JP2018002660A - Oral composition - Google Patents

Abstract

Provided is a composition for oral cavity in which the stability of appearance including the change with time in a weakly acidic to neutral pH range, and the bitterness and astringency are improved.
A molar ratio (Arel) between an organic acid and a zinc compound is at least Arel = (number of moles of organic acid) / (number of moles of zinc compound) = 0.2 or more. The composition for oral cavity which is.
[Selection] Figure 2

Description

  The present invention relates to an oral composition. More specifically, the present invention relates to a composition for oral cavity that can improve its appearance and palatability. According to the present invention, for example, an oral composition with reduced bitterness, astringency, and astringency can be obtained.

  Human bad breath is usually caused by specific bacteria in the oral cavity (Fusobacterium nucleatum). From such a viewpoint, for the purpose of preventing bad breath, an oral composition using a component having an antibacterial action against these pathogenic bacteria, for example, metals such as copper, zinc and silver has been proposed (Patent Document 1: JP-A 05-163125, Patent Document 2: JP-A 07-165544, Patent Document 3: JP-A 2006-176416, Patent Document 4: JP-A 2007-008843).

  However, oral compositions containing these metals have problems such as metal-specific bitterness, astringency, astringency (in terms of palatability), white turbidity and discoloration (in terms of appearance), etc. In order to use as a thing, there existed big subject in palatability and stability.

  As a method for improving palatability, a combination of polyoxyethylene hydrogenated castor oil and l-menthol (Patent Document 5: Japanese Patent Laid-Open No. 63-8324) A combination of polyhydric alcohol and anethole (Patent Document 6: Special) No. 2004-203894), a combination of l-menthol derivative and N-ethyl-p-menthane-1-carboxamide (Patent Document 7: Japanese Patent Application Laid-Open No. 2003-137755), a combination of betaine-type double-side active agent and sugar alcohol (Patent Document) 8: WO 2010/113688). As a method for improving the transparency of the liquid, addition of an organic acid (Patent Document 9: Japanese Patent Laid-Open No. 60-233008) has been proposed.

  Further, as a method for improving discoloration, a blend of antibacterial metal-supported zeolite (the above-mentioned Patent Document 4) has been proposed.

JP 05-163125 A Japanese Patent Laid-Open No. 07-165544 JP 2006-176416 A JP 2007-008843 A

JP 63-8324 A JP 2004-203894 A JP 2003-137755 A

International Publication No. 2010/113688 JP-A-60-233008 JP 2010-24195 A

  With regard to taste palatability, as a prior art, a combined use of polyoxyethylene hydrogenated castor oil and l-menthol (Patent Document 5: Japanese Patent Laid-Open No. 63-8324), a combined use of polyhydric alcohol and Anethole (Patent Document 6: JP 2004-203894 A) Improvement of the taste of metal salts by using a combination of 11 menthol derivatives and N-ethyl-p-menthane 3 monocarboxamide (Patent Document 7: JP 2003-137755 A) is shown. However, in these prior arts, the effect of improving taste preference is not sufficient.

  Regarding stability, as a prior art, the addition of an organic acid (Patent Document 9: Japanese Patent Laid-Open No. 60-233008, Patent Document 10: Japanese Patent Laid-Open No. 2010-24195) has a low stable pH range. There is room for improvement.

  An object of the present invention is to provide a composition for oral cavity in which the stability of the appearance including a change with the passage of time and the bitterness and astringency are improved in a weakly acidic to neutral pH range. .

  As a result of diligent research, the inventor of the present invention, when blending a zinc compound and citric acid into an oral composition, has a molar ratio (Arel) of the organic acid to the zinc compound of Arel = (number of moles of organic acid). ) / (Number of moles of zinc compound) = 0.2 or more was found to be extremely effective in achieving the above object.

  The composition for oral cavity of the present invention is based on the above knowledge, and contains at least a zinc compound and an organic acid, and the molar ratio (Arel) of the organic acid to the zinc compound is Arel = (number of moles of organic acid). / (Number of moles of zinc compound) = 0.2 or more.

  Some conventional oral compositions contain Zn and citric acid, but in the conventional oral composition, the organic acid has been regarded only as a “mere pH adjusting component”. In other words, it was thought that “Zn + citric acid + α” (α is an essential component for masking expression) is necessary for “masking expression” in the conventional oral composition. Therefore, the “masking expression” in the oral composition in which the minimum combination of the active ingredients is “Zn + organic acid (for example, citric acid)” was first discovered by the present inventors.

  It should be noted that organic acids (for example, citric acid) have been treated only as “mere pH adjusting components” under the above-described recognition (technical common sense) in the prior art. For this reason, the content of the organic acid in the conventional oral composition (that is, the molar ratio Nr = (number of moles of organic acid) / (number of moles of zinc compound)) was set to be quite small.

  In other words, under the technical common sense in the prior art, an organic acid (eg, citric acid) has been considered to have no action of masking the action of Zn (eg, bitterness, astringency, astringency). It was. On the other hand, the present inventor has first found a “Zn masking action” in an organic acid (for example, citric acid) itself as a component of the oral composition. That is, the present invention is characterized by positively utilizing the “Zn masking action” of an organic acid as a component of the oral composition first discovered in this way.

The “Zn masking action” of the organic acid can be defined quantitatively by the “Euclidean distance” described later. As shown in the example of “Example 5” to be described later, the degree of masking of the taste (astringency, astringency, etc.) of Zn was determined according to the “base formulation—zero organic acid control” in “Example 5”. “Euclidean distance between sample (zinc compound = 0.07%)” is “E ₀ ” (that is, reference), “sample in which organic acid is blended in base formulation—sample in which zinc compound and organic acid are blended in base formulation When “Euclidean distance” is “E _S ”, the ratio (E _rel (%)) = 100 × (E _S / E ₀ ) or the difference (E ₀ −E _S ) The degree of masking of the target sample can be defined quantitatively.

  The present invention can include, for example, the following aspects.

  [1] It contains at least a zinc compound and an organic acid, and the molar ratio (Arel) between the organic acid and the zinc compound is Arel = (number of moles of organic acid) / (number of moles of zinc compound) = 0.2 or more. The composition for oral cavity characterized by being.

  [2] The composition for oral cavity according to [1], wherein the molar ratio of the organic acid to the zinc compound is Arel = 0.5-20.

  [3] The oral cavity according to any one of [1] or [2], wherein the organic acid is at least one selected from the group consisting of citric acid, acetic acid, glycine, malic acid, gluconic acid, and fumaric acid. Composition.

  [4] The composition for oral cavity is a fluid composition containing water, and the blending amount of the zinc compound is 0.001 to 0.2% by mass of the whole composition. The composition for oral cavity of any one.

[5] containing the zinc compound, but does not contain the organic acid control (control) with respect to the Euclidean distance of the composition (E _0), the Euclidean distance of said zinc compound and oral compositions containing an organic acid (E _S ) Relative ratio (E _rel (%)) = 100 × (E _S / E ₀ ) is 85% or less, the composition for oral cavity according to any one of [1] to [4].

  The composition for oral cavity according to the present invention feels astringent taste and astringent feeling due to zinc by blending in a limited combination of a ratio of a zinc compound such as zinc chloride and an organic acid (for example, citric acid). In addition, it is possible to suppress bad breath with a composition that maintains the palatability of taste. In addition, high stability over time can be maintained.

  Furthermore, in the prior art, the solvent is usually acidic in order to maintain the stability of the zinc compound, but in the present invention, good stability is maintained even in a weakly acidic to neutral range. It becomes possible. Thus, according to the aspect of the present invention in which the composition for oral cavity is in a weakly acidic to neutral range, while avoiding making the oral cavity an “acidic” situation that may cause decalcification of teeth, The composition for oral cavity can be used for the purpose of mouthwashing with peace of mind.

11 is a bar graph obtained by plotting the data of “Euclidean distance” of the sample shown in Table 10 on a bar graph. It is the graph obtained by plotting the data (samples 2-11 in Tables 7-9) calculated from the measured value of the sample shown in Table 10 on an XY plane. A straight line was drawn between the samples for which the “Euclidean distance” was calculated for easy understanding. It is the graph obtained by plotting the sensory evaluation data (actual value; horizontal axis) of the sample shown in Table 10 against the data (predicted value; vertical axis) predicted by the calibration curve of the sensory evaluation score. This “predicted value” is predicted by PLS regression (the following URL can be referred to if necessary). URL: https://sites.google.com/site/esitomonokai/jie-xi-bu-wu/tahenryo/plsniyoru-hui-gui

13 is a bar graph obtained by plotting the data of “Euclidean distance” of the sample shown in Table 12 on a bar graph. It is the graph obtained by plotting the data (Sample 4, 9, 12-15 in Tables 7-9) plotted on the XY plane from the measured value of the sample shown in Table 12. A straight line was drawn so that it was easy to discriminate between samples for which the “Euclidean distance” was calculated. It is the graph obtained by plotting the sensory evaluation data (actual value; horizontal axis) of the sample shown in Table 12 against the data (predicted value; vertical axis) predicted by the calibration curve of the sensory evaluation score.

15 is a bar graph obtained by plotting the data of “Euclidean distance” of the sample shown in Table 14 on a bar graph. 15 is a graph obtained by plotting data (samples 5, 10, and 16 to 21 in Tables 7 to 9) calculated from the measured values of the samples shown in Table 14 on an XY plane. A straight line was drawn so that it was easy to discriminate between samples for which the “Euclidean distance” was calculated. It is the graph obtained by plotting the sensory evaluation data (actual value; horizontal axis) of the sample shown in Table 14 against the data (predicted value; vertical axis) predicted by the calibration curve of the sensory evaluation score.

17 is a bar graph obtained by plotting the data of “Euclidean distance” of the sample shown in Table 16 on a bar graph. It is the graph obtained by plotting on the XY plane the data computed from the measured value of the sample shown in Table 16 (samples 5, 10, 22-24 in Tables 7-9). A straight line was drawn so that it was easy to discriminate between samples for which the “Euclidean distance” was calculated. It is the graph obtained by plotting the sensory evaluation data (actual value; horizontal axis) of the sample shown in Table 16 against the data (predicted value; vertical axis) predicted by the calibration curve of the sensory evaluation score.

19 is a bar graph obtained by plotting the data of “Euclidean distance” of the sample shown in Table 18 on a bar graph. It is the graph obtained by plotting the data (Sample 5, 10, 25-28 in Tables 7-9) plotted on the XY plane from the measured value of the sample shown in Table 18. A straight line was drawn so that it was easy to discriminate between samples for which the “Euclidean distance” was calculated. It is the graph obtained by plotting the sensory evaluation data (actual value; horizontal axis) of the sample shown in Table 18 against the data (predicted value; vertical axis) predicted by the calibration curve of the sensory evaluation score.

Comparison with other patents
It is the graph obtained by plotting the data (Table 21) calculated from the measured value of the sample shown in Table 20 on the XY plane. A straight line was drawn so that it was easy to discriminate between samples for which the “Euclidean distance” was calculated. 21 is a bar graph obtained by plotting the data of “Euclidean distance” of the sample shown in Table 20 on a bar graph. It is the graph obtained by plotting the sensory evaluation data (actual value; horizontal axis) of the sample shown in Table 20 against the data (predicted value; vertical axis) predicted by the calibration curve of the sensory evaluation score.

It is the graph obtained by plotting the data (Table 25) computed from the measured value of the sample shown in Table 24 on an XY plane. A straight line was drawn between the samples for which the “Euclidean distance” was calculated for easy understanding. 25 is a bar graph obtained by plotting the data of “Euclidean distance” of the sample shown in Table 24 on a bar graph. It is the graph obtained by plotting the sensory evaluation data (actual value; horizontal axis) of the sample shown in Table 24 against the data (predicted value; vertical axis) predicted by the calibration curve of the sensory evaluation score. It is the graph obtained by plotting the sensory evaluation data (actual value; horizontal axis) of the sample shown in Table 24 against the data (predicted value; vertical axis) predicted by the calibration curve of the sensory evaluation score.

30 is a bar graph obtained by plotting the data of “Euclidean distance” of the sample shown in Table 29 on a bar graph. It is the graph obtained by plotting the data (Table 30) computed from the measured value of the sample shown in Table 29 on an XY plane. A straight line was drawn between the samples for which the “Euclidean distance” was calculated so as to be easily distinguished. It is the graph obtained by plotting the sensory evaluation data (actual value; horizontal axis) of the sample shown in Table 29 against the data (predicted value; vertical axis) predicted by the calibration curve of the sensory evaluation score.

  Hereinafter, the present invention will be described more specifically with reference to the drawings as necessary. In the following description, “parts” and “%” representing the quantity ratio are based on mass unless otherwise specified.

(Oral composition)
The oral composition of the present invention contains at least a zinc compound and an organic acid, and the molar ratio (Arel) between the zinc compound and the organic acid is Arel = (mol number of organic acid) / (mol number of zinc compound) = It is characterized by being 0.2 or more.
(Zinc compound)
The zinc compound that can be used in the present invention is not particularly limited as long as it is a “compound” containing Zn and can be “combined” with an organic acid (for example, by mixing). The zinc compounds can be used in combination of two or more as required. In this invention, it is preferable that it is a zinc compound which gives Zn ion in the water of pH 5-8 from the point of the usability | use_condition fall prevention of an oral composition. More specifically, the following zinc compounds can be suitably used.

(Suitable zinc compound)
Zinc chloride, PCA zinc (zinc salt of pyrrolidone carboxylic acid), zinc gluconate, zinc sulfate, zinc citrate, zinc malate, zinc salicylate, zinc lactate, zinc paraphenolsulfonate, zinc acetate, zinc fluoride, zinc nitrate , Zinc formate, Zinc bromate, Zinc benzoate, Zinc hydroxide, Zinc fluorophosphate, Zinc oxide, Zinc tartrate, Zinc glycine, Zinc sorbate, Zinc mandelate, Zinc pantothenate, Zinc glycerophosphate, Zinc cinnamate , Zinc phytate, zinc pyrophosphate, zinc aspartate, zinc glutamate, zinc oxalate, etc.

(Organic acid)
As long as the “combination” (for example, by mixing) with the zinc compound is possible, the organic acid that can be used in the present invention is not particularly limited. These organic acids can be used in combination of two or more as required. In this invention, it is preferable that it is an organic acid which gives an organic acid ion in the water of pH 5-8 from the point of the usability | use_condition fall prevention of an oral composition. More specifically, the following organic acids can be suitably used.

(Suitable organic acid)
Citric acid, malic acid, gluconic acid, fumaric acid, tranexamic acid, epsilon aminocaproic acid, glycyrrhetinic acid, pyrrolidone carboxylic acid, tartaric acid, lactic acid, maleic acid, aspartic acid, succinic acid, fumaric acid, glucuronic acid, adipic acid, phytic acid etc.

(Molar ratio of zinc compound to organic acid)
In the oral composition of the present invention, the ratio (Arel) of the number of moles of the zinc compound and the organic acid is Arel = (number of moles of the organic acid) :( number of moles of the zinc compound) = 0.2 or more.

(Suitable lower limit of the number of moles of organic acid)
The ratio Arel is preferably 0.25 or more, more preferably 0.3 or more, further 0.35 or more, further 0.4 or more, from the viewpoint of suitably exhibiting the effect of the organic acid. Furthermore, 0.45 or more, further 0.5 or more, further 0.55 or more, further 0.6 or more, further 0.65 or more, further 0.7 or more, further 0.8 or more. Further, 1.0 or more, further 1.2 or more, further 1.5 or more, further 2.0 or more, further 2.5 or more, further 3.0 or more, further 3.5 or more, Furthermore, it is 4.0 or more, further 4.5 or more, further 5.0 or more, further 5.5 or more, further 6.0 or more, further 6.5 or more, further 7.0 or more, Is 7.5 or more, further 8.0 or more, further 8.5 or more, further 9.0 or more, further 9.5 or more, further 10.0 or more, further 10.5 or more, 11.0 above, and particularly preferably 11.5 or more.

(Suitable upper limit of the number of moles of organic acid)
The upper limit of the molar ratio (Arel) is not particularly limited, but from a practical viewpoint (for example, suppression of excessive irritation from the oral composition), Arel is preferably 20 or less, Furthermore, it is preferable that it is 19 or less, further 18 or less, further 17 or less, further 16 or less, further 15 or less, and further 14 or less.

  In the present invention, the range of the molar ratio (Arel) is, for example, Arel = (of the organic acid) from the viewpoint of suitably exhibiting the effect of the organic acid and suppressing excessive irritation from the oral composition. The number of moles) / (number of moles of zinc compound) is preferably 0.5 to 20, more preferably 0.6 to 19, further 0.7 to 18, further 0.8 to 17, and even 0. .9 to 16, preferably 1 to 15, more preferably 1.1 to 14, and further preferably 1.2 to 13.

(Preferable combination of zinc compound and organic acid)
In the present invention, a combination of a zinc compound and an organic acid that can be suitably used is, for example, as follows.
<Zinc compound><Organicacid>
Zinc chloride Citric acid Zinc chloride Malic acid Zinc chloride Gluconic acid Zinc chloride Fumaric acid Zinc chloride Acetic acid Zinc chloride Glycine Zinc chloride EDTA-2Na
Zinc chloride Glutamic acid Zinc chloride Tartaric acid Zinc pyrrolidone carboxylic acid Zinc chloride Adipic acid Zinc formate Malic acid Zinc gluconate Citric acid Zinc gluconate Malic acid Zinc sulfate Citric acid Zinc sulfate Malate PCA zinc Citric acid

(Form of oral composition)
The form of the oral composition of the present invention is not particularly limited as long as the effect of the oral composition can be exhibited. That is, the form of the oral composition of the present invention may be, for example, any of solid, fluid, and other (gel, paste, etc.). “Solid” forms include, for example, amorphous or regular (eg, tablet) masses, powders (eg, powders, granules). Examples of the fluid include a liquid having an arbitrary viscosity, a viscous fluid, a dispersion, and an emulsion.

  More specific oral composition forms include, for example, toothpastes, powder toothpastes, water toothpastes, liquid toothpastes, and other toothpastes, mouthwashes, mouthwashes, chewing gums, oral pasta, mouth fresheners, and the like. However, the present invention is not limited to this. Moreover, according to each dosage form, the arbitrary component which can be generally used for the said dosage form can be mix | blended in the range which does not interfere substantially with the effect of this invention.

(PH)
The pH of the oral composition of the present invention is not particularly limited, but the pH is almost weakly acidic to neutral from the viewpoint that it is easy to obtain an oral composition having excellent aging stability and a deodorizing function. It is preferable to set the range. More specifically, the pH range of the oral composition of the present invention is as follows. As the pH measurement method and conditions in the present invention, the following methods and conditions can be preferably used.
Measuring device: pH meter: pH METER F-22 (HORIBA)
Measurement method: After performing “three-point calibration” using standard solutions in the order of pH 7, pH 4, and pH 9, the pH of the “sample solution” that is the object of pH measurement is measured. In addition, about the detail of a measuring method and conditions, the following site can be referred as needed.
<About 3-point calibration>
URL: http://www.horiba.com/jp/application/material-property-characterization/water-analysis/water-quality-electrochemistry-instrumentation/the-story-of-ph-and-water-quality/qa- ph / calibration / 1 /
<Standard solution used for calibration>
URL: http://www.horiba.com/jp/application/material-property-characterization/water-analysis/water-quality-electrochemistry-instrumentation/the-story-of-ph-and-water-quality/qa- ph / calibration / 2 /
<About pH measurement in general>
URL: http://www.horiba.com/jp/application/material-property-characterization/water-analysis/water-quality-electrochemistry-instrumentation/the-story-of-ph-and-water-quality/the- basis-of-ph /

  In addition, regardless of the form of the oral cavity composition of the present invention (that is, whether the form is solid, fluid, or other (gel, paste, etc.)), “Example” described later The pH of the oral composition of the present invention is measured under the conditions described in (1) (ie, “solution” state of a predetermined formulation).

(Preferable pH range)
The pH of the composition of the present invention is preferably 5.0 to 7.6, more preferably 5.1 to 7.5, further 5.2 to 7.4, further 5.3 to 7.3, and further It is preferably 5.4 to 7.2, more preferably 5.5 to 7.1, further 5.6 to 7.0, and further preferably 5.7 to 7.1.

(Euclidean distance)
The “masking effect” of the composition of the present invention can be suitably defined by the “Euclidean distance” described later. As such “Euclidean distance” measurement methods and conditions, the measurement methods and conditions described in the examples described later can be suitably used.

(Significance of Euclidean distance)
Hereinafter, the significance of the Euclidean distance will be described using actually obtained data (“Example 5” described later). The outline of the data obtained in “Example 5” (Table 10) is as follows.

(Sample 2 = Base prescription and Euclidean distance between each sample)
This measurement compares the Euclidean distance between a sample with an organic acid added to the base formulation and a sample with an additional zinc compound. Thereby, it can be shown whether the taste of only the zinc compound in each sample can be masked. Refer to Table XX for details of each sample measured. Below, Arel = (number of moles of organic acid) / (number of moles of zinc compound) and Euclidean distance between samples are shown.
<Measurement sample><Euclidean distance (relative%)>
Samples 2 and 7 (in samples 7-11, zinc chloride 0.07%; Arel = 0)
1286
Samples 3 and 8 (Arel = 0.5) 559 (43.5%)
Samples 4 and 9 (Arel = 1) 202 (15.7%)
Samples 5 and 10 (Arel = 2) 112 (8.7%)
Samples 6 and 11 (Arel = 10) 75.9 (5.9%)

  That is, in the example of “Example 5”, the Euclidean distance between the paired samples is shortened as the amount of citric acid increases. Therefore, this data shows that by increasing the amount of citric acid, the masking of zinc taste (astringency and astringency) can be “stronger” (smaller as the Euclidean distance).

As described above, the degree of masking of the zinc taste (astringency and astringency) is determined by the Euclidean distance between the “paired samples” (for example, “Euclidean distance of sample 2 to sample 7”, “sample 3” described above). -It can be defined quantitatively by the Euclidean distance of the sample 8 "). Therefore, in the present invention, "base formula-Euclidean distance between zero organic acid control sample (zinc compound = 0.07%)" as a reference (E ₀ ) When the Euclidean distance between samples in which a zinc compound and an organic acid are blended in a sample-base formulation was used as a reference (E _S ), their relative value (E _rel (%)) = 100 × (E _S / E ₀ ), The degree of masking of the sample to be measured can be defined quantitatively.

(Preferred Euclidean distance)
In the composition for oral cavity of the present invention, the value of E _rel (%) = 100 × (E _S / E ₀ ) is preferably 85% or less. The value of E _rel (%) is preferably 80% or less, more preferably 75% or less, further 72% or less, further 70% or less, further 65% or less, further 60% or less, 55% or less, further 50% or less, further 48% or less, further 46% or less, further 44% or less, further 42% or less, further 40% or less, further 38% or less, further 36%. In the following, further 34% or less, further 32% or less, further 30% or less, further 28% or less, further 26% or less, further 24% or less, further 22% or less, further 20% or less, Furthermore, it is 18% or less, further 16% or less, further 14% or less, further 12% or less, further 10% or less, further 9% or less, further 8% or less, especially 7% or less. Is preferred.

  In addition, regardless of the form of the oral cavity composition of the present invention (that is, whether the form is solid, fluid, or other (gel, paste, etc.)), “Example” described later The “Euclidean distance” of the oral composition of the present invention is measured under the conditions described in (1) (ie, “solution” state of a predetermined formulation).

(Fluid embodiment)
In the embodiment in which the oral composition of the present invention is in a fluid state, any liquid component can be used. As such a liquid component, for example, water, alcohols, and a mixture thereof can be appropriately used. When the oral composition of the present invention is in a fluid (for example, liquid) form, the amount of the zinc compound is based on the whole composition in the form of fluid from the viewpoint of preventing the disadvantage when Zn is excessive ( 100% by mass) is preferably 2% by mass or less. The blending amount of this zinc compound is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, further 1.4% by mass or less, further 1.2% by mass or less, and further 1% by mass. % Or less, further 0.8% by mass or less, further 0.6% by mass or less, further 0.4% by mass or less, more preferably 0.3% by mass or less, and particularly preferably 0.2% by mass or less. preferable.

  On the other hand, from the viewpoint of suitable effects of the zinc compound, the blending amount of the zinc compound is preferably 0.001% by mass or more based on the whole fluid composition (100% by mass). The blending amount of the zinc compound is preferably 0.002% by mass or more, more preferably 0.004% by mass or more, further 0.006% by mass or more, further 0.008% by mass or more, Is 0.01% by mass or more, further 0.015% or more, further 0.02% by mass or more, further 0.025% by mass or more, further 0.03% by mass or more, and further 0.035% by mass. In addition, 0.04% by mass or more, further 0.045% by mass or more, further 0.05% by mass or more, further 0.055% by mass or more, 0.06% by mass or more, and further 0.065% by mass. % By mass or more, further 0.07% by mass or more, further 0.075% by mass or more, further 0.08% by mass or more, further 0.085% by mass or more, further 0.9% by mass or more, Is preferably 0.95% by mass or more, more preferably 0.1% by mass or more. Arbitrariness.

  Further, from the viewpoint of the balance between the disadvantage prevention when Zn is excessive and the preferable effect of the zinc compound, the blending amount of the zinc compound is, for example, 0 on the basis of the whole fluid composition (100% by mass). It is preferable that it is 0.001-0.2 mass%. The blending amount of the zinc compound is preferably 0.002 to 0.19% by mass, more preferably 0.004 to 0.19% by mass, based on the whole fluid composition (100% by mass). %, Further 0.006 to 0.18% by mass, further 0.007 to 0.017% by mass, and more preferably 0.008 to 0.017.

(water)
Although the water which can be used in the aspect which makes the composition for oral cavity of this invention a fluid state is not restrict | limited in particular, It is preferable that it is purified water. From the viewpoint of stabilizing the pH, the water is preferably “ion exchange water”.

(Suitable viscosity)
In the aspect which makes the composition for oral cavity of this invention into a fluid state, the suitable viscosity (Vs) of this fluid is as follows. As such “viscosity” measurement method / conditions, for example, the following measurement methods / conditions can be preferably used.
・ Viscometer: B type viscometer BM type (Toki Sangyo), model BMII
・ Rotor: No. 1 or No. 2 or No. 3 or No. 4 (depending on viscosity)
・ Wetted part: SUS304 / 303
Rotational speed: 6 or 12 or 30 or 60 rpm (depending on viscosity)
For details of this viscometer, for example, the following Toki Sangyo Co., Ltd. site (including the references described at the end of the pdf file) can be referred to.
URL: http://www.tokisangyo.co.jp/pdf/viscometer/B2.pdf

(Mode of relatively low viscosity)
In the embodiment in which the oral composition of the present invention is a fluid having a relatively low viscosity, the preferred viscosity of the oral composition is not particularly limited. The suitable viscosity of the composition for oral cavity in such an aspect is usually 70 mPa · s or less.

(Aspect in which the composition for oral cavity is a fluid having a relatively high viscosity)
A mode in which the oral composition of the present invention is a fluid having a relatively high viscosity (for example, toothpastes such as toothpastes, powder dentifrices, water dentifrices, liquid dentifrices, mouthwashes, mouthwashes, chewing gums, oral pasta, cool in mouth In the aspect of an agent or the like, the preferable viscosity of the oral composition is preferably 100 mPa · s or more, for example. The viscosity is preferably 100 to 10,000 mPa · s, more preferably 200 to 5000 mPa · s, and further preferably 500 to 1000 mPa · s.

(Other ingredients)
As described above, the composition for oral cavity of the present invention comprises a zinc compound and an organic acid (for example, citric acid) as essential components. In the present invention, the following optional components may be included in the oral composition (for example, by “adding” to the essential components) as necessary. In addition, such “other components” can be used in a range that does not substantially inhibit the gist of the present invention (for example, a range that does not substantially inhibit a suitable range such as the Euclidean distance).

(Fungicide)
In the present invention, as a bactericidal agent to be used in combination with these, one kind selected from a phenolic antibacterial agent, an etheric antibacterial agent, a quaternary ammonium antibacterial agent and a pyridinium antibacterial agent alone or in combination of two or more kinds. Can be blended.

  Here, as a phenolic antibacterial agent, triclosan (2,4,4′-trichloro-2 ′) is used as a general name biosol, thymol, carvacrol known as isomers of isopropylmethylphenol, and an etheric antibacterial agent. -Hydroxydiphenyl ether), quaternary ammonium antibacterial agents include benzalkonium chloride, benzethonium chloride, and pyridinium antibacterial agents include, but are not limited to, cetylpyridinium chloride. Among these bactericides, isopropylmethylphenol, triclosan, and cetylpyridinium chloride can be preferably used.

  The total amount of the bactericidal agent selected from the above-mentioned phenolic antibacterial agent, etheric antibacterial agent, quaternary ammonium antibacterial agent and pyridinium antibacterial agent is 0.0001 to 5% of the whole composition, particularly 0.0005. 2%, especially 0.001-1% is preferred. If the blending amount is less than 0.0001%, a sufficient blending effect may not be obtained, and an excellent bactericidal effect may not be exhibited. If the blending amount exceeds 5%, it is disadvantageous in terms of stability, usability, cost, etc. of the preparation. It may become.

  In addition, when blending an antibacterial agent such as triclosan with a low water solubility and a phenolic antibacterial agent such as isopropylmethylphenol among these disinfectants, the disinfectant is preliminarily solubilized with a solvent such as alcohols, It is preferable to mix | blend with a formulation or mix | blend with a surfactant compounding formulation.

(Alcohols)
In this case, examples of alcohols include monohydric alcohols such as ethanol, isopropanol, butanol, propanol, glycerin, ethylene glycol, diethylene glycol, hexylene glycol, butylene glycol, pentanediol, propylene glycol, sorbit, polyethylene glycol 200 to 20000, Polyhydric alcohols such as polypropylene glycol 300 to 4000 can be mentioned, and one or more of these can be blended.

  When the alcohols are blended, the blending method may be blended in the fragrance, may be added separately, or may be blended in both (both in the fragrance and separately added). The total blending amount is preferably 0.1 to 70%, more preferably 0.1 to 60% of the entire composition in terms of pure content. If the blending amount is less than 0.1%, the above bactericidal agent may not be solubilized, and if it exceeds 70%, there may be a problem in terms of palatability or formulation.

(Surfactant)
As the surfactant, one or more selected from anionic surfactants, nonionic surfactants and zwitterionic surfactants may be blended. Examples of the anionic surfactant include sodium alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, sodium N-acyl sarcosinate such as sodium N-lauroyl sarcosinate, sodium N-myristoyl sarcosinate, sodium dodecylbenzene sulfonate, Hydrogenated coconut fatty acid monoglyceride sodium monosulfate, sodium lauryl sulfoacetate, N-acyl glutamate such as sodium N-palmitoyl glutamate, N-methyl-N-acyl taurine sodium, N-methyl-N-acylalanine sodium, α-olefin Sodium sulfonate and sodium dioctyl sulfosuccinate can be used. Nonionic surfactants include sugar fatty acid esters such as sucrose fatty acid esters, maltose fatty acid esters, and lactose fatty acid esters, sugar alcohol fatty acid esters such as maltitol fatty acid esters and lactitol fatty acid esters, and polyoxyethylene sorbitan monolaurate. Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene fatty acid esters such as polyoxyethylene hydrogenated castor oil, lauric acid mono- or diethanolamide, fatty acid diethanolamides such as myristic acid mono- or diethanolamide, For sorbitan fatty acid ester, fatty acid monoglyceride, polyoxyethylene higher alcohol ether, polyoxyethylene polyoxypropylene Coalescence, can be used polyoxyethylene polyoxypropylene fatty acid ester. Examples of zwitterionic surfactants include N-alkyldiaminoethylglycine such as N-lauryldiaminoethylglycine and N-myristyldiaminoethylglycine, N-alkyl-N-carboxymethylammonium betaine, and 2-alkyl-1-hydroxyethylimidazoline. Betaine sodium can be used.

  When the surfactant is blended, the blending amount is preferably 0.1 to 20%, particularly preferably 0.2 to 10% of the entire composition. If the blending amount is less than 0.1%, the bactericidal agent cannot be solubilized and a sufficient bactericidal effect may not be obtained. If it exceeds 20%, there may be a problem in formulation in terms of palatability.

(Additive in dentifrice embodiment)
For example, in the case of dentifrices, various abrasives, wetting agents, binders, sweeteners, fragrances, coloring agents, preservatives, and other active ingredients can be used.

  Examples of the abrasive include silica-based abrasives such as silica gel, precipitated silica, aluminosilicate, zirconosilicate, dicalcium phosphate dihydrate and anhydrous, calcium pyrophosphate, calcium carbonate, aluminum hydroxide, alumina, magnesium carbonate , Tertiary magnesium phosphate, zeolite, zirconium silicate, tertiary calcium phosphate, hydroxyapatite, quaternary calcium phosphate, synthetic resin-based abrasive and the like. The blending amount of these abrasives is preferably 2 to 40%, particularly 10 to 30% of the entire dentifrice composition.

  Examples of the wetting agent include sorbit, glycerin, propylene glycol, xylit, malt, lactit and the like, and sorbit and xylit are particularly preferable. These blending amounts are preferably 5 to 50%, particularly 20 to 45% of the entire composition.

Examples of the binder include sodium carboxymethyl cellulose, hydroxyethyl cellulose, carrageenan, guar gum, sodium alginate, cationized cellulose, montmorillonite, gelatin, sodium polyacrylate, and the like.
Although the compounding quantity of a binder can be adjusted with a dosage form, for example, 0.1-5% can be mix | blended with a toothpaste, and 0-5% can be mix | blended with a liquid dentifrice and a mouthwash.

  Examples of the sweetener include saccharin sodium, and examples of the preservative include paraoxybenzoic acid ester and sodium benzoate.

  Perfumes include peppermint oil, spearmint oil, anise oil, eucalyptus oil, winter green oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, mandarin oil, Lime oil, lavender oil, rosemary oil, laurel oil, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, grapefruit oil, sweetie Natural fragrances such as oil, bran oil, Iris concrete, absolute peppermint, absolute rose, orange flower, and processing of these natural fragrances (front reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction, essence Scented and powdered scents, and mentor , Carvone, anethole, cineol, methyl salicylate, cinnamic aldehyde, eugenol, 3-l-mentoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted paramentane -3-Carboxamide, pinene, octyl aldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allylcyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone , Hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, ethanol Oral compositions such as single flavors such as luthioacetate, and other flavors such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, etc. It can be used in combination with known perfume materials used in the above.

  Various active ingredients include those other than the above essential ingredients, for example, fluorides such as sodium fluoride, potassium fluoride, stannous fluoride, strontium fluoride, sodium monofluorophosphate, potassium salt of orthophosphoric acid, sodium Water-soluble phosphate compounds such as salts, glucanases such as dextranase and mutanase, allantoinchlorohydroxyaluminum, hinokitiol, ascorbic acid, lysozyme chloride, glycyrrhizic acid and its salts, sodium chloride, azulene, copper chlorophyllin sodium, copper gluconate, etc. Copper compounds, aluminum lactate, strontium chloride, potassium nitrate, berberine, hydroxamic acid and its derivatives, sodium tripolyphosphate, zeolite, amylase, methoxyethylene, maleic anhydride copolymer, polyvinyl Pyrrolidone, epi-dihydro cholesterol, benzethonium chloride, dihydrocholesterol, trichlorocarbanilide, Japanese angelica root soft extract, Phellodendron bark extract, clove, rosemary, scutellaria root, include extracts, such as safflower. In addition, the said active ingredient can be mix | blended in an effective amount in the range which does not prevent the effect of this invention.

  As the colorant, Blue No. 1, Yellow No. 4, Red No. 102, titanium dioxide and the like can be blended in usual amounts.

  The material in particular of the container which accommodates the composition for oral cavity of this invention is not restrict | limited, Usually, the container used for the composition for oral cavity can be used. Specifically, plastic containers such as polyethylene, polypropylene, polyethylene terephthalate, and nylon can be used.

  Hereinafter, the present invention will be described more specifically with reference to examples.

<Measurement method and measurement conditions for each physical property>
In the following examples, the following “measurement methods and measurement conditions” are used in principle (that is, unless otherwise specified).

<PH>
• Use the measurement method and conditions described above. For example, main methods and conditions are as follows.
Measuring device: pH meter: pH METER F-22 (HORIBA)
Measurement method: After performing “three-point calibration” using standard solutions in the order of pH 7, pH 4, and pH 9, the pH of the “sample solution” that is the object of pH measurement is measured.

<Viscosity>
• Use the measurement method and conditions described above. For example, main methods and conditions are as follows.
・ Viscometer: B type viscometer BM type (Toki Sangyo), model BMII
・ Rotor: No. 1 or No. 2 or No. 3 or No. 4 (depending on viscosity)
・ Wetted part: SUS304 / 303
・ Rotational speed: 6 or 12 or 30 or 60 rpm

<Quantitative determination of zinc>
Apparatus: X-LAB energy dispersive X-ray fluorescence spectrometer SPECTRO XEPOS (SPECTRO Analytical Instruments)
Analysis software: X-LAB PRO
X-ray tube: Fine focus End window type X-ray tube Detector: X-Flash light
Measuring method: An aqueous solution of each zinc compound concentration (example: 0.01, 0.03, 0.05%) is prepared. About 4.0 g of the adjusted solution, using a SPECTRO XEPOS apparatus, water is blanked and a calibration curve is created. About 4.0 g of sample liquid, X-ray intensity | strength is calculated | required using a SPECTRO XEPOS apparatus, and the density | concentration of a zinc compound is calculated | required from a calibration curve.
-In addition, about the detail of the measurement using this "SPECTRO XEPOS", the following site can be referred as needed.
URL: http://www.spectro.jp/products/xrf/spectro-xepos/
-For details of general energy dispersive X-ray fluorescence analysis, the following site can be referred to as necessary.
URL: http://techno-x.co.jp/en/files/nyuumon.pdf#search='technox.co.jp%2Fen%2Ffiles%2Fnyuumon.pdf '

<Quantification of organic acid>
Apparatus: Liquid Chromatograph 1220 Infinity LC (Agilent)
Column: Inert Sustain C18
Mobile phase: 50 mM ammonium dihydrogen phosphate adjusted to pH 2.0 with phosphoric acid Column temperature: 40 ° C.
Detector: Variable wavelength detector (VWD) 210 nm
Method: After weighing each organic acid to about 100 ppm, a solution diluted with water is used as a sample solution and injected into a liquid chromatograph for analysis. An internal standard method is used for quantification.
In the “internal standard method”, as the “internal standard” substance, for example, one or more substances selected from the following substances can be used.
"Internal standard" substances: malonic acid, succinic acid, fumaric acid-For details of measurement using this "1220 Infinity LC", the following sites can be referred to as necessary.
URL: http://www.chem-agilent.com/contents.php?id=1001324
・ For details on other liquid chromatography conditions suitable for organic acid analysis, as required, the Analytical Society of Japan, Kanto Branch, “High-Performance Liquid Chromatography Handbook, Rev. 2”, No. 385 388 pages, 2000, published by Maruzen Co., Ltd. can be referred to.

(Main Euclidean distance measurement methods and conditions)
・ Measuring equipment: Electronic taste system ASTREE II (Astree II; manufactured by Alpha Moss Japan Co., Ltd.)
・ Measurement environment: 25 ° C., normal pressure ・ Analysis software> Alpha Soft
Computer name: DELL OPTIPLEX 7010
The detailed measurement method and measurement conditions of “Euclidean distance” will be described later.

Example 1
(Preparation of oral composition base formulation A)
According to the formulations shown in Table 1 and Table 2 below, “Base Formula A” used for preparation of the oral composition was prepared. This “base formulation A” is mainly a base formulation used in preparing the oral composition according to the present invention (this “base formulation A” is the same formulation as “sample 2” in Table 5 described later). Is).

For example, this “base formulation A” can be prepared in the following manner. That is, in a Pyrex glass container (beaker) with an appropriate capacity, while stirring at 300 rpm with a stirrer (manufactured by ASONE, trade name: REXIM RSH-1DN), in each container in the following order: Ingredients added.
(1) Propylene glycol (wetting agent)
(2) Methyl paraben (preservative)
(3) Polyoxyethylene hydrogenated castor oil (solubilizer)
(4) Fragrance (flavoring agent)
(5) Purified water-1st time (base; add about 20-30% of the total amount here)
(6) Cetylpyridinium chloride (preservative)
(7) Xylitol (sweetener)
(8) Dipotassium glycyrrhizinate (sweetener)
(9) Glycerin (wetting agent)
(10) Na hydroxide (pH adjuster)
(11) Second time of purified water (base; add about 80-70% of the total amount, and finally adjust the amount)

  That is, the lipophilic component is added prior to the addition of the “fifth” water. However, the addition order of the “sixth” to “10th” components after the “sixth” does not necessarily have to be the above order.

(Table 1)

Example 2
(Preparation of oral composition base formulation B)
“Base formulation B” used for preparation of the oral composition was prepared in the same procedure as in Example 1 except that the formulation in Table 2 was followed. This “base formulation B” is the same formulation as “base formulation of“ Example 6 ”in Japanese Patent Application Laid-Open No. 2004-203894” and “sample 1” in the table described later).

(Table 2)

(Preparation of oral composition base formulation C)
A “base formulation C” used for preparation of the oral composition was prepared in the same manner as in Example 1 except that the formulation in Table 3 was followed. This “base formulation C” is the same formulation as “base formulation of“ Example 5 ”in Japanese Patent Application Laid-Open No. 2004-203894” and “sample 5” in the table described later).

(Table 3)

(Preparation of oral composition base formulation D)
A “base formulation D” used for preparation of the oral composition was prepared in the same procedure as in Example 1 except that the formulation in Table 4 was followed. This “base prescription D” is the same prescription as “base prescription of“ Example 5 ”of Japanese Patent Publication No. 7-47531” and “sample 9” in the table described later).

(Table 4)

Example 3
(Preparation of oral composition)
In accordance with the prescriptions in Table 5 and Table 6 below, oral composition No. 1 to 28 were prepared (components of each formulation are collectively shown in Table 3). In this example, “base formulation” is “base formulation A” prepared in Example 1 (“sample 2” in Table 5 is also this “base formulation A”).

  For example, an example of the oral composition of the present invention (based on Formulation No. 8) can be prepared by the following method. Namely, 0.07 g (0.51 mmol) of zinc chloride previously dissolved in 60 g of “base formulation A” placed in a Pyrex glass container (beaker) of an appropriate capacity; manufactured by Wako Pure Chemical Industries, Ltd. , Reagent special grade) and 0.049 g of citric acid (0.255 mmol (mmol); Wako Pure Chemicals, Wako special grade) aqueous solution 20 g were added, and at a rotation speed of 50 prm with a stirrer (manufactured by ASONE, trade name: CT-1AT). For about 10 minutes. Sodium hydroxide is added to the obtained solution so that the pH is 6.3, and the mixture is stirred for about 5 minutes at the same rotational speed as described above. The oral composition (Prescription No. 8) of the present invention was obtained by adjusting with purified water so that the whole was 100 g later.

(Table 5)

(Table 6)

The related matters regarding the data in the above “Table 5” and “Table 6” are as follows.
<Data No. >
No. 2 to 6: No zinc 7-11: Increase / decrease in amount of citric acid 12-14: Difference in pH 16-21: Difference of organic acid 22-24: Difference of zinc salt 27-28: Increase / decrease in zinc content

Example 4
(Effect of oral composition-device analysis data)
Each sample prepared in Example 1 was analyzed by an electronic taste system ASTREE II (Astri II; manufactured by Alpha Moss Japan Co., Ltd.). The details of the analysis system “ASTORY II” can be referred to the following URL.
URL: http://www.alpha-mos.co.jp/sensory/am-astree-01.html

<Measurement conditions>
According to the following procedure, the “effect” of taste masking by Samples 1 to 28 obtained in Example 3 was measured using the taste sensor ASTREE.
<Measurement and analysis method>
1) 25 ml of each sample was placed in an autosampler.
2) A cleaning liquid for cleaning (purified water 25 ml) was placed between each sample.
3) Each measurement was performed 6 times in succession for each of Samples 1 to 28.
4) Among the above “six measurements”, the average value of the results from 4 to 6 times when the numerical value is stabilized and from 100 to 120 seconds out of 0 to 120 seconds is used. To do. (For example, the average value of data for 100 to 120 seconds from the raw data for 120 seconds obtained by the single analysis of S1 is used as one analysis data. Thus, the analysis data for the fourth to sixth analysis of S1 ( The analysis data n3 of S1 is obtained by n3), and the same processing is performed for S2 to S7.)
5) In the comparison of distances, the Euclidean distance between the center of gravity of S1 (n3) and the center of gravity of Sx (n3) to be compared was calculated and presented as a distance chart and a distance table.

<Sample>
Sheet2 (refer to measurement sample)
The measurement was performed in the order of (1) a sample having a low pH and (2) a sample having a small amount of zinc so that the measurement sample “before that” was not affected.
-When changing the pH so as not to be affected by the previous measurement sample (example: Sample 2, 12, 13, etc.), the measurement was performed twice and the second measurement result was used.

<Devices and analysis software used>
Device name: Electronic taste system ASTREE II
Software: Alpha Soft
Computer name: DELL OPTIPLEX 7010
URL of ASTREE “Details”:
http://www.alpha-mos.co.jp/sensory/am-astree-01.html

  Data obtained by extracting the average value for 100 to 120 seconds during the 4th to 6th measurements of the S1 to S7 sensors from the “RAW DATE” obtained by the above measurement (ie, raw data obtained from ASTREE). Are shown in Tables 7 to 9 below.

(Table 7)

(Table 8)

(Table 9)

Example 5
(Euclidean distance calculation)
<Euclidean distance>
“Euclidean distance” is a distance between two coordinates in a space to which Euclidean geometry is applied. Generally, it can be obtained by the Pythagorean theorem (three squares theorem).
In this example, the “Euclidean distance” is indicated by the distance between the centroids of the samples to be compared (in ASTREE, the centroid obtained by analyzing the same sample three times).
-The "Euclidean distance" calculation method is as follows.
For example, in the case of the Euclidean distance between the sample p and the sample q, it is obtained by the three square theorem as follows:
Euclidean distance d (p, q) = {(p1-q1) ² +... + (Pn−qn) ² } · exp (1/2)
(Where n = number of sensors used in ASTREE; here n = 7)

  Samples used in this example are those shown in Table 10 below.

(Table 10)
In the above table, the expression “0 times that of zinc chloride” is “molar ratio”.

  For the samples shown in Table 10, various combinations of Euclidean distances were calculated based on the values described in Tables 7 to 9 above. The obtained results (that is, comparison of the relationship between the amount of citric acid and the corresponding Euclidean distance) are shown in Table 11 below. In addition, in the comparison with respect to the difference in the amount of citric acid, the pH was unified to 6.3.

(Table 11)

<Calculation of actual Euclidean distance>
For example, in the case of the Euclidean distance between the sample p and the sample q, it can be calculated by the following formula.
Euclidean distance d (p, q) = √ (p1−q1) ^ 2 +... + (Pn−qn) ^ 2
(N = number of sensors used in ASTREE. This time, 7 sensors are used.)

Therefore, the Euclidean distance between “Sample 2” (base formulation) and “Sample 7” (base formulation + zinc chloride 0.07%) in Table 10 is calculated as follows. These are Euclidean distances in the combination of “citric acid = 0 mol” (in the following “Euclidean distance” notation, “the value obtained by rounding off the numerical value of one decimal place” or “rounding method”) "Significant number based on 3 digits".
d (2,7) = √ (2104.096-1441.694) ^ 2 + (2923.502-2267.5556) ^ 2 + (1258.731-14699.889) ^ 2 + (1302.646-1022.041) ^ 2 + (2960.5555-2737.648) ^ 2 + (268.627-2050.805) ^ 2 + (2158.544-22511.473) ^ 2
= 1286

In the same manner as described above, the Euclidean distance was calculated as follows for each combination of citric acid = 0.5 mol, 1 mol, 2 mol, and 10 mol when zinc chloride = 1 mol.
<Citric acid><Euclideandistance>
0.5 mol (Sample 8) 559
1 mole (sample 9) 202
2 moles (Sample 10) 112
10 moles (sample 11) 75.9

  The data obtained above is plotted on a bar graph as shown in FIG. 1, and the data plotted on the XY plane is as shown in FIG.

  In FIG. 1, the distance between the paired samples is shortened as the amount of citric acid increases. Therefore, the graph of FIG. 2 shows that the masking of zinc taste (astringency and astringency) can be “stronger” by increasing the amount of citric acid.

In this FIG. 2, “identification index = 95”, and in this “identification index”, the closer the numerical value is to “identification index = 100”, the “discretion of taste” of each sample is “very good”. Indicates that The horizontal axis (pc1) indicates the first main component, and the vertical axis (pc2) indicates the second main component. In addition, about the detail of these horizontal axes, the numerical value of a vertical axis | shaft, and an identification index | exponent, the following URL can be referred as needed.
URL: http://www.alpha-mos.co.jp/application/documents/anti01_processed_cheese_ageing_jp.pdf

Example 6
(Correlation between instrumental analysis data and sensory evaluation)
In this example, the correlation between the instrumental analysis data obtained this time and the sensory evaluation (conventional) was evaluated.
Using the same sample as used in Example 5 (see Table 10), sensory evaluation was performed by four people (A to D) selected based on the paneler selection criteria. In addition, regarding the details of the “panel selection criteria”, the following URL can be referred to as necessary.
URL: http://www.mac.or.jp/mail/120701/03.shtml

In this example, sensory evaluation by each paneler was performed based on the following criteria, and the arithmetic average was taken as the value of “sensory evaluation”. The values obtained here are shown in FIG.
<Criteria for sensory evaluation>
5: Feel very strong 4: Feel strong 3: Feel 2: Feel a little 1: Feel a little 0: Don't feel

  By plotting the data obtained above (sensory evaluation (actual value); horizontal axis) against the data obtained in Example 5 (instrumental analysis data (predicted value); vertical axis), FIG. The graph shown was obtained (correlation coefficient = 0.006). From this figure, it can be understood that the correlation coefficient = 0.006 indicates a good “positive correlation”. Further, it can be seen from FIG. 3 that in the case of a sample having a strong astringency and astringency, the correlation between sensory evaluation and instrumental analysis data is high. On the other hand, in the case of a sample having a weak astringency and astringency, the “sensory evaluation” by each panel tends to vary.

For details on the method of calculating the “correlation coefficient” used here, the following URL can be referred to, for example.
URL: http://www1.tcue.ac.jp/home1/abek/htdocs/stat/corre.html

Example 7
(Effect of increase / decrease in pH)
Samples used in this example are those shown in Table 12 below.

(Table 12)
In the above table, the expression “0 times that of zinc chloride” is “molar ratio”.

  For the samples shown in Table 12, various combinations of Euclidean distances were calculated based on the values described in Tables 7 to 9 above. The obtained results (that is, comparison of the relationship between the amount of citric acid and the corresponding Euclidean distance) are shown in Table 13 below and the graphs of FIGS. 4 and 5. In addition, in this “comparison with respect to the difference in pH”, the molar ratio of (citric acid / zinc chloride) was unified.

(Table 13)

  As shown in Table 13 and FIG. 4, no substantial difference was observed in the masking effect of zinc taste (astringency / astringency) due to the difference in pH.

(Correlation between instrumental analysis data and sensory evaluation)
Also in this example, the correlation (about the difference in pH) between the instrumental analysis data obtained this time and the sensory evaluation (conventional) was evaluated.
Sensory evaluation was performed in the same manner as in Example 6 using the samples in Table 12 above.

Each panelist sensory evaluation (arithmetic mean) in this example is as follows. The values (correlation) obtained here are shown in FIG.
<Criteria for sensory evaluation>
5: Feel very strong 4: Feel strong 3: Feel 2: Feel a little 1: Feel a little 0: Don't feel

  The data obtained above (sensory evaluation (actually measured value); horizontal axis) is plotted against the data (instrumental analysis data (predicted value); vertical axis) obtained in the present invention, and shown in FIG. A graph was obtained (correlation coefficient = 0.9422). From this figure, it can be understood that the correlation coefficient = 0.9422 indicates a good “positive correlation”.

Example 8
(Effects of differences in organic acids)
Samples used in this example are those shown in Table 14 below.

(Table 14)
In the above table, the expression “0 times that of zinc chloride” is “molar ratio”.

  For the samples shown in Table 14, various combinations of Euclidean distances were calculated based on the values described in Tables 7 to 9 above. The obtained results (that is, comparison of the relationship between the amount of citric acid and the corresponding Euclidean distance) are shown in Table 15 below and the graphs of FIGS. In this “comparison of differences in organic acids”, the amount of organic acid when zinc chloride = 1 was set to 2 (molar ratio) and pH = 6.3).

(Table 15)

  As shown in Table 15 and FIG. 7, among the “four kinds of organic acids” used in this measurement, citric acid had the highest masking effect and gluconic acid had the lowest masking effect. Among the four organic acids, citric acid has the highest valence and gluconic acid has the lowest valence. According to the knowledge of the present inventor, such a valence is estimated as a factor causing a difference in the masking effect.

(Correlation between instrumental analysis data and sensory evaluation)
Also in this example, the correlation (about the difference in organic acids) between the instrumental analysis data obtained this time and the sensory evaluation (from the past) was evaluated.
Sensory evaluation was performed in the same manner as in Example 6 using the samples in Table 14 above.

Each panelist sensory evaluation (arithmetic mean) in this example is as follows. The values (correlation) obtained here are shown in FIG.
<Criteria for sensory evaluation>
5: Feel very strong 4: Feel strong 3: Feel 2: Feel a little 1: Feel a little 0: Don't feel

  By plotting the data obtained above (sensory evaluation (actually measured value); horizontal axis) against the data obtained in this example (instrumental analysis data (predicted value); vertical axis), FIG. The graph shown was obtained (correlation coefficient = 0.9940). From this figure, it can be seen that the correlation coefficient = 0.9940 indicates a good “positive correlation”.

Example 9
(Effects of differences in zinc salt)
Samples used in this example are those shown in Table 16 below.

(Table 16)
In the above table, the expression “0 times the zinc salt” is “molar ratio”.

  For the samples shown in Table 16, various combinations of Euclidean distances were calculated based on the values described in Tables 7 to 9 above. The obtained results (that is, comparison of the relationship between the amount of citric acid and the corresponding Euclidean distance) are shown in Table 17 below and the graphs of FIGS. In addition, in the comparison with respect to the difference of this zinc compound (salt), when the zinc compound was 1 mol, the amount of citric acid was unified to 2 mol and pH was 6.3.

(Table 17)

  As shown in Table 17 and FIG. 10, among the “zinc compounds” used in the present measurement, there was no significant difference in the masking effect due to the difference in zinc salt.

(Correlation between instrumental analysis data and sensory evaluation)
Also in this example, the correlation (about the difference in organic acids) between the instrumental analysis data obtained this time and the sensory evaluation (from the past) was evaluated.
Sensory evaluation was performed in the same manner as in Example 6 using the samples in Table 16 above.

Each panelist sensory evaluation (arithmetic mean) in this example is as follows. The values (correlation) obtained here are shown in FIG.
<Criteria for sensory evaluation>
5: Feel very strong 4: Feel strong 3: Feel 2: Feel a little 1: Feel a little 0: Don't feel

  By plotting the data (sensory evaluation (measured value); horizontal axis) obtained above with respect to the data (instrumental analysis data (predicted value); vertical axis) obtained in this example, FIG. The graph shown was obtained (correlation coefficient = 0.9949). From this figure, it can be understood that the correlation coefficient = 0.9949 indicates a good “positive correlation”.

Example 10
(Effects of differences in zinc chloride content)
Samples used in this example are those shown in Table 18 below.

(Table 18)
In the above table, the expression “0 times that of zinc chloride” is “molar ratio”.

  For the samples shown in Table 18, various combinations of Euclidean distances were calculated based on the values described in Tables 7 to 9 above. The obtained results (that is, comparison of the relationship between the amount of citric acid and the corresponding Euclidean distance) are shown in the following Table 19 and the graphs of FIGS. In addition, in the comparison with respect to the difference of this zinc compound (salt), when the zinc compound was 1 mol, the amount of citric acid was unified to 2 mol and pH was 6.3.

(Table 19)

  As shown in Table 19 and FIGS. 13 and 14, in this measurement, it was not found that the masking effect was reduced by increasing the amount of zinc chloride.

Each panelist sensory evaluation (arithmetic mean) in this example is as follows. The values (correlation) obtained here are shown in FIG.
<Criteria for sensory evaluation>
5: Feel very strong 4: Feel strong 3: Feel 2: Feel a little 1: Feel a little 0: Don't feel

  By plotting the data obtained above (sensory evaluation (actual measurement value); horizontal axis) against the data obtained in this example (instrumental analysis data (predicted value); vertical axis), FIG. The graph shown was obtained (correlation coefficient = 0.9778). From this figure, it can be seen that the correlation coefficient = 0.9778 indicates a good “positive correlation”.

<Summary of Examples 1 to 10>
・ It was possible to quantify that citric acid was able to mask the taste of zinc more than other organic acids.
-It was confirmed that the masking power of the taste of zinc increased with the increase of citric acid relative to the zinc salt. Moreover, even if the zinc chloride content was increased to 0.2%, the masking power did not decrease.
-The masking power of citric acid did not change due to the difference in pH and zinc salt.

Comparative Example 1
(Preparation of oral composition using oral composition base formulation B)
Implemented except using “Base Formula B” and “Base Formula C” prepared in Example 2 instead of “Base Formula A” prepared in Example 1 and following the formula in Table 20 below. In the same procedure as in Example 3, oral compositions “No. B1 to B4” were prepared using Base Formula B and “No. B5 to 8” using Base Formula C.

(Table 20)

Comparative Example 2
(Measurement of physical properties of oral composition Nos. B1 to B8)
Each sample prepared in Comparative Example 1 was analyzed by an electronic taste system ASTREE II (Astree II; manufactured by Alpha Mos Japan Co., Ltd.) in the same procedure as in Example 4 to obtain each “RAW DATE”. It was.

  From the “RAW DATE” obtained by the above measurement (that is, raw data obtained from ASTREE), the same procedure as in Example 4, and the average of 100 to 120 seconds at the time of the fourth to sixth measurements of the S1 to S7 sensors Data obtained by extracting values are shown in Table 21 below. In Table 20, sample No. In B1-1 to B4, “pH = 4.9” was unified, and sample No. In B5-1 to B8, “pH = 6.4” was unified.

(Table 21)

  When the data of Table 21 was plotted on the XY plane, the graph of FIG. 16 (before correction) was obtained. In FIG. 13, the horizontal axis (pc1) represents the first principal component, and the vertical axis (pc2) represents the second principal component. The identification index obtained from the graph of FIG. 16 was “identification index = 94”. (The closer the numerical value is to “identification index = 100”, the “taste identification” of each sample is “very good”. ).

  For the samples shown in Table 20, various combinations of Euclidean distances were calculated based on the values described in Table 21 in the same procedure as in Example 5. The obtained results (that is, the comparison of the Euclidean distance relationship) are shown in Table 22 below, and FIGS. 17A and 17B. FIG. 17 (A) shows the difference depending on the presence or absence of a combination of (anethole + glycerin) in each oral composition. FIG. 17B shows the difference depending on the presence or absence of a combination of (anethole + sorbitol) in each oral composition.

(Table 22)

  As described in these tables and figures, in Comparative Example 1, the distance was shortened by adding anethole, glycerin, and sorbitol, but the distance gap was small (that is, the degree of masking itself was small). It has been found.

(Correlation between instrumental analysis data and sensory evaluation)
In this comparative example 1, the correlation between the instrumental analysis data obtained this time and the sensory evaluation was evaluated in the same procedure as in Example 6. Using the sample of Comparative Example 1, sensory evaluation by four persons (A to D) selected based on the paneler selection criteria was performed, and the arithmetic average of the values by each paneler was taken as the value of “sensory evaluation”. The values obtained here are shown in Table 23 and FIG. 18 (the criteria for sensory evaluation are the same as those in Example 6).

(Table 23)

  By plotting the data obtained above (sensory evaluation (measured value); horizontal axis) against the data obtained in Comparative Example 1 (instrumental analysis data (predicted value); vertical axis), FIG. The graph shown was obtained (correlation coefficient = 0.9245). From this figure, it can be understood that the correlation coefficient = 0.9245 indicates a good “positive correlation”. Further, the prescriptions of other companies' literature (that is, prescriptions 1-1 and 1-2) have little astringency and astringency even without masking. On the other hand, it can be understood that the masking effect is smaller in the formulations of these other literatures than in the in-house formulation (ie the formulation of the example).

Comparative Example 3
(Preparation of oral composition using oral composition base formulation C)
A procedure similar to that in Example 3 except that “base formulation D” prepared in Example 2 was used instead of “base formulation A” prepared in Example 1 and that the formulation shown in Table 24 below was followed. The oral composition preparation “No. C9 to C13” was prepared. For “No. C14 to C16”, citric acid twice the number of moles of zinc chloride was added to “base formulation A” prepared in Example 1, and according to the formulation in Table 24 below, Example 3 and Adjustments were made in the same procedure.

(Table 24)

Comparative Example 4
(Measurement of physical properties of oral composition Nos. C9 to C16)
Each sample prepared in Comparative Example 3 was analyzed by an electronic taste system ASTREE II (Astree II; manufactured by Alpha Moss Japan Co., Ltd.) in the same procedure as in Example 4 to obtain each “RAW DATE”. It was.

  From the “RAW DATE” obtained by the above measurement (that is, raw data obtained from ASTREE), the same procedure as in Example 4, and the average of 100 to 120 seconds at the time of the fourth to sixth measurements of the S1 to S7 sensors Data obtained by extracting values are shown in Table 25 below. In Table 24 above, sample No. In C9 to C12, “pH = 5.1” is unified, and sample no. C13 to C16 were unified to “pH = 6.3”.

(Table 25)

  When the data of Table 25 was plotted on the XY plane, the graph of FIG. 19 was obtained. In FIG. 1, the horizontal axis (pc1) represents the first principal component, and the vertical axis (pc2) represents the second principal component. The discrimination index obtained from the graph of FIG. 19 was “discrimination index = 98” (the closer the numerical value is to “discrimination index = 100”, the “taste discrimination” of each sample is “very good”. ).

  With respect to the samples shown in Table 24, various combinations of Euclidean distances were calculated based on the values described in Table 25 by the same procedure as in Example 5. The obtained results (that is, comparison of the Euclidean distance relationship) are shown in Table 26 below, FIG. 20 (A), and FIG. 20 (B). In Table 24, the samples C9-1 to C12 are unified to pH = 5.1, and the samples C16-1 and C13 are used as a masking agent (curing) in the “in-house formulation” (that is, the formulation of Example 1). A combination of castor oil + fragrance) was used.

(Table 26)

  FIG. 20 (A) shows the difference depending on the presence or absence of a combination of (hardened castor oil + fragrance) in each oral composition according to the composition of other company's literature. FIG. 20 (B) shows the difference depending on the presence or absence of a combination of (hardened castor oil + fragrance) in each oral composition according to “in-house prescription” (that is, the prescription in Example 1).

  As described in these tables and figures, in Comparative Example 4, the distance was shortened by adding hydrogenated castor oil + fragrance, but the distance gap was small (that is, the degree of masking itself was small). It has been found.

(Correlation between instrumental analysis data and sensory evaluation)
In Comparative Example 4, the correlation between the instrumental analysis data obtained this time and the sensory evaluation was evaluated in the same procedure as in Example 6. Using the sample of Comparative Example 3, sensory evaluation by four persons (A to D) selected based on the paneler selection criteria was performed, and the arithmetic average of the values by each paneler was taken as the value of “sensory evaluation”. The values obtained here are shown in Table 27 and FIG. 21 (the criteria for sensory evaluation are the same as those in Example 6).

(Table 27)

  By plotting the data obtained above (sensory evaluation (actually measured value); vertical axis) against the data (instrumental analysis data (predicted value); horizontal axis) obtained in Comparative Example 3, FIG. The graph shown was obtained (correlation coefficient = 0.9152). From this figure, it can be understood that the correlation coefficient = 0.9152 indicates a good “positive correlation”. In addition, the prescriptions of other companies' literature (namely, prescriptions C9 to C12) have little astringency and astringency even without masking. On the other hand, it can be understood that the masking effect is smaller in the formulations of these other companies compared to those in the in-house formulation (ie the formulation of Example 1).

Comparative Example 5
(Confirmation of the effect of “cured castor oil + fragrance”)
In this comparative example, the effect of “hardened castor oil + fragrance” in the base formulation (base formulation A) according to the present invention was confirmed. The sensory evaluation with the formulation used is shown in Table 28 below. The prescription used in Table 28 is as follows.
・ In-house hardened castor oil, no fragrance: C14
・ In-house prescription (no masking): D24
・ In-house prescription (with masking): C13

(Table 28)

  By plotting the data (sensory evaluation (actually measured value); vertical axis) obtained above with respect to the data (instrumental analysis data (predicted value); horizontal axis) obtained in Comparative Example 5, FIG. The graph shown was obtained (correlation coefficient = 0.9673). From this figure, it can be understood that the correlation coefficient = 0.9673 indicates a good “positive correlation”. From FIG. 22, regarding the effect of “hardened castor oil + fragrance” in the base formulation (base formulation A) according to the present invention, the hardened castor oil and fragrance also has a “some degree” masking effect, but from the addition of citric acid. However, it can be understood that the masking effect is small.

Reference example 1
(Preparation of oral composition using oral composition base formulation A)
Oral composition preparations “No. D17 to D24” were prepared in the same procedure as in Example 3 except that the “base formulation A” prepared in Example 1 was used and the formulation in Table 29 below was followed. did.

(Table 29)

Reference example 2
(Oral composition No. D17-D24 physical property measurement)
Each sample prepared in Comparative Example 3 was analyzed by an electronic taste system ASTREE II (Astree II; manufactured by Alpha Moss Japan Co., Ltd.) in the same procedure as in Example 4 to obtain each “RAW DATE”. It was.

  From the “RAW DATE” obtained by the above measurement (that is, raw data obtained from ASTREE), the same procedure as in Example 4, and the average of 100 to 120 seconds at the time of the fourth to sixth measurements of the S1 to S7 sensors Data obtained by extracting the values are shown in Table 30 below. In addition, in each sample of the said Table 29, it unified into "pH = 6.3".

(Table 30)

  When the data of Table 30 was plotted on the XY plane, the graph of FIG. 23 was obtained. In FIG. 1, the horizontal axis (pc1) represents the first principal component, and the vertical axis (pc2) represents the second principal component. The “identification index = 0.9432” obtained from the data shown in FIG. 23 (the closer the numerical value is to “identification index = 100”, the “taste identification” of each sample is “very good”). .

  For the samples shown in Table 29, various combinations of Euclidean distances were calculated based on the values described in Table 30 by the same procedure as in Example 5. The obtained results (that is, comparison of the Euclidean distance relationship) are shown in Table 31 and FIG. In Table 29 (different organic acids), all samples were unified to pH = 6.3.

(Table 31)

As described in Table 31 and FIG. 24, the following knowledge was obtained in this reference example.
・ Citric acid has the highest masking effect.
-EDTA-Na was also the next most effective, and it is estimated that the chelating ability of organic acids is one factor in reducing the astringency and astringency of zinc salts.
・ Acetic acid and glycine also have a masking effect because the Euclidean distance is about 2/3 of that without organic acid.
・ Moleic acid, gluconic acid and fumaric acid measured last time also have Euclidean distance less than half.

(Correlation between instrumental analysis data and sensory evaluation)
In this example, the correlation between the instrumental analysis data obtained this time and the sensory evaluation was evaluated in the same procedure as in Example 6. Using the sample of this reference example, sensory evaluation by four persons (A to D) selected based on the paneler selection criteria was performed, and the arithmetic average of the values by each paneler was taken as the value of “sensory evaluation”. The values obtained here are shown in Table 32 and FIG. 25 (the criteria for sensory evaluation are the same as those in Example 6).

(Table 32)

As described in Table 32 and FIG. 25, the following findings were obtained in this reference example.
-The sensory evaluation also showed the same tendency as the measurement result by ASTREE.

<Summary of Comparative Examples and Reference Examples>
The following findings were obtained from the “summary” of the comparative examples and reference examples described above.
・ The prescriptions of other companies' literature (including partially modified prescriptions; the same applies below) measured at this time have less zinc salt masking power than the prescription under investigation.
・ The reason why there was not much difference in Euclidean distance depending on the presence or absence of masking in other companies' prescriptions was probably because citric acid was included in the prescription. From this, it can be said that citric acid has a higher masking effect than the combination of polyhydric alcohol and anethole, or hydrogenated castor oil and l-menthol.
-Since EDTA-2Na was also effective, the chelating ability of organic acids is presumed to be one factor in masking astringency and astringency.
・ Based on the previous measurement results of organic acid differences, complex structures (with side chains) tend to have higher masking power than simple structures. Also, the longer the carbon chain, the higher the masking power tended to be.

Claims (5)

  It contains at least a zinc compound and an organic acid, and the molar ratio (Arel) between the organic acid and the zinc compound is Arel = (number of moles of organic acid) / (number of moles of zinc compound) = 0.2 or more. An oral composition characterized.   The oral composition according to claim 1, wherein the molar ratio of the organic acid to the zinc compound is Arel = 0.5-20.   The composition for oral cavity according to any one of claims 1 and 2, wherein the organic acid is at least one selected from the group consisting of citric acid, acetic acid, glycine, malic acid, gluconic acid, and fumaric acid.   The composition for oral cavity is a fluid composition containing water, and the blending amount of the zinc compound is 0.001 to 0.2% by mass of the entire composition. The composition for oral cavity of description. While containing the zinc compound, relative to a control not containing the organic acid (control) for the Euclidean distance of the composition (E _0), the Euclidean distance of said zinc compound and oral compositions containing an organic acid (E _S) the ratio _{(E rel (%)) =} 100 × (E S / E 0) is oral composition according to any one of claims 1 to 4, 85% or less.