CN114430678B - 包含六偏磷酸盐和颜料的口腔护理组合物 - Google Patents
包含六偏磷酸盐和颜料的口腔护理组合物 Download PDFInfo
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- CN114430678B CN114430678B CN202080066501.3A CN202080066501A CN114430678B CN 114430678 B CN114430678 B CN 114430678B CN 202080066501 A CN202080066501 A CN 202080066501A CN 114430678 B CN114430678 B CN 114430678B
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- hexametaphosphate
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- A—HUMAN NECESSITIES
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
- A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
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- Animal Behavior & Ethology (AREA)
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Abstract
本发明涉及口腔护理组合物，其包含：(a)具有以下结构的聚合物，(I)
Description
技术领域
本发明涉及用于最小化牙齿沾污的口腔护理组合物。
背景技术
消费者对牙齿的持久增白相当感兴趣。食物和饮料如茶、咖啡和葡萄酒通过将色原直接沉积在牙齿表面上会形成牙渍。物质对牙齿表面的吸附在外源性牙齿沾污的沉积中起到关键作用。这些饮料中导致引起牙齿沾污的色原已知为单宁并且是由多酚类如儿茶素组成。这些物质由于共轭双键的存在而产生颜色。
传统的牙齿增白方法要么涉及来自试剂盒形式的过氧化物漂白，要么涉及来自牙膏形式的研磨去除沾污。这些颗粒本质上是不溶性颗粒，当用刷子施加时，这些颗粒通过研磨从牙齿的表面去除外源性沾污。本发明涉及新型口腔护理组合物，其递送有效水平的沾污防护并且通过防止牙齿沾污而延长牙齿增白的效果。本发明公开了斥沾污涂层，其具有以限定的比率所协同掺合的亲水性-疏水性嵌段共聚物与Ca2+螯合剂(磷酸盐)。这有助于在增白处理之后摄入食物/饮料的期间在牙齿表面上提供保护性防沾污涂层。
本发明中所使用的嵌段共聚物是通常已知为Pluronic的物质。通常，这些聚合物已知用于口腔护理。本发明中所使用的磷酸盐是也已用于口腔护理的六偏磷酸盐。
US2014377194A(P&G)公开了口腔护理组合物，其含有(a)柠檬酸锌；和(b)表面活性有机磷酸酯化合物。并且它还涉及预防沾污沉积在牙齿表面或其它口腔表面上的方法。
US2003124065A(P&G)公开了用于总体清洁、增白和防止、减少或去除在自然牙齿与口腔假体上所表面沉积的沾污的口腔护理组合物和方法，该组合物在口腔可接受的载体中包含至少0.1wt％的水溶性或水分散性共聚物，该共聚物通过共聚合乙烯基吡咯烷酮(VP)单体中的一种或混合物与C1-C19烷基羧酸(AC)C2-C12链烯基酯单体中的一种或混合物来制备。优选地，这些组合物另外包含其它口腔护理剂中的一种或混合物，该其它口腔护理剂选自：水溶性的三聚磷酸的碱金属或铵盐，其量以该组合物的重量计为至少约0.5wt％；研磨剂，优选沉淀二氧化硅研磨剂，其量以该组合物的重量计为至少约6wt％；和漂白剂，其量以该组合物的重量计为至少约0.1wt％。
因此，本发明的目的之一是提供最小化牙齿沾污的口腔护理组合物。
发明内容
根据本发明的第一个方面，提供了口腔护理组合物，所述组合物包含：
(a)具有以下结构的聚合物，
其中a独立地选自2至130，且b为15至67，并且所述聚合物的分子量为1,700Da至15,000Da；
(b)六偏磷酸盐；
(c)Covarine蓝(blue covarine)；和
(d)口腔可接受的基质；
其中所述聚合物与六偏磷酸盐的重量比为1:5至5:1。
根据本发明的另一个方面，提供了最小化或预防牙齿沾污的方法，所述方法包括将上述本发明的组合物施加至牙齿上的步骤。
本发明的另外一个方面涉及根据前述权利要求中的任意一项的组合物的用于缓解牙齿沾污的美容用途。
具体实施方式
除了在实施例中或其他明确指出的情况，在本说明书中表示物质的量或反应条件、物质的物理性质和/或用途的所有数值可以任选地理解为由“约”修饰。
除非另有指定，否则所有的量均以最终组合物的重量计算。
应该注意的是，在具体说明数值的任何范围时，任何特定的上限值都可以与任何特定的下限值相关联。
如本文所示的本发明的公开内容被认为涵盖了在彼此多项引用的权利要求中所限定的所有实施方案，而不论这些权利要求可能没有多项引用或冗余的事实。
在关于本发明某一特定方面(例如本发明的组合物)的特征被公开了的情况下，这种公开也被认为作必要修改后适用于本发明的任何其他方面(例如本发明的方法)。
本发明涉及口腔护理组合物，其包含具有式1的化合物结构的聚合物：
在上述化合物中，乙氧基化物基团与丙氧基化物基团的分子量比率为0.1至3.0，优选地0.1至2.5。所述聚合物的分子量为1,700Da至15,000Da，优选地10,000Da至13,000Da。本发明优选地需要具有以上结构的含有EO和PO(丙氧基化物)两部分的聚合物。所述聚合物的乙氧基化物(EO)部分的量以总聚合物计优选地为10％至80％，更优选地10％至60％。优选地用于本发明的组合物中的市售聚合物包括Pluronic L-61、Pluronic F88、Pluronic F77、Pluronic F108或Pluronic 127，更优选地Pluronic 127。所述聚合物的量以总组合物的重量计优选地以0.05wt％至4wt％，更优选地0.1wt％至3wt％，最优选地0.1wt％至2wt％的量存在。
本发明的组合物包含磷酸盐化合物，即六偏磷酸盐。六偏磷酸钠具有如下给出的结构：
所述六偏磷酸盐以总组合物的重量计优选地以0.1wt％至4wt％，更优选地0.1wt％至2.0wt％的量包含在本发明的总组合物中。
根据本发明，要求的是式1的聚合物与六偏磷酸盐的重量比为1:5至5:1，更优选地1:4至4:1。在优选的方面中，这个比率为1:3至3:1。特别优选的是，式1的聚合物与六偏磷酸盐的重量比大于1:1。
优选的是，本发明的组合物中的聚合物和六偏磷酸盐的总量以总组合物的重量计为0.1wt％至5wt％。
本发明中所使用的颜料包括酞菁蓝颜料，CI编号74160，Covarine蓝。
优选地，Covarine蓝与聚合物(a)的重量比为5:100至1:1,000，更优选地3:200至1:500。
所述总组合物中的颜料，特别是以上提及的颜料，尤其是Covarine蓝的量，为0.0005wt％至0.5wt％，更优选0.001wt％至0.1wt％，最优选0.007wt％至0.014wt％。
重量百分比是指存在的活性物质的总量，并且排除可能存在的任意载体。
根据本发明的组合物可以是任意口腔可接受的形式，例如牙膏、漱口剂、喷雾、片剂、面膜(mask)或浆液，然而喷雾和牙膏是优选的。
本发明的组合物包含口腔可接受的基质。所述口腔可接受的基质优选地包括保湿剂、水、挥发性醇或它们的组合。所述口腔可接受的基质以所述组合物的重量计优选地占96wt％至99.8wt％。
除了以上具体说明的成分以外，根据本发明的组合物通常将含有另外的成分以提高性能和/或消费者的可接受性。
根据本发明的组合物可包含聚合物沉积助剂。优选地，所述组合物包含酸酐聚合物，特别优选的是马来酸酐与甲基乙烯基醚的共聚物，其中所述酐的部分可为部分地或完全地水解或醇解的形式。优选的共聚物包括Gantrez(R)聚合物，例如：
Gantrez S-95：分子量216,000；游离酸；
Gantrez S-96：分子量700,000；游离酸；
Gantrez S-97：分子量1,500,000；游离酸；和
Gantrez MS-955：分子量1,060,000；钙/钠盐。
特别优选的马来酸与甲基乙烯基醚的共聚物，具有1,000,000或更大的分子量，并且特别优选的物质是Gantrez S-97。
根据本发明的组合物可包含水溶性的或微水溶性的金属盐源。优选的是锌离子，例如氯化锌、醋酸锌、葡萄糖酸锌、硫酸锌、氟化锌、柠檬酸锌、乳酸锌、氧化锌、一甘油锌(zinc monoglycerolate)、酒石酸锌、焦磷酸锌和马来酸锌；也优选的是亚锡离子，如氟化亚锡和氯化亚锡。
根据本发明的组合物可包含口腔护理酶系统，例如生成过氧化氢的酶系统(例如，氧化还原酶葡萄糖氧化酶)、淀粉葡糖苷酶、葡聚糖酶和/或变聚糖酶(mutanase)、(任选地存在提供锌离子的化合物和/或8-羟基喹啉的衍生物)、乳过氧化物酶、乳铁蛋白、溶菌酶和它们的混合物。
本发明的组合物可包含氟化物源，例如氟化钠、氟化亚锡、一氟磷酸钠、氟化锌铵、氟化锡铵、氟化钙、氟化钴铵和它们的混合物。
优选地，所述组合物具有20℃下6至9的pH值。
根据本发明的组合物将包含另外的本领域中常见的成分，例如：
抗菌剂，例如氯己定、血根碱提取物、甲硝唑、季铵化合物例如氯化十六烷基吡啶；双胍类，例如二葡萄糖酸氯己定、海克替啶(hexetidine)、奥替尼啶(octenidine)、阿来西定(alexidine)；和卤代双酚类化合物，例如2,2'-亚甲基二-(4-氯-6-溴苯酚)；
抗炎药，例如布洛芬、氟比洛芬、阿司匹林、吲哚美辛等；
防龋剂，例如氟化钠和氟化亚锡、氟化胺、一氟磷酸钠、三偏磷酸钠和酪蛋白；
牙菌斑缓冲液，例如尿素、乳酸钙、甘油磷酸钙和聚丙烯酸锶；
维生素，例如维生素A、C和E；
植物提取物；
植物衍生(plant-derivable)的抗氧化剂，例如类黄酮、儿茶素、多酚和单宁化合物和它们的混合物；
脱敏剂，例如柠檬酸钾、氯化钾、酒石酸钾、碳酸氢钾、草酸钾、硝酸钾和锶盐；
抗结石剂，例如焦磷酸碱金属盐、含次磷酸盐(hypophosphite)的聚合物、有机膦酸酯(organic phosphonates)和磷酸柠檬酸盐(phosphocitrates)等；
生物分子，例如细菌素、抗体、酶等；
香料，例如薄荷油和留兰香油；
蛋白质材料，例如胶原蛋白；
防腐剂；
乳化剂；
透明质酸；
氨基酸，例如精氨酸；
着色剂；
pH调节剂；
甜味剂；
药学上可接受的载体，例如淀粉、蔗糖、水或水/醇体系等；
表面活性剂，例如阴离子、非离子、阳离子和两性离子或两性表面活性剂；
保湿剂，例如甘油、山梨糖醇、丙二醇、木糖醇、乳糖醇等；
粘合剂和增稠剂，例如羧甲基纤维素钠、羟乙基纤维素黄原胶、阿拉伯树胶等以及合成聚合物，如聚丙烯酸酯和羧乙烯聚合物如/>
还可以包含可以增强活性成分例如抗菌剂的递送的聚合物；
缓冲剂和盐，以缓冲所述口腔护理组合物的pH和离子强度；并且
其它任选存在的可被包含的成分有，例如漂白剂如过氧化合物例如过氧二磷酸钾、泡腾体系如碳酸氢钠/柠檬酸体系、色变体系等。
本发明现在将通过以下非限制性实施例来说明。
本发明的实施例由数字表示，比较实施例由字母表示。
实施例
如表1中制备喷雾。
表1
| 成分 | 实施例1 | 实施例2 | 实施例3 | 实施例A |
| 山梨糖醇 | 50.00 | 50.00 | 50.00 | 52.00 |
| 糖精钠 | 0.27 | 0.27 | 0.27 | 0.27 |
| 六偏磷酸钠 | 0.50 | 0.50 | 0.50 | 0 |
| Pluronic F 127 | 1.50 | 1.50 | 1.50 | 0 |
| Covarine蓝 | 0.005 | 0.01 | 0.015 | 0 |
| Cremaphor | 2.50 | 2.50 | 2.50 | 2.50 |
| 香料 | 0.50 | 0.50 | 0.50 | 0.50 |
| 水 | 44.73 | 44.73 | 44.73 | 44.73 |
| 总计 | 100 | 100 | 100 | 100 |
测试方法
用硅基牙膏来清洁拔掉的牙齿，并且将该牙齿置于无菌的人混合唾液中2小时，以允许形成薄膜。使用比色计来测量基线牙色。用纸巾轻轻擦拭牙齿以去除多余的唾液，然后给予每颗牙齿2次喷雾施加抗沾污配制物(含有pluronic F127和六偏磷酸钠)或安慰剂配制物。在进行测色(即时增白效果)之前将该牙齿静置10秒；然后将该牙齿置于25℃下的沾污溶液(1:1:1的黑咖啡溶液、红茶溶液、红酒)中，同时轻轻搅拌(75rpm)1.5或3小时。在各个时间点取出所述牙齿，在50ml的水中冲洗，重新测量它们的颜色，然后放回所述沾污溶液中。
依据牙齿的白度指数(WIO)自基线的变化来描述所述即时增白效果，并且依据自基线的ΔE来描述随后的防沾污。在表2中显示结果。
使用以下公式来计算在接下来的不同时间点的自基线的总色变(ΔE)，因此计算沾污形成的水平：
ΔE＝√[(L*0–L*t)2+(a*0–a*t)2+(b*0–b*t)2]
其中L*0和L*t分别为基线处和时间t时的L*值；a*0和a*t分别是基线处和时间t时的a*值，b*0和b*t是基线处和时间t时的b*值。
结果
在下表2中显示了所述沾污溶液中不同时间点之后的各个处理组(n＝15)的平均ΔE(s.e.)值。在每个时间点，产品差异具有统计显著性(学生氏t检验，p<0.05)。
表2
表2中的数据表明，与比较实施例(实施例A)相比，根据本发明(实施例1-3)的口腔护理组合物提供了极其优越的防沾污功效(如通过低ΔE值明显可见)。
在每个时间点内具有不同字母的值表明处理组之间的统计学上显著的差异(p<0.05，方差分析，Tukey-Kramer)。
表2中的数据表明，将不同水平的Covarine蓝添加至所述喷雾配制物(实施例1)给出了优于比较配制物(实施例A)的即时增白益处，如通过WIO值更大且显著的变化明显可见。此外，与比较实施例(实施例A)相比，含有Covarine蓝的喷雾配制物提供了极其优越的防沾污功效(如通过显著更低的ΔE值明显可见)。
Claims (18)
1.口腔护理组合物，其包含：
(a)具有以下结构的聚合物，
其中a独立地选自2至130，且b为15至67，并且所述聚合物的分子量为1,700Da至15,000Da；
(b)六偏磷酸盐；
(c)Covarine蓝；
(d)口腔可接受的基质；
其中所述聚合物与六偏磷酸盐的重量比为1:5至5:1，
其中所述Covarine蓝的水平以总组合物计为0.001wt％至0.014wt％。
2.根据权利要求1所述的组合物，其中聚合物与六偏磷酸盐的重量比为1:4至4:1。
3.根据权利要求中的任意一项所述的组合物，其中所述聚合物的分子量为10,000Da至13,000Da。
4.根据权利要求1或2所述的组合物，所述组合物以总组合物计包含0.05wt％至4wt％的聚合物(a)。
5.根据权利要求1或2所述的组合物，所述组合物以总组合物计包含0.1wt％至2wt％的聚合物(a)。
6.根据权利要求1或2所述的组合物，所述组合物以总组合物计包含0.1wt％至4wt％的六偏磷酸盐。
7.根据权利要求1或2所述的组合物，其中聚合物和六偏磷酸盐的总量以总组合物计为0.1wt％至5wt％。
8.根据权利要求1或2所述的组合物，所述组合物为喷雾组合物。
9.根据权利要求1或2所述的组合物，所述组合物为牙膏。
10.根据权利要求1或2所述的组合物，其中所述Covarine蓝的水平以总组合物计为0.007wt％至0.014wt％。
11.根据权利要求1或2所述的组合物，其中Covarine蓝与聚合物(a)的重量比为5:100至1:1,000。
12.根据权利要求1或2所述的组合物，其中Covarine蓝与聚合物(a)的重量比为3:200至1:500。
13.根据权利要求1或2所述的组合物，其中所述组合物具有20℃下6至9的pH值。
14.根据权利要求1或2所述的组合物，其中所述口腔可接受的基质包括保湿剂、水、挥发性醇或它们的组合。
15.根据权利要求14所述的组合物，其中所述保湿剂为多元醇。
16.根据权利要求14所述的组合物，其中所述保湿剂为山梨糖醇或甘油。
17.最小化或预防牙齿沾污的非治疗性方法，所述方法包括将根据前述权利要求中的任意一项所述的组合物施加至牙齿表面上的步骤。
18.根据权利要求1至16中的任意一项的组合物在用于制备缓解牙齿的沾污的组合物中的用途。
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| PCT/EP2020/075888 WO2021063686A1 (en) | 2019-10-04 | 2020-09-16 | An oral care composition comprising hexametaphosphate and a pigment |
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| CN114430678A (zh) | 2022-05-03 |
| EP4037641B1 (en) | 2023-04-26 |
| EP4037641A1 (en) | 2022-08-10 |
| CL2022000767A1 (es) | 2023-03-03 |
| BR112022002747A2 (pt) | 2022-05-10 |
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