TWI721957B - 有效抑制牙結石形成的口腔用組合物 - Google Patents
有效抑制牙結石形成的口腔用組合物 Download PDFInfo
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- TWI721957B TWI721957B TW104139053A TW104139053A TWI721957B TW I721957 B TWI721957 B TW I721957B TW 104139053 A TW104139053 A TW 104139053A TW 104139053 A TW104139053 A TW 104139053A TW I721957 B TWI721957 B TW I721957B
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- Taiwan
- Prior art keywords
- metal ion
- chelating agent
- formation
- ion chelating
- cationic polymer
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 38
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- 229920006317 cationic polymer Polymers 0.000 claims abstract description 38
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Abstract
本發明涉及一種用於抑制牙結石形成的口腔用組合物,其含有陰離子性金屬離子螯合劑和陽離子性高分子,更具體地,涉及一種口腔用組合物可在漱口過程中,使磷酸鹽類陰離子金屬離子螯合劑和聚季銨鹽類陽離子高分子形成凝聚層而附著在牙齒表面,使得作為抑制牙結石形成的成分的陰離子類金屬離子螯合劑在漱口之後也能夠長時間殘留在口腔內。本發明的用於抑制牙結石形成的口腔用組合物能夠有效防止牙齒表面的牙結石形成,同時能夠維持牙膏的香味,提高起泡能力。
Description
本發明涉及一種用於抑制牙結石形成的口腔用組合物,其含有陰離子性金屬離子螯合劑和陽離子性高分子,更具體地,涉及一種口腔用組合物可漱口過程中,使磷酸鹽類陰離子金屬離子螯合劑和聚季銨鹽類陽離子高分子形成凝聚層而附著在牙齒表面,使得作為抑制牙結石的形成的成分的陰離子類金屬離子螯合劑在漱口之後也能夠長時間殘留在口腔內。
通常,口腔疾病是因存在於口腔中的各種細菌而引起的,對口腔有害的細菌藉由在獲得膜上取食食物等殘渣來進行增殖而形成牙菌斑,牙菌斑與唾液或血液內的鈣及鎂等的金屬離子結合,從而會形成石灰化的牙結石。這種牙菌斑和牙結石會引起諸如牙齦炎、牙周炎等的牙齦疾病,進而會損傷牙齒。規律性的刷牙有助於抑制這些沉澱物的快速形成,但是規律性的刷牙也不能充分去除附著在牙齒上的所有的結石沉澱物。因此,為了抑制牙菌斑和牙結石的形成,在物理性方面使用研磨劑,在化學性方面使用抗菌劑及金屬離子螯合劑。
在口腔用產品中使用的研磨劑有諸如碳酸鈣、二氧化矽、氫氧化鋁、磷酸鈣、碳酸氫鈉、聚乙烯及聚氯乙烯等的高分子物質,在口腔用產品中使用的抗菌劑有氯化十六烷基吡啶、hexalkonium chloride、苯紮氯銨、地喹氯銨(dequalinium chloride)、氯己定、三氯生、百里香酚、異丙基甲基苯酚及氯化烷基二氨基乙基甘氨酸等,金屬離子螯合劑有焦磷酸鹽、聚磷酸鹽及聚磷酸酯等。
如上所述,為了抑制牙結石形成,主要使用了金屬離子螯合劑,然而,當單獨使用金屬離子螯合劑時,刷牙並漱口之後,金屬離子螯合劑不會殘留在口腔中而會被洗掉,因此對於抑制牙結石形成功效方面在某種程度上存在局限性。並且,當為了提高去除牙結石的功效而添加過量的金屬離子螯合劑時,可能會產生刺激,並且因令人厭惡的味道而使使用感變差。
對此,本發明人為了尋找漱口之後也能夠使金屬離子螯合劑長時間殘留在口腔內的方法而努力的結果,確認了在含有現有的陰離子性金屬離子螯合劑的同時,還含有陽離子性高分子的口腔用組合物時,能夠獲得以下效果,從而完成了本發明。即,藉由陰離子和陽離子的沉澱反應而形成凝聚層,從而能夠使更多的陰離子類金屬離子螯合劑殘留在牙齒上,從而對抑制牙結石的形成有效。
【現有技術文獻】
【專利文獻】
韓國公開專利公報第10-2010-0052934號(2010.05.20.)
發明所欲解決之問題
本發明的目的在於,提供一種抑制牙結石形成的口腔用組合物,其藉由含有陰離子性金屬離子螯合劑及陽離子性高分子來誘導它們的凝聚,由此使得陰離子性金屬離子螯合劑殘留在牙齒表面,從而能夠抑制牙結石的形成。
解決問題之技術手段
為了實現上述目的,本發明提供一種用於抑制牙結石形成的口腔用組合物,其含有陰離子性金屬離子螯合劑及陽離子性高分子作為有效成分。
對照先前技術之功效
本發明的用於抑制牙結石形成的口腔用組合物能夠有效防止在牙齒表面上形成牙結石,同時能夠維持牙膏的香味,提高起泡能力。
對於在本說明書中使用的所有技術性及科學性術語,只要是沒有以其它方式被定義,則與本發明所屬技術領域的技術人員通常所理解的術語具有相同的意義。本說明書中使用的命名法為本技術領域所熟知且通常使用的命名法。
本發明的試驗例中,使用含有陰離子性金屬離子螯合劑及陽離子性高分子的口腔用組合物來對牙齒類比物質進行處理的結果,可以確認陰離子性金屬離子螯合劑及陽離子性高分子以凝聚層形態殘留在牙齒表面,從而殘留的陰離子性金屬離子螯合劑顯示出抑制牙結石形成的效果。
因此,本發明的一個方面,涉及一種用於抑制牙結石形成的口腔用組合物,其含有陰離子性金屬離子螯合劑及陽離子性高分子作為有效成分。口腔用組合物的特徵為陰離子性金屬離子螯合劑及陽離子性高分子相互反應,從而在牙齒表面上形成凝聚層。
對於本發明,其特徵為,口腔用組合物可以進一步含有表面活性劑。
“凝聚(coacervation)”是指,在親水性膠體溶液中,因膠體粒子的水合減少及靜電因素而使得濃縮的溶膠在分散介質中進行分離的現象,並且,經分離的液相中,一側液相的膠體濃度高,另一側液相的膠體濃度低。“凝聚層(coacervate)”是指,因陰離子性高分子電解質和陽離子性高分子電解質在特定條件下混合時產生的凝聚現象而形成的膠體物質。
本發明的口腔用組合物中含有的陰離子性金屬離子螯合劑與陽離子性高分子的離子結合來進行沉澱,從而形成凝聚層,並且形成的凝聚層能夠使具有抑制牙結石的形成效果的金屬離子螯合劑長時間殘留在牙齒表面。
對於本發明,其特徵為陰離子性金屬離子螯合劑為磷酸鹽(phosphate)類化合物。陰離子性金屬離子螯合劑可對牙結石的形成產生重要影響的金屬離子進行螯合(chelating),從而抑制牙結石的形成的物質。陰離子性金屬離子螯合劑較佳為磷酸鹽類化合物,可以選自六偏磷酸鹽(hexametaphosphate)、焦磷酸鹽(pyrophosphate)、聚磷酸鹽(polyphosphate)及上述鹽類中的一種以上。鹽類可以為1至4個鹼金屬陽離子和作為陰離子的磷酸鹽類化合物結合的形態,具體的例子有,磷酸鈉(Sodium phosphate)、磷酸氫鈉(Monosodium phosphate)、磷酸氫二鈉(Disodium phosphate)、磷酸三鈉(Trisodium phosphate)、三聚磷酸鈉(Sodium tripolyphosphate)、六偏磷酸鈉(Sodium hexametaphosphate)、焦磷酸四鈉(Tetrasodium pyrophosphate)及酸式焦磷酸鈉(Sodium acid pyrophosphate)等,但並不限定於此。
另外,對於本發明,其特徵為,陽離子性高分子為聚季銨鹽(polyquaternium)類化合物。聚季銨鹽類化合物表示中心有季銨離子的高分子化合物(聚合物),較佳地,可以為選自聚季銨鹽-10、聚季銨鹽-6及聚季銨鹽-11中的一種以上,但並不限定於此。
另外,對於本發明,其特徵為,口腔用組合物除了含有陰離子性金屬離子螯合劑及陽離子性高分子以外,進一步含有表面活性劑。對於表面活性劑,具體可列舉如甘氨酸鹽類、硫酸鹽類、磺基琥珀酸鹽類、肌氨酸鹽類、磷酸鹽類、羥乙基磺酸鹽類、谷氨酸鹽類、丙烯酸羥乙酯(taurate)類等的陰離子性表面活性劑;甜菜堿、磺基甜菜堿(sultaine)及兩性乙酸鹽(amphoacetate)類等的兩性表面活性劑;聚氧乙烯脂肪酸山梨醇酯、聚氧乙烯(硬化)蓖麻油、甘油脂肪酸酯、脂肪酸山梨醇酯、蔗糖脂肪酸酯、烷醇醯胺、烷基糖苷等的非離子表面活性劑;N-烷基二氨基乙基甘氨酸等的陽離子性表面活性劑等,較佳地,可以為選自月桂基硫酸鈉(Sodium lauryl sulfate)、甲基椰油醯基牛磺酸鈉(Sodium methyl cocoyl taurate)及月桂醇磺基琥珀酸酯二鈉(Disodium lauryl sulfosuccinate)中的一種以上,但並不限定於此。
另外,對於本發明,以組合物總重量計,可以含有0.1~10.0重量%的陰離子性金屬離子螯合劑,較佳為含有1.0~7.0重量%,更佳為含有3.0~5.0重量%。如果陰離子性金屬離子螯合劑的含量小於0.1重量%,則不會形成凝聚層,如果超過10.0重量%,則香味和起泡能力會降低,並且會產生如加重刺激感等的不好的牙膏使用感。
另外,以組合物總重量計,可以含有0.01~0.50重量%的陽離子性高分子,較佳為含有0.05~0.50重量%,更佳為含有0.10~0.50重量%。如果陽離子性高分子的含量小於0.01重量%,則不會形成凝聚層,如果超過0.50重量%,則因牙膏內的黏度高而會不方便使用。
另外,對於本發明,含有以0.2 : 1~1000 : 1的重量比混合的陰離子性金屬離子螯合劑和陽離子性高分子,較佳為含有以10 : 1~100 : 1的重量比混合的陰離子性金屬離子螯合劑和陽離子性高分子,更佳為含有以30 : 1~50 : 1的重量比混合的陰離子性金屬離子螯合劑和陽離子性高分子。由於陰離子性金屬離子螯合劑的分子量相對較小,因此,較佳以高於陽離子性高分子的比例來混合。如果陰離子性金屬離子螯合劑和陽離子性高分子的混合比例小於0.2 : 1或大於1000 : 1,則會難以形成凝聚層。
本發明的口腔用組合物在劑型方面不受特別限定,具體地,可以具有如牙膏、口腔用清洗劑、口腔用清潔劑、口香糖、糖果類、口腔噴霧、口腔漱口液、牙齒美白劑等的劑型。
本發明的口腔用組合物根據劑型及使用目的,可以含有常規使用的研磨劑、濕潤劑、輔助起泡劑、結合劑、甜味劑、pH調節劑、防腐劑、藥效成分、香料、增白劑、色素或溶劑等。
研磨劑可以使用沉澱二氧化矽(precipitated silica)、矽膠、矽酸鋯、磷酸氫鈣、無水磷酸氫鈣、含水氧化鋁、輕質碳酸鈣、重質碳酸鈣、焦磷酸鈣鹽、不溶性偏磷酸鹽及矽酸鋁等。
濕潤劑可以使用濃甘油、甘油、山梨糖醇水溶液、非結晶性山梨糖醇水溶液、聚乙二醇類及丙二醇等。
輔助起泡劑可以使用烷基硫酸鈉、月桂基硫酸鈉、蔗糖脂肪酸酯及脂肪酸山梨醇酯等的陰離子及非離子表面活性劑。
結合劑可以使用羧甲基纖維素鈉、角叉菜膠、黃原膠、羥乙基纖維素、羥丙基甲基纖維素、羥丙基纖維素、瓜爾膠、結冷膠、卡波姆、果膠、聚乙烯吡咯烷酮、聚羧乙烯(carboxyvinyl polymer)、藻酸鈉、鋰皂石、羧甲基纖維素鈉或黃原膠等。
甜味劑可以使用糖精鈉、三氯蔗糖、麥芽糖醇、阿斯巴甜、赤蘚醇、木糖醇、甘草酸及糖精鈉等,防腐劑可以使用苯甲酸、對羥基苯甲酸甲酯、對羥基苯甲酸丙酯、苯甲酸鈉及對羥基苯甲酸酯等。並且,香料可以單獨或混合使用薄荷油、留蘭香油及薄荷醇等。pH調節劑可以使用磷酸鈉、磷酸氫二鈉、檸檬酸或三乙醇胺等。
以下,將藉由實施例來更加詳細地說明本發明。這些實施例僅是為了例示本發明而提出的,對於本領域技術人員來說,本發明的範圍並不應解釋為僅限於這些實施例是顯而易見的。因此,本發明的實質性範圍由附加的申請專利範圍和它們的等效物而被定義。
[實施例1~9及比較例1~3的製備]
為了測試本發明的口腔用組合物的凝聚層的生成程度及殘留程度,以精製水、陰離子性金屬離子螯合劑(六偏磷酸鈉、焦磷酸四鈉、三聚磷酸鈉)、陽離子性高分子(聚季銨鹽-10、聚季銨鹽-6、聚季銨鹽-11)及表面活性劑(月桂基硫酸鈉、甲基椰油醯基牛磺酸鈉及月桂醇磺基琥珀酸酯二鈉)作為主要組成成分,並如下述表1的組成來分別製備總重量為100g的實施例1至9及比較例1至3。
表1
[試驗例1]凝聚層生成程度測定
選取實施例1至9及比較例1至3的樣品,並分別逐漸增加精製水的添加比例,並且逐漸降低樣品的比例,並且調整稀釋比例如下述表2中所述,並且使總重量維持在3g。利用紫外分光光度法(UV spectroscopy)來測定稀釋的各樣品的透明度(%)後,將其結果示於表2中。透明度越低,可以判斷為凝聚層形成得越多。
如上述表2中所示,不含有陽離子性高分子的比較例1沒有形成凝聚層,並且,含有陰離子性金屬離子螯合劑及陽離子性高分子而不含有表面活性劑的實施例1根據稀釋條件在凝聚層生成程度方面顯示出差異。並且可以確認,隨著含有陰離子性金屬離子螯合劑、陽離子性高分子及表面活性劑的溶液被稀釋,形成更多的凝聚層,直到超過某一點後就不再形成凝聚層。由此可以確認,為了凝聚層的形成,重要的是適當的稀釋比例。
另外,在添加陰離子性金屬離子螯合劑及陽離子性高分子的同時,還添加牙膏劑型中作為必要成分而使用的、用於形成氣泡的表面活性劑時,可以確認凝聚層的形成程度根據陽離子性高分子的種類(比較實施例2、5、6)、陰離子性金屬離子螯合劑的種類(比較實施例2、3、4)或表面活性劑的種類(比較實施例2、7、8)而存在差異,並且可以確認凝聚層的形成程度根據陰離子性金屬離子螯合劑的含量(比較實施例2、9)也會產生差異。
另外,可以知道與實施例1至9相比,陰離子性金屬離子螯合劑及陽離子性高分子的混合比例(重量比)低於30 : 1的比較例2或高於50 : 1的比較例3與落在30 : 1至50 : 1的範圍內的實施例1至9相比,不能很好地生成凝聚層。
[試驗例2]牙齒表面的金屬離子螯合劑殘留量測定
在試驗例1中確認到含有陰離子性金屬離子螯合劑、陽離子性高分子及表面活性劑的溶液中形成了凝聚層後,藉由體外試驗(in vitro test)來測定有多少形成的凝聚層會殘留在牙齒表面。
將按照表1中所記載的成分含量來製得的實施例2、7、9及比較例1的溶液稀釋10倍後,利用作為自動刷牙儀器的V-8橫向刷洗機(V-8 Cross Brushing Machine®,Sabri,美國)對作為牙齒模擬物質的羥磷灰石盤(hydroxyapatite disk)(克拉克森色層分析產品(Clarkson Chromatography Products))進行刷洗(Brushing)。為了縮小羥磷灰石盤之間的誤差,使用了4個盤,利用刷洗機並使用稀釋溶液刷洗3分鐘後,清洗5次。重複進行該步驟10次後,用氫氧化鈉溶液(0.3M)來溶解附著在羥磷灰石上的凝聚層後,利用離子色譜法(Ion chromatography,瑞士萬通(Metrohm))來測定殘留在凝聚層內的陰離子性金屬離子螯合劑的量,並將其結果示於表3中。
表3
如上述表3中所示,可以知道與未使用陽離子性高分子的情況(比較例1)相比,使用陽離子性高分子時(實施例2、7、9)的陰離子性金屬離子螯合劑的殘留量顯著多,並且可以確認表面活性劑之間雖然有一點差異,但是差異並不大(比較實施例2、7),當陰離子性金屬離子螯合劑的含量增加時,陰離子性金屬離子螯合劑的殘留量顯著增加(比較實施例2、9)。
[實施例10~11及比較例4的製備]
按照下述表4的組成來製備將含有陰離子性金屬離子螯合劑及陽離子性高分子的凝聚層溶液包含在牙膏形態的膏劑型的實施例10~11及比較例4。
表4
[試驗例3]牙結石形成抑制功效測定
以試驗例1及試驗例2的結果為基礎,測定含有陰離子性金屬離子螯合劑及陽離子性高分子的本發明的口腔用組合物是否具有抑制牙結石形成的功效。
首先,將用砂紙打磨的玻璃棒浸漬於從專家組(panel)中獲得的添加有唾液和砂糖的溶液中後,在35℃下熟化2天。在玻璃棒表面形成牙菌斑後,將玻璃棒浸漬於由25%的牙膏漿體溶液(比較例4、實施例10、11)和氯化鈣(1.5mM)組成的結晶化溶液中,並保存一晚後,第二天,清洗玻璃棒5秒鐘,然後再次浸漬於牙膏漿體溶液和結晶化溶液中而進行保存。將該步驟重複進行2周,並用強酸(1M HCl)和強鹼(1M KOH)溶解形成的牙結石後,利用離子色譜法(Ion chromatography,瑞士萬通(Metrohm))來分析鈣含量,並將其結果示於下述表5中。判斷為鈣含量越低,抑制牙結石形成的能力越好。
如表5中所示,對鈣含量進行分析的結果,可以確認當含有陽離子性高分子時(實施例10、11)與不含有時(比較例4)相比,鈣含量低,並且,鈣含量隨陰離子性金屬離子螯合劑的含量的增加(比較實施例10、11)而降低。
[試驗例4]牙膏使用感評價
以試驗例3的牙結石形成抑制力測定結果為基礎,對牙膏的使用感進行了評價。分別讓20名評價人員使用實施例10、實施例11及實施例4製得的牙膏,並且使用2周後藉由問卷調查來評價香味、起泡能力、刺激感及整體滿意度後,將其結果示於表6中。
(1分:非常不滿意/2分:不滿意/3分:一般/4分:滿足/5分:非常滿意)
如表6中所示,可以確認含有陽離子性高分子的組合物(實施例10、11)對牙膏的香味及刺激感沒有產生大的影響,反而對起泡能力有幫助。
以上,對本發明內容的特定部分進行了詳細說明,而這些具體技術對本領域技術人員來說只是較佳的實施方式,本發明的範圍並不限定於此。因此,本發明的實質性範圍由附加的申請專利範圍和它們的等效物而被定義。
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Claims (4)
- 一種用於抑制牙結石形成的口腔用組合物,以組合物總重量計,其有效成分含有:3~5重量%的陰離子性金屬離子螯合劑,其中該陰離子性金屬離子螯合劑為選自六偏磷酸鹽、焦磷酸鹽、聚磷酸鹽及它們的鹽類中的任一種以上之磷酸鹽類化合物;及0.10~0.50重量%的陽離子性高分子,其中該陽離子性高分子為選自聚季銨鹽-10、聚季銨鹽-6及聚季銨鹽-11中的任一種以上之聚季銨鹽類化合物,且該陰離子性金屬離子螯合劑和該陽離子性高分子的混合重量比為30:1~50:1。
- 如請求項1所述之用於抑制牙結石形成的口腔用組合物,其中該陰離子性金屬離子螯合劑和該陽離子性高分子相互反應,而在牙齒表面上形成凝聚層。
- 如請求項1所述之用於抑制牙結石形成的口腔用組合物,其進一步含有表面活性劑。
- 如請求項3所述之用於抑制牙結石形成的口腔用組合物,其中該表面活性劑為選自月桂基硫酸鈉、甲基椰油醯基牛磺酸鈉及月桂醇磺基琥珀酸酯二鈉中的任一種以上。
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2015
- 2015-11-19 CN CN201580075837.5A patent/CN107205892B/zh active Active
- 2015-11-19 KR KR1020150162289A patent/KR102406001B1/ko active IP Right Grant
- 2015-11-25 TW TW104139053A patent/TWI721957B/zh not_active IP Right Cessation
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TWM333174U (en) * | 2007-07-06 | 2008-06-01 | Qing-Xiu Cai | Apparatus for whitening teeth |
EP2476406A2 (de) * | 2010-12-08 | 2012-07-18 | Henkel AG & Co. KGaA | Mund- und Zahnpflege- und -Reinigungsmittel mit gesteigerter antibakterieller Wirkung II |
Also Published As
Publication number | Publication date |
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CN107205892A (zh) | 2017-09-26 |
KR102406001B1 (ko) | 2022-06-08 |
CN107205892B (zh) | 2021-01-05 |
TW201634039A (zh) | 2016-10-01 |
KR20160112919A (ko) | 2016-09-28 |
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