CN110573135B - 染毛剂 - Google Patents
染毛剂 Download PDFInfo
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- CN110573135B CN110573135B CN201980001978.0A CN201980001978A CN110573135B CN 110573135 B CN110573135 B CN 110573135B CN 201980001978 A CN201980001978 A CN 201980001978A CN 110573135 B CN110573135 B CN 110573135B
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- hair
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- acid
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- 239000000975 dye Substances 0.000 title abstract description 18
- 210000002268 wool Anatomy 0.000 title description 2
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- 238000004043 dyeing Methods 0.000 claims abstract description 90
- 239000000118 hair dye Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- NEZONWMXZKDMKF-JTQLQIEISA-N Alkannin Chemical compound C1=CC(O)=C2C(=O)C([C@@H](O)CC=C(C)C)=CC(=O)C2=C1O NEZONWMXZKDMKF-JTQLQIEISA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- UNNKKUDWEASWDN-UHFFFAOYSA-N alkannin Natural products CC(=CCC(O)c1cc(O)c2C(=O)C=CC(=O)c2c1O)C UNNKKUDWEASWDN-UHFFFAOYSA-N 0.000 claims description 9
- 241001071917 Lithospermum Species 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
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- 150000003609 titanium compounds Chemical class 0.000 abstract description 13
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 6
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- -1 iron ions Chemical class 0.000 description 35
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- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 6
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- CSFWPUWCSPOLJW-UHFFFAOYSA-N hydroxynaphthoquinone Natural products C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 description 5
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- 229910021645 metal ion Inorganic materials 0.000 description 5
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Abstract
本发明提供一种染毛剂,其具有优异的染毛性,且使用方法简单,可在短时间内染毛,并且其对于毛发、头皮的安全性也较优异。一种染毛剂,其同时或分别含有:组分(1):选自具有儿茶酚结构的色素、具有连苯三酚结构的色素、具有α‑羟基羰基结构的色素、具有β‑羟基羰基结构的色素以及它们的色素前体中的一种或两种以上色素和/或其色素前体;以及组分(2):有机钛化合物和/或有机锆化合物。另外,一种染毛方法,其将上述组分(1)和上述组分(2)同时或分别应用于毛发。
Description
[技术领域]
本发明涉及一种染毛剂,其具有优异的染毛性和便利性,并且其对于毛发、头皮的安全性较优异。
[背景技术]
以往,使用对苯二胺类的氧化染毛剂被广泛使用。这种染毛剂由含有对苯二胺、2,5-二氨基甲苯等氧化染料中间体和氨、乙醇胺等碱性剂的第一液体、以及含有过氧化氢等氧化剂的第二液体组成。已知使用氧化染毛剂的染毛剂是通过氧化染料中间体渗透到毛发内部并氧化偶联形成色素来染毛发的,因此,染色能力强,而且牢固性优异,且由洗发剂、护发素或光照造成的褪色较少。另外,还可以通过过氧化氢的作用同时进行黑色素脱色和染毛,具有还可以染毛成明亮的色调的优点。
然而,使用了上述氧化染毛剂的染毛剂存在用于染毛处理的碱性剂、过氧化氢会对毛发、头皮产生损伤的问题。另外,已指出对苯二胺、2,5-二氨基甲苯等氧化染料中间体会引起皮肤过敏,并被怀疑具有致突变性。
另一方面,作为使用方法简单的染毛剂,提出了使酸性染料、碱性染料吸附在毛发表面上的护发染剂、毛发修护剂。然而,在使用它们进行染毛时,由于染色性和洗发剂抗性不充分,需要频繁地进行染毛处理或存在皮肤着色的问题。此外,也存在由染料中包含的硝基、苯二胺结构引起的安全风险。
对于染毛剂的安全性改善,迄今为止提出了各种方案。例如,从古代开始,作为天然来源的植物色素的指甲花染料、蓝靛就被用于染毛。然而,染毛性较差,有效的染毛需要在30℃以上染毛1小时以上的条件,且色调也非常有限。另外,用于草木染的很多植物色素自古以来就被用于染毛。但是,这些色素通常染毛性非常差且缺乏实用性。因此,作为改善这一点的技术,已知一种与金属离子类媒染剂一起使用或与硫醇类等还原剂和碱性剂一起使用的方法(专利文献1、2)。
[现有技术文献]
专利文献
专利文献1:日本特开2002-138024号公报
专利文献2:日本特开2013-133320号公报
[发明内容]
发明要解决的课题
然而,根据专利文献1所述的金属离子类媒染剂,染毛性确实得到提高,但在铁离子的情况下,存在色相仅限于黑色系、饱和度也较低、并且具有铁离子特有的气味的问题。另外,在铜离子、铝离子、锡离子、镍离子、铅离子、铬离子等的情况下,担心对于人体的安全性,且染毛性也仍然不充分,洗发剂抗性方面也还存在改善的空间。另一方面,如专利文献2所述那样的与硫醇类等还原剂和碱性剂一起使用的方法,存在染毛工序复杂并且无法避免对毛发和头皮的伤害的问题。
鉴于上述现有技术,本发明的目的在于提供一种染毛剂,其具有优异的染毛性,且使用方法简单,可在短时间内染毛,并且对于毛发、头皮的安全性也较优异。
用于解决课题的手段
本发明人们经深入研究,作为解决上述课题的手段,发现将有机钛化合物和/或有机锆化合物与特定的色素和/或其色素前体组合的方法。
即,本发明提供一种同时或分别含有下述组分(1)和下述组分(2)的染毛剂。
组分(1):选自具有儿茶酚结构的色素、具有连苯三酚结构的色素、具有α-羟基羰基结构的色素、具有β-羟基羰基结构的色素以及它们的色素前体中的一种或两种以上色素和/或其色素前体。
组分(2):有机钛化合物和/或有机锆化合物
在上述染毛剂中,所述组分(1)优选为选自氧化苏木精、苏木精、氧化巴西木素、巴西木素、羟基萘醌类化合物、姜黄素、黄酮类化合物、花青苷类化合物、茜素、紫胶色素、胭脂虫红色素、咖啡酸衍生物、没食子酸衍生物以及单宁类化合物中的一种或两种以上天然来源色素。
另外,在上述染毛剂中,所述组分(2)优选为选自羟基羧酸类化合物、β-二酮类化合物、β-酮酸酯类化合物、还原酮类化合物、多元醇类化合物、多元羧酸类化合物、含氮杂环羧酸类化合物、烷醇胺类化合物以及氨基酸中的一种或两种以上化合物与钛和/或锆配位的络合物。
另一方面,本发明提供一种将下述组分(1)和下述组分(2)同时或分别应用于毛的染毛方法。
组分(1):选自具有儿茶酚结构的色素、具有连苯三酚结构的色素、具有α-羟基羰基结构的色素、具有β-羟基羰基结构的色素以及它们的色素前体中的一种或两种以上色素和/或其色素前体。
组分(2):有机钛化合物和/或有机锆化合物
在上述染毛方法中,所述组分(1)优选为选自氧化苏木精、苏木精、氧化巴西木素、巴西木素、羟基萘醌类化合物、姜黄素、黄酮类化合物、花青苷类化合物、茜素、紫胶色素、胭脂虫红色素、咖啡酸衍生物、没食子酸衍生物以及单宁类化合物中的一种或两种以上天然来源色素。
另外,在上述染毛方法中,所述组分(2)优选为选自羟基羧酸类化合物、β-二酮类化合物、β-酮酸酯类化合物、还原酮类化合物、多元醇类化合物、多元羧酸类化合物、含氮杂环羧酸类化合物、烷醇胺类化合物以及氨基酸中的一种或两种以上化合物与钛和/或锆配位的络合物。
发明效果
根据本发明,将有机钛化合物和/或有机锆化合物与特定的色素和/或其色素前体组合,因此可以获得具有优异的染毛性的染毛剂。该染毛剂使用方法简单,可在短时间内染毛,并且其对于毛发、头皮的安全性也较优异。
[具体实施方式]
本发明由以下组分构成:
组分(1):选自具有儿茶酚结构的色素、具有连苯三酚结构的色素、具有α-羟基羰基结构的色素、具有β-羟基羰基结构的色素以及它们的色素前体中的一种或两种以上色素和/或其色素前体;以及
组分(2):有机钛化合物和/或有机锆化合物。
构成上述组分(1)的色素和/或其色素前体实质上呈现浅黄色至红色,但该色素通过与构成上述组分(2)的有机钛化合物和/或有机锆化合物形成络合物,能够转化为浓色且深色(黄色、紫色乃至黑色)的色素。通过在毛发上进行该反应,该有机钛化合物和/或有机锆化合物与上述色素形成络合物,同时与毛发表面的羧基、羟基和酰胺基相互作用,从而有效地对毛发染色。结果,能够实现高染毛性和优异的洗发剂抗性。另外,构成上述组分(1)、上述组分(2)的化合物安全性高,不会引起头皮的炎症、过敏。此外,即使不使用碱性剂也能够染毛,因此也没有由碱性剂造成的毛发内部的损伤等。
作为上述组分(1),可以列举氧化苏木精、氧化苏木精的前体即苏木精、氧化巴西木素、氧化巴西木素的前体即巴西木素、羟基萘醌类化合物(指甲花醌、胡桃醌、紫草素、紫草醌、乙酰紫草素、去氢紫草素等)、姜黄素、黄酮类化合物(槲皮素、芦丁、木犀草素等)、花青苷类化合物、茜素、紫胶色素、胭脂虫红色素、咖啡酸衍生物(咖啡酸、咖啡酸乙酯、绿原酸、迷迭香酸、七叶亭等)、没食子酸衍生物(没食子酸乙酯、鞣花酸、双没食子酸等)以及单宁类化合物(五倍子、塔拉单宁、白坚木、表没食子儿茶素、柿漆等)等。这些组分可以单独使用一种,也可以两种以上一起使用。
作为上述组分(1),优选为天然来源的组分。具体地,例如氧化苏木精为洋苏木(采木)中含有的色素,氧化巴西木素为苏木中含有的色素,指甲花醌为指甲花中含有的色素,胡桃醌为黑胡桃中含有的色素,紫草素衍生物为紫草根、朱草中含有的色素,姜黄素为莪术中含有的色素。另外,槲皮素、芦丁、木犀草素等黄酮类化合物包含于以使君子科植物(例如诃子等)为首的各种树木、各种柑橘类、浆果类、蔬菜等中,没食子酸衍生物是儿茶素的一种,且大量包含于浆果类、单宁类中。茜素包含于西洋茜草、印度茜草中,咖啡酸衍生物大量包含于生咖啡豆、甘薯茎叶、向日葵种子、果实、艾蒿等中。单宁类化合物包含在广泛的植物中,大致分为水解型和缩合型。另一方面,紫胶色素及胭脂虫红色素是来自介壳虫的色素。
上述色素中,氧化苏木精和氧化巴西木素在基原植物中与其还原体共存。即,在氧化苏木精的基原植物采木(洋苏木)中含有大量还原体苏木精,氧化巴西木素的基原植物苏木中含有大量还原体巴西木素。在本发明中,虽然也可以直接使用这些还原体共存的植物提取物,但优选的是,预先将提取物用各种氧化剂(氧气、过氧化氢、氧化银、二氧化锰、过硫酸盐、高碘酸等)进行处理,例如将苏木精、巴西木素等还原体转化成氧化苏木精、氧化巴西木素等氧化体并且提高其含量后使用。
作为从植物、昆虫等天然资源获取提取物的方法,通常采用将该天然资源干燥,粉碎,并用水、乙醇、异丙醇、丙二醇、1,3-丁二醇或其混合溶剂提取的方法。
在多数情况下,上述提取物含有已被氧化的色素。可以根据需要将含有这些色素的着色提取物进一步供应到氧化步骤和纯化步骤来获得高纯度的色素含有物,但也可以将已着色的未纯化产品直接用于染毛。
作为上述组分(1),也可以不是天然来源的组分。具体地,可以列举羟基蒽醌类色素(醌茜(1,4-二羟基蒽醌)、1,4,5,8-四羟基蒽醌等)、羟基萘醌类色素(萘茜、2,5,8-三羟基-1,4-萘醌(naphthopurpurin)、2,3-二羟基-1,4-萘醌等)等。这些组分可以单独使用一种,也可以两种以上一起使用。另外,为了使染毛的色相多样化,优选采用与上述天然来源的组分一起使用。
作为上述组分(2),是钛或锆与有机配位体结合的络合物,例如,与羟基羧酸类化合物的络合物、与β-二酮类化合物的络合物、与β-酮酸酯类化合物的络合物、与还原酮类化合物的络合物、与多元醇类化合物的络合物、与多元羧酸类化合物的络合物、与含氮杂环羧酸的络合物、与烷醇胺类化合物的络合物以及与氨基酸的络合物等。通常,钛是四价六配位,锆是四价八配位,多个配位体可以通过共价键或配位键与上述组分(1)和毛发结合,从而可以赋予较高的染毛性和优异的洗发剂抗性。已知自古以来就将钛化合物用作媒染剂,但已知的钛媒染剂为含有高浓度的硫酸或盐酸的强酸性硫酸钛水溶液或氯化钛水溶液,它们不能应用于人的染毛。构成上述组分(2)的有机钛化合物实质上是中性化合物,在水溶液中的稳定性也足够高。另一方面,以往,锆几乎不用做草木染的媒染剂。其化学性质与钛非常相似。
作为钛和锆所共通的化学性质,与键合力较弱的不稳定配位体的络合物在水中容易水解,分解成氧化钛或氧化锆,因此为了获得在水中稳定的络合物,配位体的选择极其重要。作为优选的羟基羧酸配位体,可以列举乙醇酸、乳酸、扁桃酸、柠檬酸、酒石酸、苹果酸、水杨酸、磺基水杨酸等,作为优选的β-二酮或β-酮酸酯配位体,可以列举乙酰丙酮、苯甲酰丙酮、二苯甲酰甲烷、乙酰乙酸乙酯等,作为优选的还原酮配位体,可以列举抗坏血酸、异抗坏血酸、二羟基丙酮、赤藓酮糖等,作为优选的多元醇配位体,可以列举乙二醇、丙二醇、丁二醇、异戊二醇、甘油、儿茶酚、钛铁试剂等,作为优选的多元羧酸配位体,可以列举草酸、丙二酸、马来酸、谷氨酸等,作为优选的含氮杂环羧酸配位体,可以列举吡啶-2-羧酸、咪唑-2-羧酸、咪唑-4-羧酸、5-吡咯烷酮-2-羧酸、吡嗪-2-羧酸等,作为优选的烷醇胺配位体,可以列举乙醇胺、二乙醇胺、三乙醇胺等,作为优选的氨基酸配位体,可以列举丝氨酸、甘氨酸、丙氨酸、谷氨酸、赖氨酸、组氨酸等。
本发明提供一种同时或分别含有上述组分(1)和上述组分(2)的染毛剂。以下,为方便起见,将含有上述组分(1)的形式称为组合物(A),将含有上述组分(2)的形式称为组合物(B),或者将含有上述组分(A)和组分(B)两种组分的形式表示为组合物(C),并对其作为染毛剂提供的方式进行进一步详细地说明。
对于上述组合物(A)或上述组合物(B)或上述组合物(C)各自的形式没有特别限制,从易于应用于毛发的观点来看,可以优选地列举溶液状、悬浊液状、乳液状、乳膏状、泡沫状、凝胶状、糊状等形式。对于用于提供这些形式的溶剂的种类没有特别限制,例如可以使用水、甲醇、乙醇、异丙醇、乙二醇、二甘醇、丙二醇、二丙二醇、1,3-丁二醇、异戊二醇、己二醇、乙基卡必醇、甘油、双甘油、聚乙二醇、聚丙二醇等。这些溶剂可以单独使用,也可以两种以上组合使用。优选单独使用水或使用水与上述有机溶剂的混合物。
然而,从染毛性和洗发剂抗性来看,上述组分(1)和上述组分(2)优选以分开的形式提供。例如,上述形式中,特别优选以分别填充于不同容器的形式提供溶液状等的组合物(AB)和溶液状等的组合物(B)。另外,也可以在加压下与抛射剂一起封入气溶胶容器等形式提供。
另一方面,对同时含有上述组分(1)和上述组分(2)的形式进行说明,若混合上述组分(1)和上述组分(2),则发生络合,在多数情况下,会生成难溶于水、有机溶剂中的有色沉淀。若生成沉淀,通常染毛性会显著降低,因此需要采用不会生成沉淀的配方。具体地,应用优化上述组分(1)和上述组分(2)的组合、与可溶化该有色沉淀的辅助溶剂一起使用、优化混合溶剂中的溶剂比例等措施。同时含有上述组分(1)和上述组分(2)的实施方式,染毛操作简单,因此特别优选用于外出时短时间内的染毛。
对于上述组分(1)的用量没有特别限制,但在制备含有组分(1)的溶液状等的组合物(A)时,该组合物优选含有约0.03质量%至5质量%,特别优选含有约0.1质量%至3质量%。而且,例如,通过改变组分(1)的色素的浓度或混合多种色素,可以广泛地改变染毛时的色调。
对于上述组分(2)的用量没有特别限制,但在制备含有组分(2)的溶液状等的组合物(B)时,组分(2)在水中的溶解度优选为0.1质量%以上,特别优选为1.0质量%以上。另外,在该组合物中优选含有约0.05质量%至10质量%,特别优选含有约0.1质量%至5质量%。而且,例如,通过改变组分(2)的钛化合物或锆化合物的配位体、浓度、与组分(1)的色素的摩尔比等,可以大大改变染毛后毛发的色相、明度、饱和度等。
对于上述组分(1)和上述组分(2)的pH没有特别限制,但从染毛性的观点来看,在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,这些组合物(A)或组合物(B)或组合物(C)的pH优选为3至10的范围,特别优选为3至8的范围。从抑制毛发损伤的观点来看,它们的pH优选为9以下,特别优选为3.5至6.5的范围。
上述pH也可以使用由酸或碱构成的pH调节剂等适当地调节。
作为用作pH调节剂的酸,例如可以列举乙酸、乳酸、酒石酸、苹果酸、柠檬酸、乙醇酸、吡咯烷酮羧酸、乙酰丙酸、富马酸、琥珀酸、草酸、马来酸、扁桃酸、天冬氨酸、已二酸和烟酸等有机酸、磷酸等。其中,优选使用乙酸、乳酸、酒石酸、苹果酸、柠檬酸、乙醇酸、富马酸、琥珀酸、马来酸、扁桃酸、天冬氨酸、已二酸等有机酸。另外,也可以将这些酸的盐类(钠盐、钾盐或铵盐等)用作pH调节剂。
作为用作pH调节剂的碱,例如可以列举氨、乙醇胺、二乙醇胺、三乙醇胺、咪唑、氢氧化四甲铵、碳酸氢钠、醋酸钠、乳酸钠等。其中,优选使用乙醇胺、二乙醇胺、三乙醇胺、咪唑等。
上述pH调节剂可以单独使用,或者也可以两种以上组合使用。另外,对于pH调节剂的配合量没有特别限制,但是,例如,相对于染毛剂使用时的总质量,优选在0.01质量%至15质量%的范围内使用,更优选在0.1质量%至10质量%的范围内使用,特别优选在0.5质量%至5质量%的范围内使用。
另一方面,优选使用pH缓冲液来调节pH。作为pH缓冲液,例如可以列举乙酸缓冲液、磷酸缓冲液、柠檬酸缓冲液、柠檬酸磷酸缓冲液、硼酸缓冲液、酒石酸缓冲液、Tris(三羟甲基氨基甲烷)缓冲液等。特别地,优选使用乙酸缓冲液、磷酸缓冲液、柠檬酸缓冲液、柠檬酸磷酸缓冲液等。
在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,根据需要,也可以在这些组合物(A)或组合物(B)或组合物(C)中配合表面活性剂。作为表面活性剂,例如可以列举阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂等。特别地,优选使用非离子表面活性剂。
作为非离子表面活性剂,可以列举脂肪酸烷醇酰胺类、聚乙烯吡咯烷酮类、聚环氧乙烷类、聚环氧乙烷单烷基醚类、聚环氧乙烷二醚类、聚环氧乙烷单苯醚类、聚环氧丙烷类、聚环氧丙烷单烷基醚类、聚环氧丙烷二烷基醚类、聚环氧乙烷脂肪酸酯类、甘油脂肪酸酯类、甘油单醚类、山梨糖醇酐脂肪酸酯类等。
上述表面活性剂可以单独使用,或者也可以两种以上组合使用。另外,对于表面活性剂的配合量没有特别限制,但是,例如相对于染毛剂使用时的总质量,优选在0.01质量%至20质量%的范围内使用,更优选在0.1质量%至5质量%的范围内使用。
在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,根据需要,也可以在这些组合物(A)或组合物(B)或组合物(C)中配合油性组分。作为油性组分,只要能够在这些组合物(A)或组合物(B)或组合物(C)中溶解或分散即可,没有特别限制。通过配合油性组分,能够抑制染毛后对毛发的伤害,并且能够保持光泽、水润。作为油性组分,例如可以列举硅树脂类、碳化氢、油脂、蜡类、高级脂肪酸酯等。
上述油性组分可以单独使用,或者也可以两种以上组合使用。对于油性组分的配合量没有特别限制,但是,例如相对于染毛剂使用时的总质量,优选在0.01质量%至5质量%的范围内使用,更优选在0.05质量%至3质量%的范围内使用。
在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,根据需要,也可以在这些组合物(A)或组合物(B)或组合物(C)中配合高级醇。作为高级醇,只要能够在这些组合物(A)或组合物(B)或组合物(C)中溶解或分散即可,没有特别限制。例如可以列举十四醇、十六醇、油醇、十八醇等。这些高级醇可以单独使用,或者也可以两种以上一起使用。对于高级醇的配合量没有特别限制,但是,例如相对于染毛剂使用时的总质量,优选在0.01质量%至5质量%的范围内使用,更优选在0.03质量%至3质量%的范围内使用。
在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,根据需要,也可以在这些组合物(A)或组合物(B)或组合物(C)中配合高分子化合物。作为高分子化合物,只要能够在这些组合物(A)或组合物(B)或组合物(C)中溶解或分散即可,没有特别限制。例如可以列举阳离子高分子化合物、两性高分子化合物、阴离子高分子化合物、非离子高分子化合物等。
作为阳离子高分子化合物,例如可以列举阳离子化纤维素(例如氯化O-[2-羟基-3-(三甲氨基)丙基]羟乙基纤维素、氯化O-[2-羟基-3-(月桂基二甲氨基)丙基)羟乙基纤维素)、阳离子淀粉、阳离子瓜尔胶、聚二甲基二烯丙基铵盐等。
作为阴离子高分子化合物,例如可以列举丙烯酸或甲基丙烯酸与其他乙烯基单体的共聚高分子、羧甲基纤维素等。
作为非离子高分子化合物,例如可以列举聚乙烯醇、聚乙烯吡咯烷酮、纤维素、甲基纤维素、乙基纤维素、羟乙基纤维素、羟丙基纤维素、羟甲基丙基纤维素、瓜尔胶、羟丙基黄原胶、琼脂、淀粉、聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酰胺、聚甲基丙烯酰胺、聚乙二醇、聚丙二醇等。
作为其他有用的高分子化合物,例如可以列举阿拉伯胶、卡拉胶、银耳多糖、半乳聚糖、温柏籽胶、刺槐豆胶、黄蓍胶、果胶、甘露聚糖、黄原胶、葡聚糖、热凝胶、结冷胶、琥珀酰聚糖、明胶、罗望子胶、酪蛋白等天然高分子化合物。
上述高分子化合物可以单独使用,或者也可以两种以上组合使用。对于高分子化合物的配合量没有特别限制,但是,例如,相对于染毛剂使用时的总质量,优选在0.01质量%至10质量%的范围内使用,更优选在0.05质量%至5质量%的范围内使用。
在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,根据需要,也可以在这些组合物(A)或组合物(B)或组合物(C)中配合增粘剂。作为增粘剂,例如可以列举海藻酸钠、阿拉伯胶、交联丙烯酸聚合物、纤维素衍生物、黄原胶等。这些增粘剂可以单独使用,或者也可以两种以上组合使用。对于增粘剂的配合量没有特别限制,但是,例如,相对于染毛剂使用时的总质量,优选在0.01质量%至5质量%的范围内使用,更优选在0.05质量%至5质量%的范围内使用。
在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,根据需要,也可以在这些组合物(A)或组合物(B)或组合物(C)中配合香料。作为香料,可任选使用合成品或天然品,但特别地,优选使用精油(香精油)。
在制备含有上述组分(1)的溶液状等的组合物(A)时、制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,根据需要,也可以在这些组合物(A)或组合物(B)或组合物(C)中配合各种添加剂以调节染毛性。作为用于调节染毛性的添加剂,例如可以优选列举脂肪族羧酸(例如乙酸、丙酸、乳酸、乙醇酸、乙酰丙酸、富马酸、马来酸、琥珀酸、酒石酸、苹果酸、柠檬酸)、氨基酸(例如甘氨酸、α-丙氨酸、β-丙氨酸、缬氨酸、亮氨酸、异亮氨酸、苯丙氨酸、脯氨酸、丝氨酸、苏氨酸、天冬氨酸、谷氨酸、精氨酸、组氨酸、色氨酸、甲硫氨酸等)。
在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,根据需要,可以在这些组合物(A)或组合物(B)或组合物(C)中、特别是在含有有机钛化合物和/或有机锆化合物的组合物(B)中配合除钛或锆之外的金属离子作为媒染剂。如上所述,担心除铁之外的金属离子对于人体的安全性,但如果是低浓度则可以配合。作为可使用的金属离子,可以列举铜离子、铝离子、锌离子等。另一方面,虽然铁离子也存在问题,但在染成黑色系时,可以与有机钛化合物和/或有机锆化合物一起使用。作为优选的铁离子的原料,例如可以列举乳酸亚铁、乳酸铁、乙酸亚铁、乙酸铁、硫酸亚铁、硫酸铁、氯化亚铁、氯化铁等。作为配合铁离子时的配合量,优选在0.001质量%至0.3质量%的范围内使用。
在本发明中,可以向上述组分中添加各种水溶性金属盐。通过添加该金属盐,可以改善染毛性、洗发剂抗性,并且可以精细调节色相。作为该金属盐,可以使用碱金属卤化物、碱金属硫酸盐、碱土类金属卤化物、水溶性铝盐、水溶性铜盐等,作为优选的示例,可以列举氯化钠、氯化钾、溴化钠、氯化镁、溴化镁、乙酸铝、乳酸铝、硫酸铝、明矾类、乙酸铜、乳酸铜等。
在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,根据需要,可以在这些组合物(A)或组合物(B)或组合物(C)中、特别是在含色素和/或其色素前体的组合物(A)中添加已知的色素、染料来调整色调。作为已知的色素、染料,例如可以列举HC黄1、HC黄2、HC黄3、HC黄4、HC橙1、HC红1、HC红2、HC红3、HC蓝1、HC蓝2、分散紫1、分散紫3等,作为直接染料,可以列举黑色401号、蓝色1号、蓝色2号、蓝色201号、蓝色202号、蓝色203号、蓝色403号、蓝色404号、紫色201号、紫色401号、红色102号、红色106号、红色201号、红色202号、红色203号、红色204号、红色205号、红色206号、红色207号、红色208号、橙色201号、橙色203号、橙色205号、橙色206号、橙色207号、黄色201号、黄色203号、黄色204号、黄色205号、黄色401号、黄色402号、黄色403号,作为天然色素,可以列举叶绿素色素、螺旋藻色素、栀子黄色素、栀子蓝色素、愈创木薁、愈创木薁磺酸盐等。
在制备含有上述组分(1)的溶液状等的组合物(A)时、在制备含有上述组分(2)的溶液状等的组合物(B)时、或者在制备含有上述组分(1)和组分(2)的溶液状等的组合物(C)时,可以在这些组合物(A)或组合物(B)或组合物(C)中进一步添加其他物质。作为其他物质,只要不降低染毛性,并且能够在这些组合物(A)或组合物(B)或组合物(C)中溶解或分散即可,没有特别限制。作为优选的示例,可以列举胶原蛋白、角蛋白、弹性蛋白、丝心蛋白、贝壳硬蛋白、吡咯烷酮羧酸钠、乳酸钠、山梨糖醇、透明质酸、苯甲醇、苯乙醇、苄氧基乙醇、N-甲基吡咯烷酮、N-乙基吡咯烷酮、碳酸亚乙酯、尿素、羟乙基尿素、双-二乙氧基二甘醇环己烷1,4-二羧酸酯、碳酸丙烯酯、对羟基苯甲酸酯、紫外线吸收剂等。
本发明所涉及的由上述结构构成的染毛剂可用于人或动物的毛、例如毛发、体毛、动物的体毛等的染色,优选用于人的毛发的染色、狗或猫等宠物的体毛的染色,特别优选用于人的毛发的染色。
在使用本发明所涉及的由上述结构构成的染毛剂进行染毛时,对于上述组分(1)和上述组分(2)的应用顺序没有特别限制,可以以任意顺序应用。例如,可以在将含有上述组分(1)的溶液状等的组合物(A)通过涂布等应用到毛发等上之后,将含有上述组分(2)的溶液状等的组合物(B)通过涂布等应用到毛发等上,或者可以在将含有上述组分(2)的溶液状等的组合物(B)通过涂布等应用到毛发等上之后,将含有上述组分(1)的溶液状等的组合物(A)通过涂布等应用到毛发上。或者,可以将含有上述组分(1)的溶液状等的组合物(A)和含有上述组分(2)的溶液状等的组合物(B)同时通过涂布等应用到毛发等上,也可以在要使用之前将两者混合并将所得混合物通过涂布等应用到毛发等上。进一步地,还可以制备含有上述组分(1)和组分(2)两种组分的溶液状等的组合物(C),然后将其通过涂布等应用到毛发等上。
其中,特别优选在将含有上述组分(2)的溶液状等的组合物(B)通过涂布等应用到毛发等上之后,将含有上述组分(1)的溶液状等的组合物(A)通过涂布等应用到毛发上的方法。这是因为,由于构成上述组分(2)的有机钛化合物和/或有机锆化合物具有与毛发角蛋白等强烈相互作用的性质,因此通过先应用它,通常可以获得更高的染毛性。即,例如,在将上述组分(B)应用到毛发上之后,放置一段时间后再应用上述组合物(A)。对于放置时间没有特别限制,但优选为例如3至30分钟,更优选为5至20分钟。另外,应用该组合物(A)后,优选进一步放置一段时间。对于其放置时间没有特别限制,但优选为例如5至30分钟,更优选为10至20分钟。染毛处理例如可以在约20℃至40℃的温度下进行。对于含有上述组分(1)的溶液状等的组合物(A)和含有上述组分(2)的溶液状等的组合物(B)的用量没有特别限制,但优选为两者的用量比为3/1至1/3的范围。对于上述组合物(A)或上述组合物(B)的应用方法没有特别限制,可以采用将该组合物涂布到毛发等上、或者将毛发等浸泡在该组合物中等任意方法。染毛后,可以使用洗发剂和护发素来进行处理。然后,优选通过适当的方法干燥。
实施例
以下,通过实施例进一步具体地说明本发明,但本发明的范围完全不受以下实施例的限制。
<制备例1>(溶液A1的制备)
在冰冷下,向10mL丁二醇、5mL异丙醇以及2.70g乳酸的混合物中滴加2.84g四异丙醇钛(由东京化成工业株式会社制造),然后,室温下搅拌1小时。另行将1.0g羟乙基纤维素溶解于70mL纯化水中,并将该溶液一点一点地加入到乳酸钛溶液中,从而获得略微粘稠的无色透明溶液(A1)。
<制备例2>(溶液A2的制备)
在冰冷下,向10mL丁二醇、5mL正丙醇以及2.70g乳酸的混合物中滴加5.54g正丙醇锆70%丙醇溶液(由东京化成工业株式会社制造),然后,室温下搅拌1小时。另行将1.0g羟乙基纤维素溶解于70mL纯化水中,并将该溶液一点一点地加入到乳酸锆溶液中,从而获得略微粘稠的无色透明溶液(A2)。
<制备例3>(溶液B1的制备)
将0.60g氧化苏木精和0.57g木犀草素加入到5g丁二醇和10g的AMINON C-11S(由花王株式会社制造)的混合物中,并在50℃下加热溶解。接着,加入100g的2%羟乙基纤维素水溶液,并使用均质器在50℃下剧烈搅拌30分钟后,放置冷却得到橙红色乳膏状的溶液(B1)。
<制备例4>(植物色素的提取方法1)
将100g诃子干燥片(由田中染料店制造)加入到1L的50%乙醇溶液中,并回流加热2小时。放置冷却后,过滤,从滤液中减压蒸馏除去溶剂,得到6.5g含有木犀草素作为主要成分的提取物。该方法是最常用的植物色素的提取方法。
<制备例5>(植物色素的提取方法2)
将100g采木干燥片(由田中染料店制造)加入到1L的50%乙醇溶液中,并回流加热2小时。放置冷却后,过滤,向滤液中加入1.16g氧化银,在室温下搅拌2小时。过滤除去不溶物,从滤液中减压蒸馏除去溶剂,得到8.2g含有氧化苏木精作为主要成分的提取物。当从苏木中获得氧化巴西木素时,也优选采用该方法。
<制备例6>(溶液B2的制备)
将1.0g制备例4中的诃子提取物和1.2g制备例5中的采木提取物加入到5g丁二醇、5g纯化水和15g的AMINON C-11S(由花王株式会社制造)的混合物中,并在60℃下加热溶解。接着,加入100g的2%羟乙基纤维素水溶液,并使用均质器在60℃下剧烈搅拌30分钟后,放置冷却得到暗红色乳膏状的溶液(B2)。
<制备例7>(植物色素的提取方法3)
粉碎100g软紫草根干燥片(产自中国陕西省),加入1L的95%乙醇溶液,在50℃下搅拌2小时。放置冷却后,过滤,从滤液中减压蒸馏除去溶剂。将残渣溶于100mL乙酸乙酯中,用100mL的3%碳酸氢钠水溶液洗涤3次以除去共存的中级脂肪酸类,进一步用1%乳酸水溶液洗涤后,用无水硫酸镁干燥,减压蒸馏除去乙酸乙酯得到3.1g以乙酰紫草素为主要成分的粗制紫草素。
<制备例8>(植物色素的提取方法4)
粉碎100g干莪术(产自印度),加入1L的95%乙醇溶液,然后在50℃下搅拌2小时。放置冷却后,过滤,从滤液中减压蒸馏除去溶剂。在200mL乙酸乙酯中加热溶解残渣,过滤除去不溶物。从滤液中减压蒸馏除去乙酸乙酯,得到6.5g粗制姜黄素。
[试验例1](染毛试验1)
用刷子将20g制备例1的溶液A1涂抹到2g人白发(100%)束(由株式会社beaulax制造)上,并放置10分钟。接着,用刷子涂布20g制备例3的乳膏状溶液B1,再放置10分钟。用热水充分洗净发束,使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了黑褐色。当用色彩色差计(柯尼卡美能达制CR-400)测量染毛后的发束的染毛浓度(ΔE:与染毛前相比的色差)时,ΔE为50.2。
[试验例2](染毛试验2)
用刷子将20g制备例1的溶液A1涂抹到2g人白发(100%)束(由株式会社beaulax制造)上,并放置10分钟。接着,用刷子涂布20g制备例6的乳膏状溶液B2,再放置10分钟。用热水充分洗净发束,使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了暗褐色。当用色彩色差计测量染毛后的发束的染毛浓度(ΔE)时,ΔE为48.5。
[试验例3](染毛试验3)
用刷子将20g制备例2的溶液A2涂抹到2g人白发(100%)束(由株式会社beaulax制造)上,并放置10分钟。接着,用刷子涂布20g制备例6的乳膏状溶液B2,再放置10分钟。用热水充分洗净发束,使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了暗褐色。当用色彩色差计测量染毛后的发束的染毛浓度(ΔE)时,ΔE为45.2。
[试验例4](染毛试验4)
适当组合溶液A组和乳膏状溶液B组,并根据试验例1至3进行染毛试验。结果如表1所示。此外,作为溶液A组,通过制备例1或制备例2的方法,具体地,在水冷下将钛或锆与配位体的摩尔比为1:2的钛或锆的四烷氧化物加入到配位体与异丙醇或丙醇的混合物中的方法,制备了表1所示的配位体的钛或锆的络合物。另外,作为乳膏状溶液B组,通过制备例4或制备例5的方法,具体地,将100g已干燥的提取到的植物粉碎物加入到1L的50%或95%乙醇中,在搅拌下回流加热2小时后,过滤除去不溶物,从滤液中减压蒸馏除去溶剂的方法,从各种植物中提取色素,并通过制备例6的方法制备乳膏状的溶液。
[表1]
[试验例5](染毛试验5)
用刷子将20g制备例3的乳膏状溶液B1涂布到2g人白发(100%)束(由株式会社beaulax制造)上,并放置10分钟。接着,用刷子涂抹20g制备例1的溶液A1,并放置10分钟。用热水充分洗净发束,使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了黑褐色。当用色彩色差计测量染毛后的发束的染毛浓度(ΔE)时,ΔE为45.8。由此结果可知,在该试验例的情况下,即使改变溶液A和溶液B的涂布顺序,染毛性也没有太大的差异。
[试验例6](染毛试验6)
用刷子将20g制备例1的溶液A1和20g制备例3的乳膏状溶液B1毫无遗漏地涂布到2g人白发(100%)束上以使其在毛发上混合。放置30分钟后,用热水充分洗净发束,使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了褐色。当测量染毛后的发束的染毛浓度(ΔE)时,ΔE为28.7。由此结果可知,当溶液A和溶液B同时涂布到毛发上时,染毛性降低。
[试验例7](染毛试验7)
将20g制备例1的溶液A1与20g色素溶液B12(1.0g粗制紫草素和1.0g羟乙基尿素溶于100mL的95%乙醇中的溶液)混合,用刷子毫无遗漏地涂布到2g人白发(100%)束上。放置30分钟后,用热水充分洗净发束,使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了褐色。当测量染毛后的发束的染毛浓度(ΔE)时,ΔE为41.7。由此结果可知,根据溶液A和溶液B的组合,在使用时即使将两者混合并涂布到毛发上,染毛性也不会降低。
[试验例8](染毛试验8)
将50mg制备例7的粗制紫草素、60mg制备例8的粗制姜黄素、100mg苯甲醇、500mg羟乙基尿素、1.023g纯化水以及9.0g乙醇的混合物在50℃下加热搅拌,制备橙红色的色素溶液。另一方面,在冰冷下,向5mL丁二醇、5mL乙醇以及2.70g乳酸的混合物中加入2.84g四异丙醇钛,然后,室温下搅拌1小时,制备乳酸钛溶液。向上述色素溶液中加入150mg乳酸钛溶液,制备褐色的色素/钛络合物溶液。该溶液很稳定,即使放置过夜后也不会产生沉淀。
用染毛膏用迷你刷将上述溶液毫无遗漏地涂布到0.2g人白发(100%)束上。室温下放置1小时后,用热水充分洗净发束,进一步使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了酱色。另外,热水洗净后也没有发现浓度降低。进一步地,当将洗发剂洗涤后的发束的染毛浓度与刚染完发后的染毛浓度进行比较时,发现浓度降低保持在10%。由此结果可知,通过适当组合色素溶液和钛溶液,能够获得具有较高染毛性和洗发剂抗性的稳定的色素/钛络合物溶液。
[试验例9](比较染毛试验1)
用刷子将20g制备例3的乳膏状溶液B1涂布到2g人白发(100%)束(由株式会社beaulax制造)上,并用聚乙烯薄膜包裹后在35℃的恒温槽中放置30分钟。用热水充分洗净发束,使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了浅红褐色。当用色彩色差计测量染毛后的发束的染毛浓度(ΔE)时,ΔE为10.3。由此结果可知,没有钛化合物,染毛性将显著降低。
[试验例10](比较染毛试验2)
使用与制备例4同样地从黄檗中提取的、含有不与钛形成络合物的黄色色素小蘗碱的黄檗提取物,与制备例6同样地制备乳膏状溶液B,并用刷子将20g溶液B涂布到2g人白发(100%)束(由株式会社beaulax制造)上,并放置30分钟。用热水充分洗净发束,使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了浅黄色。当用色彩色差计测量染毛后的发束的染毛浓度(ΔE)时,ΔE为12.2。
[试验例11](比较染毛试验3)
用刷子将20g制备例1的溶液A1涂抹到2g人白发(100%)束(由株式会社beaulax制造)上,放置10分钟后,用刷子涂布20g上述黄檗提取物的乳膏状溶液,放置30分钟。用热水充分洗净发束,使用洗发剂和护发素进行洗涤,并用吹风机干燥。发束被染成了浅黄色。当用色彩色差计测量染毛后的发束的染毛浓度(ΔE)时,ΔE为11.8。由此结果可知,不与钛形成络合物的植物色素,即使存在钛化合物,染毛性也会显著降低。
[试验例12](洗发剂抗性试验)
将试验例1至3得到的染毛样品用含有氨基酸系洗涤剂的通用型洗发剂反复洗发5次,测量洗发前后的染毛浓度(ΔE)。结果如表2所示。
[表2]
染毛样品 | 洗发前的ΔE | 洗发后的ΔE |
试验例1 | 50.2 | 50.0 |
试验例2 | 48.5 | 48.2 |
试验例3 | 45.2 | 44.9 |
由表2的结果可知,本发明的染毛剂具有较高的洗发剂抗性。
[试验例13](对头皮的刺激性试验)
将由试验例2中使用的溶液A1和乳膏状溶液B2构成的染毛剂应用于对氧化染毛剂会引起头皮过敏的10人的人类受监测者的染毛。结果,没有一个受监测者发生过敏。另外,一个月后,再次对同一受监测者进行染毛试验,但没有发现过敏的发生。由此结果可知,本发明的染毛剂不会引起头皮过敏。
Claims (4)
1.一种染毛剂,其同时或分别含有下述组分(1)和下述组分(2):
组分(1):紫草素和/或紫草醌;
组分(2):有机钛化合物和/或有机锆化合物。
2.根据权利要求1所述的染毛剂,其中,
所述组分(2)为选自羟基羧酸类化合物及β-二酮类化合物中的一种或两种以上化合物与钛和/或锆配位而得的络合物。
3.一种染毛方法,其将下述组分(1)和下述组分(2)同时或分别应用于毛:
组分(1):紫草素和/或紫草醌;
组分(2):有机钛化合物和/或有机锆化合物。
4.根据权利要求3所述的染毛方法,其中,
所述组分(2)为选自羟基羧酸类化合物及β-二酮类化合物中的一种或两种以上化合物与钛和/或锆配位而得的络合物。
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