JP3294767B2 - Hair dye composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair dye composition, which imparts sufficient lightness to hair, has excellent hair dyeing power and fastness, and has a good feel even when used continuously. About things.

[0002]

2. Description of the Related Art Conventionally, a two-part type oxidative hair dye comprising a first agent containing an oxidation dye intermediate and a second agent containing an oxidant has been widely used as a hair dye. This hair coloring agent is a dye that causes a colorless low-molecular weight oxidation dye intermediate to penetrate into the hair and causes oxidative polymerization in the hair to form a pigment to dye the hair. These oxidative hair dyes are capable of dyeing hair in various colors as required, and have extremely excellent hair dyeing power, and are widely used in general. As the first alkaline agent, alkanolamines such as ammonia and monoethanolamine are used.

[0003] Further, in order to obtain good hair dyeing power, which is an advantage of these oxidative hair dyes, it is necessary to apply the composition evenly to the entire hair. , Jelly, aerosol and other products have been put on the market.

[0004]

However, there is a problem in that, when ammonia alone is blended as the alkali agent of the first agent, an irritating odor is generated. On the other hand, when monoethanolamine is used alone, it does not have a pungent odor, but cannot impart sufficient lightness to hair, has weak hair dyeing power, and lacks fastness. Further, when a dye solution is applied after the hair dyeing (hereinafter, referred to as plain rinse), the hair may be rough or squeaky. After the hair has been dried (hereinafter referred to as "dry"), the feel of the hair becomes stiff and the combability becomes poor, so that a good feel cannot be obtained. Further, if hair coloring is repeated continuously, there is a new problem that the stiffness of hair and the difficulty of combing increase.

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned drawbacks. As a result, by blending a specific amount of monoethanolamine and ammonia in a specific ratio, the hair can be sufficiently treated. A hair dye having excellent lightness and hair dyeing effect, excellent fastness, good feeling during plain rinsing and after drying, and good feeling even after repeated hair dyeing was obtained. Further, since the amount of ammonia to be added is smaller than the conventionally required amount, it is possible to reduce the irritating odor due to ammonia at the time of hair dyeing, thereby completing the present invention.

The present invention relates to a hair dye composition comprising (a)
Monoethanolamine and (b) ammonia are contained, and the total amount of (a) and (b) is 0.5% by weight.
To 12% by weight, more preferably 1% to 8% by weight. If it is less than 0.5% by weight, sufficient brightness, hair dyeing power,
Fastness, good rinsing and good feel after drying cannot be obtained, and if it exceeds 12% by weight, there is almost no increase in the effect of lightness, hair coloring, fastness and feel in continuous use.

The weight ratio of (a) and (b) is 1: 0.05 to 1: 0.5, more preferably 1: 0.
1-1: 0.35. If the compounding weight ratio is less than 1: 0.05, sufficient lightness cannot be obtained, hair dyeing power and fastness are poor, and the feeling during plain rinsing and after drying is poor, and a good feeling can be obtained even in continuous use. I can't. On the other hand, when the ratio exceeds 1: 0.5, there is almost no increase in the effect of lightness, hair dyeing property, fastness, and feel in continuous use.

Usually, (b) ammonia is blended as an aqueous ammonia solution which is easy to handle.

In addition to (a) and (b), by blending a cationized polymer as the component (c), the hair dyeing power and the feeling of hair during plain rinsing, after drying and during continuous use are improved. Things are obtained.

The cationized polymer used in the present invention contains an amino group or an ammonium group by bonding to a polymer chain, or has at least dimethyldiallylammonium halide as a constitutional unit. Starch, cationized guar gum derivatives, diallyl quaternary ammonium salt / acrylamide copolymers and quaternized polyvinylpyrrolidone derivatives.

As the cationized cellulose derivative, for example, those represented by the following general formula (1) are preferable.

[0012]

Embedded image In the formula (1), A represents a residue of an anhydroglucose unit, f is an integer of 50 to 20,000, and each R ₁ represents a substituent represented by the following general formula (2).

[0013]

Embedded image In the formula (2), R ₂ and R ₃ are an alkylene group having 2 or 3 carbon atoms, g is an integer of 0 to 10, h is an integer of 0 to 3, and i is 0 to
An integer of 10, R ₄ represents an alkylene group or a hydroxyalkylene group having 1 to 3 carbon atoms, R ₅ , R ₆ and R ₇ are the same or different and represent an alkyl group, an aryl group or an aralkyl group having up to 10 carbon atoms; Or a heterocyclic ring containing a nitrogen atom in the formula. X ₁ is an anion (chlorine, bromine,
Iodine, sulfuric acid, sulfonic acid, methylsulfuric acid, phosphoric acid, nitric acid, etc.). The degree of cation substitution of the cationized cellulose derivative used in the present invention is preferably from 0.01 to 1, that is, the average value of h per anhydroglucose unit is preferably from 0.01 to 1, more preferably from 0.02 to 0. 5 The sum of g + i is an average of 1 to 3. The degree of cation substitution is not sufficient if it is less than 0.01 and may be more than 1, but is preferably 1 or less from the viewpoint of the reaction yield. The molecular weight of the cationized cellulose derivative used here is about 100
It is preferably between 000 and 3,000,000. Commercially available products include LEOGARD G and GP of Lion Corporation and Polymers JR-125, JR-400 and J of Union Carbide.
R-30M, LR-400, LR-30M and the like.

Other cationized cellulose derivatives include hydroxyethylcellulose dimethyldiallylammonium chloride. Commercial products include Cellcoat H-100, manufactured by National Starch and Chemical Co., Ltd.
L-200 and the like.

The cationic starch is represented by the following general formula (3):
Is preferably represented by

[0016]

Embedded image In the formula (3), D is a starch residue, R ₈ is an alkylene group or a hydroxyalkylene group, R ₉ , R ₁₀ and R ₁₁ are the same or different, and have an alkyl group, aryl group or aralkyl having 10 or less carbon atoms. Represents a group, and may include a nitrogen atom in the formula to form a heterocyclic ring. X ₂ is an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.), and j is a positive integer. The cationic starch used in the present invention has a degree of cation substitution of 0.01 to 1, that is, 0.01 to 1, preferably 0.0 to 1, per anhydroglucose unit.
Those in which 2 to 0.5 cationic groups are introduced are preferred. A degree of cation substitution of less than 0.01 is not sufficient, and may be more than 1, but is preferably 1 or less from the viewpoint of reaction yield.

As the cationized guar gum derivative, those represented by the following general formula (4) are preferable.

[0018]

Embedded image In the formula (4), E is a guar gum residue, R ₁₂ is an alkylene group or a hydroxyalkylene group R ₁₃ , R ₁₄ and R ₁₅ are the same or different, and have an alkyl group, aryl group or aralkyl group having 10 or less carbon atoms. And a nitrogen atom in the formula may be included to form a heterocyclic ring. X ₃ is an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.), and k is a positive integer. The cationized guar gum derivative used in the present invention has a degree of cation substitution of 0.1.
It is preferably from 01 to 1, particularly preferably from 0.02 to 0.5 cationic groups introduced into the sugar unit. For example,
JP-B-58-35640, JP-B-60-46158 and JP-A-58-53996 disclose RH.
ONE-POULENC Juggler C-13S, -14S,
-17, 210, -162, HI-CARE1
000.

The cationic diallyl quaternary ammonium salt / acrylamide copolymer is represented by the following general formula (5):
Or what is shown by (6) is preferable.

[0020]

Embedded image

Embedded image In the formulas (5) and (6), R ₁₆ and R ₁₇ are the same or different, and represent hydrogen, an alkyl group (1 to 18 carbon atoms), a phenyl group, an aryl group, a hydroxyalkyl group, an amidoalkyl group, a cyano group. An alkyl group, an alkoxyalkyl group or a carboalkoxyalkyl group, R ₁₈ , R ₁₉ , R ₂₀ , R
₂₁ is the same or different; hydrogen, lower alkyl group (1 to 3 carbon atoms) or phenyl group; X ₄ is an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methylsulfuric acid, phosphoric acid, nitric acid, etc. ), P is an integer of 1 to 50, q is an integer of 0 to 50, and r is an integer of 150 to 8000. The molecular weight of the diallyl quaternary ammonium salt / acrylamide copolymer used in the present invention is preferably about 30,000 to 2,000,000,
More preferably, it is in the range of 100,000 to 1,000,000. As commercial products, Merck's Marcoat 100, 550, 28
0 and the like.

The quaternized polyvinylpyrrolidone derivative is preferably represented by the following formula (7).

[0022]

Embedded image In the formula (7), R ₂₂ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₂₃ , R ₂₄ , and R ₂₅ are the same or different and include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group, an amidoalkyl group, a cyanoalkyl group, an alkoxyalkyl group or a carboalkoxyalkyl group, Y ₁ is an oxygen atom or an NH group in an amide bond, X ₅ is an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, Alkylsulfuric acid, phosphoric acid, nitric acid, etc. having 1 to 4 carbon atoms), u is 1 to
An integer of 10 and an integer of s + t = 20 to 8000 are shown. The molecular weight of the quaternized polyvinylpyrrolidone derivative used in the present invention is preferably 10,000 to 2,000,000, and more preferably 50,000 to 1.5,000,000. Commercial products include Guff Coat 732, 755, 7
55N and the like.

Of these, cationized cellulose derivatives and / or diallyl quaternary ammonium salts / acrylamide copolymers are preferred. The compounding amount is 0.01
To 5% by weight, more preferably 0.1% to 3% by weight.
% By weight. If the amount is less than 0.01% by weight, a sufficient effect cannot be obtained. If the amount exceeds 5% by weight, the effect remains unchanged and is not economical.

Further, one or more members selected from the group consisting of ammonium salts or alkanolamine salts of sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid of the component (d) are compounded, and the compounding amount is 0.2 % To 5% by weight,
Within this range, excellent lightness and hair dyeing effects can be obtained. If the compounding amount is less than 0.2% by weight, sufficient lightness and hair dyeing effect cannot be obtained, and even if the compounding amount exceeds 5% by weight, the effect does not increase much and is not economical. Of these, ammonium sulfate, ammonium nitrate, ammonium chloride, monoethanolamine hydrochloride, ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate are preferred because particularly good results can be obtained.

The oxidation dye intermediates and couplers used in the hair dye composition of the present invention include phenylenediamines, toluylenediamines, aminophenols, aminonitrophenols, diphenylamines, diaminophenylamines, N -Phenylphenylenediamines, diaminopyridines and the like and salts thereof, resorcin, pyrogallol, catechol, α-naphthol and the like can be blended. In addition to the above substances, those listed in “Quasi-drug raw material standards” (published by Yakuji Nippo, June 1991) can be used as appropriate. Further, an acid dye can be blended.

The present hair dye composition may further contain components generally used in the hair dye composition. For example, moisturizing oil components such as higher alcohols and higher fatty acids, nonionic surfactants, anionic surfactants, amphoteric surfactants, surfactants such as cationic surfactants, and glycerin, propylene glycol, and polyethylene glycol. Agents, sulfites, stabilizers such as ascorbic acid, thickeners such as carboxymethylcellulose, xanthan gum, polyacrylic acid and its salts, silicon, and fragrances can be appropriately compounded as necessary.

[0027] The dosage form of the hair dye composition in the present invention may be any dosage form generally available on the market, for example, cream, liquid, jelly, aerosol, and the like. In particular, in the case of an aerosol foam hair dye, an effect is obtained in which the irritating odor is small, and the brightness, the hair dyeing power, and the feel of the hair after the treatment are good.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

[0029]

【Example】

 Example 1 (hair dye) <First agent>

[Table 1] <Second agent>% by weight aqueous hydrogen peroxide (35%) 15.0 cetanol 2.0 sodium lauryl sulfate 0.5 phenacetin 0.1 EDTA 0.5 amount of purified water 100 As shown in Table 1, Example 1 in which a total of 3.44% by weight of monoethanolamine and ammonia was blended at a ratio of 1: 0.32, and ammonia or monoethanolamine converted to the same amount (0.092 mol) as in Example 1 were used. In Comparative Examples 1 and 2 which were independently blended, the first agent and the second agent were mixed at a ratio of 1: 1. Either Example 1 or 2 was applied. Then at room temperature 2
After a lapse of 0 minutes, the hair of each panelist was sufficiently washed with warm water of 40 ° C. and dried. This was dyed once a month and a half and repeated three times. For each panelist who has completed such a hair dyeing treatment, the first time is a pungent smell at the time of hair dyeing, the feeling at the time of plain rinsing and after drying, the hair dyeing power, the second time is the fastness, the rinsing at the time of plain rinsing and after drying In the third test, the following evaluation criteria were used to compare the feeling during plain rinsing and the feeling after drying. Table 2 shows the average of the results. Evaluation criteria Hair dyeing power ○: Good △: Normal ×: Poor fastness ○: Good △: Normal ×: Poor irritating odor ○: Not available △: Weak ×: Strong feel at the time of plain rinse ○: No squeak and stiffness △: Slight squealing and stiffness ×: Stiffness and stiffness Feeling after drying ○: No stiffness and good combability △: Stiff but good combability ×: Stiff and poor combability

[Table 2] Example 2 (bleaching agent) <First agent>

[Table 3] <Second agent> wt% aqueous hydrogen peroxide (35%) 15.0 EDTA 0.5 cetanol 2.0 stearyltrimethylammonium chloride 1.0 propylene glycol 1.0 phenacetin 0.1 polyoxyethylene (20) oleyl ether 0.9 Amount to be 100% purified water As shown in Table 3, a total of 6.44% by weight of monoethanolamine and ammonia was blended at a ratio of 1: 0.15. In Comparative Examples 3 and 4, in which the same amount (0.141 mol) of ammonia or monoethanolamine was independently blended, the first agent and the second agent were mixed at a ratio of 1: 1. The hair was divided into left and right halves, and Example 1 was applied to one side and Comparative Example 1 or 2 was applied to the other. Then at room temperature 2
After a lapse of 0 minutes, the hair of each panelist was sufficiently washed with warm water of 40 ° C. and dried. Comparative evaluation was performed on each of the panelists after the hair dyeing treatment, and the following results were obtained.

The hair dye obtained in Example 2 has a low irritating odor, and the decolorizing power of the hair is superior to that of Comparative Example 3 which is a conventional type. On the other hand, Comparative Example 4 has no irritating odor, but has a sufficient irritating odor. No decolorizing power was obtained. . Example 3 (Aerosol foam hair dye) <First agent>% by weight Strong aqueous ammonia (28%) 4.3 Monoethanolamine 4.8 Toluene-2,5-diamine 3.0 Paraphenylenediamine 0.0 2 2-chloroparaphenylenediamine sulfate 0.5 paramethylaminophenol sulfate 0.2 paranitroorthophenylenediamine 1.0 1-amino-4-methylanthraquinone 0.1 polyoxyethylene (9) lauryl ether 1.0 cetyl Sodium sulfate 0.5 Cetyl alcohol 1.0 Vaseline 0.5 Stearic acid 1.0 Propylene glycol 8.0 Dimethyldiallylammonium chloride / acrylamide copolymer solution 0.5 Hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether 0.2 Edetate The amount the stock solution to thorium 0.1 Ascorbic acid 0.5 ammonium dihydrogen phosphate 0.3 Ammonium sulfate 0.5 Purified water 100 propellant LPG (5.0Kg / cm ^3, 25
C) at a ratio of 94: 6 to obtain a first part of an aerosol foam hair dye.

<Second agent> wt% aqueous hydrogen peroxide (35%) 15.0 EDTA 0.5 cetanol 2.0 stearyltrimethylammonium chloride 1.0 propylene glycol 1.0 phenacetin 0.1 polyoxyethylene (20 ) Oleyl ether 0.9 Amount to be purified water 100 The propellant LPG (5.0 kg / cm ³ , 25
C.) at a ratio of 94: 6 to obtain a second aerosol foam hair dye.

The first agent and the second agent were mixed at a ratio of 1: 1 and applied to the hair. Then, after 20 minutes at room temperature, 40
Washed thoroughly with warm water at ℃ and dried. As a result, a total of 6.0% by weight of monoethanolamine and ammonia was added to 1: 0.
In Example 3, which was blended at a ratio of 25, the irritating odor was small, and the lightness / hair dyeing power and the feel of the hair after the treatment were satisfactory.

[0033]

EFFECT OF THE INVENTION By blending a specific amount of monoethanolamine and ammonia in a specific ratio, a pungent odor is reduced, sufficient lightness and a hair dyeing effect are imparted to the hair, excellent in fastness, and at the time of plain rinsing, Further, a hair dye having a good feel after drying and a good feel even when hair dyeing was continuously repeated was obtained.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-99711 (JP, A) JP-A-5-97638 (JP, A) JP-A-7-316030 (JP, A) JP-A-7- 324018 (JP, A) JP-A-7-316029 (JP, A) JP-A-1-213220 (JP, A) JP-A-1-165514 (JP, A) JP-A-60-155108 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) A61K 7/13

Claims (2)

(57) [Claims] (1) monoethanolamine, (b) a
Ammonia, (c) cationic polymer and (d) sulfuric acid
Ammonium salt of acid, nitric acid, hydrochloric acid and / or phosphoric acid
Or 1 selected from the group consisting of alkanolamine salts
In a hair dye composition containing seeds or two or more ,
The total amount of (a) and (b) is 0.5% to 12% by weight, and the weight ratio of (a) and (b) is 1: 0.1 to
A hair dye composition characterized by being 1: 0.35 . 2. An aerosol foam hair dye.
The hair dye composition according to claim 1, characterized in that: