CN114177114A - 一种低成本的高效抗菌彩色一剂型染发剂及其制备方法 - Google Patents

一种低成本的高效抗菌彩色一剂型染发剂及其制备方法 Download PDF

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CN114177114A
CN114177114A CN202111539460.8A CN202111539460A CN114177114A CN 114177114 A CN114177114 A CN 114177114A CN 202111539460 A CN202111539460 A CN 202111539460A CN 114177114 A CN114177114 A CN 114177114A
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李乙文
李昊天
胡俊飞
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Sichuan University
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Abstract

本发明公开了一种低成本的高效抗菌彩色一剂型染发剂及其制备方法,该染发剂的组分为:5,6‑二羟基吲哚:4%~8%,酪氨酸:2%~8%,半胱氨酸:3%~8%,紫胶红色素:0.5%,卡波姆:1%~3%,羟乙二磷酸:0.5%~1%,亚硫酸钠:0.2%~0.5%,4‑氯间苯二酚:0.6%,2,4‑二氨基苯酚:2%~3%,m‑氨基苯酚:0.1%,三乙醇胺:10%~20%,单乙醇胺;0~10%,水余量。本发明以低廉的价格实现了抗菌染发的效果,并且不影响彩染的染色及耐洗涤性质。

Description

一种低成本的高效抗菌彩色一剂型染发剂及其制备方法
技术领域
本发明属于日化领域,特别涉及一种低成本的高效抗菌彩色一剂型染发剂及其制备方法。
背景技术
第一个有记录的天然染发剂可以追溯到古埃及人,他们用指甲花植物色素染头发和增强颜色,但天然染发剂的颜色和牢度通常不足。150年前,霍夫曼观察到苯二胺在各种底物上暴露于氧化剂时会产生棕色阴影,长期以来,它已成为最常用的染发工艺基础。自然提供丰富的头发颜色,这是由于黑色素的存在,黑色素细胞主要在皮层和髓质。色素分子的分布、浓度和混合会引起各种奇妙的颜色。黑色素在深层中的分布越多,头发就越黑。因此,利用黑色素重建头发纤维的颜色是一种基本可行的方法。
皮质层的黑色素沉积量决定着发色的不同,也是染色过程中的核心部位。吲哚类物质易渗入毛发并进入到头发的皮质层,再氧化聚合形成大分子有色物质固定于发内,且氧化条件温和。5,6-二羟基吲哚因其本身就是生物体产生的物质,所以无毒、无副作用,是合成黑色素的重要中间体,目前已在一些洗化用品中被用来取代苯胺、苯酚类化合物。
但天然黑色素具有复杂的结构和组成,很难从生物环境中分离纯化,天然黑色素的自组装和聚合需通过复杂的途径来调控,这一过程尚不完全清楚。与此同时,传统的染发剂会破坏头发结构,使其更加利于细菌的附着生长,对于免疫力低下的人或在特殊环境中工作的人(如医院和疗养院等),存在更多的卫生隐患,即使未染过的头发依旧存在相似的问题,具有抗菌作用的染发剂将会有很好的应用前景。有研究使用氨基糖苷类抗生素掺杂进行染发,但其成本的高昂限制了进一步的应用于转化。
发明内容
本发明的目的是提供一种低成本的高效抗菌彩色一剂型染发剂及其制备方法。
本发明的技术方案如下:
一种低成本的高效抗菌彩色一剂型染发剂,其为空气氧化染发剂,以质量百分比计,其组分为:5,6-二羟基吲哚:4%~8%,酪氨酸:2%~8%,半胱氨酸:3%~8%,紫胶红色素:0.5%,卡波姆:1%~3%,羟乙二磷酸:0.5%~1%,亚硫酸钠:0.2%~0.5%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:2%~3%,m-氨基苯酚:0.1%,三乙醇胺:10%~20%,单乙醇胺;0~10%,水余量,各组分质量百分比合计为100%。
上述低成本的高效抗菌彩色一剂型染发剂的优选组分为:
5,6-二羟基吲哚:4%~5%,酪氨酸:2%~8%,半胱氨酸:3%~4%,紫胶红色素:0.5%,卡波姆:1%~3%,羟乙二磷酸:0.5%~1%,亚硫酸钠:0.2%~0.5%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:2%~3%,m-氨基苯酚:0.1%,三乙醇胺:10%~20%,单乙醇胺;0~10%,水余量,各组分质量百分比合计为100%。
上述低成本的高效抗菌彩色一剂型染发剂进一步的优选组分为:
5,6-二羟基吲哚:5%,酪氨酸:2%,半胱氨酸:3%,紫胶红色素:0.5%,卡波姆:1%~3%,羟乙二磷酸:0.5%~1%,亚硫酸钠:0.2%~0.5%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:2%~3%,m-氨基苯酚:0.1%,三乙醇胺:10%~20%,单乙醇胺;0~10%,水余量,各组分质量百分比合计为100%。
在一些具体实施方式中,上述高效抗菌彩色一剂型染发剂的组分还包括0.5%的香精。
本发明中,5,6-二羟基吲哚为着色剂,其通过氧化聚合发挥染黑的主要作用;酪氨酸的自然氧化生成类黑色素,使染出的头发具备良好的耐洗及紫外防护功效;半胱氨酸发挥抗菌功能;紫胶红色素为常用且健康的色素,发挥彩染功能;卡波姆在很低的用量下就能产生高效的增稠作用,从而制备出很宽粘度范围和不同流变性的染发剂;羟乙二磷酸常用于漂染业做固色剂;亚硫酸钠起到存放时抗氧化的作用;4-氯间苯二酚、2,4-二氨基苯酚与m-氨基苯酚均为偶合剂;三乙醇胺和单乙醇胺为碱化剂;香精赋香,水作为溶剂。
本发明将5,6-二羟基吲哚与酪氨酸、半胱氨酸结合,5,6-二羟基吲哚氧化后可产生不同的酚和醌结构,酪氨酸前体分子的酶氧化和3,4-二羟基-苯丙氨酸可形成多巴喹酮,该多巴酮容易发生环化反应,并通过中间体5,6-二羟基吲哚形成最终生成黑色聚合物质。半胱氨酸对金黄色葡萄球菌有较强的抑制作用。由于酚醛羟基的存在,本发明通过氧化生成的醛基与半胱氨酸发生席夫碱反应,引入氨基分子半胱氨酸,并引入酪氨酸,使染出的头发具有抗菌功能。
具体来讲,在5,6-二羟基吲哚成功地沉积和着色头发表面后,用半胱氨酸对头发进行修饰,以提高抗菌性能。半胱氨酸相比于传统抗菌染发的银、氨基糖苷等药物,具有价格低廉、理化性质独特等优点。细菌的微酸性环境可以使其释放杀菌,使得染过的头发具有迷人的颜色和优良的抗菌性能,同时并不会对彩染的效果产生任何影响,相反的还可以使彩色的持久程度得到极大改善,有望在染发领域得到更广泛的应用。
上述高效抗菌彩色一剂型染发剂的制备方法为:
将紫胶红色素、卡波姆、羟乙二磷酸、亚硫酸钠、4-氯间苯二酚、2,4-二氨基苯酚、m-氨基苯酚、三乙醇胺、单乙醇胺和水混合,加热至50℃~80℃;再加入5,6-二羟基吲哚、酪氨酸、半胱氨酸,即得一剂型染发剂。
和现有技术相比,本发明具有如下优点和有益效果:
(1)以低廉的价格实现了抗菌染发的效果,并且不影响彩染的染色及耐洗涤性质。
(2)酪氨酸的自然氧化生成类黑色素,使染出的头发具备的良好的耐洗及紫外防护功效。
(3)原料均为无毒或低毒,对皮肤无刺激。
附图说明
图1为染出头发对金黄色葡萄球菌的杀菌效果;
图2为染出头发对大肠杆菌的杀菌效果。
具体实施方式
下面结合实施例对本发明技术方案及技术效果作更进一步地解释。其中,实施例仅用于示例性说明,但并不用来限定本发明的实施范围。以下结合具体实施例,对本发明的技术方案作进一步说明。
下述实施例和对比例中主要原料为:5,6-二羟基吲哚购自萨安化工科技有限公司;酪氨酸、半胱氨酸购自强健有限公司,三乙醇胺、单乙醇胺、氨水和乙醇均购自泰坦科技有限公司,紫胶红色素购自阿拉丁,卡波姆、羟乙二磷酸、亚硫酸钠购自成都市科隆化学品有限公司。所有其他化学品和试剂均直接使用,无需进一步纯化。
实施例1
本实施例中染发剂组分为:5,6-二羟基吲哚:8%,酪氨酸:8%,半胱氨酸:8%,紫胶红色素:0.5%,卡波姆:3%,羟乙二磷酸:1%,亚硫酸钠:0.5%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:3%,m-氨基苯酚:0.1%,三乙醇胺:20%,香精:0.5%,去离子水余量,各组分质量百分比合计为100%。
实施例2
本实施例中染发剂组分为:5,6-二羟基吲哚:5%,酪氨酸:8%,半胱氨酸:3%,紫胶红色素:0.5%,卡波姆:2%,羟乙二磷酸:0.5%,亚硫酸钠:0.2%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:3%,m-氨基苯酚:0.1%,三乙醇胺:15%,单乙醇胺:1%,香精:0.5%,去离子水余量,各组分质量百分比合计为100%。
实施例3
本实施例中染发剂组分为:5,6-二羟基吲哚:4%,酪氨酸:4%,半胱氨酸:4%,紫胶红色素:0.5%,卡波姆:1%,羟乙二磷酸:0.5%,亚硫酸钠:0.2%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:3%,m-氨基苯酚:0.1%,三乙醇胺:10%,单乙醇胺;2%,香精:0.5%,去离子水余量,各组分质量百分比合计为100%。
实施例4
本实施例中染发剂组分为:5,6-二羟基吲哚:5%,酪氨酸:2%,半胱氨酸:3%,紫胶红色素:0.5%,卡波姆:1%,羟乙二磷酸:0.5%,亚硫酸钠:0.2%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:2%,m-氨基苯酚:0.1%,三乙醇胺:10%,单乙醇胺:2%,香精:0.5%,去离子水余量,各组分质量百分比合计为100%。
实施例1~4的组分列于表1。
表1实施例1~4的组分
实施例1 实施例2 实施例3 实施例4
5,6-二羟基吲哚 8% 5% 4% 5%
酪氨酸 8% 8% 4% 2%
半胱氨酸 8% 3% 4% 3%
紫胶红色素 0.5% 0.5% 0.5% 0.5%
卡波姆 3% 2% 1% 1%
羟乙二磷酸 1% 0.5% 0.5% 0.5%
亚硫酸钠 0.5% 0.2% 0.2% 0.2%
4-氯间苯二酚 0.6% 0.6% 0.6% 0.6%
2,4-二氨基苯酚 3% 3% 3% 2%
m-氨基苯酚 0.1% 0.1% 0.1% 0.1%
三乙醇胺 20% 15% 10% 10%
单乙醇胺 0 1% 2% 2%
香精 0.5% 0.5% 0.5% 0.5%
对实施例1~4染发剂进行抗菌性评价,方法如下:
试验前,对所需采用的试剂和试管进行消毒处理。采用扩散板法对细菌的抗菌活性进行了评价。大肠杆菌(大肠杆菌ATCC 25922)和金黄色葡萄球菌分别作为模型。取细胞悬液的10μL为指数生长阶段,加入含5mL无菌LB液体培养基的试管中,加入长度为2cm的染后发丝材料,在37℃恒温摇瓶中摇匀培养。共培养12h后,从孵化器取出含有细菌的试管,用紫外可见分光光度计测定样品在600nm波长处的吸光度,并记录OD值。
在抑制区实验中,固体介质在80℃的微波炉中加热2min,冷却到表皮的温度。在冷却的10mL固体培养基中加入100μL的细菌液,摇动涂布棒,使细菌溶液在培养基中均匀分布。站立冷却后,将5根长度为2cm的头发置于培养皿中,以未修饰头发和去离子水为对照,置于37℃恒温培养箱中,培养24h后取出培养皿,染过的头发相较于未修饰头发和去离子水对照有着明显的抑菌区。
实施例1~4染发剂所染头发对大肠杆菌和金黄色葡萄球菌的抗菌效果分别见图1~2,从图中可以看出,实施例1~4染发剂所染头发对大肠杆菌和金黄色葡萄球菌的抗菌效果明显,其中实施例2~4的抗菌效果尤为显著。
对实施例1~4染发剂进行染发效果评价,方法如下:
取白发2g,取实施例1染发剂对样品白发进行涂抹实验。评分根据以下标准:1很差,2较差,3一般,4好,5很好。其中,对比例1在实施例1组分的基础上剔除酪氨酸和半胱氨酸。
表2实施例1和对比例的染发效果评价表
Figure BDA0003413804270000061
采用实施例1染发剂进行染发,将2g的白发蘸取染发剂并将其涂抹,30min后洗净,测试温度:30摄氏度平行进行三组样品的测试。测试结果见表3,表中L,a,b是标准国际色空间图的参数,L值指黑白,L值越大则越白;a值指红绿,a值越大越红;b值指黄蓝,b值越大越黄。从上表可知,实施例1的染发效果良好。
表3实施例1染发剂的染发效果
Figure BDA0003413804270000071
表4实施例1和对比例染发剂所染头发的色牢度测试结果
Figure BDA0003413804270000072
将实施例1和对比例两种染发剂所染头发洗涤10次后进行耐洗色牢度测试,测试结果见表4。从表4可知,实施例1染发剂的耐洗色牢度较好,染发效果稳定耐久。
UVA,UVB和可见光可能导致毛发光损伤,损伤程度随波长的变化而不同。UVB主要造成毛发蛋白质的流失,UVA会促进颜色的改变。毛发的紫外线防护包括毛发自身天然色素的防护和外用产品的防护,可以通过染发剂沉积在毛小皮和毛皮质上阻止紫外线损伤,不同染料的紫外线防护能力不同。采用与织物相同的抗紫外测试方法,对实施例1、对比例以及对苯二胺传统染料所染头发进行抗紫外测试,对苯二胺传统染料采用市面上的上海金寇染发膏。检测结果见表5。
表5紫外吸收能力检测结果
Figure BDA0003413804270000081
由此可见,相比于对苯二胺传统染料,对比例染出的头发即具有一定的抗紫外功效,UVA和UVB的透过率明显降低;加入酪氨酸和半胱氨酸后的实施例1,其UVA和UVB的透过率进一步降低,表明染出的黑发具有很强的紫外吸收能力,因此黑发覆盖的皮肤也会得到保护。
最后还进行了体外毒性分析,用CCK-8分析了酪氨酸和半胱氨酸氧化产物对人支气管内皮细胞(Beas-2B)活性的影响。将对数期细胞接种在96孔板上,其中含有100μL的DMEM。37℃培养24h后,用100μL(含等量样品浓度)代替培养基,加入完整培养基作为对照组,每组设3个平行实验组。加入10μL的CCK-8完全培养基(体积比为1:9)后,在37℃的黑暗中孵育4h,用倒置荧光显微镜观察活/死细胞的形态,细胞均生存良好,表明染膏无明显的体外毒性。
以上所述仅是本发明的具体实施方式,使本领域技术人员能够理解或实现本发明。对这些实施例的多种修改对本领域的技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所申请的原理和新颖特点相一致的最宽的范围。

Claims (5)

1.一种低成本的高效抗菌彩色一剂型染发剂,为空气氧化染发剂,其特征是:
以质量百分比计,其组分为:
5,6-二羟基吲哚:4%~8%,酪氨酸:2%~8%,半胱氨酸:3%~8%,紫胶红色素:0.5%,卡波姆:1%~3%,羟乙二磷酸:0.5%~1%,亚硫酸钠:0.2%~0.5%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:2%~3%,m-氨基苯酚:0.1%,三乙醇胺:10%~20%,单乙醇胺;0~10%,水余量。
2.如权利要求1所述的低成本的高效抗菌彩色一剂型染发剂,其特征是:
以质量百分比计,其组分为:
5,6-二羟基吲哚:4%~5%,酪氨酸:2%~8%,半胱氨酸:3%~4%,紫胶红色素:0.5%,卡波姆:1%~3%,羟乙二磷酸:0.5%~1%,亚硫酸钠:0.2%~0.5%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:2%~3%,m-氨基苯酚:0.1%,三乙醇胺:10%~20%,单乙醇胺;0~10%,水余量。
3.如权利要求1所述的低成本的高效抗菌彩色一剂型染发剂,其特征是:
以质量百分比计,其组分为:
5,6-二羟基吲哚:5%,酪氨酸:2%,半胱氨酸:3%,紫胶红色素:0.5%,卡波姆:1%~3%,羟乙二磷酸:0.5%~1%,亚硫酸钠:0.2%~0.5%,4-氯间苯二酚:0.6%,2,4-二氨基苯酚:2%~3%,m-氨基苯酚:0.1%,三乙醇胺:10%~20%,单乙醇胺;0~10%,水余量。
4.如权利要求1~3中任一项所述的低成本的高效抗菌彩色一剂型染发剂,其特征是:
还包括0.5%的香精。
5.权利要求1~3中任一项所述的低成本的高效抗菌彩色一剂型染发剂的制备方法,其特征是:
将紫胶红色素、卡波姆、羟乙二磷酸、亚硫酸钠、4-氯间苯二酚、2,4-二氨基苯酚、m-氨基苯酚、三乙醇胺、单乙醇胺和水混合,加热至50℃~80℃;再加入5,6-二羟基吲哚、酪氨酸、半胱氨酸,即得一剂型染发剂。
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CN105496807A (zh) * 2015-12-21 2016-04-20 济南益豪环保技术有限公司 一种单剂型染发剂
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