CN101505712A - 基于超支化缩合聚合物的组合物以及新型的超支化缩合聚合物 - Google Patents
基于超支化缩合聚合物的组合物以及新型的超支化缩合聚合物 Download PDFInfo
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- CN101505712A CN101505712A CNA200780030377XA CN200780030377A CN101505712A CN 101505712 A CN101505712 A CN 101505712A CN A200780030377X A CNA200780030377X A CN A200780030377XA CN 200780030377 A CN200780030377 A CN 200780030377A CN 101505712 A CN101505712 A CN 101505712A
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Abstract
本发明涉及一种基于超支化缩合聚合物的个人护理和家用护理组合物,所述缩合聚合物的主链上具有至少一个如下单元,所述单元包含连接到三亚甲基-氨基甲烷基团上的酰氨键,并且本发明涉及一种新型的超支化缩合聚合物。
Description
本发明涉及一种基于超支化缩合聚合物的个人护理、家用护理和织物护理组合物,以及涉及一种新型的超支化缩合聚合物。更具体地,本发明一方面涉及一种基于超支化缩合聚合物(此后也被称为本发明缩合聚合物)的个人护理和家用护理组合物,所述缩合聚合物的主链上具有至少一个如下单元,所述单元包含连接到三亚甲基-氨基甲烷基团上的酰氨键。具体地,上述缩合聚合物包含至少两个通式(I)的基团:
其中
自由键延伸至所述聚合物的主链;
A是可选被取代的(C6-C24)芳二基、或可选被取代的(C2-C24)(环)烷二基,
R1至R6各自独立地是氢、C1-20-烷基、C3-7-环烷基或C6-10-芳基;
X1、X2和X3各自独立地是氢、羟基、C1-20-烷基、C1-20-烷氧基、C3-7-环烷基、C6-10-芳基或基团-O-CO-R7、-O-CO-A-CO-N(R8,R9)、-O-CO-A-CO-OR10或-NHet;
R7是C1-20-烷基、C3-7-环烷基、C6-10-芳基、或聚合物或低聚物的残基;
R8和R9各自独立地是(C1-20)-烷基或(C6-10)-芳基,或被含有至少一个杂原子的基团取代的(C1-20)-烷基或(C6-10)-芳基;或者
R8和R9与它们连接的氮原子一起形成5元或6元环,其中,可选地一个或多个C原子被-NH、-N-(C1-20)-烷基、-N-芳基、-O-或-S-替代;
R10是C1-20-烷基、C3-7-环烷基、C6-10-芳基、或聚合物或低聚物的残基;
NHet各自独立地是通过氮原子连接到聚合物上的单环、双环或多环含氮杂环基团,所述含氮杂环基团可以是芳族基团,或者可以是部分氢化的或完全氢化的,并且可以包含额外的杂原子,诸如氮原子、氧原子或硫原子,并且所述含氮杂环基团可选被取代;并且
n、m、o各自独立地是1至4的整数,优选地,n、m和o等于1,
附加条件是,X1、X2和X3中最多只有一个是氢、C1-20-烷基、C3-7-环烷基或C6-10-芳基;并且
其中,含氮基团可以被季铵化或被质子化。
上述缩合聚合物可以用在个人护理产品和家用产品中,从而使所述产品具有如下这类产品通常需要的特征:例如低粘性,不成粉或不成片,优选是澄清、透明、光滑的。
根据本发明的典型个人护理产品和家用产品是皮肤护理制剂;沐浴和淋浴制剂;液体肥皂;棒状肥皂;含有香水、香味剂和加味成分的制剂;头发护理制剂;洁牙剂;除臭和止汗制剂;修饰制剂(decorativepreparation);光防护制剂。
本发明特别涉及如下头发护理制剂,例如护发素、洗发香波、造型啫哩和摩丝以及头发定型喷雾,其中,发现上述聚合物在这些头发护理制剂中可被用作调节剂、增强剂、成膜剂、表面活性剂、抗静电剂、保湿剂、乳化剂或头发造型试剂。在头发护理制剂中,例如成膜聚合物被用作例如调节剂,从而改善头发的梳理性、光泽度和外观以及赋予头发抗静电性质。
诸如头发护理制剂的个人护理产品还应当满足如下对其性能的要求:诸如具有细雾化状态、良好的成膜性、良好的保持力、高水平的造型保持性、长时间的卷曲保持性、改善的相容性,并且应当在采用洗发香波或肥皂清洗头发的过程中易于除去。
上述聚合物适于掺入个人护理产品或家用护理产品中,其具有制造上述产品所需的性质,即具有热稳定性、良好的溶解性、与化妆用基质的相容性、在4至9范围内的pH稳定性、容易加工形成各种产品、与其它成分的相容性以及与包装材料的相容性、具有中性颜色和气味以及具有低挥发性。
在一个实施方式中,本发明的组合物包含如下缩合聚合物,其中,至少一个通式(I)基团以R1至R6是氢的形式存在。
在另一实施方式中,本发明的组合物包含如下缩合聚合物,所述缩合聚合物中,X1、X2和X3的其中之一是甲基。
在另一实施方式中,本发明的组合物包含如下缩合聚合物,所述缩合聚合物中,X1、X2和X3中的至少一个是羟基、-O-CO-R7、-O-CO-A-CO-N(R8,R9)、-O-CO-A-CO-OR10或-NHet。
在本发明的所有实施方式中:
术语“C6-10-芳基”指具有6至10个碳原子的芳族烃的片段,特别是苯基、甲苯基、二甲苯基和萘基。
术语“C6-24-芳二基”指具有6至24个碳原子的芳族烃或氢化芳族烃的二价片段,特别是1,2-亚苯基、1,3-亚苯基、1,4-亚苯基、亚萘基、四氢或六氢亚萘基、或亚降冰片基(norbornene),这些基团可以被例如烷基或烯基取代。
术语“C1-20-烷基”指具有至多20个碳原子的直链或支化烷基,特别是甲基、乙基、丙基、异丙基、正丁基、仲丁基和叔丁基。术语“C3-7-环烷基”指具有3至7个碳原子的环烷基,特别是环丙基、环丁基、环戊基和环己基。所述C1-20-烷基可以是饱和的或不饱和的。
术语“(C2-24)-(环)烷二基”指具有2至24个碳原子的饱和的直链或支化(环)烃的二价片段,它们可以被C1-C20烷基或C2-C20烯基取代。
在本发明的所有实施方式中,A可以是饱和的或不饱和的。A可选被取代,优选被C1-C20烷基或被C2-C20烯基取代,诸如被甲基、辛烯基、壬烯基、癸烯基、十一碳烯基或十二碳烯基取代。
适当选定的A为亚乙基、亚丙基、(烷基-)1,2-亚乙基(烷基如上所述)、(甲基-)1,2-亚乙基、1,3-亚丙基、(甲基-)1,2-环己基、(甲基-)1,2-亚苯基、1,3-亚苯基、1,4-亚苯基、2,3-降冰片基、2,3-降冰片烯-5-基、四氢-1,2-亚苯基或(甲基-)1,2-环己-4-烯基。优选地,A是亚乙基、亚丙基或1,2-环己基。
R7可以选自例如饱和的或不饱和的(C1-20)烷基或C3-7-环烷基、C6-10-芳基、聚合物或低聚物。在本发明的所有实施方式中,R7优选选自(C1-20)烷基、聚合物的残基或低聚物的残基。适当聚合物的实例是聚酯、聚醚、聚(己)内酯、聚环氧乙烷、聚环氧丙烷甲基醚、聚四氢呋喃、聚硅氧烷、或氟聚合物或氟低聚物。R7可选被例如酯基、醚基、酰氨基和醇基取代。本发明缩合聚合物可以包含相同的或不同的R7基团。
优选地,R7选自苯基、甲基、乙基、丙烯、异丙基、正丁基、仲丁基、叔丁基或2-乙基己基、或者由如下天然脂肪酸衍生的基团,所述天然脂肪酸诸如为大豆脂肪酸、椰子脂肪酸或向日葵脂肪酸。如果R7是聚合物或低聚物的残基,那么其优选选自聚环氧乙烷、聚环氧丙烷或聚四氢呋喃。
如果R8和R9是(C1-C20)烷基,那么它们可以被可选含有一个或多个杂原子的取代基取代。更优选地,R8和R9是线性C2-、C3-或C6-烷基,其中一个或多个C原子可以被可选含有氮、氧或硫的取代基取代。因此,R8和R9可选被选自如下的基团取代:醇基、醚基、酯基、氰基、碳酸酯基、氨基甲酸酯基、脲基、酰氨基、酰亚氨基、氨基、亚氨基、咪唑基、肟基、硫基、硫醇基、硫脲基、砜基、亚砜基、硫酸酯基、磷酸酯基、膦基、氧化膦基、硅烷基、硅氧烷基、硅酸酯基、氟基、氯基、溴基或碘基。上述基团-N(R8,R9)的实例是二甲氨基、二乙氨基、二丁氨基、二辛氨基、乙基己基-甲基(或乙基)氨基、二-(2-乙基己基)氨基、双十八烷氨基、二烯丙基氨基、二巴豆基氨基、N-甲基(或乙基)烯丙基氨基、双(二甲基(或乙基)氨基丙基)氨基、双(二甲基(或乙基)氨基己基)氨基、双(二甲基(或乙基)氨基乙基)氨基、双(三甲基甲硅烷基丙基)氨基、双(三甲基(或三乙基)乙氧基甲硅烷基丙基)氨基、双(全氟辛基)氨基、双(全氟辛基-甲基(或乙基)氨基、双(甲氧基乙基)氨基、N-甲基(或乙基)甲氧基乙基氨基、双(甲氧基-2-丙基)氨基、双(马来酰亚氨基己基)氨基、双(辛烯基琥珀酰亚氨基丙基)氨基、双(六氢邻苯酰亚氨基己基)氨基、二糠基氨基、二氰基(甲)乙基氨基、双(二苯基膦乙基)氨基。
优选地,R8和R9是二(C1-20-烷基)氨基-C1-20-烷基,诸如N,N-二甲基氨基丙基。
其中R8和R9一起形成N-杂环的基团-N(R8,R9)的实例是吗啉基(morpholino)、硫代吗啉基、哌啶基、吡咯烷基、N-甲基哌嗪基(N-methyl piperazino)、(2-苯基)噁唑烷基、噻唑烷基、哌嗪基、2,2,6,6-四甲基哌啶基和二(苄基)氨基。
优选地,N-杂环是N-甲基哌嗪或吗啉基团。
在本发明的所有实施方式中,-OR10源自饱和的或不饱和的羟基官能化的单体、低聚物或聚合物,其中,R10可以是芳基、烷基、环烷基或聚环氧乙烷、聚环氧丙烷、聚四氢呋喃、聚硅氧烷、氟聚合物或尼龙低聚物的残基。优选地,R10是可选被取代的(C1-C26)烷基或聚环氧乙烷的残基。优选地,所述烷基选自苯基、甲基、乙基、丙基、异丙基、正丁基、仲丁基、叔丁基或2-乙基己基或由天然脂肪酸诸如大豆脂肪酸、椰子脂肪酸或向日葵脂肪酸衍生的基团。如果R10是聚合物或低聚物的残基,那么其优选选自聚环氧乙烷、聚环氧乙烷甲基醚、聚环氧丙烷、聚环氧丙烷甲基醚和/或聚四氢呋喃,具体选自聚环氧乙烷甲基醚、聚环氧丙烷甲基醚和/或聚四氢呋喃。
片段-NHet可以衍生自具有不稳定氢原子的的杂环化合物,这些杂环化合物的实例选自被取代的或未被取代的单环、双环或多环杂环,诸如吡咯、吡唑、咪唑、吡唑啉酮、吲哚、苯并咪唑、吲哚醌(isatin)、噁唑烷、2-噁唑烷酮、氧化吲哚、三唑(诸如1,2,3-三唑或1,2,4-三唑)、四唑、五唑、哒嗪酮、巴比妥酸、核酸以及诸如胞嘧啶、尿嘧啶、胸腺嘧啶或硫脲嘧啶、二氧代哌嗪、喹唑啉酮、二氮杂萘酮(phthalazinone)、嘌呤、叶黄素、蝶呤、环状内酰胺(诸如γ-丁内酰胺或α-哌啶酮)或双环脒及其衍生物。可选地,上述杂环化合物可以被完全氢化或被部分氢化,并且可以被取代。合适取代基中一个或多个可以独立地选自醇基、醚基、酯基、氰基、酰胺基、氨基、亚氨基、肟基、硫基、硫醇基、砜基、亚砜基、硫酸酯基、磷酸酯基、膦基、氧化膦基、硅烷基、硅氧烷基、硅酸酯基、氟基、氯基、溴基或碘基或羰基。最优选的是可选被取代的咪唑、苯并咪唑、1,2,4-三唑、乙内酰脲。
至少含有下述通式(I)基团的缩合聚合物是新型的化合物,其本身也是本发明的目的,所述通式(I)基团中,X1、X2和X3各自独立地是基团-O-CO-A-CO-N(R8,R9)、-O-CO-A-CO-OR10或-NHet;R1至R6、R8、R9和-NHet如上所定义,并且含氮基团可选被季铵化。
在本发明的组合物中使用的缩合聚合物通常可以具有600g/mol至50000g/mol的重均分子量,更优选具有800g/mol至25000g/mol的重均分子量,或者通常可以具有约500至15000g/mol的数均分子量,更优选具有700g/mol至4000g/mol的数均分子量。
在本发明的组合物中使用的缩合聚合物可以通过如下来制备:使通式(II)的化合物与通式(III)的二元羧酸或其环状酸酐以及可选的通式(IV)的酸、和/或通式(V)的二烷基胺、和/或通式(VI)的醇、和/或通式(VII)的杂环化合物进行缩聚;
其中,R1至R6以及n、m和o如前述式(I)所定义,X11、X21和X31具有与前述式(I)中的X1、X2和X3相同的含义,附加条件是,X11、X21、X31中的至少一个是羟基,进一步的附加条件是X11、X21和X31中最多只有一个是氢、C1-20-烷基、C3-7-环烷基,或C6-10芳基;
A(COOH)2 式(III),其中A具有与前述式(I)中相同的含义;
R7COOH 式(IV),
HN(R8R9) 式(V),
R10OH 式(VI),
H-NHet 式(VII),其中,R7、R8、R9、R10以及-NHet具有与前述式(I)相同的含义。
可选地,可以将至少一种根据式(VIII)的额外烷醇胺加入缩聚过程中,从而调节所得缩合聚合物的支化程度,
式VIII中:
Y是或者是线性、支化或环状(C1-C20)烷基;
R12、R13、R14、R15、R16和R17各自独立地是氢原子、(C6-C10)芳基、(C1-C8)烷基或CH2OH;
并且p和q是1至4的整数,优选地,p和q是1。
可选地,在缩聚反应以后,对所得缩合聚合物中的一个或多个含氮基团进行季铵化或质子化。
所述反应可以采用一步过程在室温下或者在高温下(优选在20℃至约120℃之间)实施,从而在式(II)化合物的氨基与二元羧酸或其羧酸酐的羧基之间形成酰氨键,此后,在高温下(优选在120℃至250℃之间)通过缩聚除水(优选通过蒸馏除水)得到聚酯酰胺。所述一步过程可以在溶剂存在下或者在没有溶剂的条件下进行。合适的溶剂是有机溶剂,诸如甲基-异丁基甲酮、乙酸丁酯、甲苯或二甲苯。可以在减压下或高压下(诸如在1×105Pa的压力下)、在真空下(<1×105Pa)或在共沸下进行蒸馏除水。
式(II)化合物的实例是三-羟甲基-氨基甲烷和2-氨基-2-乙基-1,3-丙二醇。
式A(COOH)2二元羧酸的环状酸酐的实例是邻苯二甲酸酐、四氢邻苯二甲酸酐、萘二羧酸酐、六氢邻苯二甲酸酐、5-降冰片烯-2,3-二羧酸酐、降冰片烯-2,3-二羧酸酐、琥珀酸酐、2-辛烯-1-基-琥珀酸酐、2-壬烯-1-基-琥珀酸酐、2-癸烯-1-基-琥珀酸酐、2-十一烷烯-1-基-琥珀酸酐、2-十二烷烯-1-基-琥珀酸酐、马来酸酐、(甲基)琥珀酸酐、戊二酸酐、4-甲基邻苯二甲酸酐、4-甲基六氢邻苯二甲酸酐、4-甲基四氢邻苯二甲酸酐、马来酸化的聚丁二烯和马来酸化的不饱和脂肪酸的烷基酯。
羧酸(IV)的实例是单官能羧酸的单体、低聚物或聚合物。适当的羧酸例如为饱和脂族(C1-C20)酸、不饱和(C1-C20)脂肪酸、芳族酸以及[α]、[β]不饱和酸或天然脂肪酸。适当的[α]、[β]不饱和酸的实例是(甲基)丙烯酸、巴豆酸以及衣康酸、马来酸、1,2-羟基硬脂酸、聚醚羧酸和富马酸的单酯或单酰胺。适当的饱和脂族酸例如为乙酸、丙酸、丁酸、2-乙基己酸、月桂酸和硬脂酸。适当的芳族酸例如为苯甲酸、叔丁基苯甲酸。天然脂肪酸的实例包括向日葵脂肪酸、椰子脂肪酸或大豆脂肪酸。
式HN(R8R9)二烷基胺(V)的实例是二甲基胺、二乙基胺、二丁基胺、二辛基胺、乙基己基-甲基(或乙基)胺、二-(2-乙基己基)胺、双十八烷胺、二烯丙基胺、二巴豆基胺、N-甲基(或乙基)烯丙基胺、双(氨基丙基)胺、双(氨基己基)胺、N-甲基(或乙基)-氨基丙基胺、双(二甲基(或乙基)氨基丙基)胺、双(二甲基(或乙基)氨基己基)胺、双(二甲基(或乙基)氨基乙基)胺、双(三甲基甲硅烷基丙基)胺、双(三甲基(或三乙基)乙氧基甲硅烷基丙基)胺、双(全氟辛基)胺、双(全氟辛基-甲基(或乙基)胺、双(甲氧基乙基)胺、N-甲基(或乙基)甲氧基乙基胺、双(甲氧基-2-丙基)胺、双(马来酰亚胺己基)胺、双(辛烯基琥珀酰亚氨基丙基)胺、双(六氢邻苯酰亚氨基己基)胺、二糠基胺、二氰基(甲)乙基胺、双(二苯基膦乙基)胺、吗啉、硫代吗啉、哌啶、吡咯烷、(2-苯基)噁唑烷、噻唑烷、哌嗪、N-甲基哌嗪、噁唑烷、2,2,6,6-四甲基哌啶和二(苄基)胺及其衍生物。
醇(VI)的实例例如为甲醇、乙醇、丙醇、丁醇、叔丁醇、2-乙基己醇、脂肪醇(诸如鲸蜡硬质醇、鲸蜡醇、硬脂醇、Polychol5)以及羟基官能化的聚合物,所述聚合物诸如为聚环氧乙烷、聚环氧丙烷、聚四氢呋喃、聚硅氧烷、氟聚合物或尼龙低聚物。优选的是聚环氧乙烷单甲基醚。
上述式(VII)杂环化合物的实例是以上具体公开的用于提供片段-NHet的那些化合物。
式VIII烷醇胺的实例是单烷醇胺或二烷醇胺。适当的单-β-烷醇胺的实例包括乙醇胺、1-乙基乙醇胺1-甲基乙醇胺、正丁基乙醇胺、1-乙基异丙基胺1-甲基异丙基胺、异丁醇胺、β-环己醇胺、正丁基异丙醇胺和正丙醇胺。
适当的二-β-烷醇胺的实例是二乙醇胺、3-氨基-1,2-丙二醇、2-氨基-1,3-丙二醇、二异丁醇胺(二(2-羟基-1-丁基)胺)、二-β-环己醇胺和二异丙醇胺(二(2-羟基-1-丙基)胺)。
除了羟基、-O-CO-R7、-O-CO-A-CO-N(R8,R9)、-O-CO-A-CO-OR10或-NHet端基以外,聚合物还可以包含某些羧基和/或β-羟基烷基酰胺基团。羧基的含量例如为0.01至2.0mg当量/(克聚合物)。β-羟基烷基酰胺基团的含量例如为0.01至5.0mg当量/(克聚合物)。可以通过式(II)化合物和可选的式(VIII)化合物与式(III)、(IV)、(V)、(VI)和(VII)反应物的比率以及转化程度来控制β-羟基烷基酰胺基团的含量。如果本发明缩合聚合物中存在羟基,那么该羟基可以在随后的步骤中与含有一个或多个可以与羟基发生反应的化合物进行反应,所述化合物例如为羧酸、羧酸酐、异氰酸酯、活化的酯或羧基卤化物,从而得到完全或部分改性的聚合物。
因此,本发明还涉及完全或部分改性的聚合物。所述改性例如可以通过如下来进行:使含有式(I)基团的缩合聚合物(其中至少一个X1、X2和/或X3是羟基)与含有反应性基团的单体、低聚物或聚合物进行反应。合适的反应性基团的实例包括羧基、羧基酯、羧酸酐、环氧基团、烷氧基硅烷基团、异氰酸酯基团、酰氯基团、环氧氯醇基团(epoxychlorohydrinegroups)、氨基、苯酚基团、羟甲基化的酰胺基团及其组合。优选地,所述单体、低聚物或聚合物仅包含一个可以与羟基发生反应的基团,结果在改性过程中未发生交联。
聚合物的支化度和官能度取决于原料和聚合物的分子量。分子量高于2000并且使用二烷醇胺和/或三烷醇胺通常获得官能度>6的高度支化的结构。
优选地,每个本发明缩合聚合物的分子中,端基X1、X2和/或X3的平均数目介于2和250之间,更优选介于3和50之间。
可选地,以季铵化形式或质子化形式存在的本发明缩合聚合物中一个或多个氮原子可以通过如下来制备:根据例如在Jerry March,“Advancedorganic chemistry”,第四版,Wiley-Interscience P.411ff中描述的标准过程使非被季铵化的缩合聚合物与常规季铵化试剂或质子化试剂进行反应。
合适的季铵化试剂例如为烷基或芳基卤化物,诸如甲基碘化物、甲基氯化物、乙基碘化物、苯基碘化物、烯丙基氯化物、乙烯基氯化物;硫酸酯,诸如硫酸二甲酯、硫酸二乙酯;缩水甘油醚和酯,诸如烯丙基缩水甘油醚和甲基丙烯酸缩水甘油酯,但并不局限于此。为了得到甜菜碱基团,合适的季铵化试剂为氯乙酸和(甲基)丙烯酸。季铵化过程可以在溶剂中进行或者可以不在溶剂中进行。合适的溶剂为水或有机溶剂,诸如乙腈。季铵化的缩合聚合物可以以在各种溶剂中的溶液形式使用,或者可以蒸发溶剂从而得到所需缩合聚合物。
优选地,氮原子被甲基和/或乙基季铵化。
合适的质子化试剂例如为无机酸,诸如HCl、H3PO4、H2SO4;以及其它化妆上可接受酸,诸如乙酸、酒石酸、富马酸、乳酸、马来酸、琥珀酸及其混合物。优选地,所述酸选自乙酸、酒石酸、盐酸、富马酸及其混合物。质子化过程可以在溶剂中进行或者可以不在溶剂中进行。合适的溶剂为水或有机溶剂,诸如乙腈。质子化的缩合聚合物可以以在各种溶剂中的溶液形式使用,或者可以蒸发溶剂从而得到所需缩合聚合物。
根据所需季铵化或质子化程度,可以相应地调整相对于氮原子的季铵化或质子化试剂的用量。
优选地,本发明缩合聚合物中的氮原子的季铵化或质子化程度为20至100%,更优选为50至100%,最优选为80至100%。
本发明的另一实施方式是含有有效量本发明缩合聚合物的个人护理产品或家用产品。
术语“有效量”通常意指,基于全部配制品,浓度至少为0.01重量%(wt%)。优选地,浓度为0.01至20wt%,最优选为0.05至10wt%。
在其它实施方式中,本发明涉及一种个人护理产品,所述产品包含上述缩合聚合物和额外的化妆用或皮肤病用佐剂和/或添加剂。
优选地,本发明的个人护理产品选自皮肤护理制剂;沐浴和淋浴制剂;液体肥皂;棒状肥皂;含有香水、香味剂和加味成分的制剂;头发护理制剂;洁牙剂;除臭和止汗制剂;修饰制剂(decorative preparation);光防护制剂和含有活性成分的制剂。
根据本发明的优选个人护理制剂是头发护理制剂,其包含在头发护理中使用的额外添加剂和佐剂。
在另一实施方式中,本发明涉及一种护理头发的方法,所述方法中,将诸如头发护理制剂的个人护理产品应用于所述头发。
在另一实施方式中,本发明涉及如上所定义的缩合聚合物作为调节剂、增强剂、成膜剂、表面活性剂、抗静电剂、保湿剂、乳化剂或头发造型试剂的用途。
本发明的个人护理产品包括额外的化妆用或皮肤病用佐剂和/或添加剂(化妆品载剂),所述佐剂和/或添加剂优选选自:
1)水
2)水溶性有机溶剂,优选C1-C4烷醇
3)油、脂肪物质、蜡
4)C6-C30一元羧酸与一价、二价或三价醇形成的与3)不同的各种酯
5)饱和的无环烃和环状烃
6)脂肪酸
7)脂肪醇
8)硅油
及它们的混合物。
本发明的个人护理产品和家用产品还可以包含其它佐剂和添加剂,例如,防腐剂/抗氧剂、脂肪物质/油、水、有机溶剂、硅氧烷、增稠剂、软化剂、乳化剂、其它遮蔽剂、消泡剂、保湿剂、芳香剂、表面活性剂、填料、螯合剂、阴离子、阳离子、非离子、两性聚合物或其混合物、推进剂(propellant)、酸化或碱化试剂、染料、着色剂、颜料或纳米颜料、光稳定剂、驱虫剂、皮肤美黑试剂、皮肤增白试剂、抗菌试剂、防腐剂或其它通常配制到化妆品中的成分。根据所需产品,本领域技术人员可以容易地对化妆用和皮肤病用佐剂和添加剂的必需用量进行选择,所述用量在如下实施例中进行阐述,但并不局限于此。
遮光试剂
额外的遮蔽剂有利地选自,UV-A、UV-B、UV-C和/或广谱滤光剂。UV-B或广谱掩蔽剂(即,在约290-340nm具有最大吸收的物质)的实例可以为有机和无机化合物。有机UV-B或广谱遮蔽剂例如为,丙烯酸酯,诸如2-氰基-3,3-二苯基丙烯酸2-乙基己酯(氰双苯丙烯酸辛酯(octocrylene),)、2-氰基-3,3-二苯基丙烯酸乙酯等;樟脑衍生物,诸如4-甲基亚苄基樟脑()、3-亚苄基樟脑、甲基硫酸樟脑苯甲烷铵(camphor benzalkonium methosulfate)、聚丙烯酰胺基甲基亚苄基樟脑、磺基亚苄基樟脑、磺甲基亚苄基樟脑、对苯二亚甲基二樟脑酰胺磺酸等;肉桂酸酯衍生物,诸如甲氧基肉桂酸乙基己酯、甲氧基肉桂酸乙氧基乙酯、甲氧基肉桂酸二乙醇胺酯、甲氧基肉桂酸异戊酯等以及键合到硅氧烷上的肉桂酸衍生物;对-氨基苯甲酸衍生物,诸如对-氨基苯甲酸、对-二甲基氨基苯甲酸2-乙基己酯、N-氧丙烯基化对-氨基苯甲酸乙酯和对-氨基苯甲酸甘油酯;二苯甲酮,诸如二苯甲酮-3、二苯甲酮-4、2,2’,4,4’-四羟基-二苯甲酮、2,2’-二羟基-4,4’-二甲氧基二苯甲酮等;亚苄基丙二酸酯,诸如4-甲氧基亚苄基丙二酸二(2-乙基己基)酯;2-(4-乙氧基苯胺亚甲基)丙二酸酯,诸如在欧洲专利公开EP 0895776中所描述的2-(4-乙氧基苯胺亚甲基)丙二酸二乙酯;欧洲专利公布EP 0358584 B1、EP 0538431 B1和EP 0709080 A1中所描述的含苯丙二酸酯(benzmalonate)基团的有机硅氧烷化合物,诸如 SLX;苯并三唑基甲基苯酚三聚硅氧烷(Drometrizoletrisiloxane)(Mexoryl XL);咪唑衍生物,诸如2-苯基苯并咪唑磺酸及其盐(2-苯基苯并咪唑磺酸盐是:例如碱金属盐(例如钠盐或钾盐)、铵盐、吗啉盐、伯胺、仲胺和叔胺盐(如,单乙醇胺盐、二乙醇胺盐等));水杨酸酯衍生物,诸如水杨酸异丙基苄酯、水杨酸苄酯、水杨酸丁酯、水杨酸乙基己酯(Neo HeliopanOS)、水杨酸异辛酯或水杨酸高薄荷酯(homosalate,Neo Heliopan HMS)等;三嗪衍生物,诸如乙基己基三嗪酮(UVINUL T-150)、二乙基己基丁酰胺基三嗪酮(UVASORBHEB)等。胶囊化的UV滤光剂,诸如胶囊化的甲氧基肉桂酸乙基己酯(Eusolex UV-珍珠)或负载有UV滤光剂的微胶囊,如例如在EP 1471995中公开的。无机化合物是诸如微粒化的TiO2等的颜料。术语“微粒化”指粒子尺寸为约5nm至约200nm,尤其是15nm至约100nm。TiO2微粒还可以被例如氧化铝或氧化锆的金属氧化物包覆,或被例如多元醇、甲基硅酮(methicone)、硬脂酸铝和烷基硅烷的有机涂层包覆。所述涂层是本领域所公知的。
广谱掩蔽剂或UV-A遮蔽剂(即,在约320-400nm具有最大吸收的物质)的例子可以为有机和无机化合物,例如,二苯甲酰甲烷衍生物,诸如4-叔丁基-4’-甲氧基二苯甲酰甲烷、二甲氧基二苯甲酰甲烷、异丙基二苯甲酰甲烷等;苯并三唑衍生物,诸如2,2’-亚甲基-二(6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)-苯酚(Tinosorb M)等;二-乙基己基氧苯酚甲氧苯基三嗪(Tinosorb S)等;亚苯基-1,4-二苯并咪唑磺酸或其盐,诸如2,2-(1,4-亚苯基)-二(1H-苯并咪唑-4,6-二磺酸)(NeoheliopanAP);经氨基取代的羟基二苯甲酮,诸如欧洲专利公开EP 1046391中描述的2-(4-二乙氨基-2-羟基苯甲酰基)-苯甲酸己酯(Uvinul A plus);在国际专利公开WO2005080341A1中所描述的离子性UV-A滤光剂;颜料,诸如微粒化的ZnO或TiO2等。术语“微粒化”指粒子尺寸为约5nm至约200nm,尤其是15nm至约100nm。TiO2微粒还可以被例如氧化铝或氧化锆的其它金属氧化物包覆,或被例如多元醇、甲基硅酮(methicone)、硬脂酸铝和烷基硅烷的有机涂层包覆。所述涂层是本领域所公知的。
因为二苯甲酰甲烷衍生物具有有限的光稳定性,因此需要对这些UV-A遮蔽剂进行光稳定。因此,术语“常规UV-A掩蔽剂”也指被下述物质稳定的二苯甲酰甲烷衍生物(例如,),所述物质例如为欧洲专利公布EP 0514491 B1和EP 0780119 A1中所描述的3,3-二苯基丙烯酸酯衍生物;美国专利No.5605680中所描述的亚苄基樟脑衍生物;欧洲专利公布EP 0358584 B1、EP 0538431 B1和EP 0709080 A1中所描述的包含苯丙二酸酯基团的有机硅氧烷化合物。
抗氧化剂
基于本发明,可以使用通常配制入个人护理产品和家用产品中的所有已知抗氧化剂。尤其优选选自下列的抗氧化剂:氨基酸(例如,甘氨酸、组氨酸、酪氨酸、色氨酸)及其衍生物、咪唑(例如,尿刊酸)和衍生物、肽(例如D,L-肌肽、D-肌肽、L-肌肽和衍生物(例如,鹅肌肽))、类胡萝卜素、胡萝卜素(例如,α-胡萝卜素、β-胡萝卜素、番茄红素)和衍生物、绿原酸和衍生物、硫辛酸和衍生物(例如,二羟基硫辛酸)、金硫代葡萄糖、丙基硫脲嘧啶和其它硫醇(例如,硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺和其糖基-、N-乙酰基-、甲基-、乙基-、丙基-、戊基-、丁基-、月桂基-、棕榈基-、油基-、y-6,7,9,10-十八碳二烯-1-基-(y-linoleyl)、胆甾醇基-和甘油基的酯)及其盐、硫代二丙酸二月桂酯、硫代二丙酸二硬脂酯、硫代二丙酸及其衍生物(酯、醚、肽、脂质、核苷酸、核苷和其盐)以及非常低剂量的(例如,pmol/kg~μmol/kg)亚砜胺(sulfoximine)化合物(例如,丁硫氨酸亚砜胺(buthioninesulfoximine)、高半胱氨酸亚砜胺、丁硫氨酸砜(buthioninsulfone)、五、六、七硫堇亚砜胺)、其它的(金属)-螯合剂(例如,α-羟基脂肪酸、棕榈酸、肌醇六磷酸、乳铁蛋白)、β-羟基酸(例如,柠檬酸、乳酸、苹果酸)、腐殖酸(huminic acid)、五倍子酸、五倍子提取物(gallic extracts)、胆红素、胆绿素、EDTA、EGTA及其衍生物、不饱和脂肪酸和其衍生物(例如,γ-亚油酸、亚油酸、油酸)、叶酸及其衍生物、泛醌和泛醌醇及其衍生物、维生素C和其衍生物(例如,棕榈酸抗坏血酸酯和四异棕榈酸抗坏血酸酯、抗坏血酸磷酸Mg、抗坏血酸磷酸Na、抗坏血酸乙酸酯)、生育酚和衍生物(例如,维生素-E-乙酸酯)、天然维生素E的混合物、维生素A和衍生物(维生素-A-棕榈酸酯和乙酸酯)以及松柏基苯甲酸酯、芸香亭酸和衍生物、α-糖基芸香苷、阿魏酸、亚糠基葡萄糖醇、肌肽、丁基羟基甲苯、丁基羟基苯甲醚、三羟基丙基苯基甲酮、脲和其衍生物、甘露糖和衍生物、锌和衍生物(例如,ZnO、ZnSO4)、硒和衍生物(例如,硒代蛋氨酸)、芪和衍生物(例如,芪氧化物、反式芪氧化物)和所述活性组分的合适衍生物(盐、酯、醚、糖、核苷酸、核苷、肽和脂质)。一种或更多种防腐剂/抗氧化剂的用量,相对于本发明组合物的总重,可以为至少0.01wt%。优选地,相对于本发明组合物的总重以约0.01wt%—约10wt%存在。优选地,一种或更多种防腐剂/抗氧化剂的用量为约0.1wt%—约1wt%。
表面活性成分
通常,个人护理产品或家用产品还包含表面活性成分,例如,乳化剂、增溶剂等。乳化剂能使两种或更多种不混溶的组分均匀组合。而且,乳化剂用于稳定组合物。可以用在本发明中以形成O/W、W/O、O/W/O或W/O/W乳液/微乳液的乳化剂包括:失水山梨糖醇油酸脂、失水山梨糖醇倍半油酸酯、失水山梨糖醇异硬脂酸酯、失水山梨糖醇三油酸酯、聚甘油基-3-二异硬脂酸酯、油酸/异硬脂酸的聚甘油酯、聚甘油基-6六蓖麻醇酸酯、聚甘油基-4-油酸酯、聚甘油基-4油酸酯/PEG-8丙二醇椰油、油酰DEA、TEA肉豆蔻酸酯、TEA硬脂酸酯、硬脂酸镁、硬质酸钠、月桂酸钾、蓖麻醇酸钾、椰油酸钠、牛油酸钠(sodium tallowate)、海狸香酸钾(potassium castorate)、油酸钠及其混合物。其它合适的乳化剂是磷酸酯及其盐,例如,磷酸十六烷酯( A)、二乙醇胺磷酸十六烷酯、十六烷磷酸钾( K)、油酸甘油酯磷酸钠(sodium glyceryl oleate phosphate)、氢化植物甘油磷酸酯及其混合物。而且,一种或更多种合成聚合物可以作为乳化剂。例如,PVP二十碳烯共聚物、丙烯酸酯/丙烯酸C10-30烷基酯交聚物、丙烯酸酯/steareth-20甲基丙烯酸酯共聚物、PEG-22/十二烷二醇共聚物、PEG-45/十二烷二醇共聚物及其混合物。其它示例性的乳化剂是脂肪醇,例如鲸蜡硬脂醇(cetearylalcohol)(Lanette O,Cognis Coopearation)、鲸蜡醇(Lanette 16,Cognis Cooperation)、硬脂醇(Lanette 18,Cognis Cooperation)、Laneth-5(Polychol 5,Croda Chemicals);其它的蔗糖和葡萄糖衍生物,例如蔗糖二硬脂酸酯(Crodesta F-10,Croda Chemicals)、葡萄糖异硬脂酸甲酯(Isolan IS,Degussa Care Chemicals);其它乙氧基化的羧酸或聚乙二醇酯和聚乙二醇醚,例如steareth-2(Brij 72,Uniqema)、steareth-21(Brij 721,Uniqema)ceteareth-25(Cremophor A25,BASFCooperation)、PEG-40氢化蓖麻油(Cremophor RH-40,BASFCooperation)、PEG-7氢化蓖麻油(Cremophor WO7,BASFCooperation)、PEG-30二聚羟基硬脂酸酯(Arlacel P 135,Uniqema);其它甘油酯和聚甘油酯,例如聚甘油基-3-二异硬脂酸酯(HostacerinTGI,Clariant Cooperation)、聚甘油-2二聚羟基硬脂酸酯(DehymulsPGPH,Cognis Cooperation)、聚甘油基-3甲基葡萄糖二硬脂酸酯(TegoCare 450,Degussa Care Chemicals)。优选的乳化剂是磷酸十六烷酯、二乙醇胺磷酸十六烷酯()、十六烷磷酸钾、PVP二十碳烯共聚物、丙烯酸酯/丙烯酸C10-30-烷酯交聚物、PEG-20失水山梨糖醇异硬脂酸酯、失水山梨糖醇异硬脂酸酯及其混合物。一种或更多种乳化剂的总用量,相对于本发明组合物的总重,为至少0.01wt%。优选地,相对于本发明组合物的总重用量为约0.01wt%-约20wt%。优选地,使用约0.1wt%-约10wt%的乳化剂。
通常个人护理产品或家用产品还包含阴离子、中性、两性或阳离子表面活性剂。示例性的阴离子表面活性剂包括,烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基芳基磺酸盐、烷基琥珀酸盐、烷基磺基琥珀酸盐、N-烷酰基肌氨酸盐(N-alkoylsarkosinate)、酰基牛磺酸盐、酰基羟乙基磺酸盐、烷基磷酸盐、烷基醚磷酸盐、烷基醚羧酸盐、α-烯烃磺酸盐、尤其是碱金属盐和碱土金属盐(如钠盐、钾盐、镁盐、钙盐)以及铵盐和三乙醇胺盐。所述烷基醚硫酸盐、烷基醚磷酸盐和烷基醚羧酸盐在分子中可以包含1至10个环氧乙烷或环氧丙烷单元,优选包含1至3个环氧乙烷单元。
合适的例如为月桂基硫酸钠、月桂基硫酸铵、月桂基醚硫酸钠、月桂基醚硫酸铵、月桂酰基肌氨酸钠、油基琥珀酸钠、月桂基磺基琥珀酸铵、十二烷基苯磺酸钠、十二烷基苯磺酸三乙醇胺盐。
合适的两性表面活性剂例如为烷基甜菜碱、烷基酰氨基丙基甜菜碱、烷基磺基甜菜碱、烷基甘氨酸酯、烷基羧基甘氨酸酯、烷基两性乙酸酯或丙酸酯、烷基两性二乙酸酯或二丙酸酯,诸如椰油二甲基磺基丙基甜菜碱、月桂基甜菜碱、椰油酰氨基丙基甜菜碱或椰油两性丙酸钠。
非离子表面活性剂的实例是,具有6至20个碳原子(其可以是线型或支化烷基链)的脂族醇或烷基酚与环氧乙烷和/或环氧丙烷的反应产物。环氧烷烃的含量相对于一摩尔醇为约6摩尔至60摩尔。而且烷基胺氧化物、单烷基或二烷基烷醇酰胺、聚乙二醇的脂肪酸酯、烷基多苷或脱水山梨糖醇醚酯适于掺入本发明的护发组合物中。
而且,个人护理产品或家用产品可以包含常规的阳离子表面活性剂,诸如季铵化的铵化合物,例如十六烷基三甲基氯化铵或溴化铵(INCI:cetrimoniumchloride或cetrimoniumbromide)、羟乙基十六烷基二甲基磷酸铵(INCI:Quaternium-44)、 Mono LS(INCI:椰油三甲基甲氧基硫酸铵(Cocotrimoniummethosulfate))、聚(氧-1,2-乙二基)、三-(羟基)磷酸(十八烷基次氮基)三-2,1-乙二基酯(INCI Quaternium-52)。为了特殊效果,可以将典型的调节剂与个人护理产品或家用产品(尤其是护发制剂)中的本发明缩合聚合物组合,诸如前述被命名为聚季铵盐(INCI:polyquaternium)的阳离子聚合物,特别是乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐的共聚物( FC, HM, MS, Ultracare)、采用二乙基磺酸盐季铵化的N-乙烯基吡咯烷酮/二甲基氨基乙基甲基丙烯酸酯的共聚物( PQ 11)、N-阳离子纤维素衍生物的共聚物(Polyquaternium-4和Polyquaternium-10)、丙烯酰胺共聚物(Polyquaternium-7)。而且,在如下硅氧烷基质上的蛋白质水解产物也可被用作调节剂,所述基质诸如为聚芳基硅氧烷、聚芳基烷基硅氧烷、聚醚硅氧烷或硅树脂。其它合适的硅氧烷化合物是dimethicondopolyole(CTFA)和氨基官能化的硅氧烷衍生物(诸如氨基二甲基硅酮(amodimethicone)(CTFA))。
而且,可以使用阳离子瓜耳胶衍生物,诸如瓜耳胶羟丙基三甲基氯化铵。
一种或更多种阴离子、中性、两性或阳离子表面活性剂的总用量,相对于组合物的总重,为至少0.01wt%。优选地,相对于本发明组合物的总重,以约0.01wt%-约20wt%的用量存在。优选地,一种或更多种表面活性剂的用量为约0.1wt%-约10wt%。
油和脂肪组分
脂质相有利地选自:矿物油和矿物蜡;油,例如,癸酸或辛酸甘油三酯或蓖麻油;油或蜡和其它天然或合成油,在优选的实施方式中,为脂肪酸与醇(例如,异丙醇、丙二醇、丙三醇)的酯或脂肪醇与羧酸或脂肪酸的酯;苯甲酸烷基酯;和/或硅油。
可以掺入本发明的乳液、微乳液、油凝胶、水分散体(hydrodispersion)或脂分散体(lipodispersion)的油相中的示例性脂肪物质有利地选自,具有3-30个碳原子的饱和/或不饱和、直链和/或支化烷基羧酸和具有3-30个碳原子的饱和/或不饱和、直链和/或支化醇的酯,以及芳族羧酸和具有3-30个碳原子的饱和/或不饱和、直链和/或支化醇的酯。这种酯可以有利地选自棕榈酸辛酯、椰油酸辛酯、异硬脂酸辛酯、辛基十二烷基肉豆蔻酸酯、鲸蜡硬脂基异壬酸酯(cetearylisononanoate)、肉豆蔻酸异丙酯、棕榈酸异丙酯、硬脂酸异丙酯、油酸异丙酯、硬脂酸正丁酯、月桂酸正己酯、油酸正癸酯、硬脂酸异辛酯、硬脂酸异壬酯、异壬酸异壬酯、棕榈酸2-乙基己酯、月桂酸2-乙基己酯、硬脂酸2-己基癸酯、棕榈酸2-辛基十二烷酯、庚酸硬脂基酯、油酸油基酯、芥酸油基酯、油酸瓢儿菜基酯、芥酸瓢儿菜基酯、硬脂酸十三烷酯、十三烷基偏苯三酸酯,以及这些酯的合成、半合成或天然混合物,例如,霍霍巴油。
其它适用在本发明的个人护理产品或家用产品中的脂肪组分包括极性油,例如,卵磷脂和脂肪酸甘油三酯,即,具有8-24个碳原子(优选12-18个碳原子)的饱和和/或不饱和、直链和/或支化羧酸的甘油三酯,其中,脂肪酸甘油三酯优选选自合成、半合成或天然油(例如,椰油酸甘油酯(cocoglyceride)、橄榄油、向日葵油、豆油、花生油、菜籽油、甜杏仁油、棕榈油、椰子油、蓖麻油、氢化蓖麻油、麦油、葡萄籽油、澳洲坚果油和其它);非极性油,例如,直链和/或支化烃和蜡(例如,矿物油、凡士林(矿脂);石蜡、角鲨烷和角鲨烯、聚烯烃、氢化聚异丁烯和异十六烷,优选的聚烯烃是聚癸烯;二烷基醚,例如二辛醚;直链或环状硅油,例如优选环甲基硅酮(八甲基环四硅氧烷);十六烷基二甲基硅酮、六甲基环三硅氧烷、聚二甲基硅氧烷、聚(甲基苯基硅氧烷)及其混合物。
可以有利地掺入本发明的个人护理产品或家用产品中的其它脂肪组分是异二十烷、新戊二醇二庚酸酯、丙二醇二辛酸酯/二癸酸酯、辛酸/癸酸/二甘油基琥珀酸酯、丁二醇辛酸酯/癸酸酯、C12-13烷基乳酸酯、二C12-13烷基酒石酸酯、三异硬脂精(triisostearin)、二季戊四醇六辛酸酯/六癸酸酯、丙二醇单异硬脂酸酯、三辛精(tricaprylin)、二甲基异山梨醇。特别优选使用苯甲酸C12-15烷基酯和异硬脂酸2-乙基己基酯的混合物、苯甲酸C12-15烷基酯和异壬酸异十三烷酯的混合物以及苯甲酸C12-15烷基酯、异硬脂酸2-乙基己基酯和异壬酸异十三烷酯的混合物。
本发明的配制剂的油相还可以包含天然植物蜡或动物蜡,例如,蜂蜡、中国蜡、大蜂蜡和其它昆虫蜡,以及牛油树脂和可可脂。
硅油
合适的硅油例如为,二甲基聚硅氧烷、二乙基聚硅氧烷、二苯基聚硅氧烷、环状硅氧烷、聚(甲基苯基硅氧烷)以及经氨基、脂肪酸、醇、聚醚、环氧、氟、糖苷和/或烷基改性的硅氧烷化合物(其在室温下为液体或固体)及其混合物。二甲基硅酮和聚(甲基苯基硅氧烷)的数均分子量优选在100至150000g/mol的范围内。优选的环状硅氧烷包括4元至8元环,其例如以环甲基硅酮(cyclomethicone)的形式商购。
油或脂肪的用量,相对于产品的总重,为约1wt%至约50wt%。油或脂肪组分的优选用量为约2wt%至约25wt%,最优选为约3wt%至约20wt%。
保湿剂
保湿剂(moisturizing agent)可被掺入本发明的产品中以保持皮肤的水合和再水合。通过提供保护层以防止水分从皮肤蒸发的保湿剂被称为润肤剂(emollient)。另外,润肤剂对皮肤表面提供软化或润肤效果,并通常被认为对局部使用是安全的。优选的润肤剂包括矿物油、羊毛脂、矿脂、癸酸/辛酸三甘油醛、胆甾醇、硅酮(例如,二甲基硅酮、环甲基硅酮)、杏仁油、霍霍巴油、鳄梨油、蓖麻油、芝麻油、向日葵油、椰子油和葡萄籽油、可可脂、橄榄油、芦荟提取物、脂肪酸(例如,油酸和硬脂酸)、脂肪醇(例如,鲸蜡醇和十六烷醇(ENJAY))、己二酸二异丙酯、羟基苯甲酸酯、C9-15醇的苯甲酸酯、异壬酸异壬基酯、醚(例如,聚环氧丙烷丁基醚和聚环氧丙烷十六烷基醚)和苯甲酸C12-15烷酯及其混合物。最优选的润肤剂是羟基苯甲酸酯、芦荟(aloe vera)、苯甲酸C12-15烷基酯及其混合物。润肤剂的用量,相对于产品的总重,为约1wt%-约50wt%。润肤剂的优选用量为约2wt%-约25wt%,最优选为约3wt%-约15wt%。
与水结合,从而将水分保持在皮肤表面的保湿剂被称为润湿剂(humectant)。可以掺入本发明产品中的合适润湿剂为,例如,甘油、丙二醇、聚丙二醇、聚乙二醇、乳酸、乳酸钠、吡咯烷酮羧酸、脲、磷脂、胶原蛋白、弹性蛋白、神经酰胺、卵磷脂、山梨糖醇、PEG-4及其混合物。其它合适的保湿剂为下类可水溶和/或可溶胀和/或水凝胶多糖类的聚合保湿剂,例如,透明质酸、壳聚糖和/或富海藻糖的多糖(可得为例如来自SOLABIA S的 1000(CAS-Nr 178463-23-5))。一种或更多种润湿剂可选在本发明产品中的用量为约0.5wt%-约8wt%,优选为约1wt%-约5wt%。
本发明的产品的水相可以包含常用化妆品添加剂,例如,醇(尤其是低级醇,优选乙醇和/或异丙醇、低级二元醇或多元醇和它们的醚,优选丙二醇、丙三醇、乙二醇、乙二醇单乙基醚或单丁基醚、丙二醇单甲基醚或单乙基醚或单丁基醚、二乙二醇单甲基醚或单乙基醚和类似产品)、聚合物、泡沫稳定剂、电解质和尤其一种或更多种增稠剂。
增稠剂
可以用在本发明的配制剂中以便有利于获得适当产品稠度的增稠剂包括卡波姆(carbomer)、二氧化硅、硅酸镁和/或铝、脂质增稠剂(例如鲸蜡醇)、棕榈酸十六烷基酯(Cutina CP,Cognis Cooperation)、肉豆蔻酸甘油酯(Estol 3650 Uniqema)、微晶蜡(A&E Connock)、肉豆蔻醇(Lanette 14,Cognis Cooperation)、肉豆蔻基乳酸酯(Crodamol ML,Croda Chemicals)、蜂蜡(A&E Connock)、硬脂酸(Lipo Chemicals)、十八烷醇(Lanette 18,Cognis Cooperation)、多糖和其衍生物(例如,黄原胶(Keltrol,CP Kelco))、羟丙基纤维素(Klucel,HerculesIncorporated)、羟乙基纤维素(Tylose H,Clariant Corporation)、聚丙烯酰胺(自乳化聚丙烯酰胺,例如Salcare SC 91、Salcare SC 96(CibaSpecialty Chemicals)、Sepigel 305(Seppic))、丙烯酸酯交聚物(优选卡波姆,例如,单独或混合使用的981、1382、2984、5984、ETD 2001、ETD 2050、Ultrez 10、Ultrez 21(Noveon Inc.))。本发明的产品中的增稠剂的用量为约0.01wt%至约8wt%,优选为0.05wt%至约5wt%。
中和剂
可以包含在本发明的产品中以中和各组分(例如乳化剂或发泡剂/稳定剂)的合适中和剂包括,但不限于,碱金属氢氧化物(例如,氢氧化钠和钾);有机碱(例如,二乙醇胺(DEA)、三乙醇胺(TEA)、氨基甲基丙醇及其混合物);氨基酸(例如精氨酸和赖氨酸),以及前述物质的任意组合。本发明的产品中的中和剂的用量为约0.01wt%-约8wt%,优选为1wt%-约5wt%。
电解质
可能需要将电解质加入本发明的产品中以改变疏水乳化剂的性能。因此,本发明的乳液/微乳液可以优选包含一种或数种含下述阴离子的盐的电解质,例如,氯离子、硫酸根、碳酸根、硼酸根、铝酸根,但不限于此。其它合适的电解质可以基于以下有机阴离子,例如但不限于,乳酸根、乙酸根、苯甲酸根、丙酸根、酒石酸根和柠檬酸根。作为阳离子,优选选择的是,铵离子、烷基铵离子、碱金属离子或碱土金属离子、镁离子、铁离子或锌离子。尤其优选的盐是氯化钾和氯化钠、硫酸镁、硫酸锌和其混合物。在本发明的产品中的电解质的用量为约0.01wt%-约8wt%。
光稳定剂
其它光稳定剂的添加可能是期望的。这类光稳定剂是例如已知的受阻胺类光稳定剂(HALS),所述受阻胺类光稳定剂可以是单体或多聚体。它们例如选自由下述物质构成的组:N,N′-双甲酰基-N,N′-双-(2,2,6,6-四甲基-4-哌啶基)-六亚甲基二胺(Uvinul 4050H)、双-(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(Uvinul 4077H)、(双-(1,2,2,6,6-五甲基-4-哌啶基)-癸二酸酯+甲基-(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯(Uvinul 4092H),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、正丁基-3,5-二叔丁基-4-羟基苄基-丙二酸双(1,2,2,6,6-五甲基哌啶基)酯、1-羟乙基-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物、N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-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-丁四酸酯、1,1′-(1,2-乙二基)-双(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰-2,2,6,6-四甲基哌啶、4-十八烷氧-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]癸烷-2,4-二酮、N,N-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的缩合物、2-氯-4,6-二(4-正丁基氨基-2,2,6,6-四-甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙胺基)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)-1,3,5-三嗪和1,2-双(3-氨基丙胺基)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]-癸烷-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-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)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物、1,2-双(3-氨基丙胺基)乙烷和2,4,6-三氯-1,3,5-三嗪和4-丁基氨基-2,2,6,6-四甲基哌啶(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]癸烷和表氯醇的反应产物,但不仅限于此。
驱虫剂
可用在本发明的产品中的驱虫剂的实例为例如N,N-二乙基-间甲苯酰胺、1,2-戊二醇或驱虫剂3535。
自美黑成分(self tanning ingredient)
美黑成分的实例为例如二羟基丙酮和/或赤藓酮糖或二羟基丙酮和/或WO 01/85124中所述的二羟基丙酮前驱体和/或赤藓酮糖。
皮肤美白成分
皮肤美白成分的实例为例如维生素C、抗坏血酸磷酸钠和抗坏血酸磷酸镁、熊果苷和α-熊果苷。
除臭活性成分
本发明考虑到的除臭活性成分的实例为止汗剂,如水合氯化铝、碱式乙酸铝和酸性铝/锆盐。可以添加酯酶抑制因子作为进一步除臭的活性成分。这类抑制因子优选为柠檬酸三烷基酯,如柠檬酸三甲酯、柠檬酸三丙酯、柠檬酸三异丙酯、柠檬酸三丁酯和特别是柠檬酸三乙酯(Hydagen CAT,Henkel),其能抑制酶活性并从而减少臭味生成。作为酯酶抑制因子所考虑的其它物质为固醇硫酸酯或磷酸酯(例如羊毛固醇、胆固醇、芸苔固醇、豆固醇和谷固醇的硫酸酯或磷酸酯)、二羧酸及其酯(例如戊二酸、戊二酸单乙酯、戊二酸二乙酯、己二酸、己二酸单乙酯、己二酸二乙酯、丙二酸和丙二酸二乙酯)和羟基羧酸及其酯(例如柠檬酸、苹果酸、酒石酸或酒石酸二乙酯)。影响微生物菌群并杀死或抑制汗分解细菌的生长的抗菌活性成分可类似地存在于制剂中(特别是棒状制剂中)。可存在的其它抗菌剂为壳聚糖、苯氧乙醇和葡萄糖酸氯己定-5-氯-2-(2,4-二氯苯氧基)-苯酚(Triclosan,Irgasan,Ciba Specialty Chemicals Inc.)。
去头屑剂
可使用的去头屑剂的例子为咪菌酮(climbazole)、羟甲辛吡酮(octopirox)和硫氧吡啶锌(zinc pyrithione)。
成膜剂
常规的成膜剂包括例如壳聚糖、微晶壳聚糖、季铵化的壳聚糖、聚乙烯吡咯烷酮、乙烯基吡咯烷酮/乙酸乙烯基酯共聚物、含高比例丙烯酸的季纤维素衍生物的聚合物、胶原、透明质酸及其盐和类似的化合物。
防腐剂
防腐剂的实例包括对羟基苯甲酸甲酯、乙酯、丙酯、丁酯;氯扎苯铵;2-溴-2-硝基-丙烷-1,3-二醇;脱氢醋酸;二唑啉基脲(DiazolidinylUrea);2-二氯苯甲醇;DMDM乙内酰脲;甲醛溶液;甲基二溴戊二腈;苯氧乙醇;羟甲基谷氨酸钠;咪唑啉基脲(Imidazolidinyl Urea);三氯生(Triclosan)和以下参考文献中所列的其它物质种类:K.F.De Polo-A shorttextbook of cosmetology,Chapter 7,Table 7-2,7-3,7-4 & 7-5,p210-219。
细菌抑制剂
细菌抑制剂的典型实例是对革兰氏阳性细菌具有特异作用的防腐剂,如2,4,4′-三氯-2′-羟基二苯醚、氯己定(1,6-二(4-氯苯基-双胍)己烷)或TCC(3,4,4′-三氯碳酰苯胺)。大量的芳香族物质和芳香油也具有抗微生物特性。典型的例子是丁香油、薄荷油和百里香油中的活性成分丁香油酚、薄荷醇和百里酚。感兴趣的天然除臭剂是萜醇法尼醇(3,7,11-三-甲基-2,6,10-十二碳三烯-1-醇),其存在于梨莓油(lime blossom oil)中。甘油醇单月桂酸酯也被证明是抑菌剂。其它细菌抑制剂的用量通常是以制剂固体含量为基础从0.1到2wt.%。
聚合物
为了获得所希望的性质,根据本发明的产品可以包括其它在化妆品上和皮肤病学上可接受的聚合物,其不同于本发明缩合聚合物。为了这个目的,可以使用所有的阴离子、阳离子、两性或中性聚合物。
阴离子聚合物的实例是丙烯酸或甲基丙烯酸及其盐的均聚物和共聚物;丙烯酸和丙烯酰胺及其盐的共聚物;聚羟基碳酸的钠盐;可水溶或可水分散聚酯;聚氨酯,诸如BASF的Luviset pur和聚脲。尤其合适的是丙烯酸叔丁酯、丙烯酸乙酯和甲基丙烯酸的共聚物(例如,100P);丙烯酸乙酯和甲基丙烯酸的共聚物(例如, Soft);N-叔丁基丙烯酰胺、丙烯酸乙酯和丙烯酸的共聚物(strong);乙酸乙烯基酯、巴豆酸和其它乙烯基酯的共聚物(e.g. grades);马来酸酐的共聚物;末端与醇发生反应的阴离子聚硅氧烷(例如羧酸官能化的)、丙烯酸叔丁酯、甲基丙烯酸的共聚物( VBM);丙烯酸和甲基丙烯酸与疏水性单体的共聚物,所述疏水性单体诸如为甲基丙烯酸C4-C30烷基酯、C4-C30烷基乙烯基酯、C4-C30烷基乙烯基醚;以及透明质酸。阴离子聚合物的实例还为乙酸乙烯基酯/巴豆酸共聚物(NationalStarch的或GAF的);乙烯基吡咯烷酮/丙烯酸乙烯基酯共聚物(例如BASF的)。其它合适的聚合物是乙烯基吡咯烷酮/丙烯酸酯三元聚合物和含有磺酸钠的聚丙烯酰胺或含有磺酸钠的聚酯。
可以与本发明缩合聚合物组合使用的其它聚合物包括 CR(National Starch;丙烯酸酯共聚物)、 0/55(National Starch;丙烯酸酯共聚物)、 47(National Starch;辛基丙烯酰胺/丙烯酸酯/甲基丙烯酸丁基氨基乙酯共聚物)、 FX 64(ISP;异丁烯/乙基马来酰亚胺/羟基乙基马来酰亚胺共聚物)、 SF-40(ISP/National Starch;乙烯基己内酰胺/DMAPA丙烯酸酯共聚物)、 LT-120(ISP/Rohm &Haas;丙烯酸酯/C1-2琥珀酸酯/羟基丙烯酸酯共聚物)、 HS(Eastman;聚酯-1)、 Z-400(Clariant;甲基丙烯酰基乙基甜菜碱/甲基丙烯酸酯共聚物)、 Z-711(Clariant;甲基丙烯酰基乙基N-氧化物/甲基丙烯酸酯共聚物)、 Z-712(Clariant;甲基丙烯酰基乙基N-氧化物/甲基丙烯酸酯共聚物)、 2000(ISP;由在乙醇中的聚(甲基乙烯基醚/马来酸)得到的单乙酯)、 HC(NationalStarch;丙烯酸酯/辛基丙烯酰胺共聚物)、 28-4910(NationalStarch;辛基丙烯酰胺/丙烯酸酯/甲基丙烯酸丁基氨基乙酯共聚物)、 HC 37(ISP;乙烯基己内酰胺/N-乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯的三元聚合物)、 LC55和LC80或LC A和LCE、 Plus(ISP;VA/马来酸丁酯/丙烯酸异冰片酯共聚物)、 (Rohm &Haas;丙烯酸酯/羟基酯丙烯酸酯共聚物)、LuvisetP.U.R.(BASF,聚氨酯-1)、 Silk(BASF)、 AQ 48(Eastman)、 CC-10(ISP;VP/DMAPA丙烯酸酯共聚物)、 2000(ISP;VP/丙烯酸酯/甲基丙烯酸月桂基酯共聚物)、DynamX(National Starch;聚氨酯-14AMP-丙烯酸酯共聚物)、Resyn XP(NationalStarch;丙烯酸酯/辛基丙烯酰胺共聚物)、Fixomer A-30(OndeoNalco;聚甲基丙烯酸和丙烯酰氨基甲基丙烷磺酸)、Fixate G-100(Noveon;AMP-丙烯酸酯/甲基丙烯酸烯丙基酯共聚物)。
阳离子聚合物的实例是聚季铵盐(INCI:Polyquaternium),例如乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐的共聚物(HM、Ultracare)、采用二乙基硫酸盐季铵化的N-乙烯基吡咯烷酮/甲基丙烯酸二甲氨基乙酯的共聚物( PQ11,INCI:聚季鎓-11)、N-乙烯基己内酰胺/N-乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐的共聚物(Hold;INCI:聚季铵盐-46)、纤维素的阳离子衍生物(聚季铵盐-4和-10)、丙烯酰氨基共聚物(聚季铵盐-7)、壳聚糖、阳离子淀粉衍生物(INCI:淀粉羟基丙基三甲基氯化铵,经改性的玉米淀粉)、阳离子瓜耳胶衍生物(INCI:羟丙基瓜耳胶羟丙基三甲基氯化铵)、阳离子向日葵籽衍生物(INCI:向日葵籽氨基丙基羟乙基二甲基氯化铵)、丙烯酸、丙烯酰胺和甲基丙烯酰氨基丙基三甲基氯化铵(INCI:聚季铵盐-53)的共聚物、聚季铵盐-32、聚季铵盐-28,但并不局限于此。此外,合适的阳离子季铵化聚合物为(基于二甲基二烯丙基氯化铵的聚合物)、(聚乙烯基吡咯烷酮与季铵化合物反应所形成的季聚合物)、聚合物JR(具有阳离子基团的羟乙基纤维素)和植物基质上的阳离子聚合物,诸如瓜耳胶聚合物,以Rhodia的等级商购。
中性聚合物的实例是聚乙烯基吡咯烷酮、N-乙烯基吡咯烷酮和乙酸乙烯基酯和/或丙酸乙烯基酯的共聚物、聚硅氧烷、聚乙烯基己内酰胺和N-乙烯基吡咯烷酮的其它共聚物、N-乙烯基吡咯烷酮和具有C1-C18烷基链的丙烯酸烷酯或甲基丙烯酸烷酯单体的共聚物、聚乙烯醇和聚亚烷基二醇的共聚物(诸如 IR(BASF))或其它乙烯基单体与聚亚烷基二醇的共聚物、聚硅氧烷、聚乙烯基己内酰铵和具有N-乙烯基吡咯烷酮、聚乙烯亚胺及其盐的共聚物、聚乙烯基胺及其盐、纤维素衍生物、壳聚糖、聚天冬氨酸盐及其衍生物、聚乙烯亚胺及其盐、聚乙烯基胺及其盐,诸如 Swing(来自BASF的部分水解的聚乙酸乙烯基酯和聚乙二醇的共聚物)。
合适的聚合物还可以为非离子、可水溶或可水分散的聚合物或低聚物,诸如聚乙烯基己内酰胺(例如 Plus(BASF))或聚乙烯基吡咯烷酮和例如具有乙烯基酯(诸如乙酸乙烯基酯)的共聚物(例如 VA 37(BASF));在DE-A-433323中所描述的例如基于衣康酸和脂族二胺的聚酰胺。
两亲性或两性聚合物的实例是辛基丙烯酰胺/甲基丙烯酸甲酯/甲基丙烯酸叔丁氨基乙酯/甲基丙烯酸2-羟基丙酯的共聚物(例如可以(Delft National)名称得到)和在例如德国专利申请DE 39 29973、DE 21 50 557、DE 28 17 369和DE 37 08 451中公开的两性聚合物。优选的两性聚合物是,丙烯酰氨基丙基三甲基氯化铵/丙烯酸或甲基丙烯酸共聚物及其碱金属盐和铵盐。其它合适的聚合物是甲基丙烯酰基乙基甜菜碱/甲基丙烯酸酯共聚物(其可以(AMERCHOL)的商品名商购)和甲基丙烯酸羟乙酯、甲基丙烯酸甲酯、甲基丙烯酸N,N-二甲氨基乙酯和丙烯酸的共聚物
其它合适的聚合物是非离子、含硅氧烷、可水溶或可水分散聚合物,例如聚醚硅氧烷,诸如Tegopren(R)(Goldschmidt)或BeIsN(R)(Wacker)。
香水和香味剂
本发明的个人护理产品和家用产品可以包含香水和香味,其包括至少一种(优选包含多种)来自天然和/或合成的加味成分。天然加味剂不仅包括易挥发组分,还包括中等挥发组分以及略微挥发组分。合成加味剂包括在实践中由所有种类的加味物质得到的代表物。
以下列出了已知加味剂的实例(其可以采用本发明的稳定组合物进行稳定),但并不局限于此:
天然产品,诸如树苔净油、罗勒油、热带水果油(诸如香柠檬油、橘皮油等)、乳香净油、香桃木油、玫瑰草油、广藿香油、橙叶油、苦艾油、熏衣草油、玫瑰油、茉莉油、依兰油等;
醇:法呢醇、香叶醇、里哪醇、橙花醇、苯基乙基醇、玫瑰醇、肉桂醇、(Z)-己-3-烯-1-醇、薄荷醇、α-萜品醇等。
醛,诸如柠檬醛、α-己基肉桂醛、铃兰醛、甲基紫罗兰酮、马鞭烯草酮、诺卡酮、香叶基丙酮等;
酯,诸如苯氧基乙酸烯丙酯、水杨酸苄酯、丙酸肉桂酯、乙酸香茅酯、乙酸癸酯、乙酸二甲基苄基卡宾酯、丁酸二甲基苄基卡宾酯、乙酰乙酸乙酯、异丁酸顺式-3-己烯酯、水杨酸顺式-3-己烯酯、乙酸里哪醇酯、二氢茉莉酮酸甲酯、丙酸苏合香酯、乙酸香根醇酯、乙酸苄酯、乙酸香叶酯等;
内酯,诸如γ-十一碳内酯、δ-癸内酯、十五碳内酯、12-氧杂十六内酯等;
缩醛,诸如Viridine(二甲醇缩苯乙醛)等;
和香料中常用的其它组分,诸如吲哚、对-薄荷-8-硫醇-3-酮、甲基丁香酚、丁香酚、茴香脑等。
着色剂
一般而言,为了使本发明的家用产品或个人护理产品着色,在电磁辐射的可见光(400-4000nm)下具有吸收的所有物质都是合适的。通常如下发色团引起吸收:偶氮-、(一、二、三或多)茋-、类胡萝卜素-、二芳基亚甲基-、三芳基亚甲基-、氧杂蒽-、吖啶-、喹啉-、次甲基-(也可以为多次甲基)噻唑-、吲达胺-、靛酚-、吖嗪-、噁嗪-、噻嗪-、蒽醌-、靛青-、酞氰染料以及其它合成、天然和/或无机发色团。
可用在本发明的家用产品或个人护理产品中的FD&C和D&C例如为,姜黄色素、核黄素(riboflavin)、核黄素(lactoflavin)、酒石黄、喹啉黄(chinolin yellow)、胭脂虫红铝、偶氮玉红、紫红色、鲜红色4R、赤藓红、红2G、靛青、叶绿素、叶绿酸、焦糖、药用碳、类胡萝卜素、胡萝卜素、胭脂树橙、降红木素、橙红、orlean、辣椒红、辣椒红玉素、番茄红素、叶黄素(flavoxanthin)、毛莨黄索、叶黄素(lutein)、玉米黄质(kryptoaxanthin)、玉红黄质、紫黄质、枚红黄质、斑蝥黄、甜菜苷、花色甙,但并不局限于此。染料的实例例如为,无机颜料,诸如氧化铁(氧化铁红、氧化铁黄、氧化铁黑等)、蓝色颜料、氧化铬绿或碳黑。可以采用本发明的稳定组合物稳定的其它着色剂和染料包括天然或合成的有机颜料、可以溶于溶剂中的分散染料(如HC型直发染料,例如HC红No.3、HC黑No.2和International Cosmetic Ingredient Dictionary Handbook 7thedition 1997中所列举的所有其它发用染料或Color Index InternationalSociety of Dyers and Colorist中所列举的分散染料、有色清漆(可溶染料的不溶盐,如阴离子染料的Ca盐、Ba盐或Al盐)、可溶的阴离子或阳离子染料(诸如酸性染料(阴离子)、碱性染料(阳离子))、直接染料、反应性染料或溶剂染料、荧光染料、荧光素和异硫氰酸酯。
活性成分
可用在本发明的个人护理产品和家用产品中的活性成分包括维生素(诸如生育酚、抗坏血酸、抗坏血酸磷酸酯、维生素Q、D和K)、视黄醇、视黄素、视黄酸、视黄醇乙酸酯、视黄醇棕榈酸酯、生物素、类胡萝卜素衍生物(诸如β胡萝卜素)、番茄红素、asthaxanthene、植物提取物、抗菌成分、不稳定氨基酸(包括二肽、寡聚肽和多肽,诸如蛋氨酸(methionen)、半胱氨酸(cystein)、胱氨酸、色氨酸、苯丙氨酸、酪氨酸、)、苯酚、多酚或类黄铜、甜没药萜醇、尿囊素、植烷三醇、泛酰醇、AHA酸、Ubichinones(诸如辅酶Q)、神经酰胺、假神经酰胺、精油、植物提取物、脱氧核糖核酸、蛋白质水解产物。
优选的身体护理产品是皮肤护理、含香水和/或香味剂的制剂、头发护理制剂、洁牙剂(dentrifices)、除臭剂和止汗剂、修饰制剂、光防护制剂和功能制剂。
皮肤护理制剂的例子具体为身体油,身体乳液、身体乳霜、身体啫哩、面部乳液、面部乳霜、面部啫哩(例如眼霜、防皱乳霜、日常护理乳液、晚霜)、修复乳霜,护肤软膏,遮光剂、剃须制剂(如剃须泡沫或睹哩)、爽肤粉(如婴儿粉)、保湿啫哩、保湿乳霜、保湿喷雾、身体复苏喷雾、橘皮组织睹哩、抗痤疮制剂、清洁乳和脱屑制剂。
根据本发明,皮肤护理制剂具有3至10的pH,优选具有4至8的pH。
含香水和/或香味剂的制剂具体是香精、花露水和剃须乳液(须后制剂)。
头发护理产品的例子为例如人用和动物用的香波、护发素、用于定型和护理头发的产品、保持剂、头发喷雾和发胶、头发睹哩、头发固定剂和染发剂或漂发剂。
洁牙剂的例子具体是牙霜(tooth cream)、牙膏、口腔洗液、口腔冲洗液、抗斑制剂和假牙用清洁剂。
修饰制剂的例子具体是唇膏、指甲油、眼影、睫毛膏、干的和湿的彩妆、腮红、散粉、脱毛剂和仿晒乳液。
功能性制剂的例子是含有活性成分如激素制剂、维生素制剂、植物提取物制剂和抗菌制剂的化妆用或皮肤病用组合物。
根据本发明的个人护理产品如化妆用和皮肤病用组合物可以是液体、乳液、增稠乳液、睹哩、乳霜、乳、软膏、膏剂、粉末、彩妆或固体管棒的形式,并能够任选地被包装为气雾剂和能够以摩丝、泡沫或喷雾泡沫、喷雾、棒或气雾剂或擦拭物(wipe)的形式提供。根据本发明的个人护理产品可被包装为安瓿。根据本发明的个人护理产品能够是在溶剂或脂质中的悬浮液或分散系的形式,或者是乳液或微乳液的形式(尤其是O/W或W/O型,O/W/O或W/O/W型),如乳霜或乳,泡状分散系、软膏、啫哩、固体管棒或气雾剂摩丝形式。乳液还能含有阴离子、非离子、阳离子或两性的表面活性剂。
本发明缩合聚合物可以存在于油相中,或存在于水相或水性醇相中。
以上所定义的缩合聚合物尤其适用于如下个人护理产品,尤其是:
·皮肤护理制剂,例如片剂形式的皮肤洗涤和清洁制剂或液体皂、无形去污剂或洗涤膏剂;
·沐浴制剂,例如液体(泡沫沐浴、乳、淋浴制剂)或固体的沐浴制剂(例如沐浴块和沐浴盐);
·护肤制剂,例如皮肤乳液、多重乳液或皮肤油;身体油、身体乳液、身体睹哩;护肤软膏;面部乳霜/乳液/啫哩;日常护理皮肤或面部乳霜/乳液/啫哩;晚霜、眼部乳霜/乳液/睹哩/安瓿;防皱乳霜/乳液/啫哩/安瓿;
·化妆品个人护理制剂,例如以下形式的面部彩妆:日霜或粉底霜(powder cream),面用散粉(干粉或粉饼),腮红或霜状彩妆,眼部护理制剂(例如眼影制剂、睫毛膏、眼线、眼霜或眼部修护霜(eye-fix cream)),唇部护理制剂(例如唇膏、唇蜜、唇线笔),指甲护理制剂(例如指甲油、洗甲水、指甲强化剂(nail hardener)或去指皮水(cuticle remover));
·足部护理制剂,例如足浴、足粉、足霜或足脂(foot balsam),特别是除臭剂和止汗剂或去胼胝制剂;
·光防护制剂,诸如放晒乳、乳液、乳霜或油,面部日常护理产品,unblocks或tropicals,晒前制剂或晒后制剂;
·皮肤美黑制剂,例如自美黑霜;
·脱色制剂,例如用于漂白皮肤的制剂或皮肤美白制剂;
·驱虫剂,例如驱虫油、乳液、喷雾或棒;
·除臭剂,例如除臭喷雾、泵作用喷雾、除臭啫哩、棒或滚擦剂(roll-on);
·止汗剂,例如止汗棒、霜或滚擦剂、泵作用喷雾;
·用于清洁和护理受损皮肤的制剂,例如合成洗涤剂(固体或液体)、去死皮制剂或磨砂制剂或去死皮面膜;
·化学品形式的脱毛制剂(脱毛作用),例如脱毛粉、液体脱毛制剂、霜或膏形式的脱毛制剂、睹哩或气雾剂形式的脱毛制剂;
·剃须制剂,例如剃须皂、泡沫剃须霜、无泡沫剃须霜、泡沫和啫哩、用于干燥剃须的须前制剂、须后水或须后乳液;
·香水或香味剂,例如含香水、香味剂和/或加味成分的制剂,诸如香精、古龙水、淡香水、香水、淡香水、香精油或香精霜;
·洁牙剂,尤其是牙霜、牙膏、口腔洗液、口腔冲洗液、抗斑制剂和假牙清洁剂;
·修饰制剂,尤其是唇膏、指甲油、眼影、睫毛膏、干和湿的彩妆、腮红、散粉、脱毛剂和仿晒乳液。
·含活性成分的化妆品配制品,尤其是激素制剂、维生素制剂、植物提取物制剂和抗菌制剂。
所列的最终配制品可以以多种存在形式存在,例如以液体制剂的形式,如W/O、O/W、O/W/O、W/O/W或PIT乳液和所有种类的微乳液,以啫哩的形式,以油、乳霜、乳或乳液的形式,以棒的形式,以喷雾(带有推进气体的喷雾或泵作用喷雾)或气雾剂的形式,以泡沫的形式,或以膏剂的形式。
尤其优选的本发明的实施方式是含有本发明缩合聚合物的头发护理制剂。
根据本发明的头发护理制剂包含的本发明缩合聚合物的浓度,基于组合物的总重,为0.1至30wt%,优选为0.5至20wt%。
优选地,头发护理制剂是化妆品头发护理制剂(例如洗发香波和护发素形式的洗发制剂),头发护理制剂(例如预护理制剂),生发油,定型霜,定型睹哩,润发油,头发冲洗剂,护理套装(treatment pack),深层头发护理剂(免洗和冲洗深层护发素),发型造型(hair-structuring)制剂(例如用于持久卷发(热卷发、适中卷发、冷卷发)的卷发制剂),头发拉直制剂,液体头发定型制剂,头发泡沫,头发喷雾,漂白制剂(例如过氧化氢溶液),闪亮香波(lightening shampoo),漂白霜,漂白粉,漂白膏或油,临时的、半永久性的或永久性的染发剂,含自身氧化染料的制剂,或天然染发剂(如散沫花或甘菊);
根据应用,头发护理制剂可以是如下形式:(气雾剂)喷雾、(气雾剂)摩丝、睹哩、啫哩喷雾、乳霜、乳液或蜡。头发喷雾包括气雾剂粉末以及不含推进剂的泵作用喷雾。头发摩丝包括气雾剂摩丝以及不含推进剂的泵作用摩丝。头发喷雾和头发摩丝主要包括或仅包括可水溶组分或可水分散组分。如果用在本发明的头发喷雾或头发摩丝中的组分是可水分散的,那么它们可以是粒子尺寸通常为1至350nm,优选为1至250nm的微分散系形式。上述制剂的固含量通常占制剂总重的0.5至20wt%。上述微分散系的稳定通常不要其它乳化剂或表面活性剂。
优选的头发护理组合物包含:
1.0.2至20wt%的本发明缩合聚合物
2.30至99.5wt%,优选40至99wt%的至少一种选自如下的溶剂:水、可与水混溶的溶剂及其混合物
3.0至70wt%的推进剂
4.0至10wt%的至少一种可水溶或可水分散发用聚合物,其不同于组分1)
5.0至0.3重量%的至少一种水不可溶硅氧烷
6.0至0.5wt%的至少一种蜡,优选至少一种脂肪酸酰胺,和
7.常规添加剂。
根据本发明的头发护理制剂可以包含至少一种其它的可水溶或可水分散发用聚合物作为组分4)。该组分的含量,基于组合物的总重,通常为约0.1至10重量%。本文中,优选使用可水溶或可水分散聚氨酯,如果需要的话,该聚氨酯额外包含共聚形式的硅氧烷基团。
根据本发明的组合物包含至少一种水不可溶硅氧烷作为组分5),特别是聚二甲基硅氧烷,例如得自Goldschmidt的该组分的含量,基于组合物的总重,通常为约0.0001至0.2重量%,优选为0.001至0.1重量%。优选的是使用至少一种脂肪酸酰胺(例如芥酸酰胺)作为组分6)。
根据本发明的头发护理制剂如果适当的话还可以包含消泡剂,例如基于硅氧烷的消泡剂。消泡剂的含量,基于组合物的总量,通常至多0.001重量%。根据本发明的组合物具有如下优点,一方面它们使头发具有所需的保持力;另一方面所述聚合物易于洗掉。一般而言,赋予头发自然的外观和光泽,即使在头发本身具有非常浓密和/或乌黑的形式。
具体地,本发明的头发护理制剂可被配制成头发护理组合物,特别是具有高含量推进剂的发用喷雾。有利地是,本发明的头发护理组合物基本上不具有“成块”效果。
在优选的实施方式中,根据本发明的头发护理制剂包含:
1.0.05至20wt%的至少一种本发明缩合聚合物
2.20至99.95wt%的水和/或醇
3.0至79.5wt%的常规添加剂
术语醇指通常用在化妆品中的所有醇,诸如乙醇、正丙醇、异丙醇,但并不局限于此。
常规添加剂例如为推进剂、消泡剂、表面活性成分(例如表面活性剂、乳化剂)、起泡剂和增溶剂。所用的表面活性成分可以是阴离子、阳离子、两亲性或中性的。其它成分可以是防腐剂、抗氧化剂、芳香油、脂质油脂(refatter)、活性和/或护理成分(诸如泛酰醇、胶原质、维生素、蛋白质水解产物、α和β羟基碳酸)、稳定剂、pH调节剂、遮光剂、着色剂、染料、凝胶形成剂、盐、保湿剂、复合物形成剂、粘度调节剂或遮光剂,但并不局限于此。而且,所有已知的造型聚合物和调节聚合物可以与本发明缩合聚合物组合使用,从而获得特定效果。
本文中明确包括,前述阳离子、阴离子、中性、非离子和两亲性聚合物可以用作常规聚合物。
为了获得某些性质,头发护理制剂还可以包含以如下硅氧烷为基础的调节化合物,所述硅氧烷例如为聚烷基硅氧烷、聚芳基硅氧烷、聚芳基烷基硅氧烷、硅氧烷树脂、聚醚硅氧烷或dimethicone copolyole(CTFA)和氨基官能化的硅氧烷化合物(诸如氨基二甲基硅酮(CTFA)、GP 4Silicone 和GP (Genesee))、Q2 (Dow Corning)、AFL(Union Carbide)或EP-B 852 488中所公开的聚合物。
含有本发明缩合聚合物的优选的头发护理制剂是造型制剂,诸如发用喷雾和发用摩丝。
在优选的实施方式中,这些制剂包含:
1.0.1至10wt%的至少一种本发明缩合聚合物
2.20至99wt%的水和/或醇
3.0至70wt%的至少一种推进剂
3.0至20wt%的常规添加剂
发用喷雾或气雾剂摩丝所用的推进剂是通常使用的推进剂。优选的是,丙烷/丁烷的混合物、戊烷、二甲基醚、1,1-二氟乙烷(HFC-152a)、二氧化碳、氮气或压缩空气。
优选的气雾剂摩丝制剂包含:
1.0.1至10wt%的至少一种本发明缩合聚合物
2.55至99.8wt%的水和/或醇
3.5至20wt%的推进剂
4.0.1至5wt%的乳化剂
5.0至10wt%的常规添加剂
气雾剂摩丝所用的乳化剂可以是所有常规使用的非离子、阴离子、阳离子或两性乳化剂。
非离子乳化剂的实例包括(INCI命名法)Laureth,例如Laureth-4;Cetheths,例如Cetheth-1,聚乙二醇十六烷基醚;Cetheareths,例如Cetheareth-25,聚乙二醇脂肪酸甘油酯、羟基化卵磷脂、脂肪酸的乳酸基酯、烷基糖苷。
阳离子乳化剂的实例是,十六烷基二甲基-2-羟乙基二氢磷酸铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、椰油三甲基甲基硫酸铵季铵-1至X(INCI)。
阴离子乳化剂可以选自:烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基芳基磺酸盐、烷基琥珀酸盐、烷基磺基琥珀酸盐、N-烷酰基肌氨酸盐(N-alkoylsarcosinate)、酰基牛磺酸盐、酰基羟乙基磺酸盐、烷基磷酸盐、烷基醚磷酸盐、烷基醚羧酸盐、α-烯烃磺酸盐、尤其是碱金属盐和碱土金属盐(如钠盐、钾盐、镁盐、钙盐)以及铵盐和三乙醇胺盐。所述烷基醚硫酸盐、烷基醚磷酸盐和烷基醚羧酸盐在分子中可以包含1至10个环氧乙烷或环氧丙烷单元,优选包含1至3个环氧乙烷单元。
优选的头发护理制剂包括发用睹哩。所述发用睹哩例如包含:
1.0.1至20wt%,优选1至10wt%的至少一种本发明缩合聚合物
2.0至10wt%的至少一种载剂(溶剂),其选自C2至C5醇,优选乙醇
3.0.01至5wt%,优选0.2至3wt%的至少一种增稠剂
4.0至50wt%的推进剂
5.0至10wt%,优选0.1至3wt%的不同于1)的造型聚合物,优选为可水溶非离子聚合物
6.0-1wt%的至少一种油脂(refatter),优选选自甘油和甘油衍生物
7.0至30wt%的其它常规添加剂,例如硅氧烷组分
8.水,添加到100wt%。
示例性的造型啫哩可以包含如下:
1.0.1至10wt%的本发明缩合聚合物
2.60至99.85wt%的水和/或醇
3.0.05至10wt%的睹哩形成剂
4.0.20wt%的其它常规添加剂
所有常用的化妆品啫哩形成剂都可以用作睹哩形成剂,诸如轻微交联的聚丙烯酸(例如卡波姆(INCI))、纤维素衍生物、多糖(例如黄原胶)、癸酸/辛酸甘油三酯、丙烯酸钠共聚物、聚季铵盐-32(和)矿物油(INCI)、丙烯酸钠共聚物(和)矿物油(和)PPG-1trideceth-6、聚季铵盐-37(和)丙二醇二癸酸酯二丙烯酸酯(和)PPG-1trideceth-6、聚季铵盐-7、聚季铵盐-44。
优选的头发护理制剂是洗发香波制剂,其包含本发明缩合聚合物作为增强和/或调节剂。
优选的洗发香波制剂包含:
1.0.05至10wt%的缩合聚合物
2.25至94.95wt%的水
3.5至50wt%的表面活性剂
4.0至5wt%的其它调节剂
5.0至10wt%的其它常规添加剂
所有常规使用的阴离子、中性、两性或阳离子表面活性剂都可以用在洗发香波制剂中。
示例性的阴离子表面活性剂包括,烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基芳基磺酸盐、烷基琥珀酸盐、烷基磺基琥珀酸盐、N-烷酰基肌氨酸盐、酰基牛磺酸盐、酰基羟乙基磺酸盐、烷基磷酸盐、烷基醚磷酸盐、烷基醚羧酸盐、α-烯烃磺酸盐、尤其是碱金属盐和碱土金属盐(如钠盐、钾盐、镁盐、钙盐)以及铵盐和三乙醇胺盐。所述烷基醚硫酸盐、烷基醚磷酸盐和烷基醚羧酸盐在分子中可以包含1至10个环氧乙烷或环氧丙烷单元,优选包含1至3个环氧乙烷单元。
合适的为例如月桂基硫酸钠、月桂基硫酸铵、月桂基醚硫酸钠、月桂基醚硫酸铵、月桂酰基肌氨酸钠、油基琥珀酸钠、月桂基磺基琥珀酸铵、十二烷基苯磺酸钠、十二烷基苯磺酸三乙醇胺盐。
合适的两性表面活性剂例如为烷基甜菜碱、烷基酰氨基丙基甜菜碱、烷基磺基甜菜碱、烷基甘氨酸酯、烷基羧基甘氨酸酯、烷基两性乙酸酯或丙酸酯、烷基两性二乙酸酯或二丙酸酯,诸如椰油二甲基磺基丙基甜菜碱、月桂基甜菜碱、椰油酰氨基丙基甜菜碱或椰油两性丙酸钠。
非离子表面活性剂的实例是,具有6至20个碳原子(其可以是线型或支化烷基链)的脂族醇或烷基酚与环氧乙烷和/或环氧丙烷的反应产物。亚烷基氧化物的含量相对于1摩尔醇为约6至60摩尔。而且烷基胺氧化物、单烷基或二烷基烷醇酰胺、聚乙二醇的脂肪酸酯、烷基多苷或脱水山梨糖醇醚酯适于掺入本发明的头发护理制剂中。
而且,洗发香波制剂可以包含常规的阳离子表面活性剂,诸如季铵化的铵化合物,例如十六烷基三甲基氯化铵或溴化铵(INCI:cetrimoniumchloride或cetrimoniumbromide)、羟乙基十六烷基二甲基磷酸铵(INCI:Quaternium-44)、 Mono LS(INCI:椰油三甲基甲氧基硫酸铵(Cocotrimoniummethosulfate))、聚(氧-1,2-乙二基)、三-(羟基)磷酸(十八烷基次氮基)三-2,1-乙二基酯(1:1)(盐)(INCIQuaternium-52)。
为了特殊效果,可以将典型的调节剂与洗发香波制剂中的本发明缩合聚合物组合,诸如前述被命名为聚季铵盐(polyquaternium)(INCI)的阳离子聚合物,特别是乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐的共聚物( FC, HM, MS,Ultracare)、采用二乙基磺酸盐季铵化的N-乙烯基吡咯烷酮/二甲基氨基乙基甲基丙烯酸酯的共聚物( PQ 11)、N-阳离子纤维素衍生物的共聚物(Polyquaternium-4和Polyquaternium-10)、丙烯酰胺共聚物(Polyquaternium-7)。而且,在如下硅氧烷基质上的蛋白质水解产物也可被用作调节剂,所述基质诸如为聚芳基硅氧烷、聚芳基烷基硅氧烷、聚醚硅氧烷或硅树脂。其它合适的硅氧烷化合物是dimethicondopolyole(CTFA)和氨基官能化的硅氧烷衍生物(诸如氨基二甲基硅酮(amodimethicone)(CTFA))。
而且,可以使用阳离子瓜耳胶衍生物,诸如瓜耳胶羟丙基三甲基氯化铵。
优选的头发护理组合物是含有本发明缩合聚合物作为增强和/或调节剂的头发护理制剂,诸如冲洗护发素和免洗护发素。
优选的护发素包含:
1.0.05至10wt%的本发明缩合聚合物;
2.25至94.95wt%的水;
3.0.1至30wt%的表面活性剂/乳化剂/表面活性成分;
4.0.1至30wt%的油/润肤剂;
5.0至5wt%的其它调节剂;
6.0至10wt%的其它常规添加剂。
所有常规使用的阴离子、中性、两性或阳离子表面活性剂都可以用在护发素制剂中。
示例性的阴离子表面活性剂包括,烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基芳基磺酸盐、烷基琥珀酸盐、烷基磺基琥珀酸盐、N-烷酰基肌氨酸盐、酰基牛磺酸盐、酰基羟乙基磺酸盐、烷基磷酸盐、烷基醚磷酸盐、烷基醚羧酸盐、α-烯烃磺酸盐、尤其是碱金属盐和碱土金属盐(如钠盐、钾盐、镁盐、钙盐)以及铵盐和三乙醇胺盐。所述烷基醚硫酸盐、烷基醚磷酸盐和烷基醚羧酸盐在分子中可以包含1至10个环氧乙烷或环氧丙烷单元,优选包含1至3个环氧乙烷单元。
合适的例如为月桂基硫酸钠、月桂基硫酸铵、月桂基醚硫酸钠、月桂基醚硫酸铵、月桂酰基肌氨酸钠、油基琥珀酸钠、月桂基磺基琥珀酸铵、十二烷基苯磺酸钠、十二烷基苯磺酸三乙醇胺盐。
合适的两性表面活性剂例如为烷基甜菜碱、烷基酰氨基丙基甜菜碱、烷基磺基甜菜碱、烷基甘氨酸酯、烷基羧基甘氨酸酯、烷基两性乙酸酯或丙酸酯、烷基两性二乙酸酯或二丙酸酯,诸如椰油二甲基磺基丙基甜菜碱、月桂基甜菜碱、椰油酰氨基丙基甜菜碱或椰油两性丙酸钠。
非离子表面活性剂的实例是,具有6至20个碳原子(其可以是线型或支化烷基链)的脂族醇或烷基酚与环氧乙烷和/或环氧丙烷的反应产物。亚烷基氧化物的含量相对于1摩尔醇为约6至60摩尔。而且烷基胺氧化物、单烷基或二烷基烷醇酰胺、聚乙二醇的脂肪酸酯、烷基多苷或脱水山梨糖醇醚酯适于掺入本发明的头发护理组合物中。
而且,护发素制剂可以包含常规的阳离子表面活性剂,诸如季铵化的铵化合物,例如十六烷基三甲基氯化铵或溴化铵(INCI:cetrimoniumchloride或cetrimoniumbromide)、羟乙基十六烷基二甲基磷酸铵(INCI:Quaternium-44)、 Mono LS(INCI:椰油三甲基甲氧基硫酸铵(Cocotrimoniummethosulfate))、聚(氧-1,2-乙二基)、三-(羟基)磷酸(十八烷基次氮基)三-2,1-乙二基酯(INCI Quaternium-52)。
对于特殊应用,典型的调节剂可以与护发素制剂中的本发明缩合聚合物组合,诸如前述被命名为聚季铵盐(polyquaternium)(INCI)的阳离子聚合物,特别是乙烯基吡咯烷酮/N-乙烯基咪唑鎓盐的共聚物(FC, HM, MS, Ultracare)、采用二乙基磺酸盐季铵化的N-乙烯基吡咯烷酮/甲基丙烯酸二甲基氨基乙酯的共聚物( PQ 11)、N-阳离子纤维素衍生物的共聚物(Polyquaternium-4和Polyquaternium-10)、丙烯酰胺共聚物(Polyquaternium-7)。而且,在如下硅氧烷基质上的蛋白质水解产物也可被用作调节剂,所述基质诸如为聚芳基硅氧烷、聚芳基烷基硅氧烷、聚醚硅氧烷或硅树脂。其它合适的硅氧烷化合物是dimethicondopolyole(CTFA)和氨基官能化的硅氧烷衍生物(诸如氨基二甲基硅酮(amodimethicone)(CTFA))。
而且,可以使用阳离子瓜耳胶衍生物,诸如瓜耳胶羟丙基三甲基氯化铵(INCI)。
而且,护发素制剂可以包含常用的表面活性成分,例如,乳化剂、增溶剂等。乳化剂能使两种或更多种不混溶的组分均匀组合。而且,乳化剂用于稳定组合物。可以用在本发明中以形成O/W、W/O、O/W/O或W/O/W乳液/微乳液的乳化剂,包括失水山梨糖醇油酸脂、失水山梨糖醇倍半油酸酯、失水山梨糖醇异硬脂酸酯、失水山梨糖醇三油酸酯、聚甘油基-3-二异硬脂酸酯、油酸/异硬脂酸的聚甘油酯、聚甘油基-6六蓖麻醇酸酯、聚甘油基-4-油酸酯、聚甘油基-4油酸酯/PEG-8丙二醇椰油、油酰DEA、TEA肉豆蔻酸酯、TEA硬脂酸酯、硬脂酸镁、硬质酸钠、月桂酸钾、蓖麻醇酸钾、椰油酸钠、牛油酸钠(sodium tallowate)、海狸香酸钾(potassium castorate)、油酸钠及其混合物。其它合适的乳化剂是磷酸酯及其盐,例如,磷酸十六烷酯、二乙醇胺磷酸十六烷酯、十六烷磷酸钾、油酸甘油酯磷酸钠(sodium glyceryl oleate phosphate)、氢化植物甘油磷酸酯及其混合物。而且,一种或更多种合成聚合物可以作为乳化剂。例如,PVP二十碳烯共聚物、丙烯酸酯/丙烯酸C10-30烷基酯交聚物、丙烯酸酯/steareth-20甲基丙烯酸酯共聚物、PEG-22/十二烷二醇共聚物、PEG-45/十二烷二醇共聚物及其混合物。其它示例性的乳化剂是脂肪醇,例如鲸蜡硬脂醇(cetearylalcohol)(Lanette O,Cognis Coopearation)、鲸蜡醇(Lanette 16,Cognis Cooperation)、硬脂醇(Lanette 18,Cognis Cooperation)、Laneth-5(Polychol 5,Croda Chemicals);其它的蔗糖和葡萄糖衍生物,例如蔗糖二硬脂酸酯(Crodesta F-10,Croda Chemicals)、葡萄糖异硬脂酸甲酯(Isolan IS,Degussa Care Chemicals);其它乙氧基化的羧酸或聚乙二醇酯和聚乙二醇醚,例如steareth-2(Brij 72,Uniqema)、steareth-21(Brij 721,Uniqema)、ceteareth-25(Cremophor A25,BASFCooperation)、PEG-40氢化蓖麻油(Cremophor RH-40,BASFCooperation)、PEG-7氢化蓖麻油(Cremophor WO7,BASFCooperation)、PEG-30二聚羟基硬脂酸酯(Arlacel P 135,Uniqema);其它甘油酯和聚甘油酯,例如聚甘油基-3-二异硬脂酸酯(HostacerinTGI,Clariant Cooperation)、聚甘油-2二聚羟基硬脂酸酯(DehymulsPGPH,Cognis Cooperation)、聚甘油基-3甲基葡萄糖二硬脂酸酯(TegoCare 450,Degussa Care Chemicals)。优选的乳化剂是磷酸十六烷酯、二乙醇胺磷酸十六烷酯、十六烷磷酸钾、PVP二十碳烯共聚物、丙烯酸酯/丙烯酸C10-30-烷酯交聚物、PEG-20失水山梨糖醇异硬脂酸酯、失水山梨糖醇异硬脂酸酯及其混合物。一种或更多种乳化剂的用量,相对于本发明组合物的总重,为至少0.01wt%。优选地,相对于本发明组合物的总重用量为约0.01wt%-约20wt%。优选地,使用约0.1wt%-约10wt%的乳化剂。
而且,护发素制剂可以包含常用的油类和脂肪类组分,其选自:矿物油和矿物蜡;油,例如,癸酸或辛酸甘油三酯或蓖麻油;油或蜡和其它天然或合成油,在优选的实施方式中,为脂肪酸与醇(例如,异丙醇、丙二醇、丙三醇)的酯、或脂肪醇与羧酸或脂肪酸的酯;苯甲酸烷基酯;和/或硅油。
可以掺入本发明的乳液、微乳液、油凝胶、水分散体(hydrodispersion)或脂分散体(lipodispersion)的油相中的示例性脂肪物质有利地选自,具有3-30个碳原子的饱和/或不饱和、直链和/或支化烷基羧酸和具有3-30个碳原子的饱和/或不饱和、直链和/或支化醇的酯,以及芳族羧酸和具有3-30个碳原子的饱和/或不饱和、直链和/或支化醇的酯。这种酯可以有利地选自棕榈酸辛酯、椰油酸辛酯、异硬脂酸辛酯、辛基十二烷基肉豆蔻酸酯、鲸蜡硬脂基异壬酸酯(cetearylisononanoate)、肉豆蔻酸异丙酯、棕榈酸异丙酯、硬脂酸异丙酯、油酸异丙酯、硬脂酸正丁酯、月桂酸正己酯、油酸正癸酯、硬脂酸异辛酯、硬脂酸异壬酯、异壬酸异壬酯、棕榈酸2-乙基己酯、月桂酸2-乙基己酯、硬脂酸2-己基癸酯、棕榈酸2-辛基十二烷酯、庚酸硬脂基酯、油酸油基酯、芥酸油基酯、油酸瓢儿菜基酯、芥酸瓢儿菜基酯、硬脂酸十三烷酯、十三烷基偏苯三酸酯,以及这些酯的合成、半合成或天然混合物,例如,霍霍巴油。
其它适用在本发明的护发素制剂中的脂肪组分包括极性油,例如,卵磷脂和脂肪酸甘油三酯,即,具有8-24个碳原子(优选12-18个碳原子)的饱和和/或不饱和、直链和/或支化羧酸的甘油三酯,其中,脂肪酸甘油三酯优选选自合成、半合成或天然油(例如,椰油酸甘油酯(cocoglyceride)、橄榄油、向日葵油、豆油、花生油、菜籽油、甜杏仁油、棕榈油、椰子油、蓖麻油、氢化蓖麻油、麦油、葡萄籽油、澳洲坚果油和其它);非极性油,例如,直链和/或支化烃和蜡(例如,矿物油、凡士林(矿脂));石蜡、角鲨烷和角鲨烯、聚烯烃、氢化聚异丁烯和异十六烷,优选的聚烯烃是聚癸烯;二烷基醚,例如二辛醚;直链或环状硅油,例如优选环甲基硅酮(八甲基环四硅氧烷);十六烷基二甲基硅酮、六甲基环三硅氧烷、聚二甲基硅氧烷、聚(甲基苯基硅氧烷)及其混合物。
可以有利地掺入本发明的护发素制剂中的其它脂肪组分是异二十烷、新戊二醇二庚酸酯、丙二醇二辛酸酯/二癸酸酯、辛酸/癸酸/二甘油基琥珀酸酯、丁二醇辛酸酯/癸酸酯、C12-13烷基乳酸酯、二C12-13烷基酒石酸酯、三异硬脂精(triisostearin)、二季戊四醇六辛酸酯/六癸酸酯、丙二醇单异硬脂酸酯、三辛精(tricaprylin)、二甲基异山梨醇。特别优选使用苯甲酸C12-15烷基酯和异硬脂酸2-乙基己基酯的混合物、苯甲酸C12-15烷基酯和异壬酸异十三烷酯的混合物以及苯甲酸C12-15烷基酯、异硬脂酸2-乙基己基酯和异壬酸异十三烷酯的混合物。
护发素制剂的油相还可以包含天然植物蜡或动物蜡,例如,蜂蜡、中国蜡、大蜂蜡和其它昆虫蜡,以及牛油树脂和可可脂。
合适的硅油例如为二甲基聚硅氧烷、二乙基聚硅氧烷、二苯基聚硅氧烷、环状硅氧烷、聚(甲基苯基硅氧烷)以及经氨基、脂肪酸、醇、聚醚、环氧、氟、糖苷和/或烷基改性的硅氧烷化合物(其在室温下为液体或固体)及其混合物。二甲基硅酮和聚(甲基苯基硅氧烷)的数均分子量优选在100至150000g/mol的范围内。优选的环状硅氧烷包括4元至8元环,其例如以环甲基硅酮的形式商购。
在上述所有制剂中,各成分的总和为100%。
本发明提供的缩合聚合物还适用于掺入如下家用护理产品和织物护理产品中,诸如家用清洁和护理剂(例如在洗涤产品和织物柔顺剂中使用的),基于非洗涤剂的织物产品,液体清洁和擦洗剂,玻璃洗涤剂,中性清洁剂(全效清洁剂),酸性家用清洁剂(沐浴),浴室清洁剂,诸如在洗涤、冲洗和洗碗剂中使用的,厨房和烤箱清洁剂,透明冲洗剂,洗碗机洗涤剂,鞋抛光剂,抛光蜡,地板洗涤剂和抛光剂,金属、玻璃和陶瓷清洁剂,织物护理制品,地垫清洁剂和地毯香波,用于除锈、除色和去污的试剂(去污盐),家具和多用途抛光剂和皮革与乙烯裹敷剂(皮革和乙烯喷雾),空气清新剂,排水管清洁剂(drain cleaner),消毒溶液,室内装潢清洁剂,汽车护理制品(例如清洁和/或抛光并保护油漆、轮胎、铬、乙烯基、皮革、织物、橡胶、塑料和织物),去污剂,抛光剂(玻璃、木头、皮革、塑料、大理石、花岗岩和瓷砖等),和金属抛光剂和清洁剂,蜡烛,凝胶蜡烛,空气清新剂和芳香油(家用)。
因此,本发明还涉及家用护理产品和织物护理产品,所述护理产品包含本发明的缩合聚合物,诸如上述具体公开的缩合聚合物。
本发明缩合聚合物可以用于使用织物后的织物处理中,被称作织物护理。这类处理包括洗涤(其使用洗涤剂、洗涤助剂和/或织物护理剂),以及包括应用基于非洗涤剂的织物护理制品(例如喷雾制品)。当以这种方式使用时,本发明缩合聚合物往往沉积在织物上,并且用于保护织物、颜色以及与所述这些织物相关的香味免受环境破坏。
在进一步的实施方式中,本发明涉及有效量的上述缩合聚合物在保护、防腐蚀或装饰涂层中;在纸张涂层配制品中;在油墨中;在生物杀灭剂中;在油田化学品中的用途,以及用于固定土壤、土壤或混凝土中的重金属的用途,但所述用途并不局限于此。
提供以下的实施例进一步阐述本发明的方法和组合物。这些实施例仅用于举例说明而非旨在以任何方式限制本发明的范围。
实施例1
含有基团(I)(其中A是亚乙基,R1-R6是氢,n、m、o=1,X1、X2和X3是羟基)的缩合聚合物的合成
将355g三(羟甲基)氨基甲烷(TRIS)和245g琥珀酸酐加入安装有搅拌器和冷凝器的玻璃反应器中,该玻璃反应器可通过油浴进行加热。将混合物缓缓加热至180℃,2小时后,施加真空以除去反应水。5小时后,冷却混合物,并得到酸值为2mg KOH/g的玻璃状聚合物。
实施例2
含有基团(I)(其中A是亚乙基,R1-R6是氢,n、m、o=1,X1、X2和X3中的至少一个是基团-O-CO-CH2CH2-CO-N(R8,R9),其中R8和R9形成N-甲基哌嗪基)的缩合聚合物的合成
将276g N-甲基哌嗪加入安装有搅拌器和冷凝器的玻璃反应器中,该玻璃反应器可通过油浴进行加热。接着加入384g琥珀酸酐,并将混合物缓缓加热至120℃。1小时后,加入139g TRIS,并将混合物加热至180℃。1/2小时后,施加真空以除去反应水。12小时后,冷却混合物,并得到酸值为47mg KOH/g的聚合物。
实施例3
含有基团(I)(其中A是1,2-环己基,R1-R6是氢,n、m、o=1,X1、X2和X3中的至少一个是基团-O-CO-(1,2-C6H4)-CO-N(R8,R9),其中R8和R9是二甲基氨基丙基)的缩合聚合物的合成
将276g二(N,N-二甲基氨基丙基)胺和295g熔融态的六氢邻苯二甲酸酐加入安装有搅拌器和冷凝器的玻璃反应器中,该玻璃反应器可通过油浴进行加热。将混合物缓缓加热至120℃。1小时后,加入80g TRIS,并将混合物加热至180℃。1/2小时后,施加真空以除去反应水。16小时后,冷却混合物,并得到酸值为25mg KOH/g的聚合物。
实施例4
含有基团(I)(其中A是亚乙基,R1-R6是氢,n、m、o=1,X1、X2和X3中的至少一个是基团-O-CO-CH2CH2-COOR10,其中R10是聚环氧乙烷基团)的缩合聚合物的合成
将407g聚环氧乙烷单甲基醚(MW=750)加入安装有搅拌器和冷凝器的玻璃反应器中,该玻璃反应器可通过油浴进行加热。接着加入68g琥珀酸酐,并将混合物缓缓加热至120℃。1小时后,加入25g TRIS,并将混合物加热至180℃。1/2小时后,施加真空以除去反应水。12小时后,冷却混合物,并得到酸值为14mg KOH/g的聚合物。
实施例5
含有基团(I)(其中A是亚乙基,R1-R6是氢,n、m、o=1,X1是甲基,X2和X3中的至少一个是基团-O-CO-CH2CH2-COOR10,其中R10是聚环氧乙烷基团)的缩合聚合物的合成
将312g聚环氧乙烷单甲基醚(MW=750)加入安装有搅拌器和冷凝器的玻璃反应器中,该玻璃反应器可通过油浴进行加热。接着加入68g琥珀酸酐,并将混合物缓缓加热至120℃。1小时后,加入37g 2-氨基-2-乙基-1,3-丙二醇,并将混合物加热至180℃。1/2小时后,施加真空以除去反应水。12小时后,冷却混合物,并得到酸值为17mg KOH/g的聚合物。
实施例6
含有基团(I)(其中X1、X2和X3中的至少一个是咪唑啉基)的缩合聚合物的合成
将246g TRIS、170g琥珀酸酐和184g咪唑加入安装有搅拌器和冷凝器的玻璃反应器中,该玻璃反应器可通过油浴进行加热。将混合物缓缓加热至180℃。2小时后,施加真空以除去反应水。5小时后,冷却混合物,并得到酸值为10mg KOH/g的玻璃状聚合物。所述缩合聚合物中咪唑啉基端基和羟基端基的比为约70wt%比30wt%。
实施例7
含有基团(I)(其中A是亚乙基和1-十二碳烯基亚乙基(1:1),R1-R6是氢,n、m、o=1,X1、X2和X3中的至少一个是基团-O-CO-R7,其中R7源自椰子脂肪酸)的缩合聚合物的合成
将183g十二碳烯基琥珀酸酐、169g琥珀酸酐、141g椰子脂肪酸和208g TRIS加入安装有搅拌器和冷凝器的玻璃反应器中,该玻璃反应器可通过油浴进行加热。将混合物缓缓加热至180℃。2小时后,施加真空以除去反应水。5小时后,冷却混合物,并得到酸值为9mg KOH/g的聚合物。所述缩合聚合物中椰子脂肪酸端基和羟基端基的比为约25wt%比75wt%。
实施例8
含有基团(I)(其中N-甲基哌嗪端基被季铵化)的缩合聚合物的合成
将50g实施例2的聚合物溶于50g水中,并在室温下缓缓加入24.2g硫酸二甲酯。开始混合物是浑浊的,然后在10分钟内将温度升高至约50℃,混合物变得澄清。24小时后,得到完全季铵化的聚合物溶液备用。
实施例9
含有基团(I)(其中二甲基氨基丙基被季铵化)的缩合聚合物的合成
将50g实施例3的聚合物溶于50g水中,并在室温下缓缓加入21.9g硫酸二甲酯。开始混合物是浑浊的,然后在10分钟内将温度升高至约50℃,混合物变得澄清。24小时后,得到完全季铵化的聚合物溶液备用。
实施例10
含有基团(I)(其中A是1,2-环己基,R1-R6是氢,n、m、o=1,X1、X2和X3中的至少一个是基团-O-CO-R7,其中R7源自向日葵脂肪酸)的缩合聚合物的合成
将184g六氢邻苯二甲酸酐、106g二异丙醇胺和73g TRIS加入安装有搅拌器和冷凝器的玻璃反应器中,该玻璃反应器可通过油浴进行加热。将混合物缓缓加热至160℃,然后加入336g向日葵脂肪酸。2小时后,施加真空以除去反应水。5小时后,冷却混合物,并得到酸值为6mg KOH/g的聚合物。
实施例11
头发造型喷雾
INCI命名 | wt.% |
无水酒精 | 添加至100 |
辛基丙烯酰胺/丙烯酸酯/甲基丙烯酸丁基氨基乙酯共聚物 | 2.50 |
羟丙基纤维素 | 0.50 |
氨甲基丙醇 | 0.50 |
香精油 | 0.200 |
本发明的缩合聚合物 | 0.01-20 |
首先将羟丙基纤维素溶解在一半的醇中并随后补加氨甲基丙醇。将除丙烯酸酯树脂以外的其它成分溶解在醇中,并在搅动下将该溶液添加至羟丙基纤维素中,随后添加丙烯酸酯树脂。
实施例12
防护型头发定型摩丝(Protective Styling Hair Mousse)
INCI命名 | wt.% |
水 | 添加至100 |
聚季铵盐-4 | 2.00 |
椰油酰胺丙基胺氧化物 | 0.40 |
PEG-12二甲基硅酮 | 0.20 |
丙二醇&二唑啉基脲&对羟基苯甲酸甲酯&对羟基苯甲酸丙酯 | 1.00 |
香精油 | 0.20 |
丙烷/丁烷 | 10.00 |
本发明的缩合聚合物 | 0.01-20 |
在搅动下按照所示顺序添加各成分。之后,与丙烷/丁烷一起充入适当的容器中。
实施例13
油性头发适用的洗发香波
INCI命名 | wt.% |
肉豆蔻醇聚醚硫酸钠 | 50.00 |
枞酰水解胶原TEA盐(TEA abietoyl collagen hydrolysate) | 3.50 |
月桂基聚醚-3(Laureth-3) | 3.00 |
膦酰基甲基壳聚糖钠盐(Phosphonomethylchitosan sodium salt) | 0.01 |
水 | 添加至100 |
着色剂(D&G Red No.33) | 0.20 |
香精油 | 0.15 |
本发明的缩合聚合物 | 0.01-20 |
将各成分在室温搅拌混合,直到它们完全溶解。
实施例14
去头屑洗发香波
INCI命名 | wt.% |
水 | 添加至100 |
月桂基醚硫酸铵(Ammonium laureth sulphate) | 35.00 |
月桂基硫酸铵 | 15.00 |
乙二醇二硬脂酸酯(Glycol disearate) | 1.00 |
二甲基硅酮 | 1.00 |
鲸蜡醇 | 0.50 |
椰子酰胺MEA(Cocamide MEA) | 3.00 |
ZPT | 1.00 |
瓜尔胶羟丙基三甲基氯化铵 | 0.20 |
氢化的聚癸烯 | 1.00 |
聚季铵盐10 | 0.10 |
PEG 7m | 0.50 |
三羟甲基丙烷三辛酸酯/三癸酸酯 | 1.00 |
防腐剂 | 适量 |
香味剂 | 0.30 |
E 104,E 110,E 132 | 0.02 |
本发明的缩合聚合物 | 0.01-20 |
实施例15
护发素香波
INCI命名 | wt.% |
水 | 添加至100 |
月桂基醚硫酸钠 | 25.00 |
椰油酰胺丙基甜菜碱 | 5.00 |
氯化钠 | 2.50 |
乙二醇二硬脂酸酯 | 1.00 |
甘油 | 2.00 |
二甲基硅酮醇(Dimethiconol) | 0.50 |
香味剂 | 0.50 |
椰油-葡萄糖苷 | 3.00 |
卡波姆 | 0.10 |
精氨酸 | 0.05 |
油酸甘油酯 | 0.05 |
硬脂酸甘油酯 | 1.00 |
瓜尔胶羟丙基三甲基氯化铵 | 0.10 |
泛醇 | 1.00 |
EDTA二钠 | 0.05 |
防腐剂 | 适量 |
水解的角蛋白 | 0.10 |
柠檬酸/氢氧化钠 | 适量 |
本发明的缩合聚合物 | 0.01-20 |
E 102,E 110,FD&C blue | 0.01 |
实施例16
含植物提取物的洗发香波
INCI命名 | wt.% |
水 | 添加至100 |
月桂基醚硫酸钠 | 25.00 |
月桂基葡糖苷 | 10.00 |
椰油酰胺丙基甜菜碱 | 5.00 |
丙二醇 | 2.0 |
香精油 | 1.25 |
柠檬酸钠 | 0.25 |
苯甲酸钠 | 0.20 |
泛醇 | 1.00 |
甲酸钠 | 0.20 |
聚季铵盐-10 | 0.20 |
羟丙基瓜尔胶羟丙基三甲基氯化铵 | 0.05 |
PEG-35蓖麻油 | 1.00 |
海盐(Maris sal) | 1.25 |
聚山梨醇酯20 | 1.00 |
醋酸生育酚 | 0.20 |
Prunus armeniaca | 0.20 |
Echinacea purpurea | 0.05 |
棕榈酸视黄酯 | 0.05 |
生育酚 | 0.05 |
亚油酸 | 0.20 |
防腐剂 | 1.00 |
本发明的缩合聚合物 | 0.01-20 |
CI77891 | 0.02 |
实施例17
闪亮香波(Shine Shampoo)
INCI命名 | wt.% |
水 | 添加至100 |
月桂基醚硫酸钠 | 15.00 |
椰油两性二乙酸二钠(Disodium cocoamphodiacetate) | 15.00 |
氯化钠 | 2.00 |
乙二醇二硬脂酸酯 | 1.00 |
椰油酰胺基丙基PYL甜菜碱(Cocoamidopropyl PYL betaine) | 2.00 |
月桂基二甲基铵羟丙基水解的小麦蛋白 | 1.00 |
PEG-12二甲基硅酮 | 1.00 |
瓜尔羟丙基三甲基氯化铵 | 0.05 |
水解的小麦蛋白 | 0.20 |
月桂基聚醚-4(Laureth-4) | 1.00 |
椰油酸PEG-7甘油酯 | 2.00 |
氢化蓖麻油 | 1.00 |
月桂基聚醚-2(Laureth-2) | 0.50 |
油酸PEG-55丙二醇酯 | 2.00 |
丙二醇 | 2.00 |
云母 | 0.20 |
柠檬酸 | 0.01 |
香味剂 | 1.00 |
E 110,E 104,E 122 | 0.05 |
本发明的缩合聚合物 | 0.01-20 |
实施例18
淋浴啫哩
INCI命名 | Wt.% |
水 | 添加至100 |
月桂基醚硫酸钠 | 12.90 |
椰油酰胺丙基甜菜碱 | 2.50 |
椰油基水解胶原钾(Potassium Cocoyl hydrolized collagen) | 1.50 |
氯化钠 | 1.00 |
香精油 | 1.00 |
水解胶原 | 0.90 |
癸基葡糖苷 | 0.90 |
聚季铵盐-10 | 0.20 |
丙二醇 | 0.18 |
5-溴-5-硝基-1,3-二氧杂环己烷 | 0.02 |
Chinoline黄E 1041%溶液 | 0.01 |
本发明的缩合聚合物 | 0.01-20 |
实施例19
彩妆/粉底/日霜
INCI命名 | wt.% |
A) | 辛基十二烷醇 | 4.00 |
硬脂酸甘油酯SE | 4.50 | |
滑石 | 1.00 | |
二氧化钛 | 6.00 | |
氧化铁 | 0.80 | |
Ricinus communis(蓖麻)籽油 | 8.00 | |
失水山梨糖醇倍半油酸酯 | 0.50 | |
Steareth-2 | 0.50 | |
醋酸生育酚酯 | 2.00 | |
EDTA二钠 | 0.10 | |
BHT | 0.05 | |
苯氧乙醇&对羟基苯甲酸甲酯&对羟基苯乙酸乙酯&对羟基苯甲酸丁酯&对羟基苯甲酸丙酯&对羟基苯甲酸异丁酯 | 0.60 | |
本发明的缩合聚合物 | 0.20 | |
鲸蜡基磷酸钾 | 2.00 | |
B) | 水 | 加至100 |
丙二醇 | 5.00 | |
卡波姆 | 1.00 | |
C) | 环甲基硅酮 | 4.00 |
二甲基硅酮 | 5.00 | |
香精油 | 0.20 |
将部分A)搅拌加热至85℃。当均匀时,添加预热到75℃的部分B)。混合,同时冷却至环境温度(不高于25℃)并在搅拌下添加部分C)。经过3-辊炼机(3-Rollmill)。
实施例20
绿色的玻璃洗涤剂
INCI命名 | wt.% |
阴离子/两性表面活性剂(Lumurol RK) | 0.70 |
丁二醇 | 5.00 |
异丙醇 | 20.00 |
着色剂(D&G Green No.2) | 0.05 |
水 | 添加至100 |
香精油 | 4.00 |
本发明的缩合聚合物 | 0.01-20 |
将各组分在室温下搅拌混合直到获得均匀的混合物。
实施例21
指甲油
INCI命名 | wt.% |
甲基乙基甲酮 | 36.00 |
异丙醇 | 28.00 |
水 | 添加至100 |
乙酸乙酯 | 20.00 |
醋酸生育酚酯 | 0.05 |
香精油 | 0.50 |
本发明的缩合聚合物 | 0.01-20 |
CI42090 | 0.01 |
在室温下搅拌混合各组分,直到获得均匀的混合物。得到了极好的结果。
实施例22
护发摩丝
INCI命名 | wt% |
聚季铵盐-11 | 5.00 |
本发明的缩合聚合物 | 0.01-20 |
羟乙基十六烷基二甲基磷酸铵 | 0.50 |
醇 | 10.00 |
香精油 | 0.40 |
防腐剂 | 适量 |
水 | 69.10 |
丙烷/丁烷 | 10.00 |
实施例23
气雾剂喷雾VOC 80
INCI命名 | wt% |
本发明的缩合聚合物 | 0.01-20 |
丙烯酸酯共聚物 | 1.00 |
氨基甲基丙醇 | 0.24 |
醇 | 35.00 |
水 | 添加至100 |
环戊基硅氧烷 | 0.10 |
香精油 | 0.10 |
丁烷 | 10.00 |
二甲基醚 | 35.00 |
加入所有成分并剧烈搅拌,直到获得均匀的混合物。
实施例24
定型乳液/溶液
INCI命名 | wt% |
本发明的缩合聚合物 | 0.01-20 |
PEG-8 | 0.20 |
香精油 | 0.10 |
水 | 10.00 |
醇 | 添加至100 |
加入所有成分并剧烈搅拌,直到获得均匀的溶液。
实施例25
发用睹哩
INCI命名 | wt% |
卡波姆 | 0.50 |
水 | 添加至100 |
三乙醇胺 | 0.70 |
本发明的缩合聚合物 | 0.01-20 |
丙烯酸酯/C1-2琥珀酸酯/羟基丙烯酸酯共聚物 | 2.00 |
氨基甲基丙醇 | 0.19 |
香精油 | 适量 |
PEG-40氢化的蓖麻油 | 适量 |
PEG-8 | 0.10 |
苯氧乙醇、对羟基苯甲酸甲酯、对羟基苯甲酸丁酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯 | 0.10 |
羟乙基纤维素 | 0.50 |
加入所有成分并剧烈搅拌,直到获得均匀的啫哩。
Claims (34)
1.一种用于个人护理、家用护理或织物护理的组合物,所述组合物包含有效量的带有至少两个通式(I)基团的缩合聚合物:
其中,
自由键延伸至所述聚合物的主链;
A是可选被取代的(C6-C24)芳二基、或可选被取代的(C2-C24)(环)烷二基,
R1至R6各自独立地是氢、C1-20-烷基、C3-7-环烷基或C6-10-芳基;
X1、X2和X3各自独立地是氢、羟基、C1-20-烷基、C1-20-烷氧基、C3-7-环烷基、C6-10-芳基或基团-O-CO-R7、-O-CO-A-CO-N(R8,R9)、-O-CO-A-CO-OR10或-NHet;
R7是C1-20-烷基、C3-7-环烷基、C6-10-芳基、或聚合物或低聚物的残基;
R8和R9各自独立地是(C1-20)-烷基或(C6-10)-芳基,或被含有至少一个杂原子的基团取代的(C1-20)-烷基或(C6-10)-芳基;或者
R8和R9与它们连接的氮原子一起形成5元或6元环,其中,可选地一个或多个C原子被-NH、-N-(C1-20)-烷基、-N-芳基、-O-或-S-替代;
R10是C1-20-烷基、C3-7-环烷基、C6-10-芳基、或聚合物或低聚物的残基;
NHet各自独立地是通过氮原子连接到所述聚合物上的单环、双环或多环含氮杂环基团,所述含氮杂环基团可以是芳族基团,或者可以是部分氢化的或完全氢化的,并且可以包含额外的杂原子,诸如氮原子、氧原子或硫原子,并且所述含氮杂环基团可选被取代;并且
n、m、o各自独立地是1至4的整数,优选地,n、m和。等于1,
附加条件是,X1、X2和X3中最多只有一个是氢、C1-20-烷基、C3-7-环烷基或C6-10-芳基;并且
其中,含氮基团可以被季铵化或被质子化。
2.如权利要求1所述的组合物,其中,在所述缩合聚合物中,至少一个通式(I)基团以其中R1至R6是氢的形式存在。
3.如权利要求1或2所述的组合物,其中,X1、X2和X3的其中之一是甲基。
4.如权利要求1或2所述的组合物,其中,在所述缩合聚合物中,至少一个通式(I)基团以其中X1、X2和X3中的至少一个是羟基的形式存在。
5.如权利要求1所述的组合物,其中,在所述缩合聚合物中,至少一个通式(I)基团以其中X1、X2和X3中的至少一个是-O-CO-R7的形式存在。
6.如权利要求5所述的组合物,其中,R7是C1-20-烷基,优选是2-乙基己基。
7.如权利要求1或2所述的组合物,其中,在所述缩合聚合物中,至少一个通式(I)基团以其中X1、X2和X3中的至少一个是-O-CO-A-CO-N(R8,R9)的形式存在。
8.如权利要求7所述的组合物,其中,R8和R9是二-(C1-20-烷基)氨基-C1-20-烷基。
9.如权利要求7所述的组合物,其中,-N(R8,R9)是5元或6元N-杂环。
10.如权利要求9所述的组合物,其中,所述5元或6元N-杂环是N-甲基哌嗪基或吗啉基。
11.如权利要求1所述的组合物,其中,在所述缩合聚合物中,至少一个通式(I)基团以其中X1、X2和X3中的至少一个是-O-CO-A-CO-OR10的形式存在。
12.如权利要求11所述的组合物,其中,R10是聚环氧乙烷甲基醚、聚环氧丙烷甲基醚和/或聚四氢呋喃。
13.如权利要求1所述的组合物,其中,在所述缩合聚合物中,至少一个通式(I)基团以其中X1、X2和X3中的至少一个是-NHet的形式存在。
14.如权利要求13所述的组合物,其中,-NHet各自独立地是通过氮原子连接到所述聚合物上的单环、双环或多环含氮杂环基团,所述含氮杂环基团可以是芳族基团,或者可以是部分氢化的或完全氢化的,并且可以包含额外的杂原子,诸如氮原子、氧原子或硫原子,并且所述含氮杂环基团可选被取代。
15.如权利要求14所述的组合物,其中,-NHet是咪唑基。
16.如权利要求1至15中任意一项所述的组合物,其中,所述缩合聚合物是一种可通过以下获得的聚合物:
使通式(II)的化合物与通式(III)的二元羧酸或其环状酸酐以及可选的通式(IV)的酸、和/或通式(V)的二烷基胺、和/或通式(VI)的醇、和/或通式(VII)的杂环化合物进行缩聚;
式(II)
其中,R1至R6以及n、m和。如前述式(I)所定义,X11、X21和X31具有与前述式(I)中的X1、X2和X3相同的含义,附加条件是,X11、X21、X31中的至少一个是羟基,进一步的附加条件是X11、X21和X31中最多只有一个是氢、C1-20-烷基、C3-7-环烷基,或C6-10芳基;
A(COOH)2 式(III),
其中,A具有与前述式(I)中相同的含义;
R7COOH 式(IV),
HN(R8R9) 式(V),
R10OH 式(VI),
H-Nhet 式(VII),
其中,R7、R8、R9、R10以及-NHet具有与前述式(I)相同的含义;
并且可选地,所获得的所述缩合聚合物中含有的氮原子被季铵化或被质子化。
18.一种缩合聚合物,所述缩合聚合物具有至少一个权利要求1所定义的通式(I)的基团,其中,X1、X2和X3各自独立地是基团-O-CO-A-CO-N(R8,R9)、-O-CO-A-CO-OR10或-NHet;R1至R6、R8、R9、R10和-NHet如权利要求1所定义;并且其中,包含在所述式(I)缩合聚合物中的氮原子可以被季铵化或被质子化。
19.如权利要求18所述的缩合聚合物,其中,X1、X2和X3各自独立地是基团-O-CO-A-CO-N(R8,R9)。
20.如权利要求19所述的缩合聚合物,其中,R8和R9是二-(C1-20-烷基)氨基-C1-20-烷基。
21.如权利要求19所述的缩合聚合物,其中,-N(R8,R9)是5元或6元N-杂环。
22.如权利要求21所述的缩合聚合物,其中,-N(R8,R9)是N-甲基哌嗪基或吗啉基。
23.如权利要求18所述的缩合聚合物,其中,X1、X2和X3各自独立地是基团-O-CO-A-CO-OR10。
24.如权利要求23所述的缩合聚合物,其中,R10是聚环氧乙烷、聚环氧丙烷甲基醚和/或聚四氢呋喃。
25.如权利要求18所述的缩合聚合物,其中,X1、X2和X3各自独立地是基团-NHet。
26.如权利要求25所述的缩合聚合物,其中,-NHet是通过氮原子连接到所述聚合物上的单环、双环或多环含氮杂环基团,所述含氮杂环基团可以是芳族基团,或者可以是部分氢化的或完全氢化的,并且可以包含额外的杂原子,诸如氮原子、氧原子或硫原子,并且所述含氮杂环基团可选被取代。
27.如权利要求25所述的缩合聚合物,其中,-NHet是咪唑基。
28.如权利要求18至27中任意一项所述的缩合聚合物,所述缩合聚合物可通过以下获得:
使通式(II)的化合物与通式(III)的二元羧酸或其环状酸酐以及可选的通式(V)的二烷基胺、和/或通式(VI)的醇、和/或通式(VII)的杂环化合物进行缩聚;
其中,R1至R6以及n、m和o如前述式(I)所定义,X11、X21和X31具有与前述式(I)中的X1、X2和X3相同的含义,附加条件是,X11、X21、X31中的至少一个是羟基,进一步的附加条件是X11、X21和X31中最多只有一个是氢、C1-20-烷基、C3-7-环烷基,或C6-10芳基;
A(COOH)2 式(III),
其中,A具有与前述式(I)中相同的含义;
HN(R8R9) 式(V),
R10OH 式(VI),
H-Nhet 式(VII),
其中,R8、R9、R10以及-NHet具有与前述式(I)相同的含义;并且可选地,所获得的所述缩合聚合物中含有的氮原子被季铵化或被质子化。
30.一种头发护理制剂,包含权利要求1至17中任意一项所述的组合物。
31.如权利要求1至17中任意一项所述的组合物,其中,所述缩合聚合物具有600g/mol至50000g/mol的重均分子量,更优选具有800g/mol至25000g/mol的重均分子量。
32.如权利要求1至17中任意一项所述的组合物,其中,每分子缩合聚合物中端基X1、X2和/或X3的平均数目介于2和250之间,更优选介于3和50之间。
33.如权利要求18至29中任意一项所述的缩合聚合物,所述缩合聚合物具有600g/mol至50000g/mol的重均分子量,更优选具有800g/mol至25000g/mol的重均分子量。
34.如权利要求18至29中任意一项所述的缩合聚合物,每分子缩合聚合物中端基X的平均数目介于2和250之间,更优选介于3和50之间。
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CN102725377A (zh) * | 2009-11-25 | 2012-10-10 | 帝斯曼知识产权资产管理有限公司 | 聚酯酰胺发泡剂 |
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CN113164345A (zh) * | 2018-11-26 | 2021-07-23 | 帝斯曼知识产权资产管理有限公司 | 包含特定的超支化共聚物和油的化妆品组合物 |
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EP2032115A2 (en) | 2009-03-11 |
JP5403361B2 (ja) | 2014-01-29 |
KR101445401B1 (ko) | 2014-09-26 |
WO2007144189A3 (en) | 2008-02-28 |
US8394500B2 (en) | 2013-03-12 |
EP2032115B1 (en) | 2021-07-21 |
JP2009540072A (ja) | 2009-11-19 |
CN101505712B (zh) | 2013-03-20 |
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