JP2008285421A - Hair modification penetrant and cosmetic for hair using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair modification penetrant effectively penetrating into the interior of hair and to provide a cosmetic for hair comprising the hair modification penetrant. <P>SOLUTION: The hair modification penetrant and the cosmetic for the hair effectively penetrating into the interior of the hair and improving the hand touch etc., of the hair are obtained by including hyaluronic acid having 5,000-20,000 average molecular weight and containing a component having ≤10,000 molecular weight in an amount of ≥40 wt.% and a component having ≥50,000 molecular weight in an amount of ≤5 wt.% in the molecular weight distribution and/or a salt thereof in the hair modification penetrant. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a hair modifying penetrant that contains hyaluronic acid and / or a salt thereof having a specific average molecular weight and a molecular weight distribution as an active ingredient and has excellent penetrability into hair, and for hair using the same Regarding cosmetics.

Hyaluronic acid is a mucopolysaccharide present in living organisms, particularly subcutaneous tissues, and has been widely used as a raw material for cosmetics as hyaluronic acid or a salt thereof due to its high moisturizing function. For example, Japanese Patent Application Laid-Open No. 59-110612 (Patent Document 1) discloses that a hair treatment agent contains hyaluronic acid having a molecular weight of 500,000 to 2,000,000 and / or salts thereof to recover damaged hair and protect it. It is described that it has the effect of giving gloss to hair. As its mechanism of action, it is described that hyaluronic acid or a salt thereof is formed by forming a protective film on the hair. However, the protective film formed by the high molecular weight hyaluronic acid and / or salt thereof is not sufficient for hair modification.

JP 59-110612 A

An object of the present invention is to use a hair modifying penetrant that has hyaluronic acid and / or a salt thereof having a specific average molecular weight and a molecular weight distribution as an active ingredient and has excellent penetrability into the hair. A cosmetic for hair is provided.

As a result of extensive research on hyaluronic acid, the present inventor surprisingly, if hyaluronic acid and / or a salt thereof having a specific average molecular weight and molecular weight distribution are used for hair, the hyaluronic acid and / or its The present inventors have found that the salt penetrates into the hair and improves the feel of the hair, such as improving the feel of the hair, and completed the present invention.

That is, the present invention
(1) The average molecular weight is 5,000 to 20,000, and in the molecular weight distribution, the proportion of components having a molecular weight of 10,000 or less is 40% by weight or more and the proportion of components having a molecular weight of 50,000 or more is 5% by weight or less. A hair modifying penetrant containing hyaluronic acid and / or a salt thereof as an active ingredient,
(2) In the molecular weight distribution, the proportion of components having a molecular weight of 10,000 or less is 40% by weight or more, and the proportion of components having a molecular weight of 50,000 or more is 1% by weight or less. Agent,
(3) The hair modifying penetrant according to (2), wherein in the molecular weight distribution, the proportion of components having a molecular weight of 10,000 or less is 50% by weight or more,
(4) A cosmetic for hair containing the hair modifying penetrant according to any one of (1) to (3),
It is.
(5) The hair cosmetic composition according to (4), wherein the content of the hair modifying penetrant is 0.001 to 5% as the hyaluronic acid and / or salt thereof,
It is.

According to the present invention, by incorporating hyaluronic acid having a specific average molecular weight and molecular weight distribution and / or a salt thereof as an active ingredient, it effectively penetrates into the hair and improves the feel of the hair. It is possible to provide a hair modifying penetrant that is excellent in modifying hair and a cosmetic for hair using the same. Therefore, further expansion of utilization of hyaluronic acid and / or its salt can be expected.

Hereinafter, the present invention will be described in detail. In the present invention, “%” means “mass%” and “part” means “part by mass”.

The hair modifying penetrant of the present invention has an average molecular weight of 5,000 to 20,000, and in the molecular weight distribution, the proportion of the component having a molecular weight of 10,000 or less is 40% by weight or more and 50,000 or more. It contains hyaluronic acid and / or a salt thereof as an active ingredient in a proportion of 5% by weight or less. By using the above hyaluronic acid and / or salt thereof, the hyaluronic acid and / or salt thereof penetrates into the hair, and a hair modifying penetrant effective for improving the feel of the hair can be obtained.

Here, “hyaluronic acid” refers to a polysaccharide having one or more repeating structural units composed of disaccharides of glucuronic acid and N-acetylglucosamine. The “hyaluronic acid salt” is not particularly limited, but is preferably a cosmetically acceptable salt, such as sodium salt, potassium salt, calcium salt, zinc salt, magnesium salt, ammonium salt and the like. It is done. Moreover, hair means eyelashes, eyebrows, etc. in addition to head hair.

The average molecular weight of hyaluronic acid or a salt thereof contained as an active ingredient of the hair modifying penetrant of the present invention is 5,000 to 20,000. Moreover, 5,000-15,000 are preferable at the point of the predominance of the permeability to the inside of hair, and it is more preferable that it is 5,000-12,000. This is because if the average molecular weight of hyaluronic acid or a salt thereof is larger than the above value, the hyaluronic acid and / or a salt thereof does not penetrate into the hair, so that the targeted hair modifying penetrant of the present invention is not obtained. Moreover, when the average molecular weight of hyaluronic acid or a salt thereof is smaller than the above value, the industrial productivity of hyaluronic acid or a salt thereof is lowered, which is not preferable.

The measurement method of the average molecular weight prescribed | regulated by this invention is demonstrated.

The average molecular weight defined in the present invention is a molecular weight calculated from the intrinsic viscosity of hyaluronic acid and / or a salt thereof. In order to determine the intrinsic viscosity of hyaluronic acid and / or its salt, first, an aqueous solution of a plurality of hyaluronic acid and / or its salt is prepared, and hyaluronic acid and / or its The specific viscosity and the reduced viscosity are calculated based on the following formulas 1 and 2 from the flowing seconds of the aqueous salt solution and the flowing seconds of the solvent. At this time, an Ubbelohde viscometer having a coefficient such that the number of seconds of flow is 200 to 1000 seconds is used. The concentration of the aqueous solution of hyaluronic acid and / or a salt thereof is selected to be suitable for the measuring instrument. The measurement is performed in a constant temperature water bath at 30 ° C. so that there is no temperature change.
(Formula 1)
(Formula 2)

Next, for each aqueous solution of hyaluronic acid and / or salt thereof, a calibration curve was prepared by plotting the obtained reduced viscosity on the vertical axis and the hyaluronic acid and / or salt concentration in terms of dry matter on the horizontal axis, By extrapolating hyaluronic acid and / or its salt concentration to zero, the intrinsic viscosity of hyaluronic acid and / or its salt is obtained. Based on the following formula 3, the average molecular weight M can be determined from the intrinsic viscosity of hyaluronic acid and / or a salt thereof.
(Formula 3)
Intrinsic viscosity (dL / g) = K′M ^α
(In the above formula 3, K ′ = 0.036 and α = 0.78.)

The hyaluronic acid and / or salt thereof used in the present invention has an average molecular weight of 5,000 to 20,000, and in the molecular weight distribution, the proportion of components having a molecular weight of 10,000 or less is 40% or more, and The proportion of components having a molecular weight of 50,000 or more is 5% or less. Further, from the viewpoint of superiority of penetrability into the hair, the proportion of components having a molecular weight of 50,000 or more is preferably 1% or less, the proportion of components having a molecular weight of 10,000 or less is 50% or more, and the molecular weight is 50,000. The proportion of the following components is more preferably 1% or less. By using hyaluronic acid and / or a salt thereof having such a molecular weight distribution, it is possible to obtain a hair modifying penetrant that is particularly excellent in penetrating into the hair.

The molecular weight distribution defined in the present invention can be obtained by liquid chromatography analysis of hyaluronic acid and / or a salt thereof using a gel filtration column. Hyaluronic acid and / or a salt thereof is a mixture of a plurality of components having different molecular weights depending on the number of repeating structural units (N-acetyl-D-glucosamine and D-glucuronic acid). Accordingly, by performing liquid chromatography analysis on an aqueous solution of hyaluronic acid and / or a salt thereof using a gel filtration column, the components constituting hyaluronic acid and / or the salt thereof can be separated by molecular size.

The molecular weight distribution of hyaluronic acid and / or a salt thereof in the present invention is determined by HPLC analysis device (trade name “Alliance PDA System”, manufactured by Nippon Waters Co., Ltd.) and gel filtration column (trade name “Diol-120”, manufactured by YMC Co., Ltd.). ) And a 0.1% (w / v) aqueous solution of hyaluronic acid and / or its salt as an analytical sample, and this analytical sample can be measured by liquid chromatography analysis.

The conditions for liquid chromatography analysis are as follows.
Column temperature: 40 ° C
Flow rate: 1 mL / min Injection volume of 0.1% (w / v) aqueous solution of hyaluronic acid and / or its salt: 20 μL
Mobile phase: 0.003 mol / L phosphate buffer (containing 0.15 mol / L NaCl, pH 7.0)
Ultraviolet detector: measured at λ = 210 nm In the liquid chromatography using the gel filtration column according to the present invention, the longer the retention time, the lower the molecular weight. In order of decreasing retention time, N-acetylglucosamine, D-glucuronic acid, hyaluronic acid (disaccharide: one repeating structural unit), hyaluronic acid (tetrasaccharide: two repeating structural units), hyaluronic acid (hexasaccharide: repeating structure) Peaks of 3 units), hyaluronic acid (octasaccharide: 4 repeating structural units)... Are obtained. The retention time and molecular weight at each peak are calculated, and a calibration curve of this retention time versus molecular weight is obtained (Formula 4).

In formula 4 described later, x represents a retention time, and y represents a molecular weight. Next, from the calibration curve shown in Equation 4, a retention time corresponding to a predetermined molecular weight (10,000 or 50,000) is calculated, and by dividing the peak by these retention times, the components in the predetermined molecular weight range are calculated. Find the percentage. The molecular weight indicated by each peak is referred to the peak in the chromatogram obtained by liquid chromatography analysis of the smallest structural unit (disaccharide) of hyaluronic acid and / or its salt with a known molecular weight in the same manner. To be identified.

For example, the ratio of components having a molecular weight of 10,000 or less is calculated by calculating a retention time corresponding to a molecular weight of 10,000 from the calibration curve shown in Equation 4, and dividing the absorption area of the component after this retention time by the total absorption area. Can be sought. Similarly, for the proportion of components having a molecular weight of 50,000 or more, the retention time corresponding to the molecular weight of 50,000 is calculated from the calibration curve shown in Equation 4, and the absorption area of the component is divided by the total absorption area before this retention time. It can ask for.

As an example, Table 1 shows the relationship between the number of repeating units of each molecular weight component obtained from the chromatogram shown in FIG.

* The molecular weight of hyaluronic acid was calculated as free acid.

(Formula 4)
y = -21.4x < ³ > + 1296.2x < ² > -267477.1x + 189427.1

A typical method for producing the hyaluronic acid and / or salt thereof used in the present invention will be described below. In addition, the manufacturing method of hyaluronic acid and / or its salt used by this invention is not limited to this.

The hyaluronic acid and / or salt thereof (hereinafter also referred to as “raw hyaluronic acid and salt thereof”), which is a raw material of the hyaluronic acid and / or salt thereof, is generally a biological tissue such as a chicken crown, umbilical cord, eyeball, skin, cartilage, Alternatively, it can be obtained by using a culture solution obtained by culturing a hyaluronic acid-producing microorganism such as a microorganism belonging to the genus Streptococcus as a raw material, and extracting (and purifying as necessary) these raw materials. For example, the molecular weight of the raw material hyaluronic acid and / or its salt extracted from a chicken crown is usually 2 million to 8 million.

The hyaluronic acid and / or salt thereof can be produced by dispersing the raw material hyaluronic acid and / or salt thereof in an acidic water-containing medium and removing the acidic water-containing medium by heating and drying. it can. Here, the degree of low molecular weight can be adjusted by adjusting the stirring speed and stirring time. Moreover, by performing the above-mentioned dispersion | distribution process on 30-70 degreeC on the heating conditions for less than 1 hour, it can be made low molecular weight stably to the target molecular weight. More specifically, the dispersion medium obtained by adding the powdered raw material hyaluronic acid and / or salt thereof to the acidic water-containing medium while stirring can be heated. Alternatively, the acidic water-containing medium may be heated in advance, and raw material hyaluronic acid and / or a salt thereof may be added thereto to maintain the temperature.

In the above production method, the water-containing medium refers to a dispersion medium of hyaluronic acid and / or a salt thereof containing water. The medium that can be used as the water-containing medium preferably has low solubility of hyaluronic acid and / or a salt thereof. The medium that can be used as the water-containing medium is not particularly limited, but for example, a liquid that is soluble in water and that can be used in the manufacturing process of cosmetics is preferable. Examples of the medium that can be used as the water-containing medium include alcohol-based media (for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol), ketone-based media (for example, acetone, methyl ethyl ketone), tetrahydrofuran, acetonitrile, and the like. These can be used alone or in combination. Among these, it is preferable that it is at least 1 sort (s) chosen from methanol, ethanol, and acetone at the point of the low boiling point and a price. The water content in the water-containing medium is not particularly specified, but if the water content is large, the hyaluronic acid and / or salt thereof cannot be maintained in a dispersed state and is dissolved in the water-containing medium, which may lead to a decrease in yield. Therefore, the ratio of water to the total amount of the water-containing medium is preferably 40% capacity or less, more preferably 30% capacity or less.

Moreover, in the said manufacturing method, as what is used in order to make a water-containing medium acidic, acids, such as hydrochloric acid and a sulfuric acid, and acidic cation exchange resin are mentioned, for example.

The method for converting hyaluronic acid into a hyaluronic acid salt and the method for converting the hyaluronic acid salt into hyaluronic acid are not particularly limited. As a method for converting the above hyaluronic acid into a hyaluronic acid salt, for example, an alkaline aqueous solution (for example, an aqueous solution of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, etc.) is used. The method of doing is mentioned. Examples of the method for converting the salt of hyaluronic acid into hyaluronic acid include, for example, a method using an aqueous acid solution (for example, an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), an acidic cation exchange resin, and the like. The method using is mentioned.

Since the hair modifying penetrant of the present invention contains the hyaluronic acid and / or salt thereof as an active ingredient, it is preferable to use the hyaluronic acid and / or salt thereof as the hair modifying penetrant as it is. A solvent such as water, an excipient such as dextrin, or other raw materials for cosmetics for hair may be added. In that case, the content of the hyaluronic acid and / or a salt thereof is preferably 0.1% or more and more preferably 1% or more in consideration of the blending amount into the hair cosmetic described later and ease of blending.

Examples of the cosmetics for hair containing the hair modifying penetrant include, for example, shampoo, rinse, rinse-integrated shampoo, hair conditioner, hair treatment, hair pack, mascara cleansing, hair color pretreatment liquid, and coloring liquid. , Undiluted hair treatment, hair cream, hair styling, hair wax, hair gel, hair foam (hair mousse), hair lotion, hair spray, hair oil, hair tonic, permanent liquid, mascara, eyeliner, eyebrow and the like.

The hair cosmetic composition of the present invention is generally used in hair cosmetic compositions as long as the effects of the present invention are not impaired, in addition to the hair modifying penetrant containing the hyaluronic acid and / or salt thereof as an active ingredient. Components can be appropriately blended. Examples of the component include an anionic surfactant (eg, alkylbenzene sulfonate, polyoxyalkyne alkyl sulfate, alkyl sulfate, olefin sulfonate, fatty acid salt, dialkyl sulfosuccinate, etc.), nonionic interface Activators (eg, polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil derivatives, etc.), cationic surfactants (eg, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl pyridinium salts, stearyl trimethyl ammonium chloride, etc.), Amphoteric surfactants (eg, alkylbetaines, alkylamidopropylbetaines, imidazolinium betaines, egg yolk lecithin, soybean lecithin, etc.), oils (eg, silicone, silicone derivatives, fluid paraffin) Tin, squalane, beeswax, carnauba wax, olive oil, avocado oil, camellia oil, jojoba oil, etc.), moisturizer (eg, polymeric hyaluronic acid and / or salt thereof, phytoglycogen, hydrolyzed eggshell membrane, trehalose, glycerin, atelocollagen Sorbitol, maltitol, etc.), higher fatty acids (eg, lauric acid, behenic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, etc.), higher alcohols (eg, cetyl alcohol, stearyl alcohol, behenyl alcohol, isostearyl alcohol, Batyl alcohol, etc.), polyhydric alcohol (eg, 1,3-butylene glycol, glycerin, diglycerin, propylene glycol, polyethylene glycol, pentylene glycol, etc.), thickener (eg, Loose ether, carboxyvinyl polymer, xanthan gum, etc.), amphoteric polymer resin compound (eg, betaineated dialkylaminoalkyl acrylate copolymer), cationic polymer resin compound (eg, vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer) Cationized products, polydimethyldiallylammonium halide type cationic polymers), cationized polysaccharides (eg, cationized hydroxyethyl cellulose, cationized guar gum, cationized starch, cationized locust bean gum, cationized dextran, cationized hyaluronic acid, etc. ), Preservatives (eg, methyl paraben, phenoxyethanol, etc.), antioxidants (eg, tocopherol, BHT, etc.), metal sequestering agents (eg, edetate, etc.), UV absorption Agents (for example, benzophenone derivatives, paraaminobenzoic acid derivatives, methoxycinnamic acid derivatives, etc.), UV reflectors (for example, titanium oxide, zinc oxide, etc.), protein hydrolysates (for example, keratin peptides, collagen peptides, soybean peptides, wheat) Peptides, milk peptides, silk peptides, egg white peptides, etc.), amino acids (eg, arginine, glutamic acid, glycine, alanine, hydroxyproline, cysteine, etc.), phospholipid polymers, fragrances, and pigments.

The content of the hair modifying penetrant in the hair cosmetic composition of the present invention is preferably 0.001 to 5%, more preferably 0.005 to 2%, as the hyaluronic acid and / or salt thereof. If the content of the hair modifying penetrant exceeds the above range, the amount of the hyaluronic acid and / or salt thereof contained as an active ingredient may exceed the amount of penetration into the hair, which is not economical. On the other hand, if the amount is less than the above range, the hair modification effect of hyaluronic acid and / or a salt thereof contained as an active ingredient hardly appears and the commercial value is lowered, which is not preferable.

The method for producing a hair cosmetic composition of the present invention uses a hair-modifying penetrant containing the water-soluble hyaluronic acid and / or salt thereof as an active ingredient as an essential blending raw material. Other than adding to the aqueous medium, it may be produced according to a conventional method.

Hereinafter, the average molecular weight used in the present invention is 5,000 to 20,000, and in the molecular weight distribution, the proportion of components having a molecular weight of 10,000 or less is 40% by weight or more and the proportion of components having a molecular weight of 50,000 or more is 5% by weight. The following hair cosmetics using hyaluronic acid and / or a salt thereof will be specifically described based on examples and the like. The present invention is not limited to these.

[Preparation Example 1] Hyaluronic acid having an average molecular weight of 9,000 In this preparation example, a sodium hyaluronate (hereinafter also referred to as “HANa”) fine powder extracted and purified from a chicken crown was prepared as a raw material. The raw material HANa had an average molecular weight of about 2.1 million and a purity of 97%.

First, a 300 L tank equipped with a stirrer and a jacket was filled with 110 L of 0.5% sulfuric acid-containing 80% water-containing acetone (acidic water-containing medium), and heated with stirring to a liquid temperature of 60 ° C. Here, 80% water-containing acetone contains 80 (w / w)% acetone and 20 (w / w)% water, and 80% water-containing acetone containing 0.5% sulfuric acid contains sulfuric acid. It contains 0.5 (w / w)% and 80% aqueous acetone containing 99.5 (w / w)%. After reaching 60 ° C., 6 kg of the prepared raw material HANa fine powder was charged into the tank while stirring. While heating so as to maintain the temperature of the sulfuric acid-containing hydrous acetone at 60 ° C., the raw material HANa fine powder was stirred so as to be in a dispersed state.

Next, after stirring for 15 minutes and allowing to stand, the supernatant sulfuric acid-containing water-containing acetone was removed by decantation to obtain a precipitate. To the obtained precipitate, 110 L of 80% water-containing acetone containing 0.5% sulfuric acid previously heated to 60 ° C. was added, and similarly stirred for 15 minutes while heating to 60 ° C. This operation was repeated a total of 3 times.

Next, 110 L of 80% water-containing acetone was added to the precipitate obtained after removing sulfuric acid-containing water-containing acetone, and stirring was performed for 15 minutes for the purpose of removing sulfuric acid. This operation was repeated until no sulfuric acid remained.

Furthermore, water-containing acetone was removed by decantation to obtain a residue. The residue was further centrifuged to remove water-containing acetone and then heat-dried at 70 ° C. under reduced pressure for 12 hours using a vacuum dryer.

Through the above steps, 5.3 kg of hyaluronic acid (yield: about 88%) was obtained as white fine powder. This hyaluronic acid has an average molecular weight of 9,000 converted from intrinsic viscosity, and in the molecular weight distribution, the proportion of components having a molecular weight of 10,000 or less is 49% or more and the proportion of components having a molecular weight of 50,000 or more is 0.5%. there were.

In this test example, the hyaluronic acid of Preparation Example 1 was used as it was as a hair-modifying penetrant, and the hair cosmetic containing the hair-modifying penetrant was used for the hair, and the penetration into hair was evaluated. .

The following three types of samples were used.
Sample 1: Hyaluronic acid obtained in Preparation Example 1 Sample 2: Hyaluronic acid (trade name “Hyaluronic Sun HA-LF”, manufactured by QP Corporation, average molecular weight 200,000)
Sample 3: Sodium hyaluronate (trade name “Hyaluronic Sun HA-LQH”, manufactured by QP Corporation, average molecular weight 1.8 million)

In order to distinguish the samples 1 to 3 from the hyaluronic acid in the hair, a sample in which hyaluronic acid was fluorescent with a fluorescent labeling substance (DMEQ-hydrazide) was used for the test. The hyaluronic acid fluorescence method is in accordance with “Effect of ultrasonic irradiation on skin absorption of keratin moisturizer sodium hyaluronate” (Drug Delivery System, 12, 415-419 (1997)). It was carried out by the method.

First, each of Samples 1 to 3 was dissolved in purified water to obtain a 7.6 mg / mL aqueous solution. 160 mL of this sample aqueous solution was taken, 3.2 mL of pyridine, 16 mL of 9 mg / mL EDC aqueous solution and 25 mL of 1.24 mg / mL DMEQ-hydrazide were added, and the mixture was stirred at room temperature for 2 hours to perform a fluorescence reaction. After the reaction, 160 mL of purified water was added to the reaction solution, dialyzed to remove the fluorescent reagent, and fluorescent hyaluronic acid or a salt thereof was obtained by lyophilization.

The hair treatment was carried out by the following method.
Fluorescent hyaluronic acid or a salt thereof (samples 1 to 3) is used as a hair modifying penetrant or additive, and the hair modifying penetrant or additive is dissolved in purified water so as to have a concentration of 1%. A cosmetic was prepared. Take 3 mL of this cosmetic, put it in a 10 mL Erlenmeyer flask, immerse 0.004 g of human hair black hair (obtained from Beaulux Co., Ltd.) cut into 5 cm lengths, warm to 40 ° C. and hold for 15 minutes with stirring did. After the treatment, the hair was taken out, washed with purified water for 10 minutes and dried.

Regarding the condition of the hair obtained by the above treatment, a polarizing microscope (Nikon ECLIPSE E600 POL), a polarizing filter (UV1A), an epifluorescence device (Nikon)
(Y-FL). Several pieces of the obtained hair were put into a vinyl chloride tube together with an adhesive, and after curing, cut into 20 μm with a microtome, and the hair cross section was observed with a fluorescence microscope. As a control, untreated hair was similarly observed. The results are shown in FIG.

From FIG. 2, the hair treated with the cosmetic for hair containing the hyaluronic acid of Sample 1 as a hair modifying penetrant was confirmed to have an even fluorescent coloration inside the hair relative to the untreated hair. It was found that the fluorescent hyaluronic acid penetrated into the hair. On the other hand, in the hair treated with the cosmetic for hair containing the hyaluronic acid of Samples 2 and 3, no fluorescent color development was observed inside the hair, so the fluorescent hyaluronic acid or its salt was not on the hair surface. It was confirmed that it did not penetrate into the hair. Therefore, the hair-modifying penetrant containing hyaluronic acid (sample 1) having a specific average molecular weight and molecular weight distribution as an active ingredient of the present invention is more effective than that containing high-molecular hyaluronic acid as an active ingredient. It was suggested that it penetrated effectively inside.

[Test Example 2]
A hair mist in which the hyaluronic acid obtained in Preparation Example 1 was used as it was as a hair modifying penetrant was prepared with the following composition. The hair mist monitoring test was conducted by 20 adult women (20-50s). The hair mist was used once a day, and the effect on the hair was examined. Table 2 shows the monitor test results.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 1.0%
Phenoxyethanol 0.4%
Methylparaben 0.1%
Remaining amount of purified water ――――――――――――――――――――――――――――――
100%

From the questionnaire results, about 60% of the users showed an effect of improving the feel of hair. Furthermore, since about 70% of the users experienced the effect by the third time after using it, it was confirmed that there was an immediate effect.

[Preparation Example 2] Hyaluronic acid having an average molecular weight of 14,000 In this preparation example, raw material hyaluronic acid extracted and purified from a hyaluronic acid-containing fermented product obtained by culturing hyaluronic acid-producing Streptococcus microorganisms as a raw material ( Hereinafter, a fine powder (also referred to as “HA”) was prepared. This raw material HA had an average molecular weight of about 1.6 million and a purity of 97%.

First, a 300 L tank equipped with a stirrer was filled with 110 L of 80% water-containing ethanol (acidic water-containing medium) containing 2% hydrochloric acid, and heated to 70 ° C. while stirring. The pH of this treatment liquid was 0.76. Here, 80% water-containing ethanol contains 80 (w / w)% ethanol and 20 (w / w)% water, and 80% ethanol containing 2% hydrochloric acid contains 2 (w / w) hydrochloric acid. / W)% and 98% (w / w)% 80% water-containing ethanol. After reaching 70 ° C., 6 kg of the prepared raw material HA fine powder was put into the tank while stirring. While heating so as to maintain the temperature of the hydrochloric acid-containing aqueous ethanol at 70 ° C., the raw material HA fine powder was stirred so as to be in a dispersed state.

Next, after stirring for 60 minutes and allowing to stand, the supernatant hydrochloric acid-containing aqueous ethanol was removed by decantation to obtain a residue. The residue was centrifuged to further remove water-containing ethanol, and then dried under reduced pressure for 12 hours at room temperature in the presence of silica gel using a vacuum dryer.

Through the above steps, 5.5 kg (yield: about 92%) of low molecular weight hyaluronic acid as white fine powder was obtained. This hyaluronic acid has an average molecular weight of 14,000 converted from intrinsic viscosity, and in the molecular weight distribution, the proportion of components having a molecular weight of 10,000 or less is 43% or more and the proportion of components having a molecular weight of 50,000 or more is 2.1%. Met.

[Test Example 3]
A hair mist using the hyaluronic acid of Preparation Example 2 as it was as a hair modifying penetrant was prepared in the same formulation as in Test Example 2, and the same test as in Test Example 2 was performed. As a result, although the effect was slightly inferior to that of Test Example 2, the effect was similarly seen in improving the feel of hair.

[Test Example 4]
Using the hyaluronic acid obtained in Preparation Example 1 as a hair modifying penetrant, a shampoo having the following composition was prepared.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.1%
Polyoxyethylene (2) sodium lauryl ether sulfate 1.0%
Palm oil fatty acid amide propyl betaine 4.0%
Coconut oil fatty acid monoethanolamide 2.0%
Sodium edetate 0.1%
Sodium benzoate 0.2%
Perfume, pigment, preservatives Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, a shampoo excellent in penetrating into the hair could be obtained by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient.

[Test Example 5]
The hyaluronic acid obtained in Preparation Example 1 was used as it was as a hair modifying penetrant to produce a rinse having the following composition.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.3%
Cetostearyl alcohol 2.0%
POE (5) cetyl ether 1.0%
Glycerol 3.0%
1,3-butylene glycol 5.0%
Silicone oil 3.0%
Wheat hydrolyzate 1.0%
Hydroxystearic acid 0.5%
Cetyl 2-ethylhexanoate 1.0%
Distearyldimethylammonium chloride 0.2%
Behenic acid dimethylaminopropylamide 0.5%
Perfume, pigment, preservatives Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient, it was possible to obtain a rinse with excellent penetration into the hair.

[Test Example 6]
Using the hyaluronic acid obtained in Preparation Example 1 as a hair modifying penetrant as it was, a rinse-integrated shampoo having the following composition was produced.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.2%
Imidazolium betaine type double-sided surfactant 16.0%
Palm oil fatty acid diethanolamide 4.0%
Stearyltrimethylammonium chloride 2.0%
N-lauroyl-N-methyl-β-alanine sodium 1.0%
Silicone derivative 1.0%
Polyoxyethylene alkyl polyamine 1.0%
Perfume, dye, pH adjuster Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, it is possible to obtain a rinse-integrated shampoo excellent in penetrating into the hair by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient. did it.

[Test Example 7]
Using the hyaluronic acid obtained in Preparation Example 1 as it was as a hair modifying penetrant, a hair conditioner having the following composition was prepared.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.5%
Stearyl alcohol 4.0%
Cetanol 1.5%
Hydroxyethyl urea 1.0%
Dimethicone 2.0%
Hydrolyzed silk 1.0%
1,3-butylene glycol 1.0%
Glycerol 3.0%
Cetyl 2-ethylhexanoate 2.0%
Isocetyl myristate 0.4%
L-Arginine 0.1%
Polyoxyethylene (4) stearyl ether 1.0%
Stearic acid dimethylaminopropylamide 1.5%
Sodium benzoate 0.3%
Perfume, pigment, preservatives Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient, a hair conditioner having excellent penetration into the hair could be obtained. .

[Test Example 8]
Using the hyaluronic acid obtained in Preparation Example 1 as it was as a hair modifying penetrant, a hair pack having the following composition was prepared.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 1.0%
Cetyl alcohol 2.0%
Stearyl alcohol 2.0%
Stearic acid hydrogenated castor oil 2.0%
Isopropyl myristate 1.0%
Stearyltrimethylammonium bromide 3.0%
Distearyldimethylammonium chloride 2.0%
1,3-butylene glycol 10.0%
Perfume, preservatives Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient, a hair pack having excellent penetration into the hair could be obtained. .

[Test Example 9]
Using the hyaluronic acid obtained in Preparation Example 1 as a hair modifying penetrant, a stock solution type hair treatment having the following composition was prepared.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 2.0%
Preservative Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient, it is possible to obtain a stock solution type hair treatment with excellent penetration into the hair. did it.

[Test Example 10]
Using the hyaluronic acid obtained in Preparation Example 1 as a hair modifying penetrant as it was, a hair cream having the following composition was prepared.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.5%
Stearic acid 2.0%
Beeswax 2.0%
Vaseline 7.0%
Liquid paraffin 40.0%
Silicon oil 0.2%
Sorbitan monostearate 1.0%
Polyoxyethylene acetylene ether 1.5%
Triethanolamine 1.0%
1,3-butylene glycol 3.0%
Polyglycolamine condensate 2.0%
Preservative Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient, a hair cream having excellent penetration into the hair could be obtained. .

[Test Example 11]
Using the hyaluronic acid obtained in Preparation Example 1 as it was as a hair modifying penetrant, a hair wax having the following composition was produced.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.5%
PEG-20 glyceryl isostearate 3.0%
Glyceryl stearate 2.0%
Microcrystalline wax 4.0%
Carnauba wax 3.0%
Behenyl alcohol 3.0%
Stearic acid 1.0%
Mineral oil 2.0%
Hydrogenated polyisobutene 2.0%
Phenyltrimethicone 3.0%
Dimethicone 1.0%
Propylparaben 0.1%
PVP 1.0%
Propylene glycol 5.0%
Perfume, pigment, preservatives Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient, a hair wax having excellent penetrability into the hair could be obtained. .

[Test Example 12]
Using the hyaluronic acid obtained in Preparation Example 1 as a hair modifying penetrant as it was, a hair gel having the following composition was produced.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 1.0%
Polyvinylhydridone 2.0%
Glycerin 5.0%
Ethanol 20.0%
Polyoxyethylene octyldodecyl ether 1.0%
Sodium hydroxide Appropriate amount of perfume and chelating agent Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, a hair gel excellent in penetrability into the hair could be obtained by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient.

[Test Example 13]
Using the hyaluronic acid obtained in Preparation Example 1 as it is as a hair modifying penetrant, a hair lotion having the following composition was prepared.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 1.0%
Polyvinylhydridone 4.0%
Ethanol 30.0%
Silicone derivative 0.5%
Glycerin 2.0%
Perfume, preservatives Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient, a hair lotion with excellent penetration into the hair could be obtained. .

[Test Example 14]
Using the hyaluronic acid obtained in Preparation Example 1 as it was as a hair modifying penetrant, a hair color pretreatment liquid having the following composition was prepared.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.5%
Imidazolinium betaine 1.0%
Keratin hydrolyzate 0.5%
Glycine 0.5%
POE lauryl ether 0.5%
Remaining amount of purified water ――――――――――――――――――――――――――――――――
100%
According to this test example, a hair color pretreatment liquid excellent in penetrating into the hair is obtained by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient. I was able to.

[Test Example 15]
Using the hyaluronic acid obtained in Preparation Example 1 as a hair modifying penetrant as it was, a coloring agent having the following composition was produced.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.5%
Benzyl alcohol 8.0%
Citric acid 1.0%
Ethanol 15.0%
Black No. 401 0.05%
Brown 201 No. 0.05%
Sodium hydroxide Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient, it is possible to obtain a coloring agent with excellent penetration into the hair. It was.

[Test Example 16]
Using the hyaluronic acid obtained in Preparation Example 1 as a hair modifying penetrant as it was, a second liquid of perm solution having the following composition was prepared.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.5%
Sodium bromate 5.0%
Silicone emulsion 1.0%
Citric acid 0.1%
Sodium citrate 0.5%
Remaining amount of purified water ――――――――――――――――――――――――――――――――
100%
According to this test example, by adding the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient, a second permanent liquid with excellent penetration into hair is obtained. I was able to.

[Test Example 17]
The hyaluronic acid obtained in Preparation Example 1 was used as it was as a hair modifying penetrant to produce an aqueous mascara having the following composition.
<Combination ratio>
Hair modifying penetrant (hyaluronic acid of Preparation Example 1) 0.5%
Isopropyl alcohol 5.0%
1,3-butylene glycol 5.0%
Potassium hydroxide 0.1%
Zinc oxide 0.1%
Pigment 2.0%
Dextrin 14.0%
Perfume, preservatives Appropriate amount of purified water Remaining amount ――――――――――――――――――――――――――――――――
100%
According to this test example, a water-based mascara excellent in permeability into the hair could be obtained by blending the hair modifying penetrant containing the hyaluronic acid obtained in Preparation Example 1 as an active ingredient. .

FIG. 1 shows an example of a chromatogram of hyaluronic acid. FIG. 2 is a photograph of the hair obtained in Test Example 1 observed with a fluorescence microscope.

Claims (5)

Hyaluron having an average molecular weight of 5,000 to 20,000 and a molecular weight distribution of 40% by weight or more of components having a molecular weight of 10,000 or less and 5% by weight or less of components having a molecular weight of 50,000 or more A hair modifying penetrant comprising an acid and / or a salt thereof as an active ingredient. The hair modifying penetrant according to claim 1, wherein the molecular weight distribution is such that the proportion of components having a molecular weight of 10,000 or less is 40% by weight or more and the proportion of components having a molecular weight of 50,000 or more is 1% by weight or less. The hair modifying penetrant according to claim 2, wherein the molecular weight distribution is such that the proportion of components having a molecular weight of 10,000 or less is 50% by weight or more. A cosmetic for hair containing the hair modifying penetrant according to any one of claims 1 to 3. The hair cosmetic composition according to claim 4, wherein the content of the hair modifying penetrant is 0.001 to 5% as the hyaluronic acid and / or salt thereof.