JPH0435151B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a food preservative and a method for producing the same. [Prior art and problems to be solved by the invention] Preservatives are added to food and drink products in order to prevent them from spoiling and improve their shelf life. Various natural and synthetic preservatives have been studied as preservatives for foods, and among the natural ones, protamine is known to have antibacterial properties, and a method of preserving food using protamine as a preservative has also been proposed. (Japanese Patent Application Laid-Open No. 61-219363). However, since protamine is a very basic protein, it is highly adsorbed to foods and drinks, especially protein-rich meat and fish paste products such as ham, wiener sausage, kamaboko, and chikuwa, milk, and dairy products made from it. It has the disadvantage that it is easily adsorbed to food and drink ingredients, and when it is adsorbed to food and drink ingredients, antibacterial activity decreases and the shelf life of food and drink products decreases. [Means for Solving the Problems] The present inventors conducted research on the relationship between the antibacterial effect of protamine and its adsorption to foods and drinks, and found that
The molecular weight of protamine from various fishes is generally 4000~
6000 or when this protamine is decomposed, its adsorption to foods and drinks decreases, but completely decomposed protamine has almost no antibacterial properties.
When it is partially decomposed by acid, alkali, or endopeptidase or an enzyme preparation containing endopeptidase so that the molecular weight is distributed in the range of 500 to 3,500, it has an antibacterial effect equal to or greater than that of protamine. Nevertheless, its adsorption to food and drink products is very low compared to protamine, and it can be added to food and drink products without the risk of reducing its antibacterial effect due to adsorption to food and drink products, as is the case with protamine. The present inventors have discovered that they can exhibit excellent antiseptic effects and have completed the present invention. That is, the present invention provides (1) that the molecular weight obtained by partially decomposing protamine is
A preservative for food and beverages, characterized by comprising partially decomposed protamine in the range of 500 to 3,500. (2) The method for producing a preservative for foods and drinks according to claim 1, characterized in that protamine is partially decomposed by endopeptidase or an enzyme preparation containing endopeptidase. (3) The method for producing a preservative for foods and drinks according to claim 1, characterized in that protamine is partially decomposed with an acid. (4) The method for producing a preservative for foods and drinks according to claim 1, characterized in that protamine is partially decomposed with an alkali. The main points are as follows. Protamine, which is the raw material for the preservative of the present invention, is a basic protein that is abundantly contained in the testes (so-called milt) of fish such as salmon and herring. ) etc.,
Although each protamine has a slightly different structure, all protamines can be used in the present invention. The preservative of the present invention has a molecular weight of 500 to 3,500, particularly preferably 500 to 3,500.
It is necessary for the molecular weight to be distributed in the range of 2,500, and those with a molecular weight of over 3,500 have too strong adsorption to foods and drinks, so if added to foods and drinks, they will be adsorbed to the food and drink ingredients and the antibacterial activity will decrease. If it is less than 100%, it has no adsorption to food and drink components, but it has almost no antibacterial effect. The amount of the preservative of the present invention added to foods and drinks varies depending on the type of food and drink, the type of protamine, etc., but usually the concentration after addition is 0.001 to 5% as solid matter.
Particularly preferred is a range of 0.01 to 1%. Addition to foods and beverages may be carried out during the manufacturing process of foods and beverages,
Alternatively, the food or drink may be immersed for a certain period of time in an aqueous solution containing the preservative of the present invention obtained by partially decomposing protamine. When added to food and beverages, it can be in any form such as liquid, paste, powder, flake, or granule, but for ease of handling and use in combination with other additives, dry powder or granule is preferred. It is preferable to use it as a form. As the drying method, for example, ordinary drying methods such as spray drying, drum drying, shelf drying, and vacuum drying can be applied. Alternatively, an organic solvent miscible with water such as ethanol or acetone may be added to precipitate and separate the decomposed product, followed by drying. The preservative of the present invention can be used to preservatives, for example, fish and meat paste products such as kamaboko, chikuwa, wiener sausage, and ham, tofu, noodles, shiumai, gyoza, tamagoyaki, confectionery such as fresh cream and shu cream, salted and dried seafood, etc. Can be used as a drug. The preservative of the present invention is obtained by partially decomposing the above-mentioned protamine to a molecular weight of 500 to 3,500 using an acid, an alkali, an enzyme, or a combination thereof.
Examples of the above acids include hydrochloric acid, sulfuric acid, etc.
Examples of the alkali include barium hydroxide, sodium hydroxide, potassium hydroxide, and the like. In addition, in the case of enzymatic degradation, endopeptidase, which is an enzyme that hydrolyzes the bonds within the peptide chain, or an enzyme preparation containing endopeptidase is used.
When using exopeptidase or an enzyme preparation containing exopeptidase, which is an enzyme that hydrolyzes amino acid residues at the amino group terminal or carboxyl terminal, protamine is easily degraded to a low molecular weight of less than 500, which is not suitable for the purpose of the present invention. The molecular weight is 500~
It becomes difficult to obtain partially degraded protamine in the 3500 range. Examples of enzyme preparations containing the above-mentioned endopeptidase include commercially available panchitase NP-
2 (manufactured by Yakult Honsha Co., Ltd.), Protease YP-SS
(manufactured by Yakult Honsha Co., Ltd.), Pectinase HL (manufactured by Yakult Honsha Co., Ltd.), Neurase F (manufactured by Amano Pharmaceutical Co., Ltd.),
Examples include protease A "Amano" (manufactured by Amano Pharmaceutical Co., Ltd.). Decomposition conditions such as the amount of enzyme added and reaction time to partially decompose protamine to a molecular weight of 500 to 3500 vary depending on the type and concentration of protamine, the type of enzyme added, the decomposition equipment, etc. Usually, an enzyme with an amount of 1/1000 to 1/5000 of protamine is added to an aqueous solution of about 3 to 15% of protamine, and the solution is decomposed at a decomposition temperature of 30 to 45°C and a decomposition time of about 1 to 10 hours. After the reaction is completed, the preservative of the present invention can be obtained by heating at about 80° C. for several minutes to inactivate the enzyme and, if necessary, performing treatments such as concentration and drying. The extent to which decomposition has progressed can be confirmed by sampling samples over time and measuring the molecular weight distribution using column chromatography. Measure the change and find the time for the molecular weight to reach 500 to 3500.
This can be determined. In the actual manufacturing process, the ninhydrin method can be used to confirm when the decomposition is complete. In other words, it is a method in which color is developed due to the presence of free amino groups generated by decomposition, and the progress of decomposition is confirmed from the absorbance at 570 nm based on a predetermined calibration curve.For example, the decomposition of a 3% protamine solution In the case of , if the reaction is stopped when the absorbance at 570 nm is 0.05 to 0.3, a partially decomposed product with a molecular weight in the range of 500 to 3500 and high antibacterial activity can be obtained. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 An enzyme preparation containing endopeptidase (manufactured by Yakult Honsha Co., Ltd.: Pectinase HL) was added to a 3% aqueous solution of protamine extracted from salmon milt so that the concentration after addition was 0.03%. After heating and stirring at .degree. C. for 2 hours, the temperature was raised to 80.degree. C. and held for 5 minutes to inactivate the enzyme, and then dried by freeze-drying to obtain a powdery decomposition product. The molecular weight of this decomposed product (preservative) was measured by column chromatography (filling material: Sephadex G-25), and the molecular weight was in the range of 500 to 2,500. The obtained preservative was added to various foods and drinks shown in Table 1 in the amounts shown in the same table, and a preservative test was conducted. The obtained results are also shown in Table 1. Example 2 Hydrochloric acid was added to a 5% aqueous solution of protamine extracted from herring milt so that the concentration after addition was 0.03N, heated and stirred at 100°C for 24 hours, cooled, and then freeze-dried. It was dried to obtain a powdery decomposition product. When the molecular weight of this decomposed product was measured by column chromatography (using the same column as in Example 1), the molecular weight was in the range of 500 to 3000.
The preservative properties of the obtained preservative were tested in the same manner as in Example 1 under the conditions shown in Table 1. The obtained results are also shown in Table 1. Example 3 Barium hydroxide was added to a 10% aqueous solution of protamine extracted from salmon milt so that the concentration after addition was 0.5N, heated and stirred at 45°C for 48 hours, cooled, and then freeze-dried. The mixture was dried to obtain a powdery decomposition product. The molecular weight of this decomposed product was measured by column chromatography (using the same column as in Example 1), and the molecular weight was 500 to 3,500. The preservative properties of the obtained preservative were tested in the same manner as in Example 1 under the conditions shown in Table 1. The obtained results are also shown in Table 1. Example 4 Endopeptidase (Punchidase NP-2, manufactured by Yakult Honsha Co., Ltd.) was added to a 5% aqueous solution of protamine extracted from salmon milt so that the concentration after addition was 0.0025%, and the mixture was incubated at 37°C. The mixture was heated and stirred for a period of time, then heated at 80° C. for 5 minutes to inactivate the enzyme, and then dried by freeze-drying to obtain a powdery decomposed product. The molecular weight of this decomposed product was measured by column chromatography (using the same column as in Example 1), and the molecular weight was 500 to 2,500. The preservative properties of the obtained preservative were tested in the same manner as in Example 1 under the conditions shown in Table 1. The obtained results are also shown in Table 1. Comparative Example 1 Protamine extracted from salmon milt was added to each of the foods and drinks shown in Table 1 in the amount shown in the same table, and the same preservative test as in each Example was conducted. The obtained results are also shown in Table 1.

【table】

〔Effect of the invention〕

As explained above, the preservative of the present invention partially decomposes protamine to have a molecular weight of 500 to 3500, so it has excellent antibacterial properties and does not have the risk of strongly adsorbing to food and drink ingredients like protamine. Therefore, there is no risk that antibacterial activity will decrease due to adsorption to food and drink components, and excellent preservative action is exhibited. Furthermore, the method of the present invention has the effect of reliably producing the above-mentioned excellent preservative.

Claims (1)

[Claims] 1. The molecular weight obtained by partially decomposing protamine is
A preservative for food and beverages, characterized by comprising partially decomposed protamine in the range of 500 to 3,500. 2. The method for producing a preservative for foods and drinks according to claim 1, characterized in that protamine is partially decomposed by endopeptidase or an enzyme preparation containing endopeptidase. 3. The method for producing a preservative for foods and drinks according to claim 1, characterized in that protamine is partially decomposed with an acid. 4. The method for producing a preservative for foods and drinks according to claim 1, characterized in that protamine is partially decomposed with an alkali.