TWI566783B - Mouthwash comprising silver polyacrylate - Google Patents

Mouthwash comprising silver polyacrylate Download PDF

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TWI566783B
TWI566783B TW104127253A TW104127253A TWI566783B TW I566783 B TWI566783 B TW I566783B TW 104127253 A TW104127253 A TW 104127253A TW 104127253 A TW104127253 A TW 104127253A TW I566783 B TWI566783 B TW I566783B
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mouthwash
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cooag
acrylic polymer
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王式禹
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銀高分子漱口水 Silver polymer mouthwash

本發明係關於一種含有銀高分子的漱口水,此漱口水中含有水溶性抗菌壓克力高分子銀鹽,本發明利用水溶性高分子的特性加上銀離子的抗菌能力,開發出有效、快速且安全的漱口水。 The present invention relates to a mouthwash containing a silver polymer, which contains a water-soluble antibacterial acrylic polymer silver salt. The present invention utilizes the characteristics of a water-soluble polymer plus the antibacterial ability of silver ions to develop an effective, Quick and safe mouthwash.

口腔的健康對人類的生活有非常大的影響,如何維持口腔的清潔是我們日常生活所必備的基本常識,維持口腔清潔最常用的方法是漱口及刷牙,一般刷牙會伴同使用牙膏,而漱口則可以僅用清水漱口,當然效果不會很好,為了有效的維護口腔清潔,一般都會使用漱口水來幫助清潔口腔。 Oral health has a great impact on human life. How to maintain oral cleansing is a basic common sense in our daily life. The most common way to maintain oral cleansing is to rinse your mouth and brush your teeth. Generally, brushing your teeth will be accompanied by toothpaste. The mouth can be rinsed with only water, of course, the effect is not very good, in order to effectively maintain oral cleaning, mouthwash is generally used to help clean the mouth.

口腔的清潔要對付的主要是食物殘渣及細菌,食物殘渣可以靠清水漱口,刷牙或使用牙線清潔等方法來去除,但是口腔中的細菌就沒有這麼簡單的除去,這些細菌會分解口腔中的有機物質產生難聞的含硫氣體,這是口臭的由來,而細菌在牙菌斑內分解含糖食物(特別是蔗糖),發酵產生酸,這些酸(主要是乳酸)從牙面結構薄弱的地方侵入, 溶解破壞牙的無機物而產生蛀牙,更嚴重的是細菌會兆呈牙齦炎和牙周病,因此將口腔中有害的細菌除去便成了日常口腔清潔的重要目標。 The cleaning of the mouth is mainly caused by food residues and bacteria. The food residue can be removed by clearing the mouth, brushing teeth or flossing, but the bacteria in the mouth are not so easily removed. These bacteria will decompose in the mouth. The organic matter produces an unpleasant smell of sulfur, which is the origin of bad breath. The bacteria break down sugary foods (especially sucrose) in the plaque and ferment to produce acid. These acids (mainly lactic acid) are weak from the tooth structure. Place to invade, It dissolves the inorganic substances that damage the teeth and causes tooth decay. What is more serious is that the bacteria will be gingivitis and periodontal disease. Therefore, removing harmful bacteria in the oral cavity becomes an important target for daily oral cleaning.

漱口水是將口腔中有害的細菌除去的最佳工 具,將抗菌成分加入漱口水中,在漱口的時候這些抗菌成分發揮作用以達到殺死細菌的目地,一般最常用在漱口水的抗菌成分是chlorhexidine gluconate和cetylpyridinium chloride兩種,這兩種抗菌成份是相對有效而且相對安全的化學物質,但是長期使用仍然可能導致口腔黏膜破損、味覺改變、口乾或有燒灼刺激感等副作用,另外還可能會把牙齒染色,在牙齒表面形成點狀色斑。 Mouthwash is the best way to remove harmful bacteria from the mouth. With antibacterial ingredients added to the mouthwash, these antibacterial ingredients act to kill the bacteria during the mouthwash. The most commonly used antibacterial ingredients in mouthwash are chlorhexidine gluconate and cetylpyridinium chloride. Ingredients are relatively effective and relatively safe chemicals, but long-term use may still cause side effects such as broken oral mucosa, altered taste, dry mouth or burning irritations, and may also stain teeth to form spotted spots on the tooth surface. .

有些漱口水則使用酒精作為抗菌成份,除了殺菌 外,另外配合一些界面活性劑可以將薄荷或一些調味成分以微乳化的形式加入入水中,可是含酒精的漱口水在漱口時會有極強的刺激性,而且對口腔黏膜也會有不良的影響,因此開發一漱口水可以安全、溫和、不刺激並有效的去除口腔中的細菌以預防口臭、蛀牙、牙齦炎和牙周病的發生實有其必要性。 Some mouthwashes use alcohol as an antibacterial ingredient, except for sterilization. In addition, with some surfactants, mint or some flavoring ingredients can be added to the water in a micro-emulsified form, but the alcohol-containing mouthwash will be extremely irritating during the mouthwash, and it will also be bad for the oral mucosa. The impact of the development of a mouthwash can be safe, gentle, non-irritating and effective in removing bacteria from the mouth to prevent the occurrence of bad breath, tooth decay, gingivitis and periodontal disease.

自古以來,銀之殺菌效果即為人們所熟知與應 用,早期人類用銀製成餐具,發覺銀餐具裝盛之牛奶或食物,比較不容易腐壞,到近期銀於殺菌應用上更是擴展到了奈米銀與銀離子的形態。 Since ancient times, the bactericidal effect of silver has been well known and should be For the early time, humans used silver to make tableware, and found that silver tableware contained milk or food, which was less prone to spoilage. In the recent silver sterilization application, it expanded to the form of nano silver and silver ions.

銀離子的應用大部分是以銀的無機鹽形式使 用,例如硝酸銀、醋酸銀和硫代硫酸銀,除了上述的銀鹽外,銀的無機鹽類幾乎都不溶於水或略溶於水。 The application of silver ions is mostly made of the inorganic salt of silver. With, for example, silver nitrate, silver acetate, and silver thiosulfate, the inorganic salts of silver are hardly soluble in water or slightly soluble in water, except for the above-mentioned silver salt.

除了銀的無機鹽類以外,銀離子也可以和有機小 分子複合或稱銀的有機鹽,最有名的是silver sulfadiazine,廣泛的被應用在燒燙傷之傷口處理以及殺菌,但是silver sulfadiazine也不溶於水。 In addition to the inorganic salts of silver, silver ions can also be small with organic Molecular compound or silver organic salt, the most famous is silver sulfadiazine, widely used in burn wound treatment and sterilization, but silver sulfadiazine is also insoluble in water.

以上不論是銀的無機鹽或有機複合物,都屬於小 分子的抗菌劑,所以他們都具有小分子抗菌劑的缺點,並不適合作為漱口水的抗菌成份使用。 Any of the above inorganic salts or organic compounds of silver are small Molecular antibacterial agents, so they all have the disadvantage of small molecule antibacterial agents, and are not suitable for use as an antibacterial ingredient in mouthwashes.

為了達到安全、溫和、不刺激並有效的去除口腔 中的細菌以預防口臭、蛀牙、牙齦炎和牙周病的目的,本發明揭露了世界上第一個使用水溶性抗菌壓克力高分子銀鹽做為抗菌成份的漱口水。 In order to achieve safe, gentle, non-irritating and effective removal of the oral cavity In order to prevent bad breath, tooth decay, gingivitis and periodontal disease, the present invention discloses the world's first mouthwash using water-soluble antibacterial acrylic polymer silver salt as an antibacterial ingredient.

本發明係關於一種含有銀高分子的漱口水,所謂之銀高分子是水溶性抗菌壓克力高分子銀鹽。 The present invention relates to a mouthwash containing a silver polymer, which is a water-soluble antibacterial acrylic polymer silver salt.

本發明中的水溶性抗菌壓克力高分子銀鹽中的壓克力高分子可以是聚丙烯酸、聚甲基丙烯酸、丙烯酸-馬來酸共聚物、甲基丙烯酸-馬來酸共聚物、丙烯酸鈉-甲基丙烯酸鈉共聚物、丙烯酸與其他壓克力單體之共聚物或甲基丙烯酸與其他壓克力單體之共聚物,這些壓克力高分子中的羧酸基 (-COOH)提供了水溶性抗菌壓克力高分子銀鹽之陰離子(-COO-)。 The acrylic polymer in the water-soluble antibacterial acrylic polymer silver salt in the present invention may be polyacrylic acid, polymethacrylic acid, acrylic acid-maleic acid copolymer, methacrylic acid-maleic acid copolymer, acrylic acid. a sodium-sodium methacrylate copolymer, a copolymer of acrylic acid with other acrylic monomers or a copolymer of methacrylic acid with other acrylic monomers, the carboxylic acid group (-COOH) in these acrylic polymers An anion (-COO - ) of a water-soluble antibacterial acrylic polymer silver salt is provided.

本發明中的水溶性抗菌壓克力高分子銀鹽中的 陽離子包含了鈉和銀或者是鉀和銀,為了讓壓克力高分子銀鹽可以具有水溶性,水溶性抗菌壓克力高分子銀鹽中-COOAg/(-COOAg+-COONa)或者-COOAg/(-COOAg+-COOK)的莫爾比例最好小於0.66。 In the water-soluble antibacterial acrylic polymer silver salt of the present invention The cation contains sodium and silver or potassium and silver. In order to make the acrylic polymer silver salt water-soluble, water-soluble antibacterial acrylic polymer silver salt -COOAg/(-COOAg+-COONa) or -COOAg/ The molar ratio of (-COOAg+-COOK) is preferably less than 0.66.

本發明之漱口水中銀的含量介於1-2000ppm之 間,當漱口水中銀的含量小於1ppm時由於銀含量過低,會導致抗菌效果不佳,使得在漱口時無法有效地除去口腔中的細菌,但是當銀的含量大於2000ppm時,漱口水會有令人無法忍受的苦味,而且成本也會過高,消費者可能無法接受。 The content of silver in the mouthwash of the present invention is between 1 and 2000 ppm. Between, when the content of silver in the mouthwash is less than 1ppm, the silver content is too low, which may result in poor antibacterial effect, so that the bacteria in the mouth cannot be effectively removed during the mouthwash, but when the content of silver is more than 2000ppm, the mouthwash will There is an unbearable bitter taste, and the cost is too high, and consumers may not accept it.

本發明之漱口水中除了水溶性抗菌壓克力高分 子銀鹽外,也可以加入其他的成分以增加漱口水之口感,這些成分中最為人所熟悉的就是薄荷。 In addition to the water-soluble antibacterial acrylic high score in the mouthwash of the present invention In addition to the silver salt, other ingredients can be added to increase the mouthfeel of the mouthwash. The most familiar of these ingredients is mint.

水溶性抗菌壓克力高分子銀鹽之製備可以使用 水溶性抗菌壓克力高分子鈉鹽或水溶性抗菌壓克力高分子鉀鹽,利用其羧酸鈉基或羧酸鉀基和銀的鹽類在水中進行金屬離子交換,以得到含有羧酸銀(-COOAg)官能基團的水溶性壓克力高分子,然後再利用超過濾(Ultrafiltration)將金屬離子交換後產生的鈉鹽去除,以得到純的水溶性抗菌壓克力高分子銀鹽。 Preparation of water-soluble antibacterial acrylic polymer silver salt can be used a water-soluble antibacterial acrylic polymer sodium salt or a water-soluble antibacterial acrylic polymer potassium salt, which is subjected to metal ion exchange in water by using a sodium carboxylate group or a potassium carboxylate group and a silver salt to obtain a carboxylic acid. A water-soluble acrylic polymer of a silver (-COOAg) functional group, and then the sodium salt produced by metal ion exchange is removed by ultrafiltration to obtain a pure water-soluble antibacterial acrylic polymer silver salt. .

水溶性抗菌壓克力高分子銀鹽交換比例之實驗: Experiment on the exchange ratio of water-soluble antibacterial acrylic polymer silver salt:

倒500cc之純水於1公升之玻璃燒杯中,將0.5克之聚羧酸鈉(分子量>8,000,000)加入燒杯中,將水溫控制在40℃,以磁石攪拌令其溶解,之後將10g之10%硝酸銀水溶液分十次加入燒杯中,每次加入之間隔為半小時,攪拌持續不斷,水溫控制在40℃,每次加入半小時後觀察溶液狀態,得到如下表之結果 Pour 500cc of pure water into a 1 liter glass beaker, add 0.5g of sodium polycarboxylate (molecular weight >8,000,000) to the beaker, control the water temperature to 40 °C, stir it with magnetite, then 10% of 10g The silver nitrate aqueous solution was added to the beaker ten times. The interval between each addition was half an hour, the stirring was continued, the water temperature was controlled at 40 ° C, and the solution state was observed after each half hour of addition, and the results of the following table were obtained.

由表中可以得知當-COOAg/(-COOAg+-COONa)大於0.77以上時所得到的聚丙烯酸銀鹽便無法溶於水,而此時銀占聚丙烯酸銀鹽的重量比是52%,保險一些,-COOAg/(-COOAg+-COONa)的比例最好小於0.66以得到可以水溶的聚丙烯酸銀鹽,或銀占聚丙烯酸銀鹽的重量比在47%以下時,聚丙烯酸銀鹽是可以水溶的。 It can be seen from the table that the polyacrylic acid silver salt obtained when -COOAg/(-COOAg+-COONa) is more than 0.77 or more is insoluble in water, and at this time, the weight ratio of silver to polyacrylic acid silver salt is 52%, insurance Some, the ratio of -COOAg / (-COOAg + -COONa) is preferably less than 0.66 to obtain a water-soluble polyacrylic acid silver salt, or when the weight ratio of silver to polyacrylic acid silver salt is 47% or less, the polyacrylic acid silver salt is water-soluble. of.

聚丙烯酸銀鹽之製備:取10g聚丙烯酸鈉(分子量>8,000,000)加入2公升40℃純水中,以每分鐘一萬轉之高速攪拌3分鐘,得到非常黏稠之透明液體,之後將10g50%之硝酸銀水溶液,分5次,在持續每分鐘一萬轉之高速攪拌下,間隔30秒的加入,加完後, 維持攪拌5分鐘至溶液呈現澄清透明的狀態,此時之溶液黏度大大的下降,成為一流動良好之透明水溶液。 Preparation of polyacrylic acid silver salt: 10 g of sodium polyacrylate (molecular weight > 8,000,000) was added to 2 liters of pure water at 40 ° C, and stirred at a high speed of 10,000 rpm for 3 minutes to obtain a very viscous transparent liquid, after which 10 g of 50% was obtained. The silver nitrate aqueous solution was divided into 5 times and added at a high speed of 10,000 rpm for 30 seconds. After the addition, Stirring was maintained for 5 minutes until the solution appeared clear and transparent, at which time the viscosity of the solution was greatly reduced to become a well-flowing clear aqueous solution.

將所得的溶液稀釋至10公升,利用一直徑3公寸 長度12公寸之螺旋捲式超過濾膜模組(薄膜之篩選分子量是10萬),將此稀釋之溶液濃縮至1公升,在濃縮過程初期,取透過液100cc,加入氯化鈉,並未發現有白色氯化銀的產生,可見所有加入之硝酸銀都已和聚丙烯酸鈉中之羧酸納基進行金屬離子交換,產生羧酸銀基,而且經金屬離子交換所得到的聚丙烯酸銀鹽仍然留在濃縮液中而未透過薄膜被濾出。 Dilute the resulting solution to 10 liters, using a diameter of 3 inches A 12-inch spiral spiral ultrafiltration membrane module (screening molecular weight of 100,000), the diluted solution is concentrated to 1 liter, in the initial stage of the concentration process, 100cc of permeate is added, sodium chloride is added, It was found that white silver chloride was produced, and it was found that all the added silver nitrate had been ion-exchanged with the sodium carboxylate in the sodium polyacrylate to produce a silver carboxylate group, and the silver polyacrylate obtained by metal ion exchange was still It is left in the concentrate and is not filtered through the membrane.

再將所得之1公升濃縮液稀釋至10公升,再濃縮 至1公升,然後再稀釋,再濃縮至1公升,如此便可以得到純度相當高之聚丙烯酸銀鹽水溶液,此聚丙烯酸銀鹽水溶液含銀量為6300ppm。 Dilute the resulting 1 liter concentrate to 10 liters and concentrate Up to 1 liter, then diluted, and then concentrated to 1 liter, so that a relatively high purity aqueous solution of silver acrylate having a silver content of 6300 ppm can be obtained.

漱口水之配製與使用口感:將前例所製備得到含銀量6300ppm之聚丙烯酸銀鹽水溶液加入純水稀釋成為含銀量100ppm之漱口水,此漱口水使用起來完全沒有任何刺激性,口感溫和。 Preparation and use of mouthwash: The aqueous solution of silver polyacrylate containing 6300 ppm of silver prepared in the previous example was diluted with pure water to make a mouthwash with a silver content of 100 ppm. The mouthwash was completely irritating without any irritation and mild taste.

漱口水之抗菌試驗:試驗標準-U.S.Pharmacopeia 35 NF 30 Micro-biological Tests(51)Antimicrobial Effectiveness Testing。 Antibacterial Test for Mouthwash: Test Standard - U.S. Pharmacopeia 35 NF 30 Micro-biological Tests (51) Antimicrobial Effectiveness Testing.

試驗方法-將漱口水與菌液以20mL:0.2mL之體積比例混合作用,於接觸時間後立即測試。 Test Method - The mouthwash and the bacterial solution were mixed in a volume ratio of 20 mL: 0.2 mL, and tested immediately after the contact time.

試驗菌種-大腸桿菌(Escherichia coli),抗藥性金黃色葡萄球菌(MRSA),肺炎桿菌(Klebsiella pneumonia),綠膿桿菌(Pseudomonas aeruginos)。 Test species - Escherichia coli, drug resistant Staphylococcus aureus (MRSA), Klebsiella pneumonia, Pseudomonas aeruginos.

試驗結果顯示如下 The test results are shown below

Claims (4)

一種含銀漱口水,成分中包含水溶性抗菌壓克力高分子銀鹽,其水溶性抗菌壓克力高分子銀鹽分子之官能基團包含有羧酸銀(-COOAg)與羧酸鈉(-COONa)或者包含有羧酸銀與羧酸鉀(-COOK),其中-COOAg/(-COOAg+-COONa)或者-COOAg/(-COOAg+-COOK)的莫爾比例小於0.66。 A silver-containing mouthwash containing a water-soluble antibacterial acrylic polymer silver salt, the functional group of the water-soluble antibacterial acrylic polymer silver salt molecule comprising silver carboxylate (-COOAg) and sodium carboxylate ( -COONa) either contains silver carboxylate and potassium carboxylate (-COOK), wherein the molar ratio of -COOAg/(-COOAg+-COONa) or -COOAg/(-COOAg+-COOK) is less than 0.66. 根據申請專利範圍第1項之含銀漱口水,其中水溶性抗菌壓克力高分子銀鹽是丙烯酸銀和丙烯酸鈉的共聚物,其丙烯酸銀和丙烯酸鈉之莫爾比例低於66/34。 The silver-containing mouthwash according to the first aspect of the patent application, wherein the water-soluble antibacterial acrylic polymer silver salt is a copolymer of silver acrylate and sodium acrylate, and the molar ratio of silver acrylate to sodium acrylate is lower than 66/34. 根據申請專利範圍第1項之漱口水,其中水溶性抗菌壓克力高分子銀鹽是丙烯酸銀和丙烯酸鈉的共聚物,其丙烯酸銀和丙烯酸鈉之莫爾比例介於66/34和11/89之間。 According to the mouthwash of the first aspect of the patent application, the water-soluble antibacterial acrylic polymer silver salt is a copolymer of silver acrylate and sodium acrylate, and the molar ratio of silver acrylate to sodium acrylate is between 66/34 and 11/ Between 89. 根據申請專利範圍第1項之含銀漱口水,其含銀量介於1到2000ppm之間。 The silver-containing mouthwash according to item 1 of the scope of the patent application has a silver content of between 1 and 2000 ppm.
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