EP3215109A1

EP3215109A1 - Hair dye

Info

Publication number: EP3215109A1
Application number: EP15794321.8A
Authority: EP
Inventors: Akira Matsutani; Masaki Kawai; Shoji Machida; Shoko NAGAFUCHI; Koji Takada; Hiroaki Fukuda
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2014-11-05
Filing date: 2015-10-27
Publication date: 2017-09-13
Also published as: JP2016088889A; WO2016072061A1

Abstract

The present invention relates to a hair dye comprising at least a first agent and a second agent, wherein the first agent contains urea and at least one benzophenone compound having three or more hydroxyl groups and the second agent contains at least one iron salt.

Description

HAIR DYE

The present invention relates to a non-oxidative hair dye which achieves an excellent hair dyeing effect and an excellent gray hair hiding effect and which imparts an excellent color tone to the hair after the hair dyeing.

A permanent hair dye is a hair dye which imparts a permanent dyeing result to the hair. An oxidative hair dye, which is used as a mixture of a first agent comprising an oxidation dye such as paraphenyldiamine and an alkaline agent and a second agent comprising an oxidizing agent such as hydrogen peroxide solution, is conventionally used generally and widely as the permanent hair dye. However, the oxidative hair dye may cause damage to the hair due to the actions of the alkaline agent and the hydrogen peroxide solution. Some oxidation dyes may cause serious allergic reactions.

On the other hand, non-oxidative hair dyes are known as hair dyes with slight damage to the hair, which tend to cause no allergic reactions. For example, hair dyes which dye the hair using a reaction between a polyhydric phenol and a metal salt are known as the non-oxidative hair dyes (see PTL 1 to 7).

A non-oxidative hair dye having an effect of preventing photobleaching, which contains in combination a first agent comprising a substance reacting with iron to develop a color and an ultraviolet absorbing agent, and a second agent comprising an iron salt, has been proposed (PTL 8).

However, the conventional non-oxidative hair dyes have no sufficient hair dyeing effect and no sufficient gray hair hiding effect.

[PTL 1] JP S48-31902 B
[PTL 2] JP S53-52633 A
[PTL 3] JP S55-154912 A
[PTL 4] JP S62-33113 A
[PTL 5] JP S64-90117 A
[PTL 6] JP H04-164017 A
[PTL 7] JP H05-170629 A
[PTL 8] JP 2011-126845 A

The conventional hair dye which uses a plant extract or an organic compound reacting with an iron salt to develop a color needs a long time to dye the hair. The hair dyeing property and the color tone are not satisfactory after dyeing the hair in this case. In the case where only tanninc acid, gallic acid and/or a derivative thereof, and iron are blended in the hair dye, when the color shade is increased to sufficiently dye gray hair, the color tone of blue is enhanced in the hair after the hair dyeing, a result of hair dyeing that imparts an excellent color tone to the hair could not be achieved.
The present invention solves the above-mentioned problems involved in the conventional art and an object thereof is to provide a non-oxidative hair dye having an excellent hair dyeing effect and an excellent gray hair hiding effect, which imparts an excellent color tone to the hair after the hair dyeing.

The present inventors have earnestly considered to solve the above-mentioned problems in respect to non-oxidative hair dyes, and achieved the present invention.

The present invention includes the following preferred embodiments.
[1] A hair dye comprising at least a first agent and a second agent, wherein the first agent contains urea and at least one benzophenone compound having three or more hydroxyl groups and the second agent contains at least one iron salt.
[2] The hair dye according to the above item [1], wherein the first agent further contains at least one organic compound, which reacts with iron to develop a color, and/or at least one plant extract containing the organic compound.

The hair dye of the present invention has an excellent hair dyeing effect and an excellent gray hair hiding effect, and imparts an excellent color tone to the hair after the hair dyeing.

The hair dye of the present invention comprises at least a first agent and a second agent. The first agent of the hair dye of the present invention contains urea to enhance the hair dyeing effect and the gray hair hiding effect.

The amount of urea in the first agent is preferably 1% by mass or more, and more preferably 3% by mass or more, based on the total amount of the first agent from the viewpoint of the hair dyeing effect and the gray hair hiding effect. The amount thereof is preferably 20% by mass or less, and more preferably 10% by mass or less from the viewpoint of the stability of the agent.

The first agent of the hair dye of the present invention comprises at least one benzophenone compound having three or more hydroxyl groups to enhance the hair dyeing effect and the gray hair hiding effect.

Examples of the benzophenone compounds having three or more hydroxyl groups include 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, and 2,3,3',4,4',5-hexahydroxybenzophenone. From the viewpoint of the tendency to enhance the hair dyeing effect and the gray hair hiding effect, a benzophenone compound having four or more hydroxyl groups is preferable, and a benzophenone compound selected from group consisting of 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, and 2,3,3',4,4',5-hexahydroxybenzophenone is more preferable.
The first agent of the hair dye of the present invention may comprise one of the compounds as the benzophenone compound having three or more hydroxyl groups, or may comprise two or more of the compounds in combination.

The amount of the benzophenone compound having three or more hydroxyl groups in the first agent is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more based on the total amount of the first agent from the viewpoint of the hair dyeing effect and the gray hair hiding effect. This amount is preferably 5% by mass or less and more preferably 3% by mass or less from the viewpoint of the stability of the agent.

It is preferable that the first agent of the hair dye of the present invention comprises an oil agent from the viewpoint that the benzophenone compound having three or more hydroxyl groups is stably blended in the first agent to enhance the hair dyeing effect and the gray hair hiding effect. Examples of the oil agents include an ester oil, a hydrocarbon oil, a silicone oil, an animal or plant oil, a higher alcohol in a liquid form at the normal temperature, and a higher fatty acid in a liquid form at the normal temperature. From the viewpoint of the stability of the first agent, the first agent more preferably comprises as the oil agent at least one oil agent selected from the group consisting of a hydrocarbon oil, an ester oil, a higher alcohol in a liquid form at the normal temperature and a silicone oil, and yet more preferably comprises at least one oil agent selected from the group consisting of a hydrocarbon oil and an ester oil. It is more preferable that the first agent of the hair dye of the present invention comprises a hydrocarbon oil from the viewpoint that a benzophenone compound having three or more hydroxyl groups is stably blended in the first agent. Examples of the hydrocarbon oils include liquid paraffin, dioctylcyclohexane, α-olefin oligomer, light isoparaffin, light liquid isoparaffin, squalane, polybutene, and liquid isoparaffin.
The amount of the oil agent is preferably 1% by mass or more, and more preferably 3% by mass or more based on the total amount of the first agent from the viewpoint of the stability of the agent. This amount is preferably 30% by mass or less, and more preferably 15% by mass or less from the viewpoint of the usability.

The first agent of the hair dye of the present invention may further comprise at least one organic compound which reacts with iron to develop a color, and/or at least one plant extract containing the organic compound. Examples of the organic compound which reacts with iron to develops a color or the plant extract containing the organic compound include, but are not limited to, tannic acid, gallic acid and a derivative thereof, gallnut, pyrogallol, logwood, hematein, catechol, salicylic acid and a derivative thereof, phthalic acid, eugenol, isoeugenol, nicotinic-acid amide, dehydroacetic acid, pyridoxine, ellagic acid, kojic acid, maltol, ferulic acid, hinokitiol, turmeric extract, curcumin, Scutellaria root extract, onion extract, quercetin, rutin, hesperetin, hesperidin, fresh coffee bean extract, caffeic acid, chlorogenic acid, tea extract, catechin, epicatechin, lithospermi radix extract, Japanese basil extract, shisonin, grape leaf extract, grape extract, enocyanin, laccaic acid, lac, cochineal, carminic acid, elderberry, red cabbage, purple sweet potato, tamarind, kaoliang, apigeninidin, and luteolinidin. It is preferable that the first agent of the hair dye of the present invention comprises tannic acid, gallic acid and a derivative thereof, and salicylic acid and a derivative thereof, from the viewpoint of the hair dyeing effect.

Examples of the tannic acids include a hydrolyzable tannin and a condensed tannin. Examples of the hydrolyzable tannins include tannin derived from Rhus chinensis, gallnut, sumac, tara, chestnut, myrobalan, oak, divi-divi, algarobilla and Geranium thunbergii. Examples of the condensed tannin include tannin derived from gambier, quebracho, mimosa, mangrove, hemlock, spruce, Burma cutch, oak bark and persimmon.

Examples of the derivative of gallic acid include an alkyl ester of gallic acid. Examples of the alkyl esters of gallic acid include an ester of gallic acid with a linear or a branched alkyl having 1 to 10 carbon atoms, preferably 2 to 5 carbon atoms. Examples of the alkyl esters include ethyl gallate, propyl gallate and isoamyl gallate. The gallic acid or a derivative thereof may be the one chemically synthesized using a known method or may be the one isolated from a plant. The gallic acid or a derivative thereof may be a substance prepared by further performing chemical synthesis on gallic acid or a derivative isolated from a plant. Furthermore, an extract obtained from a plant containing gallic acid or a derivative thereof may be directly used. For example, the gallic acid originated from tara that is a plant of the pea family, the gallic acid originated from gallnut produced by Chinese sumac of the sumac family, or an extract comprising any one of these may be used. A derivative which is obtained by chemically esterifying any one of the above gallic acids may be also used.

Examples of the derivatives of salicylic acid include esters and salts of salicylic acid. Examples of the salts of salicylic acid include alkali metal salts of salicylic acid. Specifically, the alkali metal salts of salicylic acid may be, for example, sodium salicylate. Examples of the esters of salicylic acid include a linear or a branched alkyl ester including 1 to 10 carbon atoms and a phenyl ester. Specific examples thereof include octyl salicylate, phenyl salicylate, and methyl salicylate.

The first agent of the hair dye of the present invention may comprise one type of compound or extract or may comprise two or more types of compound or extract in combination, as the organic compound which reacts with iron to develop a color, or a plant extract containing the organic compound. The first agent may comprise in combination an organic compound which reacts with iron to develop a color and a plant extract containing the organic compound.

The amount of the organic compound which reacts with iron to develop a color in the first agent is not especially limited as long as the effects of the present invention can be achieved, but the amount is preferably 0 to 10% by mass, and more preferably 0.5 to 6% by mass based on the total amount of the first agent, from the viewpoint of enhancement of the hair dyeing effect and the gray hair hiding effect.

The first agent of the hair dye of the present invention has pH of preferably 6 to 10, and more preferably 7 to 9 from the viewpoint of the hair dyeing effect and the stability of the agent.

The second agent of the hair dye of the present invention comprises at least one iron salt to enhance the hair dyeing effect and the gray hair hiding effect. The iron salt develops a color by reacting with the benzophenone compound having three or more hydroxyl groups and the organic compound which develops the color by reacting with iron, which the hair dye optionally comprises, and can fix the coloring element to the hair.

Examples of the iron salt include ferrous sulfate, ferrous chloride, ferrous acetate, ferrous phosphate, ferrous oxalate, ferric sulfate, ferric chloride, and ferric acetate. From the viewpoint of the hair dyeing effect, it is preferable that at least one iron salt selected from the group consisting of ferrous sulfate, ferrous chloride, ferrous acetate, ferric sulfate and ferric chloride is used, and more preferable that at least one iron salt selected from the group consisting of ferrous sulfate, ferrous chloride and ferrous acetate is used.
The second agent of the hair dye of the present invention may comprise the one iron salt alone, or may comprise two or more thereof in combination.

The amount of the iron may be appropriately determined within a range in which the effects of the present invention are achieved, but the amount is preferably 0.5 to 10% by mass, and more preferably 1 to 6% by mass based on the total amount of the second agent, from the viewpoint of the stability of the agent and the hair dyeing effect.

The second agent of the hair dye of the present invention has pH of preferably 2 to 6, and more preferably 3 to 5, from the viewpoint of the stability of the agent and the hair dyeing effect.

In addition to the above components, the first agent and/or the second agent of the hair dye of the present invention may comprise other components used in ordinary hair dyes. Examples of such components include a base material, a surfactant, oils, a solvent, a thickener, an organic acid, a preservative, an antioxidant, a pH adjusting agent, a wetting agent, fragrance, a metallic smell masking agent, a coloring agent, an ultraviolet absorbing agent, a hair restorer/hair growth stimulant, an anti-dandruff agent, an antibacterial agent, a softener, a moisturizer, an active oxygen removing agent, an antioxidant, an antimicrobial agent, silicone, mineral, a protein hydrolysate, a peptide, an amino acid. The amounts of each of these components may be appropriately determined within a range in which the effects of the present invention are achieved.

Examples of the base include a higher alcohol, a hydrocarbon, a fatty acid ester, a vegetable oil, and a fatty acid.
In particular, the first agent of the hair dye of the present invention comprises preferably a higher alcohol, and more preferably at least one higher alcohol selected from the group consisting of cetostearyl alcohol, cetyl alcohol, stearyl alcohol and behenyl alcohol, from the viewpoint of the stability of the agent. The amount of the higher alcohol is preferably 1% by mass or more, and more preferably 3% by mass or more based on the total amount of the first agent, from the viewpoint of the stability of the agent. The amount is preferably 20% by mass or less, and more preferably 10% by mass or less, from the viewpoint of the usability.

Examples of the surfactant include an anionic surfactant, a non-ionic surfactant, an ampholytic surfactant and a cationic surfactant. Examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylenepolyoxypropylene alkyl ether, a glycerin fatty acid ester, a polyglycerin fatty acid ester, a polyethyleneglycol fatty acid ester, and an alkyl glucoside. Examples of the anionic surfactant include a polyoxyethylene alkyl ether phosphate and a salt thereof, an N-acylamino acid salt, an alkyl ether carboxylate, an alkyl sulfate, a polyoxyethylene alkyl ether sulfate, and a sulfonate. Examples of the cationic surfactant include an alkylammonium salt. Examples of the ampholytic surfactant include alkylamidopropyl betaine.
In particular, the first agent of the hair dye of the present invention comprises preferably at least one non-ionic surfactant, and more preferably polyoxyethylene alkyl ether, from the viewpoint of the stability of the agent. From the same viewpoint, the amount of the non-ionic surfactant is preferably 0.1 to 10% by mass, and more preferably 1 to 7% by mass based on the total amount of the first agent.

Examples of the antioxidant include ascorbic acid and a derivative thereof, and sodium sulfite.

For example, citric acid, phosphoric acid, ammonia, ammonium hydrogen carbonate, ammonium bicarbonate, potassium hydroxide, sodium hydroxide, monoethanolamine, isopropanolamine, ammonium phosphate, diammoniummonohydrogen phosphate, sodium citrate, ammonium citrate, potassium phosphate, and sodium phosphate may be used as the pH adjusting agent.

Examples of the wetting agents include 1,3-butyleneglycol, propyleneglycol, glycerin, sorbitol, sodium pyrrolidone carboxylate, an amino acid and a vegetable oil.

Examples of the thickener include xanthane gum, polyethyleneglycol and hydroxyethyl cellulose.

Examples of the solvents include water, ethanol, isopropyl alcohol, 1,3-butyleneglycol, 1,2-pentanediol, 2-methyl-2,4-pentanediol, glycerin, diglycerin, propyleneglycol, dipropyleneglycol and benzyl alcohol.

The hair dye of the present invention comprises at least the first agent and the second agent, and may be a two-agent type hair dye consisting of the first agent and the second agent, may be a three-agent type hair dye consisting of the first agent, the second agent and additionally a third agent, or may be a multiple-agent type hair dye comprising more than three agents.

By mixing at least the first agent and the second agent of the present invention, dyeing the hair can be performed. As described later, the mixing may be carried out by applying the second agent to the hair after the first agent is applied to the hair, or may be carried out by mixing in advance the first agent and the second agent with each other. The mixing ratios of the first agent to the second agent (the first agent : the second agent) are preferably 1:0.5 to 1:2, more preferably 1:0.8 to 1:1.2, and yet more preferably 1:1 as the mass ratios, from the viewpoint of the usability.

The dosage forms of the first agent and the second agent which the hair dye of the present invention comprises may be a cream, a liquid, a gel, an emulsion, foam, a spray agent or an aerosol. The first agent and the second agent may have the same dosage form or may have dosage forms different from that of each other. It is preferable that the first agent is in a cream form or a gel form, from the viewpoint of the usability and the stability. It is preferable that the second agent is in a cream form or a gel form, from the viewpoint of the usability.

The preparation method of each of the first agent and the second agent which the hair dye of the present invention comprises is not especially limited and each of the agents can be produced using an ordinary method. The first agent comprises a benzophenone compound having three or more hydroxyl groups. The benzophenone compounds having three or more hydroxyl groups generally have low solubility to water. Accordingly, it is preferable that a cream as the first agent is obtained by heating and dissolving the benzophenone compound having three or more hydroxyl groups and oil phase components such as an oil agent, and then adding a water phase components into the oil phase component to emulsify these components. The storage stability of the first agent can be improved by producing the first agent in this manner.

The hair can be dyed by applying to the hair the first agent and the second agent which the hair dye of the present invention comprises. Examples of the hair dyeing method include (i) a method of dyeing hair according to which the first agent is first applied to the hair, the hair is left for a predetermined time period, and then the second agent is applied to the hair without washing away the first agent, after that the hair is left for another predetermined time period, and the hair is thereafter washed off, (ii) another method of dyeing hair according to which the first agent and the second agent are concurrently applied to the hair, the hair is left for a predetermined time period, and then the hair is washed off, and (iii) yet another method of dyeing hair according to which a composition prepared by mixing the first agent and the second agent with each other is applied to the hair, the hair is left for a predetermined time period, and then the hair is washed off. It is preferable that the hair dyeing is performed using the method of the above (i), from the viewpoint of the hair dyeing effect.

The time period for hair dyeing after the application of the hair dye to the hair is appropriately adjusted according to the type and the amount of the benzophenone compound, the amount of the hair dye applied to the hair, and a desired degree of dyeing to be fixed. When the hair dyeing is performed using the method of the above (i) or (ii), the time period for hair dyeing after the application of the hair dye to the hair is generally 1 to 60 min and preferably 5 to 40 min after the application of the first agent, and is generally 1 to 60 min and preferably 5 to 40 min after the application of the second agent.

The amount of the first agent and the second agent to be applied is preferably about 30 to 70 g for the first agent and about 30 to 70 g for the second agent and more preferably about 40 to 60 g for the first agent and about 40 to 60 g for the second agent to the hair having a length of about 20 cm, from the viewpoint of the usability. In an embodiment of the present invention, 50 g of the first agent and 50 g of the second agent may be applied to the hair having a length of about 20 cm. The temperature during the application to the hair is 15 to 45°C, from the viewpoint of the physical burden for the hair and the human body.

The present invention will be described in more detail with reference to Examples below. The present invention is not limited by Examples.

(Preparation of First Agent)
The first agent was prepared as follows.
The oil phase components such as the surfactants, the higher alcohol, the hydrocarbon oil and the benzophenone compound, and the water phase components such as gallic acid, tannic acid or sodium salicylate, and purified water, were separately weighed and were each sufficiently heated and dissolved. Thereafter, the water phase components were added to the oil phase components with sufficient stirring to emulsify them. Then, the obtained emulsion was cooled and the pH adjusting agent of the amount to adjust the pH of the first agent to 8 and urea dissolved into water were added thereto to obtain the first agent.

(Preparation of Second Agent)
The second agent of Examples 1 to 7 and Comparative Examples 1 to 7 was prepared as follows.
Ferrous sulfate or ferrous chloride was added to purified water at the normal temperature, and ascorbic acid was further added thereto. The obtained solution was stirred to dissolve the components to obtain the second agent. The obtained solution had pH of about 3.
The second agent of Examples 8 to 13 was prepared as follows.
The oil phase components which were cetostearyl alcohol and polyoxyethylene cetostearyl ether, and the water phase components which were ferrous sulfate, L-ascorbic acid, and purified water, were separately weighed and were each sufficiently heated and dissolved. Thereafter, the water phase components were added to the oil phase components with sufficient stirring to emulsify them. Then, the obtained emulsion was cooled with stirring to be completed.

(Hair Dyeing Effect, and Color Tone of Hair)
2 g of the first agent according to the composition shown in Table 1 was applied to a hair bundle of 1 g (ratio of gray hair: 100%) which was treated with a shampoo and a conditioner and was sufficiently dried. Then, the hair bundle was left for 15 min at 30°C and at the relative humidity of 65%. After that, 2 g of the second agent according to the composition shown in Table 1 was applied to the hair bundle. The hair bundle was again left for 15 min at 30°C and at the relative humidity of 65%. The hair bundle was thereafter treated with a shampoo and a conditioner, and was dried using a dryer.

The hair dyeing effect and the color tone of the hair were evaluated on the dried hair bundle as follows.

The hair dyeing effect was evaluated with visual observation according to the following criteria by five professional panelists. When the evaluation of the five panelists was split into two, the evaluation supported by the majority was employed and, when the evaluation was split into three or more, the test and the evaluation were again conducted until the evaluations of the five all matched with each other or were split into two.
Evaluation Criteria for Hair Dyeing Effect
A: The hair was deeply and strongly dyed.
B: The hair was clearly dyed.
C: The hair was slightly dyed.
D: The hair was not dyed.

The color tone (especially, the strength of blue) of the hair was evaluated with visual observation according to the following criteria by the five professional panelists. When the evaluation of the five panelists was split into two, or three or more, the evaluation was made similarly to the above.
Evaluation Criteria for Color Tone of Hair
A: Blue was very weak.
B: Blue was weak.
C: Blue was somewhat strong.
D: Blue was very strong.

(Gray Hair Hiding Effect)
4 g of the first agent according to the composition shown in Table 1 was applied to a hair bundle of 2 g (ratio of gray hair: 20%) which was treated with a shampoo and a conditioner, and was sufficiently dried. Then, the hair bundle was left for 15 min at 30°C and at the relative humidity of 65%. After that, 4 g of the second agent according to the composition shown in Table 1 was applied to the hair bundle. The hair bundle was again left for 15 min at 30°C and at the relative humidity of 65%. The hair bundle was thereafter treated with a shampoo and a conditioner, and was dried using a dryer.

The gray hair hiding effect was evaluated on the dried hair bundle as follows.

The gray hair hiding effect was evaluated with visual observation according to the following criteria by the five professional panelists. When the evaluation of the five panelists was split into two, or three or more, the evaluation was made similarly to the above.
Evaluation Criteria for Gray Hair Hiding Effect
A: No gray hair was conspicuous.
B: Gray hair was slightly conspicuous.
C: Gray hair was conspicuous.
D: No gray hair was dyed.

The hair dye of the present invention in which the first agent comprises urea and at least one benzophenone compound having three or more hydroxyl groups and the second agent comprises an iron salt achieved excellent results for the hair dyeing effect, the gray hair hiding effect, and the color tone. In contrast, the hair dyes according to Comparative Examples 1 to 4 and 7, which do not comprise at least one benzophenone compound having three or more hydroxyl groups, as well as the hair dyes according to Comparative Examples 5 and 6, which do not comprise at least one benzophenone compound having three or more hydroxyl groups and urea, achieved no sufficient effects for the hair dyeing effect, the gray hair hiding effect, and/or the color tone.

Claims

A hair dye comprising at least a first agent and a second agent, wherein the first agent contains urea and at least one benzophenone compound having three or more hydroxyl groups and the second agent contains at least one iron salt.
The hair dye according to claim 1, wherein the first agent further contains at least one organic compound, which reacts with iron to develop a color, and/or at least one plant extract containing the organic compound.