JP2002060315A - Ascorbic acid-containing thickening composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ascorbic acid derivative-containing thickening composition having excellent thickening properties, stability and sense of use by using an ionic thickener. SOLUTION: This ascorbic acid derivative-containing thickening composition is characterized in that the composition comprises ascorbic acid, its salt or its derivative and a carboxyvinyl polymer and the molecular weight of the carboxyvinyl polymer is 200,000-250,000. Preferably, the carboxyvinyl polymer shows about 11,000 cps viscosity value in 0.5% potassium hydroxide neutralization solution when measured by using a single cylindrical rotational viscometer under conditions at 12 rpm at 30 deg.C. Preferably, xanthan gum is also used as a thickener.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thickening composition containing ascorbic acid, and more particularly to an improvement of a thickener.

[0002]

2. Description of the Related Art Ascorbic acid is the most typical melanin production inhibitor and has been widely used in cosmetics and skin external preparations since ancient times due to its high safety. In recent years, various derivatives have been developed for the purpose of improving stability, and these derivatives have been used in many cases.

Many of the ascorbic acid derivatives have significantly improved stability as compared to ascorbic acid alone. However, during long-term storage, the decomposition occurs slowly, but free ascorbic acid is formed. Then, the pH of the system decreases. For this reason, in a composition containing ascorbic acid or an ascorbic acid derivative, a salt such as an organic acid, an organic base, an inorganic acid, or an inorganic base is generally used as a buffer to prevent a decrease in pH. Ascorbic acid and its derivatives are often in the form of salts.

On the other hand, thickeners are widely used in cosmetics and external preparations for the skin in order to enhance the dispersion stability, emulsion stability, usability and the like. Thickeners are broadly classified into ionic thickeners such as carboxyvinyl polymer and sodium carboxymethylcellulose, and nonionic thickeners such as xanthan gum and bentonite, but ionic thickeners in systems containing salts The effect of the thickening effect is reduced, and problems such as deterioration of product stability are likely to occur.
Therefore, when a thickener is used in a composition containing ascorbic acid, a salt thereof, or a derivative thereof, a nonionic thickener is generally used.

[0005]

However, an external preparation for skin containing a nonionic thickener has a bad feeling of use, such as stickiness and a slimy feeling, and the thickening effect is reduced to that of an ionic thickener. In order to obtain a desired thickening effect because of its relatively small size, there has been a problem that a large amount of compounding is required and stability with time is poor. On the other hand, although the ionic thickener is greatly affected by the salt, it has a good feeling in use, and the thickening effect is obtained with a small amount, and even in a system containing a salt such as an ascorbic acid derivative-containing composition. It has been desired to use such an ionic thickener.

The present invention has been made in view of the above-mentioned problems of the prior art, and the object of the present invention is to use a ionic thickener to achieve good viscosity and stability even though the system contains a salt. And to provide an ascorbic acid-containing thickening composition having usability.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to achieve the above object, certain carboxyvinyl polymers conventionally used as ionic thickeners have been developed. Found that even in a system containing ascorbic acid or a derivative thereof, the decrease in the thickening action was small, the usability was good, and the obtained composition had excellent stability over time. In addition, it was found that when the carboxyvinyl polymer and xanthan gum were used in combination with the ascorbic acid-containing composition, the thickening effect was improved as compared with the case where the carboxyvinyl polymer was used alone, and the stability with time was also good. The invention has been completed.

That is, the thickening composition containing ascorbic acid according to claim 1 of the present invention contains ascorbic acid or a salt thereof or an ascorbic acid derivative and a carboxyvinyl polymer, and the carboxyvinyl polymer has a molecular weight of 200. 2,000 to 250,000. The carboxyvinyl polymer had a viscosity value of about 11,000 cps with a 0.5% potassium hydroxide neutralized solution when measured using a single cylindrical rotary viscometer at 12 rpm and 30 ° C. Preferably, it is as shown. It is preferred that the composition of the present invention further contains xanthan gum.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described below in detail. Ascorbic acid, a salt thereof, and an ascorbic acid derivative used in the ascorbic acid-containing thickening composition according to the present invention may be those commonly used in cosmetics and pharmaceuticals. For example, ascorbic acid may be L-ascorbic acid. An acid is mentioned, and its salt includes a sodium salt, a potassium salt, a calcium salt, a magnesium salt and the like. As ascorbic acid derivatives, for example, ascorbic acid glycosides such as 2-O-α-D-glucopyranosyl-L-ascorbic acid, dl-α-tocopherol 2-L-ascorbic acid phosphoric acid diester potassium salt, L-ascorbic acid- Examples thereof include esters such as 2-sodium sulfate and magnesium ascorbic acid phosphate. In the present invention, one or more of these ascorbic acids, salts thereof, and ascorbic acid derivatives can be used. The amount of the ascorbic acid derivative to be blended is not particularly limited as long as it is within a range usually used for cosmetics and pharmaceuticals.

The carboxyvinyl polymer used in the present invention is mainly a polymer of acrylic acid,
Various grades are commercially available. The carboxyvinyl polymer used in the present invention has a molecular weight of 200,
2,000 to 250,000 and acrylic acid is not neutralized. A 0.5% potassium hydroxide neutralized solution (specifically, an aqueous solution containing 0.5% by weight of a carboxyvinyl polymer and an excess equivalent of potassium hydroxide) has a viscosity value of about 11,000 cps (a single solution). 12 rpm, 30 ° C. using a cylindrical rotational viscometer (Bismetron BL type)
Is the value measured in). Specifically, Hibiswako 1
05 (manufactured by Wako Pure Chemical Industries, Ltd.) is preferred. If the molecular weight is too large or the viscosity value is too high, the reduction of the thickening action by the salt will be large, and it will be difficult to obtain the desired thickening effect no matter how much the amount is increased. The amount of the carboxyvinyl polymer blended in the composition of the present invention can be appropriately adjusted and blended to obtain a desired thickening effect. Further, the mixing ratio of ascorbic acid or a derivative thereof to the carboxyvinyl polymer is preferably 1: 3 to 25: 1 by weight.

In the present invention, the carboxyvinyl polymer is neutralized by an alkali agent to increase the viscosity of the system.
The alkali agent is not particularly limited as long as it is an alkali agent usually used for neutralization, such as sodium hydroxide, potassium hydroxide, and monoethanolamine. Further, in the ascorbic acid-containing thickening composition of the present invention, for the purpose of preventing the pH of the product from decreasing and the like, it can contain a buffer usually used for cosmetics and external preparations for the skin.
For example, organic acids such as citric acid and oxalic acid, organic bases such as sodium citrate and potassium oxalate, inorganic acids such as hydrochloric acid and phosphoric acid, and inorganic bases such as sodium hydroxide and sodium dihydrogen phosphate are used.

The composition of the present invention may contain other components, which are generally used in cosmetics, quasi-drugs, pharmaceuticals and the like, as required, in addition to the above components. Examples include aqueous components, alcohols, oily components, surfactants, humectants, preservatives, antioxidants, chelating agents, fragrances, coloring agents, ultraviolet absorbers, medicinal components and the like.

The ascorbic acid-containing thickening composition of the present invention may contain a thickener other than the carboxyvinyl polymer as long as the effects of the present invention are not impaired. In particular, xanthan gum, which is a nonionic thickener, shows excellent thickening when used alone in an ascorbic acid derivative-containing composition, but has very poor temporal stability. However, when xanthan gum is used in combination with the carboxyvinyl polymer of the present invention, a thickening composition having an improved thickening effect of the carboxyvinyl polymer and having good stability over time can be obtained. Specific examples of xanthan gum include, for example, Celtrol (manufactured by Kelco). The mixing ratio of the carboxyvinyl polymer to the xanthan gum is preferably 6: 1 to 1: 6 by weight.

The thickening composition containing ascorbic acid according to the present invention can be applied in a wide range such as a solubilizing system, an emulsifying system and a dispersing system, and the dosage form can be arbitrarily selected. For example, dosage forms such as emulsion, cream, gel and the like can be mentioned, and they can be suitably used in the fields of cosmetics, pharmaceuticals and the like. Hereinafter, the present invention will be further described with reference to specific examples, but the present invention is not limited thereto. In addition, the following compounding amounts are shown by weight% unless otherwise specified.

[0015]

[Table 1]  Composition Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3  L-ascorbic acid 1.5 1.5 1.5 1.5 1.5 1.5 Sodium citrate 0.45 0.45 0.45 0.45 0.45 0.45 citric acid 0.05 0.05 0.05 0.05 0.05 0.05 Hi-Phiswaco 105 * 0.8 0.6 0.4---Hi-Phiswako 104 **---0.6 0.4-Xanthan cam- − − − − 1.5 Potassium hydroxide 0.47 0.46 0.45 0.46 0.45 0.40 Purified water Residue Residue Residue Residue Residue Residue  Viscosity [cps / 30 ℃]-When not contained 16,000 13,000 8,000 370,000 * 93,000 * 2,000-When contained 8,000 5,000 2,500 2,000 1,500 16,000 Stability ○ ○ ○ ○ ○ × Usability ○ ○ ○ ○ ○ ×  * Hibiswako 105: carboxyvinyl polymer (molecular weight 200,000 to 250,000) ** Hibiswako 104: carboxyvinyl polymer (molecular weight 250,000 to 300,000)

In accordance with the formulation shown in Table 1, Examples 1-3 containing L-ascorbic acid, a buffering agent and one of the following as thickeners (using potassium hydroxide as a neutralizing agent): The test liquids of Examples 1 to 3 were prepared according to a conventional method, and the viscosity, stability, and usability were evaluated. Also,
Test solutions not containing the above-mentioned (L-ascorbic acid and buffer) were also prepared, and the viscosity was measured. In addition,
The viscosity is measured by a single-type rotational viscometer (Bismetron BL type) at a rotation speed of 12 rpm and at 30 ° C. It is a value measured at a rotation speed of 10 rpm and 30 ° C. with a rotational viscometer (Bismetrone BH type).

For the feeling of use, each test solution was applied to the back of the hand and examined for stickiness or sliminess.
Regarding the stability, changes in the appearance when each test solution was stored at 50 ° C. for 2 weeks were observed. As a result, as can be seen from Table 1, in the system using hibiswako 104 as a carboxyvinyl polymer as a thickener (Comparative Examples 1 and 2), the thickening effect was not obtained when ascorbic acid and a buffer were not contained. Is extremely high, but when these are contained, the thickening effect is drastically reduced, and the thickening effect is hardly exhibited.

On the other hand, when xanthan gum which is a nonionic thickener was used as a thickener (Comparative Example 3), the thickening effect was remarkably increased by the presence of a salt, but the stability was poor.
Separation occurred upon storage at 50 ° C. for 2 weeks. Further, when applied to the skin, a slimy feeling peculiar to the nonionic thickener was felt.

On the other hand, when Hibiswako 105 is used even with the same carboxyvinyl polymer as in Examples 1 to 3, the viscosity of the system containing the ascorbic acid derivative and the buffering agent is not significantly reduced, and especially the system containing hibis When Wako 105 is added in an amount of 0.6% by weight or more,
It became clear that a high viscosity value of 000 cps or more was obtained, and a sufficient thickening effect was exhibited. Further, the test liquids of Examples 1 to 3 had good stability, and no separation or turbidity was observed. Further, the feeling of use was good without stickiness or sliminess, and no change in pH or viscosity was observed.

From the above, it can be understood that Hibiswako 105 is less affected by a salt such as ascorbic acid or a buffer on the thickening effect than Hibiswako 104, and the thickening effect is hardly reduced. Such a tendency was also observed in various ascorbate and ascorbic acid derivatives. Therefore, in the ascorbic acid-containing composition of the present invention, by using a specific type of carboxyvinyl polymer among the ionic thickeners, it is possible to obtain a sufficient thickening effect, and excellent use feeling and product stability. it can.

As a result of further studies by the present inventors, xanthan gum, which had an increased thickening effect in Table 1 but had poor stability over time, was used together with a carboxyvinyl polymer in an ascorbic acid-containing composition. As shown in the above, it was also found that a thickening composition in which the thickening effect was further improved as compared with the case of using a carboxyvinyl polymer alone, and which was excellent in stability over time was obtained.

[0022]

[Table 2]  Composition Example 4 Example 5 Comparative Example 4  L-Ascorbic acid 1.5 1.5 1.5 Sodium citrate 0.45 0.45 0.45 Citric acid 0.05 0.05 0.05 Hibiswako 105 1.35 0.75-Xanthan gum-0.60 1.35 Potassium hydroxide 0.50 0.47 0.40 Purified water Residual Residual  Viscosity [cps / 30 ℃]-When not contained 28,300 16,500 290-When contained 9,800 17,900 15,300 Stability ○ ○ × Usability ○ ○ ×

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described, but the present invention is not limited thereto. In addition, the following compounding amounts are shown by weight% unless otherwise specified.

[0024]Example 6 Daytime emulsion  A: oil phase behenyl alcohol 1.0% by weight silicon KF56 5.0 pentaerythritol-2-ethylhexanoate 5.0 POE (5) glycerin monostearate 1.5 POE (60) glycerin monostearate 1.5 octyl Methoxycinnamate 5.0 4-tert-butyl-4'-methoxybenzoylmethane 2.0 Preservatives Appropriate Chelating agent Appropriate Fragrance Appropriate B: Aqueous phase 95% Brusin denatured alcohol 10.0 Dipropylene glycol 7.0 Chondroitin sodium sulfate 0.2 Singhong Guinisin LV 0.1 Hibiswako 105 0.4 Potassium hydroxide 0.65 L-ascorbic acid 1.5 Sodium citrate 0.45 Citric acid 0.05 Ion exchange water Remainder

[0025]Example 7 Daytime emulsion  A: Oil phase Bacyl alcohol 1.0% by weight Silicon KF56 4.0 Pentaerythritol-2-ethylhexanoate 5.0 POE (5) glycerin monostearate 2.0 POE (60) glycerin monostearate 1.0 Behenic acid 0.6 stearic acid 0.2 isostearic acid 0.2 octyl methoxycinnamate 3.0 4-tert-butyl-4'-methoxybenzoylmethane 1.0 2-hydroxy-4-methoxybenzophenone 1.0 di- Paramethoxycinnamic acid-glyceryl mono-2-ethylhexanoate 1.0 Preservatives Appropriate Chelating agent Appropriate Fragrance Appropriate B: Water phase Dynamite glycerin 5.0 Dipropylene glycol 5.0 1,3-butylene glycol 4 0.0 Sodium chondroitin sulfate 0.3 Singhong Guinisin LV 0.2 Hibiswa Co 105 0.3 Potassium hydroxide 0.7 2-O-α-D-glucopyranosyl-L-ascorbic acid 1.0 Sodium citrate 0.45 Citric acid 0.05 Deionized water balance

[0026]Example 8 Emulsion  A: Oil phase Vaseline 2.0% by weight Behenyl alcohol 1.0 Bacyl alcohol 1.0 Liquid paraffin 4.0 CIO 3.0 Silicon KF56 5.0 POE (60) Glycerin monostearate 2.0 POE (5) Glycerin mono Stearate 1.5 Preservatives Appropriate Fragrance Appropriate B: Aqueous phase Dynamite glycerin 5.0 1,3-butylene glycol 5.0 Brucine-denatured ethanol 95% 5.0 Hibiswako 105 0.2 Keltrol (xanthan gum) 0 .25 Potassium hydroxide 0.57 Magnesium phosphate ascorbate 4.0 Sodium citrate 0.45 Citric acid 0.05 Chelating agent Appropriate ion exchange water balance

[0027]Example 9 Emulsion  A: oil phase petrolatum 2.0% by weight behenyl alcohol 1.0 liquid paraffin 8.0 CIO 8.0 silicon KF26 5.0 POE (60) glycerin monostearate 2.5 POE (5) glycerin monostearate 2.0 Preservatives Appropriate Perfume Appropriate B: Aqueous Dynamite Glycerin 5.0 1,3-butylene glycol 8.0 Brucine-denatured ethanol 95% 2.0 Hibiswako 105 0.2 Celtrol (xanthan gum) 0.25 Potassium hydroxide 0.57 dl-α-tocopherol 2-L-ascorbic acid phosphoric acid diester potassium salt 0.2 sodium citrate 0.45 citric acid 0.05 chelating agent as appropriate ion-exchanged water balance

[0028]Example 10 Daytime emulsion  A: oil phase behenyl alcohol 1.0% by weight batyl alcohol 0.3 silicon KF56 2.0 pentaerythritol-2-ethylhexanoate 5.0 POE (5) glycerin monostearate 1.5 POE (60) glycerin monostearate Rate 2.0 Octyl methoxycinnamate 2.0 4-tert-butyl-4'-methoxybenzoylmethane 2.0 Preservatives Appropriate Chelating agent Appropriate Flavor Appropriate B: Aqueous phase 95% brucine denatured alcohol 5.0 di Propylene glycol 3.0 Sodium chondroitin sulfate 0.3 Singhhongginisin LV 0.2 Hibiswako 105 0.4 Ketorol 0.25 Potassium hydroxide 0.02 Magnesium ascorbate phosphate 3.0 Sodium citrate 0.5 Citric Acid 0.1 Deionized water residue

[0029]Example 11 Daytime emulsion  A: Oil phase Cetyl alcohol 1.5% by weight Silicone KF56 5.0 Pentaerythritol-2-ethylhexanoate 5.0 POE (5) glycerin monostearate 2.0 POE (60) glycerin monostearate 1.5 Behenic acid 0.6 stearic acid 0.2 isostearic acid 0.2 4-tert-butyl-4'-methoxybenzoylmethane 1.0 2-hydroxy-4-methoxybenzophenone 2.0 di-paramethoxycinnamic acid -mono Glyceryl-2-ethylhexanoate 3.0 3-Methyl 3,4,5-trimethoxycinnamate-4- [methylbis (trimethylsiloxy) silyl] butyl 1.0 Preservatives Suitable Chelating Agents Suitable Flavors Suitable B: Aqueous phase dynamite glycerin 5.0 dipropylene glycol 5.0 1,3-butylene glycol 4.0 chondroitin sulfate Thorium 0.3 Singhong Guinisin LV 0.2 Hibiswako 105 0.3 Potassium hydroxide 0.255 DL-α-Tocopherol-L-ascorbic acid 0.2 Sodium citrate 0.09 Citric acid 0.01 Ion exchange water Remaining

[0030]Example 12 Cream  A: Oil phase Cetanol 2.0% by weight Vaseline 2.0 Squalane 20.0 Glycerin mono fatty acid ester 3.0 Tween 60 3.0 (POE (80) sorbitan monostearate) Isopropyl myristate 6.0 Stearyl glycyrrhetinate Glyceryl mono 2-ethylhexanoyl-diparamethoxycinnamate 0.05 4-methoxy-4'-butyldibenzoylmethane 0.05 Licorice extract 0.01 BHT 0.01 Preservatives Appropriate Fragrance Appropriate B: Aqueous phase glycerin 10.0 Propylene glycol 5.0 Hibiswako 105 0.5 Ketorol 3.0 Magnesium phosphate ascorbate 0.5 Trisodium edetate 0.1 Potassium hydroxide 1.0 Distilled water balance

[0031]Example 13 Transparent essence  Propylene glycol 1.0% by weight Glycerin 1.0 Hibiswako 105 0.2 Celtrol 0.1 Potassium hydroxide 0.4 Trisodium edetate 0.05 Magnesium ascorbate 1.0 Distilled water Balance

[0032]Example 14 translucent essence  A: Oil phase Squalane 0.5% by weight Diglycerin diisostearate 1.0 POE hydrogenated castor oil 1.0 Licorice extract 0.05 BHT 0.01 Preservative 0.2 Fragrance 0.1 B: Water phase Propylene glycol 1.0 Dipropylene glycol 2.0 Alcohol 5.0 2-O-α-D-Glucopyranosyl-L-ascorbic acid 1.0 Trisodium edetate 0.05 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid Salt 0.3 Hibiswako 105 0.3 Celtrol 0.05 Potassium hydroxide 0.3 Distilled water Residue

When the compositions of Examples 6 to 14 were prepared according to a conventional method, none of the compositions had a problem in the emulsion stability, pH stability, viscosity stability and the like over time. In addition, there was no stickiness or slimy feeling, and the usability was good.

[0034]

The thickening composition containing ascorbic acid according to the present invention has a sufficient thickening effect by using a specific kind of carboxyvinyl polymer which is an ionic thickener, even though it is a system containing a salt. , Excellent use feeling and product stability can be obtained. Further, by using xanthan gum in combination with the composition, it is possible to further improve the thickening effect without lowering the stability over time.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hiroyoshi Sato 1050 Nippa-cho, Kohoku-ku, Yokohama-shi, Kanagawa F-term in Shiseido Daiichi Research Center (reference) 4C083 AA112 AB032 AC012 AC072 AC102 AC122 AC172 AC212 AC242 AC302 AC352 AC422 AC432 AC442 AC532 AC792 AD091 AD092 AD152 AD202 AD342 AD351 AD352 AD532 AD641 AD642 CC01 CC04 CC05 EE01 EE06

Claims (3)

[Claims] 1. A carboxyvinyl polymer comprising ascorbic acid or a salt thereof, or an ascorbic acid derivative, and a carboxyvinyl polymer having a molecular weight of 20.
An ascorbic acid-containing thickening composition having a molecular weight of 0000 to 250,000. 2. The composition according to claim 1, wherein the carboxyvinyl polymer is measured at 12 rpm and 30 ° C. using a single cylinder rotational viscometer.
About 11,000 cps with 0.5% potassium hydroxide neutralized solution
A thickening composition containing ascorbic acid, which has a viscosity value of: 3. The composition according to claim 1, wherein
An ascorbic acid-containing thickening composition further comprising xanthan gum.