JPH0330639B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing absolute rose oil with low contact sensitization. [Conventional technology and its problems] Roses have been considered the most beautiful of all flowers, and have been loved by many people since more than 200 BC, as they were offered to Aphrodite, the goddess of love and beauty, in ancient Greece. It has been praised for its beauty. The main reason for this is the beauty of the roses' shape, shape, and color, but it is also true that the wonderful scent that comes with them is also a major factor. There are many fragrant flowers in the world, but many people choose roses, which have a sweet and pleasant scent. For this reason, the scent of roses has been added to all kinds of things since ancient times. Rose essential oil is widely compatible with other fragrances and is included in the base of most floral fragrances. It also has the advantage of being used in combination with synthetic fragrances and other natural fragrances to improve the scent and add elegance. For this reason, its range of use is very wide, and it has become an extremely important flower essential oil that is indispensable for cosmetics, especially perfumes and colognes. There are two ways to obtain essential oil: essential oil, which is obtained by steam distilling flowers, and absolute oil, which is extracted using a solvent. Phenyl ethyl alcohol, which is abundant in fresh flowers, is water-soluble, so its content is low in essential oil, and most of it is transferred to rose water, but absolute oil contains the entire amount as is, which improves quality. There are significant differences. In general, absolute oils (e.g., absolute diasmine oil) have been cited as one of the causes of cosmetic dermatitis in recent years, and their contact sensitization (hereinafter abbreviated as sensitization) is a problem in dermatology. There are many reports. The present inventors conducted a sensitization test on absolute rose oil produced in grass, among absolute rose oils, and confirmed that it has sensitizing properties. [Means for Solving the Problems] In view of the above circumstances, the present inventors have endeavored to obtain absolute rose oil with less sensitization, and have endeavored to fractionate absolute rose oil and its fractionation. As a result of conducting sensitization tests on substances,
We have discovered that absolute rose oil, in which specific fractions have been removed using various separation operations, has reduced sensitization, while retaining the original aroma of absolute rose oil.Based on these findings, we have As a result, the present invention was completed. That is, the present invention provides a method for producing a low sensitizing absolute rose oil, which requires removing the index peak component described below. The present invention is the first to succeed in removing the sensitizing substance in absolute rose oil, and is an epoch-making method of producing a new, low-sensitizing absolute rose oil, which has great industrial value. This is a major invention. The present invention can be applied to absolute rose oils such as grass-produced, Turkish-produced, and Morocco-produced rose oils. The present inventors conducted a sensitization test after performing a fractionation operation including at least a distillation operation, and found that a sensitizing substance was present in the following index peak components. Indicator peak component: A substance that is present at counts 51 to 54 on the chromatogram when absolute rose oil is subjected to gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions. Model: Toyo Soda HLC-802UR, Column:
4 TSKGEL G2000H ₈ in series, column temperature: 40
°C, solvent: tetrahydrofuran (THF), flow rate:
1.2ml/min, pressure: 90Kg/cm ² , sample concentration:
0.2-2% (THF solution), injection volume: 100μl, detector: UV detector (280nm) All absolute rose oils from which index peak components have been removed according to the present invention must have low sensitization properties. (See Examples below). In order to remove the index peak component from absolute rose oil according to the present invention, at least a distillation operation is required, and this distillation operation includes vacuum distillation,
Molecular distillation and the like may be used alone or in combination. In order to remove the index peak component from the absolute rose oil of the present invention, in addition to the distillation operation, gas chromatography (hereinafter abbreviated as GC) preparative separation, column chromatography treatment, alkali washing, hydrogenation, solvent Processes selected from extraction and the like can be used. Below, the means for removing the index peak component from the absolute rose oil of the present invention will be explained in detail. (1) Distillation General methods such as simple distillation and precision distillation are used. However, it is preferable to carry out the hot water bath at a temperature of 140° C. or lower and under reduced pressure from the viewpoint of preventing odor of the obtained low-sensitizing absolute rose oil. Low sensitizing absolute rose oil can be obtained as a fraction with a yield of about 60%, and the indicator peak components are removed in the residue. (2) Molecular distillation According to the present invention, a centrifugal distillation method, a wiper membrane method,
Molecular distillation methods such as falling film and pot methods can be used alone or in combination with the vacuum distillation. In the case of molecular distillation, it is preferable to suppress the distillation temperature to 125° C. or lower from the viewpoint of preventing odor of the absolute rose oil obtained. Specifically, in order to obtain a low sensitizing absolute rose oil by combining vacuum distillation and molecular distillation,
First, add absolute rose oil to a hot water bath at a temperature of 140℃.
Distillation is performed under the following reduced pressure conditions to obtain a fraction. The residue is further subjected to molecular distillation at a temperature below 125°C. Since the index peak component is removed in the residue of molecular distillation, if the above distillation fraction and the molecular distillation fraction are mixed, the yield will be about 70%, and it will be obtained as a distillation fraction. A hyposensitizing absolute rose oil with a scent closer to that of natural absolute rose oil is obtained. (3) Combination of distillation or molecular distillation and alkaline cleaning, or combination of distillation, molecular distillation and alkaline cleaning First, absolute rose oil is distilled or molecularly distilled according to the present invention. The conditions for distillation or molecular distillation are as described in (1) or (2) above. The residue purified by distillation and/or molecular distillation is then washed with alkali to remove the indicator peak component. The alkaline cleaning referred to here is a method in which absolute rose oil is dissolved in a solvent such as pentane, hexane, ether, etc. and then washed with an aqueous alkaline solution such as sodium hydroxide or potassium hydroxide. According to this method, a low sensitizing absolute rose oil from which the index peak component has been removed can be obtained at a yield of about 50%. The residue after washing with alkali is
They may be mixed with a distillation fraction, a molecular distillation fraction, or a distillation fraction and a molecular distillation fraction, respectively. The yield is improved to about 90%. (4) Combination of distillation or molecular distillation and column chromatography treatment, or combination of distillation, molecular distillation, and column chromatography treatment Similar to the combination with (3) alkaline washing above, distillation fraction or molecular distillation The residue, or the residue after distillation and molecular distillation, is treated with a nonpolar solvent (e.g., pentane, hexane, etc.) using a column packed with an adsorbent such as activated carbon, silica gel, synthetic adsorbent, or ion exchange resin. This is the way to do it. Particularly preferred adsorbents include Amberlite XAD-22, Amberlite XAD-4 (styrene-divinylbenzene copolymer), and Amberlite XAD-4 (styrene-divinylbenzene copolymer) manufactured by Organo, which are synthetic absorbents.
7. XAD-8 (acrylic acid ester polymer),
Alternatively, ion exchange resins such as Amberlyst-15, A-21 and A- manufactured by Organo Co., Ltd.
26, A-27, etc. By combining the column chromatography treatment described above, absolute rose oil containing no indicator peak component can be obtained. When the above-treated eluate is mixed with each distillate, a yield of about 90% is obtained, which does not contain any index peak components and has an excellent aroma that is closer to natural absolute rose oil. Low sensitizing absolute rose oil is obtained. A low sensitizing absolute rose oil is obtained as a fraction with a yield of around 70%, and the indicator peak component is removed from the residue. As described above, the method for removing the above index peak component can obtain a low-sensitizing absolute rose oil of sufficiently good quality even if the distillation operation is used alone. In order to obtain low-sensitizing absolute rose oil with a scent similar to that of oil in a high yield, the above-mentioned alkaline washing,
It is preferable to use a suitable combination of column chromatography treatments. [Example] Next, the present invention will be explained in more detail by giving examples. Confirmation of sensitizing properties of natural absolute rose oil Absolute rose oil from Grass (Abs.
We conducted a sensitization test using Rose de Mai Grasse as an example. The results are shown in Table 1. As is clear from Table 1, natural absolute rose oil has sensitizing properties.

[Table] The sensitization test was conducted using the following method. Test method - Guinea guinea pig sensitization test A group of 10 healthy Hartley albino guinea pigs weighing 380 to 450 g were used.
GPMT method (guinea pig maximization test)
1970Allergic contact dermatitis in the quinea
dig, Spring field, Illinois, CCThomas). First, sensitization treatment was performed as follows. Freund's complete adjuvant
An emulsion (liquid) made by emulsifying Complete Adjuvant Difco (hereinafter abbreviated as FCA) with an equal amount of water,
10 (w/w)% test substance in FCA solution (liquid) and 0 (w/w)% test substance in which 20 (w/w)% test substance in FCA solution is emulsified with an equal volume of water. Emulsions (liquids) were prepared. Inject 0.1 ml of the solution intradermally into the skin above the shaved shoulder blade of each guinea pig at a total of six locations in two rows on the left and right, symmetrical about the midline. Six days after intradermal injection, the injection site was shaved and 10 (w/
w) 0.2% white petrolatum with sodium lauryl sulfate
g was applied. The next day, 0.2 ml of the solution was applied to the injection site and kept under occlusion for 48 hours to complete the sensitization treatment. In the provocation test, 21 days after the intradermal injection, 10μ of an acetone solution of each concentration of the test substance was applied openly to the shaved back skin. For each test, 10 control animals were injected with only the solution intradermally during the sensitization treatment.
A provocation test similar to that described above was conducted at the same time to differentiate non-specific skin irritation reactions of the test substance. Judgments were made 24 and 48 hours after application according to the criteria below. Judgment criteria (1) Formation of erythema and crust Evaluation No erythema at all...0 Slight erythema...1 Clear erythema...2 Strong erythema... …3 Strong erythema with crusting …4 (2) Formation of edema Rating No edema at all …0 Slight edema …1 Obvious edema … ...2 Those with strong edema ...3 Sensitization rate = number of positive reaction animals / number of experimental animals Average score = Σ (score of erythema + score of edema) / number of experimental animals Absolute rose oil from the above glass of
The GPC chromatogram is shown in Figure 1. GPC is set to the GPC conditions for detecting the index peak component (the detector is a UV detector). Examples are shown below. In addition, the low contact sensitizing substance in the present invention is
The average evaluation score in the provocation test concentration 10% acetone was
1.0 or less. Example 1 260.0g of absolute rose oil from Grass was distilled (~60°C/0.09mmHg) to obtain 144.3g of trap fraction and distillate (hereinafter referred to as D-1). The residue (hereinafter referred to as D-R) was subjected to molecular distillation (75-125℃/0.056-0.070mmHg) using a centrifugal molecular distillation device CMS-5A manufactured by Pendex, and the trap fraction and distillate fraction were combined. (hereinafter referred to as MDI-
1) 29.8g was obtained. Residue from the above molecular distillation (hereinafter referred to as MDI-R)
20.0g was eluted with 2000ml of hexane using 100g of Amberline XAD-7, a synthetic adsorbent manufactured by Organo, and the eluted solvent was removed to form the eluate (hereinafter referred to as MDI-R-AD-1) 14.4 I got g. Next, the hexane elution residue was eluted using 1000 ml of methanol to obtain 5.4 g of the eluate (hereinafter referred to as MDI-R-AD-R). MDI-R-AD-R was subjected to GPC set to the GPC conditions for detecting the index peak component (the detector was a UV detector). The chromatogram at this time is shown in Figure 2. The sensitization potential of the indicator peak component present at counts 51-54 was tested. The results are shown in Table 2, and it can be seen that the index peak component has sensitizing properties. (The test method is the same as above, and the same applies below)

[Table] In D-1, MDI-1, and MDI-R-AD-1, the index peak component was removed, and the above-mentioned sensitization test confirmed that they were not sensitizing. The results are shown in Table 3.

[Table] In addition, D-1 has a scent unique to absolute rose oil and could be used alone as absolute rose oil, but MDI-1 and MDI-R- By adding AD-1, the product had an excellent aroma that was almost indistinguishable from natural absolute rose oil. Moreover, the yield can also be increased by mixing MDI-1 and MDI-R-AD-1. D-1 above,
FIG. 3 shows a GPC chromatogram of a low-sensitizing absolute rose oil consisting of MDI-1 and MDI-R-AD-1 (see Perfume Example 1 below for the formulation). As is clear from the figure, there was no peak between counts 51 and 54, and there was no sensitization. Incidentally, FIG. 4 shows the steps of the manufacturing method according to this embodiment. Example 2 DR obtained under the same conditions as Example 1 was subjected to column chromatography. First, after thoroughly washing with water, 100 g of the synthetic adsorbent Amberlite
-20.0g of R was processed. Using 2000ml of n-pentane as a developing solution, take the eluate and add n-pentane under reduced pressure.
Pentane was removed to obtain 16.4 g of column chromatography-treated product (hereinafter referred to as DR-AD-1). It was confirmed by GPC for detecting an index peak component that this DR-AD-1 does not contain an index peak component. The absence of sensitization was also confirmed by the sensitization test described above. A product obtained by adding an appropriate amount of D-R-AD-1 to D-1 had an excellent aroma as natural absolute rose oil. FIG. 5 shows the low sensitizing absolute rose oil (D-1) produced by the production method according to this example.
+D-R-AD-1) is shown. As is clear from the figure, there was no peak between counts 51 and 54, and there was no sensitization. Note that FIG. 6 shows the steps of the manufacturing method according to this embodiment. Example 3 10.0 g of DR obtained under the same conditions as Example 1 was dissolved in 100 ml of n-hexane, 100 ml of 1% aqueous sodium hydroxide solution was added, and the mixture was poured into a 500 ml separating funnel. After shaking this in a shaking machine for 20 minutes,
It was separated into two layers using a centrifuge. The n-hexane layer was taken, washed with water three times and separated, and the n-hexane was removed under reduced pressure to obtain 8.0 g of alkali-treated portion (hereinafter referred to as D-R-A). From this D-R-A, GPC
It was confirmed that the index peak component was removed. It was also confirmed by the sensitization test that the sensitization was reduced (Table 4).

[Table] By adding an appropriate amount to D-1, D-R-A exhibited the effect of bringing the scent of D-1 closer to that of natural absolute rose oil. FIG. 7 shows the low sensitizing absolute rose oil (D-1) produced by the production method according to this example.
+DRA) GPC chromatogram is shown.
As is clear from the figure, there was no peak between counts 51 and 54, and sensitization was also reduced. Incidentally, FIG. 8 shows the steps of the manufacturing method according to this embodiment. Example 4 10.0 g of MDI-R obtained in Example 1 was washed with alkali in the same manner as in Example 3 to obtain 8.2 g of the alkali-washed portion (hereinafter referred to as MDI-R-A). It was confirmed by GPC that the index peak component was significantly reduced in this MDI-RA. It was also confirmed by the sensitization test that the sensitization was reduced (Table 5). By combining D-1, MDI-1 and MDI-R-A, it had an excellent aroma that was almost indistinguishable from natural absolute rose oil. FIG. 9 shows the low sensitizing absolute rose oil (D-1) produced by the production method according to this example.
+MDI-1+MDI-R-A) is shown. As is clear from the figure, there was no peak between counts 51 and 54, and sensitization was also reduced. Note that FIG. 10 shows the steps of the manufacturing method according to this embodiment.

[Table] Example 5 300.0 g of absolute rose oil from Turkey was subjected to molecular distillation using the same molecular distillation apparatus used in Example 1, and the trap fraction and distillate at ~125°C/0.056 to 0.070 mmHg were combined. (hereinafter referred to as MD-1)
200.9g and the remainder (hereinafter referred to as MD-R) 87.6g
I got it. It was confirmed by GPC that MD-1 does not contain an index peak component. Then, from the sensitization test described above, it was confirmed that although the raw material Turkish absolute rose oil was found to have sensitizing properties, MD-1 did not have any sensitizing properties (Table 6). M.D.
The GPC chromatogram of -1 is shown in FIG.

[Table] MD-1 had an excellent aroma of absolute rose oil. The low-sensitizing absolute rose oil obtained in the present invention can be further perfumed by adding a perfume regulator and the like. That is, by blending a perfume regulator, it is possible to improve retention, odor balance, etc. The blending amount of the fragrance modifier is 40% by weight or less, preferably 1 to 30% by weight based on the low sensitizing absolute rose oil.
is within the range of This makes it possible to obtain an extremely safe absolute rose oil formulation with low sensitization and excellent odor. Perfume Example 1 (Using each fraction obtained in Examples) D-1 63.0 MDI-1 13.1 MDI-R-AD-1 23.9 Total 100.0% by weight Perfume Example 2 Composition of Perfume Example 1 89.3 Propylene glycol dibenzoate 3.0 Glucam P-20 (manufactured by Amacol) 5.0 Methyl eugenol 0.6 Citronellol 2.0 Dibenzothiophene 0.1 Total 100.0% by weight Perfume Example 3 Composition of Perfume Example 1 92.0 Propylene Glycol Dibenzoate 2.0 Glucam P -20 (manufactured by Amacol) 4.0 Methyleugenol 0.5 Citronellol 1.3 Dibenzothiophene 0.15 4-Methyldibenzothiophene 0.05 Total 100.0% by weight The above three perfume examples all have good odor and sensitization. However, it was better than natural absolute rose oil.

[Brief explanation of the drawing]

Figure 1 shows natural absolute rose oil.
A GPC chromatogram is shown. Figure 2 shows the polar solvent eluate (MDI-R-AD-R ) is shown. Figure 3 shows the low sensitizing absolute rose oil (D-1+MDI-1+MDI-R-
A GPC chromatogram of AD-1) is shown. FIG. 4 shows the steps of the manufacturing method according to the first embodiment. FIG. 5 shows a GPC chromatogram of the low sensitizing absolute rose oil according to the second example. 6th
The figure shows the steps of the method for producing a low sensitizing absolute rose oil according to the second example. Figure 7 is the third
1 shows a GPC chromatogram of a low sensitizing absolute rose oil according to an example. FIG. 8 shows the steps of a method for producing a low sensitizing absolute rose oil according to the third embodiment. FIG. 9 shows a GPC chromatogram of the low sensitizing absolute rose oil according to the fourth example. FIG. 10 shows the steps of the method for producing a low sensitizing absolute rose oil according to the fourth embodiment. Figure 11 shows the low sensitizing absolute rose oil (MD-1) obtained by molecular distillation of Turkish absolute rose oil in Example 5.
The GPC chromatogram of 1) is shown.

Claims (1)

[Scope of Claims] 1. A vacuum distillation step for obtaining a fraction by distilling absolute rose oil under reduced pressure at a temperature of 140°C or lower, and molecular distillation of the residue from the vacuum distillation step at a temperature of 125°C or lower. a molecular distillation step for obtaining a fraction; an adsorbent treatment step for treating the residue from the molecular distillation step with an adsorbent to obtain an eluted portion; a compounding step of combining the components, and the absolute rose oil obtained by the compounding step has components present at counts 51 to 54 in a chromatogram of gel permeation chromatography set under the following conditions. A method for producing a low contact sensitizing absolute rose oil, which is characterized in that it does not substantially contain any. [Measurement conditions] Model: Toyo Soda Kogyo HLC-802UR Column: 4 TSKGEL G2000H8 connected in series Column temperature: 40°C Solvent: Tetrahydrofuran (THF) Flow rate: 1.2ml/min Pressure: 90Kg/cm ² Sample amount: 0.2-2% tetrahydrofuran solution
100μl Detector: UV (280nm) Detector 2 A vacuum distillation process in which absolute rose oil is distilled under vacuum at a temperature of 140°C or lower to obtain a fraction, and the residue from the vacuum distillation process is treated with an adsorbent and eluted. a blending step of combining the vacuum distillation fraction and the adsorbent-treated eluate, and the absolute rose oil obtained by the blending step was set to the following conditions. 1. A method for producing an absolute rose oil with low contact sensitization properties, which is characterized in that it does not substantially contain components present in counts 51 to 54 in a gel permeation chromatogram. [Measurement conditions] Model: Toyo Soda Kogyo HLC-802UR Column: 4 TSKGEL G2000H8 connected in series Column temperature: 40°C Solvent: Tetrahydrofuran (THF) Flow rate: 1.2ml/min Pressure: 90Kg/cm ² Sample amount: 0.2-2% tetrahydrofuran solution
100μl Detector: UV (280nm) Detector 3 A vacuum distillation process in which absolute rose oil is distilled under reduced pressure at a temperature of 140°C or less to obtain a fraction, and the residue from the vacuum distillation process is treated with an alkali. and a blending step of combining the vacuum distillation fraction and the alkali-treated fraction, and the absolute rose oil obtained in the blending step is combined with gel permium under the following conditions. 1. A method for producing absolute rose oil with low contact sensitization properties, which is characterized in that it does not substantially contain components present at counts 51 to 54 in the chromatogram of ASION Chromatography. [Measurement conditions] Model: Toyo Soda Kogyo HLC-802UR Column: 4 TSKGEL G2000H8 connected in series Column temperature: 40°C Solvent: Tetrahydrofuran (THF) Flow rate: 1.2ml/min Pressure: 90Kg/cm ² Sample amount: 0.2-2% tetrahydrofuran solution
100μl Detector: UV (280nm) Detector 4 Absolute rose oil is distilled under reduced pressure at a temperature of 140°C or lower to obtain a fraction, and the residue from the vacuum distillation step is distilled into molecules at a temperature of 125°C or lower. a molecular distillation step for obtaining a fraction by distillation; an alkali treatment step for treating the residue of the molecular distillation step with an alkali to obtain an alkali-treated fraction; the vacuum distillation fraction, the molecular distillation fraction, and the alkali treatment. and a blending step in which the absolute rose oil obtained in the blending step contains components present at counts 51 to 54 in a chromatogram of gel permeation chromatography set to the following conditions. A method for producing absolute rose oil with low contact sensitization properties, characterized in that it is substantially free of contact sensitization. [Measurement conditions] Model: Toyo Soda Kogyo HLC-802UR Column: 4 TSKGEL G2000H8 connected in series Column temperature: 40°C Solvent: Tetrahydrofuran (THF) Flow rate: 1.2ml/min Pressure: 90Kg/cm ² Sample amount: 0.2-2% tetrahydrofuran solution
100μl Detector: UV (280nm) Detector 5 Absolute rose oil at a temperature of 125℃ or less,
Equipped with a molecular distillation process to obtain a fraction by molecular distillation at 0.056 to 0.070 mmHg, the fraction from the molecular distillation process has a count of 51 to 54 in the chromatogram of gel permeation chromatography set to the following conditions. A method for producing a low contact sensitizing absolute rose oil, characterized in that it is substantially free of any existing components. [Measurement conditions] Model: Toyo Soda Kogyo HLC-802UR Column: 4 TSKGEL G2000H8 connected in series Column temperature: 40°C Solvent: Tetrahydrofuran (THF) Flow rate: 1.2ml/min Pressure: 90Kg/cm ² Sample amount: 0.2-2% tetrahydrofuran solution
100μl Detector: UV (280nm) detector