一方面,近年来,家庭用及工业用洗涤剂从制造时和输送时的节能、节省资源以及减少废容器的观点出发,需要以更高的浓度配合表面活性剂。但是,表面活性剂的高浓度化又产生未想到的新问题。即,采用将表面活性剂组合物直接涂布或喷涂到污垢上,将洗涤对象浸渍到表面活性剂组合物中,然后在大量的水中边洗涤边漂洗,采用这种方法的场合下,含有高浓度表面活性剂的表面活性剂组合物,其浸透性不够,因此污垢的除去不完全。
US-A 4134854中公开了将特定的聚环氧化物加成物作为低熔点的非离子活性剂。但是,对含有该非离子活性剂的表面活性剂组合物的合适浓度没有记载,对高浓度的表面活性剂组合物的浸透性也没有任何公开。
US-A 3567784公开了其他特定的聚环氧化物加成物在高云点下显示出低凝胶化温度。但是该公报中也未记载该非离子活性剂的高浓度组合物。
另外,JP-A 47-9561号公报(=US-A 4115457)中公开了其他特定的聚环氧化物加成物的制造方法,其产物可用作精炼剂、染色助剂。但是未记载高浓度的高浸透性表面活性剂组合物。
J.A.O.C.S.,第63卷,No.9,pp.1201~1208(1986)也公开了同样的聚环氧化物加成物的物性。
发明的公开
本发明的课题是提供一种表面活性剂组合物,该组合物即使以较高的浓度配合表面活性剂,对洗涤对象也能显示出很高的润湿浸透性,而且即使是通常很稀的表面活性剂浓度(0.01~1.0重量%),也显示出高的洗净性。
本发明者们发现,含有特定量的具有特定加成形态的聚氧化烯型非离子表面活性剂的表面活性剂组合物能够解决上述课题,至此完成本发明。
本发明的表面活性剂组合物含有下述式(1)所示的平均分子量低于1 200的化合物和水,式(1)化合物对水与式(1)化合物合计量的配比为5重量%~50重量%:
RO-(EO)x-(PO)y-(EO)x′-H (1)式中,R为碳原子数12~15的直链或支链烷基或链烯基,EO为氧化亚乙基,PO为氧化亚丙基。x、x′表示环氧乙烷的平均加成摩尔数,为1以上的数,y表示环氧丙烷的平均加成摩尔数,为0.5~6的数。另外,(EO)x、(PO)y、(EO)x′按顺序依次嵌段结合。
以下详细地说明本发明的实施方案。
用于本发明的、式(1)所示的平均分子量低于1200的化合物,可以通过将环氧乙烷、其次环氧丙烷、再其次环氧乙烷按顺序依次嵌段加成到式(2)所示的醇上而获得:
R-OH (2)(式中,R的含义与上述相同)。
作为式(2)所示的醇,可以举出碳原子数12~15的饱和或不饱和的、直链或支链的伯醇或仲醇,优选R的碳原子数为12~14,由于直链烷基或链烯基的洗净力特别高而是更优选的。作为碳原子数12~15醇的具体实例,可以举出月桂醇、肉豆蔻醇等直链醇(花王(株)制,商品名“Kalcohl 2098”和“Kalcohl 4098”等)、在碳原子数12~15范围内混合的混合醇(花王(株)制,商品名“Kalcohl 2474”等)、采用羰基法或Ziegler法合成的具有支链的碳原子数12~15的醇类(协和发酵(株)制,商品名“Oxocol 1213”和“Tridecanol”、三菱化学(株)制,商品名“Dobanol 23”和“Dobanol 25”、Shell化学公司制,商品名“Neodol 23”和“Neodol 25”等)等。其中,特别优选以碳原子数12~14醇为主要成分的醇。
另外,作为将环氧化物加成到这些醇上的方法,可以举出采用公知的烷氧基化方法在催化剂的存在下加成的方法,但本发明中,环氧化物的加成顺序非常重要,应按照顺序进行嵌段加成,首先加成环氧乙烷,接着加成环氧丙烷,再加成环氧乙烷。用于该烷氧基化的催化剂可以是酸催化剂,也可以是碱催化剂,另外,也可以使用以下催化剂来合成,如特开平7-227540号中所述的MgO-ZnO、MgO-SnO、MgO-TiO2、MgO-SbO等给出窄环氧化物加成分布(narrow range)的催化剂、特开平1-164437号中所述的同样的Mg系催化剂有选择地给出窄环氧化物加成分布的催化剂。
本发明以通式(1)所示的化合物,其环氧乙烷的平均加成摩尔数x、x′为1以上。由于其合计(x+x′)为4摩尔以上时与水的相溶性特别好而是优选的,为了提高浸透性,优选20摩尔以下。特别优选6摩尔~15摩尔。
另外,通式(1)所示的化合物,其环氧丙烷的平均加成摩尔数y为0.5摩尔~6摩尔,优选1摩尔~4.5摩尔。环氧丙烷的平均加成摩尔数不足0.5摩尔的场合下,浸透性不充分,如果加成的量超过6摩尔,则洗净力降低。
本发明以通式(1)所示的化合物,其平均分子量低于1200,优选低于1000。如果平均分子量超过1200,则洗净力降低,浸透性也变差。
本发明的表面活性剂组合物中,通式(1)所示化合物对水与通式(1)所示化合物合计量的配比为5重量%~50重量%,特别优选15重量%~40重量%。如果通式(1)所示化合物的配比不足5重量%,则制造时和输送时在成本上不经济,如果高于50重量%,则浸透性降低。
本发明的表面活性剂组合物,只要不破坏本发明的效果,就可以含有其他非离子活性剂或阴离子活性剂、阳离子活性剂、两性活性剂、螯合剂、杀菌剂等,为了进一步微调所制造的表面活性剂组合物的特性,也可以添加增粘剂或减粘剂等粘度调整剂。
本发明的表面活性剂组合物中,特别是添加作为减粘剂的水相混性溶剂,可有效地提高浸透性。作为这种水相混性溶剂,可以举出乙醇、异丙醇、丁醇等低级醇;乙二醇单乙醚、乙二醇单丁醚、二乙二醇单乙醚、二乙二醇单丁醚、二乙二醇单己醚、二乙二醇单苯醚、乙二醇单苄醚等二醇醚类;乙二醇、丙二醇、1,3-丁二醇等二醇化合物。由于大量的溶剂会产生燃烧的危险性,本发明的组合物中,这种溶剂的配合量优选为0.1重量%~10重量%,更优选0.1~5重量%。
作为本发明的表面活性剂组合物中配合的其他非离子活性剂的例子,可以举出脂肪酸二乙醇胺、胺氧化物类和除上述通式(1)所示化合物以外的聚亚烷基二醇烷基醚类等。作为阴离子活性剂,可以举出烷烃磺酸盐、烷基苯磺酸盐、α-烯烃磺酸盐、烷基硫酸盐、烷基醚硫酸盐、α-磺基脂肪酸盐、高级脂肪酸盐等;作为阳离子活性剂,可以举出脂肪族胺盐类、季铵盐类等;作为两性活性剂,可以举出甜菜碱、磺基甜菜碱类、氨基酸盐类等。另外,作为螯合剂,可以举出乙二胺四醋酸钠、氮基三乙酸钠等;作为杀菌剂,可以举出氯苄烷铵等。
本发明的表面活性剂组合物,即使浓度较高,对洗涤对象也会显示出高的润湿浸透性,洗净力也很高,因此对浸透到洗涤对象内部的污垢或是对有凹凸部分的洗涤特别有效,可用作液体洗涤剂。例如,可适于用作餐具用、住宅用、浴室用、衣料用洗涤剂织物,此外,在工业用途上还可以用作纤维、金属、电子零件的洗涤剂或需要润湿浸透的有机·无机粉末的分散剂、增溶剂等。
以下用非离子活性剂的合成例和本发明的表面活性剂组合物的实施例更详细地说明本发明,但本发明不受这些实施例的限定。
应予说明,非离子活性剂的平均分子量按以下方法测定。
以式C12H25O-(EO)5-(PO)4-(EO)5-H表示的化合物的合成
向带有环氧乙烷用和环氧丙烷用的2个计量槽的5升旋转搅拌式高压釜中加入月桂醇(商品名“Kalcohl 2098”,花王(株)制)500g、氢氧化钾3.0g,氮气置换后升温至110℃,在40乇下脱水1小时。接着,升温至150℃,以3.5kg/cm2的压力将环氧乙烷592g导入高压釜中,使其反应,直到压力降低至一定值,然后冷却至120℃,以3.5kg/cm2的压力将环氧丙烷624g导入高压釜中。与环氧乙烷的情况同样使其反应,直到压力降低到一定值。然后再升温至150℃,导入环氧乙烷592g,使其反应,直到压力降低到一定值。反应结束后,使温度降低,抽出合成的样品,获得约2.3kg的目的聚亚烷基二醇月桂基醚(平均分子量858)。合成例2~14
采用与合成例1同样的方法,获得表1所示的非离子活性剂。
表1
合成例No | 非离子活性剂 | 备注 | |
结构式 | 平均分子量 | ||
合成例2 | n-C12H25O-(EO)3-(PO)1.5-(EO)3H | 537 | 本发明产品 |
合成例3 | n-C12H25O-(EO)3-(PO)4-(EO)3H | 682 | |
合成例4 | n-C12H25O-(EO)5-(PO)2-(EO)5H | 742 | |
合成例5 | n-C12H25O-(EO)7-(PO)2-(EO)5H | 830 | |
合成例6 | n-C12H25O-(EO)7-(PO)3-(EO)3H | 800 | |
合成例7 | n-C12H25O-(EO)7-(PO)4-(EO)7H | 1034 | |
合成例8 | n-C12H25O-(EO)5-(PO)4-(EO)5H | 858 | |
合成例9* | n-C12-13-羰基O-(EO)5-(PO)4-(EO)5H | 870 | |
合成例10 | n-C14H29O-(EO)5-(PO)2-(EO)5H | 770 | |
合成例11 | n-C12H25O-(EO)10-(PO)4-H | 858 | 比较产品 |
合成例12 | n-C12H25O-(PO)4-(EO)6H | 682 | |
合成例13 | n-C12H25O-(EO)10-(PO)4-(EO)10H | 1298 | |
合成例14 | n-C12H25O-(EO)5-(PO)7-(EO)5H | 1032 |
注)
*:将碳原子数12~13的羰基合成醇(商品名“Dobanol 23”,三菱化学(株)制,氢氧基价283)用作原料醇。实施例1~13和比较例1~9
配制具有表2所示组成的表面活性剂组合物,按下述方法测定浸透时间和脱脂率。其结果示于表2。<浸透时间>
使切成2cm×2cm的未精炼坯布(经过退浆处理)飘浮在表面活性剂组合物中,测定沉降所需的时间。在25℃下测定5次,将平均值作为浸透时间。
浸透时间在30秒之内的组合物被认为浸透性良好,低于10秒时浸透性特别高。<脱脂率>
(i)脱脂力评价用人工污染布的配制法
将甘油三酸酯200g溶解到80升四氯乙烯中,将阔幅细布#2003布浸渍其中,使其附着后,干燥除去四氯乙烯,制成人工污染布。
(ii)脱脂力评价方法
将上述人工污染布裁成5cm×5cm,将与每块人工污染布上有效成分0.1g相当的表面活性剂组合物涂布成2cm×2cm的面积,使5块为1组,用涤垢仪(Terg-O-Tometer)以100rpm的转速,按如下条件洗涤。
洗涤条件
洗涤时间 10分钟
水的硬度 4°DH
漂洗 自来水漂洗5分钟
洗涤后,正确地将污染布的涂布有表面活性剂组合物的部分切成2cm×2cm,使5块为1组,以氯仿为溶剂,进行12小时的索氏提取。另外,将未洗涤的人工污染布同样切成2cm×2cm,同样地进行提取。
用蒸发器从提取液中除去氯仿,求出提取的甘油三酸酯量,按下式求出脱脂率。
从表2看出,本发明的表面活性剂组合物,即使浓度比通常还高的含量即30%以上也可以使用,浸透性优良,洗净力也良好,因此可以有效地除去浸透到人工污染布细孔内的污垢。因此,作为衣料用洗涤剂,特别适用于进行预洗的衣料。另一方面,本发明范围以外的非离子活性剂(比较例1~8)不仅浸透性差,而且,即使浸透性良好,洗净力也不充分,脱脂率降低。另外,本发明范围以外的表面活性剂浓度高(比较例9)的场合下也是浸透性恶化,脱脂率降低。实施例14~16、比较例10~11
采用与实施例1同样的方法测定添加了具有表3所示组成的水溶性溶剂的表面活性剂组合物的浸透时间和脱脂率。其结果示于表3中。
从表3看出,本发明的表面活性剂组合物显示出良好的浸透性和洗净性,在使用本发明范围以外的非离子活性剂的比较例10~11中,即使添加溶剂,浸透性和脱脂率也不充分。
本发明的表面活性剂组合物,即使浓度较高,对洗涤对象也会显示出高的润湿浸透性,洗净力也很高,因此对浸透到洗涤对象内部的污垢或对有凹凸部分的洗涤特别有效,特别适于用作餐具用、住宅用、浴室用、衣料用洗涤剂,此外,在工业用途上还可以用作纤维、金属、电子零件等的洗涤剂或需要润湿浸透的有机·无机粉末的分散剂、增溶剂等。
Claims (6)
1.一种表面活性剂组合物,其中,它含有下述式(1)所示的平均分子量低于1200的化合物和水,式(1)化合物对水与式(1)化合物合计量的配比为15~40重量%:
RO-(EO)x-(PO)y-(EO)x′-H (1)式中,R为碳原子数12~15的直链或支链烷基或链烯基,EO为氧化亚乙基,PO为氧化亚丙基;x、x′表示环氧乙烷的平均加成摩尔数,为1以上的数,y表示环氧丙烷的平均加成摩尔数,为0.5~6的数;另外,(EO)x、(PO)y、(EO)x′按顺序依次嵌段结合。
2.权利要求1中所述的组合物,其中,式(1)中,x与x′之和为4~20。
3.权利要求1中所述的组合物,其中,式(1)中,y为1~4.5。
4.权利要求1中所述的组合物,其中,还含有水混合性溶剂0.1~10重量%。
5.一种液体洗涤剂,其中,含有权利要求1中所述的表面活性剂组合物,并且,对洗涤对象的浸透性优良。
6.权利要求5中所述的液体洗涤剂,其中,作为衣料用洗涤剂适用于进行预洗的方面。
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JP32127296 | 1996-12-02 | ||
JP321272/96 | 1996-12-02 |
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CN97193483A Expired - Lifetime CN1090232C (zh) | 1996-12-02 | 1997-12-02 | 表面活性剂组合物 |
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US (1) | US6140297A (zh) |
EP (1) | EP0885951B1 (zh) |
KR (1) | KR100531191B1 (zh) |
CN (1) | CN1090232C (zh) |
DE (1) | DE69731283T2 (zh) |
ES (1) | ES2231897T3 (zh) |
ID (1) | ID20303A (zh) |
TW (1) | TW349994B (zh) |
WO (1) | WO1998024867A1 (zh) |
Families Citing this family (21)
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FR2733246B1 (fr) * | 1995-04-21 | 1997-05-23 | Seppic Sa | Composition anti-mousse comprenant un tensioactif non ionique et un alkylpolyglycoside |
WO1999021949A1 (en) * | 1997-10-28 | 1999-05-06 | Colgate-Palmolive Company | Surfactant system for laundry detergent composition |
JP2000008081A (ja) * | 1998-06-25 | 2000-01-11 | Kao Corp | 洗浄剤組成物 |
KR100657134B1 (ko) * | 2000-05-03 | 2006-12-15 | 주식회사 엘지생활건강 | 에어컨 냉각핀 세척용 에어로졸형 세척제 조성물 |
US6610751B1 (en) * | 2001-12-10 | 2003-08-26 | O'lenick, Jr. Anthony J. | Bimodal guerbet alkoxylates as emulsifiers |
KR100515928B1 (ko) * | 2002-08-28 | 2005-09-20 | 이진식 | 양쪽 말단에 알콜성 기를 갖는 계면활성제를 함유한 의료기기 소독 세척제 및 그의 제조방법 1 |
KR100515929B1 (ko) * | 2002-08-28 | 2005-09-20 | 이진식 | 양쪽 말단에 알콜성 기를 갖는 계면활성제를 함유한 의료기기 소독 세척제 및 그의 제조방법 2 |
KR20050101458A (ko) * | 2004-04-19 | 2005-10-24 | 주식회사 하이닉스반도체 | 포토레지스트 세정액 조성물 및 이를 이용한 패턴 형성방법 |
JP4896475B2 (ja) * | 2005-09-16 | 2012-03-14 | ライオン株式会社 | 衣料用液体洗浄剤組成物 |
JP5295548B2 (ja) * | 2006-12-01 | 2013-09-18 | 花王株式会社 | 床水拭き用助剤 |
US8143205B2 (en) | 2008-02-21 | 2012-03-27 | S.C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion and providing residual benefits |
US8980813B2 (en) | 2008-02-21 | 2015-03-17 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits |
US9481854B2 (en) | 2008-02-21 | 2016-11-01 | S. C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
US8993502B2 (en) | 2008-02-21 | 2015-03-31 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits |
US8143206B2 (en) | 2008-02-21 | 2012-03-27 | S.C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion and providing residual benefits |
US9410111B2 (en) | 2008-02-21 | 2016-08-09 | S.C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
JP4494516B1 (ja) * | 2008-11-21 | 2010-06-30 | 花王株式会社 | 液体洗浄剤組成物 |
JP5685067B2 (ja) * | 2009-12-08 | 2015-03-18 | 花王株式会社 | 木綿布に水拡散促進能を付与する木綿布の処理方法 |
JP5380497B2 (ja) * | 2011-04-01 | 2014-01-08 | 花王株式会社 | 硬質表面用洗浄剤組成物 |
JP6104104B2 (ja) * | 2013-08-28 | 2017-03-29 | 花王株式会社 | 紙用液体嵩高剤 |
WO2019012055A1 (en) * | 2017-07-14 | 2019-01-17 | Basf Se | BIODEGRADABLE SURFACTANT |
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1997
- 1997-11-25 TW TW086117673A patent/TW349994B/zh active
- 1997-12-02 ID IDW980056D patent/ID20303A/id unknown
- 1997-12-02 ES ES97946069T patent/ES2231897T3/es not_active Expired - Lifetime
- 1997-12-02 US US09/117,182 patent/US6140297A/en not_active Expired - Lifetime
- 1997-12-02 WO PCT/JP1997/004394 patent/WO1998024867A1/ja active IP Right Grant
- 1997-12-02 CN CN97193483A patent/CN1090232C/zh not_active Expired - Lifetime
- 1997-12-02 EP EP97946069A patent/EP0885951B1/en not_active Expired - Lifetime
- 1997-12-02 KR KR1019980705984A patent/KR100531191B1/ko not_active IP Right Cessation
- 1997-12-02 DE DE69731283T patent/DE69731283T2/de not_active Expired - Lifetime
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GB1601652A (en) * | 1977-03-16 | 1981-11-04 | Mitsubishi Petrochemical Co | Liquid detergents comprising nonionic surfactants |
Also Published As
Publication number | Publication date |
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KR100531191B1 (ko) | 2006-01-27 |
KR19990082255A (ko) | 1999-11-25 |
CN1214724A (zh) | 1999-04-21 |
EP0885951A2 (en) | 1998-12-23 |
DE69731283D1 (de) | 2004-11-25 |
WO1998024867A1 (fr) | 1998-06-11 |
US6140297A (en) | 2000-10-31 |
ID20303A (id) | 1998-11-26 |
DE69731283T2 (de) | 2005-11-24 |
TW349994B (en) | 1999-01-11 |
ES2231897T3 (es) | 2005-05-16 |
EP0885951A4 (en) | 2000-08-16 |
EP0885951B1 (en) | 2004-10-20 |
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