JPH10316991A - Preparation of natural essential oil which does not contain psoralen compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove psoralen compds. from a natural essential oil contg. the same industrially easily without adversely affeting the yield, the perfume component balance of the oil, etc., by fractionating the psoralen compds. with carbon dioxide in the subcritical or supercritical state as a fluid and with a supercritical carbon dioxide extraction column chromatograph apparatus filled with a porous polymeric resin. SOLUTION: An extraction container/separation column 5 is filled with a porous polymeric resin having a specific surface area of 300-700 m<2> /g, a microproe vol. of 0.7-1.1 ml/g, and a micropore radius of 50-1,300 Å. Then, carbon dioxide in a subcritical or supercritical state at 31 deg.C or lower under a pressure of 75 kg/cm<2> or higher is supplied together with a natural essential oil contg. psoralen compds. from a bomb 1 through a spare coil 2, an indicator 3, and a six-way valve 6 to the separation column in order to cause the porous polymeric resin to adsorb the psoralen compds. to fractionate and remove them. The essential oil dissolved in carbon dioxide and contg. no psoralen compd. is separated from carbon dioxide in the gas-liq. separation column 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing a causative substance from a natural essential oil containing psoralens, which may cause a harmful effect on the skin, without causing any troubles such as operational troubles and side reactions. A method for producing a natural essential oil which is advantageously free of industrially-friendly psoralens and which can be advantageously removed by industrially easy means without adversely affecting the aroma of natural essential oil, its component balance, yield, etc. About.

More specifically, the present invention relates to a method for producing a psoralen-containing natural essential oil using a supercritical carbon dioxide extraction column chromatograph filled with a porous polymer resin using subcritical or supercritical carbon dioxide as a fluid. The present invention relates to a method for producing a natural essential oil substantially free of psoralens, which comprises fractionating psoralens in a natural essential oil.

[0003]

2. Description of the Related Art Natural essential oils are used as various fragrances for cosmetics.
For example, they are widely used in creams, lotions, lotions and other basic cosmetics; lipsticks, white powders and other cosmetics; pomades, hair creams, hair tonics and other hair styling products.

[0004] However, it is known that psoralens having a coumarin nucleus contained in natural essential oils exhibit phototoxic effects and cause, for example, dermatitis. About the cause of such inflammation, THOMAS B ・ FITZPATRICK; Sunl
According to ight and Man (University of TOKYO PRESS. 1974), such phototoxic effects are caused by compounds having a coumarin nucleus contained in natural essential oils such as psoralen,
-Methylpsoralen, 4,4′-dimethylpsoralen,
4,5′-dimethylpsoralen, 4 ′, 8-dimethylpsoralen, 4,5 ′, 8-trimethylpsoralen, 5,
7-dimethoxycoumarin, 8-methoxypsoralen, 5
It is described that psoralens represented by -methoxypsoralen are the causative substances. Therefore,
It is desired to remove only these phototoxic substances from essential oils without adversely affecting the aroma, color tone, component balance, etc. of the natural essential oils.

Conventionally, as a method for removing such phototoxic substances causing skin damage, bergamot essential oil, a kind of natural essential oil, is distilled under reduced pressure to obtain a distillate essential oil.
The distillation residue is cold-hydrolyzed with alcoholic alkali,
A method for producing bergamot essential oil which does not irritate the skin by removing psoralens by converting the hydrolyzate into an alkali salt form and combining the remaining neutral oil with the distillate essential oil has been proposed. (35-1)
No. 5363)

[0006] Lemon oil, a kind of natural essential oil,
A distillate is obtained by vacuum distillation, while a non-polar solvent is added to the distillation residue to remove and remove the flocoumarins, and the remaining flocoumarins are absorbed and removed by an inorganic adsorbent (alumina, silica gel). After that, a method is known in which oil excluding the solvent is combined with the distillate oil to produce lemon oil having no phototoxicity (JP-A-56-70096). A method of purifying bergamot oil using bergamot oil instead of lemon oil and removing bergapten by the same treatment step has also been proposed (Japanese Patent Application Laid-Open No. 58-1983).
127797).

Further, as another proposal, a natural essential oil containing psoralens and / or coumarins is distilled under reduced pressure to distill essential oil and residual essential oil, and the residual essential oil is dissolved in a water-miscible organic solvent, An aqueous solution of an alkali metal sulfite is added to the obtained solution, and after mixing, the organic solvent layer is separated and the solvent is distilled off.The obtained residue is combined with the above-mentioned distillate essential oil to obtain a natural solution free of psoralens and coumarins. A method for producing an essential oil is known (JP-A-57-5794).

Alternatively, a method for producing a natural essential oil substantially free of psoralens by subjecting a psoralen-containing natural essential oil to contact treatment with activated clay before distillation to adsorb and remove the psoralens (Japanese Patent Application Laid-Open No. 59-142297) And a non-polar solvent is added to the residue obtained by distilling orange flower essential oil, and the dissolved oil portion is adsorbed and removed by column chromatography packed with a polymer adsorbent to remove psoralens.
No. 16232) has also been proposed.

[0009] The above proposal is to distill natural essential oil, solvent extraction,
For the method of removing psoralens by adsorbent treatment,
A method for fractionating and removing psoralens by column chromatography packed with silica gel using supercritical carbon dioxide as an extractant has been proposed [J. Chromatogr. 1990, 505 , 237, and JS.
upercrit. Fluids, 7 (3), 177-183, (1994)].

[0010]

However, the method of removing psoralens by distillation, solvent extraction, and adsorbent treatment of natural essential oils is intended to remove only psoralens and reproduce the original aroma components without breaking the balance. Nevertheless, satisfactory reproduction has not always been achieved due to a chemical change due to heating during distillation, or a loss of aroma components during recovery of the used solvent.

A method for fractionating and removing psoralens by column chromatography packed with silica gel using carbon dioxide in a supercritical state as an extractant is a more preferable method than the above-mentioned method by distillation and solvent extraction. Under conditions that do not elute psoralens, polar fragrance components such as alcohols and aldehydes are adsorbed to silica gel quite strongly, so their dissolution is insufficient, and the fragrance balance from the viewpoint of reproducing the original fragrance components Have problems and are unsatisfactory. Therefore, if an attempt is made to obtain an essential oil containing substantially no psoralens, the fragrance is unsatisfactory. On the other hand, if the fragrance is emphasized, the removal of the psoralens becomes insufficient, so that the use as a fragrance for cosmetics becomes difficult. There has been a demand for further improvements in the method of removing psoralens, such as being restricted.

[0012]

The present inventors have intensively studied to improve these disadvantages. As a result, the natural essential oil containing psoralens, using subcritical or supercritical carbon dioxide as a fluid, using a supercritical carbon dioxide extraction column chromatography apparatus filled with a porous polymer resin, the psoralens in the natural essential oils The present inventors have found a method for producing a natural essential oil substantially free of psoralens and completed the present invention.

Accordingly, an object of the present invention is to provide a method for removing psoralens by distillation and organic solvent extraction, or a method for removing carbon dioxide in a supercritical state using silica gel as an adsorbent. A method for producing a natural essential oil substantially free of psoralens, which is not obtained, has no deterioration such as deterioration, and maintains the flavor component balance of the natural essential oil as it is,
Another object of the present invention is to provide a cosmetic fragrance having no phototoxicity.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the present invention, a supercritical carbon dioxide extraction column chromatograph filled with a porous polymer resin using a natural oil containing psoralens as a fluid in subcritical or supercritical carbon dioxide is used. The psoralens in the natural essential oil can be adsorbed to the porous polymer resin and fractionated and removed. The psoralen-free essential oil eluted with subcritical or supercritical carbon dioxide is separated from carbon dioxide in a gas-liquid separation column, and maintains the aroma balance of the original essential oil.

Examples of the psoralen-containing natural essential oil used in the present invention include natural essential oils such as bergamot oil, lemon oil, orange oil, grapefruit oil, petiglen oil, lime oil, mandarin oil, verbena oil and angelica oil.

The supercritical carbon dioxide extraction column chromatography apparatus used in the present invention includes a supercritical carbon dioxide supply unit,
Any device can be used as long as the device includes a sample injection unit, an extraction-chromatography separation unit, and a gas-liquid separation unit. FIG. 1 is a schematic configuration diagram of an example of a supercritical carbon dioxide extraction column chromatography apparatus.

The subcritical or supercritical carbon dioxide used in the present invention has a temperature of 31 ° C. or less and a pressure of 75 ° C.
Kg / cm ² or more are possible the use of carbon dioxide in a subcritical state, preferably, the temperature is 20 ° C. to 30 ° C., the pressure of carbon dioxide in the subcritical state of 75Kg / cm ² ~120Kg / cm ² Examples can be given. The supercritical carbon dioxide has a temperature of 31 ° C. or more and a pressure of 75 ° C.
Kg / cm ² or more are possible the use of supercritical carbon dioxide, preferably, the temperature is 30 ° C. to 50 ° C., the pressure of carbon dioxide in the supercritical state of 75Kg / cm ² ~100Kg / cm ² Examples can be given. Other than the above-described subcritical or supercritical carbon dioxide, there is a risk that psoralens may elute, which is not preferable.

Further, as the porous adsorption resin used in the present invention, a styrene / divinylbenze-based or methacrylate-based porous polymer resin (hereinafter sometimes simply referred to as a synthetic adsorbent) can be exemplified. As a styrene-divinylbenze-based porous polymer resin adsorbent, for example,
Specific surface area of about 300 to about 700 m ² / g;
7 to about 1.1 ml / g; pore radius about 50 to about 1300 °
Resins having physical properties in the range described above can be mentioned. Such synthetic adsorbents are readily available on the market,
For example, Diaion HP10, HP20, HP3
0, same HP40, same HP50, same SP206, same SP2
07 (all manufactured by Mitsubishi Chemical Corporation); Amberlite XAD-
2. XAD-4 (above, manufactured by Rohm &Haas); Hitachi Gel # 3010, # 3011, # 3019 (above, manufactured by Hitachi Chemical) and the like.

Examples of the methacrylate-based porous polymer resin adsorbent include resins having the same specific surface area, pore volume and pore radius as those of the styrene / divinylbenze-based porous polymer resin adsorbent described above. For example, Diaion HP1MG and Diaion HP2MG (manufactured by Mitsubishi Chemical Corporation); Amberlite XAD-7, XAD-8i
(All manufactured by Rohm & Haas).

The amount of the porous polymer resin adsorbent as described above may be about 2 to about 10 parts by weight, preferably about 3 to about 6 parts by weight, per 1 part by weight of the psoralen-containing natural essential oil. Can be mentioned.

According to a preferred embodiment of the method of the present invention, for example, about 1 g of the natural essential oil as exemplified above is injected into a column filled with Amberlite XAD-7 by an injector, and the temperature is 40 ° C. and the pressure is 40 ° C. 80 kg / cm ² of supercritical carbon dioxide at a flow rate of 10 ml / min.
It was fed for 0 minutes and fractionated. The carbon dioxide and the eluted essential oil were separated in the gas-liquid separation column to obtain about 0.9 g of a psoralen-free essential oil.

The essential oil obtained according to the present invention was confirmed by gas chromatography analysis to be substantially free of psoralens. Further, the obtained essential oil had a fragrance component balance of the original natural essential oil.

[0023]

The following examples further illustrate several aspects of the method of the present invention.

Example 1 A JASCO Super-201 type supercritical carbon dioxide extraction chromatograph was used. A porous adsorption resin Amberlite XAD-7 (Rohm & Ha) was applied to a 10 ml extraction column.
(manufactured by As Corporation), 3.3 g, temperature 40 ° C, pressure 80k
g / cm ² of supercritical carbon dioxide at a rate of 10 ml / min is supplied with bergamot oil (Ci Pro. Straczi
856 mg) and extracted for 30 minutes. From the gas-liquid separation column, 738 mg (86% yield) of an essential oil not containing bergapten (a type of psoralen) was obtained. Gas chromatographic analysis confirmed that psoralens were 1 ppm or less, and that psoralens were not substantially contained.

Examples 2 to 4 In the same manner as in Example 1, an essential oil containing no psoralens was obtained using bergamot oil instead of HP10 as the porous adsorption resin and lemon oil instead of bergamot oil. . They are shown in Table 1.

[0026]

[Table 1] Example Sample Adsorption resin Separation conditions Extraction time Yield 1 Balka mot XAD-7 40 ℃ 80kg / cm ² 10ml / min 30min 86% 2 Balka mot HP10 40 ℃ 80kg / cm ² 10ml / min 30min 81% 3 Lemon XAD-7 40 ° C 80kg / cm ² 10ml / min 30 minutes 90% 4 Lemon HP10 40 ° C 80kg / cm ² 10ml / min 30 minutes 87%

Comparative Examples 1-4 Essential oils from which psoralens were removed were obtained using bergamot oil and lemon oil in the same manner as in Example 1 except that silica gel was used instead of the porous adsorption resin. Table 2
It was shown to.

[0028]

TABLE 2 Comparative Sample adsorption resin separation condition extraction time yield 1 Berga Motsuto silica gel ^{40 ℃ 80kg / cm 2 10ml /} min 30 min 64% 2 Berga Motsuto silica gel ^{40 ℃ 100kg / cm 2 10ml /} min 30 minutes 76% 3 Lemon silica gel 40% 80 kg / cm ² 10 ml / min 30 minutes 71% 4 Lemon silica gel 40 ° C 100 kg / cm ² 10 ml / min 30 minutes 82%

Aroma determination results The essential oils obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were subjected to sensory evaluation by sensory evaluation by five well-trained panelists. Table 3 shows the results. In each case, the essential oil obtained according to the present invention maintained the aroma balance of the original essential oil and was judged to be preferable to the comparative examples.

[0030]

[Table 3] Odor judgment result Odor evaluation Odor judgment Example 1 Natural odor and beautiful odor. 5 Example 2 Natural feeling and smell are beautiful. 5 Comparative Example 1 Slightly sweet aroma was weak. 4 Comparative Example 2 Slightly strong terpene feeling. 3 Example 3 A natural feeling and a fresh feeling are maintained. 5 Example 4 No great difference from Example 3. 5 Comparative Example 3 Fresh feeling is weak. 4 Comparative Example 4 Somewhat strong terpene feeling. 3

The aroma evaluation and the aroma determination were performed using bergamot oil and lemon oil as standard before the psoralens removal treatment. The odor criteria are as follows. 5: not much different from standard sample 4 ... slightly different from standard sample 3 ... different from standard sample 2 ... significantly different from standard sample 1 ... significantly different from standard sample

[0032]

Industrial Applicability According to the present invention, a natural essential oil containing psoralens, which causes a harmful effect on the skin, can remove the causative substance from the natural essential oil without affecting the aroma of the natural essential oil, its component balance, yield, etc. In addition, natural essential oils which can be advantageously removed by industrially easy means and which are substantially free of psoralens of high quality can be produced.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a supercritical carbon dioxide extraction column chromatograph used in the present invention.

[Explanation of symbols]

 Reference Signs List 1 cylinder 2 preheating column 3 injector 4 hexagonal valve 5 separation column 6 constant temperature bath 7 detector 8 trap 9 safety valve v1 stop valve v2 flow control valve

Claims (1)

[Claims] 1. A method for producing a natural essential oil containing psoralens using a subcritical or supercritical carbon dioxide as a fluid, using a supercritical carbon dioxide extraction column chromatograph packed with a porous polymerized resin. A method for producing a natural essential oil containing no psoralens, comprising fractionating psoralens.