JPH0212921B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing cosmetic raw materials, and more specifically, it relates to a method for producing cosmetic raw materials, and more specifically, a new product that can withstand long-term use and is made from conchiolin, a hard protein contained in pearls and various shells. It concerns the production method of safe cosmetic raw materials. Therefore, the present invention plays an important role not only in the technical field of cosmetics, but also in the technical field of fisheries, such as pearl culture and various shell culture, and in the technical field of protein chemistry. (Prior art) Regarding cosmetics using shellfish, powdered pearls, Akoya shells, etc. have been traditionally used on a very small scale at home or as a family tradition, as they have skin conditioning and skin nourishing effects. It's just a thing. In this way, conventional cosmetics that use pearls have not received much attention other than their skin conditioning and skin nutrition effects, and only a small amount of mercury double salt stearate, which is a product of pearl protein decomposition, has been used. This cosmetic is only known for its permeability due to its fat-oil solubility (Special Publication No. 4750/1983), but this cosmetic contains mercury, which poses a safety problem, making it difficult to use in actual use. has not been reached yet. In other words, we will apply a scientific scalpel to these techniques to identify the true nature of the active ingredients, create a safe cosmetic that will not cause irritation or redness even after long-term use, and commercialize it. This has not been done at all in the past. What's more, in addition to extracting the decomposition products of conchiolin as an active ingredient, the sensitizing components, which are a source of harmful side effects, can be removed through simple operations to create extremely safe cosmetics that can withstand long-term use. The current state of technology is such that the possibility of large-scale factory production of raw materials rather than cottage industry is unimaginable. (Problems to be solved by the invention) Cosmetics made from decomposed powder of conchiolin, which is an excellent skin-conditioning ingredient found in seashells and pearls, are excellent cosmetics containing natural products, but they do not have long-term effects on the skin. If you use it, your skin may become irritated or
The present inventor was the first to discover that harmful side effects such as itching and redness occur, making it no longer tolerable to use. The present invention focused on the problem of sensitization of conchiolin, which was discovered for the first time by the present inventor, and was made for the purpose of developing a new, excellent cosmetic raw material that is safe and free of sensitization. (Means for Solving the Problems) The present invention has been made to achieve the above object, and is applicable to animal experiments, clinical trials that directly use human skin, biochemistry, cosmetic science, etc. As a result of wide-ranging studies from various technical fields, it was discovered that the cause of sensitization was a high-molecular-weight peptide in conchiolin degradation products, and moreover, a specific high-molecular-weight peptide. Furthermore, as a result of research into an industrial method for removing these polymeric peptides from conchiolin decomposition products without impairing their excellent cosmetic effects, it was found that ultrafiltration is suitable. This discovery led to the completion of the present invention. That is, the present invention first makes the new discovery that (1) Conchiolin decomposition products contain harmful sensitizing substances and cannot be used safely for a long period of time, and (2) Conchiolin degradation products contain harmful sensitizing substances. They further discovered that the chemical substance was a high-molecular peptide, and finally (3) discovered that ultrafiltration was the optimal method for removing this high-molecular peptide. Thus, the present invention has been completed. The starting material of the present invention is conchiolin. Conchiolin is known as the pearl oyster (Pinctada).
martensii), Mytilus coruscum, Mytilus edulis, Hyriopsis schlegelii, Cristaria
It is preferable to use products made from the family Uguisidae, Mucilidae, or Mucilidae, such as molluscs, but you can freely use products made from other shellfish or commercially available products, and there is no problem in terms of raw material supply. . Particularly suitable are Akoya oyster (pearl oyster) and conchiolin made from pearl. It is also possible to use crude conchiolin without purification. Since the active ingredient of the cosmetic raw material according to the present invention is a decomposition product of conchiolin protein (sometimes simply referred to as "conchiolin"), conchiolin is first hydrolyzed. For hydrolysis
Hydrolysis is carried out using a 0.5 to 35% aqueous hydrochloric acid solution for 30 minutes to 10 days while controlling the temperature at 0 to 130°C. Of course, the three requirements of hydrochloric acid concentration, hydrolysis temperature, and hydrolysis time must not be set so that conchiolin is completely decomposed into amino acids during hydrolysis. Preferably, a 2 to 20% aqueous hydrochloric acid solution is added to demineralized Akoya shells or pearl conchiolin.
After hydrolysis at 50-110°C for 5 hours to 5 days, hydrochloric acid is removed. Conventional methods are used to remove hydrochloric acid,
For example, freeze-drying or evaporation is preferred. Further, it is neutralized with an alkali such as ammonia or sodium hydroxide and desalted using a known desalting method. Also suitable is a method in which amino acids are adsorbed using an ion exchange resin after neutralization with ammonia, and then desorbed with ammonia. For example, fill a column with Amberlite IR-120H type resin, pass the previously obtained conchiolin hydrolyzate through it, desorb it with an alkali such as 1N-NH ₄ OH, and combine the effluents. If necessary, concentrate using the usual method. In addition, if necessary, it may be dried by evaporation to dryness, freeze-drying, or other appropriate methods, and distilled water may be added at the stage of moving to the next step to prepare a liquid with the desired concentration. good. In cosmetics, salt leads to the destruction of emulsions such as creams, so it is better to have as little salt as possible, and it is preferable to completely desalinate. The conchiolin hydrolyzate desalted in this way is concentrated if necessary and then subjected to ultrafiltration to remove high molecular weight peptides, which are harmful components. Ultrafiltration is carried out by a conventional method, preferably under pressure using a commercially available ultrafiltration membrane.
In the present invention, ultrafiltration is performed for the purpose of removing high-molecular peptides, and the ultrafiltration only needs to remove 6,000 or more molecular weight fractions, but an ultrafiltration membrane with a nominal molecular weight fraction of 2,000 is used. It serves this purpose. As described above, the present invention enables the ultrafiltration of hydrochloric acid hydrolyzate of conchiolin under specific conditions.
It has succeeded in having both extremely high safety and outstanding effectiveness. As the ultrafiltration membrane in the present invention, commercially available products can be appropriately used. For example, ultrafiltration using an Amicon membrane or diafiltration ultrafiltration can be advantageously used. The liquid that has passed through the ultrafiltration membrane no longer contains sensitizing polymeric peptides.
This can be freely used as a safe cosmetic raw material. If necessary, it may be dried by freeze-drying or the like, or concentrated by vacuum concentration or the like to make it convenient for storage or later use. The liquid that has passed through the ultrafiltration membrane in this way is, for example, sterilized and filtered, and in the case of nutritional cream, it is added to the nutritional cream base by about 1 to 5%, and in the case of nutritional cosmetic liquid, it is added with an alkali. The desired cosmetic products are manufactured by adding about 0.2 to 4% to the cosmetic liquid base, and about 2 to 8% to the pack base in the case of a pack. However, the cosmetic raw material according to the present invention has the active ingredient of conchiolin concentrated and harmful sensitizing ingredients have been removed, so it can exert a skin conditioning effect even when used in a very small amount, and even when used in large quantities. It has no harmful effects and is completely safe for the skin and human body. Therefore, it is not limited to the above-mentioned range of use, and can be freely used outside the range. Next, examples and test examples of the present invention will be described. Example: To 1 kg of demineralized conchiolin as a dry product, add 8 parts of concentrated hydrochloric acid and 1.2 parts of water, seal in a container, and heat at 60°C for 50 minutes.
Decomposed by heating for hours. After the decomposition is complete, add ammonia to approx.
The mixture was added little by little with sufficient stirring until the pH reached 0.5, centrifuged for 10 minutes, and then filtered through 3-micron filter paper. Dilute this 35 times with water and add hydrochloric acid or ammonia.
200 of Amberlight IR-120 after adjusting to PH2.0
After passing through the column, it was eluted with 600 ml of 1N ammonia. This liquid was passed through an ultrafiltration membrane PM-2 (molecular weight cut off: 2000) manufactured by Romicon and freeze-dried. In this way, 792 g of a cosmetic raw material containing conchiolin containing no sensitizing ingredients was obtained. As a result of examining the physical properties of the obtained cosmetic raw material, a high performance liquid chromatogram as shown in FIG. 1 (see Test Example 1 below) was obtained. Test Example 1 The product raw material obtained in Example was designated as Sample No. 1,
As a control, a substance obtained by repeating the same operations as in the example except for the ultrafiltration step was used as sample No. 2, and subjected to high performance liquid chromatography with the following specifications to examine the state of molecular weight distribution. . Column TSK-G2000G7.5mm×600mm Eluent 0.05N phosphoric acid buffer + 0.1N
NaSO ₄ (PH7.0) Flow rate 0.5ml Detector Ultraviolet absorption 210nm The results are as shown in the drawing.
The results for No. 1 are shown in Figure 1, and the results for Sample No. 2 are shown in Figure 2. As is clear from these drawings, it can be seen that harmful polymeric parts have been removed from Sample No. 1. Test Example 2 A sensitization test was conducted using the Maximization test method. Six groups of 10 healthy guinea pigs were prepared as test animals, and 2,4-
Using Dinitrochlorobenzene, sample No. 1, sample
For the three samples No. 2 and positive control, one group was used for sensitization treatment and the other group was used as control for induction. As a result, the results shown in Table 1 were obtained. The determination time is the time after 24-hour occlusive patch application for induction.

[Table] As shown above, it is clearly seen that sample No. 2 has a stronger sensitizing property. Test Example 3 In the example, the ultrafiltration membrane was used with a molecular weight cutoff of 10000.
(Toyo Roshi Co., Ltd. Q 0100) and membranes with a molecular weight cutoff of 500 (Toyo Roshi Co., Ltd. O 0005) were used instead of sample No. 3.
and 4 were prepared. Maximization tests were conducted on these samples No. 3 and 4 in the same manner as in test row 2, and the results shown in Table 2 were obtained. In addition, Table 2 shows samples No. 1 and 2 in Table 1 for comparison.
The results were also reproduced.

[Table] As is clear from the above results, it can be seen that in sample No. 3, the harmful polymer portion could not be removed and strong sensitization remained. Test Example 4 Using Samples Nos. 1, 2, and 3, Formulation Examples 1, 2, and 3 were prepared according to the following formulations, and a sensory test was conducted. A Squalane 29.0 Cetostearyl alcohol 3.0 Jojoba oil 3.0 Octyldodecyl myristate 3.0 Stearic acid monoglyceride 3.0 Sorbitan monostearate 3.0 B Purified water 39.8 Polyoxyethylene hydrogenated castor oil (60E.O.)
1.0 Polyoxyethylene sorbitan monostearate 3.0 1,3-butylene glycol 7.0 Methyl paraoxybenzoate 0.2 Sample 5.0 Weigh A and B separately, heat to 80°C, and gradually add A to B while stirring, 30 Cooled to ℃. Three types of prescription examples were created: Prescription Example 1 containing Sample No. 1, Prescription Example 2 containing Sample No. 2, and Prescription Example 3 containing Sample No. 3. 108 women were randomly divided into 4 groups, prescription example 1
Sensory evaluation was conducted for 3 weeks and the results shown in Table 3 were obtained.

[Table] It was assumed that there was no significant change.
As is clear from the results in the table above, it was found that No. 1 was the only sample with good safety and satisfactory efficacy. (Effects of the Invention) According to the present invention, by very simple operation,
A sensitizing polymeric peptide is industrially removed from conchiolin cosmetic raw materials (as is clear from Test Examples 1 to 4, this is not possible from both a chemical and biological point of view). proven). Therefore, according to the present invention, it is possible to provide cosmetics that are extremely safe and can be used for a long period of time without any cosmetic pollution. Furthermore, despite the removal of sensitizing substances, this cosmetic raw material maintains the inherent skin conditioning effect of conchiolin without any loss, and is compatible with various dosage forms and various types. Therefore, according to the present invention, cosmetics that are effective for early recovery from skin fatigue, pigment bleaching, prevention of skin aging, prevention of stiffness, shine, etc. can be freely added to cosmetics for various purposes. Can be prepared. Furthermore, conventionally, scrap pearls and Akoya shells after pearl harvesting had no effective use and were discarded, but the present invention opens up a new way of effectively utilizing these waste materials. Furthermore, conchiolin-containing shells other than pearl oysters can be widely used, and the present invention is extremely superior in terms of effective use of resources.

[Brief explanation of drawings]

FIG. 1 is a liquid chromatogram of a cosmetic raw material according to the present invention, and FIG. 2 is a liquid chromatogram of a substance that was not subjected to ultrafiltration.

Claims (1)

[Scope of Claims] 1. A method for producing a cosmetic raw material, which comprises decomposing conchiolin with hydrochloric acid, removing the hydrochloric acid, and then performing ultrafiltration to collect a fraction with a molecular weight cut off of 6000 or less. 2. The manufacturing method according to claim 1, wherein the hydrochloric acid removal step includes desalination after neutralization. 3. The manufacturing method according to claim 1, wherein the hydrochloric acid removal step comprises neutralizing with an alkali, adsorbing the amino acid using an ion exchange resin, and then desorbing it with an alkali. . 4. The molecular weight cutoff of the ultrafiltration is 2000,
A manufacturing method according to claim 1, 2, or 3, characterized in that: