JP2010024207A - Liquid cosmetic filled in spray container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid cosmetic blended with hyaluronic acid and/or its salt and filled in a spray container. <P>SOLUTION: The liquid cosmetic blended with hyaluronic acid having a quaternary ammonium group-containing group and a cationized degree of 0.15-0.6 and/or its salt are/is filled in a spray container. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a liquid cosmetic excellent in sprayability from a container for spraying containing a cationized hyaluronic acid having a specific degree of cationization and / or a salt thereof.

Hyaluronic acid and / or a salt thereof is a mucopolysaccharide present in living bodies, particularly subcutaneous tissues, and is widely used as a raw material for cosmetics due to its high water retention function and the like.

Further, the use site of the cosmetic containing hyaluronic acid and / or a salt thereof is the whole body such as hair, face, lips, limbs, elbows, knees, heels, etc., and depending on the use site, it is liquid (for example, lotion, Liquid foundation, whitening serum, body lotion, sun lotion), semi-solid (for example, hair cream, burnishing cream, shampoo, moisturizing pack), sheet (for example, moisturizing sheet), solid (for example, lip balm, powder) Various dosage forms such as foundation).

Of the cosmetics containing hyaluronic acid and / or salts thereof in various dosage forms, if liquid cosmetics containing hyaluronic acid and / or salts thereof can be sprayed from the container for spraying, hyaluronic acid and / or its An excellent feeling of use can be expected by spreading the salt on the hair and face easily and universally. However, when hyaluronic acid and / or a salt thereof is blended in a liquid cosmetic, when it is sprayed from a spray container, it is sprayed in the form of droplets rather than in the form of a mist and the usability is impaired.

For example, Japanese Patent Laid-Open No. 5-170641 (Patent Document 1) discloses 1,3-butylene glycol, polyethylene glycol, maltitol, sorbitol, fructose, glucose, polyoxyethylene methyl glucoside as a humectant. , Hyaluronic acid or a salt thereof is blended, and cosmetics having an osmotic pressure of 200 to 600 milliosmol are described. Japanese Patent Application Laid-Open No. 6-65050 (Patent Document 2) describes a skin external preparation containing hyaluronic acid and / or a salt thereof and docosahexaenoic acid or a salt or ester thereof.
Japanese Patent Laid-Open No. 5-170641 JP-A-6-65050

However, there is no disclosure of means for solving the specific problems that occur when hyaluronic acid and / or a salt thereof is sprayed from a spray container.

An object of the present invention is to provide a container-packed liquid cosmetic for spraying containing hyaluronic acid and / or a salt thereof and having excellent sprayability.

As a result of intensive research on liquid cosmetics to achieve the above object, the present inventor unexpectedly sprayed cationized hyaluronic acid and / or a salt thereof having a specific cationization degree. The present inventors have found that a liquid cosmetic excellent in sprayability from a container for use can be obtained, thereby completing the present invention.

That is, the present invention
(1) A containerized liquid cosmetic for spraying containing a quaternary ammonium group-containing group and a hyaluronic acid having a cationization degree of 0.15 to 0.6 and / or a salt thereof,
(2) The container-packed liquid cosmetic for spraying according to claim 1, wherein the quaternary ammonium group-containing group is represented by the following general formula (A):
(A)
(Wherein R ^{1 to} R ³ independently represent a hydrocarbon group, and X ⁻ represents a monovalent anion).
(3) The containerized liquid cosmetic for spraying according to (1) or (2), wherein the cationized hyaluronic acid and / or salt thereof is represented by a repeating structural unit of the following general formula (B):
(B)
(In the formula, R ^{4 to} R ⁹ independently represent a hydrogen atom or a quaternary ammonium group-containing group, except that R ^{4 to} R ⁹ all represent a hydrogen atom).
It is.

According to the present invention, a liquid that has a quaternary ammonium group-containing group and is excellent in sprayability from a container for spraying by incorporating a cationized hyaluronic acid having a specific cationization degree and / or a salt thereof. Cosmetics can be provided. Therefore, since it is possible to expect an excellent feeling of use by easily spreading the hyaluronic acid and / or salt thereof to the hair, the face, etc., further expansion of use of the hyaluronic acid and / or salt thereof can be expected.

Hereinafter, the container-packed liquid cosmetic for spraying according to an embodiment of the present invention will be described in detail. Unless otherwise specified, “%” means “mass%”.

The containerized liquid cosmetic for spraying of the present invention is characterized by blending a specific cationized hyaluronic acid and / or a salt thereof. Accordingly, the cationized hyaluronic acid and / or salt thereof, which is an essential part of the present invention, will be described in detail first.

“Hyaluronic acid” refers to a polysaccharide having one or more repeating structural units composed of disaccharides of glucuronic acid and N-acetylglucosamine. The “quaternary ammonium group-containing group” is a group having a quaternary ammonium group at least partially. In the present invention, “degree of cationization” of hyaluronic acid and / or a salt thereof refers to the number of quaternary ammonium group-containing groups per disaccharide as a constituent unit of hyaluronic acid and / or a salt thereof (substitution Number).

The cationized hyaluronic acid and / or salt thereof used for the container-packed liquid cosmetic of the present invention has a quaternary ammonium group-containing group, and the degree of cationization is 0.15 to 0.6. Furthermore, it is preferable that it is 0.2-0.6. When the degree of cationization of hyaluronic acid and / or a salt thereof is lower than the above range, it is difficult to spray from the spray container in the form of a mist and the liquid may be ejected in the form of droplets. When the degree of cationization exceeds the above range, it may not be possible to expect the effects on health and beauty.

The quaternized ammonium group-containing group of the cationized hyaluronic acid and / or salt thereof used in the container-packed liquid cosmetic of the present invention is not particularly limited, but 3-halogeno represented by the following general formula (A) -2-Hydroxypropyltrialkylammonium halide is preferred because of its excellent sprayability.
(A)
(In the formula, R ^{1 to} R ³ independently represent a hydrocarbon group, and X ⁻ represents a monovalent anion.)
In the general formula (A), the hydrocarbon group represented by R ^{1 to} R ³ is not particularly limited, but examples thereof include a linear or branched alkyl group, an unsaturated hydrocarbon group, and an aromatic carbon group. A hydrogen group is mentioned, and an alkyl group having 1 to 6 carbon atoms is preferably excellent in sprayability, more preferably an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Is more preferable. Similarly, the general formula (A), X ^- as the monovalent anion represented by is not particularly limited, for example, fluorine ion, a bromine ion, a chlorine ion, include halogen ions such as iodine ions, Chlorine ions are preferred because of their excellent sprayability. Moreover, you may use a cationizing agent individually or in combination of 2 or more types.

The structure represented by the following general formula (B) is preferable for the cationized hyaluronic acid and / or salt thereof used in the container-packed liquid cosmetic of the present invention.
(B)
(In the formula, R ^{4 to} R ⁹ independently represent a hydrogen atom or a quaternary ammonium group-containing group, except that R ^{4 to} R ⁹ all represent a hydrogen atom.)
In the general formula (B), examples of the quaternary ammonium group-containing group represented by R ^{4 to} R ⁹ include a group represented by the general formula (A).

The degree of cationization of the cationized hyaluronic acid and / or salt thereof used in the containerized liquid cosmetic for spraying of the present invention (substitution degree of the quaternary ammonium group-containing group) is first determined by the raw material sodium hyaluronate by the semi-micro Kjeldahl method. And the nitrogen content of the cationized hyaluronic acid can be obtained and calculated from the following formula based on the increase in the nitrogen content.
For example, cationization of cationized sodium hyaluronate in which the quaternary ammonium group-containing group in which R ^{1 to} R ³ are all methyl groups and X ⁻ is chlorine is bonded to sodium hyaluronate in the above general formula (A) The degree can be determined by the following method.
When the nitrogen content N _N (%) of the raw material sodium hyaluronate and the nitrogen content N _S (%) of the cationized hyaluronic acid with the degree of cationization (x) are increased (N _S −N _N ) And the degree of cationization (x) can be expressed by the following equation.
_{N S} -N N (%)
= [Atomic weight of nitrogen × x / (molecular weight of disaccharide unit of cationized sodium hyaluronate)] × 100
= [14x / {molecular weight of disaccharide unit of raw material sodium hyaluronate + (molecular weight of quaternary ammonium group-containing group-atomic weight of sodium) x}] x 100
= [14x / {401.3+ (152.5-23) x}] * 100
Therefore, the degree of cationization (the degree of substitution of the quaternary ammonium group-containing group) can be determined from the following formula.
Cation degree (x) = [(N _S −N _N ) × 401.3] / [1400-129.5 × (N _S −N _N )]
Further, the degree of cationization of cationized hyaluronic acid whose raw material hyaluronic acid is unknown can be obtained from the above formula, considering sodium hyaluronate having a purity of 99% or more as the raw material sodium hyaluronate in the above formula.

0.001-1% is preferable and, as for the compounding quantity of the said cationized hyaluronic acid and / or its salt in the container-packed liquid cosmetic of this invention, 0.001-0.5% is further more preferable. If the amount of cationized hyaluronic acid and / or salt thereof is less than the above range, it may not be possible to expect the effects of health and beauty, and if it is more than the above range, it is difficult to spray in a mist form from the spray container. In some cases, liquid droplets are ejected.

Although the container used for the container-packed liquid cosmetic for spraying of the present invention is not particularly limited as long as it can spray the container-packed liquid cosmetic for spraying in the form of a mist, the diameter of the injection nozzle is in the range of 0.1 to 2 mm. The container which sprays the content using press, such as a trigger type container, a pump type container, and an aerosol container, is mentioned. In particular, since the container-packed liquid cosmetic of the present invention can be easily sprayed without applying high pressure such as aerosol, a trigger type container or a pump type container is preferable. When the throat diameter of the injection nozzle is less than 0.1 mm, the liquid cosmetic may be clogged with the nozzle, and when it is more than 2 mm, the injection pressure may be lowered and the mist may not be injected.

The raw material hyaluronic acid and / or salt thereof used in the present invention is a raw material such as a culture solution obtained by culturing a biological tissue such as a chicken crown, umbilical cord, eyeball, skin, cartilage, or a hyaluronic acid-producing microorganism such as a microorganism belonging to the genus Streptococcus. As described above, it is obtained by extraction (further purification if necessary) from these raw materials.

The raw material hyaluronic acid and / or salt thereof used in the present invention may be either the crude extract or the purified product, but the purified product, specifically, the purity of the raw material hyaluronic acid and / or salt thereof is 90%. (Mass ratio) or more is preferable. When the purity of the raw material hyaluronic acid and / or its salt is less than 90% (mass ratio), there may be no expectation of the effects on health and beauty. The salt of hyaluronic acid is not particularly limited, but is preferably a pharmaceutically acceptable salt, and examples thereof include sodium salt, potassium salt, calcium salt, zinc salt, magnesium salt, ammonium salt and the like.

The average molecular weight of the raw material hyaluronic acid and / or salt thereof used in the present invention is not particularly limited as long as it is used as a cosmetic, and specifically, those having a molecular weight of 50,000 to 2,500,000 can be used.

The cationizing agent used in the present invention is not particularly limited as long as it has a quaternary ammonium group, but it is represented by the above general formula (A) in terms of ease of spraying from the spraying container. -Halogeno-2-hydroxypropyltrialkylammonium halide and 2,3-epoxypropyltrialkylammonium halide (glycidyltrialkylammonium salt) are preferable. Moreover, you may use a cationizing agent individually or in combination of 2 or more types.

The cationized hyaluronic acid and / or salt thereof used in the spray-packed liquid cosmetic of the present invention preferably includes a step of reacting the raw material hyaluronic acid and / or salt thereof with a cationizing agent in a basic water-containing medium. . According to the said method, the efficiency of a manufacturing process can be improved compared with the case where the raw material hyaluronic acid and / or its salt are dissolved in water and made to react with a cationizing agent, for example.

In the method for producing cationized hyaluronic acid and / or salt thereof used in the container-packed liquid cosmetic of the present invention, in the step of reacting raw material hyaluronic acid and / or salt thereof with a cationizing agent in a basic water-containing medium, The raw material hyaluronic acid and / or salt thereof is preferably reacted with a cationizing agent in a state dispersed in a basic water-containing medium. Here, the degree of cationization can be adjusted by adjusting the reaction conditions (time, temperature, etc.).

The container-packed liquid cosmetic for spraying according to the present embodiment is a range that does not impair the effects of the present invention other than cationized hyaluronic acid and / or a salt thereof, which is an essential raw material for the container-packed liquid cosmetic of the present invention. Can be appropriately selected and blended. Specifically, for example, higher alcohols, polyhydric alcohols, surfactants, polymer substances, pH adjusters, metal sequestering agents, antioxidants, ultraviolet absorbers, preservatives, anti-flame agents, amino acids, perfumes, coloring A material may be blended, and known materials can be widely used.

Next, the present invention will be described in more detail based on the following examples, comparative examples, and test examples. The present invention is not limited to these. The method described above was used for measuring the degree of cationization.

[Example 1] (Preparation of cationized hyaluronic acid and / or salt thereof)
In a 1 L beaker, 20 g of sodium hyaluronate (average molecular weight: about 1.9 million), 20 mL of 5% sodium hydroxide, 180 mL of 80% aqueous ethanol, and glycidyltrimethylammonium chloride (GTA (active ingredient about 80%, moisture about 20%) ) 30 mL was added and reacted for 1 hour at 40 ° C. with stirring using a stir bar.
Next, the liquid was removed by decantation to obtain a solid (including cationized hyaluronic acid).
Next, 400 mL of brine was added to dissolve the solid. After confirming that the solid was completely dissolved, 600 mL of ethanol was added to precipitate cationized hyaluronic acid and / or a salt thereof. After removing the liquid by decantation, 500 mL of 80% aqueous ethanol was added and stirred for 15 minutes, and the aqueous ethanol was then removed by decantation to obtain a precipitate. This operation was repeated three times to remove the cationizing agent (GTA) and salt remaining in the precipitate.
Next, the water-containing ethanol was further removed by performing a centrifugal separation treatment, followed by heat drying at 60 ° C. under reduced pressure for 5 hours using a vacuum dryer.
As a result, 20.5 g of cationized hyaluronic acid and / or a salt thereof was obtained as a white powder. The obtained cationized hyaluronic acid and / or salt thereof was dissolved in ion-exchanged water to prepare a 0.25% sample aqueous solution. In addition, the nitrogen content rate of the obtained cationized hyaluronic acid and / or its salt was measured, and the cationization degree calculated | required by the above-mentioned formula was 0.27.

[Example 2] (Preparation of cationized hyaluronic acid and / or salt thereof)
In a 1 L beaker, 20 g of sodium hyaluronate (average molecular weight: about 1.9 million), 20 mL of 5% sodium hydroxide, 180 mL of 65% aqueous ethanol, and glycidyltrimethylammonium chloride (GTA (active ingredient about 80%, moisture about 20%) ) 30 mL was added and reacted at 60 ° C. for 1 hour with stirring using a stir bar.
Next, the liquid was removed by decantation to obtain a solid (containing cationized hyaluronic acid and / or a salt thereof).
Next, 400 mL of brine was added to dissolve the solid. After confirming that the solid was completely dissolved, 600 mL of ethanol was added to precipitate cationized hyaluronic acid and / or a salt thereof. After removing the liquid by decantation, 500 mL of 80% aqueous ethanol was added and stirred for 15 minutes, and the aqueous ethanol was then removed by decantation to obtain a precipitate. This operation was repeated three times to remove the cationizing agent (GTA) and sodium chloride remaining in the precipitate.
Next, the water-containing ethanol was further removed by performing a centrifugal separation treatment, followed by heat drying at 60 ° C. under reduced pressure for 5 hours using a vacuum dryer.
As a result, 21.3 g of cationized hyaluronic acid and / or a salt thereof as white powder was obtained. The obtained cationized hyaluronic acid and / or salt thereof was dissolved in ion-exchanged water to prepare a 0.25% sample aqueous solution. In addition, the nitrogen content rate of the obtained cationized hyaluronic acid and / or its salt was measured, and the cationization degree calculated | required by the above-mentioned formula was 0.48.

[Example 3] (Preparation of cationized hyaluronic acid and / or salt thereof)
In the preparation method of the cationized hyaluronic acid and / or salt thereof in Example 2, the reaction was carried out in the same manner as in the preparation method of the cationized hyaluronic acid and / or salt thereof in Example 2, except that the reaction temperature was 50 ° C. The cationized hyaluronic acid and / or salt thereof of Example 3 was prepared.
As a result, 20.2 g of cationized hyaluronic acid and / or a salt thereof as white powder was obtained. The obtained cationized hyaluronic acid and / or salt thereof was dissolved in ion-exchanged water to prepare a 0.25% sample aqueous solution. In addition, the nitrogen content rate of the obtained cationized hyaluronic acid and / or its salt was measured, and the cationization degree calculated | required by the above-mentioned calculation formula was 0.33.

[Example 4] (Preparation of cationized hyaluronic acid and / or salt thereof)
The cationized hyaluronic acid and / or salt thereof of Example 2 except that the reaction temperature was 30 ° C. and the reaction time was 0.1 hour in the preparation method of the cationized hyaluronic acid and / or salt thereof of Example 2. The cationized hyaluronic acid and / or salt thereof of Example 4 was prepared in the same manner as in the preparation method.
As a result, 19.6 g of cationized hyaluronic acid and / or a salt thereof as white powder was obtained. The obtained cationized hyaluronic acid and / or salt thereof was dissolved in ion-exchanged water to prepare a 0.25% sample aqueous solution. In addition, the nitrogen content rate of the obtained cationized hyaluronic acid and / or its salt was measured, and the cationization degree calculated | required by the above-mentioned formula was 0.16.

[Comparative Example 1] (Preparation of cationized hyaluronic acid and / or salt thereof)
In the method for preparing the cationized hyaluronic acid and / or salt thereof of Example 2, 12 mL of 5% sodium hydroxide, 190 mL of 65% aqueous ethanol, and glycidyltrimethylammonium chloride (GTA (active ingredient about 80%, moisture about 20) %)) Was changed to 3 mL, and the cationized hyaluronic acid and / or salt thereof of Comparative Example 1 was prepared in the same manner as the preparation method of the cationized hyaluronic acid and / or salt thereof of Example 2.
As a result, 19.7 g of cationized hyaluronic acid and / or a salt thereof was obtained as a white powder. The obtained cationized hyaluronic acid and / or salt thereof was dissolved in ion-exchanged water to prepare a 0.25% sample aqueous solution. In addition, the nitrogen content rate of the obtained cationized hyaluronic acid and / or its salt was measured, and the cationization degree calculated | required by the above-mentioned calculation formula was 0.08.

[Test Example 1]
In order to investigate the sprayability from the container for spraying according to the degree of cationization, 40 mL of each of the 0.25% sample aqueous solutions of Examples 1 to 4 and Comparative Example 1 was put into a commercially available 50 mL pump spray container (nozzle diameter 0.3 mm). The product was sprayed at a product temperature of 25 ° C. so that the injection amount per injection was about 10 mL, and the sprayability from the spray container was evaluated according to the following criteria.

The evaluation of sprayability from the container for spraying was confirmed by visual inspection of the appearance, and the case of mist was A, the case of almost mist was B, and the case of droplet was C.

As shown in Table 1, when the degree of cationization was 0.15 to 0.6, the mist was sprayed from the spray container in a substantially mist form (Examples 1 to 4). In particular, when the degree of cationization was 0.2 to 0.6, it was sprayed in a mist form and exhibited very favorable properties (Examples 1 to 3). On the other hand, when the degree of cationization was less than 0.15, the liquid was sprayed from the spray container in the form of droplets, and the suitability as a spray container-packed liquid cosmetic was impaired (Comparative Example 1).

Example 5
In accordance with the usual method, the lotion which mix | blended the cationized hyaluronic acid and / or its salt obtained in Example 1 with the following prescription was prepared. 30 ml of the prepared lotion is filled in a commercially available 50 ml pump-type spray container (nozzle diameter 0.3 mm), and sprayed at a product temperature of 25 ° C. so that a single spray amount is about 10 ml. The sprayability from the container for spraying was evaluated on the basis.
Cationized hyaluronic acid and / or salt thereof (Example 1) 0.5 W / V%
Cetyl octoate 0.3W / V%
Octyl methoxycinnamate 0.15W / V%
Tocopherol acetate 0.1W / V%
EMALEX RWIS-158 2.0W / V%
(PEG-58 isostearic acid hydrogenated castor oil)
Eldew PS-306 0.5W / V%
(Lauroyl glutamate di (octyldodecyl / phytosteryl / behenyl))
Butylparaben 0.1W / V%
Methylparaben 0.2W / V%
1,3-butylene glycol 5.0 W / V%
Purified water remaining amount According to this test example, the container-packed lotion for spraying containing the cationized hyaluronic acid and / or salt thereof obtained in Example 1 is sprayed by applying pressure to the pump spray container. Was able to be injected.

Example 6
According to a conventional method, an after sun lotion was prepared by blending the cationized hyaluronic acid and / or salt thereof obtained in Example 2 with the following formulation. 150 mL of the prepared after sun lotion was packed into a commercially available 200 mL trigger spray container (0.4 mm nozzle diameter), and sprayed at a product temperature of 25 ° C. so that the injection amount per injection was about 10 mL. The sprayability from the container for spraying was evaluated according to the judgment criteria.
Cationized hyaluronic acid and / or salt thereof (Example 2) 0.4 W / V%
Ethanol 11.04W / V%
BG 4.16W / V%
Ougon extract appropriate amount stearyl alcohol 0.72W / V%
Avocado oil 0.72 W / V%
Stearic acid 0.02W / V%
Oryzanol appropriate amount polysorbate 0.23W / V%
PPG-6decyltetradeceth-20 0.2W / V%
Octoxynol-3 0.08W / V%
Methylparaben 0.14W / V%
Propylparaben 0.07W / V%
Carbomer 0.13W / V%
PVP proper amount potassium hydroxide 0.04W / V%
EDTA-2 sodium 0.01W / V%
Tocopherol Appropriate amount of purified water Remaining amount According to this test example, the after-packed after-sun lotion for spraying containing the cationized hyaluronic acid and / or salt thereof obtained in Example 2 gives pressure to the trigger type spraying container. Could be sprayed in the form of a mist.

From the above results, a containerized liquid cosmetic for spraying containing a cationized hyaluronic acid having a quaternary ammonium group-containing group and a cationization degree of 0.15 to 0.6 and / or a salt thereof, It can be said that the sprayability from the container for spraying is excellent.

Claims (3)

A containerized liquid cosmetic for spraying, characterized in that it contains a hyaluronic acid having a quaternary ammonium group-containing group and a cationization degree of 0.15 to 0.6 and / or a salt thereof. The container-packed liquid cosmetic for spraying according to claim 1, wherein the quaternary ammonium group-containing group is represented by the following general formula (A).
(A)
(In the formula, R ^{1 to} R ³ independently represent a hydrocarbon group, and X ⁻ represents a monovalent anion.) The containerized liquid cosmetic for spraying according to claim 1 or 2, wherein the cationized hyaluronic acid and / or a salt thereof is represented by a repeating structural unit of the following general formula (B).
(B)
(In the formula, R ^{4 to} R ⁹ independently represent a hydrogen atom or a quaternary ammonium group-containing group, except that R ^{4 to} R ⁹ all represent a hydrogen atom.)