KR0166059B1 - Acidic compositions for dyeing and dyeing process - Google Patents

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Description

[Name of invention]

Preparation composition for acidic hair dye, Acid hair dye composition comprising the same and hair dye method using the same

Detailed description of the invention

The present invention is for dyeing human hair or hair of dogs, cats, etc., less skin injuries, safer, and gives a natural touch, hair does not fall easily and excellent durability for hair It is about composition.

In the conventional hair dyeing method, an oxidizing dye represented by an aromatic amino compound such as paraphenylenediamine as a dye is used as a first agent, and hydrogen peroxide is used as a second agent as an oxidizing agent. A method of dyeing a hair by mixing and applying a second agent to the hair to penetrate the inside of the oxidized dye molecules into the hair, decolorizing the hair with generator oxygen generated by hydrogen peroxide, and oxidizing and coloring the oxidizing dye is known. The first agent of such a hair dye generally contains an alkali agent such as ammonia or amine to swell the hair so that dye molecules can easily penetrate into the hair and promote the generation of generator oxygen from hydrogen peroxide. To improve the expression of the hair dye effect.

However, these hair dyes have various problems in use. For example, by mixing the alkali agent, the first agent has a _P H of more than 9, and is usually 10 to 11, and is highly irritating. In addition, when ammonia is used as an alkaline agent, there is a problem in that it is unpleasant when used due to its strong irritant smell, and it becomes difficult to impart fragrance by perfume. Moreover, hair is easily damaged by the compounding of an alkali agent, and in particular, amines are nonvolatile, and thus they tend to remain in the hair after use, and the gloss of the hair is lost, the tear strength thereof is lowered, There is a problem that is crispy without gloss. Similar problems arise when using hydrogen peroxide. In other words, the decolorizing action of hydrogen peroxide can cause hair damage to the scalp as well as hair damage. On the other hand, when used for dyeing of white hair, there is also a problem that the color of the entire hair is faded even black hair.

In addition, as a more important problem, p-phenylenedridamine, which is a representative dye of an oxidizing dye, is known to cause dermatitis, and some of its similar substances have been confirmed to be carcinogenic to experimental animals.

On the other hand, a safer dyeing method is a method of using a tar-based acid dye as a dye, but it is still insufficient because it is inferior in the dyeing power to the hair and durability of the hair after dyeing compared to the method using an oxidizing dye. . For example, tar-based pigments defined in the guidelines for determining tar-based pigments that can be used in epigenetic drug products and the like are, of course, safe, but conventionally, hair dyeing using these pigments has not always been sufficient. Some of these have been put to practical use, but there are hair dyes made by dispersing or dissolving acidic dyes in benzyl alcohol. However, benzyl alcohol is not preferable in that it has an unpleasant odor, and dyeing itself is not sufficient.

Therefore, the present invention is a dyeing method which is safe for the human body hygienically without damaging the hair and causing skin disease on the scalp, and a dyeing composition and a dyeing method using the same, which exhibits at least superior dyeing property as compared with conventional oxidation dyes. To provide.

That is, the present invention is a hair dye coarse to dye the hair of human hair, cows, cats made of at least one of the emulsified squalene, squalane or partial hydrogenated additives of squalene and tar-based acid dyes, and a dyeing method using the same It is about.

That is, this invention relates to the hair dye adjuvant composition of following (1) and the hair dye composition of following (2). Furthermore, it is related with the hair dyeing method as described in following (3) and (4).

(1) squalene, squalane and squalene portions can contain as an essential component at least one member selected from hydride, nonionic surfactants, cationic surfactants and positive emulsified by any one of a surfactant _P H 3.0 or more, less than 7.0 A hair dye composition for dyeing hair with an acidic hair dye, comprising an emulsifying composition.

(2) squalene, squalane, and contains at least one kind and a sanseongyeom parent dyes the essential components selected from hydride squalene portion, nonionic surfactants, cationic surfactants and yangsyeong emulsified by any one of a surfactant _P H 3.0 or more , Dye composition for dyeing the hair by acid dyes, consisting of an emulsion composition of less than 7.0.

(3) At least one selected from squalene, squalane, and squalene partial hydride as essential components before and after the dyeing process, which is dyed with an acidic hair dye, and is used in a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. emulsified by any one _P H 3.0 or higher, characterized in that the treatment with yeommo prepared consisting of the emulsion composition is less than 7.0, sanseongyeom yeommo method of the parent dye.

4, squalene, squalane, and contains at least one kind and a sanseongyeom parent dyes the essential components selected from hydride squalene portion, nonionic surfactants, cationic surfactants and positive emulsified by any one of a surfactant _P H 3.0 or more And dyeing the hair with an acidic dyestuff consisting of an emulsion composition of less than 7.0.

Hereinafter, the present invention will be described further.

In the present invention, squalene, squalane or squalene partial hydrogenated additives are used. Squalane, squalane can be used from liver oil of fish, such as sharks, from olive plants, or from synthetic products (including fully hydrogenated squalene). These can also be mixed and used. The partial hydrogenation of squalene is manufactured by hydrogenating squalene using a catalyst by a conventional method. Although these can also be used in mixture, in this invention, the thing preferable from the point of oxidative stability is squalane or the partial hydrogenated substance of squalene whose iodine value is three or less.

In the present invention, the partially hydrogenated additive of squalene, squalane or squalene is used after emulsification. Since they are hydrophobic, their performance cannot be achieved unless emulsified.

Surfactants used include nonionic surfactants, amphoteric surfactants and anionic surfactants, but these may be used in combination. Specific surfactants include polyoxyethylene, alkyldenyl ether, sodium phosphate, polyoxyethylene oleyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene satyl ether, polyoxyethylene lauryl ether, Glycerin monostearate, sorbitan monostearate, polyoxyethylene sorbitan monolaurate and the like.

The amount of these surfactants used is 1 to 200 parts by weight, preferably 1 to 100 parts by weight based on 100 parts by weight of squalene, squalane or squalene partial hydrogenated additive.

Moreover, it is preferable that the acid dye for hair dye used here is a tar type acid dye. Such a tar-based dye is a dye whose stability to the human body is confirmed as applied to external medicines and cosmetics by the Ministry of Health and Welfare. Moreover, tar-based acid dyes are preferable because they are used in weak acidity, because they are less damaging to hair and scalp.

Specific examples thereof include Statutory Pigment Black No. 401 (chemical name: 8-amino-7-paranitrophenylazo-2-phenylazo-1-naphthol-3,6-disulfonic acid sodium salt), Yellow No. 4 ( Chemical Name: Trisodium salt of 3-carboxy-5-hydroxy-1-parasulfophenyl-4-parasulfophenylazopyrazole), yellow No. 5 (chemical name: 1-parasulfophenylazo-2-niphthol-6 Disodium salt of sulfonic acid), red No. 2 (chemical name: 1- (4-sulfo-1-naphthyl azo) -2-naphthol-3,6-trisulfate salt of disulfonic acid), red No. 102 (chemical name: Trisodium salt of 1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid), blue No. 1 (chemical name: 4- (4-N-ethyl-m-sulfobenzylamino ) -Phenyl) (2-sulfoniumphenyl) methylene (1- (N-ethyl-Nm-sulfobenzyl) -trisodium salt of ^2.5 -cyclohexadieminin), purple 401 (chemical name: 1-hydroxy -4- ( ₀ -sulfo-toluino) -monatonaphthium of anthraquinone).

Furthermore, since these tar-based acid dyes are usually water-soluble, they are used as they are, but may be dispersed in water using the above surfactant.

It is very important that squalene, squalane or squalene partial hydrogenated additives are used in an amount of 0.1 to 20% by weight, preferably 1 to 5% by weight, based on the total solids in terms of their total solids. When the amount of squalene or squalane is less than that, the effect of adding squalene, squalane, etc. is not obtained. On the contrary, the amount of added squalene, squalane, etc. is not obtained when the amount exceeds the above range. This is undesirably high because it is unnecessary.

In order to use a tar type acid dye, the acidity of the hair dye composition of this invention is adjusted to weak acidity with an acid, Preferably an organic acid etc. are used. For such acidity adjustment, lower organic carboxylic acids such as malic acid, lactic acid and succinic acid are preferably used.

In addition, the organic carboxylic acid contained in the emulsion composition of the present invention is an organic carboxylic acid having 3 to 10 carbon atoms, and specific examples thereof include succinic acid, lactic acid, salicylic acid and benzoic acid. The action of these organic carboxylic acids makes hair treated with an acidic dye a weakly acidic region, adjusts the pH value of the emulsion composition according to the present invention to 3.0 or more and less than 7.0, imparts thermal stability and storage stability to the emulsion composition, In addition, to impart mildew prevention and antiseptic properties to the composition. The amount thereof is in the range of 0.01 to 0.5 parts by weight based on 100 parts by weight of the emulsified composition, so that the pH of the composition is in the range of 4.0 to 5.0, which is close to the isoelectric point 4.5 of the hair.

In addition, the solvent and medium used for a conventional hair dye or hair dye can be added to the composition of this invention. Examples of the solvent include benzyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, alcohols such as ethylene glycol and propylene glycol, ketones such as acetone, ethers such as ethyl ether, ethylene carbonate and propylene carbonate. N-alkylpyrrolidones such as N-alkylpyrrolidones, such as lower alkylene carbonates and N-methylpyrrolidone, and hydrocarbons such as liquid paraffin and liquid isoparipin, orange essential oil and jojoba Oil, mink oil, etc. can be used in a suitable kind and quantity. The key agents include cellulose resins such as hydroxymethyl or ethylcellulose, higher fatty acids such as stearic acid, higher alcohols such as cetanol, animal and vegetable waxes such as beeswax, wax, carnauba, lanolin, and shellac, ceresin, paraffin wax, and undefined Waxes such as vaginal waxes and hydrocarbon waxes such as polyethylene waxes.

Of course, well-known additives, such as a natural or synthetic fragrance | flavor, antioxidant, and an antifungal agent used for normal cosmetics, can also be added suitably.

The composition of the present invention can be used in any of hair dyes or hair dye preparations in the form of aqueous solutions, emulsions, creams, pastes, gels and the like according to conventional methods, and can be used as shampoo, type, treatment type, pretreatment type, etc. Hair dye or hair dye. For example, an aqueous solution type is prepared and used in the following manner. That is, a solvent or the like is appropriately added, and the tar-based acidic dye is emulsified or dissolved in squalene or the like with a surfactant, and then made weakly acidic using an acidity regulator such as lactic acid and diluted with water to prepare. Squalene etc. may use what was emulsified previously, and may emulsify at the time of adjusting a composition. Preferably, emulsion zones such as squalene emulsified in advance are used. Using the prepared hair dye composition, the hair sufficiently dipped with hair detergent (shampoo) or the like is dipped or coated. It is good to warm the temperature moderately. Usually, 10 minutes at about 40 degreeC is enough. The conventional hair dye composition could not exhibit sufficient function unless it was about 50 degreeC high temperature. After dipping or coating, shampoo well and dye with water. This hair dyeing operation can be repeated as many times as needed.

The use method of the hair dye preparation composition of this invention is as follows compared with the conventional method.

That is, the conventional hair dyeing procedure is to rinse the hair sufficiently washed with a detergent (shampoo, etc.) in advance, if necessary, by using a hair dye at 50 ° C. for 15 minutes, and adding or coating the hair dye preparation of the present invention. In the pretreatment, the hair is rinsed after washing with a detergent (shampoo, etc.), and then, or simultaneously with the rinse liquid, the hair dye preparation of the present invention is used to immerse or coat the hair. After washing lightly, dye with a hair dye, rinse with water, and rinse at last. Alternatively, the hair dye of the present invention may be used, immersed or coated when lightly rinsed with water after the hair dye treatment. Dipping or coating of the hair dye preparation according to the present invention may be repeated several times as necessary.

Here, the difference between the rinse agent and the hair dye preparation of the present invention will be described. First of all, the rinse agent is a conditioning agent to make the hair softer, give natural luster and comb well after shampooing with shampoo. In the past, when hair washing with soap was performed, an acidic rinsing agent containing citric acid, tartaric acid, and the like was used for the purpose of neutralizing the alkalinity of soap, but at present, only cationic surfactants are the mainstream. Cationic surfactants adsorb to the keratin proteins in the hair to form a membrane, which gives the hair flexibility. It gives a natural luster. In other words, the purpose of the rinse is to be able to comb the hair firmly and boldly.

On the other hand, the hair dye preparation of the present invention is an acidic emulsion composition having a pH of 3.0 or more and less than 7.0, and when dyeing with an acid dye, pretreatment makes the hair acidic near the isoelectric point beforehand and coats the hair with a milk component squalane and the like. Since it is used for the purpose of improving the degree of dyeing, the purpose of use is different from that of the rinse agent.

Now, the present invention will be described in detail according to the following examples.

(Example regarding a hair dye composition)

Example 1

Hair dye compositions (1) to (5) described in Table 1 are prepared and used to dye human hair. Subsequently, the dyeing degree to the hair of the dyed person is measured. In any case, squalene and the partial hydrogenated substance of squalene are used by emulsifying with a surfactant.

The composition (5) is a comparative example using benzyl alcohol instead of squalene partial hydrogen condensate.

(Measurement method of dyeing degree)

3 g of bleached human hair are immersed in a salt bath at 40 ° C. in which the composition is placed, respectively, for 10 minutes, followed by shampoo, water washing and drying, and the treatment is repeated twice. Thereafter, a reflectance spectrophotometric colorimeter (manufactured by Sangyo Chromatic Technology Institute) is used to measure reflectance and evaluate dyeing degree.

The evaluation method obtains the reduction ratio of the reflectance when the wavelength is between 400 and 700 mm, and sets the average value as the dye value. That is, after immersing each composition, lightly rinsed with water to wash off the adherent dye, and then set the reflectance of the dried hair to 100, respectively, and calculate the sum of the degree of attenuation of the reflectance therefrom as attenuation rate (%).

The results are shown in Table 1 below.

[Examples 2-6, 1-3 in Comparison]

The composition (compositions (VI)-(VII)) of the present invention is prepared in cream form according to the formulation described in Table 2 below. For comparison purposes, three kinds of commercially available products in which the use of cream-type tar-based acid dyes are specified (compositions (VIII), (IX) and (X)) are used. Commercially available composition (VIII) specifies the use of black 401, purple 401 and benzyl alcohol, and composition (IX), which is also a commercially available product, is yellow 5, purple 401, blue 1 and benzyl alcohol. Its use is specified, and for this reason it has an unpleasant smell of benzyl alcohol.

(Dyeing test)

The bleached human hair is pre-shampooed and water-washed and spread on a wrap film, using a brush and uniformly coating 1 g of each composition on the hair. After coating, the package is wrapped in a wrap film and kept in a constant temperature dryer at 40 ° C. for 10 minutes. The shampoo, water washing and drying operations are then performed and the treatment is repeated twice.

The dyeing test is performed in the same manner as in the above example to obtain a% attenuation. The results are shown in Table 2.

(Example for hair dye preparation)

Example 1

(Combination method)

To 20 g of squalene partial hydride (iodine of 0.5) and 2.5 g of polyoxyethylene sorbitan mooleate are slowly added with stirring. Then 2,5 g of polyoxyethylene trioleate, 3.75 g of sorbitan monooleate and 5 g of n-butanol are slowly added. This is called A liquid. Separately, 0.15 g of succinic acid is precisely weighed on a balance and dissolved in 66.1 g of purified water. This is called B amount. Finally, B solution is slowly added to A solution to form an emulsion containing 20% by weight of squalene partial hydride to obtain a dyeing aid.

(Measuring method of dyeing state)

To compare hair dyeing condition, dye the hair with black tar-based acid dye and compare the degree of blackening of hair by measuring the brightness index L ^* (according to JISZ 8729). Specifically, it is as follows.

3 g of bleached human hair are thoroughly washed with a detergent (shampoo), and after rinsing, the hair dye is prepared by immersion in the hair dye prepared by the above formulation for 10 minutes at room temperature, washed with water, and then water is removed. The hair dye was immersed in a black hair dye blended with an acidic dye at 50 ° C. for 15 minutes, rinsed lightly with water to remove the adhered dye, and dried by wind.

The brightness index L ^* of this hair was measured with the colorimeter (SM color computer SM-3 type | mold by Suga Tester Co., Ltd.), and the result was shown in Table 1. The smaller the value of the brightness index L ^*, the better the staining state.

Example 2

Example 1 is repeated except that squalane (iodine is 0.01) is used instead of squalene partial hydride, n-butanol 2g and 3g benzyl alcohol instead of 5g n-butane and salicylic acid instead of succinic acid. The results are shown in Table 1.

Example 3

Example 1 is repeated except that 1 g of n-butanol and 4 g of benzyl alcohol are used instead of 5 g of n-butanol, and 0.1 g of succinic acid and 0.05 g of salicylic acid are used instead of 0.15 g of succinic acid. The results are shown in Table 1.

Example 4

Squalene instead of squalene partial hydride, 2.5 g polyoxysorbitan monooleate to 8 g, 2.5 g polyoxyethylene sorbitan trioleate to 2 g, 3.75 g sorbitan monooleate to 0 g, 0.15 g succinic acid Example 1 is repeated except that 0.15 g of salicylic acid is 64.85 g of 66.1 g of economic water. The results are shown in Table 1.

Example 5

Example 1 is repeated except that 16 g of squalane (0.01 iodine) and 4 g of isoparaffin (viscosity 20.09 _cp @ 25 ° C., Nihon Seki Oil Co., Ltd., trade name isolane-R) are used instead of 20 g of squalene partial hydride. . The results are shown in Table 1.

Comparative Example 1

Table 1 shows the results of repeating the dyeing state measurement operation of Example 1, and omitting the penetration operation (pretreatment operation with the dyeing agent of the present invention). It is clear that the brightness index L ^* has increased.

It is known that tar-based acid dyes conventionally use benzyl alcohol as a hair dye, but are insufficient in an unpleasant smell, dyeability and durability. However, by using squalene, squalane or squalene partial hydrogenated additives and tar-based acid dyes as in the present invention, they could be practically used for the first time. Although it is not clear why such a composition of the present invention has good properties, tar-based acid dyes may cause hair tissue due to its excellent permeability to animal tissues such as human hair, dogs and cat hairs of squalene, squalane or squalene partial guard additives. It is estimated that the hair dye composition of the present invention can significantly infiltrate and settle, and therefore, the dyeing power and durability after dyeing are remarkably improved and practical use as a hair dye.

In addition, the hair dye composition according to the present invention has sufficient dyeing strength without using benzyl alcohol having an unpleasant odor by using squalene, squalane or squalene partial hydrogenated additives, and it is used at a relatively lower temperature than the conventional hair dye composition. Can be dyed at temperature. This is also because of its excellent permeability to animal and plant tissues such as human hair, dog and cat hair of squalene, squalane or squalene partial hydrogenated hydrogen.

In addition, since the tar-based acid dyes having high stability are used, the safety is high, and the pH area thereof is also weakly acidic, thereby reducing damage to the hair and the scalp. Of course, it is known that it is good for the human body to use squalene for the first time on the scalp and have no problem in smells.

Therefore, the hair dye composition of the present invention is extremely safe, not to mention excellent in dyeability and durability. And when using the hair dye composition of this invention, it does not impair a natural touch and gloss.

In addition, as in the case of the conventional oxidizing dye, it is convenient because complicated labor such as mixing two kinds of drugs before use is not necessary.

In addition, the hair dye of the present invention is acidic and pH is adjusted to a value close to the isoelectric point of the hair, so it is extremely safe without hurting the hair and the scalp, and the hair dye preparation does not impair the natural feel and gloss of the hair by using the hair dye preparation. .

Although it is not clear why the hair dye preparation of the present invention gives excellent dyeing degree to the hair dye by the tar-based acid dye, it is excellent in squalene, squalane or squalene partial hydrogenation in animal tissues such as human hair, dog and cat hair. Because of its permeability, if they are given to the hair in an acidic region close to the isoelectric point of the hair, it can be reliably penetrated into the hair tissue at the same time with the tar-based acid dye, thereby improving dyeing and durability after dyeing. It is estimated.

As is apparent from the foregoing, the hair dye composition of the present invention is optimal for hair dyes such as human hair, animal hair of dogs and cats.

Claims (3)

An essential ingredient comprising at least one selected from squalene, squalane and squalene partial hydride, and consisting of an emulsified composition of pH 3.0 or more and less than 7.0 emulsified by any one of a nonionic surfactant, a cationic surfactant and an amphoteric surfactant, . Hair dye preparation for hair dyeing by acid dyeing. Emulsification of pH 3.0 or more and less than 7.0 comprising at least one selected from squalene, squalane and squalene partial hydride and an acidic hair dye as an essential component and emulsified by any one of a nonionic surfactant, a cationic surfactant and an amphoteric surfactant Dye composition for dyeing the hair by the acid dye hair dye composition. The composition according to claim 1 or 2, wherein the acidic hair dye is a tar-based acid dye.