JP3002166B2 - Production method of high quality wood vinegar liquid raw material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention removes biologically harmful components (formaldehyde, methanol) present in crude wood vinegar and bamboo vinegar, and contains active ingredients such as flavanols, tannins, polyphenols, cresol and cresol. Of high quality wood vinegar and high quality bamboo vinegar (referred to collectively as high quality wood vinegar in the present invention) and cosmetics (washing, hair, foundation, makeup, fragrance,
Sunburn, sunscreen, nails, eyeliner, lips, mouth,
Bathing) It relates to foods such as agents for treating superficial skin / mucosal infections (medicines and quasi-drugs) and soft drinks.

[0002]

2. Description of the Related Art The crude wood vinegar liquid of the present invention is:
It is an aqueous solution formed by cooling the bark, trees, and smoke generated when carbonizing mature bamboo such as bamboo.The chemical composition varies slightly depending on the type of raw material to be carbonized,
Representatives are acetic acid, propionic acid, butyric acid, methanol, formaldehyde, phenol, furfural, cresol, cresol and the like.

[0003] Since these crude wood vinegar solutions contain formaldehyde and methanol as biologically harmful components, they cannot be used as cosmetics, medicines and foods unless these are removed.

Conventionally, research and development of cosmetics, food additives and the like using wood vinegar and bamboo vinegar have been conducted. However, effective components such as phenol, tannin and flavanol can be efficiently extracted, and biological substances such as formaldehyde and methanol can be obtained. There is no way to remove harmful components, and there are currently no products licensed by the Ministry of Health and Welfare in the area of cosmetic research.

[0005] Recently, soaps and cosmetics using wood vinegar which have not been licensed for production and sale by the Ministry of Health and Welfare have been marketed. Was.

[0006]

It is well known that wood vinegar and bamboo vinegar have long contained tannins, such as phenol, which repair skin wounds and increase moisture. However, at the same time, several hundred ppm of formaldehyde and methanol, which are biologically harmful components, are contained, which has been a major obstacle to utilizing them as cosmetics, pharmaceuticals, and foods.

[0007] Wood vinegar contains tar and carcinogenic substance such as benchpirene. According to the research and development of wood vinegar so far, there is a report on the removal, deodorization and decolorization of these tar and benchpirene. Many.

Further, the wood vinegar solution and the bamboo vinegar solution contain tens of percent of a strongly acidic substance such as acetic acid, which causes a burning sensation when the wood vinegar solution is applied to the skin.

[0009] The present invention is a "body-friendly" high-quality wood vinegar liquid raw material that effectively removes bioharmful components such as whalmaldehyde and methanol contained in the crude wood vinegar solution and the crude bamboo vinegar solution and contains an active ingredient. It is intended to provide.

[0010]

According to the present invention, a crude wood vinegar solution is adjusted to pH.
It is mixed with an organic solvent under an acidity of 2.5 or less, and the active ingredient of the crude wood vinegar solution is transferred to the organic solvent phase.
H. A high-quality wood vinegar solution, wherein formaldehyde and methanol in the organic solvent phase are transferred to the aqueous phase by contact with an aqueous solution of H 4.5 to 11.0, and the organic solvent phase separated from the aqueous phase is evaporated to dryness. This is a method for producing raw materials.

In the above-mentioned present invention, the crude wood vinegar liquid 100
The amount of the organic solvent is preferably 50 to 200 parts by weight with respect to 100 parts by weight of the organic solvent phase.
More preferably, it is in the range of 5-200. In this case, pH 8.5 to pH 8.5 for specific purposes.
It is preferably 11.0.

The high-quality wood vinegar liquid raw material obtained by the production method of the present invention can be used as it is or as a cosmetic or cosmetic raw material containing the high-quality wood vinegar liquid raw material by dissolving it in an ethyl alcohol aqueous solution or squalane. is there.

The high-quality wood vinegar raw material obtained by the production method of the present invention can be used as a surface active skin / mucosa Staphylococcus aureus, an antibacterial agent for external use of MRSA infection, a superficial skin, utilizing its antibacterial action. A quasi-drug containing a topical antibacterial agent for mucosal Pseudomonas aeruginosa infection, a topical antibacterial agent for superficial skin and mucosal tinea bacillosis, and a high-quality vinegar liquid material in a range of 1 to 50% by weight. It is also possible to use as.

Furthermore, the high-quality wood vinegar liquid material of the present invention is also useful as a smoke preparation and a bactericide.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The crude wood vinegar used in the production of the high-quality wood vinegar liquid raw material of the present invention is, in the case of crude wood vinegar, a dry distillate obtained in the process of carbonizing trees and bark. The case (1) is a dry distillate obtained in the process of carbonizing an adult bamboo, and any commonly used production method can be used.

Such a crude wood vinegar solution usually contains chemical components as shown in Table 1 described later, and generally has a total amount of 1.7 to 1.7 as a total amount of solid components and volatile components. It is a smoked, sour, brownish aqueous solution containing 2.5% by weight of chemical components.

As the organic solvent used in the present invention, highly polar alcohols, acetone, ethyl acetate and the like cannot be used because they are easily dissolved in water, and the wood tar in the crude wood vinegar is easily transferred to the organic solvent phase. Low-polarity petroleum ether, benzene, chloroform can also be used, particularly preferably aliphatic single ethers such as diethyl ether, aliphatic mixed ethers, and hydrocarbons,
Among them, methane-based hydrocarbons such as n-hexane or a mixture thereof is preferably used as the extraction solvent.

The pH of the crude wood vinegar when the crude unvinegar and the organic solvent are brought into contact is also important. If the pH at the time of contact exceeds 2.5, the extraction efficiency of cresol, phenol and the like is reduced. There are obstacles.

In the present invention, when a high-quality wood vinegar is produced using an organic solvent, preferably, an aliphatic single ether and a methane-based hydrocarbon, for example, diethyl, are added to 100 parts by weight of the crude wood vinegar. Ether: n-hexane (1:
1 vol), for example, 50 to 300 parts by weight, preferably 1
A method of adding 00 to 200 parts by weight and mixing with sufficient shaking is adopted. In this case, when the amount of the organic solvent is less than 50 parts, the extraction of the active ingredient in the crude wood vinegar is not sufficient,
If the amount exceeds the weight part, the efficiency of the apparatus decreases.

Next, the organic solvent phase and the aqueous phase are separated according to a conventional method, and for example, 50 to 200 parts by weight, preferably 100 to 150 parts by weight of a 5% aqueous solution of sodium hydrogen carbonate is added to 100 parts by weight of the organic solvent phase. Is added and shaken sufficiently, and the organic solvent phase and the aqueous phase are separated.
In this case, when the amount of the aqueous sodium hydrogen carbonate solution is less than 50 parts by weight, impurities such as acetic acid, propionic acid, and acetone are not sufficiently removed from the organic solvent phase, and when the amount exceeds 200 parts by weight, The utilization efficiency of the device and the drug used is reduced.

The separated organic solvent phase is then preferably dehydrated by using a commonly used drying agent such as anhydrous sodium sulfate. The dehydrated organic solvent phase is evaporated to dryness, for example, by using a rotary evaporator.

In the above-mentioned method, in order to specifically transfer furfural, which is one of the smoked odors (aromatic components) contained in the crude wood vinegar solution and the crude bamboo vinegar solution, to the high-quality wood vinegar solution raw material, the pH 4 In the process of washing with an aqueous solution of 0.5 to 11.0,
In particular, it is preferable to use an aqueous solution having a pH of 8.5 or more. In this process, slightly dissolved proteins such as acetic acid and propion, which are denaturing components of the protein, are also removed.

In the present invention, in producing a high-quality wood vinegar liquid material containing no furfural,
Instead of the alkali carbonate aqueous solution used in the above production method,
It is preferable to use 5% sodium bisulfite, etc.
Alternatively, it is needless to say that it is selectively used depending on the use of the high-quality wood vinegar liquid raw material not containing. In particular, since furfural has an action to reduce the irritating odor of guaiacol and phenols, when used as food, it is preferable to use a high-quality wood vinegar liquid material containing furfural.

The high-quality wood vinegar liquid raw material produced by the above-mentioned production method is used by dissolving it in an organic solvent, an oily component, or an aqueous solution according to the purpose of use. In this case, the amount of liquid to be dissolved is
It is preferable that the amount is equal to or higher than the used high-quality wood vinegar liquid material.

The high-quality wood vinegar liquid raw material produced according to the present invention includes hot water, ethanol, diethyl ether,
Highly soluble in organic solvents such as n-hexane, chloroform and acetone, and soluble in jojoba oil, squalane, glycerin, etc., the high-quality wood vinegar obtained by the above production method is dissolved in these solutions to make cosmetics, pharmaceuticals and foods. Can be used as a raw material for producing or a product thereof.

Utilizing the antibacterial action of high-quality wood vinegar, superficial skin / mucosa Staphylococcus aureus, MRSA infection, superficial skin / mucosa Pseudomonas aeruginosa infection, superficial skin / mucosal ringworm, etc. When preparing a non-medicinal antibacterial agent, a high-quality wood vinegar liquid material, for example, 1 to 10 parts by weight, preferably 1 to 3 parts by weight of a high-quality wood vinegar liquid material is dissolved in, for example, a 50% aqueous ethyl alcohol solution. Can be used.

When a high-quality wood vinegar liquid material is used as a cosmetic, for example, 1 to 10 parts by weight of a high-quality wood vinegar liquid material is mixed with, for example, 100 parts by weight of squalane to form a high-quality squalane solution. 10 parts by weight, for example, is blended with 100 parts by weight of vaseline, heated and mixed, and then cooled.

[0028]

EXAMPLES Hereinafter, the present invention will be further described with reference to examples, and at the same time, the usefulness of a high-quality wood vinegar liquid raw material obtained by the production method of the present invention will be described.

Examples 1 and 2 and Comparative Example 1 Production of high-quality wood vinegar liquid raw material The used crude wood vinegar liquid contains harmful substances as shown in Table 1.

Example 1 was carried out as follows, with the aim of producing a high-quality wood vinegar liquid material relatively free of furfural. That is, 300 parts by weight of diethyl ether: n-hexane (1: 1 v / v) is added to 100 parts by weight of the crude wood vinegar solution, and the mixture is shaken sufficiently. P of aqueous phase during mixing
H was 2.4. After separating the organic solvent phase and the aqueous phase, the aqueous phase is discarded. Next, p is added to the diethyl ether / n-hexane phase.
After adding 200 parts by weight of a 5% sodium hydrogen sulfite solution of H4.6 and shaking well, the diethyl ether / n-hexane phase and the aqueous phase are separated, and the aqueous phase is discarded. The remaining diethyl ether / n-hexane phase was dehydrated by adding 5 parts by weight of anhydrous sodium sulfate, and then evaporated to dryness using a rotary evaporator. The raw material of high quality wood vinegar obtained by this production method is usually 0.170 to 0.184 g per 100 ml of crude wood vinegar.
Was in the range. The chemical components of the obtained high-quality wood vinegar liquid material were analyzed and are shown in Table 1.

Example 2 was carried out as follows in order to produce a high-quality wood vinegar liquid material containing a relatively large amount of furfural. That is, 300 parts by weight of diethyl ether: n-hexane (1: 1 v / v) is added to 100 parts by weight of the crude wood vinegar solution, and the mixture is sufficiently shaken and mixed. The pH of the aqueous phase at the time of mixing was ... After separating the organic solvent phase and the aqueous phase, the aqueous phase is discarded. Next, 200 parts by weight of a 5% sodium hydrogencarbonate solution at pH 8.7 is added to the diethyl ether / n-hexane phase, and after sufficient shaking, the diethyl ether / n-hexane phase and the aqueous phase are separated, and the aqueous phase is discarded. The remaining diethyl ether / n-hexane phase was dehydrated by adding 5 parts by weight of anhydrous sodium sulfate, and then evaporated to dryness using a rotary evaporator. The chemical components of the obtained high-quality wood vinegar solution were analyzed and the results are shown in Table 1.

Comparative Example 1 was carried out in exactly the same manner as in Example 1 except that the pH of the aqueous solution of 5% sodium bisulfite added to the diethyl ether / n-hexane phase was changed to 4.0. The chemical components of the obtained high-quality wood vinegar liquid material were analyzed and are shown in Table 1.

The results in Table 1 show that the crude wood vinegar solution 100 ml
2 shows the amounts of chemical components when the high-quality wood vinegar liquid raw material obtained from Example 1 was dissolved in 100 ml of a 50% ethyl alcohol aqueous solution, together with the chemical components of the crude wood vinegar solution.

[0034]

[Table 1] As shown in Table 1 above, in the high-quality wood vinegar liquid produced by extraction with diethyl ether / n-hexane, formaldehyde and methanol, which are biologically harmful components, were not detected. Further, by washing the diethyl ether / n-hexane extract with a 5% sodium bisulfite solution, furfural, one of the smoked odors, was not detected in the high-quality wood vinegar solution.

When the diethyl ether / n-hexane extract was washed with an aqueous solution having a pH of 4.0 (comparative example), no formaldehyde was detected, but methyl alcohol was contained in 80 ppm, and guaiacol, phenol and cresol were used in Examples. It was significantly lower than 1 and 2.

The fact that the concentrations of guaiacol, phenol and cresol were detected at a higher concentration than the crude wood vinegar solution indicates that these substances existed as condensed tannins in the crude wood vinegar solution and were freed during the production process of the present invention. Because it became.
This result is almost the same even when crude bamboo vinegar is used instead of crude wood vinegar. Table 2 shows the average recoveries of 10 samples of these substances in Examples 1 and 2.

[0037]

[Table 2]

Application Example 1 Antibacterial activity of high-quality wood vinegar liquid raw material Using 100 ml of crude wood vinegar liquid, 50% of the high-quality wood vinegar liquid raw material extracted with diethyl ether / n-hexane in Examples 1 and 2 and Comparative Example 1 was used. The antibacterial effects of two high-quality wood vinegar solutions dissolved in 100 ml of an ethyl alcohol aqueous solution were examined. Table 2 shows the results. The percentage in Table 3 indicates the effective dilution concentration of the 50% aqueous solution of ethyl alcohol.

[0039]

[Table 3]

The high-quality wood vinegar produced according to Examples 1 and 2 for staphylococci, which is the causative agent of superficial skin and mucous membrane infections, is 6.24% or more. 12.5% or more, 12.5-25% or more for Candida albicans and 1.5 for Trichophyton
6% or more, pathogenic Escherichia coli O-1 which is the causative organism of food poisoning
With respect to No. 57, an antibacterial effect was observed at a concentration of 12.5% or more. In contrast, the high-quality wood vinegar produced in Comparative Example 2 showed the same level of antibacterial activity against Trichophyton and Pseudomonas aeruginosa, but less than half that against other pathogenic bacteria. This result indicates that high-quality wood vinegar does not contain formaldehyde and methanol and exhibits antibacterial activity against certain pathogenic microorganisms. Can be expected as a topical therapeutic agent and a bactericidal agent for the pathogenic bacterium Escherichia coli O-157 which is a causative bacterium of food poisoning.

Application Example 2 Ultraviolet rays in a wide range of 250 to 400 nm reach the ground. As harmful effects of this ultraviolet ray, erythema of the skin, sunburn, blackening, aging of the skin and the like are known. The high quality wood vinegar solution dissolved in the 50% ethyl alcohol solution obtained in Example 1 was diluted with ethyl alcohol to obtain
FIG. 1 shows the results of measuring the absorbance at 00 to 400 nm and investigating the ultraviolet absorption capacity. High quality wood vinegar has a wavelength of 27
A component exhibiting a maximum absorbance at 0 to 280 nm is contained, and this substance has the ability to absorb UV-B ultraviolet light, and is identified as a phenolic substance from the characteristics of the absorption curve using a standard substance. .

In order to make a cosmetic preparation containing a high-quality wood vinegar more broadly capable of absorbing ultraviolet light, an ultraviolet absorber having a maximum absorbance at 320 to 380 nm, such as balsole A, may be added.

Application Example 3 0.18 g of the high quality wood vinegar liquid raw material produced in the above production example was
100 parts of squalane to which a surfactant was added was dissolved to prepare a cosmetic compounding material (high-quality wood vinegar liquid squalane solution). The temperature was 75 at a ratio of 3 parts by weight of high-quality wood vinegar liquid squalane solution to 97 parts by weight of white vaseline. The mixture was heated and mixed at 〜80 ° C. to prepare a high-quality wood vinegar liquid vaseline ointment, and a human patch test was performed to confirm its safety. The subjects were 43 men and women in total. The test site is the upper back, and the test method is the safety of new raw materials as described in the Ministry of Health, Labor and Welfare's "Production of cosmetics incorporating new raw materials or the range of safety data to be attached to import applications" notified on August 18, 1987. In accordance with the human patch test of test items (guidelines) to ensure Table 4 shows the test results.

[0044]

[Table 4] For both A and B, 100 ml of crude wood vinegar solution was used and dissolved in 100 ml of squalane to which a surfactant was added.
It was used as a stock solution.

C): 3 ml of the sample of B and white petrolatum 97
g blended. This product has no irritating burning odor characteristic of wood vinegar.

1) Erythema-positive case 2) Edema-positive case As shown in Table 4, both high-quality wood vinegar solution squalane-dissolved stock solution (A, B) and high-quality wood vinegar solution petrolatum ointment showed erythema and edema on the sample application site. No skin changes were observed. These results indicate that the high-quality wood vinegar liquid and the high-quality wood vinegar liquid petrolatum ointment were found to be safe for human skin.

Application Example 4 The crude wood vinegar has an antibacterial action against various pathogenic microorganisms, and the high-quality wood vinegar purified thereby has a certain concentration difference, but as with the crude wood vinegar, certain pathogenic microorganisms Has been confirmed to exhibit an antibacterial effect (for example, Table 3 above).

In the microorganism identification test, Trichophyton mentagrop
For five men with tinea pedis bacillus diagnosed according to hytes, the high-quality wood vinegar liquid Vaseline ointment prepared in Application Example 3 is applied twice a day (in the evening, when going to bed after bathing). It was applied so as to fit. In all of the five cases, the affected area was eroded and complained of itching. The effect was evaluated by visual observation and the complaint of each case in the second week.

In each case, the pruritus disappeared, the erosion of the affected part disappeared, and no scar was observed.

Conventionally, stubborn tinea pedis (aka athlete's foot)
Corticosteroids are used as treatments for
It looks as though it has been completely cured, but the symptoms worsen further,
Pigmentation to the affected area, cracking of the affected area, abnormal drying, exacerbation of inflammation, and hyperkeratosis are often observed.
Such aggravation of symptoms is the same in patients who are undergoing steroid therapy (application of corticosteroids to affected areas) for atopic dermatitis.

The high-quality wood vinegar liquid Vaseline ointment, unlike adrenal corticosteroids as described above, is expected to be a safe agent for tinea bacillosis and atopic dermatitis without side effects.

Application Example 5 An example of producing a high-quality wood vinegar liquid vaseline ointment or a cosmetic oil (oil type) for preventing cracking of heels and repairing cracked skin.

97 g of white petrolatum was added to 3 ml of squalane, a high-quality wood vinegar solution of product B of application example 3, at a temperature of 75-80.
Mix well while heating at ° C. To increase the softness if desired, it is possible to reduce white petrolatum and add squalane or jojoba oil without high quality wood vinegar.

As a cosmetic oil (oil type), a mixture of 30 g of liquid paraffin, 50 ml of olive oil, 3 ml of high-quality wood vinegar liquid squalane (product of B in Application Example 3), and 17 ml of ordinary squalane was mixed at a temperature of 70 to 85 ° C. Heated and mixed well. In addition, it is also possible to add a favorite fragrance to this.

Application Example 6 In the preparation of a cosmetic after shaving, 3.0 ml of the high-quality wood vinegar solution B produced in Example 2, 47 ml of glycerin and 50 ml of purified water are added and mixed well. Since this liquid is odorless and colorless and transparent, it is possible to add a fragrance and a pigment as desired.

[Brief description of the drawings]

FIG. 1 is an example of an absorption spectrum of a high-quality wood vinegar liquid raw material obtained by the method of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A61K 35/78 A61K 35/78 Y

Claims (4)

(57) [Claims] 1. A crude wood vinegar solution is mixed with an organic solvent under acidic conditions of pH 2.5 or less, and the active ingredient of the crude wood vinegar solution is transferred to the organic solvent phase. A method for producing a high-quality wood vinegar liquid raw material, wherein formaldehyde and methanol in an organic solvent phase are transferred to an aqueous solution phase by contact with an aqueous solution, and the organic solvent phase separated from the aqueous solution phase is evaporated to dryness. 2. The method according to claim 1, wherein the amount of the organic solvent is 50 to 200 parts by weight based on 100 parts by weight of the crude wood vinegar solution. 3. pH based on 100 parts by weight of an organic solvent phase
4.5 to 11.0 parts by weight of aqueous solution to be contacted is 75 to 2
3. The method according to claim 2, wherein the range is 00. 4. The method according to claim 1, wherein an aqueous solution having a pH of 8.5 to 11.0 is mixed with the organic solvent phase.