JPH0240317A - Hair dye composition - Google Patents

Abstract

PURPOSE:To obtain a hair dye composition, consisting of a polyvalent metal salt and one or more compounds selected from ascorbic acids, anthrone glycosides, flavone dimers, and ellagic acids, etc., and capable of slow hair dyeing of gray hair in routine hair care action without damaging hair even by repeated use thereof. CONSTITUTION:A hair dye agent composition obtained by blending 0.001-10-wt.%, preferably 0.1-7.0wt.% polyvalent metal salt (e.g., ferrous chloride, ferrous sulfate or ferric sulfate) as an ingredient (A) and 0.001-10wt.%, preferably 0.05-6wt.% one or more compounds selected from ascorbic acids, anthrone glycosides (e.g., emodin monomethyl ether), flavone dimers (e.g., 7,7''-di-o- methylcupressuflavone), falvonoid glycosides (e.g., gossypitrin), caffeic acids (e.g., caffeic acid), gossypols (e.g., hemerocallin), kojic acids and ellagic acids as an ingredient (B). The composition is preferably prepared in the form of two-pack type consisting essentially of the ingredients (A) and (B).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a hair dye composition, and more specifically to a hair dye that does not damage the hair and can gradually dye gray hair during daily hair care activities. The present invention relates to a drug composition.

[Conventional technology]

Traditionally, two-component hair dyes containing para-ferlenediamine-based oxidized dyes as the main ingredient have been commonly used, but some people with idiosyncratic conditions may experience skin irritation or allergies. It has been pointed out that there are safety problems, such as causing symptoms, etc., and suspicions regarding its mutagenicity.

To solve this problem, hair dyes containing a combination of polyvalent metal salts and sulfur or polyphenol compounds (JP-A-53-52633, JP-A-55-15491) were developed.
No. 2, JP-A-49-36838, etc.), those using plant extracts (US Pat. No. 4,183,366, JP-A-61-225259), or those using quinone compounds. Things (Unexamined Japanese Patent Publication No. 63-33320
Although many proposals have been made, such as (No. 1), they damage the hair.

Combability deteriorates. They have many drawbacks, such as staining the nails and skin, insufficient hair dyeing properties, and polyphenols are sensitizing, making them undesirable from a safety standpoint, and they do not necessarily satisfy the needs of users.

〔the purpose〕

The present invention has been made in view of the above-mentioned circumstances of the prior art, and its purpose is to be able to gradually dye hair during daily hair care activities without damaging the hair with excellent safety, and with ease of combing. An object of the present invention is to provide an excellent hair dye composition.

〔composition〕

According to the present invention, (A) a polyvalent metal salt and (B) 1 selected from ascorgolic acids, anthronic acid glycosides, flavone dimers, flavonoid glycosides, caffeic acids, gossypols, kojic acids, and ellagic acids. A hair dye composition comprising more than one type of compound is provided.

The component (^) used in the present invention is a polyvalent metal salt.

Examples of such polyvalent metal salts include ferrous sulfate,
Ferric sulfate, ferrous chloride, ferric chloride, ferrous acetate, ferric acetate, ferrous nitrate, ferric nitrate, ammonium ferrous citrate, ferrous hydroxide, ferric hydroxide iron, ferrous phosphate,
Iron salts such as ferric phosphate, potassium ferrocyanide, potassium ferricyanide, lead chloride, zinc nitrate, zinc sulfate,
Zinc hydroxide, zinc salts such as #acidzinc, lead acetate, lead sulfate, lead nitrate.

Examples include lead salts such as lead chloride, and copper salts such as copper sulfate, copper hydroxide, and copper chloride, but iron salts, particularly ferrous chloride, ferric chloride, and ferrous sulfate, are preferred in terms of effectiveness.

It is preferable to use ferric sulfate or the like.

The blending ratio of component (A) is 0.001-10% by weight, preferably 0.1-7.0% by weight.

If the blending ratio of component (A) is less than 0.001% by weight, the hair dyeing effect will not be fully exhibited, and if it exceeds 10% by weight, the stability of the hair dye composition will deteriorate, resulting in decomposition and precipitation. This is not desirable because it occurs.

In the present invention, ascorbic acids and anthrone glycosides are used as component (B) together with component (A).

Flavone dimers, flavonoid glycosides, and caffeine are
One or more compounds selected from gossypols, kojic acids, and ellagic acids are used.

The blending ratio of component (B) is 0.001 to 10% by weight, preferably 0.05 to 6% by weight.

If the blending ratio of component (B) is 0.00101% by weight, the hair dyeability will not be sufficient, and if it exceeds 10% by weight, the stability of the hair dye composition will deteriorate, which is not preferred.

The compound used as component (B) will be explained below.

Ascorbic acids include ascorbic acid, L-ascorbic acid, L-dehydroascorbic acid, or salts thereof. Examples of salts include metal salts of ascorbic acid such as magnesium ascorbyl phosphate and magnesium ascorbate sulfate; metal salts of mono-ascorbic acid such as sodium L-ascorbate, potassium L-ascorbate, and calcium ascorbate; , sodium L-dehydroascorbate, potassium L-dehydroascorbate, and calcium dehydroascorbate.

Examples of anthrone glycosides include emodins such as emodin (reum emodin), emodin monomethyl ether, emodin-anthrone, emodin-8-β-D-glucoside (anthraglycoside B), emodin-glucoside, and emodin-6-monoglucoside; Examples include moringins such as moringin, sennoside A, sennoside B, sennoside C, and ustilaginoidin A.

Examples of flavone dimers include 7,7"-di-0-methylcupresflavone, caffe jasmine, amentoflavone, 3,8"-vinaringenin-7"-0-β-glucoside, cupresflavone, fukugiside, GB-1
, GB-1a, GB-2, GB-2a, Kayaflavone,
Hinoki flavone, Hinoki flavone monomethyl ether,
Incryptomerin (cypress flavone-7″-methyl ether), gingetene, morelo flavone, neocryptomerin (cypress flavone-7-motumethyl ether),
Bodocarp Souflavone A, Bodocarp Souflavone B
, procyanidin, cycadoflavone, spicataside, volkensiflavone, xanthoquimside, and the like.

As a flavonoid glycoside, gossypetin-3-〇-β
-galactoside, gosivitrin, gosibin, chaioside, enbinin, 3.4', 5.7-tetrahydroxy-3-L-rhamnocyto, 5,7.3', 4''-tetrahydroxy-8-methoxyflavonol-3-0 -β-D
-galactoside, tetrahydroxy-methoxyflavone-α-D-glucoside, amprocyto, hiberin, 5.
4'-dihydroxyflavone-6-C-α-D-glycosylrhamnoside 7-〇-glycoside 41,511-di-0-acetylpolarin, callistefin (berargonidin-3-glucoside), azaleatin-3-rhamnoside silglucoside, azalein, pyrhein-6-glucuronide, picalin (pylrhein-7-glucuronide), biochanin-7-glucoside, 6,8-bis(C-
glucosyl) - apigenin, nelmboside, pineutcinin, eupatrin, exetrin, neohesveridin.

Sooisoriquiritin (isoliquiritigenin-4-β-glucoside), neoisorutin, neoliquiritin (liquiritigenin-7-β-glucoside), tulvaline (scutellarein-7-〇-α-L-rhamnopyranoside), sorbifolin, vitexin, vitexin -7-glucoside,
Bidexin-xyloside, ougonin.

Pyrikirein, droxylin-A, picalin rutin,
Examples include cacao pigment, safrole yellow, and the like.

Examples of caffeic acids include caffeic acid, caffeic acid dimethyl ether, 3-0-feruloylquinic acid, quinic acid-dicaffeic acid ester, 3,4-caffeoylquinic acid,
3,5-caffeoylquinic acid, 4,5-caffeoylquinic acid, fuquinolic acid, 2-0-cafnioyl-arbutin, caffeoyl-karellanin, 4-0-cafnioyl-quinic acid, 4-0 -caffeoyl-〇-quinic acid,
Examples include 3-0-cafnioyl-shikimic acid and neochlorogenic acid.

Gossypols include gossypol, hemerokalin, 6
, 6'-dimethoxy-gossypol, hemigossypol, 3
, 3'-vibulumpagin, neodiospirin, and the like.

Examples of kojic acids include compounds represented by the following general formula (% R2 = 2-pyrrolidon-5-yl group, pyridyl group), as well as 2-alkylcarbonyloxymethyl-5-hydroxy-4H-pyran-4-one. , 2-penzoyloxy-5-hydroxy-4H-pyran-4-
one, 2-cinnamoyloxymethyl-5-hydroxy-411-pyran-4-one, 2-phenoxymethyl-
Examples include 5-hydroxy-4■-pyran-4-one, kojic acid monobutyrate, and kojic acid monocabrilate.

Ellagic acids include compounds represented by the following general formula. In particular, ellagic acid in which R1 to R6 are all hydrogen, and those in which R1 to R4 are hydrogen, methyl, or ethyl, and R5 is hydrogen, hydroxyl, or methoxy are preferred. Salts can also be used, such as alkali metal salts such as sodium and potassium salts, alkaline earth metal salts, ammonium salts,
Examples include amine salts, but those in which part of the phenolic hydroxyl groups of ellagic acid are converted into alkali metal salts are preferred from the viewpoint of solubility and the like.

(In the formula, R4 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a polyalkylene oxide (2-3 carbon atoms) residue, or a sugar shown in the formula (R).

R9 is a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 8 carbon atoms. ) A specific example of the above ellagic acids is ellagic acid.

3.4-di-lowmethylellagic acid, 3.3', 4-
tri〇~methylellagic acid, 3,3'-di-0-methylellagic acid, 3.3', 4゜4'-tetra-0-methyl-
5-methoxyelagic acid, 3-ethyl-4-methyl-5-
Hydroellagic acid, 3-ethyl-4-methyl-5-hydroxyelagic acid, Amritosid
e) and various salts of these compounds, or a mixture of two or more thereof.For details of the above specific compounds, see [Handbook; Cosmetic Pharmaceutical Raw Materials, 2558-559. Revised edition; Nikko Chemicals■
Issuance”.

Although the present invention has the above-mentioned components (A) and (B) as essential components, auxiliary components commonly used in hair dye compositions of this type may be added as necessary.

Such auxiliary ingredients include liquid paraffin, petrolatum, stearic acid, cetostearyl alcohol, isopropyl palmitate, octyldodecanol, squalane, vegetable oils, isostearic acid, aromatic-hydric alcohols (such as benzyl alcohol), lanolin alcohol, and cholesterol. oils such as polyoxyethylene hydrogenated castor oil, nonionic surfactants such as polyoxyethylene stearyl ether, stearic trimethylammonium chloride,
Cationic surfactants such as dioleyldimethylammonium chloride and polyoxyethylene stearyltrimethylammonium chloride, anionic surfactants such as sodium alkyl sulfate, amphoteric surfactants such as alkylbetaine, propylene glycol, glycerin, Marpit, polyethylene glycol, ■ , humectants such as 3-butyl glycol, anionic, nonionic and cationic resins, sodium sulfite, reducing agents such as L-cysteine derivatives, citric acid,
Organic acids or salts thereof, such as apple pickle, cooling agents such as α-menthol and camphor, organic solvents such as ethanol, disinfectants such as isopropylmethylphenol, laccaic acid such as ethylene carbonate, N-methyl-2-pyrrolidone, etc. , riboflavone, pigments such as β-carotene, and fragrances such as coumarin.

The hair dye composition of the present invention can be made into various dosage forms according to conventional methods, but preferably a first liquid mainly containing the component (A) and a second liquid mainly containing the component (B). It is preferable to prepare it as a so-called two-component type.

Specifically, the first liquid is a shampoo rinse, tonic, etc. in the form of a liquid, cream, foam, spray, etc., in which the above-mentioned auxiliary ingredients are appropriately added to the polyvalent metal salt as the component (A), if necessary.
It is composed of hair cream, hair color, etc., and the two solutions contain (B) ingredients ascorbic acids, anthronic acid glycosides, flavon dimers, flavonoid glycosides, caffeic acids, gossypols, kojic acids, and ellagic acids. It consists of shampoos, conditioners, tonics, hair creams, hair colors, etc. in the form of liquids, creams, foams, sprays, etc., which are made by adding one or more compounds selected from the above and the above-mentioned auxiliary ingredients as necessary.

The dosage forms of the first liquid and the second liquid may be the same or different,
From the viewpoint of usability, it is appropriate that the first liquid be in the form of a foam or liquid, and the second liquid be in the form of a liquid, foam, or cream.

To dye hair using the hair dye composition of the present invention, (
Any method of bringing component A) and component (B) into contact during the hair dyeing process can be used, for example, first applying the first solution containing component (A) to the hair as a shampoo, conditioner, etc. for 10 minutes. Leave for ~30 minutes and wash gently. Then ([3
) A step in which the second liquid containing the ingredients is applied as a liquid, foam hair conditioner, etc. to the hair, left for 5 to 30 minutes, the first liquid and the second liquid are brought into contact, and then rinsed and optionally dried. You can repeat this every day.

〔effect〕

The hair dye composition of the present invention can dye gray hair very naturally as part of daily hair care activities, does not damage or dry hair even after repeated use, and has excellent combability. Gives a supple finish.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Examples 1-17. Comparative Examples 1 to 7 A hair dye composition consisting of a first liquid (hair rinse agent) and a second liquid (hair liquid agent) having the component composition shown in Table 1 was prepared, and the hair dyeing effect of the hair dye composition was evaluated. At the same time, the combability of the dyed hair was also evaluated. The results are shown in Table-1. The hair dyeability and combability tests were conducted as follows.

[Hair dyeability]

3g of shampooed hair (grey rate 15-20%, length 1)
Apply 0.3g of the first liquid rinse agent to 5cl) and heat at 40°C.
After leaving for 30 minutes, rinse twice with water at a bath ratio of 25 times.

Next, a second hair liquid is applied to the rinsed hair bundle and left at 40° C. for 10 minutes. The above hair dyeing process is 10
After repeating several times, measure the hair bundle glue, a, and b using a color difference meter (Model 1010).

11 (manufactured by Seishoku Kogyo Co., Ltd.), and the color difference Δ from that of untreated hair bundles
1 mm was calculated, and this value was used as an evaluation standard for hair dyeability.

Note that the lowest level value of ΔE that can be recognized as dyed hair with the naked eye is 2.0.

[Hair combability]

The hair bundles subjected to the dyeability test were left for 24 hours at 25° C. and 65% humidity, and then subjected to a sensory test by 20 panelists to determine the combability of the hair.

O Good: 80% or more" The second panel has good combability and no dryness. Q Fair: 60% to 80% or more of the panels have good combability and no dryness. ΔSlightly poor: 40% to 60% of panels had good combability and no dryness at all.Good: 40% or less of panels had good combability and no dryness at all. Toshichi's Example 18 The same treatment as in Example 1 was performed except that the first liquid shown below was a hair growth agent and the second liquid was a foam hair styling agent. ΔE was obtained.
was 4.7, and the combability of the hair was good (0).

[First liquid] (weight%)
Vitamin E acetate 0.2 Oriental chinensis extract 0.1 Ferric chloride
0.05 zinc sulfate
0.1 copper chloride
0. IQ-menthol
0.2isopropylmethylphenol
0.1 fragrance
0.2 ethanol 50.
0 water balance [2nd
Liquid] (wt%) Cationized cellulose 0.5 Polymethacrylic acid ester 3.0 Emodin
0.01 Amentoflavone
0.1 Sorbiforin
0.1 Ratu Kain Sun
0.001 fragrance
0.3 ethanol 1
5.0 Water Balance Book Foamy W hair preparation Example 19 where the above stock solution and propellant (LPG) are mixed at a weight ratio of 94=6 The first liquid shown below is a shampoo, and the second liquid is a foamy 91
When the same treatment as in Example 1 was carried out except that it was used as a hair preparation, ΔE was 4.5 and the combability of the hair was good (0).

[First liquid] (weight%
) Sodium 3.0 Coconut oil fatty acid jetanolamide sulfate sodium chloride Zinc sulfate Copper sulfate Citric acid Perfume Purified water [2nd liquid] Cationic cellulose (wt%) 1.0 Coconut oil fatty acid jetanolamide 0.3 Paraben 0.3 Ethanol
15.0 fragrance
0.5 water
Balance book Foamy hair conditioner made by mixing the above stock solution and propellant (LPG) at a weight ratio of 93.

Claims (4)

[Claims] (1) (A) a polyvalent metal salt and (B) one or more selected from ascorbic acids, anthrone glycosides, flavone dimers, flavonoid glycosides, caffeic acids, gossypols, kojic acids, and ellagic acids; A hair dye composition comprising a compound. (2) The blending ratio of component (A) is 0 based on the total weight of the hair dye composition.
．． 001 to 10% by weight of the hair dye composition according to claim 1. (3) The blending ratio of component (B) is 0 based on the total weight of the hair dye composition.
．． 001 to 10% by weight of the hair dye composition according to claim 1. (4) The hair dye composition according to claim (1), comprising one part containing component (A) and two parts containing component (B).