JPH0529429B2 - - Google Patents

Description

[Detailed description of the invention]

"Industrial Application Field" The present invention is a natural product made by combining protamine extracted from the testes of fish and shellfish with two types of antibacterial substances selected from a group of specific antibacterial substances. Concerning food preservatives mainly. "Prior Art" In recent years, with the development of distribution systems, it has become possible to easily distribute various foods over a wide range of areas. At the same time, extension of the shelf life of foods is required. However, synthetic preservatives used to extend the shelf life of foods, such as sorbic acid and benzoic acid, are subject to this requirement. Foods are limited and it is not allowed to be used in many foods, and consumers also
Foods containing synthetic preservatives and synthetic sterilizers do not have a very good impression, so there is a strong need for the development of food preservatives based on natural products. In order to satisfy this strong demand, the inventor has conducted intensive research into the development of food preservatives centered on naturally occurring antibacterial substances. On the other hand, traditionally, salmon, trout, herring, mackerel,
The testes of various seafood such as cod, squid, and scallops, commonly referred to as milt, are only partially eaten and used as meal ingredients; most of them are eaten. are being disposed of, and as an unused resource, it is hoped that they can be utilized in a more advanced manner. It is known that protamine, which exists in high concentrations in the sperm nuclei of the testes of this fish and shellfish, has antibacterial properties.
Fishes as Inhibitors on the Growth of Micro
−organisms〓ORBrekkan and G.Boge：Re
−ports on Technological Research
CCcerning Norwegian Fish Industry 1964,
4(6); Antibacterial properties of herring and salmon protamine
Nazrum Islam, Takao Itakura, Terushige Motohiro: Collection of lecture abstracts from the 1981 Autumn Conference of the Japan Society of Fisheries Science, page 164), the inventor focused on the antibacterial properties of this protamine, and developed an effective food preservative using it. We have begun research to see if this can be realized. ``Problems to be solved by the invention'' Food preservatives have antibacterial effects to varying degrees against a wide range of microorganisms, have low toxicity, and have taste, aroma, color, and physical properties of the target food. It must meet conditions such as not having a negative impact on food products, etc., and not significantly increasing the cost of the target food. Preferably, it is a natural product. Foods also include taste, aroma, color, texture, texture,
Its physical properties and other properties are extremely diverse and complex,
These should not be allowed to change due to the addition of preservatives. Moreover, in recent years, as consumers have become more natural-oriented, there is a tendency to prefer natural preservatives as much as possible. For this reason, the food industry is actively developing food preservatives based on naturally derived antibacterial substances, but a sufficiently effective product has not yet been obtained. On the other hand, although there have been academic reports on the antibacterial properties of protamine, there have been no reports on how it is actually effective as a food preservative or whether it can be put to practical use. Although protamine is highly safe for animals,
Its antibacterial properties are easily expressed in neutral or alkaline pH ranges, but the antibacterial properties are reduced in acidic ranges; it is expressed in Gram-positive bacteria, but is difficult to develop in Gram-negative bacteria; and metal ions. etc. can be a factor that inhibits the antibacterial properties of protamine, so when used as a preservative in food systems, it is difficult to ensure effectiveness when used alone. Furthermore, if the amount of protamine added is increased in order to increase the effectiveness, there are drawbacks such as having a negative effect on the taste and aroma of the food and making it extremely expensive. The present inventor conducted research to solve the above-mentioned drawbacks and technical requirements of protamine as a food preservative, and in order to solve the above-mentioned drawbacks and technical requirements of protamine, the present inventors added protamine to protamine, which was selected from a group of antibacterial substances consisting of glycine, sodium acetate, lysozyme, and licorice extract antibacterial substances. Two antibacterial substances or vitamins
When two types of antibacterial substances selected from the antibacterial substance group consisting of <sub>B1</sub> ester, polymerized phosphate, lower fatty acid monoglyceride, or sugar ester are combined, the antibacterial properties of protamine are effectively expressed and the antibacterial spectrum is also extended. It has been found that the present invention exhibits a sufficient synergistic effect even in expanded, complex, and diverse food systems, resulting in effective food preservation. Based on the above new knowledge, the present invention enables the effective discovery of the antibacterial properties of protamine by selecting and specifying two types of antibacterial substances to be combined with protamine, and the present invention has been made to effectively discover the antibacterial properties of protamine. The purpose is to embody a preservative. Also,
By combining two types of protamine antibacterial substances in this way, the amount of the constituent antibacterial substances added can be reduced, and the taste and aroma of each antibacterial substance will be diluted and will not have a negative impact on the taste and aroma of food. The aim is to provide highly practical food preservatives that are mainly made from natural products and satisfy the above requirements. "Means for Solving the Problems" The present invention takes the following means to solve the above problems. The food preservative is prepared by combining protamine with two types of antibacterial substances selected from any one of the following specific antibacterial substance groups. The specific antibacterial substances group can be classified into the following three groups. This is to clarify the selection and specification of antibacterial substances to be combined. First specific antibacterial substance group Glycine, sodium acetate, lysozyme, licorice extract antibacterial substance Second specific antibacterial substance group Vitamin B <sub>1</sub> ester, polymerized phosphate, lower fatty acid monoglyceride Third specific antibacterial substance group Vitamin B <sub>1</sub> ester, polymerized phosphate, sugar ester 2 from any one of these specific antibacterial substance groups
The antibacterial substance of the species is selected and specified, and by combining it with protamine, it is used as a food preservative. That is, there are the following three embodiments of the present invention. (1) A food preservative that combines protamine with two substances selected from the group of substances consisting of glycine, sodium acetate, lysozyme, and antibacterial substances extracted from licorice. (2) A food preservative that combines protamine with two substances selected from the group of substances consisting of vitamin B <sub>1</sub> ester, polymerized phosphate, and lower fatty acid monoglyceride. (3) A food preservative that combines protamine with two substances selected from the group of substances consisting of vitamin B <sub>1</sub> ester, polymerized phosphate, and sugar ester. The present invention focuses on the fact that protamine is originally a component derived from natural products, has high thermal stability, and is a highly safe antibacterial substance, and has great advantages as a material for food preservatives. In order to overcome the disadvantage that the antibacterial spectrum is narrow and the antibacterial properties are affected by the target bacterial species and the properties of the target food, we have conducted extensive research and found that protamine has not been used alone, but instead of using two other methods.
It was successfully developed by using the antibacterial substances of seeds as an auxiliary means. The inventors experimented with many additives used in combination as auxiliary means.
As a result, the above 2 selected from the group of specific antibacterial substances.
We have discovered that the antibacterial properties of protamine are effectively expressed by a combination of different antibacterial substances, and that a synergistic effect is exhibited. In experiments, even when one type of specific antibacterial substance was used in combination with protamine, the antibacterial properties of protamine were effectively expressed to some extent.
Although the storage life is improved and the storage period is extended, it is generally very difficult to further extend the storage period. However, in the present invention, we have demonstrated that the inventive plots containing a preservative that is a combination of protamine and two types of antibacterial substances selected from the group of specific antibacterial substances further improve preservability compared to the control plots. made possible.
The extended storage period compared to the control group obtained by the present invention is extremely significant in view of the current state of food distribution, where very strict freshness control is carried out. Furthermore, depending on the nature of the food to which it is added, the type of contaminant bacteria, processing conditions, and additives, the preservation effect may not be sufficient or the flavor of the food may be affected. A high degree of technical knowledge is required to achieve both the appropriate addition method and the preservation effect, and to ensure effectiveness. However, when commercialized as a food preservative,
Since it is not used only by those with specialized knowledge of protamine and preservatives, it is undesirable for the appropriate addition conditions to be too complex or too narrow. Therefore, the present invention satisfies the conditions required as a food preservative, such as having a fairly broad antibacterial spectrum, simple usage instructions, and not having the unique flavor and bitterness of protamine. Thus, two types of antibacterial substances to be used in combination with protamine were specifically selected and specified. The protamine used in the present invention is a strong basic protein with a relatively small molecular weight and high arginine content that exists as nucleoprotamine bound to deoxybonucleic acid in the sperm nuclei of salmon, trout, herring, mackerel, etc., and is in a free state. protamine,
Alternatively, it can be used in any form such as protamine sulfate or protamine hydrochloride. There are various methods for producing protamine, and generally speaking, the mature eggs of the fish mentioned above are ground,
Dilute hydrochloric acid is added, and condensed phosphoric acid or its salt is added to the resulting protamine extract to precipitate a sparingly soluble protamine salt, which is double decomposed with high concentration inorganic salts to produce protamine mineral salt, and then treated with an ion exchange resin. Desalting is a method used, but any method used can be used in the present invention as long as it does not contain foreign substances that cannot be added to foods due to toxicity. Antibacterial substances used in combination with the above protamine include glycine, sodium acetate, lysozyme, licorice extract antibacterial substances, lower fatty acid monoglycerides, sugar esters, vitamin B <sub>1</sub> esters, polymerized phosphates, and the like. These antibacterial substances will be briefly explained below. Glycine is known to effectively exhibit antibacterial properties against most Bacillus species. It has a synergistic effect with protamine as it inhibits bacterial cell membrane biosynthesis. Sodium acetate effectively inhibits the growth of Gram-negative bacteria, and has a large preservative effect in the acidic pH range, so its combined use with protamine is complementary. The above-mentioned glycine and sodium acetate may be of a grade that can be added to foods. Lysozyme exhibits a strong antibacterial effect mainly against Gram-positive bacteria, but its point of action is on the lysis of bacterial cell membranes.
It is highly synergistic with the action of protamine, which attaches to and destroys bacterial cell membranes. As for lysozyme, those commercially available for general food use can be used. Licorice extract antibacterial substances are mainly effective against Gram-positive bacteria, molds, and yeast. Therefore, the combination with protamine complements protamine, which has a weak effect on mold. The antibacterial substance extracted from licorice was specially applied for in 1980.
Antibacterial substances produced using the production method described in No. 172928, that is, extracted from licorice with aromatic hydrocarbons, acetone, ethanol, etc., can be used. Examples of lower fatty acid monoglycerides include caproic acid, caprylic acid, capric acid, and esters of lauric acid and glycerin. This antibacterial action mechanism is the same as that of fatty acids, which inhibits the activity of enzymes and does not have a strong bactericidal effect, but it is almost uniformly effective against mold, yeast, and bacteria, so it is effective against mold. It can compensate for the weak effect of protamine. Sugar ester exhibits antibacterial activity mainly against Gram-positive bacteria and yeast, regardless of pH, so it can supplement the action of protamine. Any sugar ester may be used as long as it is permitted as a food additive. Regarding vitamin <sub>B1</sub> sulfate, there are lauryl sulfate and cetyl sulfate. It exhibits antibacterial activity against bacteria and yeast, and is particularly effective in acidic pH ranges. Therefore, the combination with protamine is complementary in the acidic PH range. Examples of polymerized phosphates include sodium pyrophosphate, sodium metaphosphate, and sodium polyphosphate. Polymerized phosphates are effective against bacteria, especially gram-positive bacteria, but by chelating alkaline earth metals, they are effective in increasing the antibacterial properties of surfactant compounds and also increasing the antibacterial properties of protamine. . In this way, the present invention has significantly increased antibacterial activity due to the synergistic effect of combining protamine with two selected from the above antibacterial substances, and the combination of different antibacterial substances. It has a broad antibacterial spectrum and has as little effect on the flavor of food as possible, giving excellent results as a food preservative. This is because the antibacterial substance used in combination not only exerts its own antibacterial effect, but also has the effect of removing or reducing factors that inhibit the expression of protamine's antibacterial properties, so the antibacterial activity of protamine is effective. This is because the antibacterial action of the antibacterial substance itself becomes synergistic with the antibacterial action of the antibacterial substance itself, significantly improving the preservability of foods. The ratio of each component in the present invention is:
1 part of protamine to 10 to 200 parts of glycine,
5 to 100 parts of sodium acetate, 0.2 to 4 parts of lysozyme, 0.2 to 4 parts of licorice extract antibacterial substance,
Lower fatty acid monoglyceride 0.5 to 10 parts, sugar ester 0.5 to 10 parts, vitamin B <sub>1</sub> sulfate ester 0.05 to 1 part, polymerized phosphate 1.0 to 100 parts
This is within the scope of the department. In addition, the amount of the preservative of the present invention added to food is
Although it depends on the combination of its constituent components, it ranges from 0.01% to 2%, which is equivalent to protamine.
It is preferably in the range of 0.005% to 0.05%. Foods to which the food preservative of the present invention can be applied are not limited. Fishery products such as kamaboko and chikuwa, meat products such as sausages and ham, Western sweets, Japanese sweets, noodles such as raw noodles, boiled noodles, Chinese noodles, and soba noodles, seasonings such as sauces, soy sauce, and sauces, pickles,
It can be used for many foods such as vegetables. ``Action'' In the case of food preservatives, they have antibacterial effects against a wide range of microorganisms, have low toxicity, and have a negative impact on the taste, aroma, color, physical properties, etc. of the target food, albeit to varying degrees. It must meet conditions such as not giving food or significantly increasing the cost of the food in question. It is known that each of the components of the food preservative of the present invention already has an antibacterial effect. However, when used individually as a preservative, it cannot be said that the above provisions are fully satisfied. There are not many studies or reports on the antibacterial properties of protamine, and the mechanism of its antibacterial action has not been completely elucidated academically. However, it has been confirmed that protamine has the effect of inhibiting bacterial growth, including inhibiting bacterial respiration, inhibiting bacterial growth by impacting the bacterial surface layer, and particularly strong growth inhibition against Gram-positive bacteria. It has properties such as exhibiting antibacterial properties, exhibiting antibacterial properties in a relatively wide pH range from slightly acidic to alkaline, and significantly sterilizing heat-resistant spores when used in combination with heat treatment. This became clear with recent announcements. These antibacterial properties of protamine suggest that it can be applied to the food preservation field, but in particular, protamine is effective against bacterial species of the genus Bacillus, which are well known as food spoilage bacteria. Considering that most of these strains have characteristics such as being highly susceptible to growth inhibition, protamine is suitable for exerting food preservation effects such as preventing food spoilage as well as deterioration. However, when protamine is used solely as a food preservative,
The expected preservative effect is not achieved, and if the amount added is increased until the preservative effect is achieved, the flavor of the food will be spoiled and it will become expensive, making it completely impossible to put it into practical use. However, it has been found that protamine exhibits extremely strong antibacterial properties when used in combination with other antibacterial substances. The food preservative of the present invention is a food preservative made by searching for a combination of antibacterial substances that synergistically improves the antibacterial effect based on such knowledge, and further combining the selected antibacterial substance with protamine. This study was completed by confirming whether the results of adding the substance to various foods meet the expected requirements. Next, when we examine the suitability of antibacterial substances as combination targets, we find that not all of them fully satisfy the above conditions when used individually as preservatives. In other words, it is known that glycine and sodium acetate must be added in large amounts in order to provide sufficient preservability to foods, and as a result, they have a negative effect on the taste, aroma, color, etc. of foods. It is being In addition, the antibacterial properties of lysozyme and licorice extracted antibacterial substances show extremely strong antibacterial properties against certain types of bacteria, but the antibacterial spectrum is narrow and they are not suitable as preservatives for foods that spoil due to various types of bacteria. , is insufficient. In addition, these substances are extremely expensive, so adding them in large quantities to ensure sufficient shelf life will increase the cost of the food.
Undesirable. In addition, lower fatty acid monoglycerides, sugar esters, vitamin B ₁ sulfate esters, and polymerized phosphates may have a negative effect on the taste and aroma of foods if they are added to foods in amounts that provide sufficient preservability. Are known. The present invention provides two selected antibacterial substances from the above-mentioned antibacterial substances.
By combining seeds and protamine, the antibacterial effect is synergistically improved, and by combining different antibacterial substances, the antibacterial spectrum is expanded, and by reducing the amount added, the flavor of food is not impaired. It satisfies the requirements as a food preservative. "Example" The present invention will be described below with reference to Examples. Example 1 (Kamaboko) Add the additives listed in Table 1 to the basic composition of 1000 g of frozen surimi, 30 g of salt, 20 g of mirin, 10 g of monosodium glutamate, 10 g of sugar, 70 g of potato starch, and 400 g of ice water (additional amounts are as follows) After mashing for 30 minutes, it was plated and steamed for 45 minutes. After simple packaging, it was stored at 30°C and changes in appearance were observed. The results are shown in Table 1. Explanations of the symbols are shown in Table 4. It is clear that the storage stability of the test plots of the present invention is improved compared to when a single drug is added or when protamine is combined with one selected from a specific substance group. As a result of the sensory test, there was no difference in taste, color, etc. between the test plots of the present invention and the control plots, and no adverse effects on quality were observed due to the addition of the preservative of the present invention. .

[Table] Example 2 (Boiled Chinese noodles) The chemicals shown in Table 2 were added to the basic composition of 500 g of strong flour, 160 g of water, and 5 g of brine (the amount added is weight % of the basic composition), and after mixing thoroughly,
Noodle strings were made in a conventional manner using a small noodle making machine, boiled in boiling water for 4 minutes, and cooled in water. After draining the water, it was placed in a plastic bag and sealed, then stored at 25°C and observed for changes in appearance. As shown in Table 2, the results show that the preservability of the test plots to which the preservative of the present invention was added was greater than when the drug was added alone or when protamine was combined with one substance selected from a group of specific substances. It is clear that they are getting used to each other. In addition, in terms of quality, no difference was observed between the test plot of the present invention and the control. Note that the symbols are explained as shown in Table 4.

【table】

[Table] Example 3 (Boiled noodles) The basic composition was 1000 g of all-purpose wheat flour, 350 g of water, and 20 g of food, and the chemicals shown in Table 3 were added thereto (the amount added is % by weight of the basic composition), and after mixing thoroughly,
The mixture was rolled and cut in a conventional manner using a small noodle making machine to obtain noodle strings. After boiling this, put it in a plastic bag and
It was stored at ℃ and its appearance was observed. As shown in Table 3, the results show that the test plot of the present invention has a longer shelf life than when a single drug was added or when protamine was combined with one selected from a specific substance group. That is clear. In addition, in terms of quality, no difference was observed between the test plot of the present invention and the control. Note that the symbols are explained as shown in Table 4.

【table】

【table】

[Table] Example 4 (Kamaboko) Basic composition of 1000g of frozen surimi, 30g of salt, 20g of mirin, 10g of monosodium glutamate, 10g of sugar, 70g of potato starch and 400g of ice water.
Additives listed in the table were added (the amount added is % by weight relative to the basic composition), and after mashing for 30 minutes, it was plated and steamed for 45 minutes. After simple packaging, it was stored at 30°C and changes in appearance were observed. The results are shown in Table 5. The symbols in Table 5 are explained as shown in Table 8. It is clear that the storage stability of the test plots of the present invention is improved compared to when a single drug is added or when protamine is combined with one selected from a specific substance group. As a result of the sensory test, there was no difference in taste, color, odor, etc. between the test plots of the present invention and the control plots, and no adverse effects on quality were observed due to the addition of the test plots.

【table】

[Table] Example 5 (Custard cream) The agents shown in Table 2 were added to the basic composition of 32 g of egg yolk, 288 g of milk, 76 g of sugar, 13 g of wheat flour, and 13 g of cornstarch (the amount added is weight % of the basic composition), The mixture was heated while thoroughly mixed, boiled down to 10% of the total weight, and a storage test was conducted at 20°C. In addition, the 6th
Explanations of the symbols in the table are as shown in Table 8. As shown in Table 6, the results show that the test plot of the present invention has a greater shelf life than when a single drug was added or when protamine was combined with one substance selected from a group of specific substances. it is obvious. In addition, in terms of quality, no difference was observed between the test plot of the present invention and the control.

【table】

[Table] Example 6 (hamburger) Mix 1000g of minced meat and 10g of salt well in advance, and add onions (fried) to the mix.
Add 60g of well-mixed flour to 300g and 50g of water,
Furthermore, the chemicals shown in Table 7 are added (the amount added is % by weight based on the basic composition), mixed well, and then molded.
It was steamed for 25 minutes and a storage test was conducted at 20°C. As shown in Table 7, the results show that the test plot of the present invention has a greater shelf life than when a single drug was added or when protamine was combined with one selected from a specific substance group. That is clear. The symbols in Table 7 are explained as shown in Table 8. Furthermore, in terms of quality, no difference was observed between the test plots of the present invention and the control.

【table】

【table】

[Table] "Effects" As mentioned above, the present invention is a food preservative characterized by combining protamine with two types of antibacterial substances selected from the group of specific antibacterial substances. Since there are three types of specific antibacterial substance groups, specific embodiments are as follows. The first is a food preservative characterized by a combination of protamine and two types selected from a group of specific antibacterial substances consisting of glycine, sodium acetate, lysozyme, and licorice extract antibacterial substances. The second is protamine and vitamin B ₁ ester,
A food preservative characterized by a combination of two types selected from a group of specific antibacterial substances consisting of polymerized phosphates and lower fatty acid monoglycerides. The third is protamine and vitamin B ₁ ester,
A food preservative characterized by a combination of two types selected from a group of specific antibacterial substances consisting of polymerized phosphates and sugar esters. In this way, the combination of protamine and the above-mentioned specific antibacterial substances effectively expresses the antibacterial properties of protamine and exhibits a synergistic effect, significantly increasing the antibacterial activity. It has a wide spectrum and is highly effective as a food preservative that does not destroy the flavor of food. Therefore, by using the food preservative of the present invention in foods, the shelf life is significantly extended, and consumers can obtain more hygienic foods, while food manufacturers From this point of view, the extended shelf life means that products can be sold safely over a wide area, which is extremely advantageous.

Claims (1)

[Scope of Claims] 1. It is characterized by combining protamine with two types of antibacterial substances selected from the group of specific antibacterial substances listed in any one of the following (a), (b), and (c). Food preservatives. (b) Glycine, sodium acetate, lysozyme, licorice extract antibacterial substances. (b) Vitamin B ₁ ester, polymerized phosphate, lower fatty acid monoglyceride. (c) Vitamin B ₁ ester, polymerized phosphate, sugar ester.