KR102406001B1 - Oral composition for effective prevention of calculus formation - Google Patents

Abstract

The present invention relates to an oral composition for inhibiting calculus formation containing an anionic sequestering agent and a cationic polymer, and more specifically, a phosphate-based anionic sequestering agent and a polyquaternium-based cationic polymer coacervate during the brushing process. By forming, it is attached to the tooth surface and the anionic sequestering agent, which is a tartar formation inhibitory component, remains in the oral cavity for a long time even after rinsing.
The oral composition for inhibiting tartar formation of the present invention can effectively prevent tartar formation on the tooth surface, and at the same time maintain the flavor of the toothpaste and improve the foaming power.

Description

Oral composition effective for inhibiting calculus formation {Oral composition for effective prevention of calculus formation}

The present invention relates to an oral composition for inhibiting tartar formation containing an anionic sequestering agent and a cationic polymer, and more specifically, a phosphate-based anionic sequestering agent and a polyquaternium-based cationic polymer coacervate during the brushing process. By forming, it is attached to the tooth surface and the anionic sequestering agent, which is a tartar formation inhibitory component, remains in the oral cavity for a long time even after rinsing.

In general, oral diseases are caused by various bacteria living in the oral cavity, and harmful oral bacteria eat residues such as food from the acquired film and multiply to form plaque, which is formed by metal ions such as calcium and magnesium in saliva or blood It combines with calcified calculus to form. These plaques and tartar cause gum diseases such as gingivitis and periodontitis, and further damage the teeth. Although regular brushing helps prevent the rapid formation of these deposits, even regular brushing is not sufficient to remove all stone deposits adhering to the teeth. So, to suppress the formation of plaque and tartar, physically an abrasive is used, and chemically, an antibacterial agent and sequestering agent are used.

Abrasives used in oral products include high molecular substances such as calcium carbonate, silica, aluminum hydroxide, calcium phosphate, baking soda, polyethylene and polyvinyl chloride, and antibacterial agents used in oral products include cetylpyridinium chloride, hexalkonium chloride , benzalkonium chloride, decarinium chloride, chlorhexidine, triclosan, thymol, isopropylmethylphenol, and alkyldiaminoethylglycic acid chloride, and sequestering agents include pyrophosphate, polyphosphate and polyphosphorus. phonate, etc.

As above, sequestering agents have been mainly used to inhibit the formation of tartar, but when the sequestering agent is used alone, it is washed away without remaining in the oral cavity after brushing and rinsing. In addition, when an excessive amount of a sequestering agent is added to increase the tartar removal efficacy, irritation may occur and the feeling of use may deteriorate due to a foul taste.

Accordingly, the present inventors have made diligent efforts to find a way to keep the sequestering agent in the oral cavity for a long time even after rinsing the toothpaste. In this case, it was confirmed that coacervate is formed by the precipitation reaction of anions and cations, thereby leaving a larger amount of anionic sequestering agent on the teeth to be effective in inhibiting the formation of calculus, and the present invention has been completed.

Korean Patent Publication No. 10-2010-0052934 (2010.05.20.)

An object of the present invention is to provide a composition for oral cavity that contains an anionic sequestering agent and a cationic polymer to induce their coacervation, thereby inhibiting the formation of tartar by the anionic sequestering agent remaining on the tooth surface is to do

In order to achieve the above object, the present invention provides an oral composition for inhibiting the formation of calculus containing an anionic sequestering agent and a cationic polymer as active ingredients.

The composition for oral cavity suppression of tartar formation of the present invention can effectively prevent the formation of tartar on the tooth surface, while maintaining the flavor of the toothpaste and improving the foaming power.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is those well known and commonly used in the art.

In the test example of the present invention, as a result of treating the oral composition containing the anionic sequestering agent and the cationic polymer to the tooth mimic material, the anionic sequestering agent and the cationic polymer remained on the tooth surface in the form of coacervate By doing so, it was confirmed that the residual anionic sequestering agent exhibits the effect of suppressing the formation of calculus.

Accordingly, in one aspect, the present invention relates to an oral composition for inhibiting calculus formation containing an anionic sequestering agent and a cationic polymer as active ingredients, wherein the anionic sequestering agent and the cationic polymer react with each other It may be characterized in that it forms a coacervate on the tooth surface.

In the present invention, the composition may be characterized in that it further contains a surfactant.

"Coacervation" refers to a phenomenon in which a concentrated colloidal sol is separated from a dispersion medium due to reduced hydration of colloidal particles and an electrostatic factor in a hydrophilic colloidal solution, and one of the separated liquids is The colloidal concentration is high, and the colloidal concentration of the other liquid phase is low. "Coacervate" refers to a colloidal material formed due to a coacervation phenomenon when an anionic polyelectrolyte and a cationic polyelectrolyte are mixed under specific conditions.

The anionic sequestering agent contained in the oral composition of the present invention forms a coacervate by ionic bonding with a cationic polymer and precipitation, and the formed coacervate is a sequestering agent having an effect of inhibiting tartar formation on the tooth surface for a long time. let it be

In the present invention, the anionic sequestering agent may be characterized in that it is a phosphate-based compound. The anionic sequestering agent is a substance that inhibits the formation of calculus by chelating metal ions that have an important influence on the formation of calculus, and preferably a phosphate-based compound, hexametaphosphate, pyrophosphate ), polyphosphate, and may be at least one selected from the group consisting of salts thereof. The salt may be in a form in which 1 to 4 alkali metal cations and an anion, a phosphate-based compound, are combined, and specific examples include sodium phosphate, monosodium phosphate, disodium phosphate, tri Sodium phosphate (Trisodium phosphate), sodium tripolyphosphate (Sodium tripolyphosphate), sodium hexametaphosphate (Sodium hexametaphosphate), tetrasodium pyrophosphate (Tetrasodium pyrophosphate), sodium acid pyrophosphate (Sodium acid pyrophosphate), etc. It is not limited.

In addition, in the present invention, the cationic polymer may be characterized in that the polyquaternium (polyquaternium)-based compound. The polyquaternium-based compound refers to a high molecular compound (polymer) having a quaternary ammonium ion at the center, and is preferably one selected from the group consisting of polyquaternium-10, polyquaternium-6, and polyquaternium-11. or more, but is not necessarily limited thereto.

In addition, in the present invention, the composition for oral cavity may be characterized in that it further contains a surfactant in addition to the anionic sequestering agent and the cationic polymer. Specific examples of the surfactant include anionic surfactants such as glycinate, sulfate, sulfosuccinate, sarcosinate, phosphate, isethionate, glutamate, and taurate, betaine , sultaine, amphoteric surfactants such as amphoteric acetate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene (hardened) castor oil, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkylolamide, alkylgluco Nonionic surfactants such as seed, cationic surfactants such as N-alkyldiamino ethylglycine, etc., preferably sodium lauryl sulfate, sodium methyl cocoyl taurate , And disodium lauryl sulfosuccinate (Disodium lauryl sulfosuccinate) may be at least one selected from the group consisting of, but is not necessarily limited thereto.

In addition, in the present invention, the anionic sequestering agent may be contained in an amount of 0.1 to 10.0% by weight, preferably 1.0 to 7.0% by weight, more preferably 3.0 to 5.0% by weight based on the total weight of the composition. may contain. If the content of the anionic sequestering agent is less than 0.1% by weight, coacervate is not formed, and if it exceeds 10.0% by weight, flavor and foaming power are reduced, irritation is severe, etc. have.

In addition, the cationic polymer may be contained in an amount of 0.01 to 0.50% by weight, preferably 0.05 to 0.50% by weight, more preferably 0.10 to 0.50% by weight based on the total weight of the composition. If the content of the cationic polymer is less than 0.01% by weight, coacervate is not formed, and if it exceeds 0.50% by weight, the viscosity in the toothpaste is high, which may be inconvenient to use.

In addition, in the present invention, the anionic sequestering agent and the cationic polymer may be mixed and contained in a weight ratio of 0.2:1 to 1000:1, preferably 10:1 to 100:1, more preferably may be mixed and contained in a weight ratio of 30:1 to 50:1. Since the molecular weight of the anionic sequestering agent is relatively small, it is preferable to mix it in a ratio higher than that of the cationic polymer. If the mixing ratio of the anionic sequestering agent and the cationic polymer is less than 0.2:1 or more than 1000:1, it may be difficult to form coacervate.

The composition for oral use of the present invention is not particularly limited in its formulation, and specific examples thereof include toothpaste, oral cleaning agent, oral freshener, gum, candy, oral spray, oral gargle, tooth whitening agent, etc. formulations may have. .

The composition for oral use of the present invention may contain conventionally used abrasives, wetting agents, auxiliary foaming agents, binders, sweeteners, pH adjusters, preservatives, medicinal ingredients, fragrances, brighteners, pigments, solvents, etc. depending on the formulation and purpose of use. .

As the abrasive, precipitated silica, silica gel, zirconium silicate, calcium monohydrogen phosphate, anhydrous calcium monohydrogen phosphate, hydrous alumina, light calcium carbonate, heavy calcium carbonate, calcium pyrophosphate, insoluble metaphosphate, aluminum silicate, etc. can be used.

As the wetting agent, concentrated glycerin, glycerin, sorbitol aqueous solution, amorphous sorbitol aqueous solution, polyethylene glycols, propylene glycol, and the like can be used.

As the auxiliary foaming agent, anionic and nonionic surfactants such as sodium alkyl sulfate, sodium lauryl sulfate, sucrose fatty acid ester, and sorbitan fatty acid ester may be used.

The binder includes sodium carboxymethylcellulose, carrageenan, xanthan gum, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, guar gum, gellan gum, carbomer, pectin, polyvinylpyrrolidone, carboxyvinyl polymer , sodium alginate, laponite, sodium carboxymethylcellulose, xanthan gum, etc. can be used.

As the sweetener, sodium saccharin, sucralose, maltitol, aspartame, erythritol, xylitol, licoric acid, sodium saccharin, etc. can be used, and the preservative includes benzoic acid, methylparaben, propylparaben, sodium benzoate, paraoxybenzoic acid ester, and the like. can be used In addition, as the fragrance, peppermint oil, spearmint oil, menthol, etc. may be used alone or in combination, and as the pH adjusting agent, sodium phosphate, disodium phosphate, citric acid, triethanolamine, and the like may be used.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not to be construed as being limited by these examples. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

[ Example 1-9 and comparative example Preparation of 1-3]

In order to test the degree of coacervate production and residual degree of the oral composition of the present invention, purified water, anionic sequestering agents (sodium hexametaphosphate, tetrasodium pyrophosphate, sodium tripolyphosphate), cationic polymer (polyquaternium) -10, polyquaternium-6, polyquaternium-11), surfactant (sodium lauryl sulfate, sodium methylcocoyl taurate, disonium lauryl sulfosuccinate) as main components, As in the configuration, Examples 1 to 9 and Comparative Examples 1 to 3 were prepared so that the total weight was 100 g, respectively.

(Unit: % by weight) Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Purified water To 100 To 100 To 100 To
100 To
100 To
100 To
100 To 100 To
100 To
100 To
100 To
100 Sodium Hexameta
phosphate 3 0.5 7 3 3 - - 3 3 3 3 5 tetrasodium pyrophosphate - - - - - 3 - - - - - - Sodium Tripoly
phosphate - - - - - - 3 - - - - - Polyquaternium-10 - 0.1 0.1 0.1 0.1 0.1 0.1 - - 0.1 0.1 0.1 Polyquaternium-6 - - - - - - - 0.1 - - - - Polyquaternium-11 - - - - - - - - 0.1 - - - Sodium Lauryl
sulfate 2 2 2 - 2 2 2 2 2 - - 2 Sodium Methyl Cocoil
taurate - - - - - - - - - 2 - - Disodium Lauryl
sulfosuccinate - - - - - - - - - - 2 -

[ test example 1] Measurement of coacervate production level

Taking the samples of Examples 1 to 9 and Comparative Examples 1 to 3, gradually increasing the addition ratio of purified water to each, and adjusting the dilution ratio as shown in Table 2 below while gradually decreasing the ratio of the sample, but the total weight was 3 g was made to keep. After measuring the transparency (%) of each diluted sample using UV spectroscopy, the results are shown in Table 2. It was determined that the lower the transparency, the more coacervate was formed.

2x dilution 5 times dilution 10 times dilution 20 times dilution 40-fold dilution Amount of sample (g) 1.5 0.6 0.3 0.15 0.08 Amount of purified water (g) 1.5 2.4 2.7 2.85 2.93 transparency(%) Comparative Example 1 100% 100% 100% 100% 100% Comparative Example 2 99% 95% 90% 95% 99% Comparative Example 3 99% 90% 85% 88% 99% Example 1 100% 99% 76% 84% 92% Example 2 95% 30% 54% 84% 98% Example 3 99% 80% 85% 96% 99% Example 4 96% 35% 58% 88% 98% Example 5 92% 11% 36% 61% 75% Example 6 99% 98% 77% 83% 94% Example 7 90% 20% 44% 74% 88% Example 8 92% 24% 43% 77% 90% Example 9 92% 25% 40% 64% 90%

As shown in Table 2, in the case of Comparative Example 1 not containing the cationic polymer, coacervate was not formed, and the cationic polymer was contained together with the anionic sequestering agent, but the surfactant was not contained in Example 1 In the case of , there was a difference in the degree of coacervate production according to the dilution conditions. In addition, as the solution containing the anionic sequestrant, cationic polymer, and surfactant was diluted, more coacervate was formed. From this, it was confirmed that an appropriate dilution ratio is important for coacervate formation.

In addition, when a surfactant for bubble formation, which is an essential element in toothpaste formulation, is added together with the anionic sequestering agent and cationic polymer, the type of cationic polymer (compared to Examples 2, 5, and 6), anionic It was confirmed that there was a difference in the degree of coacervate generation depending on the type of sequestering agent (compared to Examples 2, 3, and 4) or the type of surfactant (compared to Examples 2, 7, and 8), and anionic metal ions It was confirmed that there was a difference in the degree of coacervate production also depending on the content of the blocking agent (compared to Examples 2 and 9).

In addition, compared to Examples 1 to 9, the mixing ratio (weight ratio) of the anionic sequestrant and the cationic polymer is 30:1 in Comparative Example 2 lower than 30:1 or Comparative Example 3 higher than 50:1, 30:1 It was found that the coacervate was not well produced compared to Examples 1 to 9, which were within the range of ~50:1.

[ test example 2] of the tooth surface sequestering agent Residual amount measurement

After confirming that coacervate was formed in the solution containing the anionic sequestrant, cationic polymer, and surfactant in Test Example 1, an in vitro test was performed to determine how much coacervate remained on the tooth surface. was measured through

After the solutions of Examples 2, 7, 9 and Comparative Example 1 prepared as shown in Table 1 were diluted 10-fold, the hydroxyapatite disc (Clarkson Chromatography Products), which is a dental mimic material, was placed on a V-8 cross-brushing machine, an automatic toothbrushing machine. (V-8 Cross Brushing Machine®, Sabri, USA) was used for brushing. To reduce the error between the hydroxyapatite disks, 4 disks were used, and after brushing the teeth with a brushing machine with a diluted solution for 3 minutes, it was washed 5 times. After repeating this 10 times, the coacervate attached to hydroxyapatite was dissolved in sodium hydroxide solution (0.3M), and then the amount of anionic sequestering agent remaining in the coacervate using ion chromatography (Metrohm). The measurement results are shown in Table 3.

(Unit: ppm) disc 1 disc 2 disc 3 disc 4 Average (ppm) Comparative Example 1 2.60 4.30 2.23 2.2 2.83 Example 2 18.13 29.42 12.30 14.05 18.48 Example 7 16.61 25.10 22.40 20.50 21.15 Example 9 35.12 30.22 33.35 36.36 33.76

As shown in Table 3, it was found that the residual amount of the anionic sequestering agent was significantly higher when the cationic polymer was present (Examples 2, 7, 9) than when the cationic polymer was absent (Comparative Example 1). , the difference between the surfactants was slightly but not large (compared to Examples 2 and 7), and when the content of the anionic sequestering agent was increased, the residual amount of the anionic sequestering agent was significantly increased (Example) 2, 9) could be confirmed.

[ Example 10-11 and comparative example 4 Manufacturing]

Examples 10 to 11 and Comparative Examples 4 in which a coacervate solution containing an anionic sequestrant and a cationic polymer were contained in a toothpaste paste formulation were prepared as shown in Table 4 below.

(Unit: % by weight) division Ingredient name Comparative Example 4 Example 10 Example 11 solvent Purified water To 100 To 100 To 100 sequestering agent Sodium Hexametaphosphate 3 3 5 cationic polymer Polyquaternium-10 - 0.1 0.1 active ingredient Sodium monofluorophosphate 0.76 0.76 0.76 wetting agent Sorbitol solution (70%) 50 50 50 sweetener sodium saccharin 0.4 0.4 0.4 abrasive silica 10 10 10 thickener Hydroxymethylcellulose 1.5 1.5 1.5 Spices combination spice One One One foaming agent Sodium Lauryl Sulfate 2 2 2

[ test example 3] tartar formation Inhibitory efficacy measurement

Based on the results of Test Examples 1 and 2, it was measured whether the oral composition of the present invention containing an anionic sequestering agent and a cationic polymer had the effect of inhibiting the formation of calculus.

First, the sanded glass rod was immersed in a solution containing saliva and sugar obtained from the panel, and then aged at 35°C for 2 days. After forming plaque on the surface of the glass rod, immerse the glass rod in a crystallization solution consisting of 25% toothpaste slurry solution (Comparative Examples 4, 10, 11) and calcium chloride (1.5 mM) and store overnight, and then store for 5 seconds the next day. After washing the glass rod, it was stored by immersing it in the toothpaste slurry solution and the crystallization solution again. The calculus formed by repeating this for 2 weeks was dissolved with a strong acid (1M HCl) and a strong base (1M KOH), and then the calcium content was analyzed using ion chromatography (Metrohm), and the results are shown in Table 5 below. It was judged that the lower the calcium content, the better the ability to inhibit the formation of calculus.

Comparative Example 4 Example 10 Example 11 Average content of calcium extracted from 4 glass rods (μg) 857 608 532

As a result of the calcium content analysis, as shown in Table 5, when the cationic polymer was contained (Examples 10 and 11), the calcium content was lower than that of the case without it (Comparative Example 4), and the content of the anionic sequestering agent It was confirmed that the calcium content decreased as the increase (compared to Examples 10 and 11) increased.

[ test example 4] toothpaste feeling evaluation

Based on the measurement result of the calculus formation inhibition of Test Example 3, the feeling of use of the toothpaste was evaluated. Each of Example 10, Example 11, and Comparative Example 4 was used by 20 people, and after two weeks of use, flavor, foaming power, stimulation, and overall satisfaction were evaluated through a questionnaire survey, and the results are shown in Table 6 indicated.

division Comparative Example 4 Example 10 Example 11 flavor 3.5 3.3 3.6 bubble power 3.7 4.2 4.0 irritation 4.0 3.9 3.9 total satisfaction 3.5 3.7 3.6

(1 point: very dissatisfied / 2 points: dissatisfied / 3 points: average / 4 points: satisfied / 5 points: very satisfied)

As shown in Table 6, it was confirmed that the compositions (Examples 10 and 11) containing the cationic polymer did not significantly affect the flavor and irritation of the toothpaste, but rather helped in the foaming power.

As described above in detail a specific part of the content of the present invention, for those of ordinary skill in the art, this specific description is only a preferred embodiment, and it is clear that the scope of the present invention is not limited thereby. something to do. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

Claims (11)

As an oral composition for inhibiting calculus formation containing an anionic sequestering agent and a cationic polymer as active ingredients,
The anionic sequestering agent is any one or more phosphoric acid-based compounds selected from the group consisting of hexametaphosphate, pyrophosphate, polyphosphate, and salts thereof,
The cationic polymer is polyquaternium-10, polyquaternium-6, and polyquaternium-11, an oral composition for inhibiting tartar formation, characterized in that at least one polyquaternium-based compound selected from the group consisting of. According to claim 1, wherein the composition for oral use is characterized in that it has an activity of enhancing the degree of coacervate production and retention on the tooth surface through the combined use of the anionic sequestering agent and the cationic polymer. Oral composition. The composition for oral use according to claim 1, wherein the composition for oral use further contains a surfactant. The composition for oral use according to claim 1, wherein the composition for oral use has an activity of enhancing the effect of inhibiting tartar formation through the combined use of the anionic sequestering agent and the cationic polymer. delete 4. The group of claim 3, wherein the surfactant is sodium lauryl sulfate, sodium methyl cocoyl taurate, and disodium lauryl sulfosuccinate. Oral composition, characterized in that any one or more selected from. delete delete The composition for oral use according to claim 1, wherein the anionic sequestering agent is contained in an amount of 0.1 to 10.0% by weight based on the total weight of the composition. The composition for oral use according to claim 1, wherein the cationic polymer is contained in an amount of 0.01 to 0.50% by weight based on the total weight of the composition. The composition for oral use according to claim 1, wherein the weight ratio of the anionic sequestrant and the cationic polymer is 0.2:1 to 1000:1.