CN1183115A - 洗涤剂条 - Google Patents

洗涤剂条 Download PDF

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CN1183115A
CN1183115A CN96193571A CN96193571A CN1183115A CN 1183115 A CN1183115 A CN 1183115A CN 96193571 A CN96193571 A CN 96193571A CN 96193571 A CN96193571 A CN 96193571A CN 1183115 A CN1183115 A CN 1183115A
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M·J·费尔
T·J·法雷尔
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Unilever NV
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Abstract

包含羟乙磺酸盐和聚亚烷基二醇的合成洗涤剂条组合物。已发现往这类组合物中加入一种有机酰胺有助于防止析相作用。

Description

洗涤剂条
            发明背景
本发明涉及条组合物，特别是合成皂条组合物，这种组合物含有最少量的聚亚烷基二醇来构造条。
肥皂是一种有效的清洗表面活性剂，历史上它被用于盥洗室条组合物中。肥皂对皮肤是刺激性的，因而多年来就需要去发现一种较为温和(即较少刺激性)的表面活性剂，它可以和肥皂一起或代替肥皂用于这类盥洗室条组合物中。例如，授权给Caswell等人的美国专利No.4,695,395讲授过一种盥洗室条组合物，它包含肥皂和酰基脂肪羟乙磺酸盐两种组分，这种组合物对皮肤远比纯肥皂要温和。
在这类非皂洗涤剂活性条中，游离的脂肪酸一般被用来构造条(即，使条免于物理性崩溃)。
然而，脂肪酸并不是唯一用来提供条构造的材料。例如，在WO95/12382中，聚亚烷基二醇被公开为一种优选的构造剂，至少是当它和醛糖二糖酸酰胺表面活性剂一起使用时是这样，因为前一种材料提供良好的构造特性，而没有抑制泡沫的形成。
在WO 94/21778中公开了一些组合物，其中含有10-60％合成的非皂表面活性剂，脂肪酸以及10-60％熔点在40-100℃范围内的水溶性表面活性剂。用于这类体系中的优选表面活性剂是聚亚烷基二醇类诸如聚乙二醇。
往合成洗涤剂条组合物中加入聚亚烷基二醇可能会引起一些加工方面的困难，因为聚亚烷基二醇类一般会在用来混合条组分的温度下熔融并容易发生析相作用。当存在多于40％的酯化羟乙磺酸盐例如DEFI时，可协助聚亚烷基二醇稳定化并防止析相作用发生。然而，使用这样高浓度的羟乙磺酸盐并不总是希望的或经济的。
出人意料地，申请人发现某些有机酰胺化合物(即，一般特征为酰基基团-CONH2连接在有机基团R上，其中R是氢、NH2或者是取代或未取代的、直链或支链的含有1-20个碳原子的烃基)，优选是一种脲类诸如尿素与这类含有PEG和相对较低浓度的DEFI的洗涤剂组合物以析相作用至少减少的方式相互作用。
有机酰胺诸如尿素已经被用于皂条组合物中，如被描述于美国专利3,491,001中那样，例如用来改善泡沫性质。然而皂条组合物并不存在上面所说的与PEG/相对低浓度的DEFI条相关的析相作用问题，并且没有认识到有机酰胺可用来制止这种析相作用并有助于条的加工。
德国专利2,627,459公开了酰胺诸如尿素在含有48.6％酰基羟乙基磺酸钠(即DEFI)的组合物中的应用。这里DEFI量足够高，可以帮助条的相形成，从而不会有当加入PEG并且DEFI的浓度降低时的那种析相作用发生(即，在洗涤剂条中DEFI按重量计的含量低于大约40％时)。
出人意料地，申请人发现，即使在含有聚亚烷基二醇并且DEFI含量按重量计低于大约40％的条中，当有机酰胺类诸如尿素存在于组合物中时，否则会发生的析相作用问题也不复存在。
            发明解说
因此，本发明提供了一种合成洗涤剂条组合物，它包含：
(a)10至60wt％的合成洗涤剂活性成分；
(b)10至60wt％的选自聚亚烷基二醇和聚环氧乙烷聚环氧丙烷嵌段共聚物的聚合物；
(c)5至25wt％的熔点在50至90℃之间的不溶于水的构造剂；
(d)0.1至15wt％的有机酰胺；以及
(e)1.00至14wt％的水；其中组分(a)包含基于总组合物计算不超过40wt％的羟乙磺酸盐。
本发明的第二个实施方案涉及一种制造均相的洗涤剂表面活性剂条的方法，这种条包含：
(a)10至60wt％的合成洗涤剂活性成分；
(b)10至60wt％的选自聚亚烷基二醇和聚环氧乙烷聚环氧丙烷嵌段共聚物的聚合物；
(c)5至25wt％的熔点在50至90℃之间的不溶于水的构造剂；
(d)1至14wt％的水；并且其中组分(a)包含基于总组合物计算不超过40wt％的羟乙磺酸盐，这种方法包括把有机酰胺加到上述(b)、(c)和(d)化合物的混合物中，再加入洗涤剂活性成分(a)，并把所说的混合物在180℃至240℃的温度下混合10至180分钟。
合适的合成洗涤剂活性成分(a)有：烷基醚硫酸盐；烷基乙氧基化物；烷基甘油醚磺酸盐；α-烯烃磺酸盐；酰基牛磺酸盐；酰基牛磺酸甲酯；N-酰基谷氨酸盐；酰基羟乙磺酸盐；阴离子酰基肌氨酸盐；烷基磷酸盐；甲基葡萄糖酯；蛋白质缩合物；乙氧基化的烷基硫酸盐；烷基多苷；烷基胺氧化物；内铵盐；磺基内铵盐；烷基磺基丁二酸酯；二烷基磺基丁二酸酯；酰基乳酸盐以及它们的混合物。上述洗涤剂优选是那些基于C8至C24；更优选基于C10至C18烷基和酰基部分的洗涤剂。
脂肪酸肥皂诸如C12-C24酸(例如硬脂酸/软脂酸混合物)的钠或钾皂可以优选地以2至10wt％，更优选以2至5wt％的量存在。一种优选的肥皂是硬脂酸钠。
优选地，合成洗涤剂活性成分(a)的含量在10至50wt％范围内，更优选10％至40wt％，最优选为含量不超过35wt％。
一种特别优选的洗涤剂合成活性成分是具有下式的酰基羟乙磺酸盐：
Figure A9619357100061
其中R是饱和的、直链或支链的烷基基团，并且M是一种碱金属或碱土金属或胺。虽然是优选的，但这一化合物的用量不应超过组合物重量的40％，优选10至40wt％。
本发明进一步的一种主要组分是选自聚亚烷基二醇和聚环氧乙烷聚环氧丙烷嵌段共聚物的聚合物。这种聚亚烷基二醇组分(b)优选是一种熔点在40°至100℃范围内的高分子量的聚亚烷基二醇，特别是聚乙二醇类或它们的混合物。
优选的聚乙二醇类(PEG)的分子量在1,500-10,000范围内。然而在本发明的某些实施方案中优选包含相当少量的分子量在50,000至500,000范围内的聚乙二醇，尤其是分子量在100,000左右的聚乙二醇。已发现这样的聚乙二醇可改善条的磨损速率。据信这是因为它们的长聚合物链即使在条组合物使用过程中被润湿时仍然保持缠在一起。
如果使用这样的高分子量聚乙二醇类(或任何其它水溶性的高分子量聚亚烷基氧化物)，其用量优选地为组合物重量的1％至5％，更优选为1.5至4.5％。这些材料一般应与大量其它水溶性的构造剂(b)诸如上述分子量为1,500至10,000的聚乙二醇联合使用。
优选的聚环氧乙烷聚环氧丙烷嵌段共聚物是在40°至100℃温度范围内熔融的那些共聚物，诸如那些嵌段共聚物，其中聚环氧乙烷含量至少占嵌段共聚物重量的40％。这样的嵌段共聚物可以单独使用或者以与聚乙二醇的混合物的形式使用。
优选地，聚亚烷基二醇的总量应为组合物重量的20％至50％，最优选至少为25％。
不溶于水的构造剂即组分(c)的熔点也应该在25-100℃范围内，更优选为至少40℃至90℃。特别设计的合适材料是脂肪酸，特别是那些含有12至24个碳原子的碳链的脂肪酸。实例有月桂酸、肉豆蔻酸、软脂酸、硬脂酸、花生四烯酸和山萮酸以及它们的混合物。这些脂肪酸的来源有椰子、拔顶椰子、棕榈、棕榈仁、巴巴苏以及牛脂脂肪酸和部分或全部硬化的脂肪酸类或蒸馏过的脂肪酸。其它合适的水不溶性构造剂包括含有8至20个碳原子的链烷醇，特别是鲸蜡醇。这些材料一般在20℃的水溶解度小于5克/升。
水溶性的聚合物构造剂组分(b)和不溶于水的构造剂(c)的相对比例控制着使用过程中条磨损的速率。不溶于水的构造剂的存在趋向于在使用过程中条暴露于水时延缓条的溶解作用并从而延缓磨损的速率。
优选地，组合物包含一种水溶性的材料(例如淀粉)，更优选地是一种“真正”水溶性的淀粉诸如，例如，麦芽糖糊精。“真正”水溶性意指淀粉在水中有10wt％或更大的溶解度并形成澄清的或基本澄清的溶液(除了少量不溶的残留物，它可能给否则是澄清的溶液造成半透明的混浊)。
被认为是操作助剂的有机酰胺存在的量应为大约0.1至15wt％，优选0.1至10wt％，更优选0.5至8wt％。
水存在的量应为组合物的1.0至14wt％。
也希望往条组合物中掺入碳链长度为8至22个碳原子的游离脂肪酸。它们可作为富脂剂、皮肤感觉和乳液形成的增进剂和/或构造剂。如果存在，则这种游离脂肪酸的含量优选为组合物的1至15wt％。然而，它们存在的量不应超过组分(b)的含量。
其它可供选择的可存在于盥洗室条组合物中的成分有润湿剂诸如甘油、山梨醇、乙氧基化的或甲氧基化的甲基葡萄糖的醚等；水溶性的聚合物诸如胶原蛋白类、改性纤维素酶(诸如聚合物JR)、瓜耳树胶和聚丙烯酸酯类；螯合剂诸如柠檬酸盐，以及润肤剂诸如聚硅氧烷、矿物油、矿脂或氟化的聚醚类。
在本发明的第二个实施方案中，本发明包括一种稳定(即防止析相作用)合成洗涤剂条的方法，所述条含有：
(a)合成洗涤剂活性成分；
(b)选自聚亚烷基二醇和聚环氧乙烷聚环氧丙烷嵌段共聚物的一种聚合物；
(c)熔点在50°至90℃之间的不溶于水的构造剂；和
(d)水；该方法包括把有机酰胺加到含有组分(b)、(c)和(d)的混合物中，加入合成洗涤剂活性成分(a)，并把得到的混合物在180℃至240℃的温度范围内混合10至180分钟。
本发明将参照以下非限制性的实施例来说明。
实施例1-4制备了具有以下组成的制剂(所有百分数均为按重量计的百分数)：
       成分 供比较的制剂   实施例1   实施例2   实施例3   实施例4
 PEG 8,000     35     34     32     30     25
 尿素     --     1     3     5     10
 椰油基羟乙磺酸钠     27.0     27.0     27.0     27.0     27.0
 软脂-硬脂酸     12     12     12     12     12
 椰油酰氨丙基内铵盐     5.0     5.0     5.0     5.0     5.0
 麦芽糖糊精     10.0     10.0     10.0     10.0     10.0
 硬脂酸钠     5.0     5.0     5.0     5.0     5.0
 二甲聚硅氧烷     0.25     0.25     0.25     0.25     0.25
 EHDP     0.02     0.02     0.02     0.02     0.02
 EDTA     0.02     0.02     0.02     0.02     0.02
 二氧化钛     0.5     0.5     0.5     0.5     0.5
 香料     0.25     0.25     0.25     0.25     0.25
 少量盐类     1.96     1.96     1.96     1.96     1.96
 水     6.0     6.0     6.0     6.0     6.0
应该注意，虽然上表中所有尿素浓度的变化是通过变化PEG8000浓度来抵偿的，但这也可以通过改变脂肪酸的浓度来抵偿。
制剂的制备方法如下：
在一台Drais混合机中把PEG和软脂酸/硬脂酸(ASAD)熔融。当熔融时加入50％NaOH(氢氧化钠)以形成硬脂酸钠，并把该混合物混合10-15分钟。然后把麦芽糖糊精分散在PEG/脂肪酸预熔物中并加入椰油酰氨丙基内铵盐使混合物增稠。混合大约10分钟后加入其余的成分。在至少88℃(190°F)、高至110℃(230°F)的温度下再继续混合30-60分钟。一旦达到所需的水量时，即从混合物中取出批料以进一步加工。
在供比较用的制剂中(即不含尿素的)，热的物料由大量不透明的被油状液体所包围的似凝乳状的区域组成。这种“酪农干酪”外观被称为析相作用，因为从物料本体中有清亮的流体分离出来。这种析相作用将导致不充分的混合和加工方面的问题并进一步影响后面的加工线。
在第一个实施例中往PEG/脂肪酸预熔物中加入了1％的尿素(它代替了1％的PEG)。申请人发现“酪农干酪”外观令人意料不到地具有较均匀的稠度并且基本上没有流体从物料本体中分离出来。
在实施例2中，加入了3％的尿素来代替PEG。这时热物料具有均匀的外观并且没有析相作用发生。实施例3和4进一步说明了这一发现。
供比较的实施例2
在下面的实施例中，加入另外的3％的脂肪酸来代替PEG。这样做是为了测定是否PEG的降低会使热物料具有均匀的外观。
成分     对比
PEG 8,000     32
尿素     --
椰油基羟乙磺酸钠     27.0
软脂-硬脂酸     15
椰油酰氨丙基内铵盐     5.0
麦芽糖糊精     10.0
硬脂酸钠     5.0
二甲聚硅氧烷     0.25
EHDP     0.02
EDTA     0.02
二氧化钛     0.5
香料     0.25
少量盐类     1.96
水     6.0
结果发现，通过加入另外的脂肪酸而不加尿素，没有观察到析相作用方面的改善。热的物料仍然保持“酪农干酪”的外观。因此，这种改善清楚地是由于使用尿素的结果。

Claims (8)

1.一种洗涤剂条组合物，它包含：
(a)按重量计10％至60％的合成洗涤剂活性成分；
(b)按重量计10％至60％的选自聚亚烷基二醇和聚环氧乙烷聚环氧丙烷嵌段共聚物的聚合物；
(c)5％至25％熔点在50℃至90℃之间的不溶于水的构造剂；
(d)按重量计0.1％至15％的有机酰胺；和
(e)按重量计1％至14％的水；其中组分(a)包含基于总的组合物计算不超过40wt％的羟乙磺酸盐。
2.一种根据权利要求1的组合物，其中的表面活性剂包含一种脂肪酸肥皂。
3.一种根据权利要求2的组合物，包含2至10％的脂肪酸肥皂。
4.一种根据权利要求1的组合物，其中b)是聚亚烷基二醇，其量在25至50wt％的范围内。
5.一种根据权利要求1的组合物，其中不溶于水的构造剂是一种C12至C24脂肪酸或它们的混合物。
6.一种根据权利要求1的组合物，其中的有机酰胺是尿素。
7.一种防止洗涤剂条发生析相作用的方法，所述洗涤剂条包括：
(a)合成洗涤剂活性成分；
(b)一种选自聚亚烷基二醇和聚环氧乙烷聚环氧丙烷嵌段共聚物的聚合物；
(c)熔点在50至90℃之间的不溶于水的构造剂；以及
(d)水；这种方法包括把一种有机酰胺加到含有组分(b)、(c)和(d)的混合物中，加入洗涤剂活性成分(a)，并把得到的混合物在180℃至240℃的温度范围内混合10至180分钟。
8.一种有机酰胺在制备合成洗涤剂条过程中作为操作助剂的用途，所述合成洗涤剂条包括：
(a)一种合成洗涤剂活性成分；
(b)一种选自聚亚烷基二醇和聚环氧乙烷聚环氧丙烷嵌段共聚物的聚合物；
(c)熔点在50至90℃之间的不溶于水的构造剂；以及
(d)水。
CN96193571A 1995-04-28 1996-04-12 洗涤剂条 Pending CN1183115A (zh)

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