CN116509756A - 一种基于氧化铈粘土复合防晒乳及其制备方法 - Google Patents
一种基于氧化铈粘土复合防晒乳及其制备方法 Download PDFInfo
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- CN116509756A CN116509756A CN202310560896.8A CN202310560896A CN116509756A CN 116509756 A CN116509756 A CN 116509756A CN 202310560896 A CN202310560896 A CN 202310560896A CN 116509756 A CN116509756 A CN 116509756A
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- cerium oxide
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Classifications
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Abstract
本发明属于防晒产品技术领域,具体公开了一种基于氧化铈粘土复合防晒乳及其制备方法,本发明在埃洛石纳米管HNTs内原位合成的CeOx纳米粒子,其具有优越分散性和强的UV吸收性能。埃洛石管壁的氧化铝和氧化硅层限制CeOx直接与皮肤接触,避免皮肤光毒性。本发明的氧化铈粘土Pickering防晒乳液涂抹性良好,具有优良的紫外吸收、屏蔽效果,可保护皮肤免受紫外辐射造成的DNA损伤和炎症,预防皮肤癌,同时具有低皮肤刺激性。本发明可满足人们对防晒霜的高效性和安全性需求,推广和应用价值高。
Description
技术领域
本发明涉及防晒产品技术领域,特别是一种基于氧化铈粘土复合防晒乳及其制备方法。
背景技术
在过去几十年里,皮肤癌发病率升高了45%,且有年轻化趋势,其主要诱因是紫外线(Ultraviolet rays,UV)辐射。UV是一种波长范围为10~400nm的电磁辐射,可引起各种不良影响,包括晒伤、光老化、氧化应激和致癌作用。UV分为三个主要波长,长波(UVA,400~320nm)、中波(UVB,315~280nm)和短波(UVC,280~200nm)。UVB诱导DNA损伤和活性氧(Reactive oxygen species,ROS),导致皮肤细胞突变、死亡、氧化应激,是晒伤和皮肤癌的主要原因。因此,防晒产品的应用对于预防皮肤癌至关重要。
防晒霜是研究最广泛的光保护措施。有机UV防护剂广泛用于防晒产品中,但这些成分刺激性强易引起过敏和皮炎。无机UV防护剂具有热稳定性高、皮肤刺激性低、化学稳定性好、UV吸收波长范围广、可见光透过率高、性价比高等优点。它们的作用原理是无机材料能吸收能量大于禁带的UV,导致电子从价带转移到导带产生空穴,电子-空穴容易复合,吸收的光子的能量通过热和光释放。铈(Ce)是储量最丰富的稀土元素,氧化铈(CeOx)为n型半导体,禁带宽度为2.94eV,可有效吸收波长小于420nm的光,对UV有很强的吸收性能,而对可见光的透过率高。CeOx纳米粒子粒径更小、比表面积大,表现出较多的氧空位,带来优异的UV吸收性能。相比氧化锌和二氧化钛对可见光的屏蔽造成的假白效应,CeOx广泛应用于防晒化妆品、UV光致发光、抗老化汽车玻璃等。但是,CeOx纳米粒子容易团聚,不利于再分散,限制了其性能。此外这些金属氧化物吸收UV时表面水活化产生羟基以捕获自由空位形成羟基自由基,而自由基吸收氧产生超氧自由基,这些ROS会导致光毒性。迫切需要使用各种修饰方法调节UV光催化性能来控制产生的ROS,可提高无机UV防护剂的安全性。
如中国专利申请号200780020132.9公开了一种防晒化妆品,含有在UV-A区具有吸收的紫外线吸收剂和用烷基烷氧基硅烷进行了表面处理的金属氧化物粉末,金属氧化物粉末为选自氧化钛、氧化锌、氧化铁、氧化铈的一种或两种以上,其目的在于提供防止在衣服上因二次附着而引起的染色的防晒化妆品。但是,该防晒化妆品中含有的氧化铈使用时会直接与皮肤接触,会造成皮肤光毒性。
Pickering乳液是由吸附到两相界面的固体微粒稳定的乳浊液。固体微粒代替传统的化学乳化剂,在两相界面形成一层薄膜,阻止了液滴之间的聚集。与传统表面活性剂稳定的乳液相比,Pickering乳液具有一定的优势:可以大大降低乳化剂的用量;减少表面活性剂带来的健康风险;对环境友好;乳液稳定性强,不易受体系pH值、盐浓度、温度及油相组成等因素的影响;固体微粒和许多活性组分的相容性更好,可提高配方功能性等。乳状液的稳定性依赖于固体颗粒的粒径、表面润湿性及固体颗粒之间的相互作用。其中润湿性是最重要的影响因素,当固体颗粒表面接触角为90度左右时,可以在油/水界面形成结构比较稳定的薄膜,有较佳的乳化性能。防晒产品货架期和在皮肤表面滞留时间都较长,这要求防晒产品需具备较好的悬浮稳定性和安全性,因此优选Pickering乳液配方可在保证稳定性的同时降低刺激性,此外选用有UV屏蔽效果的固体微粒本身可与其他防晒剂有协同增效作用。然而基于Pickering乳液配方的防晒乳仍较少。
由于为满足上述应用需求和填补市场空缺,迫切需要开发出一款安全、高效的Pickering防晒乳液用于皮肤癌预防。
发明内容
为了解决上述技术问题,本发明提供了一种基于氧化铈粘土复合防晒乳及其制备方法,以实现安全高效的UV吸收和屏蔽,保护皮肤免受UV诱发的DNA损伤,预防皮肤癌。
为达到上述目的,本发明是按照以下技术方案实施的:
本发明的第一个目的是要提供一种基于氧化铈粘土复合防晒乳的制备方法,包括以下步骤:
S1、配制浓度为0.5~2%的埃洛石纳米管HNTs乙醇分散液和浓度为0.05~0.4M的硝酸铈乙醇溶液;
S2、将HNTs乙醇分散液与硝酸铈乙醇溶液按照体积比1:1混匀后,超声处理10~40分钟得到均匀分散的HNTs-硝酸铈乙醇分散液;
S3、将HNTs-硝酸铈乙醇分散液在真空或者空气氛围下300~500rpm搅拌1~3小时后置于反应釜中,调节pH为11~13,在100℃~180℃下反应12~48小时;
S4、将S3所得的产物离心收集,用无水乙醇洗涤多遍,于-50℃冷冻干燥12h获得CeOx@HNTs复合材料;
S5、将CeOx@HNTs复合材料与去离子水混合,使CeOx@HNTs复合材料终浓度为1~4%;然后加入成膜剂,使成膜剂终浓度为2~5%;超声处理15分钟后搅拌1小时;再加入油相,使油相终浓度为10~30%,超声处理15分钟后,置于均质仪在8000~13000rpm转速下均质乳化10分钟,得到CeOx@HNTs Pickering防晒乳液。
进一步地,所述埃洛石纳米管HNTs的粒径为0.1~2μm,内径为10-20nm,外径为40-70nm,长度为100-1000nm,Zeta电位在-20~-40mV之间。
进一步地,所述步骤S1中,配制浓度为0.5~2%的埃洛石纳米管HNTs乙醇分散液具体为:将埃洛石纳米管HNTs加入无水乙醇中,300rpm搅拌12小时,之后在50Hz,功率500W条件下超声均质处理30分钟,得到均匀分散的浓度为0.5~2%HNTs乙醇分散液。
进一步地,所述超声处理是在50Hz,功率500W条件下处理。
进一步地,所述成膜剂为聚乙烯吡咯烷酮类聚合物、三甲基硅氧基硅酸酯、己二酸/二甘醇/甘油交联聚合物、聚丙烯酸、聚乙烯醇中的一种或多种组合。
进一步地,所述油相为矿油、白凡士林、橄榄油、羊毛脂、聚二甲基硅氧烷、角鲨烷、硬脂基聚二甲基硅氧烷、环五聚二甲基硅氧烷、C12~15醇苯甲酸酯、肉豆蒄酸异丙酯中的一种或多种组合。
优选地,所述成膜剂为聚乙烯醇。
优选地,所述油相为聚二甲基硅氧烷。
优选地,所述步骤S5中,CeOx@HNTs复合材料终浓度为4%,成膜剂终浓度为2%,油相终浓度为20%。
本发明的第二个目的是要提供一种利用上述方法制备的基于氧化铈粘土复合防晒乳。
本发明的机理为:
埃洛石纳米管(HNTs)是在自然条件下高岭石片层向内卷绕形成的粘土纳米管,分子式为Al2Si2O5(OH)4-nH2O(n=0或2)。它们的内径为10-20nm,外径为40-70nm,长度为100-1000nm,平均粒径约为150nm,具有独特的中空管状结构,外表面由硅氧四面体层(SiO4)和内腔的铝氧八面体层(AlO6)组成,具有丰富的结构羟基,使得合成的CeOx吸附到管腔中,限制CeOx直接与皮肤接触,避免皮肤光毒性;此外,埃洛石纳米管外表面的二氧化硅层可以反射和散射UV,再者由于外表面的二氧化硅表面带有丰富的负电荷,HNTs可在水中均匀分散形成胶体,可作为Pickering乳液油水界面的稳定剂;将CeOx@HNTs复合材料与去离子水混合后加入成膜剂和油相即可制得CeOx@HNTs Pickering防晒乳液,在保证稳定性的同时减少表面活性剂和乳化剂使用,降低刺激性,同时该防晒乳液以CeOx@HNTs为界面稳定剂协同增效UV防护效果。
与现有技术相比,本发明具有以下有益效果:
(1)本发明在埃洛石纳米管HNTs内原位合成的CeOx纳米粒子具有优越分散性和更强的UV吸收性能,埃洛石纳米管HNTs管壁的氧化铝氧化硅层还限制CeOx直接与皮肤接触,避免皮肤光毒性;
(2)本发明的基于氧化铈粘土复合防晒乳涂抹性良好,具有优良的紫外吸收、屏蔽效果,可保护皮肤免受紫外辐射造成的DNA损伤和炎症,预防皮肤癌,同时具有低皮肤刺激性。本发明可满足人们对防晒霜的高效性和安全性需求,推广和应用价值高。
附图说明
图1为CeOx@HNTs复合材料的表征。
图2为实施例1制备的CeOx@HNTs Pickering防晒乳液的表征。
图3为实施例1制备的CeOx@HNTs Pickering防晒乳液的涂抹性能。
图4为实施例1制备的CeOx@HNTs Pickering防晒乳液在动物模型中的UV防护效果。
图5为实施例1制备的CeOx@HNTs Pickering防晒乳液的安全性测试。
具体实施方式
为使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步的详细说明。此处所描述的具体实施例仅用于解释本发明,并不用于限定发明。
以下实施例中所用原料和试剂除特殊说明外均为市购所得,其中:埃洛石纳米管HNTs的粒径为0.1~2μm,内径为10-20nm,外径为40-70nm,长度为100-1000nm,Zeta电位在-20~-40mV之间。
实施例1
1)取HNTs在无水乙醇中混匀,300rpm搅拌12小时,在50Hz,功率500W条件下超声处理30分钟得到均匀分散的浓度为2%的HNTs乙醇分散液;
2)取六水合硝酸铈在无水乙醇中溶解,得到浓度为0.2M的硝酸铈乙醇溶液;
3)将HNTs乙醇分散液与硝酸铈乙醇溶液以1:1混匀,在50Hz,功率500W条件下超声处理30分钟得到均匀分散的HNTs-硝酸铈乙醇分散液;
4)HNTs-硝酸铈乙醇分散液在真空下400rpm搅拌2小时;
5)HNTs-硝酸铈乙醇分散液在聚四氟乙烯高压反应釜中,用氢氧化钠溶液调节pH为11,于180℃反应24小时;
6)将5)所得的产物在13000rpm离心条件下用无水乙醇洗涤5遍,于-50℃冷冻干燥12h获得CeOx@HNTs复合材料;
7)将CeOx@HNTs复合材料与去离子水混合,使其终浓度为4%,加入聚乙烯醇使其终浓度为2%,在50Hz,功率500W条件下超声处理15分钟后搅拌1小时;
8)加入聚二甲基硅氧烷,使其终浓度为20%,在50Hz,功率500W条件下超声处理15分钟后,置于均质仪在13000rpm转速下均质乳化10分钟,得到CeOx@HNTs Pickering防晒乳液。
实施例2
1)取HNTs在无水乙醇中混匀,300rpm搅拌12小时,在50Hz,功率500W条件下超声处理40分钟得到均匀分散的浓度为2%HNTs乙醇分散液;
2)取六水合硝酸铈在无水乙醇中溶解,得到浓度为0.2M的硝酸铈乙醇溶液;
3)将HNTs乙醇分散液与硝酸铈乙醇溶液以1:1混匀,在50Hz,功率500W条件下超声处理30分钟得到均匀分散的HNTs-硝酸铈乙醇分散液;
4)HNTs-硝酸铈乙醇分散液在空气氛围下300rpm搅拌1小时;
5)HNTs-硝酸铈乙醇分散液在聚四氟乙烯高压反应釜中,用氢氧化钠溶液调节pH为13,于180℃反应24小时;
6)将5)所得的产物在13000rpm离心条件下用无水乙醇洗涤5遍,于-50℃冷冻干燥12h获得CeOx@HNTs复合材料;
7)将CeOx@HNTs复合材料与去离子水混合,使其终浓度为4%,加入聚乙烯醇使其终浓度为2%,在50Hz,功率500W条件下超声处理15分钟后搅拌1小时;
8)加入聚二甲基硅氧烷,使其终浓度为20%,在50Hz,功率500W条件下超声处理15分钟后,置于均质仪在8000rpm转速下均质乳化10分钟,得到CeOx@HNTs Pickering防晒乳液。
实施例3
1)取HNTs在无水乙醇中混匀,300rpm搅拌12小时,在50Hz,功率500W条件下超声处理20分钟得到均匀分散的浓度为2%HNTs乙醇分散液;
2)取六水合硝酸铈在无水乙醇中溶解,得到浓度为0.2M的硝酸铈乙醇溶液;
3)将HNTs乙醇分散液与硝酸铈乙醇溶液以1:1混匀,在50Hz,功率500W条件下超声处理30分钟得到均匀分散的HNTs-硝酸铈乙醇分散液;
4)HNTs-硝酸铈乙醇分散液在真空下500rpm搅拌1小时;
5)HNTs-硝酸铈乙醇分散液在聚四氟乙烯高压反应釜中,用氢氧化钠溶液调节pH为12,于180℃反应24小时;
6)将5)所得的产物在13000rpm离心条件下用无水乙醇洗涤5遍,于-50℃冷冻干燥12h获得CeOx@HNTs复合材料;
7)将CeOx@HNTs复合材料与去离子水混合,使其终浓度为2%,加入聚乙烯醇使其终浓度为2%,在50Hz,功率500W条件下超声处理15分钟后搅拌1小时;
8)加入聚二甲基硅氧烷,使其终浓度为20%,在50Hz,功率500W条件下超声处理15分钟后,置于均质仪在10000rpm转速下均质乳化10分钟,得到CeOx@HNTs Pickering防晒乳液。
实施例4
1)取HNTs在无水乙醇中混匀,300rpm搅拌12小时,在50Hz,功率500W条件下超声处理10分钟得到均匀分散的浓度为2%HNTs乙醇分散液;
2)取六水合硝酸铈在无水乙醇中溶解,得到浓度为0.2M的硝酸铈乙醇溶液;
3)将HNTs乙醇分散液与硝酸铈乙醇溶液以1:1混匀,在50Hz,功率500W条件下超声处理30分钟得到均匀分散的HNTs-硝酸铈乙醇分散液;
4)HNTs-硝酸铈乙醇分散液在真空下350rpm搅拌2.5小时;
5)HNTs-硝酸铈乙醇分散液在聚四氟乙烯高压反应釜中,用氢氧化钠溶液调节pH为11,于180℃反应24小时;
6)将5)所得的产物在13000rpm离心条件下用无水乙醇洗涤5遍,于-50℃冷冻干燥12h获得CeOx@HNTs复合材料;
7)将CeOx@HNTs复合材料与去离子水混合,使其终浓度为4%,加入聚乙烯醇使其终浓度为2%,在50Hz,功率500W条件下超声处理15分钟后搅拌1小时;
8)加入聚二甲基硅氧烷,使其终浓度为30%,在50Hz,功率500W条件下超声处理15分钟后,置于均质仪在11000rpm转速下均质乳化10分钟,得到CeOx@HNTs Pickering防晒乳液。
实施例5
1)取HNTs在无水乙醇中混匀,300rpm搅拌12小时,在50Hz,功率500W条件下超声处理30分钟得到均匀分散的浓度为2%的HNTs乙醇分散液;
2)取六水合硝酸铈在无水乙醇中溶解,得到浓度为0.2M的硝酸铈乙醇溶液;
3)将HNTs乙醇分散液与硝酸铈乙醇溶液以1:1混匀,在50Hz,功率500W条件下超声处理30分钟得到均匀分散的HNTs-硝酸铈乙醇分散液;
4)HNTs-硝酸铈乙醇分散液在真空下400rpm搅拌2小时;
5)HNTs-硝酸铈乙醇分散液在聚四氟乙烯高压反应釜中,用氢氧化钠溶液调节pH为13,于180℃反应24小时;
6)将5)所得的产物在13000rpm离心条件下用无水乙醇洗涤5遍,于-50℃冷冻干燥12h获得CeOx@HNTs复合材料;
7)将CeOx@HNTs复合材料与去离子水混合,使其终浓度为4%,加入三甲基硅氧基硅酸酯使其终浓度为2%,在50Hz,功率500W条件下超声处理15分钟后搅拌1小时;
8)加入橄榄油,使其终浓度为20%,在50Hz,功率500W条件下超声处理15分钟后,置于均质仪在13000rpm转速下均质乳化10分钟,得到CeOx@HNTs Pickering防晒乳液。
实施例6
1)取HNTs在无水乙醇中混匀,300rpm搅拌12小时,在50Hz,功率500W条件下超声处理30分钟得到均匀分散的浓度为2%的HNTs乙醇分散液;
2)取六水合硝酸铈在无水乙醇中溶解,得到浓度为0.2M的硝酸铈乙醇溶液;
3)将HNTs乙醇分散液与硝酸铈乙醇溶液以1:1混匀,在50Hz,功率500W条件下超声处理30分钟得到均匀分散的HNTs-硝酸铈乙醇分散液;
4)HNTs-硝酸铈乙醇分散液在真空下400rpm搅拌2小时;
5)HNTs-硝酸铈乙醇分散液在聚四氟乙烯高压反应釜中,用氢氧化钠溶液调节pH为12,于180℃反应24小时;
6)将5)所得的产物在13000rpm离心条件下用无水乙醇洗涤5遍,于-50℃冷冻干燥12h获得CeOx@HNTs复合材料;
7)将CeOx@HNTs复合材料与去离子水混合,使其终浓度为4%,加入聚丙烯酸使其终浓度为2%,在50Hz,功率500W条件下超声处理15分钟后搅拌1小时;
8)加入环五聚二甲基硅氧烷,使其终浓度为20%,在50Hz,功率500W条件下超声处理15分钟后,置于均质仪在13000rpm转速下均质乳化10分钟,得到CeOx@HNTs Pickering防晒乳液。
取实施例1-6任一制备的CeOx@HNTs复合材料为例,进行表征,其结果如图1所示,由图1可以看出,氧化铈粒子在HNTs内原位合成,具有优越分散性和更强的紫外吸收性能,用于后续制备防晒乳时HNTs能够限制氧化铈直接与皮肤接触,避免皮肤光毒性。
取实施例1-6任一制备的CeOx@HNTs Pickering防晒乳液进行表征,其结果如图2所示,由图2可以看出,本实施例制备的CeOx@HNTs Pickering防晒乳液在未使用乳化剂条件下,乳滴直径较小,尺寸均匀,密度适当,且久置不分层,具有良好的稳定性。
进一步,为了测试上述实施例1~6制备的乳液的UV吸光度和UV屏蔽效果,分别设置以下对比例。
对比例1
与实施例1不同之处在于:CeOx@HNTs复合材料的最终浓度为0%,油相的添加量为20%。
对比例2
与实施例1不同之处在于:CeOx@HNTs复合材料的最终浓度为0%,油相的添加量为20%,以司班80为乳化剂,添加量为2%。
对比例3
与实施例1不同之处在于:成膜剂的添加量为0%。
对比例4
商品化的防晒乳(安耐晒金瓶防晒乳,购自日本资生堂株式会社)。
UV吸光度具体测试方法如下:将实施例1~实施例6和对比例1~对比例4中各实验组制备共8种乳液,分别通过UV吸光度测试评价防晒乳的UV吸收性能,用紫外分光光度计测量250~600nm的吸光度,结果见表1所示。
表1
组别 | 最大吸收波长,nm | 最大吸光度 |
实施例1 | 296 | 2.558 |
实施例2 | 300 | 2.478 |
实施例3 | 302 | 2.112 |
实施例4 | 300 | 2.458 |
实施例5 | 305 | 2.201 |
实施例6 | 301 | 2.418 |
对比例1 | —— | —— |
对比例2 | —— | —— |
对比例3 | 296 | 2.448 |
对比例4 | 326 | 2.047 |
从表1的结果可以看出,实施例1-实施例6制备的包含CeOx@HNTs Pickering防晒乳液最大吸收波长均偏移至更短波长处,更接近DNA的吸收波长(260nm),相比商品化的防晒乳更有效防止UV诱导的皮肤基因突变,且均有更高吸光度,有效吸收UV辐射。其中,实施例1制备的CeOx@HNTs Pickering防晒乳液的UV吸收性能最佳。实施例3降低了CeOx@HNTs复合物添加量后,吸光度降低。对比例1和2未添加CeOx@HNTs复合物,导致乳液不具备UV吸收性能。对比例3未加成膜剂,但由于CeOx@HNTs复合物的存在,UV吸收性能不受影响。对比例4为商品化防晒乳液,因为含有化学防晒剂如甲氧基肉桂酸乙基己酯,奥克立林等,因此具有较佳的UV吸收性能,但是明显低于实施例1-实施例6制备的CeOx@HNTs Pickering防晒乳液的UV吸收性能。
UV屏蔽效果具体测试方法如下:将实施例1~实施例6和对比例1~对比例4中各实验组制备共8种乳液,分别通过测量UV透过量评价防晒乳的UV屏蔽效果。将实施例1~实施例6和对比例1~对比例4的各乳液涂抹于高透光石英玻片,使面积为5×10cm,厚度为50μm。将一UV射灯固定于UV辐照仪上10cm处,并将各样品石英玻片置于UV辐照仪探头上1cm处。以空白高透光石英玻片为空白对照。计算方法为:UV透过率=样品组UV强度/空白对照UV强度×100%,结果见表2。
表2
组别 | UV透过率 |
实施例1 | 5.8±3.4% |
实施例2 | 6.2±4.5% |
实施例3 | 15.2±5.9% |
实施例4 | 8.7±2.4% |
实施例5 | 7.5±2.3% |
实施例6 | 6.8±3.7% |
对比例1 | 84.1±15.7% |
对比例2 | 91.2±14.6% |
对比例3 | 10.2±3.4% |
对比例4 | 14.1±1.4% |
从表2的结果可以看出,实施例1、实施例2和实施例4制备的CeOx@HNTs Pickering防晒乳液均有较低的UV透过率,因此具有优良的UV屏蔽性能,且实施例1制备的CeOx@HNTsPickering防晒乳液的UV屏蔽性能最佳。实施例3降低了CeOx@HNTs复合物添加量后,UV吸收和屏蔽性能下降。对比例1和2未添加CeOx@HNTs复合物,导致乳液几乎不具备UV屏蔽性能。对比例3未加成膜剂,但由于CeOx@HNTs复合物的存在,UV屏蔽性能不受影响。对比例4为商品化防晒乳液,配方含有化学防晒剂和物理防晒剂,UV透过率实施例3相当,也具有较佳的UV屏蔽性能,但是明显低于实施例1、实施例2和实施例4制备的CeOx@HNTs Pickering防晒乳液的UV屏蔽性能。
在用于人体防晒之前,我们分别对上述实施例1~实施例4和对比例1~4各乳液在动物模型的UV保护效果评价以及安全性测试。
以小鼠作为将实施例1~6和对比例1~4乳液的UV保护评价动物模型。将雌性昆明小鼠(8周龄,25-30g)麻醉,用电动剃毛刀去背部毛发,并使用脱毛膏完全清理绒毛,暴露完整皮肤。将实施例1~6和对比例1~4各乳液涂抹于小鼠背部,涂抹量为500μL/只。每只小鼠接受23700J/m2总剂量的UV照射(波长:280~320nm)后,部分小鼠在第20小时实施安乐死,收集施用防晒乳处皮肤样本。进行冷冻切片后用DNA损伤免疫荧光染色试剂盒进行染色,评价实施例1~4和对比例1~4各乳液对皮肤遗传稳定性的保护作用。部分小鼠在第3天使观察皮肤晒伤状况(红斑、水肿、水疱和脱屑),评价结果见表3,实施例1制备的CeOx@HNTsPickering防晒乳液在动物模型中的UV防护效果如图4所示。
表3
组别 | 皮肤DNA损伤 | 皮肤外观 |
实施例1 | 无 | 正常 |
实施例2 | 无 | 正常 |
实施例3 | 无 | 正常 |
实施例4 | 无 | 正常 |
实施例5 | 无 | 正常 |
实施例6 | 无 | 正常 |
对比例1 | 轻度 | 轻微红斑 |
对比例2 | 轻度 | 轻微红斑 |
对比例3 | 无 | 正常 |
对比例4 | 无 | 正常 |
从表3动物模型测试结果可以看出,实施例1~实施例6由于配方中均含有CeOx@HNTs复合物,均有优良的UV防护效果。对比例1和2未添加CeOx@HNTs复合物,导致乳液几乎不具备UV防护效果。对比例3未加成膜剂,影响涂抹性能,但UV防护效果不受影响。对比例4为商品化防晒乳液,配方含有化学防晒剂和物理防晒剂,具有优良的UV防护效果。
为了验证本发明的是否能够直接用于人体皮肤上,以实施例1-实施例6制备的CeOx@HNTs Pickering防晒乳液为例,以涂抹盐水组和0.5%十二烷基硫酸钠组分别为对照组和炎症组,评价实施例1-实施例6制备的CeOx@HNTs Pickering防晒乳液以及对照组和炎症组对小鼠皮肤刺激性和炎症反应评价安全性,具体如下:雌性昆明小鼠(8周龄,25-30g)麻醉,用电动剃毛刀去背部毛发,并使用脱毛膏完全清理绒毛,暴露完整皮肤;将实施例1~4和对比例1~4各乳液涂抹于小鼠背部,涂抹量为0.8mL/只,1次/天,共涂抹7天;实施安乐死后取涂抹部位皮肤,经4%多聚甲醛固定、石蜡包埋和切片后,用苏木精&伊红染色,观察皮肤是否有红肿,水泡,角质层增厚,炎症细胞浸润等,其结果如图5所示。
由图5可知,0.5%十二烷基硫酸钠组观察到明显的角质层增生和炎症细胞浸润。施用发明的CeOx@HNTs Pickering乳液7天后皮肤组织切片与盐水组相近,未观察到炎症细胞浸润和角质层变化,证明本发明制备的CeOx@HNTs Pickering乳液具有低皮肤刺激性和高安全性,因此,本发明制备的CeOx@HNTs Pickering乳液可作为防晒乳直接涂抹于人体皮肤上。
在确定了本发明制备的防晒乳的安全性后,再次对实施例1~6和对比例1~4的各乳液的涂抹性能评价,具体测试方法如下:将实施例1~实施例6制备的CeOx@HNTsPickering防晒乳液和对比例1~对比4中各实验组制备共8种乳液,将各乳液按照标准用量2mg/cm2,即为0.8g(mL)涂抹于志愿者手背。根据使用体验评价涂抹性能,结果见表4,实施例1制备的CeOx@HNTs Pickering防晒乳液的涂抹性能如图3所示。
表4
从表4结果可以看出,实施例1和实施例2制备的CeOx@HNTs Pickering防晒乳液均有优良的稳定性、成膜性、亲肤性,无明显假白感。由图3可以看出实施例1制备的CeOx@HNTsPickering防晒乳液优良的稳定性、成膜性、亲肤性,无明显假白感。实施例3降低了CeOx@HNTs复合物添加量后,乳化稳定性降低,导致亲肤性不佳和假白感增加。实施例4增加了油相比例至30%后乳化稳定性降低,导致亲肤性不佳。对比例1和对比例2未添加CeOx@HNTs复合物作为界面稳定剂,或添加司班80作为乳化剂,导致乳化稳定性和亲肤性下降。对比例3未加成膜剂,导致成膜性和亲肤性不佳。对比例4为商品化防晒乳液,涂抹性能均较优良。实施例1和实施例2制备的CeOx@HNTs Pickering防晒乳液均达到与成熟的商品化防晒乳液涂抹性能,进一步验证了本发明制备的CeOx@HNTs Pickering防晒乳液实用性能。
综上所述,本发明制备的CeOx@HNTs Pickering防晒乳液涂抹性良好,具有优良的紫外吸收、屏蔽效果,可保护皮肤免受紫外辐射造成的DNA损伤和炎症,预防皮肤癌,同时具有低皮肤刺激性。
本发明的技术方案不限于上述具体实施例的限制,凡是根据本发明的技术方案做出的技术变形,均落入本发明的保护范围之内。
Claims (10)
1.一种基于氧化铈粘土复合防晒乳的制备方法,其特征在于,包括以下步骤:
S1、配制浓度为0.5~2%的埃洛石纳米管HNTs乙醇分散液和浓度为0.05~0.4M的硝酸铈乙醇溶液;
S2、将HNTs乙醇分散液与硝酸铈乙醇溶液按照体积比1:1混匀后,超声处理10~40分钟得到均匀分散的HNTs-硝酸铈乙醇分散液;
S3、将HNTs-硝酸铈乙醇分散液在真空或者空气氛围下300~500rpm搅拌1~3小时后置于反应釜中,调节pH为11~13,在100℃~180℃下反应12~48小时;
S4、将S3所得的产物离心收集,用无水乙醇洗涤多遍,于-50℃冷冻干燥12h获得CeOx@HNTs复合材料;
S5、将CeOx@HNTs复合材料与去离子水混合,使CeOx@HNTs复合材料终浓度为1~4%;然后加入成膜剂,使成膜剂终浓度为2~5%;超声处理15分钟后搅拌1小时;再加入油相,使油相终浓度为10~30%,超声处理15分钟后,置于均质仪在8000~13000rpm转速下均质乳化10分钟,得到CeOx@HNTs Pickering防晒乳液。
2.根据权利要求1所述的基于氧化铈粘土复合防晒乳的制备方法,其特征在于,所述埃洛石纳米管HNTs的粒径为0.1~2μm,内径为10-20nm,外径为40-70nm,长度为100-1000nm,Zeta电位在-20~-40mV之间。
3.根据权利要求1所述的基于氧化铈粘土复合防晒乳的制备方法,其特征在于,所述步骤S1中,配制浓度为0.5~2%的埃洛石纳米管HNTs乙醇分散液具体为:将埃洛石纳米管HNTs加入无水乙醇中,300rpm搅拌12小时,之后在50Hz,功率500W条件下超声均质处理30分钟,得到均匀分散的浓度为0.5~2%HNTs乙醇分散液。
4.根据权利要求1所述的基于氧化铈粘土复合防晒乳的制备方法,其特征在于,所述超声处理是在50Hz,功率500W条件下处理。
5.根据权利要求1所述的基于氧化铈粘土复合防晒乳的制备方法,其特征在于,所述成膜剂为聚乙烯吡咯烷酮类聚合物、三甲基硅氧基硅酸酯、己二酸/二甘醇/甘油交联聚合物、聚丙烯酸、聚乙烯醇中的一种或多种组合。
6.根据权利要求1所述的基于氧化铈粘土复合防晒乳的制备方法,其特征在于,所述油相为矿油、白凡士林、橄榄油、羊毛脂、聚二甲基硅氧烷、角鲨烷、硬脂基聚二甲基硅氧烷、环五聚二甲基硅氧烷、C12~15醇苯甲酸酯、肉豆蒄酸异丙酯中的一种或多种组合。
7.根据权利要求5所述的基于氧化铈粘土复合防晒乳的制备方法,其特征在于,所述成膜剂为聚乙烯醇。
8.根据权利要求6所述的基于氧化铈粘土复合防晒乳的制备方法,其特征在于,所述油相为聚二甲基硅氧烷。
9.根据权利要求1所述的基于氧化铈粘土复合防晒乳的制备方法,其特征在于,所述步骤S5中,CeOx@HNTs复合材料终浓度为4%,成膜剂终浓度为2%,油相终浓度为20%。
10.一种如权利要求1-9任一所述方法制备的基于氧化铈粘土复合防晒乳。
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