JP2731234B2 - Method for producing clove oil with excellent aroma and low sensitization - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a substance (hereinafter, referred to as "sensitizing property") having the property of causing contact skin allergy (hereinafter, referred to as "sensitizing property") contained in clove oil. The present invention relates to a method for producing clove oil having excellent aroma (odor, residual odor) and low sensitization by blending dehydrodieugenol with essential oil removed by distillation under reduced pressure.

[Problems to be solved by conventional technology and invention]

Clove oil is produced in Madagascar and Southeast Asia
Eugenia Caryophyllata is an essential oil obtained by steam distillation of buds and has been used as a flavoring agent for foods since ancient times. In addition, it is widely used as one of the flavoring agents for general cosmetics for men, such as cologne and hair tonic.

In recent years, the presence of sensitizers in some natural essential oils used in cosmetics has been reported.

However, the safety of clove oil has not been studied.

Then, the present inventors conducted intensive studies on the safety of natural essential oils, and as a result, it was confirmed that clove oil had strong sensitizing properties.

The present inventors conducted distillation of clove oil under reduced pressure to fractionate the clove oil under reduced pressure in order to examine the aroma of clove oil and its safety in more detail, and conducted a maximization test (see below).
As a result, the sensitizing substance of clove oil was determined to be present in the high-boiling part as shown in Table 1. Since the sensitizer of clove oil is contained in the distillation residue,
A distillation method in which distillation is performed under reduced pressure to separate a distillate essential oil and a distillation residue having a high boiling point can be used.

However, the high boiling point, which is important for the aroma of clove oil, is lost in the distillation method, and its value as a perfume essential oil is reduced. (Persistence of aroma) is also poor and unsatisfactory.

[Means for Solving the Problems] The present inventors have conducted intensive studies on the components of the high boiling point portion of clove oil in order to solve the difficulties of the prior art, and obtained clovephenyl condephenylaldehyde and dehydrodioigenol B having a phenol skeleton. Identified as a source of oil sensitization.
Dehydrodieugenol was identified as a high boiling point component which is highly safe and important for the aroma of clove oil. The structural formula of each compound is shown below, and the analysis results are shown in Table 2.
Table 3 shows the results of the sensitization test. As a result of these investigations, by blending dehydrodieugenol with essential oil (low boiling point, distillate essential oil) distilled by vacuum distillation of clove oil, it does not adversely affect the aroma, color tone and component balance of clove oil. The present inventors have found that clove oil having a higher residual scent (persistence of aroma), a higher odor (perfume), and a lower sensitization can be easily obtained than the source essential oil or distillate oil, and completed the present invention.

The present invention, after obtaining a distillate essential oil by performing vacuum distillation at a temperature that does not change the aroma component of clove oil,
The distillate essential oil has a structural formula A method for producing clove oil having excellent aroma and low sensitization, characterized by incorporating dehydrodioigenol represented by the formula:

The present invention keeps the fragrance component of the low boiling point portion of clove oil with the balance as it is in natural essential oil,
It starts by distillation under reduced pressure at a temperature that does not change the aroma component of clove oil. The temperature at which the fragrance component of clove oil is not changed is that the liquid temperature in the distillation can of the distillation apparatus does not exceed 140 ° C., preferably 120 ° C.
The following are appropriate: In this case, the lower the degree of operation pressure reduction, the better, but usually a condition of 10 mmHg or less is adopted. Generally, it is preferable to select one having a lower temperature and a lower degree of pressure reduction.

In general, the distillation amount under reduced pressure is about 80% of the clove oil (crude oil) charged. It is preferable to distill as much as possible without impairing the aroma.

When the clove oil (crude essential oil) is distilled under reduced pressure under appropriate conditions as described above, the sensitizing substance in the clove oil remains in the distillation residue together with the high-boiling odor components, and is separated from the distillate essential oil.

The distillate essential oil thus obtained contains no sensitizing substances.

Next, the blending of the above-mentioned dehydrodieugenol with respect to the above-mentioned distillate essential oil is usually carried out by stirring the distillate essential oil and adding the above-mentioned dehydrodioigenol to the required amount in an appropriate amount,
It is performed by dissolving it uniformly.

The amount of dehydrodioigenol (the amount used) is 0.5 to 10% by weight, preferably 0.5 to 10% by weight, based on the weight of the distillate oil.
1.0 to 5.0% by weight. The dehydrodieugenol used in the present invention is prepared by the method of Fujita et al.
No. 9 B110-B112 (1966)). The compound is safe without skin irritation or sensitization, and is easily soluble in the distillate oil.

The dehydrodieugenol derivative used in the present invention has no skin irritation or sensitization, is safe, and is easily soluble in the distillate essential oil.

According to the present invention, natural clove oil has an excellent lingering scent without adversely affecting the aroma, color tone and component balance of natural clove oil.
A high-quality clove oil with a good odor and almost no sensitization can be obtained industrially easily and with good reproducibility, and the specificity of its action and effect is remarkable.

〔Example〕

 Hereinafter, examples will be described.

The% shown in the examples means% by weight. Sensitization,
The test methods for residual odor, standing odor, etc. are as follows.

(1) Sensitization test method Sensitization was evaluated by a maximization test.

Hartley guinea pigs (female) weighing 350-400 g were shaved onto 4 × 6 cm skin on the scapula of the guinea pig, and three intradermal injections in one row were performed in two rows in the following order.

Freund's Complete Adjuvant (Freund's
complete adjuvant: hereinafter abbreviated as FCA solution)
Intracutaneous injection of 0.05 ml at each location.

A 10% olive oil solution of test sample such as untreated clove oil was injected intradermally into each of the right and left two places at 0.05 ml each.

The same amount of sterilized water was added to an FCA solution containing 20% of test sample such as untreated clove oil and emulsified.
ml intradermal injection.

One week after these operations, the same site was shaved and rubbed with petrolatum containing 10% sodium lauryl sulfate to cause slight inflammation. Twenty-four hours after the application, 0.2 ml of an olive oil solution containing a 10% test sample such as untreated clove oil was applied to the gauze at the same site, and the ozone oil was stuck for 48 hours. On the 21st day after intradermal injection, the abdomen was shaved, and test sample 5 such as untreated clove oil was used.
% And 10% olive oil solutions were occluded for 24 hours. The judgment was made visually after 24 hours and 48 hours according to the evaluation criteria shown in Table 4.

(2) Test method of residual odor The following sensory test was employed to compare the residual odor of the essential oil and the distillate essential oil of the essential oil of the present invention obtained by the method of the present invention.

Apply 150 mg of the sample essential oil evenly to a 5.5 x 15 cm odor paper,
Sensory test room (temperature 25 ° C, humidity 60%, wind speed 0.1m / sec or less)
Leave it vertically inside. An appropriate time after application (for example, 0
(Minutes, 30 minutes, 1 hour, 2 hours, 4 hours), the comparison of the residual scent intensity of the sample essential oil attached to each odor paper is repeated 10 times by 10 panelists specializing in fragrance.

(3) Test Method for Scent (Odor) The following sensory test was employed to compare the scent of the essential oil of the present invention obtained by the method of the present invention with the scent of crude oil and distillate essential oil.

The sample essential oil is made into an 80% alcohol solution, applied in the same amount to odor paper, and the comparison of the fragrance of the sample essential oil adhering to each odor paper is repeated 10 times by 10 panelists specializing in fragrance.

Example 1 1 kg of clove oil (produced in Indonesia) was distilled under reduced pressure at a reduced pressure of 2 mmHg and a can temperature of 120 ° C to obtain 823 g of a colorless and transparent distillate essential oil.

As a result of high performance liquid chromatography analysis of the distillate, no peaks of coniferyl aldehyde and dehydrodioigenol B were observed. Next, this distillate essential oil 100
Clove oil according to the present invention was obtained by uniformly dissolving 5% by weight of dehydrodioigenol to 5% by weight. Next, a sensitization test was performed on the clove oil according to the present invention (the present invention oil), a commercially available clove oil (crude essential oil) used for vacuum distillation, and the spilled essential oil. As a result, as shown in Table 5, it was confirmed that the clove oil of the present invention (the oil of the present invention) had almost no sensitization.

Next, the residual odor of the essential oil of the present invention was compared with the residual odor of the distillate essential oil by the above-mentioned test method for residual odor. As a result, as shown in Table 6, it was confirmed that the essential oil of the present invention had a high (strongly) excellent residual scent.

Next, a sensory test was performed on the essential oil of the present invention, and the scents (odors) of the distillate essential oil and the crude essential oil by the above-described method. The results are shown in Table 7.

As is clear from the results of Table 7, the essential oil of the present invention is better than the distillate essential oil and the crude essential oil in terms of aroma (odor), and is also preferable in aroma.

Example 2 To each of the distillate essential oils obtained by distilling the commercially available clove oil used in Example 1 under reduced pressure under the same conditions, dehydrodieugenol was added in the amounts shown in Table 8 and uniformly dissolved. A clove oil according to the invention (invention oil) was obtained. A sensitization test of these clove oils (the oil of the present invention) was performed at an induced concentration of 3%, and as a result, almost no sensitization was observed. (Almost no detection was found.) Further, as a result of comparing the residual odor after 2 hours of standing with the distillate, all the oils of the present invention showed higher residual odor than the distillate. Furthermore, in the comparative test results of the scent (smell) with the above-mentioned crude oil, the oil of the present invention was more favorable and more excellent in aroma. Table 8 shows the results.

[Effects of the Invention] The clove oil obtained by the method of the present invention has no sensitizing substances, retains the aroma of natural clove oil as it is, and has a so-called natural rich scent. Moreover, its residual aroma (persistence of aroma) is superior to the distillate essential oil. Further, the odor (perfection) was better than that of the distillate essential oil or the crude oil, and skin irritation and sensitization were hardly observed.

Claims (3)

(57) [Claims] Claims: 1. After obtaining a distillate essential oil by performing vacuum distillation at a temperature that does not change the aroma component of clove oil,
The distillate essential oil has a structural formula A method for producing clove oil having excellent aroma and low sensitization, characterized by incorporating dehydrodioigenol represented by the formula: 2. The process according to claim 1, wherein the temperature at which the flavor component of the clove oil does not change is 140 ° C. or lower. 3. The process according to claim 1, wherein dehydrodieugenol is incorporated in an amount of 0.5 to 10% by weight based on the weight of the distillate essential oil.