JPH05105898A - Method for separating acid oil from essential plant oil - Google Patents

Abstract

PURPOSE:To readily separate an acid oil rapidly at a low cost by first making an acid oil contained in an essential oil from a cupresineous plant adsorbed on a specific amorphous silicate of a heavy metal and then performing extraction with a lower alcohol. CONSTITUTION:An essential oil from a cupressineous plant is optionally dissolved in a solvent to obtain a solution having a concentration of 0.01-15g/l. Added to the solution is an amorphous silicate of a heavy metal of the formula Mo(SiO2)xH2O (wherein M is a divalent metal ion and x is 2-5) in a concentration of 10-100wt.% relative to an acid oil present in the solution. The mixture is stirred at room temperature for 10-180min to have the acid oil contained in the essential plant oil selectively adsorbed on the amorphous silicate of a heave metal. Thereafter, any unadsorbed component is removed with a solvent, any drying is performed at room temperature to 120 deg.C to recover the amorphous silicate of a heavy metal having the acid oil adsorbed thereto. Next, the acid oil is extracted from the silicate with a lower alcohol.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention makes it possible to easily, quickly and inexpensively produce an acidic oil containing hinokitiol and β-drabulin from a plant essential oil such as Hiba oil by using particles composed of an amorphous heavy metal silicate. The present invention relates to a method for separating and a freshness-retaining material composed of an amorphous heavy metal silicate adsorbed with the acidic oil.

[0002]

2. Description of the Related Art Plant essential oils obtained from cypress family plants such as Asunaro, Aomori Hiba, Ibuki, Heinez, Taiwanese cypress, and Nezuko, among others, Hiba oil obtained from Aomori Hiba is rich in hinokitiol. Are known. This 7-membered tropolone compound, hinokitiol, has a strong antibacterial and insect repellent effect, and recently, hinokitiol suppresses ethylene generation in fruits and vegetables, hyphal growth suppressing effect of mushrooms, and seed germination suppressing effect. It has been found that it has various useful actions. Therefore, various attempts have been made to separate and purify hinokitiol having such excellent performance from plant essential oil.

Generally, the composition of plant essential oil containing hinokitiol is about 90% of neutral oil mainly composed of tsuyopsene which is a main component of scent, and acid oil mainly composed of hinokitiol and β-drabulin having the same action as hinokitiol. About 1
It consists of 0%. Therefore, as a refining method, a method is generally used in which an alkaline solution is added to make an acidic oil component a metal salt, and the metal salt is separated. For example, a method of diluting a vegetable essential oil with 8 to 10 times the amount of benzene and then adding a caustic soda solution to recover the precipitated hinokitiol Na salt (Japanese Patent Laid-Open No. 51-2).
No. 3244), or sodium bicarbonate is added to plant essential oil to remove organic acid, and alkali metal is added to the residual oil to form a monovalent metal salt, which is further substituted with a divalent or higher metal salt to suspend the precipitate on petroleum ether. A method of adding turbidity and adding excess dilute HCl to transfer hinokitiol to an ether layer and distilling or converting to Na salt for purification (Japanese Patent Publication No. 33-8518) and other separations by supercritical extraction are performed.

The hinokitiol thus obtained has many effects such as antibacterial properties, insect repellency, ethylene generation suppression and mycelial growth suppression as described above, and is therefore widely used for keeping freshness.

As a method for maintaining the freshness of fruits and vegetables, there are methods such as low temperature storage, CA storage and reduced pressure storage for the purpose of preventing overripening and aging of fruits and vegetables. However, these methods require a large investment in equipment, and therefore cost is not suitable unless a large amount of high value-added fruits and vegetables are stored. Therefore, as a relatively simple freshness-keeping method, there are many examples of using a freshness-keeping material containing a substance having a freshness-keeping ability such as hinokitiol. For example, a method of impregnating and adsorbing hinokitiol or a hinokitiol clathrate compound (hinokitiol-β-cyclodextrin) on paper, a non-woven fabric or the like by spraying, dipping, coating or the like (Japanese Patent Publication No. 3-1942),
A method of allowing a metabolite gas inhibitor such as hinokitiol to coexist with a water-absorbing polymer and a humidity control agent in paper or a non-woven fabric (Japanese Patent Laid-Open No. 3-65135), or by adsorbing hinokitiol on zeolite or ceramic fine powder to form a film or cardboard. Coating method (JP-A-2-15687)
No. 6), a method of directly impregnating a paper with an aqueous solution or alcohol solution of hinokitiol, or applying it to a sheet (Japanese Patent Application Laid-Open No. 1-211446).

[0006]

As described above, hinokitiol is a substance that is very effective in maintaining freshness, and if it is impregnated into paper, non-woven fabric, label, film, cardboard or the like directly or through a carrier, It becomes an excellent freshness-keeping material. However, when separating hinokitiol derived from natural products from plant essential oils such as hiba oil, those with a high purification purity require a very long purification process and a large amount of reagents and solvents, and those with a relatively short purification process require purification. It has a bad purity and contains a considerable amount of woody odor components. In addition, the currently practiced method is dangerous because it uses a large amount of acid and alkali, and the problem of wastewater treatment is serious.

When purified hinokitiol is used for keeping freshness, if it is directly impregnated into paper, nonwoven fabric or sheet, the volatility rate of hinokitiol is high and the freshness keeping effect is not sustained, or hinokitiol is adsorbed on a carrier or When an inclusion compound is included in paper, a non-woven fabric, or a sheet, the rate of volatilization of hinokitiol decreases, so that the effect is maintained but a step of adsorbing hinokitiol on the carrier is added. In the event that the fruits and vegetables become overripe and produce a bad odor as a result, they do not have the effect of removing the bad odor. Therefore, in order to prevent this, a deodorant and a deodorant must be added to the hinokitiol-containing freshness-retaining material.

Thus, when natural hinokitiol is used as a freshness-retaining material, excellent effects are exhibited. To prepare a hinokitiol-containing freshness-retaining material, (1) extraction of hinokitiol from plant essential oil such as hiba oil, (2 ) Adsorption or inclusion of the extracted hinokitiol on the carrier, and (3) weaving of the hinokitiol-containing carrier into a non-woven fabric and the like are required in many complicated steps, and in order to have a deodorizing effect, in addition to the above steps, It is also necessary to add a deodorant and weave it.

[0009]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, have reached the present invention.
That is, the present invention is a plant essential oil containing hinokitiol such as hiba oil to hinokitiol and β having an action equivalent thereto.
-A method of separating and refining hinokitiol by separating acidic oil containing drabulin as a main component and neutral oil mainly containing tsuyopsene and selectively adsorbing it on an amorphous heavy metal silicate, and this acidic oil. The present invention relates to a freshness-retaining material composed of adsorbed amorphous heavy metal silicate.

That is, the gist of the present invention is: (1) The addition of an amorphous heavy metal silicate represented by the general formula (I) to a plant essential oil obtained from a Cypressaceae plant in the presence or absence of a solvent, Selectively adsorb the acidic oil in the plant essential oil to the amorphous heavy metal silicate by mixing,
Then, a method for separating an acidic oil in a plant essential oil, which comprises extracting with a lower alcohol, and MO (SiO ₂ ) _{xH 2} O (I) (wherein, M is a divalent heavy metal ion and X is 2 to 2). (2) The present invention relates to a freshness-retaining material composed of an amorphous heavy metal silicate selectively adsorbing an acidic oil by the method (1).

According to the separation method of the present invention, a hinokitiol-containing plant essential oil such as hiba oil is dissolved in a suitable solvent such as n-hexane, and the amorphous heavy metal silicate is added and mixed into the solution. At, the acidic oil containing hinokitiol and β-drabulin as main components is selectively adsorbed.
Therefore, after washing the silicate with the solvent to remove the non-adsorbed components such as neutral oil, if extracted with a lower alcohol, only the adsorbed acidic oil is eluted, and the acidic oil from the hinokitiol-containing plant essential oil is extracted. Can be easily separated.

The amorphous heavy metal silicate used in the present invention is a compound represented by the general formula (I). MO (SiO ₂ ) _x H ₂ O (I) (In the formula, M represents a divalent heavy metal ion, and X represents a number of 2 to 5.) Here, zinc is a divalent heavy metal ion,
Copper, nickel and the like can be mentioned, but zinc is preferably used. Further, X is preferably ₂ to 5 as the amount of SiO ₂ . It is known that the compound having the above composition has a strong deodorizing effect as well as an adsorptive power (Japanese Patent Laid-Open No. 2-265).
644), and is most suitable for use in the separation method of the present invention. Examples of the amorphous heavy metal silicate satisfying the above conditions include zinc silica-based composite oxides such as ZnO (SiO ₂ ) ₂ H ₂ O.

The solvent used in the present invention is
As described above, n-hexane, cyclohexane, n-heptane and the like are used.

As an amorphous heavy metal silicate, for example, in order to separate and purify an acidic oil from Hiba oil by using a zinc-silica-based complex oxide, Hiba oil itself or Hiba oil is dissolved in a solvent and present in a solution. The zinc-silica composite oxide is usually 10 to 100% by weight, preferably 30 to 100 parts by weight of the acidic oil.
~ 70 wt% is added, and the mixture is stirred at room temperature for 10 to 180 minutes, preferably 15 to 40 minutes. In this case, in consideration of operability such as stirring and washing, a good result can be obtained by using a 10 to 70% solution of Hiba oil. After stirring, the non-adsorbed components are washed and removed with a solvent such as n-hexane, and then dried at room temperature to 120 ° C, preferably 60 to 110 ° C to obtain a zinc-silica-based composite oxide having only acidic oil adsorbed. You can

If this is stirred in, for example, ethanol,
The acidic oil is extracted and an ethanol solution of the acidic oil is obtained. The acidic oil can be easily separated by filtering off the zinc-silica-based composite oxide and then distilling off the ethanol by distillation. As the lower alcohol used for the extraction in the present invention, methanol, propanol and the like can be used in addition to ethanol as described above.

The zinc-silica-based composite oxide obtained by heating and drying the acidic oil described above is
Since it does not adsorb neutral oil containing tsuyopsene, which is the main component of odor, it hardly smells wood. The zinc-silica-based composite oxide thus obtained adsorbs hinokitiol and β-drabulin having an action equivalent to that of hinokitiol, and therefore, when used as it is, it exhibits an excellent effect as a freshness-retaining material. That is, since the amorphous heavy metal silicate obtained by the above method does not adsorb tsuyopsen, which is the main component of odor, it is woven into paper, non-woven fabric, sheet, etc. as it is, for keeping freshness of fruits and vegetables. Can be used for

The above is an example in which the acidic oil in the hiba oil is adsorbed on the amorphous heavy metal silicate, but the same treatment may be carried out after the crystalline hinokitiol is dissolved in the solvent. In this case, hinokitiol was dissolved in n-hexane so as to have a concentration of 0.01 to 15 g / L, preferably 0.1 to 15 g / L, and the hinokitiol weight in this solution was 10%.
~ 100% by weight of zinc-silica composite oxide is added and stirred at room temperature for 5 to 120 minutes, preferably 10 to 30 minutes. After that, it is washed with n-hexane, filtered to remove non-adsorbed hinokitiol, and then dried under reduced pressure at room temperature to obtain a crystalline hinokitiol-adsorbed zinc silica-based composite oxide.

In the present invention, as described above, the acid oil-adsorbed amorphous heavy metal silicate is obtained by simply stirring and mixing the hiba oil with the amorphous heavy metal silicate in the presence or absence of the solvent. Further, the obtained silicate particles can be used as they are as a freshness-keeping material by simply weaving them into a paper, a non-woven fabric, a sheet or the like. Moreover, the acidic oil-adsorbed amorphous heavy metal silicate thus obtained can exert the deodorizing action of the amorphous heavy metal silicate as it is, and is thus useful as a freshness-retaining material.

Therefore, conventional (1) purification of hinokitiol, (2) adsorption of purified hinokitiol on a carrier,
This can be shortened from 3 steps of (3) weaving the hinokitiol adsorption carrier to the nonwoven fabric to 2 steps of (1) adsorption of the acidic oil to the carrier (2) weaving of the acidic oil adsorption carrier to the nonwoven fabric. Furthermore, an ordinary rubber-based adhesive solution is applied to a polypropylene film and dried to prepare an adhesive sheet, and acidic oil or hinokitiol-adsorbed amorphous heavy metal silicate particles are evenly dispersed on the adhesive surface of this sheet. After fixing the amorphous heavy metal silicate particles to the surface of the pressure-sensitive adhesive with a pressure-bonding roll, excess particles that have not been fixed can be removed to obtain a freshness-keeping film. Also, put a surface material such as thin paper or non-woven fabric on the endless wire, and on top of this, mix thermoplastic resin such as polyethylene, polypropylene, vinyl chloride, styrene and amorphous heavy metal silicate particles in the air with a mat former. Form a mixed mat, and further layer the surface material at the entrance of the heating device into three layers,
A freshness keeping sheet can be obtained by lightly pressing after the heat treatment. Other known methods can be used to add it to cardboard, a molded container, an additional material, a coating material label and the like.

[0020]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1 Separation method of acidic oil 200 mL of hiba oil and 300 mL of n-hexane were mixed,
To this, 10 g of Shukrenz KD211G (manufactured by Lhasa Kogyo Co., Ltd.) was added and stirred at room temperature for 15 minutes, then washed and filtered with n-hexane to remove non-adsorbed components, ethanol was added, and stirred at room temperature for 30 minutes, and an ethanol eluate was obtained. 300 mL
Got When the liquid chromatography of the ethanol eluate was examined for the purpose of testing the purity of the separated acidic oil, it was found that, in comparison with the liquid chromatograph of Hiba oil, impurities other than the peak of hinokitiol and the peak considered to be β-drabulin were found. Almost no peak was observed. Then, ethanol was distilled off to obtain 10 ml of an oil containing hinokitiol and β-drabulin.

Example 2 Acid Oil Adsorbing Shuk Lens KD
Manufacturing method of 211G 1L of Hiba oil and 1.5L of n-hexane are mixed, 50g of Shukren's KD211G is added thereto, and the mixture is stirred at room temperature for 15 minutes, then washed and filtered with n-hexane to remove non-adsorbed components, and then 90 ° C. After drying for 12 hours, 55 g of acidic oil-adsorbed Shuk lens KD211G having no wood odor was obtained. As a result of measurement by an ultraviolet absorption method, 18.6 g of the KD211G contained hinokitiol 58.6 mg.

Example 3 Acid Oil Adsorbing Shuk Lens KD
211G antibacterial test Acidic oil adsorbed shuukrens 0.1 prepared in Example 2
An antibacterial test was conducted using g, 3 mL of Hiba oil and 5 mg of synthetic hinokitiol crystals. That is, Saboouraud
An agar medium is inoculated with a certain amount of a suspension of Aspergius niger spores and cells. Next, a 2 cm square filter paper was placed in the center of the medium, and acidic oil-adsorbed shuken lenses or synthetic hinokitiol crystals were placed on the filter paper, and the filter paper was impregnated with hiba oil and cultured at 28 ° C. for 7 days. As a comparative example, 0.1 g of KD211G containing no hinokitiol was used in the same manner as above. As a result of the culture, strong blocking circles were found in the medium containing the synthetic hinokitiol crystals, the medium containing acidic oil-adsorbed succulent, and the medium impregnated with hiba oil, but not in the comparative examples.

Example 4 Preservation of Lemon Acidic oil-adsorbed Shuklenz KD21 prepared in Example 2
A freshness holding paper containing 2% of 1G was prepared. Wrap 10 pieces of lemon with this paper, 1 piece each, cardboard box 50 × 50 × 2
It was stored in 0 cm and stored at 25 ° C. In the comparative example, the same experiment was performed using a paper in which the acidic oil-adsorbed Shukes lens KD211G was not incorporated. In Comparative Example, 5 lemons developed mold on the 5th day, and all 10 molds developed on the 12th day, whereas in the Examples, mold did not develop after 30 days. On the 60th day, most of the lemons were found to have mold and softening of the flesh, but the malodor generated from these was not leaked to the outside. On the other hand, in the comparative example, 12
A bad smell came out of the cardboard on the first day.

Example 5 Acid Oil Adsorbed Shuk Lens KD
Deodorization test of 211G 0.5 g of acidic oil-adsorbed shuukrens prepared in Example 2
The deodorization test was conducted using. In other words, acid oil adsorbed Shuk lens KD211G 0.5g in tetra pack of capacity 3L
Was inserted, a standard gas having a predetermined gas concentration was added, and the gas concentration was measured over time. The results are shown in Table 1, and it was shown that the odorous components can still be adsorbed on the acidic oil-adsorbed shark lens.

[0025]

[Table 1]

[0026]

INDUSTRIAL APPLICABILITY As described above, the present invention can easily, rapidly and inexpensively separate an acidic oil containing hinokitiol as a main component from a hinokitiol-containing plant essential oil such as hiba oil, and the acidic oil has a deodorizing effect. Since the adsorbed particles are separated while being adsorbed on the excellent carrier, the adsorbed particles can be directly contained in the freshness-retaining material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuji Takagi 4-28 Kitahama, Chuo-ku, Osaka Sumitomo Seika Co., Ltd. Osaka Head Office

Claims (5)

[Claims] 1. An amorphous heavy metal silicate represented by the general formula (I) is added to and mixed with a plant essential oil obtained from a cypress family plant in the presence or absence of a solvent. A method for separating an acidic oil from a plant essential oil, which comprises selectively adsorbing an acidic oil onto an amorphous heavy metal silicate and then extracting with a lower alcohol. MO (SiO ₂ ) _x H ₂ O (I) (In the formula, M represents a divalent heavy metal ion, and X represents a number of 2 to 5.) 2. A plant essential oil obtained from a cypress family plant,
The separation method according to claim 1, which is hiba oil. 3. The separation method according to claim 1, wherein the solvent is n-hexane. 4. The separation method according to claim 1, wherein the lower alcohol is ethanol. 5. An acidic oil in the plant essential oil obtained by adding and mixing an amorphous heavy metal silicate represented by the general formula (I) to a plant essential oil obtained from a cypress family plant in the presence of a solvent. A freshness-keeping material consisting of selectively adsorbed amorphous heavy metal silicate.