JPS6136724B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a preservative used to prevent oxidation and putrefaction by adding it to foods such as oil and fat foods, seafood and meat paste products, cosmetics, medicines, etc. It has been known that herbal spices have the effect of preventing the oxidation of fats and oils and oil-based foods, and various research reports on this point have been published. However, these spices have a unique and strong flavor, so adding these spices or their essential oils directly to food for the purpose of antioxidants may cause problems such as changing the flavor of the food. There are limits to what can be added. Furthermore, when blended into cosmetics, etc., the fragrance balance is disrupted, and in pharmaceuticals, there is a problem in that a characteristic odor is produced. Therefore, there is a need for a method to remove aroma components from these spices and obtain a fraction with less flavor and antioxidant effect, and US Pat. No. 3,950,266 discloses a method using rosemary or sage powder,
This is extracted with a low boiling point solvent such as ethyl ether,
After distilling off the solvent from the resulting extract to produce a crude product, the product was first washed several times with cold water and then
Wash it several times with hot water at 80℃, then dissolve it in methanol, etc., treat it with activated carbon, and distill off the solvent to obtain a purified product (this purified product still has some flavor. ), a method has also been proposed in which this purified product is dissolved in oil or fat and further steam distilled to remove flavor components, thereby obtaining an antioxidant substance with little flavor. However, this type of conventional method uses a liquid product in which the active ingredient (antioxidant substance) is dissolved in a high boiling point solvent such as edible oil, so the active ingredient is diluted and the desired antioxidant effect is not achieved. In order to achieve this effect, it is necessary to add a relatively large amount of the obtained product, and furthermore, the final product is a product in which the active ingredient is dissolved in oil or fat, etc., so when actually applied to various food manufacturing processes, various inconveniences occur,
Furthermore, it is not suitable for inclusion in cosmetics, pharmaceuticals, etc., and its range of use is limited. In this case, if the purified product, ie, the powder containing the active ingredient at a high concentration, is used as it is, there is a problem in that the characteristic flavor of spices remains. Furthermore, in the conventional method described above, after concentrating the rosemary and sage extract and washing with cold water and hot water,
This is redissolved in a solvent, then decolorized, concentrated, redissolved in fats and oils, and finally deodorized, which is a very complicated process. There is a cost issue. It has also been known that herbal spices have antibacterial effects, and when added in large quantities, they have been recognized to have antibacterial properties, but when used as is, they have a strong flavor, and their use is similar to that described above. have a problem. In addition, its antibacterial activity is generally said to be due to its essential oil components; for example, eugenol, which is known as an antibacterial agent, is extracted from essential oils. In view of the above circumstances, the inventors of the present invention have conducted extensive research on a method for easily obtaining preservatives with little flavor when incorporated into foods, etc., and have found that herbal spices such as sage, rosemary, and marjoram, and their essential oils. The collected residue, oleoresin extracted with a polar solvent, oleoresin extracted with a non-polar solvent, or its extraction residue are used as raw materials, and the extract obtained by extracting these with a polar solvent is directly decolorized. A powdery fraction can be obtained by an extremely simple method of concentrating the extract, steam distilling it, collecting the insoluble part in the residue, and drying it. It has almost no flavor characteristic of spices, making it suitable for adding to foods, etc., and this fraction has high antioxidant capacity and excellent antibacterial activity, making it suitable for use as a preservative. This discovery led to the present invention. The present invention will be explained in detail below. The spices used in the present invention include sage,
rosemary, marjoram, thyme, oregano,
These are herbal spices such as basil, and in the present invention, powders of these spices are used as raw materials; residues obtained by extracting oil from these by steam distillation and other essential oil extraction residues; or ethyl ether, ethylene chloride, dioxane, acetone, ethanol, methanol, Oleoresin extracted with polar solvents such as aqueous ethanol, ethyl acetate, propylene glycol, and glycerin; n-hexane, petroleum ether,
Oleoresin extracted with a nonpolar solvent such as ligroin, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, toluene, benzene, or the like or an extraction residue thereof is used. To obtain a preservative from these raw materials, first add a polar solvent, preferably at least an equivalent volume to the raw materials, such as ethyl ether, ethylene chloride, dioxane, acetone, ethanol, aqueous ethanol with an ethanol content of 65% or more, methanol, ethyl acetate. ,
Add propylene glycol, glycerin, etc., and extract while refluxing. This is separated into the post-extraction and extraction residue using a conventional method such as filtration, centrifugation, decantation, etc., preferably under heating, and the extraction residue is further subjected to the same operation to obtain an extract. Combine with the extract. Next, an adsorbent such as activated carbon, diatomaceous earth, or acid clay is added to this extract, and a decolorization process is performed to remove pigments such as chlorofilm in the extract. in this case,
This decolorization process uses an adsorbent containing 1 to 20% of the weight of the raw spices, and adds this to the extract for 10 to 60% of the weight of the raw spice.
It is usually sufficient to repeat the procedure of heating under reflux for a minute and then separating the adsorbent to obtain a solution portion twice. The obtained solution part (green pigment etc. is removed and exhibits a light brown to dark brown color) is heated to a temperature near the boiling point of the solvent used for the extraction, and the solvent is distilled off under reduced pressure or normal pressure. Concentrate using the method described above to obtain a dark brown to black candy-like or lump-like substance. This substance is then poured into water preferably at least 10 times its weight,
After stirring and dispersing in water, the mixture is heated under normal pressure or reduced pressure, brought to a boil, and subjected to steam distillation. Through this treatment, the essential oil components that give the aroma unique to the raw spices are volatilized together with water vapor and removed from the dispersion water. In addition, it is also possible to accelerate volatilization of essential oil components by blowing steam into the dispersion water in this steam distillation step. After continuing steam distillation until almost no essential oil components are recognized in the steam distillate, the dispersion (steam distillation residue) is heated or cooled, filtered, centrifuged,
Separate into a dark brown aqueous layer and a yellowish brown solid content (insoluble part) using a normal method such as decantation,
Collect this solid content. By drying this, a very pale light brown powder fraction is obtained. The present invention uses this solid content or powder fraction as a preservative, which has almost no flavor peculiar to spices and has an extremely strong antioxidant effect.
It also has an excellent antibacterial effect. In addition,
The dark brown aqueous layer obtained from the steam distillation residue has a strong bitter taste, and when concentrated to dryness, an extremely hygroscopic dark brown lump or powder substance is obtained.
This has almost no antioxidant effect or antibacterial effect. The preservative obtained by the above method can be used to store oil-based foods, such as oils and fats of animal or vegetable origin (fish oil, lard, tallow, head, chicken oil, soybean oil, linseed oil, cottonseed oil, surfflower oil, rice oil, etc.). oil,
Corn oil, coconut oil, palm oil, sesame oil, cacao butter, castor oil, peanut oil, etc.), butter, cheese, margarine, corn syrup, mayonnaise,
Oil-containing foods such as dressings, ham, sausages, potato chips, fried rice crackers, fried ramen noodles, and curry roux, or foods such as soybean oil, soft drinks, alcohol, fruit liquor, ketchup, jam, fish meat or meat paste products, or hair makeup. fee,
It is added to cosmetics such as skin cosmetics and mouth cosmetics, and pharmaceuticals. In this case, the amount added is 0.00001 to 2% by weight as dry powder, especially
The content is preferably 0.05 to 1% by weight. The preservative according to the present invention can be added as the insoluble part or its dry powder fraction, but if necessary, excipients such as starch and gelatin may be added to form powder or granules. It can also be used as a
In addition, fats and oils, ethanol, propylene glycol,
It can also be used as a liquid by dissolving it in glycerin or a mixture thereof. According to the method for producing a preservative according to the present invention, predetermined raw materials (herbal spices, their essential oil collection residues, oleoresin extracted with a polar solvent, oleoresin extracted with a nonpolar solvent or their extraction residues)
After extracting with a polar solvent to obtain an extract, an adsorbent is added to this to decolorize it, the adsorbent is separated, the resulting solution is concentrated, and then subjected to steam distillation. By collecting the insoluble portion of the residue, a preservative can be obtained efficiently and economically with very simple operations and extremely shortened steps. Furthermore, according to the present invention, the residual fractions that were conventionally discarded after distilling off or extracting the essential oil components can also be used as raw materials as described above, so it is possible to effectively utilize these residual fractions. You can also do it. In addition, the obtained preservative is in the form of a solid or powder that contains a large amount of active ingredients and is very easy to handle, has almost no flavor peculiar to spices, and is light brown in color, almost white. Therefore, when added to food, it does not change the flavor or color of the food, and there is no problem in terms of safety, making it very suitable for use as a food additive. Moreover, even when used in cosmetics, there is no risk of disturbing the balance of fragrances, and furthermore, it can be used in pharmaceuticals without causing changes in color, odor, etc. This preservative also exhibits extremely high antioxidant and antibacterial effects. For example, when added to lard, it prevents lard from oxidizing over a long period of time, providing an antioxidant effect equal to or greater than that of butylhydroxyanisole (BHA), which has traditionally been used as a synthetic antioxidant. It also has an excellent growth inhibiting effect on bacteria and fungi, and effectively prevents food spoilage. Next, Examples and Experimental Examples will be shown to specifically explain the present invention. [Example] Add 300 ml of 95% ethanol to 100.0 g of sample spice powder (sage, rosemary, marjoram, thyme) [Fraction A], extract while refluxing for 1 hour, and then separate the extract and the extraction residue. did. The extraction residue was further extracted with 300 ml of 95% ethanol and refluxed for 1 hour, and the extract and the extraction residue [Fraction B] were separated. The extracts were combined, 5g of activated carbon was added to this, refluxed for 30 minutes, and filtered.
Add 5g of activated carbon to the supernatant liquid from which activated carbon has been removed,
The same operation was repeated. After separating the activated carbon, the brown solution obtained by removing the green pigment (ethanol extract) is heated to about 70°C and the ethanol is distilled off under reduced pressure to obtain a brown candy-like or lump-like substance. Obtained. Next, suspend this substance in about 10 times the volume of water,
The mixture was heated to boiling while stirring, and the remaining essential oil components were removed by steam distillation. After cooling, the steam distillation residue was separated, a brown aqueous layer [Fraction C] was removed, and a pale brown insoluble portion was collected, which was dried to obtain a powder preservative [Fraction D]. The yields of each fraction A to D are shown in Table 1.

[Experiment example 1]

Antioxidant effect Next, regarding the antioxidant effect of each fraction A to D,
It was measured by the AOM method using lard. That is, adding the fractions A to D at a concentration of 0.1%,
Weigh out 20g of dissolved refined lard into a test tube,
0.23 per hour in a constant temperature oil bath set at 97.5℃±0.5℃
ml of air was forced through the tube and heated, and lard was sampled at appropriate intervals and the peroxide value (POV) was measured according to a modified Rhea method. Table 2 shows the results. For comparison, a similar experiment was conducted using 0.02% BHA.

【table】

[Experiment example 2]

Antibacterial action The above-mentioned sage fraction D was added to a tryptosoy case medium in an amount of 0.06%.
In addition to 10 ml of bioscanner (OT-
DS−12, manufactured by OTAKE WORKS) at 37℃
The turbidity was measured continuously for 60 hours (550 nm) and the results shown in the figure were obtained. The target bacterium was Bacillus subtillis, a common spoilage bacterium, taken in one platinum loopful. For comparison, a similar experiment was conducted by adding 0.2% sorbic acid. In the figure, 1 is the case when sage fraction D was used, 2 is the case when sorbic acid was used, and 3 is the control. From the results shown in the figure, it was recognized that sage fraction D showed a good antibacterial effect. [Experiment Example 3] Anti-fungal effect Using each fraction D (the preservative of the present invention) as well as fraction D (the preservative of the present invention) obtained in the same manner as in the example using oregano and cloves, anti-fungal activity was performed. (A.
The antifungal effect against P. niger and blue mold (P. For comparison, the effect of adding 5% ethanol was similarly determined. The results are shown in Table 3.

[Formulation example 1]

Creamy dressing Rapeseed salad oil 40% by weight Salt 3 Sugar 7 Egg 7 Seasoning 16 Sage fraction D 0.02 Water balance 100.0 [Formulation example 2] Hair conditioner polyoxypropylene monobutyl ether
10% by weight Liquid paraffin 10 Triol (molecular weight 4000) 10 Isostearyl palmitate 2 Polyoxyethylene lauryl ether (HLB15) 0.4 Polyoxyethylene cetyl ether (HLB8) 0.8 Stearyldimethylbenzyl ammonium chloride 1 Stearic acid 2 〃 Cetyl alcohol 5 〃 Lanolin 1 〃 Propylene glycol 5 〃 Rosemary fraction D 0.25 〃 Water balance 100.0 〃 [Formulation example 3] Ascorbic acid tablet L-Ascorbic acid 100mg Lactose 100mg α-starch 50mg Sage fraction D 1mg

[Brief explanation of the drawing]

The figure is a graph showing the antibacterial effects of a preservative from sage obtained by the method of the present invention and a conventional antibacterial agent (sorbic acid).

Claims (1)

[Scope of Claims] 1 A raw material selected from herbal spices, their essential oil collection residues, oleoresins of herbal spices extracted with polar solvents, oleoresins of herbal spices extracted with non-polar solvents, and extraction residues thereof, is polarized. After extracting with a solvent to obtain an extract, an adsorbent is added to this to decolorize it, the adsorbent is separated, the resulting solution is concentrated, and then steam distilled, and the steam distillation residue is A method for producing a preservative, comprising collecting an insoluble part of the preservative. 2. The manufacturing method according to claim 1, wherein the herbal spice is selected from sage, rosemary, marjoram, thyme, oregano, and basil.