201121574 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種新穎之齒科酸蝕凝膠組成物，可廣泛 應用於牙齒填補修復過程中作為酸蝕處理劑之用。 【先前技術】 利用壓克力樹脂填補蛀牙窩洞的處理程序，已是目前牙 醫所普遍應用的方法。一般在填補前的前處理步驟為酸钮 處理’即利用構酸將牙齒表面進行酸触與粗链化，從而將 牙齒缺瑯質或象牙質表面的髒污清潔或去礦化 (demineralize)。此酸蝕處理不僅能將牙齒表面的細微髒污 清除乾淨，同時也能使牙齒的琺瑯質產生脫鈣作用，於牙 齒表面形成粗糙化表面，而產生較大的比表面積，此步驟 有利於後續填補牙齒過程中，填補材與牙齒間的緊密黏 著。 一般酸蝕處理使用的酸蝕劑為磷酸水溶液，其濃度大多 為10至40重量％之間’由於其流動性好，塗在牙齒表面時 會任意机動，而造成健康牙齒表面也受到酸蚀產生脫的作 用’甚至可能造成牙齒周遭組織的傷害。因此，許多文獻 便開始著手開發膠體狀的酸触劑，稱為酸钮凝膠，該酸触 凝膠的作法為，添加增_劑於礙酸水溶液中，使其呈現膠 體狀’以改善賴水溶液流動性太好的缺點。由此形成之 «系酸料膠’於使用時可直接塗佈在料的牙齒表面 4位，而不會任意流動，從而可防止健康的牙齒被酸蚀脫 約。 142623.doc 201121574 早期的文獻主要疋利用石夕石（silica)當增稠劑（例如：美 國第4,802,950號專利、第6,537,563號專利及第6,753,〇〇1 號專利），使磷酸水溶液增稠，並將其充填入25G(針頭内 徑0.25 mm)針筒中’以方便能精準的將磷酸凝膠配置在牙 、齒表面的正確位置上。然而，由於矽石的保水性不佳，隨 時間增加，磷酸凝膠中的水分會逐漸蒸發，而使磷酸濃度 增加，使用時不僅可能會對牙齒造成傷害，也容易造成針 頭堵塞，導致使用上的諸多不便。 為了改善上述使用矽石當增稠劑的缺點，後續許多文獻 轉而使用保水性佳的分子當增稠劑，如甘油（glycerin ;美 國第5,954,996號專利）、蔗糖素（sucrai〇se ;美國第 6,689,343號專利）及纖維素及其衍生物（美國第6,〇27,341號 專利及第6,537,563號專利）等。其中纖維素系最常見的增 稠劑為羧曱基纖維素鈉（carb〇xyinethyl cellulose，簡稱 CMC) ’該結構具有吸水性與保水性佳之特性，適合作為 填酸水溶液之增稍劑使用。 然而’並非所有的CMC都適合用於製備磷酸酸蝕凝膠， 本案發明人們經研究後發現，CMC的黏度（visc〇sity)及鈉 鹽平均取代率（average degree of substitution)對磷酸水溶 液的最終凝膠狀態影響甚鉅，這是過去文獻中所未曾提及 的。CMC的本質黏度與其分子量及分子間作用力有關，分 子量大其容易造成分子間的糾纏（entangleinent)而使其黏度 提高’造成製備成凝膠時其流動性差，甚至黏度更高時有 可能使膠體應用時容易阻塞針頭，造成操作上的不便。另 142623.doc 201121574 方面’將CMC應用在製備酸飯凝膠時，CMC所處的環境 為酸性’而根據Le Chatelier理論，CMC之鈉鹽平均取代 率越馬時，其在酸性水溶液中的溶解度越差。當溶解度差 時，會導致CMC於磷酸溶液中，分散不均，而使用時則易 造成針頭阻塞，也會使醫師使用操作不便。所以若CMC作 為增稠劑製備磷酸酸蝕凝膠時，為了使磷酸水溶液有效增 稠（在使用上不會有阻塞針頭的現象），且同時維持酸蝕凝 膠良好的保水性，CMC的黏度及鈉鹽平均取代率等條件的 選擇疋一重要因子，但在過去的相關文獻中卻沒有提及。 美國第6,027,341號專利僅揭示可添加1-5%的CMC至乙二 胺四醋酸（EDTA)水溶液中作為增稠劑。美國第6,537,563 號專利則揭示一種包含1 〇_50重量％的磷酸及約3至約20重 里〇/〇的石夕溶膠（colloidal silica sol)之齒科酸钮凝膠組成 物’該組合物可視需要包含0.U%的CMC作為有機增稠 劑。兩者文中皆未說明是何種型態的CMC。 因此’在本專利中主要是揭露一種齒科酸蝕凝膠組成 物’藉由結合磷酸水溶液及具有特殊性質的CMC增稠劑， 所形成之酸触凝膠不會任意流動，且具備相當好的保水 性，當充填在注射容器中接上25G針頭後仍可順利擠出而 無阻塞針頭的現象’可廣泛應用於牙齒填補修復過程中作 為酸蝕處理劑之用。 【發明内容】 所以本發明之一目的為提供一種齒科酸蝕凝膠組成物， 其包含磷酸水溶液及增稠劑，其中該增稠劑為羧甲基纖維 142623.doc 201121574 素鈉（CMC)，且該CMC具有以下之性質： (a) 當加水配置成1重量％之CMC水溶液時，具有i 〇〇至 2000 cps之黏度；及 (b) 分子上的納鹽平均取代率為21 %至33%。 本發明之另一目的為提供一種增加牙齒表面粗糙度之方 法’其包括在使用填補樹脂之前’將根據本發明之齒科酸 钱凝膠組成物施加至牙齒表面’於一適當時間，使其產生 不均勻表面’再以清水將該組成物自牙齒表面移除。 【實施方式】 本發明主要是發現為了使磷酸水溶液有效增稠（在使用 上不會有阻塞針頭的現象），且同時維持酸蝕凝膠良好的 保水性’該CMC增稠劑的黏度及鈉鹽平均取代率等條件的 選擇是一重要因子，進而提出一種包含磷酸水溶液及具有 特殊性質之CMC增稠劑的齒科酸蝕凝膠組成物。 根據本發明之一實施態樣，用於齒科酸蝕凝膠組成物作 為主要成分之磷酸水溶液的濃度為1〇至40重量％，較佳為 37重量％。齒科酸蝕凝膠組成物中之磷酸含量可有效提供 2分鐘内’較佳1分鐘内，將牙齒表面酸蝕作用。所述磷酸 之有效含量一般而言可賦予凝膠組成物不高於1之pH值。 根據本發明之一實施態樣，用於齒科酸蝕凝膠組成物中 作為增稠劑使用之CMC其含量以組成物總重量計，較佳為 〇.5至7重量％，更佳為1至6重量❶/。，最佳為2至5重量％。 可使用於本發明作為增稠劑使用之CMC必須同時具有以 下性質： 142623.doc 201121574 (a) 當加水配置成1重量％之CMC水溶液時，具有100至 2000 cps ’較佳具有300至1500 cps，之黏度；及 (b) 分子上的鈉鹽平均取代率為21%至33%。 以下將說明鈉鹽平均取代率的定義。 若作為增稠劑使用之羧甲基纖維素及其鈉鹽具有如下式 (I)及（II)之結構：201121574 VI. Description of the Invention: [Technical Field] The present invention relates to a novel dental acid etching gel composition which can be widely used as an acid etching treatment agent in a dental filling and repairing process. [Prior Art] The processing procedure for filling the cavity of the cavities with acrylic resin has been widely used in dentistry. Typically, the pre-filling pre-treatment step is acid button treatment, i.e., the acid surface is acid-touched and thickened with acid, thereby cleaning or demineralizing the tooth-deficient or dentin-like surface. This acid etching treatment can not only remove the fine dirt on the tooth surface, but also decalcify the enamel of the tooth and form a rough surface on the tooth surface to produce a large specific surface area. This step is beneficial for subsequent filling. During the tooth process, the material is closely adhered to the teeth. Generally, the acid etching agent used in the acid etching treatment is an aqueous phosphoric acid solution, and the concentration thereof is mostly between 10 and 40% by weight. 'Because of its good fluidity, it is arbitrarily maneuvered when applied to the tooth surface, and the surface of the healthy tooth is also subjected to acid etching. The effect of detachment may even cause damage to the tissues surrounding the teeth. Therefore, many literatures have begun to develop colloidal acid contact agents, called acid button gels. The method of acid touch gel is to add an agent to the acid solution to make it colloidal. The disadvantage that the aqueous solution is too fluid. The resulting "acid paste" can be applied directly to the surface of the teeth of the material at the 4th position without arbitrarily flowing, thereby preventing healthy teeth from being eroded by acid etching. 142623.doc 201121574 The early literature mainly used silica as a thickener (for example, U.S. Patent No. 4,802,950, U.S. Patent No. 6,537,563 and U.S. Patent No. 6,753, No. 1) to thicken an aqueous phosphoric acid solution. It is filled into a 25G (needle inner diameter 0.25 mm) syringe to make it easy to accurately position the phosphoric acid gel on the tooth and tooth surface. However, due to the poor water retention of vermiculite, the water in the phosphate gel will gradually evaporate over time, and the concentration of phosphoric acid will increase. When used, it may not only cause damage to the teeth, but also cause needle clogging, resulting in use. Many inconveniences. In order to improve the above-mentioned disadvantages of using vermiculite as a thickener, many subsequent literatures have turned to the use of water-retaining molecules as thickeners, such as glycerin (glycerin; US Patent No. 5,954,996), sucralose (sucrai〇se; And the cellulose and its derivatives (U.S. Patent No. 6, pp. 27, 341 and U.S. Patent No. 6,537, 563). Among them, the most common thickener for cellulose is carbaryl xyinethyl cellulose (CMC). This structure has the characteristics of good water absorption and water retention, and is suitable for use as a bulking agent for aqueous acid solution. However, not all CMCs are suitable for the preparation of phosphoric acid etched gels. The inventors of the present invention found that the viscosity of CMC (visc〇sity) and the average degree of substitution of sodium salt to the final solution of aqueous phosphoric acid The state of the gel is very influential, which has not been mentioned in the past literature. The intrinsic viscosity of CMC is related to its molecular weight and intermolecular force. When the molecular weight is large, it is easy to cause entanglement between molecules and increase its viscosity. It causes poor fluidity when prepared into a gel, and even when the viscosity is higher, it may cause colloid. It is easy to block the needle during application, resulting in inconvenience in operation. 142623.doc 201121574 Aspect 'The application of CMC in the preparation of yogurt gel, the environment in which CMC is acidic' and according to Le Chatelier theory, the average substitution rate of sodium salt of CMC is the solubility in acidic aqueous solution. The worse. When the solubility is poor, it will cause the CMC to be dispersed unevenly in the phosphoric acid solution, and it is easy to cause the needle to be blocked when used, which may also make the operation of the doctor inconvenient. Therefore, if CMC is used as a thickener to prepare a phosphoric acid gel, in order to effectively thicken the phosphoric acid aqueous solution (there is no clogging of the needle in use), and at the same time maintain good water retention of the acid etching gel, the viscosity of CMC The selection of conditions such as the average substitution rate of sodium salt is an important factor, but it has not been mentioned in the related literature in the past. U.S. Patent No. 6,027,341 discloses only the addition of 1-5% of CMC to an aqueous solution of ethylenediaminetetraacetic acid (EDTA) as a thickener. U.S. Patent No. 6,537,563 discloses a dental acid gel gel composition comprising 1 〇 50% by weight of phosphoric acid and about 3 to about 20 liters of hydrazine/hydrazine of colloidal silica sol. It is necessary to contain 0. U% of CMC as an organic thickener. Neither article explains what type of CMC. Therefore, 'in this patent, it is mainly disclosed that a dental acid etching gel composition' is formed by combining an aqueous phosphoric acid solution and a CMC thickener having special properties, and the acid touch gel formed does not flow arbitrarily, and is quite good. The water retention property can be smoothly extruded without a clogging needle when the 25G needle is filled in the injection container, which can be widely used as an acid etching treatment agent in the dental filling and repairing process. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a dental acid etching gel composition comprising an aqueous phosphoric acid solution and a thickening agent, wherein the thickening agent is carboxymethyl fiber 142623.doc 201121574 sodium (CMC) And the CMC has the following properties: (a) having a viscosity of i 〇〇 to 2000 cps when the water is added in a 1% by weight aqueous solution of CMC; and (b) an average substitution rate of the nano-salt at the molecule is 21% to 33%. Another object of the present invention is to provide a method of increasing the surface roughness of a tooth which comprises 'applying a dental acid gel composition according to the present invention to a tooth surface' at a suitable time before using the filling resin An uneven surface is created' and the composition is removed from the tooth surface with fresh water. [Embodiment] The present invention mainly finds that in order to effectively thicken an aqueous phosphoric acid solution (the phenomenon that the needle is not blocked in use), and at the same time maintain good water retention of the acid etching gel, the viscosity and sodium of the CMC thickener The selection of conditions such as the average salt substitution rate is an important factor, and further, a dental acid etching gel composition comprising an aqueous phosphoric acid solution and a CMC thickener having special properties is proposed. According to an embodiment of the present invention, the concentration of the aqueous phosphoric acid solution used as the main component of the dental acid etching gel composition is from 1% to 40% by weight, preferably 37% by weight. The phosphoric acid content of the dental etched gel composition is effective to provide an acid etch on the tooth surface within 2 minutes, preferably within 1 minute. The effective level of the phosphoric acid generally imparts a pH to the gel composition of no more than one. According to an embodiment of the present invention, the CMC used as a thickener in the dental acid etching gel composition is preferably used in an amount of from 0.5 to 7% by weight based on the total weight of the composition, more preferably 1 to 6 weights /. Most preferably 2 to 5% by weight. The CMC which can be used as the thickener in the present invention must have the following properties at the same time: 142623.doc 201121574 (a) When the water is added in a 1% by weight aqueous solution of CMC, it has 100 to 2000 cps' preferably 300 to 1500 cps. , the viscosity; and (b) the average substitution rate of sodium salts on the molecule is 21% to 33%. The definition of the average substitution rate of the sodium salt will be explained below. If the carboxymethyl cellulose and its sodium salt used as a thickener have the structures of the following formulas (I) and (II):
(Π) 鈉鹽平均取代率：當n=10時，即有六十個〇H官能基，其 中若有十三個官能基的Η被-CH2COONa取代時，則CMC分 子上的鈉鹽平均取代率即為21 %，依此類推。 如前所述，CMC增稠劑的黏度及鈉鹽平均取代率等條件 的選擇是一重要因子。CMC增稠劑黏度過高時（分子殘繞 的程度過大）或分子上的鈉鹽平均取代率過高（酸性環境下 溶解度降低）時’由此形成之酸蝕凝膠過於膠結，不易自 針筒擠出’且容易阻塞針頭，降低牙醫實際操作過程中的 便利性。反之’ CMC增稠劑黏度過小時或分子上的鈉鹽平 均取代率過低時，由此形成之酸蝕凝膠流動性太好，因此 實際使用時容易隨處流動造成牙齒周圍組織的傷害。 142623.doc 201121574 本發明之齒科酸蝕凝膠組成物由於使用具有特定範圍之 黏度及分子上鈉鹽平均取代率之CMC增稠劑，從而呈現為 半膠體狀態（semi-gel type)，#填充至針筒施用時，不僅 可順利擠出而無阻塞針頭的現象，此外當施加至牙齒表面 時亦可固定在特定的部位，不致隨意流動造成牙齒周圍組 織的傷害。於本文中，「半膠體狀態」係指將酸蝕凝膠充 填至3mL的針筒並裝設在Instr〇n的夾具上以固定2爪爪^4 的速度向下壓，此時將針筒壓下所需的擠出力落於約61^至 約10N之範圍内者。 本發明之齒科酸蝕凝膠組成物中可視需要進一步含有顏 色指示劑。添加顏色指示劑之目的主要是為了使齒科酸蝕 凝膠組成物得以與牙齒的顏色作區分，從而實際使用時可 清楚的辨識牙齒與酸蝕凝膠的不同，同時酸蝕過程結束後 也可將酸蝕凝膠仔細清除乾淨。常用的顏色指示劑係為食 用顏料，例如，但不限於，曱基藍及甲基紫。一般而言， • 市面上的產品多以藍色為主。顏色指示劑的添加量，以酸 蝕凝膠組成物總重計，為〇.〇〇〇丨至1 〇重量0/〇。 另一方面，本發明之齒科酸蝕凝膠組成物中可視需要進 一步含有香精，從而在實際使用的過程中，讓病患覺得氣 味清香，而不會有磷酸的酸味。常用的香精係為食用香 料，例如，但不限於，留蘭香及水果香。香精的添加量， 以酸姓凝膠組成物總重計’為〇 〇 〇 〇 1至1 〇重量％。 除了顏色指示劑及香精之外，本發明之齒科酸蝕凝膠組 成物中可視實際應用範圍的需要進一步包含此技術領域中 142623.doc 201121574 =通常知識者所熟知但不致對本發明組成物產生不 或多種其他添力，，例如，說化物、填 抗 菌劑等。 本發明所提供之齒科酸钱凝膠組成物在實際應用上不會 有阻塞針頭的現象’並具有以下特點： ⑷可有效清除牙齒表面細微辦污，增加表面粗糖度， 有利於牙齒與填補材料之間的黏著。 W為半膠體狀態（semi_gel type)，使用 動，可固定在特定㈣位使P & (C)填充在針筒中時，可輕易擠出分配使用。 (d)可快速有效的進行牙齒表面酸蝕且使用後可輕易以 水沖洗移除。 據此，本發明進一步關於一種增加牙齒表面粗糙度之方 法，其包括在使用填補樹脂之前，將根據本發明之齒科酸 蚀凝膠組成物施加至牙齒表面，於一適當時間，使其產生 不均勻表面，再以清水將該組成物自牙齒表面移除。實際 施加時間係屬此技術領域中具有通常知識者所能推知者， 一般而言係少於1分鐘。此外，本發明之齒科酸姓凝膠組 成物可利用注射器或其他習知的施打方式施加至牙齒表 面。 以下實施例係用於對本發明作進一步說明，惟非用以限 制本發明之範圍。任何此技術技藝中具有通常知識者可輕 易達成之修飾及改變均包括於本案說明書揭示内容及所附 申請專利範圍之範圍内。 142623.doc -10· 201121574 實施例 齒科酸蝕凝膠之製備 製備例1 : 配製37%之磷酸水溶液100公克，加入〇 2公克曱基藍 水溶液’再添加0.01公克留蘭香香精，放置於容器中，利 用攪拌機以鐵弗龍攪拌棒持續攪拌，再將CMC(1%時黏度 為375 cps，平均取代率為27。/。； Aqualon(睛自台灣公利洋 _ 行股份有限公司）)5公克逐漸加入上述之磷酸溶液中，使其 授拌均勻呈凝膠狀，將攪拌均句之磷酸凝膠以高速離心機 離心脫泡，脫泡後即完成酸蝕凝膠。 製備例2 : 配製37%之磷酸水溶液ι00公克，加入〇2公克1%曱基藍 水溶液’再.添加0.01公克留蘭香香精，放置於容器中，利 用攪拌機以鐵弗龍攪拌棒持續攪拌，再將CMC(1%時黏度 為1500 cps，平均取代率為29% ; Aqual〇n(購自台灣公利 φ 洋行股份有限公司）)5公克逐漸加入上述之磷酸溶液中，使 其攪拌均勻呈凝膠狀’將攪拌均勻之磷酸凝膠以高速離心 機離心脫泡’脫泡後即完成酸蝕凝膠。 比較例1 : 配製37%之磷酸水溶液1〇〇公克，加入〇 2公克1G/。甲基藍 水溶液，再添加〇.〇〗公克留蘭香香精，放置於容器中，利 用攪拌機以鐵弗龍攪拌棒持續攪拌，再將CMC(1%時黏度 為50 cps，平均取代率為3〇% ; Aqual〇n(購自台灣公利洋 行股份有限公司））5公克逐漸加入上述之磷酸溶液中，使其 142623.doc 201121574 攪拌均勻呈凝膠狀，將攪拌均勻之磷酸凝膠以高速離心機 離心脫泡，脫泡後即完成酸蝕凝膠》 比較例2 : 配製37%之磷酸水溶液100公克，加入〇.2公克1%曱基藍 水溶液，再添加〇.〇 1公克留蘭香香精，放置於容器中，利 用攪拌機以鐵弗龍攪拌棒持續攪拌，再將CMC( 1 %時點度 為3500 cps ’平均取代率為25% ; Aqualon(購自台灣公利 洋行股份有限公司））5公克逐漸加入上述之構酸溶液中，使 其攪拌均勻呈凝膠狀，將攪拌均勻之磷酸凝膠以高速離心 機離心脫泡，脫泡後即完成酸蝕凝膠。 比較例3 : 配製37%之磷酸水溶液100公克，加入〇·2公克1%甲基藍 水溶液，再添加〇·〇 1公克留蘭香香精’放置於容器中，利 用攪拌機以鐵弗龍攪拌棒持續攪拌，再將CMC(1%時黏度 為35〇0 cps ’平均取代率為30% ; Aqualon(購，台灣公利 洋行股份有限公司））5公克逐漸加入上述之填酸溶液中，使 其攪拌均勻呈凝膠狀，將攪拌均勻之磷酸凝膠以高速離心 機離心脫泡，脫泡後即完成酸蝕凝膠。 比較例4 : 配製37%之磷酸水溶液1〇〇公克，加入〇2公克1%甲基藍 水溶液，再添加〇.〇 1公克留蘭香香精，放置於容器中利 用攪拌機以鐵弗龍攪拌棒持續攪拌，再將CMC(1%時黏度 為400 cps，平均取代率為42。/。； Aqualon(購自台灣公利洋 行股份有限公司））5公克逐漸加入上述之填酸溶液中，使其 142623.doc -12- 201121574 攪拌均勻呈凝膠狀，將攪拌均勻之磷酸凝膠以高速離心機 離心脫泡，脫泡後即完成酸姓凝膠。 比較例5 : 配製37%之磷酸水溶液1〇〇公克，加入〇·2公克1%曱基藍 水溶液’再添加0.01公克留蘭香香精，放置於容器中，利 用攪拌機以鐵弗龍攪拌棒持續攪拌，再將CMC(1%時黏度 為155〇 cps ’平均取代率為36〇/〇 ; AqUal〇n(購自台灣公利 洋行股份有限公司））5公克逐漸加入上述之填酸溶液中，使 其攪拌均勻呈凝膠狀，將攪拌均勻之磷酸凝膠以高速離心 機離心脫泡，脫泡後即完成酸蝕凝膠。 黏度量測 分別將製備例1至2及比較例1至5所使用之CMC調配成1 重里/〇之水溶液並裝在容器中’以Br〇〇kfield黏度劑 (HADV-ΠΙ Ultre)搭配4號spindle，量測其黏度，結果如表！ 中所示。 pH值量測 分別取製備例1至2及比較例丨至5所製備完成之酸蝕凝 膠，並利用酸鹼暨導電度計量測其pH值，結果如表1中所 示。 擠出力量測 取製備例1至2及比較例1至5所製備完成之酸蝕凝膠，將 其分別充填到3 mL的針筒中，並將其裝在Instr〇n的夾具 上，以固定2 mm/min的速度向下壓，使酸蝕凝膠穩定的由 針筒令被擠出，並觀察將針筒壓下所需的力，即為擠出 I42623.doc •13· 201121574 力、‘果如表1中所不。擠出力的量測值必須在約·以 下’在實際牙醫操作的過程中才不會發生擠不出來的問 題。此外’擠出力的量測值亦必須在约6N以上，才不至於 流動性太好’而於實際使用時造成病人牙齒周圍組織的傷 表1 CMC 納鹽平均取 代率(％) CMC 黏度（cps: (in 1 % solution) 凝膠pH擠出力(DisPerse by 25G needle) (N)(Π) Average substitution rate of sodium salt: When n=10, there are sixty 〇H functional groups, wherein if thirteen functional hydrazines are substituted by -CH2COONa, the sodium salt on the CMC molecule is substituted on average. The rate is 21%, and so on. As mentioned above, the selection of conditions such as the viscosity of the CMC thickener and the average substitution rate of the sodium salt is an important factor. When the viscosity of the CMC thickener is too high (the degree of molecular remnant is too large) or the average substitution rate of the sodium salt on the molecule is too high (the solubility in the acidic environment is lowered), the resulting acid-etched gel is too cemented and difficult to self-needle. The barrel is extruded and the needle is easily blocked, reducing the convenience of the dentist during actual operation. On the other hand, when the viscosity of the CMC thickener is too small or the average substitution rate of the sodium salt on the molecule is too low, the acid etching gel formed thereby has too good fluidity, so that it is easy to flow anywhere in the actual use to cause damage to the tissue surrounding the tooth. 142623.doc 201121574 The dental acid etching gel composition of the present invention exhibits a semi-gel type due to the use of a CMC thickener having a specific range of viscosity and an average sodium salt substitution rate on the molecule, # When the filling is applied to the syringe, not only the smooth extrusion but no clogging of the needle is obtained, and when applied to the surface of the tooth, it can be fixed at a specific portion without causing random flow to cause damage to the tissue surrounding the tooth. As used herein, "semi-colloidal state" means that the acid-etched gel is filled into a 3 mL syringe and mounted on a holder of Instr〇n to press down at a rate of 2 claws, at which time the syringe is pressed. The extrusion force required for pressing falls within the range of about 61^ to about 10N. The dental acid etching gel composition of the present invention may further contain a color indicator as needed. The purpose of adding a color indicator is mainly to distinguish the dental acid etching gel composition from the color of the tooth, so that the difference between the tooth and the acid gel can be clearly recognized in actual use, and the etching process is also completed. The acid gel can be carefully removed. Commonly used color indicators are food colors such as, but not limited to, fluorenyl blue and methyl violet. In general, • The products on the market are mostly blue. The amount of the color indicator added is from 〇.〇〇〇丨 to 1 〇 by weight 0/〇 based on the total weight of the acid gel composition. On the other hand, the dental acid etching gel composition of the present invention may further contain a fragrance as needed, so that in the course of actual use, the patient feels fragrant and fragrant without the acidity of phosphoric acid. Commonly used flavors are edible flavors such as, but not limited to, spearmint and fruity notes. The amount of the fragrance added is 〇 〇 〇 〇 1 to 1 〇 by weight based on the total weight of the acid composition. In addition to the color indicator and fragrance, the dental etch gel composition of the present invention may further comprise the technical field of 142623.doc 201121574, which is well known to those skilled in the art, but does not produce the composition of the present invention. No or a variety of other adding power, for example, to say a compound, to fill an antibacterial agent, and the like. The dental acid gel gel composition provided by the invention does not have the phenomenon of blocking the needle in practical application, and has the following characteristics: (4) can effectively remove the fine dirt on the surface of the tooth, increase the surface roughness, and facilitate the filling and filling of the teeth. Adhesion between materials. W is a semi-gel type. It can be easily dispensed and dispensed when it is fixed in a specific (four) position so that P & (C) is filled in the syringe. (d) The surface of the tooth can be quickly and effectively etched and can be easily removed by rinsing with water after use. Accordingly, the present invention is further directed to a method of increasing the surface roughness of a tooth comprising applying a dental acid etch gel composition according to the present invention to a tooth surface prior to use of the filling resin, at a suitable time to produce The surface is uneven and the composition is removed from the tooth surface with clear water. The actual application time is inferred by those of ordinary skill in the art, and is generally less than one minute. Further, the dental acid surname gel composition of the present invention can be applied to the tooth surface by means of a syringe or other conventional application means. The following examples are intended to be illustrative of the invention and are not intended to limit the scope of the invention. Modifications and variations that may be readily made by those skilled in the art are within the scope of the disclosure of the present disclosure and the scope of the appended claims. 142623.doc -10· 201121574 Example Preparation of Dental Acid Etching Gel Preparation Example 1 : Preparing 100 g of 37% aqueous phosphoric acid solution, adding 公2 g of thiol blue aqueous solution', adding 0.01 g of spearmint essence, and placing in a container In the middle, use a stirrer to continue stirring with the Teflon stir bar, and then CMC (the viscosity is 375 cps at 1%, the average substitution rate is 27%; Aqualon (eye from Taiwan Gongli Ocean Co., Ltd.)) 5 grams Gradually added to the above-mentioned phosphoric acid solution, the mixture is uniformly gel-like, and the phosphoric acid gel of the stirring sentence is centrifugally defoamed by a high-speed centrifuge, and the acid-etched gel is completed after defoaming. Preparation Example 2: Prepare a solution of 37% phosphoric acid in 00 g, add 公2 g of 1% hydrazine blue aqueous solution'. Add 0.01 gram of spearmint essence, place in a container, and continue stirring with a stirrer with a stirrer. CMC (having a viscosity of 1500 cps at 1%, an average substitution rate of 29%; Aqual〇n (purchased from Taiwan Gongli φ Yangxing Co., Ltd.)) 5 g gradually added to the above phosphoric acid solution, stirring it evenly into a gel The acid gel gel is completely agitated and degassed by a high-speed centrifuge. Comparative Example 1: 1 g of a 37% aqueous phosphoric acid solution was prepared, and 〇 2 g of 1 G/ was added. Methyl blue aqueous solution, add 〇.〇〗 gram gram of Fragrant Fragrance, placed in a container, stir with a stirrer with Teflon stir bar, and then CMC (1% viscosity is 50 cps, the average replacement rate is 3〇) % ; Aqual〇n (purchased from Taiwan Gongli Yangxing Co., Ltd.)) 5 grams gradually added to the above phosphoric acid solution, so that 142623.doc 201121574 is stirred evenly in the form of a gel, the homogenized phosphate gel is stirred at a high speed centrifuge Centrifugal defoaming, complete the acid etching gel after defoaming. Comparative Example 2: Prepare 100 g of 37% phosphoric acid aqueous solution, add 公.2 g of 1% hydrazine blue aqueous solution, and add 〇.〇1 g of spearmint essence. Place in a container, continue to stir with a stirrer with a Teflon stir bar, and then add CMC (average substitution rate of 2500 cps to 3500 cps '25%; Aqualon (purchased from Taiwan Gongli Yangxing Co., Ltd.)) 5 g gradually Adding to the above-mentioned acid solution, stirring it to form a gel, and uniformly stirring the phosphate gel by centrifugal defoaming in a high-speed centrifuge, and completing the acid etching gel after defoaming. Comparative Example 3: 100 g of a 37% aqueous phosphoric acid solution was prepared, and 〇·2 g of a 1% methyl blue aqueous solution was added, and then 〇·〇1 g of spearmint flavor was added to the container, and the mixture was stirred with a Teflon stir bar. Stir and then add CMC (average substitution rate of 35〇0 cps at 1% to 30%; Aqualon (purchased, Taiwan Gongli Yangxing Co., Ltd.)) 5 g gradually added to the above-mentioned acid filling solution to make it evenly stirred It is in the form of a gel, and the phosphate gel which is evenly stirred is centrifugally defoamed by a high-speed centrifuge, and the acid-etched gel is completed after defoaming. Comparative Example 4: 1 g of a 37% aqueous phosphoric acid solution was added, 2 g of a 1% methyl blue aqueous solution was added, and 1 g of spearmint essence was added, and placed in a container using a stirrer with a Teflon stir bar. Stir, and then add CMC (viscosity of 400 cps at 1%, average substitution rate of 42. /; Aqualon (purchased from Taiwan Gongli Yangxing Co., Ltd.)) 5 grams gradually added to the above acid filling solution, making it 142623. Doc -12- 201121574 Stir evenly in the form of a gel, and stir the homogenized phosphoric acid gel into a high-speed centrifuge for defoaming. After defoaming, the acid gel is completed. Comparative Example 5: Prepare 1 gram of 37% aqueous phosphoric acid solution, add 〇·2 gram of 1% thiol blue aqueous solution', add 0.01 gram of spearmint essence, place in a container, and continue stirring with a stirrer with a Teflon stir bar. Then, CMC (average substitution rate of 155 〇 cps at 1%) is 36 〇 / 〇; AqUal 〇 n (purchased from Taiwan Gongli Yangxing Co., Ltd.)) 5 gram gradually added to the above-mentioned acid filling solution, so that Stir well and gelatinous, and stir the homogenized phosphoric acid gel by centrifugal defoaming in a high-speed centrifuge. After defoaming, the acid-etched gel is completed. Viscosity measurement The CMC used in Preparation Examples 1 to 2 and Comparative Examples 1 to 5, respectively, was formulated into an aqueous solution of 1 liter/rhenium and placed in a container. 'With Br〇〇kfield viscosity agent (HADV-ΠΙ Ultre) with No. 4 Spindle, measure its viscosity, the results are like a table! Shown in . pH measurement The acid etching gels prepared in Preparation Examples 1 to 2 and Comparative Examples 丨 to 5 were respectively measured, and the pH values thereof were measured by acid-base and conductivity, and the results are shown in Table 1. Extrusion force was used to measure the acid-etched gels prepared in Preparation Examples 1 to 2 and Comparative Examples 1 to 5, which were respectively filled into a 3 mL syringe and mounted on a holder of Instr〇n for fixing. Pressing at a speed of 2 mm/min, the acid-etched gel is stabilized by the syringe, and the force required to press the syringe is observed, ie, extrusion I42623.doc •13·201121574 force, 'The fruit is not as shown in Table 1. The measurement of the extrusion force must be in the process of the actual dentist operation without the problem of being squeezed out. In addition, the 'extrusion force measurement must also be above about 6N, so that the fluidity is not too good' and the tissue around the patient's teeth is injured in actual use. Table 1 CMC average salt substitution rate (%) CMC viscosity (cps : (in 1 % solution) Gel pH Extrusion Force (DisPerse by 25G needle) (N)
由製備例2與比較例3之實驗結果可知，當鈉鹽平均取代 率相近時，隨黏度增加（相@漠度下，黏度越冑，即分子 量越大），所製備出來的酸蝕凝膠之分子殘繞的程度越 大’因此於實際使用時，不易擠出，且容易阻塞針頭:反 之，由製備例2與比較例丨之實驗結果可知，在相同鈉鹽平 均取代率的條件下，黏度越小，《分子殘繞㈣較小^流 動性太好’因此實際使用時易會造成病人牙齒_組織二 傷害。 另一方面’由製備例1與比較例4以及製備例2與比較例5 比較可知，在相同濃度下，其黏度相近的分子（分子量接 142623.doc 201121574From the experimental results of Preparation Example 2 and Comparative Example 3, it is known that when the average substitution rate of the sodium salt is similar, the viscosity is increased (the viscosity is more 胄, that is, the molecular weight is larger), and the prepared acid etching gel is prepared. The greater the degree of molecular remnant winding, so it is not easy to extrude in actual use, and it is easy to block the needle: on the contrary, from the experimental results of Preparation Example 2 and Comparative Example, it is known that under the same average sodium salt substitution rate, The smaller the viscosity, the smaller the molecular remnant (four) and the better the fluidity. Therefore, it is easy to cause damage to the patient's teeth and tissue during actual use. On the other hand, it can be seen from the comparison between Preparation Example 1 and Comparative Example 4 and Preparation Example 2 and Comparative Example 5 that the molecules having similar viscosity at the same concentration (molecular weight 142623.doc 201121574
近）的幾組，其形成膠體後，由於在酸性的環境下，CMC 分子上的納鹽平均取代率高則溶解度低’因此充填在針筒 後要將其擠出使用較不容易，且容易阻塞針頭，降低牙醫 實際操作過程中的便利性。 :容易了解本發明之各種改良是可行的並且是熟諳此技 者谷易聯想到及預期的。In recent groups, after forming a colloid, since the average substitution rate of the sodium salt on the CMC molecule is high in the acidic environment, the solubility is low. Therefore, it is not easy to extrude it after being filled in the syringe. Block the needle and reduce the convenience of the dentist during the actual operation. It is easy to understand that various modifications of the present invention are possible and are known and expected by those skilled in the art.
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