JPH0653655B2 - Keratin fiber dye composition - Google Patents

Description

Detailed Description of the Invention

[0001]

This invention relates to a keratin fiber dye composition,
In particular, the present invention relates to a keratin fiber dyeing composition containing an acid dye, having good color retention, and having a long-lasting conditioning effect.

[0002]

2. Description of the Related Art Oxidative hair dyes that have been widely used in the past basically consist of an oxidative dye and an oxidant. Since hydrogen peroxide acts under alkaline conditions during treatment, hair may be treated depending on how it is treated. There is a risk of causing skin irritation, and primary skin irritation such as redness and blisters. A hair dye containing an acid dye has been developed as a hair dye that overcomes the adverse effects of such an oxidative hair dye on the scalp and hair.

As a hair dye using such an acid dye, many hair dyes in which an acid dye and a penetration accelerator are combined have been reported (Japanese Patent Publication No. 48-23911, Japanese Patent Publication No. 55-12407).
JP-A-61-53211, JP-A-62-124612, JP-A-52
-91028, JP-A-60-28913). However, this hair dye has a problem that the feel of the hair when finished is poor because a large amount of an organic solvent is used as a penetration enhancer.

In order to improve the feel of this hair, JP-A-58:
-157713 discloses a method of imparting a continuous conditioning effect to hair by combining an oxidative dye / direct dye with a cationic polymer and an anionic surfactant. Since it is effective only in the pH range of 8 or higher and is not effective in the acidic range, it has a drawback that there is a risk of hair damage or skin irritation.

On the other hand, in JP-A-63-35514, strong dyeing power is obtained when an acidic dye and a cationic polymer are contained in a charge ratio of 0.2 to 1.0 and an amphoteric surfactant / inorganic electrolyte is used as a solubilizer. Is obtained. However, when the acidic dye and the cationic polymer are used at such a charge ratio, the acidic dye only physically coats the hair surface as an oil by forming a complex with the cationic polymer, The dye hardly penetrates into the hair.
For this reason, there is a problem that discoloration easily occurs due to rubbing or washing hair.

[0006]

As described above, in the keratin fiber dyeing composition using the acid dye, the keratin fiber dyeing composition having a good feeling of finishing and not fading due to hair washing or rubbing. Things have not been obtained yet,
The development of such compositions has been desired.

[0007]

In view of the above situation, the inventors of the present invention have made extensive studies and as a result, have found that the acid dye has a nitrogen content of 0.5 to 0.5.
By using a combination of 3.0% cationic polymer and a specific surfactant, the complex formation between the acid dye and the cationic polymer is suppressed to a low level, the color retention is improved, and the conditioning effect is maintained. The present invention has been completed and the present invention has been completed.

That is, the present invention comprises (a) an organic solvent,
(B) acid dye, (c) acid, (d) nitrogen content of 0.5-
3.0% cationic polymer, and (e) 1 selected from betaine derivatives and acylated glutamic acid derivatives
The present invention provides a keratinous fiber dye composition, which comprises one or more surfactants and has a pH of 2 to 4.

The (a) organic solvent (a) used in the keratin fiber dyeing composition of the present invention may be one that has a function of uniformly dissolving the acid dye (b) and promoting penetration into keratin fibers. If not particularly limited, for example, the following formula (1)
Alternatively, the compound represented by (2) may be mentioned.

[Chemical 1]

[Chemical 2] Above all, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, 1,3-butanediol, benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methyl. Benzyl alcohol, phenoxyethanol, 2-benzyloxyethanol, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, glycerin,
N-methylpyrrolidone, N-octylpyrrolidone, N-
Laurylpyrrolidone and the like are preferable. The organic solvent (a) is preferably added to the keratin fiber dyeing composition of the present invention in an amount of about 0.5 to 50% by weight (hereinafter, simply expressed as%), and particularly preferably 2 to 30%. If it is less than 0.5%, the effect is not sufficiently exerted, and if it is more than 50%, the effect is not improved. Also,
The mixing ratio of water and the organic solvent (a) is preferably solvent: water = 20: 80 to 50:50, although it depends on the water solubility of the solvent.

The acid dye (b) is not particularly limited as long as it is an acid dye generally used for dyeing hair. For example, Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No. 1
05, red 106, yellow 4, yellow 5, green 3
No. 1, Blue No. 1, Blue No. 2, Red No. 201, Red No. 227
No., Red 230, Red 231, Red 232, Orange 2
05, Orange 207, Yellow 202, Yellow 203, Green 201, Green 204, Green 205, Blue 202
No. 203, Blue No. 203, Blue No. 205, Brown No. 201, Red No. 401, Red No. 502, Red No. 503, Red No. 504
No., red 506, orange 402, yellow 402, yellow 4
03, Yellow 406, Yellow 407, Green 401,
Examples include green No. 402, purple No. 401, and black No. 401. The acid dye (b) is preferably added in the keratin fiber dyeing composition of the present invention in an amount of about 0.1 to 5%, particularly preferably 0.15 to 3%. If it is less than 0.1%, the dyeability is weak, and if it is added in excess of 5%, the dyeability is not improved.

As the acid (c), a wide variety of general organic acids or inorganic acids can be used. For example, citric acid, glycolic acid, succinic acid, tartaric acid, lactic acid, fumaric acid, malic acid, levulinic acid, butyric acid. , Valeric acid, oxalic acid, maleic acid, fumaric acid, mandelic acid and other organic acids; phosphoric acid, hydrochloric acid,
Inorganic acids such as sulfuric acid and nitric acid can be mentioned. In addition, to these acids (c), sodium salt, potassium salt of the acid,
It is also possible to give a buffering function in the system by combining an ammonium salt or the like. Such acid (c) is
In the keratin fiber dye composition of the present invention, 0.1 to 15%, especially 1
It is preferable to blend 10%.

As the cationic polymer (d) having a nitrogen content of 0.5 to 3.0%, those obtained by cationizing a non-nitrogen-containing polymer such as cellulose, hydroxyethyl cellulose or guar gum can be used. Cationization is carried out by adding nitrogen-free polymer to tetraalkylammonium group, hydroxyalkyltrimethylammonium group,
A quaternary ammonium group such as a dialkyldiallylammonium group is bonded, and examples of the cationic polymer (d) include a cationized cellulose derivative, hydroxyethyl cellulose dimethyldiallylammonium chloride copolymer, and cationized guar gum derivative. Can be mentioned. As the cationized cellulose derivative, hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride (CTFA, polyquaterniu
m-10) and the like, and commercially available products include polymer JR-125,
Polymer JR-400, polymer LR-400 (manufactured by Union Carbide) and the like can be mentioned. The nitrogen (N) content of these hydroxyethyl cellulose hydroxypropyltrimethylammonium chlorides is 0.5 to 2.5% according to the nitrogen determination method (method 1) described in the commentary on cosmetics material standards. Commercially available products of hydroxyethyl cellulose dimethyldiallylammonium chloride copolymer (CTFA, polyquaternium-4) include Cellcoat L-200 and Cellcoat H-60 (manufactured by National Starch). The nitrogen (N) content of these hydroxyethyl cellulose dimethyldiallylammonium chloride copolymers is 1.4 to 2.2% according to the nitrogen determination method (method 1) described in the cosmetic material standard commentary. Examples of the cationized guar gum derivative include hydroxypropyltrimethylammonium chloride guar gum, and commercially available products thereof include Jaguar C-13-S and Jaguar C-
15-S (made by Celanese Stein Hall) and the like. The nitrogen (N) content of these hydroxypropyltrimethylammonium chloride guar gums is 1.0 according to the nitrogen determination method (first method) described in the cosmetic material standard commentary.
~ 3.0%. Since these cationic polymers have a low nitrogen (N) content of 0.5 to 3.0%, complex formation with an acidic dye is suppressed to a low level, and it is recognized that the addition of this cationic polymer improves the color retention. Was given. The content of these cationic polymers is preferably 0.1 to 0.5%, more preferably 0.2 to 0.4%. When the amount of the cationic polymer is less than 0.1%, the hair finish and conditioning when combined with one or more surfactants (e) selected from the betaine derivative and the acylated glutamic acid derivative described below. The effect cannot be sustained. On the other hand, if it exceeds 0.5%, the rate of complex formation with the acid dye becomes high, and the color retention becomes poor.

Among the surfactants (e), examples of betaine derivatives include those represented by the following general formula (3) or (4).

[Chemical 3]

[Chemical 4] Specific examples include cocoamidopropyl betaine, oleamidopropyl betaine, lauramidopropyl betaine, cocobetaine, oleyl betaine, lauryl betaine, cetyl betaine, cocoamidopropyl hydroxysarteine and lauryl sultaine. Of these, cocoamidopropyl betaine and lauramidopropyl betaine are particularly preferred. The term "coco" refers to a fatty acid mixture that is mainly C ₁₂ fatty acids obtained from coconut oil.

Examples of the acylated glutamic acid derivative include those represented by the following general formula (5).

[Chemical 5] [In the formula, R ⁹ represents a linear or branched alkyl group having ⁹ to 23 carbon atoms, and X ′ represents a hydrogen atom, a potassium atom, a sodium atom, NH ₄ or an alkanolamine] Specifically, cocoyl glutamic acid , Lauroyl glutamic acid,
Examples thereof include oleoyl glutamic acid and their potassium salts, sodium salts, alkanolamine salts, ammonium salts and the like.

The above betaine derivatives or acylated glutamic acid derivatives can be used alone or in admixture of two or more. The blending amount of the component (e) is 0.1 to 0.5%, particularly 0.2 to 0.4, in the keratin fiber dyeing composition of the present invention.
% Is preferred. If the blending amount is less than 0.1%, the hair finish and conditioning effect cannot be sufficiently maintained, and if the blending amount exceeds 0.5%, the effect is not improved.

The keratin fiber dye composition of the present invention is also
It is necessary that the pH of the aqueous liquid in (2) is 2-4. pH
Adjustment of component (b), component (c), component (d) and component
It can be performed by adjusting the blending amount of (e)
In addition to this, the sodium salt of the acid of component (c),
By combining selenium salt, ammonium salt, etc.
To adjust the pH by providing a buffering capacity
More preferable. In the present composition, to the extent that the object of the present invention is not impaired,
Thickeners such as hydroxyethyl cellulose used in ordinary cosmetics, silicones, perfumes, preservatives, ultraviolet absorbers, antioxidants, bactericides and the like may be added. Using the keratin fiber dye composition of the present invention, keratin fibers such as hair
To dye textiles, the composition is applied to keratinous fibers and
The keratinous fibers are heated at 20 to 50 ° C (more preferably 30 to 45 ° C).
5 to 30 minutes (more preferably 10 to 20 minutes)
It is preferable to heat. After this, use keratinous fibers
Remains on keratinous fibers by methods such as shampooing
The composition to be used may be washed off.

[0017]

EXAMPLES The present invention will be described below with reference to examples. The concentration of each component in the prescription indicates the effective concentration.

The evaluation of the product of the present invention and the comparative product was based on the following criteria. (1) 0.5 g of the product of the present invention and the comparative product were applied to about 1 g of gray hair tress when dyed (once shampoo), and heated at 45 ° C. for 15 minutes. After allowing to cool for 5 minutes, it was rinsed with running water, shampooed / rinsed and dried. The dyed hair bundle was measured for L, a, and b values with a color difference meter (CR200 manufactured by Minolta Co., Ltd.), and the color difference (ΔE ₁ ) from the undyed hair was determined to evaluate the dyeing. It should be noted that ΔE ₁ represents that the larger the value, the better the dyeing. (2) Feeling of hair at the time of dyeing hair (1 time shampoo) 5 g was applied to about 10 g of a Japanese black hair bundle, and treated in the same manner as above, and the finish was evaluated by 5 professional panelists. ◎: Very smooth and good for fingering ○: Smooth and good for fingering △: Hair does not slip and is slightly rough ×: There is creaking and is considerably rough (3) Dyeing after 4 times shampoo (1) After the process of washing the dyed tress with a commercially available shampoo → drying was repeated 4 times, the color difference (ΔE ₂ ) from the untreated hair (undyed hair) was obtained, and the dyeing was evaluated. Note that Δ
E ₂ indicates that the larger the value, the better the dyeing, and that there is no discoloration due to shampoo. (4) Feeling of hair after 4 times shampoo Japanese black hair of (2) was treated in the same manner as (3). The feeling after 4 times of shampoo was evaluated by 5 expert panelists. ◎: Smoothness and sufficient finger passage ○: Smoothness and finger passage △: Hair is not slippery and is slightly rough ×: There is squeaky texture Has become

The components of Examples 1 to 4 and Comparative Examples 1 and 2 were blended in the compositions shown in Table 1. For example, in Example 1, red No. 102, sodium lactate, and lactic acid were dissolved in water to disperse polymer JR-400 (manufactured by Union Carbide Co.), and then hydroxyethyl cellulose dispersed in a small amount of water was added. The temperature was increased to around 60 ° C to increase the viscosity. After cooling to room temperature, ethanol, benzyl alcohol, softazoline LPB (manufactured by Kawaken Fine Chemicals)
Was added and stirred uniformly to obtain a gel-like keratinous fiber dye composition (Invention product 1). Similarly, the keratinous fiber dye composition was prepared for Examples 2 to 4 and Comparative Examples 1 and 2. In addition, the keratinous fiber dyeing agent compositions corresponding to Examples 2 to 4 were designated as the products 2 to 4 of the present invention, and the keratinous fiber dyeing agent compositions corresponding to Comparative Examples 1 and 2 were designated as the comparative products 1 and 2.

[0020]

[Table 1]

Example 5 A keratinous fiber dyeing composition having the following composition was prepared according to the method for preparing the product 1 of the present invention. (Composition)% (1) Ethanol 15.0 (2) N-methylpyrrolidone 10.0 (3) Polymer JR-400 ^{* 1} 0.4 (4) Softazoline LPB ^{* 2} 0.3 (5) Sodium lactate 1.2 (6) Lactate 6.0 (7) Orange No. 205 0.18 (8) Hydroxyethyl cellulose 1.6 (9) Water balance amount pH2.8 * 1: Cationized cellulose manufactured by Union Carbide Co., nitrogen content 1.7%. * 2: N-lauramide propalbetaine (act.31%) manufactured by Kawaken Fine Chemicals. To about 10 g of shampooed white hair, 5 g of the product of the present invention was applied, heated at 45 ° C. for 15 minutes, and allowed to cool for 5 minutes,
Rinse with running water and shampoo. As a result, the white hair bundle was dyed in a dark orange color, and the finish was very smooth, and the fingers could easily pass. This effect was fully observed even after repeating the shampoo 4 times.

Example 6 A keratinous fiber dyeing composition having the following composition was prepared according to the method for preparing the product 1 of the present invention. (Composition)% (1) Isopropanol 25.0 (2) Benzyl alcohol 5.0 (3) Polymer JR-400 ^{* 1} 0.4 (4) Softazoline LPB ^{* 2} 0.3 (5) Sodium lactate 1.2 (6) Lactate 6.0 (7) Blue No. 205 0.2 (8) Hydroxyethyl cellulose 1.6 (9) Water balance amount pH 2.8 * 1 * 2 Same as Example 5 above. To about 10 g of shampooed white hair, 5 g of the product of the present invention was applied, heated at 45 ° C. for 15 minutes, and allowed to cool for 5 minutes,
Rinse with running water and shampoo. As a result, the white hair bundle was dyed in a deep blue color, the finish was very smooth, and the fingers could easily pass. This effect was fully observed even after repeating the shampoo 4 times.

Example 7 A keratinous fiber dyeing composition having the following composition was prepared according to the method for preparing the product 1 of the present invention. (Composition)% (1) Ethanol 25.0 (2) 2-Benzyloxyethanol 10.0 (3) Polymer JR-400 ^{* 1} 0.4 (4) Softazoline LPB ^{* 2} 0.3 (5) Sodium lactate 1.2 (6) Lactate 6.0 (7) Purple No. 401 0.2 (8) Hydroxyethyl cellulose 1.6 (9) Water balance amount pH 2.8 * 1 * 2 Same as Example 5 above. To about 10 g of shampooed white hair, 5 g of the product of the present invention was applied, heated at 45 ° C. for 15 minutes, and allowed to cool for 5 minutes,
Rinse with running water and shampoo. As a result, the white hair bundle was dyed in a deep purple color, and the finish was very smooth, and the fingers could easily pass. This effect was fully observed even after repeating the shampoo 4 times.

Example 8 A keratinous fiber dyeing composition having the following composition was prepared according to the method for preparing the product 1 of the present invention. (Composition)% (1) Ethanol 25.0 (2) Benzyl alcohol 5.0 (3) Polymer JR-400 ^{* 1} 0.4 (4) Amisoft LS-11 ^{* 2} 0.3 (5) Sodium citrate 0.1 (6) Citric acid 0.5 (7) ) Lactic acid 5.0 (8) Green No. 3 0.16 (9) Hydroxyethyl cellulose 1.6 (10) Water balance amount pH 2.7 * 1: Same as Example 5 above. * 2: Monosodium salt of lauroyl glutamate from Ajinomoto Co., Inc. To about 10 g of shampooed white hair, 5 g of the product of the present invention was applied, heated at 45 ° C. for 15 minutes, and allowed to cool for 5 minutes,
Rinse with running water and shampoo. As a result, the bunch of white hair was dyed in a deep green color, and the finish was very smooth and the fingers could easily pass. This effect was fully observed even after repeating the shampoo 4 times.

Example 9 A keratinous fiber dyeing composition having the following composition was prepared according to the method for preparing the product 1 of the present invention. (Composition)% (1) Ethanol 25.0 (2) 2-Benzyloxyethanol 10.0 (3) Jaguar C-13-S ^{* 1} 0.3 (4) Softazoline LPB ^{* 2} 0.3 (5) Sodium lactate 1.2 (6) Lactate 6.0 ( 7) Purple 401 0.09 (8) Black 401 0.08 (9) Orange 205 0.17 (10) Hydroxyethyl cellulose 1.6 (11) Water Balance pH2.8 * 1: Jaguar hydroxypropyltrimethylammonium chloride guar gum, nitrogen ( N) Content is 1.5%. * 2: Same as Example 5 above. To about 10 g of shampooed white hair, 5 g of the product of the present invention was applied, heated at 45 ° C. for 15 minutes, and allowed to cool for 5 minutes,
Rinse with running water and shampoo. As a result, the white hair bundle was dyed in a dark brown color, and the finish was very smooth, and the fingers could easily pass. This effect was fully observed even after repeating the shampoo 4 times.

[0026]

According to the present invention, it is possible to obtain a keratinous fiber dyeing composition which has good dyeability, is excellent in color retention even after repeated washing of hair, and has a long-lasting conditioning effect.

Claims (1)

[Claims] 1. An organic solvent (a), an acid dye (b),
(C) an acid, (d) a cationic polymer having a nitrogen content of 0.5 to 3.0%, and (e) one or more surfactants selected from betaine derivatives and acylated glutamic acid derivatives, A horny fiber dye composition, which has a pH of 2 to 4.