JPS6323963B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is directed to a novel compound, 18α-glycyrrhizin (described later), which is obtained by isomerizing ordinary glycyrrhizin (18β-glycyrrhizin, described later, which is an extracted component from licorice) (Japanese Patent Application Laid-open No. 115797/1983).
The present invention relates to an emulsion-like (cream-like or milky lotion-like) cosmetic prepared by emulsifying an oily substance by using a specific composition consisting of 18β-glycyrrhizin and 18β-glycyrrhizin as an emulsifier. Conventional glycyrrhizin (glycyrrhizinic acid or its sodium salt, potassium salt, ammonium salt as described in "Cosmetic Raw Materials Standards", Japanese Patent Publication No. 45-21397, and Japanese Patent Application Laid-open No. 54-92633) has the following formula:
It has the structure (2), and its aqueous solution has a pH of 2.5 to 5.8.
It shows the specificity that gelation (coagulation) occurs within the range of . Gel-like (solid) skin cosmetics (Japanese Patent Publication No. 45-21397) that utilize this gelation phenomenon are well known. However, (1) the gel has poor fluidity and is difficult to adhere to fingertips, making it difficult to remove it from a container (bottle, etc.). (2) Even when the gel is pressed with fingertips or the palm of the hand, it is difficult to break down (liquefy) uniformly and is slippery, making it difficult to apply to the skin. (3) When a gel (product) is stored for a long period of time, the water in the gel separates (plasma), resulting in a significant decrease in stability and appearance. (4) Air bubbles generated during the manufacturing (blending) process remain in the gel (product) and are difficult to defoam, resulting in a poor appearance of the product. Because of these drawbacks, gel skin cosmetics have not yet been commercialized (practical). Furthermore, for example, conventional glycyrrhizin (18β-glycyrrhizin) described in JP-A No. 54-92633
In addition to the drawback of causing gelation in an acidic aqueous system with a pH of 5.5 or lower, the aqueous solution also has the drawback of being difficult to defoam for a long time once foamed. Especially for emulsified cosmetics that use large amounts of oily substances, the emulsifying power is relatively weak.
Even if 18β-glycyrrhizin is used, it is difficult to obtain cosmetics with high emulsion stability. In order to improve these drawbacks, it is known to use water-soluble polysaccharides such as pectin in combination, but in the coexistence of water-soluble polymers such as pectin, foaming tends to occur more easily.
Moreover, since the entire system exhibits remarkable structural viscosity, it must be manufactured while carefully degassing under reduced pressure. In particular, production under reduced pressure degassing requires a precise vacuum control device and skilled operating techniques, and mass production is quite difficult. On the other hand, many synthetic solubilizers (synthetic surfactants) have skin irritation properties, making them difficult to use in skin cosmetics and difficult to design formulations. In order to improve the drawbacks of the prior art, the present inventors have conducted intensive research and have developed a glycyrrhizin composition (a new composition developed by the present inventors) consisting of specific 18α-glycyrrhizin and 18β-glycyrrhizin described below: (described in Japanese Patent Application Laid-open No. 113793/1983),
When applied as an emulsifier for oily substances, any PH
Even under certain conditions, there is no gelation or reduction in emulsifying power, and there is no need to perform vacuum degassing during production.
The present invention was completed by discovering that high-quality emulsified cosmetics as described below can be produced industrially easily and advantageously. The purpose of the present invention is to act mildly without irritating the skin, provide a good feeling, and have excellent fluidity, usability, antifoaming properties, storage stability, and a good appearance. (skin eyes,
The purpose of the present invention is to provide a cream or milky lotion cosmetic with good glossiness. Another object of the present invention is to provide a novel emulsifier composition. Still another object is to provide an acidic emulsified cosmetic that can be easily and advantageously produced industrially without the use of synthetic surfactants, with easy compositional design (prescription design). It is in. For the above purpose, use the following glycyrrhizin composition as an emulsifier at 0.01 to 20.0% by weight (weight% is based on the weight of the cosmetic concerned, hereinafter the same), and use 15% oily substance as an emulsifier.
This can be achieved with a cream or milky lotion cosmetic containing ~80% by weight and water. Γ Glycyrrhizin composition: 18α- selected from the group consisting of 18α-glycyrrhizic acid, monosodium 18α-glycyrrhizinate, monopotassium 18α-glycyrrhizinate, and monoammonium 18α-glycyrrhizinate.
At least one of glycyrrhizin is 30 to 98 mol%, and 18β- selected from the group consisting of 18β-glycyrrhizic acid, monosodium 18β-glycyrrhizinate, monopotassium 18β-glycyrrhizinate, and monoammonium 18β-glycyrrhizinate.
A composition comprising 2 to 70 mol% of at least one glycyrrhizin. When 18α-glycyrrhizin is less than 30 mol%, abnormal thickening and gelation tend to occur, and
It is economically unfavorable if 18α-glycyrrhizin exceeds 98 mol%. Constituting the aforementioned glycyrrhizin composition
The combination of 18α-glycyrrhizin and 18β-glycyrrhizin is, for example, 18β-glycyrrhizic acid for 18α-glycyrrhizic acid, and 18β-glycyrrhizic acid monopotassium salt for 18α-glycyrrhizic acid monopotassium salt. , it is desirable that they are the same compounds that are in an isomer relationship with each other. The specific 18α-glycyrrhizin and glycyrrhizin composition were created by the present inventors (Akira Miyashita, Kenzo Okada, Takashi Kuramoto), and the former is a new compound (Japanese Patent Laid-Open No. 115797/1983). , the latter is a new composition (Japanese Unexamined Patent Publication No. 113793/1983). The above-mentioned 18α-glycyrrhizin is different from normal glycyrrhizin (18β-glycyrrhizin, shown in formula (1) below), except that the configuration of the hydrogen atom at position 18 is α configuration, as shown in formula (2) below. ). In addition, in the present invention, in order to distinguish between this isomer (18α-glycyrrhizin) and normal glycyrrhizin (18β-glycyrrhizin),
We added 18α to the former and called it 18α-glycyrrhizin, and added 18β to the latter and called it 18β-glycyrrhizin. The following formula (1)...18β-glycyrrhizin The following formula (2)...18α-glycyrrhizin [In the above formulas (1) and (2), A ₁ and A ₂ are hydrogen atoms, sodium, potassium,
It is an ammonium group. However, one or both of A ₁ and A ₂ is a hydrogen atom. ] Although 18α-glycyrrhizin has properties in common with 18β-glycyrrhizin, it exhibits unique and unexpected properties due to the slight difference in the configuration of one hydrogen atom. The main characteristics of 18α-glycyrrhizin will be explained below while comparing them with those of 18β-glycyrrhizin. (a) Melting point (decomposition point) Does not show a melting point. The decomposition points are as follows. Sample 18α-form 18β-form Free acid 206℃ 210℃ Monoammonium salt 212-213℃ 216℃ Monopotassium salt 248℃ 246℃ (b) Optical rotation [α] ²⁰ _D (in 50v/v% ethanol,
Measured values for lw/v% solution) Sample 18α-form 18β-form free acid +26.1° +60.4° Monoammonium salt +23.2° +57.1° Monopotassium salt +23.0° +56.0° (c) Ultraviolet absorption spectrum The results of measurements of monoammonium salts using 50v/v% ethanol as a solvent are as follows. 18α-form 18β-form λ _nax 246 nm 251 nm E1% 1 cm 128.7 136.0 ε 10810 11420 The above-mentioned glycyrrhizin composition that can be used in the present invention is produced as follows. 18β-Glycyrrhizin (free acid and any salt)
This is used as a raw material, water or lower alcohol,
70-200 using alkylene glycol etc. as a solvent
The isomerization reaction is carried out by heating to 0.degree. C. under normal pressure or increased pressure and treatment with a caustic alkali such as caustic soda or caustic potash. After finishing the treatment, a glycyrrhizin composition is obtained by adding a mineral acid and collecting the acid-precipitated precipitate, or by extracting with hexanol or butanol or the like. 18α in glycyrrhizin compositions
-The ratio of glycyrrhizin and 18β-glycyrrhizin (isomer ratio) can be appropriately obtained by adjusting the alkali treatment time. It can also be adjusted by mixing the desired amount of 18β-glycyrrhizin with the above 18α-isomerization reaction product. Ordinary glycyrrhizin (18β-glycyrrhizin) is non-irritating to the skin, but the specific glycyrrhizin composition is also safe and non-irritating to the skin. That is, using a 1% aqueous solution of each glycyrrhizin composition described in each example below as a test sample,
As a result of conducting an animal skin irritation test and a human skin irritation test according to the Draize method, both the animal skin irritation score and the human skin irritation score were 0, confirming that it is non-irritating. The specific glycyrrhizin composition used in the present invention has properties that differ from ordinary 18β-glycyrrhizin in many respects. (a) Since the glycyrrhizin has good solubility in water and dissolves in a time less than 1/10 that of 18β-glycyrrhizin, the time required for producing the cosmetic can be shortened. (b) The transparency of the aqueous solution is good. In the case of 18β-glycyrrhizin, which is an acidic monosalt with a pH of approximately 4.2, it is gel-like and opaque even if it is dissolved.
The glycyrrhizin composition described above dissolves transparently and does not gel. Therefore, it is easy to produce the liquid cosmetic with good transparency. (c) Bubbles in aqueous solution disappear easily. Since 18β-glycyrrhizin forms stable foam, its defoaming rate is slow. On the other hand, the foam of the glycyrrhizin composition is easily defoamed even in a stationary state, and the defoaming rate is fast, so that the time required for defoaming during the production of the cosmetic can be shortened. (iv) Since the viscosity of the aqueous solution is low and stable even in an acidic region, the cosmetic can maintain its liquid state with almost no change in viscosity even after long-term storage. (e) The glycyrrhizin composition described above can be used at any pH level.
It is possible to stably solubilize oily substances such as fragrances and hormones in an aqueous system without gelation even in the aqueous system. Therefore, unlike conventional glycyrrhizin (hormone-containing lotion disclosed in JP-A-52-151736), there is no need to use a solubilizing agent such as alcohol, and there is no need to adjust the pH to 6.1 or higher. . Therefore, when producing the cosmetic of the present invention, formulation design is extremely easy. (f) The glycyrrhizin composition described above can impart appropriate viscosity and pH, good fluidity, and good skin affinity to the cosmetic. Therefore, when using this cosmetic, it is easy to take out from the container, it applies evenly to the skin, has a mild effect, and, combined with its anti-inflammatory effect, leaves a refreshing and smooth skin. It can give a nice (smooth) feeling. The amount of the glycyrrhizin composition blended is 0.01 to 20% by weight, preferably 0.1 to 5% by weight, based on the total weight of the composition (formulation) of the cosmetic. When the amount is less than 0.01% by weight, the emulsifying power decreases, and when it is more than 20% by weight, the solubility in an aqueous system decreases, and it is also economically unfavorable. The oily substances used in the present invention include known oily substances for skin cosmetics, such as higher aliphatic hydrocarbons, animal oils, vegetable oils, waxes, higher alcohols, higher fatty acids, ester oils, silicone oil, etc. Examples of hydrocarbons include liquid paraffin,
Squalane, petrolatum, ceresin, solid vegetable oils such as olive oil, almond oil, avocado oil, castor oil, cacao butter, palm oil, etc.; animal oils such as cod liver oil, beef tallow, butter fat, etc.
Examples of waxes include beeswax and carnauba wax; examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, and lanolin fatty acids; examples of higher alcohols include lauryl alcohol, Examples of ester oils such as stearyl alcohol, cetyl alcohol, and oleyl alcohol include straight chain esters and branched chain esters such as butyl stearate, hexyl laurate, octyldodecyl myristate, diisopropyl adipate, and diisopropyl sebacate. . These oily substances may be used alone or in combination of two or more. Its usage amount (content) is 15 to 80% by weight, preferably 20 to 70% by weight. 15% by weight
When the amount is less than 80% by weight, the emulsion stability deteriorates, and when it is more than 80% by weight, the oil becomes extremely sticky, which is not preferable. Next, the amount of water used (content) is 10 to 90% by weight,
Preferably it is 20 to 80% by weight. Glycyrrhizin compositions that can be used in the present invention include:
It exhibits good surfactant ability (ability to lower interfacial tension) regardless of pH conditions, and can emulsify the oily substances fairly stably, but when the amount of oily substances blended is large, lecithin, Sugar ester (higher fatty acid ester of sucrose), casein soda, N-
When blending with at least one natural surfactant selected from the group consisting of (higher) acyl glutamate, pectin, xanthan gum, karaya gum, and locust bean gum, oil-based substances can be emulsified extremely stably. . Furthermore, when at least one of the glycyrrhizin compositions or this and at least one of the natural surfactants are used together as an emulsifier,
The bubbles generated during manufacturing (emulsification) disappear naturally and quickly, and are combined with water-soluble polysaccharides such as pectin.
There is no need to perform vacuum defoaming during manufacturing, which is required when using 18β-glycyrrhizin, and 18β-
Another feature of the present invention is that it does not gel under weak acidity or exhibit extreme structural viscosity, unlike when glycyrrhizin alone is used as an emulsifier. In addition, it has a mild pH for the skin, which has been frequently used recently.
Acidic cosmetics of around 5 can exhibit good fluidity and feel when applied without gelling. The above-mentioned natural surfactants can be used alone or in combination of two or more, and the blending amount is 0.1 based on the total weight in the composition of the cosmetic.
-10.0% by weight, preferably 0.5-5% by weight. In the cosmetics of the present invention, it is not necessary to add pigments in pine surge cream, cleansing cream, skin cream, skin milk, hair cream, etc., but in foundation cream and liquid makeup base, in addition to the above-mentioned ingredients, it is not necessary to add pigments. Pigments must be added and blended. The amount of pigment used is 10% by weight or less, preferably 0.5 to 7% by weight, based on the weight of the composition. Examples of pigments include titanium oxide, kaolin,
Examples include inorganic pigments such as yellow iron oxide, ferric oxide, triiron tetroxide, and talc. Furthermore, small amounts of cosmetic medicinal ingredients, fragrances, preservatives, coloring agents, and synthetic surfactants may be added as desired. The cream-like or emulsion-like cosmetic of the present invention can be produced by known methods such as heating and stirring water and the glycyrrhizin composition to dissolve the composition, and then adding the molten oily substance thereto while stirring and mixing to emulsify. manufactured by the method. The cream or milky cosmetics of the present invention include, for example, pine surge cream, cleansing cream, skin cream, skin milk, foundation cream, liquid makeup base,
It is applied to many creamy or emulsion-like cosmetics such as hair creams for skin and hair. The cream or milky lotion cosmetic of the present invention does not irritate the skin, has high safety and affinity for the skin, has fine texture, has a good appearance with high gloss, and is stable as an emulsion. Excellent properties and storage stability. The glycyrrhizin composition used in the present invention is highly safe for the skin, and even in an aqueous system, it does not gel due to the pH, compounding concentration, low temperature, addition of water-soluble metals, etc., and easily defoams when dissolved. The emulsified cosmetics made using this emulsion can be easily removed from the fingers, have good fluidity, have no uneven application, and have extremely good quality stability in terms of hardness, viscosity, feel, etc., and the feeling of use is as follows.
The finish is crisp and has a smooth feel, and its commercial value is extremely high. Such remarkable properties cannot be obtained by using conventional 18β-glycyrrhizin, and are due to the properties of the glycyrrhizin composition in an aqueous system.
This fact is also clear from the comparison results in Examples described below. The present invention will be explained below with reference to Examples. In addition, "parts" shown in the examples refer to parts by weight, and α:
β means 18α-glycyrrhizin and 18β
- means the composition ratio (molar ratio) of glycyrrhizin. The glossiness was measured according to method 2 of the glossiness measurement method of JIS-Z8741-1962. Example 1 (pine surge cream) [1] Production of monoammonium glycyrrhizinate composition 200 parts of 18β-glycyrrhizin monoammonium (purity 80%) made from licorice was mixed with 4N-NaOH100
ml and the solution was heated under reflux at normal pressure for 7.5 hours. After this, add sulfuric acid to the reaction mixture to pH
The precipitate produced by adjusting the amount of 69.6 moles of 18α-isomer and 18β-isomer
118 parts of a 30.4 mol mixture) were obtained. [2] Preparation of skin cream A Prescription 1 Cetyl alcohol 17 parts 2 Isocetyl myristate 12 3 Squalane 3 4 Liquid paraffin 22 5 Monoammonium glycyrrhizinate composition (α:β = 69.6 mol: 30.4 mol) 5 6 Methylparaben 0.2 7 Propylene Glycol 6 8 Pure water 34.6 9 Fragrance 0.2 B Production Uniformly dissolve oily components 1, 2, 3, and 4 of the above ingredients at 80°C (solution 1). Water-soluble components 5, 6, 7, and 8 of the above components are uniformly dissolved at 80°C (solution 2). Next, while stirring Solution 2 with a homomixer, Solution 1 is added and emulsified, followed by cooling. In addition, component 9 was added at 70℃ during the cooling process, and 30℃
After the temperature was lowered to ℃, stirring was stopped. The skin cream thus obtained is an O/W type emulsion that improves skin texture,
It had a good appearance including gloss, and remained extremely stable even after being stored for 3 months in a constant temperature bath at 5 to 45°C. Example 2 (pine surge cream) A Prescription 1 Liquid paraffin 50 parts 2 Cetyl alcohol 5 3 Shugar ester 2 4 Monoammonium glycyrrhizinate composition (α:β = 69.6 mol: 30.4 mol) 2 5 Methyl paraben 0.2 6 Pure water 33 7 Fragrance 0.3 B Manufacture Manufactured according to Example 1. The thus obtained pine surge cream is O/W.
The molded emulsion has a good appearance such as texture and luster.
It remained extremely stable even after being stored for 6 months in a constant temperature bath at 5-45°C. Example 3 Monoammonium glycyrrhizinate (α:β=
69.6 mol: 30.4 mol), each pine surge cream was produced in the same manner as in Example 1, except that monoammonium glycyrrhizinate with different α, β isomer ratios as shown in Table 1 was used. We investigated its hardness over time. The results are shown in Table 1. The results show that when the α isomer ratio is less than 30 mol %, gelation occurs, as with the β isomer alone, and it is difficult to remove from the fingers and does not blend well with the skin, which is poor from a practical point of view.

【table】

[Table] Hardness measurement: Use a card tensiometer.
Example 4 (Skin cream) A Prescription 1 Cetyl alcohol 6 parts 2 Castor oil 2 3 Lecithin 1 4 Liquid paraffin 20 5 Monopotassium glycyrrhizinate composition (α:β = 60.8 mol: 39.2 mol) 1.2 6 Propylene glycol 5 7 Methyl paraben 0.2 8 Pure water 64.4 9 Fragrance 0.2 B Manufacture: According to Example 1 The thus obtained skin cream is an O/W type emulsion with good appearance such as texture and gloss, and has a rating of 5~
It remained extremely stable even after 6 months in a constant temperature bath at 45°C. Comparative Example 1 Monopotassium glycyrrhizinate composition (α:β
It was produced in the same manner as in Example 4, except that monopotassium 18β-glycyrrhizinate was used instead of (=60.8 mol: 39.2 mol). As a result, the obtained skin cream is an O/W type emulsion with good appearance such as texture and gloss, but
It gels at low temperatures (5 to 30°C), becomes hard, does not come off easily on the fingers, does not blend well with the skin, and becomes slippery and uneven when applied. In addition, the texture is slippery, stringy, and sticky. Example 5 (Skin milk) A Prescription 1 Cetyl alcohol 5 parts 2 Octyldodecyl myristate 1.5 3 Liquid paraffin 20.0 4 Pectin 2.0 5 Glycyrrhizic acid composition (α:β=78 mol: 22 mol) 2.0 6 Methylparaben 0.3 7 Pure water 69.0 8 Fragrance 0.2 B Production Uniformly dissolve oily components 1, 2, and 3 of the above ingredients at 80°C (solution 1). The above components 4 to 7 are uniformly dissolved at 80°C (solution 2). Next, Solution 1 was added to Solution 2 while stirring with a homomixer, emulsified, and then cooled. In addition, component 8 was added at 70℃ during the cooling process, and 30℃
After the temperature was lowered to ℃, stirring was stopped. The skin milk thus obtained was an O/W type emulsion and was completely defoamed naturally. In addition, it had good appearance such as texture and gloss, was extremely stable even after 3 months in a constant temperature bath at 5 to 40°C, and had excellent fluidity. The viscosity ranged from 1000 to 4500 cps in each thermostatic bath. Comparative example 2 Glycyrrhizic acid (α:β=78 mol:22 mol)
The product was produced in the same manner as in Example 5, except that 18β-glycyrrhizinic acid was used instead of 18β-glycyrrhizinic acid, but since natural defoaming was not possible, further defoaming was performed by suction, but still considerable small bubbles remained. . The skin milk after suction defoaming remained stable even after 3 months in a constant temperature bath at 5 to 40°C. However, the viscosity increased over time, the fluidity deteriorated, and the solution became stringy and could no longer be released from the container. The viscosity was 1300 cps (30°C) immediately after production, but it increased to 13500 cps (30°C) the next day. Further, the skin milk of Example 5 and the skin milk of Comparative Example 2 were examined for viscosity change and emulsification state due to addition of shear using a cylinder pump filling machine. As a result, as shown in Table 2, in Comparative Example 2, the viscosity decreased significantly due to the addition of shear, and the emulsification state deteriorated significantly, while in Example 5, which used the 18α-glycyrrhizin composition, the effect of the addition of shear was small. did.

[Table] Note: Shear: Additional shear of 2Kg/cm ² by cylinder pump filling machine.
Unit: Centipoise Example 6 (Cleansing Cream) A Prescription 1 Cetyl alcohol 5 parts 2 Liquid paraffin 60 3 Monosodium glycyrrhizinate composition (α:β=35.7 mol: 64.3 mol) 5 4 Methylparaben 0.2 5 Pure water 29.5 6 Fragrance 0.3 B Manufacture Manufactured according to Example 1. The cleansing cream thus obtained is O/
The W-shaped emulsion had good appearance such as texture and gloss, and remained extremely stable even after 6 months in a constant temperature bath at 5 to 45°C. Example 7 (Cream or milky emulsion) A product was produced in the same manner as in Example 5 except that the weight part of liquid paraffin used was changed. As a result, the resulting emulsion was examined for texture, feel, and stability over time when stored at 45°C, and the results are shown in Table 3. As shown in Table 3, when the oily substance is less than 15% by weight or more than 80% by weight, the emulsion stability is poor. Furthermore, as the amount of oily substances increased, the feel became worse.

[Table] Example 8 (Cleansing Milk) A Prescription 1 Liquid paraffin 50 parts 2 Isocetyl myristate 2 3 Xanthan gum 1 4 Sodium acylglutamate 0.5 5 Monoammonium glycyrrhizinate composition
1 6 Methylparaben 0.2 7 Pure water 47 8 Fragrance 0.3 B Production: Produced according to Example 1. The cleansing milk thus obtained has a viscosity of
The emulsion was an O/W type emulsion of 4300 cps, with good appearance such as texture and gloss, and remained extremely stable even after 3 months in a constant temperature bath at 5 to 45°C. Example 9 A cream was prepared according to a conventional method using the formulation shown in Table 4. Table 5 shows the characteristics of each cream obtained.

【table】

【table】

[Table] As is clear from Table 6, good creams were obtained when the glycyrrhizin composition was 0.01 to 20% by weight. On the other hand, if it is less than 0.01% by weight, it will not emulsify.
When it exceeds 20% by weight, the solubility slightly decreases, crystallization occurs over time, and gloss and texture deteriorate. Comparative Example 3 Monoammonium glycyrrhizinate (α:β=
Example 9 except that monoammonium 18β-glycyrrhizinate was used instead of 70 mol: 30 mol)
An attempt was made to manufacture the cream in the same manner as in the case of cream sample No. 4, but it was not possible to defoamer at all by natural defoaming. Next, complete defoaming was only possible by defoaming the entire process from emulsification to stopping cooling under reduced pressure. The resulting cream was an O/W type emulsion, and its gloss level was 80 immediately after production and 55 after 6 months. Moreover, this cream gelatinized at low temperatures (5 to 30°C) and became hard, making it hard to remove from the fingers and blending into the skin, and it was slippery and uneven when applied. In addition, it was slippery and stringy, giving an unpleasant sticky feel.

Claims (1)

[Claims] 1. The following glycyrrhizin composition is used as an emulsifier.
0.01 to 20.0% by weight (weight% is based on the weight of the cosmetic concerned, the same applies hereinafter), 15% to 80% by weight of oily substances,
A cream or milky lotion cosmetic containing water and water. Γ Glycyrrhizin composition: 18α- selected from the group consisting of 18α-glycyrrhizic acid, monosodium 18α-glycyrrhizinate, monopotassium 18α-glycyrrhizinate, and monoammonium 18α-glycyrrhizinate.
At least one of glycyrrhizin is 30 to 98 mol%, and 18β- selected from the group consisting of 18β-glycyrrhizic acid, monosodium 18β-glycyrrhizinate, monopotassium 18β-glycyrrhizinate, and monoammonium 18β-glycyrrhizinate.
A composition comprising 2 to 70 mol% of at least one glycyrrhizin.