JPH0552810B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is a cream or milky water-in-oil type (W/O type) emulsified cosmetic, more specifically, it has excellent storage stability, mechanical stability, and affinity for the skin. This invention relates to a water-in-oil type emulsion cosmetic in the form of cream or emulsion that gives a refreshing feeling when used. [Prior art] Conventionally, as a base for creams, etc., W/O emulsions, which contain water particles in oil, are generally better than O/W emulsions, which contain oil particles in water. It is said to be superior in many respects, such as protecting the skin and maintaining flexibility. However, W/O emulsions have some problems such as quality stability, and in order to improve their stability, they have been improved by increasing the amount of oil or increasing the viscosity. However, as a result, the cream has disadvantages such as being more sticky than necessary and oily. In addition, in order to improve oiliness, methods have been adopted to reduce the amount of oil and add moisturizers, but these methods are insufficient in terms of affinity for the skin and stickiness, and there is no satisfactory method. The current situation is that there is none. Therefore, in order to improve these drawbacks, we proposed a cream or milky water-in-oil emulsion cosmetic containing a water-soluble ascorbic acid derivative, a nonionic surfactant with an HLB value of 10 or less, liquid oil, and water. However, it was not necessarily sufficient in terms of storage stability (Patent Application No. 63-234193). As a result of intensive research to further improve this emulsified cosmetic, the present inventors found that glycyrrhizic acid or its salts, water-soluble alkorbic acid derivatives,
Nonionic surfactant with HLB value of 10 or less, liquid oil,
A cream or milky W/O type emulsion cosmetic containing water and water not only has excellent organoleptic properties like the aforementioned W/O type cream (Japanese Patent Application No. 53-234193). They discovered that the storage stability was further improved, and completed the present invention. [Problems to be Solved by the Invention] In other words, the object of the present invention is to provide a cosmetic product that has excellent mechanical stability and affinity for the skin, provides a refreshing feeling when used, and is also superior to conventional W/O type emulsified cosmetics. The object of the present invention is to provide a W/O type emulsified cosmetic with improved stability. [Means for Solving the Problems] The present invention provides a cream comprising glycyrrhizic acid or its salts, a water-soluble ascorbic acid derivative, a nonionic surfactant with an HLB value of 10 or less, liquid oil, and water. It is a water-in-oil type emulsified cosmetic in the form of oil or emulsion. The configuration of the present invention will be explained below. Examples of glycyrrhizic acid and its salts used in the present invention include 18α-glycyrrhizic acid,
18α-monosodium glycyrrhizinate, 18α-
Monopotassium glycyrrhizinate, 18α-dipotassium glycyrrhizinate, monoammonium 18α-glycyrrhizinate, 18β-glycyrrhizic acid, 18β
Particularly preferred examples include monosodium -glycyrrhizinate, monopotassium 18β-glycyrrhizinate, dipotassium 18β-glycyrrhizinate, monoammonium 18β-glycyrrhizinate, but the present invention is not limited thereto. The content of glycyrrhizic acid and its salts is 0.005 to 2.0% by weight based on the total weight of the composition,
More preferably, it is 0.05 to 1.0% by weight. If it is less than 0.005% by weight, the stability of the cosmetic composition tends to decrease, and if it exceeds 2.0% by weight, the stability tends to decrease, which is not preferable. Examples of water-soluble alkorbic acid derivatives used in the present invention include sodium salt of L-ascorbic acid phosphate, which is a monovalent metal salt of L-ascorbic acid phosphate, potassium salt of L-ascorbic acid phosphate, and divalent metal salt of L-ascorbic acid phosphate. L is a metal salt
- ascorbic acid phosphate magnesium salt, L-ascorbic acid phosphate calcium salt, trivalent metal salt L-ascorbic acid phosphate aluminum salt, and monovalent metal salt of L-ascorbic acid sulfate; L-ascorbic acid sulfate sodium salt, L-ascorbic acid sulfate potassium salt, divalent metal salt L-ascorbic acid sulfate magnesium salt, L-ascorbic acid sulfate calcium salt, trivalent metal salt L- Ascorbic acid sulfate aluminum salt, and monovalent metal salts of L-alcorbic acid such as sodium L-ascorbate and potassium L-ascorbate, divalent metal salts of L-ascorbate magnesium and L-alcorbic acid.
-Calcium ascorbate, trivalent metal salt aluminum L-ascorbate, etc. can be mentioned as preferred examples, but are not limited to these. The content of the water-soluble ascorbic acid derivative is 0.1 to 10% by weight, more preferably 1 to 5% by weight based on the total weight of the composition. If it is less than 0.1% by weight, the texture, appearance, such as gloss, and stability of the cosmetic will tend to deteriorate, and if it exceeds 10% by weight, the stability will tend to deteriorate, which is not preferable. Nonionic surfactants with an HLB value of 10 or less used in the present invention include, for example, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquistearate, sorbitan tristearate, and sorbitan tristearate. Monooleate, sorbitan sesquioleate, sorbitan trioleate, sorbitan monoisostearate, glyceryl monoisostearate, glyceryl monostearate, glyceryl monooleate for glycerin fatty acid esters, polyoxyethylene sol for polyoxyethylene esters Bithexastearate (6.E.0.), Polyoxyethylene Sorbitotetraoleate (6.E.0.), Polyoxyethylene Monostearate (1.E.0.), Poxyoxyethylene Monostearate (2.E.0.), Polyoxyethylene Monostearate (4.E.0.), Polyoxyethylene Monooleate (2.E.0.), Polyoxyethylene Cetyl Ether (2.E.0. ), polyoxyethylene stearyl ether (2.E.0.), polyoxyethylene stearyl ether (4.E.0.), polyoxyethylene oleyl ether (2.E.0.), polyoxyethylene nonylph enyl ether (2.E.0.), polyoxyethylene octyl phenyl ether (3.
E.0.), polyoxyethylene castor oil (3.E.0.),
Polyoxyethylene castor oil (10.E.0.), polyoxyethylene hydrogenated castor oil (5.E.0.), polyoxyethylene hydrogenated castor oil (10.E.0.), polyoxyethylene sorbitol Preferred examples include beeswax (6.E.0.), but are not limited thereto. Those having an HLB value of more than 10 are hydrophilic surfactants, which generally do not form W/O type emulsified cosmetics, and are not suitable here. However, even if the HLB value exceeds 10,
By combining with those with an HLB value of 10 or less, it can be used with an overall HLB value of 10 or less. Nonionic surfactants with an HLB value of 10 or less may be used alone or in combination of two or more. Its content is preferably 1 to 6% by weight, more preferably 1.5 to 5% by weight. Generally, if it is less than 1% by weight, emulsifying properties, stability, and appearance deteriorate, and if it exceeds 6% by weight, stability tends to deteriorate, which is not preferable. The liquid oils used in the present invention are oils that are liquid at room temperature, such as hydrocarbons (liquid paraffin, squalane), liquid synthetic ester oils (isopropyl myristate, isopropyl palmitate, octyldodecyl myristate). ), vegetable oils (olive oil, soybean oil, rice bran oil, cottonseed oil, etc.). However, it is not limited to these. Liquid oils may be used alone or in combination of two or more. Its content is preferably 5 to 40% by weight, more preferably 10 to 30% by weight. Generally, if it is less than 5% by weight, it will not spread well during use, and if it exceeds 40% by weight, it will tend to soften easily. The water used in the present invention is generally purified water such as ion exchange water. The water content is preferably 40 to 80% by weight, more preferably 50 to 70% by weight. If it is less than 40% by weight, the refreshing feeling during use will be poor and the affinity for the skin will be poor. If it exceeds 80% by weight, the emulsifying property and the appearance of the cosmetic may deteriorate, which is not preferable. In addition to the above-mentioned ingredients, the emulsified cosmetic of the present invention includes:
Raw materials commonly used in cosmetics, such as fragrances, preservatives, humectants, pigments, and ultraviolet absorbers, can be appropriately blended within the range that achieves the purpose of the present invention. The W/O type emulsified cosmetic of the present invention can be easily produced industrially, for example, by the production method (preparation method) described below. A mixed composition containing a nonionic surfactant with an HLB value of 10 or less and a liquid oil, and an aqueous solution containing glycyrrhizic acid and its salts and a water-soluble ascorbic acid derivative are mixed by stirring. The temperature of the mixed composition containing a nonionic surfactant and liquid oil when stirring is about 70°C, and the temperature of the aqueous solution of a water-soluble ascorbic acid derivative when stirring is about 50°C. When using moisturizers, fragrances, ultraviolet absorbers, preservatives, and pigments, use a mixture consisting of a nonionic surfactant with an HLB value of 10 or less and a liquid oil, or a mixture containing glycyrrhizic acid and its salts and a water-soluble ascorbic acid derivative. Operationally, it is preferable to include it in an aqueous solution. When stirring and mixing the above-mentioned mixture and an aqueous solution, use a normal mixer such as a homomixer or an emulsifying device, stir and mix the main components while heating them to 40-85℃, and after emulsifying, gradually Cool to room temperature. Appropriate amounts of fragrances and the like are added during this cooling process. The emulsified cosmetic composition of the present invention can be used in various cream-like or emulsion-like products such as protective creams, skin creams, hand creams, foundation creams, skin milks, and sunscreens. (Example) Examples will be described below. In the Examples, parts refer to parts by weight, and % refers to % by weight. The methods for the storage stability test and sensory property test described in the Examples are as follows. (1) Storage stability test Place the sample in a constant temperature bath at 45℃ and observe the emulsification state and appearance after leaving it for 10 days. If any abnormality is observed (if oil separates, if particles become coarse) If an abnormality is observed after being left for 1 month, it is represented by ×. If an abnormality is found after being left for 3 months, it is represented by △. If an abnormality is found after being left for 5 months, it is represented by ○, and if it is left unused for 6 months. If no abnormalities are observed (if the emulsification state is uniform and a homogeneous emulsion is formed), ◎
It was expressed as (2) Sensory properties during use 20 subjects used the sample for 10 days and then evaluated the properties of the sample. The test results were ``Good spread during application'' for test items such as spreadability, viscosity, and affinity.
It is indicated by the number of people who answered that it did not have a sticky or slimy feel and that it had good affinity with the skin. Examples 1 to 36, Comparative Examples 1 to 5 [Protective cream] As shown in the composition below, the type and amount of surfactant and the type and amount of water-soluble ascorbic acid derivative are as shown in Table 1. , each W/O type protective cream was prepared and the various tests described above were conducted. (1) Composition

[Table] (2) Preparation method (A) was uniformly dissolved at 70℃ and (B) at 50℃, and while stirring (A), (B) was poured into (A) to emulsify and disperse. After that, it is prepared by cooling to a temperature of 30°C while stirring. However, when monoammonium glycyrrhizinate is used as the glycyrrhizinate, the monoammonium glycyrrhizinate should be heated at 80°C.
After dissolving in purified water and cooling to 50℃,
Dissolve methyl paraoxybenzoate, a water-soluble ascorbic acid derivative. (3) Characteristics Table 1 shows the results of testing the various characteristics of each Example and Comparative Example.

【table】

【table】

【table】

[Table] As shown in Table 1, HLB is used as a surfactant.
Comparative Example 1 using a nonionic surfactant with a value higher than 10 had poor storage stability and sensory characteristics, and Comparative Example 2 using sodium cetyl sulfate, an anionic surfactant, also had poor storage stability and sensory characteristics. bad. Furthermore, as is clear from Comparative Example 3, the storage stability is slightly inferior when L-ascorbate is not contained, and furthermore, as is clear from Comparative Example 4, there are cases where 18α-glycyrrhizic acid and its salts are not contained. , storage stability is slightly inferior. Furthermore, as is clear from Comparative Example 5, when no surfactant is contained, the storage stability is poor and the organoleptic properties are also poor. On the other hand, an example of the present invention using 1 to 6% by weight of a nonionic surfactant with an HLB value of 10 or less, 0.005 to 2.0% by weight of glycyrrhizic acid or its salt, and 0.1 to 10% by weight of a water-soluble ascorbic acid derivative as emulsifier components. 1 to 36 have excellent storage stability and sensory properties. Example 37 (Skin cream) (1) Composition

[Table] (2) Preparation method Monoammonium 18β-glycyrrhizinate
Dissolve in purified water at 80℃, and when the temperature of the solution drops to 50℃, add the remaining component (B) and disperse uniformly. Disperse (A) uniformly at 70°C, and while stirring (A), pour (B) into (A) to emulsify and disperse it, then add (C) and cool to 30°C while stirring. Prepare. (3) Characteristics In a sensory test conducted by 20 subjects, 17 people answered that the product felt refreshing when used. The skin cream thus obtained is W/O
A molded emulsion with a fine texture and good appearance.
It also had good water repellency and remained extremely stable even when stored indoors at 45°C for 6 months. Example 38 (hand cream) (1) Composition

[Table] (2) Preparation method Monoammonium 18β-glycyrrhizinate
Dissolve in purified water at 80℃, and when the temperature of the solution drops to 50℃, add the remaining component (B) and disperse uniformly. Melt (A) uniformly at 70℃, pour (B) into (A) while stirring and emulsify and disperse component (C).
Prepare by adding and cooling to a temperature of 30℃ while stirring. (3) Characteristics In a sensory test conducted by 29 test subjects, 17 people answered that the product felt refreshing when used. The hand cream thus obtained is W/O
It was a type emulsion and remained extremely stable even when stored indoors at 45°C for 6 months. Example 39 (Foundation Cream) (1) Composition

【table】

[Table] (2) Preparation method Disperse (A) uniformly at 75℃ and (B) at 50℃, then pour (B) into (A) while stirring (A) to emulsify and disperse. , (C) is added and cooled to a temperature of 30°C while stirring. (3) Characteristics In a sensory test conducted by 20 subjects, 19 people answered that the product felt refreshing when used. The foundation cream thus obtained is a W/O emulsion with a fine texture and good appearance. It also had good water repellency, excellent makeup retention, and was extremely stable even when stored indoors at 45°C for 6 months. Example 40 (Skin milk) (1) Composition

【table】

[Table] (2) Preparation method Monoammonium 18α-glycyrrhizinate
Dissolve in purified water at 80℃, and when the temperature of the solution drops to 50℃, add the remaining component (B) and disperse uniformly. Dissolve (A) uniformly at 70℃, pour (B) into (A) while stirring and emulsify and disperse component (C).
Prepare by adding and cooling to a temperature of 30℃ while stirring. (3) Characteristics In a sensory test conducted by 20 subjects, 17 people answered that the feeling of use was refreshing. The skin milk obtained in this way is a W/O type emulsion (viscosity is 7000 cps at room temperature).
It remained extremely stable even when stored indoors at ℃ for 6 months. Example 41 (Sunscreen cream) (1) Composition

[Table] (2) Preparation method Dissolve or disperse (A) uniformly at 70℃ and (B) at 50℃, and while stirring (A), pour (B) into (A) to emulsify. After that, add (C) and cool to 30°C while stirring to prepare. (3) Characteristics In a sensory test conducted by 20 subjects, 19 people answered that the product felt refreshing when used. The sunscreen cream thus obtained was a W/O type emulsion, had a fine appearance, had good water repellency, and was extremely stable even when stored indoors at 45°C for 6 months. Example 42 (Sunscreen milk) (1) Composition

【table】

〔Effect of the invention〕

As described above, the emulsified cosmetic of the present invention is a W/O type emulsion that exhibits a fine and homogeneous appearance, does not have excessive stickiness or oiliness, and provides a refreshing feeling when used. In addition, it has the property of being easily compatible with the skin, and is also considerably superior in terms of storage stability compared to conventional W/O type creams.

Claims (1)

[Claims] 1. A water-in-oil emulsion in the form of a cream or milky liquid, characterized by containing glycyrrhizic acid or its salts, a water-soluble ascorbic acid derivative, a nonionic surfactant with an HLB value of 10 or less, liquid oil, and water. Cosmetics.