JPH0884577A - Freshness retaining agent for food - Google Patents

Abstract

PURPOSE: To obtain a freshness retaining agent for a food, capable of preserving the freshness of meats, vegetables or fruits in a refrigerator or a food storage box for a long period and having sustained release properties by using allyl isothiocyanate which is an extract of a Japanese horseradish or a mustard. CONSTITUTION: This freshness retaining agent for a food is obtained by converting allyl isothiocyanate which is a principal ingredient of an extract separated from a Japanese horseradish, a mustard, etc., into an aqueous solution, gelatinizing or adsorbing the allyl isothiocyanate on an adsorbent granular material and forming an atmosphere at 2-3 concentration in order to suppress the volatility thereof for a prescribed period. Thereby, the functions of the allyl isothiocyanate to retain the freshness can be maintained for 20-60 days.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a food freshness-retaining agent for maintaining the freshness of foods stored in a refrigerator or a food storage box for a certain period.

[0002]

2. Description of the Related Art As such a freshness-retaining agent, there is powdered activated carbon having adsorbed ethylene, but it has no bactericidal effect itself, and there is also a factor due to the putrefaction of the stored foods themselves, which is an effect of maintaining freshness. Cannot be said to be fully exerted.

In this sense, allyl isothiocyanate (CH ₂ ═CHCH ₂ NCS) contained in wasabi, mustard, etc.
Is an antibacterial agent that suppresses the growth of pathogenic bacteria and suppresses the growth of E. coli, Staphylococcus aureus, Proteus spp., Enterobacter vibrio, etc., which cause food poisoning, and also aging vegetables and fruits. It is known to be effective as a freshness-retaining agent for vegetables and fruits as well as fish meat because it also has the effect of suppressing the generation of the hormone ethylene to prevent aging.

This allyl isothiocyanate is available from Japan Food Science 1992 Vol. 31, No. 9, pp. 50-51, Antbact, Antfung Ag
ents, Vol. 23, No4, 1995 233
As reported on page 240, etc., it is a poorly water-soluble liquid with a high melting point of -100 ° C and a boiling point of 151.9 ° C and a low volatility (about 0.03 ppm). It has the effect of maintaining freshness by gas-phase contact with other substances. Further, it is harmless in itself, and is recognized as a food additive, and can be safely used as a freshness-retaining agent in a domestic food refrigerator.

As a utilization form of allyl isothiocyanate having a function of keeping the freshness of such foods, wasabi,
It has been tried to put a paper pulp impregnated with an extract from mustard etc. in a refrigerator, a food storage box or a lunch box for use. Further, in order to improve its utility, a freshness-retaining agent using a clay mineral such as sepiolite as an impregnating base material is also disclosed in JP-A-2-113876.

[0006]

However, when allyl isothiocyanate, which itself has lipophilicity, is adsorbed to a base material such as pulp or sepiolite as it is, it volatilizes in several tens of minutes, It cannot be expected to be effective as a freshness-retaining agent in the refrigerator for a relatively long period of time. As a freshness-keeping agent for keeping the freshness of foods in refrigerators and food storage boxes, suppressing rapid volatilization of allyl isothiocyanate,
It is necessary to keep an appropriate volatile atmosphere concentration for a certain period of time, even about 30 days, at all times.

The object of the present invention is to control the release of meat, vegetables and fruits in a refrigerator and a food storage box for a long period of time by using allyl isothiocyanate which is an extract of horseradish or mustard. It is intended to provide a freshness-retaining agent for food having properties.

[0008]

The present invention has been completed based on the finding that the function of allyl isothiocyanate to maintain the freshness of foods is sufficiently maintained at a concentration of about 2 to 3 ppm in a food storage atmosphere. It is characterized in that allyl isothiocyanate, which is the main component of wasabi extract or mustard extract, is treated so as to have a sustained release property that maintains its volatility stably for a certain period of time.

As a result, it is possible to suppress the volatilization amount of allyl isothiocyanate itself and to keep 2-3 p around the stored food products.
The atmosphere of allyl isothiocyanate having a concentration of about pm is set to 2
It can be maintained for 0 to 60 days.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As a first mode of the treatment for imparting sustained release while maintaining an appropriate amount of volatilization, allyl isothiocyanate is used as a surfactant or in combination with polyhydric alcohol. It can be an aqueous solution.

When the solution is made into an aqueous solution, a surfactant such as a nonionic surfactant or an amphoteric surfactant which has low evaporability and compatibility with lipophilic allyl isothiocyanate and has dispersibility in water is used. Combined.

When allyl isothiocyanate is made into an aqueous solution, even if it is dispersed with a polyhydric alcohol having a function of dissolving allyl isothiocyanate, it is volatilized in a short period of time. Therefore, when diluting to a predetermined concentration to give sustained release, allyl isothiocyanate is added to HLB in an amount of 10 to 16
Dissolve in water using a surfactant with a relatively high hydrophilic group, a nonionic amphoteric surfactant, and a polyhydric alcohol, and impregnate this with paper or an inorganic water-absorbing substrate as in the past. Let me use it.

The most desirable form of use is to gel the aqueous solution of allyl isothiocyanate with a gelling agent such as duran gum (Kelcogel), and put it in a plastic container of an appropriate size for use. is there. In addition, the aqueous solution of allyl isothiocyanate may be gelled.

As a gelling agent in combination with a surfactant of allyl isothiocyanate, duragan gum (trade name) manufactured by Kelco can be preferably used.

Kelcogel is a natural polysaccharide obtained by fermentation. That is, it is a product obtained by separating and purifying a polysaccharide produced by Pseudomonas erodea, which is a microorganism collected from aquatic plants, outside of the cells using glucose or the like as a nutrient source.

Kelcogel was developed by Kelco Division of Merck & Co., Inc. in the same manner as xanthan gum, and is an industrially produced natural gum having extremely unique properties. It is a gelling and stabilizing agent for food products. It is one of the most stable natural gums that shows strong acid resistance, heat resistance, and enzyme resistance, with strong oxidization and gelation at low concentration in the presence of ions.

Another form of this gelation is as follows.
An oily gel can be prepared by dissolving allyl isothiocyanate in an isoparaffin compound and then using a gelling agent such as 1-1 hydroxystearic acid.

The amount of allyl isothiocyanate in the gel is
The amount of the surfactant relative to the allyl isothiocyanate is a weight ratio in order to maintain the effect for 20 to 30 days which is a normal functional period, though it may be arbitrarily changed depending on the target food and its expected duration. A compounding amount of 1 to 10 times or more is desirable. Examples of the polyhydric alcohols used include propylene glycol, ethylene glycol, glycerin and the like, and the ratio of allyl isothiocyanate and propylene glycol or the like or a mixture of two or more thereof is 1: 1 to 1: 3, particularly 1: 2. Is desirable.

Among the surfactants used in the aqueous solution of allyl isothiocyanate, especially in gelation, the following nonionic surfactants [A] to [F] are available.

[A] Polyoxyethylene alkylphenyl ether

Embedded image The carbon number of R is preferably 8, 9, 12. HLB is 8 ~
16 is preferred.

[B] Fatty acid polyoxyethylene sorbitan

Embedded image The ester portion of R is preferably lauric acid, oleic acid, and stearic acid, and HLB is preferably 10-18.

[C] Polyoxyethylene fatty acid ester

[Chemical 3] The fatty acid is preferably oleic acid, stearic acid and lauric acid, and HLB is preferably 8-18.

[D] Polyoxyethylene alkyl ether RO (CH ₂ CH ₂ O) nHR is preferably an ether type of lauryl group, cetyl group and stearyl group, and HLB is preferably 8-18.

[E] Sorbitan fatty acid ester

[Chemical 4] HLB is preferably 6 or higher.

[F] Glycerin fatty acid ester

[Chemical 5] R is preferably stearic acid or oleic acid.

There are 6 groups.

Further, as the amphoteric and anionic type of the amino acid type surfactant, cocoamidopropyl betaine is used.

[Chemical 6] And glutamic acid forms such as lupoxymethyl-N-droxyethylimidazolium betaine, and (N-coconut oil fatty acid acylglutamic acid)

[Chemical 7] Is mentioned.

Further, nonionic polyoxyethylene alkylphenyl ether type, polyoxyethylene sorbitan ester type, polyoxyether type, sorbitan ester type, polyhydric alcohol ester type, amphoteric surfactants include cocoamidopropyl betaine and lupoxymethyl- N
-Droxyethyl imidazolium betaine is good, especially in the range HLB 8-16.

Most of those having a low HLB, such as sorbitan ester type and polyhydric alcohol (glycerin monosterate), are effective when used in combination with those having a high HLB, such as polyoxyethylene nonylphenyl ether.

A substance having a sustained release can be obtained by mixing one or more of these surfactants and gelling, and in the case of an aqueous gel, water occupies about 80% or more. OW type.

Further, as another mode of gelation, allyl isothiocyanate may be dissolved in an isoparaffin solution to form an oily gel.

Further, as another form, the solution-formulated sustained-release allyl isothiocyanate can be granulated.

In addition, means such as adsorbing it to a solid substance compatible with allyl isothiocyanate can be adopted.

As described above, by using together with the surfactant during gelation, the molecule of allyl isothiocyanate is wrapped in the micelle and attracts the surfactant having no evaporative property, so that the allyl isothiocyanate is attracted. Molecules attract each other in water and stay in water for a long time to prevent early volatilization.

In order to adsorb allyl isothiocyanate to the granular or powdery substance, for example, powdery or granular stearic acid is placed in a closed container, and the inside is evacuated while stirring to vaporize an equivalent amount of allyl isothiocyanate. After that, the vacuum can be broken so that the stearic acid can be uniformly adsorbed. Examples of the granular substance to be attached include the following.

Sodium Acrylate Copolymer Water Absorption Polymer Adipic Acid Malic Acid Glucose Maltose Maltose Serubiose Cellulose Carboxymethyl Cellulose Carboxyethyl Cellulose Glycerin Monostearate Organic fatty acids such as stearic acid Alginic acid Locust bean gum Xanthan gum Other polysaccharides.

[0037]

【Example】

 Example 1 This example illustrates an example of gelation.

The following are examples of formulations in this example.

Allyl isothiocyanate: 3 g Polyoxyethylene nonylphenyl ether (HLB15.2): 5 g Kelcogel (gelling agent manufactured by Kelco): 1 g Water: 93 g Water 93 g is put in a container. , 1 g of kelco gel is dissolved.

Next, this is heated to 90 ° C., polyoxyethylene nonylphenyl ether is added and stirred, and after heating is stopped, allyl isothiocyanate is added and cooled to gel.

That is, in this state, 60 from the solution state
At about ° C, gelation occurs rapidly and solidification occurs. At the interface with air, lipophilic groups are arranged on the air surface, and hydrophilic groups are arranged inside the gel to form a film of the active agent.

Further, allyl isothiocyanate is contained in the micellar form of the surfactant and attracts each other to suppress evaporation. Furthermore, since there is a film of a surfactant that is compatible with allyl isothiocyanate at the interface with air,
Furthermore, evaporation is suppressed and sustained release is maintained.

The wasabi extract and allyl isothiocyanate, which are the main components of the mustard extract, and those selected from the group of various surfactants were gelated by the above-mentioned method and subjected to the test.

Next, the gel of each of these combinations is subjected to 20 ° C.
After leaving it in an open state in 65% RH for 1, 5, 10, 15, 20 days, it was sealed in a 200 liter refrigerator, and after 1 hour, the gas in the refrigerator was sampled and analyzed by gas chromatography. The analysis conditions for gas chromatography are ... Column packing material Salmon 3,000 Column temperature 120 ° C Carrier gas N ₂ Carrier gas pressure 0.5 kg / m ^{2 The} following table shows 1 g of Kelcogel and the addition amount and water of the following table. 1
This is the value set to 00g.

[0045]

[Table 1] In addition, the gel that was left for 25 days was left in a refrigerator of 200 liters for beef, broccoli, and mushrooms, and the appearance change was compared with the blank. After one week, the result was compared with the blank, and it was found that the freshness was extremely maintained. It was effective.

[Table 2] Example 2 This example illustrates an example of oily gelation.

Isoparaffin is heated to about 80 ° C. Next, 1.1 hydroxy stearic acid (or 1.2
Hydroxystearic acid) is added and dissolved. After heating was stopped, allyl isothiocyanate was added and cooled to gel.

(A) (B) (C) Allyl isothiocyanate 5g-isoparaffin 100-250 ° C fraction 85g 85g 8g 1.1 hydroxy stearic acid 10g-1.2 hydroxystearic acid-10g 10g The above gel 100g Were left open for 5, 15 and 30 days, respectively, placed in a 200 liter food storage box at 20 ° C. and sealed for 1 hour to measure the concentration of allyl isothiocyanate in the food storage box.

After leaving for 5 days, after leaving for 15 days, after leaving for 30 days A 30 ppm 23 ppm 10 ppm B 32 ppm 25 ppm 10 ppm C 30 ppm 20 ppm 10 ppm Isoparaffin compounds are phased with wasabi extract, mustard extract and its main component, allyl isothiocyanate. It has good solubility, and its fraction at 120 to 250 ° C volatilizes at the same ratio as allyl isothiocyanate. Therefore, the evaporation rate of allyl isothiocyanate was greatly suppressed in the state of being dissolved in isoparaffin, and a constant evaporation amount could be maintained for about 30 days in the state of 30 ° C or lower.

Example 3 This example shows an example in which a solution obtained by gradually releasing allyl isothiocyanate was attached to the following granules and used as the granules.

(1) Kelzan (trade name: Kelco) 99 g Allyl isothiocyanate 1 g (2) Glucose 99.9 g Allyl isothiocyanate 0.1 g The granular materials obtained by the above (1) and (2) are respectively nonwoven fabrics (3 ×). Enclose 1g in 3), 100g broccoli
Was put in a box and tested for its freshness-preserving effect.

As shown in the following test results, the effect was sufficient even with the granulated product.

Number of days left to stand 0 15 7 Appearance observation Blank − − ± + (1) − − − − (2) − − − − + Change, ± Slight change, − No change In this way, from the wasabi extract By mixing the extract and one or more of the aforementioned surfactants and gelling,
Similarly, with regard to the oily gel and the granular material, it was possible to obtain a sustained-release product that maintains the freshness of the food in the refrigerator.

The embodiments of the present invention are not limited to the above-mentioned embodiments, and it is obvious to those skilled in the art that there are various modes within the scope of the technical idea of the present invention.

[0054]

According to the present invention, the following effects can be obtained.

(1) In a closed space such as a refrigerator, a food storage box, and a lunch box, while keeping a constant evaporation amount of allyl isothiocyanate, meat,
The function of suppressing the propagation of pathogenic bacteria in not only fish meat but vegetables and fruits can be maintained.

(2) Further, when the product of the present invention is prepared, it is not visible due to the volatilization of gas at the time of the sealing work in the closed space.

Claims (7)

[Claims] 1. A freshness-retaining agent for foods, wherein allyl isothiocyanate, which is a main component of extracts from horseradish, mustard, and the like, is subjected to a treatment for imparting a sustained-release property that suppresses its volatility for a certain period of time. 2. The freshness-retaining agent for food according to claim 1, wherein an atmosphere of allyl isothiocyanate having a concentration of 2-3 ppm is formed around the target food. 3. The freshness-retaining agent for food according to claim 1, wherein allyl isothiocyanate is dissolved in a solution with a surfactant. 4. An aqueous solution obtained by dissolving allyl isothiocyanate in a polyhydric alcohol together with a surfactant.
Alternatively, the freshness-retaining agent for the food according to claim 2. 5. The freshness-retaining agent for foods according to claim 3 or 4, wherein allyl isothiocyanate in the form of an aqueous solution is gelled. 6. The freshness-retaining agent for food according to claim 1 or 2, wherein allyl isothiocyanate is dissolved in an isoparaffin solution to form an oily gel. 7. The freshness-retaining agent for food according to claim 3 or 4, wherein the aqueous solution of allyl isothiocyanate is adsorbed on the adsorptive granular material.