CN1180071C - 铸造洗涤剂组合物 - Google Patents
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Abstract
一种熔体铸造固体成形洗涤剂条组合物,它包含:2~60%不溶于水的结构剂和2~50%洗涤活性剂,其特征在于,它包含0.5~30%盐溶电解质和30~80%水。
Description
技术领域
本发明涉及熔体铸造固体成形(melt-cast solid shaped)的洗涤剂组合物。
片状洗涤剂在传统上采用以下两种方法之一制造:(i)配制物的剪切混炼/均化,然后挤出和冲压,或者(ii)铸造(casting)。
在片状洗涤剂采用剪切混炼并挤出的制造中,可结合到配制剂中的水量小于约15%。此种体系是多相复合物,表现为“砖悬浮在灰泥中”的形态类型。砖是固体颗粒,在香皂的情况下,它是长链饱和脂肪酸的结晶盐、无机填料等。灰泥是由各种含水易溶的液晶或各向同性溶液相、液体添加剂以及相对地可溶于水的肥皂或表面活性剂组成的混合物。此类组合物一般由50~60%固体、20~30%亲液液晶相和约10%各向同性液体组成。
在采用铸造制造洗涤剂组合物中,配制的体系通过提高温度而转变为流体状态,注入到模具中,然后冷却。此种技术通常用于制造透明个人洗涤片剂,除其他成分(如肥皂和合成表面活性剂)之外,铸造时通常包含15~50%昂贵成分如乙醇、多羟基醇、糖等。US4,165,293(Amway,1979);WO96/04361(P&G,1996)公开一种固体透明皂条,包含肥皂、合成表面活性剂和水溶性有机溶剂如丙二醇。此种组合物中的含水量为约10~32%。
通过采用铸造而制造不透明洗涤剂片剂的问题是,典型组合物不能在高温形成可倾注液体。US5,340,492(P&G,1994)公开一种具有三维骨架结构的可铸造组合物,包含中和的结晶羧酸(肥皂)的相对刚性互锁网络、合成表面活性剂和高含量水以及其他液体。然而,该专利并未表明在组合物中不需要使用约15%丙二醇这一点。
公开在US5,340,492中的组合物将是软的,表现出当采用干酪金属丝切割器具(cheese wire cutter apparatus)测定时小于75kPa的屈服应力,因此不能用作刚挺到足以方便地拿在手中使用的刚挺片剂。为了增加皂条的刚性,该专利中的实施例假借所谓“条外观助剂”在组合物中采用诸如多元醇(例如,丙二醇)之类的成分。该专利却未公开任何一种当组合物中还存在合成表面活性剂时不含“条外观助剂”的组合物。此种条外观助剂既昂贵,又会减少起泡量和速度。
本发明的目的是获得一种固体成形洗涤剂组合物,它具有非常高的水和液体有益剂(benefit agents)含量,刚挺并且经济,同时保持良好使用性能。
现已发现,少量盐溶电解质在含有非常高含量水或液体有益剂的熔体铸造洗涤剂组合物中的加入能产生一种表现出当采用干酪金属丝切割器具测定时大于75kPa屈服应力的刚性固体成形制品。此种组合物可拿在手中,并且经济、高起泡,显示良好使用性能。
按照本发明第一方面,提供一种熔体铸造固体成形洗涤剂组合物,它包含:
a)2~60%不溶于水的结构剂(structurant);
b)2~50%洗涤活性种物质(species);
c)0.5~30%盐溶电解质;
d)30~80%水;
以及任选地其他液体有益剂。
按照一个优选的方面,本发明涉及一种熔体铸造固体成形洗涤剂组合物,它包含:
a)2~50%不溶于水的结构剂,选自包含一种或多种中和的C6~C24脂肪酸的饱和脂肪酸皂,
b)2~40%洗涤活性物质,
c)0.5~20%盐溶电解质,以及
d)30~80%水
以及任选地其他液体有益剂。
按照更优选的方面,本发明涉及一种熔体铸造固体成形洗涤剂组合物,它包含:
a)5~40%含一种或多种C12~C24脂肪酸的饱和脂肪酸皂,
b)2~20%洗涤活性物质,
c)0.5~15%盐溶电解质,以及
d)35~70%水
以及任选地其他液体有益剂。
优选的是,洗涤活性剂主要是非皂类。
按照本发明另一个方面,提供一种制造固体成形洗涤剂组合物的方法,包括下列步骤:
a)制造上述组合物的熔体,
b)将所述熔体倾倒入模具中以获得要求的形状,以及
c)在静止条件下冷却该模具以发生凝固。
本发明方法可用来制造铸入式包装(cast-in-pack)固体成形洗涤剂组合物,包括下列步骤:
a)制造上述组合物的熔体,
b)将所述熔体倾倒入预成形聚合物模具中以获得要求的形状,以及
c)密封所述模具,以及
d)在静止条件下冷却该模具以发生凝固。
本发明涉及一种关键在于包含盐溶电解质的熔体铸造固体成形洗涤剂组合物及其制造方法。
本发明组合物的固体成形制品刚挺到足以方便地拿在手里,经济,高起泡,并且显示良好使用性能。该组合物显示当采用干酪金属丝切割器具测定时大于75kPa的屈服应力值。
本发明组合物中使用的盐溶电解质选自开列在“Hofmeister”或“易溶的”(“Lyotropic”)系列中的那些。盐溶电解质是其电解质阴离子的感胶离子数大于10的那些电解质,并且选自NO2 -,ClO3 -,Br-,NO3 -,ClO4 -,I-,CNS-,C6H5SO3 -,C6H4CH3SO3 -和Cr2O7 2-。本发明组合物使用的盐溶电解质的优选例子是上述阴离子的碱金属盐。本发明组合物使用的盐溶电解质的最优选例子是甲苯磺酸钠、枯烯磺酸钠和二甲苯磺酸钠。
不溶于水的结构剂优选地选自含一种或多种C6~C24脂肪酸的饱和脂肪酸皂。术语“(肥)皂”是指脂肪羧酸的盐。作为不溶于水的结构剂的皂可以是饱和脂肪酸的钠、钾、镁、铝、钙或锂盐。尤其优选的是具有以饱和脂肪酸钠或钾盐形式获得的皂。该皂可由一种或多种C12~C24饱和脂肪酸制取。
组合物中不溶于水的结构剂优选占组合物重量的5~50wt%,更优选5~40wt%。
本发明组合物包含洗涤活性剂,它可以是皂基或非皂基的。优选使用选自阴离子、非离子、阳离子、两性或两性离子表面活性剂、或它们的混合物的非皂洗涤活性剂。
合适的阴离子洗涤活性化合物是有机硫反应产物的水溶性盐,其分子结构中具有8~22个碳原子烷基基团以及选自磺酸或硫酸酯基团及其混合物的基团。合成阴离子洗涤活性化合物的某些例子是线型烷基苯磺酸盐、月桂基硫酸钠、月桂基醚硫酸钠、α-烯烃磺酸盐、烷基醚硫酸盐、磺酸脂肪族甲基酯(fatty methyl ester sulphonate)、烷基羟乙基磺酸盐等。另一些阴离子表面活性剂是皂,后者可选自下列酸的盐:不饱和脂肪酸如油酸、蓖麻油酸、月桂烯酸、十一烷酸、肉豆蔻脑酸(myristolic acid)、棕榈炔酸、芥酸(erusic acid)、亚油酸、亚麻酸或其混合物。
最适合上述洗涤活性物质中的阳离子是钠、钾、铵以及各种各样胺,例如一乙醇胺、二乙醇胺和三乙醇胺。
合适的非离子洗涤活性化合物可广义地描述为通过烯化氧基团,其本身为亲水性的,与脂族或烷基芳族性质的有机疏水化合物缩合所生成的化合物。常见非离子表面活性剂是具有8~22个碳原子的或者直链或支化链构型的脂族醇与环氧乙烷的缩合产物,例如每摩尔椰子醇具有2~15mol环氧乙烷的椰子油环氧乙烷缩合物。非离子表面活性剂的某些例子是烷基酚环氧乙烷(EO)缩合物、牛油醇10EO缩合物、烷基二甲基(demethyl)胺氧化物、月桂基一乙醇酰胺等。
两性洗涤活性剂的某些例子是椰油酰氨基丙基甜菜碱、椰油甜菜碱等。
也可任选地在本发明组合物中包括进阳离子或两性离子洗涤活性剂。
另一些适宜洗涤活性物质的例子在下面著名教科书中给出:(i)《表面活性剂》,卷I,Schwartz和Perry,(ii)《表面活性剂与洗涤剂》,卷II,Schwartz、Perry和Berch,(iii)《表面活性剂手册》,M.R.Porter,Chapman和Hall,纽约,1991。
本发明洗涤剂组合物中使用的洗涤活性剂优选是阴离子的并且通常高至50%,更优选2~30%。
按照本发明优选的方面,液态有益皮肤材料如润湿剂、润肤剂、防晒剂、抗老化化合物被结合到该组合物中。合适的润湿剂和保湿剂的例子包括多元醇、甘油、鲸蜡醇、丙烯酸聚合物(Carbopol)934、乙氧基化蓖麻油、石蜡油、羊毛脂及其衍生物。硅氧烷化合物如硅氧烷表面活性剂,像DC3225C(Dow Corning)和/或硅氧烷润肤剂、硅油(DC-200 Ex-Dow Corning)也可包括在内。防晒剂,如4-叔丁基-4’-甲氧基二苯甲酰甲烷(按商品名PARSOL 1789由Givaudan供应)和/或肉桂酸2-乙基己基甲氧基酯(按商品名PARSOL MCX由Givaudan供应)或者其他UV-A和UV-B防晒剂。
其他任选的成分如头发调理剂、填料、着色剂、香料、不透明剂、防腐剂、一种或多种水溶性粒料如滑石粉、高岭土,多糖以及其他传统成分也可结合到该组合物中。
制造本发明固体成形洗涤剂组合物的方法包括下列步骤:
i.将例如不溶于水的结构剂、洗涤活性剂、盐溶电解质和水在搅拌器/混合机中在大于50℃的高温下进行混合,以获得可倾倒熔体。
ii.将熔体倾倒入刚性或柔性模具中。优选使用接近网形状(nearnet shape)的柔性聚合物模具,这可采用热成形技术按要求的形状取得。
iii.让组合物在模具中冷却以发生凝固。
iv.洗涤剂制品可被脱模。
可适宜地选择模具用来生产接近网形状的(near net shape)片剂或生产条/块。条/块还可进一步成形为洗涤剂制品。
如果固体洗涤剂制品采用接近网形状的热成形聚合物生产,则将模具密封以获得铸入式包装洗涤剂组合物。为获得铸入式包装洗涤剂组合物,模具优选在模具注满之后立即密封起来。
下面,将通过例子来说明本发明,但下面的例子仅为说明给出,并且不具有限制性。
实例:
组合物制备
包含下面给出的脂肪酸、非皂洗涤剂和盐溶电解质的混合物,在2L容积的圆底烧瓶中进行混合。批料温度升高到80℃。在该混合物中加入氢氧化钠水溶液,以便使脂肪酸皂化。批料温度维持在80℃以便获得澄清溶液。80℃的皂的熔体倒入热成形聚合物模具中,密封住模具的进口。让模具冷却,从而使皂发生凝固,从而获得铸入式包装洗涤剂组合物。用上述制造方法制备表1和2中所列皂条。制成的皂条的刚性采用下面所描述的程序用屈服应力表示加以测定。
屈服应力是采用“干酪金属丝切割器具”测定的。该设备由干酪金属丝安装在靠球轴承可自由摆动的臂上组成。皂料坯位于金属丝下面,使金属丝刚好接触料坯。一个已知重量直接位于干酪金属丝上方,使金属丝切入到料坯中。1min后,拿去重量,采用游标卡尺测定切口长度。屈服应力(Y.S.),以帕(Pa)为单位,采用下式计算:
其中l=切口长度,cm
d=金属丝直径,cm,
w=干酪金属丝上方的重量,g
表1
成分(wt%) | 1 | 2 | 3 | 4 | 5 | 6 | |
结构剂 | 硬脂酸钠 | 12 | 12 | 12 | 20 | 20 | 20 |
洗涤活性剂 | 月桂基醚硫酸钠 | 10 | 10 | 17 | 15 | 15 | 25 |
盐溶电解质 | 甲苯磺酸钠 | 7 | 0 | 0 | - | - | - |
硫氰酸钾 | - | - | - | 10 | 0 | 0 | |
任选的成分 | 丙二醇 | 0 | 0 | 0 | 10 | 10 | 10 |
水 | 水 | 71 | 78 | 71 | 45 | 55 | 45 |
屈服应力(kPa) | 138 | 35 | 17 | 372 | 66 | 27 |
表1中所给出的数据显示,感胶离子数大于10的盐溶电解质在洗涤剂组合物中的加入对生产表现出大于75kPa屈服应力从而可方便地拿在手中使用的含45~71%水的刚挺片剂很关键。相比之下,不加盐溶电解质所获得的组合物呈膏体般粘稠,无法作为刚挺片剂拿在手中方便地使用。
表2给出几个例子,展示感胶离子数大于10的盐溶电解质在洗涤剂组合物中的加入对生产表现出大于75kPa屈服应力的刚挺片剂很关键。在表2中给出的例子中,不加盐溶电解质所获得的组合物(1a~12a)如膏体般粘稠(屈服应力小于75kPa),无法作为刚挺片剂拿在手中方便地使用。相比之下,采用盐溶电解质所获得的组合物(1b~12b)则刚挺,显示大于75kPa的屈服应力,因而可方便地拿在手中使用。
表2(i)
组分 | 1a | 1b | 2a | 2b | 3a | 3b | 4a | 4b |
硬脂酸钠 | 15 | 15 | 20 | 20 | - | - | 7.7 | 7.7 |
棕榈酸钠 | - | - | - | - | 15 | 15 | 9.4 | 9.4 |
羟基硬脂酸钠 | - | - | - | - | - | - | - | - |
肉豆蔻酸钠 | - | - | - | - | - | - | - | - |
月桂酸钠 | - | - | - | - | - | - | - | - |
山萮酸钠 | - | - | - | - | - | - | - | - |
月桂基醚硫酸钠 | 10 | 10 | 15 | 15 | 10 | 10 | 8.6 | 8.6 |
椰油甜菜碱 | - | - | - | - | - | - | - | - |
椰油酰氨基丙基甜菜碱 | - | - | - | - | - | - | - | - |
油酸钠 | - | - | - | - | - | - | - | - |
蓖麻油酸钠 | - | - | - | - | - | - | - | - |
甲苯磺酸钠 | - | 10 | - | - | - | 10 | - | 15 |
碘化钾 | - | - | - | - | - | - | - | - |
硫氰酸钾 | - | - | - | 10 | - | - | - | - |
硝酸钠 | - | - | - | - | - | - | - | - |
丙二醇 | - | - | 10 | 10 | - | - | - | - |
水 | 75 | 65 | 55 | 45 | 75 | 65 | 74.3 | 59.3 |
屈服应力(kPa) | 48 | 154 | 66 | 372 | 75 | 103 | 25 | 230 |
表2(ii)
组分 | 5a | 5b | 6a | 6b | 7a | 7b | 8a | 8b |
硬脂酸钠 | 14 | 14 | 16 | 16 | 18.8 | 18.8 | 13 | 13 |
棕榈酸钠 | - | - | - | - | - | - | - | - |
羟基硬脂酸钠 | - | - | - | - | - | - | - | - |
月桂酸钠 | - | - | - | - | - | - | - | - |
山萮酸钠 | - | - | - | - | - | - | - | - |
月桂基醚硫酸钠 | 15 | 15 | 15 | 15 | 15.6 | 15.6 | - | - |
椰油甜菜碱 | - | - | - | - | - | - | - | - |
椰油酰氨基丙基甜菜碱 | - | - | - | - | - | - | 10 | 10 |
油酸钠 | - | - | - | - | - | - | - | - |
蓖麻油酸钠 | - | - | - | - | - | - | - | - |
甲苯磺酸钠 | - | - | - | - | - | 10 | - | 7 |
碘化钾 | - | - | - | 15 | - | - | - | - |
硫氰酸钾 | - | - | - | - | - | - | - | - |
硝酸钠 | - | 10 | - | - | - | - | - | - |
丙二醇 | 2 | 2 | 4 | 4 | 8.3 | 8.3 | - | - |
水 | 69 | 59 | 65 | 50 | 57.3 | 47.3 | 77 | 70 |
屈服应力(kPa) | 27 | 141 | 22 | 274 | 25 | 230 | 18 | 96 |
表2(iii)
组分 | 9a | 9b | 10a | 10b | 11a | 11b | 12a | 12b |
硬脂酸钠 | 6.8 | 6.8 | 14 | 14 | 10.8 | 10.8 | 16.2 | 16.2 |
棕榈酸钠 | 7.2 | 7.2 | - | - | - | - | - | - |
羟基硬脂酸钠 | 2.2 | 2.2 | - | - | - | - | - | - |
肉豆蔻酸钠 | - | - | - | - | 2.2 | 2.2 | - | - |
月桂酸钠 | - | - | 4.4 | 4.4 | 2.2 | 2.2 | - | - |
山萮酸钠 | - | - | - | - | 2.1 | 2.1 | - | - |
月桂基醚硫酸钠 | 30 | 30 | 30 | 30 | 30 | 30 | - | - |
椰油甜菜碱 | - | - | - | - | - | - | 10 | 10 |
椰油酰氨基丙基甜菜碱 | - | - | - | - | - | - | - | - |
油酸钠 | 4.3 | 4.3 | - | - | - | - | - | - |
蓖麻油酸钠 | 2.2 | 2.2 | - | - | - | - | - | - |
甲苯磺酸钠 | - | - | - | 15 | - | 15 | - | 10 |
碘化钾 | - | - | - | - | - | - | - | - |
硫氰酸钾 | - | 15 | - | - | - | - | - | - |
硝酸钠 | - | - | - | - | - | - | - | - |
丙二醇 | 15 | 15 | 15 | 15 | 15 | 15 | - | - |
水 | 32.3 | 17.3 | 36.6 | 21.6 | 37.7 | 22.7 | 73.8 | 63.8 |
屈服应力(kPa)) | <15★ | 204 | <15★ | 279 | <15★ | 100 | 32 | 200 |
☆获得的产物为膏体般粘稠,且无法作为刚挺片剂拿在手中方便地使用。屈服应力无法测定,因为干酪金属丝切透了4cm厚样品。
Claims (4)
1.一种熔体铸造固体成形洗涤剂条组合物,它包含2~60重量%不溶于水的结构剂和2~50重量%洗涤活性剂,其特征在于,它包含0.5~30重量%盐溶电解质和30~80重量%水,其中盐溶电解质具有大于10的电解质阴离子的感胶离子数,并且是NO2 -,ClO3 -,Br-,NO3 -,ClO4 -,I-,CNS-,C6H5SO3 -、C6H4CH3SO3 -或Cr2O7 2-。
2.权利要求1的组合物,其中不溶于水的结构剂是饱和脂肪酸皂,它包含一种或多种中和的C12~C24脂肪酸。
3.权利要求1的组合物,其中盐溶电解质是甲苯磺酸钠、枯烯磺酸钠或二甲苯磺酸钠。
4.制造权利要求1~3任一项的熔体铸造固体成形洗涤剂条组合物的方法,包括下列步骤:
a)制造洗涤剂条组合物的熔体;
b)将所述熔体倾倒入模具中以获得要求的形状;以及
c)在静止条件下冷却该模具以发生凝固。
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CN (1) | CN1180071C (zh) |
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CA2433045A1 (en) * | 2000-12-29 | 2002-07-11 | Unilever Plc | Detergent composition |
DE10338043A1 (de) * | 2003-08-19 | 2004-12-02 | Henkel Kgaa | Verfahren zur Herstellung von Wasch-oder Reinigungsmitteln |
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US4201743A (en) * | 1971-05-27 | 1980-05-06 | Colgate-Palmolive Company | Method of making soap bars |
US4165293A (en) | 1977-05-16 | 1979-08-21 | Amway Corporation | Solid transparent cleanser |
DE3684180D1 (de) | 1985-06-07 | 1992-04-16 | Dow Consumer Products | Schmutz- und fleckenentferner fuer waesche. |
GB8928902D0 (en) * | 1989-12-21 | 1990-02-28 | Unilever Plc | Detergent bar |
US5340492A (en) * | 1990-11-26 | 1994-08-23 | The Procter & Gamble Company | Shaped solid made with a rigid, interlocking mesh of neutralized carboxylic acid |
US5759982A (en) * | 1994-06-17 | 1998-06-02 | The Procter & Gamble Company | Laundry bars with polyethylene glycol as a processing aid |
US5968892A (en) * | 1994-06-17 | 1999-10-19 | Hutchins; James Peyton | Non-brittle laundry bars comprising coconut alkyl sulfate and polyethylene glycol |
US5703025A (en) | 1994-08-03 | 1997-12-30 | The Procter & Gamble Company | Monohydric alcohol-free process for making a transparent pour molded personal cleansing bar |
WO1998011864A2 (en) * | 1996-09-23 | 1998-03-26 | The Procter & Gamble Company | Lathering and cleansing personal cleansing bar compositions which contain elongated lipid particles |
US5916856A (en) * | 1996-10-16 | 1999-06-29 | Lever Brothers Company | Pourable cast melt bar compositions comprising low levels of water and minimum ratios of polyol to water |
US5929011A (en) * | 1996-10-30 | 1999-07-27 | Sunburst Chemicals, Inc. | Solid cast chlorinated cleaning composition |
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BR0014964A (pt) | 2002-07-02 |
MY125934A (en) | 2006-09-29 |
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