JPH0644929B2 - Deodorants - Google Patents

Description

TECHNICAL FIELD The present invention relates to a deodorant, and more particularly to a multi-stage organic solvent extract of thyme or a separated product of the extract by silica gel chromatography. The present invention relates to a deodorant as a component.

Therefore, the present invention is not only heavily used in the industrial fields of deodorants and deodorants, but is also widely used in various industrial fields such as sanitary chemicals, foods and drinks, cosmetics, and pharmaceuticals.
It is also important in the field of natural product organic chemistry.

[Conventional technology]

Thyme is a type of herb spice that belongs to the Labiatae family,
It has already been reported that it has a taste and smell effect on foods, particularly meat and fish.

(Oil Chemistry 29 , 7 (1980)).

It has also been proposed to mix dried leaves of Labiatae plants with chewing gum to remove halitosis (JP-A-54-8407).
0). Further, the raw material selected from the extract of the Lamiaceae plant obtained by extracting the Lamiaceae plant with a polar solvent and / or a non-polar solvent and a raw material selected from the extraction residue are subjected to a solvent extraction treatment to collect the extract. Alternatively, a method has been proposed in which both the extraction treatment and the steam distillation treatment are carried out to obtain a deodorant substance from the above-mentioned raw material (JP-A-57-404278).
In addition, sage, rosemary, an extract obtained by extracting these with a polar solvent / or a nonpolar solvent, and a raw material selected from the extraction residue are subjected to a solvent extraction treatment to collect the extract. Then, deodorizing treatment with an adsorbent is performed to obtain a deodorant substance, or the extract is subjected to both a decolorizing treatment with an adsorbent and a steam distillation treatment, and the residue is collected. Kai 57-203445) has also been proposed.

[Problems to be solved by the invention]

However, in the above proposal, the deodorant substance collected from the Lamiaceae plant has a drawback that it is difficult to completely remove the unique aroma derived from the raw material plant, and the use is significantly limited, Further, it is effective for those having a sulfur compound such as methyl mercaptan as a bad odor source, but has no effect for ammonia odor, amine odor and acid odor. The present invention has been made in view of the state of the art as described above, and the present invention has a strong deodorizing action on methyl mercaptan and also against various malodorous components such as hydrogen sulfide and ammonia. At the same time, the purpose is to develop a broad and strong deodorant that exhibits a deodorant action. Furthermore, the present invention has a mechanism that is fundamentally different from a product that simply masks a malodor with a strong fragrance as a main component, which has been the mainstream of conventional products, and is of a type that destroys malodor from its source. Its purpose is to develop a safe deodorant without pollution.

[Structure of Invention]

In order to achieve the above purpose, the extraction conditions of components having a deodorizing effect were examined from time.

Since the solvent extract of Thyme contains a large amount of other plant components in addition to the components having a deodorizing effect, the deodorizing effect is not complete, and therefore various aspects were investigated.

After extracting thyme with paraffin hydrocarbons to remove essential oils and components that do not have a deodorizing effect, the extraction residue is sequentially extracted with an organic solvent. The alkyl ether extract has a strong deodorizing effect. Admitted. As a result of further research based on this novel and useful knowledge, the present invention has been completed.

The raw material of the deodorant according to the present invention is Thmus vulgaris.
The whole plant or foliage of L. or Thymus serpyllum is mainly used, and it may be raw, or a dried product or a crushed product thereof may be used as appropriate.

According to the present invention, thyme is first extracted with a paraffinic hydrocarbon to extract components such as essential oils, fats and oils, lipoids and resins. The extraction is preferably cold or at room temperature. When heated, some of the components that have a deodorizing effect are extracted into hydrocarbons, so it is necessary to avoid them. Petroleum ether, n-pentane, n-hexane, n-heptane and the like are used as the paraffinic hydrocarbon, but n-hexane is preferable from the economical viewpoint.

Then, the extraction residue subjected to the hydrocarbon extraction treatment is extracted with alkyl ether. Diethyl ether, isopropyl ether, and dibutyl ether are used as the alkyl ether, and isopropyl ether is preferable in terms of workability and economic efficiency. The extraction may be carried out under cold conditions or under warm conditions. The amount of isopropyl ether used for the extraction is preferably 5 to 10 times, and economically 5 to 6 times, the amount of thyme with respect to the n-hexane insoluble portion subjected to the n-hexane extraction treatment. Removal of isopropyl ether from the extract gives a pale yellow powder extract.

In this way, the extract, which is the active ingredient of the present invention, is a pale yellow powder and contains no essential components such as essential oils, resins, and lipoids. felt. This extract (hereinafter abbreviated as Extract A) can be used as it is as an active ingredient of a deodorant, but can be concentrated if necessary. Extract A (isopropyl ether extract) is extracted with a ketone solvent. Acetone is economically preferable as the ketone solvent. Removal of acetone from the extract gives a tan solid. It was confirmed that the active ingredient of this product was concentrated about twice as much as the extract A, and the solubility in organic solvents was significantly increased. Hereinafter, the acetone extract of the extract A is abbreviated as the extract B.

The extract B was separated and purified by silica gel column chromatography to obtain a pale yellow powdery active ingredient from the elution part of ethyl acetate: n-hexane = 1: 1. This product showed a maximum absorption at 228,293 nm (EtOH solution) in the ultraviolet absorption spectrum, and the presence of functional groups such as hydroxyl group and carbonyl group in the infrared absorption spectrum. Melting point: 187-200 ℃, optical rotation [α] _D
The property was + 37 ± 5 °. It is a pale yellow powder in which the active ingredient is concentrated about 5 times that of Extract A, has no offensive odor, and has a faint forest-like scent. (Hereinafter, it will be abbreviated as extract B and column product).

The thus-obtained Extract A and Extract B can be used as they are as deodorants, but powders, granules, tablets, aerosols, pastes, pastes, It may be formulated into capsules, liquids and the like. It can also be used as a food or beverage.

The deodorant according to the present invention has a completely different mechanism of action from those which have hitherto been commercially available. Since it has a wide range of deodorant action, it can be used for any deodorant application. And the action is strong and lasting. Since the active ingredient of this deodorant is derived from a natural plant, it is extremely safe for humans and animals and extremely effective in preventing pollution.

The deodorant according to the present invention is used in rooms such as toilets, kitchens, refrigerators, automobiles, precision work rooms, clean rooms, hospitals, laboratories, barns, and laboratory animal rooms; toilet ventilation fans, ventilation cylinders; toilet bowls, flush toilets. It can be used as sanitary chemicals in various places such as water tanks, sewage treatment tanks, vacuum cars, garbage collection boxes and collection rooms, shoes, dressing rooms for pools and baths. In addition, since the deodorant is non-toxic, it can be used in the fields of medicine and cosmetics as a oral formulation or as a component of mussel or toothpaste for suppressing bad breath. Of these, the deodorant can be widely used in the technical fields of foods and drinks and favorite products by being mixed with chewing gum.

[Test Example 1] 100 g of thyme was used for 24 hours at room temperature using 600 m of n-hexane.
After extracting for a period of time, the mixture was filtered and hexane was recovered from the filtrate to obtain an extract (1.7 g).

Then, the hexane extraction insoluble part was replaced with isopropyl ether 600.
m was used for extraction at 70 ° C. for 24 hours. After cooling, the mixture was filtered, and isopropyl ether was recovered from the filtrate to obtain an extract A.
(3.0g).

Further, the isopropyl ether insoluble portion was replaced with chloroform 600.
Extraction was carried out at 60 ° C. for 3 hours using m, filtered after cooling, and chloroform was recovered from the filtrate to obtain an extract (1.8 g). Finally, the chloroform-insoluble portion was extracted with 600 m of methanol at 70 ° C. for 3 hours, cooled and filtered to obtain methanol from the filtrate. (10.9 g) The deodorizing effect of each extract on methylcaptan was as follows.

As is clear from this test example, it was demonstrated that the target active ingredient was present only in the extract A, that is, the isopropyl ether extract.

The test method for the deodorizing effect was performed as follows.

Test method A 50 m Nessler tube is charged with 15 m of pH 7.5 phosphate buffer and 1 m of each extract A, 1% acetone solution. 0.15% methyl mercaptan / methanol solution 0.1m
, Shake well, keep at 37 °, and after 30 minutes measure the concentration with a detector tube and compare with the blank.

Specific examples and formulation examples are shown below.

Example 1 5 kg of thyme is extracted with n-hexane 50 at 30 ° C. for 24 hours.
After cooling, the mixture is filtered and the insoluble portion in n-hexane is extracted with isopropyl ether 50 at 70 ° C for 24 hours. After cooling, filter and collect isopropyl ether from the filtrate to obtain 150 g of pale yellow powder.
Got (Extract A) Extract 100 A is extracted with acetone 1 at 30 ° C. for 10 hours.
After cooling, the mixture was filtered and acetone was distilled off to obtain 45 g of an active ingredient, a greenish brown powder. (Extract B) 10 g of Extract B was subjected to column chromatographic purification using 100 g of silica gel to obtain 3 g of a pale yellow powder from the elution part of ethyl acetate: n-hexane = 1: 1. Almost no offensive odor, with a faint forest-like scent. 228,29 in the UV absorption spectrum
It has a maximum absorption at 3 nm (EtOH solution), and its infrared absorption spectrum suggests the presence of hydroxyl and carbonyl groups. Melting point: 187-1
It exhibited the properties of 00 ° C and optical rotation degree [α] _D = + 37 ± 5 ° (EtOH). (Extract B, column product) The deodorizing effect measured by a detector tube by adding a thyme active ingredient to each malodorous ingredient is shown below.

Test method In a 50 m Nessler tube, put 15 m of pH 7.5, 0.1 M phosphate buffer and 1 m of acetone solution of specified concentration. Methyl mercaptan is added to this, shaken well, kept at 37 ° C, and after 30 minutes, 1 hour and 30 hours, measure the concentration with a detector tube and compare with the blank.

The same test was conducted for hydrogen sulfide and ammonia.

[Example 2] A comparison between the active ingredient extract B of the present invention and a commercially available natural deodorant is shown below.

(Deodorizing power test) A head space of a solution of a malodorous substance (methyl mercaptan, ammonia, hydrogen sulfide) is injected into 5 bottles with a gas-tight disposable syringe so as to have a predetermined concentration. 10 g of the test object (extract B, natural deodorant M type, natural deodorant G type, natural deodorant P type) are quickly sprayed into 5 bottles and stoppered. 30 minutes after injection,
After 1 hour and 3 hours, the concentration of the malodorous substance was measured with a detector tube.

According to this example, the active ingredient according to the present invention has a deodorizing effect on any of ammonia, methyl mercaptan and hydrogen sulfide, and has a very strong effect, and has a broad and strong deodorizing effect. It was proved to be effective as an agent.

[Formulation Example 1] Aerosol formulation Active ingredient of the present invention Extract B 1 part by weight 80% Ethanol 10 parts by weight Difluoromethane 70 parts by weight [Formulation Example 2] Tablet Active ingredient of the present invention Extract A 1 part Propylene Glycol 10 parts Lactose 75 Part Dextrin 10 parts talc 4 parts Mold into tablets by a conventional method.

[Formulation Example 3] Chewing gum Vinyl acetate resin 20 parts Plasticizer 3 parts Polyisobutylene 3 parts Wax 2 parts Calcium carbonate 2 parts Powdered sugar 45 parts Glucose 23 parts Active ingredient of the present invention Extract A 1 part Fragrance 1 part After being placed in a mixer and heated and stirred in this order, the mixture was cut into blocks and extruded with an extruder to obtain sheets. After cutting this sheet, place it in a conditioning room at 21-24 ° C and 45-50% for 6-8
A plate gum product for preventing bad breath was manufactured by keeping it warm for an hour and packaging it.

[Formulation Example 4] Granules Active ingredient of the present invention Extract A 1 part Propylene Glycol 10 parts Lactose 74 parts Dextrin 15 parts After kneading with water, the mixture is molded into a granule using a granulator.

Claims (3)

[Claims] 1. Extraction of thyme with paraffinic hydrocarbons,
A deodorant characterized in that a pale yellow solid obtained by extracting the extraction residue with alkyl ethers after removing essential oils, fats and oils, resins and the like and removing the solvent from the extract is the active ingredient. 2. A deodorant characterized in that the active ingredient according to claim 1 is extracted with a ketone solvent, the solvent is removed from the extract, and the green-brown solid obtained is used as the active ingredient. 3. The active ingredient according to claim 2 is separated and purified by silica gel column chromatography to obtain ethyl acetate:
A separated product obtained from the elution part of n-hexane = 1: 1, showing a maximum absorption at 228,293 nm (EtOH solution) in the ultraviolet absorption spectrum, and suggesting the presence of a hydroxyl group and a carbonyl group in the infrared absorption spectrum, Melting point: 187-200 ° C, optical rotation [α] _D
A deodorant characterized by containing as an active ingredient a component of = + 37 ± 5 °.