JP6045863B2 - Diketone action inhibitor - Google Patents

Description

  The present invention relates to a body odor inhibitor. More specifically, the present invention is suitable for suppressing events caused by the action of body odor inhibitors and diketone compounds useful for cosmetics, quasi-drugs, pharmaceuticals, sundries, etc. suitable for humans who care about body odor. The present invention relates to a diketone action inhibitor useful for external preparations, quasi drugs, pharmaceuticals, miscellaneous goods and the like.

  The body odor is a mixture of a plurality of odors generated from each part such as the axilla, head, trunk, toe, and sole. Among these parts, for example, in the axilla and head, the components contained in sweat are decomposed by skin resident microorganisms together with sebum, dirt, etc., and a substance that emits a strong odor is generated. Therefore, the smell of the axilla (hereinafter referred to as “smelling odor”) and the smell of the head (hereinafter referred to as “head odor”) are strong and easily perceived by others.

  As a causative substance of odor, short chain fatty acids such as 3-methyl-2-hexenoic acid and volatile steroids such as androstenone (5α-16-androsten-3-one) are known (for example, patents). Reference 1). As causative substances of head odor, for example, fatty acids such as acetic acid and propionic acid are known (see, for example, Patent Document 2).

  As a deodorant agent that suppresses the generation of these body odor-causing substances and suppresses the generation of body odor, for example, the synthesis and secretion of apolipoprotein D, which is a carrier protein of 3-methyl-2-hexenoic acid, is suppressed to 3- It is involved in the production of deodorant agents (for example, see Patent Document 3) consisting of extracts of plants such as buckwheat to suppress the generation of methyl-2-hexenoic acid, androste 16-enes, which are volatile steroids. There has been proposed a deodorant agent (for example, see Patent Document 4) composed of an extract of a plant such as urgon to suppress the activity of β-glucuronidase and suppress the generation of androste 16-enes.

  However, the deodorant may not be able to sufficiently suppress body odor, particularly acid odor in the armpit and oil odor in the head. Accordingly, there is a need for a body odor inhibitor that can effectively suppress such body odor.

Japanese Patent Laying-Open No. 2005-062159 JP 2001-220593 A JP 2006-152003 A JP 2002-255776 A

  The present invention has been made in view of the prior art, and an object thereof is to provide a body odor inhibitor capable of effectively suppressing body odor, in particular, acid odor in the armpit and oil odor in the head. To do. Moreover, an object of this invention is to provide the diketone action inhibitor which can suppress effectively the effect | action of the diketone compound resulting from a skin component.

That is, the gist of the present invention is as follows.
(1) a body odor inhibitor comprising an ascorbic acid fatty acid ester compound,
(2) Ascorbic acid fatty acid ester compound is represented by the general formula (I):

(Wherein R ¹ is an optionally substituted acyl group having 6 to 22 carbon atoms, R ² is a hydrogen atom or an optionally substituted acyl group having 6 to 22 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an optionally substituted acyl group having 6 to 22 carbon atoms or phosphono group)
The body odor suppressor according to (1), which is a compound represented by:
(3) Ascorbic acid fatty acid ester compound is at least selected from the group consisting of ascorbyl hexadecanoate, ascorbyl dihexadecanoate, ascorbyl tetraisohexadecanoate, ascorbyl octadecanoate, ascorbyl hexadecanoate and trisodium hexadecanoate ascorbyl phosphate The body odor suppressor according to (1) or (2), which is one type
(4) General formula (II) resulting from skin components:
R ^5- (CO)-(CO) -R ⁶ (II)
(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms)
A diketone action inhibitor that suppresses the action of the diketone compound represented by the formula, wherein the diketone action inhibitor contains an ascorbic acid fatty acid ester compound,
(5) The ascorbic acid fatty acid ester compound has the general formula (I):

(Wherein R ¹ is an optionally substituted acyl group having 6 to 22 carbon atoms, R ² is a hydrogen atom or an optionally substituted acyl group having 6 to 22 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an optionally substituted acyl group having 6 to 22 carbon atoms or phosphono group)
And the diketone action inhibitor according to (4) above, and (6) an ascorbic acid fatty acid ester compound, wherein The diketone action inhibitor according to (4) or (5), which is at least one selected from the group consisting of acid ascorbyl, hexadecanoic acid ascorbyl phosphoric acid, and hexadecanoic acid ascorbyl trisodium phosphate.

  The body odor suppressor of the present invention has an excellent effect that it can effectively suppress body odor, particularly acid odor in the armpit and oil odor in the head. Moreover, the diketone action inhibitor of this invention has the outstanding effect that the effect | action of the diketone compound resulting from a skin component can be suppressed effectively.

It is a graph which shows the result of having investigated the diacetyl production | generation suppression rate in Staphylococcus aureus NBRC13276 and Staphylococcus epidermidis (Staphylococcus epidermidis IAM1296) in Test example 1. FIG. (A) is a graph showing the results of examining the relationship between the test substance and 50% inhibitory concentration of diacetyl production in Staphylococcus aureus NBRC13276 in Test Example 2, and (B) is a test example 2. It is a graph which shows the result of having investigated the relationship between a test substance and the 50% inhibitory concentration of diacetyl production in Staphylococcus epidermidis IAM1296. In Experiment 4, it is a graph which shows the result of having investigated the relationship between a test sample and odor intensity | strength.

1. Body odor suppressor The body odor suppressor of the present invention is characterized by containing an ascorbic acid fatty acid ester compound as described above. The ascorbic acid fatty acid ester compound has the general formula (II) derived from skin components:
R ^5- (CO)-(CO) -R ⁶ (II)
(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms)
It has the property which suppresses body odor by suppressing the effect | action of the diketone compound represented by these. Therefore, since the body odor suppressor of the present invention contains the ascorbic acid fatty acid ester compound, it suppresses the action of the diketone compound caused by skin components, and body odor caused by the diketone compound, particularly in the axillary region. Acid odor and oil odor in the head can be effectively suppressed.

  In the present specification, “body odor” refers to an odor generated from the surface of the skin. In this specification, the concept of “head” includes scalp and hair. Further, in the present specification, the “oil odor” is similar to the scent of stale oil and refers to a smell that has been fermented. Further, in the present specification, the “acid odor” refers to a sour smell that is steamed.

  Further, in the present specification, the concept of “body odor suppression” includes reducing the degree of body odor and suppressing the occurrence of body odor itself. In the present specification, “suppression of the action of the diketone compound” means to suppress the production of a diketone compound in human skin, a contact object in contact with the skin, or a human living space, and / or human skin. Removing the diketone compound present in the contact object or the human living space in contact with the skin to reduce the amount thereof, thereby reducing the amount of the human skin, the contact object in contact with the skin or the diketone in the human living space It refers to inhibiting the action of a compound.

  Examples of the contacted object include clothing and bedding, but the present invention is not limited to such examples. In addition, examples of the living space include an indoor space and a vehicle interior space such as an automobile, but the present invention is not limited to such illustration.

  Examples of the ascorbic acid fatty acid ester compound include the general formula (I):

(Wherein R ¹ is an optionally substituted acyl group having 6 to 22 carbon atoms, R ² is a hydrogen atom or an optionally substituted acyl group having 6 to 22 carbon atoms, R ³ and R ⁴ each independently represent a hydrogen atom or an optionally substituted acyl group having 6 to 22 carbon atoms or phosphono group)
And a salt of the compound represented by the general formula (I), but the present invention is not limited only to such examples.

In general formula (I), R ¹ is an acyl group having 6 to 22 carbon atoms which may have a substituent. The number of carbon atoms of the acyl group is 6 or more, preferably 12 or more, more preferably 16 or more from the viewpoint of obtaining a sufficient diketone action suppressing effect, and 22 or less, preferably from the viewpoint of easy handling during use. Is 20 or less, more preferably 18 or less. Examples of the acyl group having 6 to 22 carbon atoms include hexanoyl group, octanoyl group, nonanoyl group, decanoyl group, dodecanoyl group, tetradecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, eicosyl group, Although a docosanoyl group etc. are mentioned, this invention is not limited only to this illustration. Among these acyl groups having 6 to 22 carbon atoms, a dodecanoyl group, a tetradecanoyl group, a hexadecanoyl group and an octadecanoyl group are preferable from the viewpoint of obtaining a sufficient diketone action suppressing effect, and a hexadecanoyl group and An octadecanoyl group is more preferred. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, but the present invention is limited only to such examples. It is not a thing.

In general formula (I), R ² is an acyl group of a hydrogen atom or a carbon atoms which may have a substituent 6-22. An acyl group having 6 to 22 carbon atoms which may have a substituent in R ² are the same as with carbon atoms which may 6 to 22 have a substituent in R ^1.

In the general formula (I), R ³ and R ⁴ are each independently a hydrogen atom, an acyl group, or a phosphono group which has carbon atoms which may 6 to 22 have a substituent. The acyl group having 6 to 22 carbon atoms which may have a substituent in R ³ and R ⁴ is the same as the carbon group having 6 to 22 carbon atoms which may have a substituent in R ¹ .

  Examples of the salt of the compound represented by the general formula (I) include general formulas such as an alkali metal salt of the compound represented by the general formula (I) and an alkaline earth metal salt of the compound represented by the general formula (I) ( Inorganic salts of the compounds represented by I); organic salts of the compounds represented by the general formula (I) such as organic amine salts of the compounds represented by the general formula (I). It is not limited. Examples of the alkali metal salt include a sodium salt, a potassium salt, and a lithium salt, but the present invention is not limited to such examples. Examples of alkaline earth metal salts include magnesium salts and calcium salts, but the present invention is not limited to such examples. Examples of the organic amine salt include a monoethanolamine salt, a diethanolamine salt, a triethanolamine salt, and the like, but the present invention is not limited to such examples. When the salt of the compound represented by the general formula (I) is used by dissolving in a solvent such as water, alcohol, or an aqueous alcohol solution, from the viewpoint of enhancing the solubility in the solvent, the salt of the compound represented by the general formula (I) Among them, the alkali metal salt of the compound represented by the general formula (I) is preferable, the sodium salt of the compound represented by the general formula (I) and the potassium salt of the compound represented by the general formula (I) are more preferable. The sodium salt of the compound represented by (I) is more preferable.

  Ascorbic acid fatty acid ester compounds include, for example, ascorbyl hexanoate, ascorbyl octoate, ascorbyl nonanoate, ascorbyl decanoate, ascorbyl dodecanoate, ascorbyl hexadecanoate, ascorbyl dihexadecanoate, ascorbyl tetraisohexadecanoate, ascorbyl heptadecanoate, octadecane Examples include ascorbyl acid, ascorbyl nonadecanoate, ascorbyl hexadecanoate, trisodium ascorbyl hexadecanoate, and the like, but the present invention is not limited to such examples. Among these ascorbic acid fatty acid ester compounds, from the viewpoint of obtaining a sufficient diketone action inhibitory effect, ascorbyl hexadecanoate, ascorbyl dihexadecanoate, ascorbyl tetraisohexadecanoate, ascorbyl octadecanoate, ascorbyl hexadecanoate and ascorbyl hexadecanoate Trisodium phosphate is preferred, ascorbyl hexadecanoate, ascorbyl dihexadecanoate, ascorbyl octadecanoate, ascorbyl hexadecanoate and trisodium ascorbyl hexadecanoate are more preferred, ascorbyl hexadecanoate, ascorbyl octadecanoate, ascorbyl hexadecanoate And trisodium ascorbyl phosphate hexadecanoate is more preferred. The ascorbic acid fatty acid ester compound may be used alone or in combination of two or more.

In general formula (II), R < ⁵ > and R < ⁶ > are respectively independently a C1-C4 alkyl group. The number of carbon atoms of the alkyl group is 1 to 4 because it has a great influence on the human body odor, particularly the acid odor in the axilla and the oil odor in the head, but preferably 1 to 3, more preferably 1 or 2, more preferably 1. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. It is not limited to illustration only. Among these, a methyl group is preferable because it has a great influence on human body odor, particularly acid odor in the axilla and oil odor in the head.

  Examples of the diketone compound include diacetyl, 2,3-pentanedione, and 2,3-hexanedione, but the present invention is not limited to such examples. Among the diketone compounds, diacetyl and 2,3-pentanedione are preferable, and diacetyl is more preferable because it has a great influence on human body odor, particularly acid odor in the axilla and abra odor in the head.

  The diketone compound can be produced from skin components by, for example, skin resident microorganisms. Examples of the skin resident microorganism include Staphylococcus aureus and Staphylococcus epidermidis, but the present invention is not limited to such examples. Examples of Staphylococcus aureus include Staphylococcus aureus NBRC13276, but the present invention is not limited to such examples. Examples of Staphylococcus epidermidis include Staphylococcus epidermidis IAM1296, but the present invention is not limited to such examples. Staphylococcus aureus and Staphylococcus epidermidis are genetically related species and may be species having the ability to produce diketone compounds.

  In the present specification, the “skin component” refers to a compound that is a precursor of a diketone compound. Examples of the compound serving as a precursor of the diketone compound include lactic acid and pyruvic acid, but the present invention is not limited to such examples.

  Examples of the diketone compound resulting from the skin component include a diketone compound produced on the skin, a diketone compound present in a contact object in contact with human skin, and a diketone compound produced on a contact object in contact with the skin. The diketone compound produced in the human living space, the diketone compound existing in the human living space, and the like can be mentioned, but the present invention is not limited to such examples. Examples of the action of the diketone compound produced on the skin include body odor, particularly acid odor in the axilla and generation of oil odor in the head. However, the present invention is limited only to such examples. is not. In addition, a diketone compound present in a contact object in contact with the skin, a diketone compound generated on the contact object in contact with the skin, a diketone compound generated in a human living space, or a diketone compound present in a human living space Examples of the action include generation of an odor similar to the body odor in a contact object or human living space in contact with the skin, but the present invention is not limited to such an example.

  The body odor inhibitor of the present invention may be a dosage form that does not contain substances other than the ascorbic acid fatty acid ester compound, or may be a liquid dosage form in which the ascorbic acid fatty acid ester compound is mixed in a solvent. Examples of the solvent include water, alcohol, and an aqueous alcohol solution, but the present invention is not limited to such examples.

  When the body odor suppressor of the present invention is the liquid agent, the content of the ascorbic acid fatty acid ester compound in the body odor suppressor of the present invention varies depending on the type of the ascorbic acid fatty acid ester compound, the use of the body odor suppressor, etc. Since it cannot be determined, it is preferable to set as appropriate according to the type of the ascorbic acid fatty acid ester compound, the use of the body odor suppressor, and the like. Usually, the content of the ascorbic acid fatty acid ester compound in the body odor suppressor of the present invention is preferably 0.0001 from the viewpoint of more effectively suppressing the human body odor, particularly the acid odor in the axilla and the oil odor in the head. From the viewpoint of ease of handling during use, it is preferably 10% by mass or less, more preferably 5% by mass or less.

The amount of the body odor suppressor used at the time of contact between the body odor suppressor of the present invention and the application site is the use of the body odor suppressor, the type of the ascorbic acid fatty acid ester compound, the ascorbic acid fatty acid ester compound contained in the body odor suppressor. Since it differs depending on the amount etc. and cannot be determined in general, it is appropriately determined according to the use of the body odor inhibitor, the type of the ascorbic acid fatty acid ester compound, the amount of the ascorbic acid fatty acid ester compound contained in the body odor inhibitor, etc. It is preferable to set. Usually, the amount of the body odor suppressor used at the time of contact between the body odor suppressor of the present invention and the application site is converted into the mass of the ascorbic acid fatty acid ester compound used per 1 cm ^{2 of} application site, From the viewpoint of more effectively suppressing the acid odor in the axilla and the oil odor in the head, it is preferably 0.00001 mg or more, more preferably 0.001 mg or more, preferably from the viewpoint of easy handling during use. Is 1.0 mg or less, more preferably 0.5 mg or less.

  The body odor suppressor of the present invention may further contain an antiperspirant, a disinfectant, an adsorbent and the like as long as the object of the present invention is not hindered.

  Examples of the location where the body odor suppressor of the present invention is applied include, for example, skin parts such as axilla, trunk, soles, and head, locations where the body odor may adhere, and the same odor as the body odor occurs. Although the location etc. which may be mentioned are mentioned, this invention is not limited only to this illustration.

  The body odor suppressing agent of the present invention can effectively suppress body odor caused by the diketone compound, in particular, acid odor in the axilla and oil odor in the head. It can be used by blending it with a food, a quasi-drug, a pharmaceutical product and the like.

  Such dosage forms such as cosmetics, quasi drugs, and pharmaceuticals can be appropriately selected depending on the use of the external preparation. Examples of the dosage forms of the cosmetics, quasi drugs, pharmaceuticals and the like include aerosols, roll-on, sticks, cleaning agents, creams, sheet agents, lotions, emulsions, gels, powders, etc. However, the present invention is not limited to such examples.

  Examples of cosmetics, quasi-drugs, and pharmaceuticals containing the body odor inhibitor of the present invention include deodorant agents (eg, deodorant lotion, deodorant gel, deodorant spray, deodorant roll-on, deodorant paper, deodorant stick). Lotion, lotion, emulsion, skin care cream, tonic, stick cosmetic, lip balm, body cleanser (eg body shampoo, bar soap, etc.), sheet cosmetic (eg wipe sheet, sheet pack etc.), Although cosmetics for hair washing (for example, shampoo, rinse, etc.), patches and the like can be mentioned, the present invention is not limited to such examples.

  When the body odor suppressor of the present invention is used in combination with the cosmetics, quasi drugs, pharmaceuticals, etc., raw materials usually used for cosmetics, quasi drugs, pharmaceuticals, for example, oils, surfactants, Components such as alcohol, preservatives, chelating agents, antioxidants, thickeners, and fragrances can be added to the cosmetics, quasi drugs, pharmaceuticals, and the like.

  As described above, the body odor suppressor of the present invention contains the ascorbic acid fatty acid ester compound having the property of suppressing body odor by suppressing the action of the diketone compound on the skin. It can be suitably used for cosmetics, quasi-drugs, pharmaceuticals and the like suitable for humans who are concerned about the acid odor and the oil odor on the head.

2. Diketone Action Inhibitor The diketone action inhibitor of the present invention is a diketone action inhibitor that suppresses the action of the diketone compound resulting from skin components, and contains an ascorbic acid fatty acid ester compound. Since the diketone action inhibitor of the present invention contains the ascorbic acid fatty acid ester compound, the action of the diketone compound resulting from skin components can be effectively suppressed.

  The ascorbic acid fatty acid ester compound is the same as the ascorbic acid fatty acid ester compound used for the body odor inhibitor described above.

  The diketone action inhibitor of the present invention may be a dosage form containing no substance other than the ascorbic acid fatty acid ester compound, or may be a liquid dosage form in which the ascorbic acid fatty acid ester compound is mixed in a solvent. Examples of the solvent include water, alcohol, and an aqueous solution of alcohol, but the present invention is not limited to such examples.

  When the diketone action inhibitor of the present invention is the liquid agent, the content of the ascorbic acid fatty acid ester compound in the diketone action inhibitor of the present invention is preferably 0 from the viewpoint of more effectively suppressing the action of the diketone compound. From 0.001 mass% or more, More preferably, it is 0.01 mass% or more, From a viewpoint of the ease of handling at the time of use, Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less.

  In addition, when using the diketone action inhibitor of this invention, the usage-amount of the said diketone action inhibitor at the time of a contact with an application location is content of the said ascorbic-acid fatty-acid ester compound in a diketone action inhibitor, diketone action inhibitor Since it differs depending on the use and the like and cannot be determined in general, it is preferably set appropriately depending on the content of the ascorbic acid fatty acid ester compound in the diketone action inhibitor, the use of the diketone action inhibitor, and the like.

  The diketone action inhibitor of the present invention may contain, for example, an auxiliary agent for sufficiently expressing the diketone compound inhibitory property by the ascorbic acid fatty acid ester compound.

  The diketone action inhibitor of the present invention can effectively suppress the action of the diketone compound caused by skin components, and can be suitably used, for example, for suppressing body odor caused by the action of the diketone compound. .

  As described above, the diketone action inhibitor of the present invention suppresses the production of a diketone compound in human skin, a contact object in contact with the skin, or a human living space, and / or human skin, the skin. The action of diketone compounds in human skin, contact objects in contact with human skin or human living space by removing the amount of diketone compounds present in the contact objects or human living space in contact with human skin Therefore, it is useful for the development of external preparations, quasi-drugs, pharmaceuticals, miscellaneous goods and the like suitable for suppressing events caused by the action of diketone compounds.

  Next, the present invention will be described in more detail based on examples. However, the present invention is not limited to the examples.

Example 1
Basic medium (composition of basic medium: yeast extract 0.0002% by mass, potassium dihydrogen phosphate 0.003% by mass, dipotassium hydrogen phosphate 0.0019% by mass, magnesium sulfate heptahydrate 0.0002% by mass, Sodium chloride 0.0014% by mass, ammonium chloride 0.001% by mass, magnesium chloride 0.00001% by mass, ferrous chloride 0.00001% by mass, calcium chloride 0.00001% by mass and the balance water) Ascorbyl 6-hexadecanoate as a test substance was added so that the concentration of sodium lactate was 2 mM and the concentration of the test substance was 0.0005% by mass to obtain a medium. Lactic acid is a substance considered to be a precursor of diacetyl, which is one of diketone compounds represented by the general formula (II).

(Test Example 1)
Production of diketone compounds typified by diacetyl in the axilla and formation of diketone compounds typified by diacetyl in the head were observed in humans with acid odor in the axilla and humans with oil odor in the head, respectively. From this, it was confirmed that the production of diketone compounds represented by diacetyl was related to the acid odor in the axilla and the oil odor in the head. Further, it was confirmed that such diacetyl was produced from lactic acid by skin resident microorganisms.

Among the skin resident microorganisms, Staphylococcus aureus and Staphylococcus epidermidis were confirmed to be particularly excellent in diacetyl-producing ability. Therefore, whether ascorbyl 6-hexadecanoate can suppress body odor using as an index the presence or absence of diacetyl production from lactic acid by Staphylococcus aureus or Staphylococcus epidermidis I investigated. First, Staphylococcus aureus NBRC13276 or Staphylococcus epidermidis IAM1296 was added to the medium obtained in Example 1 so that its concentration was 1 × 10 ⁷ CFU / mL. Incubated at 36 ° C. for 6 hours with shaking at 210 rpm.

  Of the obtained culture, 0.2 mL of the culture was collected. The components contained in the collected culture were derivatized with 2,4-dinitrophenylhydrazine, and the obtained product was filtered through a membrane filter to obtain a measurement sample. The obtained measurement sample was subjected to high performance liquid chromatography (HPLC), and the amount of diacetyl contained in the measurement sample (the amount of diacetyl when cultured in the presence of the test substance) was measured. The HPLC measurement conditions for measuring the amount of diacetyl are as follows.

[HPLC measurement conditions when measuring the amount of diacetyl]
Detection wavelength: 365 nm
Column used: YMC, trade name: Hydrosphere C18
(Column size: 250 mm x 4.6 mm)
Column temperature: 50 ° C
Flow rate: 1 mL / min
Injection volume: 0.1 mL
Moving bed: A solution in which acetonitrile and water are mixed at a ratio of 1: 1.

  Further, instead of the medium obtained in Example 1, sodium lactate and ethanol (control substance) were added to the basic medium so that the concentration of sodium lactate was 2 mM and the concentration of ethanol was 1.0 mass%. The same operation as described above was performed except that a control medium was used, and the amount of diacetyl contained in the measurement sample (the amount of diacetyl when cultured in the presence of a control substance) was measured.

  Then formula (III):

Thus, the diacetyl production inhibition rate was calculated. In Test Example 1, S.M. aureus and S. The result of investigating the diacetyl production inhibition rate in epidermidis is shown in FIG. In the figure, “S. aureus” indicates Staphylococcus aureus NBRC13276, and “S. epidermidis” indicates Staphylococcus epidermidis IAM1296.

  From the results shown in FIG. 1, it can be seen that the inhibition rate of diacetyl production by the test substance in Staphylococcus aureus NBRC13276 and Staphylococcus epidermidis IAM1296 is 100%. From these results, it can be seen that the medium obtained in Example 1 strongly suppresses diacetyl production by Staphylococcus aureus NBRC13276 and diacetyl production by Staphylococcus epidermidis IAM1296.

  From these results, it can be seen that according to ascorbyl 6-hexadecanoate (Example 1), the production of diketone compounds represented by diacetyl by skin resident microorganisms can be suppressed. In addition, since it was confirmed that the acid odor in the axilla and the oil odor in the head are related to the production of diketone compounds represented by diacetyl as described above, according to ascorbyl 6-hexadecanoate, This suggests that the body odor caused by the diketone compound, particularly the acid odor in the axilla and the oil odor in the head can be suppressed.

(Example 2)
To the basal medium, sodium lactate and ascorbyl 6-hexadecanoate as a test substance are added so that the concentration of sodium lactate is 2 mM and the concentration of the test substance is 100, 30, 10, 3 or 1 μM. A medium with an ascorbyl hexadecanoate concentration of 100, 30, 10, 3 or 1 μM was obtained.

Next, Staphylococcus aureus NBRC13276 or Staphylococcus epidermidis IAM1296 is added to each medium at a temperature of 36 ° C. so that the concentration is 1 × 10 ⁷ CFU / mL. And cultured with shaking at 210 rpm. Of the obtained culture, 0.2 mL of the culture was collected. The components contained in the collected culture were derivatized with 2,4-dinitrophenylhydrazine, and the obtained product was filtered through a membrane filter to obtain a measurement sample.

(Comparative Example 1)
In Example 2, a measurement sample was obtained in the same manner as in Example 2 except that isopropylmethylphenol was used instead of ascorbyl 6-hexadecanoate as a test substance.

(Test Example 2)
The measurement samples obtained in Example 2 and Comparative Example 1 were each subjected to HPLC, and the amount of diacetyl contained in the measurement sample (the amount of diacetyl when cultured in the presence of the test substance) was measured.

  In Example 2, a measurement sample was obtained by performing the same operation as in Example 2 except that ethanol as a control substance was used instead of ascorbyl 6-hexadecanoate as a test substance. The measurement sample was subjected to HPLC, and the amount of diacetyl contained in the measurement sample (the amount of diacetyl when cultured in the presence of a control substance) was measured.

  The HPLC measurement conditions for the measurement of the amount of diacetyl are the same as the HPLC measurement conditions for the measurement of the amount of diacetyl in Test Example 1.

  Then, the diacetyl production | generation suppression rate was computed according to Formula (III). Based on the calculated diacetyl production inhibition rate, a 50% inhibition concentration of diacetyl production was calculated. In Test Example 2, the test substance and S.I. The results of examining the relationship with the 50% inhibitory concentration of diacetyl production in Aureus are shown in FIG. FIG. 2B shows the result of examining the relationship with the 50% inhibitory concentration of diacetyl production in epidermidis. In the figure, lane 1 is a 50% inhibitory concentration of diacetyl formation when using ascorbyl 6-hexadecanoate, and lane 2 is diacetyl generation when using isopropylmethylphenol, which is generally used as a bactericidal component for external preparations for skin. 50% inhibitory concentration is indicated. In the figure, “S. aureus” represents Staphylococcus aureus NBRC13276, and “S. epidermidis” represents Staphylococcus epidermidis IAM1296.

  From the results shown in FIG. 2, the 50% inhibitory concentration of diacetyl formation in Staphylococcus aureus NBRC13276 when using ascorbyl 6-hexadecanoate (Example 2) is 6 μM, and staphylococcus It can be seen that the 50% inhibitory concentration of diacetyl formation in Epidermidis (Staphylococcus epidermidis IAM1296) is 2 μM. In contrast, 50% inhibitory concentration of diacetyl formation in Staphylococcus aureus NBRC13276 when using isopropylmethylphenol (Comparative Example 1) and diacetyl formation in Staphylococcus epidermidis IAM1296 It can be seen that the 50% inhibitory concentrations of are 225 μM and 273 μM, respectively.

  Therefore, it can be seen from these results that ascorbyl 6-hexadecanoate has an effect of suppressing the production of diketone compounds typified by diacetyl by skin resident microorganisms even at extremely low concentrations. Moreover, it turns out that ascorbyl 6-hexadecanoate suppresses the production | generation of a diketone compound more effectively compared with the isopropyl methyl phenol generally used as a disinfection component of a skin external preparation.

(Examples 3 to 7)
In the basic medium, sodium lactate and ascorbyl 6-octadecanoate (Example 3), 6-hexadecanoic acid ascorbyl (Example 4), 2-phosphate 6-hexadecanoic acid ascorbyl (Example 5), 2 , 6-dihexadecanoic acid ascorbyl (Example 6) or 2,3,5,6-tetraisohexadecanoic acid ascorbyl (Example 7), sodium lactate concentration 2 mM and test substance concentration 0.01 mass % Was added to obtain a medium.

(Comparative Examples 2 to 5)
To the basic medium, sodium lactate and hexadecanoic acid (Comparative Example 2), ascorbic acid (Comparative Example 3), ascorbyl-2-glucoside (Comparative Example 4) or ascorbyl magnesium phosphate (Comparative Example 5) as a test substance The medium was added so that the concentration of sodium lactate was 2 mM and the concentration of the test substance was 0.01% by mass.

(Test Example 3)
In Test Example 1, the same operation as in Test Example 1 was performed, except that the media obtained in Examples 3 to 7 and Comparative Examples 2 to 5 were used instead of the media obtained in Example 1. The inhibition rate against diacetyl production by Staphylococcus aureus NBRC13276 and Staphylococcus epidermidis IAM1296 was calculated. Table 1 shows the results of examining the relationship between the type of extract contained in the medium and the diacetyl production inhibitory effect in Test Example 3. In Table 1, “S. aureus” represents Staphylococcus aureus NBRC13276, and “S. epidermidis” represents Staphylococcus epidermidis IAM1296. Moreover, the evaluation criteria of the diacetyl production inhibitory action in Table 1 are as follows.
[Evaluation criteria for diacetyl production inhibitory action]
◎ Diacetyl production inhibition rate is 60% or more and 100% or less (the diacetyl production inhibition action is very strong).
○ Diacetyl production inhibition rate is 20% or more and less than 60% (diacetyl production inhibition effect is strong).
X Diacetyl production inhibition rate is less than 20% (diacetyl production inhibition action is very weak).

  From the results shown in Table 1, hexadecanoic acid (Comparative Example 2) constituting the fatty acid moiety in the molecular structure of ascorbyl 6-hexadecanoate is only for diacetyl production by Staphylococcus epidermidis IAM1296. Ascorbic acid (Comparative Example 3) constituting the ascorbic acid moiety in the molecular structure of ascorbyl 6-hexadecanoate, which shows an inhibitory action, is produced by diacetyl production and staphylo Suppresses most of diacetyl production by Staphylococcus epidermidis IAM1296 Etc. It can be seen that does not show. In contrast, ascorbyl 6-hexadecanoate (Example 4) having a fatty acid moiety (hexadecanoic acid moiety) and an ascorbic acid moiety is produced by Staphylococcus aureus NBRC13276 and produced by Staphylococcus epidermidis ( It can be seen that, against any diacetyl production by Staphylococcus epidermidis IAM1296), it exhibits a very strong inhibitory action that cannot be obtained with fatty acid (hexadecanoic acid) alone or ascorbic acid alone.

  Further, from the results shown in Table 1, ascorbyl 6-octadecanoate (Example 3) having a fatty acid part and an ascorbic acid part in the same manner as Ascorbyl 6-hexadecanoate (Example 4), 6-hexadecane 2-phosphate Ascorbyl acid (Example 5), Ascorbyl 2,6-dihexadecanoate (Example 6) and Ascorbyl 2,3,5,6-tetraisohexadecanoate (Example 7) were obtained from Staphylococcus aureus. NBRC13276) and diacetyl production by Staphylococcus epidermidis IAM1296 show very strong inhibitory action. However, ascorbyl-2-glucoside (Comparative Example 4) and magnesium ascorbyl phosphate (Comparative Example 5) are diacetyl produced by Staphylococcus aureus NBRC13276 and Staphylococcus epidermidis IAM12 It can be seen that there is almost no inhibitory effect on any of the production.

  Therefore, from these results, ascorbyl 6-octadecanoate (Example 3), ascorbyl 6-hexadecanoate (Example 4), ascorbyl 6-hexadecanoate (Example 5), 2,6-dihexadecane Ascorbyl fatty acid ester compounds having a fatty acid moiety and an ascorbic acid moiety, such as acid ascorbyl (Example 6) and 2,3,5,6-tetraisohexadecanoic acid ascorbyl (Example 7) and salts thereof According to this, it can be seen that the production of diketone compounds represented by diacetyl by skin resident microorganisms can be effectively suppressed.

(Example 8)
Ascorbyl 6-hexadecanoate was dissolved in sterilized water so as to have a concentration of 0.2% by mass to obtain a test sample.

(Test Example 4)
The axilla of 6 subjects was washed with unscented soap. Thereafter, each subject was allowed to wear a T-shirt with a non-brominated cotton sheet affixed to the axilla, and the cotton sheet was brought into contact with the axilla of the subject. After 18 hours from the start of wearing the T-shirt, each subject exercised to sweat. Thereafter, a cotton sheet was collected from each subject's T-shirt.

  About 1.0 mL of the test sample obtained in Example 8 was sprayed on the obtained cotton sheet. Half of the cotton sheet after spraying was incubated at 35 ° C. for 20 hours. Thereafter, three specialist panels were allowed to evaluate the odor generated from the cotton sheet. The evaluation standard of odor intensity is as follows.

[Evaluation criteria for odor intensity]
0 point: not smelling 1 point: faintly smelling 2 points: weakly smelling 3 points: clearly smelling 4 points: smelling slightly strong 5 points: smelling very strongly

  Moreover, except having used ethanol as a placebo test sample instead of the test sample obtained in Example 8, the same operation as the above was performed and the odor generated from the cotton sheet was evaluated.

  In Test Example 4, the results of examining the relationship between the test sample and the odor intensity are shown in FIG. In the figure, lane 1 shows a placebo test sample, and lane 2 shows a test sample obtained in Example 8.

  From the results shown in FIG. 3, it can be seen that when a test sample containing ascorbyl 6-hexadecanoate was used (Example 8), the odor generated from the cotton sheet was reduced. The Wilcoxon code for the difference in odor intensity between the cotton sheet when using the test sample (Example 8) containing ascorbyl 6-hexadecanoate and the cotton sheet when using the placebo test sample When the rank test was performed, it was confirmed that the difference was statistically significant.

  Since the odor in the axilla, particularly the acid odor, as well as the oil odor in the head, is related to the formation of diketone compounds represented by diacetyl, according to ascorbyl 6-hexadecanoate, the oil odor in the head It is suggested that can also be reduced.

  In addition, also when a compound and its salt other than 6-hexadecanoic acid ascorbyl are used among the compounds represented with general formula (I) and its salt, the same tendency as 6-hexadecanoic acid ascorbyl is seen.

  Therefore, from the above results, the ascorbic acid fatty acid ester compound represented by the compound represented by the general formula (I) and the salt thereof has a body odor caused by the action of the diketone compound represented by the general formula (II), particularly the axillary part. This suggests that it is useful for suppressing the generation of acid odor in the head and the oil odor in the head.

  From the above results, ascorbic acid fatty acid ester compounds represented by the compounds represented by the general formula (I) and salts thereof are effective in suppressing the action of diketone compounds represented by diacetyl derived from skin components and body odors, particularly in the axilla region. This suggests that it is useful for suppressing the generation of acid odor in the head and the oil odor in the head.

  Also, in bedding such as clothes and pillowcases that come into contact with the skin, a precursor of a diketone compound such as lactic acid and skin resident microorganisms that are present on the skin adhere to the skin, and the diketone compound is generated by the skin resident microorganism. Alternatively, it is considered that a diketone compound produced on the skin adheres. From these results, ascorbic acid fatty acid ester compounds represented by the compounds represented by the general formula (I) and salts thereof suppress the action of diketone compounds in bedding such as clothes and pillowcases in contact with the skin, and body odor, This suggests that it is useful for suppressing the generation of odors similar to the acid odor in the axilla and the oil odor in the head.

  From the above results, it is suggested that ascorbic acid fatty acid ester compounds and / or salts thereof are useful as diketone action inhibitors and body odor inhibitors.

(Prescription example)
Hereinafter, the formulation example of the external preparation which concerns on this invention is shown. Note that “EO” in parentheses in the raw material name represents an oxyethylene group. The number described before “EO” indicates the number of added moles of oxyethylene group.

(Prescription Example 1 Deodorant Spray)
Deodorant spray by filling an aerosol container from a stem with a stock solution having the following composition and a propellant having the following composition so that the mass ratio (stock solution / propellant) is 5/95, and attaching a button suitable for the stem. It was.
(Composition of stock solution)
Talc 20.0% by mass
Silic anhydride 20.0% by mass
Chlorhydroxyaluminum 10.0% by mass
Ascorbyl 6-hexadecanoate 1.0% by mass
Menthol 1.5% by mass
Triclosan 0.1% by mass
Dimethylpolysiloxane 15.0% by mass
Perfume Appropriate amount Isopropyl tetradecanoate Balance Total 100.0%
(Propellant composition)
LPG 100.0% by mass

(Prescription Example 2 Deodorant Stick)
The following raw materials were mixed so as to have the following composition to obtain a deodorant stick.
Isopropyl methylphenol 0.2% by mass
Potassium aluminum sulfate 20.0% by mass
Chlorohydroxyaluminum 10.0% by mass
Octadecyl alcohol 5.0% by mass
Glycerol monooctadecanoate 3.0% by mass
Silica anhydride 35.0% by mass
Candelilla wax 0.5% by mass
Castor oil 0.1% by mass
Ascorbyl 6-hexadecanoate 1.0% by mass
Citral 0.04% by mass
Eugenol 0.05% by mass
Decamethylcyclopentasiloxane balance 100.0% by mass

(Prescription Example 3 Deodorant Gel)
The following raw materials were mixed so as to have the following composition to obtain a deodorant gel.
Ascorbyl 6-hexadecanoate 1.0% by mass
Menthol 0.5% by mass
Acrylic acid / alkyl methacrylate copolymer 0.2% by mass
Potassium hydroxide 0.02% by mass
Isononyl isononanoate 1.5% by mass
Triclosan 0.1% by mass
Ethyl alcohol 30.0% by mass
Perfume Appropriate amount Purified water balance Total 100.0% by mass

(Prescription example 4 Deodorant roll-on)
The following raw materials were mixed so as to have the following composition to obtain a deodorant roll-on.
Ascorbyl 6-hexadecanoate 1.0% by mass
Menthol 0.1% by mass
Triclosan 0.1% by mass
Chlorhydroxyaluminum 10.0% by mass
Isononyl isononanoate 1.0% by mass
Hydroxypropyl cellulose 1.0% by mass
Ethyl alcohol 60.0% by mass
Perfume Appropriate amount Purified water balance Total 100.0% by mass

(Formulation Example 5 Wipe Sheet Cosmetic)
A sheet cosmetic for wiping was prepared by impregnating 1 g of a nonwoven fabric with 5 g of a composition having the following composition.
[Sheet composition for wiping off]
Ascorbyl 6-hexadecanoate 1.0% by mass
Menthol 0.1% by mass
Talc 10.0% by mass
Polyoxyethylene polyoxypropylene 2-decyltetradecyl ether
0.2% by mass
Ethyl alcohol 40.0% by mass
Perfume Appropriate amount Purified water balance Total 100.0% by mass

(Formulation Example 6 Latex)
The following raw materials were mixed so as to have the following composition to obtain an emulsion.
Ascorbyl 6-hexadecanoate 1.0% by mass
Liquid paraffin 15.0% by mass
Beeswax 2.0% by mass
Lanolin 1.5% by mass
(9Z) -9-octadecenoic acid sorbitan 2.5% by mass
Polyoxyethylene sorbitan monooleate 1.0% by mass
1,2-octanediol 0.05% by mass
1,3-butylene glycol 13.0% by mass
Xanthan gum 0.5% by mass
Purified water balance 100.0% by mass

(Formulation example 7 lotion)
The following raw materials were mixed so as to have the following composition to obtain a lotion.
Ascorbyl 6-hexadecanoate 1.0% by mass
1,3-butylene glycol 6.0% by mass
Glycerin 4.0% by mass
Hydrolyzed hyaluronic acid 0.1% by mass
Polyoxyethylene polyoxypropylene 2-decyltetradecyl ether
0.2% by mass
Ethylene glycol phenyl ether 0.3% by mass
Perfume proper amount Ethyl alcohol 3.0 mass%
Purified water balance 100.0% by mass

(Prescription Example 8 Skin Care Gel)
The following raw materials were mixed so as to have the following composition to obtain a skin care gel.
Ascorbyl 6-hexadecanoate 1.0% by mass
1,3-butylene glycol 10.0% by mass
Glycerin 3.0% by mass
Dipropylene glycol 5.0% by mass
Acrylic acid / alkyl methacrylate copolymer 0.4% by mass
Xanthan gum 0.01% by mass
Potassium hydroxide 0.15% by mass
Decamethylpolysiloxane 5.0% by mass
Trimethylglycine 10.0% by mass
1.2-pentanediol 0.1% by mass
Glycerin mono 2-ethylhexyl ether 0.05% by mass
Dipotassium glycyrrhizinate 0.1% by mass
Ethyl alcohol 3.0 mass%
Ethylenediaminetetraacetic acid disodium appropriate amount Fragrance appropriate amount Purified water balance 100.0% by mass

(Prescription Example 9 Skin Care Cream)
The following raw materials were mixed so as to have the following composition to obtain a skin care cream.
Liquid paraffin 5.0% by mass
Paraffin 5.0% by mass
Hydrogenated palm oil 3.0% by mass
Docosyl alcohol 3.0% by mass
Octadecanoic acid 1.0% by mass
Glyceryl tri-2-ethylhexanoate 5.0% by mass
Xanthan gum 0.05% by mass
Carboxyvinyl polymer 0.4% by mass
1.5% by mass of polyoxyethylene sorbitan monooctadecanoate
Glyceryl octadecanoate 0.5% by mass
1,3-butylene glycol 10.0% by mass
1,2-octanediol 0.2% by mass
Ascorbyl 6-hexadecanoate 1.0% by mass
Glycerin mono-2-ethylhexyl ether 0.35% by mass
Glycerin 5.0% by mass
Potassium hydroxide Appropriate amount Tocopherol Appropriate amount Disodium ethylenediaminetetraacetate Appropriate amount Fragrance Appropriate amount Purified water Remaining Total 100.0% by mass

(Prescription Example 10 Body lotion)
The following raw materials were mixed so as to have the following composition to obtain a body lotion.
Ascorbyl 6-hexadecanoate 1.0% by mass
Menthol 0.5% by mass
1,3-butylene glycol 5.0% by mass
Nylon powder 5.0% by mass
Ethyl alcohol 50.0% by mass
Perfume Appropriate amount Purified water balance Total 100.0% by mass

(Prescription Example 11 Tonic)
The following raw materials were mixed so as to have the following composition to make a tonic.
Ascorbyl 6-hexadecanoate 1.0% by mass
Menthol 0.5% by mass
D-pantothenyl alcohol 0.2% by mass
Nicotinamide 0.1% by mass
Dl-α-tocopherol acetate 0.1% by mass
Camphor 0.001% by mass
Polyoxyethylene hydrogenated castor oil (50 EO) 0.3% by mass
Sodium lactate 0.5% by mass
Citric acid 0.05% by mass
Ethyl alcohol 50.0% by mass
Perfume Appropriate amount Purified water balance Total 100.0% by mass

(Prescription Example 12 Face Wash)
The following raw materials were mixed so as to have the following composition to obtain a face wash.
30% by mass dodecyldimethylaminoacetic acid betaine solution 3.0% by mass
Dodecanoic acid 5.0% by mass
Tetradecanoic acid 6.0% by mass
Hexadecanoic acid 4.0% by mass
Octadecanoic acid 9.0% by mass
Polyethylene glycol dioctadecanoate (150E.O.)
5.0% by mass
10% by weight vinylpyrrolidone / dimethylaminopropylmethacrylamide / dodecyldimethylaminopropylmethacrylamide chloride copolymer solution
10.0% by mass
Polyethylene glycol 20.0% by mass
Propylene glycol 3.0% by mass
Glycerin 5.0% by mass
1,2-octanediol 0.5% by mass
Hydroxypropyl methylcellulose 0.5% by mass
Potassium hydroxide 5.0% by mass
Ascorbyl 6-hexadecanoate 1.0% by mass
Ethylenediaminetetraacetate appropriate amount perfume appropriate amount purified water remainder total 100.0% by mass

(Prescription Example 13 Body Shampoo)
The following raw materials were mixed so as to have the following composition to obtain a body shampoo.
Dodecanoic acid 5.0% by mass
Tetradecanoic acid 7.0% by mass
Propylene glycol 4.0% by mass
Dodecyldimethylaminoacetic acid betaine 3.5% by mass
Potassium hydroxide 3.6% by mass
Sodium sulfite 0.03% by mass
Methyl paraoxybenzoate 0.3% by mass
Ethylene glycol phenyl ether 0.8% by mass
Ascorbyl 6-hexadecanoate 1.0% by mass
Ethylenediaminetetraacetate appropriate amount perfume appropriate amount purified water remainder total 100.0% by mass

(Prescription Example 14 Shampoo)
The following raw materials were mixed so as to have the following composition to obtain a shampoo.
Sodium polyoxyethylene lauryl ether sulfate 6.0% by mass
Dodecyldimethylaminoacetic acid betaine 2.0% by mass
Polyoxyethylene lauryl ether sodium acetate 3.0% by mass
Disodium lauryl sulfosuccinate 1.0% by mass
Palm oil fatty acid diathanamide 5.0% by mass
O- [2-hydroxy-3- (trimethylammonio) propyl] chloride
Hydroxyethyl cellulose
0.2% by mass
Dipotassium glycyrrhizinate 0.2% by mass
Menthol 1.0% by mass
Ascorbyl 6-hexadecanoate 1.0% by mass
Ethyl alcohol 3.0 mass%
Sodium chloride Appropriate amount Ethylenediaminetetraacetate Appropriate amount Sodium benzoate Appropriate amount Perfume Appropriate amount Purified water Remaining Total 100.0%

  Moreover, in the prescription examples 1-14, instead of using ascorbyl 6-hexadecanoate, ascorbic acid fatty acid ester compounds represented by the general formula (I) other than ascorbyl 6-hexadecanoate and salts thereof are used. The raw materials are mixed so that the composition is the same as that shown in Formulation Examples 1 to 14, and deodorant spray, deodorant stick, deodorant gel, deodorant roll-on, wiping sheet cosmetic, emulsion, makeup Water, skin care gel, skin care cream, body lotion, tonic, face wash, body shampoo and shampoo can be obtained.

Claims (1)

General formula (II) due to skin components by skin resident microorganisms:
R ^5- (CO)-(CO) -R ⁶ (II)
(Wherein R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms)
A in by suppressing the generation represented by diketone compound diketones action inhibitor to inhibit the action of the diketone compound, octadecanoic acid ascorbyl group consisting of hexadecanoic acid ascorbyl phosphate and ascorbyl phosphate trisodium hexadecanoic acid A diketone action inhibitor comprising at least one compound selected from the group.