JP2019085341A - Cosmetics having skin-whitening effect and antibacterial properties - Google Patents

Abstract

To provide cosmetics having skin-whitening effect and antibacterial properties and being inexpensive.SOLUTION: The present invention provides cosmetics containing at least one of phenyl ethanol derivatives represented by formula (1) and a protamine carbonate [R-Rindependently represent an aldehyde group, a sulfone group, a carboxyl group, an amino group, OH, H or salts thereof; Ris H or an alkali metal, or an alkaline earth metal].SELECTED DRAWING: None

Description

  The present invention relates to a cosmetic having a whitening effect and an antibacterial property. In particular, the present invention relates to a cosmetic that is safe and inexpensive, and has high whitening effect and antibacterial properties.

  Blackening of the skin observed by spots, freckles, sunburn, etc. is considered to be caused by excessive production of melanin pigment by melanin-producing cells contained in the skin due to hormonal abnormalities or ultraviolet rays contained in sunlight. ing. Ascorbic acid (vitamin C) has been used as one of the methods for suppressing such overproduction of melanin pigment (Patent Document 1).

  In addition, conventionally, it is a whitening cosmetic that contains hydroquinone monobenzyl ether, hydrogen peroxide, kojic acid, etc., which has the function of suppressing excessive formation of melanin in order to prevent skin blackening, stains and freckles and to maintain the original skin. Have been proposed (Patent Document 2).

  However, although the above components can be incorporated into cosmetics and can provide a certain whitening effect, the effect is temporary, and it is difficult to achieve both a high whitening effect and high safety. .

  Further, in recent years, several health problems caused by specific substances contained in cosmetics have been reported, and development of safer cosmetics is desired (Non-patent Document 1).

  In view of such circumstances, the present inventor paid attention to polyphenol compounds generally regarded as safe, and among them, it was possible to confirm a whitening effect on phenyl ether compounds and their analogs.

  Furthermore, among them, as a novel compound, a phenylethanol derivative represented by hydroxytyrosol is most preferable in terms of safety, and since a whitening effect can also be expected, the use of the present compound is effective as a countermeasure against the above situation. (Non-Patent Document 2).

  In addition, the present inventor was able to use it safely and at ease in the body by containing protamine extracted from seafood for eating and drinking as a natural product in the form of protamine carbonate, and had long-term antibacterial activity and stability. We are developing cosmetics (Patent Document 3).

Unexamined-Japanese-Patent No. 05-229931 gazette Patent No. 3455470 Patent No. 4939782

Hiraguna Makiko and 1 other person, "hydrolyzed wheat", allergy, 63 (1), 63-64, 2014 (Heira 26) EFSA Journal 2017; 15 (3): 4728 [23 pp. ]

  Although a phenylethanol derivative represented by hydroxytyrosol is most preferable in terms of safety, and a whitening effect can also be expected, the amount thereof added to cosmetics is naturally limited because it is expensive itself.

  Therefore, it is an object of the present invention to provide inexpensive cosmetics having high safety, whitening effect and long-term antibacterial activity, even when used for cleansing the body or for whitening. Do.

  The present inventor has found that the skin-whitening effect of a phenylethanol derivative can be further enhanced by incorporating protamine in the form of a carbonate in a cosmetic containing a phenylethanol derivative represented by hydroxytyrosol. As a result, the above problems have been solved. That is, by adding protamine carbonate, which is cheaper than phenylethanol derivatives, to cosmetics containing hydroxyphenol derivatives, it is possible to improve not only long-term antibacterial activity but also the whitening effect as compared with hydroxyphenol derivatives alone. It became clear.

（式中、Ｒ₁〜Ｒ₅は、それぞれ独立して、アルデヒド基、スルホン基、カルボキシル基、アミノ基、水酸基、水素原子またそれぞれの塩から選択される。Ｒ₆は水素原子又はアルカリ金属、アルカリ土類金属から選択される。）
（２）前記フェニルエタノール誘導体が、２−（４−ヒドロキシフェニル）エタノール、２−（１，２−ジヒドロキシフェニル）エタノール、２−（１，３−ジヒドロキシフェニル）エタノール、２−（１，４−ジヒドロキシフェニル）エタノール、２−（１，５−ヒドロキシフェニル）エタノール、２−（２，３−ジヒドロキシフェニル）エタノール、２−（２，４−ジヒドロキシフェニル）エタノール、２−（２，５−ジヒドロキシフェニル）エタノール、２−（３，４−ジヒドロキシフェニル）エタノール、２−（１，２，３−トリヒドロキシフェニル）エタノール、２−（１，２，３，４−テトラヒドロキシフェニル）エタノール、２−（ペンタヒドロキシフェニル）エタノール又はこれらの塩であることを特徴とする（１）に記載の化粧料。
（３）前記フェニルエタノール誘導体が、２−（３，４−ジヒドロキシフェニル）エタノール又はそのアルコールの塩であることを特徴とする（２）に記載の化粧料。
（４）前記フェニルエタノール誘導体の含有量が０．０００１ｗｔ％〜１０ｗｔ％であることを特徴とする（１）〜（３）のいずれかに記載の化粧料。
（５）前記プロタミン炭酸塩の含有量が０．０００１ｗｔ％〜１０ｗｔ％であることを特徴とする（１）〜（４）のいずれかに記載の化粧料。
（６）洗浄用化粧料であることを特徴とする（１）〜（５）のいずれかに記載の化粧料。
（７）身体洗浄用の洗剤であることを特徴とする（６）に記載の化粧料。
（８）固形又は液体石鹸であることを特徴とする（６）又は（７）に記載の化粧料。
（９）ｐＨが８以上であることを特徴とする（１）〜（８）のいずれかに記載の化粧料。
（１０）食品の取り扱いに際して身体の洗浄に用いられることを特徴とする（１）〜（９）のいずれかに記載の化粧料。
（１１）医療又は看護への従事に際して身体の洗浄に用いられることを特徴とする（１）〜（９）のいずれかに記載の化粧料。
（１２）美白用であることを特徴とする（１）〜（９）のいずれかに記載の化粧料。 Therefore, the present invention is specified as follows.
(1) A cosmetic comprising at least one or more of phenylethanol derivatives represented by the following chemical formula (1), and protamine carbonate.

(Wherein, R _{1 to} R ₅ are each independently selected from an aldehyde group, a sulfone group, a carboxyl group, an amino group, a hydroxyl group, a hydrogen atom or a salt thereof. R ₆ is a hydrogen atom or an alkali metal, Selected from alkaline earth metals)
(2) The phenylethanol derivative is 2- (4-hydroxyphenyl) ethanol, 2- (1,2-dihydroxyphenyl) ethanol, 2- (1,3-dihydroxyphenyl) ethanol, 2- (1,4- (1,4-dihydroxyphenyl) ethanol) Dihydroxyphenyl) ethanol, 2- (1,5-hydroxyphenyl) ethanol, 2- (2,3-dihydroxyphenyl) ethanol, 2- (2,4-dihydroxyphenyl) ethanol, 2- (2,5-dihydroxyphenyl) ) Ethanol, 2- (3,4-dihydroxyphenyl) ethanol, 2- (1,2,3-trihydroxyphenyl) ethanol, 2- (1,2,3,4-tetrahydroxyphenyl) ethanol, 2- (2) Pentahydroxyphenyl) ethanol or salts thereof, described in (1) Cosmetics.
(3) The cosmetic according to (2), wherein the phenylethanol derivative is 2- (3,4-dihydroxyphenyl) ethanol or a salt of an alcohol thereof.
(4) The cosmetic according to any one of (1) to (3), wherein the content of the phenylethanol derivative is 0.0001 wt% to 10 wt%.
(5) The cosmetic according to any one of (1) to (4), wherein the content of the protamine carbonate is 0.0001 wt% to 10 wt%.
(6) The cosmetic according to any one of (1) to (5), which is a cosmetic for cleaning.
(7) The cosmetic according to (6), which is a detergent for body washing.
(8) The cosmetic according to (6) or (7), which is a solid or liquid soap.
(9) The cosmetic according to any one of (1) to (8), which has a pH of 8 or more.
(10) The cosmetic according to any one of (1) to (9), which is used for cleansing the body when handling food.
(11) The cosmetic according to any one of (1) to (9), which is used for cleansing the body when engaged in medical care or nursing.
(12) The cosmetic according to any one of (1) to (9), which is characterized by being for whitening.

  ADVANTAGE OF THE INVENTION According to this invention, the cheap cosmetics which have a high skin-whitening effect can be provided, maintaining an antimicrobial effect with high safety | security and long-term stability stably.

（式中、Ｒ₁〜Ｒ₅は、それぞれ独立して、アルデヒド基、スルホン基、カルボキシル基、アミノ基、水酸基、水素原子またそれぞれの塩から選択される。Ｒ₆は水素原子又はアルカリ金属、アルカリ土類金属から選択される。） The present invention is a cosmetic containing at least one or more kinds of phenylethanol derivatives represented by the following chemical formula (2).

(Wherein, R _{1 to} R ₅ are each independently selected from an aldehyde group, a sulfone group, a carboxyl group, an amino group, a hydroxyl group, a hydrogen atom or a salt thereof. R ₆ is a hydrogen atom or an alkali metal, Selected from alkaline earth metals)

  The phenylethanol derivative represented by the above chemical formula (2) basically has a whitening effect, and examples thereof include 2- (4-hydroxyphenyl) ethanol, 2- (1,2-dihydroxyphenyl) ethanol, 2- (1,3-dihydroxyphenyl) ethanol, 2- (1,4-dihydroxyphenyl) ethanol, 2- (1,5-hydroxyphenyl) ethanol, 2- (2,3-dihydroxyphenyl) ethanol, 2- (2,4-dihydroxyphenyl) ethanol, 2- (2,5-dihydroxyphenyl) ethanol, 2- (3,4-dihydroxyphenyl) ethanol, 2- (1,2,3-trihydroxyphenyl) ethanol, 2 -(1,2,3,4-tetrahydroxyphenyl) ethanol, 2- (pentahydroxyphenyl) ) Ethanol or may be selected from these salts.

  In addition, as a phenylethanol derivative represented by the above chemical formula (2), although a compound of natural origin is also present, 2- (3,4-dihydroxyphenyl) ethanol or a salt of alcohol thereof is most safe. preferable.

  The method for producing hydroxytyrosol (2- (3,4-dihydroxyphenyl) ethanol) is not particularly limited. In particular, in order to increase the effect of the present invention, it is preferable to use an extract from a plant material containing a large amount of hydroxytyrosol, but there is no problem in using a commercial product or chemical synthesis. When hydroxytyrosol is added in an amount of less than 0.0001 wt%, the whitening effect is not exhibited well. Even if the amount is more than 10% by weight, the effect corresponding to the increase of the addition amount can not be obtained. Therefore, although 0.0001 wt% to 10 wt% is preferably added and used, 0.001 wt% to 5 wt% is more preferable, and most preferably 0.01 wt% to 1 wt%.

  The present invention is also a cosmetic containing protamine carbonate. By including protamine carbonate, it exhibits long-term antibacterial activity.

  Protamine carbonate is conventionally known as an antibacterial agent, but when used in the present invention, it has been recognized that the whitening effect of cosmetics is further improved. The detailed reason is unclear, but it is speculated that it may be due to the solubilizing power of protamine carbonate. That is, protamine contains a large amount of arginine, and this arginine constitutes a protein as one of the amino acids, but even the monomer exhibits interesting properties, and among them, the solubilizing effect is mentioned. In particular, the solubilizing power is effective for a compound having an aromatic ring, and the solubilizing effect on the cosmetic works on the phenylethanol derivative contained in the cosmetic of the present invention, and the whitening effect is improved. It is guessed that it is connected to

  Protamine used in the present invention is known to be effectively extracted from fish, in particular silkworm and silkworm, and is used as a safe food preservative of biological origin because of its high antibacterial activity. . Since the antibacterial property of protamine is excellent in alkalinity, it may be considered to be used for detergents and soaps having excellent detergency.

  In addition, the amount of protamine carbonate is adjusted in consideration of the maintenance of the antibacterial property and the ease of adjustment. When the content of carbonate of protamine is less than 0.0001 wt%, the antibacterial effect is not exhibited well. The addition of more than 10 wt% does not increase the antibacterial effect to the extent of the increase. Therefore, 0.0001 wt% to 10 wt% is preferably added and used, but 0.001 wt% to 1 wt% is more preferable, and most preferably 0.01 wt% to 1 wt%.

  The cosmetic composition of the present invention can be used as a cleansing cosmetic composition, particularly as a body cleansing detergent. Although the form is not limited, it can be used as a solid or liquid soap. The confirmation of the pH of the cosmetic can be easily performed, for example, by using a 1% aqueous solution thereof, and it is desirable that the pH is 8 or more. Such detergents and soaps are suitably used for body washing or for cosmetic purposes such as whitening when handling food or engaging in medical care or nursing as an application.

  In the case of a solid soap, the cosmetic of the present invention can be produced by kneading, for example, hydroxytyrosol or a derivative thereof and protamine carbonate in a soap base. The soap base is not limited to the composition etc., and so-called soap base can be used. For example, fats and oils such as tallow, palm oil, palm stearin and coconut oil are saponified, if necessary Water can be used.

  In the case of a liquid soap, the cosmetic of the present invention can be produced by adding, for example, hydroxytyrosol or a derivative thereof and protamine carbonate to an aqueous surfactant solution or an aqueous emulsion and stirring and mixing. .

  In addition, in the cosmetic of the present invention, components that are generally added to cosmetics can be blended as needed and in a range that does not impair the effects of the present invention. For example, perfumes, dyes, pH adjusters, dispersants, oil components, saccharides, alcohols, moisturizers, thickeners, antioxidants and the like.

  EXAMPLES Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples, and arbitrary modifications can be made within the scope of the technical idea of the present invention.

(Comparative example 1)
A soap base made from beef tallow and purified water was prepared. The soap itself was taken as Comparative Example 1.

(Comparative example 2)
With respect to the soap base of Comparative Example 1, 0.05 wt% of protamine carbonate was added and kneaded to obtain Comparative Example 2.

(Comparative example 3)
With respect to the soap base of Comparative Example 1, 0.01 wt% of hydroxytyrosol was added and kneaded to obtain Comparative Example 3.

(Comparative example 4)
With respect to the soap base of Comparative Example 1, 0.05 wt% of ascorbic acid was added and kneaded to obtain Comparative Example 4.

(Comparative example 5)
Comparative Example 5 was obtained by adding 0.05 wt% of protamine carbonate to a 15 wt% aqueous polyoxyethylene lauryl ether sulfate surfactant solution and stirring and mixing.

(Comparative example 6)
Comparative Example 6 was obtained by adding 0.01 wt% of hydroxytyrosol to a 15 wt% aqueous solution of polyoxyethylene lauryl ether sulfate surfactant and stirring and mixing.

Example 1
With respect to the soap base of Comparative Example 1, 0.05 wt% of protamine carbonate and 0.01 wt% of hydroxytyrosol were added and kneaded to obtain Example 1.

(Example 2)
With respect to the liquid detergent raw material of Comparative Example 5, 0.01 wt% of hydroxytyrosol was added, stirred and mixed to obtain Example 2.

(Example 3)
With respect to the liquid detergent raw material of Comparative Example 5, 0.01 wt% of 2- (2,3-dihydroxyphenyl) ethanol was added, stirred and mixed to obtain Example 3.

(Example 4)
With respect to the liquid detergent raw material of Comparative Example 5, 0.01 wt% of 2- (1,2,3-trihydroxyphenyl) ethanol was added, stirred and mixed to obtain Example 4.

(Example 5)
With respect to the liquid detergent raw material of Comparative Example 5, 0.01 wt% of hydroxytyrosol carboxylic acid ester salt was added, stirred and mixed to obtain Example 5.

<Antibacterial confirmation test>
Two samples of each of the above Comparative Examples 1 to 6 and Examples 1 to 5 contained in a zippered polyethylene bag are prepared, one in a household freezer at -5 ° C and the other at 40 ° C. Each of the samples was stored for 1 year in a thermostatic chamber, and samples for antimicrobial confirmation test were prepared. The samples stored at minus 5 ° C. were distinguished by the symbol L, and the samples stored at 40 ° C. by the symbol H. Samples stored at -5 ° C are considered not to age.

  The sample for confirming the antibacterial property was boiled and then dissolved in pure water to prepare a 1% aqueous solution. According to a conventional method, petri dishes placed in agar medium were prepared, and about 0.01 g of each of the above aqueous solutions was sprayed. Each petri dish was left outdoors for 24 hours and then heated at 36 ° C. ± 2 ° C. for one week. Then, it observed with the microscope of 800 times.

  In the petri dishes of Comparative Examples 1L and 1H, remarkable growth of bacteria was observed. Moreover, compared with Comparative Example 1, Comparative Examples 3L and 3H were recognized although growth of bacteria was slightly suppressed. On the other hand, remarkable growth of bacteria was not confirmed in petri dishes of Comparative Examples 2L, 2H, 5L, 5H, Examples 1L, 1H, 2L, 2H, 3L, 3H, 4L, 4H, 5L, 5H. In addition, although the degree of the comparison examples 4L, 4H and 6L, 6H was weaker compared to the case where protamine carbonate was mixed, the growth inhibitory effect of the bacteria was recognized.

<Whitening effect test for human skin>
The cosmetic of the present invention (Examples 1 to 5) and the comparative examples (Comparative Examples 1 to 6) were used for about one month each for 20 female subjects who are concerned about the blackness of the skin and skin spots. The skin condition after use was evaluated on the basis of the following criteria.
◎: Simi and buckwheat, the blackness of the skin was significantly improved.
○: Simi, buckwheat, the blackness of the skin was improved.
:: Simi, buckwheat, the skin blackness was slightly improved.
X: Simi and buckwheat, the blackness of the skin was unchanged.

  In addition, as a numerical determination, the degree of blackness of the skin of the region of particular concern was previously measured using a spectrocolorimeter (Konica Minolta CM-77d), and the change before and after the test was quantified. In the present invention, L *, a * and b * color systems are used, and in the present invention, “L *” values indicating the brightness and darkness of the skin are determined and analyzed.

  The L * value gradually increases when the cosmetic of the example and the comparative example is used, and there is an effect. The effect was determined by the L * value (ΔL *) of the skin color before and at the start of the test. As the ΔL * value, the arithmetically averaged value of 20 subjects was used. The above test results are shown in Table 1 below.

  As is clear from Table 1 above, it was found that the effects on whitening were very excellent in Examples 1 to 5 of the present invention, as compared with the comparative examples not containing hydroxytyrosol or its derivative. It also became clear that the effect on skin lightening was further improved when protamine carbonate was included.

  As described above, in addition to having high safety and the ability to maintain the antibacterial effect without being denatured over a long period of time, the present invention has a high whitening effect even if the amount of phenylethanol derivative used is small. It is also obvious that it can provide inexpensive detergents and soaps not only for body washing but also for whitening.

Claims (12)

A cosmetic comprising at least one or more kinds of phenylethanol derivatives represented by the following chemical formula (1), and protamine carbonate.

(Wherein, R _{1 to} R ₅ are each independently selected from an aldehyde group, a sulfone group, a carboxyl group, an amino group, a hydroxyl group, a hydrogen atom or a salt thereof. R ₆ is a hydrogen atom or an alkali metal, Selected from alkaline earth metals)   The phenylethanol derivative is 2- (4-hydroxyphenyl) ethanol, 2- (1,2-dihydroxyphenyl) ethanol, 2- (1,3-dihydroxyphenyl) ethanol, 2- (1,4-dihydroxyphenyl) Ethanol, 2- (1,5-hydroxyphenyl) ethanol, 2- (2,3-dihydroxyphenyl) ethanol, 2- (2,4-dihydroxyphenyl) ethanol, 2- (2,5-dihydroxyphenyl) ethanol, 2- (3,4-Dihydroxyphenyl) ethanol, 2- (1,2,3-trihydroxyphenyl) ethanol, 2- (1,2,3,4-tetrahydroxyphenyl) ethanol, 2- (pentahydroxyphenyl) 2.) A preparation according to claim 1, characterized in that it is ethanol or a salt thereof. Fee.   The cosmetic according to claim 2, wherein the phenylethanol derivative is 2- (3,4-dihydroxyphenyl) ethanol or a salt of alcohol thereof.   The cosmetic according to any one of claims 1 to 3, wherein the content of the phenylethanol derivative is 0.0001 wt% to 10 wt%.   The cosmetic according to any one of claims 1 to 4, wherein the content of the protamine carbonate is 0.0001 wt% to 10 wt%.   The cosmetic according to any one of claims 1 to 5, which is a cosmetic for cleaning.   The cosmetic according to claim 6, which is a body washing detergent.   The cosmetic according to claim 6 or 7, which is a solid or liquid soap.   The cosmetic according to any one of claims 1 to 8, which has a pH of 8 or more.   The cosmetic according to any one of claims 1 to 9, which is used for cleansing the body when handling food.   The cosmetic according to any one of claims 1 to 9, which is used for cleansing the body when engaged in medical or nursing care.   The cosmetic according to any one of claims 1 to 9, which is for whitening.