CN102648222B - 用于人工指甲涂料的可去除的彩色层及其制备方法 - Google Patents
用于人工指甲涂料的可去除的彩色层及其制备方法 Download PDFInfo
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- CN102648222B CN102648222B CN201080052134.8A CN201080052134A CN102648222B CN 102648222 B CN102648222 B CN 102648222B CN 201080052134 A CN201080052134 A CN 201080052134A CN 102648222 B CN102648222 B CN 102648222B
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Classifications
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- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
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Abstract
本发明涉及包括底漆、彩色层和面漆的指甲涂料体系。本发明的所述体系可以涂覆于天然的和/或早已存在的人工的指甲涂料上。本发明通常涉及用于天然的和人工的指甲涂料组合物,并且特别是,但并不作为限定方式,本发明涉及可聚合组合物和由此聚合的彩色层。本发明进一步涉及制备聚合彩色层的方法。
Description
技术领域
本发明通常涉及用于指甲涂料的组合物,特别是,但并不作为限定方式,本发明涉及可聚合组合物和由此聚合的彩色层。
背景技术
下面提供的信息不是对本发明的现有技术的认可,而只是用于帮助读者理解。
以指甲涂料和补充剂(extenders)的形式的人工手指甲和脚趾甲组合物是众所周知的并且已成为外观和美容行业中的主要产品线。人的手指甲(在许多情况下也有脚趾甲)外观对许多追逐时尚的个体是很重要的。包括将易碎的指甲表面加固的商用的人工指甲组合物已经用于提升天然指甲的外观而且也用于增强天然指甲的物理性能。
可以将常规天然指甲涂料划分为两类:指甲油(nail polishes)和人工指甲;所述指甲油也称为挥发性漆(lacquers)、清漆(varnish)或者瓷漆(enamels);所述人工指甲也称为凝胶(gels)或者丙烯酸树脂(arylics)。指甲油一般地含有溶解和/或悬浮于非活性溶剂中的各种固体组分。当涂覆并且干燥时,所述固体沉积在指甲表面成为清亮的、半透明的或者彩色的膜。通常,指甲油易于划痕且易于用溶剂来去除,通常在1分钟内如果不能如上所述地去除,那么指甲油将在1-5天内从天然指甲上破裂(chip)掉或者剥离掉。
常规的人工指甲是由化学活性单体和/或低聚物与活性或非活性聚合物结合以创建出通常为100%固体且不需要非活性溶剂的体系。预混合以及随后涂覆到指甲板上,或者涂覆且暴露于紫外线(UV)辐射中时,发生化学反应,结果形成难以去除的、持续时间长的、耐久性长的交联热固性指甲涂料。与指甲油相比,人工指甲具有大大增强的粘合性,耐久性,以及抗划痕和抗溶剂性。然而,因为这些固有的特性,导致这些热固性材料比消费者期望的更加难于去除。通常需要浸泡在非活性溶剂中30-90分钟(对于丙烯酸树脂和目前可得到的“可浸泡的凝胶”;可能需花费90分钟以上也很难用溶剂来去除传统的UV指甲凝胶)来去除,且通常也需要用木质的或金属的探头(probe)猛烈地磨蚀或刮擦表面以助于去除过程。
仍然存在对化妆品的需要,所述化妆品具有增强的热固性材料的粘合性,也具有与指甲油更相似的易去除性。
本发明形成指甲覆盖层体系的一部分,所述指甲覆盖层体系含有底漆粘合层(申请号12/555,571,2009年9月8日提交的发明,目前待审(pending)中)、现有申请、中间物、起装饰作用的彩色层(申请号12/573,633,2009年10月5日提交,目前待审中),以及起保护作用的面漆(申请号12/573,640,2009年10月5日提交,目前待审中)。相互引用每个申请的全部内容到其它的每个申请中以用于所有目的的参考。
从下面的公开中其他的目的和优势将变得显而易见。
发明内容
当与相关公开结合时,本发明方面提供了一种底漆,其特征在于,所述底漆与诱导“解聚”、“速释(quick-release)”特性的溶剂结合在一起牢固地粘附于指甲表面,提供了易去除性。当与相关公开结合时,本发明方面提供了一种彩色层,所述彩色层与诱导“解聚”、“速释”特性的溶剂结合在一起牢固地粘附于聚合物表面,提供了易去除性。当与相关公开结合时,本发明方面提供了一种保护面漆,所述保护面漆与诱导“解聚”、“速释”特性的溶剂结合在一起牢固地粘附到聚合物表面,提供了易去除性。
本发明一方面提供了一种含有由网状物互相贯穿(interpenetrate)的三维(3-D)热固性晶格(lattice)的指甲涂料,所述网状物含有可有机溶剂溶解的树脂(organic solvent dissolvable resin)。根据本发明的一方面,3-D热固性晶格提供了常规人工指甲的增强的粘合性、韧性和抗划痕性。根据本发明的一方面,空隙(voids)间的互连体系和可有机溶剂溶解的树脂的互相贯穿的网状物提供了溶剂的易去除性。
根据一个方面,本发明提供了一种含有至少一种单体,和/或低聚物,和/或聚合成3-D热固性聚合物的液体组合物。根据一个方面,本发明提供了一种含有至少一种可有机溶剂溶解的树脂的液体组合物。根据一个方面,所述可有机溶剂溶解的树脂在3-D热固性晶格中形成内含物的网状物。
根据一个方面,本发明提供了含有一种或多种可加成聚合的(addition-polymerizable)、烯键式不饱和单体(ethylenically-unsaturated monomers)的黏性液体组合物。
根据一个方面,本发明提供了一种赋予所述聚合晶格易去除性的“解聚”性能的单体。根据一个方面,所述单体可以是聚丙二醇-4-单甲基丙烯酸酯(polypropylene glycol-4-monomethacrylate)(PPG4单甲基丙烯酸酯(monomethacrylate))。根据一个方面,适合的单体可以包括聚乙二醇(PEG)或聚丙二醇(PPG)家族中任意的丙烯酸酯(acrylated)或甲基丙烯酸酯(methacrylated)单体。根据一个方面,所述“解聚”单体的含量为约0至约70重量%(wt%)。
根据一个方面,所述液体组合物包括活性单体,和/或低聚物,和/或提供聚合组合物增加的粘合性的聚合物。根据一个方面,所述活性单体,和/或低聚物,和/或聚合物可以是(甲基)丙烯酸酯。正如聚合物领域中的技术人员所知的,所述术语(甲基)丙烯酸酯包含丙烯酸酯和/或甲基丙烯酸酯。
根据一个方面,所述活性单体,和/或低聚物,和/或聚合物可以选自由甲基丙烯酸羟乙酯(hydroxyethylmethacrylate,HEMA)、甲基丙烯酸羟丙酯(hydroxypropylmethacrylate,HPMA)、甲基丙烯酸乙酯(ethyl methacrylate,EMA)、甲基丙烯酸四氢糠酯(tetrahydrofurfuryl methacrylate,THFMA)、苯均四酸二酐二甲基丙烯酸酯(pyromellitic dianhydride di(meth)acrylate)、苯均四酸二酐丙三基二甲基丙烯酸酯(pyromellitic dianhydride glyceryldimethacrylate)、1,2,4,5-苯四二甲基丙烯酸酯(pyromellitic dimethacrylate)、甲基丙烯酰氧乙基马来酸酯(methacroyloxyethyl maleate)、2-羟乙基甲基丙烯酸酯/琥珀酸酯(2-hydroxyethyl methacrylate/succinate)、1,3-丙三醇二甲基丙烯酸酯/琥珀酸酯加合物(1,3-glycerol dimethacrylate/succinate adduct)、邻苯二甲酸一乙基甲基丙烯酸酯(phthalic acid monoethyl methacrylate)、乙酰乙酸基甲基丙烯酸乙酯(acetoacetoxy ethyl methacylate,AAEMA)以及它们的混合物组成的组。根据一个方面,所述活性单体,和/或低聚物,和/或聚合物可以具有酸性功能。根据一个方面,所述单体、低聚物或提供聚合组合物增加的粘合性的聚合物的含量为约0至约50重量%。
本发明的一方面提供了一种含有非活性的、可溶剂溶解的聚合物的可聚合液体组合物。根据一个方面,所述非活性的、可溶剂溶解的聚合物是纤维素酯(cellulose ester)。根据特定的一个方面,所述非活性的、可溶剂溶解的聚合物是乙酸纤维素烷基化物(cellulose acetate alkylate)。根据更特定的一个方面,所述非活性的、可溶剂溶解的聚合物是乙酸丁酸纤维素(celluloseacetate butyrate)或者乙酸丙酸纤维素(cellulose acetate propionate)。根据进一步的一个方面,为易去除而提供的成分含量可以为约0.1至约75重量%。
根据本发明的一个方面,所述彩色层组合物可以含有达到10重量%的颜料和/或染料。
本发明的一个方面提供了一种去除的方法。根据一个方面,提供了对有机溶剂,尤其是,对丙酮敏感的由所公开的组合物聚合得到的所述热固性可聚合组合物。根据所公开的一个方面,提供了将有机溶剂分布到聚合物/天然指甲界面的方法。根据一个方面,将合适的溶剂导出到聚合物/天然指甲界面会导致解聚作用,所述解聚作用导致粘合剂的粘结界面快速瓦解且极为有利于快速而温和地从天然指甲上去除。
通过下面详细的描述,对本领域技术人员而言本发明的其他的观点和优势将变得显而易见,其中,通过阐述实施本发明的最好的实施例简单地表明和描述了本发明的优选实施方式。所能认识到的是本发明能够有其他的和不同的实施方式,并且,在不偏离本发明的情况下,本发明的一些细节能够在各种明显的方面上进行修改。因此,所描述的应看作是自然而非受限定的阐述。
具体实施方式
指甲涂料通常由应用于角质化(keratin)的指甲表面的材料组成。现有技术的涂料可以至少通过两种机理损伤指甲。第一,天然指甲增强物的充分粘合可能需要磨蚀以使指甲表面变粗糙。第二,增强物的去除可能需要长时间暴露在可能有害的溶剂中和/或所述人工指甲表面的进一步磨蚀。
本发明的实施方式提供了一种含有由网状物互相贯穿的三维(3-D)热固性晶格的指甲涂料,所述网状物含有可有机溶剂溶解的树脂。根据本发明的一方面,3-D热固性晶格提供了常规人工指甲的增强的粘合性、韧性以及抗划痕性。根据一种实施方式,底漆介于所述天然指甲表面和所存在的彩色层之间。
所述术语“指甲”和“指甲表面”是指天然的、角质化的指甲表面,或者粘结有预先形成的人工指甲或指甲末端的天然指甲。换句话说,可以将本发明的可聚合组合物直接应用到所述天然指甲的角质化的表面上,或者应用到粘结有预先形成的人工指甲或指甲末端增强物的指甲表面上。
本发明含有的可聚合组合物用于涂覆指甲并由此聚合以产生人工指甲结构。所述可聚合组合物优选为无水液体,所述无水液体的稠度在室温下介于半流动性凝胶至自由流动液体之间。在立即使用之前,将所述可聚合组合物应用到所述指甲表面并由指甲技师将所述可聚合组合物成形。聚合之后得到人工指甲结构。
所述液体组合物的实施方式含有活性单体、和/或低聚物、和/或提供可聚合组合物增加粘合性的聚合物。在某种实施方式中,所述活性的单体、和/或低聚物、和/或聚合物可以是(甲基)丙烯酸酯。正如在聚合物领域中的技术人员所公知的,所述术语(甲基)丙烯酸酯包含丙烯酸酯和/或甲基丙烯酸酯。根据一个方面,所述活性单体、和/或低聚物、和/或聚合物可以选自由甲基丙烯羟丙酯(HPMA)、甲基丙烯酸羟乙酯(HEMA)、甲基丙烯酸乙酯(EMA)、甲基丙烯酸四氢糠酯(THFMA)、苯均四酸二酐二甲基丙烯酸酯、苯均四酸二酐丙三基二甲基丙烯酸酯、1,2,4,5-苯四二甲基丙烯酸酯、甲基丙烯酰氧乙基马来酸酯、2-羟乙基甲基丙烯酸酯/琥珀酸酯、1,3-丙三醇二甲基丙烯酸酯/琥珀酸酯加合物、邻苯二甲酸一乙基甲基丙烯酸酯、乙酰乙酸基甲基丙烯酸乙酯(AAEMA)以及它们的混合物组成的组。根据一个方面,所述活性单体、和/或低聚物、和/或聚合物可以具有酸性功能。根据一个方面,所述单体、低聚物或提供聚合组合物增加的粘合性的聚合物含量约0至约50重量%。
所述烯键式不饱和反应物可以为单、双、三或多官能的作为可加成聚合的烯键。很多种烯键式不饱和反应物是适合的,只要所述反应物在暴露于适当的色质时能够聚合而产生聚合的人工指甲结构。适合的烯键式不饱和反应物在美国专利6,818,207中公开,引入美国专利6,818,207以作参考。
所述液体组合物的某种实施方式至少含有一种通过使所述界面粘结对有机溶剂敏感以赋予所述“解聚”性能的单体。根据一个方面,所述至少一种单体可以是聚丙二醇-4-单甲基丙烯酸酯(PPG-4单甲基丙烯酸酯)。根据一个方面,适合的单体可以包括PPG或聚乙二醇(polyethylene glycol,PEG)家族中任意的丙烯酸酯或甲基丙烯酸酯单体。根据一个方面,所述“解聚”单体的含量可以为约0至约70重量%。
本发明的一种实施方式提供了一种可聚合的液体组合物,所述可聚合的液体组合物含有提供改进的粘合性、粘度、耐磨性和耐久性的甲基丙烯酸酯单体。在某种实施方式中,所述甲基丙烯酸酯单体是甲基丙烯酸四氢糠酯。在其它的实施方式中,部分或全部所述甲基丙烯酸四氢糠酯可以由单体取代,所述单体包括,但并不限定于甲基丙烯酸乙酯(EMA)、甲基丙烯酸羟丙酯(HPMA)和其他单体例如苯均四酸二酐丙三基二甲基丙烯酸酯,和类似的(甲基)丙烯酸酯单体。甲基丙烯酸酯单体可以为约0至约70重量%。
本发明的可聚合液体组合物的某些实施方式可以含有可提供柔韧性和硬度给聚合产品的(甲基)丙烯酸聚氨酯树脂(urethane (meth)acrylate resin)。在某些实施方式中,优选甲基丙烯酸聚氨酯。所述(甲基)丙烯酸聚氨酯单体的含量可以为约0至约50重量%。在某些实施方式中,所述(甲基)丙烯酸聚氨酯的分子量(克/摩尔)可以为约100至约20,000。在某些实施方式中,所述(甲基)丙烯酸聚氨酯的重均分子量可以为约300至约15,000。在某些实施方式中,所述(甲基)丙烯酸聚氨酯的分子量可以为约500至约13,000。在某些实施方式中,所述(甲基)丙烯酸聚氨酯可以具有的分子量约500至约6,000。
在本发明的某些实施方式中,所述3-D热固性晶格被非活性溶剂释放留下的空隙间的网状物互相贯穿。在固化过程中,在交联聚合物基质(matrix)中形成非活性、可有机溶剂溶解的树脂的区域(domains)。当想要去除指甲覆盖物时,所述聚合物暴露于溶剂中,所述溶剂渗入空隙间的网状物到可有机溶剂溶解的树脂的区域中。所述树脂的溶解允许溶剂进一步渗入到所述热固性材料的内部并且也渗入到所述底漆/彩色层界面处。
本发明的可聚合液体组合物的某些实施方式可以含有非活性的、可溶剂溶解的聚合物。根据一个方面,所述非活性的、可溶剂溶解的聚合物是纤维素酯。根据特定的一个方面,所述非活性的、可溶剂溶解的聚合物是乙酸纤维素烷基化物。根据更特定的一个方面,所述非活性的、可溶剂溶解的聚合物是乙酸丁酸纤维素或乙酸丙酸纤维素。所述非活性的、可溶剂溶解的聚合物可以是任意可采用的非活性的、可溶剂溶解的聚合物的混合物。根据进一步的一个方面,所述非活性的、可溶剂溶解的聚合物的含量可以为约0.1至约75重量%。
根据某些实施方式,所述彩色层进一步含有至少一种流变改性剂(rheology modifying agent)。在某些实施方式中,所述流变改性剂的含量达到10重量%。在某些实施方式中,所述流变剂可以为所述组合物提供触变性能以使颜料粒子处于悬浮状态。在某些实施方式中,所述流变剂可以为热解法二氧化硅。在某些实施方式中,所述流变剂可以为聚酰胺。
本发明的所述组合物可以含有约塑化剂(plasticizer)的0.001-5重量%。所述塑化剂促使所述聚合的指甲结构具有改善的柔韧性并降低易碎性。适合的塑化剂可以为酯,低挥发性溶剂或非离子材料例如非离子有机表面活性剂或(聚)硅氧烷。
适合的酯具有一般结构RCO-OR′,其中,RCO--代表羧酸基,而--OR′为醇残留物(residue)。优选R和R′为具有6-30个碳原子并且可以为饱和或不饱和的脂肪基(fatty radicals)。适合的酯的实例是1997年第七版C.T.F.A.化妆品成分字典和手册(C.T.F.A.Cosmetic Ingredient Dictionary andHandbook)中1558至1564页列出的那些,引入本文以作参考。在本发明的优选组合物中,所述塑化剂为化学式为RCO--OR′的酯,其中,每个R和R′各自为直链或支链的C6-30烷基。一种适合的塑化剂为异硬脂醇异壬酸酯(isostearyl isononanoate)。其他适合的塑化剂在美国专利6,818,207中公开,引入美国专利6,818,207以作参考。
根据某些实施方式,所述彩色层进一步含有至少一种紫外线稳定剂。在某些实施方式中,所述紫外线稳定剂的含量达到2重量%。
本发明的所述组合物可以含有一种或多种紫外线吸收剂,所述紫外线吸收剂帮助降低在人工指甲中常见的发黄。紫外线吸收剂具有将入射的紫外线辐射转化成损害较小的红外线(热量)或可见光的能力。推荐的紫外线吸收剂的量为组合物总量的0.001-5重量%。适合的紫外线吸收剂包括羟基苯并三唑(hydroxy benzotriazole)化合物和苯(甲)酮(benzophenone)化合物,例如在美国专利6,818,207中公开,引入美国专利6,818,207以作参考。
可以适当的含有一种或多种聚合调节剂。聚合调节剂帮助防止单体组合屋的聚合发生的太快。氢醌(Hydroquinone)和类似材料为合适的聚合调节剂。聚合调节剂的建议范围为组合物总重量的约0.0001-5重量%。合适的聚合调节剂为美国专利6,818,207公开的,引入以作参考。
没有被理论束缚,本发明的发明人通过促进溶剂进入到所述涂料的内部来使指甲覆盖物易于去除。常规的可聚合指甲涂料通过表面摩擦随后长时间(30-90分钟)地暴露于有机溶剂而会削弱。所述溶剂在所述热固性材料的外表面处和边缘处缓慢地渗入并最终使所述涂料膨胀。所述膨胀最终使整体基质结构削弱,同时使所述指甲表面的粘结性瓦解。即便较弱附着的指甲涂料可能需要磨蚀以增强溶剂贯穿和加速去除。然而,溶剂扩散到所述热固性材料中的低速率限制了膨胀速率。
本发明提供了一种通过可溶剂溶解的通道和内含物(solvent-dissolvablechannels and inclusions)的网状物互相贯穿的3-D热固性材料。当暴露于有机溶剂时,所述纤维素酯或其他非活性的、可溶于有机溶剂中的聚合物在所述涂料中溶化并浸出。结果是在整个热固性材料中布满一系列溶剂可通过的通道。在这种条件下,溶剂可以进攻到所述热固性材料的内部,而不再受扩散速率慢的束缚。
本发明的可聚合组合物的某些实施方式可以为黏性凝胶或液体。凝胶或液体实施方式可以通过暴露于辐射能量例如热量、可见光、紫外线或电子束辐射中来聚合。将液体或凝胶实施方式应用到指甲并且可以形成期望的形状。将涂覆的指甲暴露到辐射能量中,然后发生聚合。
所发明的组合物可以通过光化辐射(actinic radiation)聚合。所述光化辐射可以为可见光、紫外线或电子束辐射。所述紫外线辐射特征在于可以是某一波长或一段波长,但是不限于约320至约420纳米。
所述液体组合物涂覆到表面,特别是底漆表面之后,所述液体固化。所述液体组合物含有可以通过紫外光引发(UV-initiated)、自由基聚合方法固化的烯键式不饱和甲基丙烯酸酯(ethylenic unsaturated(meth)acrylates)。聚合领域的技术人员为使用本发明可容易地决定适合的光引发剂。下面阐明的是适合本发明目的的没有限定的有代表性的光引发剂。
没有限定的适合的光引发剂是2,4,6-三甲基苯甲酰基二苯基亚磷衍生物(2,4,6-trimethylbenzoyldiphenylphosphorous derivative),适合的衍生物为乙基-2,4,6-三甲基苯甲酰基二苯基亚膦酸酯(ethyl-2,4,6-trimethylbenzoyl-diphenylphosphinate),它可以以商品名(巴斯夫股份有限公司,路德维希港,德国)(BASF Aktiengesellschaft,Ludwigshafen,DE)获得。另一种非限定的适合的衍生物为2,4,6-三甲基苯甲酰基二苯基氧化膦(2,4,6-trimethylbenzoyldiphenyl phosphine oxide),它可以以商品名(BASF)或作为TPO(拉恩,Rahn)获得。所述2,4,6-三甲基苯甲酰基二苯基亚膦酸酯光引发剂的含量可以为约0%至约20重量%。
非限定性的适合的光引发剂是羟基环己基苯基酮(hydroxycyclohexylphenyl ketone),可以以商品名获得且其含量可以为约0至约20重量%。
非限定性的适合的光剂是苄基二甲醛缩苯乙酮(benzil dimethyl ketal,BDK),可以以商品名(雅保,巴吞鲁日,路易斯安那州,美国)(Albemarle,Baton Rouge,LA,US)获得且其含量可以为约0至约20重量%。
本发明彩色层的某些实施方式可以含有达到10重量%的颜料和/或染料。本发明的实施方式中相关底漆和面漆可以具有达到1重量%的颜料和/或染料。颜料和/或染料的高浓度可以吸收紫外线辐射。因此为了补偿,本发明的某些实施方式可以含有达到20重量%的更高浓度的光引发剂。
常规的热固性指甲涂料含有100%的固体并且不含有非活性溶剂。本发明的可聚合液体组合物进一步含有至少一种非活性溶剂。适合的非活性溶剂在室温下易于挥发并且是保留成分的良溶剂。当应用时,所述非活性溶剂易于挥发留下逐渐增加的多孔性区域。这些多孔性区域随后便于去除溶剂进入,所述去除溶剂可以是丙酮。
适合的非活性溶剂包括但并不限定于酮、乙酸烷基酯(alkyl acetates)、醇、烷烃、烯烃以及它们的混合物。适合的非活性溶剂可以选自由丙酮、乙酸乙酯、乙酸丁酯、异丙醇、乙醇、甲基乙基酮、甲苯、己烷以及它们的混合物组成的组。特别地,适合的非活性溶剂是丙酮。通常地,非活性溶剂或者非活性溶剂混合物含量达到约70重量%。
为了精细调整粘合性和去除性能,配方(formulation)的某些实施方式可选择性地含有(甲基)丙烯酸酯单体和/或聚合物。所述(甲基)丙烯酸酯的非限定性实例包括:(甲基)丙烯酸酯或聚(甲基)丙烯酸酯、甲基丙烯酸羟丙酯(HPMA)、甲基丙烯酸羟乙酯(HEMA)、苯均四酸二酐二甲基丙烯酸酯、苯均四酸二酐丙三基二甲基丙烯酸酯、1,2,4,5-苯四二甲基丙烯酸酯、甲基丙烯酰氧乙基马来酸酯、2-羟乙基甲基丙烯酸酯/琥珀酸酯、1,3-丙三醇二甲基丙烯酸酯/琥珀酸酯加合物、邻苯二甲酸一乙基甲基丙烯酸酯、甲基丙烯酸乙酯、甲基丙烯酸四氢糠酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯(isobutyl methacrylate)、PEG-4二甲基丙烯酸酯(PEG-4 dimethacrylate)、PPG单甲基丙烯酸酯(PPG monomethacrylate)、三羟甲基丙烷三甲基丙烯酸酯(trimethylolpropane trimethacrylate)、甲基丙烯酸羟乙酯(hydoxyethylmethacrylate)、异亚丙基二苯基双缩水甘油基甲基丙烯酸酯(isopropylidenediphenyl bisglycidyl methacrylate)、甲基丙烯酸月桂酯(laurylmethacrylate)、甲基丙烯酸环己酯(cyclohexyl methacrylate)、甲基丙烯酸己酯(hexyl methacrylate)、甲基丙烯酸聚氨酯(urethane methacrylate)、甲基丙烯酸羟丙酯(hydroxypropylmethacrylate)、三乙二醇二甲基丙烯酸酯(triethylene glycol dimethacrylate)、二甲基丙烯酸乙二醇酯(ethylene glycoldimethacrylate)、四甘醇二甲基丙烯酸酯(tetraethylene glycol dimethacrylate)、三羟甲基丙烷三甲基丙烯酸酯(trimethylolpropane trimethacrylate)、新戊二醇二甲基丙烯酸酯(neopentylglycol dimethacylate)、乙酰乙酸基甲基丙烯酸乙酯(acetoacetoxy ethyl methacylate,AAEMA)以及它们的混合物。
配方的某些实施方式可以可选择性地含有树脂,例如,但没有限定为聚乙烯醇缩丁醛(polyvinylbutyral)和/或对甲苯磺酰胺甲醛(tosylamideformaldehyde)树脂。这些树脂也可以起膜成型剂、粘合促进剂(adhesionpromoters)以及去除剂的作用。这些树脂也可以作为可溶剂溶解的树脂,所述树脂能够被萃取出以创建用于溶剂吸收和迁移的通道。
配方的某些实施方式可以可选择性地含有塑化剂,例如,但并不限定于己二酸二异丁酯。塑化剂作用为将暴露于紫外线太阳光和空气后随后形成的聚合物的脆性最小化。还发现塑化剂能轻微缩短去除时间。塑化剂的含量可以为0至约25重量%。聚合领域的技术人员可以领会到含有的塑化剂在上述某限定内是不良的,因为它们可能减少(impare)所述涂料的完整性和耐久性。
所述未聚合的彩色层可以有液体或凝胶的稠度。所述未聚合的彩色层可以被涂覆在聚合的底漆表面上。在一种实施方式中,所述聚合的底漆可以是共待审(co-pending)(代理案件(Attorney Docket)017535-0376694)中的实施方式。所述聚合的底漆可以被涂覆在指甲表面上且与彩色层接触。所述指甲表面-底漆-彩色层体系可以暴露于紫外线辐射中。所述底漆和彩色层可以聚合从而将所述彩色层粘合到所述指甲表面上。
在一种实施方式中,没有磨蚀所述人工指甲表面,可以将彩色层从所述天然指甲表面上去除掉。
与常规的指甲涂料相对比,本发明涉及的主要优势在于本发明能够使持久的彩色层粘合到天然指甲上超过两周而且所述涂料没有破裂。与常规涂料相对比,本发明涉及对指甲无损伤的紫外线凝胶体系,因为所述涂覆过程不需要对天然指甲进行磨蚀锉屑。并且所述去除过程至多需要使用木签轻微地触碰。而且,与常规体系比较中,本发明涉及可更快速地去除的指甲涂料体系,所述指甲涂料体系可以对于用20分钟去除整个体系的情况下只用20秒即可去除底漆。
本发明的可聚合底漆可以借助氢键粘合到角质化的指甲表面上。借助有机溶剂方式可以将所述底漆和彩色层从指甲表面上去除。非限定性的溶剂包括丙酮、乙酸丁酯、异丙醇、乙醇、乙酸乙酯、甲基乙基酮以及它们的混合物。
实施例1:耐化学性测试
根据本发明比较商业磨光面漆配方(commercial polish topcoatformulation)和商业增强型面漆配方(commercial enhancement type topcoatformulation)以对比面漆配方的耐化学性。除了用丙酮代替甲基乙基酮之外,我们采用常规的甲基乙基酮双摩擦测试(MEK double rub test)。在玻璃显微镜片上制备每种配方的薄膜。形成的每种膜湿厚为5毫升。通过将商业增强型配方和本发明的配方使用BrisaTM灯暴露于紫外光下而固化。使用99重量%的异丙醇擦拭非常薄、未聚合的发黏的(tacky)顶层使其干燥。所述磨光配方没有固化,但在外界条件下干燥。所有样本在外界光和温度条件下持续24小时发生老化。下面老化中的每个样品分别用浸入99重量%丙酮中的化妆棉擦拭。所述磨光配方通过两次擦拭后完全去除掉。本发明的配方通过两次擦拭后变得模糊(dulled),但是残留的未受损伤的(intact)至少需要150次擦拭。所述增强的配方残留的反光的(shiny)并且未受损伤的至少需要200次擦拭。
实施例2:铅笔硬度测试
为了测试耐划痕性,我们记录出现凹痕测试样品最软“H”型铅笔的制备如实施例1给出的一样。我们也记录所述最软“H”型铅笔能够撕开测试膜。所述磨光配方分别被3H铅笔压出凹痕并被4H铅笔撕裂。本发明的配方分别被3H铅笔压出凹痕并被6H铅笔撕裂。所述增强的配方被4H铅笔压出凹痕但是即使通过最硬的铅笔(6H)也没有被撕裂。这个测试表明本发明比所述指甲磨光配方具有明显更好的抗划痕性。
工业应用
本发明提供的组合物及其方法具有工业化使用性,所述组合物及其方法用于改进指甲涂料和天然指甲之间的粘合性,不需要对所述天然指甲进行磨蚀。本发明进一步提供了用于去除指甲涂料的方法,所述方法不需要对所述天然指甲表面进行延长在溶剂中的浸泡时间或磨蚀。
Claims (31)
1.一种可聚合组合物,所述可聚合组合物含有:
至少一种可加成聚合的烯键式不饱和单体;
至少一种(甲基)丙烯酸聚氨酯树脂;
至少一种增塑剂,该增塑剂具有通式结构RCO-OR′,其中RCO-表示羧酸基,-OR′为醇的残基,并且R和R′为具有6-30个饱和或不饱和的碳原子的脂肪基;
至少一种非活性的、可溶剂溶解的聚合物,以及
至少一种非活性溶剂;
其中,当暴露于聚合促进源时,所述可聚合组合物固化为其中限定有空隙的丙烯酸热固性材料。
2.根据权利要求1所述的可聚合组合物,其中,所述聚合促进源选自由热传导和/或辐射、可见光辐射、紫外线辐射、电子束辐射、胺、过氧化物以及它们的组合物组成的组。
3.根据权利要求1所述的可聚合组合物,其中,所述至少一种非活性的、可溶剂溶解的聚合物为纤维素酯。
4.根据权利要求3所述的可聚合组合物,其中,所述纤维素酯为乙酸纤维素烷基化物。
5.根据权利要求4所述的可聚合组合物,其中,所述乙酸纤维素烷基化物选自由乙酸丁酸纤维素、乙酸丙酸纤维素以及它们的混合物组成的组。
6.根据权利要求1所述的可聚合组合物,其中,所述至少一种非活性的、可溶剂溶解的聚合物的含量为5重量%至70重量%。
7.根据权利要求1所述的可聚合组合物,其中,所述至少一种非活性的、可溶剂溶解的聚合物的含量为10重量%至60重量%。
8.根据权利要求1所述的可聚合组合物,其中,所述至少一种非活性的、可溶剂溶解的聚合物的含量为20重量%至50重量%。
9.根据权利要求1所述的可聚合组合物,其中,所述可聚合组合物进一步含有促进粘结的(甲基)丙烯酸酯。
10.根据权利要求9所述的可聚合组合物,其中,所述促进粘结的(甲基)丙烯酸酯选自由甲基丙烯酸四氢糠酯、甲基丙烯酸乙酯、甲基丙烯酸羟丙酯、苯均四甲酸二酐丙三基二甲基丙烯酸酯以及它们的混合物组成的组。
11.根据权利要求1所述的可聚合组合物,其中,所述可聚合组合物进一步含有苯均四甲酸丙三基二甲基丙烯酸酯。
12.根据权利要求1所述的可聚合组合物,其中,所述可聚合组合物进一步含有至少一种着色剂。
13.根据权利要求12所述的可聚合组合物,其中,所述至少一种着色剂的含量达到10重量%。
14.根据权利要求12所述的可聚合组合物,其中,所述至少一种着色剂选自由颜料和染料组成的组。
15.根据权利要求1所述的可聚合组合物,其中,所述可聚合组合物进一步含有至少一种流变剂。
16.根据权利要求15所述的可聚合组合物,其中,所述至少一种流变剂为热解法二氧化硅。
17.根据权利要求16所述的可聚合组合物,其中,所述热解法二氧化硅的表面用聚二甲基硅氧烷改性。
18.根据权利要求15所述的可聚合组合物,其中,所述至少一种流变剂为聚酰胺。
19.根据权利要求15所述的可聚合组合物,其中,所述至少一种流变剂的含量达到10重量%。
20.根据权利要求1所述的可聚合组合物,其中,所述至少一种(甲基)丙烯酸聚氨酯具有以g/mol计100至20000的分子量。
21.根据权利要求20所述的可聚合组合物,其中,所述至少一种(甲基)丙烯酸聚氨酯具有200至10000的分子量。
22.根据权利要求20所述的可聚合组合物,其中,所述至少一种(甲基)丙烯酸聚氨酯具有300至5000的分子量。
23.根据权利要求20所述的可聚合组合物,其中,所述至少一种(甲基)丙烯酸聚氨酯具有300至1000的分子量。
24.根据权利要求1所述的可聚合组合物,其中,所述至少一种非活性溶剂选自由酮、乙酸烷基酯、醇、烷烃、烯烃以及它们的混合物组成的组。
25.根据权利要求24所述的可聚合组合物,其中,所述至少一种非活性溶剂选自由丙酮、乙酸乙酯、乙酸丁酯、异丙醇、乙醇、甲基乙基酮、甲苯、己烷以及它们的混合物组成的组。
26.根据权利要求24所述的可聚合组合物,其中,所述至少一种非活性溶剂为丙酮。
27.根据权利要求1所述的可聚合组合物,其中,所述至少一种非活性溶剂的含量达到70重量%。
28.根据权利要求1所述的可聚合组合物,其中,所述可聚合组合物进一步含有至少一种光引发剂。
29.根据权利要求28所述的可聚合组合物,其中,所述至少一种光引发剂选自由苯甲酰基苯基亚膦酸酯、环己基苯基酮、苯甲基缩酮以及它们的混合物组成的组。
30.根据权利要求28所述的可聚合组合物,其中,所述至少一种光引发剂选自由2,4,6-三甲基苯甲酰基二苯基亚膦酸酯、羟基环己基苯基酮、苄基二甲醛缩苯乙酮以及它们的混合物组成的组。
31.根据权利要求28所述的可聚合组合物,其中,所述至少一种光引发剂的含量达到20重量%。
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US12/573,633 US8492454B2 (en) | 2009-10-05 | 2009-10-05 | Removable color layer for artificial nail coatings and methods therefore |
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PCT/US2010/047171 WO2011043880A1 (en) | 2009-10-05 | 2010-08-30 | Removable color layer for artificial nail coatings and methods therefore |
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- 2010-08-30 IN IN3004DEN2012 patent/IN2012DN03004A/en unknown
- 2010-08-30 KR KR1020127011613A patent/KR20120100972A/ko not_active Application Discontinuation
- 2010-08-30 RU RU2012116778/05A patent/RU2560249C2/ru not_active IP Right Cessation
- 2010-08-30 MX MX2012004069A patent/MX2012004069A/es active IP Right Grant
- 2010-08-30 JP JP2012533182A patent/JP5851407B2/ja active Active
- 2010-08-30 CN CN201080052134.8A patent/CN102648222B/zh not_active Expired - Fee Related
- 2010-08-30 EP EP10751752A patent/EP2486068A1/en not_active Ceased
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2012
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- 2012-04-05 CL CL2012000890A patent/CL2012000890A1/es unknown
- 2012-04-13 CR CR20120178A patent/CR20120178A/es unknown
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US20110081306A1 (en) | 2011-04-07 |
IL219077A (en) | 2016-04-21 |
WO2011043880A1 (en) | 2011-04-14 |
US20140050682A1 (en) | 2014-02-20 |
AU2010303836B2 (en) | 2015-08-13 |
EP2486068A1 (en) | 2012-08-15 |
MA33653B1 (fr) | 2012-10-01 |
IL219077A0 (en) | 2012-06-28 |
RU2012116778A (ru) | 2013-11-10 |
US20120083547A1 (en) | 2012-04-05 |
CR20120178A (es) | 2012-11-09 |
ZA201202507B (en) | 2014-06-25 |
CA2776961C (en) | 2017-07-11 |
US20150044151A1 (en) | 2015-02-12 |
IN2012DN03004A (zh) | 2015-07-31 |
JP2013506710A (ja) | 2013-02-28 |
RU2560249C2 (ru) | 2015-08-20 |
BR112012007773A2 (pt) | 2017-08-29 |
MX2012004069A (es) | 2012-06-28 |
US8492454B2 (en) | 2013-07-23 |
US8367742B2 (en) | 2013-02-05 |
CL2012000890A1 (es) | 2012-09-07 |
CN102648222A (zh) | 2012-08-22 |
CA2776961A1 (en) | 2011-04-14 |
KR20120100972A (ko) | 2012-09-12 |
AU2010303836A1 (en) | 2012-05-10 |
JP5851407B2 (ja) | 2016-02-03 |
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