CN103370049B - 用具有amps且富含丙烯酸的聚合物的碱可溶胀乳液增稠化妆品制剂的方法 - Google Patents
用具有amps且富含丙烯酸的聚合物的碱可溶胀乳液增稠化妆品制剂的方法 Download PDFInfo
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Abstract
本发明涉及一种通过使用ASE或HASE型聚合物的碱可溶胀的直接(水包油)乳液来增稠化妆品组合物的方法,所述聚合物是富含丙烯酸且具有一定量AMPS的。这样的乳液的使用同时允许不必使用表面活性剂和非水的有机溶剂,并且允许对于小于7的pH值触发增稠现象:后一个特征对于准备用于与皮肤接触的制剂特别有利。
Description
本发明涉及一种增稠化妆品组合物的方法,其利用富含丙烯酸并且具有一定量AMPS的ASE或HASE型聚合物在水中的直接乳液,所述乳液是碱可溶胀的。使用这样的乳液同时允许不必使用表面活性剂和非水的有机溶剂和允许对于小于7的pH值的增稠现象被激活,后一个特征对于意图用于与皮肤接触的制剂是特别有利的。
许多化妆品制剂目前都是为施加到皮肤上而设计的:这是美容产品、化妆产品和身体护理产品的固有特征。非常自然地,寻求在与皮肤的pH范围相匹配的pH范围内,即在5–7之间的pH值,优选在5–6.5之间的pH值,更优选在5.5–6之间的pH值增稠这样的制剂。
针对该问题有许多技术方案,这些技术方案可以分成四类:使用较高分子量且处于粉末形式的聚合物,依赖于聚合物颗粒在水中的直接乳液中的丙烯酸类聚合物的称为“回酸(back-acid)”的技术,使用其他也处于直接乳液形式的聚合物,以及使用反相乳液。
在第一类中,可以引用文献EP1138703A1,其描述了一种化妆品局部用组合物,包含高分子量的聚合物,具有至少一种具有游离强酸基团的单体与至少一种酯化单体共聚并且通过具有8–30个碳原子的疏水基团封端的基体。
上述聚合物是一种乳化聚合物,处于固体形式;它可以分散在水中并且它能使含有它的组合物得以增稠,尤其是针对接近5的pH值。
但是,这些聚合物具有与使用粉末相关的缺点:输送和清洁困难、与其粉末状、刺激性和特定性质相关的产品的危险性。此外,必须通过引入表面活性剂来使这些聚合物在要增稠的介质中增溶。所述表面活性剂构成了使得制剂更复杂的额外的制剂添加剂,并且其可以与所述制剂中已经含有的表面活性剂相互作用,有时产生不希望的作用(尤其是相分离或者形成不可溶的残留物)。
称为“回酸”的技术也是已知的,如在文献WO01/76552中所述。这是一种包括向含水介质中引入表面活性剂和碱可溶胀的丙烯酸类共聚物的方法。这在其羧酸基团被中和时产生增稠效果:此时产生三维网络,导致水相的粘度增加。这样的效果可以在接近6的pH区域内触发,表面活性剂的作用是即使在pH值降低时也保持增稠效果。
除了上述离子机理以外,还存在缔合机理,其基于疏水单体的存在:这是由文献WO03/62288所描述的,其也寻求增稠具有酸性pH值的制剂。相同的机理适用于文献US4529773A1。如同回酸方法,附加产物形式的表面活性剂的存在因此是必要的,这导致前述的缺点。
描述使用其他在乳液中的聚合物的许多文献也是已知的。在这方面,文献EP0824914B1描述了含有胺化的阳离子单体的聚合物。所寻求的增稠效果通过胺化的阳离子单体的离子化用酸性pH值获得。在文献WO2004/024779中,设想的聚合物的阳离子性由取代的氨基乙烯基单体提供。在这种情况下,也可以增稠具有酸性pH值的含水介质。
然而,阳离子聚合物对水生动物的毒性是众所周知的:并且不幸的是在通过家用水******到的大小河流中的生活周期末端发现它们。
最后,反相乳液及其在化妆品领域中作为增稠剂的用途也是已知的,如文献WO2004063228A1和GB2422605A1中所公开的。但是,这些结构体要求存在表面活性剂和溶剂以保证其稳定性,并且因此产生上述缺点。
因此,为了使尤其是具有小于7的pH值的含水组合物增稠同时克服现有技术方法的缺点而继续进行研究,本申请人已经开发了一种使用新颖结构体的增稠方法。这些是碱可溶胀的(甲基)丙烯酸聚合物在水中的直接乳液,其3个基本特征是:
-不存在表面活性剂和非水的有机溶剂,
-与甲基丙烯酸比较,大量存在丙烯酸,
-和存在一定量的特定单体,所述特定单体是2-丙烯酰胺基-2-甲基丙
磺酸(或AMPS,CASno:40623-75-4)。
这些产物有利地能使化妆品制剂得以增稠,而没有向制剂中引入新的表面活性剂或者非水的有机溶剂。此外,可以在5–7之间的pH范围内触发增稠现象,而不使用“回酸”技术。
但是,在发现AMPS在富含丙烯酸并且没有表面活性剂和非水的有机溶剂的碱可溶的乳液中的重要性之前,还不知道如何制备这样的乳液。正是一定量的AMPS的存在使得能够生产这样的产品,其具有以前提及的关注点,这在化妆品领域中是特别有利的,尤其是为了使pH值小于7,特别是在5–6.5之间,更优选在5.5–6之间的制剂增稠。这些乳液在以FR1055080和FR1055077的申请号提交的尚未公开的法国专利申请中首次描述。
本申请人规定,表述“聚合物在水中的直接乳液”表示聚合物颗粒在水中的稳定且均匀的分散体(这里不参考水包油或油包水型乳液,它们是指存在两个分离的相,一个是基于水的,另一个是基于油的)。关于表述“碱可溶胀的聚合物”,它表示当介质为碱性时,所述聚合物能够引入一定量的水从而形成凝胶并且因此增大粘度。
在本申请中提及的乳液包括2个主要的增稠剂族:ASE型的那些(碱可溶胀的乳液)和HASE型的那些(疏水改性的碱可溶胀的乳液)。前者表示(甲基)丙烯酸与这些酸的非水溶性酯的共聚物,后者表示具有(甲基)丙烯酸的非水溶性酯和具有称为“缔合”基团的疏水基团的单体的(甲基)丙烯酸基体的共聚物。这些共聚物也可以是交联的。
这些产品的作用机理,尤其是这些乳液的碱可溶胀的特性及其增稠pH接近中性的含水介质的能力,已经描述于文献WO2007/144721和“Practicalquidetoassociativethickeners”(ProceedingsoftheAnnualMeetingTechnicalProgramoftheFSCT,2000,78th,644–702)。ASE和HASE型的增稠剂一般以碱可溶胀的聚合物在水中的直接乳液的形式制备,其活性产品含量为其总重量的10%-45%之间。
相应的合成方法尤其是描述在下列出版物中:“Synthesisofanalkali-swellableemulsionanditseffectontherateofpolymerdiffusioninpoly(vinylacetate-butylacrylate)latexfilms”(JournalofPolymerScience,PartA:PolymerChemistry,2005,43(22),第5632–5642页),“Structuralandrheologicalpropertiesofhydrophobicallymodifiedalkali-solubleemulsionsolutions”(JournalofPolymerScience,PartB:PolymerPhysics,2002,40(18),第1985–1994页)。它也是许多专利申请的主题(关于ASE的EP0089213A1、EP0646606A1、EP0979833A1和关于HASE的EP0013836A1、WO93/2454A1、US4268641A1、US4421902A1、US3915921A1)。
因此,本发明的第一个目的在于一种增稠化妆品制剂的方法,其通过使所述制剂与聚合物的直接含水乳液接触,然后调节pH值到5–7之间,优选在5–6.5之间,更优选在5.5–6之间,其特征在于所述乳液不含表面活性剂和非水的有机溶剂,并且在于用每种单体的重量%表示,所述聚合物由以下单体构成:
a)20重量%-60重量%的甲基丙烯酸和丙烯酸,
b)40重量%-80重量%的选自丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯及其混合物的至少一种单体,
c)0.05重量%-22重量%的2-丙烯酰胺基-2-甲基丙磺酸,
d)0–1重量%的至少一种交联单体,
其中a)+b)+c)+d)的总量等于100%,
或
a)20重量%-60重量%的甲基丙烯酸和丙烯酸,
b)40重量%-80重量%的选自丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯及其混合物的至少一种单体,
c)0.5重量%-25重量%的含有疏水基团的单体,
d)0.05重量%-22重量%的2-丙烯酰胺基-2-甲基丙磺酸,
e)0–1重量%的至少一种交联单体,
其中a)+b)+c)+d)+e)的总量等于100%,
其中,相对于丙烯酸和甲基丙烯酸的总重量,丙烯酸的重量%为50%-100%,优选为80%-100%,更优选为98%-100%,最优选为该重量%为100%(因此不存在甲基丙烯酸)。
上述第一种类型的组合物是富含丙烯酸的ASE型乳液,第二种是富含丙烯酸的HASE型乳液。
该方法的特征还在于含有疏水基团的单体具有通式R-(EO)m-(PO)n-R’,其中:
-m和n表示小于或等于150的整数,其至少一个是非零的,
-EO和PO分别表示亚乙基氧基和亚丙基氧基,
-R表示可聚合基团,优选为甲基丙烯酸酯基团或甲基丙烯酰基氨基甲酸酯基团,
-R’表示具有至少6个且最多36个碳原子的疏水基团。
该方法的特征还在于所述交联单体选自二甲基丙烯酸乙二醇酯、三羟甲基丙烷三丙烯酸酯、邻苯二甲酸二烯丙基酯、丙烯酸烯丙基酯、马来酸烯丙基酯、亚甲基-二-丙烯酰胺、亚甲基-二-甲基丙烯酰胺、四烯丙氧基乙烷、三聚氰酸三烯丙基酯、烯丙基醚以及由多元醇获得的丙烯酸酯、甲基丙烯酸酯和甲基丙烯酰基氨基甲酸酯。
该方法的特征还在于所述含水乳液具有相对于其总重量以干重计10%-50%的聚合物的干提取物。
该方法的特征还在于所述乳液的粒径为50nm–500nm。
该方法的特征还在于所述聚合物的重均摩尔质量为20000克/摩尔–1000000克/摩尔。
最后,该方法的特征在于所述化妆品制剂选自含有至少一种表面活性剂的制剂,尤其是选自准备用于皮肤的制剂(护理霜、化妆产品、发泡剂、香波等)。
以下实施例能够使本发明更好地被理解,但是不限制本发明的范围。
实施例
实施例1
本实施例涉及pH值为5.5的水的增稠。
测试3种根据本发明的HASE型乳液,使用具有表1中给出的质量组成的聚合物。
表1
AA:丙烯酸
AMA:甲基丙烯酸
AE:丙烯酸乙酯
甲基丙烯酸C22(EO)25酯:通式为R–(EO)m–(PO)n–R’的单体,其中,m=25,n=0,EO和PO分别表示亚乙基氧基和亚丙基氧基,R表示甲基丙烯酸酯基团,R’表示具有22个碳原子的线性烷基。
AMPS:2-丙烯酰胺基-2-甲基丙磺酸
在测试编号4中,还使用了以名称AquaSF-1由LubrizolTM公司销售的聚合物。
对于每次测试,相对于待增稠的水的总重量,使用以干重计1%的聚合物。在100转/分和25℃测量凝胶的以mPa.s表示的BrookfieldTM粘度随pH值的变化,pH值通过逐渐加入氢氧化钠来提高。
图1表示在测试编号1(菱形)、2(方形)、3(叉号)和4(圆形)的情况下的这种变化。
可以清楚地看出,使用具有AMPS的乳液的根据本发明的方法能够对于比用商业聚合物低得多的pH值触发增稠现象。
此外,在5.5–6的pH值范围内的增稠能力在本发明聚合物的情况下比现有技术聚合物的更大。
实施例2
本实施例涉及pH值为5.5的水的增稠。
测试几种根据本发明的HASE型乳液,使用具有表1给出的质量组成的聚合物。
表2
AA:丙烯酸
AMA:甲基丙烯酸
AE:丙烯酸乙酯
甲基丙烯酸TSP(EO)25酯:通式为R–(EO)m–(PO)n–R’的单体,其中m=25,n=0,EO和PO分别表示亚乙基氧基和亚丙基氧基,R表示甲基丙烯酸酯基团,R’表示三苯乙烯基苯酚(TSP)基团。
甲基丙烯酸异C16(EO)25酯:通式为R–(EO)m–(PO)n–R’的单体,其中m=25,n=0,EO和PO分别表示亚乙基氧基和亚丙基氧基,R表示甲基丙烯酸酯基团,R’表示衍生自Guerbet醇2-己基1-癸醇的烷基链。
甲基丙烯酸C18(EO)30酯:通式为R–(EO)m–(PO)n–R’的单体,其中m=25,n=0,EO和PO分别表示亚乙基氧基和亚丙基氧基,R表示甲基丙烯酸酯基团,R’表示具有18个碳原子的线性烷基链。
AMPS:2-丙烯酰胺基-2-甲基丙磺酸。
对于每次测试,相对于待增稠的水的总重量,使用以干重计1%的聚合物。在100转/分和25℃测量凝胶的以mPa.s表示的BrookfieldTM粘度随pH值的变化,pH值通过逐渐加入氢氧化钠来提高。
然后对于达到Brookfield粘度值等于400mPa.s时确定pH值,注意图1表明,对于说明现有技术的测试编号1,该pH值等于约6.4。
对于这些测试编号5、6和7,获得分别等于5.7、5.8和5.9的pH值。这清楚地表明,在低于根据现有技术的聚合物观察到的pH值下发生增稠现象。
Claims (13)
1.一种增稠化妆品制剂的方法,其通过使所述制剂与聚合物的直接含水乳液接触,然后调节pH值到5–7,其中所述聚合物的直接含水乳液表示聚合物颗粒在水中的稳定且均匀的分散体,其特征在于所述乳液不含表面活性剂和非水的有机溶剂,并且其特征在于,用每种单体的重量%表示,所述聚合物由以下单体构成:
a)20重量%-60重量%的甲基丙烯酸和丙烯酸,
b)40重量%-80重量%的选自丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯及其混合物的至少一种单体,
c)0.05重量%-22重量%的2-丙烯酰胺基-2-甲基丙磺酸,
d)0–1重量%的至少一种交联单体,
其中a)+b)+c)+d)的总量等于100%,
或
a)20重量%-60重量%的甲基丙烯酸和丙烯酸,
b)40重量%-80重量%的选自丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸甲酯及其混合物的至少一种单体,
c)0.5重量%-25重量%的含有疏水基团的单体,其中所述含有疏水基团的单体具有通式R-(EO)m-(PO)n-R’,其中:
m和n表示小于或等于150的整数,其至少一个是非零的,
EO和PO分别表示亚乙基氧基和亚丙基氧基,
R表示可聚合基团,
R’表示具有至少6个且最多36个碳原子的疏水基团,
d)0.05重量%-22重量%的2-丙烯酰胺基-2-甲基丙磺酸,
e)0–1重量%的至少一种交联单体,
其中a)+b)+c)+d)+e)的总量等于100%,
其中,相对于丙烯酸和甲基丙烯酸的总重量,丙烯酸的重量%为50%-100%。
2.根据权利要求1的方法,其中调节pH值到5–6.5。
3.根据权利要求1的方法,其中调节pH值到5.5–6。
4.根据权利要求1的方法,其特征在于相对于丙烯酸和甲基丙烯酸的总重量,丙烯酸的重量%为80%-100%。
5.根据权利要求1的方法,其特征在于相对于丙烯酸和甲基丙烯酸的总重量,丙烯酸的重量%为98%-100%。
6.根据权利要求1的方法,其特征在于相对于丙烯酸和甲基丙烯酸的总重量,丙烯酸的重量%为100%。
7.根据权利要求1的方法,其特征在于R表示甲基丙烯酸酯基团或甲基丙烯酰基氨基甲酸酯基团。
8.根据权利要求1–7的任一项的方法,其特征在于所述交联单体选自二甲基丙烯酸乙二醇酯、三羟甲基丙烷三丙烯酸酯、邻苯二甲酸二烯丙基酯、丙烯酸烯丙基酯、马来酸烯丙基酯、亚甲基-二-丙烯酰胺、亚甲基-二-甲基丙烯酰胺、四烯丙氧基乙烷、三聚氰酸三烯丙基酯、烯丙基醚以及由多元醇获得的丙烯酸酯、甲基丙烯酸酯和甲基丙烯酰基氨基甲酸酯。
9.根据权利要求1–7的任一项的方法,其特征在于所述含水乳液具有相对于其总重量以干重计10%-50%的聚合物的干提取物。
10.根据权利要求1–7的任一项的方法,其特征在于所述乳液的粒径为50nm–500nm。
11.根据权利要求1–7的任一项的方法,其特征在于所述聚合物的重均摩尔质量为20000克/摩尔–1000000克/摩尔。
12.根据权利要求1–7的任一项的方法,其特征在于所述化妆品制剂选自含有至少一种表面活性剂的制剂。
13.根据权利要求12的方法,其特征在于所述化妆品制剂选自准备用于皮肤的制剂。
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FR1151812A FR2972370B1 (fr) | 2011-03-07 | 2011-03-07 | Procede d'epaississement d'une formulation cosmetique a partir d'une emulsion alkali gonflable d'un polymere a l'amps et riche en acide acrylique. |
PCT/IB2011/003126 WO2012120330A1 (fr) | 2011-03-07 | 2011-12-14 | Procédé d'épaississement d'une formulation cosmétique à partir d'une émulsion alkali gonflable d'un polymère à l'amps et riche en acide acrylique |
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EP3704168A1 (en) * | 2017-11-03 | 2020-09-09 | Dow Global Technologies, LLC | Anti-settling, thickening polymer and aqueous cleansing formulations containing same |
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US10610471B2 (en) * | 2018-02-01 | 2020-04-07 | The Procter & Gamble Company | Cosmetic ink composition comprising a surface tension modifier |
US10813857B2 (en) | 2018-02-01 | 2020-10-27 | The Procter & Gamble Company | Heterogenous cosmetic ink composition for inkjet printing applications |
US10849843B2 (en) | 2018-02-01 | 2020-12-01 | The Procter & Gamble Company | Stable cosmetic ink composition |
WO2020144060A1 (en) | 2019-01-09 | 2020-07-16 | Unilever Plc | Shampoo composition and method of use |
FR3101247A1 (fr) | 2019-09-30 | 2021-04-02 | Coatex | Composition cosmetique anti-uv |
CN114276484B (zh) * | 2022-01-19 | 2023-03-28 | 广东星狮能源科技有限公司 | 粉末增稠剂的制备方法、消毒免洗搓手凝胶 |
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US20120231056A1 (en) | 2012-09-13 |
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US20170027846A1 (en) | 2017-02-02 |
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EP2683354A1 (fr) | 2014-01-15 |
EP2683354B1 (fr) | 2017-05-24 |
WO2012120330A1 (fr) | 2012-09-13 |
AU2011361923A1 (en) | 2013-09-05 |
BR112013016884A2 (pt) | 2016-08-09 |
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PL2683354T3 (pl) | 2017-09-29 |
ES2638291T3 (es) | 2017-10-19 |
US20140112966A1 (en) | 2014-04-24 |
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