CN1767765A - 皮肤外用剂组合物 - Google Patents

皮肤外用剂组合物 Download PDF

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CN1767765A
CN1767765A CN 200480008797 CN200480008797A CN1767765A CN 1767765 A CN1767765 A CN 1767765A CN 200480008797 CN200480008797 CN 200480008797 CN 200480008797 A CN200480008797 A CN 200480008797A CN 1767765 A CN1767765 A CN 1767765A
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上沼三纪子
末继胜
小川滋之
横田江利子
原英二郎
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Shiseido Co Ltd
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Abstract

皮肤外用剂组合物,含有式(I)、(II)、(III)或(IV)表示的二醇化合物或其衍生物。(式中,R表示苄基或苯基。)

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皮肤外用剂组合物
技术领域
本发明涉及皮肤外用剂组合物和抗菌剂。更详细地说,涉及可优选使用于皮肤外用剂组合物、洗涤剂、食品、日用品等的、对广泛微生物有优良抗菌活性、含有对人体安全的二醇化合物或其衍生物,既充分确保防腐性,又显著提高使用性、安全性的皮肤外用剂组合物和抗菌剂。
其利用领域可用于药品、准药品、化妆品领域(也包括人和其它动物所用的各种制剂)的各种皮肤外用剂组合物,具体来说可举出用于化妆水、乳液、乳膏(包含软膏)、防晒霜、粉底、油、面膜、肥皂(也包括药用皂)、香皂、口红、指甲化妆品、眉眼化妆品、香水、洗面奶、口腔用类(牙膏、漱口液等)、除臭剂(腋臭、脚臭等)、浴用剂、洗发剂、焗油剂、发油、发胶、染发剂等。此外,可用于医疗器械类或以患部的消毒洗涤为目的的医疗用洗涤剂、杀菌洗涤餐具等的家用洗涤剂、食品工业用洗涤剂等。还可用于纤维制品(床单类、衣服类等)、食品包装薄膜、合成树脂、木材、日用品等的抗菌加工、各种形态的口服药剂、卫生棉类、湿纸巾或擦拭用纸类、灭菌用布等无纺布,并且还可用于口腔用组合物(口香糖、糖果等)或鱼糕、鱼卷等水产熟食品,香肠、火腿等畜产品,西式糕点类,日式糕点类,生面、煮面、中式面、日本面、荞麦面、通心面等面类,酱油、汤汁、作料汁等调味料,家常菜、果汁、汤汁等普通饮食类。
背景技术
至今为止为抑制微生物增殖,广泛使用山梨酸、脱氢乙酸及其盐、对羟基苯甲酸衍生物等作为食品、药品、化妆品类等的抗菌、防腐剂,但存在安全性问题,添加量或对象食品受到限制(例如,山梨酸及其盐在食品中的配比上限为0.2%,脱氢乙酸及其盐只能用于奶酪、黄油和奶油,此外,对羟基苯甲酸甲酯钠在化妆品类中的配比上限为1.0%)。
此外,为抑制微生物增殖,通过对机体在皮肤或粘膜上采用物理的或所谓分布杀菌性物质或粘液的化学方法抑制微生物入侵。进一步地,对入侵到机体内的微生物,可通过免疫球蛋白阻止附着、吞噬细胞的吞噬作用、溶菌酶的溶菌作用等先天非特异性免疫或对特定病原菌的免疫应答等进行抵抗。
但是,如果微生物的感染力超过机体的抵抗力,机体内就会出现感染症状,例如,有产生金黄色葡萄球菌引起的脓皮症等感染性皮炎、食物中毒,败血症,枯草杆菌引起的结膜炎、虹膜炎,大肠杆菌引起的尿道感染症、痢疾等,此外,还有产生放线菌等引起的牙周病、生龋性菌引起的龋齿、及粉刺菌(丙酸杆菌粉刺),头皮屑菌(卵圆形糠秕孢子菌(pityrosprum ovale))等引起的粉刺、头皮屑或头皮屑伴有的瘙痒等各种各样症状的危险性。
因此,至今为止,对机体内外感染症的预防和治疗使用了各种各样的药物,占其绝大多数的抗生素或抗菌-防腐剂确实效果很强,但安全性存在问题,须严格注意它们的使用,因而正致力寻求在功效、安全性等方面更有用的物质。
近年来,正在寻求对肌肤有益而安全的皮肤外用剂组合物。另一方面,也不得不重视皮肤外用剂组合物的保存性,必须考虑防腐防霉,实际中大多数皮肤外用剂组合物配合对羟基苯甲酸酯,通称尼泊金类作为防腐剂来确保防腐力。
但是,作为防腐剂配合尼泊金类时,有时少部分敏感的使用者也会出现使用时刺痛等皮肤刺激,也不满意使用性。当然也可以不配合尼泊金类而制备皮肤外用剂组合物,但此时为确保防腐性,必须采用每单次使用量的小装量容器,或在管状容器中设置无内衬结构等其他复杂装置,缺乏可通用性。
发明内容
因此,本发明的目的是提供充分确保防腐性,且同时满足使用性、安全性的皮肤外用剂组合物。
本发明的另一目的是提供对细菌、酵母、霉等微生物引起的感染症、疾病有抗菌、防腐效果,即,有杀菌或防止经时繁殖效果,且在各种领域也能安全利用的抗菌剂。
根据本发明,可提供含有相对于组合物总重量在0.001质量%以上的式(I)、(II)、(III)或(IV)表示的二醇化合物或其衍生物以及剩余部分的基质而成的皮肤外用剂组合物。
Figure A20048000879700062
(式中,R表示苄基或苯基。)
Figure A20048000879700063
Figure A20048000879700064
根据本发明,还可提供含有式(I)、(II)、(III)或(IV)表示的二醇化合物或其衍生物的抗菌剂。
Figure A20048000879700071
Figure A20048000879700072
(式中,R表示苄基或苯基。)
Figure A20048000879700073
Figure A20048000879700074
具体实施方式
本发明人等鉴于上述课题,确认前述式(I)~(IV)的二醇化合物或其衍生物对各种微生物具有强的抗菌和防腐效果,对人或动物使用安全,发现其作为新型抗菌剂在各个领域中应用非常有效,至此完成了本发明。
此外,本发明人等对细菌、酵母、霉等微生物引起的感染症、疾病有抗菌、防腐效果,即具有杀菌或防止经时繁殖的效果、且在各种领域中利用也安全的物质进行反复努力研究的结果,确认前述式(I)~(IV)表示的二醇化合物或其衍生物对各种微生物有强的抗菌、防腐效果,确认其对人或动物安全,发现其作为新型抗菌剂在各种领域中应用非常有效,至此完成本发明。
以下详述本发明的构成。
本发明所用的上述式(1)的3-己炔-2,5-二醇虽是公知物质,但作为抗菌剂属新型用途。
本发明所用的3-己炔-2,5-二醇可通过乙炔和乙醛容易地制造。并且例如东京化成工业株式会社、关东化学株式会社、ALDRICH公司等均有市售,容易购得。本发明所用的3-己炔-2,5-二醇可以任意是旋光体、外消旋体、内外消旋体或它们的混合物。
本发明所用的上述式(II)的甘油衍生物虽是公知物质,但作为抗菌剂属新型用途。该甘油衍生物可通过普通的合成方法制造。例如可以通过糖醇、甘油、氯醇或溴醇等卤代醇和苯酚或苄醇容易地制造。还可通过制造苯基缩水甘油醚或苄基缩水甘油醚后水解而得。3-苯氧基-1,2-丙二醇例如由东京化成工业株式会社市售,3-苄氧基-1,2-丙二醇例如由SIGMA公司等市售,容易购得。本发明所用的甘油衍生物可以任意是旋光体、外消旋体或它们的混合物。并且3-苯氧基-1,2-丙二醇和3-苄氧基-1,2-丙二醇既可以分别单独使用,也可以以任意比例组合使用。
本发明所用的前述式(III)的2,2-二甲基-1-苯基-1,3-丙二醇虽是公知物质,但作为抗菌剂属新型用途。该2,2-二甲基-1-苯基-1,3-丙二醇可通过普通的合成方法制造。例如可由苯甲醛和异丁醛容易地制造。(例如可通过Wolter ten Hoeve等人的方法(J.Org.Chem.1985,50,4508-4514)获得。)并且2,2-二甲基-1-苯基-1,3-丙二醇例如由Aldrich公司等市售,可容易购得。本发明所用的2,2-二甲基-1-苯基-1,3-丙二醇可以任意是旋光体、外消旋体或它们的混合物。
本发明所用的前述式(IV)的2,4,7,9-四甲基-5-癸炔-4,7-二醇虽是公知物质,但作为抗菌剂属新型用途。
本发明所用的2,4,7,9-四甲基-5-癸炔-4,7-二醇可通过普通的合成方法制造。例如可由乙炔和4-甲基-2-戊酮合成。并且2,4,7,9-四甲基-5-癸炔-4,7-二醇例如由东京化成株式会社等市售,容易购得。本发明所用的2,4,7,9-四甲基-5-癸炔-4,7-二醇可以任意是旋光体,外消旋体或它们的混合物。
本发明抗菌剂可任意配合于皮肤外用剂组合物。此外,本发明抗菌剂也可以配合作为用于以医疗器械类或以患部的消毒洗涤为目的的医疗用洗涤剂,杀菌洗涤餐具等的家用洗涤剂,食品工业用洗涤剂,食品包装薄膜、纤维、合成树脂、木材、日用品等的抗菌加工用的抗菌剂;抗菌性涂料,口腔用组合物(口香糖、糖果等)或鱼糕、鱼卷等水产熟食品,香肠、火腿等畜产品,糕点类,面类,汤汁、酱油等调味料,家常菜,饮料等食品用的抗菌剂等。
本发明抗菌剂的使用方法没有特殊限制,适用于各种对象。例如可直接使用添加到对象物的方法、喷洒方法、涂布方法、浸渍方法、含浸方法、成形加工等时掺入的方法等通常使用的方法。
本发明抗菌剂可直接使用,但作为抗菌剂配合时的配合量因制品形态、所期待作用的程度而不同,虽无特殊限定,但通常在100ppm以上,优选1000ppm以上,更优选1000~5000ppm。
此外,本发明抗菌剂配合在各种组合物中时,在不损害本发明效果的范围内,可与食品、化妆品、药品、准药品等一般常用的各种成分一起配合,例如:砂糖、炼乳、小麦粉、起酥油、食盐、葡萄糖、鸡蛋、黄油、人造奶油、糖稀、钙、铁分、调味料、香辛料或油分(动植物油、矿物油、酯油、蜡油、硅油、高级醇、磷脂质类、脂肪酸类等)、表面活化剂(阴离子性、阳离子性、两性或非离子性表面活化剂)、维生素类(维生素A族、维生素B族、叶酸类、烟酸类、泛酸类、生物素类、维生素C族、维生素D族、维生素E族、其它阿魏酸、γ-谷维素等)、紫外吸收剂(对氨基苯甲酸、邻氨基苯甲酸、水杨酸、香豆素、苯并三唑、四唑、咪唑啉、嘧啶、二噁烷、呋喃、吡喃酮、樟脑、核酸、尿素囊及它们的衍生物、氨基酸类化合物、紫草素、黄芩苷、黄芩黄素、黄连素等)、抗氧化剂(硬脂酸酯、降二氢愈疮木酸、二丁羟基甲苯、丁羟基苯甲醚、对羟基苯甲醚、没食子酸丙酯、芝麻酚、麻油酚、棉酚等)、增粘剂(羟乙基纤维素、乙基纤维素、羧乙基纤维素、甲基纤维素、羧甲基纤维素、羧甲基纤维素钠、羟丙基纤维素、硝化纤维素、聚乙烯醇、聚乙烯甲醚、聚乙烯吡咯烷酮、聚甲基丙烯酸乙烯酯、聚丙烯酸盐、聚羧乙烯、阿拉伯胶、黄蓍胶、琼脂、酪蛋白、糊精、明胶、果胶、淀粉、褐藻酸及其盐等)、保湿剂(丙二醇、1,3-丁二醇、聚乙二醇、甘油、1、2-戊二醇、己二醇、硫酸软骨素及其盐、透明质酸及其盐、乳酸钠等),除此以外,还有低级醇、多元醇、水溶性高分子、pH调节剂、防腐-防霉剂、着色剂、香料、清凉剂、稳定剂、动-植物提取物、动植物性蛋白质及其分解物、动植物性多糖类及其分解物、动植物性糖蛋白及其分解物、微生物培养代谢成分、血流促进剂、消炎剂、抗炎剂、抗过敏剂、细胞活化剂、氨基酸及其盐、角质溶解剂、收敛剂、创伤治疗剂、增泡剂、口腔用剂、消臭脱臭剂、乳化剂等,也可以同时使用。
此外、有关将本发明抗菌剂配合于皮肤外用剂组合物时的剂型是任意的,可使用常规方法配合,例如可采用化妆水、乳剂、软膏、乳液、粉底、油、面膜、肥皂(也包括药用皂)、香皂、口红、指甲化妆品、眉眼化妆品、香水、洗面奶、口腔用类(牙膏、漱口液等)、防臭剂(腋臭、脚臭等)、浴用剂、洗发剂、焗油剂、发油、发胶、染发剂等剂型。
此外,有关向其它组合物中配合本发明抗菌剂时的剂型是任意的,可使用常规方法配合,例如可采用口服药剂,纤维制品(衬衫类、衣服类等),还有卫生棉类、湿纸巾或擦拭用纸类,除菌用布等无纺布,或口腔用组合物(口香糖、果糖等)或鱼糕、鱼卷等水产熟食品,香肠、火腿等畜产品,西式糕点类,日式糕点类,中式面、日本面、荞麦面等面类,汤汁、酱油、作料汁等调味料,家常菜、果汁、汤汁等普通饮食类的剂型。
并且,配合了本发明抗菌剂的各种组合物的形态是任意的,可使用溶液状、乳膏状、糊状、凝胶状、胶冻状、泡状、固状或粉末状。
含有本发明前述式(I)~(IV)的二醇化合物或其衍生物的抗菌剂可以任意配合到皮肤外用剂组合物中。其配合量根据制品形态而不同,没有特殊限定,但通常考虑到皮肤外用剂组合物的防腐性,必须在0.001质量%以上,优选0.1质量%以上。在更优选1.0质量%以上的配合下能更显著地发挥本发明的效果。配合上限从皮肤外用剂组合物的性质上难以特殊限定,但显著过剩配合时发现有发粘等使用性的劣化,因此优选配合在10.0质量%以下。
配合了本发明式(I)~(IV)的抗菌剂的皮肤外用剂组合物的基质只要是常用的皮肤外用剂组合物基质均可使用。即,可使用液状、凝胶状、糊状、乳液状、乳膏状等基质。还可同时使用通常能够配合入皮肤外用剂组合物中的成分,例如粉末成分、液体油脂、固体油脂、蜡、烃油、高级脂肪酸、高级醇、酯油、硅油、阴离子表面活化剂、阳离子表面活化剂、两性表面活化剂、非离子表面活化剂、保湿剂、水溶性高分子、增粘剂、成膜剂、紫外吸收剂、金属离子封闭剂、低级醇、多元醇、糖、氨基酸、有机胺、高分子乳液、pH调节剂、皮肤营养剂、维生素、抗氧化剂、抗氧化助剂、其它药剂、色素、香料、水等。
并且还可以通过配合普通的二元醇等增强抗菌作用。
本发明的式(II)的甘油衍生物从结构来看属两性介质,易溶于水或醇分或油分等中或易于与它们溶合在一起而容易配合。并且有使用感良好的优点。
以下具体列举了配合本发明抗菌剂的皮肤外用剂组合物的可配合的成分,可与下述成分的一种或二种以上配合来制备皮肤外用剂组合物。
粉末成分可举出例如:无机粉末(例如:滑石粉、高岭土、云母、绢云母(丝云母)、白云母、金云母、合成云母、红云母、黑云母、蛭石、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、二氧化硅、沸石、硫酸钡、烧结硫酸钙(烧石膏)、磷酸钙、氟磷灰石、羟基磷灰石、陶瓷粉末、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、苯并二氨基三嗪树脂粉末、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);无机红色类颜料(例如:氧化铁(红丹)、钛酸铁等);无机褐色类颜料(例如:γ-氧化铁等);无机黄色类颜料(例如:氧化铁黄、黄土等);无机黑色类颜料(例如:氧化铁黑、低价氧化钛等);无机紫色类颜料(例如:芒果紫、钴紫等);无机绿色类颜料(例如:氧化铬、氢氧化铬、钛酸钴等);无机蓝色类颜料(例如:群青、绀青等);珠光颜料(例如:氧化钛包覆云母、氧化钛包覆氯氧化铋、氧化钛包覆滑石粉、着色氧化钛包覆云母、氯氧化铋、鱼鳞箔等);金属粉末颜料(例如:铝粉、铜粉等);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、和蓝色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号和蓝色1号等);天然色素(例如:叶绿素、β-胡萝卜素等)等。
液体油脂可举出例如:鳄梨油、山茶油、马卡达姆坚果油、玉米油、橄榄油、菜籽油、芝麻油、小麦胚芽油、山茶油、蓖麻油、亚麻籽油、红花油、棉籽油、大豆油、花生油、茶籽油、米糠油、西蒙得木油、胚芽油、三甘油等。
固体油脂可举出例如:可可树脂、椰油、固化椰油、棕榈油、棕榈仁油、木蜡核油、固化油、木蜡、固化蓖麻油等。
蜡可举出例如:蜂蜡、朱树蜡、巴西棕榈蜡、羊毛脂、乙酸羊毛脂、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、西蒙得木蜡、硬质羊毛脂、虫胶蜡、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。
烃油可举出例如:液体石蜡、地蜡、角鲨烷、降植烷、石蜡、纯地蜡、角鲨烯、凡士林、微晶蜡、费歇尔-托普希蜡(Fischer-Tropsch Wax)等。
高级脂肪酸可举出例如:月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山萮酸、油酸、十一碳烯酸、异硬脂酸、亚油酸、亚麻酸、二十碳五烯酸(EPA)、廿二碳六烯酸(DHA)等。
高级醇可举出例如:直链醇(例如:月桂醇、鲸蜡醇、硬脂醇、山萮醇、肉豆蔻醇、油醇、油硬脂醇(十六醇十八醇混合物)等);支链醇(例如:单硬脂酸甘油醚(鲨肝醇)、2-癸基十四烷醇、月桂醇、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。
酯油可举出肉豆蔻酸异丙酯、辛酸鲸蜡酯、肉豆蔻酸辛基十二烷酯、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、乙酸羊毛脂、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-乙基己酸乙二醇酯、二季戊四醇脂肪酸酯、单异硬脂酸N-烷基醇酯、二癸酸新戊二醇酯、苹果酸二异硬脂酸酯、二-2-戊基十一烷酸甘油酯、三-2-乙基己酸三羟甲基丙烷酯、三异硬脂酸三羟甲基丙烷酯、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酯、2-乙基己酸十六酯、棕榈酸2-乙基己酯、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、油酸油酯、乙酰甘油、棕榈酸2-庚基十一烷酯、己二酸二异丁酯、N-月桂酰基-L-谷氨酸-2-辛基十二烷酯、己二酸二-2-庚基十一烷酯、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。
硅油可举出例如:链状聚硅氧烷(例如:聚二甲基硅氧烷、聚甲基苯基硅氧烷、聚二苯基硅氧烷等);环状聚硅氧烷(例如:八甲基环四硅氧烷、十甲基环戊硅氧烷、十二甲基环六硅氧烷等)、甲基三甲氧基硅烷、形成三维网络结构的聚硅氧烷树脂、硅橡胶、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。
阴离子表面活化剂可举出例如: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:月桂硫酸钠、月桂硫酸钾等);烷基醚硫酸酯盐(例如:POE-月桂硫酸三乙醇胺、POE-月桂硫酸钠等);N-酰基肌氨酸(例如:月桂酰肌氨酸钠等);高级脂肪酸氨基磺酸盐(例如:N-肉豆蔻基-N-甲基牛磺酸钠、椰油脂肪酸甲基牛磺酸钠、椰油脂肪酸甲基牛磺酸牛磺酸钠、月桂基甲基牛磺酸钠、月桂基甲基牛磺酸甲基牛磺酸钠等);磺基琥珀酸盐(例如:二-2-乙基己基磺基琥珀酸钠、单月桂酰单乙醇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:线性十二烷基苯磺酸钠、线性十二烷基苯磺酸三乙醇胺、线性十二烷基苯磺酸等);高级脂肪酸酯硫酸酯盐(例如:固化椰油脂肪酸甘油酯硫酸钠等);N-酰基谷氨酸盐(例如:N-月桂酰谷氨酸一钠、N-硬脂酰谷氨酸二钠、N-肉豆蔻酰-L-谷氨酸一钠等);POE-烷基醚羧酸;POE-烷基烯丙基醚羧酸盐;α-烯烃磺酸盐;月桂酰单乙醇酰胺琥珀酸钠;N-棕榈酰天冬氨酸二三乙醇胺等。
阳离子表面活化剂可举出例如:烷基三甲铵盐(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:十六烷基氯化吡啶鎓等);二硬脂基二甲基氯化铵二烷基二甲基铵盐;聚氯(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;苯扎氯铵;氯化苄乙铵等。
两性表面活化剂可举出例如:咪唑啉类两性表面活化剂(例如:2-十-烷基-N,N,N-(羟乙基羧甲基)-2-咪唑啉钠、2-可可基-2-咪唑啉鎓氢氧化物-1-羧乙氧基二钠盐等);甜菜碱类表面活化剂(例如:2-十七烷基-N-羧甲基-N-羟乙基咪唑啉鎓甜菜碱、酰胺基胺型两性表面活化剂、月桂基二甲氨基乙酸甜菜碱、烷基甜菜碱、酰胺甜菜碱、磺基甜菜碱等)等。
亲油性非离子表面活化剂可举出例如:山梨糖醇酐脂肪酸酯类(例如:山梨糖醇酐单油酸酯、山梨糖醇酐单异硬脂酸酯、山梨糖醇酐单月桂酸酯、山梨糖醇酐单棕榈酸酯、山梨糖醇酐单硬脂酸酯、山梨糖醇酐倍半油酸酯、山梨糖醇酐三油酸酯、山梨糖醇酐五-2-乙基己酸二甘油酯、山梨糖醇酐四-2-乙基己酸二甘油酯等);甘油聚甘油脂肪酸类(例如:甘油单棉子油脂肪酸酯、甘油一芥酸酯、甘油倍半油酸酯、甘油单硬脂酸酯、甘油α,α’-焦谷氨酸油酯、甘油单硬脂酸酯苹果酸酯等);丙二醇脂肪酸酯类(例如:单硬脂酸丙二醇酯等);固化蓖麻油衍生物;甘油烷基醚等。
亲水性非离子表面活化剂可举出例如:POE-山梨糖醇酐脂肪酸酯类(例如:POE-山梨糖醇酐单油酸酯、POE-山梨糖醇酐单硬脂酸酯、POE-山梨糖醇酐单油酸酯、POE-山梨糖醇酐四油酸酯等);POE山梨醇脂肪酸酯类(例如:POE-山梨醇单月桂酸酯、POE-山梨醇单油酸酯、POE-山梨醇五油酸酯、POE-山梨醇单硬脂酸酯等);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-月桂醚、POE-油醚、POE-硬脂醚、POE-山萮醚、POE-2-辛基十二烷醚、POE-胆甾醇醚等);嵌段聚醚型类(例如:普路罗尼克(Pluronic)等);POE-POP-烷醚类(例如:POE-POP-鲸蜡醚、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:特强尼(Tetronic)等);POE-蓖麻油固化蓖麻油衍生物(例如:POE-蓖麻油、POE-固化蓖麻油、POE-固化蓖麻油单异硬脂酸酯、POE-固化蓖麻油三异硬脂酸酯、POE-固化蓖麻油单焦谷氨酸单异硬脂酸二酯、POE-固化蓖麻油马来酸酯等);烷醇酰胺(例如椰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);蔗糖脂肪酸酯;烷基乙氧基二甲胺氧化物;磷酸三油基酯等。
保湿剂可举出例如: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、乙酰化透明质酸、硫酸粘液素等粘多糖及其盐、胆甾醇-12-羟基硬脂酸酯、乳酸、乳酸钠、d1-吡咯烷酮羧酸盐、三甲基甘氨酸、二甘油(EO)PO加成物、刺梨提取物、西洋蓍草提取物、黄香草木樨提取物等。
天然水溶性高分子可举出例如:植物类高分子(例如:阿拉伯胶、黄蓍胶、半乳聚糖、瓜尔胶、角叉莱胶、果胶、琼脂、刺槐豆胶、榅桲(Cydonia oblonga Mill)、海藻胶(海藻提取物)、淀粉(大米、玉米、马铃薯、小麦);微生物类高分子(例如:黄原胶、葡聚糖、琥珀葡聚糖、结冷胶、茁霉多糖等)等。
半合成水溶性高分子可举出例如:淀粉类高分子(例如:羧甲基淀粉、羟丙甲基淀粉等);纤维素类高分子(甲基纤维素、乙基纤维素、羟丙甲基纤维素、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、纤维素粉末等);褐藻酸类高分子(例如:褐藻酸钠、褐藻酸丙二醇酯等)等。
合成水溶性高分子可举出例如:乙烯类高分子(例如:聚乙烯醇、聚乙烯甲醚、聚乙烯吡咯烷酮、聚羧乙烯、烷基改性羧乙烯聚合物等);聚氧乙烯类高分子(例如:聚乙二醇20000、40000、60000的聚氧乙烯-聚氧丙烯共聚物等);丙烯酸类高分子(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。
增粘剂除上述水溶性高分子以外,可举出例如:硅酸铝镁、膨润土、有机改性膨润土、锂蒙脱石、硅酸AlMg(维格姆(Veegum))、硅酸锂镁钠盐、无水硅酸等。
紫外吸收剂可举出例如:苯甲酸类紫外吸收剂(例如:对氨基苯甲酸(以下简称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丁酯、N,N-二甲基PABA乙酯等);水杨酸类紫外吸收剂(例如:水杨酸戊酯、水杨酸薄荷酯、水杨酸高薄荷酯、水杨酸辛酯、水杨酸苯酯、水杨酸苄酯、水杨酸酯对异丙醇苯酯等);肉桂酸类紫外吸收剂(例如:肉桂酸辛酯、4-异丙基肉桂酸乙酯、2,5-二异丙基肉桂酸甲酯、2,4-二异丙基肉桂酸乙酯、2,4-二异丙基肉桂酸甲酯、对甲氧基肉桂酸丙酯、对甲氧基肉桂酸异丙酯、对甲氧基肉桂酸异戊酯、对甲氧基肉桂酸辛酯(对甲氧基肉桂酸2-乙基己酯)、对甲氧基肉桂酸2-乙氧基乙酯、对甲氧基肉桂酸环己酯、单2-乙基己酰基-二对甲氧基肉桂酸甘油酯等);3-(4’-甲基苯叉)-d,1-莰烷、3-苯叉-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、二苯叉吖嗪、二茴香基甲烷、4-甲氧基-4’-叔丁基二苯甲酰基甲烷、5-(3,3-二甲基-2-亚降冰片烷基)-3-戊烷-2-酮、双-乙基己氧基苯酚-甲氧基苯基-三嗪、2,4,6-三[4-(2-乙基己氧基羧基)苯胺基]1,3,5-三嗪等。
金属离子封闭剂可举出例如:1-羟乙烷-1,1-二膦酸、1-羟乙烷-1,1-二膦酸四钠盐、依地酸二钠、依地酸三钠、依地酸四钠、六偏磷酸钠、柠檬酸钠、聚磷酸钠、偏磷酸钠、葡糖酸、磷酸、柠檬酸、抗坏血酸、琥珀酸、依地酸、乙二胺羟乙基三乙酸三钠等。
低级醇可举出例如:乙醇、异丙醇、异丁醇、叔丁醇等。
多元醇可举出例如: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:二甘醇、一缩二丙二醇、三甘醇、聚丙二醇、四甘醇、二甘油、聚乙二醇、三甘油、四甘油、聚甘油等);二元醇的烷基醚类(例如:乙二醇一甲醚、乙二醇一乙醚、乙二醇一丁醚、乙二醇一苯醚、乙二醇一己醚、乙二醇单2-甲基己醚、乙二醇异戊醚、乙二醇苄醚、乙二醇异丙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚等);二元醇烷醚类(例如:二甘醇一甲醚、二甘醇一乙醚、二甘醇一丁醚、二甘醇二甲醚、二甘醇二乙醚、二甘醇丁醚、二甘醇甲基乙醚、三甘醇一甲醚、三甘醇一乙醚、丙二醇一甲醚、丙二醇一乙醚、丙二醇一丁醚、丙二醇异丙醚、一缩二丙二醇甲醚、一缩二丙二醇乙醚、一缩二丙二醇丁醚等);二元醇醚酯(例如:乙二醇一甲醚乙酸酯、乙二醇一乙醚乙酸酯、乙二醇一丁醚乙酸酯、乙二醇一苯醚乙酸酯、乙二醇二己二酸酯(アジベ一ト)、乙二醇二琥珀酸酯、二甘醇一乙醚乙酸酯、二甘醇一丁醚乙酸酯、丙二醇一甲醚乙酸酯、丙二醇一乙醚乙酸酯、丙二醇单丙基醚乙酸酯、丙二醇一苯醚乙酸酯等);甘油一烷基醚(例如:木酮醇、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、赤藓醇、葡萄糖、果糖、淀粉分解糖、麦芽糖、木糖醇、淀粉分解糖还原醇等);Glysolid;四氢糠醇;POE-四氢糠醇;POP-丁醚;POP-POE-丁醚;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。
单糖可举出例如: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、景天庚糖等);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-氨基葡萄糖、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-葡糖醛酸、D-半乳糖醛酸、L-艾杜糖醛酸等)等。
低聚糖可举出例如:蔗糖、グンチアノ一ス、伞形糖、乳糖、车前子糖、异剪秋罗糖类、α,α-海藻糖、棉子糖等。
氨基酸可举出例如: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。此外,氨基酸衍生物可举出例如:三甲基甘氨酸、谷胱甘肽、吡咯烷酮羧酸等。
有机胺可举出例如: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。
高分子乳液可举出例如:丙烯酸树脂乳液、聚丙烯酸乙酯乳液、丙烯酸树脂液、聚丙烯酰烷酯乳液、聚乙酸乙烯酯树脂乳液、天然橡胶乳等。
pH调节剂可举出例如:乳酸-乳酸钠、柠檬酸-柠檬酸钠、琥珀酸-琥珀酸钠等缓冲剂等。
维生素可举出例如: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。
抗氧化剂可举出例如:生育酚类、二丁羟基甲苯、丁羟基苯甲醚、没食子酸酯类等。
抗氧化助剂可举出例如: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。
其它可配合的成分可举出例如:消炎剂(例如:甘草酸衍生物、甘草亭酸衍生物、水杨酸衍生物、日扁柏醇、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、氨甲环酸、4-甲氧基水杨酸钾等);各种提取物(例如:黄柏、黄连、紫草、芍药、当药、白桦、鼠尾草、枇杷、人参、芦荟、棉葵、鸢尾、葡萄、薏苡仁、丝瓜、百合、藏红花、川芎、生姜、藤黄、刺芒、蒜、辣椒、陈皮、当归、海藻等)、活化剂(例如:蜂王浆、感光素、胆甾醇衍生物等);血液循环促进剂(例如:壬酸香草酰胺、烟酸苄酯、烟酸β-丁氧基乙酯、辣椒辣素、姜油酮、斑蝥酊剂、鱼石脂、丹宁酸、α-冰片、烟酸生育酚、六烟酸肌醇酯、环扁桃酯、桂利嗪、妥拉唑啉、乙酰胆碱、维拉帕米、风箱树素、γ-谷维素等);抗皮脂溢剂(例如:硫黄、二甲基噻蒽等);抗炎剂(例如:硫代牛磺酸、亚牛磺酸等);稳定剂(4,5-二吗啉代-3-羟基哒嗪)等。
实施例
下面列举实施例更具体地说明本发明。但本发明并不限定于此。配合量用质量%表示。
实施例I-1:抗菌效果
求出对各种菌的最小抑菌浓度(MIC)。
采用琼脂平板法,对细菌,在配合各浓度3-己炔-2,5-二醇的SCD琼脂培养基(荣研制)上接种下述各细菌,在30℃下培养24小时,求出不形成菌落的3-己炔-2,5-二醇的浓度(最小抑菌浓度:MIC)。此外,对真菌,在配合各种浓度3-己炔-2,5-二醇的马铃薯葡萄糖琼脂培养基上接种下述各真菌,在25℃下培养48小时,求出不形成菌落的3-己炔-2,5-二醇的浓度(最小抑菌浓度:MIC)。对对羟基苯甲酸甲酯也进行同样的处理。判定结果根据以下评价标准示于表1。
(试验菌)
Ps:绿脓杆菌(菌株名:Pseudomonas aerug inosa ATCC15442)
E:大肠杆菌(菌株名:Escherichia coli ATCC8739)
S:金黄色葡萄球菌(菌株名:Staphylococcus aureus ATCC6538)
Can:白色假丝酵母菌(酵母)标准株(菌株名:Candida albicansATCC10231)
Asp:黑曲霉(菌株名:Aspergillus niger ATCC16404)
(评价标准)
A:最小抑菌浓度为小于1000ppm
B:最小抑菌浓度为1000ppm以上~小于5000ppm
C:最小抑菌浓度为5000ppm以上~小于10000ppm
D:最小抑菌浓度为10000ppm以上~小于30000ppm
E:最小抑菌浓度为30000ppm以上
表I-1
试验菌     抗菌效果
3-己炔-2,5-二醇 对羟基苯甲酸甲酯
绿脓杆菌(菌株名:Pseudomonasaeruginosa ATCC15442) A C
大肠杆菌(菌株名:Escherichia coliATCC8739) A B
金黄色葡萄球菌(菌株名:Staphylococcus aureus ATCC6538) A B
白色假丝酵母菌(菌株名:Candidaalbicans ATCC10231) A B
黑曲霉(菌株名:Aspergillus nigerATCC16404) A B
实施例I-2:安全性试验
进行本发明的3-己炔-2,5-二醇的安全性试验。进行单次给药毒性试验的结果,判断毒性极弱。此外,进行皮肤单次刺激性试验和皮肤连续刺激性试验的结果,判断皮肤刺激性极弱。进一步进行皮肤敏感性试验、遗传毒性试验的结果为阴性。
综上所述,本发明的3-己炔-2,5-二醇的安全性良好。
以下,更详细地说明本发明的利用方法,但本发明并不限定于以下实施例,可用于配合各种药品、准药品、化妆品领域的皮肤外用剂组合物、洗涤剂、食品、日用品等。并且,各实施例采用各制品制造中的常规方法制造即可,这里只显示配合量。
实施例I-3:化妆水
                                                     质量%
乙醇                                                 5.0
1,3-丁二醇                                          6.0
甘油                                                 4.0
油醇                                                 0.1
POE(20)山梨糖醇酐单月桂酸酯                          0.5
POE(15)月桂醚                                        0.5
3-己炔-2,5-二醇                                     1.0
香料                                                 适量
纯化水                                               剩余量
实施例I-4:乳液
                                                     质量%
3-己炔-2,5-二醇                                     3.0
甘油                                                 3.0
鲸蜡醇                                               1.5
硬脂醇                                               1.8
聚二甲基硅氧烷(20cs)                                 1.5
角鲨烷                                               2.0
凡士林                                               2.0
肉豆蔻酸异丙酯                                       2.5
甘油单硬脂酸酯                                       1.8
聚氧乙烯(POE=5)甘油单硬脂酸酯                       1.8
聚氧乙烯(POE=20)鲸蜡醚                              1.5
聚羧乙烯                                             0.25
氢氧化钾                                             0.05
L-精氨酸                                             0.2
一缩二丙二醇                                         5.0
1,3-丁二醇                                          3.0
依地酸三钠                                              0.2
对羟基苯甲酸甲酯                                        0.01
纯化水                                                  剩余量
实施例I-5:乳膏
                                                        质量%
3-己炔-2,5-二醇                                        10.0
硬脂醇                                                  3.5
硬脂酸                                                  2.0
角鲨烷                                                  10.5
肉豆蔻酸异丙酯                                          7.5
聚氧乙烯(POE=25)鲸蜡醇醚                               3.0
甘油单硬脂酸酯                                          2.0
生育酚乙酸酯                                            0.2
甘草酸一铵                                              0.05
甘油                                                    3.0
一缩二丙二醇                                            5.0
1,3-丁二醇                                             3.0
苯氧乙醇                                                0.2
依地酸三钠                                              0.01
羟苯乙酯                                                0.1
纯化水                                                  剩余量
实施例I-6:洗面奶
                                                        质量%
3-己炔-2,5-二醇                                        0.5
硬脂酸                                                  8.0
棕榈酸                                                  6.0
肉豆蔻酸                                                6.0
月桂酸                                                  4.0
氢氧化钾                                                5.2
甘油单硬脂酸酯                                         2.0
丙二醇                                                 1.0
蜂蜡                                                   1.5
聚乙二醇1500                                           5.0
甘油                                                   10.0
纯化水                                                 剩余量
实施例I-7:洗发剂
                                                       质量%
月桂基聚氧乙烯(3)硫酸酯钠盐(30%水溶液)                25.0
月桂硫酸酯钠盐(30%水溶液)                             8.0
椰油脂肪酸二乙醇酰胺                                   4.0
异戊二醇                                               4.0
一缩二丙二醇                                           1.0
1,3-丁二醇                                            1.0
依地酸三钠                                             0.01
3-己炔-2,5-二醇                                       0.1
色素                                                   适量
香料                                                   适量
纯化水                                                 剩余量
实施例I-8:透明胶状面膜
                                                       质量%
3-己炔-2,5-二醇                                       0.1
聚氧乙烯油醇醚                                         0.5
甘草酸一铵                                             0.05
羧甲基纤维素                                           5.0
乙醇                                                   12.0
聚乙烯醇                                               12.0
1,3-丁二醇                                            5.0
依地酸三钠                                             0.01
纯化水                                          剩余量
实施例I-9:眼线膏
                                                质量%
3-己炔-2,5-二醇                                3.0
氧化铁(黑)                                      14.0
肉豆蔻酸异丙酯                                  1.5
聚氧乙烯山梨糖醇酐单油酸酯                      1.0
乙酸乙烯酯树脂乳剂                              45.0
甘草酸一铵                                      0.05
聚羧乙烯                                        1.5
柠檬酸乙酰三丁酯                                1.0
一缩二丙二醇                                    5.0
1,2-戊二醇                                     3.0
依地酸三钠                                      0.01
纯化水                                          剩余量
实施例I-10:发油(hairtonic)
                                                质量%
固化蓖麻油环氧乙烷(40摩尔)加成物                2.0
乙醇                                            60.0
香料                                            适量
3-己炔-2,5-二醇                                0.01
纯化水                                          剩余量
实施例I-11:浴用剂
                                                质量%
碳酸氢钠                                        60.0
无水硫酸钠                                      35.0
3-己炔-2,5-二醇                                5.0
实施例I-12:中式面
                                                质量%
小麦粉                                           98.0
食盐                                             1.0
甜味剂                                           0.5
3-己炔-2,5-二醇                                 0.5
实施例I-13:面汤汁
                                                 质量%
酱油                                             80.0
醋                                               1.0
葡萄糖                                           15.0
谷氨酸钠                                         2.0
砂糖                                             1.0
3-己炔-2,5-二醇                                 1.0
实施例I-14:荞麦面
                                                 质量%
荞麦粉                                           96.0
食盐                                             0.9
水                                               3.0
3-己炔-2,5-二醇                                 0.1
实施例I-15:面包
                                                 质量%
小麦粉                                           90.0
食盐                                             1.2
砂糖                                             2.0
水                                               6.0
3-己炔-2,5-二醇                                 0.8
实施例I-16:火腿
                                                 质量%
肉馅                                             95.0
鸡蛋                                             4.0
食盐                                              0.5
香辛料                                            0.4
3-己炔-2,5-二醇                                  0.1
实施例I-17:果汁饮料
                                                  质量%
葡萄糖液                                          13.0
橙汁                                              85.0
香料                                              1.0
3-己炔-2,5-二醇                                  1.0
使用试验及防腐力试验
参照以下制法制备表II-1所示处方的化妆水,实施使用试验及防腐力试验。
化妆水的制法
向纯化水中溶解3-己炔-2,5-二醇、柠檬酸、柠檬酸三钠、依地酸三钠(水相)。溶解乙醇、甘油、1,3-丁二醇、POE(60)固化蓖麻油、对羟基苯甲酸甲酯(醇相)。混合水相和醇相。
使用试验方法
对过去使用配合了尼泊金的皮肤外用剂组合物时有刺激感的皮肤敏感的10名评判员,以每日2次的频率使用1周,报告使用感的满意度和有无皮肤刺激。使用感的评价按以下4个等级的标准进行分类,此外,确认主诉刺激感的人数。
A:认为使用感良好的评判员8名以上
B:认为使用感良好的评判员5名以上~不到8名
C:认为使用感良好的评判员3名以上~不到5名
D:认为使用感良好的评判员不到3名
防腐力判定试验方法
给实施例及比较例的样品30ml接种菌液后,通过涂抹法检查菌数的变化。接种菌使用霉(菌株名:Aspergillus niger ATCC16404;接种量104cfu(菌落形成单位,colony forming unit)/g)、酵母(菌株名:Candida albicans ATCC10231;接种量105cfu/g)、细菌(大肠杆菌:菌株名:Escherichia coli ATCC8739;接种量106cfu/g,金黄色葡萄球菌:菌株名:Staphylococcus aureus ATCC6538;接种量106cfu/g,绿脓杆菌:菌株名:Pseudomonas aeruginosa ATCC15442;接种量106cfu/g),以直至2周后的菌数变化来评价抗菌力,所得效果按以下4个等级的标准进行分类。
A:1周以内,霉、酵母、细菌都减少到100cfu/g以下
B:2周以内,霉、酵母、细菌都减少到100cfu/g以下
C:2周后,霉、酵母、细菌的任意一种仍残存在100cfu/g以上
D:2周后,霉、酵母、细菌都仍残存在100cfu/g以上
予以说明,皮肤外用剂组合物的防腐力为A至B时判定为合格。使用试验及防腐力试验的结果如表II-1所述。
表II-1
  实施例II-1   实施例II-2   实施例II-3   比较例II-1   比较例II-2   比较例II-3
  3-己炔-2,5-二醇   5   3   1   -    -   -
  乙醇   2   2   2   2   10   2
  甘油   2   2   2   2   2   2
  1,3-丁二醇   3   3   3   3   3   3
  POE(60)固化蓖麻油   0.4   0.4   0.4   0.4   0.4   0.4
  柠檬酸   0.03   0.03   0.03   0.03   0.03   0.03
  柠檬酸三钠   0.07   0.07   0.07   0.07   0.07   0.07
  依地酸三钠   0.02   0.02   0.02   0.02   0.02   0.02
  羟苯甲酯    -   -    -   -    -   0.2
  纯化水   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量
  防腐力试验结果   A   A   A   D   B   A
  使用试验结果   A(10/10)   A(9/10)   A(8/10)   B(7/10)   C(4/10)   B(6/10)
  主诉刺激感的人数   0/10   0/10   0/10   0/10   1/10   4/10
实施例II-1、II-2和II-3中无主诉皮肤刺激者,并且满意使用性者的比例多,也能确保防腐力。此为本发明效果。另外,比较例II-1虽皮肤刺激少、满意使用性者的比例也多,但防腐力差。比较例II-2虽无防腐力问题,但使用性的满意度低,认为是乙醇配比过多引起的主诉皮肤刺激者有1名。比较例II-3虽使用性、防腐力优良,但主诉皮肤刺激者多,皮肤刺激尚存课题。
接下来参照以下制法制备表II-2所示处方的乳液,使用试验及防腐力试验采用与前述同样的方法实施。使用试验和防腐力试验的结果如表II-2所示。
乳液的制法
向纯化水中加入3-己炔-2,5-二醇、1,3-丁二醇、聚乙二醇1500、依地酸三钠、三乙醇胺、加热调节到70℃(水相)。溶解硬脂酸、鲸蜡醇、凡士林、角鲨烷,向其中加入山梨糖醇酐单油酸酯,对羟基苯甲酸甲酯后调节到70℃(油相)。向油相中加入水相进行预乳化,再用匀浆器均匀乳化后冷却。
表II-2
  实施例II-4   实施例II-5   实施例II-6   比较例II-4   比较例II-5
  3-己炔-2,5-二醇   1   0.5   0.3   -   -
  1,3-丁二醇   3   3   3   3   3
  聚乙二醇1500   2   2   2   2   2
  山梨糖醇酐单油酸酯   0.4   0.4   0.4   0.4   0.4
  硬脂酸   2   2   2   2   2
  鲸蜡醇   1.5   1.5   1.5   1.5   1.5
  凡士林   3   3   3   3   3
  角鲨烷   6   6   6   6   6
  三乙醇胺   1   1   1   1   1
  依地酸三钠   0.02   0.02   0.02   0.02   0.02
  羟苯甲酯    -   -    -   -   0.2
  纯化水   剩余量   剩余量   剩余量   剩余量   剩余量
  防腐力试验结果   A   A   A   D   A
  使用试验结果   A(9/10)   A(9/10)   A(8/10)   B(6/10)   B(5/10)
  主诉刺激感的人数   0/10   0/10   0/10   0/10   5/10
实施例II-4、II-5和II-6中无主诉皮肤刺激者,并且满意使用性者的比例多,也能确保防腐力。此为本发明效果。另外,比较例II-4虽皮肤刺激少、满意使用性者的比例也多,但防腐力差。比较例II-5虽使用性、防腐力优良,但主诉皮肤刺激者多,皮肤刺激尚存课题。
接下来参照以下制法制备表II-3所示处方的乳膏,使用试验及防腐力试验采用与前述同样的方法实施。使用试验和防腐力试验的结果如表II-3所示。
乳膏的制法
向纯化水中加入3-己炔-2,5-二醇、1,3-丁二醇、丙二醇、加热调节到70℃(水相)。加热溶解硬脂醇、硬脂酸、氢化羊毛脂、角鲨烷、辛基十二烷醇后、加入POE(25)鲸蜡醇醚、甘油单硬脂酸酯、对羟基苯甲酸甲酯后调节到70℃(油相)。向油相中加入水相,用匀浆器乳化后冷却。
表II-3
  实施例II-7   实施例II-8   实施例II-9   比较例II-6   比较例II-7
  3-己炔-2,5-二醇   3   1   0.3   -   -
  1,3-丁二醇   3   3   3   3   3
  丙二醇   4   4   4   4   4
  甘油单硬脂酸酯   2   2   2   2   2
  POE(25)鲸蜡醇醚   3   3   3   3   3
  硬脂醇   7   7   7   7   7
  硬脂酸   2   2   2   2   2
  氢化羊毛脂   5   5   5   5   5
  角鲨烷   9   9   9   9   9
  辛基十二烷醇   10   10   10   10   10
  羟苯甲酯   -   -    -   -   0.2
  纯化水   剩余量   剩余量   剩余量   剩余量   剩余量
  防腐力试验结果   A   A   A   D   A
  使用试验结果   A(10/10)   A(9/10)   A(8/10)   B(7/10)   B(6/10)
  主诉刺激感的人数   0/10   0/10   0/10   0/10   4/10
实施例II-7、II-8和II-9中无主诉皮肤刺激者,并且满意使用性者的比例多,也能确保防腐力。此为本发明效果。另外,比较例II-6虽皮肤刺激少、满意使用性者的比例也多,但防腐力差。比较例II-7虽使用性、防腐力优良,但主诉皮肤刺激者多,皮肤刺激尚存课题。
以下,例示本发明的各种皮肤外用剂组合物,所有实施例均能维持良好的防腐力,无皮肤刺激性、使用性良好。
实施例II-10:化妆水
(醇相)                                    质量%
乙醇                                      5.0
油醇                                      0.2
POE(20)山梨糖醇酐单月桂酸酯               0.5
POE(15)月桂醚                             0.5
4,5-二吗啉代-3-羟基哒嗪                  0.1
苯氧乙醇                                  0.3
香料                                      适量
(水相)                                    质量%
1,3-丁二醇                               6.0
1,2-戊二醇                               2.0
3-己炔-2,5-二醇                          0.5
甘油                                      5.0
纯化水                                    剩余量
(制法)
分别制备好水相、醇相后进行混合。
实施例II-11:化妆水
(醇相)                                    质量%
乙醇                                      5.0
POE(20)油醚                               0.5
3-己炔-2,5-二醇                          0.1
香料                                      适量
(水相)                                质量%
一缩二丙二醇                          6.0
山梨糖醇                              4.0
PEG1500                               5.0
甲基纤维素                            0.2
榅桲                                  0.1
纯化水                                剩余量
(制法)
将一部分纯化水与甲基纤维素和榅桲相混合、搅拌,制成粘稠液。混合溶解剩余的纯化水和其它水相成分,向其中加入前述粘稠液,得到均匀的水相。制备完醇相后添加到水相中进行混合。
实施例II-12:乳膏
                                          质量%
硬脂酸                                    5.0
硬脂醇                                    4.0
肉豆蔻酸异丙酯                            18.0
甘油单硬脂酸酯                            3.0
丙二醇                                    10.0
1,2-己二醇                               3.0
3-己炔-2,5-二醇                          3.0
氢氧化钾                                  0.2
苯氧乙醇                                  0.3
亚硫酸氢钠                                0.01
香料                                      适量
纯化水                                    剩余量
(制法)
向纯化水中加入丙二醇和氢氧化钾溶解,加热后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例II-13:乳膏
                                                  质量%
硬脂酸                                            6.0
山梨糖醇酐单硬脂酸酯                              2.0
POE(20)山梨糖醇酐单硬脂酸酯                       1.5
丙二醇                                            10.0
3-己炔-2,5-二醇                                  10.0
甘油三辛酸酯                                      10.0
角鲨烯                                            5.0
亚硫酸氢钠                                        0.01
香料                                              适量
纯化水                                            剩余量
(制法)
向纯化水中加入丙二醇溶解,加热后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例II-14:乳液
                                                      质量%
硬脂酸                                                2.5
鲸蜡醇                                                1.5
凡士林                                                5.0
液体石蜡                                              10.0
POE(10)单油酸酯                                       2.0
PEG1500                                               3.0
三乙醇胺                                              1.0
3-己炔-2,5-二醇                                      5.0
亚硫酸氢钠                                            0.01
聚羧乙烯                                              0.05
香料                                                  适量
纯化水                                    剩余量
(制法)
向少量纯化水中加入聚羧乙烯溶解(A相)。向剩余纯化水中加入PEG1500和三乙醇胺,加热溶解后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例II-15:胶冻
                                               质量%
95%乙醇                                       5.0
一缩二丙二醇                                   15.0
1,2-辛二醇                                    3.0
POE(50)油醚                                    2.0
聚羧乙烯                                       1.0
氢氧化钠                                       0.15
3-己炔-2,5-二醇                               0.1
香料                                           适量
纯化水                                         剩余量
(制法)
在纯化水中均匀溶解聚羧乙烯(A相)。将POE(50)油醚溶于95%的乙醇后添加到A相中。添加氢氧化钠以外的成分后,再添加氢氧化钠进行中和,使粘度增加。
实施例II-16:美容液
                                                   质量%
95%乙醇                                           5.0
POE(20)辛基十二烷醇                                1.0
泛酰醇乙醚                                         0.1
氢氧化钾                                           0.1
甘油                                               5.0
一缩二丙二醇                                       10.0
亚硫酸氢钠                            0.03
聚羧乙烯                              0.2
3-己炔-2,5-二醇                      0.3
苯氧乙醇                              0.3
纯化水                                剩余量
(制法)
在一部分纯化水中溶解聚羧乙烯(A相)。同样地,在另一部分纯化水中溶解氢氧化钾(B相)。将水溶性成分溶解于剩余的纯化水中(C相)。使POE(20)辛基十二烷醇、泛酰醇乙醚溶解在乙醇中,再添加先前制备的C相,混合搅拌后,再向其中搅拌混合A相,然后加入B相,用匀浆器搅拌混合。
实施例II-17:面膜
(A相)                                    质量%
一缩二丙二醇                             5.0
POE(60)固化蓖麻油                        5.0
(B相)                                    质量%
橄榄油                                   5.0
生育酚乙酸酯                             0.2
香料                                     0.2
(C相)                                    质量%
亚硫酸氢钠                               0.03
聚乙烯醇(皂化度90,聚合度2000)           13.0
乙醇                                     5.0
3-己炔-2,5-二醇                         0.5
纯化水                                   剩余量
(制法)
分别均匀溶解A相、B相、C相,向A相中加入B相使之互溶。然后将它们加入到C相中混合。
实施例II-18:固体粉末状粉底
                                         质量%
(1)滑石粉                                15.0
(2)绢云母                                10.0
(3)球状尼龙粉末                          10.0
(4)多孔性无水硅酸粉末                    15.0
(5)氮化硼                                5.0
(6)二氧化钛                              5.0
(7)氧化铁                                3.0
(8)硬脂酸锌                              5.0
(9)液体石蜡                              剩余量
(10)三异辛酸甘油酯                       15.0
(11)山梨糖醇酐倍半油酸酯                 1.5
(12)3-己炔-2,5-二醇                     1.0
(13)香料                                 适量
(制法)
在混合粉碎(1)~(8)的各成分的同时,加入(9)~(13)的各成分的混合物搅拌混合,在容器中成形,得到固体粉底。
实施例II-19:油包水型乳状粉底
                                            质量%
(1)球状尼龙                                  10.0
(2)多孔性无水硅酸粉末                        8.0
(3)云母钛                                    2.0
(4)聚硅氧烷处理绢云母                        2.0
(5)聚硅氧烷处理云母                          12.0
(6)聚硅氧烷处理二氧化钛                      5.0
(7)聚硅氧烷处理氧化铁                        2.0
(8)纯化水                                    剩余量
(9)3-己炔-2,5-二醇                          3.0
(10)十甲基环戊硅氧烷                         18.0
(11)聚二甲基硅氧烷                                   5.0
(12)角鲨烷                                           1.0
(13)聚氧乙烯改性聚二甲基硅氧烷                       2.0
(14)香料                                             适量
(制法)
向均匀混合(9)~(14)的各成分的溶解物中加入混合粉碎后的(1)~(7)使之分散。向该分散液中加入(8)后进行乳化,填充到容器中,得到油包水型乳状粉底。
实施例II-20:白粉
                                                      质量%
(1)滑石粉                                             剩余量
(2)绢云母                                              10.0
(3)球状尼龙粉末                                        10.0
(4)氮化硼                                              5.0
(5)氧化铁                                              3.0
(6)碳酸镁                                              5.0
(7)角鲨烷                                              3.0
(8)三异辛酸甘油酯                                      2.0
(9)山梨糖醇酐倍半油酸酯                                2.0
(10)3-己炔-2,5-二醇                                   3.0
(11)香料                                               适量
(制法)
在混合粉碎(1)~(6)的各成分的同时,加入(7)~(11)的各成分的混合物搅拌混合,得到白粉。
实施例II-21:眼影
                                                       质量%
(1)滑石粉                                              剩余量
(2)云母                                                15.0
(3)球状尼龙粉末                                        10.0
(4)氮化硼                                          5.0
(5)氧化铁                                          3.0
(6)氧化钛包覆云母                                  5.0
(7)角鲨烷                                          3.0
(8)三异辛酸甘油酯                                  2.0
(9)山梨糖醇酐倍半油酸酯                            2.0
(10)3-己炔-2,5-二醇                               0.5
(11)香料                                           适量
(制法)
在混合粉碎(1)~(6)的各成分的同时,加入(7)~(11)的各成分的混合物搅拌混合,得到眼影。
实施例II-22:口红
                                                   质量%
(1)巴西棕榈蜡                                      0.5
(2)小烛树蜡                                        5.0
(3)纯地蜡                                          10.0
(4)角鲨烷                                          剩余量
(5)甘油三异硬脂酸酯                                10.0
(6)甘油二异硬脂酸酯                                20.0
(7)3-己炔-2,5-二醇                                0.2
(8)马卡达姆坚果油脂肪酸胆甾醇酯                    4.0
(9)合成硅酸钠镁                                    0.5
(10)疏水性二氧化硅                                 0.5
(11)纯化水                                         2.0
(12)颜料                                           适量
(13)香料                                           适量
(制法)
使(9)、(10)分散于加热到60℃的(8)中,向其中加入(11)充分搅拌。再将之加入加热溶解到70℃的(1)~(7)中充分搅拌,再加入(12)、(13)分散搅拌,然后倒入容器,冷却成形,得到口红。
实施例II-23:发胶
(原液处方)                                      质量%
(1)丙烯酸树脂烷醇胺溶液(50%)                    8.0
(2)聚氧乙烯固化蓖麻油                            1.0
(3)液体石蜡                                      5.0
(4)甘油                                          3.0
(5)香料                                          适量
(6)3-己炔-2,5-二醇                              0.01
(7)乙醇                                          5.0
(8)纯化水                                        剩余量
(填充处方)                                      质量%
(1)原液                                          90.0
(2)液化石油气                                    10.0
(制法)
向甘油和聚氧乙烯固化蓖麻油的溶解物中添加液体石蜡,用匀浆器均匀乳化。将其添加到其它成分的溶液中。填充为向罐中装入原液,装上阀门后,充入气体。
实施例II-24:洗发剂
                                                    质量%
月桂基聚氧乙烯(3)硫酸酯钠盐(30%水溶液)              30.0
月桂硫酸酯钠盐(30%水溶液)                           10.0
椰油脂肪酸二乙醇酰胺                                 4.0
甘油                                                 1.0
3-己炔-2,5-二醇                                     3.0
苯甲酸钠                                             0.5
色素                                                 适量
香料                                                 适量
金属离子封闭剂                                       适量
纯化水                                      剩余量
(制法)
将纯化水加热到70℃,加入其它成分均匀溶解后冷却。
实施例II-25:焗油剂
                                                 质量%
硅油                                              3.0
液体石蜡                                          1.0
鲸蜡醇                                            1.5
硬脂醇                                            1.0
硬脂基三甲基氯化铵                                0.7
3-己炔-2,5-二醇                                  5.0
甘油                                              3.0
色素                                              适量
香料                                              适量
纯化水                                            剩余量
(制法)
向纯化水中加入硬脂基三甲基氯化铵、甘油、色素,保持在70℃(水相),再与其它成分混合,加热溶解后保持在70℃(油相)。向水相中加入油相,用匀浆器乳化后,边搅拌边冷却。
实施例II-26:乳膏
                                                      质量%
液体石蜡                                               10.0
聚二甲基硅氧烷                                         2.0
甘油                                                   10.0
1,3-丁二醇                                            2.0
赤藓醇                                                 1.0
聚乙二醇1500                                           5.0
角鲨烷                                                 15.0
四 2-乙基己酸季戊四醇酯                                5.0
氢氧化钾                                              0.1
六偏磷酸钠                                            0.05
生育酚乙酸酯                                          0.05
3-己炔-2,5-二醇                                      3.0
羟丙甲基纤维素                                        0.3
聚乙烯醇                                              0.1
聚羧乙烯                                              0.2
丙烯酸-甲基丙烯酸烷酯共聚物(Pemulen TR-2)             0.1
纯化水                                                剩余量
(制法)
制作在少量纯化水中溶有聚羧乙烯和丙烯酸-甲基丙烯酸烷酯共聚物的溶液(A相)。向剩余的纯化水中溶解水溶性成分,加热后保持在70℃(水相)。向液状油中混合油性成分,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例II-27:乳膏
                                               质量%
凡士林                                         2.0
聚二甲基硅氧烷(6mPa.s)                         2.0
乙醇                                           5.0
山萮醇                                         0.5
鲨肝醇                                         0.2
甘油                                           7.0
1,3-丁二醇                                    5.0
聚乙二醇20000                                  0.5
西蒙得木油                                     3.0
角鲨烷                                         2.0
羟基硬脂酸植物甾醇酯                           0.5
四 2-乙基己酸季戊四醇酯                         1.0
聚氧乙烯(60)固化蓖麻油                      1.0
氢氧化钾                                    0.1
焦亚硫酸钠                                  0.01
六偏磷酸钠                                  0.05
硬脂基甘草亭酸酯                            0.1
泛酰醇乙醚                                  0.1
熊果苷                                      7.0
氨甲环酸                                    1.0
生育酚乙酸酯                                0.1
透明质酸钠                                  0.05
3-己炔-2,5-二醇                            3.0
依地酸三钠                                  0.05
4-叔丁基-4’-甲氧基二苯甲酰甲烷             0.1
二对甲氧基肉桂酸单-2-乙基己酸               0.1
氧化铁黄                                    适量
黄原胶                                      0.1
聚羧乙烯                                    0.2
纯化水                                      剩余量
(制法)
制成在少量纯化水中溶解了聚羧乙烯和黄原胶的溶液(A相)。向剩余的纯化水中溶解水溶性成分,加热后保持在70℃(水相)。向液状油中混合油性成分,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例II-28:乳膏
                                                  质量%
十甲基环戊硅氧烷                                  30.0
聚氧乙烯-聚甲基硅氧烷共聚物(分子量6000)           1.5
三甲基甲硅烷氧基硅酸                              0.5
甘油                                                   2.0
一缩二丙二醇                                           5.0
3-己炔-2,5-二醇                                       2.0
滑石粉                                                 5.0
球状无水硅酸                                           0.5
棕榈酸糊精包覆微粒氧化钛(30nm)                         7.0
球状聚乙烯粉末                                         2.0
聚(氧乙烯-氧丙烯)-聚甲基硅氧烷共聚物(分子量55000)      1.0
苯氧乙醇                                               0.2
依地酸三钠                                             0.02
二甲基二硬脂基铵锂蒙脱石                               0.5
纯化水                                                 剩余量
(制法)
加热溶解油分后,聚氧乙烯-聚甲基硅氧烷共聚物,聚(氧乙烯-氧丙烯)-聚甲基硅氧烷共聚物,二甲基二硬脂基铵锂蒙脱石及其它油性成分,调节到70℃,均匀分散溶解后得到油性凝胶。向纯化水中加入甘油、一缩二丙二醇、3-己炔-2,5-二醇,调节到70℃。将其边搅拌边缓慢添加到先前制备的油性凝胶中,用匀浆器均匀混合后,冷却至30℃。
实施例II-29:乳液
                                                     质量%
液体石蜡                                             7.0
凡士林                                               3.0
十甲基环戊硅氧烷                                     2.0
山萮醇                                               1.0
甘油                                                 5.0
一缩二丙二醇                                         7.0
聚乙二醇1500                                         2.0
3-己炔-2,5-二醇                                     2.0
西蒙得木油                                           1.0
异硬脂酸                                            0.5
硬脂酸                                              0.5
山萮酸                                              0.5
四 2-乙基己酸季戊四醇酯                             3.0
2-乙基己酸鲸蜡酯                                    3.0
甘油单硬脂酸酯                                      1.0
聚氧乙烯甘油单硬脂酸酯                              1.0
氢氧化钾                                            0.1
六偏磷酸钠                                          0.05
硬脂基甘草亭酸酯                                    0.05
L-精氨酸                                            0.1
蜂王浆提取物                                        0.1
生育酚乙酸酯                                        0.1
乙酰化透明质酸钠                                    0.1
依地酸三钠                                          0.05
4-叔丁基-4’-甲氧基二苯甲酰甲烷                     0.1
对甲氧基肉桂酸2-乙基己酯                            0.1
聚羧乙烯                                            0.15
纯化水                                              剩余量
(制法)
制作在少量纯化水中溶解了聚羧乙烯的溶液(A相)。向剩余的纯化水中溶解水溶性成分,加热后保持在70℃(水相)。向液状油中混合油性成分,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
试验例III-1:抗菌效果
求出对各种菌的最小抑菌浓度(MIC)。对3-苯氧基-1,2-丙二醇、3-苄氧基-1,2-丙二醇、对羟基苯甲酸甲酯进行以下的试验。
采用琼脂平板法,对细菌,在配合各浓度各试验化合物的SCD琼脂培养基(荣研制)上接种下述各细菌,在30℃下培养24小时,求出不形成菌落的各试验化合物的浓度(最小抑菌浓度:MIC)。此外,对真菌,在配合各浓度各试验化合物的马铃薯葡萄糖琼脂培养基上接种下述各真菌,在25℃下培养48小时,求出不形成菌落的各试验化合物的浓度(最小抑菌浓度:MIC)。判定结果根据以下评价标准示于表1。
(试验菌)
Ps:绿脓杆菌(菌株名:Pseudomonas aeruginosa ATCC15442)
E:大肠杆菌(菌株名:Escherichia coli ATCC8739)
S:金黄色葡萄球菌(菌株名:Staphylococcus aureus ATCC6538)
Can:白色假丝酵母菌(酵母)标准株(菌株名:Candida albicansATCC10231)
Asp:黑曲霉(菌株名:Aspergillus niger ATCC16404)
(评价标准)
A:最小抑菌浓度为小于1000ppm
B:最小抑菌浓度为1000ppm以上~小于5000ppm
C:最小抑菌浓度为5000ppm以上~小于10000ppm
D:最小抑菌浓度为10000ppm以上~小于30000ppm
E:最小抑菌浓度为30000ppm以上
表III-1
  试验菌                    抗菌效果
  3-苯氧基-1,2-丙二醇   3-苄氧基-1,2-丙二醇   对羟基苯甲酸甲酯
  绿脓杆菌(菌株名:Pseudomonasaeruginosa ATCC15442)   A   A   C
  大肠杆菌(菌株名:Escherichia coliATCC8739)   A   A   B
  金黄色葡萄球菌(菌株名:Staphylococcus aureus ATCC6538)   A   A   B
  白色假丝酵母菌(酵母)标准株(菌株名:Candida albicans ATCC10231)   A   A   B
  黑曲霉(菌株名:Aspergillus nigerATCC16404)   A   A   B
试验例III-2:安全性试验
进行了本发明的甘油衍生物3-苯氧基-1,2-丙二醇和3-苄氧基-1,2-丙二醇的安全性试验。进行单次给药毒性试验的结果,判断毒性极弱。此外,进行皮肤单次刺激性试验和皮肤连续刺激性试验的结果,判断皮肤刺激性极弱。进一步进行皮肤敏感性试验、遗传毒性试验的结果是阴性。
综上所述,本发明的甘油衍生物3-苯氧基-1,2-丙二醇和3-苄氧基-1,2-丙二醇的安全性良好。
实施例III-1:化妆水
                                                    质量%
乙醇                                                5.0
1,3-丁二醇                                         6.0
甘油                                                4.0
油醇                                                0.1
POE(20)山梨糖醇酐单月桂酸酯                         0.5
POE(15)月桂醚                                       0.5
3-苯氧基-1,2-丙二醇                                1.0
香料                                                适量
纯化水                                              剩余量
实施例III-2:化妆水
                                                    质量%
乙醇                                                5.0
1,3-丁二醇                                         6.0
甘油                                                4.0
油醇                                                0.1
POE(20)山梨糖醇酐单月桂酸酯                         0.5
POE(15)月桂醚                                       0.5
3-苄氧基-1,2-丙二醇                                1.0
香料                                                适量
纯化水                                       剩余量
实施例III-3:化妆水
                                            质量%
乙醇                                         5.0
1,3-丁二醇                                  6.0
甘油                                         4.0
乙基己二醇                                   0.2
2,2-二乙基-1,3-丙二醇                      0.3
2,2,4-三甲基-1,3-戊二醇                   0.5
油醇                                         0.1
POE(20)山梨糖醇酐单月桂酸酯                  0.5
POE(15)月桂醚                                0.5
3-苯氧基-1,2-丙二醇                         0.7
3-苄氧基-1,2-丙二醇                         0.4
香料                                         适量
纯化水                                       剩余量
实施例III-4:化妆水
                                            质量%
乙醇                                         5.0
1,3-丁二醇                                  6.0
甘油                                         5.0
油醇                                         0.1
乙基己二醇                                   0.3
2,2-二羟甲基戊烷                            0.2
POE(20)山梨糖醇酐单月桂酸酯                  0.5
POE(15)月桂醚                                0.5
3-苯氧基-1,2-丙二醇                         0.7
香料                                         适量
纯化水                                       剩余量
实施例III-5:化妆水
                                               质量%
乙醇                                           5.0
1,3-丁二醇                                    6.0
甘油                                           5.0
油醇                                           0.1
乙基己二醇                                     0.2
POE(20)山梨糖醇酐单月桂酸酯                    0.5
POE(15)月桂醚                                  0.5
3-苯氧基-1,2-丙二醇                           0.7
苯氧乙醇                                       0.2
香料                                           适量
纯化水                                         剩余量
实施例III-6:化妆水
                                               质量%
乙醇                                           4.0
1,3-丁二醇                                    6.0
甘油                                           4.0
油醇                                           0.1
2,2-二乙基-1,3-丙二醇                        0.1
乙基己二醇                                     0.3
POE(20)山梨糖醇酐单月桂酸酯                    0.5
POE(15)月桂醚                                  0.5
3-苄氧基-1,2-丙二醇                           0.8
苯氧乙醇                                       0.2
香料                                           适量
纯化水                                         剩余量
实施例III-7:化妆水
                                               质量%
山梨糖醇                                      4.0
1,3-丁二醇                                   6.0
甘油                                          2.0
POE(20)油醇醚                                 0.5
甲基纤维素                                    0.2
榅桲                                          0.1
2,2-二乙基-1,3-丙二醇                       0.1
乙基己二醇                                    0.3
3-苄氧基-1,2-丙二醇                          0.8
对羟基苯甲酸甲酯                              0.2
香料                                          适量
纯化水                                        剩余量
实施例III-8:乳液
                                              质量%
3-苯氧基-1,2-丙二醇                          3.0
甘油                                          3.0
乙基己二醇                                    1.0
鲸蜡醇                                        1.5
硬脂醇                                        1.8
聚二甲基硅氧烷(20cs)                          1.5
角鲨烷                                        2.0
凡士林                                        2.0
肉豆蔻酸异丙酯                                2.5
甘油单硬脂酸酯                                1.8
聚氧乙烯(POE=5)甘油单硬脂酸酯                1.8
聚氧乙烯(POE=20)鲸蜡醚                       1.5
聚羧乙烯                                      0.25
氢氧化钾                                      0.05
L-精氨酸                                      0.2
一缩二丙二醇                                 5.0
1,3-丁二醇                                  3.0
依地酸三钠                                   0.2
对羟基苯甲酸甲酯                             0.01
纯化水                                       剩余量
实施例III-9:乳液
                                             质量%
3-苯氧基-1,2-丙二醇                         1.0
甘油                                         5.0
乙基己二醇                                   2.0
鲸蜡醇                                       1.5
硬脂醇                                       1.8
聚二甲基硅氧烷(20cs)                         1.5
角鲨烷                                       2.0
凡士林                                       2.0
肉豆蔻酸异丙酯                               2.4
甘油单硬脂酸酯                               1.8
聚氧乙烯(POE=5)甘油单硬脂酸酯               1.8
聚氧乙烯(POE=20)鲸蜡醚                      1.5
聚羧乙烯                                     0.25
氢氧化钾                                     0.05
L-精氨酸                                     0.2
一缩二丙二醇                                 5.0
1,3-丁二醇                                  3.0
依地酸三钠                                   0.2
苯氧乙醇                                     0.02
纯化水                                       剩余量
实施例III-10:乳液
                                             质量%
3-苄氧基-1,2-丙二醇                            3.0
甘油                                            3.0
鲸蜡醇                                          1.5
乙基己二醇                                      1.0
硬脂醇                                          1.8
聚二甲基硅氧烷(20cs)                            1.5
角鲨烷                                          2.0
凡士林                                          2.0
肉豆蔻酸异丙酯                                  2.5
甘油单硬脂酸酯                                  1.8
聚氧乙烯(POE=5)甘油单硬脂酸酯                  1.8
聚氧乙烯(POE=20)鲸蜡醚                         1.5
聚羧乙烯                                        0.25
氢氧化钾                                        0.05
L-精氨酸                                        0.2
一缩二丙二醇                                    5.0
1,3-丁二醇                                     3.0
依地酸三钠                                      0.2
对羟基苯甲酸甲酯                                0.01
纯化水                                          剩余量
实施例III-11:乳液
                                                质量%
3-苯氧基-1,2-丙二醇                            1.0
3-苄氧基-1,2-丙二醇                            2.0
甘油                                            3.0
鲸蜡醇                                          1.5
硬脂醇                                          1.8
乙基己二醇                                      1.0
2,2,4-三甲基-1,3-戊二醇                      0.5
聚二甲基硅氧烷(20cs)                                  1.5
角鲨烷                                                2.0
凡士林                                                2.0
肉豆蔻酸异丙酯                                        2.5
甘油单硬脂酸酯                                        1.8
聚氧乙烯(POE=5)甘油单硬脂酸酯                        1.8
聚氧乙烯(POE=20)鲸蜡醚                               1.5
聚羧乙烯                                              0.25
氢氧化钾                                              0.05
L-精氨酸                                              0.2
一缩二丙二醇                                          5.0
1,3-丁二醇                                           3.0
依地酸三钠                                            0.2
对羟基苯甲酸甲酯                                      0.01
纯化水                                                剩余量
实施例III-12:乳膏
                                                      质量%
3-苯氧基-1,2-丙二醇                                  10.0
硬脂醇                                                3.5
硬脂酸                                                2.0
角鲨烷                                                10.5
肉豆蔻酸异丙酯                                        7.5
聚氧乙烯(POE=25)鲸蜡醇醚                             3.0
甘油单硬脂酸酯                                        2.0
生育酚乙酸酯                                          0.2
甘草酸一铵                                            0.05
甘油                                                  3.0
一缩二丙二醇                                          5.0
1,3-丁二醇                                           3.0
苯氧乙醇                                        0.2
依地酸三钠                                      0.01
羟苯乙酯                                        0.1
纯化水                                          剩余量
实施例III-13:乳膏
                                                质量%
3-苄氧基-1,2-丙二醇                            10.0
硬脂醇                                          3.5
硬脂酸                                          2.0
角鲨烷                                          10.5
肉豆蔻酸异丙酯                                  7.5
聚氧乙烯(POE=25)鲸蜡醇醚                       3.0
甘油单硬脂酸酯                                  2.0
生育酚乙酸酯                                    0.2
甘草酸一铵                                      0.05
甘油                                            3.0
一缩二丙二醇                                    5.0
1,3-丁二醇                                     3.0
依地酸三钠                                      0.01
羟苯乙酯                                        0.1
纯化水                                          剩余量
实施例III-14:乳膏
                                                质量%
3-苄氧基-1,2-丙二醇                            4.0
3-苯氧基-1,2-丙二醇                            5.0
乙基己二醇                                      3.0
2,2,4-三甲基-1,3-戊二醇                      1.0
2,2-二乙基-1,3-丙二醇                         0.5
2,2-二羟甲基戊烷                               0.2
硬脂醇                                           3.5
硬脂酸                                           2.0
角鲨烷                                           10.5
肉豆蔻酸异丙酯                                   7.5
聚氧乙烯(POE=25)鲸蜡醇醚                        3.0
甘油单硬脂酸酯                                   2.0
生育酚乙酸酯                                     0.2
甘草酸一铵                                       0.05
甘油                                             3.0
一缩二丙二醇                                     5.0
1,3-丁二醇                                      3.0
苯氧乙醇                                         0.2
依地酸三钠                                       0.01
羟苯乙酯                                         0.1
纯化水                                           剩余量
实施例III-15:洗面奶
                                                 质量%
3-苯氧基-1,2-丙二醇                             0.5
硬脂酸                                           8.0
棕榈酸                                           6.0
肉豆蔻酸                                         6.0
月桂酸                                           4.0
氢氧化钾                                         5.2
甘油单硬脂酸酯                                   2.0
丙二醇                                           1.0
蜂蜡                                             1.5
聚乙二醇1500                                     5.0
甘油                                             10.0
纯化水                                           剩余量
实施例III-16:洗面奶
                                                质量%
3-苄氧基-1,2-丙二醇                            0.5
硬脂酸                                          8.0
棕榈酸                                          6.0
肉豆蔻酸                                        6.0
月桂酸                                          4.0
氢氧化钾                                        5.2
甘油单硬脂酸酯                                  2.0
丙二醇                                          1.0
蜂蜡                                            1.5
聚乙二醇1500                                    5.0
甘油                                            10.0
纯化水                                          剩余量
实施例III-17:洗面奶
                                                质量%
3-苄氧基-1,2-丙二醇                            0.3
3-苯氧基-1,2-丙二醇                            0.2
硬脂酸                                          8.0
棕榈酸                                          6.0
肉豆蔻酸                                        6.0
月桂酸                                          4.0
乙基己二醇                                      0.5
2,2,4-三甲基-1,3-戊二醇                      0.5
2,2-二乙基-1,3-丙二醇                         0.5
2,2-二羟甲基戊烷                               0.2
氢氧化钾                                        5.2
甘油单硬脂酸酯                                  2.0
丙二醇                                          1.0
蜂蜡                                              1.5
聚乙二醇1500                                      5.0
甘油                                              10.0
纯化水                                            剩余量
实施例III-18:洗发剂
                                                  质量%
月桂基聚氧乙烯(3)硫酸酯钠盐(30%水溶液)           25.0
月桂硫酸酯钠盐(30%水溶液)                        8.0
椰油脂肪酸二乙醇酰胺                              4.0
异戊二醇                                          4.0
一缩二丙二醇                                      1.0
1,3-丁二醇                                       1.0
依地酸三钠                                        0.01
2-丁基-2-甲基-1,3-丙二醇                         0.2
3-苯氧基-1,2-丙二醇                              0.1
色素                                              适量
香料                                              适量
纯化水                                            剩余量
实施例III-19:洗发剂
                                                  质量%
月桂基聚氧乙烯(3)硫酸酯钠盐(30%水溶)             25.0
月桂硫酸酯钠盐(30%水溶液)                        8.0
椰油脂肪酸二乙醇酰胺                              4.0
异戊二醇                                          3.0
一缩二丙二醇                                      1.0
1,3-丁二醇                                       1.0
乙基己二醇                                        0.5
2,2-二基-1.3-丙二醇                              0.4
依地酸三钠                                        0.01
3-苯氧基-1,2-丙二醇                                0.1
色素                                                适量
香料                                                适量
纯化水                                              剩余量
实施例III-20:洗发剂
                                                    质量%
月桂基聚氧乙烯(3)硫酸酯钠盐(30%水溶液)             25.0
月桂硫酸酯钠盐(30%水溶液)                          8.0
椰油脂肪酸二乙醇酰胺                                4.0
异戊二醇                                            4.0
一缩二丙二醇                                        1.0
2,2-二乙基-1,3-丙二醇                             0.5
1,3-丁二醇                                         1.0
依地酸三钠                                          0.01
3-苄氧基-1,2-丙二醇                                0.1
色素                                                适量
香料                                                适量
纯化水                                              剩余量
实施例III-21:透明胶状面膜
                                                    质量%
3-苯氧基-1,2-丙二醇                                0.1
聚氧乙烯油醇醚                                      0.5
甘草酸一铵                                          0.05
羧甲基纤维素                                        5.0
乙醇                                                12.0
聚乙烯醇                                            12.0
1,3-丁二醇                                         5.0
依地酸三钠                                          0.01
纯化水                                              剩余量
实施例III-22:透明胶状面膜
                                                      质量%
3-苄氧基-1,2-丙二醇                                  0.05
3-苯氧基-1,2-丙二醇                                  0.1
聚氧乙烯油醇醚                                        0.5
2,2-二乙基-1,3-丙二醇                               0.1
乙基己二醇                                            0.1
2,2,4-三甲基-1,3-丙二醇                            0.1
2,2-二羟甲基戊烷                                     0.1
甘草酸一铵                                            0.05
羧甲基纤维素                                          5.0
乙醇                                                  12.0
聚乙烯醇                                              12.0
1,3-丁二醇                                           5.0
依地酸三钠                                            0.01
纯化水                                                剩余量
实施例III-23:透明胶状面膜
                                                      质量%
3-苄氧基-1,2-丙二醇                                  0.1
聚氧乙烯油醇醚                                        0.5
甘草酸一铵                                            0.05
羧甲基纤维素                                          5.0
乙醇                                                  12.0
聚乙烯醇                                              12.0
1,3-丁二醇                                           5.0
依地酸三钠                                            0.01
纯化水                                                剩余量
实施例III-24:眼线膏
                                                      质量%
3-苯氧基-1,2-丙二醇                                 3.0
氧化铁(黑)                                           14.0
肉豆蔻酸异丙酯                                       1.5
聚氧乙烯山梨糖醇酐单油酸酯                           1.0
乙酸乙烯酯树脂乳剂                                   45.0
甘草酸一铵                                           0.05
聚羧乙烯                                             1.5
柠檬酸乙酰三丁酯                                     1.0
一缩二丙二醇                                         5.0
乙基己二醇                                           1.0
2,2,4-三甲基-1,3-戊二醇                           1.0
2,2-二基-1,3-戊二醇                                1.0
2,2-二羟甲基戊烷                                    0.5
1,2-戊二醇                                          2.0
依地酸三钠                                           0.01
纯化水                                               剩余量
实施例III-25:眼线膏
                                                     质量%
3-苄氧基-1,2-丙二醇                                 3.0
氧化铁(黑)                                           14.0
肉豆蔻酸异丙酯                                       1.5
聚氧乙烯山梨糖醇酐单油酸酯                           1.0
乙酸乙烯酯树脂乳剂                                   45.0
甘草酸一铵                                           0.05
聚羧乙烯                                             1.5
柠檬酸乙酰三丁酯                                     1.0
一缩二丙二醇                                         5.0
乙基己二醇                                           1.0
2,2-二乙基-1,3-戊二醇                              1.0
2,2,4-三甲基-1,3-戊二醇                              0.5
1,2-戊二醇                                             3.0
依地酸三钠                                              0.01
纯化水                                                  剩余量
实施例III-26:眼线膏
                                                        质量%
3-苄氧基-1,2-丙二醇                                    2.0
3-苯氧基-1,2-丙二醇                                    1.0
氧化铁(黑)                                              14.0
肉豆蔻酸异丙酯                                          1.5
聚氧乙烯山梨糖醇酐单油酸酯                              1.0
乙酸乙烯酯树脂乳剂                                      45.0
甘草酸一铵                                              0.05
聚羧乙烯                                                1.5
柠檬酸乙酰三丁酯                                        1.0
一缩二丙二醇                                            5.0
2,2-二羟甲基戊烷                                       1.0
2,2,4-三甲基-1,3-戊二醇                              1.0
2,2-二乙基-1,3-丙二醇                                 0.5
乙基己二醇                                              1.0
苯氧乙醇                                                0.1
依地酸三钠                                              0.01
纯化水                                                  剩余量
实施例III-27:发油
                                                        质量%
固化蓖麻油环氧乙烷(40摩尔)加成物                        2.0
乙醇                                                    60.0
香料                                                    适量
3-苯氧基-1,2-丙二醇                                    0.01
纯化水                                                剩余量
实施例III-28:发油
                                                      质量%
固化蓖麻油环氧乙烷(40摩尔)加成物                      2.0
乙醇                                                  60.0
香料                                                  适量
3-苄氧基-1,2-丙二醇                                  0.01
纯化水                                                剩余量
实施例III-29:浴用剂
                                                      质量%
碳酸氢钠                                              60.0
无水硫酸钠                                            35.0
3-苯氧基-1,2-丙二醇                                  5.0
实施例III-30:浴用剂
                                                      质量%
碳酸氢钠                                              60.0
无水硫酸钠                                            35.0
3-苄氧基-1,2-丙二醇                                  5.0
实施例III-31:浴用剂
                                                      质量%
碳酸氢钠                                              60.0
无水硫酸钠                                            35.0
3-苄氧基-1,2-丙二醇                                  3.0
3-苯氧基-1,2-丙二醇                                  2.0
实施例III-32:中式面
                                                      质量%
小麦粉                                                98.0
食盐                                                  1.0
甜味剂                                                0.5
3-苯氧基-1,2-丙二醇                                0.5
实施例III-33:中式面
                                                    质量%
小麦粉                                              98.0
食盐                                                1.0
甜味剂                                              0.5
3-苄氧基-1,2-丙二醇                                0.5
实施例III-34:中式面
                                                    质量%
小麦粉                                              98.0
食盐                                                1.0
甜味剂                                              0.5
3-苯氧基-1,2-丙二醇                                0.2
3-苄氧基-1,2-丙二醇                                0.2
实施例III-35:面汤汁
                                                    质量%
酱油                                                80.0
醋                                                  1.0
葡萄糖                                              15.0
谷氨酸钠                                            2.0
砂糖                                                1.0
3-苯氧基-1,2-丙二醇                                1.0
实施例III-36:面汤汁
                                                    质量%
酱油                                                80.0
醋                                                  1.0
葡萄糖                                              15.0
谷氨酸钠                                            2.0
砂糖                                                1.0
3-苄氧基-1,2-丙二醇                              1.0
实施例III-37:面汤汁
                                                  质量%
酱油                                              80.0
醋                                                1.0
葡萄糖                                            15.0
谷氨酸钠                                          2.0
砂糖                                              1.0
3-苄氧基-1,2-丙二醇                              0.5
3-苯氧基-1,2-丙二醇                              0.3
实施例III-38:荞麦面
                                                  质量%
荞麦粉                                            96.0
食盐                                              0.9
水                                                3.0
3-苯氧基-1,2-丙二醇                              0.1
实施例III-39:荞麦面
                                                  质量%
荞麦粉                                            96.0
食盐                                              0.9
水                                                3.0
3-苄氧基-1,2-丙二醇                              0.1
实施例III-40:荞麦面
                                                  质量%
荞麦粉                                            96.0
食盐                                              0.9
水                                                3.0
3-苯氧基-1,2-丙二醇                              0.03
3-苄氧基-1,2-丙二醇                              0.06
实施例III-41:面包
                                                   质量%
小麦粉                                             90.0
食盐                                               1.2
砂糖                                               2.0
水                                                 6.0
3-苯氧基-1,2-丙二醇                               0.8
实施例III-42:面包
                                                   质量%
小麦粉                                             90.0
食盐                                               1.2
砂糖                                               2.0
水                                                 6.0
3-苄氧基-1,2-丙二醇                               0.8
实施例III-43:面包
                                                   质量%
小麦粉                                             90.0
食盐                                               1.2
砂糖                                               2.0
水                                                 6.0
3-苯氧基-1,2-丙二醇                               0.1
3-苄氧基-1,2-丙二醇                               0.7
实施例III-44:火腿
                                                   质量%
肉馅                                               95.0
鸡蛋                                               4.0
食盐                                               0.5
香辛料                                             0.4
3-苯氧基-1,2-丙二醇                               0.1
实施例III-45:火腿
                                                 质量%
肉馅                                             95.0
鸡蛋                                             4.0
食盐                                             0.5
香辛料                                           0.4
3-苄氧基-1,2-丙二醇                             0.1
实施例III-46:火腿
                                                 质量%
肉馅                                             95.0
鸡蛋                                             4.0
食盐                                             0.5
香辛料                                           0.4
3-苯氧基-1,2-丙二醇                             0.3
3-苄氧基-1,2-丙二醇                             0.6
实施例III-47:果汁饮料
                                                质量%
葡萄糖液                                        13.0
橙汁                                            85.0
香料                                            1.0
3-苯氧基-1,2-丙二醇                            1.0
实施例III-48:果汁饮料
                                               质量%
葡萄糖液                                       13.0
橙汁                                           85.0
香料                                           1.0
3-苄氧基-1,2-丙二醇                           1.0
实施例III-49:果汁饮料
                                               质量%
葡萄糖液                                    13.0
橙汁                                        85.0
香料                                        1.0
3-苯氧基-1,2-丙二醇                        0.3
3-苄氧基-1,2-丙二醇                        0.6
使用试验和防腐力试验
参照以下制法制备表IV-1所示处方的化妆水,实施了使用试验和防腐力试验。
化妆水的制法
向纯化水中加入3-苯氧基-1,2-丙二醇制成实施例1、2、3,加入3-苄氧基-1,2-丙二醇制成实施例4、5、6。分别向其中溶解柠檬酸、柠檬酸三钠、依地酸三钠(水相)。溶解乙醇、甘油、1,3-丁二醇、POE(60)固化蓖麻油、对羟基苯甲酸甲酯(醇相)。混合水相和醇相。
使用试验方法
对过去使用配合了尼泊金的皮肤外用剂组合物时有刺激感的皮肤敏感的10名评判员,以每日2次的频率使用1周,报告使用感的满意度和有无皮肤刺激。使用感的评价按以下4个等级的标准进行分类,并确认主诉刺激感的人数。
A:认为使用感良好的评判员8名以上
B:认为使用感良好的评判员5名以上~不到8名
C:认为使用感良好的评判员3名以上~不到5名
D:认为使用感良好的评判员不到3名
防腐力判定试验方法
向实施例和比较例的样品30ml接种菌液后,通过涂抹法检查菌数的变化。接种菌使用霉(菌株名:Aspergillus niger ATCC16404;接种量104cfu(colony forming unit)/g)、酵母(菌株名:Candida albicansATCC10231;接种量105cfu/g)、细菌(大肠杆菌:菌株名:Escherichiacoli ATCC8739;接种量106cfu/g,金黄色葡萄球菌:菌株名:
Staphylococcus aureus ATCC6538;接种量106cfu/g,绿脓杆菌:菌株名:Pseudomonas aeruginosa ATCC15442;接种量106cfu/g),以直至2周后的菌数变化来评价抗菌力,所得效果按以下4个等级的标准进行分类。
A;1周以内,霉、酵母、细菌都减少到100cfu/g以下
B;2周以内,霉、酵母、细菌都减少到100cfu/g以下
C;2周后,霉、酵母、细菌中的任意一种仍残存在100cfu/g以上
D;2周后,霉、酵母、细菌都仍残存在100cfu/g以上
予以说明,皮肤外用剂组合物的防腐力为A至B时判定为合格。使用试验和防腐力试验的结果如表IV-1所述。
表IV-1
  实施例IV-1   实施例IV-2   实施例IV-3   实施例IV-4   实施例IV-5   实施例IV-6   比较例IV-1   比较例IV-2   比较例IV-3
  3-苯氧基-1,2-丙二醇 5 3 1 - - - - - -
  3-苄氧基-1,2-丙二醇 - - - 5 3 1 - - -
  乙醇   2   2   2   2   2   2   2   10   2
  甘油   2   2   2   2   2   2   2   2   2
  1,3-丁二醇   3   3   3   3   3   3   3   3   3
  POE(60)固化蓖麻油   0.4   0.4   0.4   0.4   0.4   0.4   0.4   0.4   0.4
  柠檬酸   0.03   0.03   0.03   0.03   0.03   0.03   0.03   0.03   0.03
  柠檬酸三钠   0.07   0.07   0.07   0.07   0.07   0.07   0.07   0.07   0.07
  依地酸三钠   0.02   0.02   0.02   0.02   0.02   0.02   0.02   0.02   0.02
  羟苯甲酯   -    -   -    -   -   -    -    -   0.2
  纯化水   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量
  防腐力试验结果   A   A   A   A   A   A   D   B   A
  使用试验结果   A(10/10)   A(10/10)   A(9/10)   A(10/10)   A(9/10)   A(8/10)   B(7/10)   C(4/10)   B(6/10)
  主诉刺激感的人数   0/10   0/10   0/10   0/10   0/10   0/10   0/10   1/10   4/10
实施例IV-1~IV-6中无主诉皮肤刺激者,并且满意使用性者的比例多,也能确保防腐力。此为本发明效果。另外,比较例IV-1虽皮肤刺激少、满意使用性者的比例也多,但防腐力差。比较例IV-2虽无防腐力问题,但使用性的满意度低,认为是乙醇配比过多引起的主诉皮肤刺激者有1名。比较例IV-3虽使用性、防腐力优良,但主诉皮肤刺激者多,皮肤刺激尚存课题。
接下来参照以下制法制备表IV-2所示处方的乳液,采用与前述同样的方法实施使用试验和防腐力试验。使用试验和防腐力试验的结果如表IV-2所示。
乳液的制法
向纯化水中加入3-苯氧基-1,2-丙二醇制成实施例IV-7、IV-8、IV-9,加入3-苄氧基-1,2-丙二醇制成实施例10、11、12。分别向其中加入1,3-丁二醇、聚乙二醇1500、依地酸三钠、三乙醇胺,加热调节到70℃(水相)。溶解硬脂酸、鲸蜡醇、凡士林、角鲨烷,向其中山梨糖醇酐单油酸酯,加入对羟基苯甲酸甲酯后调节到70℃(油相)。向油相中加入水相进行预乳化,再用匀浆器均匀乳化后冷却。
表IV-2
  实施例IV-7   实施例IV-8   实施例IV-9   实施例IV-10   实施例IV-11   实施例IV-12   比较例IV-4   比较例IV-5
  3-苯氧基-1,2-丙二醇   1   0.5   0.3   -   -   -   -   -
  3-苄氧基-1,2-丙二醇   -   -   -   1   0.5   0.3   -   -
  1,3-丁二醇   3   3   3   3   3   3   3   3
  聚乙二醇1500   2   2   2   2   2   2   2   2
  山梨糖醇酐单油酸酯   0.4   0.4   0.4   0.4   0.4   0.4   0.4   0.4
  硬脂酸   2   2   2   2   2   2   2   2
  鲸蜡醇   1.5   1.5   1.5   1.5   1.5   1.5   1.5   1.5
  凡士林   3   3   3   3   3   3   3   3
  角鲨烷   6   6   6   6   6   6   6   6
  三乙醇胺   1   1   1   1   1   1   1   1
  依地酸三钠   0.02   0.02   0.02   0.02   0.02   0.02   0.02   0.02
  羟苯甲酯   -   -   -   -   -   -   -   0.2
  纯化水   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量
  防腐力试验结果   A   A   A   A   A   A   D   A
  使用试验结果   A(10/10)   A(10/10)   A(9/10)   A(9/10)   A(9/10)   A(9/10)   B(6/10)   B(5/10)
  主诉刺激感的人数   0/10   0/10   0/10   0/10   0/10   0/10   0/10   5/10
实施例IV-7~IV-12中无主诉皮肤刺激者,并且满意使用性者的比例多,也能确保防腐力。此为本发明效果。另外,比较例IV-4虽皮肤刺激少、满意使用性者的比例也多,但防腐力差。比较例IV-5虽使用性、防腐力优良,但主诉皮肤刺激者多,皮肤刺激尚存课题。
接下来参照以下制法制备表IV-3所示处方的乳膏,采用与前述同样的方法实施使用试验和防腐力试验。使用试验和防腐力试验的结果如表IV-3所示。
乳膏的制法
向纯化水中加入3-苯氧基-1,2-丙二醇制成实施例13、14、15,3-苄氧基-1,2-丙二醇制成实施例IV-16、IV-17、IV-18。分别向其中加入1,3-丁二醇、丙二醇,加热调节到70℃(水相)。加热溶解硬脂醇、硬脂酸、氢化羊毛脂、角鲨烷、辛基十二烷醇后,加入POE(25)鲸蜡醇醚、甘油单硬脂酸酯、对羟基苯甲酸甲酯后调节到70℃(油相)。向油相中加入水相,用匀浆器乳化后冷却。
表IV-3
  实施例IV-13   实施例IV-14   实施例IV-15   实施例IV-16   实施例IV-17   实施例IV-18   比较例IV-6   比较例IV-7
  3-苯氧基-1,2-丙二醇   3   1   0.3   -   -   -   -   -
  3-苄氧基-1,2-丙二醇   -   -   -   3   1   0.3   -   -
  1,3-丁二醇   3   3   3   3   3   3   3   3
  丙二醇   4   4   4   4   4   4   4   4
  甘油单硬脂酸酯   2   2   2   2   2   2   2   2
  POE(25)鲸蜡醇醚   3   3   3   3   3   3   3   3
  硬脂醇   7   7   7   7   7   7   7   7
  硬脂酸   2   2   2   2   2   2   2   2
  氢化羊毛脂   5   5   5   5   5   5   5   5
  角鲨烷   9   9   9   9   9   9   9   9
  辛基十二烷醇   10   10   10   10   10   10   10   10
  羟苯甲酯   -   -   -   -   -   -   -   0.2
  纯化水   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量
  防腐力试验结果   A   A   A   A   A   A   D   A
  使用试验结果   A(10/10)   A(10/10)   A(9/10)   A(10/10)   A(10/10)   A(8/10)   B(7/10)   B(6/10)
  主诉刺激感的人数   0/10   0/10   0/10   0/10   0/10   0/10   0/10   4/10
实施例IV-13~IV-18中无主诉皮肤刺激者,并且满意使用性者的比例多,也能确保防腐力。此为本发明效果。另外,比较例IV-6虽皮肤刺激少、满意使用性者的比例也多,但防腐力差。比较例IV-7虽使用性、防腐力优良,但主诉皮肤刺激者多,皮肤刺激尚存课题。
以下,例示本发明的各种皮肤外用剂组合物,所有实施例均能维持良好的防腐力,无皮肤刺激性、使用性良好。
实施例IV-19:化妆水
(醇相)                                      质量%
乙醇                                        5.0
油醇                                        0.2
2,2,4-三甲基-1,3-戊二醇                  0.5
2,2-二羟甲基戊烷                           0.1
乙基己二醇                                  0.3
2,2-二乙基-1,3-丙二醇                     0.1
2,2-二乙基丙二醇                           0.1
POE(20)山梨糖醇酐单月桂酸酯                 0.5
POE(15)月桂醚                               0.5
4,5-二吗啉代-3-羟基哒嗪                    0.1
苯氧乙醇                                    0.2
对羟基苯甲酸甲酯                            0.1
香料                                        适量
(水相)                                      质量%
1,3-丁二醇                                 6.0
1,2-戊二醇                                 1.0
3-苯氧基-1,2-丙二醇                        1.0
甘油                                        5.0
纯化水                                      剩余量
(制法)
分别制备好水相、醇相后进行混合。
实施例IV-20:化妆水
(醇相)                                                 质量%
乙醇                                                   5.0
油醇                                                   0.2
乙基己二醇                                             1.0
2,2,4-三甲基-1,3-戊二醇                             0.3
2,2,-二乙基-1,3-丙二醇                              0.5
2,2-二甲基-1,3-丙二醇                                0.1
2,2-二羟甲基戊烷                                      0.1
POE(20)山梨糖醇酐单月桂酸酯                            0.5
POE(15)月桂醚                                          0.5
4,5-二吗啉代-3-羟基哒嗪                               0.1
苯氧乙醇                                               0.3
香料                                                   适量
(水相)                                                 质量%
1,3-丁二醇                                            6.0
1,2-戊二醇                                            1.0
3-苯氧基-1,2-丙二醇                                   0.7
3-苄氧基-1,2-丙二醇                                   0.5
甘油                                                   5.0
纯化水                                                 剩余量
(制法)
分别制备好水相、醇相后进行混合。
实施例IV-21:化妆水
(醇相)                                                 质量%
乙醇                                                   5.0
油醇                                                   0.2
乙基己二醇                                             1.0
2,2,4-三甲基-1,3-戊二醇                            0.3
2,2,-二乙基-1,3-丙二醇                             0.5
2,2-二甲基-1,3-丙二醇                               0.1
POE(20)山梨糖醇酐单月桂酸酯                           0.5
POE(15)月桂醚                                         0.5
4,5-二吗啉代-3-羟基哒嗪                              0.1
对羟基苯甲酸甲酯                                      0.1
香料                                                  适量
(水相)                                                质量%
1,3-丁二醇                                           6.0
1,2-戊二醇                                           1.0
3-苯氧基-1,2-丙二醇                                  0.7
3-苄氧基-1,2-丙二醇                                  0.5
甘油                                                  5.0
纯化水                                                剩余量
(制法)
分别制备好水相、醇相后进行混合。
实施例IV-22:化妆水
(醇相)                                                质量%
乙醇                                                  5.0
POE(20)油醚                                           0.5
2,2-二羟甲基戊烷                                     0.3
乙基己二醇                                            0.2
2,2,4-三甲基-1,3-丙二醇                            0.1
2,2-二乙基丙二醇                                     0.1
对羟基苯甲酸甲酯                                      0.1
香料                                                  适量
(水相)                                                质量%
一缩二丙二醇                                          6.0
3-苄氧基-1,2-丙二醇                      0.5
山梨糖醇                                  4.0
PEG1500                                   5.0
甲基纤维素                                0.2
榅桲                                      0.1
纯化水                                    剩余量
(制法)
在一部分纯化水中混合甲基纤维素和榅桲,搅拌,制成粘稠液。混合溶解剩余的纯化水和其它水相成分,向其中加入前述粘稠液,得到均匀的水相。制备完醇相后添加到水相中进行混合。
实施例IV-23:化妆水
(醇相)                                         质量%
乙醇                                           5.0
POE(20)油醚                                    0.5
1,3-二羟甲基丙烷                              0.1
乙基己二醇                                     0.5
2,2-二乙基-1,3-丙二醇                        0.1
2,2-二甲基-1,3-丙二醇                        0.1
2,2,4-三甲基-1,3-丙二醇                     0.1
香料                                           适量
苯氧乙醇                                       0.1
对羟基苯甲酸甲酯                               0.2
(水相)                                         质量%
一缩二丙二醇                                   6.0
山梨糖醇                                       4.0
PEG1500                                        5.0
3-苄氧基-1,2-丙二醇                           0.3
3-苯氧基-1,2-丙二醇                           0.2
甲基纤维素                                     0.2
榅桲                                            0.1
纯化水                                          剩余量
(制法)
在一部分纯化水中混合甲基纤维素和榅桲,搅拌,制成粘稠液。混合溶解剩余的纯化水和其它水相成分,向其中加入前述粘稠液,得到均匀的水相。制备完醇相后添加到水相中进行混合。
实施例IV-24:化妆水
(醇相)                                              质量%
乙醇                                                5.0
POE(20)油醚                                         0.5
3-苯氧基-1,2-丙二醇                                0.5
2,2,4-三甲基-1,3-戊二醇                          0.1
2,2-二乙基丙二醇                                   0.1
乙基己二醇                                          0.5
香料                                                适量
(水相)                                              质量%
一缩二丙二醇                                        6.0
山梨糖醇                                            4.0
PEG1500                                             5.0
甲基纤维素                                          0.2
榅桲                                                0.1
纯化水                                              剩余量
(制法)
在一部分纯化水中混合甲基纤维素和榅桲,搅拌,制成粘稠液。混合溶解剩余的纯化水和其它水相成分,向其中加入前述粘稠液,得到均匀的水相。制备完醇相后添加到水相中进行混合。
实施例IV-25:化妆水
(醇相)                                                  质量%
乙醇                                                    5.0
乙基己二醇                                       0.2
POE(20)油醚                                      0.5
3-苯氧基-1,2-丙二醇                             0.5
3-苄氧基-1,2-丙二醇                             0.5
2,2-二乙基-1,3-丙二醇                          0.1
2,2,4-三甲基-1,3-戊二醇                       0.5
苯氧乙醇                                         0.1
对羟基苯甲酸甲酯                                 0.1
香料                                             适量
(水相)                                           质量%
一缩二丙二醇                                     6.0
山梨糖醇                                         4.0
PEG1500                                          5.0
甲基纤维素                                       0.2
榅桲                                             0.1
纯化水                                           剩余量
(制法)
在一部分纯化水中混合甲基纤维素和榅桲,搅拌,制成粘稠液。混合溶解剩余的纯化水和其它水相成分,向其中加入前述粘稠液,得到均匀的水相。制备完醇相后添加到水相中进行混合。
实施例IV-26:乳膏
                                                    质量%
硬脂酸                                               5.0
硬脂醇                                               4.0
肉豆蔻酸异丙酯                                      18.0
甘油单硬脂酸酯                                       3.0
丙二醇                                              10.0
1,2-己二醇                                          3.0
2,2-二乙基-1,3-丙二醇                              0.1
3-苯氧基-1,2-丙二醇                          3.0
氢氧化钾                                      0.2
苯氧乙醇                                      0.3
亚硫酸氢钠                                    0.01
香料                                          适量
纯化水                                        剩余量
(制法)
向纯化水中加入丙二醇和氢氧化钾溶解,加热后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-27:乳膏
                                                  质量%
硬脂酸                                            6.0
山梨糖醇酐单硬脂酸酯                              2.0
POE(20)山梨糖醇酐单硬脂酸酯                       1.5
丙二醇                                            10.0
2,2-二乙基-1.3-丙二醇                            0.1
3-苄氧基-1,2-丙二醇                              5.0
甘油三辛酸酯                                      10.0
角鲨烯                                            5.0
亚硫酸氢钠                                        0.01
香料                                              适量
纯化水                                            剩余量
(制法)
向纯化水中加入丙二醇溶解,加热后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-28:乳膏
                                                  质量%
硬脂酸                                               6.0
山梨糖醇酐单硬脂酸酯                                 2.0
POE(20)山梨糖醇酐单硬脂酸酯                          1.5
丙二醇                                               10.0
3-苄氧基-1,2-丙二醇                                 3.0
3-苯氧基-1,2-丙二醇                                 2.0
2,2-二乙基-1,3-丙二醇                              0.1
甘油三辛酸酯                                         10.0
角鲨烯                                               5.0
亚硫酸氢钠                                           0.01
苯氧乙醇                                             0.1
香料                                                 适量
纯化水                                               剩余量
(制法)
向纯化水中加入丙二醇溶解,加热后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-29:乳膏
                                                   质量%
硬脂酸                                             6.0
山梨糖醇酐单硬脂酸酯                               2.0
POE(20)山梨糖醇酐单硬脂酸酯                        1.5
丙二醇                                             10.0
3-苄氧基-1,2-丙二醇                               2.0
3-苯氧基-1,2-丙二醇                               3.0
2,2-二乙基-1,3-丙二醇                            0.1
甘油三辛酸酯                                       10.0
角鲨烯                                             5.0
亚硫酸氢钠                                         0.01
对羟基苯甲酸甲酯                                0.05
苯氧乙醇                                        0.1
香料                                            适量
纯化水                                          剩余量
(制法)
向纯化水中加入丙二醇溶解,加热后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-30:乳液
                                                质量%
硬脂酸                                          2.5
鲸蜡醇                                          1.5
凡士林                                          5.0
液体石蜡                                        10.0
POE(10)单油酸酯                                 2.0
PEG1500                                         3.0
三乙醇胺                                        1.0
3-苯氧基-1,2-丙二醇                            5.0
亚硫酸氢钠                                      0.01
聚羧乙烯                                        0.05
香料                                            适量
纯化水                                          剩余量
(制法)
向少量纯化水中加入聚羧乙烯溶解(A相)。向剩余纯化水中加入PEG1500和三乙醇胺,加热溶解后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-31:乳液
                                               质量%
硬脂酸                                             2.5
鲸蜡醇                                             1.5
凡士林                                             5.0
液体石蜡                                           10.0
POE(10)单油酸酯                                    2.0
PEG1500                                            3.0
三乙醇胺                                           1.0
3-苄氧基-1,2-丙二醇                               5.0
亚硫酸氢钠                                         0.01
聚羧乙烯                                           0.05
香料                                               适量
纯化水                                             剩余量
(制法)
向少量纯化水中加入聚羧乙烯溶解(A相)。向剩余的纯化水中加入PEG1500和三乙醇胺,加热溶解后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-32:乳液
                                                   质量%
硬脂酸                                             2.5
鲸蜡醇                                             1.5
乙基己二醇                                         1.0
2,2,4-三甲基-1,3-丙二醇                         0.5
2,2-二羟甲基丙烷                                  0.3
2,2-二乙基-1,3-丙二醇                            0.2
凡士林                                             5.0
液体石蜡                                           10.0
POE(10)单油酸酯                                    2.0
PEG1500                                            3.0
三乙醇胺                                           1.0
3-苄氧基-1,2-丙二醇                               3.0
3-苯氧基-1,2-丙二醇                               2.0
亚硫酸氢钠                                         0.01
聚羧乙烯                                           0.05
苯氧乙醇                                           0.1
对羟基苯甲酸甲酯                                   0.1
香料                                               适量
纯化水                                             剩余量
(制法)
向少量纯化水中加入聚羧乙烯溶解(A相)。向剩余的纯化水中加入PEG1500和三乙醇胺,加热溶解后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-33:乳液
                                                 质量%
硬脂酸                                           2.5
鲸蜡醇                                           1.5
乙基己二醇                                       1.0
2,2,4-三甲基-1,3-丙二醇                       0.5
2,2-二羟甲基丙烷                                0.3
2,2-二乙基-1,3-丙二醇                          0.2
凡士林                                           5.0
液体石蜡                                         10.0
POE(10)单油酸酯                                  2.0
PEG1500                                          3.0
三乙醇胺                                         1.0
3-苄氧基-1,2-丙二醇                             3.0
3-苯氧基-1,2-丙二醇                             2.0
亚硫酸氢钠                                   0.01
聚羧乙烯                                     0.05
对羟基苯甲酸甲酯                             0.2
香料                                         适量
纯化水                                       剩余量
(制法)
向少量纯化水中加入聚羧乙烯溶解(A相)。向剩余的纯化水中加入PEG1500和三乙醇胺,加热溶解后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-34:胶冻
                                            质量%
95%乙醇                                    5.0
一缩二丙二醇                                15.0
1,2-辛二醇                                 2.0
乙基己二醇                                  1.0
2,2-二羟甲基戊烷                           0.1
POE(50)油醚                                 2.0
聚羧乙烯                                    1.0
氢氧化钠                                    0.15
3-苯氧基-1,2-丙二醇                        0.1
香料                                        适量
纯化水                                      剩余量
(制法)
在纯化水中均匀溶解聚羧乙烯(A相)。将POE(50)油醚溶于95%的乙醇后添加到A相中。添加氢氧化钠以外的成分后,添加氢氧化钠进行中和,使粘度增加。
实施例IV-35:胶冻
                                            质量%
95%乙醇                                        5.0
一缩二丙二醇                                    15.0
1,2-辛二醇                                     2.0
乙基己二醇                                      1.0
2,2-二羟甲基戊烷                               0.1
POE(50)油醚                                     2.0
聚羧乙烯                                        1.0
氢氧化钠                                        0.15
3-苄氧基-1,2-丙二醇                            0.2
香料                                            适量
纯化水                                          剩余量
(制法)
在纯化水中均匀溶解聚羧乙烯(A相)。将POE(50)油醚溶于95%的乙醇后添加到A相中。添加氢氧化钠以外的成分后,添加氢氧化钠进行中和,使粘度增加。
实施例IV-36:胶冻
                                              质量%
95%乙醇                                      5.0
一缩二丙二醇                                  15.0
1,2-辛二醇                                   2.0
乙基己二醇                                    1.0
2,2-二羟甲基戊烷                             0.1
2,2-二甲基-1,3-丙二醇                       0.1
2,2-二乙基-1,3-丙二醇                       0.1
2,2,4-三甲基-1,3-丙二醇                    0.05
POE(50)油醚                                   2.0
聚羧乙烯                                      1.0
氢氧化钠                                      0.15
3-苄氧基-1,2-丙二醇                          0.05
3-苯氧基-1,2-丙二醇                                0.05
苯氧乙醇                                            0.1
对羟基苯甲酸甲酯                                    0.1
香料                                                适量
纯化水                                              剩余量
(制法)
在纯化水中均匀溶解聚羧乙烯(A相)。将POE(50)油醚溶于95%的乙醇后添加到A相中。添加氢氧化钠以外的成分后,添加氢氧化钠进行中和,使粘度增加。
实施例IV-37:胶冻
                                                    质量%
95%乙醇                                            5.0
一缩二丙二醇                                        15.0
1,2-辛二醇                                         2.0
乙基己二醇                                          1.0
2,2-二羟甲基戊烷                                   0.1
2,2-二甲基-1,3-丙二醇                             0.1
2,2-二乙基-1,3-丙二醇                             0.1
2,2,4-三甲基-1,3-丙二醇                          0.05
POE(50)油醚                                         2.0
聚羧乙烯                                            1.0
氢氧化钠                                            0.15
3-苄氧基-1,2-丙二醇                                0.05
3-苯氧基-1,2-丙二醇                                0.05
对羟基苯甲酸甲酯                                    0.08
香料                                                适量
纯化水                                              剩余量
(制法)
在纯化水中均匀溶解聚羧乙烯(A相)。将POE(50)油醚溶于95%的乙醇后添加到A相中。添加氢氧化钠以外的成分后,添加氢氧化钠进行中和,使粘度增加。
实施例IV-38:美容液
                                               质量%
95%乙醇                                       5.0
POE(20)辛基十二烷醇                            1.0
泛酰醇乙醚                                     0.1
氢氧化钾                                       0.1
甘油                                           5.0
一缩二丙二醇                                   10.0
亚硫酸氢钠                                     0.03
聚羧乙烯                                       0.2
3-苯氧基-1,2-丙二醇                           0.3
苯氧乙醇                                       0.3
纯化水                                         剩余量
(制法)
在一部分纯化水中溶解聚羧乙烯(A相)。同样地,在另一部分纯化水中溶解氢氧化钾(B相)。将水溶性成分溶解于剩余的纯化水中(C相)。使POE(20)辛基十二烷醇、泛酰醇乙醚溶解在乙醇中,再添加先前制备的C相,混合搅拌后,再向其中搅拌混合A相,然后加入B相,用匀浆器搅拌混合。
实施例IV-39:美容液
                                              质量%
95%乙醇                                      5.0
POE(20)辛基十二烷醇                           1.0
泛酰醇乙醚                                    0.1
氢氧化钾                                      0.1
甘油                                          5.0
一缩二丙二醇                                  10.0
亚硫酸氢钠                                    0.03
聚羧乙烯                                      0.2
3-苄氧基-1,2-丙二醇                          0.4
苯氧乙醇                                      0.3
纯化水                                        剩余量
(制法)
在一部分纯化水中溶解聚羧乙烯(A相)。同样地,在另一部分纯化水中溶解氢氧化钾(B相)。将水溶性成分溶解于剩余的纯化水中(C相)。向乙醇中溶解POE(20)辛基十二烷醇、泛酰醇乙醚,再添加先前制备的C相,混合搅拌后,再向其中搅拌混合A相,然后加入B相,用匀浆器搅拌混合。
实施例IV-40:美容液
                                            质量%
95%乙醇                                    5.0
POE(20)辛基十二烷醇                         1.0
乙基己二醇                                  0.1
泛酰醇乙醚                                  0.1
氢氧化钾                                    0.1
甘油                                        5.0
一缩二丙二醇                                10.0
亚硫酸氢钠                                  0.03
聚羧乙烯                                    0.2
3-苄氧基-1,2-丙二醇                        0.3
3-苯氧基-1,2-丙二醇                        0.2
对羟基苯甲酸甲酯                            0.1
苯氧乙醇                                    0.1
纯化水                                      剩余量
(制法)
在一部分纯化水中溶解聚羧乙烯(A相)。同样地,在另一部分纯化水中溶解氢氧化钾(B相)。在剩余的纯化水中溶解水溶性成分(C相)。使POE(20)辛基十二烷醇、泛酰醇乙醚溶解在乙醇中,再添加先前制备的C相,混合搅拌后,再向其中搅拌混合A相,然后加入B相,用匀浆器搅拌混合。
实施例IV-41:面膜
(A相)                                       质量%
一缩二丙二醇                                5.0
POE(60)固化蓖麻油                           5.0
(B相)                                       质量%
橄榄油                                      5.0
生育酚乙酸酯                                0.2
香料                                        0.2
(C相)                                       质量%
亚硫酸氢钠                                  0.03
聚乙烯醇(皂化度90,聚合度2000)              13.0
乙醇                                        5.0
3-苯氧基-1,2-丙二醇                        0.5
3-苄氧基-1,2-丙二醇                        0.6
对羟基苯甲酸甲酯                            0.1
纯化水                                      剩余量
(制法)
分别均匀溶解A相、B相、C相,向A相中加入B相,使之互溶。然后将它们加入到C相中混合。
实施例IV-42:面膜
(A相)                                      质量%
一缩二丙二醇                               5.0
POE(60)固化蓖麻油                          5.0
(B相)                                      质量%
橄榄油                                     5.0
生育酚乙酸酯                                          0.2
香料                                                  0.2
(C相)                                                质量%
亚硫酸氢钠                                            0.03
聚乙烯醇(皂化度90,聚合度2000)                        13.0
乙醇                                                  5.0
3-苄氧基-1,2-丙二醇                                  0.6
3-苯氧基-1,2-丙二醇                                  0.3
苯氧乙醇                                              0.1
对羟基苯甲酸甲酯                                      0.1
纯化水                                                剩余量
(制法)
分别均匀溶解A相、B相、C相,向A相中加入B相,使之互溶。然后将它们加入到C相中混合。
实施例IV-43:固体粉末状粉底
                                                     质量%
(1)滑石粉                                            15.0
(2)绢云母                                            10.0
(3)球状尼龙粉末                                      10.0
(4)多孔性无水硅酸粉末                                15.0
(5)氮化硼                                            5.0
(6)二氧化钛                                          5.0
(7)氧化铁                                            3.0
(8)硬脂酸锌                                          5.0
(9)液体石蜡                                          剩余量
(10)三异辛酸甘油酯                                   15.0
(11)山梨糖醇酐倍半油酸酯                             1.5
(12)3-苯氧基-1,2-丙二醇                             1.0
(13)3-苄氧基-1,2-丙二醇                             1.0
(14)对羟基苯甲酸甲酯                                  0.2
(15)香料                                              适量
(制法)
在混合粉碎(1)~(8)的各成分的同时,加入(9)~(15)的各成分的混合物搅拌混合,在容器中成形得到固体粉底。
实施例IV-44:油包水型乳状粉底
                                                      质量%
(1)球状尼龙                                           10.0
(2)多孔性无水硅酸粉末                                 8.0
(3)云母钛                                             2.0
(4)聚硅氧烷处理绢云母                                 2.0
(5)聚硅氧烷处理云母                                   12.0
(6)聚硅氧烷处理二氧化钛                               5.0
(7)聚硅氧烷处理氧化铁                                 2.0
(8)纯化水                                             剩余量
(9)3-苯氧基-1,2-丙二醇                               3.0
(10)3-苄氧基-1,2-丙二醇                              3.0
(11)十甲基环戊硅氧烷                                  18.0
(12)聚二甲基硅氧烷                                    5.0
(13)角鲨烷                                            1.0
(14)聚氧乙烯改性聚二甲基硅氧烷                        2.0
(15)对羟基苯甲酸甲酯                                  0.2
(16)苯氧乙醇                                          0.1
(17)香料                                              适量
(制法)
向均匀混合(9)~(17)的各成分的溶解物中,加入混合粉碎后的(1)~(7)中使之分散。向该分散液中加入(8)后进行乳化,填充到容器中,得到油包水型乳状粉底。
实施例IV-45:油包水型乳状粉底
                                                      质量%
(1)球状尼龙                                           10.0
(2)多孔性无水硅酸粉末                                 8.0
(3)云母钛                                             2.0
(4)聚硅氧烷处理绢云母                                 2.0
(5)聚硅氧烷处理云母                                   12.0
(6)聚硅氧烷处理二氧化钛                               5.0
(7)聚硅氧烷处理氧化铁                                 2.0
(8)纯化水                                             剩余量
(9)3-苯氧基-1,2-丙二醇                               3.0
(10)3-苄氧基-1,2-丙二醇                              3.0
(11)乙基己二醇                                        1.0
(12)2,2-二羟甲基戊烷                                 1.0
(13)2,2-二乙基-1,3-丙二醇                           1.0
(14)2,2-二甲基-1,3-丙二醇                           0.2
(15)2,2,4-三甲基-1,3-戊二醇                        1.0
(16)十甲基环戊硅氧烷                                  18.0
(17)聚二甲基硅氧烷                                    5.0
(18)角鲨烷                                            1.0
(19)聚氧乙烯改性聚二甲基硅氧烷                        2.0
(20)苯氧乙醇                                          0.1
(21)对羟基苯甲酸甲酯                                  0.1
(22)香料                                              适量
(制法)
向均匀混合(9)~(22)的各成分的溶解物中,加入混合粉碎后的(1)~(7)使之分散。向该分散液中加入(8)后进行乳化,填充到容器中,得到油包水型乳状粉底。
实施例IV-46:白粉
                                                      质量%
(1)滑石粉                                          剩余量
(2)绢云母                                          10.0
(3)球状尼龙粉末                                    10.0
(4)氮化硼                                          5.0
(5)氧化铁                                          3.0
(6)碳酸镁                                          5.0
(7)角鲨烷                                          3.0
(8)三异辛酸甘油酯                                  2.0
(9)山梨糖醇酐倍半油酸酯                            2.0
(10)3-苯氧基-1,2-丙二醇                           3.0
(11)3-苄氧基-1,2-丙二醇                           2.0
(12)香料                                           适量
(制法)
在混合粉碎(1)~(6)的各成分的同时,加入(7)~(12)的各成分的混合物搅拌混合,得到白粉。
实施例IV-47:白粉
                                                    质量%
(1)滑石粉                                           剩余量
(2)绢云母                                           10.0
(3)球状尼龙粉末                                     10.0
(4)氮化硼                                           5.0
(5)氧化铁                                           3.0
(6)碳酸镁                                           5.0
(7)角鲨烷                                           3.0
(8)三异辛酸甘油酯                                   2.0
(9)山梨糖醇酐倍半油酸酯                             2.0
(10)乙基己二醇                                      0.5
(11)3-苯氧基-1,2-丙二醇                            1.0
(12)3-苄氧基-1,2-丙二醇                            2.0
(13)对羟基苯甲酸甲酯                             0.1
(14)香料                                         适量
(制法)
在混合粉碎(1)~(6)的各成分的同时,加入(7)~(14)的各成分的混合物搅拌混合,得到白粉。
实施例IV-48:眼影
                                                质量%
(1)滑石粉                                       剩余量
(2)云母                                         15.0
(3)球状尼龙粉末                                 10.0
(4)氮化硼                                       5.0
(5)氧化铁                                       3.0
(6)氧化钛包覆云母                               5.0
(7)角鲨烷                                       3.0
(8)三异辛酸甘油酯                               2.0
(9)山梨糖醇酐倍半油酸酯                         2.0
(10)乙基己二醇                                  1.0
(11)2,2-二羟甲基-1,3-戊二醇                   0.1
(12)2,2-二乙基-1,3-戊二醇                     0.1
(13)2,2-二甲基-1,3-戊二醇                     0.1
(14)2,2,4-三甲基-1,3-丙二醇                  0.1
(15)3-苯氧基-1,2-丙二醇                        0.5
(16)3-苄氧基-1,2-丙二醇                        0.5
(17)对羟基苯甲酸甲酯                            0.1
(18)香料                                        适量
(制法)
在混合粉碎(1)~(6)的各成分的同时,加入(7)~(18)的各成分的混合物搅拌混合,得到眼影。
实施例IV-49:口红
                                                    质量%
(1)巴西棕榈蜡                                       0.5
(2)小烛树蜡                                         5.0
(3)纯地蜡                                           10.0
(4)角鲨烷                                           剩余量
(5)甘油三异硬脂酸酯                                 10.0
(6)甘油二异硬脂酸酯                                 20.0
(7)3-苯氧基-1,2-丙二醇                             0.2
(8)3-苄氧基-1,2-丙二醇                             0.1
(9)乙基己二醇                                       0.2
(10)马卡达姆坚果油脂肪酸胆甾醇酯                    4.0
(11)合成硅酸钠镁                                    0.5
(12)疏水性二氧化硅                                  0.5
(13)纯化水                                          2.0
(14)颜料                                            适量
(15)香料                                            适量
(制法)
使(11)、(12)分散于加热到60℃的(10)中,向其中加入(13)充分搅拌。再把它们加入到加热溶解到70℃的(1)~(9)中充分搅拌,再加入(14)、(15)进行分散搅拌,然后倒入容器,冷却成形,得到口红。
实施例IV-50:发胶
(原液处方)                                        质量%
(1)丙烯酸树脂烷醇胺溶液(50%)                     8.0
(2)聚氧乙烯固化蓖麻油                             1.0
(3)液体石蜡                                       5.0
(4)甘油                                           3.0
(5)香料                                           适量
(6)3-苯氧基-1,2-丙二醇                           0.01
(7)3-苄氧基-1,2-丙二醇                              0.01
(8)乙醇                                              5.0
(9)纯化水                                            剩余量
(填充处方)                                           质量%
(1)原液                                              90.0
(2)液化石油气                                        10.0
(制法)
向甘油和聚氧乙烯固化蓖麻油的溶解物中添加液体石蜡,用匀浆器均匀乳化。将其添加到其它成分的溶液中。填充为向罐中装入原液,装上阀门后,充入气体。
实施例IV-51:洗发剂
                                                    质量%
月桂基聚氧乙烯(3)硫酸酯钠盐(30%水溶液)             30.0
月桂硫酸酯钠盐(30%水溶液)                          10.0
椰油脂肪酸二乙醇酰胺                                4.0
甘油                                                1.0
3-苯氧基-1,2-丙二醇                                3.0
3-苄氧基-1,2-丙二醇                                3.0
苯甲酸钠                                            0.5
色素                                                适量
香料                                                适量
金属离子封闭剂                                      适量
纯化水                                              剩余量
(制法)
将纯化水加热到70℃,加入其它成分均匀溶解后冷却。
实施例IV-52:焗油剂
                                                   质量%
硅油                                               3.0
液体石蜡                                           1.0
鲸蜡醇                                           1.5
硬脂醇                                           1.0
硬脂基三甲基氯化铵                               0.7
 3-苯氧基-1,2-丙二醇                            5.0
 3-苄氧基-1,2-丙二醇                            5.0
甘油                                             3.0
色素                                             适量
香料                                             适量
纯化水                                           剩余量
(制法)
向纯化水中加入硬脂基三甲基氯化铵、甘油、色素后保持在70℃(水相),再与其它成分混合,加热溶解后保持在70℃(油相)。向水相中加入油相,用匀浆器乳化后,边搅拌边冷却。
实施例IV-53:乳膏
                                                  质量%
液体石蜡                                          10.0
聚二甲基硅氧烷                                    2.0
甘油                                              10.0
1,3-丁二醇                                       2.0
赤藓醇                                            1.0
乙基己二醇                                        0.1
2,2-二羟甲基丙烷                                 1.0
2,2,4-三甲基-1,3-戊二醇                        0.5
2,2-二乙基-1,3-丙二醇                           0.1
聚乙二醇1500                                      5.0
角鲨烷                                            15.0
四 2-乙基己酸季戊四醇酯                           5.0
氢氧化钾                                          0.1
六偏磷酸钠                                        0.05
生育酚乙酸酯                                      0.05
3-苯氧基-1,2-丙二醇                              3.0
3-苄氧基-1,2-丙二醇                              2.0
苯氧乙醇                                          0.1
羟丙甲基纤维素                                    0.3
聚乙烯醇                                          0.1
聚羧乙烯                                          0.2
丙烯酸-甲基丙烯酸烷酯共聚物(Pemulen TR-2)         0.1
纯化水                                            剩余量
(制法)
制备在少量纯化水中溶解了聚羧乙烯和丙烯酸-甲基丙烯酸烷酯共聚物的溶液(A相)。向剩余的纯化水中溶解水溶性成分,加热后保持在70℃(水相)。向液状油中混合油性成分,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-54:乳膏
                                                质量%
凡士林                                          2.0
聚二甲基硅氧烷(6mPa.s)                          2.0
乙醇                                            5.0
山萮醇                                          0.5
鲨肝醇                                          0.2
甘油                                            7.0
1,3-丁二醇                                     5.0
乙基己二醇                                      1.0
聚乙二醇20000                                   0.5
西蒙得木油                                      3.0
角鲨烷                                          2.0
羟基硬脂酸植物甾醇酯                            0.5
2-乙基己酸季戊四醇酯                             1.0
聚氧乙烯(60)固化蓖麻油                           1.0
氢氧化钾                                         0.1
焦亚硫酸钠                                       0.01
六偏磷酸钠                                       0.05
硬脂基甘草亭酸酯                                 0.1
泛酰醇乙醚                                       0.1
熊果苷                                           7.0
氨甲环酸                                         1.0
生育酚乙酸酯                                     0.1
透明质酸钠                                       0.05
3-苯氧基-1,2-丙二醇                             3.0
3-苄氧基-1,2-丙二醇                             3.0
依地酸三钠                                       0.05
4-叔丁基-4’-甲氧基二苯甲酰甲烷                  0.1
二对甲氧基肉桂酸单-2-乙基己酸甘油酯              0.1
氧化铁黄                                         适量
黄原胶                                           0.1
聚羧乙烯                                         0.2
纯化水                                           剩余量
(制法)
制备在少量纯化水中溶解了聚羧乙烯和黄原胶的溶液(A相)。向剩余纯化水中溶解水溶性成分,加热后保持在70℃(水相)。向液状油中混合油性成分,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例IV-55:乳膏
                                               质量%
十甲基环戊硅氧烷                               30.0
聚氧乙烯-聚甲基硅氧烷共聚物(分子量6000)                     1.5
三甲基甲硅烷氧基硅酸                                        0.5
甘油                                                        2.0
一缩二丙二醇                                                5.0
3-苯氧基-1,2-丙二醇                                        2.0
3-苄氧基-1,2-丙二醇                                        2.0
滑石粉                                                      5.0
球状无水硅酸                                                0.5
棕榈酸糊精包覆微粒氧化钛(30nm)                              7.0
球状聚乙烯粉末                                              2.0
聚(氧乙烯-氧丙烯)-聚甲基硅氧烷共聚物(分子量55000)           1.0
苯氧乙醇                                                    0.2
对羟基苯甲酸甲酯                                            0.1
依地酸三钠                                                  0.02
二甲基二硬脂基铵锂蒙脱石                                    0.5
纯化水                                                      剩余量
(制法)
加热溶解油分后,加入聚氧乙烯-聚甲基硅氧烷共聚物、聚(氧乙烯-氧丙烯)-聚甲基硅氧烷、二甲基二硬脂基铵锂蒙脱石及其它油性成分,调节到70℃,均匀分散溶解后得到油性凝胶。向纯化水中加入甘油、一缩二丙二醇、3-苯氧基-1,2-丙二醇,调节到70℃。将其边搅拌边缓慢添加到先前制备的油性凝胶中,用匀浆器均匀混合后,冷却至30℃。
实施例IV-56:乳液
                                                       质量%
液体石蜡                                               7.0
凡士林                                                 3.0
十甲基环戊硅氧烷                                       2.0
山萮醇                                                 1.0
甘油                                                   5.0
一缩二丙二醇                                         7.0
聚乙二醇1500                                         2.0
3-苯氧基-1,2-丙二醇                                 2.0
3-苄氧基-1,2-丙二醇                                 2.0
西蒙得木油                                           1.0
异硬脂酸                                             0.5
硬脂酸                                               0.5
山萮酸                                               0.5
2-乙基己酸季戊四醇酯                                 3.0
2-乙基己酸鲸蜡酯                                     3.0
甘油单硬脂酸酯                                       1.0
聚氧乙烯甘油单硬脂酸酯                               1.0
氢氧化钾                                             0.1
六偏磷酸钠                                           0.05
硬脂基甘草亭酸酯                                     0.05
L-精氨酸                                             0.1
蜂王浆提取物                                         0.1
生育酚乙酸酯                                         0.1
乙酰化透明质酸钠                                     0.1
依地酸三钠                                           0.05
4-叔丁基-4’-甲氧基二苯甲酰甲烷                      0.1
对甲氧基肉桂酸2-乙基己酯                             0.1
聚羧乙烯                                             0.15
纯化水                                               剩余量
(制法)
制作在少量纯化水中溶解了聚羧乙烯的溶液(A相)。向剩余的纯化水中溶解水溶性成分,加热后保持在70℃(水相)。向液状油中混合油性成分,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
〔使用试验和防腐力试验〕
参照以下制法制备表V-1所示处方的化妆水,实施了使用试验和防腐力试验。
化妆水的制法
向纯化水中加入2,2-二甲基-1-苯基-1,3-丙二醇制成实施例1、2、3,分别向其中溶解柠檬酸、柠檬酸三钠、依地酸三钠(水相)。溶解乙醇、甘油、1,3-丁二醇、POE(60)固化蓖麻油、对羟基苯甲酸甲酯(只有比较例V-3)(醇相)。混合水相和醇相。
使用试验方法
对过去使用配合了尼泊金的皮肤外用剂组合物时有刺激感的皮肤敏感的10名评判员,以每日2次的频率使用1周,报告使用感的满意度和有无皮肤刺激。使用感的评价按以下4个等级的标准进行分类,此外,确认主诉刺激感的人数。
A:认为使用感良好的评判员8名以上
B:认为使用感良好的评判员5名以上~不到8名
C:认为使用感良好的评判员3名以上~不到5名
D:认为使用感良好的评判员不到3名
防腐力判定试验方法
向实施例和比较例的样品30ml接种菌液后,通过涂抹法检查菌数的变化。接种菌使用霉(菌株名:Aspergillus niger ATCC16404;接种量104cfu(colony forming unit)/g)、酵母(菌株名:Candida albicansATCC10231;接种量105cfu/g)、细菌(大肠杆菌:菌株名:Escherichiacoli ATCC8739;接种量106cfu/g,金黄色葡萄球菌:菌株名:Staphylococcus aureus ATCC6538;接种量106cfu/g,绿脓杆菌:菌株名:Pseudomonas aeruginosa ATCC15442;接种量106cfu/g),以直至2周后的菌数变化来评价抗菌力,所得效果按以下4个等级的标准进行分类。
A;1周以内,霉、酵母、细菌都减少到100cfu/g以下
B;2周以内,霉、酵母、细菌都减少到100cfu/g以下
C;2周后,霉、酵母、细菌的任意一种仍残存在100cfu/g以上
D;2周后,霉、酵母、细菌都仍残存在100cfu/g以上
予以说明,皮肤外用剂组合物的防腐力为A至B时判定为合格。使用试验和防腐力试验的结果如表V-1所述。
表V-1
  实施例V-1   实施例V-2   实施例V-3   比较例V-1   比较例V-2   比较例V-3
  2,2-二甲基-1-苯基-1,3-丙二醇 0.3 0.2 0.1 - - -
  乙醇   2   2   2   2   10   2
  甘油   2   2   2   2   2   2
  1,3-丁二醇   3   3   3   3   3   3
  POE(60)固化蓖麻油   0.4   0.4   0.4   0.4   0.4   0.4
  柠檬酸   0.03   0.03   0.03   0.03   0.03   0.03
  柠檬酸三钠   0.07   0.07   0.07   0.07   0.07   0.07
  依地酸三钠   0.02   0.02   0.02   0.02   0.02   0.02
  羟苯甲酯   -    -   -   -   -   0.2
  纯化水   剩余量   剩余量   剩余量   剩余量   剩余量   剩余量
  防腐力试验结果   A   A   A   D   B   A
  使用试验结果   A(10/10)   A(10/10)   A(9/10)   B(7/10)   C(4/10)   B(6/10)
  主诉刺激感的人数   0/10   0/10   0/10   0/10   1/10   4/10
实施例V-1~V-3中无主诉皮肤刺激者,并且满意使用性者的比例多,也能确保防腐力。此为本发明效果。另外,比较例V-1虽皮肤刺激少、满意使用性者的比例也多,但防腐力差。比较例V-2虽无防腐力问题,但使用性的满意度低,认为是乙醇配比过多引起的主诉皮肤刺激者有1名。比较例V-3虽使用性、防腐力优良,但主诉皮肤刺激者多,皮肤刺激尚存课题。
接下来参照以下制法制备表V-2所示处方的乳液,采用与前述同样的方法实施使用试验和防腐力试验。使用试验和防腐力试验的结果如表V-2所示。
乳液的制法
向纯化水中加入2,2-二甲基-1-苯基-1,3-丙二醇制成实施例V-4、V-5、V-6。分别向其中加入1,3-丁二醇、聚乙二醇1500、依地酸三钠、三乙醇胺,加热调节到70℃(水相)。溶解硬脂酸、鲸蜡醇、凡士林、角鲨烷,向其中加入山梨糖醇酐单油酸酯、对羟基苯甲酸甲酯(只有比较例V-5)、调节到70℃(油相)。向油相中加入水相进行预乳化,再用匀浆器均匀乳化后冷却。
表V-2
  实施例V-4   实施例V-5   实施例V-6   比较例V-4   比较例V-5
  2,2-二甲基-1-苯基-1,3-丙二醇   0.5   0.4   0.3   -   -
  1,3-丁二醇   3   3   3   3   3
  聚乙二醇1500   2   2   2   2   2
  山梨糖醇酐单油酸酯   0.4   0.4   0.4   0.4   0.4
  硬脂酸   2   2   2   2   2
  鲸蜡醇   1.5   1.5   1.5   1.5   1.5
  凡士林   3   3   3   3   3
  角鲨烷   6   6   6   6   6
  三乙醇胺   1   1   1   1   1
  依地酸三钠   0.02   0.02   0.02   0.02   0.02
  羟苯甲酯   -   -   -   -   0.2
  纯化水   剩余量   剩余量   剩余量   剩余量   剩余量
  防腐力试验结果   A   A   A   D   A
  使用试验结果   A(10/10)   A(10/10)   A(9/10)   B(6/10)   B(5/10)
  主诉刺激感的人数   0/10   0/10   0/10   0/10   5/10
实施例V-4~V-6中无主诉皮肤刺激者,并且满意使用性者的比例多,也能确保防腐力。此为本发明效果。另外,比较例V-4虽皮肤刺激少、满意使用性者的比例也多,但防腐力差。比较例V-5虽使用性、防腐力优良,但主诉皮肤刺激者多,皮肤刺激尚存课题。
接下来参照以下制法制备表V-3所示处方的乳膏,采用与前述同样的方法实施使用试验和防腐力试验。使用试验和防腐力试验的结果如表V-3所示。
乳膏的制法
向纯化水中加入2,2-二甲基-1-苯基-1,3-丙二醇制成实施例V-7、V-8、V-9。分别向其中加入1,3-丁二醇、丙二醇,加热调节到70℃(水相)。加热溶解硬脂醇、硬脂酸、氢化羊毛脂、角鲨烷、辛基十二烷醇,然后加入POE(25)鲸蜡醇醚、甘油单硬脂酸酯、对羟基苯甲酸甲酯(只有比较例V-7),调节到70℃(油相)。向油相中加入水相,用匀浆器乳化后冷却。
表V-3
  实施例V-7   实施例V-8   实施例V-9   比较例V-6   比较例V-7
  2,2-二甲基-1-苯基-1,3-丙二醇 1 0.5 0.3 - -
  1,3-丁二醇   3   3   3   3   3
  丙二醇   4   4   4   4   4
  甘油单硬脂酸酯   2   2   2   2   2
  POE(25)鲸蜡醇醚   3   3   3   3   3
  硬脂醇   7   7   7   7   7
  硬脂酸   2   2   2   2   2
  氢化羊毛脂   5   5   5   5   5
  角鲨烷   9   9   9   9   9
  辛基十二烷醇   10   10   10   10   10
  羟苯甲酯   -   -   -   -   0.2
  纯化水   剩余量   剩余量   剩余量   剩余量   剩余量
  防腐力试验结果   A   A   A   D   A
  使用试验结果   A(10/10)   A(10/10)   A(9/10)   B(7/10)   B(6/10)
  主诉刺激感的人数   0/10   0/10   0/10   0/10   4/10
实施例V-7~V-9中无主诉皮肤刺激者,并且满意使用性者的比例多,也能确保防腐力。此为本发明效果。另外,比较例V-6虽皮肤刺激少、满意使用性者的比例也多,但防腐力差。比较例V-7虽使用性、防腐力优良,但主诉皮肤刺激者多,皮肤刺激尚存课题。
以下,例示本发明的各种皮肤外用剂组合物,所有实施例均能维持良好的防腐力,无皮肤刺激性、使用性良好。
实施例V-10:化妆水
(醇相)                                            质量%
乙醇                                               5.0
油醇                                               0.2
2,2,4-三甲基-1,3-戊二醇                         0.5
2,2-二羟甲基戊烷                                  0.1
乙基己二醇                                         0.3
2,2-二乙基-1,3-丙二醇                            0.1
2,2-二甲基-1,3-丙二醇                            0.1
2,2-二甲基-1-苯基-1,3-丙二醇                     0.3
3-己炔-2,5-二醇                                   0.1
POE(20)山梨糖醇酐单月桂酸酯                        0.5
POE(15)月桂醚                                      0.5
4,5-二吗啉代-3-羟基哒嗪                           0.1
苯氧乙醇                                           0.2
对羟基苯甲酸甲酯                                   0.1
香料                                               适量
(水相)                                            质量%
1,3-丁二醇                                        6.0
1,2-戊二醇                                        1.0
3-苯氧基-1,2-丙二醇                               1.0
3-苄氧基-1,2-丙二醇                               1.0
甘油                                               5.0
纯化水                                             剩余量
(制法)
分别制备好水相、醇相后进行混合。
实施例V-11:化妆水
(醇相)                                                质量%
乙醇                                                  5.0
POE(20)油醚                                           0.5
2,2-二羟甲基戊烷                                     0.3
乙基己二醇                                            0.2
2,2,4-三甲基-1,3-戊二醇                            0.1
2,2-二乙基-1,3-丙二醇                               0.1
2,2-二甲基-1,3-丙二醇                               0.1
2,2-二甲基-1-苯基-1,3-丙二醇                        0.3
3-己炔-2,5-二醇                                      0.1
苯氧乙醇                                              0.1
对羟基苯甲酸甲酯                                      0.1
香料                                                  适量
(水相)                                               质量%
一缩二丙二醇                                          6.0
3-苄氧基-1,2-丙二醇                                  0.5
3-苯氧基-1,2-丙二醇                                  0.5
山梨糖醇                                              4.0
PEG1500                                               5.0
甲基纤维素                                            0.2
榅桲                                                  0.1
纯化水                                                剩余量
(制法)
在一部分纯化水中混合甲基纤维素和榅桲,搅拌,制成粘稠液。混合溶解剩余的纯化水和其它水相成分,向其中加入前述粘稠液,得到均匀的水相。制备完醇相后添加到水相中进行混合。
实施例V-12:乳膏
                                                      质量%
硬脂酸                                                 5.0
硬脂醇                                                 4.0
肉豆蔻酸异丙酯                                         18.0
甘油单硬脂酸酯                                         3.0
丙二醇                                                 10.0
1,2-己二醇                                            1.0
乙基己二醇                                             2.0
2,2,4-三甲基-1,3-戊二醇                             1.0
2,2-二羟甲基戊烷                                      1.0
2,2-二甲基-1-苯基-1,3-丙二醇                         2.0
2,2-二乙基-1,3-丙二醇                                0.1
3-苯氧基-1,2-丙二醇                                   1.0
3-苄氧基-1,2-丙二醇                                   3.0
3-己炔-2,5-二醇                                       0.1
氢氧化钾                                               0.2
苯氧乙醇                                               0.3
对羟基苯甲酸甲酯                                       0.1
亚硫酸氢钠                                             0.01
香料                                                   适量
纯化水                                                 剩余量
(制法)
向纯化水中加入丙二醇和氢氧化钾溶解,加热后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例V-13:乳膏
                                                    质量%
硬脂酸                                              6.0
山梨糖醇酐单硬脂酸酯                                    2.0
POE(20)山梨糖醇酐单硬脂酸酯                             1.5
乙基己二醇                                              2.0
2,2-二基-1,3-丙二醇                                   1.0
2,2-二羟甲基戊烷                                       1.0
2,2,4-三甲基-1,3-戊二醇                              1.0
丙二醇                                                  10.0
2,2-二甲基-1-苯基-1,3-丙二醇                          3.0
3-苄氧基-1,2-丙二醇                                    3.0
3-苯氧基-1,2-丙二醇                                    1.0
3-己炔-2,5-二醇                                        0.1
甘油三辛酸酯                                            10.0
角鲨烯                                                  5.0
亚硫酸氢钠                                              0.01
对羟基苯甲酸甲酯                                        0.01
苯氧乙醇                                                0.1
香料                                                    适量
纯化水                                                  剩余量
(制法)
向纯化水中加入丙二醇溶解,加热后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例V-14:乳液
                                                      质量%
硬脂酸                                                2.5
鲸蜡醇                                                1.5
乙基己二醇                                            1.0
2,2,4-三甲基-1,3-丙二醇                            0.5
2,2-二羟甲基戊烷                                     0.3
2,2-二乙基-1,3-丙二醇                                   0.2
2,2-二甲基-1-苯基-1,3-丙二醇                            1.5
3-己炔-2,5-二醇                                          0.2
凡士林                                                    5.0
液体石蜡                                                  10.0
POE(10)单油酸酯                                           2.0
PEG1500                                                   3.0
三乙醇胺                                                  1.0
3-苯氧基-1,2-丙二醇                                      2.0
3-苄氧基-1,2-丙二醇                                      1.0
苯氧乙醇                                                  0.2
对羟基苯甲酸甲酯                                          0.1
亚硫酸氢钠                                                0.01
聚羧乙烯                                                  0.05
香料                                                      适量
纯化水                                                    剩余量
(制法)
在少量纯化水中溶解聚羧乙烯(A相)。向剩余的纯化水中加入PEG1500和三乙醇胺,加热溶解后保持在70℃(水相)。再与其它成分混合,加热熔融后保持在70℃(油相)。向水相中加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例V-15:胶冻
                                                        质量%
95%乙醇                                                5.0
一缩二丙二醇                                            15.0
1,2-辛二醇                                             2.0
乙基己二醇                                              1.0
2,2-二羟甲基戊烷                                       0.1
2,2-二甲基-1,3-丙二醇                                 0.1
2,2-二乙基-1,3-丙二醇                                    0.1
2,2,4-三甲基-1,3-丙二醇                                 0.05
POE(50)油醚                                                2.0
聚羧乙烯                                                   1.0
氢氧化钠                                                   0.15
3-苄氧基-1,2-丙二醇                                       0.05
3-苯氧基-1,2-丙二醇                                       0.05
2,2-二甲基-1-苯基-1,3-丙二醇                             0.3
3-己炔-2,5-二醇                                           0.1
苯氧乙醇                                                   0.1
对羟基苯甲酸甲酯                                           0.1
香料                                                       适量
纯化水                                                     剩余量
(制法)
在纯化水中均匀溶解聚羧乙烯(A相)。将POE(50)油醚溶于95%的乙醇后添加到A相中。添加氢氧化钠以外的成分后,添加氢氧化钠进行中和,使粘度增加。
实施例V-16:美容液
                                                          质量%
95%乙醇                                                   5.0
POE(20)辛基十二烷醇                                        1.0
泛酰醇乙醚                                                 0.1
乙基己二醇                                                 0.1
2,2-二羟甲基戊烷                                          0.1
2,2-二甲基-1,3-丙二醇                                    0.1
2,2-二乙基-1,3-丙二醇                                    0.1
2,2,4-三甲基-1,3-丙二醇                                 0.05
2,2-二甲基-1-苯基-1,3-丙二醇                             0.3
氢氧化钾                                                   0.1
甘油                                              5.0
一缩二丙二醇                                      10.0
亚硫酸氢钠                                        0.03
聚羧乙烯                                          0.2
3-苯氧基-1,2-丙二醇                              0.2
3-苄氧基-1,2-丙二醇                              0.1
苯氧乙醇                                          0.3
对羟基苯甲酸甲酯                                  0.1
纯化水                                            剩余量
(制法)
在一部分纯化水中溶解聚羧乙烯(A相)。同样地,在另一部分纯化水中溶解氢氧化钾(B相)。将水溶性成分溶解于剩余的纯化水中(C相)。使POE(20)辛基十二烷醇、泛酰醇乙醚溶解在乙醇中,再添加先前制备的C相,混合搅拌后,再向其中搅拌混合A相,然后加入B相,用匀浆器搅拌混合。
实施例V-17:面膜
(A相)                                             质量%
一缩二丙二醇                                      5.0
POE(60)固化蓖麻油                                 5.0
(B相)                                             质量%
橄榄油                                            5.0
乙基己二醇                                        0.1
2,2,4-三甲基-1,3-戊二醇                        0.1
2,2-二乙基-1,3-丙二醇                           0.2
2,2-二羟甲基戊烷                                 0.05
生育酚乙酸酯                                      0.2
香料                                              0.2
(C相)                                             质量%
亚硫酸氢钠                                        0.03
聚乙烯醇(皂化度90,聚合度2000)                           13.0
乙醇                                                     5.0
2,2-二甲基-1-苯基-1,3-丙二醇                           0.3
3-苯氧基-1,2-丙二醇                                     0.5
3-苄氧基-1,2-丙二醇                                     0.6
3-己炔-2,5-二醇                                         0.1
对羟基苯甲酸甲酯                                         0.1
苯氧乙醇                                                 0.2
纯化水                                                   剩余量
(制法)
分别均匀溶解A相、B相、C相,向A相中加入B相,使之互溶。然后将它们加入到C相中混合。
实施例V-18:固体粉末状粉底
                                                     质量%
(1)滑石粉                                            15.0
(2)绢云母                                            10.0
(3)球状尼龙粉末                                      10.0
(4)多孔性无水硅酸粉末                                15.0
(5)氮化硼                                            5.0
(6)二氧化钛                                          5.0
(7)氧化铁                                            3.0
(8)硬脂酸锌                                          5.0
(9)液体石蜡                                          剩余量
(10)三异辛酸甘油酯                                   15.0
(11)山梨糖醇酐倍半油酸酯                             1.5
(12)3-苯氧基-1,2-丙二醇                             0.5
(13)3-苄氧基-1,2-丙二醇                             0.3
(14)2,2-二甲基-1-苯基-1,3-丙二醇                   0.1
(15)乙基己二醇                                       0.2
(16)2,2,4-三甲基-1,3-戊二醇                            0.1
(17)2,2-二乙基-1,3-丙二醇                               0.2
(18)2,2-二羟甲基戊烷                                     0.05
(19)3-己炔-2,5-二醇                                      0.1
(20)对羟基苯甲酸甲酯                                      0.2
(21)香料                                                  适量
(制法)
在混合粉碎(1)~(8)的各成分的同时,(9)~(21)的加入各成分的混合物搅拌混合,在容器中成形得到固体粉底。
实施例V-19:油包水型乳状粉底
                                                        质量%
(1)球状尼龙                                             10.0
(2)多孔性无水硅酸粉末                                   8.0
(3)云母钛                                               2.0
(4)聚硅氧烷处理绢云母                                   2.0
(5)聚硅氧烷处理云母                                     12.0
(6)聚硅氧烷处理二氧化钛                                 5.0
(7)聚硅氧烷处理氧化铁                                   2.0
(8)纯化水                                               剩余量
(9)3-苯氧基-1,2-丙二醇                                 3.0
(10)3-苄氧基-1,2-丙二醇                                3.0
(11)乙基己二醇                                          1.0
(12)2,2-二羟甲基戊烷                                   1.0
(13)2,2-二乙基-1,3-丙二醇                             1.0
(14)2,2-二甲基-1,3-丙二醇                             0.2
(15)2,2,4-三甲基-1,3-戊二醇                          1.0
(16)2,2-二甲基-1-苯基-1.3-丙二醇                       0.7
(17)3-己炔-2,5-二醇                                    0.1
(18)十甲基环戊硅氧烷                                    18.0
(19)聚二甲基硅氧烷                                   5.0
(20)角鲨烷                                           1.0
(21)聚氧乙烯改性聚二甲基硅氧烷                       2.0
(22)苯氧乙醇                                         0.1
(23)对羟基苯甲酸甲酯                                 0.1
(24)香料                                             适量
(制法)
向均匀混合(9)~(24)的各成分的溶解物中加入混合粉碎后的(1)~(7)中使之分散。向该分散液中加入(8)后进行乳化,填充到容器中,得到油包水型乳状粉底。
实施例V-20:白粉
                                                    质量%
(1)滑石粉                                           剩余量
(2)绢云母                                           10.0
(3)球状尼龙粉末                                     10.0
(4)氮化硼                                           5.0
(5)氧化铁                                           3.0
(6)碳酸镁                                           5.0
(7)角鲨烷                                           3.0
(8)三异辛酸甘油酯                                   2.0
(9)山梨糖醇酐倍半油酸酯                             2.0
(10)乙基己二醇                                      0.5
(11)3-苯氧基-1,2-丙二醇                            1.0
(12)3-苄氧基-1,2-丙二醇                            2.0
(13)乙基己二醇                                      1.0
(14)2,2-二羟甲基戊烷                               1.0
(15)2,2-二乙基-1,3-丙二醇                         1.0
(16)2,2-二甲基-1,3-丙二醇                         0.2
(17)2,2,4-三甲基-1,3-戊二醇                      1.0
(18)2,2-二甲基-1-苯基-1.3-丙二醇                            0.7
(19)3-己炔-2,5-二醇                                         0.1
(20)对羟基苯甲酸甲酯                                         0.3
(21)香料                                                     适量
(制法)
在混合粉碎(1)~(6)的各成分的同时,加入(7)~(21)的各成分的混合物搅拌混合,得到白粉。
实施例V-21:眼影
                                                      质量%
(1)滑石粉                                             剩余量
(2)云母                                               15.0
(3)球状尼龙粉末                                       10.0
(4)氮化硼                                             5.0
(5)氧化铁                                             3.0
(6)氧化钛包覆云母                                     5.0
(7)角鲨烷                                             3.0
(8)三异辛酸甘油酯                                     2.0
(9)山梨糖醇酐倍半油酸酯                               2.0
(10)乙基己二醇                                        1.0
(11)2,2-二羟甲基戊烷                                 0.3
(12)2,2-二乙基-1,3-戊二醇                           0.1
(13)2,2-二甲基-1,3-戊二醇                           0.1
(14)2,2,4-三甲基-1,3-丙二醇                        0.1
(15)3-苯氧基-1,2-丙二醇                              0.5
(16)3-苄氧基-1,2-丙二醇                              0.5
(17)2,2-二甲基-1-苯基-1.3-丙二醇                     0.7
(18)3-己炔-2,5-二醇                                  0.3
(19)对羟基苯甲酸甲酯                                  0.1
(20)香料                                              适量
(制法)
在混合粉碎(1)~(6)的各成分的同时,加入(7)~(20)各成分的混合物搅拌混合,得到眼影。
实施例V-22:口红
                                                质量%
(1)巴西棕榈蜡                                   0.5
(2)小烛树蜡                                     5.0
(3)纯地蜡                                       10.0
(4)角鲨烷                                       剩余量
(5)甘油三异硬脂酸酯                             10.0
(6)甘油二异硬脂酸酯                             20.0
(7)3-苯氧基-1,2-丙二醇                         0.2
(8)3-苄氧基-1,2-丙二醇                         0.1
(9)2,2-二甲基-1-苯基-1.3-丙二醇                0.3
(10)乙基己二醇                                  1.0
(11)2,2-二羟甲基戊烷                           0.1
(12)2,2-二乙基-1,3-戊二醇                     0.1
(13)2,2-二甲基-1,3-戊二醇                     0.1
(14)2,2,4-三甲基-1,3-丙二醇                  0.1
(15)3-己炔-2,5-二醇                            0.7
(16)马卡达姆坚果油脂肪酸胆甾醇酯                4.0
(17)合成硅酸钠镁                                0.5
(18)疏水性二氧化硅                              0.5
(19)纯化水                                      2.0
(20)颜料                                        适量
(21)香料                                        适量
(制法)
使(17)、(18)分散到于加热到60℃的(16)中,向其中加入(19)充分搅拌。再将之加入到加热到70℃溶解的(1)~(15)中充分搅拌,再加入(20)、(21)分散搅拌后,倒入容器,冷却成形,得到口红。
实施例V-23:发胶
(原液处方)                                          质量%
(1)丙烯酸树脂烷醇胺溶液(50%)                       8.0
(2)聚氧乙烯固化蓖麻油                               1.0
(3)液体石蜡                                         5.0
(4)甘油                                             3.0
(5)香料                                             适量
(6)3-苯氧基-1,2-丙二醇                             0.01
(7)3-苄氧基-1,2-丙二醇                             0.01
(9)2,2-二甲基-1-苯基-1.3-丙二醇                    0.3
(10)乙基己二醇                                      0.2
(11)2,2-二羟甲基戊烷                               0.1
(12)2,2-二乙基-1,3-戊二醇                         0.1
(13)2,2-二甲基-1,3-戊二醇                         0.1
(14)2,2,4-三甲基-1,3-丙二醇                      0.1
(15)3-己炔-2,5-二醇                                0.3
(16)乙醇                                            5.0
(17)纯化水                                          剩余量
(填充处方)                                          质量%
(1)原液                                             90.0
(2)液化石油气                                       10.0
(制法)
向甘油和聚氧乙烯固化蓖麻油的溶解物中添加液体石蜡,用匀浆器均匀乳化。将其添加到其它成分的溶液中。填充为向罐中装入原液,装上阀门后,充入气体。
实施例V-24:洗发剂
                                                    质量%
月桂基聚氧乙烯(3)硫酸酯钠盐(30%水溶液)             30.0
月桂硫酸酯钠盐(30%水溶液)                            10.0
椰油脂肪酸二乙醇酰胺                                  4.0
甘油                                                  1.0
乙基己二醇                                            0.2
2,2,4-三甲基-1,3-戊二醇                            0.2
2,2-二乙基-1,3-丙二醇                               0.1
2,2-二羟甲基戊烷                                     0.05
2,2-二甲基-1-苯基-1,3-丙二醇                        0.1
3-苯氧基-1,2-丙二醇                                  1.0
3-苄氧基-1,2-丙二醇                                  1.0
3-己炔-2,5-二醇                                      0.5
苯甲酸钠                                              0.5
色素                                                  适量
香料                                                  适量
金属离子封闭剂                                        适量
纯化水                                                剩余量
(制法)
将纯化水加热到70℃,加入其它成分均匀溶解后冷却。
实施例V-25:焗油剂
                                                   质量%
硅油                                               3.0
液体石蜡                                           1.0
鲸蜡醇                                             1.5
硬脂醇                                             1.0
硬脂基三甲基氯化铵                                 0.7
乙基己二醇                                         0.3
2,2,4-三甲基-1,3-戊二醇                         0.1
2,2-二乙基-1,3-丙二醇                            0.1
2,2-二羟甲基戊烷                                  0.07
2,2-二甲基-1-苯基-1,3-丙二醇                           0.3
3-苯氧基-1,2-丙二醇                                     1.0
3-苄氧基-1,2-丙二醇                                     2.0
3-己炔-2,5-二醇                                         0.7
甘油                                                     3.0
色素                                                     适量
香料                                                     适量
纯化水                                                   剩余量
(制法)
向纯化水中加入硬脂基三甲基氯化铵、甘油、色素,保持在70℃(水相),再与其它成分混合,加热溶解后保持在70℃(油相)。向水相中加入油相,用匀浆器乳化后,边搅拌边冷却。
实施例V-26:乳膏
                                                        质量%
液体石蜡                                                10.0
聚二甲基硅氧烷                                          2.0
甘油                                                    10.0
1,3-丁二醇                                             2.0
赤藓醇                                                  1.0
乙基己二醇                                              0.1
2,2-二羟甲基戊烷                                       1.0
2,2,4-三甲基-1,3-戊二醇                              0.5
2,2-二乙基-1,3-丙二醇                                 0.1
2,2-二甲基-1-苯基-1,3-丙二醇                          2.0
聚乙二醇1500                                            5.0
角鲨烷                                                  15.0
四 2-乙基己酸季戊四醇酯                                 5.0
氢氧化钾                                                0.1
六偏磷酸钠                                              0.05
生育酚乙酸酯                                      0.05
3-苯氧基-1,2-丙二醇                              1.0
3-苄氧基-1,2-丙二醇                              1.0
3-己炔-2,5-二醇                                  0.2
苯氧乙醇                                          0.1
对羟基苯甲酸甲酯                                  0.1
羟丙甲基纤维素                                    0.3
聚乙烯醇                                          0.1
聚羧乙烯                                          0.2
丙烯酸-甲基丙烯酸烷酯共聚物(Pemulen TR-2)         0.1
纯化水                                            剩余量
(制法)
制成在少量纯化水中溶有聚羧乙烯和丙烯酸-甲基丙烯酸烷酯共聚物的溶液(A相)。向剩余的纯化水中溶解水溶性成分,加热后保持在70℃(水相)。向液状油中混合油性成分,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例V-27:乳膏
                                                质量%
凡士林                                          2.0
聚二甲基硅氧烷(6mPa.s)                          2.0
乙醇                                            5.0
山萮醇                                          0.5
鲨肝醇                                          0.2
甘油                                            7.0
1,3-丁二醇                                     5.0
聚乙二醇20000                                   0.5
西蒙得木油                                      3.0
角鲨烷                                          2.0
羟基硬脂酸植物甾醇酯                              0.5
2-乙基己酸季戊四醇酯                              1.0
聚氧乙烯(60)固化蓖麻油                            1.0
氢氧化钾                                          0.1
焦亚硫酸钠                                        0.01
六偏磷酸钠                                        0.05
硬脂基甘草亭酸酯                                  0.1
泛酰醇乙醚                                        0.1
熊果苷                                            7.0
氨甲环酸                                          1.0
生育酚乙酸酯                                      0.1
透明质酸钠                                        0.05
3-苯氧基-1,2-丙二醇                              1.0
3-苄氧基-1,2-丙二醇                              1.0
依地酸三钠                                        0.05
乙基己二醇                                        1.0
2,2-二甲基-1-苯基-1,3-丙二醇                    0.6
2,2-二羟甲基戊烷                                 0.2
2,2,4-三甲基-1,3-戊二醇                        0.1
2,2-二乙基-1,3-丙二醇                           0.2
3-己炔-2,5-二醇                                  0.2
4-叔丁基-4’-甲氧基二苯甲酰甲烷                   0.1
二对甲氧基肉桂酸单-2-乙基己酸甘油脂               0.1
苯氧乙醇                                          0.1
对羟基苯甲酸甲酯                                  0.05
氧化铁黄                                          适量
黄原胶                                            0.1
聚羧乙烯                                          0.2
纯化水                                            剩余量
(制法)
制成在少量纯化水中溶解了聚羧乙烯和黄原胶的溶液(A相)。向剩余的纯化水中溶解水溶性成分,加热后保持在70℃(水相)。向液状油中混合油性成分,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
实施例V-28:乳膏
                                                    质量%
十甲基环戊硅氧烷                                    30.0
聚氧乙烯-聚甲基硅氧烷共聚物(分子量6000)             1.5
三甲基甲硅烷氧基硅酸                                0.5
甘油                                                2.0
乙基己二醇                                          1.0
2,2-二甲基-1-苯基-1,3-丙二醇                      0.7
2,2-二羟甲基戊烷                                   0.2
2,2,4-三甲基-1,3-戊二醇                          0.1
2,2-二乙基-1,3-丙二醇                             0.3
一缩二丙二醇                                        5.0
3-苯氧基-1,2-丙二醇                                0.5
3-苄氧基-1,2-丙二醇                                1.0
3-己炔-2,5-二醇                                    0.5
滑石粉                                              5.0
球状无水硅酸                                        0.5
棕榈酸糊精包覆微粒氧化钛(30nm)                      7.0
球状聚乙烯粉末                                      2.0
聚(氧乙烯-氧丙烯)-聚甲基硅氧烷共聚物(分子量55000)   1.0
苯氧乙醇                                            0.2
对羟基苯甲酸甲酯                                    0.1
依地酸三钠                                          0.02
二甲基二硬脂基铵锂蒙脱石                           0.5
纯化水                                             剩余量
(制法)
加热溶解油分后,加入聚氧乙烯-聚甲基硅氧烷共聚物、聚(氧乙烯-氧丙烯)-聚甲基硅氧烷、二甲基二硬脂基铵锂蒙脱石及其它油性成分,调节到70℃,均匀分散溶解后得到油性凝胶。向纯化水中加入甘油、一缩二丙二醇、3-苯氧基-1,2-丙二醇,调节到70℃。将其边搅拌边缓慢添加到先前制备的油性凝胶中,用匀浆器均匀混合后,冷却至30℃。
实施例V-29:乳液
                                                  质量%
液体石蜡                                          7.0
凡士林                                            3.0
十甲基环戊硅氧烷                                  2.0
山萮醇                                            1.0
甘油                                              5.0
一缩二丙二醇                                      7.0
聚乙二醇1500                                      2.0
乙基己二醇                                        1.0
3-己炔-2,5-二醇                                  1.0
2,2-二甲基-1-苯基-1,3-丙二醇                    1.5
2,2-二羟甲基戊烷                                 0.2
2,2,4-三甲基-1,3-戊二醇                        0.1
2,2-二乙基-1,3-丙二醇                           0.2
3-苯氧基-1,2-丙二醇                              2.0
3-苄氧基-1,2-丙二醇                              2.0
西蒙得木油                                        1.0
异硬脂酸                                          0.5
硬脂酸                                            0.5
山萮酸                                            0.5
四 2-乙基己酸季戊四醇酯                               3.0
2-乙基己酸鲸蜡酯                                      3.0
甘油单硬脂酸酯                                        1.0
聚氧乙烯甘油单硬脂酸酯                                1.0
氢氧化钾                                              0.1
六偏磷酸钠                                            0.05
硬脂基甘草亭酸酯                                      0.05
L-精氨酸                                              0.1
蜂王浆提取物                                          0.1
生育酚乙酸酯                                          0.1
乙酰化透明质酸钠                                      0.1
依地酸三钠                                            0.05
4-叔丁基-4’-甲氧基二苯甲酰甲烷                       0.1
对甲氧基肉桂酸2-乙基己酯                              0.1
聚羧乙烯                                              0.15
纯化水                                                剩余量
(制法)
制作在少量纯化水中溶解了聚羧乙烯的溶液(A相)。向剩余的纯化水中溶解水溶性成分,加热后保持在70℃(水相)。向液状油中混合油性成分,加热熔融后保持在70℃(油相)。向水相中缓慢加入油相进行预乳化,再加入A相,用匀浆器均匀乳化后,边充分搅拌边冷却至30℃。
试验例VI-1:抗菌效果
求出对各种菌的最小抑菌浓度(MIC)。对2,2-二甲基-1-苯基-1,3-丙二醇、羟基苯甲酸甲酯进行以下的试验。
采用琼脂平板法,对细菌,在配合各浓度各试验化合物的大豆酪蛋白消化琼脂培养基(荣研制)上接种下述各细菌,在30℃下培养24小时,求出不形成菌落的各试验化合物的浓度(最小抑菌浓度:MIC)。此外,对真菌,在配合各浓度各试验化合物的马铃薯葡萄糖琼脂培养基上接种下述各真菌,在25℃下培养48小时,求出不形成菌落的各试验化合物的浓度(最小抑菌浓度:MIC)。判定结果按以下评价标准示于表VI-1。
(试验菌)
Ps:绿脓杆菌 标准株(菌株名:Pseudomonas aeruginosa ATCC15442)
E:大肠杆菌 标准株(菌株名:Escherichia coli ATCC8739)
S:金黄色葡萄球菌 标准株(菌株名:Staphylococcus aureus ATCC6538)
Can:白色假丝酵母菌(酵母)标准株(菌株名:Candida albicansATCC10231)
Asp:黑曲霉 标准株(菌株名:Aspergillus niger ATCC16404)
(评价标准)
A:最小抑菌浓度为小于1000ppm
B:最小抑菌浓度为1000ppm以上、小于5000ppm
C:最小抑菌浓度为5000ppm以上、小于10000ppm
D:最小抑菌浓度为10000ppm以上、小于30000ppm
E:最小抑菌浓度为30000ppm以上
表VI-1
  试验菌                     抗菌效果
  2,2-二甲基-1-苯基-1,3-丙二醇   对羟基苯甲酸甲酯
  绿脓杆菌 标准株(菌株名:Pseudomonas aeruginosa ATCC15442) A C
  大肠杆菌 标准株(菌株名:Escherichia coli ATCC8739) A B
  金黄色葡萄球菌 标准株(菌株名:Staphylococcus aureus ATCC6538) A B
  白色假丝酵母菌(酵母)标准株(菌株名:Candida albicans ATCC10231) A B
  黑曲霉 标准株(菌株名:Aspergillus niger ATCC16404) A B
试验例VI-2:安全性试验
对本发明的2,2-二甲基-1-苯基-1,3-丙二醇进行安全性试验进行。进行单次给药毒性试验的结果,判断毒性极弱。此外,进行皮肤单次刺激性试验和皮肤连续刺激性试验的结果,判断皮肤刺激性极弱。进一步进行皮肤敏感性试验、遗传毒性试验的结果是阴性。
综上所述,本发明的2,2-二甲基-1-苯基-1,3-丙二醇的安全性良好。
实施例VI-1:化妆水
                                                  质量%
乙醇                                              5.0
1,3-丁二醇                                       6.0
甘油                                              4.0
油醇                                              0.1
POE(20)山梨糖醇酐单月桂酸酯                       0.5
POE(15)月桂醚                                     0.5
2,2-二甲基-1-苯基-1,3-丙二醇                    0.3
香料                                              适量
纯化水                                            剩余量
实施例VI-2:化妆水
                                                  质量%
乙醇                                              5.0
1,3-丁二醇                                       6.0
甘油                                              5.0
油醇                                              0.1
乙基己二醇                                        0.3
2,2-二乙基-1,3-丙二醇                           0.3
2,2,4-三甲基-1,3-戊二醇                        0.5
2,2-二羟甲基戊烷                                 0.2
POE(20)山梨糖醇酐单月桂酸酯                       0.5
POE(15)月桂醚                                              0.5
2,2-二甲基-1-苯基-1,3-丙二醇                             0.2
3-苄氧基-1,2-丙二醇                                       0.3
3-苯氧基-1,2-丙二醇                                       0.2
3-己炔-2,5-二醇                                           0.1
苯氧乙醇                                                   0.2
对羟基苯甲酸甲酯                                           0.1
香料                                                       适量
纯化水                                                     剩余量
实施例VI-3:化妆水
                                                           质量%
山梨糖醇                                                   4.0
1,3-丁二醇                                                6.0
甘油                                                       2.0
POE(20)油醇醚                                              0.5
甲基纤维素                                                 0.2
榅桲                                                       0.1
2,2-二乙基-1,3-丙二醇                                    0.1
乙基己二醇                                                 0.3
2,2,4-三甲基-1,3-戊二醇                                 0.2
2,2-二羟甲基戊烷                                          0.2
2,2-二甲基-1-苯基-1,3-丙二醇                             0.2
3-苄氧基-1,2-丙二醇                                       0.3
3-苯氧基-1,2-丙二醇                                       0.2
3-己炔-2,5-二醇                                           0.1
苯氧乙醇                                                   0.2
对羟基苯甲酸甲酯                                           0.2
香料                                                       适量
纯化水                                                     剩余量
实施例VI-4:乳液
                                                       质量%
2,2-二甲基-1-苯基-1,3-丙二醇                         2.0
甘油                                                   3.0
2,2-二乙基-1,3-丙二醇                                0.2
2,2,4-三甲基-1,3-戊二醇                             0.5
2,2-二羟甲基戊烷                                      0.5
乙基己二醇                                             1.0
鲸蜡醇                                                 1.5
硬脂醇                                                 1.8
聚二甲基硅氧烷(20cs)                                   1.5
角鲨烷                                                 2.0
凡士林                                                 2.0
肉豆蔻酸异丙酯                                         2.5
甘油单硬脂酸酯                                         1.8
聚氧乙烯(POE=5)甘油单硬脂酸酯                         1.8
聚氧乙烯(POE=20)鲸蜡醚                                1.5
聚羧乙烯                                               0.25
氢氧化钾                                               0.05
L-精氨酸                                               0.2
一缩二丙二醇                                           5.0
1,3-丁二醇                                            3.0
依地酸三钠                                             0.2
3-苄氧基-1,2-丙二醇                                   0.2
3-苯氧基-1,2-丙二醇                                   0.1
3-己炔-2,5-二醇                                       0.1
苯氧乙醇                                               0.1
对羟基苯甲酸甲酯                                       0.01
纯化水                                                 剩余量
实施例VI-5:乳膏
                                                          质量%
2,2-二甲基-1-苯基-1,3-丙二醇                            1.0
3-苄氧基-1,2-丙二醇                                      0.2
3-苯氧基-1,2-丙二醇                                      0.1
2,2-二乙基-1,3-丙二醇                                   0.2
2,2,4-三甲基-1,3-戊二醇                                0.5
2,2-二羟甲基戊烷                                         0.5
乙基己二醇                                                1.0
3-己炔-2,5-二醇                                          0.1
硬脂醇                                                    3.5
硬脂酸                                                    2.0
角鲨烷                                                    10.5
肉豆蔻酸异丙酯                                            7.5
聚氧乙烯(POE=25)鲸蜡醇醚                                 3.0
甘油单硬脂酸酯                                            2.0
生育酚乙酸酯                                              0.2
甘草酸一铵                                                0.05
甘油                                                      3.0
一缩二丙二醇                                              5.0
1,3-丁二醇                                               3.0
苯氧乙醇                                                  0.2
依地酸三钠                                                0.01
羟苯乙酯                                                  0.1
纯化水                                                    剩余量
实施例VI-6:洗面奶
                                                          质量%
2,2-二甲基-1-苯基-1,3-丙二醇                            0.5
3-苄氧基-1,2-丙二醇                                      0.2
3-苯氧基-1,2-丙二醇                                     0.1
2,2-二乙基-1,3-丙二醇                                  0.2
2,2,4-三甲基-1,3-戊二醇                               0.5
2,2-二羟甲基戊烷                                        0.5
乙基己二醇                                               0.1
3-己炔-2,5-二醇                                         0.1
硬脂酸                                                   8.0
棕榈酸                                                   6.0
肉豆蔻酸                                                 6.0
月桂酸                                                   4.0
氢氧化钾                                                 5.2
甘油单硬脂酸酯                                           2.0
丙二醇                                                   1.0
蜂蜡                                                     1.5
聚乙二醇1500                                             5.0
甘油                                                     10.0
对羟基苯甲酸甲酯                                         0.01
苯氧乙醇                                                 0.1
纯化水                                                   剩余量
实施例VI-7:洗发剂
                                                         质量%
月桂基聚氧乙烯(3)硫酸酯钠盐(30%水溶液)                  25.0
月桂硫酸酯钠盐(30%水溶液)                               8.0
椰油脂肪酸二乙醇酰胺                                     4.0
异戊二醇                                                 4.0
苯甲酸钠                                                 0.5
一缩二丙二醇                                             1.0
1,3-丁二醇                                              1.0
依地酸三钠                                               0.01
3-苄氧基-1,2-丙二醇                                    0.1
3-苯氧基-1,2-丙二醇                                    0.1
2,2-二乙基-1,3-丙二醇                                 0.2
2,2,4-三甲基-1,3-戊二醇                              0.5
2,2-二羟甲基戊烷                                       0.5
乙基己二醇                                              0.1
3-己炔-2,5-二醇                                        0.1
2,2-二甲基-1-苯基-1,3-丙二醇                          0.1
色素                                                    适量
香料                                                    适量
纯化水                                                  剩余量
实施例VI-8:透明胶状面膜
                                                        质量%
3-苄氧基-1,2-丙二醇                                    0.05
3-苯氧基-1,2-丙二醇                                    0.1
2,2-二甲基-1-苯基-1,3-丙二醇                          0.1
聚氧乙烯油醇醚                                          0.5
2,2-二乙基-1,3-丙二醇                                 0.1
乙基己二醇                                              0.1
2,2,4-三甲基-1,3-丙二醇                              0.1
2,2-二羟甲基戊烷                                       0.1
3-己炔-2,5-二醇                                        0.1
甘草酸一铵                                              0.05
羧甲基纤维素                                            5.0
乙醇                                                    12.0
聚乙烯醇                                                12.0
1,3-丁二醇                                             5.0
依地酸三钠                                              0.01
纯化水                                                  剩余量
实施例VI-9:眼线膏
                                                       质量%
2,2-二甲基-1-苯基-1,3-丙二醇                         1.0
3-苄氧基-1,2-丙二醇                                   0.2
3-苯氧基-1,2-丙二醇                                   0.5
氧化铁(黑)                                             14.0
肉豆蔻酸异丙酯                                         1.5
聚氧乙烯山梨糖醇酐单油酸酯                             1.0
乙酸乙烯酯树脂乳剂                                     45.0
甘草酸一铵                                             0.05
聚羧乙烯                                               1.5
柠檬酸乙酰三丁酯                                       1.0
一缩二丙二醇                                           4.0
异丙醇                                                 1.0
乙基己二醇                                             1.0
2,2-二乙基-1,3-戊二醇                                1.0
2,2-二甲基-1,3-戊二醇                                1.0
2,2,4-三甲基-1,3-戊二醇                             0.5
2,2-二羟甲基戊烷                                      0.5
1,2-戊二醇                                            3.0
3-己炔-2,5-二醇                                       0.1
苯氧乙醇                                               0.1
对羟基苯甲酸甲酯                                       0.02
依地酸三钠                                             0.01
纯化水                                                 剩余量
实施例VI-10:发油
                                                       质量%
固化蓖麻油环氧乙烷(40摩尔)加成物                       2.0
乙醇                                                   60.0
香料                                                   适量
2,2-二甲基-1-苯基-1,3-丙二醇                         0.01
纯化水                                                 剩余量
实施例VI-11:浴用剂
                                                       质量%
碳酸氢钠                                               64.5
无水硫酸钠                                             35.0
2,2-二甲基-1-苯基-1,3-丙二醇                         0.5
实施例VI-12:中式面
                                                       质量%
小麦粉                                                 98.0
食盐                                                   1.0
甜味剂                                                 0.5
2,2-二甲基-1-苯基-1,3-丙二醇                         0.5
实施例VI-13:面汤汁
                                                       质量%
酱油                                                   80.7
醋                                                     1.0
葡萄糖                                                 15.0
谷氨酸钠                                               2.0
砂糖                                                   1.0
2,2-二甲基-1-苯基-1,3-丙二醇                         0.3
实施例VI-14:荞麦面
                                                       质量%
荞麦粉                                                 96.0
食盐                                                   0.9
水                                                     3.0
2,2-二甲基-1-苯基-1,3-丙二醇                         0.1
实施例VI-15:面包
                                                  质量%
小麦粉                                            90.0
食盐                                              1.2
砂糖                                              2.0
水                                                6.5
2,2-二甲基-1-苯基-1,3-丙二醇                    0.3
实施例VI-16:火腿
                                                  质量%
肉馅                                              95.0
鸡蛋                                              4.0
食盐                                              0.5
香辛料                                            0.4
2,2-二甲基-1-苯基-1,3-丙二醇                    0.1
实施例VI-17:果汁饮料
                                                  质量%
葡萄糖液                                          13.0
橙汁                                              85.0
香料                                              1.0
2,2-二甲基-1-苯基-1,3-丙二醇                    1.0
前述实施例均显示良好的防腐性。
试验例VII-1:抗菌结果
求出对各种菌的最小抑菌浓度(MIC)。对2,4,7,9-四甲基-5-癸炔-4,7-二醇、对羟基苯甲酸甲酯进行以下的试验。
采用琼脂平板法,对细菌,在配合各浓度试验化合物的色氨酸大豆琼脂培养基(荣研制)上接种下述各细菌,在30℃下培养24小时,求出不形成菌落的各试验化合物的浓度(最小抑菌浓度:MIC)。此外,对真菌,在配合各浓度试验化合物的马铃薯葡萄糖琼脂培养基上接种下述各真菌,在25℃下培养48小时,求出不形成菌落的各试验化合物的浓度(最小抑菌浓度:MIC)。判定结果根据以下评价标准示于表1。
(试验菌)
Ps:绿脓杆菌 标准株(菌株名:Pseudomonas aeruginosa ATCC15442)
E:大肠杆菌 标准株(菌株名:Escherichia coli ATCC8739)
S:金黄色葡萄球菌 标准株(菌株名:Staphylococcus aureus ATCC6538)
Can:白色假丝酵母菌(酵母)标准株(菌株名:Candida albicansATCC10231)
Asp:黑曲霉标准株(菌株名:Aspergillus niger ATCC16404)
(评价标准)
A:最小抑菌浓度为小于1000ppm
B:最小抑菌浓度为1000ppm以上、小于5000ppm
C:最小抑菌浓度为5000ppm以上、小于10000ppm
D:最小抑菌浓度为10000ppm以上、小于30000ppm
E:最小抑菌浓度为30000ppm以上
表VII-1
 试验菌                      抗菌效果
  2,4,7,9-四甲基-5-癸炔-4,7-二醇 对羟基苯甲酸甲酯
 绿脓杆菌 标准株(菌株名:Pseudomonasaeruginosa ATCC15442) A C
 大肠杆菌 标准株(菌株名:Escherichiacoli ATCC8739) A B
 金黄色葡萄球菌 标准株(菌株名:Staphylococcus aureus ATCC6538) A B
 白色假丝酵母菌(酵母)标准株(菌株名:Candida albicans ATCC10231) A B
 黑曲霉标准株(菌株名:Aspergillusniger ATCC16404) A B
试验例VII-2:安全性试验
进行本发明的2,4,7,9-四甲基-5-癸炔-4,7-二醇的安全性试验。进行单次给药毒性试验的结果,判断毒性极弱。此外,进行皮肤单次刺激性试验和皮肤连续刺激性试验的结果,判断皮肤刺激性极弱。进一步进行皮肤敏感性试验、遗传毒性试验的结果是阴性。
综上所述,本发明2,4,7,9-四甲基-5-癸炔-4,7-二醇的安全性良好。
实施例VII-1:化妆水
                                                      质量%
乙醇                                                  5.0
1,3-丁二醇                                           6.0
甘油                                                  4.0
油醇                                                  0.1
POE(20)山梨糖醇酐单月桂酸酯                           0.5
POE(15)月桂醚                                         0.5
2,4,7,9-四甲基-5-癸炔-4,7-二醇                    0.3
香料                                                  适量
纯化水                                                剩余量
实施例VII-2:化妆水
                                                      质量%
乙醇                                                  5.0
1,3-丁二醇                                           6.0
甘油                                                  5.0
油醇                                                  0.1
乙基己二醇                                            0.3
1,2-戊二醇                                           0.1
2,2-二乙基-                                          0.3
2,2,4-三甲基-1,3-戊二醇                            0.5
2,2-二羟甲基戊烷                                     0.2
2,2-二甲基-1-苯基-1,3-丙二醇                        0.3
POE(20)山梨糖醇酐单月桂酸酯                           0.5
POE(15)月桂醚                                           0.5
2,4,7,9-四甲基-5-癸炔-4,7-二醇                      0.2
3-苄氧基-1,2-丙二醇                                    0.3
3-苯氧基-1,2-丙二醇                                    0.2
3-己炔-2,5-二醇                                        0.1
苯氧乙醇                                                0.2
对羟基苯甲酸甲酯                                        0.1
香料                                                    适量
纯化水                                                  剩余量
实施例VII-3:化妆水
                                                        质量%
山梨糖醇                                                4.0
1,3-丁二醇                                             6.0
甘油                                                    2.0
POE(20)油醇醚                                           0.5
甲基纤维素                                              0.2
榅桲                                                    0.1
2,2-二乙基-1,3-丙二醇                                 0.1
乙基己二醇                                              0.3
1,2-戊二醇                                             0.1
2,2,4-三甲基-1,3-戊二醇                              0.2
2,2-二羟甲基戊烷                                       0.2
2,4,7,9-四甲基-5-癸炔-4,7-二醇                      0.2
2,2-二甲基-1-苯基-1,3-丙二醇                          0.1
3-苄氧基-1,2-丙二醇                                    0.3
3-苯氧基-1,2-丙二醇                                    0.2
3-己炔-2,5-二醇                                        0.1
苯氧乙醇                                                0.2
对羟基苯甲酸甲酯                                        0.2
香料                                                       适量
纯化水                                                     剩余量
实施例VII-4:化妆水
(醇相)                                                     质量%
乙醇                                                       5.0
油醇                                                       0.2
2,2,4-三甲基-1,3-戊二醇                                 0.5
2,2-二羟甲基戊烷                                          0.1
乙基己二醇                                                 0.3
2,2-二甲基-1-苯基-1,3-丙二醇                             0.05
2,2-二乙基-1,3-丙二醇                                    0.1
2,2-二甲基-1,3-丙二醇                                    0.1
2,4,7,9-四甲基-5-癸炔-4,7-二醇                         0.3
3-己炔-2,5-二醇                                           0.1
POE(20)山梨糖醇酐单月桂酸酯                                0.5
POE(15)月桂醚                                              0.5
4,5-二吗啉代-3-羟基哒嗪                                   0.1
苯氧乙醇                                                   0.2
对羟基苯甲酸甲酯                                           0.1
香料                                                       适量
(水相)                                                     质量%
1,3-丁二醇                                                6.0
1,2-戊二醇                                                1.0
3-苯氧基-1,2-丙二醇                                       1.0
3-苄氧基-1,2-丙二醇                                       1.0
甘油                                                       5.0
纯化水                                                     剩余量
实施例VII-5:化妆水
(醇相)                                                     质量%
乙醇                                                  5.0
POE(20)油醚                                           0.5
2,2-二羟甲基戊烷                                     0.3
乙基己二醇                                            0.2
2,2,4-三甲基-1,3-戊二醇                            0.1
2,2-二乙基-1,3-丙二醇                               0.1
2,2-二甲基-1-苯基-1,3-丙二醇                        0.1
2,2-二甲基-1,3-丙二醇                               0.1
2,4,7,9-四甲基-5-癸炔-4,7-二醇                    0.3
3-己炔-2,5-二醇                                      0.1
苯氧乙醇                                              0.1
对羟基苯甲酸甲酯                                      0.1
香料                                                  适量
(水相)                                                质量%
一缩二丙二醇                                          6.0
3-苄氧基-1,2-丙二醇                                  0.5
3-苯氧基-1,2-丙二醇                                  0.5
山梨糖醇                                              4.0
PEG1500                                               5.0
甲基纤维素                                            0.2
榅桲                                                  0.1
纯化水                                                剩余量
实施例VII-6:乳液
                                                      质量%
2,4,7,9-四甲基-5-癸炔-4,7-二醇                    1.0
甘油                                                  3.0
2,2-二乙基-1,3-丙二醇                               0.2
2,2,4-三甲基-1,3-戊二醇                            0.5
2,2-二羟甲基戊烷                                     0.5
2,2-二甲基-1-苯基-1,3-丙二醇                               0.1
乙基己二醇                                                   1.0
鲸蜡醇                                                       1.5
硬脂醇                                                       1.8
聚二甲基硅氧烷(20cs)                                         1.5
角鲨烷                                                       2.0
凡士林                                                       2.0
肉豆蔻酸异丙酯                                               2.5
甘油单硬脂酸酯                                               1.8
聚氧乙烯(POE=5)甘油单硬脂酸酯                               1.8
聚氧乙烯(POE=20)鲸蜡醚                                      1.5
聚羧乙烯                                                     0.25
氢氧化钾                                                     0.05
L-精氨酸                                                     0.2
一缩二丙二醇                                                 5.0
1,3-丁二醇                                                  3.0
1,2-戊二醇                                                  0.1
依地酸三钠                                                   0.2
3-苄氧基-1,2-丙二醇                                         0.2
3-苯氧基-1,2-丙二醇                                         0.1
3-己炔-2,5-二醇                                             0.1
苯氧乙醇                                                     0.1
对羟基苯甲酸甲酯                                             0.01
羟苯乙酯                                                     0.01
羟苯丁酯                                                     0.01
纯化水                                                       剩余量
实施例VII-7:乳液
                                                             质量%
硬脂酸                                                       2.5
鲸蜡醇                                                    1.5
乙基己二醇                                                1.0
2,2,4-三甲基-1,3-丙二醇                                0.5
2,2-二羟甲基戊烷                                         0.3
2,2-二乙基-1,3-丙二醇                                   0.2
2,2-二甲基-1-苯基-1,3-丙二醇                            0.3
2,4,7,9-四甲基-5-癸炔-4,7-二醇                        1.5
3-己炔-2,5-二醇                                          0.2
凡士林                                                    5.0
液体石蜡                                                  10.0
POE(10)单油酸酯                                           2.0
PEG1500                                                   3.0
三乙醇胺                                                  1.0
3-苯氧基-1,2-丙二醇                                      2.0
3-苄氧基-1,2-丙二醇                                      1.0
苯氧乙醇                                                  0.2
对羟基苯甲酸甲酯                                          0.1
羟苯乙酯                                                  0.02
羟苯丁酯                                                  0.01
亚硫酸氢钠                                                0.01
聚羧乙烯                                                  0.05
香料                                                      适量
纯化水                                                    剩余量
实施例VII-8:乳液
                                                          质量%
液体石蜡                                                  7.0
凡士林                                                    3.0
十甲基环戊硅氧烷                                          2.0
山萮醇                                                    1.0
甘油                                                    5.0
一缩二丙二醇                                            7.0
聚乙二醇1500                                            2.0
乙基己二醇                                              1.0
3-己炔-2,5-二醇                                        1.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                      1.5
2,2-二羟甲基戊烷                                       0.2
2,2,4-三甲基-1,3-戊二醇                              0.1
2,2-二甲基-1-苯基-1,3-丙二醇                          0.2
2,2-二乙基-1,3-丙二醇                                 0.2
3-苯氧基-1,2-丙二醇                                    2.0
3-苄氧基-1,2-丙二醇                                    2.0
西蒙得木油                                              1.0
异硬脂酸                                                0.5
硬脂酸                                                  0.5
山萮酸                                                  0.5
四-2-乙基己酸季戊四醇酯                                 3.0
2-乙基己酸鲸蜡酯                                        3.0
甘油单硬脂酸酯                                          1.0
聚氧乙烯甘油单硬脂酸酯                                  1.0
氢氧化钾                                                0.1
六偏磷酸钠                                              0.05
硬脂基甘草亭酸酯                                        0.05
L-精氨酸                                                0.1
蜂王浆提取物                                            0.1
生育酚乙酸酯                                            0.1
乙酰化透明质酸钠                                        0.1
依地酸三钠                                              0.05
4-叔丁基-4’-甲氧基二苯甲酰甲烷                         0.1
对甲氧基肉桂酸2-乙基己酯                                  0.1
聚羧乙烯                                                  0.15
纯化水                                                    剩余量
实施例VII-9:胶冻
                                                          质量%
95%乙醇                                                  5.0
一缩二丙二醇                                              15.0
1,2-辛二醇                                               2.0
乙基己二醇                                                1.0
2,2-二羟甲基戊烷                                         0.1
2,2-二甲基-1,3-丙二醇                                   0.1
2,2-二基-1,3-丙二醇                                     0.1
2,2,4-三甲基-1,3-丙二醇                                0.05
POE(50)油醚                                               2.0
聚羧乙烯                                                  1.0
氢氧化钠                                                  0.15
3-苄氧基-1,2-丙二醇                                      0.05
3-苯氧基-1,2-丙二醇                                      0.05
2,2-二甲基-1-苯基-1,3-丙二醇                            0.1
2,4,7,9-四甲基-5-癸炔-4,7-二醇                        0.3
3-己炔-2,5-二醇                                          0.1
苯氧乙醇                                                  0.1
对羟基苯甲酸甲酯                                          0.1
羟苯乙酯                                                  0.03
羟苯丁酯                                                  0.01
香料                                                      适量
纯化水                                                    剩余量
实施例VII-10:美容液
                                                          质量%
95%乙醇                                                  5.0
POE(20)辛基十二烷醇                                       1.0
泛酰醇乙醚                                                0.1
乙基己二醇                                                0.1
2,2-二羟甲基戊烷                                         0.1
2,2-二甲基-1,3-丙二醇                                   0.1
2,2-二乙基-1,3-丙二醇                                   0.1
2,2-二甲基-1-苯基-1,3-丙二醇                            0.1
2,2,4-三甲基-1,3-丙二醇                                0.05
2,4,7,9-四甲基-5-癸炔-4,7-二醇                        0.3
氢氧化钾                                                  0.1
甘油                                                      5.0
一缩二丙二醇                                              10.0
亚硫酸氢钠                                                0.03
聚羧乙烯                                                  0.2
3-苯氧基-1,2-丙二醇                                      0.2
3-苄氧基-1,2-丙二醇                                      0.1
苯氧乙醇                                                  0.3
对羟基苯甲酸甲酯                                          0.1
纯化水                                                    剩余量
实施例VII-11:面膜
(A相)                                                     质量%
一缩二丙二醇                                              5.0
POE(60)固化蓖麻油                                         5.0
(B相)                                                     质量%
橄榄油                                                    5.0
乙基己二醇                                                0.1
2,2,4-三甲基-1,3-戊二醇                                0.1
2,2-二乙基-1,3-丙二醇                                   0.2
2,2-二羟甲基戊烷                                         0.05
生育酚乙酸酯                                              0.2
香料                                                      0.2
(C相)                                                     质量%
亚硫酸氢钠                                                0.03
聚乙烯醇(皂化度90,聚合度2000)                            13.0
乙醇                                                      5.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                        0.3
2,2-二甲基-1-苯基-1,3-丙二醇                            0.2
3-苯氧基-1,2-丙二醇                                      0.5
3-苄氧基-1,2-丙二醇                                      0.6
3-己炔-2,5-二醇                                          0.1
对羟基苯甲酸甲酯                                          0.1
苯氧乙醇                                                  0.2
纯化水                                                    剩余量
实施例VII-12:乳膏
                                                          质量%
2,4,7,9-四甲基-5-癸炔-4,7-二醇                        1.0
2,2-二甲基-1-苯基-1,3-丙二醇                            0.5
3-苄氧基-1,2-丙二醇                                      0.2
3-苯氧基-1,2-丙二醇                                      0.1
2,2-二乙基-1,3-丙二醇                                   0.2
2,2,4-三甲基-1,3-戊二醇                                0.5
2,2-二羟甲基戊烷                                         0.5
乙基己二醇                                                1.0
3-己炔-2,5-二醇                                          0.1
硬脂醇                                                    3.5
硬脂酸                                                    2.0
角鲨烷                                                    10.5
肉豆蔻酸异丙酯                                            7.5
聚氧乙烯(POE=20)鲸蜡醇醚                                 3.0
甘油单硬脂酸酯                                            2.0
生育酚乙酸酯                                              0.2
甘草酸一铵                                                0.05
甘油                                                      3.0
一缩二丙二醇                                              5.0
1,2-戊二醇                                               0.1
1,3-丁二醇                                               3.0
苯氧乙醇                                                  0.2
依地酸三钠                                                0.01
对羟基苯甲酸甲酯                                          0.1
羟苯乙酯                                                  0.1
羟苯丁酯                                                  0.05
纯化水                                                    剩余量
实施例VII-13:乳膏
                                                          质量%
硬脂酸                                                    6.0
山梨糖醇酐单硬脂酸酯                                      2.0
POE(20)山梨糖醇酐单硬脂酸酯                               1.5
乙基己二醇                                                2.0
2,2-二乙基-1,3-丙二醇                                   1.0
2,2-二羟甲基戊烷                                         1.0
2,2,4-三甲基-1,3-戊二醇                                1.0
丙二醇                                                    10.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                        3.0
2,2-二甲基-1-苯基-1,3-丙二醇                            0.5
3-苄氧基-1,2-丙二醇                                      3.0
3-苯氧基-1,2-丙二醇                                      1.0
3-己炔-2,5-二醇                                         0.1
甘油三辛酸酯                                             10.0
角鲨烯                                                   5.0
亚硫酸氢钠                                               0.01
对羟基苯甲酸甲酯                                         0.01
羟苯乙酯                                                 0.01
羟苯丁酯                                                 0.01
苯氧乙醇                                                 0.1
香料                                                     适量
纯化水                                                   剩余量
实施例VII-14:乳膏
                                                         质量%
液体石蜡                                                 10.0
聚二甲基硅氧烷                                           2.0
甘油                                                     10.0
1,3-丁二醇                                              2.0
赤藓醇                                                   1.0
乙基己二醇                                               0.1
2,2-二羟甲基戊烷                                        1.0
2,2,4-三甲基-1,3-戊二醇                               0.5
2,2-二甲基-1-苯基-1,3-丙二醇                           0.2
2,2-二乙基-1,3-丙二醇                                  0.1
2,4,7,9-四甲基-5-癸炔-4,7-二醇                       2.0
聚乙二醇1500                                             5.0
角鲨烷                                                   15.0
四 2-乙基己酸季戊四醇酯                                  5.0
氢氧化钾                                                 0.1
六偏磷酸钠                                               0.05
生育酚乙酸酯                                             0.05
3-苯氧基-1,2-丙二醇                                      1.0
3-苄氧基-1,2-丙二醇                                      1.0
3-己炔-2,5-二醇                                          0.2
苯氧乙醇                                                  0.1
对羟基苯甲酸甲酯                                          0.2
羟苯乙酯                                                  0.1
羟苯丁酯                                                  0.05
羟丙甲基纤维素                                            0.3
聚乙烯醇                                                  0.1
聚羧乙烯                                                  0.2
丙烯酸-甲基丙烯酸烷酯共聚物(Pemulen TR-2)                 0.1
实施例VII-15:乳膏
                                                          质量%
凡士林                                                    2.0
聚二甲基硅氧烷(6mPa.s)                                    2.0
乙醇                                                      5.0
山萮醇                                                    0.5
鲨肝醇                                                    0.2
甘油                                                      7.0
1,3-丁二醇                                               5.0
聚乙二醇20000                                             0.5
西蒙得木油                                                3.0
角鲨烷                                                    2.0
羟基硬脂酸植物甾醇酯                                      0.5
2-乙基己酸季戊四醇酯                                      1.0
聚氧乙烯(60)固化蓖麻油                                    1.0
氢氧化钾                                                  0.1
焦亚硫酸钠                                                0.01
六偏磷酸钠                                                0.05
硬脂基甘草亭酸酯                                      0.1
泛酰醇乙醚                                            0.1
熊果苷                                                7.0
氨甲环酸                                              1.0
生育酚乙酸酯                                          0.1
透明质酸钠                                            0.05
3-苯氧基-1,2-丙二醇                                  1.0
3-苄氧基-1,2-丙二醇                                  1.0
依地酸三钠                                            0.05
乙基己二醇                                            1.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                    0.6
2,2-二羟甲基戊烷                                     0.2
2,2-二甲基-1-苯基-1,3-丙二醇                        0.2
2,2,4-三甲基-1,3-戊二醇                            0.1
2,2-二乙基-1,3-丙二醇                               0.2
3-己炔-2,5-二醇                                      0.2
4-叔丁基-4’-甲氧基二苯甲酰甲烷                       0.1
二对甲氧基肉桂酸单-2-乙基己酸甘油酯                   0.1
苯氧乙醇                                              0.1
对羟基苯甲酸甲酯                                      0.05
羟苯乙酯                                              0.02
羟苯丁酯                                              0.03
氧化铁黄                                              适量
黄原胶                                                0.1
聚羧乙烯                                              0.2
纯化水                                                剩余量
实施例VII-16:乳膏
                                                      质量%
十甲基环戊硅氧烷                                      30.0
聚氧乙烯-聚甲基硅氧烷共聚物(分子量6000)                         1.5
三甲基甲硅烷氧基硅酸                                            0.5
甘油                                                            2.0
乙基己二醇                                                      1.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                              0.8
2,2-二羟甲基戊烷                                               0.2
2,2,4-三甲基-1,3-戊二醇                                      0.1
2,2-二乙基-1,3-丙二醇                                         0.3
一缩二丙二醇                                                    5.0
3-苯氧基-1,2-丙二醇                                            0.5
3-苄氧基-1,2-丙二醇                                            1.0
2,2-二甲基-1-苯基-1,3-丙二醇                                  0.2
3-己炔-2,5-二醇                                                0.5
滑石粉                                                          5.0
球状无水硅酸                                                    0.5
棕榈酸糊精包覆微粒氧化钛(30nm)                                  7.0
球状聚乙烯粉末                                                  2.0
聚(氧乙烯-氧丙烯)-聚甲基硅氧烷(分子量55000)                     1.0
苯氧乙醇                                                        0.2
对羟基苯甲酸甲酯                                                0.1
羟苯乙酯                                                        0.05
羟苯丁酯                                                        0.05
依地酸三钠                                                      0.02
二甲基二硬脂酰铵锂蒙脱                                          0.5
纯化水                                                          剩余量
实施例VII-17:洗面奶
                                                                质量%
2,4,7,9-四甲基-5-癸炔-4,7-二醇                              0.5
2,2-二甲基-1-苯基-1,3-丙二醇                                  0.3
3-苄氧基-1,2-丙二醇                                        0.2
3-苯氧基-1,2-丙二醇                                        0.1
2,2-二乙基-1,3-丙二醇                                     0.2
2,2,4-三甲基-1,3-戊二醇                                  0.5
2,2-二羟甲基戊烷                                           0.5
乙基己二醇                                                  0.1
1,2-戊二醇                                                 0.1
 3-己炔-2,5-二醇                                           0.1
硬脂酸                                                      8.0
棕榈酸                                                      6.0
肉豆蔻酸                                                    6.0
月桂酸                                                      4.0
氢氧化钾                                                    5.2
甘油单硬脂酸酯                                              2.0
丙二醇                                                      1.0
蜂蜡                                                        1.5
聚乙二醇1500                                                5.0
甘油                                                        10.0
对羟基苯甲酸甲酯                                            0.01
苯氧乙醇                                                    0.1
纯化水                                                      剩余量
实施例VII-18:洗发剂
                                                            质量%
月桂基聚氧乙烯(3)硫酸酯钠盐(30%水溶液)                     25.0
月桂硫酸酯钠盐(30%水溶液)                                  8.0
椰油脂肪酸二乙醇胺                                          4.0
异戊二醇                                                    4.0
苯甲酸钠                                                    0.5
一缩二丙二醇                                                1.0
1,3-丁二醇                                        1.0
1,2-戊二醇                                        0.1
依地酸三钠                                         0.01
2,2-二甲基-1-苯基-1,3-丙二醇                     0.1
3-苄氧基-1,2-丙二醇                               0.1
3-苯氧基-1,2-丙二醇                               0.1
2,2-二乙基-1,3-丙二醇                            0.2
2,2,4-三甲基-1,3-戊二醇                         0.5
2,2-二羟甲基戊烷                                  0.5
乙基己二醇                                         0.1
3-己炔-2,5-二醇                                   0.1
2,4,7,9-四甲基-5-癸炔-4,7-二醇                 0.1
色素                                               适量
香料                                               适量
纯化水                                             剩余量
实施例VII-19:焗油剂
                                                   质量%
硅油                                               3.0
液体石蜡                                           1.0
鲸蜡醇                                             1.5
硬脂醇                                             1.0
硬脂基三甲基氯化铵                                 0.7
乙基己二醇                                         0.5
2,2,4-三甲基-1,3-戊二醇                         0.3
2,2-二甲基-1-苯基-1,3-丙二醇                     0.2
2,2-二乙基-1,3-丙二醇                            0.1
2,2-二羟甲基戊烷                                  0.07
2,4,7,9-四甲基-5-癸炔-4,7-二醇                 0.4
3-苯氧基-1,2-丙二醇                               1.0
3-苄氧基-1,2-丙二醇                                   1.0
3-己炔-2,5-二醇                                       0.7
甘油                                                   3.0
色素                                                   适量
香料                                                   适量
纯化水                                                 剩余量
实施例VII-20:透明胶状面膜
                                                       质量%
3-苄氧基-1,2-丙二醇                                   0.05
3-苯氧基-1,2-丙二醇                                   0.1
2,4,7,9-四甲基-5-癸炔-4,7-二醇                     0.1
聚氧乙烯油醇醚                                         0.5
2,2-二乙基-1,3-丙二醇                                0.1
乙基己二醇                                             0.1
2,2-二甲基-1-苯基-1,3-丙二醇                         0.2
2,2,4-三甲基-1,3-丙二醇                             0.1
2,2-二羟甲基戊烷                                      0.1
3-己炔-2,5-二醇                                       0.1
甘草酸一铵                                             0.05
羧甲基纤维素                                           5.0
乙醇                                                   12.0
聚乙烯醇                                               12.0
1,3-丁二醇                                            5.0
1,2-戊二醇                                            0.3
依地酸三钠                                             0.01
纯化水                                                 剩余量
实施例VII-21:固体粉末状粉底
                                                       质量%
滑石粉                                                 15.0
绢云母                                               10.0
球状尼龙粉末                                         10.0
多孔性无水硅酸粉末                                   15.0
氮化硼                                               5.0
二氧化钛                                             5.0
氧化铁                                               3.0
硬脂酸锌                                             5.0
液体石蜡                                             剩余量
三异辛酸甘油酯                                       15.0
山梨糖醇酐倍半油酸酯                                 1.5
3-苯氧基-1,2-丙二醇                                 0.5
3-苄氧基-1,2-丙二醇                                 0.3
2,4,7,9-四甲基-5-癸炔-4,7-二醇                   0.2
乙基己二醇                                           0.2
2,2,4-三甲基-1,3-戊二醇                           0.1
2,2-二甲基-1-苯基-1,3-丙二醇                       0.2
2,2-二乙基-1,3-丙二醇                              0.2
2,2-二羟甲基戊烷                                    0.05
3-己炔-2,5-二醇                                     0.1
对羟基苯甲酸甲酯                                     0.2
羟苯乙酯                                             0.1
香料                                                 适量
实施例VII-22:油包水型乳状粉底
                                                     质量%
球状尼龙                                             10.0
多孔性无水硅酸粉末                                   8.0
云母钛                                               2.0
聚硅氧烷处理绢云母                                   2.0
聚硅氧烷处理云母                                     12.0
聚硅氧烷处理二氧化钛                                   5.0
聚硅氧烷处理氧化铁                                     2.0
纯化水                                                 剩余量
3-苯氧基-1,2-丙二醇                                   3.0
3-苄氧基-1,2-丙二醇                                   3.0
乙基己二醇                                             1.0
2,2-二羟甲基戊烷                                      1.0
2,2-二乙基-1,3-丙二醇                                1.0
2,2-二甲基-1,3-丙二醇                                0.2
2,2,4-三甲基-1,3-戊二醇                             1.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                     0.8
2,2-二甲基-1-苯基-1,3-丙二醇                         0.2
3-己炔-2,5-二醇                                       0.1
十甲基环戊硅氧烷                                       18.0
聚二甲基硅氧烷                                         5.0
角鲨烷                                                 1.0
聚氧乙烯改性聚二甲基硅氧烷                             2.0
苯氧乙醇                                               0.1
对羟基苯甲酸甲酯                                       0.1
香料                                                   适量
实施例VII-23:白粉
                                                       质量%
滑石粉                                                 剩余量
绢云母                                                 10.0
球状尼龙粉末                                           10.0
氮化硼                                                 5.0
氧化铁                                                 3.0
碳酸镁                                                 5.0
角鲨烷                                                 3.0
三异辛酸甘油酯                                       2.0
山梨糖醇酐倍半油酸酯                                 2.0
乙基己二醇                                           0.5
3-苯氧基-1,2-丙二醇                                 1.0
3-苄氧基-1,2-丙二醇                                 2.0
乙基己二醇                                           1.0
2,2-二羟甲基戊烷                                    1.0
2,2-二乙基-1,3-丙二醇                              1.0
2,2-二甲基-1,3-丙二醇                              0.2
2,2,4-三甲基-1,3-戊二醇                           1.0
2,2-二甲基-1-苯基-1,3-丙二醇                       0.1
2,4,7,9-四甲基-5-癸炔-4,7-二醇                   0.4
3-己炔-2,5-二醇                                     0.1
对羟基苯甲酸甲酯                                     0.3
香料                                                 适量
实施例VII-24:眼线膏
                                                     质量%
2,4,7,9-四甲基-5-癸炔-4,7-二醇                   1.0
2,2-二甲基-1-苯基-1,3-丙二醇                       0.3
3-苄氧基-1,2-丙二醇                                 0.2
3-苯氧基-1,2-丙二醇                                 0.5
氧化铁(黑)                                           14.0
肉豆蔻酸异丙酯                                       1.5
聚氧乙烯山梨糖醇酐单油酸酯                           1.0
乙酸乙烯酯树脂乳剂                                   45.0
甘草酸一铵                                           0.05
聚羧乙烯                                             1.5
柠檬酸乙酰三丁酯                                     1.0
一缩二丙二醇                                         4.0
异丙醇                                                 1.0
乙基己二醇                                             1.0
2,2-二基-1,3-戊二醇                                  1.0
2,2-二甲基-1,3-戊二醇                                1.0
2,2,4-三甲基-1,3-戊二醇                             0.5
2,2-二羟甲基戊烷                                      0.5
1,2-戊二醇                                            3.0
3-己炔-2,5-二醇                                       0.1
苯氧乙醇                                               0.1
对羟基苯甲酸甲酯                                       0.02
依地酸三钠                                             0.01
纯化水                                                 剩余量
实施例VII-25:眼影
                                                       质量%
滑石粉                                                 剩余量
云母                                                   15.0
球状尼龙粉末                                           10.0
氮化硼                                                 5.0
氧化铁                                                 3.0
氧化钛包覆云母                                         5.0
角鲨烷                                                 3.0
三异辛酸甘油酯                                         2.0
山梨糖醇酐倍半油酸酯                                   2.0
乙基己二醇                                             1.0
2,2-二羟甲基戊烷                                      0.3
2,2-二乙基-1,3-戊二醇                                0.1
2,2-二甲基-1,3-戊二醇                                0.1
2,2,4-三甲基-1,3-丙二醇                             0.1
3-苯氧基-1,2-丙二醇                                   0.5
3-苄氧基-1,2-丙二醇                                      0.5
2,4,7,9-四甲基-5-癸炔-4,7-二醇                        0.6
2,2-二甲基-1-苯基-1.3-丙二醇                             0.2
3-己炔-2,5-二醇                                          0.3
对羟基苯甲酸甲酯                                          0.1
香料                                                      适量
实施例VII-26:口红
                                                          质量%
巴西棕榈蜡                                                0.5
小烛树蜡                                                  5.0
纯地蜡                                                    10.0
角鲨烷                                                    剩余量
甘油三异硬脂酸酯                                          10.0
甘油二异硬脂酸酯                                          20.0
3-苯氧基-1,2-丙二醇                                      0.2
3-苄氧基-1,2-丙二醇                                      0.1
2,4,7,9-四甲基-5-癸炔-4,7-二醇                        0.5
乙基己二醇                                                1.0
2,2-二羟甲基戊烷                                         0.1
2,2-二乙基-1,3-戊二醇                                   0.1
2,2-二甲基-1,3-戊二醇                                   0.1
2,2,4-三甲基-1,3-丙二醇                                0.1
3-己炔-2,5-二醇                                          0.7
2,2-二甲基-1-苯基-1.3-丙二醇                             0.1
马卡达姆坚果油脂肪酸胆甾醇酯                              4.0
合成硅酸钠镁                                              0.5
疏水性二氧化硅                                            0.5
纯化水                                                    2.0
颜料                                                      适量
香料                                                     适量
实施例VII-27:发胶
(原液处方)                                               质量%
丙烯酸树脂烷醇胺溶液(50%)                               8.0
聚氧乙烯固化蓖麻油                                       1.0
液体石蜡                                                 5.0
甘油                                                     3.0
香料                                                     适量
3-苯氧基-1,2-丙二醇                                     0.01
3-苄氧基-1,2-丙二醇                                     0.01
2,4,7,9-四甲基-5-癸炔-4,7-二醇                       0.3
乙基己二醇                                               0.2
2,2-二羟甲基戊烷                                        0.1
2,2-二乙基-1,3-戊二醇                                  0.1
2,2-二甲基-1,3-戊二醇                                  0.1
2,2,4-三甲基-1,3-丙二醇                               0.1
3-己炔-2,5-二醇                                         0.3
2,2-二甲基-1-苯基-1.3-丙二醇                            0.1
乙醇                                                     5.0
纯化水                                                   剩余量
(填充处方)                                               质量%
原液                                                     90.0
液化石油气                                               10.0
实施例VII-28:发油
                                                         质量%
固化蓖麻油环氧乙烷(40摩尔)加成物                         2.0
乙醇                                                     60.0
香料                                                     适量
2,4,7,9-四甲基-5-癸炔-4,7-二醇                       0.01
纯化水                                                 剩余量
实施例VII-29:浴用剂
                                                       质量%
碳酸氢钠                                               64.5
无水硫酸钠                                             35.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                     0.5
实施例VII-30:中式面
                                                       质量%
小麦粉                                                 98.0
食盐                                                   1.0
甜味剂                                                 0.5
2,4,7,9-四甲基-5-癸炔-4,7-二醇                     0.5
实施例VII-31:面汤汁
                                                       质量%
酱油                                                   80.7
醋                                                     1.0
葡萄糖                                                 15.0
谷氨酸钠                                               2.0
砂糖                                                   1.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                     0.3
实施例VII-32:荞麦面
                                                       质量%
荞麦粉                                                 96.0
食盐                                                   0.9
水                                                     3.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                     0.1
实施例VII-33:面包
                                                       质量%
小麦粉                                                 90.0
食盐                                                         1.2
砂糖                                                         2.0
水                                                           6.5
2,4,7,9-四甲基-5-癸炔-4,7-二醇                           0.3
实施例VII-34:面包
                                                             质量%
肉馅                                                         95.0
鸡蛋                                                         4.0
食盐                                                         0.5
香辛料                                                       0.4
2,4,7,9-四甲基-5-癸炔-4,7-二醇                           0.1
实施例VII-35:果汁饮料
                                                             质量%
葡萄糖液                                                     13.0
橙汁                                                         85.0
香料                                                         1.0
2,4,7,9-四甲基-5-癸炔-4,7-二醇                           1.0
前述实施例均显示良好的防腐性。
工业实用性
本发明抗菌剂对各种微生物具有增殖抑制作用,对人或动物更安全。因此,作为抗菌剂使用能够防止各种形态的制剂、制品的腐败和污染,适用于药品、准药品、化妆品领域(也包括人和其它动物所用的各种制剂)的各种皮肤外用剂组合物、医疗器械类或以患部的消毒洗涤为目的的医疗用洗涤剂,杀菌洗涤餐具等的家用洗涤剂,食品工业用洗涤剂,纤维制品(床单类、衣服类等),食品包装薄膜、合成树脂、木材、日用品等的抗菌加工,各种形态的口服药剂,卫生棉类、湿纸巾或擦拭用纸类,除菌用布等无纺布,或口腔用组合物(口香糖、硬糖等)或鱼糕、鱼卷等水产熟食品,香肠、火腿等畜产品,西式糕点类,日式糕点类,中式面、日本面、荞麦面等面类,汤汁、酱油、作料汁等调味料,家常菜、果汁、汤汁等普通饮食类。
本发明抗菌剂可用于药品、准药品、化妆品领域(也包括人和其它动物所用的各种制剂)的各种皮肤外用剂组合物,具体来说,可举出应用于化妆水、乳液、乳膏(包含软膏)、防晒霜、粉底、油、面膜、肥皂(也包括药用皂)、香皂、口红、指甲化妆品、眉眼化妆品、香水、洗面奶、口腔用类(牙膏、漱口液等)、防臭剂(腋臭、脚臭等)、浴用剂、洗发剂、焗油剂、发油、发胶、染发剂等。此外,可应用于医疗器械类或以患部的消毒洗涤为目的的医疗用洗涤剂,杀菌洗涤餐具等的家用洗涤剂,食品工业用洗涤剂等。还可应用于纤维制品(衬衫类、衣服类等),食品包装薄膜、合成树脂、木材、日用品等的抗菌加工,各种形态的口服药剂,卫生棉类、湿纸巾或擦拭用纸类,除菌用布等无纺布,或口腔用组合物(口香糖、糖果等)或鱼糕、鱼卷等水产熟食品,香肠、火腿等畜产品,西式糕点类,日式糕点类,生面、煮面、中式面、日本面、荞麦面、通心面等面类,酱油、汤汁、作料汁等调味料,家常菜、果汁、汤汁等普通饮食类。

Claims (11)

1.皮肤外用剂组合物,含有相对于组合物总重量在0.001质量%以上的式(I)、(II)、(III)或(IV)表示的二醇化合物或其衍生物以及剩余部分的基质而成:
式中,R表示苄基或苯基,
Figure A2004800087970002C2
2.权利要求1所述的皮肤外用剂组合物,二醇化合物为式(I)的3-己炔-2,5-二醇。
3.权利要求1所述的皮肤外用剂组合物,二醇衍生物为式(II)的甘油衍生物。
4.权利要求1所述的皮肤外用剂组合物,二醇化合物为式(III)的2,2-二甲基-1-苯基-1,3-丙二醇。
5.权利要求1所述的皮肤外用剂组合物,二醇化合物为式(IV)的2,4,7,9-四甲基-5-癸炔-4,7-二醇。
6.权利要求1所述的皮肤外用剂组合物,二醇化合物或其衍生物的含量为组合物总重量的0.001~10质量%。
7.抗菌剂,含有式(I)、(II)、(III)或(IV)表示的二醇化合物或其衍生物。
式中,R表示苄基或苯基,
8.权利要求7所述的抗菌剂,二醇化合物为式(I)的3-己炔-2,5-二醇。
9.权利要求7所述的抗菌剂,二醇衍生物为式(II)的甘油衍生物。
10.权利要求7所述的抗菌剂,二醇化合物为式(III)的2,2-二甲基-1-苯基-1,3-丙二醇。
11.权利要求7所述的抗菌剂,二醇化合物为式(IV)的2,4,7,9-四甲基-5-癸炔-4,7-二醇。
CN 200480008797 2003-04-04 2004-04-02 皮肤外用剂组合物 Pending CN1767765A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102481242A (zh) * 2009-08-26 2012-05-30 巴斯夫欧洲公司 1,3-二醇作为杀生物剂的用途
CN113476610A (zh) * 2021-08-13 2021-10-08 云南中医药大学 甘油衍生物与抗真菌药物组成的抗真菌药物组合物

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CN101401775B (zh) * 2008-11-18 2010-08-25 董萍 被动靶向夜用和日用皮肤美白功效纳米乳及其制备方法
CN104758198B (zh) * 2014-01-08 2017-11-21 南京美纯生物科技有限公司 一种含黑莓提取物的强抗氧化护肤品及其制备方法和用途
CN109892364B (zh) * 2017-12-11 2022-12-09 丰益(上海)生物技术研发中心有限公司 加速面团醒发的添加剂及方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102481242A (zh) * 2009-08-26 2012-05-30 巴斯夫欧洲公司 1,3-二醇作为杀生物剂的用途
CN113476610A (zh) * 2021-08-13 2021-10-08 云南中医药大学 甘油衍生物与抗真菌药物组成的抗真菌药物组合物

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