CN102046141A - 皮肤外用剂 - Google Patents
皮肤外用剂 Download PDFInfo
- Publication number
- CN102046141A CN102046141A CN2009801197118A CN200980119711A CN102046141A CN 102046141 A CN102046141 A CN 102046141A CN 2009801197118 A CN2009801197118 A CN 2009801197118A CN 200980119711 A CN200980119711 A CN 200980119711A CN 102046141 A CN102046141 A CN 102046141A
- Authority
- CN
- China
- Prior art keywords
- acid
- poe
- salt
- ether
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 50
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 44
- 239000002211 L-ascorbic acid Substances 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 235000000069 L-ascorbic acid Nutrition 0.000 claims abstract description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 75
- 239000000203 mixture Substances 0.000 claims description 48
- -1 fatty acid ester Chemical class 0.000 abstract description 162
- 239000000194 fatty acid Substances 0.000 abstract description 43
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 40
- 229930195729 fatty acid Natural products 0.000 abstract description 40
- 150000001875 compounds Chemical class 0.000 abstract description 31
- 229930006000 Sucrose Natural products 0.000 abstract description 14
- 239000005720 sucrose Substances 0.000 abstract description 14
- QYIXCDOBOSTCEI-QCYZZNICSA-N (5alpha)-cholestan-3beta-ol Chemical compound C([C@@H]1CC2)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CCCC(C)C)[C@@]2(C)CC1 QYIXCDOBOSTCEI-QCYZZNICSA-N 0.000 abstract description 6
- 150000005215 alkyl ethers Chemical class 0.000 abstract description 5
- QYIXCDOBOSTCEI-UHFFFAOYSA-N alpha-cholestanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 QYIXCDOBOSTCEI-UHFFFAOYSA-N 0.000 abstract description 5
- 125000002328 sterol group Chemical group 0.000 abstract description 4
- 150000003712 vitamin E derivatives Chemical class 0.000 abstract description 4
- 229930188104 Alkylresorcinol Natural products 0.000 abstract description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical group OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 abstract 1
- IFVWLEMMYISKHW-UHFFFAOYSA-N 4-(2-methylpropyl)benzene-1,3-diol Chemical compound CC(C)CC1=CC=C(O)C=C1O IFVWLEMMYISKHW-UHFFFAOYSA-N 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 62
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 58
- 239000000843 powder Substances 0.000 description 46
- 239000000284 extract Substances 0.000 description 44
- 229960001755 resorcinol Drugs 0.000 description 41
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- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 33
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 24
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- 235000011187 glycerol Nutrition 0.000 description 21
- ZGSCRDSBTNQPMS-UJURSFKZSA-N 3-O-Ethylascorbic acid Chemical compound CCOC1=C(O)C(=O)O[C@@H]1[C@@H](O)CO ZGSCRDSBTNQPMS-UJURSFKZSA-N 0.000 description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
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- 230000004075 alteration Effects 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 16
- 239000004205 dimethyl polysiloxane Substances 0.000 description 16
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 16
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- 239000002585 base Substances 0.000 description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 238000013329 compounding Methods 0.000 description 14
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- 235000002378 plant sterols Nutrition 0.000 description 13
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 13
- 239000000454 talc Substances 0.000 description 13
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- 239000012138 yeast extract Substances 0.000 description 13
- 229940058015 1,3-butylene glycol Drugs 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
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- 238000004519 manufacturing process Methods 0.000 description 12
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- 229910052618 mica group Inorganic materials 0.000 description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 12
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- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 11
- 229920000945 Amylopectin Polymers 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 239000006071 cream Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- KBJXDTIYSSQJAI-UHFFFAOYSA-N propylcarbamic acid Chemical compound CCCNC(O)=O KBJXDTIYSSQJAI-UHFFFAOYSA-N 0.000 description 11
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 11
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 11
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical group OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 10
- 239000004375 Dextrin Substances 0.000 description 10
- 229920001353 Dextrin Polymers 0.000 description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Natural products C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 10
- 235000019425 dextrin Nutrition 0.000 description 10
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 9
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- 235000021355 Stearic acid Nutrition 0.000 description 9
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 9
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 9
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- RUHCWQAFCGVQJX-RVWHZBQESA-N (3s,8s,9s,10r,13r,14s,17r)-3-hydroxy-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-1-one Chemical group C1C=C2C[C@H](O)CC(=O)[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 RUHCWQAFCGVQJX-RVWHZBQESA-N 0.000 description 8
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 8
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Abstract
本发明提供一种温度稳定性(尤其是高温稳定性)、光稳定性优异的皮肤外用剂,该皮肤外用剂含有烷基间苯二酚类。一种皮肤外用剂,其含有:0.01~5质量%的(a)4-异丁基间苯二酚或其盐、和0.01~5质量的(b)选自L-抗坏血酸或其盐、3-O-烷基-L-抗坏血酸或其盐中的1种或2种以上。还可以根据期望配合(c)选自(c-1)具有甾醇骨架的化合物(例如,POE植物甾醇类、POE胆甾烷醇类等);(c-2)维生素E衍生物;(c-3)聚甘油脂肪酸酯、聚氧丁烯聚甘油烷基醚、蔗糖脂肪酸酯等化合物;及(c-4)具有失水山梨醇骨架的化合物中的1种或2种以上化合物。
Description
技术领域
本发明涉及皮肤外用剂。进一步具体而言,涉及温度稳定性(尤其是高温稳定性)、光稳定性优异的皮肤外用剂,该皮肤外用剂含有烷基间苯二酚类。
背景技术
已知烷基间苯二酚类具有黑色素产生抑制作用和抗菌作用,为了达到美白、抗菌等目的而被含有在化妆品中(例如,参照专利文献1~2)。作为具有美白效果的物质,除了上述烷基间苯二酚类以外,还已知有L-抗坏血酸、L-抗坏血酸衍生物,从而还提出了含有烷基间苯二酚类、L-抗坏血酸类(=L-抗坏血酸、L-抗坏血酸衍生物)等的皮肤外用剂(例如,参照专利文献3~4)。但是,烷基间苯二酚类、L-抗坏血酸类均存在容易因温度、光而发生变色的问题,到目前为止,有关有效抑制烷基间苯二酚类、L-抗坏血酸类的变色的技术还未充分得以研究。
现有技术文献
专利文献
专利文献1:日本特开平2-049715号公报
专利文献2:日本特开平4-169511号公报
专利文献3:日本特开2004-277352号公报
专利文献4:日本特开2005-120023号公报
发明内容
发明要解决的问题
本发明的目的在于提供温度稳定性(尤其是高温稳定性)、光稳定性优异的皮肤外用剂,该皮肤外用剂含有烷基间苯二酚类、L-抗坏血酸类。
用于解决问题的方案
为了解决上述问题,本发明人等反复进行了深入研究,结果发现,虽然在仅配合烷基间苯二酚类、L-抗坏血酸类中的任一者时,均会因温度、光而发生变色,但是通过分别组合特定量的烷基间苯二酚类中的尤其是4-异丁基间苯二酚或其盐和L-抗坏血酸类中的尤其是L-抗坏血酸或其盐、3-O-烷基-L-抗坏血酸或其盐,能够发挥出非常优异的光稳定性效果、温度(高温)稳定性效果,从而完成了本发明。
即,本发明涉及一种皮肤外用剂,其含有:0.01~5质量%的(a)4-异丁基间苯二酚或其盐、和0.01~5质量%的(b)选自L-抗坏血酸或其盐、3-O-烷基-L-抗坏血酸或其盐中的1种或2种以上。
上述中,(b)成分为3-O-烷基-L-抗坏血酸或其盐的方式是优选的。
发明的效果
根据本发明,能够提供温度稳定性(尤其是高温稳定性)、光稳定性优异的皮肤外用剂,该皮肤外用剂含有烷基间苯二酚类、L-抗坏血酸衍生物。
具体实施方式
以下,详细说明本发明。另外,以下中,“POE”表示聚氧乙烯,“POP”表示聚氧丙烯。
本发明中使用的作为(a)成分的4-异丁基间苯二酚或其盐为下述式(I)所示的化合物或其盐。
作为上述式(I)所示的4-异丁基间苯二酚的盐,没有特别的限定,可列举出例如钠盐、钾盐、锂盐等碱金属盐,镁盐、钙盐等碱土金属盐,以及铵盐、氨基酸盐等。但是并非限定于这些列举的例子。
在本发明皮肤外用剂中,(a)成分的配合量为0.01~5质量%,优选为0.1~3质量%,更优选为0.1~1质量%。配合量低于0.01质量%时,美白效果、抗菌效果等不足,另一方面,从对皮肤的刺激性的方面等来看,超过5质量%的配合是不优选的。
本发明中使用的(b)成分为选自L-抗坏血酸或其盐、3-O-烷基-L-抗坏血酸或其盐中的1种或2种以上。作为3-O-烷基-L-抗坏血酸或其盐,可列举出例如3-O-甲基-L-抗坏血酸、3-O-乙基-L-抗坏血酸、3-O-正丙基-L-抗坏血酸、3-O-异丙基-L-抗坏血酸、3-O-正丁基-L-抗坏血酸、3-O-异丁基-L-抗坏血酸、3-O-叔丁基-L-抗坏血酸、3-O-正戊基-L-抗坏血酸、3-O-正己基-L-抗坏血酸、3-O-正庚基-L-抗坏血酸、3-O-正辛基-L-抗坏血酸、3-O-正壬基-L-抗坏血酸等L-抗坏血酸的3-O-烷基醚或它们的盐等。
作为盐,没有特别的限定,可列举出例如钠盐、钾盐、锂盐等碱金属盐,镁盐、钙盐等碱土金属盐,以及铵盐,氨基酸盐等。但是,并非限定于这些列举的例子。
本发明中,3-O-烷基-L-抗坏血酸或其盐尤其最优选3-O-C1-6烷基-L-抗坏血酸或其盐。
在本发明皮肤外用剂中,(b)成分的配合量为0.01~5质量%,优选为0.05~3质量%,尤其优选为0.1~3质量%。配合量低于0.01质量%时,对温度稳定性的贡献不足,另一方面,在对皮肤的刺激性的方面等来看,超过5质量%的配合是不优选的。
本发明皮肤外用剂通过组合上述(a)成分、(b)成分,不仅有效抑制(a)成分和(b)成分这两种成分的变色即温度稳定性(高温稳定性)优异,而且尤其是抑制由日光、氙引起的变色的效果非常优异。
本发明中,从光稳定性的方面来看,作为(c)成分,还可以根据期望使用选自(c-1)具有甾醇骨架的化合物、(c-2)维生素E衍生物、(c-3)式(II)(后述)所示的化合物、及(c-4)具有失水山梨醇骨架的化合物中的1种或2种以上化合物。也可以使用这些各化合物的盐。
作为(c-1)成分即具有甾醇骨架的化合物,可列举出在植物甾醇类、植物甾烷醇(phytostanol)类、胆甾烷醇类、胆甾醇醚类等上加成聚合了环氧乙烷(EO)、环氧丙烷(PO)等而成的化合物等。这些化合物可以用下述式(IV)来表示。
式(IV)中,R5表示植物甾醇残基、植物甾烷醇残基、胆甾烷醇残基、胆甾醇醚残基中的任一种,s表示0~100的数值,t表示5~100的数值。
作为上述具有胆甾醇骨架的化合物的具体例,可列举出例如POE(5)植物甾醇、POE(10)植物甾醇、POE(20)植物甾醇、POE(25)植物甾醇、POE(30)植物甾醇等聚氧乙烯植物甾醇类;POE(20)植物甾烷醇、POE(25)植物甾烷醇及POE(30)植物甾烷醇等聚氧乙烯植物甾烷醇类;POE(20)胆甾烷醇、POE(25)胆甾烷醇、POE(30)胆甾烷醇等聚氧乙烯胆甾烷醇类;POE(5)胆甾醇醚、POE(10)胆甾醇醚、POE(15)胆甾醇醚、POE(20)胆甾醇醚、POE(24)胆甾醇醚、POE(30)胆甾醇醚等聚氧乙烯胆甾醇醚类等。其中,从光稳定性的方面来看,优选POE(20)植物甾醇、POE(30)植物甾醇、POE(30)胆甾烷醇等,尤其优选POE(30)植物甾醇。
作为(c-2)成分即维生素E衍生物,没有特别的限定,但优选使用例如下述式(V)或(VI)所示的化合物。
上述式(V)或(VI)中,各取代基表示以下含义。另外,式中,EO表示氧亚乙基,PO表示氧亚丙基,BO表示氧亚丁基。
R6、R7、R8分别独立地表示氢原子或甲基。作为R6、R7、R8的优选组合,可列举出R6、R7和R8表示甲基的组合(5,7,8-三甲基体。原料维生素E为α-生育酚的情况);R6和R8表示甲基、R7表示氢原子的组合(5,8-二甲基体。原料维生素E为β-生育酚的情况);R6表示氢原子、R7和R8表示甲基的组合(7,8-二甲基体。原料维生素E为γ-生育酚的情况)或者R6和R7表示氢原子、R8表示甲基的组合(8-甲基体。原料维生素E为δ-生育酚的情况)。
R9表示氢原子、碳原子数1~6的烷酰基、碳原子数1~6的烷基、SO3H基、P(O)(OH)2基、CH2COOH基或COCH2CH(SO3H)COOH基。
上述碳原子数1~6的烷酰基可以为直链状或支链状任一种,具体而言,可列举出例如乙酰基、丙酰基、丁酰基、异丁酰基、新戊酰基等,其中,优选乙酰基、丙酰基、新戊酰基等,从合成的方面来看,尤其优选乙酰基。
上述碳原子数1~6的烷基可以为直链状或支链状任一种,具体而言,可列举出例如甲基、乙基、丙基、丁基、异丁基、叔丁基、戊基、己基等,其中,优选甲基、乙基、丙基、丁基等,从合成的方面来看,尤其优选甲基、乙基。
SO3H基、P(O)(OH)2基、CH2COOH基或COCH2CH(SO3H)COOH基可以与碱结合而形成盐。作为碱,只要是毒性低、不影响上述式(V)或(VI)所示的维生素E衍生物的抗氧化活性和保湿性等,则没有特别的限定。作为此类盐,可列举出例如钠盐、钾盐、锂盐等碱金属盐;钙盐、镁盐等碱土金属盐;铝盐、铁盐、锌盐、铜盐、镍盐、钴盐等金属盐;铵盐等无机盐;叔辛基胺盐、二苄基胺盐、吗啉盐、葡糖胺盐、苯基甘氨酸烷基酯盐、乙二胺盐、N-甲基葡糖胺盐、胍盐、二乙基胺盐、三乙基胺盐、二环己基胺盐、N,N’-二苄基乙二胺盐、氯普鲁卡因盐、普鲁卡因盐、二乙醇胺盐、N-苄基-苯乙基胺盐、哌嗪盐、四甲基铵盐、三(羟甲基)氨基甲烷盐等有机盐等胺盐。但是,并非限定于这些列举的例子。其中,从合成的方面来看,优选碱金属盐、碱土金属盐、铵盐等,更优选钠盐、钾盐、1/2镁盐、1/2钙盐、铵盐等,尤其优选钠盐、铵盐。
k、y分别表示0~30的数值,优选为0~25,尤其优选为0~20(其中,k和y不同时为0)。x表示1~30的数值,优选为1~10,尤其优选为1~5。作为尤其优选的k、x、y的组合,可列举出k、y分别为0~20(其中,k和y不同时为0)、x为1~5的组合。
(c-3)成分为下述式(II)所示的化合物。
式(II)中,R2表示碳原子数12~22的直链状或支链状的烷基或烯基。
n表示0或1的数值。q表示1~3的整数,q=1时R3表示下述式(III)所示基团或糖残基,q=2或3时R3表示糖残基。
式(III)中,R4表示氢原子或碳原子数12~22的脂肪族酰基,m、p分别独立地表示0~40的整数,且m+p≥5。
作为上述式(II)所示的化合物,作为优选的化合物,可列举出聚甘油脂肪酸酯、聚氧丁烯聚甘油烷基醚、蔗糖脂肪酸酯等。
作为聚甘油脂肪酸酯的聚甘油的部分,可优选列举出甘油的5~20聚体,作为脂肪酸部分,可优选列举出月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸、亚油酸或山萮酸等。即,上述式(II)中,n=1,q=1,R3为式(III)所示的基团(其中,式中,m=5~20,p=0),作为R2,优选月桂基、肉豆蔻基、棕榈基、硬脂基、油基、亚油基(linolyl)等。优选酯化度为每1分子平均1~3、且具有至少3个自由的羟基的方式。即,在式(II)所示的聚甘油脂肪酸酯中,R3为式(III)所示的基团(式中,m=5~20、p=0的聚甘油部分),聚甘油部分的1~3个R4表示碳原子数12~22的脂肪族酰基,至少3个R4为氢。另外,作为R4的碳原子数12~22的脂肪族酰基,优选月桂酰基、肉豆蔻酰基、棕榈酰基、硬脂酰基、油酰基、亚油酰基(linoloyl)等。
已市售有大量的此类聚甘油脂肪酸酯,作为尤其优选的聚甘油脂肪酸酯,可优选列举出市售品中的十甘油单月桂酸酯、十甘油单油酸酯、十甘油单硬脂酸酯等。
作为聚氧丁烯聚甘油烷基醚,优选氧化丁烯基的加成摩尔数(平均聚合度)平均为10~20、聚甘油的平均加成摩尔数(平均聚合度)为10~20的聚氧丁烯聚甘油烷基醚。即,式(II)中,n=0,q=1,R3为式(III)所示的基团(式中,m=10~20,p=10~20),作为R2,优选硬脂基、油基等。
上述聚氧丁烯聚甘油烷基醚还存在市售品,也可以利用市售品。尤其优选的市售品,可列举出聚氧丁烯(13)聚甘油(14)硬脂醚(“ハイグリオ一ルS-26”;日本サ一フアクタント(株)制造)等。
作为蔗糖脂肪酸酯,可优选列举n=1且q=1的蔗糖单脂肪酸酯、q=2的蔗糖二脂肪酸酯、q=3的蔗糖三脂肪酸酯。其中,更优选蔗糖单脂肪酸酯。作为脂肪酸部分,可优选列举出月桂酸、棕榈酸、硬脂酸、油酸。即,式(II)中,R3为以糖残基的形式存在的蔗糖,作为R2优选月桂基、肉豆蔻基、棕榈基、硬脂基、油基等。具体而言,作为优选的蔗糖单脂肪酸酯,尤其优选蔗糖单月桂酸酯、蔗糖单硬脂酸酯等。
作为(c-4)成分即具有失水山梨醇骨架的化合物,可列举出例如失水山梨醇脂肪酸酯、聚氧乙烯失水山梨醇脂肪酸酯等,作为构成所述酯的脂肪酸,可优选列举出肉豆蔻酸、棕榈酸、异硬脂酸、硬脂酸、油酸等,其中,从提高稳定性的方面来看,尤其优选硬脂酸。另外,在聚氧乙烯失水山梨醇脂肪酸酯中,聚氧乙烯的加成摩尔数优选为5~40,更优选为10~30。作为(c-4)成分的具体例,可列举出单硬脂酸聚氧乙烯(20)失水山梨醇〔=Polysorbate 60〕等。
在配合(c)成分的情况下,本发明皮肤外用剂中,(c)成分的配合量优选为0.01~7质量%,更优选为0.05~5质量%,尤其优选为0.1~3质量%。配合量低于0.01质量%时,在将本发明皮肤外用剂调制成透明化妆水的情况下,变得难以调制成透明体系,另一方面,超过7质量%时,在使用性(黏腻增加)、刺激性方面是不优选的。
本发明的皮肤外用剂是以上述成分为基剂按照常规方法调制而成的。本发明的皮肤外用剂,除上述成分以外,在不损害本发明效果的范围内,可以根据需要适当配合通常用于皮肤外用剂中的其他成分,例如粉末成分、液体油脂、固体油脂、蜡类、烃油、高级脂肪酸、高级醇、合成酯油、硅油、阴离子表面活性剂、阳离子表面活性剂、两性表面活性剂、非离子表面活性剂、保湿剂、水溶性高分子、皮膜剂、紫外线吸收剂、金属离子螯合剂、低级醇、多元醇、糖、氨基酸、有机胺、高分子乳胶、pH调节剂、皮肤营养剂、维生素类、抗氧化剂、抗氧化助剂、香料、水等。以下列举出具体的能够配合的成分,但并非限定于这些列举的例子。
作为粉末成分,可列举出例如无机粉末(例如滑石、高岭土、云母、绢云母(sericite)、白云母、金云母、合成云母、红云母、黑云母、蛭石(vermiculite)、碳酸镁、碳酸钙、硅酸铝、硅酸钡、硅酸钙、硅酸镁、硅酸锶、钨酸金属盐、镁、硅石、沸石、硫酸钡、煅烧硫酸钙(烧石膏)、磷酸钙、氟磷灰石、羟基磷灰石、陶瓷粉、金属皂(例如肉豆蔻酸锌、棕榈酸钙、硬脂酸铝)、氮化硼等);有机粉末(例如聚酰胺树脂粉末(尼龙粉末)、聚乙烯粉末、聚甲基丙烯酸甲酯粉末、聚苯乙烯粉末、苯乙烯与丙烯酸的共聚物树脂粉末、苯并胍胺树脂粉末、聚四氟乙烯粉末、纤维素粉末等);无机白色颜料(例如二氧化钛、氧化锌等);无机红色系颜料(例如氧化铁(铁丹)、钛酸铁等);无机褐色系颜料(例如γ-氧化铁等);无机黄色系颜料(例如黄氧化铁、黄土等);无机黑色系颜料(例如黑氧化铁、低维氧化钛等);无机紫色系颜料(例如锰紫、钴紫等);无机绿色系颜料(例如氧化铬、氢氧化铬、钛酸钴等);无机蓝色系颜料(例如群青、绀青等);珠光颜料(例如氧化钛被覆云母、氧化钛被覆氯氧化铋、氧化钛被覆滑石、着色氧化钛被覆云母、氯氧化铋、鱼鳞箔等);金属粉末颜料(例如铝粉末、铜粉末等);锆、钡或铝色淀等有机颜料(例如,红色201号、红色202号、红色204号、红色205号、红色220号、红色226号、红色228号、红色405号、橙色203号、橙色204号、黄色205号、黄色401号、及蓝色404号等有机颜料,红色3号、红色104号、红色106号、红色227号、红色230号、红色401号、红色505号、橙色205号、黄色4号、黄色5号、黄色202号、黄色203号、绿色3号及蓝色1号等);天然色素(例如叶绿素、β-胡萝卜素等)等。
作为液体油脂,例如可列举出鳄梨油、山茶油、海龟油、澳洲坚果油、玉米油、貂油、橄榄油、菜籽油、蛋黄油、芝麻油、桃仁油、小麦胚芽油、山茶花油、蓖麻油、亚麻籽油、红花油、棉籽油、紫苏子油、大豆油、花生油、茶籽油、榧子油、米糠油、泡桐油、日本桐油、霍霍巴油、胚芽油、三甘油等。
作为固体油脂,例如可列举出可可脂、椰子油、马脂、氢化椰子油、棕榈油、牛脂、羊脂、氢化牛脂、棕榈仁油、猪脂、牛骨脂、木蜡核油、氢化油、牛脚脂、木蜡、氢化蓖麻油等。
作为蜡类,例如可列举出蜂蜡、小烛树蜡、棉蜡、巴西棕榈蜡、杨梅蜡、白蜡、鲸蜡、褐煤蜡、米糠蜡、羊毛脂、木棉蜡、乙酰化羊毛脂、液状羊毛脂、甘蔗蜡、羊毛脂脂肪酸异丙酯、月桂酸己酯、还原羊毛脂、霍霍巴蜡、硬质羊毛脂、紫胶蜡、POE羊毛脂醇醚、POE羊毛脂醇乙酸酯、POE胆甾醇醚、羊毛脂脂肪酸聚乙二醇、POE氢化羊毛脂醇醚等。
作为烃油,例如可列举出液体石蜡、地蜡、角鲨烷、姥鲛烷、石蜡、纯地蜡、角鲨烯、凡士林、微晶蜡等。
作为高级脂肪酸,可列举出例如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山萮酸、油酸、十一碳烯酸、妥尔酸、异硬脂酸、亚油酸、亚麻酸、二十碳五烯酸(EPA)、二十二碳六烯酸(DHA)等。
作为高级醇,例如可列举出直链醇(例如,月桂醇、鲸蜡醇、硬脂醇、山萮醇、肉豆蔻醇、油醇、鲸蜡硬脂醇(CetostearylAlcohol)等);支链醇(例如,单硬脂基甘油醚(鲨肝醇)、2-癸基十四碳炔醇、羊毛脂醇、胆甾醇、植物甾醇、己基十二烷醇、异硬脂醇、辛基十二烷醇等)等。
作为合成酯油,可列举出肉豆蔻酸异丙酯、辛酸鲸蜡酯、肉豆蔻酸辛基十二烷基酯、棕榈酸异丙酯、硬脂酸丁酯、月桂酸己酯、肉豆蔻酸肉豆蔻酯、油酸癸酯、二甲基辛酸己基癸酯、乳酸鲸蜡酯、乳酸肉豆蔻酯、醋酸羊毛脂、硬脂酸异鲸蜡酯、异硬脂酸异鲸蜡酯、12-羟基硬脂酸胆甾醇酯、二-2-乙基己酸乙二醇、二季戊四醇脂肪酸酯、单异硬脂酸N-烷二醇、二癸酸新戊二醇酯、苹果酸二异硬脂醇酯、二-2-庚基十一烷酸甘油酯、三-2-乙基己酸三羟甲基丙烷、三异硬脂酸三羟甲基丙烷、四-2-乙基己酸季戊四醇酯、三-2-乙基己酸甘油酯、三辛酸甘油酯、三异棕榈酸甘油酯、三异硬脂酸三羟甲基丙烷、鲸蜡基2-乙基己酸酯、2-乙基己基棕榈酸酯、三肉豆蔻酸甘油酯、三-2-庚基十一烷酸甘油酯、蓖麻油脂肪酸甲酯、油酸油醇酯、乙酰甘油、棕榈酸2-庚基十一烷基酯、己二酸二异丁酯、N-月桂酰基-L-谷氨酸-2-辛基十二烷基酯、己二酸二-2-庚基十一烷基酯、月桂酸乙酯、癸二酸二-2-乙基己酯、肉豆蔻酸2-己基癸酯、棕榈酸2-己基癸酯、己二酸2-己基癸酯、癸二酸二异丙酯、琥珀酸2-乙基己酯、柠檬酸三乙酯等。
作为硅油,例如可列举出链状聚硅氧烷(例如,二甲基聚硅氧烷、甲基苯基聚硅氧烷、二苯基聚硅氧烷等);环状聚硅氧烷(例如,八甲基环四硅氧烷、十甲基环五硅氧烷、十二甲基环六硅氧烷等)、形成三维网状结构的硅酮树脂、硅酮橡胶、各种改性聚硅氧烷(氨基改性聚硅氧烷、聚醚改性聚硅氧烷、烷基改性聚硅氧烷、氟改性聚硅氧烷等)等。
作为阴离子表面活性剂,例如可列举出脂肪酸皂(例如,月桂酸钠、棕榈酸钠等);高级烷基硫酸酯盐(例如,月桂基硫酸钠、月桂基硫酸钾等);烷基醚硫酸酯盐(例如,POE-月桂基硫酸三乙醇胺、POE-月桂基硫酸钠等);N-酰基肌氨酸(例如,月桂酰基肌氨酸钠等);高级脂肪酸酰胺磺酸盐(例如,N-肉豆蔻酰基-N-甲基牛磺酸钠、椰子油脂肪酸甲基牛磺酸钠、月桂基甲基牛磺酸钠等);磷酸酯盐(POE-油醚磷酸钠、POE-硬脂醚磷酸等);磺基琥珀酸盐(例如,二-2-乙基己基磺基琥珀酸钠、单月桂酰基单乙醇酰胺聚氧乙烯磺基琥珀酸钠、月桂基聚丙二醇磺基琥珀酸钠等);烷基苯磺酸盐(例如,直线型十二烷基苯磺酸钠、直线型十二烷基苯磺酸三乙醇胺、直线型十二烷基苯磺酸等);高级脂肪酸酯硫酸酯盐(例如,氢化椰子油脂肪酸甘油硫酸钠等);N-酰基谷氨酸盐(例如,N-月桂酰基谷氨酸单钠、N-硬脂酰基谷氨酸二钠、N-肉豆蔻酰基-L-谷氨酸单钠等);硫酸化油(例如,土耳其红油等);POE-烷基醚羧酸;POE-烷基烯丙基醚羧酸盐;α-烯烃磺酸盐;高级脂肪酸酯磺酸盐;仲醇硫酸酯盐;高级脂肪酸烷基醇酰胺硫酸酯盐;月桂酰基单乙醇酰胺琥珀酸钠;N-棕榈酰基天冬氨酸双三乙醇胺;酪蛋白钠等。
作为阳离子表面活性剂,例如可列举出烷基三甲基铵盐(例如,硬脂基三甲基氯化铵、月桂基三甲基氯化铵等);烷基吡啶鎓盐(例如,鲸蜡基氯化吡啶等);二硬脂基二甲基氯化铵、二烷基二甲基铵盐;氯化聚(N,N’-二甲基-3,5-亚甲基哌啶鎓);烷基季铵盐;烷基二甲基苄基铵盐;烷基异喹啉鎓盐;二烷基吗啉鎓盐;POE-烷基胺;烷基胺盐;多胺脂肪酸衍生物;戊醇脂肪酸衍生物;苯扎氯铵;苄索氯铵等。
作为两性表面活性剂,例如可列举出咪唑啉系两性表面活性剂(例如,2-十一烷基-N,N,N-(羟乙基羧甲基)-2-咪唑啉钠、2-椰油基-2-咪唑啉鎓氢氧化物-1-羧基乙氧基二钠盐等);甜菜碱系表面活性剂(例如,2-十七烷基-N-羧甲基-N-羟乙基咪唑啉甜菜碱、月桂基二甲基氨基醋酸甜菜碱、烷基甜菜碱、酰胺甜菜碱、磺基甜菜碱等)等。
作为亲油性非离子表面活性剂,可列举出例如丙二醇脂肪酸酯类(例如,单硬脂酸丙二醇等);氢化蓖麻油衍生物等。
作为亲水性非离子表面活性剂,例如可列举出POE山梨糖醇脂肪酸酯类(例如,POE-山梨糖醇单月桂酸酯、POE-山梨糖醇单油酸酯、POE-山梨糖醇五油酸酯、POE-山梨糖醇单硬脂酸酯等);POE-甘油脂肪酸酯类(例如,POE-甘油单硬脂酸酯、POE-甘油单异硬脂酸酯、POE-甘油三异硬脂酸酯等POE-单油酸酯等);POE-脂肪酸酯类(例如,POE-二硬脂酸酯、POE-单二油酸酯、二硬脂酸乙二醇酯等);POE-烷基醚类(例如,POE-月桂基醚、POE-油醚、POE-硬脂醚、POE-山萮醚、POE-2-辛基十二烷基醚、POE-胆甾烷醇醚等);Pluronic型类(例如,Pluronic等);POE/POP-烷基醚类(例如,POE/POP-鲸蜡基醚、POE/POP-2-癸基十四烷基醚、POE/POP-单丁醚、POE/POP-氢化羊毛脂、POE/POP-甘油醚等);四POE/四POP-乙二胺缩合物类(例如,Tetronic等);POE-蓖麻油氢化蓖麻油衍生物(例如,POE-蓖麻油、POE-氢化蓖麻油、POE-氢化蓖麻油单异硬脂酸酯、POE-氢化蓖麻油三异硬脂酸酯、POE-氢化蓖麻油单焦谷氨酸单异硬脂酸二酯、POE-氢化蓖麻油马来酸等);POE-蜂蜡/羊毛脂衍生物(例如,POE-山梨糖醇蜂蜡等);烷醇酰胺(例如,椰子油脂肪酸二乙醇酰胺、月桂酸单乙醇酰胺、脂肪酸异丙醇酰胺等);POE-丙二醇脂肪酸酯;POE-烷基胺;POE-脂肪酸酰胺;蔗糖脂肪酸酯;烷基乙氧基二甲基氧化胺;三油基磷酸等。
作为保湿剂,例如可列举出聚乙二醇、丙二醇、甘油、1,3-丁二醇、木糖醇、山梨糖醇、麦芽糖醇、硫酸软骨素、透明质酸、硫酸粘多糖、栝楼仁酸、去端肽胶原、胆甾醇基-12-羟基硬脂酸酯、乳酸钠、胆汁酸盐、dl-吡咯烷酮羧酸盐、短链可溶性胶原、二甘油(EO)PO加成物、刺梨提取物、欧蓍草提取物、草木樨提取物等。
作为天然的水溶性高分子,例如可列举出植物系高分子(例如,阿拉伯胶、黄蓍胶、半乳糖、瓜尔胶、角豆树胶、刺梧桐树胶、角叉菜胶、果胶、琼脂、榅桲籽(marmelo)、海藻胶体(海藻提取物)、淀粉(大米、玉米、马铃薯、小麦)、甘草酸);微生物系高分子(例如,黄原胶、葡聚糖、琥珀酰葡聚糖、普鲁兰多糖等);动物系高分子(例如,胶原、酪蛋白、白蛋白、明胶等)等。
作为半合成的水溶性高分子,例如可列举出淀粉系高分子(例如,羧甲基淀粉、甲基羟丙基淀粉等);纤维素系高分子(甲基纤维素、乙基纤维素、甲基羟丙基纤维素、羟乙基纤维素、纤维素硫酸钠、羟丙基纤维素、羧甲基纤维素、羧甲基纤维素钠、结晶纤维素、纤维素末等);海藻酸系高分子(例如,海藻酸钠、海藻酸丙二醇酯等)等。
作为合成的水溶性高分子,例如可列举出乙烯基系高分子(例如,聚乙烯醇、聚乙烯基甲醚、聚乙烯基吡咯烷酮、羧基乙烯基聚合物等);聚氧乙烯系高分子(例如,聚乙二醇20,000、40,000、60,000的聚氧乙烯聚氧丙烯共聚物等);丙烯酸系高分子(例如,聚丙烯酸钠、聚丙烯酸乙酯、聚丙烯酰胺等);聚乙烯亚胺;阳离子聚合物等。
作为无机的水溶性高分子,可列举出膨润土、硅酸铝镁(Veegum)、锂藻土、锂蒙脱石、无水硅酸等。
作为紫外线吸收剂,例如可列举出苯甲酸系紫外线吸收剂(例如,对氨基苯甲酸(以下,简称为PABA)、PABA单甘油酯、N,N-二丙氧基PABA乙酯、N,N-二乙氧基PABA乙酯、N,N-二甲基PABA乙酯、N,N-二甲基PABA丁基酯、N,N-二甲基PABA乙酯等);邻氨基苯甲酸系紫外线吸收剂(例如,三甲基环己基(homomenthyl)-N-乙酰基邻氨基苯甲酸酯等);水杨酸系紫外线吸收剂(例如,水杨酸戊酯、水杨酸薄荷酯、水杨酸三甲基环己酯、水杨酸辛基酯、水杨酸苯基酯、水杨酸苄基酯、对异丙醇苯基水杨酸酯等);肉桂酸系紫外线吸收剂(例如,肉桂酸辛基酯、乙基-4-异丙基肉桂酸酯、甲基-2,5-二异丙基肉桂酸酯、乙基-2,4-二异丙基肉桂酸酯、甲基-2,4-二异丙基肉桂酸酯、丙基-对甲氧基肉桂酸酯、异丙基-对甲氧基肉桂酸酯、异戊基-对甲氧基肉桂酸酯、辛基-对甲氧基肉桂酸酯(2-乙基己基-对甲氧基肉桂酸酯)、2-乙氧基乙基-对甲氧基肉桂酸酯、环己基-对甲氧基肉桂酸酯、乙基-α-氰基-β-苯基肉桂酸酯、2-乙基己基-α-氰基-β-苯基肉桂酸酯、甘油单-2-乙基己酰基-二对甲氧基肉桂酸酯等);二苯甲酮系紫外线吸收剂(例如,2,4-二羟基二苯甲酮、2,2’-二羟基-4-甲氧基二苯甲酮、2,2’-二羟基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-甲氧基-4’-甲基二苯甲酮、2-羟基-4-甲氧基二苯甲酮-5-磺酸盐、4-苯基二苯甲酮、2-乙基己基-4’-苯基-二苯甲酮-2-羧酸酯、2-羟基-4-正辛氧基二苯甲酮、4-羟基-3-羧基二苯甲酮等);3-(4’-甲基亚苄基)-d,1-樟脑、3-亚苄基-d,1-樟脑;2-苯基-5-甲基苯并噁唑;2,2’-羟基-5-甲基苯基苯并三唑;2-(2’-羟基-5’-叔辛基苯基)苯并三唑;2-(2’-羟基-5’-甲基苯基苯并三唑;二苄连氮(dibenzalazine);二茴香酰基甲烷;4-甲氧基-4’-叔丁基二苯甲酰基甲烷;5-(3,3-二甲基-2-亚降冰片烯基)-3-戊烷-2-酮等。
作为金属离子螯合剂,例如可列举出1-羟基乙烷-1,1-双膦酸、1-羟基乙烷-1,1-双膦酸四钠盐、乙二胺四乙酸二钠、乙二胺四乙酸三钠、乙二胺四乙酸四钠、柠檬酸钠、聚磷酸钠、偏磷酸钠、葡萄糖酸、磷酸、柠檬酸、抗坏血酸、琥珀酸、乙二胺四乙酸、乙二胺羟乙基三醋酸三钠等。
作为低级醇,例如可列举出乙醇、丙醇、异丙醇、异丁醇、叔丁醇等。
作为多元醇,例如可列举出二元醇(例如,乙二醇、丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、2-丁烯-1,4-二醇、己二醇、辛二醇等);三元醇(例如,甘油、三羟甲基丙烷等);四元醇(例如,1,2,6-己三醇等的季戊四醇等);五元醇(例如,木糖醇等);六元醇(例如,山梨糖醇、甘露糖醇等);多元醇聚合体(例如,二乙二醇、二丙二醇、三乙二醇、聚丙二醇、四乙二醇、二甘油、聚乙二醇、三甘油、四甘油、聚甘油等);二元醇烷基醚类(例如,乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、乙二醇单苯基醚、乙二醇单己醚、乙二醇单2-甲基己醚、乙二醇异戊基醚、乙二醇苄基醚、乙二醇异丙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁基醚等);二元醇烷基醚类(例如,二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇丁醚、二乙二醇甲基乙醚、三乙二醇单甲醚、三乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单丁醚、丙二醇异丙醚、二丙二醇甲醚、二丙二醇乙醚、二丙二醇丁醚等);二元醇醚酯(例如,乙二醇单甲醚乙酸酯、乙二醇单乙醚乙酸酯、乙二醇单丁醚乙酸酯、乙二醇单苯基醚乙酸酯、乙二醇二己二酸酯、乙二醇二琥珀酸酯、二乙二醇单乙醚乙酸酯、二乙二醇单丁醚乙酸酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、丙二醇单丙基醚乙酸酯、丙二醇单苯基醚乙酸酯等);甘油单烷基醚(例如,鲛肝醇、鲨油醇、鲨肝醇等);糖醇(例如,山梨糖醇、麦芽糖醇、麦芽三糖、甘露糖醇、蔗糖、赤藓糖醇、葡萄糖、果糖、淀粉分解糖、麦芽糖、木糖、淀粉分解糖还原醇等);Glysolid;四氢糠醇;POE-四氢糠醇;POP-丁基醚;POP-POE-丁基醚;三聚氧丙烯甘油醚;POP-甘油醚;POP-甘油醚磷酸;POP-POE-季戊四醇醚、聚甘油等。
作为单糖,例如可列举出三碳糖(例如,D-甘油醛、二羟基丙酮等);四碳糖(例如,D-赤藓糖、D-赤藓酮糖、D-苏糖、赤藓糖醇等);五碳糖(例如,L-阿拉伯糖、D-木糖、L-来苏糖、D-阿拉伯糖、D-核糖、D-核酮糖、D-木酮糖、L-木酮糖等);六碳糖(例如,D-葡萄糖、D-塔罗糖、D-阿洛酮糖、D-半乳糖、D-果糖、L-半乳糖、L-甘露糖、D-塔格糖等);七碳糖(例如,庚醛糖、庚糖等);八碳糖(例如,辛酮糖等);脱氧糖(例如,2-脱氧-D-核糖、6-脱氧-L-半乳糖、6-脱氧-L-甘露糖等);氨基糖(例如,D-葡糖胺、D-半乳糖胺、唾液酸、氨基糖醛酸、胞壁酸等);糖醛酸(例如,D-葡糖醛酸、D-甘露糖醛酸、L-古洛糖醛酸、D-半乳糖醛酸、L-艾杜糖醛酸等)等。
作为低聚糖,例如可列举出蔗糖、龙胆三糖、伞形糖、乳糖、车前糖、异木质素(Isolignose)类、α,α-海藻糖、蜜三糖、木质素(Lignose)类、Umbilicin、水苏糖、毛蕊花糖类等。
作为多糖,例如可列举出纤维素、榅桲籽、硫酸软骨素、淀粉、半乳聚糖、硫酸皮肤素、糖原、阿拉伯胶、硫酸乙酰肝素、透明质酸、黄蓍胶、硫酸角质素、软骨素、黄原胶、硫酸粘多糖、瓜尔胶、葡聚糖、硫酸角质、刺槐豆胶、琥珀酰葡聚糖、栝楼仁酸等。
作为氨基酸,例如可列举出中性氨基酸(例如,苏氨酸、半胱氨酸等);碱性氨基酸(例如,羟基赖氨酸等)等。另外,作为氨基酸衍生物,例如可列举出酰基肌氨酸钠(月桂酰基肌氨酸钠)、酰基谷氨酸盐、酰基β-丙氨酸钠、谷胱甘肽、吡咯烷酮羧酸等。
作为有机胺,例如可列举出单乙醇胺、二乙醇胺、三乙醇胺、吗啉、三异丙醇胺、2-氨基-2-甲基-1,3-丙二醇、2-氨基-2-甲基-1-丙醇等。
作为高分子乳胶,例如可列举出丙烯酸树脂乳胶、聚丙烯酸乙酯乳胶、丙烯酸树脂液、聚丙烯酸烷基酯乳胶、聚醋酸乙烯酯树脂乳胶、天然橡胶胶乳等。
作为维生素类,例如可列举出维生素A、B1、B2、B6、C、E及其衍生物、泛酸及其衍生物、生物素等。
作为抗氧化剂,例如可列举出生育酚类、二丁基羟基甲苯、丁基羟基茴香醚、没食子酸酯类等。
作为抗氧化助剂,例如可列举出磷酸、柠檬酸、抗坏血酸、马来酸、丙二酸、琥珀酸、富马酸、脑磷脂、六偏磷酸盐、植酸、乙二胺四乙酸等。
作为其他可配合的成分,例如可列举出防腐剂(对羟基苯甲酸乙酯、对羟基苯甲酸丁酯等);消炎剂(例如,甘草酸衍生物、甘草次酸衍生物、水杨酸衍生物、日扁柏醇(hinokitiol)、氧化锌、尿囊素等);美白剂(例如,胎盘提取物、虎耳草提取物、熊果苷等);各种提取物(例如,黄柏、黄莲、紫根、芍药、日本獐牙菜、桦木(birch)、鼠尾草、枇杷、人参、芦荟、锦葵、鸢尾、葡萄、薏苡仁、丝瓜、百合、藏红花、川芎、生姜、小连翘、芒柄花、大蒜、辣椒、陈皮、当归、海藻等)、赋活剂(例如,蜂王浆、感光素、胆甾醇衍生物等);促进血液循环剂(例如壬酸香草酰胺(Nonylic acid vanillylamide))、烟酸苄酯、烟酸β-丁氧基乙酯、辣椒素、姜油酮、斑蝥酊、鱼石脂、鞣酸、α-龙脑、烟酸生育酚、六烟酸肌醇酯、环扁桃酯、肉桂苯哌嗪、苯甲唑啉、乙酰胆碱、戊脉安、千金藤素、γ-谷维素等);抗脂溢剂(例如硫磺、二甲硫蒽等);抗炎剂(例如凝血酸、甘草酸二钾等)等。
本发明的皮肤化妆品的剂型是任意的,可列举出可溶化系、乳化系、粉末分散系、油-水的2层系、油-水-粉末的3层系等,但并非限定于这些剂型。另外,本发明的皮肤化妆品的产品形态也是任意的,可以用于化妆水、乳液、乳霜、面膜等面部皮肤化妆品、身体皮肤化妆品、芳香皮肤化妆品。
实施例
以下列举实施例进一步具体说明本发明,但本发明并不受这些实施例的任何限定。配合量没有特别限定,以其成分相对于配合体系的质量%表示。
(实施例1:4-异丁基间苯二酚对日光照射下(50℃)抗坏血酸或其衍生物的变色、变臭的防止效果)
[色差(ΔE),L值]
对下述表1所示的试样1~6照射日光(50MJ,50℃)。照射结束后,用色差计(GretagMacbeth Color-Eye 7000A)测定了恢复到室温后的各试样的色差(ΔE)。色差(ΔE)越小表示变色越少。并且,使用积分球式分光光度仪(“Color-Eye7000A”,GretagMacbeth公司制造)测定了各试样的透明度L值(L值越接近100则越透明)。结果如表1所示。
[气味]
对下述表1所示的试样1~6照射日光(50MJ,50℃)。照射结束后,专业评委(5名)对于恢复到室温的各试样进行气味的感官评价,按照非常好(5分)、好(4分)、普通(3分)、差(2分)、非常差(1分)这五个等级进行了评价。求出5名评委评价的平均值,并按照以下基准示出了评价结果。
(评价)
◎:5名评委评价的平均值为4.0~5.0
○:5名评委评价的平均值为3.0~3.9
Δ:5名评委评价的平均值为2.0~2.9
×:5名评委评价的平均值为1.0~1.9
[色差减少率(%)]
试样1~2、试样3~4、试样5~6中,按照[{(未配合4-异丁基间苯二酚的试样的色差(ΔE))-(配合有4-异丁基间苯二酚的试样的色差(ΔE))}/(未配合4-异丁基间苯二酚的试样的色差(ΔE))]×100(%)进行计算。由此可见4-异丁基间苯二酚对L-抗坏血酸或其衍生物具有变色防止效果。色差减少率(%)越接近100(%),则变色防止效果越优异。结果如表1所示。
[表1]
由表1所示的结果可以确认:在单独配合4-异丁基间苯二酚、或单独配合抗坏血酸或其衍生物时,光稳定性、温度(高温)稳定性差,但通过并用两者,可获得光稳定性效果、温度(高温)稳定性效果。
越是4-异丁基间苯二酚的效果高的试样,则色差大幅减少(色差减少率大)。总之,4-异丁基间苯二酚可以防止抗坏血酸类的变色,其中,使用了3-O-乙基-L-抗坏血酸、L-抗坏血酸作为L-抗坏血酸类的试样3、5的色差减少率高,其中,使用了3-O-乙基-L-抗坏血酸的试样3的色差减少率为约97%,且色差也为0.091,通过4-异丁基间苯二酚能够大体上完全抑制3-O-乙基-L-抗坏血酸的变色。
(实施例2:烷基间苯二酚类中的4-异丁基间苯二酚的变色防止效果的显著性)
[色差(ΔE),L值]
将下述表2所示的试样7~20于50℃(遮光)的恒温槽放置2周后,使用色差计(GretagMacbeth Color-Eye 7000A)测定了恢复到室温后的各试样的色差(ΔE)。色差(ΔE)越小则表示变色越少。并且,使用积分球式分光光度仪(“Color-Eye7000A”,GretagMacbeth公司制造)测定了各试样的透明度L值(L值越接近100则越透明)。结果如表2所示。
[表2]
另外,表2中,4-异丁基间苯二酚的配合量为0.1质量%,调整其他烷基间苯二酚类的配合量使其与4-异丁基间苯二酚为等摩尔量。由于变色测定对象为烷基间苯二酚类,因此使这些烷基间苯二酚类的摩尔数保持一致。
由表2所示的结果可以确认:本发明范围的试样15可以获得色差、L值均表现为变色少的测定结果,可知其变色防止效果最优异。
以下进一步示出配方例。
(实施例3:化妆水)
(配合成分) (质量%)
(1)乙醇 5.0
(2)甘油 1.0
(3)1,3-丁二醇 5.0
(4)POE/POP癸基十四烷基醚 0.2
(5)六偏磷酸钠 0.03
(6)聚天冬氨酸钠 0.1
(7)3-O-乙基-L-抗坏血酸 5.0
(8)4-异丁基间苯二酚 0.1
(9)绿茶提取物 0.1
(10)小连翘提取物 0.1
(11)西洋薄荷提取物 0.1
(12)α-葡萄糖基橙皮苷 0.01
(13)香根鸢尾根提取物 0.1
(14)乙二胺四乙酸三钠 0.1
(15)羧乙烯基聚合物 0.05
(16)丙烯酸钠/2-丙烯酰胺-2-甲基丙磺酸共聚物 0.05
(17)氢氧化钾 0.02
(18)苯氧基乙醇 适量
(19)纯化水 余量
(20)香料 适量
(实施例4:化妆水)
(配合成分) (质量%)
(1)乙醇 10.0
(2)甘油 2.0
(3)二丙二醇 1.0
(4)异硬脂酸 0.1
(5)POE/POP甲基聚硅氧烷共聚物 1.0
(6)月桂基二甲基氨基醋酸甜菜碱 0.1
(7)柠檬酸 0.01
(8)柠檬酸钠 0.09
(9)六偏磷酸钠 0.01
(10)洋甘菊提取物 0.1
(11)黄芩提取物 0.1
(12)白花地胆草叶提取物 0.1
(13)3-O-乙基-L-抗坏血酸 0.01
(14)4-异丁基间苯二酚 0.01
(15)薰衣草油 0.001
(16)苯氧基乙醇 适量
(17)活性氢水 1.0
(18)纯化水 余量
(实施例5:化妆水)
(配合成分) (质量%)
(1)乙醇 10.0
(2)甘油 2.0
(3)二丙二醇 1.0
(4)异硬脂酸 0.1
(5)POE/POP甲基聚硅氧烷共聚物 1.0
(6)月桂基二甲基氨基醋酸甜菜碱 0.1
(7)柠檬酸 0.01
(8)柠檬酸钠 0.09
(9)六偏磷酸钠 0.01
(10)洋甘菊提取物 0.1
(11)刺梨果实提取物 0.1
(12)黄芩提取物 0.1
(13)L-抗坏血酸 1.0
(14)4-异丁基间苯二酚 1.0
(15)POE(30)胆甾醇 1.0
(16)薰衣草油 0.001
(17)苯氧基乙醇 适量
(18)活性氢水 1.0
(19)纯化水 余量
(实施例6:化妆水)
(配合成分) (质量%)
(1)乙醇 10.0
(2)甘油 2.0
(3)二丙二醇 1.0
(4)异硬脂酸 0.1
(5)POE/POP甲基聚硅氧烷共聚物 1.0
(6)月桂基二甲基氨基醋酸甜菜碱 0.1
(7)柠檬酸 0.09
(8)柠檬酸钠 0.01
(9)六偏磷酸钠 0.01
(10)地黄提取物 0.1
(11)洋甘菊提取物 0.1
(12)黄芩提取物 0.1
(13)3-O-乙基-L-抗坏血酸 1.0
(14)4-异丁基间苯二酚 0.1
(15)薰衣草油 0.001
(16)苯氧基乙醇 适量
(17)活性氢水 1.0
(18)纯化水 余量
(实施例7:化妆水)
(配合成分) (质量%)
(1)乙醇 5.0
(2)甘油 1.0
(3)1,3-丁二醇 5.0
(4)POE/POP癸基十四烷基醚 0.2
(5)六偏磷酸钠 0.03
(6)聚天冬氨酸钠 0.1
(7)3-O-乙基-L-抗坏血酸 5.0
(8)4-异丁基间苯二酚 0.01
(9)绿茶提取物 0.1
(10)牡丹皮提取物 0.1
(11)西洋薄荷提取物 0.1
(12)α-葡萄糖基橙皮苷 0.01
(13)香根鸢尾根提取物 0.1
(14)乙二胺四乙酸三钠 0.1
(15)羧乙烯基聚合物 0.05
(16)丙烯酸钠/2-丙烯酰胺-2-甲基丙磺酸共聚物 0.05
(17)氢氧化钾 0.02
(18)苯氧基乙醇 适量
(19)纯化水 余量
(20)香料 适量
(实施例8:化妆水)
(配合成分) (质量%)
(1)乙醇 5.0
(2)甘油 1.0
(3)1,3-丁二醇 5.0
(4)POE/POP癸基十四烷基醚 0.2
(5)六偏磷酸钠 0.03
(6)聚天冬氨酸钠 0.1
(7)3-O-乙基-L-抗坏血酸 0.01
(8)4-异丁基间苯二酚 1.0
(9)绿茶提取物 0.1
(10)虎耳草提取物 0.1
(11)西洋薄荷提取物 0.1
(12)α-葡萄糖基橙皮苷 0.01
(13)香根鸢尾根提取物 0.1
(14)乙二胺四乙酸三钠 0.1
(15)羧乙烯基聚合物 0.05
(16)丙烯酸钠/2-丙烯酰胺-2-甲基丙磺酸共聚物 0.05
(17)氢氧化钾 0.02
(18)苯氧基乙醇 适量
(19)纯化水 余量
(20)香料 适量
(实施例9:O/W乳霜)
(配合成分) (质量%)
(1)液体石蜡 3.0
(2)凡士林 1.0
(3)二甲基聚硅氧烷 1.0
(4)硬脂醇 1.8
(5)山萮醇 1.6
(6)澳洲坚果油 2.0
(7)氢化棕榈油 3.0
(8)角鲨烷 6.0
(9)硬脂酸 2.0
(10)2-乙基己酸鲸蜡酯 4.0
(11)POE氢化蓖麻油 0.5
(12)自乳化型单硬脂酸甘油酯 3.0
(13)4-叔丁基-4′-甲氧基二苯甲酰基甲烷 0.05
(14)对羟基苯甲酸酯 适量
(15)二对甲氧基肉桂酸单-2-乙基己酸甘油酯 0.05
(16)3-O-乙基-L-抗坏血酸 5.0
(17)4-异丁基间苯二酚 5.0
(18)硬脂酸蔗糖酯 7.0
(19)氢氧化钾 0.15
(20)六偏磷酸钠 0.05
(21)三甲基甘氨酸 2.0
(22)甘油 8.0
(23)二丙二醇 5.0
(24)甜茶提取物 0.1
(25)酵母提取物 0.1
(26)乙二胺四乙酸三钠 0.05
(27)羧乙烯基聚合物 0.05
(28)云母钛 0.1
(29)着色剂 适量
(30)纯化水 余量
(实施例10:皮肤紧致用W/O乳霜)
(配合成分) (质量%)
(1)二甲基聚硅氧烷 3.0
(2)十甲基环五硅氧烷 13.0
(3)十二甲基环六硅氧烷 5.0
(4)POE甲基聚硅氧烷共聚物 1.0
(5)对羟基苯甲酸酯 适量
(6)L-薄荷醇 适量
(7)三甲基甲硅烷氧基硅酸 2.0
(8)乙醇 2.0
(9)甘油 3.0
(10)二丙二醇 5.0
(11)聚乙二醇6000 5.0
(12)3-O-乙基-L-抗坏血酸 0.01
(13)4-异丁基间苯二酚 0.01
(14)六偏磷酸钠 0.05
(15)咖啡因 0.1
(16)茴香提取物 0.1
(17)金缕梅提取物 0.1
(18)人参提取物 0.1
(19)乙二胺四乙酸三钠 0.05
(20)二吗啉基哒嗪酮 0.01
(21)三甲氧基肉桂酸甲基双(三甲基硅烷)甲硅烷基异戊酯 0.1
(22)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 5.0
(23)黄氧化铁 适量
(24)钛酸钴 适量
(25)二硬脂二甲铵锂蒙脱石 1.5
(26)聚乙烯醇 0.1
(27)羟乙基纤维素 0.1
(28)丙烯酸钠/2-丙烯酰胺-2-甲基丙磺酸共聚物 0.1
(29)(丙烯酰二甲基牛磺酸铵/VP)共聚物(AristoflexAVCTM;Clariant公司制造) 0.1
(30)香料 适量
(31)纯化水 余量
(实施例11:O/W乳液)
(配合成分) (质量%)
(1)二甲基聚硅氧烷 3.0
(2)十甲基环五硅氧烷 4.0
(3)乙醇 5.0
(4)甘油 6.0
(5)1,3-丁二醇 5.0
(6)聚氧乙烯甲基葡萄糖苷 3.0
(7)葵花油 1.0
(8)角鲨烷 2.0
(9)氢氧化钾 0.1
(10)六偏磷酸钠 0.05
(11)羟丙基-β-环糊精 0.1
(12)L-抗坏血酸 1.0
(13)4-异丁基间苯二酚 5.0
(14)POE/POB二醇-单-DL-α-生育酚[式(VI)。式中k+y=30(k=16,y=14),x=2,R6、R7、R8为CH3,R9为H] 1.0
(15)甘草酸二钾 0.05
(16)枇杷叶提取物 0.1
(17)L-谷氨酸钠 0.05
(18)茴香提取物 0.1
(19)薰衣草油 0.1
(20)地黄提取物 0.1
(21)被孢霉油(Mortierella Oil) 0.5
(22)乙酰基透明质酸钠 0.1
(23)甜马郁兰提取物 0.1
(24)二吗啉基哒嗪酮 0.1
(25)黄原胶 0.1
(26)羧乙烯基聚合物 0.1
(27)丙烯酸/甲基丙烯酸烷基酯共聚物(ペミユレンTR-2TM) 0.1
(28)(丙烯酰二甲基牛磺酸铵/VP)共聚物(AristoflexAVCTM;Clariant公司制造) 1.0
(29)铁丹 适量
(30)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 1.0
(31)云母钛 0.1
(32)对羟基苯甲酸酯 适量
(33)纯化水 余量
(实施例12:W/O日用乳液)
(配合成分) (质量%)
(1)二甲基聚硅氧烷 2.0
(2)十甲基环五硅氧烷 25.0
(3)十二甲基环六硅氧烷 10.0
(4)聚氧乙烯·甲基聚硅氧烷共聚物 1.5
(5)烷基交联聚甲基硅氧烷的十甲基环五硅氧烷配合物(Dow Corning 9045 Silicone Elastomer Blend TM:Dow Corning公司制造) 5.0
(6)三甲基甲硅烷氧基硅酸 1.0
(7)1,3-丁二醇 5.0
(8)角鲨烷 0.5
(9)滑石 5.0
(10)甘草酸二钾 0.1
(11)酵母提取物 0.1
(12)3-O-乙基-L-抗坏血酸 5.0
(13)4-异丁基间苯二酚 0.1
(14)L-丝氨酸 1.0
(15)通草提取物 0.1
(16)乙二胺四乙酸三钠 0.05
(17)4-叔丁基-4′-甲氧基二苯甲酰基甲烷 1.0
(18)对甲氧基肉桂酸2-乙基己酯 5.0
(19)二对甲氧基肉桂酸单-2-乙基己酸甘油酯 1.0
(20)硅酮被覆微粒氧化钛(40nm) 4.0
(21)二硬脂二甲铵锂蒙脱石 0.5
(22)球状聚乙烯粉末 3.0
(23)丙烯酸钠/2-丙烯酰胺-2-甲基丙磺酸共聚物 0.1
(24)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 1.0
(25)云母钛 0.1
(26)苯氧基乙醇 适量
(27)纯化水 余量
(28)香料 适量
(实施例13:面膜)
(配合成分) (质量%)
(1)乙醇 10.0
(2)1,3-丁二醇 6.0
(3)聚乙二醇4000 2.0
(4)橄榄油 1.0
(5)澳洲坚果油 1.0
(6)羟基硬脂酸植物甾醇 0.05
(7)乳酸 0.05
(8)乳酸钠 0.1
(9)3-O-乙基-L-抗坏血酸 0.01
(10)4-异丁基间苯二酚 0.01
(11)POE/POP二醇-单-DL-α-生育酚[式(V)。式中k+y=30(k=16,y=14),x=2,R6、R7、R8为CH3,R9为H] 1.0
(12)鱼胶原 0.1
(13)糖蜜提取物 1.0
(14)软骨素硫酸钠 0.1
(15)酵母提取物 3.0
(16)羧甲基纤维素钠 0.2
(17)聚乙烯醇 12.0
(18)(丙烯酰二甲基牛磺酸铵/VP)共聚物(AristoflexAVCTM;Clariant公司制造) 2.0
(19)丙烯酸钠/2-丙烯酰胺-2-甲基丙磺酸共聚物 0.1
(20)烷基交联聚甲基硅氧烷的二甲基聚硅氧烷配合物(Dow Corning 9041 Silicone Elastomer Blend TM:Dow Corning公司制造) 3.0
(21)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 5.0
(22)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 1.0
(23)对羟基苯甲酸酯 适量
(24)纯化水 余量
(25)香料 适量
(实施例14:粉状固形粉底)
(配合成分) (质量%)
(1)二甲基聚硅氧烷 5.0
(2)烷基交联聚甲基硅氧烷的十甲基环五硅氧烷配合物(Dow Corning 9045 Silicone Elastomer Blend TM:Dow Corning公司制造) 5.0
(3)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 0.5
(4)异硬脂酸 0.5
(5)3-O-乙基-L-抗坏血酸 1.0
(6)4-异丁基间苯二酚 5.0
(7)硬脂酸蔗糖酯 3.0
(8)苹果酸二异硬脂酸酯 3.0
(9)三2-乙基己烷甘油酯 1.0
(10)失水山梨醇倍半异硬脂酸酯 1.0
(11)球状PMMA被覆云母 6.0
(12)Prismtone powder YR 1.0
(13)微粒氧化锌 0.5
(14)微粒氧化钛 2.0
(15)合成金云母 2.0
(16)金属皂处理滑石 8.0
(17)球状无水硅酸 5.0
(18)刺梨提取物 0.1
(19)酵母提取物 0.1
(20)对羟基苯甲酸酯 适量
(21)三甲氧基肉桂酸甲基双(三甲基硅烷)甲硅烷基异戊酯 1.0
(22)对甲氧基肉桂酸2-乙基己酯 3.0
(23)球状聚丙烯酸烷基酯粉末 6.0
(24)甲基氢聚硅氧烷被覆滑石 余量
(25)甲基氢聚硅氧烷被覆绢云母 5.0
(26)甲基氢聚硅氧烷被覆氧化钛 15.0
(27)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 10.0
(28)云母钛 1.0
(29)甲基氢聚硅氧烷被覆颜料(着色剂) 5.0
(实施例15:粉状固形粉底)
(配合成分) (质量%)
(1)地蜡 0.5
(2)二甲基聚硅氧烷 2.0
(3)甲基苯基聚硅氧烷 1.0
(4)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 5.0
(5)烷基交联聚甲基硅氧烷的十甲基环五硅氧烷配合物(Dow Corning 9040 Silicone Elastomer Blend TM:Dow Corning公司制造) 5.0
(6)角鲨烷 7.0
(7)角鲨烷(植物性) 1.0
(8)失水山梨醇倍半异硬脂酸酯 1.0
(9)甘油改性硅酮树脂被覆煅烧绢云母 16.0
(10)甘油改性硅酮树脂被覆绢云母 7.0
(11)黄氧化铁被覆云母钛 0.1
(12)微粒氧化钛 5.0
(13)滑石 10.0
(14)氧化钛被覆绢云母 0.1
(15)氮化硼 2.5
(16)铁丹被覆云母钛 0.1
(17)植物甾醇 0.1
(18)抗坏血酸二棕榈酸酯 0.1
(19)3-O-乙基-L-抗坏血酸 5.0
(20)4-异丁基间苯二酚 0.1
(21)POE(30)植物甾醇 7.0
(22)酵母提取物 0.1
(23)对羟基苯甲酸酯 适量
(24)对甲氧基肉桂酸2-乙基己酯 1.0
(25)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 10.0
(26)球状聚丙烯酸烷基酯粉末 8.0
(27)甲基氢聚硅氧烷被覆云母 余量
(28)甲基氢聚硅氧烷被覆氧化铁氧化钛烧结物 5.0
(29)甲基氢聚硅氧烷被覆绢云母 5.0
(30)甲基氢聚硅氧烷被覆氧化钛 4.0
(31)甲基氢聚硅氧烷被覆薄片状氧化钛 5.0
(32)甲基氢聚硅氧烷被覆颜料(着色剂) 5.0
(33)香料 适量
(实施例16:粉状固形粉底)
(配合成分) (质量%)
(1)α-烯烃低聚物 3.0
(2)凡士林 3.0
(3)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 5.0
(4)烷基交联聚甲基硅氧烷的十甲基环五硅氧烷配合物(Dow Corning 9040 Silicone Elastomer Blend TM:Dow Corning公司制造) 3.0
(5)澳洲坚果油 0.1
(6)失水山梨醇倍半异硬脂酸酯 1.0
(7)烷基改性硅酮树脂被覆黄氧化铁 2.0
(8)烷基改性硅酮树脂被覆铁丹 1.0
(9)烷基改性硅酮树脂被覆黑氧化铁 0.5
(10)L-抗坏血酸 1.0
(11)4-异丁基间苯二酚 0.01
(12)黄氧化铁被覆云母钛 5.0
(13)合成金云母 5.0
(14)氧化钛 1.0
(15)氧化锌 1.0
(16)低温煅烧氧化锌 4.0
(17)煅烧绢云母 10.0
(18)金云母 1.0
(19)氧化铝 1.0
(20)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 15.0
(21)滑石 余量
(22)合成金云母 5.0
(23)交联型硅酮粉末(トレフイルE-506TM:Dow CorningToray Silicone Co.,Ltd.制造) 10.0
(24)酵母提取物 5.0
(25)对羟基苯甲酸酯 适量
(26)对甲氧基肉桂酸2-乙基己酯 1.0
(27)海藻酸钙粉末 1.0
(28)香料 适量
(实施例17:固形粉底)
(配合成分) (质量%)
(1)α-烯烃低聚物 10.0
(2)微晶蜡 0.5
(3)烷基交联聚甲基硅氧烷的二甲基聚硅氧烷配合物(Dow Corning 9041 Silicone Elastomer Blend TM:Dow Corning公司制造) 3.0
(4)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 1.0
(5)地蜡 5.0
(6)二甲基聚硅氧烷 15.0
(7)甲基苯基聚硅氧烷 10.0
(8)澳洲坚果油 0.1
(9)巴西棕榈蜡 0.1
(10)三2-乙基己酸甘油酯 7.0
(11)2-乙基己酸鲸蜡酯 10.0
(12)失水山梨醇倍半异硬脂酸酯 1.5
(13)云母 0.5
(14)硬脂酸铝 1.0
(15)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 3.0
(16)交联型硅酮粉末(トレフイルE-506TM:Dow CorningToray Silicone Co.,Ltd.制造) 8.0
(17)N-月桂酰基-L-赖氨酸 0.1
(18)3-O-乙基-L-抗坏血酸 0.01
(19)4-异丁基间苯二酚 5.0
(20)酵母提取物 0.1
(21)铁红 适量
(22)黄氧化铁 适量
(23)海藻酸钙粉末 1.0
(24)尼龙粉末 余量
(25)球状无水硅酸 1.0
(26)氧化钛 1.0
(实施例18:乳状粉底)
(配合成分) (质量%)
(1)微晶蜡 1.0
(2)二甲基聚硅氧烷 15.0
(3)十甲基环五硅氧烷 2.0
(4)烷基交联聚甲基硅氧烷的十甲基环五硅氧烷配合物(Dow Corning 9045Silicone Elastomer Blend TM:Dow Corning公司制造) 3.0
(5)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 0.5
(6)1,3-丁二醇 6.0
(7)小烛树蜡 3.0
(8)异硬脂酸 1.0
(9)3-O-乙基-L-抗坏血酸 0.01
(10)4-异丁基间苯二酚 0.1
(11)Polysorbate 60 7.0
(12)乙二醇脂肪酸酯 0.1
(13)羊毛脂脂肪酸辛基十二烷基酯 0.5
(14)2-烷基-N-羧甲基-N-羟乙基咪唑啉甜菜碱 4.0
(15)氧化钛 7.5
(16)硫酸钡 5.0
(17)氧化钛 7.0
(18)滑石 3.0
(19)无水硅酸 4.0
(20)交联型硅酮粉末(トレフイルE-506TM:Dow CorningToray Silicone Co.,Ltd.制造) 0.1
(21)六偏磷酸钠 0.1
(22)羟丙基-β-环糊精 0.1
(23)金缕梅提取物 0.1
(24)芍药提取物 0.1
(25)软骨素硫酸钠 0.1
(26)酵母提取物 0.1
(27)阿仙药提取物 0.1
(28)对羟基苯甲酸酯 适量
(29)铁丹 适量
(30)黄氧化铁 适量
(31)黑氧化铁 适量
(32)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 1.0
(33)黄原胶 0.1
(34)羧甲基纤维素钠 0.1
(35)丙烯酸钠/2-丙烯酰胺-2-甲基丙磺酸共聚物 0.5
(36)纯化水 余量
(实施例19:W/O粉底)
(配合成分) (质量%)
(1)二甲基聚硅氧烷 3.0
(2)十甲基环五硅氧烷 10.0
(3)POE/甲基聚硅氧烷共聚物 3.0
(4)十二甲基环六硅氧烷 5.0
(5)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 0.1
(6)烷基交联聚甲基硅氧烷的十甲基环五硅氧烷配合物(Dow Corning 9040 Silicone Elastomer Blend TM:Dow Corning公司制造) 5.0
(7)甘油 4.0
(8)1,3-丁二醇 5.0
(9)棕榈酸 0.5
(10)L-抗坏血酸 5.0
(11)4-异丁基间苯二酚 0.01
(12)二硬脂酰基二甲基氯化铵 0.2
(13)金属皂处理滑石 2.0
(14)交联型硅酮粉末(トレフイルE-506TM:Dow CorningToray Silicone Co.,Ltd.制造) 0.1
(15)铁丹被覆云母钛 0.5
(16)N-月桂酰基-L-丝氨酸 2.0
(17)L-谷氨酸钠 2.0
(18)对羟基苯甲酸酯 适量
(19)苯氧基乙醇 0.2
(20)球状尼龙粉末 1.0
(21)球状聚丙烯酸烷基酯粉末 3.0
(22)射干提取物 1.0
(23)酵母提取物 5.0
(24)纯化水 余量
(25)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 2.0
(26)糊精脂肪酸酯处理滑石 3.0
(27)糊精脂肪酸酯处理二氧化钛 15.0
(28)糊精脂肪酸酯处理黄氧化铁 3.0
(29)糊精脂肪酸酯处理黑氧化铁 0.5
(实施例20:O/W粉底)
(配合成分) (质量%)
(1)二甲基聚硅氧烷 8.0
(2)烷基交联聚甲基硅氧烷的十甲基环五硅氧烷配合物(Dow Corning 9040 Silicone Elastomer Blend TM:Dow Corning公司制造) 20.0
(3)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 5.0
(4)山萮醇 0.5
(5)鲨肝醇 0.5
(6)1,3-丁二醇 5.0
(7)澳洲坚果油 0.1
(8)异硬脂酸 1.5
(9)硬脂酸 1.0
(10)3-O-乙基-L-抗坏血酸 1.0
(11)4-异丁基间苯二酚 5.0
(12)山萮酸 0.5
(13)2-乙基己酸鲸蜡酯 5.0
(14)单硬脂酸聚氧乙烯甘油酯 1.0
(15)自乳化型单硬脂酸甘油酯 1.0
(16)黄氧化铁被覆云母钛 2.0
(17)氧化钛 4.0
(18)滑石 0.5
(19)高岭土 3.0
(20)合成金云母 0.1
(21)交联型硅酮粉末 0.1
(22)无水硅酸 5.0
(23)氢氧化钾 0.2
(24)三乙醇胺 0.8
(25)酵母提取物 0.1
(26)地椒提取物 0.1
(27)对羟基苯甲酸酯 适量
(28)对甲氧基肉桂酸2-乙基己酯 1.0
(29)铁丹 适量
(30)黄氧化铁 适量
(31)黑氧化铁 适量
(32)黄原胶 0.1
(33)丙烯酸钠/2-丙烯酰胺-2-甲基丙磺酸共聚物 1.0
(34)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 5.0
(35)澎润土 1.0
(36)羧甲基纤维素钠 0.1
(37)纯化水 余量
(38)香料 适量
(实施例21:粉底)
(配合成分) (质量%)
(1)十二甲基环六硅氧烷 15.0
(2)十甲基环五硅氧烷 余量
(3)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 5.0
(4)烷基交联聚甲基硅氧烷的二甲基聚硅氧烷配合物(Dow Corning 9041 Silicone Elastomer Blend TM:Dow Corning公司制造) 30.0
(5)乙醇 10.0
(6)异硬脂酸 0.5
(7)肉豆蔻酸处理氧化锌 0.5
(8)糊精棕榈酸酯被覆氧化钛 10.0
(9)糊精棕榈酸酯被覆滑石 7.0
(10)硅酮表面处理氧化钛(30nm) 5.0
(11)交联型硅酮粉末 1.0
(12)球状无水硅酸 2.0
(13)3-O-乙基-L-抗坏血酸 0.01
(14)4-异丁基间苯二酚 0.1
(15)苦参提取物 0.1
(16)柴胡提取物 1.0
(17)酵母提取物 2.0
(18)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 1.0
(19)对甲氧基肉桂酸2-乙基己酯 5.0
(20)糊精棕榈酸酯被覆铁丹 适量
(21)糊精棕榈酸酯被覆黄氧化铁 适量
(22)糊精棕榈酸酯被覆黑氧化铁 适量
(23)香料 适量
(实施例22:打底霜)
(配合成分) (质量%)
(1)二甲基聚硅氧烷 5.0
(2)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 0.1
(3)烷基交联聚甲基硅氧烷的十甲基环五硅氧烷配合物(Dow Corning 9045 Silicone Elastomer Blend TM:Dow Corning公司制造) 30.0
(4)十甲基环五硅氧烷 余量
(5)乙醇 8.0
(6)绀青被覆云母钛 0.5
(7)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 5.0
(8)甲基硅氧烷网状聚合物 5.0
(9)交联型硅酮粉末(トレフイルE-506TM:Dow CorningToray Silicone Co.,Ltd.制造) 5.0
(10)柠檬酸 0.02
(11)柠檬酸钠 0.08
(12)3-O-乙基-L-抗坏血酸 5.0
(13)4-异丁基间苯二酚 0.01
(14)POE/POP二醇-单-DL-α-生育酚[式(V)。式中k+y=30(k=16,y=14),x=2,R6、R7、R8为CH3,R9为H] 0.01
(15)郁金提取物 0.01
(16)酵母提取物 0.1
(17)纯化水 1.0
(18)POE/POP甲基聚硅氧烷共聚物 5.0
(实施例23:打底霜)
(配合成分) (质量%)
(1)二甲基聚硅氧烷 5.0
(2)烷基交联聚甲基硅氧烷的十甲基环五硅氧烷配合物(Dow Corning 9040 Silicone Elastomer Blend TM:Dow Corning公司制造) 5.0
(3)3-三(三甲基甲硅烷氧基)甲硅烷基丙基氨基甲酸支链淀粉 5.0
(4)十甲基环五硅氧烷 25.0
(5)聚氧乙烯/甲基聚硅氧烷共聚物 3.0
(6)甘油 1.0
(7)1,3-丁二醇 5.0
(8)木糖醇 0.5
(9)异硬脂酸 0.5
(10)无机复合粉体(カバ一リ一フAR-80TM;触媒化成工业株式会社制造) 10.0
(11)烷基改性硅酮树脂被覆无水硅酸 2.0
(12)滑石 0.5
(13)L-抗坏血酸 1.0
(14)4-异丁基间苯二酚 5.0
(15)硬脂酸铝 1.0
(16)铁丹被覆云母钛 0.1
(17)六偏磷酸钠 0.05
(18)甘草酸二钾 0.1
(19)L-丝氨酸 0.1
(20)小连翘提取物 0.1
(21)刺梨提取物 0.1
(22)芍药提取物 0.1
(23)溶血卵磷脂 0.01
(24)虎耳草提取物 0.1
(25)酵母提取物 0.1
(26)对羟基苯甲酸酯 适量
(27)苯氧基乙醇 适量
(28)糊精棕榈酸酯被覆黄氧化铁 0.1
(29)二硬脂二甲铵锂蒙脱石 1.0
(30)纯化水 余量
(31)三甲基甲硅烷氧基硅酸 1.5
(32)球状无水硅酸 1.0
(33)球状聚乙烯粉末 5.0
(34)香料 适量
产业上的可利用性
本发明的皮肤外用剂尽管含有一直以来容易因温度、光而发生变色的烷基间苯二酚类、L-抗坏血酸类,其温度稳定性(尤其是高温稳定性)、光稳定性也优异。
Claims (2)
1.一种皮肤外用剂,其含有:0.01~5质量%的(a)4-异丁基间苯二酚或其盐、和0.01~5质量%的(b)选自L-抗坏血酸或其盐、3-O-烷基-L-抗坏血酸或其盐中的1种或2种以上。
2.根据权利要求1所述的皮肤外用剂,其中,(b)成分为3-O-烷基-L-抗坏血酸或其盐。
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PCT/JP2009/059870 WO2009145300A1 (ja) | 2008-05-29 | 2009-05-29 | 皮膚外用剤 |
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CN106659662A (zh) * | 2014-06-10 | 2017-05-10 | 味之素株式会社 | 含有3‑o‑烷基‑l‑抗坏血酸或其盐的化妆品组合物 |
CN107595663A (zh) * | 2017-11-09 | 2018-01-19 | 武汉励合生物医药科技有限公司 | 一种高温稳定性皮肤外用剂 |
CN112120947A (zh) * | 2020-10-20 | 2020-12-25 | 伯德创研(广州)生物科技有限公司 | 一种祛斑美白组合物及其应用 |
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US5874463A (en) * | 1994-10-24 | 1999-02-23 | Ancira; Margaret | Hydroxy-kojic acid skin peel |
JPH11199426A (ja) * | 1998-01-05 | 1999-07-27 | Nippon Haipokkusu:Kk | 化粧料 |
RU2212229C1 (ru) * | 2002-06-14 | 2003-09-20 | Открытое акционерное общество "Косметическое объединение "Свобода" | Дневной восстанавливающий крем |
JP2004277352A (ja) | 2003-03-17 | 2004-10-07 | Sansho Seiyaku Co Ltd | 皮膚外用剤 |
JP4080946B2 (ja) * | 2003-05-28 | 2008-04-23 | 株式会社クラレ | 皮膚外用剤 |
JP2005120023A (ja) | 2003-10-16 | 2005-05-12 | Shiseido Co Ltd | 皮膚外用剤 |
KR101161568B1 (ko) * | 2003-12-15 | 2012-07-04 | 포라 가세이 고교 가부시키가이샤 | 피부 외용제 |
JP4546228B2 (ja) * | 2004-12-02 | 2010-09-15 | 株式会社資生堂 | 経皮吸収促進用油性皮膚外用組成物 |
WO2006126675A1 (ja) * | 2005-05-27 | 2006-11-30 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | 皮膚外用剤 |
CN101282708B (zh) * | 2005-10-05 | 2013-03-20 | 江崎格力高株式会社 | 含有磷酸化糖的皮肤外用剂 |
WO2007077770A1 (ja) * | 2005-12-26 | 2007-07-12 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | アルキルレゾルシノール配糖体とその製造方法並びに用途 |
JP5081432B2 (ja) * | 2006-07-04 | 2012-11-28 | 株式会社クラレ | 油中水乳化剤形の皮膚外用剤 |
JP5069965B2 (ja) * | 2007-07-19 | 2012-11-07 | 株式会社クラレ | 皮膚外用剤 |
JP5074134B2 (ja) * | 2007-09-14 | 2012-11-14 | 株式会社 資生堂 | 皮膚外用剤 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106659662A (zh) * | 2014-06-10 | 2017-05-10 | 味之素株式会社 | 含有3‑o‑烷基‑l‑抗坏血酸或其盐的化妆品组合物 |
CN107595663A (zh) * | 2017-11-09 | 2018-01-19 | 武汉励合生物医药科技有限公司 | 一种高温稳定性皮肤外用剂 |
CN112120947A (zh) * | 2020-10-20 | 2020-12-25 | 伯德创研(广州)生物科技有限公司 | 一种祛斑美白组合物及其应用 |
CN114642609A (zh) * | 2021-04-27 | 2022-06-21 | 上海科黛生物科技有限公司 | 一种改善维生素c稳定性的组合物及其在化妆品中的应用 |
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EP2292208A1 (en) | 2011-03-09 |
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KR20110013502A (ko) | 2011-02-09 |
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AU2016204668B2 (en) | 2018-03-08 |
KR101455969B1 (ko) | 2014-10-31 |
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US20110213030A1 (en) | 2011-09-01 |
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EP2292208A4 (en) | 2015-04-08 |
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BRPI0912134A2 (pt) | 2015-11-03 |
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