CN100358489C - 洗涤剂组合物 - Google Patents

洗涤剂组合物 Download PDF

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CN100358489C
CN100358489C CNB008151938A CN00815193A CN100358489C CN 100358489 C CN100358489 C CN 100358489C CN B008151938 A CNB008151938 A CN B008151938A CN 00815193 A CN00815193 A CN 00815193A CN 100358489 C CN100358489 C CN 100358489C
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春日健一
宫岛哲也
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Abstract

洗涤剂组合物，其中包含：(A)阴离子表面活性剂，(B)抗菌剂，和(C)含C4-12烷基或烯基的甘油醚。该洗涤剂组合物具有优异的洗涤性、快速发泡性，可表现出高抗菌活性，并能对头皮或身体产生令人满意的抗瘙痒和去臭作用，并且对头皮具有抗头屑作用。

Description

洗涤剂组合物
技术领域
本发明涉及洗涤剂组合物，其具有优异的洗涤性、快速发泡性，可表现出高抗菌活性，并能对头皮或身体产生令人满意的抗瘙痒和去臭作用，并且对头皮具有抗头屑作用。
背景技术
头发或体用洗涤组合物一般都包含阴离子表面活性剂作为主要基质，用以令其具有优异的洗涤性、发泡力和迅速发泡特性。这些洗涤剂组合物除具有清洁作用之外，还需要具有杀菌或抗菌作用。已知含有抗菌剂三氯生、吡罗克酮或阳离子表面活性剂的洗涤剂组合物可预防头屑和瘙痒。
但将阴离子表面活性剂和抗菌剂结合共用会导致以下问题，如洗涤性或快速发泡性的劣化、以及所表现出的抗菌作用不足。
本发明的目的是提供具有优异洗涤性和快速发泡性、并能产生高效抗菌作用的洗涤剂组合物。
本发明公开
本发明发现了具有优异洗涤性和快速发泡性的洗涤剂组合物，并且其能产生高效抗菌作用，和表现出充分的抗瘙痒、去臭和去头屑作用，其中是将特定的甘油醚与阴离子表面活性剂和抗菌剂共用达到的。
本发明提供了一种洗涤剂组合物，其中包含以下组分(A)、(B)和(C)：
(A)阴离子表面活性剂，
(B)抗菌剂，和
(C)含C4-12烷基或烯基的甘油醚。
本发明的最佳实施方式
本发明中用作组分(A)的阴离子表面活性剂优选是：硫酸盐、磺酸盐和羧酸盐类。其实例包括烷基硫酸盐、聚氧化烯烷基醚硫酸盐、聚氧化烯链烯基醚硫酸盐、烷基磺基琥珀酸盐、聚氧化烯烷基磺基琥珀酸盐、烷基苯磺酸盐、α-烯烃磺酸盐、聚氧化烯烷基苯基醚硫酸盐、硫酸甘油酯、酰氨基醚硫酸盐、高级脂肪酸盐、链烷磺酸盐和α-磺基脂肪酸酯盐。
这些阴离子表面活性剂中，优选烷基硫酸盐、聚氧化烯烷基醚硫酸盐和聚氧化烯链烯基醚硫酸盐，其中更优选如下式(5)所示的烷基硫酸盐，以及如下式(6)所示的聚氧化烯烷基醚硫酸盐和聚氧化烯链烯基醚硫酸盐。
R7OSO3M    (5)
R8O(CH2CH2O)mSO3M    (6)
其中R7代表C10-18烷基，R8代表C10-18烷基或烯基，M代表碱金属、碱土金属、铵、烷醇胺或碱性氨基酸，并且m以重均计表示1-5。
至少可采用一种阴离子表面活性剂用作组分(A)。其用以令该洗涤剂组合物具有优异的洗涤性和发泡特性，优选其用量占组合物总量的5-50％(重量)，特别是8-30％(重量)，更优选是10-22％(重量)。
作为组分(B)用于本发明的抗菌剂的实例包括：三氯生、三氯卡班、吡罗克酮油胺(olamine)，巯氧吡啶锌、二硫化硒和3-甲基-4-(1-甲基乙基)苯酚，以及抗菌剂如《化妆品和药品抗菌剂和杀菌剂》(John.J.Kavala编，Fragrance Journal出版)中描述的那些，其中特别优选三氯生、三氯卡班、吡罗克酮油胺和巯氧吡啶锌。
用作组分(B)的阳离子表面活性剂的实例包括：如式(1)所示的季铵盐、如式(2)所示的苄烷铵盐或苄乙氧铵盐、如式(3)所示的洗必太盐和如式(4)所示的吡啶_盐。
Figure C0081519300051
其中R1和R2可相同或不同，分别代表含6-14个碳原子和总数含16-26个原子的长链烷基、长链烯基或长链羟烷基，R3和R4可相同或不同，分别代表C1-3烷基或羟烷基，或平均加成摩尔数为10或10以下的聚氧乙烯基，Z代表卤素原子，氨基酸、脂肪酸、含直链或支链C1-30烷基或烯基的磷酸酯、膦酸酯、磺酸酯或硫酸酯的阴离子残基，或阴离子低聚物或聚合物，其中含有磺化多环芳族化合物的福尔马林缩聚物，其中包含聚合度为3或3以上的苯乙烯磺酸，或含有烃基取代基。
其中R5代表C8-14烃基或如下式所示的基团：
Figure C0081519300062
并且Z的定义与上文相同。
其中Z′代表葡糖酸、乙酸或盐酸。
其中R6代表直链或支链C6-18烷基，并且Z的定义与上文相同。
式(1)中，优选R1和R2为C8-12烷基，而优选R3和R4为C1-3烷基。
式(2)中，优选R5是C8-14烃基。式(4)中，优选R6是C8-16烷基。
式(1)、(2)和(4)中，特别优选卤素原子用作Z。
阳离子表面活性剂的具体优选实例包括：苯扎氯铵、苄索氯铵、鲸蜡基氯化吡啶_、葡萄糖酸洗必太、乙酸洗必太和盐酸洗必太，特别优选式(2)所示的那些，如苯扎氯铵和苄索氯铵。
组分(B)可将抗菌阳离子表面活性剂与其他抗菌剂共用，达到更高作用。组分(B)的用量优选占组合物总量的0.005-5％(重量)，特别是0.1-4％(重量)、更优选0.4-3％(重量)。在上述范围内可达到足够的抗菌作用。
组分(C)的甘油醚包含直链或支链C4-12烷基或烯基。优选的甘油醚包含C4-12烷基如正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、异己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基或正月桂基。其中优选含C4-11烷基、特别是C6-10烷基、更优选是C8烷基的甘油醚，其中烷基数优选是1或2，特别是1。
可将一种或多种这些甘油醚用作组分(C)。甘油醚的用量可占组合物总量的0.1-30％(重量)，特别是0.5-15％(重量)，更优选1-10％(重量)，用以令所得洗涤剂组合物具有优异的发泡特性。
本发明的洗涤剂组合物中还可加入金属螯合剂以进一步加强其抗菌作用。对金属螯合剂并无特殊限制，只要其具有螯合金属离子的能力。其实例包括氨基多羧酸螯合剂、芳族或脂族羧酸螯合剂、氨基酸螯合剂、醚多羧酸螯合剂、膦酸螯合剂、羟基羧酸螯合剂、磷酸螯合剂、高分子电解质(包括低聚电解质)螯合剂和丁二酮肟(DG)。这些螯合剂可以是游离酸或盐，如钠盐、钾盐或铵盐。或者其也可是以上成分的可水解酯类衍生物。
氨基多羧酸螯合剂的具体实例包括：
(a)式R11(Y)2所示的化合物
(b)式N(Y)3所示的化合物
(c)式R11-N(Y)-CH2CH2-N(Y)-R11所示的化合物
(d)式R11-N(Y)-CH2CH2-N(Y)2所示的化合物
(e)式(Y)2N-R12-N(Y)2所示的化合物
(f)化合物(e)的类似物，并且其中含有至少4个Y，例如是下式所示的化合物：
Figure C0081519300081
在上式中，Y代表-CH2COOH或-CH2CH2COOH，R11代表可构成已知螯合剂的基团，如H、烷基、羟基或羟烷基，R12代表可构成已知螯合剂的基团，如烯基或环烯基。
氨基多羧酸螯合剂的典型实例包括乙二胺四乙酸(EDTA)，环己二胺四乙酸(CDTA)、氨三乙酸(NTA)、亚氨基二乙酸(IDA)、N-(2-羟乙基)亚氨二乙酸(HIMDA)、二亚乙基三胺五乙酸(DTPA)、N-(2-羟乙基)乙二胺三乙酸(EDTA-OH)、以及二醇醚二胺四乙酸(GEDTA)及其盐。
芳族或脂族羧酸螯合剂的实例包括：草酸、丙二酸、琥珀酸、戊二酸、己二酸、衣康酸、乌头酸、三聚氰酸、水杨酸、富马酸、乙酰水杨酸、羟基苯甲酸、氨基苯甲酸(包括邻氨基苯甲酸)、邻苯二甲酸、1，2，4-苯三酸和没食子酸，以及这些酸的盐、甲酯或乙酯。
氨基酸螯合剂的实例包括：甘氨酸、丝氨酸、丙氨酸、赖氨酸、胱氨酸、半胱氨酸、乙硫氨酸、酪氨酸、甲硫氨酸，以及它们的盐或衍生物。
醚多羧酸螯合剂的实例包括：二乙醇酸，如下式所示的化合物，这些化合物的类似物和它们的盐(例如钠盐)。
Figure C0081519300082
其中X1代表H、-CH2COOH或-COOH，X2代表H、-CH2COOH或
Figure C0081519300083
膦酸螯合剂的实例包括：亚氨基二甲基膦酸(IDP)、烷基二膦酸(ADPA)和1-羟基乙烷-1，1-二膦酸(DEQUESTTM2010)。
羟基羧酸螯合剂的实例包括：苹果酸、柠檬酸、乙二醇酸、葡糖酸、庚酸、酒石酸和乳酸，以及它们的盐。
磷酸螯合剂的实例包括：正磷酸、焦磷酸、三磷酸和聚磷酸。
高分子电解质(包括低聚电解质)的实例包括：丙烯酸聚合物、马来酸酐聚合物、α-羟基丙烯酸聚合物、衣康酸聚合物、由这些聚合物中的至少两种单体构成的共聚物，以及环氧琥珀酸聚合物。
此外，抗坏血酸、氢硫基醋酸、肌醇六磷酸、乙醛酸以及它们的盐也可优选用作螯合剂。
其中优选的金属螯合剂包括：乙二胺四乙酸(EDTA)、琥珀酸、水杨酸、草酸、乳酸、富马酸、酒石酸和1-羟基乙烷-1，1-二膦酸，或它们的盐。
可将以上列举的至少一种螯合剂用作金属螯合剂，其用量优选占组合物总量的0.1-10％(重量)，特别是2-5％(重量)。
本发明的洗涤剂组合物中还可根据需要加入普通洗涤剂组合物中常用的组分，例如：保湿剂如丙二醇、甘油、二甘醇单乙醚、山梨醇和泛醇；调理组分如阳离子聚合物、聚硅氧烷化合物及其衍生物；珠光剂如二硬脂酸乙二醇酯；非离子表面活性剂如聚氧乙烯烷基醚和烷基聚糖苷；两性表面活性剂如酰氨基丙基甜菜碱；除组分(B)之外的阳离子组分；着色剂如染料和颜料；粘度调节剂如甲基纤维素、聚乙二醇和乙醇；pH调节剂如柠檬酸和氢氧化钾；以及盐如氯化钠，植物提取物，除组分(B)之外的抗菌剂、杀菌剂，维生素制剂，抗炎剂，去头屑剂，香精，色料，紫外线吸收剂，抗氧剂和水。
本发明的洗涤剂组合物可以本领域已知的方法进行制备，并且其适用作毛发用或身体用洗涤剂，如香波、浴液、洁面剂和洁手剂。
实施例
实施例1
由本领域已知的方法制备具有表1所示配方的洗涤剂组合物，并且对组合物的洗涤性、迅速发泡特性、去头屑作用和去臭作用进行评估。所得的结果列于表1中。
[评估方法]
(1)洗涤力和迅速发泡特性
由健康男性和女性各5名组成的测试小组每日采用洗涤剂组合物洗发，共经1周，根据下述标准对洗涤性和迅速发泡性进行评估。计算10名小组成员的平均评估值。平均值为4.0或4.0以上、3.2-3.9、2.5-3.1、以及2.4或2.4以下分别被级分为“A”、“B”、“C”、“D”。
5：使用感优异
4：使用感较好
3：使用感一般
2：使用感较差
1：使用感差
(2)去头屑作用
5名男性成员每日采用洗涤剂组合物洗发，共经1个月。最后一次洗发后，经48小时，然后洗发2次，每次用3g洗涤剂组合物。收集洗发后的水，并经预先称重的255尼龙筛(100×100μm)过滤。将尼龙筛在室温下风干约48小时，经该255尼龙筛收集的角质细胞层的重量被认为是头皮屑。计算5人的头屑平均重量，并用下述标准表征。
A：头屑重量≤30mg
B：30mg＜头屑重量≤40mg
C：40mg＜头屑重量≤50mg
D：50mg＜头屑重量
(3)去臭作用
由男性和女性各5名组成的测试小组每日1次对各洗涤剂组合物进行应用试验，共经2周。最后一次洗涤后，由受过训练的评估小组成员根据下述标准对试验人员的体味进行评估。计算10人的平均评估值。平均值为4.0或4.0以上、3.2-3.9、2.5-3.1、以及2.4或2.4以下分别被级分为“A”、“B”、“C”、“D”。
5：无体味
4：体味较轻
3：有体味
2：体味明显
1：体味强烈
表1
组分(重量％)     本发明产品     对照产品
    1     2     3     4     1     2     3
聚氧乙烯月桂基醚硫酸钠(EO＝2)     15     15     10     15     15     15
月桂基硫酸钠     15     5
正辛基甘油基醚     3     3     3     3     3
吡罗克酮油胺     1     1
苯扎氯铵(C<sub>12</sub>/C<sub>14</sub>＝50/50)     0.5     0.2     0.5     0.5
乙二胺四乙酸二钠     0.5
pH调节剂/防腐剂/着色剂/香精     适量     适量     适量     适量     适量     适量     适量
水     余量     余量     余量     余量     余量     余量     余量
洗涤性     A     A     A     A     C     B     C
迅速发泡性     A     A     A     A     C     B     C
去头屑作用     A     A     A     A     C     D     D
去臭作用     A     A     A     A     C     D     D
实施例2
由本领域已知的方法制备具有下述配方的浴液。
(组分)                              ％(重量)
聚氧乙烯椰油基醚硫酸钠(EO＝3)       16
正辛基甘油醚                        3
鲸蜡基氯化吡啶_                    1
琥珀酸二钠                          1
1-羟基乙烷-1，1-二膦酸溶液(60％)    0.3
对羟基苯甲酸甲酯                    0.2
鲸蜡醇                              0.5
香精                                0.1
水                                  余量
                                                               
总量                                100.0
实施例3
由本领域已知的方法制备具有下述配方的洗发剂.
(组分)                           ％(重量)
聚氧乙烯月桂基醚硫酸钠(EO＝3)    18
正辛基甘油醚                     3
巯氧吡啶锌                       0.5
苯扎氯铵(C12/C14＝50/50)         0.5
琥珀酸二钠                       0.6
对羟基苯甲酸丁酯                 0.2
香精                             0.2
水                               余量
                                                       
总量                             100.0
实施例4
由本领域已知的方法制备具有下述配方的洁手剂。
(组分)                           ％(重量)
聚氧乙烯月桂基醚硫酸铵(EO＝2)    20
正辛基甘油醚                     1
苯扎氯铵(C12/C14＝50/50)         1
琥珀酸二钠                       0.8
草酸二钠                         0.2
聚乙烯醇                         1
丙二醇                           0.5
对羟基苯甲酸丁酯                 0.2
珠光剂(二硬脂酸乙二醇酯)         2
香精                             0.3
水                               余量
                                                           
总量                             100.0
实施例5
由本领域已知的方法制备具有下述配方的洗发剂。
(组分)                           ％(重量)
聚氧乙烯月桂基醚硫酸钠(EO＝2)    14
2-乙基己基甘油醚                 2
巯氧吡啶锌                       0.8
苯扎氯铵(50％)                   1.5
琥珀酸                           0.3
氢氧化钠                         适量
香精                             0.3
水                               余量
                                                      
总量                             100.0
由实施例2-5所得的各洗涤剂组合物均具有优异的洗涤性和迅速发泡特性，并且具有较高的抗菌作用。
工业实用性
本发明的洗涤剂组合物具有优异的洗涤性和迅速发泡特性，可表现出较高的抗菌作用，并能对头皮或身体产生令人满意的抗瘙痒和去臭作用，并且对头皮具有去头屑作用。

Claims (5)

1.一种头发或体用洗涤剂组合物，其中包含以下组分(A)、(B)和(C)：
(A)选自烷基硫酸盐、聚氧化烯烷基醚硫酸盐或聚氧化烯链烯基醚硫酸盐的阴离子性表面活性剂，
(B)抗菌剂，和
(C)含C4-12烷基或烯基的甘油醚。
2.权利要求1的洗涤剂组合物，其中组分(B)是抗菌剂，其选自：三氯生、三氯卡班、吡罗克酮油胺、巯氧吡啶锌、二硫化硒和3-甲基-4-(1-甲基乙基)苯酚。
3.权利要求1的洗涤剂组合物，其中组分(B)是抗菌剂，选自三氯生、三氯卡班、吡罗克酮油胺和巯氧吡啶锌。
4.权利要求1的洗涤剂组合物，其中组分(B)是由下式(1)-(3)之一所示的抗菌剂
Figure C008151930002C1
其中，R5代表C8-14烃基或如下式所示的基团：
Figure C008151930002C2
其中，Z代表卤素原子，氨基酸、脂肪酸、含直链或支链C1-30烷基或烯基的磷酸酯、膦酸酯、磺酸酯或硫酸酯的阴离子残基，或阴离子低聚物或聚合物，其中含有磺化多环芳族化合物的福尔马林缩聚物，其中包含聚合度为3或3以上的苯乙烯磺酸，或含有烃基取代基，
其中，Z′代表葡糖酸、乙酸或盐酸，
其中，R6代表直链或支链C6-18烷基，并且Z的定义与以上定义相同。
5.权利要求1-4中任一权利要求的洗涤剂组合物，其中还含有金属螯合剂。
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JP3371098B2 (ja) 2003-01-27
DE60009740D1 (de) 2004-05-13
EP1226814A4 (en) 2003-03-05
WO2001032134A1 (fr) 2001-05-10
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JP2001131592A (ja) 2001-05-15
CN1387426A (zh) 2002-12-25

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