JPH10279452A - Oxidative hair dye composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition that has still more increased dyeability with increased dye fastness to sun light and hair washing and lessen extremely hair damage by using a specific polysaccharide originating from a microorganism as an active ingredient. SOLUTION: This oxidative hair dye composition contains a succinoglycan as an active ingredient. The succinoglycan is a water-soluble polymer comprises the galactose units with an average molecular weight of <= about 6,000,000, the glucose units, the succinic acid units, and the pyruvic acid units at a ratio of 1:7:0.8:1 and an optional acetic acid units. The formulation of a polypeptide and/or its derivative to this system containing succinoglycan as active ingredients manifests more increased effect of the glycan. The amount of the succinoglycan to be added is 0.01-50.0 wt.% based on the whole amount of the composition and those of the polypeptide and/or its derivative are 0.01-20.0 wt.% based on the succinoglycan.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a hair dye composition,
In particular, the invention relates to a composition for an oxidative hair dye.

[0002]

2. Description of the Related Art Hair dyes for dyeing hair are widely used as, for example, "white hair dyeing" and "fashionable dyeing". As this hair dye, in addition to the temporary hair dye and the semi-permanent hair dye, a “permanent hair dye” for imparting a permanent hair dyeing effect is widely used. Among them, the "oxidative hair dye" that performs color development by allowing an oxidizing agent to act on an oxidation dye is one of the permanent hair dyes.
Especially since the effect is permanent and it is possible to make the color lighter than the original hair with the bleaching effect,
It is one of the most widely used hair dyes. This oxidative hair dye usually takes the form of a two-part type consisting of a first part containing an oxidizing dye and a second part containing an oxidizing agent. Dosage form). That is, first, a low molecular weight oxidation dye is penetrated into the hair using the first agent, and then the oxidative hair dye is oxidatively polymerized in the hair and on the surface of the hair using the second agent to form a dye. It is a hair dye to be worn.

[0003] However, although oxidative hair dyes which have been conventionally used are excellent in hair dyeing power, there is a problem in that the hair is damaged at the time of use, the hair loses moistness and luster, and the combability deteriorates. Was. Furthermore, "permanent hair dye"
However, since hair dyes tend to fade gradually by being exposed to sunlight or using shampoo, oxidative hair dyes with even higher durability are desired. Various studies have been made to compensate for such disadvantages, but satisfactory results have not yet been sufficiently recognized.

For example, attempts have been made to solve these problems by blending dextrin pullulan, which is a polysaccharide, in an oxidative hair dye (Japanese Patent Publication No. 4-32).
06), when this dextrin pullulan is used, the dyeing property is certainly good, but the fastness of the dyeing to sunlight and hair washing is not sufficient, and the problem of "damage to hair" has been completely solved. I couldn't say. further,
When dextrin pullulan is used, there is a problem in stability over time depending on the system of the oxidative hair dye, and as a result, it was undeniable that it was not suitable for blending into the composition for the oxidative hair dye.

[0005]

The problem to be solved by the present invention is to provide a composition for an oxidative hair dye having excellent properties in view of the above prior art. More specifically, the dyeing property is further improved, the fastness of the dyeing to sunlight and hair washing is also improved, the damage of the hair is extremely small, and the gloss of the hair can be further improved, and furthermore, the aging An object of the present invention is to provide a composition for an oxidative hair dye which is excellent in stability.

[0006]

Means for Solving the Problems As a result of intensive studies conducted by the present inventor to solve these problems, the composition for oxidative hair dye containing succinoglycan has an oxidation dye having desirable and excellent properties. The present invention was completed by finding that the composition was a hair preparation composition.

More specifically, the composition for oxidative hair dye containing succinoglycan has further improved dyeing properties, improved fastness to sunlight and washing, and extremely reduced damage to hair. In addition to the fact that the gloss of the hair can be further improved, the stability over time has been found to be much better than that of the oxidized hair dye containing dextrin pullulan.

[0008] That is, the present invention is to provide a composition for oxidative hair dye containing succinoglycan.

In the present invention, the term "composition for oxidative hair dye" as described above means that the oxidizing agent is acted on the compounded oxidative dye to cause oxidative polymerization to dye the hair with a desired color. It refers to the composition for the hair dye to be performed, and does not matter whether the composition is a two-part composition or a one-part composition.
Further, it does not matter whether only the dye precursor is used as the oxidation dye or the coupler is used as the oxidation dye in combination with the dye precursor.

[0010]

Embodiments of the present invention will be described below. Succinoglycan blended in the composition for oxidative hair dye of the present invention is a kind of polysaccharide derived from microorganisms, and in addition to a sugar unit derived from galactose and glucose, succinic acid and pyruvic acid and as an optional component And polysaccharides derived from microorganisms containing units derived from acetic acid or salts of these acids.

More specifically, succinoglycan has an average molecular weight of about 6 million and has the following structural formula: galactose unit: 1, glucose unit: 7, succinic acid unit: 0.1.
8 and pyruvate unit: 1 is a water-soluble polymer containing an acetic acid unit as an optional component.

[0012]

Embedded image (In the formula, Gluc represents a glucose unit, Galac represents a galactose unit, and the notation in parentheses represents a binding mode between sugar units. For example, (β1,4) represents a β1-4 bond.)

[0013] Microorganisms that serve as sources of succinoglycans include, for example, Pseudomonas spp., Rhizobium spp.
Bacteria belonging to the genus Alcaligenes or Agrobacterium can be mentioned. Among these bacteria, Agrobacterium tumefaciens I-736, a bacterium belonging to the genus Agrobacterium, [Collecting Organization for Microbial Culture (C) on March 1, 1988 in accordance with the Budapest Treaty
NCM) and is publicly available under the number I-736. Is particularly preferred as a source of succinoglycan.

Succinoglycans can be produced by culturing these microorganisms in a medium. More specifically, carbon sources such as glucose, sucrose and starch hydrolysates; organic nitrogen sources such as casein, caseinate, vegetable powder, yeast extract and corn steep liquor (CSL); metal sulfates and phosphoric acid It can be produced by culturing the above-described microorganism in a medium containing inorganic salts such as salts and carbonates, and optional trace elements.

In general, this culture is preferably carried out at 25 to 35 ° C. under a pressure of 1 to 4 bar under aerobic conditions such as stirring culture. The pH of the medium is 5 to 9, preferably 6 to 8. After completion of the culture, the culture medium is heat-treated and then brought into continuous contact with an organic solvent such as isopropanol to isolate succinoglycan. When isolating succinoglycan from the culture medium, it is preferably filtered, centrifuged, pressurized, and dried to obtain succinoglycan to be added to the hair dye composition of the present invention. Can be.

In addition, the succinoglycan thus produced can be added to the composition for oxidative hair dye of the present invention as it is, and if necessary, acid decomposition, alkali decomposition, enzyme decomposition, ultrasonic wave A decomposition product such as a treatment can be similarly blended.

The composition for oxidative hair dye of the present invention (the weight of the composition which is the basis of the percentage by weight in the composition for hair dye of the present invention is the composition for oxidative hair dye used in the two-part hair dye. In the case of a product, the weight of the composition of the first agent or the second agent containing the component to be indicated is included. The same applies to the following.), The amount of succinoglycan in the composition is approximately 0.0
It is blended in a range of 1% by weight or more and 50.0% by weight or less,
Preferably, it is blended in the range of 0.1% by weight or more and 5.0% by weight or less.

If the amount of the succinoglycan is less than 0.01% by weight based on the whole composition, it becomes difficult to sufficiently exhibit the effect of dyeing hair and the effect of preventing damage to hair. If the amount exceeds 50.0% by weight, the effect corresponding to the increase of the amount cannot be expected to be improved, which is not preferable.

Under normal conditions, succinoglycan exhibits rheological properties comparable to those of xanthan gum, which is widely used as a thickener, and is extremely stable even under severe temperature, pH and in the presence of salt. It is. The composition for an oxidized hair dye of the present invention containing this succinoglycan is a composition for a hair dye having very excellent characteristics.

First, surprisingly, the composition for oxidative hair coloring of the present invention surprisingly does not cause decomposition behavior such as viscosity change, coloration or odor deterioration even if the pH or salt concentration changes over time. It is stable.

More surprisingly, the composition for oxidative hair dyes of the present invention is excellent in the fastness of dyeing, can suppress damage to hair, and can impart further gloss to hair. That is, the succinoglycan blended in the composition for oxidative hair dye of the present invention is adsorbed in the gaps between cuticles and chemically interacts with keratin protein to form a relatively robust thin film having a three-dimensional structure on the hair surface. Is formed, which has the effect of suppressing damage to the hair and improving the hair itself.

Further, the composition for an oxidative hair dye of the present invention has thixotropy, is excellent in extensibility, applicability, leveling properties and dyeing properties with a viscosity not dripping. Further, in the composition for an oxidative hair dye of the present invention, when a polypeptide and / or a derivative thereof is blended together with the above-mentioned succinoglycan, the intended effect of the present invention can be further improved. Here, examples of the polypeptide and / or a derivative thereof to be combined with the oxidative hair dye composition of the present invention together with succinoglycan include degradation products of natural proteins such as collagen hydrolyzate and keratin hydrolyzate.

The amount of these polypeptides and / or their derivatives in the composition for oxidative hair dye of the present invention is such that the weight ratio to the amount of succinoglycan in the composition for oxidative hair dye of the present invention is as follows. It is preferable that the weight of the glycan is 1 and about 0.01 to 20.0.

As described above, the oxidative hair dye usually takes the form of a two-part system comprising a first part containing an oxidizing dye and a second part containing an oxidizing agent. In the present invention, succinoglycan is used. Can be blended into the constituent units of the two-part oxidative hair dye of the first and second parts. Also, 1
The present invention can also be applied to oxidative hair dyes in the form of agents.

Therefore, the composition for oxidative hair dye of the present invention comprises
As a oxidized hair dye of the form in which succinoglycan is blended with the first agent of the oxidative hair dye of the dosage form, a form which is blended with the second agent, a form which is blended with the first and second agents, or a one-pack type oxidative hair dye Any of the following forms can be adopted. In addition, in the composition for oxidative hair dye of the present invention, in addition to the above-mentioned essential components, other components that are usually compounded in oxidative hair dye should be compounded within a range that does not impair the intended effect of the present invention. Can be.

For example, in a two-part oxidative hair dye, the first
Examples of the oxidation dye precursor to be incorporated in the agent include phenylenediamines, aminophenols, toluylenediamines, aminonitrophenols, diaminopyridines, and salts thereof.

The amount of these oxidation dye precursors in the composition for an oxidation hair dye of the present invention is usually about 0.01% by weight or more and 10.0% by weight or less based on the whole composition. Further, as a coupler, for example, resorcin, metaaminophenol, metaphenylenediamine and the like can be blended together with a corresponding oxidation dye precursor.

Further, in the first agent, surfactants such as polyoxyethylene alkyl ether salts and polyoxyethylene alkylamine fatty acid amides; humectants such as glycerin and propylene glycol; oily components such as lanolin and liquid paraffin; Stabilizers such as sulfites and ascorbic acid; thickeners such as carboxymethylcellulose and carboxyvinyl polymers; alkaline agents such as aqueous ammonia, monoethanolamine, sodium hydroxide and potassium hydroxide; Can be.

On the other hand, as the oxidizing agent of the second agent, hydrogen peroxide is usually used. In the second agent, for example, stabilizers such as terpinal and sodium stannate; oils and fats such as paraffin; higher alcohols , Surfactant, acid, pH adjuster,
Flavors and the like can be blended. Such a two-part composition for an oxidative hair dye of the present invention is usually used immediately before use by mixing the first part and the second part and subjecting the mixture to hair dyeing for 10 to 30 minutes.

In one-part oxidative hair dyes, for example, 2,4-diaminophenol sulfate, stearyltrimethylammonium chloride / triethanolamine, ammonium thioglycolate, propylenediglycol, L
Components such as PG (gas) can be blended in addition to the above essential components. Specific forms and the like of the composition for an oxidative hair dye of the present invention will be described in Examples described later.

[0031]

The present invention will be specifically described below with reference to examples. Note that the present invention is not limited to these examples.

[Production Example] Production of succinoglycan Succinoglycan was produced according to the description of Japanese Patent Publication No. 6-74283. That is, fermentation was performed using Agrobacterium tumefaciens I-736 in a culture medium having the composition described below. That is, the culture medium was inoculated with Agrobacterium tumefaciens I-736 strain, and 20 liters of Biol having a used volume of 15 liters was used.
In the affite (registered trademark) container, stirring culture was performed at 28 ° C using a Ruston (registered trademark) type stirrer at 400 rpm, and the medium was aerated at a flow rate of 825 liters / hour. After 90 hours of stirring cultivation, which corresponds to the total consumption of the sucrose or substantially the entire consumption, the heteropolysaccharide 6 defined in terms of the weight of sucrose used
6% by weight were obtained. Cylindrical spindle N at 30 rpm
o. 4 using Brookfield LTV (registered trademark)
The viscosity of the fermented liquid measured by a viscometer was 6,800 Pa · s.

Succinoglycan was recovered from 2 kg of the above fermented broth heat treated at 90 ° C. for 30 minutes. That is, 2300 ml of isopropyl alcohol was added to the fermented solution thus heat-treated, and a precipitate was formed with 150 g of sodium sulfate. Next, the fiber resulting from the precipitation is subjected to dehydration treatment twice with 1200 ml of isopropyl alcohol, and the dehydrated fiber is pressed to tear apart,
Dry in an oven at 85 ° C. The obtained dried product was pulverized and sieved. Thus, a cream-colored succinoglycan powder was obtained.

Composition of culture medium :% by weight of the culture medium CSL (corn steep liquor) 11.0 K ₂ HPO ₄ 4.0 MgSO ₄ .7H ₂ O 0.5 sucrose 25.0 Ion-exchanged water Residual amount Obtained as described above. Succinoglycan was used in the following examples.

[Evaluation of Composition for Hair Coloring Agent] The composition for oxidized hair coloring agent prepared according to each of the following formulations was evaluated through a dyeing test, a fastness test, and a hair damage test.

Hair dyeing method The first and second oxidized hair dyes of the following formulation were combined with 15
g: 15 g, mixed at room temperature on hair [white hair (5 g)], and allowed to stand for 20 minutes. The hair was then rinsed thoroughly with 40 ° C. hot water and dried at 40 ° C. for 15 minutes (this hair dyeing method is common to all test systems).

Dyeing test: With respect to the oxidized hair dye prepared according to the following formulation, the dying with five types of hair strands was determined, and the oxidized hair dye was prepared by removing succinoglycan from the components of the oxidized hair dye of the formula. The dyeing of each oxidative hair dye was evaluated by comparison with the dye (comparative example). In addition, the gloss of the hair was visually evaluated.

Evaluation criteria ：: Examples are more excellent in dyeing properties than comparative examples. Δ: Examples and Comparative Examples have the same level of dyeability. ×: The example is inferior to the comparative example.

Fastness test: Oxidized hair dyes prepared according to the following formulation (Examples and Comparative Examples having the above-mentioned relationship with each other) were used, and the following five hair strands were dyed using the hair dyes in the following manner. The color fastness was compared.

(A) Evaluation of Shampoo Resistance The dyed hair was shampooed twice with a 2% aqueous solution of sodium lauryl sulfate (40 ° C., 10 minutes), and then in a thermostatic bath (40 ° C., 1 minute).
5 minutes). This operation was repeated 10 times, and the color change (fading and discoloration) of the dyed hair was confirmed, and evaluated according to the following criteria.

Evaluation Criteria : The example is superior to the comparative example. Δ: Examples and Comparative Examples are comparable. ×: The example is inferior to the comparative example.

(B) Evaluation of light fastness The dyed hair was exposed to sunlight for 60 days (integrated solar radiation amount of 27,000ca)
l / cm), and the change in the color of the dyed hair (fading and discoloration) was confirmed using the dyed hair not subjected to the sun exposure treatment as a control, and evaluated based on the following criteria.

Evaluation Criteria : The example is superior to the comparative example. Δ: Examples and Comparative Examples are comparable. ×: The example is inferior to the comparative example.

Hair damage test: With respect to the oxidized hair dye prepared according to the following formulation, the surface of the hair before and after dyeing the five types of hair strands dyed using the same was observed with an electron microscope (magnification: 3000 times). The degree of damage to the hair pelts of these hairs was evaluated by comparison with an oxidized hair dye of a prescription in which succinoglycan was removed from the components of the oxidized hair dye of the prescription (Comparative Example).

Evaluation criteria ○: Same as before dyeing, no damage was observed. Δ: Cuticles are slightly damaged such as bumps, cracks, and peeling. X: The cuticle is considerably damaged such as bulges, cracks and peeling.

Stability test with time A sample of the oxidized hair dye prepared according to the following formulation (Examples 3, 4, 5) was filled into a 50 ml screw tube,
Each sample was stored according to each temperature condition [-5 ° C, 0 ° C, room temperature (RT), 50 ° C], and a one-month stability test was performed. The evaluation of the stability over time was comprehensively judged from the viewpoints of change in appearance, change in viscosity and amount of free ammonia.

Evaluation criteria ○: No change was observed even after one month. Δ: Change was observed to such an extent that practical use was not hindered. X: A change was found that made it difficult to actually use.

Example 1 Oxidative hair dye (1) blending amount (% by weight) (first agent) paraphenylenediamine 1.0 propylene glycol 10.0 sodium edetate 0.3 sodium sulfite 0.5 ascorbic acid Sodium 0.5 Succinoglycan 1.0 Aqueous ammonia pH 10.0 Amount of ion-exchanged water Remaining amount (second agent) 30% hydrogen peroxide solution 6.0 Ion-exchanged water remaining amount

<Production method> Each of the first and second agents was prepared by mixing the respective components. About this oxidation hair dye (1),
The above dyeing test, fastness test ((a) evaluation of shampoo resistance, (b) evaluation of light resistance) and a hair damage test were performed. These test results are shown in Table 1 (dying test),
The results are shown in Table 2 (fastness test) and Table 3 (hair damage test).

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

In the visual observation performed during the dyeing test, each strand was excellent in gloss. Based on these results, the oxidized hair dye according to the present invention, which contains succinoglycan, has been considered to be an important problem of hair dyes, and has excellent dyeing properties and fastness of hair dye. It was found that the hair was hardly damaged and that the gloss of the hair could be further improved.

Example 2 Oxidative Hair Dye (2) Compounding Amount (First Agent) Paraphenylenediamine 1.0 Resorcinol 0.8 Propylene Glycol 10.0 Sodium Edetate 0.3 Sodium Sulfite 0.5 Ascorbic Acid Sodium 0.5 Succinoglycan 1.0 Aqueous ammonia pH 10.0 Amount of ion-exchanged water Remaining amount (second agent) 30% hydrogen peroxide solution 6.0 Ion-exchanged water remaining amount

<Production method> Both the first and second agents were prepared by mixing the respective components. Oxidative hair dye of this Example 2 (2)
In the above-mentioned dyeing test, fastness test ((a) evaluation of shampoo resistance, (b) evaluation of light resistance) and hair damage test, the above test was carried out. The same good result as that of ()) could be obtained.

In the oxidative hair dye (2) of Example 2, the polypeptide (collagen hydrolyzate) was used in the same manner as in 1.
In the case of the oxidative hair dye containing 0% by weight in the first agent, the results of the dyeing test were similar to those of the oxidative hair dye (2), but the fastness test, especially the shampoo resistance test Then
The oxidative hair dye containing the polypeptide was remarkably excellent (all the strands were evaluated as “○”, and all the strands were remarkably superior to Comparative Example 2).
From this result, it was found that the oxidative hair dye of the present invention containing the polypeptide was excellent in the fastness of dyeing especially to shampoo.

Example 3 Creamy Oxidative Hair Coloring Compounding Amount (% by Weight) (First Agent) Paraphenylenediamine 1.5 Metaphenylenediamine 1.0 Polyoxyethylene alkyl ether salt 3.0 Cetostearyl alcohol 15 3.0 Liquid paraffin 3.0 Succinoglycan 2.0 Keratin hydrolyzate 1.0 Perfume Appropriate amount Aqueous ammonia Amount to reach pH 10.0 Ion-exchanged water Remaining amount (Second agent) 30% hydrogen peroxide solution 6. 0 Edetic acid 0.5 Cetanol 2.0 Sodium alkylate 0.5 Sodium stannate 0.1 Deionized water Residue <Preparation method> Prepared in the same manner as in Example 2 above.

The aging hair dye of the present invention of Example 3 was subjected to the above-mentioned stability test with time, and the results are shown in Table 4 below. The oxidative hair dye of Comparative Example 3 in Table 4 is an oxidative hair dye containing dextrin pullulan instead of succinoglycan in the formulation of the oxidative hair dye of Example 3.

[0059]

[Table 4]

From these results, it has been found that the oxidative hair dye composition of the present invention also improves the temporal stability, which has conventionally been a problem, by incorporating succinoglycan. In addition, the composition for an oxidative hair dye of the present invention of Example 3 in all of the other tests described above obtains substantially the same results as the composition for an oxidative hair dye of the present invention of Example 1 described above. I was able to.

Example 4 Gel Oxidation Hair Coloring Agent Compounding Amount (% by Weight) (First Agent) Paraphenylenediamine 20.0 Paraaminophenol 0.5 Resorcin 0.5 Polyoxyethylene alkylphenyl ether 20.0 Olein Acid 5.0 Polyethylene glycol 20.0 Sodium sulfite 0.5 Succinoglycan 1.0 Perfume Appropriate amount Monoethanolamine Amount to pH 10.0 Ion-exchanged water balance (2nd agent) 30% hydrogen peroxide 6 0.0 Edetic acid 0.5 Cetanol 2.0 Sodium alkylate 0.5 Sodium stannate 0.1 Deionized water balance

<Preparation method> Preparation was carried out in the same manner as in the above example. The composition for an oxidized hair dye of the present invention of Example 4 was used for the oxidative hair dye of the present invention of Example 1 in each of the above-mentioned tests to (dying test, fastness test and hair damage test). The results were comparable to the composition. In addition, in the test (stability test with time), the same result as that of the composition for an oxidative hair dye of the present invention in Example 3 was able to be obtained.

Example 5 Shampoo-Type Oxidative Hair Dye Compounding Amount (% by Weight) (First Agent) Paraphenylenediamine 0.8 Orthoaminophenol 1.0 Resorcinol 1.5 Polyoxyethylene alkylphenyl ether 22.0 Oleic acid 3.0 Isopropyl alcohol 10.0 Succinoglycan 0.5 Aqueous ammonia pH 10.0 Amount of perfume Appropriate amount Remaining amount of ion-exchanged water (Second agent) 30% hydrogen peroxide solution 6.0 Edetic acid 0 0.5 Cetanol 2.0 Sodium alkylate 0.5 Sodium stannate 0.1 Deionized water balance

<Preparation method> Preparation was carried out in the same manner as in the above example. The composition for an oxidative hair dye of the present invention of Example 5 was used for the oxidative hair dye of the present invention of Example 1 in each of the above-mentioned tests to (dying test, fastness test and hair damage test). The results were comparable to the composition. In addition, in the test (stability test with time), the same result as that of the composition for an oxidative hair dye of the present invention in Example 3 was able to be obtained.

[0065]

Industrial Applicability According to the present invention, the dyeing property is excellent, the fastness of dyeing to sunlight and hair washing is good, the damage of the hair is extremely small, and the gloss of the hair can be further improved. Provided is a composition for an oxidative hair dye which is excellent in stability over time.

Claims (2)

[Claims] 1. An oxidative hair dye composition containing succinoglycan. 2. The composition for a hair dye according to claim 1, wherein the composition for an oxidative hair dye is a composition for an oxidative hair dye further comprising a polypeptide and / or a derivative thereof.