JP6614071B2 - Liquid oral composition - Google Patents

Description

  The present invention relates to a liquid oral composition containing no paraoxybenzoic acid ester, which is excellent in appearance stability by suppressing the precipitation of menthol even when stored at a low temperature.

  In recent years, with regard to oral compositions, paraben-free oral products that do not contain paraoxybenzoic acid esters (parabens) have been desired due to the increased safety orientation.

  Parabens are widely used as a preservative in oral compositions, but this paraben is known to affect the stability (precipitation) of menthol, which is generally incorporated as a cooling agent in oral compositions. Patent Document 1 (Japanese Patent No. 4985905) contains a combination of methyl paraoxybenzoate and ethyl paraoxybenzoate in combination with a specific nonionic surfactant, and has a low ethanol composition containing a cationic fungicide. A technique that prevents precipitation of L-menthol after low-temperature storage with a liquid oral composition has been proposed.

Japanese Patent No. 4985905

  However, in the product design, when parabens are not used, it is difficult to ensure the stability of menthol. Therefore, it has been desired to develop a menthol precipitation suppression technique using a paraben-free liquid oral composition.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid oral composition containing no paraoxybenzoic acid ester, in which precipitation of menthol is suppressed even after low-temperature storage and excellent appearance stability is provided. To do.

  As a result of intensive studies to achieve the above object, the present inventors combined eugenol and methyl salicylate in a specific ratio with a liquid oral composition containing no menthol, but containing paraoxybenzoate. It has been found that, when blended, menthol is stabilized even after low-temperature storage, precipitation is suppressed, and appearance stability is improved. That is, according to the present invention, (B) eugenol and (C) salicylic acid are contained in a liquid oral composition containing 0.001 to 0.15 mass% of menthol without containing a paraoxybenzoic acid ester. Methyl is blended, and (B) / (C) is 0.25 to 4 as a mass ratio and ((B) + (C)) / (A) is 0.65 or more as a mass ratio. It is possible to provide a liquid oral composition containing no paraoxybenzoic acid ester (paraben-free), in which precipitation of menthol is suppressed even after storage, which gives excellent appearance stability, and also has a good taste because it is suppressed in taste. The present invention has been found and the present invention has been made.

According to the present invention, when (B) eugenol and (C) methyl salicylate are combined in a liquid oral composition such as a paraben-free mouthwash, the mass ratio of (B) / (C) is within a specific range. In addition, when the mass ratio of ((B) + (C)) / (A) is not less than a specific value, (A) as a menthol stabilizer, it acts to suppress precipitation of menthol even after low-temperature storage. Thus, excellent appearance stability without crystal precipitation due to menthol even after storage at −5 ° C. for 1 month is given. In this case, eugenol and methyl salicylate, which are well-known as oral flavors, have a unique taste, but when they are used in combination with components (B) and (C) at an appropriate ratio, the taste is expressed. It is possible to improve the appearance stability by suppressing the precipitation of menthol without giving a remarkable remarkable effect that cannot be achieved by the mere addition of an inappropriate oral flavor.
In the present invention, even if the paraben-free liquid oral composition is a hypoallergenic non-alcohol or low-alcohol composition or a composition in which the amount of surfactant added is reduced, menthol precipitation is suppressed. In addition, the appearance stability is excellent, and a bactericidal power against oral bacteria can be satisfactorily expressed by adding a cationic bactericidal agent, and a refreshing feeling by menthol can also be satisfactorily imparted.

Therefore, the present invention provides the following liquid oral composition and the method for inhibiting menthol precipitation in the liquid oral composition.
[1]
It is a liquid composition for oral cavity containing no paraoxybenzoic acid ester and containing 0.001 to 0.15% by mass of (A) menthol,
(B) Eugenol and
(C) It contains methyl salicylate, and (B) / (C) is 0.25 to 4 as a mass ratio, and ((B) + (C)) / (A) is 0.65 or more as a mass ratio. A liquid oral composition characterized by being.
[2]
(B) The liquid oral composition according to [1], wherein the content of eugenol is 0.00013 to 0.2% by mass, and the content of (C) methyl salicylate is 0.00013 to 0.2% by mass.
[3]
The liquid oral composition according to [1] or [2], wherein the total content of (B) eugenol and (C) methyl salicylate is 0.00065 to 0.4 mass%.
[4]
Furthermore, (D) Composition for liquid oral cavity in any one of [1]-[3] whose content of ethanol is 0-15 mass%.
[5]
Furthermore, (E) polyoxyethylene hydrogenated castor oil having an average addition mole number of ethylene oxide of 40 to 100 moles and polyoxyethylene having a carbon chain length of 16 to 18 and an average addition mole number of ethylene oxide of 10 to 50 moles The liquid oral cavity composition in any one of [1]-[4] which contains 0.1-0.5 mass% of 1 type, or 2 or more types of nonionic surfactant chosen from alkyl ether.
[6]
Furthermore, (F) The composition for liquid oral cavity in any one of [1]-[5] containing 0.01-0.1 mass% of cationic bactericides.
[7]
A liquid oral composition containing 0.001 to 0.15% by mass of (A) menthol without blending paraoxybenzoate ester,
(B) Eugenol and
(C) Methyl salicylate is blended, and (B) / (C) is 0.25 to 4 with mass ratio, and ((B) + (C)) / (A) is 0.65 or more with mass ratio A method for inhibiting menthol precipitation in the liquid composition for oral cavity.

  ADVANTAGE OF THE INVENTION According to this invention, the composition for liquid oral cavity which does not contain paraoxybenzoic acid ester which the precipitation of menthol is suppressed and the external appearance stability is excellent after low-temperature storage can be provided. Moreover, according to this invention, the method of suppressing precipitation of menthol in the liquid oral cavity composition which does not contain a paraoxybenzoic acid ester can be provided.

  Hereinafter, the present invention will be described in more detail. The liquid oral composition of the present invention is a paraben-free liquid preparation containing no paraoxybenzoic acid ester, and (B) eugenol and (C) methyl salicylate together with (A) menthol. In a specific proportion.

  In the present invention, specific examples of the paraoxybenzoic acid ester include alkyl esters of paraoxybenzoic acid such as methyl paraoxybenzoate, ethyl paraoxybenzoate, and butyl paraoxybenzoate, and these are not blended in the composition of the present invention. .

(A) Menthol is a refreshing component and L-menthol can be used.
The content of (A) menthol is 0.001 to 0.15% (mass%, the same applies hereinafter) of the entire composition, preferably 0.005 to 0.1%. As the content increases, the refreshing feeling increases, but when it exceeds 0.15%, the precipitation of menthol cannot be suppressed and the appearance stability decreases. In addition, the feeling of use deteriorates because the stimulation is too strong.

  In the present invention, by using a combination of (B) eugenol and (C) methyl salicylate as perfume components, the combined system of components (B) and (C) suppresses its precipitation as a menthol stabilizer. As a result, the appearance stability is excellent even after storage at a low temperature, the clarity can be maintained, and the both tastes can be suppressed. When the component (B) or (C) is lacking, the taste is not suppressed because the taste is not suppressed.

  (B) The content of eugenol is preferably 0.00013 to 0.2%, more preferably 0.003 to 0.1% of the entire composition. As the content increases, the effect of suppressing menthol precipitation increases, and if it is 0.00013% or more, sufficient appearance stability can be obtained. A content of 0.2% or less is suitable for suppressing taste. If it exceeds 0.2%, even if it is combined with (C) methyl salicylate, there is a possibility that it may feel unpleasant, and the unpleasant taste may not be sufficiently suppressed.

  (C) The content of methyl salicylate is preferably 0.00013 to 0.2%, more preferably 0.003 to 0.1% of the entire composition. As the content increases, the effect of suppressing menthol precipitation increases, and if it is 0.00013% or more, sufficient appearance stability can be obtained. 0.2% or less is suitable for the suppression of off-flavors, and if it exceeds 0.2%, there is a possibility that even if combined with (B) eugenol, the off-flavors may be felt, and the off-flavors may not be sufficiently suppressed. is there.

  The total content of (B) eugenol and (C) methyl salicylate can be 0.00026 to 0.4% of the total composition, but is particularly preferably 0.00065 to 0.4%, more preferably 0.006 to 0.2%. Within this range, the precipitation of menthol is sufficiently suppressed, the appearance stability is increased, and the taste is sufficiently suppressed. If it is less than 0.00026%, the effect of suppressing menthol precipitation may be low and appearance stability may be poor, and if it exceeds 0.4%, a nasty taste may occur and the feeling of use may be deteriorated.

  In this invention, (B) / (C) which shows the content ratio of (B) eugenol and (C) methyl salicylate is 0.25-4 as a mass ratio, Preferably it is 0.26-3.8. is there. When (B) / (C) is out of the above range, the nasty taste derived from the components (B) and (C) cannot be suppressed, the nasty taste may not be suppressed, and the scent may also be strong, resulting in poor usability. .

  (A) The content ratio of (B) eugenol and (C) methyl salicylate relative to menthol ((B) + (C)) / (A) is 0.65 or more as a mass ratio, preferably 0.7 That's it. If it is less than 0.65, the precipitation of menthol cannot be suppressed and the appearance stability is poor. Moreover, the upper limit of the mass ratio of ((B) + (C)) / (A) is preferably 3 or less, more preferably 2 or less, and still more preferably 1.5 or less, from the viewpoint of refreshing feeling.

The composition for liquid oral cavity of the present invention may be (D) ethanol-free (content 0%) non-alcohol composition, but when (D) ethanol is further added, the effect of inhibiting menthol precipitation increases. Appearance stability is further improved.
(D) The content of ethanol is preferably 0 to 15% of the entire composition, and when added, it is preferably 1 to 15%, particularly 2 to 10%, and more preferably 4 to 8%. Appearance stability improves as the content increases, but 15% or less is suitable for suppression of irritation. In addition, when ethanol is contained in a fragrance | flavor, it is preferable that the total amount of ethanol in the composition including this is in the said range.

  Furthermore, it is preferable to add (E) nonionic surfactant as the surfactant. When (E) nonionic surfactant is added, the perfume component is sufficiently solubilized and the effect of inhibiting menthol precipitation is enhanced. Appearance stability is further improved. Specifically, polyoxyethylene hydrogenated castor oil having an average added mole number (EO) of ethylene oxide of 40 to 100 moles, a carbon chain length of 16 to 18 and an average added mole number of ethylene oxide of 10 to 50. One or two or more selected from polyoxyethylene alkyl ethers that are moles are preferred from the viewpoint of solubilization of the fragrance and the feeling of use. O. Is more preferably 60-100 mol of polyoxyethylene hydrogenated castor oil from the viewpoint of suppressing taste.

  (E) Content of nonionic surfactant is 0.5% or less with respect to the whole composition, 0.1 to 0.5% is especially preferable. If it is 0.1% or more, the fragrance is sufficiently solubilized, but if it is added too much, there is a concern that the sterilizing power is reduced when a bactericide is added.

In the liquid oral cavity composition of the present invention, (F) a cationic bactericidal agent can be further added. When a cationic disinfectant is added, in addition to excellent appearance stability and unpleasant taste, a bactericidal effect on oral bacteria is effectively expressed.
Examples of the (F) cationic fungicide include quaternary ammonium salts such as cetylpyridinium chloride and benzalkonium chloride, and chlorhexidine salts such as chlorhexidine hydrochloride and chlorhexidine gluconate. Can be used. Among them, quaternary ammonium salts such as cetylpyridinium chloride and benzalkonium chloride, particularly cetylpyridinium chloride are more preferable in terms of effect expression.
(F) When adding a cationic disinfectant, the content is preferably 0.01 to 0.1% of the whole composition, more preferably 0.02 to 0.05%. The greater the content, the greater the bactericidal effect against oral bacteria, but if too much is added, the feeling of use may be reduced.

  The liquid oral composition of the present invention can be prepared and applied as a general mouthwash, a mouthwash such as a concentrated type mouthwash, a freshener in the mouth, etc. In addition to the above components, other known components can be appropriately blended. For example, for the mouthwash, wetting agents, thickeners, surfactants, pH adjusters, preservatives other than paraoxybenzoic acid esters, perfumes other than (A), (B) and (C) ingredients, active ingredients, Sweetening agents, coloring agents and the like can be added.

Examples of the wetting agent include glycerin, sorbitol, propylene glycol, ethylene glycol, polyethylene glycol, xylit, maltite, and lactit.
Examples of the thickener include xanthan gum, carrageenan, hydroxymethyl cellulose, sodium alginate, polyvinyl alcohol and the like.

  As surfactants, in addition to (E) nonionic surfactants, other surfactants such as sodium myristyl sulfate, N-lauroyl sarcosinate, lauroyl methyl taurine, acylamino acid salts, sodium dodecylbenzenesulfonate , Α-sulfo fatty acid alkyl ester / sodium, anionic surfactants such as alkyl phosphate ester salts, betaine acetate type amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, N-fatty acid acyl Examples include imidazoline-type amphoteric surfactants such as —N-carboxymethyl-N-hydroxyethylethylenediamine salt, and amino acid-type surfactants such as N-fatty acid acyl-L-alginate salts, and one or more of these. Can be added. The addition amount of these surfactants is preferably 0 to 5%, more preferably 0.01% or more, and further preferably 0.01 to 1%.

Examples of pH adjusters include phthalic acid, phosphoric acid, citric acid, succinic acid, acetic acid, fumaric acid, malic acid, carbonic acid and their potassium salts, sodium salts, ammonium salts, ribonucleic acid or salts thereof, sodium hydroxide, and the like. 1 type or 2 types or more can be used. In particular, a combination of phosphoric acid or citric acid and a sodium salt thereof is preferable.
The liquid oral composition of the present invention preferably has a pH at 25 ° C. adjusted to 5.5 to 7.5. As a pH adjuster in the vicinity thereof, two liquids of sodium dihydrogen phosphate and sodium monohydrogen phosphate are used. Or a combination of citric acid and sodium citrate can be used.

  As a preservative, for example, sodium benzoate, alkyldiaminoethylglycine hydrochloride, potassium sorbate and the like can be added within a range not impeding the effects of the present invention.

As perfumes, natural essential oils such as spearmint oil, eucalyptus oil, winter green oil, clove oil, thyme oil, sage oil, cardamom oil, rosemary oil, marjoram oil, lemon oil, nutmeg oil, lavender oil, paracres oil, and Perfume ingredients contained in the above natural essential oils such as l-carvone, 1,8-cineole, thymol, linalool, limonene, menthone, menthyl acetate, citral, camphor, borneol, pinene, spirantol, etc., and ethyl acetate, ethyl butyrate , Isoamyl acetate, hexanal, hexenal, methyl anthranilate, ethyl methyl phenyl glycidate, benzaldehyde, vanillin, ethyl vanillin, furaneol, maltol, ethyl maltol, gamma / delta decalactone, Perfume ingredients such as Numa / Deltown Decalactone, N-ethyl-p-menthane-3-carboxamide, menthyl lactate, ethylene glycol-1-menthyl carbonate, and further a combination of several perfume ingredients and natural essential oils. One or more kinds of blended flavors such as apple, banana, strawberry, blueberry, melon, peach, pineapple, grape, muscat, wine, cherry, squash, coffee, brandy, yogurt can be used. The blending amount is preferably 0.00001 to 3%, and can be used within a range not impeding the effects of the present invention.
In addition, when (A), (B) or (C) component is contained in a fragrance | flavor, content of (A), (B) or (C) component can be used within the said range.

  As active ingredients, in addition to (F) cationic fungicides, other active ingredients such as anti-inflammatory agents such as tranexamic acid, epsilon-aminocaproic acid, dextranase, amylase, protease, mutanase, lysozyme, lytechenzyme, etc. Enzymes, sodium fluoride, sodium monofluorophosphate, fluoride such as stannous fluoride, vitamins such as aluminum chlorohydroxy allantoin, allantoin, azulene, lysozyme chloride, ascorbic acid, dihydrocholesterol, glycyrrhetin salts, glycyrrhetinic acids , Hydrocholesterol, chlorophyll, copper chlorophyllin sodium, thyme, hornon, clove, hamamelis and other plant extracts, copper gluconate, caropeptide, sodium polyphosphate, water-soluble inorganic phosphate Compound, polyethylene glycol, polyvinyl pyrrolidone, sodium lauroyl sarcosinate, anti-tartar agents, anti-plaque agents, potassium nitrate, may be added to aluminum lactate and the like. In addition, the compounding quantity of these active ingredients is an effective quantity in the range which does not prevent the effect of this invention.

Examples of the sweetener include saccharin sodium and stevocytes.
As a colorant, a highly safe water-soluble pigment such as Blue No. 1, Green No. 3, Yellow No. 4, Red No. 105 can be added.

  EXAMPLES Hereinafter, although an experimental example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, “%” means “% by mass” unless otherwise specified.

[Experimental Example 1]
Liquid oral compositions (mouthwashes) having the compositions shown in Tables 1 to 3 were prepared by a conventional method, and these were used as samples. The appearance stability after low-temperature storage and the absence of taste were evaluated by the following methods. The results are shown in Tables 1-3.

<Appearance stability evaluation method>
The sample mouthwash was filled with 450 mL of a 500 mL PET (polyethylene terephthalate) container, and the appearance stability after 1 month storage in a -5 ° C. constant temperature bath was visually determined according to the following criteria. The ◯ or ◎ samples were judged to have good menthol precipitation and good appearance stability.
Evaluation criteria for appearance stability;
A: There is no difference from the initial product, and no precipitation of needle crystals is observed.
○: A very small amount of orientation is observed.
Δ: Precipitation of a small amount of crystals is observed.
X: Precipitation of acicular crystals is observed.

<Assessment method of tastelessness>
The sample was rinsed with 10 mL of mouthwash in the mouth and rinsed for 30 seconds. The average score of 10 people was calculated, and 2.0 or higher was regarded as acceptable.
Evaluation criteria for tastelessness;
3 points: No nasty taste was observed 2 points: Somewhat tasty taste was observed 1 point: Nasty taste was found

＊香料は、メントール、オイゲノール及びサリチル酸メチルを含まない（以下、同様。）。

* The fragrance does not contain menthol, eugenol and methyl salicylate (the same shall apply hereinafter).

[Experiment 2]
No. shown in Table 1. The liquid oral cavity composition (mouthwash) of 1-11 was used as a sample, and the bactericidal effect and the refreshing feeling were evaluated by the following method. The result is No. The results are shown in Table 4 as 2-1 to 2-11.

<Method for evaluating bactericidal effect on oral bacteria>
For the bacterial count measurement test, Dentocult-SM (manufactured by Orion Diagnostics Inc., Finland), which is a kit for measuring the number of mutans in saliva, was used. In advance, the number of bacteria in saliva was evaluated according to the method of using Dentocult-SM, and 10 people with 2 or more points were targeted according to the following evaluation criteria.
Mouth samples containing 10 mL of mouthwash were rinsed for 30 seconds, and after 3 hours, the number of mutans bacteria in the saliva was similarly measured using Denocult-SM, and in accordance with the evaluation criteria shown below. The bactericidal effect was evaluated. The average score of 10 people was calculated. The smaller the score, the higher the bactericidal effect.
Evaluation criteria for bactericidal effect;
3 points: the number of mutans bacteria is 10 ⁶ or more 2 points: the number of mutans bacteria is 10 ⁵ or more and less than 10 ⁶ 1 point: the number of mutans bacteria is less than 10 ⁵

<Method for evaluating refreshment>
The sample was rinsed with 10 mL of mouthwash in the mouth and rinsed for 30 seconds, and the refreshing feeling after the mouthwashing was evaluated in the following three stages. The average score of 10 people was calculated. A score of 2.0 or higher was accepted.
Evaluation criteria for refreshing feeling after mouthwash;
3 points: A refreshing sensation was observed 2 points: A slight refreshing sensation was observed 1 point: A refreshing sensation was not recognized

Claims (7)

It is a liquid composition for oral cavity containing no paraoxybenzoic acid ester and containing 0.001 to 0.15% by mass of (A) menthol,
(B) Eugenol and
(C) It contains methyl salicylate, and (B) / (C) is 0.25 to 4 as a mass ratio, and ((B) + (C)) / (A) is 0.65 or more as a mass ratio. A liquid oral composition characterized by being.   The liquid oral composition according to claim 1, wherein the content of (B) eugenol is 0.00013 to 0.2 mass%, and the content of (C) methyl salicylate is 0.00013 to 0.2 mass%.   The liquid oral composition according to claim 1 or 2, wherein the total content of (B) eugenol and (C) methyl salicylate is 0.00065 to 0.4 mass%.   Furthermore, (D) Ethanol content is 0-15 mass%, The composition for liquid oral cavity of any one of Claims 1-3.   Furthermore, (E) polyoxyethylene hydrogenated castor oil having an average addition mole number of ethylene oxide of 40 to 100 moles and polyoxyethylene having a carbon chain length of 16 to 18 and an average addition mole number of ethylene oxide of 10 to 50 moles The liquid oral cavity composition of any one of Claims 1-4 which contains 0.1-0.5 mass% of 1 type, or 2 or more types of nonionic surfactant chosen from alkyl ether.   Furthermore, the liquid oral cavity composition of any one of Claims 1-5 which contains 0.01-0.1 mass% of (F) cationic disinfectants. A liquid oral composition containing 0.001 to 0.15% by mass of (A) menthol without blending paraoxybenzoate ester,
(B) Eugenol and
(C) Methyl salicylate is blended, and (B) / (C) is 0.25 to 4 with mass ratio, and ((B) + (C)) / (A) is 0.65 or more with mass ratio A method for inhibiting menthol precipitation in the liquid composition for oral cavity.