JPH0333684B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel application of Yokuinin. The gist of the present invention is to focus on the starches, proteins, fibers, and lipids contained in Yokuinin, decompose them with hydrochloric acid, reduce the molecular weight, and convert starches, proteins, and fibers into sugars and amino acids. On the other hand, lipids (fatty acid esters) are separated as free fatty acids, and then the free fatty acids are transferred to trichlorotrifluoroethane using trichlorotrifluoroethane.
In other words, while obtaining a mixture of sugars and amino acids,
On the other hand, although it is a method of recovering yokuinin oil, the mixed extract of sugars and amino acids obtained is excellent as a moisturizing agent, and can be added to cosmetics to prevent dry skin and hair. prevent and give flexibility. In addition, this product has a tyrosinase activity inhibiting effect and suppresses the production of melanin pigment, so it can be expected to have a whitening effect. On the other hand, the oil that can be simultaneously obtained in the present invention is a liquid oil that is smooth and non-sticky, and has the characteristic of imparting luster to the skin or hair when applied or rubbed onto the skin or hair. Yokuinin has been used in Chinese herbal medicine since ancient times, and is one of the herbal medicines listed in the Japanese Bureau of Medicine. Its medical effects include diuretic, anti-inflammatory, analgesic, edema, pain relief for neuralgia and rheumatism, and purulent drainage, and it has also been used as a nourishing and tonic agent. In folk medicine, it is used to remove warts and rough skin, and traditionally these active ingredients are substances derived from the lipid components contained in Yokuinin.
It was said to have the main effect. However, recently, nutritionally speaking, not only lipid components but also nutritional ingredients have been added.
Starches and proteins are also attracting attention, and on the other hand, it is also said that starch-derived saccharides or certain glycosides or polysaccharides are significantly involved in anti-inflammatory effects. On the other hand, when looking at the application to cosmetics, extracts mainly extracted from the lipid components of Yokuinin are mostly used. For example,
"Special Publication No. 45-18998" and "Japanese Patent Publication No. 52-1042",
There is ``Japanese Unexamined Patent Publication No. 52-156936'', and recently, ``Japanese Unexamined Patent Publication No. 55-35052'' uses yokuinin oil obtained by the pressing method. As mentioned above, all of these are extracts containing mainly the lipids in Yokuinin, and it is clear from the extraction method that they are extracts or oils from which sugars and proteins have been removed. In other words,
Because it is extracted in a highly concentrated (almost 100%) organic solvent, the proteins contained in the extracted extract may be coagulated and denatured by the organic solvent, resulting in protein removal. Therefore, the extracts used in cosmetics to date have essentially been so-called yokuinin oil, which is mainly composed of the lipids in yokuinin, from which sugars and proteins have been removed. It was. On the other hand, the extract of the present invention is composed of sugars and amino acids and does not contain lipids, and the extract obtained by separating at the same time in the process does not require any protein removal procedure, which is advantageous. It is something. "Example 1" Add about 10 grams of 2N hydrochloric acid to 1 kg of JP Yokuinin powder, stir well to uniformly disperse, and maintain the temperature of the solution at around 98°C for 2.5 hours.
By this operation, most of it becomes a solubilized muddy fluid, so heating is stopped and the solution is left at room temperature to wait for cooling. When the temperature reaches room temperature, add the same amount of trichlorotrifluoroethane (Central Glass Manufacturing's trade name: CG Triflon) as the solubilized slurry fluid.
Stir well. Stirring speed is approximately 300rpm, 15~
It is best to do this for about 20 minutes. As a result, all of the fat-soluble components (lipids) contained in the solubilized slurry are transferred to trichlorotrifluoroethane.
Let stand for 2 hours. By standing still, three layers are separated. In other words, an aqueous layer containing hydrochloric acid is formed in the upper layer, a solubilized muddy fluid layer is formed in the middle layer, and a trichlorotrifluoroethane layer is formed in the lower layer. Once fractionated, this will be referred to as Solution B for convenience. On the other hand, the middle layer and the upper layer are mixed and taken out to form a liquid A. After separating into liquids A and B, the following operations are performed separately to obtain a water-soluble extract containing mainly saccharides and amino acids of Yokuinin from liquid A.
On the other hand, from liquid B, a liquid oil is obtained which is mainly composed of free fatty acids of Yokuinin lipid. Both A and B solutions are filtered in advance using filter paper, etc., and then the filtrate is concentrated under reduced pressure (using an evaporator) at 40°C. In Part A, most of the hydrochloric acid used in the process is removed by vacuum concentration, but a trace amount of hydrochloric acid may still remain, so the vacuum concentrated viscous starch syrup (approx. 800-1200g), about 3
Add twice the amount of water to dilute and dissolve, then 2N
Add sodium hydroxide solution to make the pH slightly acidic, filter through filter paper, concentrate again under reduced pressure at about 40°C, and evaporate to dryness. This allows for solids to have approx.
700-850g of extract is obtained. In addition, the obtained extract may have a dark brown color,
Usually, before concentrating liquid A under reduced pressure, add 0.5~
When 4% activated carbon is added, stirred for 30 to 60 minutes, and then filtered with paper, the liquid A becomes highly transparent and pale in color, making it easier to use in cosmetics. Therefore, it is advisable to perform such pretreatment as necessary. This also applies to the operation of liquid B described below. Now, the operation for liquid B is to concentrate it under reduced pressure at 40℃ (using an evaporator), so that the trichlorotrifluoroethane in liquid B is easily removed, and the oil is left behind smoothly, and the yield is about 50 to 52 g. . This oil is a liquid oil with a transparent light yellow-brown color. Yokuinin oil produced by this method is
The conventional deproteinization operation is not necessary at all; in other words, by separating the hydrolyzate into liquid A and liquid B using trichlorotrifluoroethane, the protein can also be removed without removing the protein. , in liquid A,
The amino acids are transferred as amino acids to obtain their hydrolyzed extract (hereinafter, the extract obtained from this liquid A is simply referred to as extract), while the liquid oil mainly composed of free fatty acids (hereinafter obtained from liquid B) is obtained from liquid B. The resulting liquid oil is simply referred to as oil), and compared to the conventional production of Yokuinin extract (Yokuinin oil), it is a more rational production method and has superior operability. Both the extract or oil according to the present invention can be applied to cosmetics and the like. In other words, one of them may be used alone or both may be used in combination, but the oil may be used according to a known method. The application area of extracts is not just limited to cosmetics, but because they are low molecular weight and can be taken orally,
Because it is easily digested and absorbed, it can be used for nutritional and tonic purposes in medicines and health foods, or as an excipient for tablets, capsules, granules, powders, etc. It can also be easily used in processed foods. Furthermore, although the extract is water-soluble, it may be used after being emulsified (dispersed) in oil. Products to which extracts are added exhibit the moisturizing effect of the extract itself, and when used in cosmetics or processed foods, for example, this enhances the moisturizing effect and helps prevent products from drying out. Also, in products that require emulsification, 3
When it is contained in an amount of up to 6%, the stability of the emulsified state is improved. Furthermore, when processed foods or cosmetics contain oil, it prevents the oxidation of the lipids.
Improved stability. For example, the antioxidant effect on fats and oils was determined by using edible lard and adding 3% extract to AOM.
When heated to around 98℃ in a test machine and looking at the oxidized state, it was found that with additive-free lard, the POV value increased rapidly after about 3 hours, but with the addition of extract, the stability continued. be done. It was presumed that the amino groups in the amino acids in the extract played an important role in stabilizing it. Therefore, the extract obtained according to the present invention is advantageous as a stabilizer in cream or emulsion-like products that are emulsified or suspended using oil. In addition, since the extract becomes a transparent and viscous aqueous solution, it is easy to incorporate into water-soluble transparent liquid products. Next, regarding the extract or oil according to the present invention, its physicochemical properties or actions (properties, effects), etc. are as shown in experimental examples. "Experimental Example" The extract and oil obtained in Example 1 above were tested for inhibitory effect on tyrosinase activity, and the results are shown in Table 1. It was found that the effect is high. The test method involves treating tyrosine with tyrosinase and measuring the melanin pigment produced.
A method of measuring with an absorbance meter at 640 nm was adopted. The reaction system composition is as shown below. still,
This effect was not observed in Yokuinin oil or a lipid-based extract from Yokuinin. (Reaction composition) L-tyrosine (1.0 mg/ml) …0.5 ml Phosphate buffer (PH6.8) …2.0 ml Distilled water or specimen …2.0 ml Copper ion (1% solution) …0.05 ml Tyrosinase (1 mg/ml ) …1.0ml

[Table] As shown in Table 1 above, no extracts other than those obtained from Solution A in Examples according to the present invention showed any inhibitory effect on tyrosinase activity. That is,
It was found that one of the skin-whitening factors present in Yokuinin was not transferred to the extract or oil, which mainly consists of fat-soluble components. moreover,
It was also found that the inhibitory effect on tyrosinase activity was due to the low molecular weight amino acids or peptides rather than the sugars in the extract. On the other hand, the present inventors investigated the conventional extraction method regarding the application of Yokuinin to cosmetics.
We examined its quality, and the results are shown in Table 2. In other words, in the evaluation of each extraction method and extraction solvent, the present invention is superior in terms of yield and operability, there is no waste, and there is less danger during extraction due to the characteristics of the solvent used. Although it has many advantages, especially in terms of operability, extracts obtained using known extraction solvents such as benzene and petroleum ether are difficult to purify. In other words, since it is difficult to remove the characteristic odor of the organic solvent that remains, there is a drawback that the proteins contained in the extract must also be removed in the end. Additionally, even if you try to remove specific odors such as benzene from the crude extract during the purification process, it is difficult to remove them.The reason for this is that some of the extracted lipid components are bound to benzole. It is estimated that In addition, although benzene extraction contains a considerably larger amount of protein components in the crude extract than acetone, ethanol, or methanol extraction, it ends up forming a precipitate over time, so conventional organic solvent extraction It was found that this method requires a protein removal operation during purification, and the resulting product is mainly composed of fats and oils (oil). If only the lipids in Yokuinin were extracted using an organic solvent, it would be more likely that
- It was also found that hexane and the like are advantageous.
In addition, in lotions, etc., extracts extracted with low concentration 10-70% ethanol or a mixture of low concentration 10-70% ethanol and propylene glycol are stable; in this case, An extract containing trace amounts of protein and saccharide as well as fat in Yokuinin is obtained.

[Table] Next, regarding the extract according to the present invention, as shown in FIGS. 1 and 2, it has an excellent moisturizing effect. In both experiments, the results were measured using a constant temperature and humidity chamber. The measurement method is
Using a constant temperature and humidity machine (manufactured by Takasugi Seisakusho), the relative humidity at 30℃ is adjusted to 30%, 50%, 70%, and 90%.
The moisture absorption effect and water loss rate were determined after the sample was allowed to stand for a period of time. Next, the ultraviolet absorption spectrum of the extract according to the present invention and the oil obtained during the process is as shown in FIG. In other words, extracts have maximum absorption at 280 nm, while oils have maximum absorption at 270 nm. Furthermore, when the amino acids in the extract were examined by thin layer chromatography, spots as shown in Figure 4 were obtained. The measurement conditions are shown below. "Measurement conditions shown in Figure 4" Support: Silica gel G, 0.25 mm Developing solvent: n-propanol, water (64:36) Developing distance: 10 cm After development, dry the plate at 110°C for about 5 minutes and spray the ninhydrin test. and heat it to develop color. Next, the fatty acids of the oil obtained according to the present invention are extracted (oil) using two to three known extraction methods.
When compared by thin layer chromatography, spots as shown in FIG. 5 were obtained.
In other words, it was found that the composition of the fatty acids obtained differs depending on the extraction solvent, and the oil of the present invention is mainly composed of free fatty acids. "Measurement conditions shown in Figure 5" Support: Silica gel G, 0.25 mm Developing solvent: Petroleum ether, ether, acetic acid (82:18:1) Developing distance: 10 cm Coloring conditions: 10% sulfuric acid, 150°C, 15 minutes. Furthermore, looking at the content ratio of sugars and amino acids in the extract according to the present invention, sugars account for 80 to 90%.
And amino acids account for 12-18%. Sugar was determined as glucose using the Somogi method, and amino acids were converted based on the Nitrogen determination method of the Japanese Bureau. In addition, in the measurement, the extract was a solid dry product, and this was diluted 10 times with water in advance and then subjected to the measurement. A summary of these figures is shown in Table 3.

[Table] Table 3 is a study based on the extraction method according to the above-mentioned known literature.These known extracts are extracts mainly extracted from the lipids in Yokuinin. The starch and protein contained in Yokuinin are removed without being used. In other words, about the amount that makes up Yokuinin
In comparison, 90% of the components were not utilized, but in the production method of the present inventors, most of the components can be effectively utilized through hydrochloric acid decomposition. or,
The manufacturing method is as shown in the examples.
If the production method according to the present invention is applied, for example, after obtaining an extract (Yokuinin oil) by a known extraction method, a large amount of the residue (mainly starch, protein, and fiber) that is removed can be extracted. Furthermore, even if hydrochloric acid decomposition is performed, an extract mainly composed of sugars and amino acids can be obtained. In other words, the feature of the present invention lies in the effective use of the large amounts of starch, protein, and fiber contained in Yokuinin. that's why,
In Example 1 above, the procedure is to first perform hydrochloric acid decomposition and then use trichlorotrifluoroethane to extract the fat-soluble component (Yokuinin oil). Lipid component (Yokuinin oil) with various known solvents
Even if the residue is extracted in advance and decomposed with hydrochloric acid, an extract mainly composed of sugars and amino acids can be obtained.
However, the solvent in such a case may be the residue obtained by first extracting the lipid component (Yokuinin oil) with n-hexane, or the
35052" is advantageous in terms of operation and effective use of the raw material Yokuinin. That is, the present invention eliminates the waste of the raw material Yokuinin powder by obtaining a hydrolyzed extract of Yokuinin, and the obtained extract can be used as a moisturizing agent. It is also used in cosmetics. "Example 2" A large amount of residue (with a lipid content of 0 to 2% or less, consisting mainly of starch, sugars, proteins, and fibers) obtained in the extraction process of known Yokuinin extract (Yokuinin oil) ), for this
Add 10 times the amount of 2N hydrochloric acid, stir well, and once it is evenly dispersed, keep the solution at around 98°C for 2.5 hours. This operation turns most of the material into solubilized muddy fluid, so stop heating, leave it at room temperature, and wait for cooling. When the temperature reaches room temperature, add the same amount or 1/2 amount of trichlorotrifluoroethane or n-hexane as the solubilized slurry and stir well. After stirring for about 5 to 10 minutes, when placed in a separating funnel, the trace amount of remaining lipids will migrate to the trichlorotrifluoroethane layer (lower layer), and when n-hexane is used, Now, let's move on to the upper layer. Since three layers are formed in any case, remove the trichlorotrifluoroethane layer or the n-hexane layer, and remove the remaining water layer and muddy layer. Once the fluid is taken out and mixed together, it is filtered through a filter paper (Toyo Roshi No. 2 type), and the filtrate is concentrated under reduced pressure at 40°C (using an evaporator). 800-900g of candy can be obtained from 1kg of the product. The following operations are carried out in accordance with the operations for liquid A in Example 1, and as a result, the hydrolyzed extract of Yokuinin has a concentration of 650 ~
You get 700g. The characteristics and properties of the obtained extract are
It is almost the same as the hydrolyzed extract obtained in Example 1, has a moisturizing effect, and also exhibits a tyrosinase activity inhibiting effect. However, the inhibitory effect on tyrosinase activity was somewhat uneven, and the amount of amino acids was also lower than that of the extract obtained from Solution A of Example 1 in some cases. The results are as shown in the following table "Table 4". The cause of this was presumed to be related to the characteristics of the solvent (effect on protein) used in the known procedure for obtaining the fat-soluble components in Yokuinin. In other words, using the residue after obtaining the extract using benzol, petroleum ether, and acetone,
It was found that, compared to the extract obtained by decomposing this, the residue obtained by press extraction and the residue obtained by hydrolysis using the residue after n-hexane extraction had a higher amino acid content. However, it was found that the moisturizing effect was almost unchanged, and it exhibited sufficient moisturizing effect and could be used in cosmetics and the like.

【table】

[Table] As described above, in the examples of the present invention, extracts containing sugars and amino acids, which have excellent moisturizing effects, as well as yokuinin oil can be reasonably obtained from yokuinin, and both can be used in cosmetics. It has excellent blendability. An example of its prescription is given below. Although they are indicated as A extract and B extract in the prescription, A extract indicates the extract obtained from liquid A of Example 1 of the present invention and the extract obtained in Example 2, and the extract B indicates indicates a liquid oil (Yokuinin oil) obtained from Solution B of Example 1, and Extract A refers to an extract mainly composed of saccharides and amino acids. (Prescription example 1: Cream) Extract A 3.0 Extract B 3.0 Stearic acid 14.0 Vaseline 2.0 Glyceryl monostearate 2.5 Polyoxyethylene sorbitan Monostearate (20E.O.) 1.5 Fragrance 0.5 Antioxidant Appropriate amount Preservative Appropriate amount 1,3 -Butylene glycol 8.0 Purified water Total amount 100.0 (Formulation example 2: Emulsion) Extract A 0.2 Extract B 2.0 Squalane 5.0 Vaseline 2.0 Beeswax 0.5 Sorbitan sesquioleate 0.8 Polyoxyethylene oleyl ether (20E.
D.) 1.2 Fragrance 0.5 Antioxidant Appropriate amount Preservative Appropriate amount 1,3-butylene glycol 5.0 Ethyl alcohol 5.0 Carboxy vinyl polymer (1.0% water soluble)
20.0 Potassium hydroxide 0.1 Purified water Total amount 100.0 (Formulation example 3: lotion) Extract A 2.0 Glycerin 5.0 1,3-butylene glycol 4.0 Oleyl alcohol 0.1 Polyoxysorbitan monolaurate (20E.D.) 1.5 Polyoxyethylene lauryl ether (20E.
O.) 0.5 Ethyl alcohol 10.0 Fragrance 0.1 Pigment Appropriate amount UV absorber Appropriate amount Preservative Appropriate amount Purified water Total amount 100.0 (Formulation example 4: Hair liquid) A extract 0.5 B extract 5.0 Polyoxypropylene alkyl ether phosphate ester 19.0 Triethanolamine 1.0 Ethyl alcohol 48.0 Fragrance Appropriate amount Preservative Appropriate amount Purified water Total amount 100.0 (Formulation example 5: Hair shampoo) A extract 5.0 Lauryl sulfate triethanolamine acid 15.0 Coconut oil fatty acid monoethanolamide 2.0 Fragrance Appropriate amount Pigment Appropriate amount Water Total amount 100.0 (Formulation example 6: Hair rinse) Extract A 2.0 Extract B 1.0 Alkyldimethylammonium chloride 3.0 Glyceryl monostearate 3.0 Fragrance Appropriate amount Pigment Appropriate amount Water Total amount 100.0 (Formulation example 7: Hair Tonik) A extract 2.0 B extract 2.0 Benzoic acid 1.0 Salicylic acid 1.0 Resorcinol 3.0 Isopropyl myristate 3.0 Rose water 1 0.0 Ethyl alcohol total amount 100.0

[Brief explanation of the drawing]

1 and 2 are obtained by the present invention,
It is a graph showing the effect of an extract mainly composed of sugars and amino acids on the moisturizing effect. however,
Figure 2 shows the effect of adding 10% extract to a 50% aqueous solution of 1,3-butylene glycol. FIG. 3 is a graph showing the ultraviolet absorption spectrum of trumpet oil, which is composed of an extract mainly composed of saccharides and amino acids obtained according to the present invention, and free fatty acids. A is an extract mainly composed of sugars and amino acids. B is Yokuinin oil consisting of free fatty acids. FIG. 4 shows thin layer chromatography spots for amino acids in the extract mainly composed of saccharides and amino acids obtained according to the present invention. FIG. 5 shows the thin layer chromatography spots of the trumpet oil obtained according to the present invention and the extract (the main component is oil and fat) obtained using a conventional known organic solvent. 1) A is a sagebrush oil obtained according to the present invention. The others are Yokuinin oil obtained using various known extraction solvents, and the extraction solvents are shown below.

Claims (1)

[Claims] 1. A skin cosmetic product characterized by containing an extract mainly composed of saccharides and amino acids obtained by hydrolyzing Yokuinin.