CN1128870C - 用于稳定含表面活性剂制剂的抗氧剂 - Google Patents
用于稳定含表面活性剂制剂的抗氧剂 Download PDFInfo
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- CN1128870C CN1128870C CN99105199A CN99105199A CN1128870C CN 1128870 C CN1128870 C CN 1128870C CN 99105199 A CN99105199 A CN 99105199A CN 99105199 A CN99105199 A CN 99105199A CN 1128870 C CN1128870 C CN 1128870C
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- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- IBYFOBGPNPINBU-UHFFFAOYSA-N tetradecenoic acid Natural products CCCCCCCCCCCC=CC(O)=O IBYFOBGPNPINBU-UHFFFAOYSA-N 0.000 description 1
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0084—Antioxidants; Free-radical scavengers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/2034—Monohydric alcohols aromatic
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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- C11D3/2093—Esters; Carbonates
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2096—Heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
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Abstract
本发明涉及包含下列组分的清洁组合物:(a1)式(1)和/或(2)的苯酚抗氧剂;和/或(a2)式(3)的抗氧剂;及(b)含有长链烷基或链烯基的表面活性剂。用于本发明的抗氧剂具有极好的反应性,对水解有良好的稳定性,特别是在碱性介质中,而且,由于该抗氧剂的溶解性使它们可以很容易地被用于制造肥皂制剂。
Description
固体和液体肥皂被用来清洁人体皮肤已经很久了。肥皂组合物的稳定性是无问题使用或长期保存的重要指标。
已知自由基反应对肥皂组合物有不利影响。自由基引发链式反应,这种反应会影响清洁组合物中肥皂、游离酸或合成表面活性剂的长链烃的分解。这种反应还会带来其它副作用,例如,褪色和酸败。
在清洁组合物中加入抗氧剂可以防止长链烃的降解,所说抗氧剂有,例如,丁基化羟基甲苯(BHT),它既可以防止某些自由基的催化作用,又可以作为自由基终止自由基的链式反应。
但是,使用BHT会在肥皂组合物中引起稳定性的问题,例如,褪色,或形成黄褐色副产物。
WO97/27839公开了一些肥皂组合物,其中具体用到苯酚抗氧剂作稳定剂。但是,这些化合物溶解性很差,而且很难掺入。
因此,本发明的目的是要寻找在肥皂制剂中有较好溶解性并且可以毫无问题地掺入相应肥皂组合物的苯酚抗氧剂。
因此,本发明提供了包含下列组分的清洁组合物:
(a2)式(3)的抗氧剂;
在式(1)、(2)和(3)中,
R1是氢;C1-C22烷基;C1-C22烷硫基;C5-C12环烷基;苯基;或C7-C9苯基烷基;
R2是C1-C22烷基;C5-C12环烷基;苯基;C7-C9苯基烷基;或-SO3M;
V是-O-;或-NH-;
a是0;1;或2;
b、c和d分别是0;或1;
e和f分别是1至3的整数;及
m、n和p分别是1至3的整数;
当e是1时
其中,当R3是C1-C22烷基时,b=0;或Q是式(1a)或(1b)基团;
g是0或1;
M是碱金属;铵;
当e是2时
当e是3时
其中,当R3是式(1k)基团时,c=1;以及
R4和R5分别是氢;或C1-C22烷基;及
(b)含有长链烷基或链烯基的表面活性剂。
C1-C22烷基是直链或支链烷基,例如,甲基,乙基,正丙基,异丙基,正丁基,仲丁基,叔丁基,戊基,异戊基或叔戊基,庚基,辛基,异辛基,壬基,癸基,十一烷基,十二烷基,十四烷基,十五烷基,十六烷基,十七烷基,十八烷基或二十烷基。
C1-C22烷硫基是直链或支链烷硫基,例如,甲硫基,乙硫基,正丙硫基,异丙硫基,正丁硫基,仲丁硫基,叔丁硫基,戊硫基,庚硫基,辛硫基,异辛硫基,壬硫基,癸硫基,十一烷硫基,十二烷硫基,十四烷硫基,十五烷硫基,十六烷硫基,十七烷硫基,十八烷硫基或二十烷硫基。
C2-C18链烯基是,例如,烯丙基,甲代烯丙基,异丙烯基,2-丁烯基,3-丁烯基,异丁烯基,正戊-2,4-二烯基,3-甲基-丁-2-烯基,正辛-2-烯基,正十二-2-烯基,异十二烯基,正十二-2-烯基或正十八-4-烯基。
C5-C7环烷基是环戊基,环庚基,特别是环己基。
C7-C9苯基烷基是苯丙基,苯乙基,特别是苄基。
在新组合物中,优选这样的式(1)抗氧剂,其中
Q是-CmH2m-,特别是亚甲基或亚乙基,及
m同式(1)中定义。
特别是式(1)中的V是-O-。
其中
R1和R2分别是C1-C5烷基;
a是1或2;及
R3,Q,V,T,b,c,d和e同式(1)中定义。
特别优选的式(2)化合物是其中e为1.
其中
R6是-O-M;或
M是氢;铵;或碱金属;及
R1,R2,Q,a和b同权利要求8中定义。
而且,组分(a1)优选式(4)化合物,
其中
R1和R2分别是C1-C5烷基;
Q是-CmH2m-或-CmH2m-NH-;
R3是一个直接键;-O-或-S-;
a是1或2;
m是1-5;及
T同式(1)中定义。
优选的式(3)化合物是其中
Q是亚乙基;
R3是一个直接键;及
R1,R2,T和a同式(3)中定义。
特别优选的式(4)化合物是其中T为-O-CH2。
其它可以根据本发明使用的令人感兴趣的化合物是式(5)化合物,
其中
R1和R2分别是C1-C5烷基;及
式(2)至(5)化合物中优选
R1和R2分别是叔丁基;及
a是1。
其中
Q是-CmH2m-;
T是-CnH2n-;
R1和R2分别是C1-C5烷基;
R3是式(1g);(1h);(1i)或(1k)基团;
m和n分别是1-3;
a是1或2;及
b和d分别是0或1;
而且,特别优选式(7)化合物,
其中
R1,R2和R3分别是C1-C5烷基;及
m是1-3。
其中
R1和R2分别是C1-C5烷基;
V是-O-;或-NH-;
a是1或2;
m是1-3;及
n是0-3。
对应于组分(a1)和(a2)的抗氧剂可以单个组分或几种单个化合物的混合物形式用于新型清洁剂。
新型清洁剂中组分(a)的浓度一般为50-1000ppm。
用于本发明的抗氧剂具有极好的反应性,因此利于用于低温环境。而且,它们还显示出对水解有良好的稳定性,特别是在碱性介质中。由于它们具有良好的溶解性,所以它们可以被很容易地掺入肥皂制剂中。
这种新型组合物表现出对褪色和化学分解有高稳定性。这些都有利于所用抗氧剂的效率,颜色稳定性,易于掺入和水解稳定性。
新型清洁剂中的组分(b)是可以除去皮肤表面赃物,同时对导致褪色和/或异味(讨厌气味)的氧化降解作用敏感的任何表面活性剂。
合适的实例有阴离子、非离子或两性离子和两性合成的去污物质。
适宜的阴离子去污物质有:
-硫酸盐,例如,脂肪醇硫酸盐,其烷基链有8-18个碳原子,如硫酸化的月桂醇;
-脂肪醇醚硫酸盐,例如,2-30mol环氧乙烷与1mol C8-C22脂肪醇形成的聚加合物的酸酯或其盐;
-被称为肥皂的C8-C20脂肪酸如椰子脂肪酸的碱金属盐、铵盐或胺盐;
-烷基酰氨基硫酸盐;
-烷基氨基硫酸盐,例如,一乙醇胺月桂基硫酸盐;
-烷基酰胺醚硫酸盐;
-烷基芳基多醚硫酸盐;
-一甘油酯硫酸盐;
-烷基磺酸盐,其烷基链有8-20个碳原子,例如,十二烷基磺酸盐;
-烷基酰氨基磺酸盐;
-烷基芳基磺酸盐;
-α-链烯烃磺酸盐;
-磺基琥珀酸衍生物,例如,烷基磺基琥珀酸盐,烷基醚磺基琥珀酸盐或烷基磺基琥珀酰胺衍生物;
其中
X是氢;C1-C4烷基或-COOM+;
Y是氢或C1-C4烷基;
Z是-(CH2)m1-1;
m1是1-5的整数;
n1是6-18的整数;
M是碱金属阳离子或铵阳离子;
-式(34)CH3-X-Y-A的烷基和烷基芳基醚羧酸盐,
其中
R是氢或C1-C4烷基;
Y是-(CHCHO)1-50-;
A是-(CH2)m2-1COO-M+;或
m2是1-6;及
M是碱金属阳离子或胺阳离子。
所用的其它阴离子表面活性剂是脂肪酸甲基牛磺酸化物(tauride),alkylisethionate,脂肪酸多肽缩合物和脂肪醇磷酸酯。这些化合物中的烷基优选有8-24个碳原子。
这些阴离子表面活性剂通常以它们的水溶性盐如碱金属盐,铵盐或胺盐形式使用。这些盐的实例有锂、钠、钾、铵、三乙胺、乙醇胺,二乙醇胺或三乙醇胺盐,尤其是常用钠、钾或铵(NR1R2R3)盐,其中R1,R2和R3分别是氢,C1-C4烷基或C1-C4羟基烷基。
特别优选用于新型组合物的阴离子表面活性剂是一乙醇胺月桂基硫酸盐或脂肪醇硫酸酯的碱金属盐,尤其是月桂基硫酸钠,以及2-4mol环氧乙烷与月桂基醚硫酸钠的反应产物。
适宜的两性离子和两性表面活性剂是C8-C18甜菜碱,C8-C18磺基甜菜碱,C8-C24烷基酰氨基C1-C4亚烷基甜菜碱,咪唑啉羧酸盐,烷基两性(ampho)羧基羧酸,烷基两性羧酸(例如,月桂基两性甘氨酸盐)和N-烷基-b-氨基丙酸盐或-亚氨基二丙酸盐,C10-C20烷基酰氨基-C1-C4亚烷基甜菜碱,尤其优选椰子脂肪酸酰氨基丙基甜菜碱。
适宜的非离子表面活性剂的实例有分子量为1000-15,000的环氧丙烷/环氧乙烷加合物的衍生物,脂肪醇乙氧化物(1-50EO),烷基苯酚聚乙二醇醚(1-50EO),乙氧基化碳水化合物,脂肪酸乙二醇偏酯如乙二醇一硬脂酸酯,脂肪酸链烷醇酰胺类和二链烷醇酰胺类,脂肪酸链烷醇酰胺乙氧化物和脂肪胺氧化物。
另外,组分(b)可以是饱和或不饱和的单个C8-C22脂肪酸的盐,或它们彼此的混合物,或它们与组分(b)中提到的其它去污物质的混合物。这些脂肪酸的实例有癸酸,月桂酸,肉豆蔻酸,棕榈酸,硬脂酸,花生酸,榆树酸,癸烯酸,十二碳烯酸,十四碳烯酸,十八碳烯酸,油酸,二十碳烯酸和芥子酸,以及这些酸的工业级混合物,例如,椰子脂肪酸。这些酸是以盐的形式参与混合,合适的阳离子有碱金属阳离子如钠和钾阳离子,金属原子如锌和铝原子,或充分碱性的含氮有机化合物如胺或乙氧基化胺。这些盐也可以当场制备。
新型组合物中的组分(b)优选是肥皂,即支链或非支链长链烷基-或链烯基-羧酸盐,例如,钠、钾、铵或取代的铵盐。
另外,除了组分(a)和(b)之外,新型组合物还可以含有作为组分(c)的空间位阻的胺类光保护剂。
其中,G是氢或甲基,尤其是氢。
可以用作组分(c)的四烷基哌啶衍生物的实例可以在EP-A-356677(第3-17页,第a)至f)部分)查到。该专利中的所述章节被视为本说明书的一部分。
下面各四烷基哌啶衍生物特别适于使用:
双(2,2,6,6-四甲基哌啶-4-基)癸二酸酯,双(2,2,6,6-四甲基哌啶-4-基)琥珀酸酯,双(1,2,2,6,6-五甲基哌啶-4-基)癸二酸酯,双(1-辛氧基-2,2,6,6-四甲基哌啶-4-基)癸二酸酯,双(1,2,2,6,6-五甲基哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯,1-羟乙基-2,2,6,6-四甲基-4-羟基哌啶与琥珀酸的缩合物,N,N-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛氨基-2,6-二氯-1,3,5-s-三嗪的缩合物,三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯,四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷tetraoate,1,1’-(1,2-乙二基)双(3,3,5,5-四甲基哌嗪酮),4-苯甲酰基-2,2,6,6-四甲基哌啶,4-硬脂酰氧基-2,2,6,6-四甲基哌啶,双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯,3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸-2,4-二酮,双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯,双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯,N,N’-双(2,2,6,6-四甲基-4-哌啶基)-六亚甲基二胺与4-吗啉基-2,6-二氯-1,3,5-三嗪的缩合物,2-氯-4,6-二(4-正丁氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙氨基)乙烷的缩合物,2-氯-4,6-二(4-正丁氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙氨基)乙烷的缩合物,8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸-2,4-二酮,3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮,3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮,4-十六烷氧基-和4-十八烷氧基-2,2,6,6-四甲基哌啶的混合物,N,N’-双(2,2,6,6-四甲基-4-哌啶基)-六亚甲基二胺与4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物,1,2-双(3-氨基丙氨基)乙烷与2,4,6-三氯-1,3,5-三嗪及4-丁氨基-2,2,6,6-四甲基哌啶(CA登记号(CAS Reg.No.)[136504-96-6])的缩合物,(2,2,6,6-四甲基-4-哌啶基)正十二烷基琥珀酰亚胺,(1,2,2,6,6-五甲基-4-哌啶基)正十二烷基琥珀酰亚胺,2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷与环氧氯丙烷的反应产物,四(2,2,6,6-四甲基哌啶-4-基)丁烷-1,2,3,4-四羧酸酯,四(1,2,2,6,6-五甲基哌啶-4-基)丁烷-1,2,3,4-四羧酸酯,2,2,4,4-四甲基-7-氧杂-3,20-二氮杂-21-氧代二螺[5.1.11.2]二十烷,8-乙酰基-3-十二烷基-1,3,8-三氮杂-7,7,9,9-四甲基螺[4.5]癸-2,4-二酮,或下式化合物
R=H or CH3
新组合物可以是固体、胶状、合成洗涤剂或液体肥皂形式,可用常规方法制成。
所说肥皂(固体肥皂,合成洗涤剂,液体肥皂)可用肥皂工业制造这类产品的惯用方法以及文献(见,例如,L.Spitz(Ed.),《肥皂和洗涤剂,理论和实践综述》(Soaps and Detergents,A Theroeticaland Practical Review),AOCS Press,Champaign,III,USA(1996))所述方法制造。固体肥皂制造中的重要因素是挤压之前充分搅拌肥皂组合物(的各种组分),使各种组分,特别是抗氧剂均匀分布。通常在组合物被挤压或浇铸之前将抗氧剂直接加到肥皂组合物中,或者,如果适合,预先溶解于香料中,经过搅拌(例如,在导流搅拌机中)和揉合(例如,在充分揉合机中)使其均匀分布。类似地,液体肥皂也是将各种组分放在合适的搅拌设备(例如,Pfaudler生产的Sulzer搅拌机、Erestat搅拌机或DAT搅拌机)内制成的。由于各种组分的粘度较低,所以抗氧剂一般比在固体肥皂中更快地达到分布均匀。另一种方法是将抗氧剂掺入肥皂组合物基底(薄片,带状物)中,如果需要,通过加热(熔化)实现。
下列实施例用以说明本发明。
除非另有说明,份额和百分比均为重量。温度为℃。
肥皂组合物的制备实施例
实施例1:固体肥皂的制备
组分
%重量A 动物脂肪,椰子和棕榈核肥皂(钠盐)混合物 85B 水 加到100C 甘油 1二氧化钛 0.2乳酸(88%) 0.2式(14),(15),(17),(21),(22),(23),(25)0.005-0.1或(28)抗氧剂 0.1依地酸(EDTA)二钠
制备:在20℃充分搅拌肥皂基底(A)并加水(B)。用定子旋转器将所得粘稠浆糊均化,然后在剧烈搅拌的同时按上列顺序加入组分(C)。将混合物再均化15分钟,然后用台式挤压机挤压。挤压(成批挤压)得到肥皂棒。
实施例2:液体肥皂的制备 组分
%重量甘油一硬脂酸酯(40%) 5.0月桂基硫酸铵(28%) 25.0可可酰氨基丙基羟基sultaine 3.5依地酸(EDTA)二钠 0.1丙二醇 1.0’月桂基二乙醇酰胺 0.5式(14),(15),(17),(21),(22),(23),(25)或0.001-0.05(28)抗氧剂 Q.S.香料,防腐剂水 加到100柠檬酸 Q.S.(pH5.5-
6.5)
制备:首先,将上列各组分依次加入,然后加水混合。用柠檬酸将pH调至5.5-6.5。然后在20℃均化混合物10分钟。最后将得到的液体肥皂倒入瓶中。
实施例3:合成洗涤剂肥皂的制备 组分
%重量A cocoylisethionate钠 20月桂基磺基乙酸钠 16石蜡 19蜡,微晶体 1B 水 加到100C 式(14),(15),(17),(21),(22),(23),(25)0.002-0.05或(28)抗氧剂 8玉米淀粉 2椰子脂肪酸 2月桂基二乙醇酰胺 21糊精 1乳酸(88%)
制备:在20℃充分搅拌肥皂基底(A)并加水(B)。用定子旋转器将所得浆糊均化,然后在剧烈搅拌的同时按上列顺序加入组分(C)。将混合物再均化15分钟,然后用台式挤压机挤压。挤压(成批挤压)得到肥皂棒。
应用实施例
实施例4:关于(抗氢剂)氢化环境中的肥皂中的褪色试验
试验用抗氧剂:式(11),(15),(16),(25),(32)和(33)化合物。
将参与试验的各抗氧剂500ppm与500ppm苯甲酰过氧化物和0.2%二氧化钛一起在台式搅拌机中剧烈搅拌和揉合,使之均匀分散在常用肥皂基底(动物脂肪,椰子和棕榈核肥皂的混合物)中。将该混合过程重复几次以保证抗氧剂在肥皂中分布均匀。
用台式挤压机挤压混合物,生产出的试验肥皂棒重量约为1g。将这些肥皂存放在40℃干燥箱内两个月,每周检查一次各肥皂棒的褪色情况。定量检查采用比色计,反射分光镜法更利于检查。这种方法在文献(例如,见《比色计》,第2版,国际照明委员会(CIE),CIE出版15.2(1986))中有详细论述。通过比较试验制剂与标准(用同样组合物新制成的样品)的比色结果来测定所用抗氧剂的颜色稳定性。
试验结果说明,采用抗氧剂可以获得良好的颜色稳定性。
实施例5:关于(抗氧剂)在肥皂中的溶解性试验
试验用抗氧剂:式(11),(15),(16),(21),(23),(24),(32)和(33)化合物。
为了确定溶解性将各0.1%抗氧剂与常用肥皂基底(动物脂肪,椰子和棕榈核肥皂的混合物)在40℃充分混合。然后将混合物冷却到室温,用光学显微镜观察抗氧剂是否已经均匀分布在肥皂组合物中(没有结晶,无混合相)。
此项试验的结果表明,试验化合物具有非常好的溶解性,并且能够迅速和完全掺入肥皂组合物中。
实施例6:关于(抗氧剂)对水解的稳定性试验
试验用抗氧剂:式(11),(14),(15),(16),(17),(21),(22),(24),(28),(32)和(33)化合物。
抗氧剂在碱性物质中的稳定性可以用简单的试验方法迅速得出结论。为此,将各0.05%抗氧剂在台式搅拌机中搅入常用肥皂底片中,该底片通常含有10-15%水分和0.02-0.1%游离碱(如Na2O)(总量的重量%)。重复该搅拌过程多次以保证抗氧剂在肥皂中均匀分布。将样品存放在40℃干燥箱内两个月,然后用HPLC分析测定未变化抗氧剂的相对含量。所用参考值(100%值)是各抗氧剂在新制备的肥皂制剂中的HPLC数据(高度或面积)。
结果:
上述试验表明,被试验的抗氧剂在肥皂制剂中有良好的稳定性。存放两个月后的HPLC分析结果说明,它们在碱性肥皂中的含量实际上没有改变。
因此,新型组合物(肥皂)对变色和化学分解具有良好的稳定性。
Claims (24)
1.一种个人护理清洁组合物,含有
和/或
(a2)式(3)的抗氧剂;
在式(1)、(2)和(3)中,
R1是氢;C1-C22烷基;C1-C22烷硫基;C5-C12环烷基;苯基;或C7-C9苯基烷基;
R2是C1-C22烷基;C5-C12环烷基;苯基;C7-C9苯基烷基;或-SO3M;
V是-O-;或-NH-;
a是0;1;或2;
b、c和d分别是0;或1;
e和f分别是1至3的整数;及
m、n和p分别是1至3的整数;
当e是1时
其中,当R3是C1-C22烷基时,b=0;或Q是式(1a)或(1b)基团;
g是0或1;
M是氢;碱金属;或铵;
当e是2时
当e是3时
其中,当R3是式(1k)基团时,c=1;以及
R4和R5分别是氢;或C1-C22烷基;及
(b)含有长链烷基或链烯基的表面活性剂。
2.根据权利要求1的组合物,其中,在式(1)中
Q是-CmH2m-;其中
m同权利要求1中定义。
3.根据权利要求1的组合物,其中
Q是亚甲基或亚乙基。
4.根据权利要求1的组合物,其中
V是-O-。
5.根据权利要求1的组合物,其中
R1和R2分别是C1-C22烷基。
6.根据权利要求5的组合物,其中
R1和R2分别是C1-C5烷基。
7.根据权利要求1的组合物,其中
a是1。
8.根据权利要求1的组合物,其中组分(a1)是式(2)化合物,
其中
R1和R2分别是C1-C5烷基;
a是1或2;及
R3,Q,V,T,b,c,d和e同权利要求1中定义。
9.根据权利要求8的组合物,其中
e是1。
12.根据权利要求11的组合物,其中
Q是亚乙基;
R3是一个直接键;及
R1,R2,T和a同权利要求11中定义。
13.根据权利要求11的组合物,其中
T是-O-CH2-。
17.根据权利要求15的组合物,其中用到式(8)化合物,
其中
B是式(8a)基团
R1和R2分别是C1-C5烷基;
V是-O-;或-NH-;
a是1或2;
m是1-3;及
n是0-3。
18.根据权利要求1的清洁组合物,其中对应于组分(a1)和(a2)的抗氧剂被作为单个化合物或几个单个化合物的混合物使用。
19.根据权利要求1的清洁组合物,其中组分(a1)或(a2)或组分(a1)和(a2)的总含量为50-1000ppm。
20.根据权利要求1的清洁组合物,其中组分(b)是阴离子、非离子或两性离子和两性合成的去污物质。
21.根据权利要求20的清洁组合物,其中阴离子去污物质是C8-C20脂肪酸的碱金属盐、铵盐或胺盐。
22.根据权利要求1的清洁组合物,其中组分(c)是空间位阻的胺类光保护剂。
24.根据权利要求1的清洁组合物,为固体,胶状物,合成洗涤剂或液体制剂形式。
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US4900469A (en) * | 1986-10-21 | 1990-02-13 | The Clorox Company | Thickened peracid precursor compositions |
ES2045106T3 (es) * | 1987-03-17 | 1994-01-16 | Procter & Gamble | Composiciones de blanqueo. |
US5252643A (en) | 1991-07-01 | 1993-10-12 | Ciba-Geigy Corporation | Thiomethylated benzofuran-2-ones |
JP2576923B2 (ja) * | 1991-10-04 | 1997-01-29 | 花王株式会社 | 容 器 |
AU3008695A (en) | 1994-07-26 | 1996-02-22 | Procter & Gamble Company, The | Rinse added fabric softener compositions containing antioxidants for sun-fade protection for fabrics |
JP3661231B2 (ja) * | 1995-07-06 | 2005-06-15 | 三菱化学株式会社 | 熱可塑性樹脂成形用ロールの洗浄液 |
JPH0931497A (ja) * | 1995-07-18 | 1997-02-04 | Nippon Oil & Fats Co Ltd | 脂肪酸塩組成物 |
US5712237A (en) * | 1995-11-27 | 1998-01-27 | Stevens; Edwin B. | Composition for cleaning textiles |
ES2160324T3 (es) | 1996-01-30 | 2001-11-01 | Colgate Palmolive Co | Composicion limpiadora que comprende estabilizante(s) de color y tensioactivo(s). |
US5843876A (en) * | 1996-01-30 | 1998-12-01 | Colgate-Palmolive Co. | Composition |
US5728663A (en) * | 1996-07-02 | 1998-03-17 | Johnson & Johnson Consumer Products, Inc. | Clear, colorless soap bar with superior mildness, lathering and discolorization resistence |
ES2157549T3 (es) * | 1996-07-15 | 2001-08-16 | Ciba Sc Holding Ag | Acidos propionicos beta-ditiofosforilados en lubricantes. |
JPH10204479A (ja) * | 1997-01-21 | 1998-08-04 | Lion Corp | 界面活性剤粉体および粒状洗剤組成物 |
US5994286A (en) | 1997-07-22 | 1999-11-30 | Henkel Corporation | Antibacterial composition containing triclosan and tocopherol |
JPH11189793A (ja) * | 1997-12-26 | 1999-07-13 | Japan Energy Corp | 洗浄剤組成物 |
-
1999
- 1999-04-27 ID IDP990391A patent/ID22517A/id unknown
- 1999-04-27 CN CN99105199A patent/CN1128870C/zh not_active Expired - Fee Related
- 1999-04-27 BR BR9902371-7A patent/BR9902371A/pt not_active IP Right Cessation
- 1999-04-28 JP JP11121157A patent/JPH11349988A/ja active Pending
-
2000
- 2000-12-07 US US09/734,234 patent/US20010000173A1/en not_active Abandoned
-
2002
- 2002-12-18 US US10/323,123 patent/US20030148916A1/en not_active Abandoned
-
2007
- 2007-10-25 US US11/977,633 patent/US7410940B2/en not_active Expired - Fee Related
-
2009
- 2009-10-30 JP JP2009250313A patent/JP2010059432A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
ID22517A (id) | 1999-10-28 |
US20010000173A1 (en) | 2001-04-05 |
BR9902371A (pt) | 2000-01-18 |
US20080108540A1 (en) | 2008-05-08 |
CN1236008A (zh) | 1999-11-24 |
US7410940B2 (en) | 2008-08-12 |
US20030148916A1 (en) | 2003-08-07 |
JPH11349988A (ja) | 1999-12-21 |
JP2010059432A (ja) | 2010-03-18 |
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