KR100844227B1 - Composition of hairdye and method of manufacturing thereof - Google Patents

Abstract

New hair dyes containing reactive dyes and methods for their preparation are disclosed. Such hair dyes of the present invention include reactive dyes having thickeners, penetrants and vinylsulfone reactors. The reactive hair dye composition according to the present invention dyes hair keratin by forming a covalent bond by chemical reaction between the reactor of the dye and the reactor of hair keratin under acidic conditions. No skin irritation and relatively simple to use. In addition, excellent color development, and can express a variety of colors. It also has good water washability and relatively long lasting power.

Vinyl sulfone reactor, thickener, penetrant, reducing agent

Description

Hair dye composition and its manufacturing method {COMPOSITION OF HAIRDYE AND METHOD OF MANUFACTURING THEREOF}

The present invention relates to hair dye compositions, and more particularly to hair dyes comprising reactive dyes.

Hair dyes are used to artificially change the color of hair, and have recently been used as a means of expressing appearance more attractively beyond the dyeing of white hair or swordfish. Hair dyes A variety of hair dyes have been developed since the dyeing of hair using dyes extracted from plants called henna or chamomile by the Egyptians about 4,000 years ago.

Recently, hair dyes generally used can be divided into permanent hair dyes and semi-permanent hair dyes in terms of their persistence. Permanent hair dyes penetrate through the outermost layer of hair, hair dye, and into the cortex and hair medulla. The effect of dyeing lasts for a long time. It becomes discoloration little by little.

Permanent hair dyes include oxidative hair dyes and non-oxidative hair dyes, and among them, oxidative hair dyes having relatively long persistence are mainly used. The oxidation hair dye consists of a dye first intermediate, a second intermediate, an antioxidant, an alkali, a surfactant, and the like, and is usually provided in a powder, cream, or liquid type. Oxidative hair dye is a colorless dye precursor (precursor) penetrating into the hair color by the oxidation-coupling reaction by hydrogen peroxide and maintains color until the hair grows out. The composition of the drug consists of the first agent and the second agent, and the first agent is composed of an alkali ammonia and an oxidation dye intermediate, and the second agent is composed of hydrogen peroxide. Alkaline 1 swells and softens the epidermis, allowing the oxidized dye and hydrogen peroxide of 2 agent to penetrate into the cortex inside the hair, while hydrogen peroxide reaching the cortex decolorizes the existing pigments in the hair. Pigmentation of the oxidized dye to express the color to complete the dyeing. That is, when the oxidizing agent and the alkaline agent react, the generator oxygen comes out to decolor the melanin pigment in the hair, and when acting on the oxidizing dye intermediate, the water-soluble low molecular oxidizing dye intermediate is oxidized to develop color, and the pigment particles condensate. It becomes insoluble particles and becomes dye. At this time, the swelling and softened cuticles are damaged by washing or friction, and the hairs lose their gloss and have a negative effect on the aesthetics. In addition, alkaline ammonia and oxidant hydrogen peroxide damage the scalp and skin, and low molecular weight oxidized dye intermediates have been reported to cause itching and allergy by irritating the skin with paraphenylenediamine and aniline derivatives as main components. . The final color is determined by the combination of the oxidized dye precursor, diimine, and the coupler, and is affected by the degree of hydrolysis, oxidation, and polymerisation of the diimine, making color prediction difficult and usually determined by experience. In addition, the oxidized dye intermediate, which is not oxidized due to the penetration inside the cuticle, is continuously oxidized by oxygen in the air, causing color change.

Semi-permanent hair dyes are also called acid hair dyes because they mainly use acid dyes as hair dye components. Acidic dyes do not contain alkali or oxidizing agents, so relatively little damage to the scalp or hair, while the low persistence is often inconvenient to dye. Acidic hair dyes infiltrate the acid dye having a molecular weight of about 300 to 900 into the hair using a solvent such as benzyl alcohol to form dyes in the hair by forming ionic bonds with proteins. At that time, the pH is lowered to below the isoelectric point of the hair, thereby increasing the dyeing site having a positive charge in the hair, thereby improving the dyeability. However, the penetrating area of the dye is limited to the outer side of the cortex, and the dye flows out gradually by repeating trituration, and usually fades in two to three weeks.

The present invention has been made to solve the problems of the prior art as described above, the object of the present invention to minimize the damage to the skin or hair to minimize the use of harmful components to the human body and to provide an easy to use hair dye composition.

Another object of the present invention is to provide a method for producing the hair dye composition described above.

The hair dye composition according to the object of the present invention includes a reactive dye having a thickener, a penetrant and a vinylsulfone reactor.

Specifically, 1 to 10 wt% thickener, 1 to 20 wt% penetrant, 0.01 to 5 wt% reactive dye having a vinylsulfone reactor, the balance may be water.

In addition, the pH adjusting agent may further comprise 1 to 5% by weight.

In addition, it may be further included a reducing agent for reducing the -S-S-bond of hair keratin.

Method for producing a hair dye composition according to another object of the present invention, (1) to form a homogeneous mixture, the balance of which is at least 1 to 10% by weight of water, (2) 1 to 20% by weight of the penetrant in the homogeneous mixture Adding% to form a base liquid comprising at least a thickener and a penetrant, and (3) mixing 0.01-5% by weight of a reactive dye having a vinylsulfone reactor with the base liquid.

Preferably in the step of forming a homogeneous mixture, it may further comprise 1 to 5% by weight pH adjuster.

In addition, the reducing agent for reducing the -S-S-bond of hair keratin may be further included in any one of steps (1) to (3).

Hereinafter, the present invention will be described in more detail.

The present invention is a novel hair dye composition using a reactive dye having a vinyl sulfone reactor and a method for producing the same, having no skin irritation, excellent coloring and sustaining power, and various colors. The reactive hair dye composition according to the present invention dyes hair keratin by forming a covalent bond by chemical reaction between the reactor of the dye and the reactor of hair keratin, preferably under acidic conditions. The present invention not only has excellent water washability but also excellent light resistance and hardly damages hair after dyeing.

The hair dye composition of the present invention basically includes a reactive dye, a thickener, and a penetrant having a vinyl sulfone reactive group. The remainder is water, and a solvent for uniformly mixing other components may be included together. In addition, the hair dye composition of the present invention may preferably further include a reducing agent. In addition, the hair dye composition of the present invention may further include a pH adjusting agent, a surfactant, a moisturizing agent, a perfume, and a conditioning agent.

In the permanent dyeing of the present invention, a reactive dye and a reactor of hair keratin are formed by forming a covalent bond by nucleophilic substitution reaction or nucleophilic addition reaction. After the dyeing is completed the color of the dye remains the same. The dyeing reaction mechanism using the dye including the vinylsulfone reactor of the present invention is shown in the following scheme.

Here, Y may be -NH-, -NH ₂ or -SH.

Hair is a keratin protein fiber consisting of 18 amino acids. Arginine, lysine and histidine comprise an amine reactor and cystine can be converted to cysteine with a thiol reactor if reduced. Since the reactivity with respect to the reactive dye is about 100 times higher than that of the amine group, the cystine can be reduced to cysteine using a reducing agent in the method of the present invention. Such a reduction in cysteine can achieve a high concentration of dyeing effect.

In the present invention, the reactive dye is a reactive dye having a vinylsulfone reactor that can be used, in particular may be one or more selected from the group consisting of the following formula (1) to (5). Therefore, they may be included alone or in combination, or may be used by mixing one or more in advance to have a specific color.

Yellow reactive dye with vinyl sulfone reactive group

Orange reactive dyes with vinylsulfone reactive groups

Red reactive dye with vinyl sulfone reactive group

Red reactive dye with vinyl sulfone reactive group

Blue reactive dye with vinyl sulfone reactive group

M may be H, Li or Na, K in the above.

The reactive dyes of Chemical Formulas 1 to 5 applied to the present invention are newly developed dyes, and in particular, the blue reactive dyes of Chemical Formula 5 are described in detail in Applicant's Patent No. 10-494834.

Among the dyes having a reactor used for the hair dye, dyes having a reactor capable of nucleophilic addition rather than nucleophilic substitution are more preferable, and a reactive dye including a vinyl sulfone reactor is particularly suitable.

Reactive dyes having a vinylsulfone reactor are preferably used in the range of 0.01 to 5% by weight, more preferably 0.1 to 1.0% by weight. If less than 0.1% by weight, the dyeing effect is insignificant, and if it exceeds 5% by weight, the economy is inferior, and too much may cause contamination problems.

The thickener may be guar gum, acacia gum, gum arabic, xanthan gum, gelatin as proteins, and polyvinyl alcohol and cellulose derivatives as synthetic gums. These may be used alone or at least one of them. The amount used is in the range of 1 to 10% by weight, the viscosity is too high or too low to be easy to use for hair.

An aromatic alcohol and an organic solvent can be used as a penetrant. For example, benzyl alcohol, phenyl ethanol, isopropanol, phenoxyethanol, phenyl ethyl alcohol, cinnamon alcohol, butanol, resorcin, pyrocaterol, pyrogarol and alkylpyrrolidone may be used alone or in at least one. have. The amount used is 1 to 20% by weight. If it is lower than 1% by weight, the penetration effect is insignificant, and if it is higher than 20% by weight, phase separation may occur.

Solvents for uniformly mixing the other components of the hair dye may be included with the components. As a solvent which may be contained, a C1-C6 linear or branched alcohol etc. are possible. For example, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, carbitol, propyl alcohol, 1,3-butylene glycol, etc. are mentioned. These may be used alone or at least one or more, preferably ethanol is used. The amount used is in the range of 1 to 20% by weight based on the total amount of the hair dye.

Reducing agents can be used to improve dyeability. The reducing agent here is one for reducing the -S-S-bond of hair keratin, and cysteine, homocysteine, N-acetylcysteine, thioglycolic acid, ascorbic acid and the like can be used. These may be used alone or at least one.

As the pH adjusting agent, any of inorganic and organic acids can be used. As an example, organic acids, such as citric acid (fruit acid), succinic acid, tartaric acid, lactic acid (lactic acid), malic acid, fumaric acid, maleic acid, glycolic acid, and inorganic acids, such as hydrochloric acid, a sulfuric acid, phosphoric acid, nitric acid, are mentioned. These may be used alone or at least one or more, preferably an organic acid is used. Moreover, these acids and the sodium salt, potassium salt, or ammonium salt of these acids can be used in combination for the purpose of imparting buffering capacity and the like. The amount used is in the range of 1 to 5% by weight.

The surfactant may be an alkylallyl sulfate, lauryl sodium sulfate, lauryl sulfate triethanolamine salt as an anion, an alkanolamide fatty acid ester as a nonionic, a water-soluble amine fatty acid soap as a soap and a soap. These may also be used alone or in at least one or more.

The manufacturing process of the hair dye comprising the reactive dye having a vinyl sulfone reactor of the present invention is as follows.

First, a process of preparing a hair dye base liquid is performed. The hair dye base liquid preparation first forms a homogeneous mixture containing water and a thickener, and then includes a penetrant.

Therefore, water, a thickener such as hydroxyethyl cellulose, a solvent such as propylene glycol, and a pH adjuster are added to the vessel at room temperature and stirred for 10 to 30 minutes using a homogenizer. Stirring here and after may be applied, for example, by stirring at a rate of 20 to 40 r.p.m.

Then, in order to appropriately adjust the viscosity, a thickener such as xanthan gum and a solvent example of propylene glycol are added together and stirred for 5 to 15 minutes.

Subsequently, a mixture of a penetrating agent such as benzyl alcohol and a solvent such as ethanol is added and stirred for 10 to 30 minutes to complete the dye base.

Next, a mother liquor of a reactive dye having a vinylsulfone reactor is added to the dye base and stirred sufficiently to complete the hair dye.

 In addition, surfactants, humectants, fragrances, conditioning agents and the like can be added to the dye base or finished hair dye.

<Example>

Hereinafter, the present invention will be described in detail with reference to preferred embodiments.

In the embodiment of the present invention, three kinds (Examples 1 to 3) of blue dyes each including a vinyl sulfone reactor were prepared, and the composition thereof is shown in Table 1 below.

Composition of Examples 1 to 3 of a hair dye comprising a reactive dye having a bithyl sulfone reactor of the present invention Ingredient (% by weight) Example 1 Example 2 Example 3 Purified water To 100 To 100 To 100 Hydroxyethyl cellulose 1.4 1.4 1.4 Xanthan Gum 0.2 0.2 0.2 Lactic acid 4.9 2.5 2.5 Thioglycolic acid - 2.4 Cysteine - - 2.4 ethanol 16 16 16 Benzyl alcohol 8 8 8 Propylene glycol 5 5 5 dyes 0.5 0.5 0.5

The total weight is 100 to represent the weight% of each component, and water represents the balance other than the contained components. In addition, Examples 2 and 3 used a reducing agent, Example 2 used thioglycolic acid as a reducing agent, and Example 3 used cysteine as a reducing agent.

dyeing

The hair dyes of Examples 1 to 3 prepared as described above were applied to no wash tropical wool, fifth grade bleaching hair, and ten grade bleaching hair, respectively. Examples 1-3 used blue reactive dyes with vinylsulfone reactors.

The dyeing procedure was to apply the hair dyes of Examples 1 to 3 to the white hair, the 5th grade bleaching hair and the 10th grade bleaching hair, respectively, and to leave it for 10 minutes at room temperature and humidity of 50% at approximately 24 ° C. The following test was conducted to observe the color difference after dyeing and the color difference after washing with water and after solvent extraction.

In the following tests, brightness (L *: 0-100), saturation (a *) using Spectralflash 500, Datacolor's Computer Color Matching System (CCM), was used. : The CIE color difference (ΔE) system calculated from the values of + →-, red → green) and saturation (b *: + →-, yellow → blue) was used.

Flush  exam

The hydrophobicity test of the white hair, 5th grade bleaching hair, and 10th grade bleaching hair dyed using Examples 1-3 was carried out, and the color change with water washing was measured. The test was carried out once and three times the drying process after the shampoo, respectively.

Flush test results of blue reactive hair dyes of Examples 1 to 3 according to the present invention sample Shampoo count Example 1 Example 2 Example 3   White blanket  1 time shampoo L * 39.68 36.89 36.81 a * -9.74 -8.18 -9.32 b * -12.43 -10.82 -12.60  3 times shampoo L * 40.91 37.10 37.43 a * -9.65 -7.80 -8.82 b * -12.38 -10.74 -12.50 ΔE 1.238 0.445 0.798   Class 5 Bleached Hair  1 time shampoo L * 26.35 25.98 25.88 a * -5.65 -4.19 -6.46 b * 2.46 2.02 1.80  3 times shampoo L * 28.69 27.00 26.85 a * -4.94 -3.87 -5.78 b * 3.70 3.33 3.19 ΔE 2.746 1.688 1.208   Grade 10 Bleached Hair  1 time shampoo L * 32.04 31.75 30.42 a * -11.68 -9.19 -10.12 b * -9.48 -8.78 -9.93  3 times shampoo L * 36.89 36.60 34.89 a * -11.69 -9.67 -10.92 b * -8.42 -7.74 -9.06 ΔE 4.996 4.990 4.624

As can be seen in Table 2, after washing, the white hair was hardly discolored, and decolorization occurred a little more in the 10th grade bleaching hair than the 5th grade bleaching hair. However, this is a bit faded in color. Better results were shown in Examples 2 and 3 with reducing agents. In addition, Example 3 with cysteine showed slightly better results than Example 2 with thiocyclic acid.

Solvent extraction test

Solvent extraction test results of the blue reactive hair dye of Examples 1 to 3 according to the present invention sample Example 1 Example 2 Example 3   White blanket  Before extraction (3 times shampoo) L * 40.91 37.10 37.43 a * -9.65 -7.80 -8.82 b * -12.38 -10.74 -12.50  After extraction (3 times shampoo) L * 37.79 37.97 33.75 a * -11.92 -9.67 -10.82 b * -13.24 -10.99 -13.22 ΔE 3.952 6.412 4.243   Class 5 Bleached Hair  Before extraction (3 times shampoo) L * 28.69 27.00 26.42 a * -4.94 -3.87 -4.92 b * 3.70 3.33 2.21  After extraction (3 times shampoo) L * 32.80 30.00 29.56 a * 0.18 0.10 -1.72 b * 10.20 8.88 7.21 ΔE 9.238 7.456 6.722   Grade 10 Bleached Hair  Before extraction (3 times shampoo) L * 36.89 36.60 30.42 a * -11.69 -9.19 -10.12 b * -8.42 -7.74 -9.93  After extraction (3 times shampoo) L * 41.97 42.82 38.11 a * -13.45 -11.25 -13.61 b * -3.44 -0.60 -5.21 ΔE 7.322 9.559 5.692

The solvent extraction result is a measure of the degree of the dye covalently bonded to the hair, it can be seen that a lot of the color of the applied dye is fixed, although the color is lighter than the case of washing with water. Example 2 with thioglycolic acid decolored slightly more than Example 3 with cysteine.

Example  4-5, and Comparative example

Hereinafter, orange (Example 4) and orange (Example 5) were prepared in a reactive dye having a vinylsulfone reactor according to the present invention, and compared with an acid dye (Comparative Example).

The comparative test was evaluated using a CIE chrominance (ΔE) system through the water flush test and the solvent extraction test after staining the white hair as described above.

Flush Test Results for Examples 4, 5 and Comparative Examples According to the Invention Item Example 4 (orange) Example 5 (orange) Comparative Example (Acid Dyes)   Defensive  1 time shampoo L * 53.54 46.70 77.38 a * 43.57 54.40 8.47 b * 59.04 35.53 101.99  3 times shampoo L * 53.76 46.90 78.10 a * 43.45 54.54 7.08 b * 59.71 35.80 90.95 ΔE 0.718 0.362 11.150

Solvent Extraction Test Results for Examples 4, 5 and Comparative Examples According to the Invention Item Example 4 (orange) Example 5 (orange) Comparative Example (Acid Dyes)   Solvent extraction  Before extraction L * 53.76 46.90 78.39 a * 43.45 54.54 -0.06 b * 59.71 35.80 90.84  After extraction L * 59.20 50.35 84.80 a * 40.10 53.71 -0.66 b * 68.82 37.04 18.19 ΔE 11.123 3.760 72.934

In both the water washing test and the solvent extraction test, the color change was much less than that of the acidic hair dye, which was the case where the reactive dye covalently bonded to the hair as in Examples 4 and 5 according to the present invention. This means that Examples 3 and 4 of the present invention show superior color development and sustainability as compared with the comparative examples.

In particular, the commercially available black acid hair dye nail polish of the comparative example showed a result of almost discoloration of the dyed color after solvent extraction. In the case of white hair, the color remained slightly, but it was bleached in a light blue color instead of black. The data was not described here, but the hair was not bleached and was almost bleached to be close to the color before dyeing.

The present invention is a novel hair dye using a reactive dye having a vinyl sulfone reactive group and a method for producing the same, since it does not use a harmful aromatic amine, there is no skin irritation, and there is no hair damage after dyeing. It is also relatively simpler to use than conventional permanent hair dyes. It also has good flushing ability and excellent color development, and can express various colors. It also has a relatively long lasting power.

Claims (3)

As the hair dye composition: 1 to 10 weight percent thickener; 1 to 20% by weight penetrant; 0.01 to 5% by weight reactive dyes having a vinylsulfone reactor; And The balance contains water, The reactive dye is a hair dye composition, characterized in that the formula (2). [Formula 2]

Where M is an alkali metal ion and is H, Li, Na or K. The method according to claim 1, The hair dye composition further comprises 1 to 5% by weight of the pH adjusting agent. The method according to claim 1, A hair dye composition further comprising a reducing agent for reducing -S-S-bond of hair keratin.