CN1050363C - 滤光剂,含该滤光剂的防晒化妆组合物及其用途 - Google Patents
滤光剂,含该滤光剂的防晒化妆组合物及其用途 Download PDFInfo
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- CN1050363C CN1050363C CN95120079A CN95120079A CN1050363C CN 1050363 C CN1050363 C CN 1050363C CN 95120079 A CN95120079 A CN 95120079A CN 95120079 A CN95120079 A CN 95120079A CN 1050363 C CN1050363 C CN 1050363C
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
- A61K8/585—Organosilicon compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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Abstract
本发明提出链状或环状短链二或三有机硅氧烷类新化合物,该化合物具有所有包括至少一个来自N,N’-草酰二苯胺(或草酰替苯胺)并且含有亚烷氧基的滤光单元的化合物的共同特征,这些化合物尤其可在旨在保护皮肤和毛发、使其不受紫外光线照射的化妆组合物中用作有机防晒剂或光保护剂。本发明还涉及上述化合物在上述化妆方面的用途以及含有这些化合物的高性能化妆组合物。
Description
本发明涉及新的链状或环状短链二有机(聚)硅氧烷类或三有机硅烷类化合物,这些化合物具有所有包括至少一个来自N,N’-草酰二苯胺(或草酰替苯胺)并且含有亚烷基或亚烷氧基的滤光单元或防晒单元或光保护单元的化合物的共同特征,这些化合物尤其可在旨在保护皮肤和头发或毛发、使其不受紫外线照射的化妆组合物中用作为有机防晒剂或有机滤光剂或有机防光照剂,或称为光保护剂。本发明还涉及这些化合物在上述化妆领域中的应用或用途以及含有这些化合物的高性能或高品质化妆组合物。
已知受波长为280-400nm的光线照射可使人体皮肤或表皮晒黑,尤其是波长为280-320nm的光线,也称为UV-B的光线可引起红斑并使皮肤灼伤,而这会妨碍天然黑色或黑素的产生或形成,因此应当滤出或滤除UV-B光线。
还已知可使皮肤晒黑的波长为320-400nm的UV-A光线容易诱使皮肤产生不利的变化,尤其是在过敏性皮肤或连续受阳光照射的皮肤情况下就更是如此。更具体地讲,UV-A光线可使皮肤失去弹性并且出现皱纹,从而导致皮肤过早衰老或老化。这类光线在某些个案情况下更有助于引发红斑反应或加剧这种反应,甚至可成为光中毒或光过敏反应的根源。因此,也需要滤出或滤除UV-A光线。
为保护皮肤、使其免受(UV-A和/或UV-B)光照,到目前为止,已提出许多化合物。
大多数这类化合物均为芳族或芳香化合物,可在280-315nm范围内或在315-400nm范围内或在这两个范围内吸收UV光线。这些化合物通常配制成防阳光照射或防晒组合物,其形式为水包油类乳液(即由连续分散水相和不连续分散油相构成的化妆用载体),该组合物因此可含有各种浓度的一或多种常用有机滤光剂,这些滤光剂可选择性吸收有害的UV光线,其中含有亲脂和/或亲水芳族官能团,这些滤光剂(及其用量)可根据所要求的保护因子进行选择(在数学上,保护因子(IP)可表示为在用UV滤光剂的情况下开始产生红斑所需光照时间与不用UV滤光剂的情况下开始产生红斑所需光照时间之比)。
除了其固有滤光能力而外,这些具有抗UV活性的化合物还应当具有在含有这些化合物的组合物中显示出优良化妆性能,在常用溶剂,尤其是脂肪物质如油和脂中的优良溶解性以及优良的耐水耐汗性(持久保持)。而且,还要求这些滤光物质不会渗透进入皮肤并且是非毒性的。
在为此提出的所有化合物中,许多这类化合物并不具有在防阳光照射或防晒组合物中用作UV滤光剂所要求的全部性能。更具体地讲,这些化合物固有的滤光能力不足,而且为了用这类产品获得令人满意的滤光性能,常需应用相当大量的这类产品,这也通过含有这些化合物的最终配方显示出不良或差的化妆性能而反映出来。此外,在用于防阳光照射的各种配方中的溶解性(尤其是其脂溶性)也并不总是足够高,另外这些化合物受光照的稳定性(光稳定性)可能不够高并且其耐水和耐汗性也可能差。
本发明提出一类新的化合物,这些化合物尤其可在化妆组合物中用作具有抗UV作用或具有UV吸收作用的防晒剂或光保护剂,而且这些化合物没有上述缺陷。
更具体地讲,本发明已发现通过亚烷基或亚烷氧基类特殊连接链单元经过接枝过程,尤其是经过氢化硅烷化反应将一或多个特殊滤光单元,即N,N’-草酰二苯胺(或称为草酰替苯胺)衍生物连接到适当选定的链状或环状(聚)硅氧烷链上或连接到适当选定的硅烷上,就能够获得具有显著性能的新化合物,并且根据其化学结构,这些化合物不管是在UV-A范围内还是在UV-B范围内均具有很高的滤光性能,而且在常用有机溶剂,尤其是脂肪物质如油中具有极好的溶解性,优异的光稳定性以及优异的化妆性能,这使其特别适宜于在旨在保护皮肤和/或毛发、使其不致于受紫外线照射的化妆组合物中用作为防光照或防晒剂或光保护剂,或者用于制备这种化妆组合物。
这一发现即奠定了本发明的基础。
因此,本发明第一方面就是提出新化合物,其特征在于这些化合物如下列式(1)至(3)之一所示:
A-Si(R’)3 (3)式(1)至(3)中:
R可相同或不同,选自C1-C10烷基,苯基和3,3,3-三氟丙基,其中按数目计至少80%的R是甲基,
B可相同或不同,选自上述基团R和下述基团A,
R’可相同或不同,选自C1-C8烷基或苯基,
r是0-50的整数(含0和50),s是等于0或1的整数,条件是如果s是0,则两个基团B中至少一个是A,
t是2-10的整数(含2和10),
R2是氢或C1-C4烷基,
p是0-10的整数(含0和10),
m是0或1,
端部-CH2-直接与硅原子相连;
*Z是氢或二价基团-Y-,
*q是0-3的整数(含0和3),
*R1可相同或不同,分别选自C1-C8烷基或C1-C6烷氧基,应注意到的是在后一种情况下,两个相邻的基团R1(q≥2)可共同形成其中亚烷基含1或2个碳原子的亚烷二氧基。
上式(1)和(3)中,A为来源于N,N’-草酰二苯胺(或称为草酰替苯胺)的基团,在将其连到初始(聚)硅氧烷短链上或连到初始硅烷上之后可使链状二有机(聚)硅氧烷类化合物(式(1))或环状二有机(聚)硅氧烷类化合物(式(2))或三有机硅烷类化合物(式(3))对波长范围为280-400nm的紫外光线具有吸收性能。如上所述,并且如上列式(4)的定义所示,该基团须带有至少一个对应于可保证将N,N’-草酰二苯胺(或草酰替苯胺)连接到(聚)硅氧烷链上或连接到硅烷上的链单元的亚烷基或亚烷氧基官能团。本发明化合物的优点之一在于可根据该滤光单元A所带有的各种取代基的性质和/或位置而获得既可纯粹滤出或滤除UV-A或相反纯粹滤出或滤除UV-B并且具有特别高的消光系数的滤光剂。
正如上列定义所示,链单元-(O)m-(CH2)P-CH(R2)-CH2-(即如式(5)所示二价基团-Y-)可根据本发明连接到来自N,N’-草酰二苯胺(或草酰替苯胺)的滤光单元上,该单元因而保证上列单元与(聚)硅氧烷链或硅烷链中的硅原子相连,该连接可按本发明在由N,N’-草酰二苯胺(或草酰替苯胺)的两个芳环中X和Z占据的位置中任何一个位置上进行,而所说链单元中的-(O)m-端部则与来自N,N’-草酰二苯胺(或草酰替苯胺)的单元相连,并且其-CH2-端部则与(聚)硅氧烷链或硅烷链中的硅原子相连。而且,应当强调的是:来自N,N’-草酰二苯胺(或草酰替苯胺)的滤光单元因而可具有单一的连接链单元(在Z是氢的情况下),或相反具有两条连接链单元(在Z是二价基团-Y-的情况下)并且因而可连到两条不同的(聚)硅氧烷链上或连到两个不同的甲硅烷基化单元上。
按照本发明,优选的是,在带有X的芳环中X处于该芳环的邻位或对位上。
同样,在Z是第二连接链单元-Y-的情况下,优选的是Z处于带有Z的芳环的邻位或对位上。
在上式(1)至(3)中,烷基可为直链或支链,尤其可选自甲基,乙基,正丙基,异丙基,正丁基,异丁基,叔丁基,正戊基,异戊基,新戊基,正己基,正庚基,正辛基,2-乙基己基和叔辛基。本发明中烷基R,R’和B优选是甲基,乙基,丙基,正丁基,正辛基和2-乙基己基。更为优选的是,基团R,R’和B均是甲基。烷氧基尤其可选自甲氧基,乙氧基,正丙氧基,异丙氧基,正丁氧基和异丁氧基。
在上式(1)至(3)的化合物中,优选用式(1)或式(2)的化合物,即链状或环状短链二有机硅氧烷。
本发明范围内的链状或环状二有机硅氧烷中,尤其优选至少具有下列定义之一,特别优选具有下列全部定义的无规衍生物或明确定义的嵌段衍生物:
R是烷基,优选是甲基,
B是烷基,优选是甲基(在式(1)的链状化合物情况下),
r是0-3(含0和3)(在式(1)的链状化合物情况下),
t是2-4(含2和4)(在式(2)的环状化合物情况下),
q是0或1,
R1是H(q=0)或甲氧基(q≠0),
p是0或1,
R2是H或甲基。
为了得到式(1)和(2)的(聚)硅氧烷滤光剂,可按普通程序(途径1)进行加氢甲硅烷基化(或叫氢化硅烷化)反应:其中用例如所有基团A均为氢的相应(聚)硅氧烷开始进行操作。这种起始(聚)硅氧烷以下称为含SiH的衍生物,SiH基可存在于(聚)硅氧烷链之中或端部。这些含SiH的衍生物是(聚)氧烷工业上已众所周知的产品并且一般可在市场上买到。这些化合物例如已在美国专利US3,220,972,US3,697,473和US4,340,709中作了说明。
因此,这种含SiH的衍生物可根据情况表示为下式(1bis):式中R,r和s同上式(1)定义,可相同或不同的基团B’选自基团R和氢原子,但应当注意到的是在s=0时,基团B’之一并且仅有一个应是氢原子,
所以,可在有效催化量铂催化剂存在下用式(1bis)或(2bis)所示含SiH的这种衍生物与选自下列式(4bis)所示化合物的N,N’-草酰二苯胺(或草酰替苯胺)有机衍生物进行普通的氢化硅烷化反应,式中R1和q同上式(4)定义,而X’不是上列式(5)的二价基团-Y-,在这种情况下是下式(5bis)的相应不饱和同系一价基团-Y’:式中R2,m和p同上式(5)定义,
Z’是上述一价基团-Y’。
在特别适合于本发明范围的上式(4bis)化合物中,可具体举出:
a)N,N’-双[4-(2-甲基烯丙氧基)苯基]草酰胺,
b)N,N’-双[2-(2-甲基烯丙氧基)苯基]草酰胺,以及
c)N,N’-双[2-烯丙氧基-5-甲氧基苯基)草酰胺。
上列式(4bis)的产品的适当制备方法尤其是已在专利FR-B-1,506,632和FR-B-1,516,276中作了说明。因此,根据这些专利所述,可按如下已知方法得到上述产品。
然后在第二步,用下式(7)的卤化物将所得衍生物烷基化:式中R2和p同上式(5)定义,而Hal是选自氯和溴的卤原子,因此得到式(4bis)中Z’是-Y’的要求衍生物。
2)对于非对称衍生物:反应式(6)所示获得衍生物的反应可分两步进行:(i)将草酸二甲酯或二乙酯与一当量含羟基的芳族胺反应,然后(ii)将(i)中所得产物与第二当量不含羟基的胺反应。(ii)所得反应产物然后再用上列式(7)的卤化物烷基化,因此可得到式(4bis)中Z’=H的要求衍生物。
3)式(5bis)中m是0的式(4bis)衍生物可用m=1的相应式(4bis)衍生物得到,其中经Claisen重排之后自由羟基用C1-C8烷基卤烷基化。
用于进行上式(1bis)或(2bis)的化合物与上式(4bis)的化合物之间的氢化硅烷化(加氢甲硅烷化)反应的铂催化剂已众所周知并已在文献中作了广泛的说明,其例子尤其可举出美国专利US3,159,601,US3,159,602,US3,220,972及欧洲专利申请EP-A-0,057,459,EP-A-0,188,978和EP-A-0,190,530中所述的铂和有机产品的配合物以及美国专利US3,419,593,US3,377,432和US3,814,730中所述铂和含乙烯基的有机聚硅氧烷的配合物。为了将式(1bis)或(2bis)的化合物与式(4bis)的化合物进行反应,铂催化剂的用量以金属铂重量计一般为5-600ppm,优选10-200ppm,均以式(1bis)或(2bis)的化合物重量为基准。该氢化硅烷化反应可在本体中进行或在挥发性有机溶剂如甲苯,庚烷,二甲苯,四氢呋喃或四氯乙烯中进行。在反应完成所要求的时间内一般要求将反应混合物加热到60-120℃的温度。式(1bis)或(2bis)的化合物也可滴加到式(4bis)的化合物在含催化剂的有机溶剂中的溶液中。式(1bis)或(2bis)的化合物和式(4bis)的化合物还可同时加到催化剂在有机溶剂中的悬浮体中。建议用醇中氢氧化钾测试剩余的SiH来检查反应是否已完全进行,然后去除溶剂,如经减压蒸馏去除溶剂。所得粗油状物例如要经过二氧化硅吸收柱而得以提纯。
至于上式(3)的三有机硅烷滤光剂的制备过程,可按上述进行该工艺过程,仍然是进行氢化硅烷化反应,这次用式(R’)3SiH(式(3bis)中R’同上式(3)定义)的起始硅烷与上式(4bis)的N,N’-草酰二苯胺(或草酰替苯胺)的有机衍生物反应。
如上所述,上式(1)至(3)的化合物针对紫外光线具有优异的固有滤光能力(根据产品的结构适用于UV-A和/或UV-B)以及优异的光稳定性。将不同结构的产品混合在一起,即具体地讲将本发明中纯粹具有UV-A滤光活性的产品与本发明中纯粹具有UV-B滤光活性的产品混合在一起,就可得到在整个UV范围(UV-A+UV-B)内均具有滤光活性的组合物,这是一大优点。此外,由于具有很高的脂溶性,所以上式(1)至(3)的化合物可以高浓度应用,从而使最终组合物达到极高的保护因子,而且这些化合物可均匀分散在含有至少一种脂肪相或化妆用有机溶剂的普通化妆载体中,因此可将其涂抹在皮肤或毛发上而形成有效的保护膜。最后,这些化合物的化妆性能很好,尤其是这些产品与现有的滤光性(聚)硅氧烷比起来不那么粘手并且更为柔和。
本发明主题还包括化妆组合物,其中于优选含至少一种脂肪相或有机溶剂的化妆用载体中含有有效量至少一种上式(1)至(3)的化合物。
式(1)至(3)的化合物用量以组合物总重量计一般为0.1-20wt%(重量百分比,下同),优选0.5-10wt%。
本发明化妆组合物可用作保护人体表皮或皮肤或毛发、使其不受紫外线照射的组合物,用作防阳光照射或防晒组合物或用作化妆产品。
该组合物尤其可制成洗液,增稠洗液,凝胶,乳膏,奶液,粉末或固体棒状形式,并且可任选调成气溶胶以及呈泡沫或喷剂形式。
该组合物还可以含有化妆领域中常用的化妆添加剂如脂肪物质,有机溶剂,(聚)硅氧烷,增稠剂,软化剂,补充防晒剂或光保护剂,防沫剂,润肤剂,香料,防腐剂,表面活性剂,填料,螯合剂,阴离子、阳离子、非离子或两性聚合物或其混合物,推进剂,碱化或酸化剂,染色剂,颜料或纤细颜料,尤其是旨在通过物理方式达到排除紫外线照射的补充光保护效果的添加剂,或任何其它常用于化妆品,特别是用于制造防晒组合物的成分。
有机溶剂中可举出低级醇和多元醇如乙醇,异丙醇,丙二醇,甘油和山梨(糖)醇。
脂肪物质可由油或蜡或其混合物,脂肪酸,脂肪酸酯,脂肪醇,凡士林,石蜡,羊毛脂,氢化羊毛脂或乙酰化羊毛脂构成。油可选自动物,植物,矿物或合成油,尤其是氢化棕榈油,氢化蓖麻油,凡士林油,石蜡油,Purcellin油,挥发性或非挥发性(聚)硅氧烷油和异链烷烃。
更具体地讲,本发明化妆组合物用于保护人体表皮或皮肤、使其不受紫外光照射或用作防晒的组合物时,可将其在溶剂或脂肪物质中制成悬浮体或分散体形式,或制成乳液形式(尤其是H/E(水包油)或E/H(油包水),但优选H/E类形式)如乳膏或雪花膏或奶液,或制成脂囊体或脂质分散体,香脂或软膏,凝胶,固体棒或气溶胶形式。乳液另外还可含有阴离子、非离子、阳离子或两性表面活性剂。
本发明化妆组合物用于保护毛发时,可将其制成洗发膏,洗发液或护发素,定型胶或有待冲洗,或有待在洗发前后,将毛发染色或脱色前后,将毛发卷成或烫成波浪形或拉直之前,之间或之后进行涂抹的组合物形式,或制成制做发式或治疗或处理用洗剂或发胶,梳理或定型用洗剂或发胶,洗发或护发浆,电烫毛发或将毛发拉直所用组合物或将头发染色或脱色所用的组合物形式。
本发明化妆组合物用作睫毛,眉毛,皮肤或毛发的化妆品如处理皮肤的乳液或雪花膏,染色或化妆底霜,唇膏,眼睑或眼影膏,面部化妆品,俗称“eye-liner”的眼线膏,mascara或染色凝胶时,可将其制成固体或浆糊状无水或含水形式如水包油或油包水乳液,悬浮液或胶料。
本发明主题还包括保护皮肤和毛发、使其不受紫外线照射,尤其是不受阳光照射的方法,其中在皮肤或毛发上涂抹有效量的上述化妆组合物或上式(1),(2)或(3)的化合物。
以下实施例说明本发明,但并不限制本发明。
实施例1
该实施例说明N,N’-双{4-[3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]二硅氧烷基]-2-甲基丙氧基]苯基}草酰胺,即本发明下式化合物的制备方法:(该产品对应于式(1)中R=B=甲基;r=0,s=1;q=0,X=Z=-Y-(对位)且Y中m=p=1和R2=甲基的化合物)。
a)第一步
将对氨基苯酚(109g;1mol),草酸二甲酯(59g;0.5mol)和500ml邻二氯苯放入装备齐全的圆底烧瓶中,混合物140℃加热4小时,生成的甲醇蒸发后,170℃持续加热1小时,冷却后将反应混合物过滤,因此得到的蓝色糊状物先用甲苯后用乙醇洗涤,之后真空干燥,最后得到61g(收率:44%)N,N’-双(4-羟基苯基)草酰胺,其特征如下:
灰紫色粉状
Pf(熔点):>250℃
b)第二步
将27.2g上述产物,200ml无水DMSO和28g碳酸钾加入装备齐全的圆底烧瓶中。混合物在氮气中加热到65℃。然后20分钟内向其中滴加入甲基烯丙基氯(20g;0.22mol)。混合物在氮气中65℃下持续搅拌6小时。冷却后加入200ml甲醇。所得固体滤出后用甲醇洗涤并用400mlDMF重结晶而得到14.3gN,N’-双[4-(2-甲基烯丙氧基)苯基]草酰胺,其特征如下:
白色粉状
Pf:239-240℃
c)第三步
将7.6g(即0.02mol)上述产物和16ml甲苯加入装备齐全的圆底烧瓶中。混合物在氮气中加热到80℃。然后加入氢化硅烷化催化剂(环状乙烯基甲基硅氧烷中含3-3.5%Pt的配合物,得自Hüls Petrarch PC085,100μl),之后再加入9.79g七甲基三硅氧烷。氮气中80℃下6小时后将反应介质浓缩并用二氧化硅在压力下进行色层分离(洗涤液:CH2Cl2/庚烷60/40)而回收得到16.5g(收率:78%)要求的最终产物,其特征如下:
白色粉状
Pf:84-86℃
元素分析:
理论值:C 52.38 H 8.30 N 3.39 Si 20.41
实测值:C 52.58 H 8.34 N 3.37 Si 19.93
该产品的UV吸收特性(乙醇中测定)如下:
λmax=293nm εmax=23,000
该产品可极其有效地用作在UV-B范围内具有活性的防晒剂或光保护剂。
实施例2
该实施例说明N,N’-双{2-[3-[1,3,3,3-四甲基-1-[(三甲基甲硅烷基)氧基]二硅氧烷基]-2-甲基丙氧基]苯基}草酰胺,即本发明下式化合物的制备方法:(该产品对应于式(1)中R=B=甲基;r=0,s=1;q=0;X=Z=-Y-(邻位)且Y中m=p=1和R2=甲基的化合物)。
a)第一步
将邻氨基苯酚(65.5g;0.6mol),草酸二甲酯(35.4g;0.3mol)和300ml1,2-二氯苯放入装备齐全的圆底烧瓶中,混合物140℃加热4小时,生成的甲醇蒸发后,170℃持续加热1小时,冷却后将反应混合物过滤,得到的固体用乙醇洗涤,因此回收得到69.8g(收率:85%)N,N’-双(2-羟基苯基)草酰胺,其特征如下:
浅灰褐色粉状
Pf(熔点):>250℃
b)第二步
将59.8g上述产物,440ml无水DMSO和61.6g碳酸钾加入装备齐全的圆底烧瓶中。混合物在氮气中加热到65℃。然后30分钟内向其中滴加入甲基烯丙基氯(43.8g;0.484mol)。混合物在氮气中65℃下持续搅拌4小时。冷却后加入200ml甲醇。所得固体滤出后先用甲醇后用水,之后再用甲醇洗涤而得到77.4gN,N’-双[2-(2-甲基烯丙氧基)苯基]草酰胺,其特征如下:
淡灰褐色粉状
Pf:184℃
c)第三步
将19g(即0.05mol)上述产物和30ml甲苯加入装备齐全的圆底烧瓶中。混合物在氮气中加热到80℃。然后加入氢化硅烷化催化剂(环状乙烯基甲基硅氧烷中含3-3.5%Pt的配合物,得自Hüls Petrarch PC085,100μl),之后再加入24.5g七甲基三硅氧烷。氮气中回流3小时后将反应介质浓缩并用甲醇重结晶而回收得到28g(收率:68%)要求的最终产物,其特征如下:
白色粉状
Pf:77℃
元素分析:
理论值:C 52.38 H 8.30 N 3.39 Si 20.41
实测值:C 52.36 H 8.27 N 3.56 Sil 19.15
该产品的UV吸收特性(乙醇中测定)如下:
λmax=307nm εmax=18,425
该产品可极其有效地用作在UV-B范围内具有活性的防晒剂或光保护剂。
实施例3
以下列出本发明防晒化妆组合物或光保护性化妆组合物,即水包油类防晒香脂的具体配方:
实施例1的化合物 3g
鲸蜡基硬脂醇和用33mol EO氧乙
烯化或环氧乙烷化的鲸蜡基硬脂醇
(TENSIA的“DEHSCONET 390”)的混合物 8g
非自乳化的甘油一和二硬脂酸
酯的混合物 1.5g
鲸蜡醇 1.5g
苯甲酸C12-C15烷基酯(FINETEX的“FINSOLV TN”) 12g
聚二甲基硅氧烷(Rhone-Poulenc的“SILBIONE HUILE
70 047 V 300) 1g
对甲氧基肉桂酸2-乙基己基酯
(Givaudan-Roure以商名“PARSOL MCX”
销售的补充防晒剂或光保护剂) 5g
纤细颜料级二氧化钛(TAYCA的“MT 100 T”) 1g
甘油 15g
苯-1,4-二(3-亚甲基-10-樟脑磺酸)
(FR-2,528,420所述的补充防晒剂或光保护剂) 6.06g
三乙醇胺 1.2g
香料,防腐剂 qs(适量)
水 qsp(适量至) 100g
可按制备乳液的普通工艺得到该香脂,其中将脂溶性滤光剂溶于含有乳化剂的脂肪相中,将该脂肪相加热到约70-80℃后充分搅拌条件下加入已加热到同一温度的水。持续搅拌10-15分钟后温和搅拌条件下放冷,达到40℃后再加入香料和防腐剂。
实施例4
以下列出本发明防晒化妆组合物或光保护性化妆组合物,即水包油类防晒奶液或乳液的具体配方:
实施例1的化合物 2g
鲸蜡基硬脂醇和用33mol EO氧乙
烯化或环氧乙烷化的鲸蜡基硬脂醇
(TENSIA的“DEHSCONET390”)的混合物 3g
非自乳化的甘油一和二硬脂酸
酯的混合物 1g
鲸蜡醇 1g
苯甲酸C12-C15烷基酯(FINTEX的“FINSOLV TN”) 9g
聚二甲基硅氧烷(Rhone-Poulenc的“SILBIONE HUILE
70 047 V 300) 1g
2-氰基-3,3-二苯基丙烯酸2-乙基己基酯
(BASF以商名“UNINUL N 539”
销售的补充防晒剂或光保护剂 6g
4-叔丁基-4’-甲氧基二苯甲酰甲烷
(Givaudan-Roure以商名“PARSOL 1789”
销售的补充防晒剂或光保护剂) 2g
甘油 15g
香料,防腐剂 qs(适量)
水 qsp(适量至) 100g
可按制备乳液的普通工艺得到该奶液或乳液,其中将脂溶性滤光剂溶于含有乳化剂的脂肪相中,将该脂肪相加热到约70-80℃后充分搅拌条件下加入已加热到同一温度的水。持续搅拌10-15分钟后温和搅拌条件下放冷,达到40℃后再加入香料和防腐剂。
Claims (13)
2.权利要求1的化合物,其特征在于X处于带有该基团的芳环中的邻位或对位。
3.权利要求1的化合物,其特征在于Z是二价基团-Y-并且处于带有该基团的芳环中的邻位或对位。
4.权利要求2的化合物,其特征在于Z是二价基团-Y-并且处于带有该基团的芳环中的邻位或对位。
5.权利要求1-4中任何一项的化合物,其特征在于q等于1,并且R1是甲氧基。
6.权利要求1-4中任何一项的化合物,其特征在于q等于0。
7.滤除紫外光的化妆组合物,其特征在于其中于化妆用载体中包括有效量的至少一种权利要求1-6中任何一项所定义的化合物。
8.权利要求7的化妆组合物,其特征在于所说化妆用载体含有至少一种脂肪相或有机溶剂。
9.权利要求8的化妆组合物,其特征在于所说化妆用载体呈水包油或油包水类乳液形式。
10.权利要求9的化妆组合物,其特征在于所说化妆用载体呈水包油类乳液形式。
11.权利要求7-10中任何一项的化妆组合物,其特征在于滤光化合物含量按组合物总重量计为0.1-20wt%。
12.权利要求11的化妆组合物,其特征在于所说含量为0.5-10wt%。
13.权利要求1-6中任何一项所定义的化合物作为在UV-A和/或UV-B范围内具有活性的防晒剂或光保护剂的用途。
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FR9413770A FR2727114B1 (fr) | 1994-11-17 | 1994-11-17 | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
FR9413770 | 1994-11-17 |
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FR2726562B1 (fr) * | 1994-11-08 | 1996-12-27 | Oreal | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
FR2727115B1 (fr) * | 1994-11-17 | 1996-12-27 | Oreal | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
FR2727113B1 (fr) * | 1994-11-17 | 1996-12-27 | Oreal | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
FR2767689B1 (fr) * | 1997-08-26 | 1999-10-15 | Oreal | Utilisation de derives oxamates comme agents depigmentants |
US6036946A (en) | 1997-12-24 | 2000-03-14 | Shaklee Corporation | Methods for protecting skin from damaging effects of ultraviolet light |
US6146664A (en) * | 1998-07-10 | 2000-11-14 | Shaklee Corporation | Stable topical ascorbic acid compositions |
US6462168B1 (en) | 2001-04-25 | 2002-10-08 | General Electric Company | Weatherable polycarbonates comprising oxanilide structural units, method, and articles made therefrom |
WO2003030856A1 (en) * | 2001-10-08 | 2003-04-17 | Roche Vitamins Ag | Siloxane sunscreen compositions |
CN101182372B (zh) * | 2002-07-05 | 2010-12-01 | 沙伯基础创新塑料知识产权有限公司 | 含n,n'-草酰二苯胺结构单元的耐气候性聚碳酸酯、其制造方法及由其制得的制品 |
US7576170B2 (en) * | 2003-12-19 | 2009-08-18 | Momentive Performance Materials | Cyclic siloxane compositions for the release of active ingredients |
US7767754B2 (en) | 2005-11-08 | 2010-08-03 | Momentive Performance Materials Inc. | Silicone composition and process of making same |
US7479522B2 (en) | 2005-11-09 | 2009-01-20 | Momentive Performance Materials Inc. | Silicone elastomer composition |
FR2908769B1 (fr) * | 2006-11-17 | 2008-12-26 | Oreal | Nouveaux composes derives dithiolanes silicies et leur utilisation |
CN101796017A (zh) * | 2007-09-21 | 2010-08-04 | 塞诺菲-安万特股份有限公司 | (羧基亚烷基苯基)苯基草酰胺、其生产方法以及作为药物的用途 |
EP2311844A1 (en) * | 2009-10-15 | 2011-04-20 | Interquim, S.A. | Silyl polymeric benzoic acid ester compounds, uses, and compositions thereof |
KR101860085B1 (ko) * | 2009-11-25 | 2018-05-21 | 다우 실리콘즈 코포레이션 | 휘발성 고리형 실록산 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5198498A (en) * | 1990-02-06 | 1993-03-30 | Ciba-Geigy Corporation | Light-stabilized binders for coating compositions |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3068153A (en) * | 1958-11-13 | 1962-12-11 | Union Carbide Corp | Sunburn preventive compositions |
US3159602A (en) | 1962-06-07 | 1964-12-01 | Olin Mathieson | Preparation of polymeric phosphates |
US3220972A (en) | 1962-07-02 | 1965-11-30 | Gen Electric | Organosilicon process using a chloroplatinic acid reaction product as the catalyst |
US3159601A (en) | 1962-07-02 | 1964-12-01 | Gen Electric | Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes |
NL133821C (zh) | 1964-07-31 | |||
NL131800C (zh) | 1965-05-17 | |||
CH500259A (de) * | 1967-04-11 | 1970-12-15 | Ciba Geigy Ag | Verwendung von Bis-oxalsäurediamiden als Ultraviolettabsorptionsmittel ausserhalb der Textilindustrie |
US3906041A (en) * | 1968-02-19 | 1975-09-16 | Sandoz Ltd | Oxalic acid derivatives |
CH511806A (de) * | 1968-02-19 | 1971-08-31 | Sandoz Ag | Vunfahren zur Herstellung neuer asymmetrischer Diaryloxalamide und deren Verwendung als Stabilisatoren und UV-Absorder für Kunststoffe |
US3814730A (en) | 1970-08-06 | 1974-06-04 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
US3697473A (en) | 1971-01-04 | 1972-10-10 | Dow Corning | Composition curable through si-h and si-ch equals ch2 with improved properties |
US4340709A (en) | 1980-07-16 | 1982-07-20 | General Electric Company | Addition curing silicone compositions |
US4394317A (en) | 1981-02-02 | 1983-07-19 | Sws Silicones Corporation | Platinum-styrene complexes which promote hydrosilation reactions |
FR2575086B1 (fr) | 1984-12-20 | 1987-02-20 | Rhone Poulenc Spec Chim | Complexe platine-alcenylcyclohexene comme catalyseur de reaction d'hydrosilylation et son procede de preparation |
FR2575085B1 (fr) | 1984-12-20 | 1987-02-20 | Rhone Poulenc Spec Chim | Complexe platine-triene comme catalyseur de reaction d'hydrosilylation et son procede de preparation |
GB8608315D0 (en) * | 1986-04-04 | 1986-05-08 | Sandoz Ltd | Organic compounds |
IT1262915B (it) * | 1992-01-14 | 1996-07-22 | Enichem Sintesi | Stabilizzanti ossammidici |
FR2695560B1 (fr) * | 1992-09-17 | 1994-11-04 | Oreal | Composition cosmétique filtrante photostable contenant un filtre UV-A et un polymère filtre du type silicone benzotriazole. |
FR2727115B1 (fr) * | 1994-11-17 | 1996-12-27 | Oreal | Nouveaux filtres solaires, compositions cosmetiques photoprotectrices les contenant et utilisations |
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1995
- 1995-10-16 AT AT95402308T patent/ATE162793T1/de active
- 1995-10-16 EP EP95402308A patent/EP0712856B1/fr not_active Expired - Lifetime
- 1995-10-16 ES ES95402308T patent/ES2117369T3/es not_active Expired - Lifetime
- 1995-10-16 DE DE69501542T patent/DE69501542T2/de not_active Expired - Fee Related
- 1995-10-20 AU AU34381/95A patent/AU678912B2/en not_active Ceased
- 1995-10-26 ZA ZA959068A patent/ZA959068B/xx unknown
- 1995-11-01 BR BR9504906A patent/BR9504906A/pt not_active IP Right Cessation
- 1995-11-08 MX MX9504682A patent/MX9504682A/es unknown
- 1995-11-14 JP JP7295823A patent/JP2821404B2/ja not_active Expired - Fee Related
- 1995-11-15 AR AR33424095A patent/AR000135A1/es unknown
- 1995-11-16 RU RU95120189A patent/RU2126010C1/ru not_active IP Right Cessation
- 1995-11-16 PL PL95311398A patent/PL181211B1/pl unknown
- 1995-11-16 CA CA002163072A patent/CA2163072C/fr not_active Expired - Fee Related
- 1995-11-16 HU HU9503280A patent/HUT74043A/hu unknown
- 1995-11-16 CN CN95120079A patent/CN1050363C/zh not_active Expired - Fee Related
- 1995-11-17 KR KR1019950041963A patent/KR100217969B1/ko not_active IP Right Cessation
- 1995-11-17 US US08/560,489 patent/US5587151A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5198498A (en) * | 1990-02-06 | 1993-03-30 | Ciba-Geigy Corporation | Light-stabilized binders for coating compositions |
Also Published As
Publication number | Publication date |
---|---|
MX9504682A (es) | 1997-04-30 |
AU3438195A (en) | 1996-05-23 |
HU9503280D0 (en) | 1996-01-29 |
KR960016879A (ko) | 1996-06-17 |
PL181211B1 (pl) | 2001-06-29 |
AU678912B2 (en) | 1997-06-12 |
JP2821404B2 (ja) | 1998-11-05 |
DE69501542D1 (de) | 1998-03-05 |
CN1131671A (zh) | 1996-09-25 |
RU2126010C1 (ru) | 1999-02-10 |
BR9504906A (pt) | 1997-09-02 |
EP0712856A1 (fr) | 1996-05-22 |
ZA959068B (en) | 1996-05-17 |
CA2163072C (fr) | 2000-06-06 |
US5587151A (en) | 1996-12-24 |
FR2727114A1 (fr) | 1996-05-24 |
JPH08208669A (ja) | 1996-08-13 |
ATE162793T1 (de) | 1998-02-15 |
CA2163072A1 (fr) | 1996-05-18 |
EP0712856B1 (fr) | 1998-01-28 |
ES2117369T3 (es) | 1998-08-01 |
AR000135A1 (es) | 1997-05-21 |
FR2727114B1 (fr) | 1996-12-27 |
DE69501542T2 (de) | 1998-05-14 |
HUT74043A (en) | 1996-10-28 |
KR100217969B1 (ko) | 1999-10-01 |
PL311398A1 (en) | 1996-05-27 |
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