CN103402584A - 口腔护理组合物 - Google Patents
口腔护理组合物 Download PDFInfo
- Publication number
- CN103402584A CN103402584A CN2012800125699A CN201280012569A CN103402584A CN 103402584 A CN103402584 A CN 103402584A CN 2012800125699 A CN2012800125699 A CN 2012800125699A CN 201280012569 A CN201280012569 A CN 201280012569A CN 103402584 A CN103402584 A CN 103402584A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- oral care
- polymer
- dental surface
- care composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
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Abstract
本发明提供适于向牙齿表面提供临时增白效果的口腔护理组合物，该组合物包含：包含水或多元醇或其混合物的连续相；分散在该连续相中的颗粒状牙齿表面增白剂，和用于该颗粒状牙齿表面增白剂的沉积助剂；其特征在于该沉积助剂是在其结构中具有以下单体的聚-(磺酸)聚合物：-[CH2-C(R)(C(O)NH-C(R1)(R2)-CH2-SO3-X)]-其中R是氢或甲基；X选自氢、铵、碱金属或碱土金属；并且R1和R2各自独立地选自氢和1至4个碳原子的烷基；并且其中该颗粒状牙齿表面增白剂是酞菁蓝颜料。
Description
发明领域
本发明涉及口腔护理组合物。更特别地，本发明涉及含有颗粒状齿面增白剂的口腔护理组合物。
发明背景
牙齿的颜色受到其固有的颜色以及所存在的可能在牙齿表面上形成的任何外源性色斑的组合的影响。外源性颜色与材料吸附到牙釉质表面上的获得性膜中有关，其最终会导致着色。影响外源性色斑形成的因素包括不良的刷牙方法，吸烟，饮食摄入带有颜色的食物（如红葡萄酒），对象的年龄和某些阳离子试剂(例如双氯苯双胍己烷，或像锡和铁的金属盐)的使用。
消费者对于洁白的牙齿一直都有一个强烈的期望，并且许多人不满于他们目前的牙齿颜色。这种对于洁白牙齿的期望导致了对于牙齿增白产品的使用产生不断增加的需求。
目前的增白牙膏依赖于使研磨剂和化学成分最优化从而最大限度地去除和预防污渍。在刷牙过程中，研磨剂颗粒被暂时性地困在牙刷和着色的牙齿表面之间并磨去所述色斑。通常也可以与研磨剂颗粒一起使用化学组分，并且其包括钙螯合剂，聚合物，表面活性剂，酶和氧化剂。
EP 1
935 395描述了一种新的用于牙齿增白的光学方法。在使用在该公开文献中所描述的牙膏刷牙的时候，蓝色颜料（特别是Covarine蓝）被沉积到牙齿表面上，在这里其能够改变牙齿表面的光学效果，并且提高牙齿白度的测量值和感知。这种牙膏意在用于产生暂时性的牙齿增白效果，由于其不包含刺激化学品，因此可以根据需要频繁地重复使用，但是其并不意在对牙齿颜色产生任何的永久性改变。可以通过使用沉积助剂提高蓝色颜料在齿面上的沉积，所述沉积助剂最优选是GANTREZ®型聚合物，即，马来酸酐与甲基乙烯基醚的共聚物。
本发明人已经发现，可以通过使用某些聚-(磺酸)聚合物作为沉积助剂来增强EP 1 935 395中描述的系统所提供的临时牙齿增白效果。
发明概述
本发明提供适于向牙齿表面提供临时增白效果的口腔护理组合物，该组合物包含：
包含水或多元醇或其混合物的连续相；
分散在该连续相中的颗粒状牙齿表面增白剂，和
用于该颗粒状牙齿表面增白剂的沉积助剂；
其特征在于该沉积助剂是在其结构中具有以下单体的聚-(磺酸)聚合物：
-[CH2-C(R)(C(O)NH-C(R1)(R2)-CH2-SO3X)]-
其中R是氢或甲基；X选自氢、铵、碱金属或碱土金属；并且R1和R2各自独立地选自氢和1至4个碳原子的烷基；
并且其中该颗粒状牙齿表面增白剂是酞菁蓝颜料。
发明详述
牙齿表面增白剂
本发明的组合物包含分散在该组合物的连续相中的颗粒状牙齿表面增白剂。
该颗粒状牙齿表面增白剂通过沉积到牙齿上并由此改变它们的外观来起作用。通过该沉积助剂辅助该颗粒状牙齿表面增白剂沉积到牙齿上。
该颗粒状牙齿表面增白剂是酞菁蓝颜料。
酞菁是含有以由交替的碳和氮原子连结的16元环形式连接的四个对称布置的异吲哚环的有机金属化合物。大多数酞菁含有中心共配位金属离子，如铜。铜酞菁具有以下基础结构：
酞菁蓝颜料表现出超过一种的结晶变体，其在色彩方面不同。已经开发了相稳定该酞菁颜料分子的方法以防止转化至不同结晶变体。一种实例是分子的轻微化学改性，例如部分氯化。还已经开发了针对颜料应用过程中絮凝的稳定酞菁颜料分子的方法。一种实例是向该分子中混合其它试剂，例如向颜料分子中混合表面活性添加剂。
下列颜料是示例性酞菁蓝颜料：
| C.I.通用名 | C.I.结构数字 | 结晶变体：类型 | 氢原子数 |
| 颜料蓝 15 | 74 160 | α | - |
| 颜料蓝 15:1 | 74 160 | α；相稳定的 | 0.5-1 Cl |
| 颜料蓝 15:2 | 74 160 | α；相和絮凝稳定的 | 0.5-1 Cl |
| 颜料蓝 15:3 | 74 160 | β | - |
| 颜料蓝 15:4 | 74 160 | β；絮凝稳定的 | - |
| 颜料蓝 15:6 | 74 160 | ε | - |
| 颜料蓝 16 | 74 100 | γ；不含金属 | - |
用于本发明的最优选的颗粒状牙齿表面增白剂是如上表中所述的分别指定为C.I. 颜料蓝15、C.I. 颜料蓝15:1或C.I. 颜料蓝 15:2的那些α铜酞菁。市售实例是来自Sensient
Cosmetic Technologies/LCW的Covarine蓝 W 6795。
上述材料的任意混合物也可使用。
本发明组合物中颗粒状牙齿表面增白剂（如上定义）的量按颗粒状牙齿表面增白剂（如上定义）总重量计合适地为该组合物总重量的0.001至3%、优选0.001至1%、更优选0.005至0.3%。
沉积助剂
本发明的组合物包含用于该颗粒状牙齿表面增白剂的沉积助剂。该沉积助剂是在其结构中具有以下单体的聚-(磺酸)聚合物：
-[CH2-C(R)(C(O)NH-C(R1)(R2)-CH2-SO3X)]-
其中R是氢或甲基；X选自氢、铵、碱金属或碱土金属；并且R1和R2各自独立地选自氢和1至4个碳原子的烷基；
适于在本发明中用作沉积助剂的聚-(磺酸)聚合物通常具有50,000至10,000,000、优选80,000至8,000,000和更优选100,000至7,000,000的重均分子量。测定此类聚合材料的重均分子量的合适方法是相对于聚乙二醇标样的凝胶渗透色谱法。
适于在本发明中用作沉积助剂的聚-(磺酸)聚合物可以是水溶性或水分散性的。术语“水溶性或水分散性的”在本发明上下文中通常是指当在25℃下以等于1质量%的浓度引入到水相中时能够获得宏观均质和透明溶液（也就是说，在等于500纳米的波长下，穿过1厘米厚的样品，具有至少60%、优选至少70%的最大透光率值）的聚合物。
在本发明中用作沉积助剂的聚-(磺酸)聚合物还可以是两亲的，即它们含有亲水性部分或结构部分和包含至少一个脂肪链的疏水性部分或结构部分两者。
术语“沉积助剂”在本发明的上下文中是指在该组合物使用过程中辅助该颗粒状牙齿表面增白剂由该组合物的连续相沉积到牙齿表面上的材料。在本发明的上下文中该组合物的用途通常涉及将该组合物应用于口腔，接着刷和/或冲洗。
合适的沉积助剂通过对该颗粒状牙齿表面增白剂（如上定义）和牙齿表面均具有亲和力来起作用。
优选的沉积助剂能够辅助颗粒状牙齿表面增白剂染料沉积至牙齿上，以使得牙齿表面的白度，与利用含相同量的颗粒状牙齿表面增白剂染料但不含沉积助剂的对比配方以相同的方式处理牙齿所获得的数值相比，提高至少20%，并且更优选提高至少100%。
提高的牙齿表面白度的一个便捷的度量为使用色度计测定的Δb*。负的Δb*值表示黄色至蓝色的转换，其已被证明是消费者所感知的牙齿表面白度的主要原因之一。
据此，优选的沉积助剂能够辅助颗粒状牙齿表面增白剂染料在牙齿上的沉积，以使得负的Δb*值，与利用含相同量的颗粒状牙齿表面增白剂染料但不含沉积助剂的对比配方以相同的方式处理牙齿所获得的数值相比，提高至少20%并且更优选至少100%。
证实沉积助剂的作用的简化实验模型如下：
首先将打磨的羟基磷灰石圆盘放置在无菌人类唾液中2小时以便形成薄膜。然后将所述圆盘在水中冲洗并确定基准颜色（例如使用Minolta色度计CR300）。之后利用（a）颗粒状牙齿表面增白剂染料在水中的悬浮液；或者（b），与（a）浓度相同的颗粒状牙齿表面增白剂染料在水中的悬浮液加沉积助剂来刷洗所述圆盘。所述刷洗最好使用刷洗机来进行。冲洗后，再次测定圆盘的颜色，并且对于处理（a）和处理（b）二者都记录Δb*的变化。根据这些数据的对比，很容易看出沉积助剂的作用。
优选的一类在本发明中用作沉积助剂的聚-(磺酸)聚合物在其结构中具有单体：
-[CH2-C(R)(C(O)NH-C(R1)(R2)-CH2-SO3X)]-
其中R是氢，R1和R2各自独立地选自1至3个碳原子的烷基，且X代表氢、铵或碱金属。
特别优选的一类在本发明中用作沉积助剂的聚-(磺酸)聚合物在其结构中具有单体：
-[CH2-C(R)(C(O)NH-C(R1)(R2)-CH2-SO3X)]-
其中R是氢，R1和R2各自是甲基，且X代表氢、铵、钠或钾。此类单体下文中称为2-丙烯酰氨基-2-甲基丙磺酸或AMPS®单体。
上述类别的合适的聚-(磺酸)聚合物可以是2-丙烯酰氨基-2-甲基丙磺酸（AMPS®）单体的均聚物或共聚物。该聚合物可以是交联或非交联的。当该聚合物是交联的时，交联剂可以选自通常用于通过自由基聚合获得的聚合物的交联的烯属多不饱和化合物。交联剂的实例包括亚甲基双丙烯酰胺、甲基丙烯酸烯丙酯和三羟甲基丙烷三丙烯酸酯（TMPTA）。
AMPS®共聚物的实例包括AMPS®与一种或多种阴离子共聚单体和/或一种或多种非离子共聚单体的共聚物。
合适的阴离子共聚单体的实例包括丙烯酸、甲基丙烯酸、丙烯酸β-羧乙酯、丙烯酰氧基丙酸、衣康酸、衣康酸的单烷基酯、马来酸、马来酸的单烷基酯、巴豆酸、富马酸、富马酸的单烷基酯，和它们的盐。
阴离子共聚单体的优选实例包括丙烯酸和衣康酸和它们的盐。
合适的非离子共聚单体的实例包括丙烯酰胺、甲基丙烯酰胺、N-乙烯基乙酰胺和N-甲基-N-乙烯基乙酰胺、N-乙烯基甲酰胺和N-甲基-N-乙烯基甲酰胺、N-烷基丙烯酰胺和N,N-二烷基丙烯酰胺、N-烷基甲基丙烯酰胺和N,N-二烷基甲基丙烯酰胺、丙烯酸烷基酯、甲基丙烯酸烷基酯、丙烯酸苄酯、甲基丙烯酸苄酯、含有具有4至9个碳原子的环烷基的N-乙烯基内酰胺（如N-乙烯基吡咯烷酮、N-乙烯基丁内酰胺和N-乙烯基己内酰胺）、乙烯基酯、乙烯基醇、丙二醇或乙二醇，其中这些单体的烷基优选含有1至7个、更优选1至3个碳原子。其它合适的非离子共聚单体包括丙烯酸或甲基丙烯酸与烷基乙氧基化物的酯，如下式的单体：
-[CH2-C(R1)(C(O)-O-[CH2-CH2-O]n-R2)]-
其中n是3至100、优选3至50、更优选7至25的整数，R1是氢或甲基，R2代表含有6至30个碳原子、优选10至22个碳原子、更优选14至22个碳原子的直链或支化烷基。
非离子共聚单体的优选实例包括丙烯酰胺、甲基丙烯酰胺、N-乙烯基甲酰胺、N-甲基丙烯酰胺和N,N-二甲基丙烯酰胺、N-甲基甲基丙烯酰胺和N,N-二甲基甲基丙烯酰胺、N-乙基丙烯酰胺和N,N-二乙基丙烯酰胺、N-乙基甲基丙烯酰胺和N,N-二乙基甲基丙烯酰胺、N-乙烯基吡咯烷酮和丙烯酸或甲基丙烯酸与含有7至25个乙氧基基团的聚乙氧基化C14-C22脂肪醇的酯。
适用于本发明的AMPS®共聚单体可以例如以商标ARISTOFLEX®购自Clariant，如ARISTOFLEX® AVC（INCI名称：丙烯酰基二甲基牛磺酸铵/VP共聚物）、ARISTOFLEX® AVS（INCI名称：丙烯酰基二甲基牛磺酸钠/VP共聚物）、ARISTOFLEX® HMB（INCI名称：丙烯酰基二甲基牛磺酸铵/山嵛醇聚醚（Beheneth）-25甲基丙烯酸酯交联共聚物）和ARISTOFLEX® TAC（INCI名称：丙烯酰基二甲基牛磺酸铵/丙烯酸羧乙酯交联共聚物）。
优选的用于本发明的2-丙烯酰氨基-2-甲基丙磺酸（AMPS®）共聚物按总重量计包含该聚合物总重量的至少25%、更优选至少50%和最优选至少75%的AMPS®单体。
采用AMPS®均聚物已经获得了特别良好的结果。
上述材料的任意混合物也可使用。
本发明的组合物中沉积助剂（如上定义）的量按沉积助剂（如上定义）总重量计合适地为该组合物总重量的0.001至5.0%、优选0.005至3.0%、更优选0.01至1.0%。
产品形式
本发明的组合物包含含有水或多元醇或其混合物的连续相。
本发明的组合物的合适产品形式实例包括洁牙剂、嗽口水、口香糖、糖锭（lozenges）、生物附着性贴剂或条、口腔喷雾和液体制剂，如涂料（paint）或漆，其设计为使用涂施器如刷子或海绵尖涂施器直接施加到牙齿表面。
本发明的组合物的优选产品形式是适于刷洗和/或漂洗口腔表面的那些。
在此类优选产品形式中，水和/或多元醇的量按水和/或多元醇总重量计通常为该组合物总重量的至少10%、优选至少30%、更优选至少50%。
在本发明的上下文中一类优选的产品形式的实例为洁牙剂。术语“洁牙剂”通常是指用于清洁口腔表面的制剂。洁牙剂为口用组合物，其不用于为治疗试剂的全身给药的目的而被故意吞咽，但是其被应用于口腔，用于对口腔进行处理并随后吐出。典型地，洁牙剂与清洁用具，如牙刷，一起使用，通常将其施加于所述牙刷的刷毛并随后刷洗口腔内可达到的表面。优选所述洁牙剂呈软膏或凝胶的形式（或其组合）。
根据本发明的洁牙剂组合物将通常包含基于洁牙剂的总重量计40-99wt%的液体连续相。这样的液体连续相通常将包括不同相对含量的水和多元醇的混合物，水的含量通常为10-45wt%（基于洁牙剂的总重量计），多元醇的含量通常为30-70wt%（基于洁牙剂的总重量计）。典型的多元醇包括润湿剂，如甘油、山梨糖醇、聚乙二醇、聚丙二醇、丙二醇、木糖醇（及其它可食用的多元醇）、氢化的部分水解的多糖及其混合物。
根据本发明的洁牙剂组合物通常将包含其它成分以提高性能和/或消费者可接受性，例如研磨清洁剂、粘结剂或增稠剂、和表面活性剂。
举例来说，洁牙剂通常将包含基于洁牙剂的总重量计3-75wt%的研磨清洁剂。合适的研磨清洁剂包括二氧化硅干凝胶、水凝胶和气凝胶，以及沉淀的颗粒状二氧化硅；碳酸钙、磷酸二钙、磷酸三钙、煅烧氧化铝、偏磷酸钠和钾、焦磷酸钠和钾、三偏磷酸钠、六偏磷酸钠、颗粒状羟基磷灰石及其混合物。
此外，所述洁牙剂通常将包含0.5-10wt%的粘结剂或增稠剂，其用量为，基于洁牙剂的总重量计。合适的粘结剂或增稠剂包括羧乙烯基聚合物（例如与聚烯丙基蔗糖或聚烯丙基季戊四醇交联的聚丙烯酸），羟乙基纤维素，羟丙基纤维素，纤维素醚的水溶性盐（如羧甲基纤维素钠和羧甲基羟乙基纤维素钠），天然胶（如角叉菜胶，刺梧桐胶，瓜尔豆胶，黄原胶，阿拉伯胶和黄蓍胶），细碎的二氧化硅，锂皂石，胶态硅酸镁铝及其混合物。
此外，所述洁牙剂通常将包含基于洁牙剂的总重量计0.2-5wt%的表面活性剂。合适的表面活性剂包括阴离子表面活性剂，如钠、镁、铵或乙醇胺的C8-C18烷基硫酸盐（例如月桂基硫酸钠）、C8-C18烷基磺基琥珀酸盐（例如二辛基磺基琥珀酸钠）、C8-C18烷基磺基醋酸盐（例如月桂基磺基醋酸钠）、C8-C18烷基肌氨酸盐（如月桂基肌氨酸钠）、C8-C18烷基磷酸盐（其可以任选地包含最多10个环氧乙烷和/或环氧丙烷单元）和硫酸盐化的单甘酯。其它合适的表面活性剂包括非离子表面活性剂，例如任选地聚乙氧基化的脂肪酸山梨醇酯、乙氧基化的脂肪酸、聚乙二醇的酯、脂肪酸单甘酯和双甘酯的乙氧基化物、以及环氧乙烷/环氧丙烷嵌段聚合物。其它合适的表面活性剂包括两性表面活性剂，例如甜菜碱或磺基甜菜碱。也可以使用任意如上所述材料的混合物。
在本发明的上下文中另一类优选的产品形式的实例为漱口剂。术语“漱口剂”通常是指液体制剂，其被用于冲洗口腔表面并提供给使用者以口部清洁和清爽的感觉。所述漱口剂为口用组合物，其不用于为治疗试剂的全身给药的目的而被故意吞咽，但是其被应用于口腔，用于对口腔进行处理并随后吐出。
根据本发明的漱口剂组合物通常将包含水连续相。水的量通常为基于漱口剂的总重量计70-99wt%。
根据本发明的漱口剂组合物通常将包含其它成分以提高性能和/或消费者可接受性，例如在上文提及的用于洁牙剂的润湿剂和表面活性剂。润湿剂的量通常为基于漱口剂的总重量计5-20wt%，表面活性剂的量通常为基于漱口剂的总重量计0.1-5wt%。
本发明的组合物（如特别是洁牙剂或漱口剂）还可以包含本领域常用的其它任选组分，如氟化物离子源、抗牙菌斑剂、缓冲剂、调味剂、增甜剂、着色剂、遮光剂、防腐剂、抗过敏剂和抗菌剂。
本发明还将通过参照下文的非限制性实施例进行说明。
实施例
进行评估以评价使用聚-(磺酸)聚合物作为沉积助剂时蓝色颜料至模型牙齿表面的输送。相对于代表描述在EP 1 935 395中的优选的蓝色颜料与沉积助剂组合（即0.025% w/w的蓝Covarine颜料加0.1% w/w的获自ISP的GANTREZ®S97沉积助剂）的制剂对输送进行比较。
因此，制备具有下表1中所示成分的测试制剂。
所有成分表示为总制剂的重量%，并以活性成分的含量形式表示。
表
1
| 成分 | 对比例 | 实施例1 | 实施例2 |
| GANTREZ® S-97 | 0.1 | 0 | 0 |
| 聚(2-丙烯酰氨基-2-甲基-1-丙磺酸)(1) | 0 | 0.1 | 0 |
| RHEOCARE®HSP-1180(2) | 0 | 0 | 0.1 |
| 蓝Covarine (C.I.74160)；40% a.i. | 0.025 | 0.025 | 0.025 |
| 水 | 至100 | 至100 | 至100 |
(1) 平均Mw
2,000,000，15重量%在水中，来自Sigma-Aldrich®
(2) 聚(2-丙烯酰氨基-2-甲基-1-丙磺酸)，14-18重量%在水中，来自Cognis Care
Chemicals。
试验方法
使用P1200碳化硅砂纸打磨羟基磷灰石（HA）圆盘并用水彻底冲洗。将所述圆盘浸入无菌的全人类唾液中最少两个小时的时间以便形成薄膜。将所述HA圆盘从唾液中取出，用水冲洗，并利用色度计以CIELAB模式测定所述圆盘的基准颜色。然后将所述HA圆盘放置在刷洗机中，并且每个圆盘添加10ml的测试制剂。将所述圆盘在375g的刷洗负载下刷洗1分钟。刷洗之后，在水中冲洗所述HA圆盘并再次测定所述圆盘的颜色。计算颜色坐标b*以及白度指数（WIO）的变化。所述WIO指数是已经为特别是评价牙齿白度而最优化的指数（如在Journal
of Dentistry，第36卷，Supplement 1，2008，第2至7页中所述）。
结果
b*与白度（WIO）的改变显示在下表2中。
表
2
| 制剂 | b*的改变 | WIO的改变 |
| 对比例 | -12.17 | 19.3 |
| 实施例1 | -18.78 | 30.1 |
| 实施例2 | -19.07 | 28.7 |
该结果证明，与对比例相比，由实施例1和2提供了优异的增白效果。
Claims (7)
1.适于向牙齿表面提供临时增白效果的口腔护理组合物，该组合物包含：
包含水或多元醇或其混合物的连续相；
分散在该连续相中的颗粒状牙齿表面增白剂，和
用于该颗粒状牙齿表面增白剂的沉积助剂；
其特征在于该沉积助剂是在其结构中具有以下单体的聚-(磺酸)聚合物：
-[CH2-C(R)(C(O)NH-C(R1)(R2)-CH2-SO3X)]-
其中R是氢或甲基；X选自氢、铵、碱金属或碱土金属；并且R1和R2各自独立地选自氢和1至4个碳原子的烷基；
并且其中该颗粒状牙齿表面增白剂是酞菁蓝颜料。
2.如权利要求1所述的口腔护理组合物，其中该酞菁蓝颜料选自指定为C.I. 颜料蓝 15、C.I. 颜料蓝 15:1或C.I. 颜料蓝 15:2的那些α铜酞菁。
3.如前述权利要求任一项所述的口腔护理组合物，其中该聚-(磺酸)聚合物在其结构中具有单体：
-[CH2-C(R)(C(O)NH-C(R1)(R2)-CH2-SO3X)]-
其中R是氢，R1和R2各自独立地选自1至3个碳原子的烷基，且X代表氢、铵或碱金属。
4.如权利要求3所述的口腔护理组合物，其中该聚-(磺酸)聚合物在其结构中具有单体：
-[CH2-C(R)(C(O)NH-C(R1)(R2)-CH2-SO3X)]-
其中R是氢，R1和R2各自是甲基，且X代表氢、铵、钠或钾。
5.如权利要求4所述的口腔护理组合物，其中该聚-(磺酸)聚合物是以下单体的均聚物：
-[CH2-C(R)(C(O)NH-C(R1)(R2)-CH2-SO3X)]-
其中R是氢，R1和R2各自是甲基，且X代表氢、铵、钠或钾。
6.如前述权利要求任一项所述的口腔护理组合物，其中该聚-(磺酸)聚合物具有100,000至7,000,000的重均分子量。
7.如前述权利要求任一项所述的口腔护理组合物，其为洁牙剂或漱口剂的形式。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11157896 | 2011-03-11 | ||
| EP11157896.9 | 2011-03-11 | ||
| PCT/EP2012/053248 WO2012123241A2 (en) | 2011-03-11 | 2012-02-27 | Oral care compositions |
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| CN103402584B CN103402584B (zh) | 2016-02-24 |
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| CN201280012569.9A Expired - Fee Related CN103402584B (zh) | 2011-03-11 | 2012-02-27 | 口腔护理组合物 |
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| EP (1) | EP2683447B1 (zh) |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105828796A (zh) * | 2013-12-23 | 2016-08-03 | 高露洁-棕榄公司 | 牙齿美白口腔护理产品 |
| CN107567327A (zh) * | 2015-04-28 | 2018-01-09 | 巴斯夫欧洲公司 | 用于稳定过氧化物化合物的聚合物 |
| CN109069361A (zh) * | 2016-04-01 | 2018-12-21 | 宝洁公司 | 包含凝胶网络相和硝酸钾的口腔护理组合物 |
| CN111417375A (zh) * | 2017-12-13 | 2020-07-14 | 高露洁-棕榄公司 | 口腔护理组合物和用于提高其稳定性的方法 |
| CN112839625A (zh) * | 2018-05-21 | 2021-05-25 | 荷兰联合利华有限公司 | 口腔护理组合物 |
| CN114430678A (zh) * | 2019-10-04 | 2022-05-03 | 联合利华知识产权控股有限公司 | 包含六偏磷酸盐和颜料的口腔护理组合物 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112015015872B1 (pt) * | 2013-02-01 | 2020-02-27 | Unilever N.V. | Composição de tratamento oral |
| CN105209124B (zh) * | 2013-05-15 | 2018-10-26 | 荷兰联合利华有限公司 | 口腔护理组合物 |
| EP3651722B1 (en) | 2017-07-13 | 2022-02-02 | Unilever Global IP Limited | A composite material for whitening teeth and composition comprising the same |
| WO2019034346A1 (en) | 2017-08-17 | 2019-02-21 | Unilever N.V. | COMPOSITION FOR THE WHITENING OF TEETH |
| CN112512489B (zh) | 2018-07-13 | 2023-04-28 | 联合利华知识产权控股有限公司 | 口腔护理组合物 |
| BR112020023740B1 (pt) | 2018-08-17 | 2023-10-10 | Unilever Ip Holdings B.V | Composições de cuidados orais e método para branquear os dentes de um indivíduo |
| EP3628375A1 (en) | 2018-09-27 | 2020-04-01 | Unilever N.V. | Oral care composition |
| BR102019020257A2 (pt) | 2019-09-27 | 2021-04-20 | Mmf&T Desenvolvimento Tecnológico E Inovação Ltda | composição para saúde oral e processo de elaboração de composição para saúde oral |
| EP4054519B1 (en) | 2019-11-06 | 2023-08-09 | Unilever IP Holdings B.V. | Oral care composition for whitening teeth |
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| EP1935395B1 (en) * | 2006-12-20 | 2013-06-05 | Unilever PLC | Oral composition |
| KR20200057256A (ko) * | 2018-11-16 | 2020-05-26 | 삼성전자주식회사 | 디스플레이 장치 및 그 구동 방법 |
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- 2012-02-27 CN CN201280012569.9A patent/CN103402584B/zh not_active Expired - Fee Related
- 2012-02-27 EP EP12705875.8A patent/EP2683447B1/en not_active Not-in-force
- 2012-02-27 WO PCT/EP2012/053248 patent/WO2012123241A2/en active Application Filing
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| EP0321650A1 (en) * | 1987-12-21 | 1989-06-28 | The B.F. Goodrich Company | Dental calculus inhibiting compositions |
| CN101080212A (zh) * | 2004-12-17 | 2007-11-28 | 强生消费者公司 | 包含聚合乳化剂的清洁组合物及其使用方法 |
| CN101204358A (zh) * | 2006-12-20 | 2008-06-25 | 荷兰联合利华有限公司 | 口腔护理组合物 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105828796A (zh) * | 2013-12-23 | 2016-08-03 | 高露洁-棕榄公司 | 牙齿美白口腔护理产品 |
| CN105828796B (zh) * | 2013-12-23 | 2020-04-07 | 高露洁-棕榄公司 | 牙齿美白口腔护理产品 |
| CN107567327A (zh) * | 2015-04-28 | 2018-01-09 | 巴斯夫欧洲公司 | 用于稳定过氧化物化合物的聚合物 |
| CN109069361A (zh) * | 2016-04-01 | 2018-12-21 | 宝洁公司 | 包含凝胶网络相和硝酸钾的口腔护理组合物 |
| CN111417375A (zh) * | 2017-12-13 | 2020-07-14 | 高露洁-棕榄公司 | 口腔护理组合物和用于提高其稳定性的方法 |
| CN112839625A (zh) * | 2018-05-21 | 2021-05-25 | 荷兰联合利华有限公司 | 口腔护理组合物 |
| CN114430678A (zh) * | 2019-10-04 | 2022-05-03 | 联合利华知识产权控股有限公司 | 包含六偏磷酸盐和颜料的口腔护理组合物 |
| CN114430678B (zh) * | 2019-10-04 | 2024-03-26 | 联合利华知识产权控股有限公司 | 包含六偏磷酸盐和颜料的口腔护理组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112013021953A2 (pt) | 2018-06-12 |
| EP2683447A2 (en) | 2014-01-15 |
| CN103402584B (zh) | 2016-02-24 |
| EP2683447B1 (en) | 2016-11-09 |
| WO2012123241A3 (en) | 2012-11-15 |
| BR112013021953B1 (pt) | 2019-01-29 |
| WO2012123241A2 (en) | 2012-09-20 |
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