RU2595875C1 - Use of zinc or copper (ii) salt as component of oral care composition and oral care composition - Google Patents

Abstract

FIELD: hygiene.

SUBSTANCE: group of inventions relates to oral care compositions and can be used in perfume-cosmetic industry for producing said compositions. Disclosed is use of a zinc or copper (II) salt of general formula

, where M is Zn or Cu, R¹ is hydrogen or methyl, R² is selected from a group comprising hydrogen, substituted or unsubstituted alkyl, alkenyl, alkadienyl, substituted or unsubstituted aryl, as a component of an oral care composition and an oral care composition, containing said salt in an amount of 0.5 to 5% of weight of composition. Orally acceptable base can contain a polyatomic alcohol, surfactant, taste, flavouring and other functional additives and deionised water.

EFFECT: use of zinc or copper (II) salts of formula (1), in oral care agents enables to maintain in oral cavity bactericidal and/or fungicidal, anti-erosion and reparative action of composition for a long period of time after use of composition due to ability of said compounds to penetrate surface layer of enamel and be retained in it for a long time.

7 cl, 7 tbl, 69 ex

Description

The invention relates to the use of metal salts in compositions for caring for the oral cavity and in fact to compositions for caring for the oral cavity and can be used in the perfume and cosmetic industry for the production of these compositions.

Oral care products, such as toothpastes, gels, rinses, therapeutic compositions, are regularly used by consumers as an element of hygiene, since they can bring both therapeutic and hygienic benefits to consumers (V. Suntsov, V.K. Leontyev , Distel V.A., Wagner V.D. Dental prophylaxis in children.M .: Medical book; N. Novgorod: Publishing house of the Novosibirsk State Medical Academy, 2001, p. 86-90). The therapeutic benefits include the prevention of caries and gingivitis, hypersensitivity control, and resistance to dental erosion. The cosmetic benefits of oral care formulations include the prevention of tartar formation, the elimination or prevention of plaque, tooth whitening, breath freshening, and an overall improvement in oral sensations.

It is known to use zinc and copper ions in the form of simple salts of zinc or copper (II), in particular citrate, lactate, gluconate, acetate, glycinate, in oral care preparations, namely in toothpastes, gels, rinses, therapeutic compositions chloride, zinc sulfate and / or chloride, fluoride, sulfate, acetate, glycinate of copper (II) (RU 2311901, A61K 8/73, A61K 8/69, A61K 8/64, A61K 8/44, A61K 8/19, A61K 8/42, A61K 8/36, A61K 8/24, A61K 8/21, A61Q 11/00, 2007; RU 2497496, A61K 8/25, A61K 8/41, A61Q 11/00, 2013; RU 2519204, A61K 8/27, A61K 8/365, A61K 8/72, A61Q 11/00, 2014; RU 2535088, A61K 8/19, A61K 8/24, A61K 8/27, A61K 8/36, A61K 8/41, A61K 8/72, A61Q 11/00, 2 014; RU 2546004, A61K 8/27, A61K 8/34, A61K 8/41, A61K 8/60, A61K 8/90, A61K 8/97, A61Q 11/00, A61C 17/00, 2015). It is indicated that the use of these salts in oral care compositions is due, in particular, to the presence of their antibacterial effect, the ability to increase the resistance to dental erosion, and also to promote restoration of tooth tissues. However, these salts alone do not have the ability to stay on the surface of the teeth for a sufficiently long time, and therefore their introduction into compositions for caring for the oral cavity is carried out, for example, using a polymer matrix (RU 2519204, A61K 8/27, A61K 8/365, A61K 8/72, A61Q 11/00, 2014).

To ensure the long-term antibacterial effect of zinc or copper ions, the use of a zinc or copper (II) salt of the general formula

where M is Zn or Cu, R ¹ is hydrogen or methyl, R ^{2 is} selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkadienyl, substituted or unsubstituted aryl, as a component of the oral composition.

For the same purpose, an oral composition has been proposed that includes an acceptable oral base and a zinc or copper (II) salt, characterized in that it contains a zinc or copper (II) salt of the general formula (1), where M is Zn or Cu, R ¹ is hydrogen or methyl, R ^{2 is} selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkadienyl, substituted or unsubstituted aryl, in an amount of from 0.5 to 5% by weight of the composition.

The composition may be a toothpaste, anti-inflammatory gel or mouthwash. An acceptable oral base composition may include polyhydric alcohol, a surfactant, a sweetener, essential oils and deionized water. In the case where the composition is an oral rinse, an acceptable base for the composition of the composition may include deionized water.

Compounds meeting the above general formula (1) for various R ² values are known (RU 2315793, C09D 5/14, C09D 131/02, C09D 133/10, 2008; RU 2497857, C09D 5/14, C07C 69/78 , 2013; RU 2550361, С01G 3/00, С01G 9/00, С07С 229/54, С07С 229/24, С07С 229/06, С07С 55/02, С07С 59/01, С07С 59/235, С07С 59/50 , A01N 55/02, B27K 3/34, C09D 5/14, D21H 25/02, 2015; RU 2014134076, A01N 55/02, 2015; RU 2014137615, A01N 55/02, 2015); it is also known that they have a bactericidal and fungicidal effect.

The technical result of the invention is the unexpectedly discovered ability of these compounds to penetrate into the surface layer of tooth enamel and stay in it for a long time. Due to this, in the oral cavity for a long period of time after using the composition, the bactericidal and / or fungicidal, as well as the reparative effect of the compositions containing these compounds is preserved, and resistance to dental erosion is ensured.

The invention is illustrated by the following examples 1-69. Examples 1-19 illustrate the effect of the compounds used according to the invention on the acid resistance of tooth enamel, examples 20-38 show the ability of these compounds to stably hold in tooth enamel, examples 39-56 show the fungicidal and bactericidal properties of teeth treated with these compounds. Examples 57-69 show embodiments of a particular embodiment of the compositions of the invention.

Example 1. The effect of zinc acrylate-benzoate (R ¹ = H, R ² = C ₆ H ₅ ) on the resistance of tooth enamel to acid was investigated. Before the experiment, human teeth removed according to indications in the dental clinic were treated for contamination with saliva, plaque, etc. Then, two sections of the tooth surface, equal in area, were covered with sheets of paper, after which the tooth was covered with special nail polish, so that there was no varnish on the surfaces of the tooth sections covered with paper. One of the sites was opened and the tooth was treated with a 3% solution of zinc acrylate-benzoate for 30 minutes, stirring the solution with a magnetic stirrer, after which the tooth was kept for 10 minutes in 0.01 N. hydrochloric acid and determined the increase in the content of Ca ²⁺ in solution (ΔCa ²⁺ ). For control, after that, the treated area was again closed with paper, the second area was opened, the tooth was treated for 30 minutes with water, stirring it with a magnetic stirrer, after which the tooth was kept for 10 minutes in 0.01 N. hydrochloric acid and ΔСа ^{2+ was} determined. The value of ΔСа ²⁺ for the solution after exposure to the tooth treated with the solution of zinc acrylate-benzoate was 21 ppm, whereas in the control experiment it was 38.3 ppm, i.e. almost twice as much.

Examples 2-17. The experiment of Example 1 was repeated using other compounds of the general formula (1). Data on the results of the experiments are shown in table 1. In the control experiment in all cases, the value of ΔСа ²⁺ was 38 ± 1 ppm.

Examples 18-19 (comparative). The experiment of Example 1 was repeated using the zinc salts used in the known oral care compositions. Data on the results of the experiments are shown in table 1. The results of the experiments show that the zinc salts used do not affect the stability of tooth enamel with respect to acid.

Example 20. We studied the accumulation of zinc acrylate-benzoate in the surface layer of tooth enamel and its subsequent leaching with water. Before the experiment, human teeth removed according to indications in the dental clinic were treated for contamination with saliva, plaque, etc. Then a 3% solution of zinc acrylate-benzoate was applied to the surface of the teeth with a toothbrush for 5 or 10 minutes. After that, the teeth were washed with running distilled water for 2-3 minutes and dried. The content of Zn ²⁺ in the surface layer of tooth enamel (depth 20 μm) was determined before treatment with zinc acrylate-benzoate and after treatment, and then the teeth were washed with running distilled water for 1-3 hours, and then for 30 days and the Zn content was again determined ²⁺ in the surface layer of tooth enamel. To determine the Zn ²⁺ content, an X-ray fluorescence analysis method using an X-ray tube and an energy dispersive X-ray fluorescence analyzer EDX-720 (Shimadzu, Japan) was used. The method allows you to determine the ratio of the intensities of the characteristic lines of Zn ²⁺ and Ca ²⁺ ; calibration was performed using specially prepared samples of mixtures of zinc oxide and calcium orthophosphate. The content of Zn ²⁺ in the surface layer of tooth enamel was determined from the found ratio of intensities and the known content of Ca ²⁺ in tooth enamel. The results obtained are presented in table 2. From table 2 it follows that a significant amount of Zn ²⁺ passes into the surface layer of enamel and the connection of zinc acrylate-benzoate with enamel is quite strong, since even after 3 hours washing out in running water, the Zn ²⁺ content ^is practically does not change, and after washing for 30 days, the surface layer of enamel still contains 30-70% of the amount of zinc initially transferred to this layer.

Examples 21-36. The experiment of Example 19 was repeated using other compounds of the general formula (1). Data on the results of the experiments are shown in table 3.

Examples 37-38 (comparative). The experiment of Example 19 was repeated using the zinc salts used in the known oral care compositions. The data on the experimental results are shown in Table 3. The experimental results show that when treating a tooth with zinc lactate or zinc citrate, the Zn ²⁺ content in the surface layer of tooth enamel changes slightly, i.e. Zn ²⁺ enters the surface layer of enamel in a very small amount.

Examples 39-54. We studied the effect of teeth in the enamel of which a zinc or copper (II) salt was introduced according to examples 2-17 on the growth of mold spores or bacterial strains. The fungicidal and bactericidal properties of the treated tooth enamel were evaluated by the width of the annular inhibitory zone (the zone of the absence of fungus or bacteria) around the tooth treated with salt of zinc or copper (II), placed in a Petri dish with Chapek-Doks nutrient medium with agar (GOST 9.048-89), in which a suspension of mold spores (Aspergillus, Penicillium, Chaetomium, Paecilomyces, Trichoderma, Alternaria) or bacteria of the genera Pseudomonas, Bacillus, Proteus, etc. was added. The tests were carried out at a temperature of 29 ± 2 ° С and relative humidity of more than 90% for 24% hours. Data on the results of the experiments are shown in table 4.

Examples 55-56 (comparative). The experiments of Examples 39-54 were repeated using the zinc salts used in the known oral care compositions. Data on the results of the experiments are shown in table 4. The results of the experiments show that teeth treated with lactate or zinc citrate do not have fungicidal and bactericidal effects on the environment in which they are placed.

Examples 57-62. Toothpastes were prepared according to the usual technology, which is an acceptable oral basis, including commonly used ingredients, including abrasive components, polyhydric alcohols, surfactants, flavoring, flavoring and other functional additives and deionized water, and salts were introduced into the base zinc or copper (II), corresponding to the formula (1). The ingredients of the compositions and their amounts are shown in table 5. To refer to the salts of zinc or copper (II) introduced in the composition in table 5, as well as in the following tables 6 and 7, references are made to examples 1-17, where these salts are mentioned. The compositions described in these and subsequent examples have good consumer properties, their use provides resistance to dental erosion and a reduction in the size of areas of destruction of bone tissue that have previously undergone erosion (reparative effect).

Examples 63-65. Oral rinse formulations were prepared using conventional technology, which is an acceptable oral basis, including commonly used ingredients, including polyhydric alcohols, surfactants, flavors, flavorings and other functional additives, and deionized water, and zinc salts were introduced into the base or copper (II) corresponding to the formula (1). The ingredients of the compositions and their amounts are shown in table 6.

Example 66. A rinse aid composition was prepared, which was a solution of zinc methacrylate butyrate in deionized water. The amounts of ingredients are shown in table 6.

Examples 67-69. Formulations of anti-inflammatory gels were prepared using conventional technology, which are an acceptable oral basis, including commonly used ingredients, including anti-inflammatory ingredients, polyhydric alcohols, surfactants, flavors, aromas and other functional additives and deionized water, and salts were introduced into the base zinc or copper (II) in accordance with the invention. The ingredients of the compositions and their amounts are shown in table 7.

Claims (7)

1. The use of zinc or copper (II) salts of the general formula

where M is Zn or Cu, R ¹ is hydrogen or methyl, R ^{2 is} selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkadienyl, substituted or unsubstituted aryl, as a component of the oral composition. 2. The composition for caring for the oral cavity, including an acceptable base for the oral cavity and a salt of zinc or copper (II), characterized in that it contains a salt of zinc or copper (II) of the General formula

where M is Zn or Cu, R ¹ is hydrogen or methyl, R ^{2 is} selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, alkenyl, alkadienyl, substituted or unsubstituted aryl, in an amount of from 0.5 to 5% by weight of the composition. 3. The composition according to p. 2, characterized in that an acceptable oral base includes a polyhydric alcohol, a surfactant, flavoring, flavoring and other functional additives and deionized water. 4. The composition according to p. 2 or 3, characterized in that it is a toothpaste. 5. The composition according to p. 2, characterized in that it is a mouth rinse and an acceptable basis for the oral cavity includes deionized water. 6. The composition according to p. 5, characterized in that an acceptable base for the oral cavity also includes polyhydric alcohol, a surfactant, flavoring, flavoring and other functional additives. 7. The composition according to p. 2 or 3, characterized in that it is an anti-inflammatory gel.