CN101573097B - 用于口腔组合物的风味剂 - Google Patents
用于口腔组合物的风味剂 Download PDFInfo
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- CN101573097B CN101573097B CN2007800239097A CN200780023909A CN101573097B CN 101573097 B CN101573097 B CN 101573097B CN 2007800239097 A CN2007800239097 A CN 2007800239097A CN 200780023909 A CN200780023909 A CN 200780023909A CN 101573097 B CN101573097 B CN 101573097B
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- 239000000551 dentifrice Substances 0.000 claims abstract description 15
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 claims abstract description 14
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Classifications
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- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/10—Natural spices, flavouring agents or condiments; Extracts thereof
- A23L27/12—Natural spices, flavouring agents or condiments; Extracts thereof from fruit, e.g. essential oils
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- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
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- A—HUMAN NECESSITIES
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- 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
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- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
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- A—HUMAN NECESSITIES
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- 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
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
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- A—HUMAN NECESSITIES
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- A—HUMAN NECESSITIES
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- A—HUMAN NECESSITIES
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
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- A—HUMAN NECESSITIES
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Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Inorganic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Cosmetics (AREA)
- Fats And Perfumes (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
- Confectionery (AREA)
Abstract
本发明涉及口腔护理组合物,所述组合物包含亚锡离子、薄荷型风味油、防止组合物中产生恶臭和异味的保护剂组分、以及口部可接受的载体。所述薄荷型油包括胡椒薄荷、留兰香和薄荷。适宜的保护剂组分包括铜盐和羰基化合物,例如抗坏血酸;顺式茉莉酮;2,5-二甲基-4-羟基-3(2H)-呋喃酮;5-乙基-3-羟基-4-甲基-2(5H)-呋喃酮;香草醛;乙基香草醛;茴香醛;3,4-亚甲基二氧苯甲醛;3,4-二甲氧基苯甲醛;4-羟基苯甲醛;2-甲氧基苯甲醛;4-甲氧基苯甲醛;苯甲醛;肉桂醛(3-苯基-2-丙烯醛);己基肉桂醛;α-甲基肉桂醛;邻甲氧基肉桂醛;α-戊基肉桂醛;以及它们的组合。所述口腔护理组合物可以是洁齿剂。
Description
发明领域
本发明涉及包含风味剂组合物和亚锡离子的美观悦人的口腔护理制剂。
发明背景
亚锡离子适合用于口腔组合物中。通常使用由氟化亚锡和其它亚锡盐提供的亚锡离子来提供抗牙斑、抗齿龈炎功效以及改善口气和过敏。然而已证实,由于已知包含亚锡离子的制剂不美观悦人,因此用亚锡离子配制具有挑战性。当与某些口腔护理风味化合物组合使用时,亚锡离子会产生恶臭。仍期望提供可有效递送具有美观悦人风味的亚锡离子的口腔护理组合物。没有任何现有技术可提供本发明的所有美学优点和有益效果。
发明概述
本发明涉及口腔护理组合物,所述组合物包含亚锡离子、薄荷型风味油、防止组合物中产生恶臭和异味的保护剂组分、以及口部可接受的载体。所述薄荷型油包括胡椒薄荷、留兰香和田野薄荷。适宜的保护剂组分包括羰基化合物例如抗坏血酸;顺式茉莉酮;2,5-二甲基-4-羟基-3(2H)-呋喃酮;5-乙基-3-羟基-4-甲基-2(5H)-呋喃酮;香草醛;乙基香草醛;茴香醛;3,4-亚甲基二氧苯甲醛;3,4-二甲氧基苯甲醛;4-羟基苯甲醛;2-甲氧基苯甲醛;苯甲醛;肉桂醛;己基肉桂醛;α-甲基肉桂醛;邻甲氧基肉桂醛;α-戊基肉桂醛;以及它们的组合。
对于本领域的技术人员来讲,通过阅读本说明书的公开内容,本发明的这些和其它特征、方面和优点将变得显而易见。
发明详述
虽然在说明书之后提供了特别指出和清楚地要求保护本发明的权利要求书,但据信通过下列优选实施方案的说明可更好地理解本发明。
除非另外指明,本文所用的所有百分比均按所述洁齿剂组合物的重量计。除非另外指明,本文所用的比率均为总组合物的摩尔比。除非另外指明,所有的测量均在25℃进行。
本文中“包含/包括”是指可加入不影响最终结果的其它步骤和成分。该术语包括术语“由...组成”和“基本上由...组成”。
如本文所用,单词“包含/包括”和它的变体旨在为非限制性的,因此列表中条目的叙述不排除其它也可能在本发明的材料、组合物、装置和方法中有用的类似条目。
如本文所用,单词“优选的”、“优选地”和它们的变体是指在特定环境下能提供特定有益效果的本发明的实施例。然而,其它的实施例在相同或其它的环境下也可以是优选的。此外,一个或多个优选实施例的详述不是表示其它实施例是无用的,并且并非旨在从本发明的范畴中排除其它的实施例。
本文中,“有效量”是指化合物或组合物的量足以显著促成积极的有益效果,优选口腔健康有益效果,但有足够低以避免严重的副作用,即,在技术人员的合理判断范围内提供合理的效险比。
“口腔护理组合物”是指在一般使用过程中不是被故意吞咽以用于特定治疗剂的全身给药,而是可在口腔中保留足够长的时间以基本上接触所有的牙齿表面和/或口腔组织以得到具有口腔活性的产物。所述口腔护理组合物可为多种形式,包括牙膏、洁齿剂、牙胶、齿龈胶、漱口水、摩丝、泡沫、假牙护理产品、口喷剂、药糖块、咀嚼片或口香糖。该口腔护理组合物还可掺入到牙贴或薄膜上以直接施用或粘附到口腔表面。
除非另外指明,本发明使用的术语“洁齿剂”是指糊剂、凝胶或液体制剂。洁齿剂组合物既可为单相组合物也可为两种或多种单独洁齿剂组合物的组合。洁齿剂组合物可以呈任何所需形式,如深条纹的、浅条纹的、多层的、糊剂周围有凝胶的、或它们的任意组合。在包括两种或多种单独洁齿剂组合物的洁齿剂中,每种洁齿剂组合物可被装入到物理上独立的分配器腔室中,并排分配。
如本文所用,术语“分配器”是指任何适于分配组合物如洁齿剂的泵、管或容器。
如本文所用,术语“牙齿”是指自然牙齿以及人造牙齿或假牙。
术语“风味油”是指用作调味剂的精油,其为从植物中蒸馏或提取出的挥发性油以及这些挥发性油的组分。如本文所用,当涉及薄荷和薄荷型油时,术语“风味油”包括各种等级的油,所述油通常是指初始天然的或未加工的(刚从植物源提起出来),和精致的或精馏的以使油符合标准并且除去不需要的风味/气味特征(例如通过分馏)。精馏级一般为提供给最终使用者以用作调味剂和香料的商业等级。典型的精油以及它们的主要组分是得自以下的那些:例如百里香(百里酚、香芹酚)、牛至(香芹酚、萜烯)、柠檬(柠檬烯、萜品烯、水芹烯、蒎烯、柠檬醛)、柠檬香草(柠檬醛、甲基庚烯酮、香茅醛、香叶醇)、橙花(里哪醇、β-蒎烯、柠檬烯)、橙(柠檬烯、柠檬醛)、茴芹(对丙烯基茴香醚、黄樟脑)、丁香(丁子香酚、乙酸丁子香酯、石竹烯)、玫瑰(香叶醇、香茅醇)、迷迭香(龙脑、冰片酯、樟脑)、老鹳草(香叶醇、香茅醇、里哪醇)、熏衣草(乙酸里哪酯、里哪醇)、香茅(香叶醇、香茅醇、香茅醛、莰烯)、桉树(桉叶油素);胡椒薄荷(薄荷醇、薄荷酯)、荷兰薄荷(香芹酮、柠檬烯、蒎烯);鹿蹄草(水杨酸甲酯)、樟脑(黄樟脑、乙醛、樟脑)、月桂树(丁子香酚、月桂烯、佳味醇)、肉桂(肉桂醛、乙酸肉桂酯、丁子香酚)、茶树(萜品-4-醇、桉树脑)、和柏叶(α-守酮、β-守酮、葑酮)。精油、它们的组合物和制备更详细地描述于Kirk-Othmer的“Encyclopedia of ChemicalTechnology”第4版和“The Merck Index”第13版中。
术语“口部可接受的载体”包括用于口腔护理组合物中的安全和有效的材料、赋形剂或添加剂,包括但不限于氟离子源、抗牙结石或抗牙垢剂、缓冲液、研磨剂例如二氧化硅、碱金属碳酸氢盐、增稠物质、湿润剂、水、表面活性剂、二氧化钛、风味剂、甜味剂、木糖醇、着色剂、以及它们的混合物。
可用于本发明的活性成分和其它成分可根据其美容和/或治疗有益效果或其假定的作用模式来分类或描述。然而应当理解,在某些情况下,可用于本发明的活性物质和其它成分可提供一种以上的美容和/或治疗有益效果或作用,或通过一种以上的方式起作用或运转。因此,本文的分类只是为了方便起见,而非旨在将成分限制在所列的特别指出的一种或几种应用中。
在本文中,术语“牙垢”和“牙结石”可互换使用,并且是指矿物化的牙斑生物膜。
本发明组合物包含基本组分以及任选组分。本发明组合物中的基本组分和任选组分描述于以下段落中。
本发明涉及以下发现:当含亚锡组合物中含有薄荷油、尤其是薄荷或薄荷类精油时,通常会出现存在于所述组合物中的恶臭。所述恶臭可被描述为异味或“臭”味,其还会造成口腔组合物中的异味。虽然可选择除薄荷油以外可与亚锡一起配制并且不产生恶臭的可供选择的风味剂,但是风味剂中的薄荷组分是通常所期望的。甚至更期望所述口腔组合物完全具有薄荷味,因为薄荷是口腔护理组合物中最主要的风味剂。还已发现,存在于风味油中的主要恶臭前体物质是含硫的化合物,例如二甲基亚砜(DMSO)、二甲硫醚(DMS)、二甲基二硫醚和二甲基砜,样本所具有的含量高达300ppm或更高。下表显示了留兰香和胡椒薄荷样本中DMSO和DMS的含量。如下所示,主要物质是DMSO。DMS在风味油中显著以较低的含量存在。
表1:胡椒薄荷和留兰香油给料中DMSO和DMS的含量
样本 | DMSO(ppm,w/v) | DMS(ppm,w/v) |
胡椒薄荷给料#1 | 318 | 10.3 |
胡椒薄荷给料#2 | 312 | 22.1 |
胡椒薄荷给料#3 | 181 | 46.8 |
留兰香(1%切头) | 235 | <1 |
薄荷油,由I.P.Callison提供;留兰香油,由Labbeemint提供
据报导,自然中存在DMSO。例如,所选水果、蔬菜、谷物和饮料中DMSO的天然存在量报导于“J.Agric.Food Chem.”(1981,29,第1089-91页)中。所报导的最高含量是黑茶饮料中的16ppm。在大多数样本中,所发现的含量小于1ppm。浓缩或处理样本例如番茄糊剂中所发现的含量更高。DMSO含量的增加被认为是由于商业处理期间二甲硫醚(DMS)的氧化所致。DMS在自然界中普遍存在,并且是造成许多食品特征气味的原因。还报导DMSO存在于留兰香油[“Anais de Academia Brasileira deCiencias”,1972,44(Suppl.),273-7]和薄荷油[“Agric.Biol.Chem.”,1980,44(7),1535-43]中。没有在本文薄荷风味油中所发现含量的报导。
不受理论的束缚,据信薄荷油中的含硫化合物(具体地讲DMSO)与亚锡离子反应并且生成物质,例如硫醇(thiols)或硫醇(mercaptans),其是造成所察觉恶臭和异味的原因。亚锡离子具有相当强的还原特性。当与DMSO反应时,亚锡离子可被氧化成四价锡形式,所述DMSO继而被还原成恶臭物质DMS,以及被进一步还原成甲硫醇(CH3SH)。为防止产生恶臭,一种方法是净化薄荷油以除去恶臭前体,如题目为“FLAVOR OILS WITH REDUCEDSULFUR CONTENT AND USE IN ORAL CARE COMPOS ITIONS”的共同提交的共同未决的专利申请中所述。作为另外一种选择,本发明人已发现,可通过使用与薄荷油组合的某些“保护剂”组分来预防恶臭。据信,这些保护剂是用作捕获剂的化合物,其结合恶臭硫物质,从而防止恶臭。有利的是,许多这些保护剂还是风味剂成分,因此可作为风味剂体系的一部分掺入还可提供特定的风味特征。本发明的风味剂体系可提供丰富均衡的风味,同时薄荷组分可用于含亚锡组合物中而没有恶臭。所述口腔组合物将主要具有薄荷风味而没有恶臭或异味。
风味剂体系
本发明的风味剂体系包含薄荷油、保护剂组分以及任选的其它传统风味剂成分,包括甜味剂和冷却剂。可存在一种或多种薄荷油。可使用一种或多种保护剂。也可使用其它风味剂组分例如冷却剂或其它风味剂来形成风味剂体系。所述风味剂体系在口腔组合物中的典型含量按所述组合物的重量计为约0.01%至约5%。所述风味剂体系的含量按所述组合物的重量计优选为约0.02%至约4%,更优选约0.1%至约3%,并且最优选约0.5%至约2%。下面描述风味剂体系的组分。
薄荷油
薄荷油包括指定为薄荷类精油的那些,例如椒样薄荷或胡椒薄荷、绿薄荷、小叶薄荷或留兰香。所述薄荷油包括通常被称为胡椒薄荷、田野薄荷和留兰香的那些。所述薄荷油可以是天然或合成的,或天然与合成组分的组合。可使用标准蒸馏和/或提取设备将薄荷油分馏或精馏以除去任何不需要的组分。所述薄荷油的含量通常为2ppm至1300ppm。
保护剂组分
适宜的保护剂组分包括铜盐和羰基化合物,例如抗坏血酸[3-氧代-L-古洛呋喃内酯];顺式茉莉酮[3-甲基-2-(2-戊烯基-2-环戊烯酮];2,5-二甲基-4-羟基-3(2H)-呋喃酮;5-乙基-3-羟基-4-甲基-2(5H)-呋喃酮;香草醛[4-羟基-3-甲氧基苯甲醛];乙基香草醛;茴香醛[4-甲氧基苯甲醛];3,4-亚甲基二氧苯甲醛;3,4-二甲氧基苯甲醛;4-羟基苯甲醛;2-甲氧基苯甲醛;苯甲醛;肉桂醛[3-苯基-2-丙烯醛];己基肉桂醛;α-甲基肉桂醛;邻甲氧基肉桂醛;α-戊基肉桂醛;以及它们的组合。
据信,通过使用上述保护剂来减少挥发性恶臭硫化合物例如甲硫醇(硫醇)和二甲硫醚(DMS)的主要作用机理示于下文化学反应中。通过与硫醇或硫化物反应并且形成气味影响较小的产物,所述保护剂可用作“捕获剂”。涉及羰基化合物的反应如下所示:
a)硫醇或烷基硫化物与迈克尔反应受体即α,β-不饱和羰基化合物的迈克尔反应,得到如下所示的加成化合物,其可能具有较低的挥发性或无挥发性,因此气味较淡。
R=烷基、芳基
b)酮和醛可与硫醇反应,得到如下所示的硫代缩酮和硫代缩醛:
R=烷基、芳基
R″=H+、SnF2
为研究保护剂对包含氟化亚锡和天然薄荷油的体系中恶臭产生的抑制功效,准备20mL的玻璃小瓶,以包含3mL精馏薄荷油(由I.P.Callison提供)、3mL水和225mg氟化亚锡。除了对照物以外,向所有小瓶中加入保护剂,其量为薄荷油量的1%(v/v)。将封口的小瓶在50℃下储存72小时。在室温下平衡后,用固相微萃取(SPME)纤维对每个小瓶的顶部空间取样。对从每个小瓶中取出的样本,使SPME纤维于GC入口中解吸;在GC柱上分离挥发性物质;并且用硫化学发光检波器(SCD)对流出物进行分析。将甲硫醇(MM)和二甲硫醚(DMS)的峰面积相对于这些化合物的对照含量进行评定,并且如下表所示,保护剂导致氟化亚锡/薄荷油混合物中恶臭化合物MM和DMS测定含量的显著降低。
保护剂组分的量取决于口腔组合物中所选的具体保护剂、所选的具体薄荷油的量、亚锡离子的量、所加的其它风味剂组分、以及所期望的风味特征。一些保护剂具有调味特性,并且将提供风味剂特征,例如香草味、醇厚细腻感或肉桂味。这些保护剂中的每一个均可单独使用,或与其它保护剂一起使用。已发现,有效的保护剂与薄荷油的比率按重量计为约2∶1至约1∶300。当使用保护剂例如抗坏血酸、顺式茉莉酮、2,5-二甲基-4-羟基-3(2H)-呋喃酮、5-乙基-3-羟基-4-甲基-2(5H)-呋喃酮、乙基香草醛、香草醛、茴香醛、3,4-亚甲基二氧苯甲醛、3,4-二甲氧基苯甲醛、4-羟基苯甲醛或2-甲氧基苯甲醛时,所述比率优选为约1∶1至约1∶200。对于任何一种肉桂醛化合物,保护剂与薄荷油的比率按重量计优选为约1∶2至约1∶16,更优选约1∶3至约1∶12。在保护剂与薄荷油的比率高时,非薄荷风味剂可占优势。
保护剂在包含亚锡离子的口腔组合物中的典型浓度在以下范围内:13至2000ppm的顺式茉莉酮、2,5-二甲基-4-羟基-3(2H)-呋喃酮、5-乙基-3-羟基-4-甲基-2(5H)-呋喃酮、乙基香草醛或香草醛;6至700ppm的茴香醛、3,4-亚甲基二氧苯甲醛、3,4-二甲氧基苯甲醛、4-羟基苯甲醛或2-甲氧基苯甲醛;10至100ppm的苯甲醛;200至2700ppm的肉桂醛、己基肉桂醛、α-甲基肉桂醛、邻甲氧基肉桂醛或α-戊基肉桂醛。
除了薄荷油和保护剂以外,风味剂体系还包含附加的风味成分,包括但不限于冬青油、丁香芽油、桂皮、鼠尾草、欧芹油、牛至属植物、柠檬、橙、丙烯基乙基愈创木酚、天芥菜精、4-顺式-庚烯醛、联乙酰、甲基对-叔丁基苯基乙酸酯、薄荷醇、水杨酸甲酯、水杨酸乙酯、乙酸1-薄荷酯、噁烷酮、α-紫罗兰酮、肉桂酸甲酯、肉桂酸乙酯、肉桂酸丁酯、丁酸乙酯、乙酸乙酯、邻氨基苯甲酸甲酯、乙酸异戊酯、丁酸异戊酯、己酸烯丙酯、丁子香酚、桉树脑、百里酚、肉桂醇、辛醇、辛醛、癸醇、癸醛、苯乙醇、苄醇、α-萜品醇、里哪醇、苧烯、柠檬醛、麦芽酚、乙基麦芽酚、茴香脑、二氢茴香脑、香芹酮、薄荷酮、β-大马酮、紫罗酮、γ-癸内酯、γ-壬内酯、γ-十一烷酸内酯以及它们的混合物。一般来讲,适宜的风味成分是结构特征和官能团较不倾向于氧化还原反应的化合物。这些包括饱和的或包含稳定芳环或酯基的风味剂化合物的衍生物。可经历某些氧化或降解反应却不会导致风味剂特性或特征显著变化的风味剂化合物也是适宜的。可以单一或纯化合物的形式来提供风味成分,或者通过加入天然油或提取物以组合物的形式来提供,所述天然油或提取物优选已经过某些精炼处理以除去下述组分,所述组分较不稳定并且会降解和改变所期望的风味特征,从而获得影响器官感觉方面较不可接受的产物。
所述风味剂体系还可包含凉爽剂或冷却剂,例如薄荷醇、薄荷酯、羧酰胺、缩酮、二醇、以及它们的混合物。适用于本发明组合物中的冷却剂实例是对薄荷羧酰胺试剂,例如商业名为“WS-3”的N-乙基对薄荷-3-羧酰胺;商业名为“WS-23”的N,2,3-三甲基-2-异丙基丁酰胺;N-对-苯乙腈薄荷羧酰胺;以及系列中的其它物质,例如WS-5、WS-11、WS-14和WS-30。其它适宜的冷却剂包括由Takasago制备的称为TK-10的3-1-薄荷氧基丙-1,2-二醇;薄荷酮甘油缩醛(MGA);薄荷酯,例如乙酸薄荷酯、乙酰乙酸薄荷酯、乳酸薄荷酯(ML,由Haarmann andReimer提供)、和琥珀酸单薄荷酯(以商品名Physcool由V.Mane提供)。本文所用术语薄荷醇和薄荷基包括这些化合物的右旋和左旋异构体、以及它们的外消旋混合物。TK-10描述于1984年7月10日公布的授予Amano等人的美国专利4,459,425中。WS-3和其它试剂描述于1979年1月23日公布的授予Watson等人的美国专利4,136,163中。
所述风味剂体系通常包含甜味剂。合适的甜味剂包括本领域熟知的那些,包括天然的和人造的甜味剂。一些适宜的水溶性甜味剂包括单糖、二糖、多糖和衍生物,例如木糖、核糖、葡萄糖(右旋糖)、甘露糖、半乳糖、果糖(左旋糖)、蔗糖(砂糖)、麦芽糖、转化糖(衍生自蔗糖的果糖和葡萄糖的混合物)、部分水解的淀粉、玉米糖浆固体、二氢查尔酮、应乐果甜蛋白、蛇菊苷、甘草素、木糖醇和赤藓醇。合适的水溶性人造甜味剂包括可溶解的糖精盐,即糖精钠或糖精钙盐、环磺酸盐、3,4-二氢-6-甲基-1,2,3-噁噻嗪-4-酮-2,2-二氧化物的钠盐、铵盐或钙盐、3,4-二氢-6-甲基-1,2,3-噁噻嗪-4-酮-2,2-二氧化物的钾盐(丁磺氨-K)、游离酸形式的糖精,等等。其它适宜的甜味剂包括基于二肽的甜味剂,例如L-天冬氨酸衍生的甜味剂,例如L-天冬氨酰基-L-苯基丙氨酸甲酯(天冬甜素)和美国专利3,492,131中描述的物质,L-α-天冬氨酰基-N-(2,2,4,4-四甲基-3-硫化三亚甲基)-D-丙氨酸酰胺水合物,L-天冬氨酰基-L-苯基甘油和L-天冬氨酰基-L-2,5-二氢苯基甘氨酸、L-天冬氨酰基-2,5-二氢-L-苯基丙氨酸、L-天冬氨酰基-L-(1-环己烯基)-丙氨酸的甲酯等。可以使用衍生自天然存在的水溶性甜味剂的水溶性甜味剂,例如普通砂糖(蔗糖)的氯化衍生物(例如对已知三氯蔗糖的产品描述),以及蛋白质基甜味剂例如西非竹竽(非洲甜果素I和II)。所述组合物优选包含按重量计约0.1%至约10%,优选约0.1%至约1%的甜味剂。
此外,所述风味剂体系可包含流涎剂、加温剂和麻木剂。这些试剂以按所述组合物的重量计约0.001%至约10%,优选约0.1%至约1%的含量存在于组合物中。适宜的流涎剂包括由Takasago生产的加温剂的实例是辣椒和烟酸酯,如烟酸苄酯。适宜的麻木剂包括苯佐卡因、利多卡因、丁香芽油和乙醇。
亚锡离子
本发明还包括亚锡离子。亚锡离子来自亚锡源,其可以是可溶的或微溶的亚锡化合物。实例包括亚锡的氟化物、氯化物、氟氯化物、乙酸盐、六氟锆酸盐、硫酸盐、酒石酸盐、葡糖酸盐、柠檬酸盐、苹果酸盐、甘氨酸盐、焦磷酸盐、偏磷酸盐、草酸盐、磷酸盐、碳酸盐和氧化物。亚锡离子的含量通常为至少约1000ppm,优选约2,000ppm至约15,000ppm亚锡。更优选地,亚锡离子的含量为约3,000ppm至约13,000ppm。这是所述组合物中存在的用于向牙齿表面递送的亚锡离子总量。所述亚锡离子源的含量按所述最终组合物的重量计通常为约0.25%至约11%。优选地,所述亚锡离子源的含量为约0.4%至约7%,并且更优选约0.45%至约5%。
在实际使用所述组合物前,所述组合物中的亚锡离子源在储存期间优选未被完全离子化。当刷牙时唾液和/或水与所述组合物接触时,亚锡离子源被完全离子化并且活性离子将向口腔递送。包含亚锡盐、尤其是氟化亚锡和氯化亚锡的洁齿剂描述于授予Majeti等人的US5,004,597中。亚锡盐洁齿剂的其它描述可见于US5,578,293中。优选的亚锡盐是氟化亚锡。其它适宜的亚锡盐包括二水合氯化亚锡、乙酸亚锡、酒石酸亚锡和柠檬酸亚锡二钠。
口部可接受的载体材料
口部可接受的载体描述于下文中。它们包括可安全用于口腔组合物中的任何物质。所述载体材料可为活性剂或非活性剂。适宜的载体材料优选基本上不含作为恶臭物质前体的硫化合物。
任选的活性剂
1.牙齿增白活性物质
牙齿增白活性物质可包括在本发明的口腔护理物质中。适于增白的活性物质选自由下列组成的组:过氧化物、金属亚氯酸盐、过硼酸盐、过碳酸盐、过氧酸、过硫酸盐、以及它们的组合。适合的过氧化物包括过氧化氢、过氧化脲、过氧化钙、以及它们的混合物。适合的金属亚氯酸盐包括亚氯酸钙、亚氯酸钡、亚氯酸镁、亚氯酸锂、亚氯酸钠和亚氯酸钾。附加的增白活性物质可以是次氯酸盐和二氧化氯。优选的过碳酸盐是过碳酸钠。优选的过硫酸盐是过硫酸氢钾。
2.抗牙垢剂
已知用于牙齿护理产品中的抗牙垢剂包括磷酸盐。磷酸盐包括焦磷酸盐、多磷酸盐、聚膦酸盐以及它们的混合物。其中最常见用于牙齿护理产品中的是焦磷酸盐。衍生自焦磷酸盐或多磷酸盐的焦磷酸和多磷酸离子被递送到牙齿上。可用于本发明组合物中的焦磷酸盐包括二碱金属焦磷酸盐、四碱金属焦磷酸盐、以及它们的混合物。焦磷酸二氢二钠(Na2H2P2O7)、焦磷酸四钠(Na4P2O7)和焦磷酸四钾(K4P2O7)的未水合和水合形式是优选物质。虽然可使用上述任何焦磷酸盐,但优选焦磷酸四钠盐。例如,多磷酸钠和三乙醇胺多磷酸盐也是有用的。
在Kirk&Othmer的Encyclopedia of Chemical Technology,第三版,第17卷,Wiley-Interscience Publishers(1982)中更详细地描述了焦磷酸盐。附加的抗牙结石剂包括1986年5月20日公布的美国专利4,590,066中公开的焦磷酸盐或多磷酸盐;聚丙烯酸盐和其它聚羧酸盐,例如1969年2月25日公布的美国专利3,429,963和1981年12月8日公布的美国专利4,304,766以及1987年4月28日公布的美国专利4,661,341中所公开的那些;聚环氧琥珀酸盐,例如1989年7月11日公布的美国专利4,846,650中所公开的那些;乙二胺四乙酸,如1937年2月15日登记的英国专利No.490,384中所公开的那些;氨三乙酸和相关化合物,如1972年7月18日公布的美国专利3,678,154中所公开的那些;聚膦酸盐,如1973年6月5日公布的美国专利3,737,533、1976年10月26日公布的美国专利3,988,443和1989年10月31日公布的美国专利4,877,603中所公开的那些。
可用于代替焦磷酸盐或者可以与焦磷酸盐组合的其它抗牙结石剂包括已知物质,例如合成的阴离子聚合物,包括聚丙烯酸盐以及马来酸酐或马来酸与甲基乙烯基醚的共聚物(例如Gantrez),例如美国专利4,627,977中所述;以及例如聚氨基丙烷磺酸(AMPS)、三水合柠檬酸锌、多磷酸盐(例如三聚磷酸盐;六偏磷酸盐)、二膦酸盐(例如EHDP;AHP)、多肽(例如聚天冬氨酸和聚谷氨酸)、以及它们的混合物。
3.氟离子源
氟离子源是熟知的用于口腔护理组合物的防龋剂。鉴于此目的,将氟离子包含于众多口腔护理组合物中,尤其是牙膏中。公开此类牙膏的专利包括1970年11月3日的美国专利3,538,230;1972年9月5日的美国专利3,689,637;1973年1月16日的美国专利3,711,604;1975年10月7日的美国专利3,911,104;1976年1月27日的美国专利3,935,306;和1977年8月9日的美国专利4,040,858。
将氟离子施用到牙釉质上可用于防止蛀牙。多种氟离子形成材料可被用作本发明组合物中的可溶性氟离子源。适宜的氟离子形成材料的实例可见于1970年10月20日公布的美国专利3,535,421和1972年7月18日公布的美国专利3,678,154中,例如氟化钠、氟化钾,氟化亚锡和氟化铵。在一个实施方案中,当与本发明的递送体系一起使用时,本发明的组合物可提供约50ppm至10,000ppm的接触牙齿表面的氟离子。在另一个实施方案中,所述组合物可提供约100至3000ppm的接触牙齿表面的氟离子。
4.抗微生物剂
抗微生物剂也可存在于本发明的口腔护理组合物或物质中。上述试剂可包括但不限于5-氯-2-(2,4-二氯苯氧基)-苯酚,通常是指三氯生,并描述于“Merck Index”第11版(1989)1529页(编号9573)和美国专利3,506,720以及1988年1月7日公布的欧洲专利申请No.0,251,591中;邻苯二甲酸及其盐,包括但不限于1991年2月19日美国专利4,994,262中公开的那些,优选邻苯二甲酸单钾镁、氯己定(Merck Index,编号2090)、阿来西定(Merck Index,编号222);合克替啶(Merck Index,编号4624);血根碱(Merck Index,编号8320);烷基苄基二甲基氯化铵(Merck Index,编号1066);N-水杨酰苯胺(Merck Index,编号8299);杜灭芬(Merck Index,编号3411);氯化十六烷基吡啶鎓(CPC)(Merck Index,编号2024);氯化十四烷基吡啶鎓(TPC);氯化N-十四烷基-4-乙基吡啶(TDEPC);癸双辛胺啶;地莫匹醇,辛哌乙醇和其它哌啶子基衍生物;乳链菌素配制物;锌/亚锡/铜离子试剂;抗生素如沃格孟汀、阿莫西林、四环素、强力霉素、米诺环素和甲硝唑以及上述的类似物和盐;精油包括麝香草酚、香叶醇、香芹酚、柠檬醛、日扁柏素、桉油精、儿茶酚(尤其是4-烯丙基儿茶酚)以及它们的混合物;水杨酸甲酯;过氧化氢;亚氯酸金属盐,以及上述物质的混合物。
5.抗炎剂
抗炎剂也可存在于本发明的口腔护理组合物或物质中。此类试剂可包括但不限于非甾族抗炎剂(或NSAID),例如酮咯酸、氟比洛芬、布洛芬、萘普生、吲哚美辛、阿斯匹林、酮洛芬、吡罗昔康和甲氯芬那酸。NSAID如酮咯酸的使用,受1997年5月6日公布的美国专利5,626,838权利要求书的保护。其中公开了通过向口腔或口咽局部施用有效量的NSAID,预防和/或治疗口腔或口咽中原发性和复发性鳞状细胞癌的方法。
6.营养物质
营养物质可改善口腔环境,并且可包含在本发明的口腔护理组合物或本发明的物质中。营养物包括矿物、维生素、口服营养增补剂、肠内营养增补剂、以及它们的混合物。
可以包括在本发明组合物中的矿物质包括钙、磷、氟化物、锌、锰、钾及其混合物。这些矿物质公开于Drug Facts and Comparisons(活页医药品信息服务),Wolters Kluer Company,St.Louis,Mo.,第10至17页。
维生素可与矿物质一起被包含或者分别使用。维生素包括维生素C、D和E、硫胺素、核黄素、泛酸钙、烟酸、叶酸、烟酰胺、吡哆素、氰钴胺、对-氨基苯甲酸、生物类黄酮、以及它们的混合物。此类维生素公开于DrugFacts and Comparisons,Wolters Kluer Company,第3至10页。
口服营养增补剂包括氨基酸、抗脂肪肝剂、鱼油、以及它们的混合物,如Drug Facts and Comparisons,Wolters Kluer Company,St.年,第54至54e页中所公开的。氨基酸包括但不限于L-色氨酸、L-赖氨酸、甲硫氨酸、苏氨酸、左旋肉毒碱或L-肉毒碱、以及它们的混合物。抗脂肪肝剂包括但不限于胆碱、肌醇、甜菜碱、亚油酸、亚麻酸、以及它们的混合物。鱼油含有大量ω-3(N-3)多不饱和脂肪酸、二十碳五烯酸和二十二碳六烯酸。
肠内营养增补剂包括但不限于蛋白质产品、葡萄糖聚合物、玉米油、红花油、中碳链甘油三酯,如在Drug Facts and Comparisons,WoltersKluer Company,St.年,第55至57页中所公开的。
7.口腔和喉部产品
可与本发明一起使用的其它物质包括通常所知的口腔和喉部产品。这些产品公开于Drug Facts and Comparisons,Wolters Kluer Company,St.Louis,Mo.,第520b至527中。这些产品包括但不限于抗真菌剂、抗生素和止痛药剂。
8.抗氧化剂
抗氧化剂通常被认为可用于组合物中,例如本发明的那些组合物。抗氧化剂公开于教科书中,例如Cadenas和Packer的The Handbook ofAntioxidants(抗氧化剂手册),由Marcel Dekker,Inc.出版。可包含在本发明的口腔护理组合物或物质中的抗氧化剂包括但不限于:维生素E、抗坏血酸、尿酸、类胡萝卜素、维生素A、黄酮类化合物和多酚、草本植物抗氧化剂、褪黑激素、氨基吲哚、硫辛酸、以及它们的混合物。
9.H-2拮抗剂
组胺-2(H-2或H2)受体拮抗剂化合物(H-2拮抗剂)可用于本发明的口腔护理组合物中。如本文所用,选择性的H-2拮抗剂为阻滞H-2受体的化合物,但在阻滞组胺-1(H-1或H1)受体方面不具备有意义的活性。选择性的H-2拮抗剂包括符合上述标准的化合物,所述化合物公开于分别公布于3/15/94和11/15/94的并且转让给Procter&Gamble的美国专利5,294,433和5,364,616中。
10.止痛活性物质
止痛剂或去敏剂也可存在于本发明的口腔护理组合物或物质中。这些药剂可包括但不限于氯化锶、硝酸钾、天然草药如五倍子、细辛、荜澄茄素、高良姜、黄芩、两面针、白芷等。
11.抗病毒活性物质
可用于本组合物中的抗病毒活性物质包括任何已知的常规用于处理病毒感染的活性物质。这些抗病毒活性物质公开于Drug Facts andComparisons,Wolters Kluer Company,第402(a)至407(z)页中。具体实例包括1998年5月5日公布的美国专利5,747,070中所公开的抗病毒活性物质。此专利公开了亚锡盐在控制病毒方面的用途。亚锡盐和其它抗病毒活性物质详细描述于Kirk&Othmer的Encyclopedia of ChemicalTechnology,第3版,第23卷,Wiley-lnterscience Publishers(1982,第42至71页。可用于本发明中的亚锡盐可包括有机亚锡羧酸盐和无机的亚锡卤化物。如果氟化亚锡被使用,则其通常只与另一亚锡卤化物或一种或多种亚锡羧酸盐或另一种治疗剂组合使用。
12.酚类
得自植物源例如茶、越橘、石榴和橡树皮的酚类及衍生物,由于它们作为抗微生物、抗炎以及抗氧化活性物质的用途,因此也可被掺入到本发明的组合物中。在这些酚类及衍生物中,有许多也可被用作调味剂。此酚类包括儿茶素、没食子儿茶素没食子酸酯、表儿茶素(EC)、表没食子儿茶素(EGC)、表没食子儿茶素没食子酸酯(EGCG)、表儿茶素没食子酸酯(ECG)、茶黄素、茶红素、花色素/原花青素和花青素(例如矢车菊素、飞燕草素、花葵素、芍药花青素、锦葵色素和牵牛花色素);鞣酸;没食子酸;鞣花酸;鞣花单宁;姜黄素。所述酚类可作为纯化合物或作为植物提取物来提供。可用作口腔护理活性物质的酚类公开于共同转让的作为US2007/0053849A1公布的美国专利申请11/595,530中。
许多在口腔护理组合物中用作活性物质或风味剂的酚类易被氧化,即具有还原特性,因此可以与亚锡产生恶臭硫物质相同的方式与DMSO反应。
其它试剂
除了上述材料之外,许多其他组分还可根据需要加入。
1.水
本组合物的范围为基本上非水至含水。所谓基本上非水是指组合物可包含非常少量的水,少于约5%,这是通常与其它材料(如山梨醇或其它吸湿材料)一起引入到组合物中的含量。在制备商业上合适的含水组合物时使用的水应该优选为低离子含量并且不含有机杂质。通常,水的含量按本发明的含水组合物的重量计为约5%至约70%,优选约20%至约50%。这些水的量包括被添加的游离水以及与其他材料一起引入的水。
2.粘合剂体系
本发明的洁齿剂组合物掺有由增稠剂和至少一种湿润剂组成的粘合剂体系,所述增稠剂选自由下列组成的组:多糖、卡波姆、泊洛沙姆、改性纤维素以及它们的混合物。所述增稠剂的含量按所述组合物的重量计为约0.05%至约3%,并且优选约0.1%至1.5%。这些粘合剂体系可向所述组合物提供适宜的稠度和凝胶性。所述粘合剂体系还包含附加的无机增稠剂。湿润剂可用于防止牙膏组合物因暴露于空气中而变硬,并且某些湿润剂也可赋予牙膏组合物期望的甜味。适用于本发明中的湿润剂包括甘油、山梨醇、聚乙二醇、丙二醇、木糖醇和其它可食用的多元醇。优选甘油、聚乙二醇、聚丙二醇以及它们的混合物,尤其是它们的混合物。湿润剂的含量按所述组合物的重量计一般为约0.1%至70%,优选约1%至约60%,并且更优选约15%至55%。
所述粘合剂体系还可包含附加的无机增稠剂,例如胶态硅酸铝镁或细分的二氧化硅,以进一步改善纹理。如果存在的话,则附加的无机增稠剂用量按所述洁齿剂组合物的重量计为约0.1%至约15%,更优选约0.1%至约5%。
3.缓冲剂
本组合物可包含缓冲剂。如本文所用的缓冲剂是指能够用于将所述组合物pH值范围调节为约3.0至约10的试剂。所述缓冲剂包括碱金属氢氧化物、氢氧化铵、有机铵化合物、碳酸盐、倍半碳酸盐、硼酸盐、硅酸盐、磷酸盐、咪唑、以及它们的混合物。具体的缓冲剂包括磷酸一钠、磷酸三钠、苯甲酸钠、苯甲酸、氢氧化钠、氢氧化钾、碱金属碳酸盐、碳酸钠、咪唑、焦磷酸盐、柠檬酸和柠檬酸钠。缓冲剂的用量按本组合物的重量计为约0.1%至约30%,优选为约0.1%至约10%,并且更优选为约0.3%至约3%。
4.磨料抛光物质
磨料抛光物质也可包含在牙膏组合物中。设想用于本发明的组合物的磨料抛光物质可以是任何不过度磨损牙质的物质。典型的磨料抛光物质包括:二氧化硅,包括凝胶和沉淀;氧化铝;磷酸盐,包括正磷酸盐、聚偏磷酸盐和焦磷酸盐;以及它们的混合物。具体的实例包括二碱式磷酸钙二水合物、焦磷酸钙、磷酸三钙、聚偏磷酸钙、不溶性聚偏磷酸钠、水合氧化铝、β-焦磷酸钙、碳酸钙和树脂磨料例如脲和甲醛的颗粒状缩合产物,以及其它物质,如1962年12月25日公布的Cooley等人的美国专利3,070,510中所公开。还可使用研磨剂的混合物。如果洁齿剂组合物或颗粒相包含平均链长为约4或更长的多磷酸盐,则含钙的研磨剂和氧化铝不是优选的研磨剂。最优选的研磨剂是二氧化硅。
优选多种类型的二氧化硅牙齿研磨剂,因为它们具有使牙齿特别清洁但又不过度磨损牙釉或牙质的磨光性能的独特有益效果。本发明的二氧化硅磨料抛光物质,以及其它研磨剂的平均粒径通常在约0.1至约30微米,并且优选约5至约15微米的范围内。所述研磨剂可以是沉淀二氧化硅或硅胶,如在公布于1970年3月2日授予Pader等人的美国专利3,538,230和公布于1975年1月21日授予DiGiulio的美国专利3,862,307中所描述的二氧化硅干凝胶。实例包括W.R.Grace&Company,Davison ChemicalDivision以商品名“Syloid”销售的二氧化硅干凝胶和例如J.M.HuberCorporation以商品名销售的沉淀二氧化硅,尤其是具有119、118、109和129命名的二氧化硅。可用于本发明牙膏中的这类二氧化硅牙齿研磨剂更详细地描述于1982年7月29日授予Wason的美国专利4,340,583和共同转让的美国专利5,603,920、5,589,160、5,658,553、5,651,958、5,716,601和6,740,311中。
可应用的研磨剂混合物如上面所列的的不同等级的二氧化硅研磨剂。本主题发明的洁齿剂组合物中研磨剂的总量按重量计通常在约6%至约70%的范围内。牙膏优选包含按所述组合物的重量计约10%至约50%的研磨剂。本主题发明的牙齿溶液、口喷剂、漱口水和非研磨性凝胶组合物通常含有很少研磨剂或完全不含研磨剂。
4.牙齿亲和剂
本发明可包括牙齿亲和剂,例如聚合物表面活性剂(PMSA),该聚合物表面活性剂为高分子电解质,更具体地讲为阴离子聚合物。所述聚合物表面活性剂包含阴离子基团,例如磷酸根、膦酸根、羧酸根或它们的混合物,因此具有与阳离子或带正电实体相互作用的能力。“矿物质”描述词旨在表明聚合物的表面活性或亲和性针对矿物质表面,例如磷酸钙矿物或牙齿。
由于聚合物表面活性剂具有抗色斑有益效果,因此可用于本发明的组合物中。据信,所述聚合物表面活性剂可提供防色斑有益效果,这是因为它们对矿物质表面具有反应性或亲和性,导致不期望被吸附的薄膜蛋白质部分解吸,具体地讲是与结合染污牙齿的颜色本体、牙结石发展以及吸引不可取微生菌种相伴的那些。这些聚合物表面活性剂在牙齿上的保持力还可防止色斑产生,这应归因于对颜色本体在牙齿表面上结合位点的破坏。
据信,聚合物表面活性剂结合口腔护理产品中促生色斑成分例如亚锡离子和阳离子抗微生物剂的能力也是有益的。所述PMSA还可提供牙齿表面调理效果,其对表面热力学性质和表面薄膜性质产生适宜的影响,这在漱洗或刷洗期间并且最重要的是在漱洗或刷洗后,赋予改善的清洁感美观性。当应用于口腔组合物中时,许多这些聚合物试剂还已知或者期待可提供控制牙垢的有益效果,从而在牙齿外观以及它们给消费者的触感方面提供改善。
适宜的表面效果包括:1)处理后立即产生亲水性牙齿表面;和2)产品使用后长期保持表面调理效果和对薄膜的控制,包括刷洗或漱洗后以及更长的整个期间。造成表面亲水性增加的有益效果可通过水接触角的相对减小测得。重要的是,在使用产品后,亲水表面在牙齿表面上长期保持。
聚合矿物质表面活性剂包括对牙齿表面具有强亲和力、在牙齿表面沉积成聚合物层或覆盖层并且产生所需表面改性效果的任何试剂。这类聚合物的合适的实例为高分子电解质,例如缩聚磷酸化聚合物、聚膦酸酯、含磷酸根-或膦酸酯的单体或聚合物与如下物质的共聚物:烯键式不饱和单体和氨基酸或其它聚合物,例如蛋白质、多肽、多糖、聚丙烯酸酯、聚丙烯酰胺、聚甲基丙烯酸酯、聚乙基丙烯酸酯、聚甲基丙烯酸羟基烷基酯、聚乙烯醇、聚马来酸酐、聚马来酸酯、聚酰胺、聚乙烯胺、聚乙二醇、聚丙二醇、聚乙酸乙烯酯和聚乙烯基苄基氯、聚羧酸酯和羧基取代的聚合物、以及它们的混合物。适宜的聚合矿物质表面活性剂包括均授予Degenhardt等人的美国专利5,292,501、5,213,789、5,093,170、5,009,882和4,939,284中所述的羧基取代的醇聚合物和授予Benedict等人的美国专利5,011,913中所述的二膦酸酯衍生的聚合物;合成阴离子聚合物,包括聚丙烯酸酯以及马来酸酐或马来酸与甲基乙烯基醚的共聚物(如Gantrez),如授予Gaffar等人的美国专利4,627,977中所述。优选的聚合物是二膦酸酯改性的聚丙烯酸。具有活性的聚合物具有足够的表面粘附特性以将薄膜蛋白质解吸并保持附于釉质表面上。对于牙齿表面,具有末端或侧链磷酸盐或膦酸酯官能团的聚合物是优选的,然而具有矿物质结合活性的其它聚合物可根据吸附亲和力来证明有效性。
适宜的含膦酸酯聚合矿物质表面活性剂的其它实例包括授予Degenhardt等人的US4,877,603中公开的作为抗牙结石剂的偕二膦酸酯聚合物;授予Dur s ch等人的US4,749,758和GB1,290,724(均转让给Hoechst)中公开的含膦酸酯基团的共聚物,其适用于洗涤剂和清洁组合物中;和授予Zakikhani等于的US5,980,776和授予Davis等人的US6,071,434中公开的可用于包括抑制牙垢和腐蚀、涂层、接合剂和离子交换树脂的应用中的共聚物和共调聚物。其它聚合物包括GB1,290,724中公开的乙烯基磷酸和丙烯酸及其盐的水溶性共聚物,其中所述共聚物包含按重量计约10%至约90%的乙烯基磷酸和按重量计约90%至约10%的丙烯酸,更具体地讲,其中所述共聚物具有的乙烯基磷酸与丙烯酸的重量比率为70%的乙烯基磷酸比30%的丙烯酸;50%的乙烯基磷酸比50%的丙烯酸;或30%的乙烯基磷酸比70%的丙烯酸。其它适宜的聚合物包括由Zakikhani和Davis公开的水溶性聚合物,其通过二膦酸酯或聚膦酸酯单体与至少一种具有不饱和C=C键的其它化合物(如,丙烯酸酯和甲基丙烯酸酯单体)的共聚化制得,所述聚膦酸酯单体具有一个或多个不饱和的C=C键(如,亚乙烯基-1,1-二膦酸和2-(羟基氧膦基)亚乙基-1,1-二膦酸),所述聚合物例如具有如下结构的那些:
1.具有以下结构的丙烯酸和2-(羟基氧膦基)亚乙基-1,1-二膦酸的共调聚物:
2.具有以下结构的丙烯酸和乙烯基二膦酸的共聚物:
合适的聚合物包括二膦酸酯/丙烯酸酯聚合物,其由Rhodia以商品名ITC1087(平均分子量为3000至60,000)和Polymer1154(平均分子量为6000至55,000)提供。
优选的聚合物表面活性剂在口腔护理组合物中的其它组分如氟离子和金属离子的存在下是稳定的。还优选在水含量高的制剂中具有有限水解度的聚合物,从而可能得到简单的单相洁齿剂或漱口水制剂。如果聚合物表面活性剂不具有这些稳定特性,一种选择是双相制剂,其中使聚合矿物质表面活性剂与氟化物或其它不相容的组分分开。另一种选择是配制非水性、基本非水性或具有有限量水的组合物,以将PMSA与其它组分间的反应最小化。
优选的聚合物表面活性剂为多磷酸盐。尽管存在一些环状聚磷酸盐衍生物,但通常认为聚磷酸盐由主要以线性构型排列的两个或多个磷酸盐分子组成。尽管焦磷酸盐(n=2)从技术上说是多磷酸盐,但是所需的多磷酸盐为具有约三个或更多个磷酸根基团的那些,以使得有效浓度的表面吸附能产生足够的非结合磷酸根官能团,这增强了表面的阴离子表面电荷以及亲水特性。在所有磷酸盐中,期望的无机磷酸盐包括三聚磷酸盐、四聚磷酸盐和六偏磷酸盐。比四聚磷酸盐大的聚磷酸盐通常以无定形玻璃质材料出现。在本发明中优选的是具有下式的直链多磷酸盐:
XO(XPO3)nX
其中X为钠、钾或铵,并且n平均值为约3至约125。优选的多磷酸盐是n平均值为约6至约21的那些,例如由FMC Corporation和Astaris生产的以商品名Sodaphos(n≈6)、Hexaphos(n≈13)和Glass H(n≈21)销售的那些。这些多磷酸盐可以单独使用或者组合使用。多磷酸盐在酸性pH下,尤其是低于pH5时,易于在水含量高的制剂中水解。因此,优选使用长链多磷酸盐,具体地讲平均链长为约21的Glass H。据信,当经历水解时,此类长链多磷酸盐可产生短链多磷酸盐,其仍可有效地沉积在牙齿上并提供防色斑有益效果。
除了多磷酸盐以外或作为多磷酸盐的替代,可使用其它多磷酸化的化合物,具体地讲多磷酸化肌醇化合物,例如植酸、肌醇五(二氢磷酸酯)、肌醇四(二氢磷酸酯)、肌醇三(二氢磷酸酯)和它们的碱金属盐、碱土金属盐或铵盐。本文优选的是植酸以及它的碱金属盐、碱土金属盐或铵盐。植酸也被称为肌醇1,2,3,4,5,6-六(二氢磷酸酯)或肌醇六磷酸。在本文中,术语“肌醇六磷酸”包括植酸和它的盐以及其它多磷酸化肌醇化合物。
牙齿亲和剂的量按所述总口腔组合物的重量计通常为约0.1%至约35%。在洁齿剂制剂中,所述量优选为约2%至约30%,更优选约5%至约25%,并且最优选约6%至约20%。在漱口水组合物中,牙齿亲和剂的量优选为约0.1%至5%,并且更优选为约0.5%至约3%。
除了产生表面改性效果以外,牙齿亲和剂还可用于稳定不溶解的盐。例如,已发现Glass H多磷酸盐可溶解不溶性亚锡盐。因此,在包含亚锡盐的组合物中,Glass H有助于降低亚锡的色斑促生效应。
5.附加的口部可接受的载体
本组合物还可包含表面活性剂,其通常也被称为起泡剂。适宜的表面活性剂是指那些在整个宽的pH值范围内具有适度稳定性和泡沫的物质。表面活性剂可以是阴离子的、非离子的、两性的、两性离子的、阳离子的、或它们的混合物。可用于本发明的阴离子表面活性剂包括烷基中含有8至20个碳原子的烷基硫酸的水溶性盐(如烷基硫酸钠)和含有8至20个碳原子的脂肪酸的磺化单酸甘油酯的水溶性盐。这类阴离子表面活性剂的实例是月桂基硫酸钠和椰子基单酸甘油酯磺酸钠。其他合适的阴离子表面活性剂为肌氨酸盐如月桂酰肌氨酸钠、牛磺酸盐、月桂基磺基乙酸钠、月桂酰羟乙基磺酸钠、月桂基聚氧乙烯醚羧酸钠和十二烷基苯磺酸钠。也可使用阴离子表面活性剂的混合物。许多合适的阴离子表面活性剂公开于1976年5月25日授予Agricola等人的美国专利3,959,458中。可用于本发明组合物中的非离子表面活性剂可广义地定义为由氧化亚烷基团(本身亲水的)与本身可为脂族或烷基芳族的有机疏水化合物缩合而生成的化合物。适宜的非离子表面活性剂的实例包括泊洛沙姆(以商品名Pluronic和Pluraflo出售)、聚氧乙烯、聚氧乙烯脱水山梨糖醇酯(以商品名Tweens出售)、Polyoxyl40氢化蓖麻油、脂肪醇乙氧基化物、烷基酚与聚环氧乙烷的缩合物、衍生自环氧乙烷与氧化丙烯和乙二胺的反应产物的缩合产物、脂肪醇的环氧乙烷缩合物、长链叔胺氧化物、长链叔膦氧化物、长链二烷基亚砜,以及这些物质的混合物。可用于本发明的两性表面活性剂可被广泛地描述为脂族仲胺和叔胺的衍生物,其中脂族基团可以是直链或支链的,并且其中一个脂族取代基包含约8至约18个碳原子,并且一个包含水溶性的阴离子基团,例如羧酸根、磺酸根、硫酸根、磷酸根或膦酸根。其它合适的两性表面活性剂是甜菜碱,具体地讲为椰油酰氨基丙基甜菜碱。也可使用两性表面活性剂的混合物。在这些适宜的非离子和两性表面活性剂中,有许多公开于1977年9月27日公布的Gieske等人的美国专利4,051,234中。本发明的组合物通常包含一种或多种表面活性剂,每种的含量按重量计为约0.25%至约12%,优选为约0.5%至约8%,并且最优选为约1%至约6%。
其中泊洛沙姆是优选用于本发明组合物中的表面活性剂。泊洛沙姆还可用作乳化剂、粘合剂、稳定剂、以及其它相关的功能。适用于本发明的泊洛沙姆是Poloxamer407和Pluraflo L4370。
本发明也可包括碱金属碳酸氢盐,它可以提供许多功能,包括研磨、除臭、缓冲和调节pH值。碳酸氢钠也称为发酵粉,其为常用的碱金属碳酸氢盐。本组合物可包含约0.5%至约30%,优选约0.5%至约15%,最优选约0.5%至约5%的碱金属碳酸氢盐。
可将二氧化钛也加入到本组合物中。二氧化钛是能给组合物提供不透明性的白色粉末。二氧化钛的含量按所述洁齿剂组合物的重量计一般为约0.25%至约5%。
也可将着色剂加入到本发明的组合物中。着色剂可以是水溶液的形式,优选为含1%着色剂的水溶液。有色溶液的含量按所述组合物的重量计一般为约0.01%至约5%。
其它可用于本组合物的任选试剂包括选自烷基聚二甲基硅氧烷共聚多元醇和烷氧基聚二甲基硅氧烷共聚多元醇的聚二甲基硅氧烷共聚多元醇,如C12至C20烷基聚二甲基硅氧烷共聚多元醇以及它们的混合物。高度优选是商品名Abil M90的鲸蜡基聚二甲硅氧烷共聚多元醇。通常,聚二甲基硅氧烷共聚多元醇的含量按重量计为约0.01%至约25%,优选约0.1%至约5%,更优选约0.5%至约1.5%。该聚二甲基硅氧烷共聚多元醇辅助提供积极的牙齿感觉有益效果。
使用方法
本发明也涉及牙齿清洁和预防令人讨厌的口腔病症的方法,所述口腔病症包括龋齿、微生物感染、牙斑、牙结石、色斑和口腔恶臭和牙齿侵蚀。
本发明的使用方法包括将试验者的牙釉质表面和口腔粘膜与本发明的口腔组合物接触。使用方法可以为用洁齿剂刷洗、用洁齿剂浆液或漱口剂漂洗、或咀嚼口香糖产品。其它方法包括将局部用口腔凝胶、口喷剂或其它形式与患者的牙齿和口腔粘膜接触。受试者可以是其牙齿表面接触所述口腔组合物的任何人或动物。“动物”旨在包括家庭宠物或其它家畜,或关在笼中的动物。
例如,处理方法可包括某个人使用一种洁齿剂组合物来刷洗狗的牙齿。另一个实例包括用口腔组合物将猫的嘴漂洗足够长时间以看到有益效果。可以配制包含本口腔组合物的宠物护理产品如咀嚼物和玩具。将所述组合物包含在相对柔软但坚固耐用的材料,如生皮、由天然或合成纤维制成的绳子、和由尼龙、聚酯或热塑性聚氨酯制成的聚合物制品中。当动物咀嚼、舌舔或啃咬上述产品时,所含的活性组分被释放到动物的口腔中的唾液基质中,这相当于有效的刷洗或漂洗。
实施例
下列实施例进一步描述和证明了本发明范围内的实施方案。所给的这些实施例仅用于说明之目的,不可理解为是对本发明的限制,因为在不背离本发明的实质和范围的情况下其许多变型是可能的。
下面描述包含薄荷油和保护剂组分的风味剂体系。
实施例I
成分 | 重量% |
田野薄荷 | 40% |
对丙烯基茴香醚 | 15% |
薄荷醇 | 10% |
胡椒薄荷 | 30% |
肉桂醛 | 5% |
实施例II
成分 | 重量% |
WS-3冷却剂 | 10% |
留兰香油 | 15% |
薄荷油 | 30% |
对丙烯基茴香醚 | 4) |
薄荷醇 | 24% |
乙基香草醛 | 7% |
天芥菜精 | 3% |
香草醛 | 7% |
下面描述包含亚锡离子、如实施例I和II中的风味剂体系和口部可接受载体的口腔组合物,所述风味剂体系包含薄荷油和保护剂。包含亚锡和风味剂体系的口腔组合物将没有臭味和异味,所述风味剂体系包含薄荷油和保护剂。包含相同量亚锡和薄荷油但不包含保护剂的口腔组合物将具有显著的恶臭和异味,使得所述口腔组合物不美观悦人。
实施例III
1碳酸锌AC,由Bruggemann Chemical:Newtown Square,PA,USA供应
本文所公开的量纲和值不旨在被理解为严格地限于所述的精确值。相反,除非另外指明,每个这样的量纲是指所引用的数值和围绕该数值的功能上等同的范围。例如,公开为“40mm”的量纲旨在表示“约40mm”。
在发明详述中引用的所有文件都在相关部分中以引用方式并入本文中。对于任何文件的引用不应当解释为承认其是有关本发明的现有技术。当本发明中术语的任何含义或定义与以引用方式并入的文件中术语的任何含义或定义矛盾时,应当服从在本发明中赋予该术语的含义或定义。
虽然已经举例说明和描述了本发明的具体实施方案,但是对于本领域技术人员来说显而易见的是,在不背离本发明实质和范围的情况下可以做出多个其他改变和变型。因此,权利要求书意欲包括在本发明范围内的所有这样的改变和变型。
Claims (12)
1.一种口腔护理组合物,所述组合物包含:
a.亚锡离子;
b.风味剂体系,所述风味剂体系包含(i)薄荷油,和(ii)保护剂组分,所述保护剂组分选自顺式茉莉酮、2,5-二甲基-4-羟基-3(2H)-呋喃酮、5-乙基-3-羟基-4-甲基-2(5H)-呋喃酮、香草醛、乙基香草醛、茴香醛、以及它们的混合物;和
c.口部可接受的载体;
其中所述保护剂组分与薄荷油的比率按重量计为2∶1至1∶300。
2.如权利要求1所述的口腔组合物,其中所述保护剂组分与薄荷油的比率按重量计为1∶1至1∶200。
3.如权利要求1所述的口腔组合物,其中所述保护剂组分与薄荷油的比率按重量计为1∶2至1∶16。
4.如权利要求1所述的口腔组合物,其中所述保护剂组分与薄荷油的比率按重量计为1∶3至1∶12。
5.如权利要求1所述的口腔组合物,其中所述薄荷油选自胡椒薄荷、留兰香、田野薄荷以及它们的混合物。
6.如权利要求1所述的口腔组合物,其中所述口腔组合物为洁齿剂。
7.如权利要求1所述的口腔组合物,其中所述口腔组合物具有小于70%的水。
8.如权利要求1所述的口腔组合物,其中所述亚锡离子来自氟化亚锡。
9.如权利要求1所述的口腔组合物,其中所述风味剂体系按重量计为0.01%至5%。
10.如权利要求1所述的口腔组合物,所述组合物包含一种或多种附加的风味成分。
11.如权利要求10所述的口腔组合物,其中所述附加的风味成分选自冬青油、丁香芽油、桂皮、鼠尾草、欧芹油、牛至属植物、柠檬、橙、丙烯基乙基愈创木酚、天芥菜精、4-顺式-庚烯醛、联乙酰、甲基对-叔丁基苯基乙酸酯、薄荷醇、水杨酸甲酯、水杨酸乙酯、乙酸1-薄荷酯、噁烷酮、α-紫罗兰酮、肉桂酸甲酯、肉桂酸乙酯、 肉桂酸丁酯、丁酸乙酯、乙酸乙酯、邻氨基苯甲酸甲酯、乙酸异戊酯、丁酸异戊酯、己酸烯丙酯、丁子香酚、桉树脑、百里酚、肉桂醇、辛醇、辛醛、癸醇、癸醛、苯乙醇、苄醇、α-萜品醇、里哪醇、苧烯、柠檬醛、麦芽酚、乙基麦芽酚、茴香脑、二氢茴香脑、香芹酮、薄荷酮、β-大马酮、紫罗酮、γ-癸内酯、γ-壬内酯、γ-十一烷酸内酯、以及它们的混合物 。
12.如权利要求1所述的口腔组合物,所述组合物还包含选自由下列组成的组的成分:多磷酸盐、肌醇六磷酸、乙二胺四乙酸、以及它们的组合。
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