JPS641146B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides deodorizing substances from sage and rosemary.
In particular, the present invention relates to a method for producing an effective deodorizing substance for those whose odor source is a sulfur compound such as methyl mercaptan. Foul odors emitted from sewage treatment plants, fish processing plants, fishmeal manufacturing plants, livestock or poultry manure drying plants, pulp factories, etc. have long been a social problem, and there is also a lot of garbage and filth in the living environment. There are sources of bad odors, and it is desired to suppress their generation or eliminate odors. Furthermore, it is also desired to suppress and deodorize bad breath, which is one of the sources of bad odor. Various substances are known to cause unpleasant odors, but sulfur compounds such as hydrogen sulfide and mercaptans are particularly problematic, and conventional deodorization methods include activated carbon, silica gel, zeolite,
Adsorption to cyclodextrin, direct combustion,
Oxidation using catalysts, ozone, hypochlorous acid, potassium permanganate, masking with aroma components, methods using chemical bonding reactions, etc. are adopted depending on the type of subodor source. There is a demand for ingredients that are effective against sulfur compounds such as methyl mercaptan. Traditionally, sage and rosemary have been widely used as spices that have a burning taste and odor effect on foods, especially meat and fish, and dried leaves of mint family plants are also added to chewing gum to remove bad breath. It has also been proposed to
No. 84070). However, when sage and rosemary are used directly as a deodorant, it takes time for the effects to appear, and while it is good to use it in cooking simply for the taste and odor, it is not fast-acting. It is unsuitable as a deodorant, and when sage or rosemary is added to toothpaste to remove bad breath, the scent is too strong and is impractical. The present inventors conducted various studies on deodorizing substances that have an excellent deodorizing effect on sulfur compounds such as methyl mercaptan, and found that sage, rosemary, Raw materials selected from the extracted sage and rosemary extracts obtained by extraction and their extraction residues are extracted with a solvent and the extract is collected, and then extracted with an adsorbent such as activated carbon. If a step of decolorization is performed, or a step of collecting the residue by steam distillation before the solvent extraction step, between the solvent extraction step and the decolorization step, or after the decolorization step, methyl mercaptan A substance with high deodorizing effect is obtained, and this substance can be used as an industrial deodorant, household deodorant, toothpaste, mouthwash, chewing gum, etc.
The present invention was based on the discovery that the present invention can be suitably used as an active ingredient in oral deodorants such as Candy. The present invention will be explained in more detail below. When producing the deodorizing substance according to the present invention, raw materials include whole plants of sage and rosemary, cut or powdered aerial parts, sage and/or rosemary mixed with water, ethyl ether, ethylene chloride, dioxane, etc. , polar solvents such as acetone, ethanol, methanol, ethyl acetate, propylene glycol, or n-hexane, petroleum ether, ligroin, cyclohexane, carbon tetrachloride,
Non-polar solvents such as chloroform, dichloromethane, 1,2-dichloroethane, toluene, benzene,
Alternatively, one selected from extracts obtained by extraction with mixed solvents thereof and extraction residues thereof is used. In order to obtain a deodorizing substance from the above-mentioned raw materials, first, the above-mentioned raw materials are extracted with an organic solvent and the extract is collected. In the extraction process, a solvent is added to the above raw materials and kept at room temperature or the reflux temperature of the solvent for 0.5 to 24 hours, especially for 1 to 24 hours.
It is preferable to carry out the treatment for 10 hours. The solvent used in this extraction process may be an organic solvent or an inorganic solvent, or may be a mixed solvent of an organic solvent and an inorganic solvent. Specific examples of organic solvents include ethyl ether, ethylene chloride, dioxane, acetone, ethanol, methanol, ethyl acetate, propylene glycol, n-hexane, petroleum ether, ligroin, silohexane, carbon tetrachloride, chloroform, dichloromethane, 1,2 - Dichloroethane, toluene, benzene and the like. In addition, water and aqueous solutions of acids, alkalis, or their salts can be used as inorganic solvents, and specifically, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, carbonic acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, water Calcium oxide, sodium chloride, potassium chloride,
Examples include ammonium chloride, sodium hydrogen carbonate, sodium carbonate, and sodium sulfate. In addition, it is preferable to use these acids, alkalis, and salts at a concentration of 2 mol or less. Further, it is preferable that the amount of the above-mentioned solvent used be at least equal to the volume of the raw material or the steam distillation residue described below. After the extraction process, the extract is separated into an extract and an extraction residue by a conventional method such as filtration, centrifugation, decantation, etc., preferably under heating, and the extract is collected. Note that the extraction residue may be subjected to the above-mentioned extraction process again if necessary to obtain an extract, which may be combined with the previous extract. In this case, it is also possible to use a different solvent from the previous solvent as the extraction solvent. The extract obtained in this way is preferably treated by distilling off the solvent (in the case of an inorganic solvent extraction process, especially an acid, alkali, or salt extraction process, it is treated by ion exchange, dialysis, etc.). It is preferable to distill off the solvent after washing) and collect it as a deodorizing substance. Note that, if necessary, the product from which the solvent has been distilled off may be further subjected to extraction treatment using another solvent. In the present invention, after performing the solvent extraction treatment step, a decolorization treatment is performed. Decolorization treatment is carried out by adding the above-mentioned extract or, if the steam distillation treatment described below is performed before this decolorization treatment, to the steam distillation residue, if it is solid, after dissolving it in an appropriate solvent to make it liquid. This is preferably carried out by adding an adsorbent such as activated carbon, diatomaceous earth, or acid clay, and stirring for about 10 to 60 minutes at room temperature or under heat.
In addition, if it is in liquid form, it can be treated by adding an adsorbent as it is. In this case, the amount of adsorbent used is 0.5 to 8% by weight based on the raw materials, 2 to 6% by weight especially for cut or powdered materials and extraction residues, and 0.5 to 2% by weight for extracted extracts. It is preferable that After decolorization treatment, separate the adsorbent and collect the liquid.
Preferably, an adsorbent is added to this liquid and decolorization treatment is performed two to three times. When the decolorization treatment is the final step, the liquid thus obtained is preferably concentrated and dried by distilling off the solvent under reduced pressure.
Collected as a deodorizing substance. In addition, in the present invention, it is necessary to perform the solvent extraction treatment and the decolorization treatment as described above, and thereby a fraction with a high deodorizing effect can be obtained. In the present invention, steam distillation treatment can be performed before the solvent extraction treatment step, between the solvent extraction treatment step and the decolorization treatment step, or after the decolorization treatment step. In the steam distillation treatment, the above-mentioned raw material or the extract after the above-mentioned extraction treatment or the decolorized one is poured into water preferably 10 times or more in weight, stirred, and dispersed in water, and then the mixture is placed under normal pressure or reduced pressure. This is done by heating to a boil and bringing it to a boil. This removes the essential oil components along with the steam, but the deodorizing components remain in the steam distillation residue. Note that in this steam distillation step, steam can also be blown into the dispersion to promote volatilization of the essential oil components. After continuing steam distillation until almost no essential oil components are recognized in the steam distillate, the steam distillation residue is recovered. If this steam distillation residue is subjected to extraction treatment or decolorization treatment after steam distillation treatment, it is subjected to extraction treatment or decolorization treatment, and if steam distillation treatment is performed as the final step, the steam distillation residue is collected as a deodorizing substance. . In addition, when performing solvent extraction treatment after steam distillation treatment, when using an organic solvent, acid, or inorganic solvent such as alkali as the solvent, the dispersion after steam distillation treatment is filtered, centrifuged, or decanted after heating or cooling. Generally, an aqueous layer and a solid content are separated by a method such as a dispersion process, and an extraction process is performed on this solid content. This extract can be collected as a steam distillation residue and simultaneously collected as an extract of the extraction process by combining both the distillation residue collection and the extraction process. In this case, the extract (steam distillation residue) of the dispersion using an organic or inorganic solvent may be subjected to the above extraction treatment again. Also,
In some cases, the aqueous layer separated from the dispersion may be subjected to extraction treatment. In addition, when performing the solvent extraction step after the steam distillation treatment, if water is used for this solvent extraction, the solid content is separated from the dispersion after the steam distillation treatment and an aqueous layer is collected, and this aqueous layer or this The concentrated product undergoes decolorization treatment. Furthermore, when performing extraction treatment with acid, alkali, or salt, a method may be adopted in which the acid, alkali, or salt is added to the concentrated solution to a predetermined concentration. When performing decolorization treatment after steam distillation treatment, when performing decolorization treatment on the solid content, the solid content is dissolved in an appropriate solvent before treatment, and the aqueous layer is also subjected to decolorization treatment. In some cases, the treatment can be carried out by directly introducing an adsorbent into this aqueous layer. Furthermore, an adsorbent can be added to the solvent extract of the dispersion after steam distillation treatment. In addition, when steam distillation is performed at the end, the steam distillation residue is collected as a deodorizing substance. It can be recovered as a dispersion or its concentrate. It is also possible to perform an extraction treatment on the dispersion using an organic solvent or an inorganic substance such as an acid or an alkali, and collect the extract (preferably from which the solvent has been distilled off) as a deodorizing substance. The deodorizing substance obtained by the above-mentioned method has a fast-acting and excellent deodorizing effect particularly on methyl mercaptan, effectively suppresses and deodorizes the bad odor of methyl mercaptan, and is therefore useful in food processing factories, It is used as an active ingredient in industrial deodorizers for malodor sources generated in pulp factories, etc., and as an active ingredient in household deodorants for household deodorizers for malodor sources generated in food waste, trays, etc., and as an oral deodorant, toothpaste, and mouthwash. It can be incorporated into oral compositions such as lozenges, troches, chewing gum, and candy as an active deodorizing ingredient for preventing bad breath. In this case, especially for the purpose of preventing bad breath, it is preferable to use one obtained by steam distillation because the essential oil components are removed and the odor is therefore reduced. The deodorizing substance of the present invention may be used alone as a deodorant, or may be used in combination with other deodorizing active ingredients, or may be blended with ingredients commonly used in deodorants. For example, oxidizing agents such as sodium perborate, hypochlorous acid, manganese dioxide, permanganate, benzoquinone, naphthoquinone, aldehydes such as glyoxal and acrolein, ketones, 1,2-propylene oxide, 1,2-n
-α, β of epoxy compounds such as butylene oxide, methacrylic acid esters, maleic acid derivatives, etc.
- Unsaturated compounds Metal salts such as copper sulfate and zinc sulfate, adsorbents such as activated carbon, silica gel, and alumina may be mixed together. The deodorant may be in the form of a solution prepared by dissolving the deodorant substance of the present invention in an appropriate solvent, or may be in the form of powder, granules, blocks, or the like. When the deodorizing substance of the present invention is added to oral compositions, etc., the amount to be added is
The content is preferably 0.0001 to 50% by weight, more preferably 0.001 to 10% by weight, and still more preferably 0.01 to 5% by weight. In this case, the deodorizing substance of the present invention has increased deodorizing power through decolorization treatment, and essential oil components have been removed by steam distillation treatment, so it is derived from sage and rosemary. It has almost no characteristic odor, and since it has been decolorized, it has a light color, so when it is blended into oral compositions, it does not impair the feeling of use. In addition, when the deodorizing substance of the present invention is blended into an oral composition, appropriate components depending on the type of composition can be used as the components of the oral composition. For example, in the case of toothpaste, abrasives such as dicalcium phosphate, calcium carbonate, calcium pyrophosphate, inert sodium metaphosphate, amorphous silica, crystalline silica, aluminosilicate, aluminum oxide, aluminum hydroxide, resin, etc. Blend amount usually 20~
60% by weight), binders such as carboxymethylcellulose, hydroxyethylcellulose, alginates, carrageenan, gum arabic, and polyvinyl alcohol (usually 0.3 to 5% by weight), thickening agents such as polyethylene glycol, sorbitol, glycerin, propylene glycol, etc. (Usually 10-70% by weight), sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium hydrogenated coconut fatty acid monoglyceride monosulfate, sodium lauryl sulfoacetate, sodium N-lauroyl sarcosinate, N-acylglutamate, sucrose fatty acid ester Foaming agents such as (usually 0.1 to 5% by weight),
And essential oils such as peppermint and spearmint, l
- Flavoring materials such as menthol, cambon, eugenol, anethole, etc., saccharin sodium, stevioside, neohesperidyl dihydrochalcone, glycyrrhizin, perillartine, p
- Mix ingredients such as a sweetener such as methoxycinnamic aldehyde and a preservative with water and produce according to a conventional method. Furthermore, in mouthwashes and other mouthwashes, ingredients are appropriately blended depending on the properties of the product. In addition to the above-mentioned deodorizing substances, the oral cavity composition also contains lysothyls chloride, dextranase,
Lytic enzyme, mutanase, chlorhexidine, sorbic acid, alexidine, hinokitiol, cetylpyridinium chloride, alkylglycine, alkyldiaminoethylglycine salt, allantoin, ε-aminocaproic acid, tranexamic acid, azulene, vitamin E, sodium monofluorophosphate, fluoride Active ingredients such as sodium, stannous fluoride, water-soluble primary or secondary phosphates, quaternary ammonium compounds, and sodium chloride may also be incorporated. According to the method for producing a deodorant substance of the present invention,
A substance that is fast-acting and has a high deodorizing effect on methyl mercaptan can be obtained by a simple operation, and this substance can be suitably used as an active deodorizing ingredient in various deodorants. When this is done, there is almost no scent derived from sage and rosemary, the color is pale, and it is highly safe to use, so it is very effective as an active deodorizing ingredient for the oral cavity. Hereinafter, the present invention will be specifically explained with reference to Examples. Example 1 20g of dried sage powder was extracted with n-hexane for 5 hours using a Soxhlet extractor to obtain a dark green n-hexane.
- A hexane phase was obtained. 1 g of activated carbon was added to this, stirred and filtered, and the liquid was concentrated to obtain 1.7 g of a colored paste (deodorizing substance). Example 2 Add 300 ml of water to 50 g of dry rosemary powder,
Extraction was carried out at 80°C for 2 hours. Next, the residue was separated from the aqueous solution, fresh water was added to the residue, and the same operation was repeated twice. These aqueous solutions were combined and concentrated to 1/3, and then 2 g of activated carbon was added and stirred. After filtering, the liquid was then concentrated and 5.4 g of a colored powder (deodorizing substance) was obtained. Example 3 Extraction residue of oleoresin obtained by extracting rosemary powder with n-hexane 100
g was extracted with ethyl ether using a Soxhlet extractor for 5 hours, and concentrated to obtain 13.8 g of a green colored solid. Next, add 5g of this solid to 50ml
was dissolved in ethyl ether, 1 g of activated carbon was added, stirred and filtered twice, and the liquid was concentrated to obtain 15 g of a pale yellow powder (deodorizing substance). Example 4 25 g of dry rosemary powder was extracted with n-hexane for 5 hours using a Soxhlet extractor to obtain 2.9 g of a dark green paste. 100 ml of water was added to this and steam distillation was performed on a mantle heater to remove the essential oil.The steam distillation residue was collected by filtration and dried to obtain 2.1 g of a dark green solid. This was dissolved in 50 ml of ethyl ether, 1 g of activated carbon was added, the stirring and filtering procedure was repeated twice, the liquid was concentrated, and 1.8 g of a colored paste (deodorizing substance) was obtained. Example 5 10 g (dark green) of oleoresin (extract) obtained by extracting sage powder with ethanol was extracted with benzene using a Soxhlet extractor.
After time extraction, 3.5 g of dark green paste was obtained. This was dissolved in 100 ml of ethanol, 2 g of activated carbon was added thereto, stirred, and then filtered twice, and the liquid was concentrated to obtain 2.7 g of colored paste (deodorizing substance). Example 6 200 ml of water was added to 30 g of rosemary powder and stirred at room temperature for 3 hours. Next, separate the aqueous solution, add new water to the residue, and repeat the same process twice, totaling 3 times.
Extraction operations were performed twice. After steam distilling 600ml of this aqueous solution, the process of adding 3g of activated carbon, stirring and filtering was repeated twice, and finally the liquid was concentrated.
3 g of colored powder (deodorizing substance) was obtained. Next, the deodorizing power of each deodorizing substance was examined by the following method. The results are shown in Table 1. Deodorizing power test: Ethanol solution or aqueous solution containing 0.02% by weight of sample (deodorizing substance) in a test tube with a content of approximately 22 to 23 ml (for control, use only ethanol or water)
1 ml and 1.5 ml of 0.1M phosphate buffer were added to adjust the pH to 7.5. Contains 1ppm of methyl mercaptan
0.5 ml of an aqueous solution of 10% by volume ethanol was added, and the mixture was immediately capped with a rubber stopper and stirred vigorously for 1 minute. Thereafter, the tube was allowed to stand at 37.degree. C. for 6 minutes, and then 5 ml of air was injected into the test tube by piercing the rubber stopper with a gas syringe for gas chromatography. After stirring vigorously for 300 seconds, 5 ml of the head space was sampled using the same gas syringe and immediately injected into a gas chromatograph to measure the integral count of methyl mercaptan. Note that a gas chromatograph 163 manufactured by Hitachi, Ltd. was used. The results were expressed as deodorization rate using the following formula. Deodorization rate = C-S/C x 100 (%) C: Integral count of control S: Integral count of sample

【table】

[Table] Examples of the use of the deodorizing substance of the present invention are shown below. In addition,
All % indicates weight %. Usage example 1 Kyandei sugar 50% water candy 33 Organic acid 2 Flavor 0.2 Deodorizing substance of Example 1 0.1 Water Remaining 100.0% Usage example 2 Kyandei sugar 50% Water Candy 33 Organic acid 2 Flavor 0.2 Example 2 Deodorizing substance 0.2 Water remaining 100.0% Usage example 3 Toothpaste calcium carbonate 50.0% Glycerin 20.0 Carrageenan 0.5 Carboxymethyl cellulose 1.0 Lauryl diethanolamide 1.0 Sucrose monolaurate 2.0 Fragrance 1.0 Satucalin 0.1 Deodorizing substance of Example 3 0.15 Chlorhexidine 0.01 Ki Stranase 0.01 Water remaining 100.0% Usage example 4 Toothpaste dicalcium phosphate dihydrate 50.0% Glycerin 20.0 Carboxymethyl cellulose 2.0 Sodium lauryl sulfate 2.0 Fragrance 1.0 Satucalin 0.1 Deodorizing substance of Example 4 0.2 Chlorhexidine 0.01 Water remaining 100.0% Usage example 5 Chewing gum gum base 20% Sugar Sugar 53 Glucose 10 Water Candy 16.4 Flavor 0.5 Deodorizing substance of Example 5 0.1 100.0% Usage example 6 Chewing gum gum base 20% Sugar Sugar 55 Corn syrup 12 Water Candy 9.3 Fragrance Materials 0.5 Deodorizing substance of Example 6 0.2 100.0% Usage example 7 Liquid toothpaste sodium polyacrylate 50.0% Glycerin 30.0 Fragrance 0.9 Satucalin 0.1 Deodorizing substance of Example 4 0.05 Ethanol 3.0 Chlorhexidine 0.01 Linoleic acid 0.04 Water Remaining 100.0% Use Example 8 Mouthwash ethanol 20.0% Fragrance 1.0 Saccharin 0.05 Deodorizing substance of Example 4 0.1 Example 6 0.1 Sodium monofluorophosphate 0.1 Chlorhexidine 0.01 Lauryl diethanolamide 0.3 Water Remaining 100.0% Usage example 9 Gargle tablet carbonated Sodium hydrogen 54.0% Dibasic sodium phosphate 10.0 Polyethylene glycol 3.0 Citric acid 17.0 Anhydrous sodium sulfate 13.25 Fragrance 2.0 Example 5 Deodorizing substance 0.3 Example 6 〃 0.2 Oleic acid 0.1 Sodium monofluorophosphate 0.1 Chlorhexidine 0.05 100.0% Usage example 10 Deodorizing spray ethanol 50% Gyrolodifluoromethane 49.5 Deodorizing substance of Example 1 0.5 100.0% Usage example 11 Liquid deodorant ethanol 99.4% Fragrance 0.1 Deodorizing substance of Example 2 0.5 100.0%

Claims (1)

[Claims] 1. Solvent extraction treatment is performed on raw materials selected from sage, rosemary, extracts obtained by extracting these with polar and/or non-polar solvents, and their extraction residues. A method for producing a deodorizing substance, characterized in that the deodorizing substance is obtained from the raw material by performing a step of collecting an extract thereof and a subsequent step of decolorizing it with an adsorbent. 2. Perform solvent extraction treatment on raw materials selected from sage, rosemary, extracted extracts obtained by extracting these with polar solvents and/or non-polar solvents, and their extraction residues, and collect the extracts. step, followed by a step of decolorizing with an adsorbent, and performing a steam distillation treatment before the solvent extraction treatment, between the solvent extraction treatment step and the decolorization treatment step, or after the decolorization treatment step to remove the residue. A method for producing a deodorizing substance, the method comprising: obtaining a deodorizing substance from the raw material by performing a step of collecting the raw material.