JPS63183518A - Composition for hair - Google Patents

Abstract

PURPOSE:To obtain a composition for hair capable of promoting melanin formation, preventing and improving gray hair by external use to scalp, containing, a nucleic acid-related substance such as adenosine 3',5'-cyclic-phosphate compound, etc., and flavin adenine dinucleotide, etc. CONSTITUTION:A composition for hair containing 0.01-2% nucleic acid-related substance selected from a compound having a basis skeleton shown by formula I, flavin adenine dinucleotide and a salt thereof. The composition is applied to scalp, activates melanoctye, promotes melanin formation, can prevent and improve gray hair. A compound shown by formula II (R1-R3 are H, 1-22C acyl or alkyl; X1 and X2 are H, halogen, thio-containing group, amino or OH; M1 is H or salt-forming cation) is preferable as the compound shown by formula I and adenosine 3',5'-cyclic-phosphate wherein R1-R3, X1 and X2 are all H may be cited.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applied externally to the scalp to activate melanocytes in the hair roots, promote melanin production, and prevent gray hair.
It relates to hair compositions, such as hair tonics, which can be improved.

[Conventional technology]

Although a large number of hair growth and tonics have been developed to date, there are currently very few reports on the development results of hair cosmetics that have the effect of preventing or improving gray hair. Among them, JP-A-60-1747'05 has
The use of vitamin D3 and its derivatives has been described. However, this method has the following drawbacks: (i) Vitamin D3 and its derivatives used are extremely unstable in the air and easily oxidized, making it difficult to formulate formulations; however, when used continuously as an external preparation, it is not sufficiently effective; (ii) Vitamin D and its derivatives may cause symptoms of hypervitaminosis D, that is, hypercalcemia (anorexia, vomiting, constipation, weight loss, growth arrest, etc.);
There were problems such as doubts about safety, and the technology described in the publication was not practical.

[Problem that the invention seeks to solve]

Therefore, an object of the present invention is to provide a hair composition that exhibits excellent gray hair prevention and improvement effects when applied externally to the scalp and is extremely safe for the skin.

[Means for solving problems]

The present invention can effectively solve the above problems by incorporating specific nucleic acid-related substances and derivatives thereof, which exist in trace amounts in each tissue and cell in the living body and have various regulatory functions and physiological effects, into a cosmetic base material. This was done based on the knowledge that

That is, the present invention provides a hair product containing at least one nucleic acid-related substance selected from the group consisting of a compound having a basic skeleton represented by the following formula [I], flavin adenine dinucleotide, and salts thereof. A composition is provided.

In the present invention, any compound can be used as long as it has a skeleton represented by the above general formula [■] in the molecule, but among these, the compound represented by the following general formula [■] is preferred. preferable.

(In formula [■], R1, R2, R3 are hydrogen, carbon number 1-
22, preferably 1 to 15 acyl group or carbon number 1 to 2
2, preferably an alkyl group of 1 to 15, Xl, X
2 is halogen such as hydrogen, bromine, iodine, chlorine, fluorine,
Thio-containing groups such as mercapto group, thioalkyl group having 1 to 4 carbon atoms, 4-chlorophenylthio group, thiobenzyl group,
They are an amino group, an aminoalkyl group having 1 to 4 carbon atoms, or a hydroxyl group. Ml also represents hydrogen, salt-forming cations, such as alkali metals such as sodium, potassium, and lithium;
Indicates tris(hydroxymethyl)aminomethane. still,
The acyl group and the alkyl group may have a substituent such as a halogen, and may contain an aromatic ring. Alternatively, it may be an acyl group derived from a dibasic acid. ) The compound represented by the above general formula [■] includes adenosine 3',5'-cyclic monophosphate (in the formula, R1, R2, R3,
A compound in which xl, x2, and MI are all hydrogen; hereinafter referred to as cAM
It is abbreviated as P. ), certain derivatives thereof and salts thereof.

Next, these compounds, flavin adenine dinucleotide (hereinafter abbreviated as FAD), and salts thereof will be explained in detail.

Compound represented by the general formula [ID] cAMP used in the present invention is a physiologically important substance that has the ability to regulate various hormone actions in vivo, and has already been used as a biochemical reagent and a cardiac drug.

Currently, they are produced industrially by fermentation or synthesis methods, but various derivatives with improved cell membrane permeability or in vivo stability are also commercially available.

Specific examples of the compound represented by the general formula [■] used in the present invention include one or a mixture of two or more of the compounds shown in Table 1 and their sodium salts, potassium salts, lithium salts, etc. be done.

Note that c p phs used in Table 1 represents a 4-chlorophenylthio group (the same applies hereinafter).

Among these compounds, R1-R3, xl in formula [■]
, X2 are all not hydrogen. Furthermore, it is preferable that R,, R3 are hydrogen or an acyl group, R2 and xl are hydrogen, and x2 is hydrogen, a halogen, a thio-containing group, an amine group, or a hydroxyl group. Among these, when X2 is hydrogen, one or both of R+SRa is an acyl group, and when the acyl group is derived from a monocarboxylic acid, it is particularly preferable that the acyl group has 5 to 5 carbon atoms.
Those having 15 carbon atoms are preferred, and those derived from dicarboxylic acids are preferably those having 2 to 15 carbon atoms.

In addition, when X2 is a halogen, a thio-containing group, an amino group, or a hydroxyl group, R, R3 is hydrogen or has 1 to 1 carbon atoms.
5 is preferably an acyl group.

FAD and its salt FAD are known as important substances that are involved in the general oxidation of organic compounds in vivo as coenzymes of oxidoreductases. FAD is widely used as a pharmaceutical raw material in the treatment of dermatitis, allergic diseases, stomatitis, and beriberi, and as an active ingredient in eye drops.

Currently, FAD is produced industrially by fermentation or synthesis, and is easily available.

Note that salts of FAD can also be used in the present invention, specifically FAD sodium salt (FAD 2Na), FA
Examples include D potassium salt (FAD 2K).

The present invention takes advantage of the hitherto unknown effect of preventing and improving gray hair by directly applying the nucleic acid-related substance as an essential ingredient to the scalp. Can be blended at any concentration. Usually, depending on the product form and frequency of use, various hair compositions contain o, o o i to 5% by weight (hereinafter abbreviated as %).

), preferably 0.01 to 2%.

In addition to the above-mentioned essential ingredients, the composition of the present invention includes other pharmaceutical ingredients, such as vitamins such as vitamin A1, vitamin B6, vitamin E1, pantothenic acid, and biotin; amino acids such as methionine, cysteine, cystine, and tyrosine; Bactericidal agents such as salicylic acid, hinokitiol, resorcinol, trichlorocarbanilide, etc., hormones such as ethinyl estradiol, progesterone, etc. can be blended, and preferably 0.0001 to 3% in the hair composition.
It is good to add it.

Furthermore, raw materials commonly used in cosmetics such as oil, water, surfactants, humectants, lower alcohols, thickeners, antioxidants, chelating agents, pH adjusters, preservatives, fragrances, and pigments can be added. . Specifically, the oils include olive oil,
Oils and fats such as jojoba oil and hydrogenated oils, waxes such as spermaceti wax, beeswax, and lanolin, hydrocarbons such as liquid paraffin, ceresin, and squalane, fatty acids such as stearic acid and oleic acid, cetanol, stearyl alcohol, and lanolin. These include alcohols, alcohols such as hexyldecanol, and esters such as isopropyl myristate and butyl stearate. It is preferable that the hair composition contains oil in an amount of 0.5 to 85%. Examples of surfactants include anionic surfactants such as sodium stearate, sodium cetyl sulfate, polyoxyethylene lauryl ether phosphate, and sodium N-acylglutamate, and cationic surfactants such as stearyldimethylbenzylammonium chloride and stearyltrimethylammonium chloride. Active agent, alkylaminoethylglycine hydrochloride solution, amphoteric surfactant such as lecithin, glycerin monostearate, sorbitan monostearate, sucrose fatty acid ester, propylene glycol monostearate, polyoxyethylene oleyl ether, polyethylene glycol monostearate Examples include nonionic surfactants such as polyoxyethylene sorbicun monopalmitate, polyoxyethylene coconut fatty acid monoethanolamide, polyoxyethylene polyoxypropylene glycol, polyoxyethylene castor oil, and polyoxyethylene lanolin. can. The surfactant is preferably contained in the hair composition in an amount of 0.1 to 15%. Furthermore, as humectants, glycerin, 1,3-butylene glycol, propylene glycol, etc. are used, as lower alcohols, ethanol, inpropatol, etc. are used, as thickeners, polyethylene glycol, carboxymethyl cellulose sodium, etc., and oxidized As inhibitors, dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, etc. are used. As chelating agents, disodium edetate, ethane hydroxy diphosphate, etc. are used. As pH adjusters, citric acid, sodium citrate, boron, etc. are used. Examples of preservatives include methyl paraoxybenzoate, etinopedehydroacetic acid paraoxybenzoate, salicylic acid, and benzoic acid. Note that the optional components are not limited to these. By appropriately blending the above-mentioned essential components and optional components, it can be used in a variety of product forms, including hair tonics, creams, lotions, emulsions, ointments, etc., as long as they can be used externally.

Specifically, the hair tonic contains 0.0% of the above essential ingredients.
01-2%, lower alcohol 40-98%, drug ingredients 0
~3%, moisturizer 0-15%, purified water 0-60%, fragrance
Examples include compositions containing trace amounts of the above essential ingredients, 0.01 to 2% of the above essential ingredients, 20 to 80% of oil content,
An example is a composition containing 0.5 to 15% surfactant, 0 to 15% humectant, 15 to 80% purified water, and a trace amount of preservative. In addition, as an emulsion, 0.01 to 2% of the above essential ingredients
Examples include compositions containing 5 to 30% oil, 0.5 to 15% surfactant, 0 to 15% humectant, 50 to 95% purified water, and a trace amount of preservative.

The details of the effect of the nucleic acid-related substance used in the present invention on preventing and improving gray hair when applied externally are unknown, but it activates melanocytes present in the hair bulb of the scalp hair roots to promote melanin production, resulting in the production of melanin. By incorporating the granules into hair matrix cells, it has the effect of preventing and improving gray hair.
Furthermore, it is presumed that it also exhibits hair nourishing and restoring effects by activating hair matrix cells.

In addition, the nucleic acid-related substance of the present invention is extremely safe because it is widely present in living organisms. No practical problems were observed in terms of performance, etc.

〔Effect of the invention〕

According to the present invention, there is provided a hair cosmetic that exhibits excellent gray hair prevention and improvement effects when applied externally to the scalp and is extremely safe for the skin.

According to the present invention, in addition to the above-mentioned effects, hair nourishing and hair growth effects are also achieved.
Demonstrated.

Therefore, the hair composition of the present invention can be applied to hair in various forms, such as hair tonics, creams, lotions, emulsions, ointments, hair treatments, hair conditioners, and other hair cosmetics, and externally applicable formulations. It can be used widely in various forms.

Next, the present invention will be explained by examples.

In addition, the following abbreviations were used in the examples.

MB: monobutyryl MH: monohexanoyl MO = monooctanoyl MS: monosuccinyl DA nidiacetyl DB nidibutyryl DM = dimalonyl DS nidisuccinyl CβPhS: 4-chlorophenylthio Further, the positions of the substituents of the cAMP derivative are shown as follows.

N6: Indicates the bonding position when R or R2 is other than hydrogen.

0'': Indicates the bonding position when R3 is other than hydrogen.

8: Shows the bonding position when X2 is other than hydrogen.

〔Example〕

Example 1 A fragrance was added to ethanol and dissolved uniformly. Separately, a solution was prepared by adding other ingredients to purified water and uniformly dissolved therein, and the ethanol solution was added thereto to prepare a hair tonic. The composition is shown in Table 2, and the numerical values in the table are the blending amount (% by weight) (the same applies hereinafter).

Table 2 The above hair tonic was applied to 20 men and women with gray hair (30~
(60 years old) twice a day (morning and evening) for 3 consecutive months, the product of the present invention and the comparative example were used separately on the left and right scalp using the half-head method, and the condition of the application site was observed before and after the test. We compared the results and investigated their effectiveness in preventing and improving gray hair. The results are shown below.

Table-3 From the results of Table-3, N6.0''-DBcAMP-Na
It can be seen that the hair tonic of the present invention containing the above can reduce the amount of gray hair compared to a hair tonic without additives, and exhibits a remarkable effect of preventing and improving gray hair.

In addition, no abnormal symptoms were observed in the skin condition during or after using the hair tonic for three months.

N6. A tweet test was conducted to check the safety of O''-DBcAMP-Na. The test items and results are summarized in Table 4.

From the results in Table-4, N6. O”-DBcAMP-N
It was confirmed that the safety of a was extremely high.

Example 2 Components 1 to 5 and components 6 to 10 shown in Table 5 were separately prepared at 80%
After heating and dissolving at ℃, the two were mixed and emulsified, and while cooling,
Component 11 was added and further uniformly dispersed to prepare a hair emulsion. In addition, in the table, T indicates the average number of added moles of ethylene oxide (the same applies hereinafter).

Table 5 In the same manner as in Example 1, the effect of the milky lotion on preventing and improving gray hair was investigated. The results are shown in Table-6.

Table 6 From the results in Table 6, when using the emulsion of the present invention containing FAD/2Na, the amount of gray hair was smaller than when using an additive-free emulsion, and there was significant prevention and improvement of gray hair. It was shown to be effective.

In addition, no abnormal skin symptoms were observed during or after using the emulsion for three months.

Furthermore, the same emulsion was also tested for hair growth effect as described below.

That is, six C57 black mice were made into one group, hairs were pricked from both sides of the abdomen to the back of the mice, and the emulsion of the present invention was applied to one side and the comparative example was applied once a day for two consecutive weeks for two consecutive weeks. Then, the length of hair that grew in the pricked area was measured every week to compare the hair growth effects. The results are shown in Table-7. The numerical values in Table 2 are the hair length (mm) expressed as the standard deviation above the average value.

Table 7 As is clear from the results in Table 7, FAD ・2Na
The emulsion of the present invention containing the above showed a remarkable hair-nourishing effect compared to the emulsion without additives.

When testing the safety of FAD 2Na using the same method as in Example 1, no problems such as skin irritation were observed, and it was confirmed that the safety was extremely high.

Example 3 Components 1 to 6 and components 7 to 10 shown in Table-8 were separately prepared at 80%
After heating and dissolving at ℃, the mixture was mixed and emulsified, and while cooling, component 11 was added and uniformly dispersed to prepare the hair cream shown in Table 8.

In the same manner as in Example 1, the effect of the hair cream on preventing and improving gray hair was investigated. The results are shown in Table-9.

Table-9 From the results of Table-9, N6. O”-DScAMP-Na
When the cream of the present invention containing the following was used, the amount of gray hair was smaller than when using a cream without additives, and it showed a remarkable effect of preventing and improving gray hair.

Furthermore, during and after using the above cream for three months, no abnormal symptoms were observed in the condition of the skin. Furthermore, when the safety of N6.0"-DScAMP-Na was tested in the same manner as in Example 1, no problems such as skin irritation were observed, and it was confirmed that the safety was extremely high.

Example 4 After separately mixing and dissolving components 1 to 4 and components 5 to 9 shown in Table 10, the solution of components 1 to 4 was added thereto while stirring the solution of components 5 to 9, and the solution of components 1 to 4 was added to the solution shown in Table 1. A hair emulsion shown in No. 10 was prepared.

In the same manner as in Example 1, the effect of the emulsion on preventing and improving gray hair was investigated. The results are shown in Table-11.

Table 11 From the results in Table 11, when using the emulsion of the present invention containing O"-MSc and AMP-Na, the amount of gray hair was less and more noticeable than when using an additive-free emulsion. It has been shown to be effective in preventing and improving gray hair.

In addition, no abnormal skin symptoms were observed during or after using the emulsion for three months.

Furthermore, when testing the safety of O''-MScAMP-Na using the same method as in Example 1, no problems such as skin irritation were observed, and it was confirmed that the safety was extremely high.

Example 5 A hair cream having the composition shown in Table 12 was prepared, and Example 1
In the same manner as above, the effect of preventing and improving gray hair was investigated. The results are shown in Table-13.

Table 13 From the results in Table 13, when using the hair cream of the present invention containing N6-MBcAMP-Na, the amount of gray hair was less and more noticeable than when using additive-free hair cream. It has been shown to be effective in preventing and improving gray hair.
“In addition, no abnormal symptoms were observed in the skin condition during or after using the above hair cream for 3 months.In addition, the safety of N6-MBcAMP-Na was tested using the same method as in Example 1. When tested, no problems such as skin irritation were observed, confirming that the product is extremely safe.

Example 6 N6. used in Example 3. O”-DScAMl”Na
instead of 8-BrcAMt'Na, 8-C12cA
MP-Na, 8-Cjl! PhScAMP・Na,
8-3fl8-3flcA, 8-OHc8-0Hc
A, O”-MB-8-BrcAMP・Na or N
A hair tonic containing 6.0"-D^-8-NH2CAMP-Na was prepared and evaluated in the same manner as in Example 1. As a result, almost the same gray hair prevention and improvement effect as in Example 3 was obtained.

Example 7 A hair tonic was prepared by sequentially adding other ingredients to ethanol and uniformly dissolving them. The composition is shown in Table-14.

Table 14 In the same manner as in Example 1, the hair tonic was used to prevent gray hair,
The improvement effect was investigated. The results are shown in Table-15.

Table 15 From the results in Table 15, when using the hair tonic of the present invention containing FAD/2Na, the amount of gray hair was smaller than when using the hair tonic without additives, and there was significant prevention of gray hair. , showed an improvement effect.

Furthermore, even during and after using the above hair tonic for three months, I could not bear any unusual symptoms in my skin condition.

Example 8 Instead of FAD・2Na used in Example 7, Na-MS
cAMl”Na, %N6-MHcAMP-Na, 0”
-MOcAMP-Na or Na, O”-DMcA
A hair tonic containing Mt'Na was prepared and Example 1
When evaluated in the same manner as in Example 7, almost the same gray hair prevention and improvement effects as in Example 7 were obtained.

Claims (2)

[Claims] (1) A hair composition comprising at least one nucleic acid-related substance selected from the group consisting of a compound having a basic skeleton represented by the following formula [I], flavin adenine dinucleotide, and salts thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・〔I
] (2) The compound having the basic skeleton represented by the formula [I] is adenosine 3',5' represented by the following general formula [II]
- The hair composition according to claim (1), which is a cyclic phosphoric acid compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] (In the formula [II], R_1, R_2, R_3 are hydrogen, an acyl group having 1 to 22 carbon atoms, or an acyl group having 1 to 22 carbon atoms. is an alkyl group, X_1 and X_2 are hydrogen, halogen, thio-containing group, amino group, aminoalkyl group or hydroxyl group, and M_1 represents hydrogen or a salt-forming cation.)