CN1267715A - 交联聚乙烯基吡咯烷酮在增加密实粒状洗涤剂和清洁剂的碎裂速率中的应用 - Google Patents
交联聚乙烯基吡咯烷酮在增加密实粒状洗涤剂和清洁剂的碎裂速率中的应用 Download PDFInfo
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Abstract
本发明涉及交联聚乙烯基吡咯烷酮作为密实粒状洗涤剂和清洁剂的添加剂的应用,以便在其与水接触时增加其碎裂速率,还涉及粒度为50~400μm的交联聚乙烯基吡咯烷酮颗粒、制备密实粒状洗涤剂和清洁剂的方法、和密实粒状洗涤剂和清洁剂本身。
Description
本发明涉及交联聚乙烯基吡咯烷酮作为密实粒状洗涤剂和清洁剂的添加剂的应用,以便在其与水接触时增加其碎裂速率,还涉及粒度为50~400μm的交联聚乙烯基吡咯烷酮颗粒、制备密实粒状洗涤剂和清洁剂的方法、和密实粒状洗涤剂和清洁剂本身。
制造致密或密实洗涤剂和清洁剂组合物的方法包括各种团聚、密实或造粒技术。在以如粒状存在的密实洗涤剂和清洁剂产品情况下,难以实现在水的作用下适宜的强度性能和足够快地溶解或碎裂之间的适当平衡。例如,置于洗涤机运转室内的洗涤剂颗粒必须在其与水接触之后1分钟以内碎裂。当洗涤剂颗粒仅仅有微小的密实度时,可得到满意的碎裂速率,但是,这在应用中经常以牺牲所要求的抗碎性或耐磨性为代价。如此制备的颗粒仅仅有低抗碎性,并且在运输期间有粉碎和破碎倾向。另一方面,在生产洗涤剂颗粒时施加过度的密实或压缩,会导致在使用中的洗涤剂颗粒的碎裂时间或溶解时间过长,以致达到不能令人满意。
已知各种密实或超密实洗涤剂和清洁剂,参见EP-A 340,013、EP-A 0,518,888、DE-A19、649,560和DE-A 19,649,565。为了改善颗粒洗涤剂配方的溶解速度,使用增溶添加剂,它包括例如疏水和亲水单体的共聚物,如苯乙烯和丙烯酸的共聚物,参见WO-A97/46657。按照WO-A 97/46529所述,颗粒洗涤配方的溶解速率是通过使用诸如环氧乙烷和/或环氧丙烷和多元醇的加成物达到的。
制造药物片剂的方法展现了许多制备具有所要求的强度性能和碎裂时间的颗粒的可能途径。使颗粒碎裂的主要作用机理可叙述为润湿、毛细管作用(芯吸作用)和溶胀,参见“药物研究及工业制药”(Drug Development and Industrial Pharma),卷6(5)511~536(1980)。在改进片剂可溶性的产品中,提及了化交联溶胀产物,如微晶交联、羧甲基纤维素、交联羧甲基淀粉钠或交联聚乙烯基吡咯烷酮(参见,Volker Buehler,Kollidon-药物工业用聚乙烯基吡咯烷酮)(Polyvingl pyrrolidone for the pharmaceutical industry,BASF, 993年8月,第156页以下等)。
由于洗涤剂中非离子表面活性剂和其它低熔蜡状可塑性变形组合物的原因,将由制药已知的片剂碎裂剂加入到密实洗涤剂和清洁剂中很少成功,特别是在洗衣用的密实洗涤剂的情况下更是难以成功。
已知,当密实洗涤剂和清洁剂(具有洗涤剂和清洁剂作用的成形颗粒)含有特殊粒状的、象制药学中所知的那样的、并能够增加成形粒子孔隙度或毛细现象的和具有高吸水能力的碎裂剂时,其碎裂速率会增加。(参见DE 197 10 254 A1。)
以这种方法制备的密实洗涤剂和清洁剂的碎裂速率的确有所增加,但是增加得还不够高,特别是在密实洗涤剂和清洁剂是经受较高压实压力以增加其尺寸稳定性和耐破碎性的情况下。另外,这样制备的密实洗涤剂和清洁剂还存在的缺点是,碎裂剂在压实工序之前必须在加工工序中转变成粒状。
因此,本发明的目的是提供一种添加剂,它进一步增加密实粒状洗涤剂和清洁剂的碎裂速率,而又没有上述缺点。
在本发明中,通过使用交联聚乙烯基吡咯烷酮作密实粒状洗涤剂和清洁剂的添加剂以增加其在与水接触时的碎裂速率达到了上述目的,交联聚乙烯基吡咯烷酮颗粒的粒度为50~400μm的。
所谓密实粒状洗涤剂和清洁剂,在本发明是指具有洗涤剂或清洁剂作用的成形颗粒,特别是诸如洗涤剂颗粒、洗碗颗粒、漂白颗粒、除污斑颗粒或水软化颗粒,特别是家用洗衣用洗涤剂颗粒,特别是机用洗涤剂颗粒。
术语“成形颗粒”并不限于球团粒。
在理论上,诸如颗粒、球、挤出物、环、条或片之类的任何三维形状都是可能的,例如可借助包皮层使原料具有这些形状。
所谓交联聚乙烯基吡咯烷酮,是优选系指在药物工业中用作片剂碎裂剂的交联聚乙烯基吡咯烷酮,例如Killidon CL或Luvicross(商品名,BASF股份有限公司,Ludwigshafen,参见,VolkerBuehler,Kollidon-药物工业用聚乙烯基吡咯烷酮,BASF,1993年8月,第156页以下等)。
所使用的交联聚乙烯基吡咯烷酮颗粒的粒度为50~400μm,优选为80~300μm。
按照本发明,特别优选使用交联聚乙烯基吡咯烷酮,其粒度为50~400μm,优选其粒度为80~300μm,并且至少10%重量、优选15%(重量)、更优选25%(重量)的粒子的粒度在200μm以下。
为了得到这种优选的粒度分布,使通过诸如爆米花状的聚合和干燥、以赋予宽粒度分布的已知方法生产的聚乙烯基吡咯烷酮固体(Kollidon CL或Luvicross),经诸如过筛或气动分级之类的适当分级方法直接进行粒度分级,而不需要为得到所要求的粒度分布而实施另外的造粒工序。干燥按已知方法进行,例如采用转鼓干燥。
本发明还涉及含有0.5~20%(重量)、优选含有0.5~10%(重量)、更优选0.5~5%(重量)的上述交联聚乙烯基吡咯烷酮的密实颗粒洗涤剂和清洁剂,以便其与水接触时增加碎裂速率。
在一个优选的实施方案中,交联聚乙烯基吡咯烷酮的颗粒,按其优选应用,粒度为50~400μm,并且至少10%(重量)的粒子的粒度在200μm以下。
上述已经说明了密实粒状洗涤剂和清洁剂。所优选的密实颗粒洗涤剂和清洁剂是适用于水洗衣物的成形颗粒,也就是说它是一种除了含有本发明提出的交联聚乙烯基吡咯烷酮之外,还含有各种用于洗涤衣物的洗涤剂的通用成分的密实颗粒洗涤剂和清洁剂。
本发明的密实粒状洗涤剂和清洁剂是按已知方法通过将粉状成分成形,特别是通过密实或压缩,优选通过压块制成的,所谓的粉状成分包括:作为碎裂剂的交联聚乙烯基吡咯烷酮和洗涤剂或清洁剂的通用成分、漂白剂和水软化剂(″Tablettieren:Stand der Technik″(制片法:工艺现状),SFW-Journal,1996,第122年刊,P1016~1021)。
密实粒状洗涤剂和清洁剂的普通成分是,例如离子、非离子、阳离子、两性和两性离子表面活性剂;无机和有机、水熔性或水不溶性助洗剂和共助洗剂;漂白剂,特别是过氧漂白剂,而且还有活性氯化合物,其有利的是被涂敷的漂白活化剂和漂白催化剂;酶和酶稳定剂;消泡剂;防灰化剂;染料传递抑制剂;光学增白剂;防止物再沉积在纺织品上的物质,即,防护剂;还有诸如硫酸盐之类的通用无机盐和诸如膦酸盐的有机盐;光学增白剂;着色剂和香料或阻蚀剂。
所优选的洗涤剂是含有至少一种表面活性剂和至少一种助洗剂作为其成分的所谓的密实洗涤剂。
为了制备本的密实粒状洗涤剂和清洁剂,加入上述交联聚乙烯基吡咯烷酮,以增加碎裂速率,其加入量按具有洗涤剂和清洁剂活性的成形粒子的重量计优选为0.5~20%(重量),更优选为0.5~10%(重量),最优选为0.5~5%(重量),在最终密实或造粒之前将其加到通常的粉状洗涤剂或清洁剂成分、漂白剂和水软化剂或其粉状前体或部分组分中。洗涤剂或清洁剂的通常的粉状成分,漂白剂和水软化剂、其前体或部分组分以诸如粉状、粒状或挤出物等形式存在。它们的粒度范围为,例如,200μm~3mm,优选为250μm~2mm。
在将通常的粉状洗涤剂或清洁剂成分、漂白剂和水软化剂或其部分组分与按照本发明使用的交联聚乙烯基吡咯烷酮混合之后,将所得混合物,还可在进一步的混合步骤之后,通过诸如挤压或压块之类的手段加工,以形成团聚的密实的质量密度增加的成形块体。如此制成了例如粒状体、球状体、挤出物、环状体或片状体。该混合物可以下述方式分割,即,例如,所得到的粒状体或球状体这样的大小,即在洗涤机中一次洗涤仅需1~3个粒状体或球状体。从如此形成的混合物制的成形块体的直径为例如1~50mm,优选2~35mm。
按照本发明使用交联聚乙烯基吡咯烷酮作为密实粒状洗涤剂和清洁剂的添加剂,致使该密实颗粒洗涤剂和清洁剂在与水接触时,其碎裂速率显著增加。甚至这种碎裂、强压缩成形的块体在几秒钟内碎裂。这样不仅能够借助定量给料设备将该密实粒状洗涤剂和清洁剂直接加到机械法水成液中,而且也能够把该密粒粒状洗涤剂和清洁剂直接置于市售家用机特别是洗涤设备的水槽中。
下面参见如下实施例,叙述本发明。
实施例1~4
在混合器中加工如下所给的粉状颗粒洗涤剂组合物A(堆积密度约770g/L)和交联聚乙烯基吡咯烷酮(实施例1和2:粒度80~400μm,实施例3和4:粒度小于100μm),得到均匀共混物;采用普通偏心式压机(Korsch出售,EK O DMS型)在表中所叙条件下将共混物压制成颗粒,所得颗粒重约3g(直径20mm)所有混合物均含有按照本发明使用的5%的交联聚乙烯基吡咯烷酮。检验颗粒,测定其在水中的碎裂特性(见表)。
借助购自Kraemer公司(Darmstadt)的颗粒检测仪测定颗粒硬度。该仪器测定使颗粒破碎所必须的水平力。
为测定溶解性,采用购自Erweka公司的碎裂计时器。为此,将颗粒置于具有筛底的碎裂笼检测器中,并在温控水浴中受到搅拌(往复运动速率:每分钟上下运动30次,距离20mm)。测定从筛子除去所有微量洗涤剂所需要的时间。结果列于下表。
洗涤剂组合物A(均为重量百分数)烷基苯磺酸盐 8钾椰子皂 1.2非离子表面活性剂 6(1mol C13~C15脂肪醇与7mol环氧
乙烷反应)沸石A 35碳酸钠 8硅酸钠×5.5H2O 6柠檬酸钠 4过碳酸钠 18四乙酰乙二胺(TAED) 5配位剂 0.3(乙二胺四亚甲基膦酸酯)聚(丙烯酸-共-马来酸)70∶30,分子量70,000 4硫酸钠 3其它组分 2.5(香料,消泡剂,酶、光学增白剂)堆积密度 约770g/l粒度 约700~1000μm
比较实例1和2
为了进行比较,从粉状洗涤剂A制取重约3g直径为20mm的粒状体,并进行测试评定其在水中的碎裂性能(见下表)。象实施例1~4所述进行读数。
洗涤剂颗粒性能
实例 | 洗涤剂A含有的PVD粒度 | 密实力kN | 密实力MPa | 破碎力N | 破裂时间 |
1 | 80 to 400μm | 6.48 | <3 | <5秒 | |
2 | 80 to 400μm | 29.41 | 12 | <10秒 | |
3 | <100μm | 5.98 | <3 | 30分 | |
4 | <100μm | 26.39 | 14 | 30分 | |
比较例 | 未加入PVD | 4.09 | 13 | 8 | >30分 |
比较例 | 未加入PVD | 7.97 | 25 | 11 | >30分 |
显而易见,在本发明中加入直径为80~400μm的粒状交联聚乙烯基吡咯烷酮,致使洗涤剂颗粒的碎裂显然进行得更快,并且其耐破裂性显然更高。
Claims (5)
1.一种使用交联聚乙烯基吡咯烷酮作为密实粒状洗涤剂和清洁剂的添加剂的方法,以便使其与水接触时增加其碎裂速率,其中交联聚乙烯基吡咯烷酮颗粒的粒度为50~400μm。
2.权利要求1的方法,其中至少10%(重量)的交联聚乙烯基吡咯烷酮颗粒的粒度为200μm以下。
3.权利要求1或权利要求2的方法,其中颗粒是通过将聚合和干燥制备的聚乙烯基吡咯烷酮固体经直接分级得到的。
4.一种密实粒状洗涤剂或清洁剂,其含有0.5~20%(重量)的交联聚乙烯基吡咯烷酮,以便在使其与水接触时增加其碎裂速率,交联聚乙烯基吡咯烷酮颗粒的粒度为50~400μm,而至少10%(重量)的所述颗粒的粒度小于200μm。
5.一种制造含有以交联聚乙烯基吡咯烷酮作碎裂剂的密实粒状洗涤剂或清洁剂的方法,其中交联聚乙烯基吡咯烷酮以0.5~20%(重量)的含量与粉状洗涤剂成分混合,交联聚乙烯基吡咯烷酮颗粒的粒度为50~400μm,而至少10%(重量)的所述颗粒的粒度为200μm以下,在混合之后,压缩该混合物使其成为密实状。
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DE19912031A DE19912031A1 (de) | 1999-03-17 | 1999-03-17 | Verwendung von quervernetztem Polyvinylpyrrolidon zur Erhöhung der Zerfallgeschwindigkeit von kompakten teilchenförmigen Wasch- und Reinigungsmitteln |
DE19912031.5 | 1999-03-17 |
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CN1267715A true CN1267715A (zh) | 2000-09-27 |
CN1165605C CN1165605C (zh) | 2004-09-08 |
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US (1) | US6329334B1 (zh) |
EP (1) | EP1036839A3 (zh) |
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CN110184129A (zh) * | 2019-06-24 | 2019-08-30 | 东莞市水卫仕日化有限公司 | 洗涤剂组合物及其制备方法和应用 |
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US6974789B1 (en) * | 1999-01-23 | 2005-12-13 | The Procter & Gamble Company | Detergent tablet |
DE50102470D1 (de) | 2000-03-10 | 2004-07-08 | Basf Ag | Verwendung von quervernetztem polyvinylpyrrolidon als sprengmittel in kompakten, teilchenförmigen wasch- und reinigungsmitteln |
KR100366399B1 (ko) * | 2000-07-06 | 2003-01-09 | 주식회사피죤 | 크림상 세탁용 세제 조성물 |
WO2002033037A1 (en) * | 2000-10-18 | 2002-04-25 | The Procter & Gamble Company | Detergent tablet |
EP1389230A1 (en) * | 2000-11-24 | 2004-02-18 | Unilever N.V. | Cleaning compositions |
EP1219700A1 (en) * | 2000-12-28 | 2002-07-03 | Unilever Plc | Cleaning compositions |
US6586386B2 (en) | 2001-10-26 | 2003-07-01 | Isp Investments Inc. | Tablet of compacted particulate cleaning composition |
US6821941B2 (en) | 2002-10-23 | 2004-11-23 | Isp Investments Inc. | Tablet of compacted particulated cleaning composition |
ES2403167T3 (es) * | 2005-12-21 | 2013-05-14 | Basf Se | Polivinilpirrolidona entrelazada finamente dividida como agente desintegrador de tabletas |
US8568780B2 (en) | 2007-06-06 | 2013-10-29 | Basf Se | Pharmaceutical formulation for the production of rapidly disintegrating tablets |
BRPI0812064B8 (pt) | 2007-06-06 | 2021-05-25 | Basf Se | formulação farmacêutica na forma de aglomerados, comprimidos, e, processo para a produção de uma formulação farmacêutica |
DE102010051226A1 (de) * | 2010-11-12 | 2012-05-31 | Dental Care Innovation Gmbh | Ausspültablete mit abrasiven Bestandteilen |
EP3377549A4 (en) | 2015-11-20 | 2019-07-03 | ISP Investments LLC | PROLIFERATIVE POLYMERS WITH LACTINE UNITS |
US10626350B2 (en) | 2015-12-08 | 2020-04-21 | Ecolab Usa Inc. | Pressed manual dish detergent |
CN110505867A (zh) | 2017-02-02 | 2019-11-26 | 洁碧有限公司 | 用于牙齿清洁的包括研磨剂的片剂 |
JP7195771B2 (ja) | 2018-06-11 | 2022-12-26 | 株式会社日本触媒 | ポリビニルピロリドン重合体の製造方法 |
WO2023117494A1 (en) | 2021-12-20 | 2023-06-29 | Basf Se | Polypropylene imine polymers (ppi), their preparation, uses, and compositions comprising such ppi |
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DE4007601A1 (de) | 1990-03-09 | 1991-09-12 | Henkel Kgaa | Verfahren zum herstellen von granulaten eines wasch- oder reinigungsmittels |
GB9015504D0 (en) * | 1990-07-13 | 1990-08-29 | Unilever Plc | Detergents composition |
GB9015503D0 (en) * | 1990-07-13 | 1990-08-29 | Unilever Plc | Detergent composition |
GB9114184D0 (en) * | 1991-07-01 | 1991-08-21 | Unilever Plc | Detergent composition |
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