JP6774677B2 - Hair dye composition - Google Patents

Description

The present invention relates to a hair dye composition.

As one of the hair dyeing techniques, there is a technique of coloring with an acid dye, which is applied to, for example, a hair dye called hair manicure. Hair dyes that dye hair with acid dyes have the advantage of being less damaging to hair and less irritating to the skin, unlike two-agent hair dyes that dye hair using oxidation dyes. However, since acid dyes do not easily penetrate into the hair, it is recommended to add a penetration promoter such as an aromatic compound, a urea compound, or pyrrolidone to the base for the purpose of promoting the penetration of the dye and enhancing the hair dyeing effect. It is common. However, since these penetration promoters enhance the penetration of dyes not only into the hair but also into the skin, there is a problem that when the coloring on the hair is improved, the coloring on the scalp is also increased at the same time. On the other hand, it is widely practiced to apply face cream to the hairline of the hair before the treatment to prevent the hair dye from coming into contact with the scalp, but in areas where the hair is densely grown, it is applied to the skin. Since it is difficult to selectively apply the cream only, the coloring of the scalp is unavoidable when trying to improve the coloring of the hair.

In order to solve this problem, a hair dye composition in which a hydrocarbon oil and a polyether-modified silicone are used in combination with a penetration accelerator has been proposed (Patent Document 1). However, although the skin coloring is reduced by this technique, the hair dyeing property is also lowered, and it cannot be said that the hair dyeing agent is sufficiently satisfactory. Further, by utilizing the hydrophobic nature of the hair surface, a colorant is encapsulated in core-shell particles having a core portion containing a hydrophobic polymer as a constituent component, and the colorant is selectively adsorbed on the hair at the same time. A technical proposal for suppressing skin coloring has also been made (Patent Document 2). In this technology, coloring materials such as oil-soluble dyes and pigments that have an affinity with the core of the particles are used, but oil-soluble dyes are inferior to acid dyes in terms of hair dyeability, and pigments are inferior in hair dyeability. Although it is excellent, it does not penetrate into the hair and only adheres to the surface, so it was a technical proposal with room for further improvement that the color would fade with a single wash. On the other hand, even if this technical proposal is applied to an acid dye having excellent hair dyeing property in combination with a penetration accelerator, there is a problem that core shell particles cannot be produced because the affinity between the acid dye and the hydrophobic polymer in the core portion is low. there were.

JP-A-2002-205927 Japanese Unexamined Patent Publication No. 2000-53545

Therefore, the present invention relates to a hair dye composition that does not easily color the skin and has excellent hair dyeing properties.

In such a situation, the present inventors have reduced skin coloring and high hair dyeing property by encapsulating the permeation promoter in the particles to act on the hair surface while reducing the contact of the permeation promoter with the skin. I came up with the idea of achieving both. Further research is carried out, and Patent Document 2 states that an aromatic alcohol, which is a permeation accelerator, is encapsulated in hydrogel particles and dispersed in an aqueous solvent, and an acid dye is dissolved in a continuous phase containing an aqueous solvent. The present invention has been completed by finding that a hair dye composition satisfying the above-mentioned requirements can be obtained by using a form opposite to the technique described in 1.

The present invention provides a hair dye composition in which an acid dye is dissolved in an aqueous solvent and hydrogel particles containing an aromatic alcohol are dispersed in the aqueous solvent.

The hair dye composition of the present invention does not easily color the skin and has excellent hair dyeing properties.

In the hair dye composition of the present invention, the hydrogel particles are dispersed in a continuous phase containing an aqueous solvent in which an acid dye is dissolved.

[Aqueous solvent]
The aqueous solvent used in the present invention comprises water and a hydrophilic solvent, and examples of the hydrophilic solvent include lower aliphatic alcohols such as ethanol, propanol and isopropanol; propylene glycol, 1,3-butanediol, diethylene glycol and the like. Polyphiles such as glycerin; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as ethyl carbitol and butyl carbitol can be mentioned.

[Acid dye]
In the hair dye composition of the present invention, the acid dye is dissolved in the aqueous solvent. The acid dye is not limited as long as it is a water-soluble acid dye, for example, blue No. 1 (CI42090), purple No. 401 (CI60730), black No. 401 (CI20470), orange 205 (CI15510), red 106 (red. CI45100), red No. 227 (CI17200), acid orange 3 (CI10385) and the like.

The acid dyes can be used alone or in combination of two or more. The content of the acid dye in the hair dye composition of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less. Is.

[Hydrogel particles]
The hydrogel particles used in the hair dye composition of the present invention are substantially spherical particles of hydrogel having a three-dimensional structure dispersed in water using a water-soluble polymer having a gelling ability as a gelling agent. The oily component is dispersed or dissolved in the hydrogel particles. In the present specification, such a dispersed or dissolved state of the oily component is referred to as a state in which the oily component is contained in the hydrogel particles. In the present invention, an aromatic alcohol is essential as an oily component, and the hydrogel particles containing the aromatic alcohol are dispersed in the continuous phase containing the aqueous solvent.

In the present invention, examples of the water-soluble polymer having a gelling ability to form hydrogel particles include non-crosslinked polymers such as agar, gelatin, collagen, and curdlan, sodium alginate, sodium polyacrylate, and pectin. Cross-linked type such as carrageenan can be mentioned. Of these, the non-crosslinked type is preferable, and agar is more preferable, because it easily disintegrates on the hair when applied to the hair and has excellent hair dyeability.

The hydrogel particles referred to in the present specification can be prepared, for example, according to the methods described in JP-A-2002-159838 or JP-A-2002-20227.

The content of the water-soluble polymer having gelling ability in the hair dye composition improves the feel at the time of use, and at the time of washing and removing the non-gelled component at the time of preparing hydrogel particles and at the time of cleaning and removing the hair dye composition. From the viewpoint of preventing the particles from breaking when blended into the product, 0.2% by mass or more is preferable, 0.75% by mass or more is more preferable, 1% by mass or more is further preferable, and the particles when the hair dye composition is used. From the viewpoint of appropriate fragility, 4% by mass or less is preferable, 3% by mass or less is more preferable, and 2% by mass or less is further preferable. In addition, the content of the water-soluble polymer having gelling ability in the hydrogel particles improves the feel at the time of use, and at the time of washing and removing the non-gelled components at the time of preparing the hydrogel particles and the composition of the hair dye. From the viewpoint of preventing the particles from breaking when blended into the product, 0.4% by mass or more is preferable, 1.5% by mass or more is more preferable, 2% by mass or more is further preferable, and the particles when the hair dye composition is used. From the viewpoint of appropriate fragility, 8% by mass or less is preferable, 6% by mass or less is more preferable, and 4% by mass or less is further preferable.

Aromatic alcohol is contained in the hydrogel particles. Examples of the aromatic alcohol include benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol and the like. Of these, benzyl alcohol and 2-benzyloxyethanol are preferable, and benzyl alcohol is more preferable.

Aromatic alcohols can be used alone or in combination of two or more. The content of the aromatic alcohol in the hair dye composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, from the viewpoint of excellent hair dyeing property. Further, from the viewpoint of suppressing coloring on the skin, it is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

It is desirable that substantially the entire amount of the aromatic alcohol in the hair dye composition is contained in the hydrogel particles, but a small amount of aromatic alcohol leaks from the particles into the aqueous solvent unintentionally. In some cases, this is not excluded. However, from the viewpoint of not impairing the effect of the present invention that it is difficult to color the skin, the content of aromatic alcohol in the continuous phase is preferably 2% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.5% by mass. It is preferable that the absolute amount is not more than% and the absolute amount does not exceed the absolute amount of aromatic alcohol contained in the hydrogel particles.

In addition to the aromatic alcohol, the hydrogel particles preferably contain an oily component other than the aromatic alcohol from the viewpoint of suppressing leakage of the aromatic alcohol from the hydrogel particles. Hereinafter, when the term "oil component" is simply used, it refers to a concept including "aromatic alcohol" and "oil component other than aromatic alcohol". The content of aromatic alcohol in the oily component is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and to the skin from the viewpoint of excellent hair dyeing property. From the viewpoint of suppressing coloring, it is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.

The oily component other than the aromatic alcohol is preferably a mixture of a solid fat and a liquid oil from the viewpoint of suppressing leakage of the oily component from the hydrogel particles. The solid fat referred to in the present specification means an oily component having a melting point of 35 ° C. or higher, and the liquid oil means an oily component having a melting point of less than 35 ° C.

The melting point of the solid fat is 35 ° C. or higher, more preferably 40 ° C. or higher, further preferably 55 ° C. or higher, and 65 ° C. or higher from the viewpoint of suppressing leakage of oily components from the hydrogel particles during high-temperature storage. More preferred. Further, from the viewpoint that it can be easily mixed with the liquid oil during production, the melting point of the solid fat is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 90 ° C. or lower. All of these melting points are values measured by the differential scanning calorimetry method.

Examples of the solid fat include one or more selected from the group consisting of paraffin, higher alcohol, petrolatum, silicone, hydrogenated oil, and higher fatty acid, and paraffin and higher alcohol are preferable.

The content of the solid fat in the oily component is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 10% by mass or more, from the viewpoint of suppressing leakage of the oily component from the hydrogel particles. More preferably, it is more preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, from the viewpoint of ease of spreading on hair.

Liquid oils have a melting point of less than 35 ° C and are derived from paraffins, ester oils, higher alcohols, squalanes, glycerides, polymer emulsions or suspensions, hydrocarbon oils, vegetable oils, fatty acids, ethylene glycol difatty acid esters, dialkyl ethers and silicones. One or more species selected from the group of

Examples of the components that may be included in the hydrogel particles of the present invention include, in addition to the above oily components, water-soluble organic compounds such as sugars and water-soluble polymer compounds, and components such as pH adjusters and preservatives. ..

The content of the hydrogel particles in the hair dye composition is preferably 25% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, and to the skin from the viewpoint of excellent hair dyeing property. From the viewpoint of suppressing coloration, 80% by mass or less is preferable, 70% by mass or less is more preferable, and 60% by mass or less is further preferable.

The average particle size of the hydrogel particles is preferably 5 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, further preferably 25 μm, and preferably 1000 μm or less from the same viewpoint from the viewpoint of appearance and productivity. , 500 μm or less is more preferable, 300 μm or less is further preferable, and 150 μm or less is further preferable. The average particle size of the hydrogel particles is measured by a laser diffraction / scattering method using a laser diffraction / scattering type particle size distribution measuring device (manufactured by HORIBA, Ltd., model number: LA-920).

Hydrogel particles can be produced as follows. For example, a water-soluble polymer having a gelling ability as an aqueous component is mixed with ion-exchanged water and heated to a temperature equal to or higher than the dissolution temperature to sufficiently dissolve the polymer. Separately, aromatic alcohol as an oily component and other oily components as necessary are mixed and dissolved by heating. At a temperature equal to or higher than the gelling temperature, the aqueous component and the oily component are mixed to prepare an oil-in-water emulsion. The method for preparing the oil-in-water emulsion is not limited, but a known technique using various stirrers, dispersers and the like can be used. From the viewpoint of the stability of the emulsion, it is preferable to add the emulsion dispersant to the aqueous component and / or the oily component, and it is more preferable to add the emulsion dispersant to the aqueous component.

Here, as the emulsification dispersant, one or more selected from the group consisting of a polymer emulsification dispersant, a nonionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant can be mentioned. Be done.

Among the emulsifying dispersants, nonionic surfactants and anionic surfactants are used from the viewpoints of ease of spreading the hair dye composition on the hair and handleability at the time of washing and blending into the hair dye composition. It is preferable to use one or more surfactants selected from the group consisting of activators, cationic surfactants and amphoteric surfactants in combination with a high molecular weight emulsion dispersant, and a nonionic surfactant and a high molecular weight emulsion dispersion. The combined use of agents is more preferable. Further, from the viewpoint of reducing the addition of the surfactant and reducing the stickiness due to the surfactant when applied onto the hair, it is more preferable to use the polymer emulsification dispersant alone.

The amount of the emulsion dispersant is not limited, but is 0.001% by mass or more based on the total amount of the emulsion from the viewpoint of the feel during use, the stability of the emulsion, and the suppression of leakage of the aromatic alcohol contained in the hydrogel particles. Preferably, 0.01% by mass or more is more preferable, 0.05% by mass or more is further preferable, and 20% by mass or less is preferable, and 5% by mass or less is more preferable from the viewpoint of fragility of particles when the hair dye composition is used. It is preferable, and 1% by mass or less is more preferable.

Hydrogel particles are produced from the emulsion thus obtained by a general dropping method or stirring method. From the viewpoint of preventing leakage of aromatic alcohol from the hydrogel particles, the hydrogel particles are preferably produced by a dropping method. When using a crosslinked water-soluble polymer that is solidified by ions such as Ca ²⁺ or other coagulants, add a metal salt containing the ions, a coagulant, or an aqueous solution thereof to the emulsion, and then cool the emulsion. It should be solidified.

The dropping method is a method in which an emulsion is discharged from a hole, and the discharged emulsion is produced by utilizing the property of becoming droplets due to its surface tension or interfacial tension.

In the dropping method, the place where the droplet is generated may be a gas phase or a liquid phase. When it is formed in a liquid phase, it may be formed in a static liquid having no liquid flow, but it is preferable to form it in a static liquid having no liquid flow, but it is preferably formed by accompanying a downward flow, an upward flow or a parallel flow using a droplet forming tube. .. The end face of the pore may be present in either the gas phase or the liquid phase, but when droplets are formed in the liquid phase, it is preferably present in the liquid phase.
The method for discharging the emulsion is not limited, but for example, the dispersion is sprayed into the gas phase from a spray nozzle having a spray hole, and the formed droplets are cooled and solidified to produce hydrogel particles. In the present invention, when agar is used as the water-soluble polymer having a gelling ability, the method for producing agar hydrogel particles described in JP-A-2007-160277 is preferable because it does not necessarily require cooling equipment.

In the stirring method, the emulsion has a property of being substantially immiscible with the emulsion, and the emulsion is added to a liquid adjusted to a temperature equal to or higher than the gelation temperature of the hydrogel, and the emulsion is atomized by the shearing force of stirring. It is a method of producing by utilizing the property of forming droplets by interfacial tension. The droplets formed by the stirring method are cooled and solidified in a liquid that is substantially immiscible with the emulsion to become particles.

[Thickener]
The hair dye composition of the present invention contains an anionic or nonionic thickening water-soluble polymer in a continuous phase in order to improve usability as a composition such as stability and ease of spreading during application. It is preferable to do so. As anionic polymers, xanthan gum, hydroxypropyl xanthan gum, welan gum, gellan gum, carboxyvinyl polymer, guar gum, acrylic acid methacrylate copolymer, methyl vinyl ether / maleic anhydride copolymer, partially crosslinked with 1,9-decadien. Examples of the nonionic polymer include polyethylene glycol, hydroxyethyl cellulose, polyvinylpyrrolidone, and polyvinylpyrrolidone / vinyl acetate copolymer, and xanthan gum and hydroxypropyl xanthan gum are preferable. Two or more of these thickening water-soluble polymers can be used in combination.

The content of the thickening water-soluble polymer in the hair dye composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of stability of the composition and ease of spreading at the time of application. 0.5% by mass is further preferable, 10% by mass or less is preferable, 7% by mass or less is more preferable, and 5% by mass or less is further preferable.

[PH]
The pH (25 ° C.) of the hair dye composition of the present invention is preferably 2 or more, more preferably 2.5 or more, and even more preferably 2.7 or more. Further, 6 or less is preferable, 5 or less is more preferable, and 4 or less is further preferable. Here, the pH is a value measured as it is for the composition stock solution without being diluted.

As the acid used for adjusting the pH, an organic acid such as citric acid, malic acid, lactic acid, glycolic acid, malonic acid, succinic acid or a salt thereof or a salt thereof; an inorganic acid such as phosphoric acid or hydrochloric acid is used. Of these, citric acid, lactic acid, and glycolic acid are preferable. Inorganic alkaline agents such as sodium hydroxide and potassium hydroxide; organic alkaline agents such as monoethanolamine and aminopropanol; ammonia; ammonium chloride; carbonates such as ammonium carbonate, potassium carbonate, sodium carbonate and guanidine carbonate. Examples include salts, with alkali metal hydroxides, ammonia and monoethanolamine being preferred.

[Other optional ingredients]
In addition to the above-mentioned components, the hair dye composition of the present invention appropriately contains components used in ordinary cosmetics, such as pigments, chelating agents, fragrances, preservatives, ultraviolet absorbers, antioxidants, and bactericides. It can be manufactured according to the usual method.

[Dosage form]
The form of the hair dye composition of the present invention can be, for example, a dosage form suitable for dyeing hair such as emulsion, cream, gel, and paste.

In order to carry out a hair dyeing treatment using the hair dye composition of the present invention, the hair dye composition having a substantially equal mass may be applied to the hair, left to stand, and then washed away. The leaving time is preferably 1 minute or longer, more preferably 3 minutes or longer, still more preferably 5 minutes or longer, and preferably 60 minutes, from the viewpoint of time for the dye to sufficiently penetrate into the hair and convenience. Below, it is more preferably 40 minutes or less, still more preferably 20 minutes or less. The hair dye composition of the present invention can be satisfactorily dyed without heating when it is left to stand, and thus damage to the hair can be prevented. Therefore, the hair dye composition can be left without heating. More preferred. Further, when the hair dye composition of the present invention is washed away, it may be simply washed away with warm water, but it is preferable to wash it off with shampoo, and it is more preferable to wash it off with shampoo repeatedly twice.

Example 1, Comparative Examples 1-2
Particles 1 and 2 in Table 1 were prepared according to the method described in JP-A-2007-160277. That is, the oily component in Table 1 was heated to 80 ° C. to prepare an oily component solution. Separately, the aqueous component of Table 1 was heated to 90 ° C. to prepare a solution, and after cooling to 80 ° C., the oily component solution was added and stirred to obtain an emulsion. Particles 1 and 2 were produced by a dropping method of spray-cooling the obtained emulsion using a two-fluid external mixing nozzle. Particle 1 is an agar hydrogel particle containing benzyl alcohol as an aromatic alcohol, and is the hydrogel particle of the present invention. On the other hand, the particles 2 do not contain aromatic alcohol and are hydrogel particles outside the scope of the present invention.

Next, using these, a hair manicure gel having the composition shown in Table 2 was prepared according to a conventional method, and the hair dyeing property and the skin coloring property were evaluated. The hair and skin treatment methods and evaluation methods are as follows. The results are shown in Table 2.

[Hair treatment method]
After applying 1 g of the hair dye composition to 1 g of human gray hair tress, it was left at 30 ° C. for 15 minutes. After that, it was rinsed with hot water at 40 ° C and dried with warm air from a dryer.

[Skin treatment method]
A circle (0.785 cm ² ) with a diameter of 1 cm was marked on the pig skin, and 0.05 g of the hair dye composition was applied. After leaving it at 30 ° C for 15 minutes, it was rinsed with hot water at 40 ° C, placed on a paper towel and gently drained.

[Evaluation method for hair dyeing and skin coloring]
Using a color difference meter (Konica Minolta Co., Ltd., color difference meter CR-300), the shades of hair and pig skin dyed according to the above-mentioned hair treatment method and skin treatment method are subjected to a CIE color system (L ^* , a ^* , b). ^* ) Was measured, and ΔE ^* was calculated by the following formula using the difference between the values before and after the treatment (ΔL ^* , Δa ^* , Δb ^* ), and the hair dyeability and skin colorability were evaluated. The larger ΔE ^* , the greater the hair dyeing property and the skin coloring property.

In addition, regarding skin coloring, a visual evaluation was also conducted by 10 evaluators, and the number of people who answered that they were not concerned about skin coloring was shown.

The composition of Example 1 containing the hydrogel particles of the present invention has equivalent hair dyeability as compared with Comparative Example 1 containing hydrogel particles outside the scope of the present invention and Comparative Example 2 not containing hydrogel particles. However, skin coloring was remarkably suppressed.

Claims (7)

A hair dye composition in which an acid dye is dissolved in an aqueous solvent and hydrogel particles containing an aromatic alcohol are dispersed in the aqueous solvent. The hair dye composition according to claim 1, wherein the hydrogel particles are formed by using a non-crosslinked water-soluble polymer having a gelling ability as a gelling agent. The hair dye composition according to claim 2, wherein the water-soluble polymer having a non-crosslinked gelling ability is agar. The hair dye composition according to any one of claims 1 to 3, wherein the hydrogel particles further contain an oily component other than an aromatic alcohol. The hair dye composition according to claim 4, wherein the oily component other than the aromatic alcohol is a mixture of a solid fat and a liquid oil. Claimed that the aromatic alcohol is one or more selected from the group consisting of benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol and 2-benzyloxyethanol. Item 8. The hair dye composition according to any one of Items 1 to 5. A method for dyeing hair using the hair dye composition according to any one of claims 1 to 6.