CN109689016B

CN109689016B - Liquid oral composition

Info

Publication number: CN109689016B
Application number: CN201780054135.8A
Authority: CN
Inventors: 西山佑树; 二阶堂亚纪子
Original assignee: Lion Corp
Current assignee: Lion Corp
Priority date: 2016-09-05
Filing date: 2017-08-24
Publication date: 2022-01-14
Anticipated expiration: 2037-08-24
Also published as: WO2018043275A1; JP6614071B2; KR20190046774A; KR102270933B1; JP2018039739A; CN109689016A

Abstract

A liquid oral composition containing 0.001 to 0.15 mass% of (A) menthol without containing parabens, characterized in that the composition contains (B) eugenol and (C) methyl salicylate, and the mass ratio of (B)/(C) is 0.25 to 4 and the mass ratio of ((B) + (C))/(A) is 0.65 or more. A method for suppressing the deposition of menthol in the liquid oral composition, wherein the components (B) and (C) are mixed in a liquid oral composition in which the component (A) is mixed without mixing a paraben, and the mass ratio of (B)/(C) is 0.25 to 4, and the mass ratio of ((B) + (C))/(A) is 0.65 or more.

Description

Liquid oral composition

Technical Field

The present invention relates to a liquid oral composition containing no paraben, which is suppressed in precipitation of menthol even when stored at low temperatures and has excellent appearance stability.

Background

In recent years, for oral compositions, there has been an increasing demand for paraben (paraben free) free oral products that do not contain paraben (paraben) for reasons such as improvement of safety.

Parabens are widely used as preservatives in oral compositions, but it is known that these parabens have an effect on the stability (deposition) of menthol which is usually mixed as a cooling agent in oral compositions, and patent document 1 (japanese patent No. 4985905) proposes the following technique: methyl p-hydroxybenzoate and ethyl p-hydroxybenzoate are mixed in combination with a specific nonionic surfactant, and the precipitation of L-menthol after low-temperature storage is prevented in a liquid oral composition comprising low ethanol and containing a cationic bactericide.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 4985905

Disclosure of Invention

Problems to be solved by the invention

However, in terms of product design, it is difficult to ensure stability of menthol without using parabens, and therefore it is desired to develop a technique for suppressing precipitation of menthol in a liquid oral composition containing no parabens.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid oral composition containing no paraben, which is suppressed in precipitation of menthol even when stored at low temperatures and provides excellent appearance stability.

Means for solving the problems

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that: when eugenol and methyl salicylate are mixed in a specific ratio in a liquid oral composition containing menthol without paraben, menthol is stabilized and precipitation is suppressed even after storage at low temperature, and appearance stability is improved. Namely, it was found that: according to the present invention, a liquid oral composition containing no paraben, in which the precipitation of menthol is suppressed even after storage at low temperature, and excellent appearance stability is brought about, and further, off-flavor is suppressed, and a feeling of use is good, can be provided by mixing (B) eugenol and (C) methyl salicylate (B)/(C) in a mass ratio of 0.25 to 4 and ((B) + (C))/(a) in a mass ratio of 0.65 or more into a liquid oral composition containing no paraben and containing 0.001 to 0.15 mass% of (a) menthol without paraben, and the present invention has been completed.

According to the present invention, when eugenol (B) and methyl salicylate (C) are combined in a liquid oral composition such as a mouth wash containing no paraben, the mass ratio of (B)/(C) is within a specific range and the mass ratio of ((B) + (C))/(a) is at least a specific value, and the composition exhibits an effect of suppressing menthol precipitation after low-temperature storage as a stabilizer for menthol (a), thereby imparting excellent appearance stability in which crystals are not precipitated by menthol even after 1 month of storage at-5 ℃. In this case, although eugenol and methyl salicylate, which are known as oral flavors, have unique unpleasant odors, when the components (B) and (C) are used in combination at an appropriate ratio, the precipitation of menthol is suppressed without causing any unpleasant odor, the appearance stability is improved, and an extraordinarily significant action effect which cannot be achieved by adding an inappropriate oral flavor alone is brought about.

In the present invention, even if the liquid oral composition containing no paraben is composed of a non-alcohol or low-alcohol with low irritation or a composition in which the amount of the surfactant added is reduced, the precipitation of methanol is suppressed, the appearance stability is excellent, and further, a cationic bactericidal agent can be added to satisfactorily exhibit bactericidal power against bacteria in the oral cavity, and a cooling sensation obtained from menthol can be satisfactorily imparted.

Accordingly, the present invention provides the following liquid oral composition and a method for suppressing precipitation of menthol in the liquid oral composition.

[1]

A liquid oral composition containing 0.001 to 0.15 mass% of (A) menthol without containing parabens, characterized in that the composition contains (B) eugenol and (C) methyl salicylate, and the mass ratio of (B)/(C) is 0.25 to 4 and the mass ratio of ((B) + (C))/(A) is 0.65 or more.

[2]

The liquid oral composition according to item [1], wherein the content of eugenol (B) is 0.00013 to 0.2 mass%, and the content of methyl salicylate (C) is 0.00013 to 0.2 mass%.

[3]

The liquid oral composition according to [1] or [2], wherein the total content of eugenol (B) and methyl salicylate (C) is 0.00065 to 0.4 mass%.

[4]

The liquid oral composition according to any one of [1] to [3], wherein the composition further contains (D) ethanol, if necessary, in an amount of 0 to 15 mass%.

[5]

The liquid oral composition according to any one of [1] to [4], further comprising 0.1 to 0.5 mass% of (E) 1 or 2 or more nonionic surfactants selected from polyoxyethylene hydrogenated castor oil having an average molar number of addition of ethylene oxide of 40 to 100 moles and polyoxyethylene alkyl ether having a carbon chain length of 16 to 18 and an average molar number of addition of ethylene oxide of 10 to 50 moles.

[6]

The liquid oral composition according to any one of [1] to [5], further comprising (F) a cationic bactericidal agent in an amount of 0.01 to 0.1 mass%.

[7]

A method for suppressing the deposition of menthol in the liquid oral composition, characterized by adding eugenol (B) and methyl salicylate (C) to a liquid oral composition containing 0.001 to 0.15 mass% of menthol (A) without paraben so that the mass ratio of (B)/(C) is 0.25 to 4 and the mass ratio of ((B) + (C))/(A) is 0.65 or more.

Effects of the invention

According to the present invention, there can be provided a liquid oral composition which is free from parabens, is suppressed in the deposition of menthol even after storage at low temperatures, and has excellent appearance stability. Further, the present invention can provide a method for suppressing the precipitation of menthol in a liquid oral composition containing no paraben.

Detailed Description

The present invention is described in further detail below, and the liquid oral composition of the present invention is a paraben-free liquid preparation containing (a) menthol and, at the same time, (B) eugenol and (C) methyl salicylate in a specific ratio.

In the present invention, specific examples of the paraben include alkyl parabens such as methyl paraben, ethyl paraben and butyl paraben. These materials are not incorporated into the compositions of the present invention.

(A) Menthol is a component that imparts a cooling sensation, and L-menthol can be used.

(A) The content of menthol is 0.001 to 0.15% (mass%, the same applies hereinafter) of the entire composition, and preferably 0.005 to 0.1%. The cooling sensation is enhanced as the content is increased, but when it exceeds 0.15%, precipitation of menthol is not suppressed, and the appearance stability is lowered. In addition, the stimulation is too strong, and the feeling of use is deteriorated.

In the present invention, by using the fragrance component (B) eugenol and the fragrance component (C) methyl salicylate in combination, the combined system of the components (B) and (C) acts as a stabilizer for menthol to suppress the precipitation thereof, and thus, after storage at low temperature, the appearance stability is also excellent, the clarity can be maintained, and the odor caused by both can be suppressed. If the component (B) or (C) is absent, the odor is not suppressed and the odor is deteriorated.

(B) The content of eugenol is preferably 0.00013 to 0.2%, more preferably 0.003 to 0.1% of the total composition. The effect of suppressing the precipitation of menthol increases as the content increases, and sufficient appearance stability is obtained at 0.00013% or more. For suppressing the off-flavor, the content of eugenol (B) is preferably 0.2% or less. If the amount exceeds 0.2%, the odor may be perceived even in combination with (C) methyl salicylate, and the odor 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 total composition. The effect of suppressing the precipitation of menthol increases as the content increases, and sufficient appearance stability is obtained at 0.00013% or more. For suppressing the off-flavor, the content of eugenol (B) is preferably 0.2% or less. If the content exceeds 0.2%, the odor may be perceived even when the composition is combined with eugenol (B), and the odor may not be sufficiently suppressed.

(B) The total content of eugenol and methyl salicylate (C) may be set to 0.00026 to 0.4% by mass of the total composition, but is particularly preferably 0.00065 to 0.4% by mass, and more preferably 0.006 to 0.2% by mass. Within this range, the precipitation of menthol is sufficiently suppressed, the appearance stability is improved, and the odor is also sufficiently suppressed. When the content is less than 0.00026%, the effect of suppressing the precipitation of menthol may be low, and the appearance stability may be poor, and when the content is more than 0.4%, an unpleasant odor may be generated, resulting in poor feeling.

In the present invention, (B)/(C) representing the content ratio of eugenol (B) to methyl salicylate (C) is 0.25 to 4, preferably 0.26 to 3.8, in terms of mass ratio. (B) When the content is outside the above range, the odor derived from the components (B) and (C) is increased, and the odor cannot be suppressed, and the odor may be increased, resulting in poor feeling in use.

In the present invention, ((B) + (C))/(a) showing the content ratio of eugenol (B) and methyl salicylate (C) to menthol (a) is 0.65 or more, preferably 0.7 or more in terms of a mass ratio. If the amount is less than 0.65, precipitation of menthol is not suppressed, resulting in poor appearance stability. From the viewpoint of the cooling sensation, 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.

The liquid oral composition of the present invention may be a non-alcoholic composition containing no (D) ethanol (content: 0%), but if (D) ethanol is further added, the effect of suppressing precipitation of menthol increases, and the appearance stability further improves.

(D) The content of ethanol is preferably 0 to 15% of the total composition, and in the case of addition, it is preferably 1 to 15%, particularly 2 to 10%, and more preferably 4 to 8%. The more the content is, the more the appearance stability is improved, but 15% or less is preferable for suppressing the irritation. Further, when ethanol is contained in the perfume, it is preferable that the total amount of ethanol in the composition including ethanol is within the above range.

Further, it is preferable to add (E) a nonionic surfactant as the surfactant, and when (E) a nonionic surfactant is added, the flavor component is sufficiently solubilized, the effect of suppressing the precipitation of menthol is increased, and the appearance stability is further improved. Specifically, from the viewpoint of solubilizing the perfume and feeling upon use, 1 or 2 or more selected from polyoxyethylene hydrogenated castor oil having an average addition mole number (E.O.) of ethylene oxide of 40 to 100 moles and polyoxyethylene alkyl ether having a carbon chain length of 16 to 18 and an average addition mole number of ethylene oxide of 10 to 50 moles are preferable, and in particular, polyoxyethylene hydrogenated castor oil having an e.o. of 60 to 100 moles is more preferable from the viewpoint of suppressing an offensive odor.

(E) The content of the nonionic surfactant is 0.5% or less, particularly preferably 0.1 to 0.5% of the total composition. When the content is 0.1% or more, the perfume is sufficiently solubilized, but if the content is too large, the bactericidal activity may be reduced when the bactericide is added.

The liquid oral composition of the present invention may further contain (F) a cationic bactericidal agent. When the cationic bactericidal agent is added, the bactericidal effect against oral bacteria is effectively exhibited in addition to excellent appearance stability and no odor.

Examples of the cationic bactericidal agent (F) include quaternary ammonium salts such as cetylpyridinium chloride and benzalkonium chloride; chlorhexidine hydrochloride, chlorhexidine gluconate, and other chlorhexidine salts, 1 or more than 2 of these materials can be used. Among them, cetyl pyridinium chloride and benzalkonium chloride, which are quaternary ammonium salts, are more preferable from the viewpoint of effect expression.

When the cationic bactericide (F) is added, the content thereof is preferably 0.01 to 0.1%, more preferably 0.02 to 0.05% of the total composition. The higher the content, the higher the bactericidal effect on oral bacteria, but the more excessive the content, the less the feeling of use may be.

The liquid oral composition of the present invention can be used as a mouthwash such as a general mouthwash or a concentrated mouthwash; mouth freshener, etc. In addition, other known components may be mixed in addition to the above components depending on the dosage form. For example, a mouth wash may contain a wetting agent, a thickener, a surfactant, a pH adjuster, a preservative other than parabens, a flavor other than the components (A), (B) and (C), an active ingredient, a sweetener, a coloring agent, and the like.

Examples of the humectant include glycerin, sorbitol, propylene glycol, ethylene glycol, polyethylene glycol, xylitol, maltitol, and lactitol.

Examples of the thickener include xanthan gum, carrageenan, hydroxymethyl cellulose, sodium alginate, and polyvinyl alcohol.

Examples of the surfactant include, in addition to the nonionic surfactant (E), anionic surfactants such as sodium tetradecyl sulfate, N-lauroylsarcosine salt, lauroylmethyltaurine, acylamino acid salt, sodium dodecylbenzenesulfonate, sodium alkyl α -sulfofatty acid ester, and alkyl phosphate salt; betaine acetate type surface amphoteric surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amide propyldimethylaminoacetic acid betaine; 1 or 2 or more of them may be added to an imidazoline type amphoteric surfactant such as N-fatty acid acyl-N-carboxymethyl-N-hydroxyethyl ethylenediamine salt, or an amino acid type surfactant such as N-fatty acid acyl-L-alginic acid ester salt. The amount of these surfactants added is preferably 0 to 5%, more preferably 0.01% or more, and still more preferably 0.01 to 1%.

Examples of the pH adjuster include phthalic acid, phosphoric acid, citric acid, succinic acid, acetic acid, fumaric acid, malic acid, carbonic acid, and potassium salts, sodium salts, and ammonium salts of these; ribonucleic acid or a salt thereof; sodium hydroxide, etc., and 1 or 2 or more species can be used. Particularly preferred are those obtained by combining phosphoric acid, citric acid and their sodium salts.

The liquid oral composition of the present invention is preferably adjusted to a pH of 5.5 to 7.5 at 25 ℃, and both of sodium dihydrogen phosphate and sodium monohydrogen phosphate, or both of citric acid and sodium citrate may be used as a pH adjuster in the vicinity thereof.

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

As the perfume, natural essential oils such as spearmint oil, eucalyptus oil, wintergreen oil, clove oil, senecio oil, sage oil, cardamom oil, rosemary oil, marjoram oil, lemon oil, nutmeg oil, lavender oil, and spica flower oil; and perfume components contained in the above natural essential oils such as l-carvone, 1, 8-cineole, thymol, linalool, limonene, menthone, menthyl acetate, citral, camphor, borneol, pinene, spilanthol (spilanthol), etc.; and perfume components such as ethyl acetate, ethyl butyrate, isoamyl acetate, hexanal, hexenal (hexenol), methyl anthranilate, ethyl methylphenylglycidate, benzaldehyde, vanillin, ethyl vanillin, furanone, maltol, ethyl maltol, γ/δ -decalactone, γ/δ -undecalactone, N-ethyl-p-menthane-3-carboxamide, menthyl lactate, ethylene glycol-l-menthol carbonate, and the like; further combining several perfume components and natural essential oil to obtain 1 or more than 2 of apple flavor, banana flavor, strawberry flavor, blueberry flavor, melon flavor, peach flavor, pineapple flavor, grape flavor, muscadine flavor, wine flavor, cherry flavor, winter squash flavor, coffee flavor, brandy flavor, yogurt flavor and other blended flavors. The amount of the compound may be 0.00001 to 3%, and the compound may be used within a range not interfering with the effects of the present invention.

When the component (a), (B) or (C) is contained in the perfume, the content of the component (a), (B) or (C) may be used within the above range.

As the active ingredient (F), other active ingredients such as an anti-inflammatory agent such as tranexamic acid and epsilon-aminocaproic acid; enzymes such as dextranase, amylase, protease, mutanase, lysozyme, and lyase; fluorides such as sodium fluoride, sodium monofluorophosphate, stannous fluoride and the like; vitamins such as allantoin chlorohydroxyaluminum, allantoin, chamomile blue, lysozyme chloride, ascorbic acid, etc.; dihydrocholesterol; glycyrrhizin salts; glycyrrhetinic acids; hydrogenated cholesterol; chlorophyll; sodium copper chlorophyllin; thyme, radix Scutellariae, flos Caryophylli, and Hamamelis mollis; copper gluconate; seal peptide (carpopeptide); sodium polyphosphate; a water-soluble inorganic phosphoric acid compound; polyethylene glycol; polyvinylpyrrolidone; sodium lauroyl salicylate; a tartar control agent; a tartar control agent; sodium nitrate; aluminum lactate, and the like. Further, the mixing amount of these effective ingredients is an effective amount within a range not to impair the effects of the present invention.

Examples of the sweetener include sodium saccharin and stevioside.

As the colorant, highly safe water-soluble coloring matters such as blue No.1, green No. 3, yellow No. 4, red No. 105, etc. can be added.

Examples

The present invention will be specifically described below with reference to examples, examples and comparative examples, but the present invention is not limited to the following examples. In the following examples,% represents% by mass unless otherwise specified.

[ Experimental example 1]

Liquid oral compositions (mouth washes) having compositions shown in tables 1 to 3 were prepared by a conventional method, and these compositions were used as samples, and appearance stability and presence or absence of an offensive odor after low-temperature storage were evaluated by the following methods. The results are shown in tables 1 to 3.

< evaluation method of appearance stability >

A450 mL sample of the mouthwash was filled in a 500mL PET (polyethylene terephthalate) container and stored in a thermostatic bath at-5 ℃ for 1 month, and then the appearance stability was visually evaluated according to the following criteria. The samples "o" and "x" were regarded as showing that the precipitation of menthol was suppressed and the appearance stability was acceptable.

Evaluation criteria for appearance stability;

very good: no difference from the initial product was observed, and no needle-like crystals were observed.

O: very trace amounts of dross were visible.

And (delta): a slight amount of crystals were observed to precipitate.

X: needle-like crystals were observed to precipitate.

< method for evaluating the Presence or absence of an odor >

After a sample of 10mL of the mouthwash was contained in the mouth for 30 seconds, the presence or absence of an offensive odor after the gargling was evaluated in the following 3 stages. The average score of 10 persons was calculated, and the score of 2.0 or more was regarded as a pass.

Whether the evaluation criterion is peculiar or not is judged;

and 3, dividing: no peculiar smell

And 2, dividing: smell the peculiar smell slightly

1 minute: smelling peculiar smell

[ Table 1]

The flavors do not include menthol, eugenol, and methyl salicylate (the same below).

[ Table 2]

[ Table 3]

[ Experimental example 2]

The liquid oral compositions (mouth rinses) of nos. 1 to 11 shown in table 1 were used as samples, and the bactericidal effect and cooling sensation were evaluated by the following methods. The results are shown in Table 4 as Nos. 2-1 to 2-11.

< method for evaluating Sterilization Effect against intraoral bacteria >

A simple cell count assay kit for Streptococcus mutans in saliva, Dentocult-SM (Orion diagnostic, Finland), was used for the cell count assay. The number of bacteria in saliva was evaluated in advance according to the method of use of Dentocult-SM, and 10 persons with a score of 2 or more were used as subjects according to the evaluation criteria described below.

The number of Streptococcus mutans in saliva after rinsing with 10mL of the sample mouthwash in the mouth for 30 seconds and 3 hours was measured by the Dentocult-SM, and the bactericidal effect was evaluated according to the evaluation criteria shown below. The average score of 10 was calculated. The smaller the score, the higher the bactericidal effect, and a score of 1.5 or less was evaluated as passed.

Evaluation criteria of bactericidal effect;

and 3, dividing: the number of Streptococcus mutans is 10⁶The above

And 2, dividing: the number of Streptococcus mutans is 10⁵Above and less than 10⁶

1 minute: the number of Streptococcus mutans is less than 10⁵

< method for evaluating Cool feeling >

The mouth was rinsed with 10mL of the sample mouthwash for 30 seconds, and the cooling sensation after rinsing was evaluated in the following 3 stages. The average score of 10 was calculated. The score of 2.0 or more was judged to be acceptable.

Evaluation criteria of cooling sensation after gargling;

and 3, dividing: the appearance of a cool feeling was confirmed

And 2, dividing: slight cooling sensation was confirmed

1 minute: the feeling of coolness cannot be confirmed

[ Table 4]

Claims

1. A liquid oral composition containing 0.001 to 0.15 mass% of (A) menthol without containing parabens, characterized in that the composition contains (B) eugenol and (C) methyl salicylate, and the mass ratio of (B)/(C) is 0.25 to 4 and the mass ratio of ((B) + (C))/(A) is 0.65 or more, and the composition further contains (E) a nonionic surfactant.

2. The liquid oral composition according to claim 1, wherein the eugenol (B) is contained in an amount of 0.00013 to 0.2% by mass, and the methyl salicylate (C) is contained in an amount of 0.00013 to 0.2% by mass.

3. The liquid oral composition according to claim 1 or 2, wherein the total content of eugenol (B) and methyl salicylate (C) is 0.00065 to 0.4% by mass.

4. The liquid oral composition according to claim 1 or 2, wherein the composition further contains (D) ethanol in an amount of 0 to 15% by mass.

5. The liquid oral composition according to claim 1 or 2, wherein the content of the (E) nonionic surfactant is 0.1 to 0.5% by mass, and the (E) nonionic surfactant is 1 or 2 or more selected from polyoxyethylene hydrogenated castor oil having an average molar number of addition of ethylene oxide of 40 to 100 moles, and polyoxyethylene alkyl ether having a carbon chain length of 16 to 18 and an average molar number of addition of ethylene oxide of 10 to 50 moles.

6. The liquid oral composition according to claim 1 or 2, further comprising (F) a cationic bactericidal agent in an amount of 0.01 to 0.1 mass%.

7. A method for suppressing the deposition of menthol in a liquid oral composition, characterized by adding (B) eugenol and (C) methyl salicylate to a liquid oral composition containing 0.001 to 0.15 mass% of (A) menthol without parabens so that the mass ratio of (B)/(C) is 0.25 to 4 and the mass ratio of ((B) + (C))/(A) is 0.65 or more, and adding (E) a nonionic surfactant.