JPH0329840B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing a low contact sensitizing diasmine oil, and particularly to an improvement in a method for removing contact sensitizing substances. [Prior Art] Diyasmine oil is an extremely important flower essential oil that is indispensable for cosmetics, especially perfumes and colognes. However, in recent years, it has been reported that natural diasmine oil is one of the causes of cosmetic dermatitis, and its contact sensitization properties have become a problem from a dermatological point of view, such as the following:
Many reports have been made as shown in (1) to (4). (1) Hideo Nakayama: Fragrance allergy and cosmetic dermatitis,
Journal of the Japanese Dermatological Association, Vol. 84, pp. 659-667,
1974(2) Nakayama, H., Hanaoka, H., Ohsiro,
A.：Allergen Controlled System (ASC) No. 19
Page, Kanehara Publishing, 1974 (3) Larsem, W, G.: Dermatitis due to a perfume, Contact Dermatitis.
Volume 1, pages 142-145, published in 1975. (4) Chubu Patch Test Research Group (Hiroshi Ueda, Ritsuko Hayakawa) Fragrance-based Patch Test, Skin, Vol. 20, No.
Pages 195-199, 1978 Various sensitizing fragrances have been discovered in addition to diasmine oil, but the search for the sensitizing substance is generally extremely difficult. Although this is not an example of sensitization, the technique described in JP-A-55-3434, for example, is known as a method for removing substances that cause phototoxicity. That is, natural essential oils containing psoralen compounds, which cause phototoxicity, are distilled under reduced pressure to obtain distilled essential oils containing no psoralen compounds. On the other hand, the distillation residue is treated with a nonpolar solvent to crystallize and remove psoralen compounds. Next, the essential oil obtained by removing the nonpolar solvent from the distillation residue is combined with the distilled essential oil to obtain a low phototoxic essential oil. Natural essential oils that can reduce phototoxicity by removing psoralen in this way include bergamot oil, lemon oil, orange oil,
grapefruit oil, petitgrain oil, lime oil,
Examples include mandarin oil, verbena oil, angelica oil, and the like. [Problems to be Solved by the Invention] Although several studies have been reported regarding chemical component analysis of diasmine oil, it is not clear what kind of structure the contact sensitizing substance contained in diasmine oil has. No reported cases have been found. Of course, the reduction of sensitization characteristic of natural diasmine oil,
Although attempts have been made to identify the causative substance, the sensitizing substance has not yet been identified, and at present, it has not been possible to obtain a low-sensitizing natural diasmine oil. The present invention has been made in view of the problems of the prior art, and its purpose is to provide a method for producing natural diasmine oil with excellent safety. [Means for Solving the Problems] As a result of intensive studies by the present inventors to achieve the above object, they have discovered the sensitizing substance in natural diasmine oil, and have made it possible to produce a low-sensitizing natural diasmine oil. That's what I did. That is, in the first invention of the present application, natural diasmine oil is distilled under reduced pressure at a temperature of 110°C or less and a pressure of 5 mmHg or less, and 37 parts by weight of natural diasmine oil is
a first vacuum distillation step to obtain a first fraction as less than parts by weight; and a distillation residue from the first vacuum distillation step at a temperature of 110°C.
℃ or less and a pressure of 0.1 mmHg or less to obtain a fraction and a residue; and a molecular distillation step in which the fraction obtained in the molecular distillation step is subjected to molecular distillation at a temperature of 132 mmHg or less.
℃ or less and a pressure of 1 mmHg or less to obtain a second fraction; and a first adsorbent treatment step in which the distillation residue from the molecular distillation step is treated with an adsorbent to obtain a first eluate. and a blending step of combining the first fraction, the second fraction, and the first elution part. Further, the second invention of the present application is to obtain a first fraction by distilling natural diasmine oil under reduced pressure at a temperature of 110°C or less and a pressure of 5 mmHg or less to obtain a first fraction of 37 parts by weight or less based on 100 parts by weight of natural diasmine oil. a vacuum distillation step and the distillation residue from the first vacuum distillation step at a temperature of 110°C.
℃ or less and a pressure of 0.1 mmHg or less to obtain a fraction and a residue, and a second adsorbent to treat the fraction obtained in the molecular distillation step with an adsorbent to obtain a second elution part. a first adsorbent treatment step in which the distillation residue obtained in the molecular distillation step is treated with an adsorbent to obtain a first elution part; the first fraction, the second elution part, and the first elution part; and a blending step of combining the parts. That is, the present inventors used a gel permeation gram measured by gel permeation chromatography (hereinafter referred to as GPC) under specific conditions as a means of confirmation, and found that It was discovered that the peak component present in the count was a sensitizing substance, and by removing it, natural diasmine oil with low contact sensitization was obtained. Here, the low contact sensitizing diasmine oil includes not only those having no contact sensitization at all, but also those having sufficiently reduced sensitization. [Example] Hereinafter, preferred examples of the present invention will be described. Note that the present invention is not limited to the examples. Method of sensitization test In the present invention, contact sensitization was evaluated using a guinea pig contact sensitization test. A group of 10 healthy Hartley albino guinea pigs weighing 380 to 450 g were used, and Magnusson and
Kligman's GPMT method (guinea pig
maximization test，1970Allergic contact
dermatitis in the guinea pig，Spring field，
IU.CCThomas). The sensitization treatment was carried out as follows. 0.1ml Freund's complete adjuvant (hereinafter abbreviated as FCA, manufactured by Difco) water emulsion (FCA: H ₂ O =
1:1V/V) 0.1ml test substance solution (10W/V%/FCA) 0.1ml 20W/V% test substance FCA solution:
Each reagent of the H ₂ O=1:1 (V/V) emulsion was prepared and injected intradermally into the guinea pigs in two rows on the left and right sides of the shoulder in the order of ~, at a total of 6 locations. After 7 days, 0.2 ml of the test substance solution (10 W/V%/liquid paraffin) was applied under occlusion for 48 hours to the injection site where a small amount of 10W/V% sodium lauryl sulfate/white petrolatum had been applied after shaving the day before. , the sensitization treatment was completed. A provocation test was conducted two weeks after the above procedure by applying 10 µ of acetone solution of each concentration of the test substance to the shaved back and abdominal skin for 24 hours in the open. For each test, the same number of animals that had been injected intradermally with FCA alone were used simultaneously as a control to distinguish non-specific skin irritation reactions. Judgments were made 24 to 48 hours after application according to the criteria in Table 1.

[Table] Number of sensitized animals
Σ(erythema score + edema
rating)
Evaluation score =

Claims (1)

[Claims] 1 Natural diasmine oil is distilled under reduced pressure at a temperature of 110°C or less and a pressure of 5 mmHg or less to obtain natural diasmine oil 100%
a first vacuum distillation step to obtain a first fraction with a concentration of 37 parts by weight or less based on the weight part; and a distillation residue from the first vacuum distillation step at a temperature of 110%.
℃ or less and a pressure of 0.1 mmHg or less to obtain a fraction and a residue; and a molecular distillation step in which the fraction obtained in the molecular distillation step is subjected to molecular distillation at a temperature of 132 mmHg or less.
℃ or less and a pressure of 1 mmHg or less to obtain a second fraction; and a first adsorbent treatment step in which the distillation residue from the molecular distillation step is treated with an adsorbent to obtain a first eluate. and a blending step of combining the first fraction, the second fraction, and the first elution part, and a gel permeation chromatograph in which the diasmine oil obtained by the blending step is set to the following conditions. Gel permeation chromatogram drop counter measured by E.
A method for producing natural diasmine oil with low contact sensitization, characterized by obtaining natural diasmine oil that does not substantially contain peak components in the 48.0 to 50.0 count range. [Measurement conditions] Column: 4 G2000H8 manufactured by Toyo Soda Industries connected in series Column temperature: 40℃ Flow rate: 1.0ml/min Solvent: Tetrahydrofuran Pressure: 80Kg/cm ² Sample amount: 2% by weight tetrahydrofuran solution
100μ Detector: UV (280nm) detector The G2000H8 column manufactured by Toyo Soda Kogyo Co., Ltd.
These are as follows. Size of one column: inner diameter 7.5 mm, length 600 mm Packing agent: Styrene-divinylbenzene copolymer (porous polymer with average pore size 200 Å and particle size 10 μm) Amount of packing agent: 24 ml/Number of theoretical plates per column : 16000 stage 2 Natural diasmine oil is distilled under reduced pressure at a temperature of 110℃ or less and a pressure of 5mmHg or less to produce 100% natural diasmine oil.
a first vacuum distillation step to obtain a first fraction with a concentration of 37 parts by weight or less based on the weight part; and a distillation residue from the first vacuum distillation step at a temperature of 110%.
℃ or less and a pressure of 0.1 mmHg or less to obtain a fraction and a residue, and a second adsorbent to treat the fraction obtained in the molecular distillation step with an adsorbent to obtain a second elution part. a first adsorbent treatment step in which the distillation residue obtained in the molecular distillation step is treated with an adsorbent to obtain a first elution part; the first fraction, the second elution part, and the first elution part; and a blending step in which the diasmine oil obtained in the blending step is measured by gel permeation chromatography under the following conditions. at the counter
A method for producing natural diasmine oil with low contact sensitization, characterized in that it does not substantially contain peak components in the 48.0 to 50.0 count range. [Measurement conditions] Column: 4 Toyo Soda G2000H8 columns connected in series Column temperature: 40°C Solvent: Tetrahydrofuran Flow rate: 1.0ml/min Pressure: 80Kg/cm ² Sample amount: 2% by weight tetrahydrofuran solution
100μ Detector: UV (280nm) detector The G2000H8 column manufactured by Toyo Soda Kogyo Co., Ltd.
These are as follows. Size of one column: inner diameter 7.5 mm, length 600 mm Packing agent: Styrene-divinylbenzene copolymer (porous polymer with average pore size 200 Å and particle size 10 μm) Amount of packing agent: 24 ml/Number of theoretical plates per column :16000 stages