CN113226254A - 含有视黄醇的水包油型乳化化妆品 - Google Patents
含有视黄醇的水包油型乳化化妆品 Download PDFInfo
- Publication number
- CN113226254A CN113226254A CN201980085013.4A CN201980085013A CN113226254A CN 113226254 A CN113226254 A CN 113226254A CN 201980085013 A CN201980085013 A CN 201980085013A CN 113226254 A CN113226254 A CN 113226254A
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- Prior art keywords
- oil
- alkyl
- extract
- water type
- retinol
- Prior art date
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- 239000002537 cosmetic Substances 0.000 title claims abstract description 64
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- 239000001257 hydrogen Substances 0.000 claims description 2
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Abstract
本发明的目的在于，提供一种使视黄醇保持稳定且乳化稳定性也优异，而且涂抹时的服贴感良好，具有水润且清爽的使用感的含有视黄醇的水包油型乳化化妆品。本发明涉及一种水包油型乳化化妆品，其特征在于，其含有(a)视黄醇、(b)烷基改性羧乙烯基聚合物及(c)油分，上述(c)油分的配合量相对于化妆品总量为10～40质量％，且上述(c)油分含有相对于油分总量为50质量％以上的酯油。
Description
技术领域
本发明涉及一种含有视黄醇的水包油型乳化化妆品。更详细而言，涉及一种可使视黄醇长期保持稳定且乳化稳定性优异，而且涂抹时的服贴感良好，可实现水润且清爽的使用感的化妆品、尤其是适合用于眼周的水包油型乳化化妆品。
背景技术
视黄醇等维生素A类已知为具有各种生理作用的物质。例如市售有较多含有视黄醇等维生素A类作为表现出皱纹改善效果的美容成分的化妆品。然而，视黄醇为极不稳定的物质，有因热、光、空气(即氧)等而容易变质的倾向。
因此，为了抑制由视黄醇的氧化所导致的劣化，一般与抗氧化剂一同配合。尤其通用的是即使少量也发挥优异的抗氧化效果的生育酚或二丁基羟基甲苯(BHT)等酚系抗氧化剂。然而，生育酚或BHT等酚系抗氧化剂通过它们本身被氧化而防止共存的物质的氧化，故而存在产生抗氧化效果随时间经过劣化，并且有时产生变色或异臭等问题。另外，若预料到经时劣化而大量配合抗氧化剂，则也存在尤其在低温下保管时抗氧化剂会析出的问题。
因此，想出各种即便减少或不配合抗氧化剂也可使视黄醇保持稳定的办法。
例如专利文献1中记载的化妆品组合物为包含可溶于液态油中的视黄醇类及聚合物乳化剂的化妆品水包油乳液组合物。专利文献1中，上述聚合物乳化剂通过将水在油相中的扩散设为最低限度，并将视黄醇在水中的暴露设为最低限度，从而改善视黄醇类的稳定性。然而，作为上述液态油，确认到效果者为硅油及二辛基醚，由于其配合量较少(5％以下)，故而涂抹于皮肤时的使用性不充分。
专利文献2公开有通过在含有视黄醇等油溶性有效物质的O/W型乳液组合物中配合烷基改性羧乙烯基聚合物作为实质上唯一的乳化剂，将组合物pH调整为4.0～8.0，并且将乳液颗粒的平均粒径设为2～30μm，从而可维持乳化稳定性并改善油溶性有效物质的保存稳定性及安全性。但是，专利文献2的组合物中配合的油分为角鲨烷等烃油、硅油及高级醇，与专利文献1的组合物同样地使用性差。
先前已知专利文献1及2中使用的烷基改性羧乙烯基聚合物与在室温下为液状的高级醇共同提升乳化稳定性(专利文献3)，及聚乙二醇及/或聚丙二醇对使视黄醇稳定化有效(专利文献4)，但尚且不知在保持视黄醇的稳定性及乳化稳定性的状态下改善使用性的例子。尤其鉴于在应用于眼周的化妆品中，涂抹时的服贴感、水润且清爽的使用感较重要，谋求这种使用性优异的含有视黄醇的化妆品。
现有技术文献
专利文献
专利文献1：日本专利特表2004-513959号公报
专利文献2：日本专利特开2013-241406号公报
专利文献3：日本专利特开平8-126831号公报
专利文献4：日本专利特开平6-32710号公报
发明内容
发明要解决的问题
因此，本发明的课题在于，提供一种使视黄醇保持稳定并且乳化稳定性也优异，而且涂抹时的服贴感良好，具有水润且清爽的使用感的含有视黄醇的水包油型乳化化妆品。
用于解决问题的方案
本发明人为解决上述问题而进行努力研究，结果发现在含有视黄醇及烷基改性羧乙烯基聚合物作为有效成分的水包油型乳化化妆品中，通过将配合的油分量及酯油占油分总量的比率调整为特定范围，可获得实质上不使用抗氧化剂也使视黄醇保持稳定，并且乳化稳定性优异，而且涂抹于皮肤时的服贴感良好，带来水润且清爽的使用感的化妆品，从而完成本发明。
即，本发明提供一种水包油型乳化化妆品，其特征在于，其含有
(a)视黄醇、
(b)烷基改性羧乙烯基聚合物、及
(c)油分，
上述(c)油分的配合量相对于化妆品总量为10～40质量％，且上述(c)油分含有相对于油分总量为50质量％以上的酯油。
发明的效果
本发明的水包油型乳化化妆品可使视黄醇长期保持稳定，维持高乳化稳定性，并且涂抹时的服贴感良好，带来水润且清爽的使用感。
另外，可不含有固体油分作为油分，故而制造时无须加热。进而，可实质上不含有抗氧化剂，故而不担心产生经时变色、变臭或析出。
具体实施方式
本发明的水包油型乳化化妆品(以下也简称为“化妆品”)含有(a)视黄醇、(b)烷基改性羧乙烯基聚合物及(c)酯油占50质量％以上的油分作为必需成分。以下对构成本发明的乳化化妆品的各成分进行详细叙述。
(a)视黄醇
本发明的化妆品中的“视黄醇”(成分(a))包含视黄醇及其衍生物。作为视黄醇衍生物，一般已知有视黄醇棕榈酸酯、视黄醇乙酸酯、Cylasphere Retinol、生育酚视黄酸酯等。本发明中，优选使用不为衍生物的视黄醇(也称为纯视黄醇)。本说明书中，“视黄醇”意指纯视黄醇。视黄醇与衍生物相比，皱纹改善等效果虽高，但是为非常不稳定的物质。但是，若将视黄醇配合于本发明的化妆品中，则即便不添加抗氧化剂也可长期保持稳定。
相对于本发明的乳化化妆品总量，本发明的化妆品中的视黄醇的配合量为0.001～0.5质量％，优选0.01～0.1质量％。此处，若不足0.001质量％，则无法充分地发挥通过配合视黄醇所带来的效果，另一方面，若超过0.5质量％而配合，则存在对皮肤带来刺激的情况。
(b)烷基改性羧乙烯基聚合物
本发明的化妆品中的“烷基改性羧乙烯基聚合物”(成分(b))包含烷基改性羧乙烯基聚合物及其盐。
本发明中使用的烷基改性羧乙烯基聚合物的烷基可为直链状也可为支链状，构成烷基的碳数并无特别限定，例如为8～35，优选10～30。
作为本发明的烷基改性羧乙烯基聚合物，例如可使用使经碳数8～35(优选10～30)的长链烷基改性的(甲基)丙烯酸酯单体与烯属不饱和羧酸单体共聚合而获得的共聚物。作为典型例，可列举使1～50重量％的(甲基)丙烯酸长链烷基酯单体与50～99重量％的烯属不饱和羧酸单体共聚合而获得的共聚物等。视情况，也可使用具有为了调整共聚物的特性而进一步配合烯属多官能性单体进行聚合而成的交联结构的共聚物(例如参照日本专利特开2002-193731号公报)。
作为构成烷基改性羧乙烯基聚合物的(甲基)丙烯酸长链烷基酯单体，可使用下述通式(1)所示的单体。
(R为碳数8～35、优选10～30的直链状或支链状烷基，R’为氢或甲基。)
作为具体例，可列举选自丙烯酸癸酯、丙烯酸月桂酯、丙烯酸棕榈酯、丙烯酸硬脂酯、丙烯酸山萮酯等碳数8～35、优选10～30的丙烯酸烷基酯及相当于它们的甲基丙烯酸酯的组中的1种以上的单体。
另外，作为与上述(甲基)丙烯酸长链烷基酯单体共聚合的烯属不饱和羧酸单体，例如可列举选自丙烯酸、甲基丙烯酸、α-氯-丙烯酸、α-苯基丙烯酸、山梨酸、肉桂酸、马来酸、富马酸、或马来酸酐等包含烯烃系双键及至少1个羧基的聚合性化合物的组中的1种以上的单体。其中，优选容易获取且具有优异的聚合能力的丙烯酸。
作为由(甲基)丙烯酸长链烷基酯与烯属不饱和羧酸单体形成的共聚物，也可使用具有如下交联结构的共聚物，该交联结构除(甲基)丙烯酸长链烷基酯与烯属不饱和羧酸单体以外，为了调整共聚物的特性而进一步添加亚甲双丙烯酰胺、丙烯酸烯丙酯、甲基丙烯酸甲基烯丙酯、二乙烯醚、烯丙基蔗糖、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、三丙烯酸甘油酯等烯属多官能性单体进行聚合而成。相对于(甲基)丙烯酸长链烷基酯单体与烯属不饱和羧酸单体的总量，上述烯属多官能性单体的添加量优选0.01～4.0质量％，进而优选0.2～1.0质量％。这些具有交联结构的共聚物例如可利用日本专利特开昭51-6190号公报等中记载的方法制造。
本发明中使用的(b)烷基改性羧乙烯基聚合物的平均分子量并无特别限定，优选设为约500000～约5000000。
需要说明的是，作为本发明的化妆品中使用的(b)烷基改性羧乙烯基聚合物，优选使用化妆品成分表示名称被称为“丙烯酸(酯)类/C10-30烷醇丙烯酸酯交联聚合物”、或“丙烯酸(酯)类/C12-22烷醇甲基丙烯酸酯共聚物”者。这些聚合物以PEMULEN TR-1(Lubrizol公司制造)、PEMULEN TR-2(Lubrizol公司制造)、CARBOPOL 1342(Lubrizol公司制造)、CARBOPOL ETD2020(Lubrizol公司制造)、AllianzOPT(Ashland公司制造)的产品名市售，可使用这些市售品。
本发明的化妆品中的(b)烷基改性羧乙烯基聚合物的配合量并无特别限定，通常相对于乳化化妆品总量为0.01～4.0质量％，优选0.01～2.0质量％，进而优选0.01～1.0质量％，尤其优选0.01～0.5质量％。
烷基改性羧乙烯基聚合物可使用1种或混合使用2种以上。
(c)油分
本发明的化妆品通过以相对于化妆品总量将油分(成分(c))的配合量设为10～40质量％，而且酯油占该油分总量的50质量％以上的方式进行调整，除稳定性以外，也达成涂抹时的服贴感及水润的使用感。
本发明的油分(成分(c))中配合的“酯油”只要为化妆品中可配合的酯油，则并无特别限定。本说明书中的“酯油”包含酸与醇进行酯键合而成的化合物、氨基酸的羧基与醇进行酯键合而成的化合物、及二聚酸及/或二聚醇的二酯体。
作为酸与一元醇进行键合而成的酯油，例如可列举：肉豆蔻酸异丙酯、辛酸鲸蜡酯(2-乙基己酸鲸蜡酯)、肉豆蔻酸辛基十二烷基酯、棕榈酸异丙酯、棕榈酸2-乙基己酯、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、乙酰化羊毛脂、硬脂酸异鲸蜡酯、异硬脂酸异鲸蜡酯、胆甾醇12-羟基硬脂酸酯、蓖麻油脂肪酸甲酯、油酸油脂、棕榈酸2-庚基十一烷基酯、月桂酸乙酯、肉豆蔻酸2-己基癸酯、棕榈酸2-己基癸酯、乙酸乙酯、乙酸丁酯及乙酸戊酯等。
作为酸与多元醇进行键合而成的酯油，例如可列举：乙二醇二-2-乙基己酸酯、二季戊四醇脂肪酸酯、单异硬脂酸正烷基二醇酯、二癸酸新戊二醇酯、苹果酸二异硬脂酯、甘油二-2-庚基十一烷酸酯、三羟甲基丙烷三-2-乙基己酸酯、三羟甲基丙烷三异硬脂酸酯、季戊四醇四(乙基己酸)酯、甘油三-2-乙基己酸酯、三羟甲基丙烷三异硬脂酸酯、甘油三肉豆蔻酸酯、甘油三-2-庚基十一烷酸酯、己二酸二异丁酯、己二酸二-2-庚基十一烷酯、癸二酸二-2-乙基己酯、己二酸2-己基癸酯、癸二酸二异丙酯及柠檬酸三乙酯等。
作为氨基酸的羧基与醇进行酯键合而成的酯油，例如可列举：N-月桂酰-L-谷氨酸-2-辛基十二烷基酯、N-月桂酰-谷氨酸二(植物甾醇/2-辛基十二烷基)酯、N-月桂酰-谷氨酸二(植物甾醇/山萮基/2-辛基十二烷基)酯、N-月桂酰-谷氨酸二(胆甾醇基/2-辛基十二烷基)酯、N-月桂酰-谷氨酸二(胆甾醇基/山萮基/2-辛基十二烷基)酯、N-月桂酰-肌氨酸异丙酯等。
作为二聚酸及/或二聚醇的二酯体，例如可列举：二聚二亚麻油酸二(植物甾醇/异硬脂基/鲸蜡基/硬脂基/山萮基)酯、二聚二亚麻油酸二(异硬脂基/植物甾醇)酯、二聚二亚麻油酸二亚麻酯、二异硬脂酸二聚二亚麻酯、乙酸甘油酯等。
本发明的化妆品中配合的酯油可为1种或2种以上的混合物。尤其优选使用由脂肪酸与多元醇形成的酯油、例如季戊四醇四(乙基己酸)酯。
作为构成本发明的化妆品中的油分(成分(c))且除酯油以外的油分，只要为化妆品中通常可配合的油性成分则并无特别限定。
若列举具体例，则包含鳄梨油、山茶油、澳洲坚果油、貂油、橄榄油、蓖麻油、霍霍巴油等液体油脂；可可脂、椰子油、棕榈油、棕榈仁油、牛油、猪油、羊油、马油、氢化油、氢化蓖麻油、木蜡、乳木果油等固体油脂；蜂蜡、小烛树蜡、棉蜡、巴西棕榈蜡、虫蜡、鲸蜡、褐煤蜡、米糠蜡、羊毛脂、氢化羊毛脂、硬质羊毛脂、木棉蜡、甘蔗蜡、霍霍巴蜡、虫胶蜡等蜡类；液体石蜡、角鲨烷、石蜡、地蜡、角鲨烯等烃；月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山萮酸、油酸、12-羟基硬脂酸、异硬脂酸、亚油酸(linoleic acid)、亚麻酸(linolenic acid)等高级脂肪酸；月桂醇、鲸蜡醇、硬脂醇、山萮醇、油醇、单硬脂基甘油醚、单棕榈基甘油醚、胆甾醇、植甾醇、异硬脂醇等高级醇；硅油等。可使用1种这些油分或组合使用2种以上。
本发明的化妆品可采用不配合固体油脂或蜡类等在常温(25℃)下为固体状的油分(固体油分)作为油分的配方。通过采用不含固体油分的配方，无须在制造过程中设置加热步骤，可在常温下制备，故而优选。
另外，在使用丙烯酸(酯)类/C10-30烷醇丙烯酸酯交联聚合物作为(b)烷基改性羧乙烯基聚合物时，若配合在常温下为固体的高级醇作为(c)油分，则有时发生凝胶化而无法获得稳定的水包油型乳化物。因此，本发明的化妆品包含不含有在常温下为固体的高级醇的方式。
相对于化妆品总量，本发明的化妆品中的(c)油分的配合量为10～40质量％，优选15～35质量％，更优选20～30质量％。若(c)油分的配合量不足10质量％，则无法获得涂抹时的服贴感，若超过40质量％而配合，则稳定性降低，无法获得水润的使用感。
酯油必须相对于油分总量配合50质量％以上、优选60质量％以上。酯油相对于油分总量的比率的上限值并无特别限定，例如可设为100质量％以下、90质量％以下或80质量％以下等。若酯油相对于油分总量的质量比率不足50质量％，则服贴感及水润感不充分。
本发明的乳化化妆品除上述必需成分(a)～(c)以外，也可在不损害本发明的效果的范围内适当配合水包油型乳化化妆品中可配合的其他成分。具体而言，可列举：增稠剂、保湿剂、中和剂、各种药剂、各种提取物、稳定剂、防腐剂、螯合剂、掩蔽剂、着色剂、香料、精油等。
需要说明的是，本发明的化妆品可使视黄醇保持稳定，故而无须实质上配合以往的含有视黄醇的组合物中配合的抗氧化剂(例如生育酚或二丁基羟基甲苯(BHT)等酚系抗氧化剂)。但是，可在不影响本发明的效果的范围内适当配合。
作为增稠剂，可列举：黄原胶、罗望子胶、海藻酸钠、结冷胶、琼脂、聚乙烯醇、榅桲籽胶、未经烷基改性的羧乙烯基聚合物(在本说明书中简称为“卡波姆”)等。作为未经烷基改性的羧乙烯基聚合物的市售品，例如有CARBOPOL941聚合物、CARBOPOL980聚合物、CARBOPOL981聚合物(Lubrizol Advanced Materials公司制造)、Synthalen K、SynthalenL(3VSIGMA公司制造)等。
作为保湿剂，例如可列举：1,3-丁二醇(BG)、聚乙二醇、丙二醇、一缩二丙二醇(DPG)、己二醇、甘油、二甘油、木糖醇、麦芽糖醇、麦芽糖、D-甘露醇、海藻糖、赤藓糖醇、丙二醇、葡萄糖、聚氧乙烯甲基葡萄糖苷等。
作为螯合剂，可列举：依地酸钠、偏磷酸钠、磷酸等。
作为各种药剂，可列举：肌醇、盐酸吡哆醇、烟酸苄酯、烟酰胺、dl-α-生育酚烟酸酯、抗坏血酸磷酸镁、抗坏血酸2-葡萄糖苷、dl-α-生育酚2-L抗坏血酸磷酸二酯钾盐、泛酸、生物素等维生素类、尿囊素、薁等抗炎剂、熊果苷、4-甲氧基水杨酸或其盐、传明酸或其衍生物等美白剂、鞣酸等收敛剂、盐酸溶菌酶、盐酸吡哆醇、γ-谷维素、海洋胶原蛋白、海洋弹力蛋白等。
作为各种提取物，可列举：儿茶钩藤提取物、山毛榉芽提取物、姜黄根提取物、鱼腥草提取物、黄檗树皮提取物、草木犀提取物、短柄野芝麻提取物、甘草提取物、芍药提取物、肥皂草叶/根提取物、丝瓜提取物、鸡纳树树皮提取物、草莓虎耳草提取物、苦参提取物、日本萍蓬草根提取物、无患子果提取物、茴香果提取物、樱草花提取物、蔷薇提取物、中国地黄根提取物、柠檬提取物、紫草根提取物、芦荟提取物、地椒提取物、蓝桉提取物、问荆提取物、药鼠尾草提取物、麝香草提取物、茶提取物、甜茶叶提取物、海藻提取物、黄青提取物、丁香花提取物、树莓提取物、香蜂花提取物、人参提取物、胡萝卜提取物、欧洲七叶树提取物、桃提取物、桃叶提取物、桑叶提取物、矢车菊花提取物、北美金缕梅提取液、(动物)胎盘蛋白、胸腺提取物、蚕丝提取液、酵母提取物等各种提取物。
本发明的乳化化妆品可依据以往使用的方法制造。例如可通过分开混合油相成分及水相成分而分别制备油相及水相，将油相及水相加以混合并利用均质混合器等进行乳化而制造。
本发明的化妆品可使具有皱纹改善效果的视黄醇保持稳定，并且涂抹时的服贴感及水润感优异。本发明的化妆品利用这些特征，适合作为用于脸、尤其是眼周的乳液、乳霜、美容液等加以提供。
实施例
以下列举实施例更详细地说明本发明，但本发明并不限定于这些实施例。
需要说明的是，关于以下实施例等中的含量，只要无特别说明则表示质量％。
制备下述表1所示的组成的水包油型乳化化妆品(试样)，依照下述评价方法及评价基准评价它们的特性。将评价结果一并示于表1。
(1)乳化稳定性
将各试样于50℃下放置4周后，恢复至室温，目视观察试样的状态，利用以下基准进行评价。
A：完全未见油分离。
B：略微可见油分离。
C：明显可见油分离。
(2)使用感的实际使用试验
·水润感
8名专业官能检查员实际使用，进行水润感的判定。
评价基准：
S：8名中7～8名回答水润且清爽的使用性良好。
A：8名中5～6名回答水润且清爽的使用性良好。
B：8名中3～4名回答水润且清爽的使用性良好。
C：8名中2名以上回答感觉不到水润感，使用性不佳。
·涂抹时的服贴感
8名专业官能检查员实际使用，进行涂抹时的服贴感的判定。
评价基准：
S：8名中7～8名回答涂抹时的服贴感优异，使用性良好。
A：8名中5～6名回答涂抹时的服贴感优异，使用性良好。
B：8名中3～4名回答涂抹时的服贴感优异，使用性良好。
C：8名中2名以上回答涂抹时的服贴感不优异，使用性不佳。
[表1]
制造方法：
上述各试样大致利用以下方法制造。
将油相成分(季戊四醇四(乙基己酸)酯、氢化聚癸烯、角鲨烷及视黄醇)及水相成分(上述以外的成分)分别分开混合后，边将油相成分添加到水相成分中，边利用乳化机进行乳化，从而获得水包油型乳化物。
根据表1所示的结果，可知包含丙烯酸(酯)类/C10-30烷醇丙烯酸酯交联聚合物作为(b)烷基改性羧乙烯基聚合物，且相对于化妆品总量含有特定范围内的量(25质量％)的相对于油分总量酯油(季戊四醇四(乙基己酸)酯)占50质量％以上(60质量％)的油分的乳化化妆品(实施例1)的服贴感良好，获得水润且清爽的使用感。
另一方面，在油分的配合量为不满足本发明特定范围的8质量％的化妆品(比较例1)中，涂抹时的服贴感明显降低。另外，在油分的配合量为超过本发明特定范围的41质量％的化妆品(比较例2)中，缺乏水润感。进而，在油分量虽为本发明特定范围内(27质量％)，但酯油相对于油分总量的比率为44质量％(不足50质量％)的化妆品(比较例3)中，服贴感及水润感均不充分。
以下示出本发明的水包油型乳化化妆品的配方例，但本发明并不限定于这些。
配方例1：
配方例2：
Claims (9)
1.一种水包油型乳化化妆品，其特征在于，
其含有(a)视黄醇、(b)烷基改性羧乙烯基聚合物、及(c)油分，
所述(c)油分的配合量相对于化妆品总量为10～40质量％，且所述(c)油分含有相对于油分总量为50质量％以上的酯油。
2.根据权利要求1所述的水包油型乳化化妆品，其中，(b)烷基改性羧乙烯基聚合物为下述通式(1)所示的(甲基)丙烯酸长链烷基酯单体与烯属不饱和羧酸单体的共聚物：
其中，R为碳数8～35的直链状或支链状烷基，R’为氢或甲基。
3.根据权利要求2所述的水包油型乳化化妆品，其中，(b)烷基改性羧乙烯基聚合物为选自丙烯酸(酯)类/C10-30烷醇丙烯酸酯交联聚合物及丙烯酸(酯)类/C12-22烷醇甲基丙烯酸酯共聚物中的至少1种。
4.根据权利要求3所述的水包油型乳化化妆品，其中，(b)烷基改性羧乙烯基聚合物为丙烯酸(酯)类/C10-30烷醇丙烯酸酯交联聚合物。
5.根据权利要求1至4中任一项所述的水包油型乳化化妆品，其中，(b)烷基改性羧乙烯基聚合物的配合量相对于化妆品总量为0.01～4.0质量％。
6.根据权利要求1至5中任一项所述的水包油型乳化化妆品，其中，酯油为多元醇的脂肪酸酯。
7.根据权利要求6所述的水包油型乳化化妆品，其中，多元醇的脂肪酸酯包含季戊四醇四(乙基己酸)酯。
8.根据权利要求1至7中任一项所述的水包油型乳化化妆品，其不含有固体油分。
9.根据权利要求1至8中任一项所述的水包油型乳化化妆品，其实质上不含有抗氧化剂。
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| JP2018247049 | 2018-12-28 | ||
| JP2018-247049 | 2018-12-28 | ||
| PCT/JP2019/049789 WO2020137785A1 (ja) | 2018-12-28 | 2019-12-19 | レチノール含有水中油型乳化化粧料 |
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| US (1) | US20220125689A1 (zh) |
| EP (1) | EP3903762A4 (zh) |
| JP (1) | JP7456939B2 (zh) |
| CN (1) | CN113226254B (zh) |
| TW (1) | TW202038891A (zh) |
| WO (1) | WO2020137785A1 (zh) |
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| JP7374755B2 (ja) * | 2019-12-20 | 2023-11-07 | 株式会社ナリス化粧品 | 皮膚外用組成物 |
| JP2024064065A (ja) | 2022-10-27 | 2024-05-14 | Ｊｎｔｌコンシューマーヘルス株式会社 | 化粧品組成物 |
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Also Published As
| Publication number | Publication date |
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| WO2020137785A1 (ja) | 2020-07-02 |
| JP7456939B2 (ja) | 2024-03-27 |
| EP3903762A4 (en) | 2022-10-26 |
| JPWO2020137785A1 (ja) | 2021-11-18 |
| TW202038891A (zh) | 2020-11-01 |
| CN113226254B (zh) | 2024-02-23 |
| US20220125689A1 (en) | 2022-04-28 |
| EP3903762A1 (en) | 2021-11-03 |
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