CN1870902A - 糖果组合物 - Google Patents
糖果组合物 Download PDFInfo
- Publication number
- CN1870902A CN1870902A CN02809798.XA CN02809798A CN1870902A CN 1870902 A CN1870902 A CN 1870902A CN 02809798 A CN02809798 A CN 02809798A CN 1870902 A CN1870902 A CN 1870902A
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- quadrafos
- metal cation
- described composition
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- Prior art date
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- 239000002184 metal Substances 0.000 claims abstract description 69
- 150000001768 cations Chemical class 0.000 claims abstract description 68
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- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
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- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- MSXHSNHNTORCAW-GGLLEASOSA-M sodium;(2s,3s,4s,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].O[C@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O MSXHSNHNTORCAW-GGLLEASOSA-M 0.000 description 1
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- JEYKZWRXDALMNG-UHFFFAOYSA-N sufotidine Chemical compound CN1N=C(CS(C)(=O)=O)N=C1NCCCOC1=CC=CC(CN2CCCCC2)=C1 JEYKZWRXDALMNG-UHFFFAOYSA-N 0.000 description 1
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- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 1
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- 235000019364 tetracycline Nutrition 0.000 description 1
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- 235000019157 thiamine Nutrition 0.000 description 1
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- 239000011721 thiamine Substances 0.000 description 1
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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- 229960000790 thymol Drugs 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
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- 235000019165 vitamin E Nutrition 0.000 description 1
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- 239000011709 vitamin E Substances 0.000 description 1
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- WTARULDDTDQWMU-UHFFFAOYSA-N β-pinene Chemical compound C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
- A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
- A23G3/36—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
- A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
- A23G3/343—Products for covering, coating, finishing, decorating
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
- A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
- A23G3/36—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
- A23G3/362—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds containing inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G4/00—Chewing gum
- A23G4/06—Chewing gum characterised by the composition containing organic or inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G4/00—Chewing gum
- A23G4/06—Chewing gum characterised by the composition containing organic or inorganic compounds
- A23G4/064—Chewing gum characterised by the composition containing organic or inorganic compounds containing inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G4/00—Chewing gum
- A23G4/18—Chewing gum characterised by shape, structure or physical form, e.g. aerated products
- A23G4/20—Composite products, e.g. centre-filled, multi-layer, laminated
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G2210/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing inorganic compounds or water in high or low amount
-
- 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
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
- Confectionery (AREA)
Abstract
糖果组合物,所述组合物包括:(i)具有平均阴离子链长大于或等于3的聚磷酸盐物质;(ii)大于约10ppm的第一金属阳离子,所述金属离子选自元素周期表的第5、6、7、8、9、10、11、12、14、16族金属;(ii i)少于约10%的水;和(iv)合适的糖果载体物质,其中聚磷酸盐阴离子与金属阳离子的摩尔比为约10∶1至约1∶1。本发明涉及稳定的可携带的口腔护理糖果组合物,所述组合物提供增强的控制口腔异味有益效果以及增强的抗牙结石有益效果。
Description
发明领域
本发明涉及糖果组合物,该组合物包括具有平均阴离子链长大于3或等于3的聚磷酸盐;金属阳离子,其中聚磷酸盐与金属阳离子的比率为约10∶1至约1∶1,且其中按组合物的重量计,该糖果组合物包括小于10%的水。优选地,本发明涉及不生龋齿或所谓的“无糖”口香糖糖果组合物。更特别地是,本发明涉及治疗或防止口腔异味,治疗或防止牙结石和对使用者口腔内具有表面调理效果的组合物。本发明的组合物适用于人或动物。
发明背景
口腔异味或口臭通常指难闻气味,其是由口腔中积聚的挥发性硫化合物、羧酸和胺所引起。恶臭化合物主要是由口腔微生物对硫化物的腐败作用而产生,该硫化物包括口中存在的氨基酸、蛋白胨或蛋白质。此类微生物很容易在唾液和牙斑中找到,且可来源于截留在牙齿间、在齿龈缝中或粘附于舌头的黏液膜和不规则表面的蛋白质类食物颗粒,以及脱落的口腔皮膜、食物残渣等。此外,口腔异味可由不良的口腔卫生、消化系统问题、疾病、饮食或这些因素的任意组合所引起。口腔异味不仅令人讨厌,而且它的存在也表明不良的口腔卫生,并且还可能是一些更严重的潜在问题的最初征兆之一,这是因为产生异味的腐烂物质的积聚还可导致牙斑的形成、龋齿、齿龈炎和牙结石的产生。定期刷牙可帮助最大程度地减少口腔异味。然而,即使定期刷牙也不足以去除所有的粘附于口腔表面的食物和口腔细菌沉淀,而且在严重的情况下,它不能够消除口腔异味。
到目前为止,配制的治疗口腔异味产品包括许多能杀死产生口腔异味的细菌的物质。此类物质包括例如下列物质:三氯生、洗必太、季铵盐和含樟脑的对氯苯酚。然而,这些物质可能涩口,且每日仅能以有限量摄入,因此未必适用于每日使用数次的产品中。在某些情况下,它们还可导致不良的副作用如变色、变味等。
最近的趋势趋向于使用所谓的天然物质,尤其是提取物,以在个人护理产品中提供多种有益效果。已报导日本黄莲和忍冬的草本植物提取物(日本专利57-85319/美国专利5,741,138);日本专利10-182,388中公布草本植物咖喱草提取物用于防治口臭;WO 96/28135专利中公布了酸果蔓果实提取物,其具有抗微生物和抗菌的性能;和德国专利4,221,103公布了包括多种草本植物提取物的组合物用于口腔卫生。已确定在多种草本植物提取物中多酚为重要的活性物质。口腔护理公开内容的实施例包括WO 01/17494,其中公开了包括茶多酚的洁齿剂组合物;US/PCT/00/11258,其中公开了包括多酚草本植物提取物的洁齿剂组合物;和欧洲专利1,013,261,其中公开了包括多酚的喷剂液体用于遮蔽口臭。然而现有技术的教导主要涉及具有有限的去除异味或抗菌性能的组合物,这使得产品本身具有有限的活性且不稳定,导致随着时间的流逝而缓慢变色和功效进一步下降。因此,需要稳定的口腔护理产品,该产品能递送有效的异味控制有益效果。
在用于治疗口腔异味的口腔组合物中还考虑包括金属阳离子。公开内容包括美国专利5,833,952,其中公开了包括锡盐的组合物,可任选地与锌盐联合使用;WO 99/17735,其中公开了金属离子氨基酸螯合物;美国专利6,123,925,其中公开了包括与抗菌金属离子联合使用的陶瓷颗粒的洁齿剂。然而,在制备用于防治口腔异味的包括金属离子的组合物中仍存在一些问题。这些问题包括:高含量的金属阳离子的存在可能常造成组合物中其它元素不稳定;金属离子容易与其它产物螯合且因此变得无效;严格控制的调节限制和产品趋向于较高涩味,因此具有不能接受的口感特征。尽管有这些不利条件,但是使用金属阳离子用于防治口腔异味仍具有一些有益效果。这些有益效果包括:材料非常便宜;原料容易使用且金属阳离子具有良好的有记载的功效。因此,仍然希望继续使用金属阳离子,以发展稳定的令人愉悦的口腔护理产品,使其递送有效且持久的防治异味有益效果。
口腔异味与牙斑的积聚密切相关。牙斑是指在牙齿和口腔邻近表面上积聚的物质的沉淀。它是口腔中微生物增长的产物,主要来源于口中的食物/糖残渣。存在于唾液中的粘蛋白、矿物质和食物沉淀以及在口中的死亡细胞也有助于形成牙斑。牙斑的积聚增加结石的形成,该结石是一种沉积于牙齿上的硬的矿物质,当牙斑膜上纠缠在一起的磷酸钙晶体变得足够紧密以致发生聚集并具有抗变形能力时,就会形成结石。牙齿上的牙斑和结石的积聚导致口腔健康的普遍下降,由此导致龋齿形成速率的增加,牙床疾病流行的增加,并还可能促使牙齿变色和产生异味。如果对这些状况不治疗,则可导致严重的口腔疾病和齿龈与牙齿的退化。
本领域已知有多种抗牙斑和抗牙结石剂。此类物质中的一种为线性或环状脱水聚磷酸盐,该物质已知为有效的钙/镁离子抑制剂、多价螯合剂和/或螯合剂和有效的结石形成抑制剂。已知的实施例为水溶性六偏磷酸盐、三聚磷酸盐、焦磷酸盐及类似物。这些物质广泛地公开于口腔护理组合物如洁齿剂中。这些公开内容的实施例包括美国专利5,094,844,其中公开了包括三聚磷酸盐的口腔组合物;美国专利4,460,565,其中公开了口腔组合物,该组合物包括两种或多种氟化物和能向牙齿提供钙离子的试剂,及可选择性地与环状磷酸盐联合;WO99/12517,其中公开了包括三聚磷酸盐、焦磷酸盐和PVP的口腔组合物;日本专利10-182388,其中公开了包括环状和线性的浓缩磷酸和咖喱草提取物的组合物;和日本专利9-295942,其中公开了包括至少一种间位磷酸盐的用于防止牙齿腐化的试剂。还已知此类聚磷酸盐在包括锌的口腔组合物中能提供缓冲效应(Wagenknecht的美国专利4,170,632和美国专利4,170,633)。此外,未决专利申请PCT/US00/30808报导了平均阴离子链长大于或等于4的长链线性聚磷酸盐,向牙齿和粘膜提供新的表面调理有益效果。这导致提高的清洁印象。然而,聚磷酸盐,尤其是长链聚磷酸盐的一个常见的问题是它们会快速水解,因此它们的功效将随着时间而降低。而且,当将聚磷酸盐引入口腔时,唾液酶快速水解该物质,这又导致其所需的功效降低。因此,有可能进一步优化包括聚磷酸盐的口腔护理产品制剂,以克服这些水解问题。
给定口腔异味形成与牙斑的密切联系,理想的是研发一种口腔护理产品,该产品不仅具有优良的防治口腔异味的有益效果,而且还具有抗牙斑有益效果。尽管日本专利10-182388公开了包括环状和线性浓缩磷酸和咖喱草提取物的组合物,其中咖喱草提取物具有防止口臭的有益效果,然而目前在本领域几乎没有为此目的作出任何努力。给定金属阳离子用于防治口腔异味的已知的有益效果,理想的是研发一种包括聚磷酸盐和金属阳离子组合的口腔组合物,用于治疗和防止口腔异味和牙斑。目前在单相口腔护理组合物中将金属阳离子与聚磷酸盐结合的努力鲜有成功。本领域的公开内容包括:美国专利5,833,952,其中公开了包括锡盐,优选任选地与锌盐联合的磷酸锡的组合物;WO 99/17735,其中公开了可任选与焦磷酸盐联合的金属离子氨基酸螯合物;美国专利5,094,842,其中公开了包括维生素C、铜盐的组合物,其中优选的锡盐为磷酸锡;美国专利5,188,820,其中公开了包括锡盐和锌盐混合物的口腔组合物,其中优选的锡盐为磷酸锡;未决专利申请PCT/US00/17177,其中公开包括了长链聚磷酸盐和乳酸锌的口香糖组合物;和欧洲专利528,458,其中公开了包括磷酸肽、可溶性聚磷酸盐和锌盐,及可任选包括锡盐的组合物。虽然现有技术的公开内容教导金属离子与焦磷酸盐和短链聚磷酸盐的联合,但仍需要研发能递送有效抗牙斑和抗口腔异味功效的组合物。而且,仍然需要配制有效的去除口腔异味的组合物,该组合物具有可接受的涩味含量。
此外,在口腔护理行业中,目前趋向于发展可携带的口腔护理产品形式,该形式可一天使用几次,尤其是在饭后。希望此类产品能提高消费者的口腔卫生。此外,此类产品能更容易地为不太容易和不可能定期刷牙的儿童和宠物提供口腔卫生。
糖果组合物受到儿童和成人的欢迎,且在消费过程中,在口腔中停留相当长的一段时间,它似乎是生产可携带口腔护理产品的理想形式。已知多种糖果组合物的生产技术和进展。然而,此类糖果组合物的高糖含量已被公认为是导致不良牙齿健康的一种因素。已研发生产“无糖”或不生龋齿的糖果,该糖果保留感官上的性质,但不会有助于牙斑的形成。新近的研究已转向发展糖果组合物,尤其是“无糖”糖果组合物,尤其是口香糖组合物,该组合物包括一种或多种口腔护理剂。此类实例中的一种为WO 99/44436,其公开了涂敷口香糖组合物,该组合物包括具有已知口腔护理有益效果的物质。然而,尽管口香糖产品具有一些有益效果,但它们也具有一些不利因素,因为一些消费者认为咀嚼口香糖不雅观,并且在某些群体中不被接受。此外,口香糖产品形式对于给宠物和儿童施用不理想。因此,需要一种糖果口腔护理产物形式或系列形式,其不仅可被广泛的群体接受,而且还保持高度的口腔护理功效,尤其是抗牙斑和抗牙结石功效。
在本领域中已报道了糖果组合物中聚磷酸盐的使用。实施例包括欧洲专利309,414,其中公开了包括树胶基质和抗牙垢活性物质的口香糖组合物,该抗牙垢活性物质选自聚磷酸盐、柠檬酸盐和苹果酸盐;美国专利4,908,211,其中公开了包括血根碱和可任选的聚磷酸盐的口香糖;美国专利5,702,687,其中公开了可任选地包括焦或聚磷酸盐组合物的口香糖组合物,和美国专利4,151,270,其中公开了可任选地包括三聚磷酸盐的口香糖组合物。尽管现有技术的教导提供了关于研发包括短链聚磷酸盐的口香糖组合物的有用指导,但它们没有指导如何研发多种包括链长为3或大于3的聚磷酸盐的糖果组合物,以使聚磷酸盐在组合物中保持配方稳定,并在消费组合物时具有所需的抗牙结石功效。仍需要成功地配制包括金属阳离子的糖果组合物,该金属阳离子具有持久有效的口腔异味控制有益效果。
令人吃惊的是,现已发现当制备口腔组合物,该口腔组合物包括具有平均阴离子链长大于或等于3的聚磷酸盐,第一金属阳离子,少于10%的水,其中聚磷酸盐与金属离子的比率为约10∶1至约1∶1时;所得组合物具有有效和持久的抗牙斑和抗口腔异味有益效果。此外还发现,在使用期间和之后的延长时间段内,该组合物提供表面调理效果,以使口腔表面呈现显著的清洁印象和良好的口感特征,因此提高消费者能注意到的对牙齿的有益效果。
不受理论的约束,据信当配制包括与金属阳离子结合的具有链长大于或等于3的聚磷酸盐物质的组合物时,阳离子可与聚磷酸盐络合,这将降低它们的防口臭功效。然而,通过确保金属阳离子与聚磷酸盐的比率为约10∶1至1∶1,未络合的金属阳离子将保持足够高的含量以至能保持防治口腔异味的有益效果。此外,据信这种络合控制也导致足够的金属阳离子被络合,以使产品不会具有在此种物质中常有的令人不悦的涩味。此外,长链聚磷酸盐改变了粘膜和牙齿表面的表面亲水和疏水性能,这将使使用者体验到表面调理效果。而且,已惊奇地发现,当该组合物包括少于10%的水时,非常易于水解的长链聚磷酸盐在组合物中保持稳定配制,并因此而保持其抗牙结石功效。据信,这是因为聚磷酸盐是作为一种不被溶解的干物质加入,并且由于组合物中水的低含量,因此它不会水解。此低含量水还能够使具有不同溶解度的金属盐的不同性质被利用,从而导致金属阳离子的可控释放的效果。
据信在此类组合物中,金属阳离子容易与聚磷酸盐物质络合,从而减小了它们的防治异味功效。然而,在本发明的组合物中,通过确保金属阳离子与聚磷酸盐的比率为约10∶1至1∶1,未络合的金属阳离子的含量将维持足够高,以保持防治口腔异味的有益效果。此外,据信这种络合控制也导致足够的金属阳离子被络合,以使产品不会具有在此种物质中常有的令人不悦的涩味。据信这些效果可通过使用一种或多种金属阳离子的混合物得到进一步地提高,该混合物还能帮助克服任何给定金属阳离子通常的低的规定限量。此外,认为金属阳离子通过与挥发性的异味络合产生化合物,以提供持久的异味减少来显示其防止口腔异味的效果。最后,据信金属阳离子与口腔微生物相互作用,抑制细胞活性并最终杀死有机体,从而进一步减少口腔异味和牙斑。通过金属阳离子和聚磷酸盐的联合使用,金属阳离子聚磷酸盐配合物与游离物质形成平衡。这起到了金属阳离子缓慢释放赋形剂的作用,因此延长金属阳离子对口腔内微生物作用的效果。还据信通过使用金属阳离子的组合可增强这种效果。
本发明的一个目标是提供低水含量的可携带口腔护理组合物,该组合物包括聚磷酸盐物质和金属阳离子,以提供具有组合的和持久的抗牙结石和口腔异味控制有益效果的产品。本发明的另一目标是提供组合物,该组合物提供改善的口腔内清洁印象和光滑牙齿表面印象,以增强口腔护理有益效果的明显性。本发明的另一目标是提供具有减少涩味的口腔组合物。最后,本发明的另一目标是提供适于成人、儿童和宠物使用的组合物。本发明的这些和其它目标从随后的详细描述中将变得显而易见。
发明概述
糖果组合物,该组合物包括:
(i)平均阴离子链长大于3或等于3的聚磷酸盐物质;
(ii)大于约10ppm的第一金属阳离子,所述离子选自元素周期表的第5、6、7、8、9、10、11、12、14、16族金属;
(iii)少于约10%的水;和
(iv)合适的糖果载体物质,
其中聚磷酸盐阴离子和金属阳离子的摩尔比为约10∶1至约1∶1。
发明详述
除非另外指明,本文中使用的所有百分比和比率均以组合物的总重量计,并且所有的测量均在25℃进行。
除非另外指明,本文引用的所有出版物均全文引入本文以供参考。
本文使用的术语“安全和有效量”是指化合物、组分或组合物的量足以产生显著的正面有益效果,但又足够低以避免副作用,即在可靠的医学判断范围内,提供合理的有益效果与风险的比率。
本文使用的术语“口腔活性物质”是指能在口腔中提供美容、预防疾病和治疗有益效果的物质。
本文所定义的术语“糖果”是指固体、胶状、似胶状或玻璃状组合物,该组合物可任选地具有液体中心填料和/或可任选地涂敷包括大于约25%的糖或糖醇的涂层。此类组合物通常具有甜味。糖果产品的实施例包括但不限于口气清新薄荷糖、软糖、口香糖、硬糖、具有涂层的糖、药糖块、口胶、压制薄荷糖、咽喉滴剂等。
本文所定义的术语“口香糖”是指糖果组合物,该组合物适于口嚼,且以组合物的重量计包括2%或2%以上的弹性体。
本文所定义的术语“弹性体”是指不易消化的聚合物质或混合物质,例如典型地用于口香糖组合物中的物质。
本文所定义的术语“发嘎吱声的”是指该产品具有坚硬的和轻微砂砾般的结构,并且在使用过程中,该结构产生轻微的破裂声。该组合物优选地具有砂糖结构。
本文所定义的术语“表面调理”是指在处理后立刻产生亲水牙齿表面;并在使用后延长的时间段里保持这些效果。
可用于本发明的活性物质和其它成分可以按照其美容和/或治疗有益效果或其假定的作用方式在本发明中进行分类或描述。然而,应该了解可用于本发明的活性物质和其他成分在一些实施例中可提供一种以上的治疗和/或美容有益效果或以一种以上的作用方式实施。因此,本发明的分类只是为了方便,而非旨在将成分限制在具体陈述的应用或所列应用上。
组合物的组成和本发明的方法在下面进行详细描述。
聚磷酸盐
本发明的组合物包括聚磷酸盐物质,优选按重量计包括大于约1%、优选约1.5%至约50%、更优选约2%至约15%、甚至更优选约3%至约12%、最优选约5%至约10%的聚磷酸盐。
聚磷酸盐是广泛使用的术语,其涉及通过脱水作用形成磷酸根阴离子聚合物的已被聚合的磷酸根阴离子。聚磷酸盐可以以线性物质或环状物质或其混合物的形式存在。优选聚磷酸盐为仅包括低含量环状物质的线性物质。聚磷酸盐的特征还在于其聚合物阴离子的平均阴离子链长。为了本发明的目的,所指聚磷酸盐为那些平均阴离子链长为3或大于3的物质。优选地,聚磷酸盐具有约3至约40、优选约6至约30、更优选约10至约25、甚至更优选约18至约25的平均阴离子链长,及其混合物。而且,聚磷酸盐以盐形式存在。优选地,聚磷酸盐为碱金属盐或其混合物,优选钠盐或钾盐或其混合物,且更优选钠盐。
具有大于4的平均阴离子链长的聚磷酸盐通常为玻璃状物质。本文所定义的“玻璃状”物质是一种非晶形物质。本发明优选具有下式的线性“玻璃状”聚磷酸盐:
XO(XPO3)nX
其中X为钠、钾或氢,且n平均大于或等于6或其混合物。此类聚磷酸盐由FMC Corporation制造,且已知以商品名Sodaphos(n≈6)、Hexaphos(n≈13)和Glass H(n≈21)市售。优选Hexaphos和Glass H,且Glass H为最优选的聚磷酸盐。这些聚磷酸盐可单独使用或组合使用。在Kirk & Othermer的Encyclopediaof Chemical Technology,第四版,第18卷,Wiley-Interscience Publishers(1996)书中,描述了多种磷酸盐及其来源,该文及包括Kirk & Othermer引用的所有文献均全文引入本文以供参考。
希望糖果组合物能持续释放聚磷酸盐剂。这可以通过以下来实现,向组合物中掺入其它聚磷酸盐物质,尤其是二价阳离子盐,如钙盐,该盐与主要的聚磷酸盐物质相比具有较低的水溶性。这可用于将聚磷酸盐释放速率改变至一所需参数。按重量百分比计,低溶解度聚磷酸盐通常占低于更易溶的磷酸盐的含量的一半,优选低于其四分子一。例如,按组合物的重量计,阳离子物质低溶解度聚磷酸盐典型地以高达约10%、优选约0.05%至约5%、更优选约0.1%至约3%的量存在。
如上述的那些聚磷酸盐不仅具有抗牙结石有益效果,而且它们还提供对牙齿和口腔其它表面的表面调理效果。该表面调理效果包括有效解吸不期望的表皮蛋白质部分;使用后立刻产生亲水性牙齿表面;和在使用后延长的时间段内维持这些效果。这些效果产生清洁感,这种清洁感将在糖果产品本身完全消耗后持续,并且进一步有助于消费者的体验。
在使用者牙齿表面和口腔粘膜上的表面调理效果可在体内测量。这些测量包括消费者对关于清洁和光滑牙齿的问题的回答。产生亲水表面的效果可根据在空气中晾干的牙齿和粘膜表面与水的接触角的相对减少来测量,其依据Baeir等人在“Biophysical Modeling of Acquired Pellicle Formation on Substrataof Varying Surface Energies-an in vivo study”,Caries Research,1984,18:408-415中描述的方法测量。整体表面调理效果还可通过定量的消费者调查来测量。表面测量在两个独立的牙齿和齿龈表面的两个独立位置上进行三次记录。
金属阳离子
本发明组合物包括大于约10ppm的第一金属阳离子。该金属阳离子选自第5族(V,Nb,Ta);第6族(Cr,Mo,W);第7族(Mn,Tc,Re);第8族(Fe,Ru,Os);第9族(Co,Rh,Ir);第10族(Ni,Pd,Pt);第11族(Cu,Ag,Au);第12族(Zn,Cd,Hg);第14族(Ge,Sn,Pb);第16族(Se,Te,PO);及其混合物。优选地,该金属阳离子选自任何一价或二价阳离子,其选自锌、锰、铜、铁、钴、银、硒、锡和钒;优选选自锌、锰、铜、铁、银和锡;更优选选自锌、铜、银和锡;最优选选自锌和锡。对于口香糖组合物,优选地,金属阳离子不选自单独的锌或锡,而选这些阳离子中的任何一种与至少另一种的组合。
在本发明中可使用多种金属阳离子盐。这些包括在25℃下每100ml中溶解少于0.5g的所谓的“水不溶性盐”和在25℃下每100ml中溶解大于或等于0.5g的“水溶性盐”。也可以使用这些盐的混合物。在本发明的组合物中此类混合物可能具有几个益处,因为它们可能具有不同的与聚磷酸盐阴离子的络合性质。此外,它们在唾液中具有不同的释放速率,因此能起到提供控制释放曲线的作用。适用于本文的盐的实施例包括醋酸盐、硫酸铵、溴化物、氯化物、铬酸盐、柠檬酸盐、连二硫酸盐、氟硅酸盐、酒石酸盐、氟化物、甲酸盐、碘化物、硝酸盐、硫酸苯酚、水杨酸盐、硫酸盐、葡萄糖酸盐、琥珀酸盐、甘油磷酸盐、乳酸盐及其混合物;优选的为醋酸盐、溴化物、氯化物、柠檬酸盐、连二硫酸盐、酒石酸盐、氟化物、甲酸盐、碘化物、硝酸盐、硫酸盐、葡萄糖酸盐、琥珀酸盐、乳酸盐及其混合物;和更优选为醋酸盐、氯化物、柠檬酸盐、硫酸盐、葡萄糖酸盐、琥珀酸盐、乳酸盐及其混合物。如果使用含氯化亚锡,在将盐掺入组合物前,最好将氯化亚锡与葡萄糖酸钠预先混合,因为这有助于稳定二价锡离子。当组合物为口香糖时,优选不使用乳酸锌。而且,对于口香糖组合物,优选不使用氟化锡盐。
控制本发明组合物包括的金属阳离子及其盐的含量,以使该组合物符合地方管理标准是重要的。这些标准因物质和国家而异,但都为本领域的专业人员所熟知。本发明组合物包括大于10ppm、优选大于15ppm、更优选大于20ppm、甚至更优选大于25ppm的口腔活性金属阳离子。按组合物的重量计,本发明组合物优选包括约0.001%至约5%、优选约0.01%至约2%、更优选约0.1%至约1%、最优选约0.1%至约0.5%的包括口腔活性金属阳离子的金属盐。高度优选地,如果组合物是口香糖组合物且包括乳酸锌、氟化锡或其混合物,按组合物的重量计,这些盐以大于1%的含量存在。
当将金属阳离子掺入另外包括聚磷酸盐的本发明的组合物中时,将获得减少在该组合物中金属阳离子的涩味的附加有益效果,因此改善了口味。为最大化该有益效果,聚磷酸盐阴离子与金属阳离子总含量的摩尔比应为约10∶1至约1∶1、优选约5∶1至约1∶1、优选约3∶1至约1∶1。如果使用一种以上的金属阳离子,那么采用的比率应使用金属阳离子的总的组合含量。本文使用的术语“聚磷酸盐阴离子”是指单个阴离子,不考虑链长。聚磷酸盐阴离子的含量应以假定所有聚磷酸盐物质具有生产者标注的该物质的平均阴离子链长来计算。
如果使用一种以上的金属阳离子,优选地,第一金属阳离子与第二金属阳离子的摩尔比为约50∶1至约1∶50、优选约20∶1至约1∶20、更优选约10∶1至1∶10。这将最大化使用两种金属阳离子的有益效果。
最后,对于口香糖组合物,高度优选地,如果优选的口腔活性金属阳离子是锌盐、锡盐及其混合物,该盐与第二种口腔异味控制剂联合使用。该另一种口腔异味控制剂可选自抗微生物剂、天然提取物、精油或吸收剂,这些成分将稍后在申请书中讨论。在口香糖组合物中,高度优选的是另一种试剂与锌或锡盐的联合使用,从而通过两种物质一起作用的协同效应来改善口腔异味控制。
水
按组合物的重量计,本发明组合物包括少于约10%、优选少于约8%、更优选少于约5%、甚至更优选少于约3%、最优选少于约2%的水。需要低含量的水以确保植物提取物的多酚组分不会被氧化,并且如果包括任何长链聚磷酸盐,其不会在最终组合物中水解。
在制备适于市售的组合物中,使用的水优选应为低离子含量且无有机杂质。在组合物中的水量应考虑其不仅是作为游离水添加,而且是作为引入其它物质如山梨醇、二氧化硅、表面活性剂溶液和/或着色溶液的水。而且以最终组合物计,应适当将水量与涂层和/或填料考虑为一个整体。
载体物质
本发明组合物为包括口香糖的糖果组合物。合适的物理形式包括细棒、糖衣丸、园锥形和棒。尽管每个产品的提取成分随各产品而异,但具体技术为本领域专业人员所熟知。然而,有一些通用成分适于所有产品形式,这些成分在下面进行详细讨论。优选的产品形式为按组合物的重量计,配制含有少于约10%的水的压制片剂、软糖、硬糖和口香糖。
本发明的糖果组合物包括载体物质。该载体物质根据使用的糖果类型的不同而异,且为本领域专业人员所熟知。该载体物质可选自可口嚼和不可口嚼的物质。推荐组合物包括至少10%可口嚼物质。可口嚼物质选自包括琼脂胶和明胶等的树胶;软糖基质和树胶基质材料。优选地,本发明的组合物的载体物质不是可搅打起泡的或可充气的乳液形式。硬糖和软糖载体,压制片剂等通常包括大于约70%的整体甜味剂,该甜味剂包括会产生龋齿和不会产生龋齿的糖和糖浆。软糖还可包括黄油以形成可口嚼的乳脂糖。对于果冻和橡皮糖组合物,载体包括大于约25%的整体甜味剂,且还额外地包括树胶,例如阿拉伯树胶、明胶、琼脂粉及类似物。
本发明的组合物优选为口香糖形式。因此,优选地,按组合物的重量计,该组合物包括大于约10%、优选大于约15%、更优选大于约20%、最优选大于约25%、最高达约75%的树胶基质。树胶基质包括选自弹性体、树脂或蜡的载体物质或载体物质的混合物。树胶基质载体物质为非水溶性物质,该物质典型地不能在口中释放。此类物质包括:
(i)弹性体和弹性体溶剂
本发明的组合物优选地包括弹性体或几种不同弹性体的混合物。弹性体物质通常为本领域所熟知,但示范性实施例包括苯乙烯-丁二烯橡胶(SBR);合成树脂;聚异丁烯和异丁烯-异戊二烯共聚物;天然树胶;糖胶树胶;天然橡胶;节路顿胶;巴拉塔树胶;马来树胶;lechi caspi;香豆乳汁;及其混合物。以重量计,本发明的组合物优选包括约2%至约30%、更优选约5%至约25%的弹性体。这些含量由所需的口香糖的最终结构确定,因为当弹性体总含量低于约2%时,基质组合物缺乏弹性、口嚼结构和粘结性,而当高于约30%时,制剂硬而有弹性,并保持紧密的口嚼感。
在本发明的组合物中优选存在弹性体溶剂,因为它们有助于软化弹性体组分。本文使用的弹性体溶剂的优选实施例包括部分氢化的木松香的季戊四醇酯、木松香的季戊四醇酯、部分二聚的松香的甘油酯、多聚松香的甘油酯、妥尔油的甘油酯、木或树胶松香、部分氢化的木松香的甘油酯、部分氢化的木松香的甲酯,及其混合物。以重量计,本发明的组合物优选包括约2%至约50%、更优选约10%至约35%的弹性体溶剂。
(ii)树脂和蜡
树脂为任选择的,但期望的本发明口香糖组合物的成分。它们用于塑化树胶基质。合适的树脂包括醋酸盐聚乙烯酯(PVA);萜树脂,包括聚萜和α-蒎烯或β-蒎烯的聚合物;及其混合物。以重量计,此类组合物优选包括约3%至约25%、优选约5%至约20%的树脂。
口香糖组合物还可包括一种或多种蜡。合适的蜡包括石蜡;微晶蜡;Fischer-Tropsch石蜡;天然蜡如坎台里蜡、巴西棕榈和蜂蜡;聚烯烃蜡如聚乙烯蜡;及其混合物。以重量计,组合物包括高达约25%、优选约5%至约20%的蜡。
本发明的糖果组合物可为中心填充型。按组合物的重量计,此类产品优选包括约60%至约95%、更优选约75%至约85%的可食用的壳;和约5%至约40%、优选约15%至约25%的填料。中心填充型糖果组合物可在可食用的壳中包括口腔护理活性物质,和/或在可食用的填料中包括不同的口腔护理活性物质或活性物质的混合物。此外,该组合物可在壳和填料中包括不同的调味剂。
本发明的组合物可包括一种或多种可嘎吱嘎吱地咬嚼的固体颗粒,该颗粒分散于整个载体物质中。该优选的可嘎吱嘎吱咬嚼的颗粒具有最小粒径以使该颗粒能被0.1mm筛、优选0.112mm筛、更优选0.16mm筛、甚至更优选0.18mm筛和最优选0.2mm筛保留下来,其中该筛选自DIN 4188筛系列。而且,颗粒优选地具有最大粒径以使它能通过2mm筛、优选1mm筛、更优选0.8mm筛、甚至更优选0.5mm筛、最优选0.4mm筛,同样其中该筛选自DIN 4188筛系列。颗粒的溶解度优选为在25℃下至少1g/100ml、更优选至少5g、甚至更优选至少8g、最优选至少15g。最后,优选地,该颗粒材料具有以Mohs硬度等级计大于1、优选大于2的硬度。粒径、溶解度和硬度性质给予糖果自身发嘎吱声的结构。此类颗粒可以以上述列举的口腔护理活性物质中的其中一种的固体形式存在,在此情况下,口腔护理活性物质为固体,或可为进一步的颗粒如糖晶体、干果、坚果等。可发嘎吱声结构可用于加强对消费者的口腔护理的有益效果。不同的发嘎吱声结构可通过磨制颗粒至所需尺度或通过混合不同市售等级的颗粒而获得,以得到期望的可发嘎吱声。优选地,那种可发嘎吱声的感觉维持在让消费者可注意到的状态至少1分钟30秒、优选至少2分钟、最优选至少2分钟30秒。然而还优选发嘎吱声的结构在5分钟后、优选4分钟后消失,以使该物质不会磨损牙质,或使产品不会有沙砾般的残余物。
而且,本发明的糖果组合物也可以为涂层的。外层涂敷可为硬的或可嘎吱嘎吱咬嚼的。典型地,外层涂敷将基本上由山梨醇、麦芽糖醇、木糖醇、异麦芽和其它可结晶的多醇组成。而且,该涂层典型地由几个不透明层组成,以使透过涂层本身糖果核心不可见,可任选地再涂敷另一层或多层透明层用于美观、结构和保护性用途。外层涂层还可包括少量水和阿拉伯树胶。多元醇涂层可进一步涂上蜡。以常用方式进行涂层,通过连续的使用涂层溶液,在每个涂层间干燥,如WO99/44436所述。当涂层干燥时,尽管可添加其它着色剂,其通常变得不透明且通常为白色。多元醇涂层可进一步涂上蜡。涂层还可包括有色的薄片和颗粒。如果该组合物包括涂层,可能一种或多种口腔护理活性物质分散于整个涂层中。当一种或多种口腔护理活性物质在单相组合物中不能与其它活性物质相容时,这是尤其优选的。
组合物的平衡
本发明的组合物优选包括安全和有效含量的一种或多种附加成分组分。此类物质为本领域专业人员所熟知,并且本领域专业人员基于口腔护理、制备组合物的所需的物理和美观的性质能够容易选择。此类物质的实施例包括但不限于脂肪、溶剂、蜡、乳化剂、软化剂、增量剂、阳离子物质、缓冲剂、增白剂、碱金属二碳酸盐、增稠剂、湿润剂、水、表面活性剂、二氧化钛、调味剂、着色剂,及其混合物。最常用的那些成分在下面进行详细描述。
口腔护理活性物质
本发明的组合物包括口腔护理活性物质,该活性物质选自下列物质:抗牙结石剂、抗牙斑剂、脱敏剂、氟化物离子源、口腔异味控制剂、H2拮抗剂,及其混合物。优选地,口腔护理活性物质选自下列物质:抗牙结石剂;抗牙斑剂组;去敏剂组;口腔异味控制剂;更优选地,口腔护理活性物质为抗牙结石剂;更优选地,口腔护理活性物质为聚磷酸盐。列于下列组中的活性物质并不意味着相互排斥,单个活性物质可包括在本发明的组合物中以提供几种效果。
按重量计,本发明的组合物优选包括约0.01%至约50%、更优选约0.1%至约15%、甚至更优选约0.25%至约10%、最优选约0.5%至约7%的口腔护理活性物质。
抗牙结石剂:已知用于牙齿护理产品中的抗牙结石剂包括磷酸盐、焦磷酸盐、聚磷酸盐(如上述所讨论)、膦酸酯、聚膦酸酯及其混合物。在牙齿护理产品中最为熟知的是焦磷酸盐。在本组合物中有用的焦磷酸盐包括焦磷酸二碱金属盐、焦磷酸四碱金属盐及其混合物,它们的脱水和水合物形式为优选种类,如焦磷酸二氢二钠(Na2H2P2O7)、焦磷酸四钠(Na4P2O7),和焦磷酸四钾(K4P2O7)及其混合物。在Kirk和Othmer的Encyclopedia of Chemical Technology,第3版,第17卷,Wiley Interscience Publishers(1982)书中,对焦磷酸盐有更详细地描述。
附加的抗牙结石剂包括聚丙烯酸酯和其它聚羧酸酯,如那些在1969年2月25日授予Shedlovsky的美国专利3,429,963和在1981年12月8日授予Chang的美国专利4,304,766中,和在1987年4月28日授予Benedict和Sunberg的美国专利4,661,341中公开的物质;聚环氧琥珀酸酯,如那些在1989年7月11日授予Bendict,Bush和Sunberg的美国专利4,846,650中公开的物质;乙二胺四乙酸,如在1937年2月15日的英国专利490,384所公开的;氨三乙酸和相关化合物,如在1972年7月18日授予Widder和Briner的美国专利3,678,154所公开的;聚膦酸酯如在1973年6月5日授予Francis的美国专利3,737,533,在1976年10月26日授予Ploger,Schmidt-Dunker和Gloxhuber的美国专利3,988,443,在1989年10月31日授予Degenhardt和Kozikowski的美国专利4,877,603中所公开的。抗结石磷酸盐包括焦磷酸钾和焦磷酸钠;三聚磷酸钠;二膦酸盐如乙烷-1-羟基-1,1-二膦酸盐、1-氮杂环庚烷-1,1-二膦酸盐,和线性烷基二膦酸盐;线性羧酸;和柠檬酸钠锌和其它可溶的锌盐。
抗牙斑剂:抗牙斑剂包括抗牙斑剂和氟化物离子来源。抗牙斑剂为任何能够抑制口腔表面上细菌沉淀积累的物质。实施例包括木糖醇和抗微生物剂。
氟化物离子来源:氟化物离子应用于牙釉以防止牙齿腐烂。可使用多种产生氟化物离子的物质作为在本组合物中的可溶性氟化物来源。合适的产生氟化物离子的物质的实例可参见下列专利:在1970年10月20日授予Briner等人的美国专利3,535,421和1972年7月18日授予Widder等人的美国专利3,678,154。用于本发明的优选的氟化物离子来源包括氟化钠、氟化钾、氟化锡、氟化铵及其混合物。尤其优选氟化钠。优选地,本组合物提供约50ppm至约10,000ppm、更优选约100ppm至约3000ppm的氟化物离子。
去敏剂:去敏剂或止痛剂也可存在本发明的本口腔护理组合物或物质中。此类试剂可包括但不限于氯化锶、硝酸钾,天然草本植物如五倍子坚果、细辛、荜澄茄素、高良姜、黄芩、两面针、白芷等。可使用止痛药作为去敏剂,该止痛药包括低含量的非甾族抗炎剂,如酮咯酸、氟比洛芬、布洛芬、萘普生、消炎痛、阿司匹林、酮洛芬、吡罗昔康和甲氯芬那酸。
口腔异味控制剂:口腔异味控制剂包括各种物质。最常用的为抗微生物剂,它可在口腔护理组合物或本发明的物质中存在。此类试剂包括但不限于5-氯-2-(2,4-二氯苯氧基)-苯酚,通常称为三氯生,且在美国专利3,506,720中的MerckIndex,第11版,(1989),1529页(9573条),和1988年1月7日公布的Beecham Group,Plc的欧洲专利申请0,251,591中进行了描述;邻苯二甲酸及其盐,其包括但不限于那些在1991年2月19日公布的美国专利4,994,262中公开的物质,优选邻苯二甲酸单钾镁,洗必太(Merck Index,第2090号);双胍啶(Merck Index,第222号);合克替啶(Merck Index,第4624号);血根碱(Merck索引,第8320号);烷基苄基二甲基铵氯化铵(Merck Index,第1066号);N-水杨酰苯胺(Merck Index,第8299号);溴化杜灭芬(Merck Index,第3411号);氯化十六烷基吡啶(CPC)(Merck索引,第2024号);氯化十四烷基吡啶(TPC);氯化N-十四烷基-4-乙基毗啶(TDEPC);octenifine;delmopinol;octapinol;和其它哌啶衍生物;烟酸配制品(nicin preparations);锌/锡离子试剂;抗生素如沃格孟汀、羟氨苄青霉素、四环素、强力霉素、米诺环素和甲硝唑;以及类似物和上述物质的盐;水杨酸甲酯;和所有上述物质的混合物。
第二类物质为抗菌天然植物提取物。这些提取物包括从植物任何部分如叶、干、树皮、浆、种子、肉、果汁、根及其混合物中获得的提取物。优选地,该提取物从叶、浆和种子中获得,更优选地从叶或种子中获得。可使用许多不同的植物或植物的不同部分以提供这些提取物。植物包括茶,尤其是绿茶、木兰、日本黄莲、忍冬、葡萄、香柠檬、柚子、桔子、柠檬、橘子、中国柑桔、无核小蜜橘、克莱门小柑橘、酸橙,及其混合物;优选来自葡萄、柚子及其混合物。此类提取物包括多种生物活性物质。这些物质包括花青素、黄烷醇、可水解的丹宁酸、生物碱、类脂、碳水化合物、简单糖、蛋白质和氨基酸、醇、多酚、有机酸及其混合物。已知精油也具有抗菌性能。这些物质包括百里酚、香叶醇、香芹酚、扁柏酚、桉油精、儿茶酚(尤其是4-烯丙基儿茶酚)及其混合物。优选地,按组合物的重量计,本发明的组合物包括约0.0001%至约30%、优选约0.001%至约15%、更优选约0.01%至约10%、甚至更优选约0.1%至约5%、最优选约0.25%至约3%的提取物。
本发明的组合物可任选地包括肌醇六磷酸锌,与天然提取物联合。据信肌醇六磷酸锌能增强多酚对呼吸气味的保护功效并且增加多酚提取物的稳定性。按组合物的重量计,本发明的组合物优选包括约0.1%至约10%、更优选约0.5%至约5%、最优选约1%至约3%的肌醇六磷酸锌。
另一类口腔异味控制剂包括吸收剂。这些吸收剂用于吸收、结合或络合挥发性的口腔异味物质。此类试剂的实施例包括滑石、蘑菇提取物、沸石、环糊精、二氧化硅壳及其混合物。按组合物的重量计,此类物质优选使用含量为约0.5%至约10%、优选约1%至约5%。
H-2拮抗剂:组胺-2(H-2)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。本文使用的选择性H-2拮抗剂为嵌段H-2受体的混合物,而不具有嵌段组胺-1(H-1)受体的有意义的活性。选择性的H-2拮抗剂包括那些分别公开于1994年3月15日和1994年11月15日的Singer等人并转让给宝洁的美国专利5,294,433和5,364,616,其中选择性H-2拮抗剂选自下列物质:西咪替丁、丙炔替丁、雷尼替丁、ICIA-5165、硫替丁、ORF-17578、卢皮替丁(lupitidine)、冬尼替丁(donetidine)、法莫替丁、罗沙替丁、哌芳酯丁、拉姆替丁(lamtidine)、BL-6548、BMY-25271、扎尔替丁(zaltidine)、尼扎替丁、米芬替丁(mifentidine)、BMY-52368、SKF-94482、BL-6341A、ICI-162846、ramixotidine、Wy-45727、SR-58042、BMY-25405、氧替丁(loxtidine)、DA-4634、bisfentidine、sufotidine、乙溴替丁、HE-30-256、D-16637、FRG-8813、FRG-8701、impromidine、L-643728和HB-408.4。尤其优选西咪替丁(SKF-92334)、N-氰基-N’-甲基-N”-(2-(((5-甲基-1H-咪唑-4-基)甲基)硫代)乙基)胍。
西咪替丁也公开于Merck Indes,第11版(1989),第354页(第2279条),和Physicians’Desk Reference,第46版(1992),第2228页。相关的优选H-2拮抗剂包括丁咪胺和甲硫咪胺。
抗氧化剂:通常认为抗氧化剂在组合物(如本发明的那些)中是有用的。抗氧化剂公开于文本如Cadenas和Packer的《抗氧化剂手册》(The Handbook ofAntioxidants),1996,Marel Dekker,Inc。在本发明的口腔护理组合物中可包括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、类黄素和多酚、草本植物抗氧化剂、抗黑变激素、氨基吲哚、硫辛酸及其混合物。
牙齿颜色改变物质:牙齿颜色改变物质被认为在本发明的口腔护理活性物质中是有用的。这些物质适于改变牙齿的颜色以使消费者满意,如那些列于CTFACosmetic Ingredient Handbook,第3版,Cosmetic and FragrancesAssociation Inc.,Washington DC(1982)中的物质,该文件引入本文以供参考。具体的实施例包括滑石、云母、碳酸镁、碳酸钙、硅酸镁、碳酸镁铝、二氧化硅、二氧化钛、氧化锌、红色氧化铁、褐色氧化铁、黄色氧化铁、黑色氧化铁、氰亚铁酸铵铁、锰紫、群青颜料、尼龙粉、聚乙烯粉、异丁烯酸酯粉、聚苯乙烯粉、丝粉、结晶纤维素、淀粉、钛酸云母、氧化铁钛酸云母、氯氧化铋,及其混合物。按组合物的重量计,典型的颜料含量为约0.05%至约20%、优选约0.1%至约15%、最优选约0.25%至约10%。
用于本发明的的组合物还可包括去除或漂白牙齿表面上或其中的内在或外来污渍的物质。此类物质选自下列物质: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,及其组合。合适的过氧化物包括过氧化氢、过氧化脲、过氧化钙、过氧化脲及其混合物。合适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。附加的漂白物质可为次氯酸盐和二氧化氯。优选的过碳酸盐为过碳酸钠。优选的过硫酸盐为过硫酸氢钾。这些物质的含量取决于可获得的氧或氯。按组合物的重量计,在本发明的组合物中该含量通常为约0.1%至约35%、优选约1%至约25%、最优选约5%至约10%。
营养物质
营养物质可改善口腔环境,并且可包括在本发明的口腔护理组合物或本发明的物质中。营养物质包括矿物质、维生素、口腔营养补充物、肠营养补充物、草本植物补充物、天然提取物及其混合物,如公开于Drug Facts and Comparisons(loose leaf drug information service),Wolters Kluer Company,StLouis,Mo.,1997中的那些。本发明的组合物中可包括的矿物质包括钙、磷、氟化物、锌、锰、钾及其混合物。维生素可与矿物质一起被包含或单独使用。维生素包括维生素C和D、硫胺素、核黄素、泛酸钙、烟酸、叶酸、烟酰胺、吡哆素、维生素B12、对氨基苯甲酸、生物类黄酮,及其混合物。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。
甜味剂
甜味剂主要有两种类型:整体甜味剂和高密度甜味剂。通常,甜味剂的用量依据甜味剂和整体期望的美观效果而不同,但使用含量应足够高以使能不使用调味剂即可获得所需的甜味。当使用整体甜味剂时,它们可用作组合物内的增量剂或填充剂。
整体生龋齿的甜味剂:本发明的组合物可包括甜味剂物质。此类物质包括单糖、二糖、聚糖及其混合物。实施例包括木糖、核糖、葡萄糖、甘露糖、半乳糖、果糖、葡萄糖、蔗糖、麦芽糖、果寡糖浆、部分水解的淀粉或玉米糖浆固体及其混合物。然而,此类物质常导致龋齿的形成,因为它们容易被口腔中的细菌和其它微生物新陈代谢。优选地,按组合物的重量计,本发明的组合物包括低于约10%、优选低于约5%、更优选低于约2%、甚至更优选低于约1%、最优选低于约0.5%的生龋齿的甜味剂。如需要,本发明的组合物可包括0%的生龋齿的甜味剂。
整体不生龋齿的甜味剂:本发明的组合物优选地包括不生龋齿的甜味剂。本文使用的术语“不生龋齿的”是指不能被口腔的微生物新陈代谢的甜味剂,因此不会有助于生成龋齿。优选地,按组合物的重量计,本发明的组合物包括大于约10%、优选大于约20%、更优选大于约30%、最优选大于约40%的不生龋齿的甜味剂。以组合物的重量计,本发明的组合物可包括高达约99%的不生龋齿的甜味剂。
优选的不生龋齿的甜味剂为糖醇如山梨醇、木糖醇、甘露糖醇、麦芽糖醇、异麦芽、氢化淀粉水解物、胰岛素和其它不生龋齿的可食用的多元醇,如甘油和赤藓醇及其混合物。最优选的不生龋齿的甜味剂选自麦芽糖醇、甘露糖醇、木糖醇、山梨醇、三氯蔗糖、天门冬酰苯丙氨酸甲酯和其盐,及其混合物。一般地讲,以重量计,组合物包括约10%至约80%、更优选约30%至约70%的该整体甜味剂。
高密度甜味剂:高密度甜味剂是较整体甜味剂而言更优选用于本发明的组合物,因为由于其它一些原因,高密度甜味剂可延长在口嚼过程中最终口香糖的滋味。合适的高密度甜味剂包括:基于二肽的甜味剂如L-天冬氨酰基-L-苯基丙氨酸甲酯(天冬甜素)和其等价物(在美国专利3,492,131中所描述的),L-α-天冬氨酰基-N-(2,2,4,4-四甲基-3-三乙基)-D-丙氨酸酰胺水合物(阿力甜)和类似物;糖精及其可溶解盐如糖精钠和钙;环已氨基磺酸盐如Acesulfame-K等;蔗糖的氯化衍生物如氯化脱氧蔗糖等;和基于蛋白质的甜味剂,如索马甜(甜蛋白)。以重量计,本发明的组合物优选包括约0.01%至约2.0%、更优选约0.05%至约0.5%的高密度甜味剂。
增量剂
增量剂(如填充剂)也可用于糖果中。合适的填充剂和增量剂通常为非磨擦性的,优选具有低于5μm、更优选低于3μm、最特别地低于1μm的平均粒径。示例性增量剂包括碳酸钙或重质碳酸钙、滑石、氢氧化铝、氧化铝、硅酸铝、磷酸二钙及其混合物。以重量计,组合物优选包括高达约50%、更优选高达约30%、最优选高达约10%的增量剂。
附加的口香糖成分
有几种成分通常被加入到口香糖组合物中,但通常不在其它类型的糖果中使用。下面列出该物质的实施例,但该列表不是为了限制。如果需要,类似地,此类成分可用于其它类型的糖果。
本发明的口香糖组合物可包括除树脂组分外的增塑剂。合适的增塑剂包括三醋酸甘油酯、乙酰化单酸甘油酯、三丁酸甘油酯、月桂酸乙酯、乙酰乙酸乙酯、酒石酸二乙酯、乳酸乙酯或乳酸丁酯、苹果酸二乙酯、油酸乙酯、蓖麻子油、琥珀酰单酸甘油酯或其混合物。优选三醋酸甘油酯和乙酰化单酸甘油酯。以重量计,组合物优选包括高达约10%、优选约0.1%至约3%的增塑剂。
本发明的组合物优选包括软化剂或软化剂混合物,该软化剂当掺入树胶基质中时,有助于改变结构和稠度。尤其是,它们帮助软化口香糖,并在一个延伸的时间段内维持口香糖的柔软。合适的软化剂包括脂肪物质如羊毛脂、硬脂酸、硬脂酸钠和硬脂酸钾;多元醇如甘油醇、丙二醇等;及其混合物。以重量计,组合物优选包括高达约30%、更优选约0.1%至约10%的软化剂。在优选实施方案中,口香糖组合物以重量计包括约0.1%至约10%的脂肪软化剂,该软化剂选自硬脂酸、硬脂酸钠、硬脂酸钾及其混合物,优选硬脂酸。
口香糖组合物优选包括乳化剂如一硬脂酸甘油酯、卵磷脂、脂肪酸单酸甘油酯、甘油二酯、一硬脂酸丙二醇酯及其混合物。以重量计,组合物包括高达约10%、优选约2%至约6%的乳化剂。
在本发明的口香糖组合物中可包括多种脂肪。优选的脂肪包括氢化菜油如氢化棕榈油、氢化大豆油、氢化棉籽油和多种其它的氢化菜油及其混合物。以口香糖组合物的重量计,脂肪的合适用量为高达约20%、优选约1%至约10%。
调味剂
本发明的组合物可优选地包括调味剂。本文使用的术语“调味剂”指那些香料和等价合成物质,加入该物质以给组合物调味。调味剂还可包括特殊物质,该物质被加入以提高暖感或冷感。
调味剂为本领域所熟知。它们包括合成香料和/或油和/或来自植物、根、豆、坚果、叶、花、果实等的香精,及其混合物。合适的香料实施例包括柠檬、桔子、香蕉、葡萄、酸橙、杏、柚子、苹果、草莓、樱桃、巧克力、菠萝、咖啡、可可、可乐、花生、杏仁、甘草、桂皮等。调味剂的用量通常取决于个人的喜好,但一般以组合物的重量计,它们的用量高达约4%、优选约0.1%至约1%。
本发明的组合物可任选地包括凉爽剂和WO 97/06695中描述的合适的物质。本文优选使用生理凉爽剂,该凉爽剂选自下列物质:薄荷醇、薄荷油、N-取代的-对薄荷烷-3-甲酰胺、无环叔和仲甲酰胺、3-1-甲氧基丙-1,2-二醇及其混合物。尤其优选的为薄荷醇和含油如薄荷油的薄荷醇。按组合物的重量计,凉爽剂的优选用量为约0.001%至约5%、更优选约0.05%至约3.5%。
本发明的组合物可任选地包括暖剂。优选的试剂包括那些选自下列的物质:香草醇正丁酯、香草醇正丙酯、香草醇异丙酯、香草醇异丁酯、香草醇正胺酯、香草醇异胺酯、香草醇正己酯、香草醇甲酯、香草醇乙酯、ginerol、姜烯酚、豆寇醇、姜油酮、辣椒碱、二氢辣椒碱、非二氢辣椒碱、同型辣椒碱、同型二氢辣椒碱、乙醇、异丙醇、异戊醇、苯甲醇、氯仿、丁子香酚、肉桂油、肉桂醛及其混合物。按组合物的重量计,暖剂优选用量为约0.001%至约5%、更优选约0.05%至约3.5%。
制备组合物
采用本领域专业人员公知的标准技术制备本发明的组合物。优选地,聚磷酸盐在加入组合物前在水中预沉淀以防止水解。如果组合物包括一种以上的相,不同的相通常单独制备,同样相分区的物质可以任何顺序加入。然后通过剧烈搅拌将两相混合以形成多相体系,如乳液和悬浊液。在制剂中任何高挥发性的成分或在高温下易于水解的成分,通常在各相混合后,在轻微搅拌下加入。典型的糖果制造方法高度适用于制备本发明的组合物。最后,如果产品为涂层的糖果组合物,涂层步骤为最后一步。可通过挂糖衣或喷雾干燥技术实施涂层,该技术通常为本领域专业人员所公知。
实施例
下列实施例进一步详细说明本发明范围内的优选实施方案。给出这些实施例仅仅是为了说明本发明,而非解释为限制本发明,因为在不背离本发明精神和范围的条件下可以对本发明进行许多改变。除非另外指明,所有成分均表示为组合物的重量百分比。
成分 | I%w/w | II%w/w | III%w/w | IV%w/w | V%w/w | VI%w/w |
糖 | 31.44 | 31.74 | - | - | - | - |
葡萄糖 | 22.00 | 26.00 | - | - | - | - |
树胶基质 | 30.00 | 30.00 | 28.00 | 30.00 | 30.00 | 32.00 |
山梨醇 | - | - | 41.02 | 39.10 | 40.13 | 38.49 |
木糖醇 | - | - | 20.00 | 20.00 | 20.00 | 20.00 |
甘油 | 8.00 | 8.00 | 5.00 | 5.00 | 5.00 | 5.00 |
明胶 | - | - | - | - | - | - |
水 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 |
乙酸锌 | 0.48 | 0.23 | 0.90 | - | - | 0.46 |
柠檬酸锌 | - | - | - | 0.82 | 0.82 | - |
六偏磷酸钠(n=6) | - | - | 2.00 | - | - | - |
聚磷酸钠(n=21)* | 5.00 | 1.00 | - | 2.00 | 1.00 | 1.00 |
调味剂 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 |
卵磷脂 | 0.03 | 0.03 | 0.03 | 0.03 | - | - |
Acesulfam K | - | - | 0.05 | 0.05 | 0.05 | 0.05 |
总计 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
涂层(20-30%w/w) | ||||||
山梨醇 | - | - | - | - | 94.80 | 94.80 |
水 | - | - | - | - | 2.00 | 2.00 |
二氧化钛 | - | - | - | - | 1.50 | 1.50 |
Acesulfam K | - | - | - | - | 0.05 | 0.05 |
聚山梨酸酯60 | - | - | - | - | 0.15 | 0.15 |
调味剂 | - | - | - | - | 1.50 | 1.50 |
总计 | - | - | - | - | 100.00 | 100.00 |
*市售等级,平均粒径为133μm;**粗磨等级,平均粒径大于200μm
实施例I至VI:口香糖:在δ叶片式混砂机中熔化树胶基质至55℃至60℃。加入整体甜味剂和甘油,混合。加入活性物质并混合。最后混入调味剂。移去热源并在模制和切割前冷却。将涂层预制溶液喷洒到冷却的树脂上成薄层,在加上后续层前将其干燥。添加足够的涂层以使涂层的总重量为最终完成的小球重量的20%至30%。
成分 | VII%w/w | VIII%w/w | IX%w/w | X%w/w | XI%w/w | XII%w/w |
树胶基质 | 28.000 | 28.000 | 28.00 | 28.00 | - | - |
山梨醇 | 42.918 | 38.370 | 42.09 | 38.42 | - | 92.77 |
木糖醇 | 20.000 | 20.000 | 20.00 | 20.00 | - | - |
异麦芽 | - | - | - | - | 90.37 | - |
甘油 | 5.000 | 5.000 | 5.00 | 5.00 | - | - |
明胶 | - | - | - | - | - | 0.10 |
水 | 0.500 | 0.500 | 0.50 | 0.50 | 3.00 | 0.50 |
乙酸锌 | - | 0.58 | 0.69 | 0.58 | 0.58 | 0.58 |
氯化锡 | 0.032 | - | - | - | - | - |
三聚磷酸钠 | - | - | 1.00 | - | - | - |
聚磷酸盐钠(n=21)* | 1.000 | 5.00 | - | 5.00 | 5.00 | 5.00 |
调味剂 | 2.500 | 2.500 | 2.50 | 2.50 | 1.00 | 1.00 |
卵磷脂 | - | - | - | - | - | - |
Acesulfam K | 0.050 | 0.050 | 0.05 | 0.05 | 0.05 | 0.05 |
总计 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
*市售等级,平均粒径为133μm;**粗磨等级,平均粒径大于200μm
实施例VII至X:口香糖:在δ叶片式混砂机中熔化树胶基质至55℃至60℃。加入整体甜味剂和甘油,混合。加入活性物质并混合。最后混入调味剂。移去热源并在模制和切割前冷却。将涂层预制溶液喷洒到冷却的树脂上成薄层,在加上后续层前将其干燥。添加足够的涂层以使涂层的总重量为最终完成的小球重量的20%至30%。
实施例XI:药糖块。将异麦芽溶解于水中并在搅拌下加热至110℃至112℃,然后煮至141℃至145℃,以煮去水分。在真空下取出一批,并在低湿度环境下于约90℃下加入聚磷酸盐/调味剂。在将其转入成型浴和冲切设备前,在热桌上将反应浴包起,然后在冷桌(20℃)上冷却。最终产物具有类似玻璃的半透明外观。
实施例XII:压片。制备明胶和树胶产品的预形成溶液,喷洒在糖或葡萄糖或异麦芽糖醇上,以形成颗粒状混合物。将其干燥并过滤,然后压缩形成片剂。
Claims (17)
1.糖果组合物,所述组合物包括:
(i)平均阴离子链长大于或等于3的聚磷酸盐物质;
(ii)大于约10ppm的第一金属阳离子,所述金属阳离子选自元素周期表的第5、6、7、8、9、10、11、12、14、16族金属;
(iii)少于约10%的水;和
(iv)合适的糖果载体物质
其中聚磷酸盐阴离子与金属阳离子的所述摩尔比为约10∶1至约1∶1。
2.如权利要求1所述的组合物,其中所述聚磷酸盐阴离子具有约3至约40、优选约6至约30、更优选约10至约25、最优选约18至约25的平均阴离子链长。
3.如权利要求1至2中任一项所述的组合物,其中所述聚磷酸盐为碱金属盐、优选为钠盐或钾盐、更优选为钠盐。
4.如权利要求1至3中任一项所述的组合物,其中所述组合物按重量计包括大于约1%、优选约1.5%至约50%、更优选约2%至约15%、甚至更优选约3%至约12%、最优选约5%至约10%的聚磷酸盐。
5.如权利要求1至4中任一项所述的组合物,其中所述第一金属阳离子和第二金属阳离子为一价的或二价的阳离子,所述阳离子选自锌、锰、铜、铁、钴、银、硒、锡和钒;优选地选自锌、锰、铜、铁、银和锡;更优选地选自锌、铜、银和锡;最优选地选自锌和锡。
6.如权利要求1至5中任一项所述的组合物,其中所述金属阳离子以金属盐形式提供,所述盐选自下列物质:醋酸盐、硫酸铵盐、溴化物、氯化物、铬酸盐、柠檬酸盐、连二硫酸盐、氟硅酸盐、酒石酸盐、氟化物、甲酸盐、碘化物、硝酸盐、硫酸苯酚盐、水杨酸盐、硫酸盐、葡萄糖酸盐、琥珀酸盐、甘油磷酸盐、乳酸盐及其混合物;优选的为醋酸盐、溴化物、氯化物、柠檬酸盐、连二硫酸盐、酒石酸盐、氟化物、甲酸盐、碘化物、硝酸盐、硫酸盐、葡萄糖酸盐、琥珀酸盐、乳酸盐及其混合物;更优选的为醋酸盐、氯化物、柠檬酸盐、硫酸盐、葡萄糖酸盐、琥珀酸盐、乳酸盐及其混合物。
7.如权利要求1至6中任一项所述的组合物,其中所述组合物包括大于约15ppm、优选大于约20ppm、优选大于约25ppm的所述金属阳离子。
8.如权利要求1至7中任一项所述的组合物,其中按组合物的重量计,所述组合物包括约0.001%至约5%、优选约0.01%至约2%、更优选约0.1%至约1%、甚至更优选约0.1%至约0.5%的包括所述金属阳离子的金属盐。
9.如权利要求1至8中任一项所述的组合物,其中所述聚磷酸盐与金属阳离子的摩尔比为约5∶1至约1∶1、优选约3∶1至约1∶1。
10.如权利要求1至9中任一项所述的组合物,其中所述组合物包括另外的抗微生物剂,所述抗微生物剂选自洗必太、三氯生、天然提取物、氯化十六烷基吡啶、去氧苯经妥、海克替丁及其混合物;优选地,另外的抗微生物剂为天然提取物,所述提取物选自葡萄籽提取物、柚子籽提取物、绿茶提取物、玉兰提取物及其混合物。
11.如权利要求1至10中任一项所述的组合物,其中所述糖果载体物质选自口香糖基质、硬糖基质、软糖基质、明胶基质、压制糖基质或其混合物;优选口香糖基质。
12.如权利要求11所述的组合物,其中按所述组合物的重量计,所述组合物包括大于约10%、优选大于约15%、更优选大于约20%、最优选大于约25%的树胶基质。
13.如权利要求1至12中任一项所述的组合物,其中按所述组合物的重量计,所述组合物包括少于约8%、优选少于约5%、更优选少于约3%、最优选少于约2%的水。
14.如权利要求1至13中任一项所述的组合物,其中按所述组合物的重量计,所述组合物包括大于约10%、优选大于约20%、更优选大于约30%、最优选大于约40%的不生龋齿的甜味剂。
15.如权利要求14所述的组合物,其中所述不生龋齿的甜味剂为糖醇,所述糖醇优选选自麦芽糖醇、甘露糖醇、木糖醇、山梨醇、三氯蔗糖、天冬甜素及其混合物。
16.如权利要求1至15中任一项所述的组合物,其中所述糖果组合物具有外部涂层。
17.如权利要求16所述的组合物,其中所述聚磷酸盐分散于整个所述载体物质且所述金属离子分散于整个所述涂层物质,反之亦然。
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WO2002092027A2 (en) * | 2001-05-15 | 2002-11-21 | The Procter & Gamble Company | Confectionery compositions |
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-
2002
- 2002-05-14 WO PCT/US2002/015259 patent/WO2002092027A2/en not_active Application Discontinuation
- 2002-05-14 EP EP02769736A patent/EP1448060A2/en not_active Withdrawn
- 2002-05-14 AU AU2002308717A patent/AU2002308717A1/en not_active Abandoned
- 2002-05-14 CN CNB02809798XA patent/CN100438769C/zh not_active Expired - Fee Related
- 2002-05-15 US US10/146,258 patent/US6726897B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102510726A (zh) * | 2009-09-16 | 2012-06-20 | 森永制果株式会社 | 软糖及软糖的制造方法 |
CN105767438A (zh) * | 2016-03-08 | 2016-07-20 | 漯河医学高等专科学校 | 口腔保健及口腔疾病预防口香糖 |
Also Published As
Publication number | Publication date |
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US20030007997A1 (en) | 2003-01-09 |
AU2002308717A1 (en) | 2002-11-25 |
US6726897B2 (en) | 2004-04-27 |
WO2002092027A3 (en) | 2004-06-03 |
CN100438769C (zh) | 2008-12-03 |
EP1448060A2 (en) | 2004-08-25 |
WO2002092027A2 (en) | 2002-11-21 |
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