JP2770211B2 - Natural hiba oil-based fungicide and method for producing same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fungicide containing natural hiba oil as a main component and a treating agent used for foods and the like, which is called an antiseptic in a broad sense and has antibacterial properties (hereinafter referred to as a fungicide) It is about.

[0002]

2. Description of the Related Art In the production and preservation of foods and the like, a treatment agent called a preservative in a broad sense is added to prevent the generation of mold and the generation and spread of various harmful bacteria, thereby preventing the generation of mold and preventing various kinds of harm. It is widely practiced to prevent the occurrence and spread of bacteria. As the treating agent used in this case, that is, a fungicide, a substance using a natural material as it is, a processed product thereof, a substance selected from various chemicals, and the like are selected according to the purpose of use. As the various chemicals, synthetic compounds containing sulfur, nitrogen, oxygen and the like in their molecules, synthetic compounds containing arsenic, and the like are well known and widely used.

[0003] Many natural materials are used as they are, or are used after being slightly processed. For example, what is generally called spice, or a certain kind of plant is used. However, although those using these natural materials are well known, there are few examples of those which are industrially practical. Although it is known that it has antifungal properties, it can be considered that there are a wide variety of causes that are not practically used.As an important cause, natural materials show sufficient antifungal properties, but once processed, Alternatively, it is conceivable that the drug effect is substantially lost when diluted.

[0004]

SUMMARY OF THE INVENTION The present invention relates to hiba oil, which is one of the natural materials having antifungal properties, and uses an emulsifier while maintaining antifungal properties. It is intended to provide a natural hiba oil-based fungicide which is diluted without using an active ingredient and a method for producing the same.

[0005]

The present invention provides: Caustic addition to Hiba oil heated to Hiba oil
Saponifies the oil component that undergoes the saponification action of the oil, and emulsifies the oil component.
The treated product was granted, and diluted with water and alcohol
Natural hiba oil based antifungal agent characterized by comprising. 2. 2. The natural fungicide based on hiba oil according to the above 1, wherein the content of hiba oil is 10% or less. 3. 3. The natural hiba oil-based fungicide according to the above 1 or 2 , wherein the content of the alcohol is 40% or more. 4. 4. The natural hiba oil-based fungicide according to any one of the above items 1 to 3, wherein the alcohol is a lower alcohol having 4 or less carbon atoms. 5. Add caustic alkali to Hiba oil and heat it to remove
Saponifies the oil component undergoing saponification action to emulsify the oil component.
A method for producing a natural fungus oil-based fungicide, characterized in that after obtaining the treated product , water and alcohol are added and stirred to adjust the pH to a substantially uniform solution with or without pH adjustment. 6. 6. The method for producing a natural Hiba oil-based fungicide according to the above item 5, wherein the amount of water used is at least the same as or greater than that of Hiba oil. 7. 7. The method for producing a natural Hiba oil-based fungicide according to the above 5 or 6 , wherein the amount of alcohol used is twice or more that of Hiba oil. By doing so, the purpose is achieved.

The details will be described below. Hinokitiol is well known as an active ingredient of natural product-based fungicides. This hinokitiol is contained in Taiwan cypress and is said to have been effective, but at present it is the most abundant in hiba oil obtained by steam distillation of natural Aomori hiba, which is mainly produced in Aomori Prefecture. It is supposed to be. It is said that hiba oil contains effective ingredients other than hinokitiol, but in any case, the total content of the active ingredients is not large and only a trace amount. Therefore, it is considered that even if a simple dilution of Hiba oil containing only a trace amount of the active ingredient is used, the antifungal property is reduced and the substantial effect cannot be obtained.

[0007] In fact, hiba oil is an aggregate of various oil components, but it is difficult to simply dilute it with water. Even if an attempt was made to use an emulsifier for dilution, emulsification was difficult, and the effect was reduced even when emulsification was successful.
This is presumably because the emulsifier covers the active ingredient of hiba oil with a multimolecular layer. Some emulsifiers are not edible and cannot always be used, even if emulsification is successful. Furthermore, even when emulsification is successfully performed using an emulsifier, the unique odor of Hiba oil is hard to decrease and cannot be used depending on the application.
Hiba oil is soluble in lower alcohols such as ethanol, but it was difficult to maintain the antifungal properties of Hiba oil by dilution with lower alcohol. In such a state, there is no other way but to use the hiba oil as it is. It is practically difficult to use.

The present invention focuses on diluting hiba oil while maintaining its antifungal properties, and has succeeded in obtaining a fungicide containing dilute hiba oil as a main component. Moreover, the obtained antifungal agent can make the smell peculiar to Hiba oil extremely small. The present invention succeeds in diluting Hiba oil while maintaining the fungicidal properties of Hiba oil by adding an alkali to heat treatment and then dissolving by adding an alcohol, particularly a lower alcohol and water. It was done. In this case, as the alkali to be used, commonly used alkali compounds such as caustic soda and potassium hydroxide are allowed.

Due to the addition of alkali and heating, some of the component oils of Hiba oil contain saponifiable components.
It is expected to undergo a saponification action, and as a result, the treated Hiba oil is thought to have increased water affinity. For this reason, regardless of whether an emulsifier is used, the treated material imparts hydrophilicity as an anionic activator contained in Hiba oil itself, and even if it has an emulsifying action, it does not lose the fungicidal properties of Hiba oil and can be treated with an aqueous dispersion. It is considered that there is a possibility. Alternatively, it is conceivable that an antifungal property is separately added by alkali treatment.

However, in the case where an alkali is added and heat-treated, an oil layer and an aqueous layer are separated when a small amount of water is added. Therefore, a lower alcohol such as ethanol was added to obtain a substantially uniform solution. For example, it was confirmed that a sufficient antifungal property was exhibited even with a 20-fold diluted solution. Moreover, the smell peculiar to Hiba oil is very weakened. The alcohol content of the obtained fungicide is not particularly limited, but is preferably at least 40% from the viewpoint of ensuring the dispersibility and uniformity of the hiba oil. Also,
The amount of hiba oil may be large or small, but if it is large, the significance of dilution is lost, and if too small, there is a problem in securing mold resistance. The lower limit is 2-3%, depending on the purpose of use
And 5% is useful for most purposes. Although there is no particular upper limit, generally speaking, it can be said to be 30 to 40% because of dilution. The term "lower alcohol" as used herein means an alcohol having 4 or less carbon atoms, which is very commonly used.

The amount of water used in the production is preferably at least the same as or higher than that of hiba oil, and the upper limit is about 25, 26 times in relation to other components. Generally, a range of 2 to 15 times is particularly preferable. If the amount of water deviates from this range, problems may occur with the uniform dilution of Hiba oil. The amount of alcohol used in the production is preferably in the range of 2 to 40 times the amount of Hiba oil, particularly 4 to 4
A range of 0 times is preferred. If the amount of alcohol is less than this range, the dilution of hiba oil will be reduced, and an effective target product will not be obtained. If too much, the dilution is too large,
This is because the content of hiba oil becomes too thin.

[0012]

Example 1 30 g of Hiba oil from Aomori was placed in a flask equipped with a cooling tube, and 15.5 g of a 3% aqueous solution of sodium hydroxide was added thereto. Heating from 40 ° C to over 90 ° C, mostly 96-98 ° C
At 90 ° C., and then heated for 90 minutes. Next, 100 grams of water was added. After the water had been added and the two layers were stirred well, 432.4 g of 89.5% ethanol was added. The ethanol-added one had a pH of 9.5, but was neutralized with a 1.54% aqueous hydrochloric acid solution to adjust the pH to 7.5 and the pH 6.1.
The final adjustment was made with water to obtain a 5% hiba oil and about 64.5% ethanol. The obtained product was a yellow transparent liquid, but traces of oil droplets were observed at the bottom. The smell unique to hiba oil was only slightly felt. The supernatant was used as a fungicide.

A fungicide test was carried out using the obtained yellow transparent liquid. An aqueous agar solution containing glucose and honey was prepared, cooled and solidified in a petri dish, and used as a culture. The culture test is to treat the above 5% Hiba oil-based fungicide,
After air-drying to evaporate ethanol, blue mold was planted on the culture bed, and a white test was added for comparison to perform a comparative test.
When left at room temperature, in the white test, mold propagation was observed on the entire surface in 7 to 10 days, but no blue mold propagation was observed in the treated culture after 30 days.

[0014]

Example 2 30 g of hiba oil as in Example 1 was placed in a flask, 25 g of 1.54% caustic soda was added, and the mixture was heated over an open flame. When heating was continued while stirring to prevent bumping, the water gradually evaporated, and the water layer was brown and formed a lower layer, but in about 30 minutes, the entire layer became a uniform layer and only an oil layer. Then stop heating, cool naturally, and add 100
Grams were added, stirred well, and allowed to stand. It was neutralized with 1.54% hydrochloric acid and adjusted to pH 7.5. Next, 432.4 grams of 89.5% ethanol was added, and a little more water was added to bring the total to 600 grams. The obtained product was a yellow transparent liquid having a hiba oil content of 5% and an ethanol content of 64.5%. The odor was slightly felt as in Example 1. Using the obtained liquid as a fungicide, the same test as in Example 1 was performed using the same culture and blue mold as in Example 1. As a result of the test, as in the case of Example 1, no propagation of blue mold was observed even after 30 days.

Comparative Example 1 For comparison, Hiba oil was used
A water emulsion was made using 0% of a nonionic surfactant of the nonylphenylethylene oxide ether type. (Comparison A)
Furthermore, a 5% solution was prepared using 89.5% ethanol of Hiba oil as it was. (Comparative B) Comparative odors of Comparative A and Comparative B were clearly unique to Hiba oil as compared with Examples 1 and 2. Using Comparative A and Comparative B, a test was performed under the same conditions as in Example 1. Both Comparative A and Comparative B were better than the white test, but blue mold breeding was observed from about the 15th, and no mold resistance was exhibited.

Table 1 shows the evaluation results of Example 1, Example 2, and Comparative Example.

[Table 1] Note: The meanings of the symbols in the evaluation results are as follows. ○: Effective △: Insufficient ×: No effect

[0017]

As described above, according to the present invention, hiba oil, which is a kind of natural antifungal agent which has been difficult to use by dilution, is emulsified with a limited emulsifier. Even if it succeeded, it was not able to secure mold resistance, and it still had the unique smell of Hiba oil, without using an emulsifier,
It is possible to dilute and use it, and it is possible to extremely eliminate a unique smell, and to obtain a natural hiba oil-based fungicide having a sufficient antifungal property in a diluted state Was made. Therefore, it has been possible to use Hiba oil, which is a natural antifungal agent, up to the field where the medicinal effect has been confirmed but it is practically difficult to supply, or the application of use has been hindered. The effect can be obtained.

Claims (7)

(57) [Claims] 1. A method of adding a caustic alkali to hiba oil and subjecting it to heat treatment.
Saponifies the oil component in Hiba oil which is subject to saponification
Natural hiba oil based antifungal agent characterized by comprising diluting with a treated product obtained by imparting emulsifying effect, water and alcohol. 2. The natural fungicide according to claim 1, wherein the content of hiba oil is 10% or less. 3. A natural hiba oil based antifungal agent according to claim 1, wherein in that the content of alcohol is 40%. Wherein the alcohol is one of the claims 1 to 3, characterized in that a lower alcohol having 4 or less carbon atoms
The natural hiba oil-based fungicide according to any of the above items . 5. The caustic was added to Hiba oil, heated to
Saponification of saponified oil component in Hiba oil
After obtaining a treated product having an emulsifying action , water and alcohol are added and stirred, and the pH is adjusted or not, and a method for producing a natural Hiba oil-based fungicide, characterized in that the solution is substantially uniform. . 6. The method for producing a natural Hiba oil-based fungicide according to claim 5, wherein the amount of water used is at least the same as or greater than Hiba oil. 7. The method according to claim 5, wherein the amount of alcohol used is twice or more of the amount of Hiba oil.
6. The method for producing a natural hiba oil-based fungicide according to 6 .