JP7624697B2 - Acidic hair dye composition - Google Patents

Description

The present invention relates to an acidic hair dye composition.

Acid hair dyes are one-component coloring agents that are also called hair manicures or acid colors. Because acid hair dyes do not contain oxidizing agents such as hydrogen peroxide, when dyeing hair with acid hair dyes, it is common to dye hair without bleaching it.

Hair dyed with acidic hair dyes has the problem that the dye gradually washes out of the hair due to sweat, shampooing, and chemical processes such as permanent waving, causing the color to fade in as little as a few weeks.

For example, Patent Document 1 discloses a hair dye composition that contains a specific acid dye in a specific content and ratio, thereby improving dye fastness and dyeing the hair in a color that looks natural and beautiful even under various lighting conditions.

Patent Document 2 discloses an acid hair dye composition that contains a specific acid dye, an acid, and an aromatic alcohol to improve the dye fastness of hair and reduce discoloration of washing liquid and sweat during hair washing.

JP 2011-157290 A JP 2004-18505 A

However, in the technology of Patent Document 1, when dyeing gray hair with an acidic hair dye, black hair and gray hair are dyed in different colors, and the gray hair appears undyed, which is a phenomenon known as gray hair floating. In particular, in the dyeing process of hair containing a mixture of black hair and gray hair, the gray hair does not blend well, and the quality is not satisfactory.
In the technique of Patent Document 2, since color fading occurs due to permanent wave treatment, the color fastness is not of satisfactory quality.

In view of the above, the present invention aims to provide an acidic hair dye composition that blends well with gray hair and has high durability against permanent wave treatment.

The present inventors have conducted extensive research to solve the above problems, and as a result have found that an acidic hair dye composition having the following composition can solve the above problems, thereby completing the present invention.
The present invention relates to, for example, the following [1] to [8].

[1] The composition contains an acid dye containing at least one acid dye A selected from the group consisting of (A1) Yellow No. 406, (A2) Red No. 104 (1), and (A3) Purple No. 401, and the acid dye contains at least one combination selected from the group consisting of (A1) Yellow No. 406 and (A3) Purple No. 401 (I), (A2) Red No. 104 (1) and (B9) Green No. 201 (II), and (B4) Orange No. 205 and (B8) Black No. 401 (III), and when the composition contains the combination (I), (A 1) An acidic hair dye composition in which the mass ratio ((A1):(A3)) between Yellow No. 406 and (A3) Purple No. 401 is 1:5 to 1:1, and in the case where the combination (II) is included, the mass ratio ((A2):(B9)) between (A2) Red No. 104 (1) and (B9) Green No. 201 is 8:3 to 9:1, and in the case where the combination (III) is included, the mass ratio ((B4):(B8)) between (B4) Orange No. 205 and (B8) Black No. 401 is 1:2 to 9:1, and the proportion of the acidic dye A is 60% by mass or more when the total amount of the acidic dyes is taken as 100% by mass.

[2] The acidic hair dye composition according to [1], wherein the acidic dye includes a combination (I) of (A1) Yellow No. 406 and (A3) Purple No. 401, and a combination (III) of (B4) Orange No. 205 and (B8) Black No. 401, and when the total mass of (A1) Yellow No. 406 and (A3) Purple No. 401 ((A1) + (A3)) is 100 parts by mass, the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4) + (B8)) is 10 parts by mass or more.

[3] The acidic hair dye composition according to [1], wherein the acidic dye includes a combination (II) of (A2) Red No. 104 (1) and (B9) Green No. 201, and a combination (III) of (B4) Orange No. 205 and (B8) Black No. 401, and when the total mass of (A2) Red No. 104 (1) and (B9) Green No. 201 ((A2) + (B9)) is 100 parts by mass, the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4) + (B8)) is 10 parts by mass or more.

[4] The acidic hair dye composition according to [1], wherein the acidic dyes include a combination (I) of (A1) Yellow No. 406 and (A3) Purple No. 401, a combination (II) of (A2) Red No. 104 (1) and (B9) Green No. 201, and a combination (III) of (B4) Orange No. 205 and (B8) Black No. 401.

[5] The acidic hair dye composition according to [1], wherein the acidic dye includes a combination (I) of (A1) Yellow No. 406 and (A3) Purple No. 401, a combination (II) of (A2) Red No. 104 (1) and (B9) Green No. 201, and a combination (III) of (B4) Orange No. 205 and (B8) Black No. 401, and when the total mass of (A1) Yellow No. 406 and (A3) Purple No. 401 ((A1) + (A3)) is 100 parts by mass, the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4) + (B8)) is 10 parts by mass or more.

[6] The acidic hair dye composition according to [1], wherein the acidic dye includes a combination (I) of (A1) Yellow No. 406 and (A3) Purple No. 401, a combination (II) of (A2) Red No. 104 (1) and (B9) Green No. 201, and a combination (III) of (B4) Orange No. 205 and (B8) Black No. 401, and when the total mass of (A2) Red No. 104 (1) and (B9) Green No. 201 ((A2) + (B9)) is 100 parts by mass, the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4) + (B8)) is 10 parts by mass or more.

[7] The acidic hair dye composition according to any one of [1] to [6], wherein the acidic dye comprises the acidic dye A and the acidic dye B, and the acidic dye B is at least one selected from the group consisting of (B1) Yellow No. 203, (B2) Yellow No. 403 (1), (B3) Yellow No. 407, (B4) Orange No. 205, (B5) Red No. 106, (B6) Red No. 227, (B7) Red No. 230 (1), (B8) Black No. 401, and (B9) Green No. 201.

[8] An acidic hair dye composition according to any one of [1] to [7], which is used for dyeing gray hair.

The present invention provides an acidic hair dye composition that blends well with gray hair and has high durability against permanent wave treatment.

Next, the acidic hair dye composition of the present invention will be specifically described.
<Acidic hair dye composition>
The acidic hair dye composition of the present invention contains an acid dye including at least one acid dye A selected from the group consisting of (A1) Yellow No. 406, (A2) Red No. 104 (1), and (A3) Purple No. 401, and the acidic dye includes at least one combination selected from the group consisting of a combination (I) of (A1) Yellow No. 406 and (A3) Purple No. 401, a combination (II) of (A2) Red No. 104 (1) and (B9) Green No. 201, and a combination (III) of (B4) Orange No. 205 and (B8) Black No. 401. When the acidic hair dye composition contains the combination (I), 3) When the mass ratio (A1):(A3) of (A2) Red No. 104(1) to (B9) Green No. 201 is 1:5 to 1:1 and the combination (II) is included, the mass ratio (A2):(B9) of (A2) Red No. 104(1) to (B9) Green No. 201 is 8:3 to 9:1 and the combination (III) is included, the mass ratio (B4):(B8) of (B4) Orange No. 205 to (B8) Black No. 401 is 1:2 to 9:1 and, when the total amount of the acid dyes is taken as 100 mass%, the proportion of the acid dye A is 60 mass% or more, preferably 63 mass% or more and 98 mass% or less, more preferably 63 mass% or more and 83 mass% or less.

If the proportion of acid dye A is less than 60% by mass, the coloring in the thioglycolic acid permanent wave first agent solution tends to be dark, and the fastness in permanent wave treatment using the thioglycolic acid permanent wave first agent solution may also be reduced, which is undesirable. In addition, if the coloring in the thioglycolic acid permanent wave first agent solution tends to be dark, it may give the practitioner the impression that the hair has faded, which is also undesirable.

In the present invention, the acid dye A refers to an acid dye of the group consisting of (A1) Yellow No. 406, (A2) Red No. 104 (1) and (A3) Purple No. 401.
In the present invention, Acid Dye B refers to an Acid Dye of the group consisting of (B1) Yellow No. 203, (B2) Yellow No. 403 (1), (B3) Yellow No. 407, (B4) Orange No. 205, (B5) Red No. 106, (B6) Red No. 227, (B7) Red No. 230 (1), (B8) Black No. 401, and (B9) Green No. 201.

In the acid dyes of the present invention, the combination of (A1) Yellow No. 406 and (A3) Purple No. 401 is indicated as combination (I), the combination of (A2) Red No. 104 (1) and (B9) Green No. 201 is indicated as combination (II), and the combination of (B4) Orange No. 205 and (B8) Black No. 401 is indicated as combination (III).

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A. When the acid dye includes combination (I), the mass ratio of (A1) Yellow No. 406 to (A3) Purple No. 401 ((A1):(A3)) is 1:5 to 1:1, which tends to blend well with gray hair, dye gray hair more strongly, and may cause less coloring in a thioglycolic acid solution, and is therefore preferably 2:3 to 1:2 ((A1):(A3)).

When the ratio ((A1):(A3)) is less than 1:5, i.e., when the content ratio of (A3) is high, the purple color becomes stronger and the saturation becomes too high, which can result in an unnatural finish and poor compatibility with gray hair, which is undesirable.

When the ratio ((A1):(A3)) is greater than 1:1, i.e., when the content ratio of (A1) is high, the yellow color becomes stronger and the saturation becomes too high, which can result in an unnatural finish and poor compatibility with gray hair, which is undesirable.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A. When the acid dye includes combination (II), the mass ratio of (A2) Red No. 104 (1) to (B9) Green No. 201 ((A2):(B9)) is 8:3 to 9:1, which tends to blend well with gray hair and dye gray hair well, and is therefore preferably 3:1 to 6:1 ((A2):(B9)).

When the ratio of ((A2):(B9)) is less than 8:3, i.e., when the content ratio of (B9) is high, the green color becomes stronger and the saturation becomes too high, which can result in an unnatural finish and poor compatibility with gray hair, which is undesirable.

When the ratio ((A2):(B9)) is greater than 9:1, i.e., when the content ratio of (A2) is high, the red color becomes stronger and the saturation becomes too high, which can result in an unnatural finish and poor compatibility with gray hair, which is undesirable.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combination (III), the mass ratio of (B4) Orange No. 205 to (B8) Black No. 401 ((B4):(B8)) is 1:2 to 9:1, which is particularly good at blending with gray hair and tends to dye gray hair well, and therefore preferably ((B4):(B8)) is 2:3 to 5:1.

When the ratio ((B4):(B8)) is less than 1:2, i.e., when the content ratio of (B8) is high, the blue color becomes stronger and the saturation becomes too high, which can result in an unnatural finish and poor compatibility with gray hair, which is undesirable.

When the ratio ((B4):(B8)) is greater than 9:1, i.e., when the content ratio of (B4) is high, the orange color becomes stronger and the saturation becomes too high, which can result in an unnatural finish and poor compatibility with gray hair, which is undesirable.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combination (I) and combination (III), the mass ratio of (A1) Yellow No. 406 to (A3) Purple No. 401 ((A1):(A3)) is preferably 2:3 to 1:2, and the mass ratio of (B4) Orange No. 205 to (B8) Black No. 401 ((B4):(B8)) is preferably 2:3 to 5:1.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combination (II) and combination (III), the mass ratio of (A2) Red No. 104 (1) to (B9) Green No. 201 ((A2):(B9)) is preferably 3:1 to 6:1, and the mass ratio of (B4) Orange No. 205 to (B8) Black No. 401 ((B4):(B8)) is preferably 2:3 to 5:1.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combination (I) and combination (II), the mass ratio of (A1) Yellow No. 406 to (A3) Purple No. 401 ((A1):(A3)) is preferably 2:3 to 1:2, and the mass ratio of (A2) Red No. 104(1) to (B9) Green No. 201 ((A2):(B9)) is preferably 3:1 to 6:1.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combinations (I), (II), and (III), the mass ratio of (A1) Yellow No. 406 to (A3) Purple No. 401 ((A1):(A3)) is preferably 2:3 to 1:2, the mass ratio of (A2) Red No. 104(1) to (B9) Green No. 201 ((A2):(B9)) is preferably 3:1 to 6:1, and the mass ratio of (B4) Orange No. 205 to (B8) Black No. 401 ((B4):(B8)) is preferably 2:3 to 5:1.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combination (I) and combination (III), when the total mass of (A1) Yellow No. 406 and (A3) Purple No. 401 ((A1) + (A3)) is taken as 100 parts by mass, the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4) + (B8)) is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more and 500 parts by mass or less, and even more preferably 20 parts by mass or more and 65 parts by mass or less, because it tends to blend well with gray hair and dye gray hair strongly.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combination (II) and combination (III), when the total mass of (A2) Red No. 104 (1) and (B9) Green No. 201 ((A2) + (B9)) is taken as 100 parts by mass, the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4) + (B8)) is preferably 10 parts by mass or more, and since it tends to blend well with gray hair, it is more preferably 20 parts by mass or more and 500 parts by mass or less, and even more preferably 20 parts by mass or more and 220 parts by mass or less.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combinations (I), (II), and (III), the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4)+(B8)) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more and 500 parts by mass or less, when the total mass of (A1) Yellow No. 406 and (A3) Purple No. 401 ((A1)+(A3)) is taken as 100 parts by mass.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combinations (I), (II), and (III), the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4)+(B8)) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more and 500 parts by mass or less, when the total mass of (A2) Red No. 104(1) and (B9) Green No. 201 ((A2)+(B9)) is taken as 100 parts by mass.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and when the acid dye includes combinations (I), (II), and (III), when the total mass of (A1) Yellow No. 406 and (A3) Purple No. 401 ((A1) + (A3)) is taken as 100 parts by mass, the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4) + (B8)) is It is preferably 10 parts by mass or more, more preferably 20 parts by mass or more and 500 parts by mass or less, and when the total mass of (A2) Red No. 104 (1) and (B9) Green No. 201 ((A2) + (B9)) is taken as 100 parts by mass, the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4) + (B8)) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more and 500 parts by mass or less.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and the acid dye includes combination (I) and combination (III), and further preferably includes at least one selected from the group consisting of (A2) Red No. 104 (1), (B1) Yellow No. 203, (B2) Yellow No. 403 (1), (B3) Yellow No. 407, (B5) Red No. 106, (B6) Red No. 227, (B7) Red No. 230 (1), and (B9) Green No. 201.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, and it is more preferable that the acid dye includes combination (I) and combination (III), and further includes (A2) Red No. 104 (1). By including the acid dye includes combination (I) and combination (III), and further includes (A2) Red No. 104 (1), it is preferable because it causes less coloring in the thioglycolic acid solution and is less likely to give the impression to the practitioner that the hair has faded.

The acid hair dye composition of the present invention contains at least one acid dye including Acid Dye A, and the acid dye includes Acid Dye A and Acid Dye B, and it is preferable that Acid Dye B is at least one selected from the group consisting of (B1) Yellow No. 203, (B2) Yellow No. 403 (1), (B3) Yellow No. 407, (B4) Orange No. 205, (B5) Red No. 106, (B6) Red No. 227, (B7) Red No. 230 (1), (B8) Black No. 401, and (B9) Green No. 201.

It is more preferable that the acid dye B is at least one selected from the group consisting of (B4) Orange No. 205, (B8) Black No. 401, and (B9) Green No. 201.
From the viewpoint of less coloring in the thioglycolic acid permanent wave first agent solution, it is more preferable that the acid dye B is at least one selected from the group consisting of (B1) Yellow No. 203, (B3) Yellow No. 407, and (B4) Orange No. 205, and it is even more preferable that the acid dye B is (B4) Orange No. 205.

From the viewpoint of high fastness in permanent wave treatment using a thioglycolic acid permanent wave first agent solution, it is preferable that the acid dye B is at least one selected from the group consisting of (B2) Yellow No. 403 (1), (B5) Red No. 106, (B6) Red No. 227, (B7) Red No. 230 (1), (B8) Black No. 401, and (B9) Green No. 201, and it is even more preferable that the acid dye B is at least one selected from the group consisting of (B8) Black No. 401 and (B9) Green No. 201.

The acid hair dye composition of the present invention contains at least one acid dye including an acid dye A, the acid dye including the acid dye A and an acid dye B, and the acid dye B is preferably at least one selected from the group consisting of (B1) Yellow No. 203, (B2) Yellow No. 403 (1), (B3) Yellow No. 407, (B4) Orange No. 205, (B5) Red No. 106, (B6) Red No. 227, (B7) Red No. 230 (1), (B8) Black No. 401, and (B9) Green No. 201, and when the total amount of the acid dyes is taken as 100% by mass, the proportion of the acid dye A is 60% by mass or more, and the proportion of the acid dye B is preferably 2% by mass or more and 40% by mass or less.

[Acid dyes]
In the present invention, the acid dye refers to an acid dye in tar dyes described in the Ministerial Ordinance (Ministry of Health and Welfare Ordinance No. 30 of 1966) that specifies tar dyes that can be used in medicines, etc. The acid dye can be applied to hair together with a penetrating agent or the like to dye the hair.

The acidic hair dye composition of the present invention may contain acidic dyes other than Acid Dye A and Acid Dye B, HC dyes, and basic dyes, as long as the effects of the present invention are not impaired. Examples of acidic dyes include Red No. 2, Red No. 3, Red No. 102, Red No. 105 (1), Red No. 201, Red No. 213, Red No. 230 (2), Red No. 231, Red No. 232, Red No. 401, Red No. 502, Red No. 503, Red No. 504, Red No. 506, Orange No. 207, Orange No. 402, Yellow No. 4, Yellow No. 5, Yellow No. 202 (1), Yellow No. 202 (2), Yellow No. 402, Blue No. 1, Blue No. 2, Examples of the HC dyes include Blue No. 202, Blue No. 203, Blue No. 205, Green No. 205, Green No. 401, Green No. 402, and Brown No. 201. Examples of the HC dyes include HC Blue 2, HC Blue 6, HC Blue 7, HC Blue 8, HC Orange 1, HC Orange 2, HC Orange 3, HC Red 1, HC Red 3, HC Red 7, HC Red 10, HC Red 13, HC Red 14, HC Purple 1, HC Purple 2, HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, 1-amino-2-methyl Examples of the basic dyes include red 213, red 214, basic blue 7, basic blue 9, basic blue 26, basic blue 75, basic blue 99, basic red 2, basic red 22, basic red 51, basic red 76, basic yellow 57, basic yellow 87, basic orange 31, basic brown 16, basic brown 17, basic purple 3, basic purple 4, and basic purple 14. Among these, acid dyes and HC dyes are preferred because they are dyed with acid.

[Natural colorants and other ingredients]
The acidic hair dye composition of the present invention may contain a natural colorant, if necessary, within a range that does not impair the effects of the present invention. As the natural colorant, those that have been used for a long time in food and cosmetics are preferred from the viewpoints of safety and color tone, and for example, natural colorants described in the Cosmetic Raw Material Standards, Cosmetic Type Approval Standards I to V, Quasi-drug Raw Material Standards, and Food Additives Official Standards can be used.

Specific examples of natural pigments that are preferred include gardenia pigment, turmeric pigment, annatto pigment, copper chlorophyll, paprika pigment, and lac pigment.
The natural dyes may be used alone or in combination of two or more kinds, and an acid dye may be used in combination with one or more natural dyes.

The acidic hair dye composition of the present invention may contain other ingredients as necessary, provided that the effects of the present invention are not impaired. Examples of other ingredients include oily ingredients (hydrocarbons, oils and fats, waxes, higher alcohols, higher fatty acids, esters), thickeners, penetrating agents, moisturizing agents, surfactants (anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants), silicones, chelating agents, antioxidants, stabilizers, pH adjusters, protective agents, solvents, anti-inflammatory agents, fragrances, preservatives, UV absorbers, propellants, plant extracts, herbal extracts, vitamins, and resins.

Specific examples of other components that can be used include benzyl alcohol as a penetrating agent, ethanol and water as a solvent, and the pH adjuster can be, for example, the above-mentioned acidic components, preferably lactic acid (e.g., 90% lactic acid) and sodium lactate. As water, it is preferable to use ion-exchanged water. The other components can be used alone or in combination of two or more.

<Production of Acidic Hair Dye Composition>
The acidic hair dye composition of the present invention can be produced by, for example, stirring, mixing, heating, dissolving, dispersing, or the like in a known manner, except that each of the above-mentioned components is used in the amounts described above, and the production method is not particularly limited.

[pH]
The pH of the acidic hair dye composition of the present invention is preferably 2.0 to 5.0, more preferably 2.0 to 3.5.

[Dosage form]
The formulation of the acidic hair dye composition of the present invention is not particularly limited, but may be, for example, a milk, cream, gel, lotion, liquid, or foam. Of these, the cream or gel formulation is preferred.
The acidic hair dye composition of the present invention can also be used as a spray composition by using it together with a propellant.

[Application]
The acidic hair dye composition of the present invention can be applied or sprayed onto hair. When applying to hair, an appropriate amount can be applied with a comb or brush. After application to hair, it is preferable to heat the composition to 20 to 50°C, preferably 45°C, for 1 to 20 minutes, if necessary.

The acidic hair dye composition of the present invention is preferably used for dyeing gray hair.
The acidic hair dye composition of the present invention can be applied to the entire hair, and can also be used for dyeing a specific part of the hair, for example, a gray hair part.

The acidic hair dye composition of the present invention is preferably used for dyeing all or part of gray hair.
Generally, when a portion of hair is gray, specifically, when the proportion of gray hair in the total hair is 30% to 50%, even if a dyeing process is performed, the black hair and the gray hair will not be dyed the same color, and the gray hair may appear to be undyed, and a phenomenon known as gray hair floating may occur.

The acidic hair dye composition of the present invention does not cause gray hair to float and blends well with gray hair, so it is preferably used on hair in which the proportion of gray hair in the total hair is 30% to 50%.
The acidic hair dye composition of the present invention can be applied or sprayed onto hair to perform a dyeing treatment, and then the dyed hair can be subjected to a permanent wave treatment.

When permanent waving is performed on hair dyed with the acidic hair dye composition of the present invention, it is preferable that the permanent waving is performed using thioglycolic acid or cysteamine.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these.

[Examples 1 to 42, Comparative Examples 1 to 34]
In the examples and comparative examples, commercially available products shown in Table 1 were used.

The numerical values in the formulations in Tables 2 to 11 represent the mass percentage of each component when the acidic hair dye composition is taken as 100 mass%, and are expressed as values converted into pure content.

[Hair dye test]
The components were mixed according to the formulation shown in Table 2 to prepare a base for an acidic hair dye composition.

The acidic hair dye compositions were prepared by mixing this base with the acidic dyes shown in Tables 6 to 11, and used as samples.

[Hair bundle]
(Hair bundle 1) 10 cm long human hair bundle containing 30% mixed gray hair (BM-MIX-A manufactured by Bealux) 1 g
(Hair bundle 2) 10 cm long human hair bundle of 50% mixed gray hair (BM-MIX-K50-A, manufactured by Bealux) 1 g
(Hair bundle 3) 10 cm long human gray hair bundle (BM-W-A, manufactured by Bealux) 1 g
Each sample was applied to the above three types of hair bundles, and a hair dyeing test was carried out.

[Hair dye test]
2 g of the sample was applied to one dry hair bundle with a brush. The hair bundle was then left to stand at 45°C for 15 minutes and dyed (dyeing treatment). The dyed hair bundle was washed with a 10% aqueous solution of Alscope DA-330S (Toho Chemical Industry Co., Ltd.) and then dried. After drying, hair bundle 1 was evaluated for compatibility with gray hair in evaluation item 1, and hair bundle 2 was evaluated for evaluation item 2. Hair bundle 3 was evaluated for dyeing of gray hair in evaluation item 3.
After the above evaluation, the hair bundle 3 used in evaluation item 3 was used to carry out a fastness test by treating it with three types of permanent wave agent 1 solutions.

[Robustness test]
The formulation of the thioglycolic acid permanent wave first agent solution is shown in Table 3, the formulation of the cysteamine permanent wave first agent solution is shown in Table 4, and the formulation of the permanent wave second agent solution is shown in Table 5.

One hair bundle from hair bundle 3 used in evaluation item 3 was immersed in 10 mL of thioglycolic acid permanent wave agent 1 solution or cysteamine permanent wave agent 1 solution. After immersion for 15 minutes at 25°C, the hair bundle was removed. After removing the hair bundle, the coloring in the thioglycolic acid permanent wave agent 1 solution or cysteamine permanent wave agent 1 solution was visually evaluated.

Before the hair bundle was immersed in the thioglycolic acid permanent wave No. 1 solution and the cysteamine permanent wave No. 1 solution, both were colorless and transparent.
The hair bundle removed from the immersion was rinsed with tap water for 30 seconds, towel-dried, and immersed in 10 ml of permanent wave agent 2 solution. After immersion at 25°C for 15 minutes, the hair bundle was removed, washed with a 10% aqueous solution of Arscope DA-330S (Toho Chemical Industry Co., Ltd.), and dried with a dryer (permanent wave treatment). This permanent wave treated hair bundle was visually compared with the hair bundle 3 used in evaluation item 3 that had not been permanent wave treated, and fastness was evaluated in evaluation items 5 and 7.

In addition, coloring of the thioglycolic acid permanent wave 1st agent solution or the cysteamine permanent wave 1st agent solution after permanent wave treatment was evaluated in evaluation items 4 and 6.

[Evaluation method]
A sensory evaluation was carried out by 10 expert panelists (hairdressers) one at a time according to the evaluation criteria described for each item (1) to (7).

The average of the scores of the 10 panelists for each item was calculated and rated as follows:
⊚: The average of the evaluation points of 10 professional panelists (beauticians) is 3 points or more and 4 points or less.
◯: The average of the evaluation points of 10 professional panelists (beauticians) is 2.5 points or more and less than 3 points.
Δ: The average score of 10 professional panelists (beauticians) is 2 points or more and less than 2.5 points.
×: The average of the evaluation points of 10 professional panelists (hairdressers) is 1 point or more and less than 2 points.

[Evaluation items and evaluation criteria]
(1) Adaptability to Gray Hair of 30% Gray Hair Mix (Hair Bundle 1) The adaptability of the dyed hair bundle to gray hair was evaluated visually under sunlight.
4 points: Gray hair blends well. 3 points: Gray hair blends well. 2 points: Gray hair blends poorly. 1 point: Gray hair blends poorly, gray hair looks out of place.

(2) Adaptation to Gray Hair of 50% Gray Hair Mix (Hair Bundle 2) The adaptation to gray hair of the dyed hair bundle was evaluated visually under sunlight.
4 points: Gray hair blends well. 3 points: Gray hair blends well. 2 points: Gray hair blends poorly. 1 point: Gray hair blends poorly, gray hair looks out of place.

(3) Dyeing of White Hair Bundle (Hair Bundle 3) The dyeing intensity of the dyed hair bundle was evaluated visually under sunlight.
4 points: Strong dyeing of gray hair 3 points: Slightly strong dyeing of gray hair 2 points: Slightly weak dyeing of gray hair 1 point: Weak dyeing of gray hair

(4) Coloration of Thioglycolic Acid Permanent Wave First Agent Solution After permanent wave treatment using a thioglycolic acid permanent wave first agent solution, the color intensity of the first agent solution was evaluated visually under sunlight.
4 points: Almost no coloring 3 points: Slight coloring 2 points: Slightly dark coloring 1 point: Dark coloring

(5) Durability in Permanent Wave Treatment Using Thioglycolic Acid Permanent Wave First Agent Solution Hair tresses that had been permanently waved using thioglycolic acid were compared under sunlight with hair tresses that had not been permanently waved (unpermed hair tresses) and visually evaluated.
4 points: No discoloration or fading, high fastness 3 points: Almost no discoloration or fading, slightly high fastness 2 points: Some discoloration or fading, slightly low fastness 1 point: Significant discoloration or fading, low fastness

(6) Coloration of Cysteamine Permanent Wave No. 1 Solution After permanent wave treatment using a cysteamine permanent wave No. 1 solution, the color intensity of the solution was evaluated visually under sunlight.
4 points: Almost no coloring 3 points: Slight coloring 2 points: Slightly dark coloring 1 point: Dark coloring

(7) Durability in Perm Treatment Using Cysteamine Perm Treatment Agent 1 Solution Hair tresses that had been permanently treated using cysteamine were compared under sunlight with hair tresses that had not been permanently treated (unpermed hair tresses) and visually evaluated.
4 points: No discoloration or fading, high fastness 3 points: Almost no discoloration or fading, slightly high fastness 2 points: Some discoloration or fading, slightly low fastness 1 point: Significant discoloration or fading, low fastness

All of the dyeing methods of Examples 1 to 42 gave good results.
It can be seen that the acidic hair dye composition of the present invention is an acidic hair dye composition that blends well with gray hair and has high fastness to permanent wave treatment.

The acidic hair dye compositions of Comparative Examples 1 to 24 did not contain at least one combination selected from the group consisting of combination (I), combination (II), and combination (III), and therefore tended to be poorly compatible with gray hair.

Comparative Examples 25 and 26 contain combination (I), but the mass ratio ((A1):(A3)) of (A1) Yellow No. 406 and (A3) Purple No. 401 is not within the range of 1:5 to 1:1, and therefore tend to not blend well with gray hair.

Comparative Examples 27 and 28 contain combination (II), but the mass ratio ((A2):(B9)) of (A2) Red No. 104 (1) to (B9) Green No. 201 is not within the range of 8:3 to 9:1, and therefore tend to not blend well with gray hair.

Comparative Examples 29 and 30 contain combination (III), but the mass ratio of (B4) Orange No. 205 to (B8) Black No. 401 ((B4):(B8)) is not within the range of 1:2 to 9:1, and therefore tend to not blend well with gray hair.

In the acid hair dye compositions of Comparative Examples 31 to 33, when the total amount of the acid dyes was taken as 100% by mass, the proportion of the acid dye A was not 60% by mass or more, and therefore the durability tended to be low in permanent wave treatment using a thioglycolic acid permanent wave first agent solution.

In the acid hair dye composition of Comparative Example 34, when the total amount of the acid dyes was taken as 100% by mass, the proportion of the acid dye A was not 60% by mass or more, so the coloring in the thioglycolic acid permanent wave first agent solution tended to be darker.

Claims (7)

(A1) Yellow No. 406, (A2) Red No. 104 (1), and (A3) Purple No. 401;
The acid dye is
( A2) Red No. 104 (1) and (B9) Green No. 201 (II )
Including ,
In the combination (II) , the mass ratio of (A2) Red No. 104 (1) to (B9) Green No. 201 ((A2):(B9)) is 8:3 to 9:1 ;
The acidic hair dye composition, wherein the proportion of the acidic dye A is 60% by mass or more when the total amount of the acidic dyes is 100% by mass. The acid dye is
(A2) Red No. 104 (1) and (B9) Green No. 201 (II)
(B4) Orange No. 205 and (B8) Black No. 401 (III),
2. The acidic hair dye composition according to claim 1, wherein in the combination (III), the mass ratio of (B4) Orange No. 205 to (B8) Black No. 401 ((B4):(B8)) is 1:2 to 9:1. The acid dye is
(A2) A combination (II) of Red No. 104 (1) and Green No. 201 (B9) and a combination (III) of Orange No. 205 (B4) and Black No. 401 (B8),
3. The acidic hair dye composition according to claim 2, wherein the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4)+(B8)) is 10 parts by mass or more when the total mass of ( A2 ) Red No. 104(1) and (B9) Green No. 201 ((A2)+(B9)) is 100 parts by mass. The acid dye is
The combination includes (I) of (A1) Yellow No. 406 and (A3) Purple No. 401, (II) of (A2) Red No. 104 (1) and (B9) Green No. 201, and (III) of (B4) Orange No. 205 and (B8) Black No. 401,
In the combination (I), the mass ratio ((A1):(A3)) of (A1) Yellow No. 406 and (A3) Purple No. 401 is 1:5 to 1:1.
The acidic hair dye composition according to claim 2 . The acid dye is
The combination includes (I) of (A1) Yellow No. 406 and (A3) Purple No. 401, (II) of (A2) Red No. 104 (1) and (B9) Green No. 201, and (III) of (B4) Orange No. 205 and (B8) Black No. 401,
5. The acidic hair dye composition according to claim 4, wherein the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4)+(B8)) is 10 parts by mass or more when the total mass of (A1) Yellow No. 406 and (A3) Purple No. 401 ((A1)+(A3)) is 100 parts by mass . The acid dye is
The combination includes (I) of (A1) Yellow No. 406 and (A3) Purple No. 401, (II) of (A2) Red No. 104 (1) and (B9) Green No. 201, and (III) of (B4) Orange No. 205 and (B8) Black No. 401,
5. The acidic hair dye composition according to claim 4, wherein the total mass of (B4) Orange No. 205 and (B8) Black No. 401 ((B4)+(B8)) is 10 parts by mass or more when the total mass of (A2) Red No. 104( 1 ) and (B9) Green No. 201 ((A2)+(B9)) is 100 parts by mass. The acidic hair dye composition according to any one of claims 1 to 6 , which is used for dyeing gray hair.