JPH0798935B2 - Quality deterioration inhibitor - Google Patents

Description

TECHNICAL FIELD The present invention relates to a quality deterioration preventing agent. More specifically, the present invention relates to additives for preventing deterioration of quality of cosmetics, foods, pharmaceuticals or raw materials thereof due to oxidation and growth of microorganisms.

[Conventional technology]

It is generally said that cosmetics, foods, pharmaceuticals, or raw materials thereof are preferably those that are not colored, changed in odor, or deteriorated by oxidation, and that are not decomposed or deteriorated by the growth of microorganisms. Therefore, as the antioxidant, for example, dibutylhydroxytoluene (BHT), tocopherol, propyl gallate, etc. have been conventionally used. Further, as preservatives, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate,
Butyl paraoxybenzoate, sodium dehydroacetate, sodium benzoate, sorbic acid, benzalkonium chloride, cetylpyridinium chloride, tetramethylthiuram disulfide and the like are used.

[Problems to be solved by the invention]

The most commonly used means at present to prevent the deterioration of fats and oils is the addition of antioxidants.
Although synthetic antioxidants, especially BHT, have strong antioxidant power, their use is limited due to safety issues. In addition, natural products are said to have higher safety than synthetic products, but tocopherol is inferior to synthetic products in terms of stability in food and antioxidant power, and spice extract is antioxidant. Although excellent in power, it has a unique flavor, and therefore can be used only for foods that can advantageously utilize the flavor.

Further, generally, a preservative is added to cosmetics, foods, pharmaceuticals, raw materials thereof or the like as a means for preventing the growth of microorganisms. However, preservatives are a problem in terms of safety, and the amount used is severely limited.

The present invention is a novel antioxidant that does not have the drawbacks found in the conventional antioxidants as described above, that is, a highly safe substance composed of a substance derived from a natural product, which has no limitation on the intended use, and has an excellent antioxidant power. It is to provide an antioxidant having an antibacterial effect.

In view of these circumstances, the present inventors have conducted repeated studies on antioxidant and antiseptic properties of cosmetics, foods, pharmaceuticals, or raw materials thereof, and as a result, identified extracts of Junsai as cosmetics, foods, pharmaceuticals or raw materials thereof, etc. It was found that the addition in a ratio significantly suppresses the oxidation and the growth of microorganisms and prevents the deterioration of quality, and as a result of further research, the present invention has been completed.

[Means for solving problems]

The present invention is an agent for preventing quality deterioration of cosmetics, foods, pharmaceuticals or raw materials thereof, which contains a solvent extract of Junsai.

The quality deterioration preventive agent of the present invention is an agent that prevents oxidation of cosmetics, foods, pharmaceuticals, raw materials thereof, and the like, and also prevents the growth of microorganisms.

The term "oxidation" as used in the present invention means to exhibit so-called rancidity, which is the absorption of molecular oxygen in the air to cause autoxidation.

Junsai used in the present invention is a dicotyledonous plant net, a leaflet subweb, buttercups, water lily family, Junsai of the genus Junsai, and refers to a plant with a scientific name of Brasenia Schreberi JFG mel. For example, cultivated products can be used.

The solvent extract of Junsai of the present invention is a plant of Junsai, for example, leaves or stems and a viscous substance wrapping the surroundings extracted with a solvent, and examples of the solvent include water and alcohols ( Solvents such as methanol, ethanol, propanol etc.), ethers (diethyl ether etc.), ketones (acetone etc.), hydrocarbons (hexane, heptane etc.) and the like can be mentioned. What was extracted using a mixed solvent of one kind or two or more kinds of these solvents,
It may be one extracted by heating or one extracted at room temperature. The solvent extract may be a solvent-containing product or a solvent-distilled product regardless of the degree of concentration.

The quality deterioration inhibitor of the present invention, additives within the range of not losing the effect of the solvent extract of Junsai, such as foods, pharmaceuticals,
The raw materials for cosmetics, the above-mentioned antioxidants and preservatives, etc. can be added.

The cosmetics, foods, and pharmaceuticals referred to in the present invention include oils and fats, waxes, hydrocarbons, fatty acids, alcohols, esters, amine / amide / metal soaps, processed oils and fats such as surfactants, flavors, and gums. It refers to processed products produced from quality and water-soluble polymer compounds or vitamins as raw materials.

Examples of the oils and fats as raw materials for cosmetics, foods, and pharmaceuticals referred to in the present invention include avocado oil, almond oil, olive oil, sesame oil, safflower oil, soybean oil, corn oil,
Examples include rapeseed oil, castor oil, peanut oil, and palm oil.

Examples of waxes include beeswax, carnauba wax, whale wax, lanolin, and candelilla wax.

Examples of hydrocarbons include liquid paraffin, petrolatum,
Squalane etc. are mentioned.

Examples of the fatty acids include lauric acid, myristic acid,
Examples thereof include eicosapentaenoic acid, γ-linolenic acid and linoleic acid.

Examples of alcohols include lauryl alcohol, stearyl alcohol, and lanolin alcohol.

Examples of the esters include isopropyl myristate, butyl stearate, hexyl laurate, propylene glycol dioleate, lanolin acetate, oleyl oleate, decyl oleate, and octyldodecyl myristate.

Examples of the amine / amide / metal soap include octadecylamine, nonadecylamine, diheptylamine, didodecylamine, tetradecylamine, octylamide, decylamide, zinc stearate, aluminum stearate, and zinc lanolinate.

Examples of processed oils and fats such as surfactants include, for example, sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil,
Examples include hydrogenated castor oil.

Examples of the fragrance include anise oil, ylang-ylang oil, fennel oil, orange oil, black letter oil, cinnamon oil, cedarwood oil, jasmine oil, spearmint oil, rose oil, lavender oil, lemon oil, or a mixed fragrance thereof. .

Examples of gum and water-soluble polymer compounds include gum arabic, guaiac butter, tragacanth gum, quince seed, casein, sodium gelatinate, methyl cellulose, hydroxypropyl cellulose and the like.

Examples of vitamins include vitamin A, vitamin E,
Vitamin D, vitamin B ₁ , vitamin B ₂ , vitamin B _{6 and the} like can be mentioned.

Cosmetics manufactured using these materials as raw materials,
Examples thereof include pomade, cream, emulsion, shampoo, perfume, cologne, lotion, foundation, lip balm, lipstick and the like.

Examples of the processed food include butter, margarine, edible oil, biscuits, cookies, ice cream, potato chips and the like.

Pharmaceuticals include extracts, capsules, granules, powders, eye ointments, suspensions, emulsions, plasters, suppositories, fine granules,
Examples include tablets, syrups, dips, decoctions, injections, eye drops, troches, ointments, poultices, liniments, lotions and the like.

The amount of the quality deterioration preventing agent used for the purpose of preventing oxidation and preserving cosmetics, foods, medicines or raw materials thereof of the present invention is
As a solid component obtained by distilling off the solvent in the solvent extract of Junsai to the processed product or raw material, 0.0005 ~
It is added in a proportion of 10 weight percent, preferably 0.005 to 1 weight percent. If it is less than 0.0005% by weight, the effect is poor, and if it exceeds 10% by weight, an increase in hard fruits cannot be expected.

Regarding the addition method, it may be added in advance or may be added during the production, and may be appropriately selected in consideration of workability.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. The percentages (%) are weight percentages unless otherwise specified.

(Example) Example 1 400 g of raw Junsai is crushed and 400 ml of water is added every 2 hours for 2 hours.
The extract was heated and extracted once, and then freeze-dried in a vacuum to obtain 4 g of a hot water extract.

Example 2 100 g of raw Junsai was crushed, heated and extracted twice with 100 ml of water for 2 hours each time, and further concentrated to obtain 50 ml of the extract (2
% Solids).

Example 3 20 g of dried Junsai was ground and mixed with water and methanol (1:
1) Heat extraction with 100 ml for 5 hours and further concentration to obtain 4 g of an extract (containing 50% solid matter).

Example 4 20 g of dried Junsai was crushed, 300 ml of methanol was added,
Leave at room temperature for 1 month. By further concentrating, 1 g of an extract (containing 99% or more solid matter) was obtained.

Example 5 20 g of dried Junsai was crushed, heated and extracted twice with 100 ml of propanol for 2 hours each time, and further concentrated to obtain 1 g of an extract (containing 70% solid matter).

Example 6 20 g of dried Junsai was crushed, extracted by heating with 100 ml of butanol twice for 2 hours each time, and further concentrated to obtain an extract.
1 g (containing 60% solids) was obtained.

Example 7 20 g of dried Junsai was crushed, heated and extracted twice with 100 ml of acetone for 2 hours each time, and further concentrated to obtain an extract 50.
0 mg (containing 99% or more solid) was obtained.

Example 8 1 g of the hot water extract obtained in Example 1 is heated and extracted twice with 40 ml of ethanol for 2 hours each. By further concentrating, 250 mg of an extract (containing 99% or more solid matter) was obtained.

Example 9 O / W Nutrition Cream A) Stearic acid 4.0 (%) Cetyl alcohol 3.0 Liquid paraffin 5.5 Vaseline 10.0 Stearate monoglyceride 3.0 Sorbitan monostearate 0.6 B) 1,3-Butylene glycol 6.0 Triethanolamine 1.5 Polyoxyethylene sorbitan 0.4 Monostearate Purified water 65.7 Junsai hot water extract * 0.1 Methyl paraoxybenzoate 0.1 C) Perfume 0.1 * This extract contains 96% as a solid.

Production method: Oil phase component A and aqueous phase component B are 70 to 75 ° C, respectively.
After heat-dissolving, add A and B to emulsify, add C while cooling and mix, and cool to 30 ° C. to obtain a product.

Example 10 Emulsion A) Stearic acid 5.0 (%) Cetyl alcohol 5.0 Liquid paraffin 2.0 Vaseline 5.0 Monoglyceride stearate 1.3 Sorbitan monostearate 1.5 B) 1,3-Butylene glycol 6.0 Triethanolamine 0.7 Polyoxyethylene sorbitan 0.8 Monostearate Purified water 62.5 Quality deterioration inhibitor * 10.0 Methyl paraoxybenzoate 0.1 C) Perfume 0.1 * This quality deterioration inhibitor contains 5% solids, 40% glycerin and 55% water in the hot water extract of Junsai. .

Production method: A product is produced in the same manner as in Example 9.

Example 11 Biscuit soft flour 600 parts White sugar 270 parts Shortening 150 parts Ammonium bicarbonate 2.4 parts Sodium bicarbonate 1.2 parts Salt 3.3 parts Water 100 parts Junsai hot water extract * 1.3 parts Manufacturing method: Soft flour and shortening are mixed and further topped Add white sugar and mix. Next, Junsai hot water extract, salt, ammonium bicarbonate, sodium bicarbonate are added and mixed,
Use the dough. The dough is rolled to a thickness of 2 mm, molded and then baked in an oven at 200 ° C for 8 minutes to obtain a product.

* This extract contains 50% as a solid.

Example 12 Pound cake Flour 100 parts Sugar 100 parts Fluidity shortening 60 parts Egg white 100 parts Milk 15 parts Fluff flour 3 parts Hot water extract of Junsai * 2 parts * This extract contains 2% as a solid.

Manufacturing method: Add egg white, sugar, fluidity shortening, add flour, puffer powder, milk, Junsai hot water extract,
Roast in an oven at 180-200 ° C to obtain products.

Example 13 Edible Oil Edible Oil 100 parts Junsai ethanol extract * 0.05 parts * This extract contains 99% as a solid.

〔The invention's effect〕

Cosmetics, foods, pharmaceuticals or base materials thereof using the quality deterioration inhibitor containing the solvent extract of Junsai of the present invention are preferable because their oxidation is not promoted and also have antibacterial activity and are safe. Is also preferable in terms of flavor.

The effects of the present invention will be described below with reference to experimental examples.

(Example) Experimental example 1 The effect of the antioxidant activity of the extract obtained in Example 1 was examined by the iron rodan method.

Principle: Fe ²⁺ becomes Fe ³⁺ by the peroxide generated by the autoxidation of fats and oils, which reacts with NH ₄ SCN to produce red rodan iron, Fe (SCN) ₃ , so from its absorbance On the contrary, it is a method of determining the amount of peroxide.

Reagent preparation method: phosphate buffer (pH 7.0); 0.2M KH ₂ PO ₄ and 0.2M Na ₂ HPO ₄
The aqueous solution was mixed and adjusted to pH 7.0 with a pH meter.

30% NH ₄ SCN solution; ₃ g of NH ₄ SCN was dissolved by adding 7 ml of water.

0.002M ferrous chloride / hydrochloric acid solution; FeCl ₂ nH ₂ O 0.2575 g was made up exactly to 100 ml with a 10-fold dilution of special grade hydrochloric acid.

Preparation of sample solution: Add 0.8 ml of linoleic acid to 40 ml of absolute ethanol and dissolve, 40 ml of phosphate buffer solution (PH7.0)
And 1 ml of a 0.5% aqueous solution of Junsai hot water extract was added to make 100 ml with water. For comparison, the system with no sample added and B
A system in which HT and dl-α-tocopherol were added was similarly prepared.

Measurement method: The sample solution was left in a 60 ° C incubator to oxidize the sample, and the amount of peroxide of linoleic acid was measured over time.
For the measurement, 30% NH ₄ SCN solution and 0.02M ferrous chloride hydrochloride were added to the sample solution to develop color, and the absorbance at 500 nm was measured.

A graph of the measurement results is shown in Fig. 1. As is clear from this figure, the Junsai hot water extract showed a strong antioxidant activity equivalent to that of BHT.

When the extracts obtained in Examples 2 to 8 were tested in the same manner, they showed the same good antioxidant effect as that of Example 1.

Experimental Example 2 The antioxidant activity of the extract obtained in Example 1 was measured by the thiobarbituric acid method.

Principle: The thiobarbituric acid method is a method in which thiobarbituric acid reacts with malonaldehyde, which is an oxidative decomposition product of fats and oils, to form a red reaction substance having a maximum absorption around 530 nm, and is oxidized from the absorbance. This is a method for quantifying decomposition products.

Reagent preparation method: 20% trichloroacetic acid aqueous solution; 5 g of trichloroacetic acid was dissolved in 20 ml of water.

0.67% thiobarbituric acid aqueous solution; thiobarbituric acid
0.335 g was dissolved in 50 ml water.

Preparation of sample solution: A sample solution was prepared in the same manner as in Example 1.

Measurement method: In the same manner as in Experimental Example 1, the sample solution was left in a 60 ° C incubator to oxidize the sample, and the measurement was performed with time. The measurement is
20% trichloroacetic acid and 0.67% thiobarbituric acid aqueous solution were added to the sample solution to develop color, and the absorbance at 532 nm was measured.

The graph of the result is shown in Fig.2. As is clear from the figure, the Junsai extract showed almost the same antioxidant activity as BHT.

When the extracts obtained in Examples 2 to 8 were tested in the same manner, they showed the same good antioxidant effect as that of Example 1.

Experimental Example 3 An acute toxicity test was conducted as a safety test. The extract obtained in Example 1 was used as a sample, SD rats were used as animals, and the dose of specific body weight was adjusted, and oral gavage was performed using a metal gastric tube. Dosages of 32, 40 and 50 ml / K
The administration group of g (1600, 2000, 2500 mg / Kg as a solid product) was set, and 12 males and 12 females were provided for each administration group, and the animals were reared and observed for 14 days.

As a result, all of the treatment groups survived and no death was observed. In addition, body weight changes also showed a steady increase in each administration group,
No abnormalities were observed in appearance or behavior.

Therefore, the LD50 value is 50 ml / Kg or more (2,500 mg / Kg as a solid product), which is the highest dose that can be administered, and the toxicity is extremely low.
Compared with the LD50 of HT being 1700-2000 mg / Kg,
Junsai is very safe.

Also, when the extracts obtained in Examples 2 to 8 were tested in the same manner, they were as safe as Example 1.

Experimental Example 4 As a safety test, a patch test was performed on 30 humans. As the sample, the extract obtained in Example 1 was used, the patch concentration was 10% aqueous solution, and the purified water used as the base was used as a control. As a patch material, fin chamber (EP
It was applied for 48 hours using ITEST).

As a result, the Junsai hot water extract showed only a slight erythema in 2 out of 30 people, while it was 5 in the control purified water.
A slight erythema was noted in the name. These results show that Junsai extract is very safe for skin.

Also, when the extracts obtained in Examples 2 to 8 were tested in the same manner, they were as safe as Example 1.

Experimental Example 5 As an antibacterial activity test, the minimum inhibitory concentration of Junsai extract was measured by the agar plate dilution method.

The extracts used as samples were the hot water extract obtained in Example 1 and the ethanol extract obtained in Example 8.

Test method: 1 platinum loop of each of the bacterial solutions was smeared on the agar medium in which the sample was dissolved and cultured to confirm the growth of the bacteria. Regarding the culture conditions, bacteria were cultured on SCD agar at 37 ° C for 1 day,
Yeast and mold were cultured on GP agar medium at 25 ° C for 3 to 7 days. For bacterial preparation, tryptosoy broth for bacteria at 30 ° C for 1 day, yeast for GP medium at 25 ° C,
After culturing for 2 days, adjust to 10 ⁶ / ml, and for mold, 5m
1 platinum loop of fresh cells was dispersed and used in 1 l of phosphate buffer (PH7.2). Table 1 shows the results of the measured bacterial species and the minimum inhibitory concentration thereof. As is clear from the table, the extract has antibacterial activity and can reduce the amount of preservative used.

When the extracts obtained in Examples 2 to 7 were tested in the same manner, they showed the same good antibacterial properties as in Example 1.

Furthermore, in Examples 9 to 13, the products containing the quality deterioration inhibitor of the present invention had good oxidation prevention and had no problem in flavor. Furthermore, the amount of methyl paraoxybenzoate as a preservative used could be reduced or eliminated, and a good preservative power was exhibited.

[Brief description of drawings]

FIG. 1 shows that linoleic acid measured by the iron iron rhodanate is oxidized with time. The vertical axis represents absorbance at 500 nm, and the horizontal axis represents time. As an explanation of the abbreviations shown in the figure, JUN refers to Junsai hot water extract (0.005% as solid).
%), BHT is dibutylhydroxyltoluene 0.005%, TO
C means dl-α-tocopherol 0.005% and CON means control. FIG. 2 shows that linoleic acid measured by the thiobarbituric acid method is oxidized with time. The vertical axis represents absorbance at 532 nm, and the horizontal axis represents time. The meanings of the abbreviations JUN, BHT, TOC, and CON described in the figure are the same as in FIG.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area A61K 47/46 K

Claims (1)

[Claims] 1. A quality deterioration inhibitor comprising a solvent extract of Junsai.