CN104160008B - 织物柔软活性组合物 - Google Patents

织物柔软活性组合物 Download PDF

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CN104160008B
CN104160008B CN201380007393.2A CN201380007393A CN104160008B CN 104160008 B CN104160008 B CN 104160008B CN 201380007393 A CN201380007393 A CN 201380007393A CN 104160008 B CN104160008 B CN 104160008B
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D·A·帕里什
J·希尔德布兰德
久本宮子
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Abstract

本发明涉及一种组合物,其特征在于存在酯季铵盐,所述酯季铵盐具有在低温下可促进分散的特性。酯季铵盐的重要特征是碘值为65‑85,并且分布为:33‑38%单酯、52‑55%二酯和7‑12%三酯。

Description

织物柔软活性组合物
技术领域
本发明涉及一种酯季铵盐组合物,其在30℃或更低温度下具有良好分散性。该组合物在用于洗衣过程的织物柔软剂形成中特别有用。
背景技术
平均每分子被两个脂肪酸基酯化的烷醇胺的季铵盐,通常被称为酯季铵盐,已被广泛用作织物柔软剂。使用这些化合物的一个问题是,在低于约40℃的温度下它们通常很难分散在水或水溶液中。这使得制剂的制备更加困难和昂贵。
Gallotti等人(WO2008/003454)试图解决酯季铵盐的可分散性问题。这个参考文献公开了可用于织物柔软剂,尤其适用于低温工艺的浓缩酯季铵盐组合物。该组合物包含(a)酯季铵盐化合物,特别是二(乙酯)二甲基氯化铵(DEEDMAC)类、(b)有机溶剂、(c)水、以及(d)稳定剂。
US 5830845公开了可以在室温下制备的浓缩水性织物柔软剂组合物。所述的活性物质具有碘值高于80的脂肪酸烷基部分。通常来说,组合物具有超过10%的多元不饱和含量,和低于20重量%的单酯季铵盐含量。
EP 1 584 674 Al公开了酯季铵盐浓缩物,其被建议可以在较低温度下生产织物柔软剂。组合物包含:(a)酯季铵盐化合物,(b)有机溶剂,(c)水,(d)pH调节剂。该参考文献建议,对于低温可分散性而言,水是必不可少的。
WO97/42279公开了用于生产织物柔软剂的三乙醇胺酯季铵盐浓缩物。基于季铵盐的总量,该组合物包括大于55重量%的二酯季铵盐,和低于25重量%的三酯季铵盐。在水中分散这些酯季铵盐浓缩物以制成水性织物柔软剂,这需要将水预加热至45-60℃。
尽管已经作出各种努力,但是仍然需要改进,使酯季铵盐组合物在低温下就很容易分散在水中或水溶液中,并且保持有效作为织物柔软剂的能力。
发明内容
本发明涉及含有在低温下具有良好可分散性的酯季铵盐的组合物。该组合物可以在洗衣过程中用作织物柔软剂。
第一个方面,本发明涉及织物柔软活性组合物,包含一种或多种如结构式(I)的酯季铵盐:
(I)
其中R1、R2和R3是氢或C(O)R5基团;
R5是包含11-21个碳原子的烷基或烯基;
A-是与织物柔软剂可相容的阴离子;
R4是甲基或乙基。
与织物柔软剂可相容的阴离子A-优选是硫酸甲酯或硫酸乙酯,最优选是硫酸甲酯。R4基团优选是甲基。
基于标准化的重量百分数,33-38%的酯季铵盐是单酯,即R1是C(O)R5基团,R2和R3是氢;52-55%是二酯,即R1和R2是C(O)R5基团,R3是氢;和7-12%是三酯,即R1、R2和R3是C(O)R5基团。标准化的重量百分数的基础是单酯、二酯和三酯的重量之和。
R5基团可以衍生自纯脂肪酸R5COOH或结构式为R5COOH的脂肪酸的混合物,其中R5是支链或非支链的烷基或烯基基团,优选是非支链的。合适的饱和脂肪酸的例子有棕榈酸和硬脂酸。合适的单不饱和脂肪酸的例子有油酸和棕榈油酸。同样优选的是,结构式(I)中R5基团的烷基或烯基链具有平均15到17个碳原子的链长。平均链长是基于脂肪酸的混合物中每种脂肪酸的重量分数来计算的。支链脂肪酸链的链长是指连续最长的碳原子链。
计算出的游离脂肪酸R5COOH中R5基团的碘值是从65到85,优选从65到75,最优选约70。碘值是衡量酯化的脂肪酸碳链的不饱和程度的参数,即、100g脂肪酸的双键反应消耗的碘的克数。碘值可以通过ISO3961方法确定。R5基团优选具有低于10%的多元不饱和水平。这里描述的R5的碘值范围在温度低于30℃时提供流动性和可分散性,以及良好的柔软性能。单酯含量和碘值的范围的结合是特别重要的。碘值的范围是从65到85,尤其是从65到75,单酯值低于约33重量%,往往导致组合物在所述程序中对于方便使用而言太粘稠,基本为糊状结构。当二酯值大体上增加超过55重量%时,在温度低于30℃时可分散性会减少。
优选地,R5烯基基团的不饱和键的顺式和反式之比小于12:1,更优选在5:1和9:1之间。
织物柔软活性组合物应该包含10-25%的醇类溶剂,如乙醇、2-丙醇、甘油、乙二醇、丙二醇、二丙二醇、或乙二醇的C1-C4烷基单醚。
在温度大于15℃和高达至少25℃,织物柔软活性组合物呈透明液态。
在织物柔软活性组合物中,应该存在优选大于50%的结构式(I)的酯季铵盐。这些织物柔软活性组合物可以与水和其他成分结合使用,以形成可用于织物洗涤的水性织物柔软剂。
在0-30℃、优选5-25℃和更优选15-25℃的温度下,通过将上述织物柔软活性组合物与水或水溶液混合来制备液体水性织物柔软剂组合物。混合后,水性织物柔软剂组合物一般具有2-30重量%的根据结构式I的酯季铵盐。织物柔软活性组合物或水溶液也可以任选地包括添加剂,如粘度助剂、防腐剂、或增稠剂。芳香水性织物柔软剂可以通过将香料放入织物柔软活性组合物中,然后再将其与根据上述程序的水溶液混合,或同时将织物柔软活性组合物和香料与水或水溶液混合而制得。
作为织物柔软剂,文中所述的酯季铵盐组合物可以用作在洗衣机漂洗循环中的液体水性织物柔软剂组合物,或作为在织物滚筒烘干时添加的烘干机活性组合物。在后一种情况下,织物柔软剂通常会以烘干机片材的形式,包括浸渍有所述织物柔软活性组合物之水性分散体的无纺布材料基材。基底片材的例子包括但不限于纤维素纤维或合成纤维,尤其是聚酯、尼龙或聚丙烯纤维。
发明描述
织物柔软活性组合物的制备
本发明的酯季铵盐可以如下制备:任选存在溶剂或催化剂的情况下,用游离脂肪酸或甘油三酸酯对三乙醇胺进行酯化。可以使用的脂肪酸与胺的摩尔比为1.40:1到1.70:1,优选1.45:1到1.60:1。该反应可以在90-220℃的温度下进行。脂肪酸与胺的最优选摩尔比为1.50比1。该反应可以通过将温度冷却至约80℃以下来结束。可以通过蒸馏将水从反应混合物中除去,任选利用减压蒸馏。
脂肪酸的平均链长和碘值对于在5-30℃的温度下能同时实现良好的性能和良好的可分散性是非常重要的。酯化反应中使用的脂肪酸应该具有12-22碳原子的平均碳链长度,碘值从65到85,优选从65到75。它们可以是合成的或天然来源的,例如牛油脂、菜籽油、大豆油和棕榈油。平均链长度是以混合物中各种脂肪酸的重量分数为基础来计算的。所需的碘值可以如下获得:使用已经具有理想碘值的自然来源的脂肪酸混合物,混合不同碘值的组合物,或部分氢化具有更高碘值的脂肪酸混合物或甘油三酸酯混合物。不饱和脂肪酸部分的双键的顺式和反式之比优选是在5:1和9:1之间。
在第二步中,三乙醇胺脂肪酸酯与合适的季铵化试剂如硫酸二甲酯进行季铵化反应。季铵化试剂与胺的摩尔比通常从0.90到0.97,反应应在60-100℃的温度下进行,直到反应混合物的总胺值的范围在1-8mg KOH/g。总胺值是通过根据美国石油化学家协会的Tf2a-64方法,利用高氯酸进行非水滴定测定,并以每克样品的mgKOH计算总胺值。
在上述的季铵化反应过程中或之后添加醇类溶剂,使得最终的酯季铵盐活性组合物具有10-25重量%的溶剂。
制备水性织物柔软剂
上述织物柔软活性组合物与水或者水溶液混合,以形可用于洗衣程序的成水性织物柔软剂组合物。有效混合可能发生在5-30℃,优选在5-25℃,更优选在15-25℃。混合可在低剪切,并且没有任何其它促进分散的助剂的条件下发生。这样使得在混合发生的温度下,例如15-20℃时,形成液体分散物。与织物柔软活性组合物相比,得到的水性织物柔软剂组合物是基本不透明的。可以添加到水性组合物中的其它成分包括但不限于香料、防腐剂、增稠剂、染料和荧光增白剂。
水性织物柔软剂的使用
这里所述的组合物可用于各种各样的清洗程序,但是相信它们在衣服洗涤程序中特别有用。通常,这些清洁操作包括使用洗涤剂除去污垢的初始步骤,随后是除去所使用的洗涤剂的漂洗过程。在后者,漂洗步骤中,通常可以使用这里描述的组合物。
烘干机活化织物柔软剂片材的制备
上述织物柔软活性组合物可与水或水溶液混合,并应用于无纺布基材上,以制备适用于滚筒式烘干机的烘干机活化片材。这种烘干机活化片材是如下制备的:将织物柔软活性组合物与水混合形成水性分散体,随后使水性分散体接触或应用于基材。所述的水性分散体可以任选包含其他成分,包括但不限于不易燃烧的溶剂、辅助表面活性剂、防腐剂、粘度助剂和香料。
烘干机活化织物柔软剂片材的使用
上述烘干机活化片材可以用在洗涤和漂洗程序之后,在滚筒式烘干机的烘干周期中。烘干机片材与潮湿衣物一起添加到滚筒式烘干机中。在烘干周期中,组合物分布于织物上以提供柔软和抗静电效果,以及可任选提供香味和另外的活性成分。
本发明通过下列非限制性实施例阐明。
实施例
所有实施例都是用三乙醇胺酯季铵盐织物柔软剂活性物质进行的,所述三乙醇胺酯季铵盐织物柔软剂活性物质是如下制备的:用脂肪酸对三乙醇胺进行酯化,然后用硫酸二甲酯进行季铵化。除非另有指定,所述织物柔软剂活性物质含有乙醇作为溶剂。脂肪酸、它们的碘值和多元不饱和脂肪酸的分数、以及用于制备TEA酯季铵盐的脂肪酸(FA)和三乙醇胺(TEA)的摩尔比都在表1中列出。根据NMR测量的酒精含量,单酯季铵盐(MEQ)、二酯季铵盐(DEQ)和三酯季铵盐(TEQ)的标准化含量,以及织物柔软剂活性物质的外观情况都在表2中列出。50重量%油酸和50重量%牛油脂肪酸的混合物中烯键的顺式和反式比例约为7。
表1:TEA酯季铵盐的脂肪酸数据
*不是根据本发明
表2:织物柔软剂活性物质的组成和外观
*不是根据本发明
**溶剂是二丙二醇正丁基醚
织物柔软剂在高温(40-60℃)下的配制,得到浆状或固体产物(比较实施例)
将去离子水加热到50℃,用架空搅拌器(overhead mixter)以500min-1的速度搅拌。将织物柔软剂活性物质预热至50℃,使其处于熔融状态并以缓慢而平稳的方式添加。可根据需要添加25%活性溶液形式的氯化钙,以保持一定涡流。一旦织物柔软剂活性物质添加完成后,分散体在50℃下以500min-1搅拌10分钟,然后在连续搅拌中降温。在冷却期间可根据需要添加氯化钙溶液来控制粘度。到达30℃时,可以添加任选成分如香料、增稠剂和防腐剂,接着额外混合10分钟时间。最后通过添加氯化钙溶液调整粘度。
织物柔软剂在低温(20-30℃)下的配制,得到液态产物
去离子水平衡至25℃,用架空搅拌器以500min-1搅拌。将平衡至25℃的织物柔软剂活性物质以缓慢而平稳的方式添加。可根据需要添加25%活性溶液形式的氯化钙,以保持一定涡流。一旦织物柔软剂活性物质添加完成后,分散体在25℃下以500min-1搅拌10分钟。混合后,可以添加任选成分如香料、增稠剂和防腐剂,接着额外混合10分钟。最后通过添加氯化钙溶液调整粘度。
表3总结了根据这些织物柔软剂配制过程得到的产品A到L,使用给定的分散温度和织物柔软剂活性物质含量的结果。无法到达目标指示的活性物质含量,因为在所有织物柔软剂活性物质添加之前,混合物已凝胶化。
表3:TEA酯季铵盐的分散条件和结果
产品 分散温度℃ 活性物质含量重量% 分散结果
A* 50 15 常规分散过程,毫无问题
A* 25 -- 季铵盐不是液体;不能分散
B* 50 15 常规分散过程,毫无问题
B* 25 -- 季铵盐不是液体;不能分散
C* 50 16 常规分散过程,毫无问题
C* 25 -- 季铵盐不是液体;不能分散
D* 50 15(目标) 分散过程中形成胶体
D* 25 15(目标) 分散过程中形成胶体
E* 45 10(目标) 分散过程中形成胶体
E* 30 20(目标) 分散过程中形成胶体
F* 24 20 不易分散
G* 25 20 易于分散
H* 23 20(目标) 分散过程中形成胶体
I* 23 20 不易分散
J 30 5 非常易于分散
J 20 22 非常易于分散
J 21 5 非常易于分散
J 23 20 非常易于分散
K* 23 20 非常易于分散
L 22 20 非常易于分散
*不是根据本发明
所有此处引用的参考文献通过引用全部并入本文。现在已经充分描述本发明,本领域技术人员将会理解,本发明可以在条件、参数等广泛且等效的范围内,且不会影响本发明或者其任何实施方式的精神和领域下实现。

Claims (24)

1.一种织物柔软活性组合物,包括:
a)结构式(I)的酯季铵盐:
其中R1、R2和R3是氢或C(O)R5基团;
R5是包含11-21个碳原子的烷基或烯基;
A-是与织物柔软剂可相容的阴离子;
R4是甲基或乙基;
并且,其中:
i)基于标准化的重量%:33-38%的所述酯季铵盐是单酯;52-55%的所述酯季铵盐是二酯;和7-12%的所述酯季铵盐是三酯;以及
ii)以游离脂肪酸R5COOH计算,所述R5基团的碘值是65到85,所述R5基团中不饱和键的顺式与反式之比小于12:1;和
b)10-25重量%醇类溶剂;
并且其中,在大于15℃且高达25℃的温度下,所述组合物呈透明液体形式。
2.如权利要求1所述的织物柔软活性组合物,其中碘值为65到75。
3.如权利要求1或2所述的织物柔软活性组合物,其中不饱和键的顺式和反式之比在5:1和9:1之间。
4.如权利要求1或2所述的织物柔软活性组合物,其中所述R5基团具有低于10%的多不饱和水平。
5.如权利要求1或2所述的织物柔软活性组合物,其中所述酯季铵盐中R5基团的平均链长是15-17个碳原子。
6.如权利要求1或2所述的织物柔软活性组合物,其中所述醇类溶剂是乙醇或2-丙醇。
7.如权利要求1或2所述的织物柔软活性组合物,其中所述醇类溶剂是乙二醇的C1-C4烷基单醚。
8.如权利要求1或2所述的织物柔软活性组合物,其中所述醇类溶剂是乙二醇、丙二醇或二丙二醇。
9.如权利要求1或2所述的织物柔软活性组合物,其中存在至少50重量%的根据结构式(I)的酯季铵盐。
10.如权利要求4所述的织物柔软活性组合物,其中所述不饱和键的顺式和反式之比在5:1和9:1之间。
11.一种水性织物柔软剂组合物,其包括如权利要求1至10任意一项所述的织物柔软活性组合物和足够的水,使得结构式(I)的酯季铵盐的存在量为2-30重量%。
12.如权利要求11所述的水性织物柔软剂组合物,还包括粘度助剂、防腐剂、增稠剂或香料。
13.一种制备如权利要求11所述的水性织物柔软剂组合物的方法,包括将权利要求1至10任意一项所述的织物柔软活性组合物与水或水溶液在5-30℃的温度下混合。
14.如权利要求13所述的方法,其中所述织物柔软活性组合物与所述水或水溶液在5-25℃的温度下混合。
15.如权利要求13所述的方法,其中所述织物柔软活性组合物与所述水或水溶液在15-25℃的温度下混合。
16.一种洗涤织物的方法,包括将所述织物与权利要求11的水性织物柔软剂接触的步骤。
17.如权利要求16所述的方法,其中所述方法包括在洗衣机的漂洗循环中使所述织物与所述水性织物柔软剂接触。
18.一种制备芳香水性织物柔软剂的方法,包括将权利要求1至10任意一项所述的织物柔软活性组合物与香料和水混合,其中所述混合是在5-30℃的温度下进行。
19.如权利要求18所述的方法,其中所述织物柔软活性组合物与所述香料同时与水或水溶液混合。
20.如权利要求18所述的方法,其中所述织物柔软活性组合物首先与所述香料在5-30℃的温度下先混合,然后与水或水溶液混合。
21.一种在烘干机中使用的烘干机活化片材,包括浸渍有权利要求1至10任意一项所述的织物柔软活性组合物的水性分散体的无纺布材料基底片材。
22.如权利要求21所述的烘干机活化织物柔软剂片材,其中所述基底片材是由纤维素纤维或合成纤维制成。
23.如权利要求21所述的烘干机活化织物柔软剂片材,其中所述基底片材是由聚酯、尼龙或聚丙烯纤维制成。
24.一种处理织物的方法,包括在存在权利要求21的烘干机活化片材的烘干机中烘干所述织物。
CN201380007393.2A 2012-01-30 2013-01-30 织物柔软活性组合物 Active CN104160008B (zh)

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