KR101586787B1 - Polymer gel for release of chlorine dioxide gas and packaging method of food comprising the same - Google Patents

Abstract

The present invention relates to a polymer gel for releasing a chlorine dioxide gas and a packaging method for foods containing the same, wherein a chlorine dioxide aqueous solution containing a sodium chlorite solution and a buffer solution having a buffer region at a pH of 3 to 4 is absorbed by the polymer, It is possible to continuously release 0.2 to 5 ppm chlorine dioxide gas for a day to inhibit proliferation of harmful microorganisms during the distribution period and to maintain the freshness and prolong the shelf life compared to the past.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer gel for releasing a chlorine dioxide gas and a method for packaging the same,

The present invention relates to a polymer gel for chlorine dioxide gas release capable of continuously releasing chlorine dioxide gas at a constant concentration for a long period of time, a method for producing the polymer gel, and a packaging method for foods containing the polymer gel.

Water-soluble chlorine dioxide (ClO ₂ ) is used as a disinfectant in beverage plants, food manufacturing, handling and storage facilities (US Environmental Protection Agency, 2007), and also as a disinfectant for food processing facilities (US Food and Drug Administration , 1977).

In particular, water-soluble chlorine dioxide has emerged as a disinfectant that can compensate for the advantages and disadvantages of ultraviolet rays (UV), chlorine, and ozone, while minimizing damage to the natural environment in the food manufacturing process, water purification plant and sewage treatment plant Recently, there has been an increase in the disinfection treatment systems using these as well as advanced countries.

In addition, water-soluble chlorine dioxide has been shown to be effective in a wide range of pH, with fast action (Bernarde et al., 1965, 1967; McGuire and Dishinger, 1984; Rav-Acha, 1984) Long et al., 1999), so Escherichia coli ) O157: H7, Enterobacter ( Enterobacter sakazakii ), Listeria monocytogenes ( Listeria monocytogenes), Bacillus cereus (Bacillus cereus , and Bacillus thuringiensis (Han et al., 2001; Singh et al., 2002; Beuchat et al., 2004; Rodgers et al., 2004; Ryu and Beuchat , 2005; Kim et al., 2006).

However, one of the disadvantages of chlorine dioxide as a disinfectant is instability during manufacture and storage.

Because of the low stability of chlorine dioxide, chlorine dioxide has to be manufactured on site and is difficult to store for long periods.

One of the traditional methods of producing water-soluble chlorine dioxide uses sodium chlorite (NaClO ₂ ) and hydrochloric acid (HCl) as reactants:

[Reaction Scheme]

_{5NaClO 2 + 4HCl → 4ClO 2 +} 5NaCl + 2H 2 O

The amount of chlorine dioxide produced by this reaction is harmful to the human body and can not be used for the purpose of food sterilization because it produces a large amount of chlorine dioxide gas by reaching its maximum concentration through rapid dissociation of hydrogen ions contained in hydrochloric acid.

Accordingly, there is a demand for a method capable of continuously releasing a low concentration of chlorine dioxide gas so that it can be used for sterilizing food.

Korea Patent No. 0973826 Korea Patent No. 1098782

It is an object of the present invention to provide a polymer gel for chlorine dioxide gas release capable of continuously releasing a constant concentration of chlorine dioxide gas for a long period of time.

Another object of the present invention is to provide a method for producing the polymer gel.

It is still another object of the present invention to provide a packaging method of food using the polymer gel.

In order to achieve the above object, the polymer gel for releasing chlorine dioxide gas of the present invention is a polymer solution containing a chlorine dioxide aqueous solution containing a sodium chlorite solution and a buffer solution having a buffer area of pH 7 or less.

The chlorine dioxide aqueous solution may further include one kind of organic acid selected from the group consisting of citric acid, acetic acid, succinic acid and phosphoric acid.

The concentration of sodium chlorite in the sodium chlorite solution may be 1000 to 15000 ppm, and the chlorine dioxide gas-releasing polymer gel may continuously release chlorine dioxide gas of 0.2 to 5 ppm.

The pH of the chlorine dioxide aqueous solution may be 5 or less, and the buffer may be at least one selected from the group consisting of a universal buffer, a hydrochloric acid-sodium hydroxide buffer, and a citrate buffer.

The polymer may be an acrylic polymer such as itaconic acid ester, maleic acid ester, methacrylic acid ester, (meth) acrylic acid, styrene, alkyl vinyl ether and vinyl acetate And a polymerizable monomer containing one kind of monomer selected from the group consisting of

The chlorine dioxide gas-releasing polymer gel may be packaged in a linear low density polyethylene (LLDPE) film or a low density polyethylene (LDPE) film, and the film has a chlorine dioxide gas permeability of 5000 to 8000 cc / m 2 揃 day 揃 atm.

According to another aspect of the present invention, there is provided a method of preparing a polymer gel for releasing chlorine dioxide gas comprising the steps of: (a) adding a buffer solution having a buffer region of pH 7 or less to a sodium chlorite solution; And (b) absorbing the prepared mixed solution to the polymer.

In step (a), one or more organic acids selected from the group consisting of citric acid, acetic acid, succinic acid, and phosphoric acid may be further added. When the organic acid is further added, it may be added to the sodium chlorite solution after mixing the buffer solution and the organic acid .

In the step (a), the pH is 5 or less, and the concentration of sodium chlorite in the sodium chlorite solution may be 1000 to 15000 ppm.

The polymer absorbing the mixed solution in the step (b) can continuously release chlorine dioxide gas at 0.2 to 5 ppm.

According to another aspect of the present invention, there is provided a method of producing a polymer gel for releasing chlorine dioxide gas comprising the steps of: (a) absorbing sodium hypochlorite solution into a polymer; And (b) drying the moisture-absorbing polymer.

The polymer gel and the buffer solution having the buffer region of pH 7 or less may be separated into the diaphragm and reacted by the removal of the diaphragm.

The buffer solution may further comprise one kind of organic acid selected from the group consisting of citric acid, acetic acid, succinic acid and phosphoric acid.

According to another aspect of the present invention, there is provided a food packaging method comprising the steps of: (A) injecting a polymer gel for releasing chlorine dioxide gas according to any one of claims 1 to 10 into a plastic packaging material; (B) feeding the food into the plastic packaging material into which the chlorine dioxide gas-releasing polymer gel is introduced; And (C) sealing the gas-filled plastic casing.

In the step (A), the chlorine dioxide gas-releasing polymer gel may continuously release 0.2 to 5 ppm chlorine dioxide gas.

After the food is introduced in the step (B), it may be replaced with a gas containing at least one of oxygen, carbon dioxide and nitrogen.

The oxygen, the carbon dioxide, or the mixed gas thereof in the gas substituted in the step (B) may be 3 vol% or more.

In the gas substituted in the step (B), 3 to 10% by volume of oxygen and 5 to 30% by volume of carbon dioxide may be present.

The plastic packaging material may be a laminate of at least one selected from the group consisting of polyethylene, polypropylene, nylon and polyethylene terephthalate.

The chlorine dioxide gas-releasing polymer gel of the present invention can continuously release stable chlorine dioxide gas of 0.2 to 5 ppm for 14 to 18 days, so that the growth of harmful microorganisms can be suppressed and sterilized during the distribution period, So that the shelf life can be extended as compared with the conventional one.

In addition, foods such as potatoes or apples that easily browse when peeled off are inhibited from browning, and there is no change in odor and food appearance due to chlorine dioxide gas.

The present invention relates to a polymer gel for releasing chlorine dioxide gas, which can continuously prolong the shelf life by keeping the freshness and extending the shelf life compared with the conventional one, by continuously releasing the chlorine dioxide gas at a constant concentration for a long time to inhibit growth of harmful microorganisms during the distribution period, A method for producing the polymer gel, and a packaging method for food containing the same.

The chlorine dioxide gas is a gas emitted from a chlorine dioxide aqueous solution produced using sodium chlorite.

Hereinafter, the present invention will be described in detail.

The polymer gel for releasing chlorine dioxide gas of the present invention is a polymer solution containing a chlorine dioxide aqueous solution containing a sodium chlorite solution and a buffer solution having a buffer area of pH 7 or lower. The chlorine dioxide aqueous solution may further contain one kind of organic acid selected from the group consisting of citric acid, acetic acid, succinic acid and phosphoric acid.

The sodium chlorite solution is a substance for producing an aqueous chlorine dioxide solution by reacting with a buffer solution, and sodium chlorite at a concentration of 1000 to 15000 ppm, preferably 1000 to 10000 ppm is used. The sodium chlorite solution is conventionally reacted with hydrochloric acid to form chlorine dioxide gas at a high concentration. In the present invention, since a low concentration of chlorine dioxide gas is released by using the buffer solution, high concentration of sodium chlorite in the above- Can be obtained.

If the concentration of sodium chlorite is less than the lower limit, chlorine dioxide gas may not be produced. If the concentration exceeds the upper limit, chlorine dioxide gas may not be continuously released and chlorine gas may be released for only 1 to 2 days .

The buffer solution is a buffer solution having a buffer area of pH 7 or less, and is mixed with a sodium chlorite solution using a buffer solution of 0.05M to 0.1M to produce an aqueous solution of chlorine dioxide. The buffer is adjusted so that the pH of the aqueous solution of chlorine dioxide is 5 or less, preferably 3 to 5, so that the chlorine dioxide gas can be continuously released at low concentration for 14 to 18 days. When a buffer solution alone is used as a substance to be mixed with the sodium chlorite solution, a buffer solution having a pH of 5 or less, preferably a pH of 3 to 5 is used. As a material to be mixed with a sodium chlorite solution, a buffer solution and an organic acid are mixed and used , The pH of the aqueous chlorine dioxide solution is adjusted to 5 or less by using a buffer solution having a pH of 7 or less.

When the pH of the aqueous solution of chlorine dioxide is over 5, the concentration of chlorine dioxide gas generated gradually decreases from 3 to 4 days, and chlorine dioxide gas is hardly released in about 14 days. When the pH is 5 or less, It releases chlorine gas at about the same level as the first 14 days. In particular, a pH of 3 continuously generates chlorine dioxide gas at a concentration of 0.5 to 0.7 ppm higher than that at pH 5.

The buffer may be at least one selected from the group consisting of a universal buffer, a hydrochloric acid-sodium hydroxide buffer, and a citric acid buffer, preferably 0.1 M KCl, 0.1 M citric acid, 0.1 M KH ₂ PO ₄ , 0.1 M Na ₂ b ₄ O ₇ , 0.1 M Tris base and HCl to adjust the pH to 3 to 8.

When the aqueous solution of the chlorine dioxide is absorbed to the polymer, a larger amount of chlorine dioxide aqueous solution can be used than in the case of using the chlorine dioxide aqueous solution itself on the basis of the same volume, so that the chlorine dioxide gas at a higher concentration can be continuously released for a long time have.

The polymer is preferably an acrylic polymer, and the acrylic polymer is selected from the group consisting of itaconic acid ester, maleic acid ester, methacrylic acid ester, (meth) acrylic acid, styrene, alkyl vinyl ether And vinyl acetate. [0033] The term " monomer "

Further, when the organic acid is further added, the chlorine dioxide gas can be continuously generated (based on the same pH) at a concentration higher by about 0.2 to 0.5 ppm than the case of using only the buffer, But not at all. Even when the organic acid is further added, the pH of the resulting aqueous solution of chlorine dioxide should be 5 or less, preferably 3 to 5, as in the case of using only the buffer solution.

The polymer gel thus prepared has a concentration of sodium chlorite of 1000 to 15000 ppm and chlorine dioxide gas of 0.2 to 5 ppm is continuously released for 14 to 18 days based on the pH of the aqueous solution of chlorine dioxide being 5.

When the polymer gel is applied directly to another place, the polymer gel may be wrapped in a film because it may cause a consumer's disgust if the polymer adheres to the substance to be eaten or touched. Preferably, the film is a linear low density polyethylene (LLDPE) film or a low density polyethylene (LDPE) film having a chlorine dioxide gas permeability of 5000 to 8000 cc / m < 2 > A polypropylene (PP) film, a polypropylene stretched (OPP) film, a high density polyethylene (HDPE) film and an unleaded polypropylene (CPP) film other than the above films have a chlorine dioxide gas permeability of 300 to 700 cc / The amount of chlorine dioxide gas permeating out of the film is reduced, so that it can not be used.

The present invention also provides a method for producing a polymer gel for releasing chlorine dioxide gas.

A method for preparing a polymer gel according to an embodiment of the present invention comprises the steps of: (a) adding a buffer solution having a buffer region of pH 3 to 4 to a sodium chlorite solution; And (b) moisture-absorbing the mixed solution by polymer.

First, in step (a), a buffer solution is added to the sodium chlorite solution to adjust the pH to 5 or less.

In the case of preparing a polymer gel by further adding an organic acid, it is necessary to add the buffer solution and the organic acid in the step (a), and then add the mixed solution to the sodium chlorite solution so that a similar concentration of chlorine dioxide gas stably flows continuously for 14-18 days .

Next, in the step (b), the mixed solution prepared in the step (a) is absorbed in the polymer to prepare a polymer gel for releasing chlorine dioxide gas. The molding may be omitted if necessary.

According to another embodiment of the present invention, there is provided a method of preparing a polymer gel, comprising: (a) absorbing sodium hypochlorite solution into a polymer; And (b) drying the moisture-absorbing polymer.

First, the sodium hypochlorite solution is absorbed in the polymer and dried by freeze drying or hot air drying to prepare a polymer gel. The polymer gel and the buffer solution thus prepared are separated into diaphragms, and chlorine dioxide gas can be generated by removing the diaphragm and reacting during use. The buffer solution may further contain an organic acid.

The polymer gel prepared by this method is easy to apply and can maximally increase the release time of chlorine dioxide gas.

The present invention also provides a food packaging method using a polymer gel for releasing chlorine dioxide gas.

A food packaging method of the present invention comprises the steps of: (A) injecting a chlorine dioxide gas-releasing polymer gel into a plastic packaging material; (B) feeding the food into the plastic packaging material into which the chlorine dioxide gas-releasing polymer gel is introduced; And (C) sealing the gas-filled plastic casing.

First, in step (A), a polymer gel is continuously introduced into the plastic packaging material so that chlorine dioxide gas is continuously released at a concentration of 0.2 to 5 ppm.

Next, in the step (B), the food is put into the plastic packaging material into which the polymer gel is introduced. In addition, after the food is put into the plastic packaging material, it can be replaced with at least one gas selected from the group consisting of oxygen, carbon dioxide and nitrogen (MAP packaging).

The oxygen, the carbon dioxide, or the mixture gas thereof in the gas replaced in the plastic packaging material is 3 vol% or more. Specifically, in the case of 100% by volume of carbon dioxide, the oxygen content is 3 to 20% by volume, preferably 5 to 10% by volume; The carbon dioxide is 10 to 90% by volume; Nitrogen is filled with the balance. Depending on the type of food, the vegetables and fruits may have 10 to 30% by volume of carbon dioxide and 40 to 100% by volume of meat.

If the volume percentage of oxygen is less than the lower limit value, the amount of oxygen required for circulation of food is insufficient and freshness is lowered. If the oxygen content is above the upper limit value, the growth of harmful microorganisms may not be inhibited. In addition, when the volume percentage of carbon dioxide is less than the lower limit value, the inhibition of microorganisms may not be improved even when mixed with chlorine dioxide gas, and the freshness of the food may be lowered when the upper limit is exceeded.

The plastic packaging material may be a laminate of at least one selected from the group consisting of polyethylene, polypropylene, nylon and polyethylene terephthalate.

Next, in the step (C), the gas-filled plastic packaging material is sealed.

Since the chlorine dioxide gas released from the polymer gel is decomposed by the contact with the light and the packaging material and is discharged to the outside of the packaging material, The chlorine dioxide gas at an appropriate concentration is maintained in the inside of the food.

On the other hand, if the chlorine dioxide gas is not continuously supplied to the inside of the packaged food, the microorganisms start to grow in the food and the freshness of the food decreases because the chlorinated gas does not exist inside the packaged food after a certain period of time.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

One. Sodium hypochlorite  As the reaction solution Buffer  Comparison of hydrochloric acid

Manufacturing Example  One.

A sodium chlorite solution with a sodium chlorite concentration of 10000 ppm and a 0.1 M universal buffer at pH 3 were mixed at room temperature to prepare a chlorine dioxide aqueous solution having a pH of 3.

Manufacturing Comparative Example  One.

A chlorine dioxide aqueous solution was prepared by mixing the sodium chlorite solution and the hydrochloric acid (HCl) solution in the same manner as in Preparation Example 1, except that the sodium chlorite concentration was 1000 ppm.

Test Example  One.

The chlorine dioxide aqueous solution prepared in Preparation Example 1 and Comparative Production Example 1 was stored in a closed plastic box and the concentration (ppm) of chlorine dioxide gas was measured over time. At this time, the samples were stored in a space in which light having the same intensity was stored.

division 1day 5day 8day 11day 14day Production Example 1 1.9 1.8 1.9 1.8 1.7 Manufacturing Comparative Example 1 50.1 16.2 6.1 5.4 3.0

As shown in Table 1, in Comparative Example 1 using hydrochloric acid, it was confirmed that the amount of chlorine dioxide gas abruptly decreased rapidly over time after an excessive amount of chlorine dioxide gas was generated. Although the chlorine dioxide gas is released by about 14 days of chlorine dioxide gas discharge, an excessive amount of chlorine dioxide gas is released until about 1 to 5 days, causing a problem that the food is discolored and deteriorated, which is inappropriate for food.

2. An aqueous solution of chlorine dioxide pH Measurement of chlorine dioxide gas generation

Manufacturing Example  2.

A chlorine dioxide aqueous solution having a pH of 5 was prepared in the same manner as in Preparation Example 1 except that 0.1 M Universal Buffer at pH 5 was used.

Manufacturing Example  3.

Prepared in the same manner as in Preparation Example 1 except that citric acid and a 0.1 M universal buffer solution having a pH of 4-5 were mixed and then added to a sodium chlorite solution to prepare a chlorine dioxide aqueous solution having a pH of 3.

Manufacturing Example  4.

A chlorine dioxide aqueous solution having a pH of 5 was prepared using citric acid and a 0.1 M universal buffer solution having a pH of 6-7.

Manufacturing Example  5.

Acetic acid and 0.1 M universal buffer solution of pH 4-5 were mixed in the same manner as in Preparation Example 1 and added to sodium chlorite solution to prepare a chlorine dioxide aqueous solution having a pH of 3.

Manufacturing Example  6.

Prepared in the same manner as in Preparation Example 5, but using a 0.1 M universal buffer solution of acetic acid and pH 6-7, a chlorine dioxide aqueous solution having a pH of 5 was prepared.

Manufacturing Comparative Example  2.

A chlorine dioxide aqueous solution having a pH of 6 was prepared in the same manner as in Preparation Example 1 except that 0.1 M Universal Buffer at pH 6 was used.

Manufacturing Comparative Example  3.

A chlorine dioxide aqueous solution having a pH of 8 was prepared in the same manner as in Preparation Example 1 except that 0.1 M Universal Buffer at pH 8 was used.

Manufacturing Comparative Example  4.

A chlorine dioxide aqueous solution having a pH of 7 was prepared in the same manner as in Preparation Example 3 except that citric acid and 0.1 M universal buffer having pH 8 were used.

Test Example  One.

The chlorine dioxide aqueous solution prepared in the above-mentioned Production Examples and Comparative Comparative Examples was stored in a closed plastic box and the concentration (ppm) of chlorine dioxide gas was measured over time. At this time, the samples were stored in a space in which light having the same intensity was stored.

division 1day 5day 8day 11day 14day Production Example 1 1.9 1.8 1.9 1.8 1.7 Production Example 2 1.4 1.3 1.3 1.2 1.2 Production Example 3 2.1 2.0 2.1 2.0 2.0 Production Example 4 1.7 1.6 1.6 1.7 1.6 Production Example 5 2.1 2.0 2.0 1.9 1.9 Production Example 6 1.6 1.5 1.5 1.5 1.4 Manufacturing Comparative Example 2 1.3 1.1 0.4 0.1 0.0 Manufacturing Comparative Example 3 1.1 0.8 0.2 0.0 0.0 Manufacturing Comparative Example 4 1.2 0.9 0.3 0.0 0.0

As shown in Table 2 above, it was confirmed that the chlorine dioxide gas released from the aqueous solution of chlorine dioxide prepared according to Production Examples 1 to 6 was maintained at a concentration similar to one day until 14 days. Particularly, when organic acid was used, chlorine dioxide It was confirmed that the gas was kept more constant and the concentration of chlorine dioxide gas was lowered as the pH was higher (pH 5 compared to pH 3).

On the other hand, Comparative Production Examples 2 to 4 showed that chlorine dioxide gas was released from about 3 to 4 days, and chlorine dioxide gas was hardly released after 8 days, and chlorine dioxide gas remained in the plastic box was not found.

3. Measurement of the permeability of chlorine dioxide gas according to the type of packaging paper

Manufacturing Example  7.

The chlorine dioxide aqueous solution prepared in Preparation Example 1 was absorbed by the acrylic polymer polymerized including the itaconic acid ester moiety to prepare a polymer gel for releasing chlorine dioxide gas.

Test Example  3.

The polymer gel prepared in Example 1 was applied to a linear low density polyethylene (LLDPE) film, a low density polyethylene (LDPE) film, a polypropylene (PP) film, a polypropylene stretched (OPP) film, a high density polyethylene (HDPE) The film was packed with a polypropylene (CPP) film and placed in a plastic box. One day later, the concentration of chlorine dioxide gas present in the plastic box was measured to determine the extent to which the chlorine dioxide gas emitted from the polymer gel passed through the film (transmittance) . At this time, the samples were stored in a space in which light having the same intensity was stored.

division LLDPE LDPE PP OPP HDPE CPP Transmittance (cc / mm2 / day / atm) 7000 5000 400 600 620 390

As shown in Table 3 above, it was confirmed that the linear low density polyethylene (LLDPE) film and the low density polyethylene (LDPE) film have excellent permeability to chlorine dioxide gas. Therefore, the polymer gel may be packed into the LLDPE film or the LDPE film where the polymer gel itself is not used.

Example  1 to 6. chlorine dioxide gas + oxygen + carbon dioxide + nitrogen

The polymer gel prepared in Preparative Example 7, which was packaged in a linear low density polyethylene (LLDPE) film, was added to a food packaging material (polyethylene terephthalate), and then apple was added. Then, the inside of the packaging material was filled with oxygen, carbon dioxide and nitrogen And then packed and sealed to produce packaged food. Wherein the volume percent of carbon dioxide and oxygen in the displaced gas is 10 vol.% And 5 vol.%, Respectively; 10% by volume and 10% by volume; 20% by volume and 5% by volume; 20% by volume and 10% by volume; 30% by volume and 5% by volume; 30% by volume and 10% by volume.

Example  7. chlorine dioxide gas + carbon dioxide

The same procedure as in Example 1 was carried out except that meat was used instead of apples and the inside of the package was replaced with 100 vol% of carbon dioxide and sealed to prepare a packaged food.

Example  8. Chlorine dioxide gas + oxygen + nitrogen

The same procedure as in Example 1 was carried out except that carbon dioxide was not used as the substituted gas and 10% by volume of oxygen was used as a packaged food.

Example  9. Chlorine dioxide gas

A packaged food was prepared in the same manner as in Example 1 except that no replacement gas was used.

Comparative Example  1 to 6. Oxygen + carbon dioxide + nitrogen

The packaged food was prepared in the same manner as in Examples 1 to 6 except that the polymer gel prepared in Preparation Example 7 was not used.

Comparative Example  7. Carbon dioxide

A packaged food was prepared in the same manner as in Example 7 except that chlorine dioxide gas was not used.

Test Example  4.

Bacillus cereus was artificially contaminated on the surface of the apple. One day after packaging as in the above Examples and Comparative Examples, 25 g of apple surface and 225 ml of sterilized physiological saline were added to a stomacher bag After shaking, 0.1 ml of the dilution diluted by decimal dilution method was taken out of the stomacher, and the plate was stained and cultured at 37 ° C for 24 hours. In the packaged foods in the above Examples and Comparative Examples, chlorine dioxide gas was basically present in a quantity of 1.9 mm.

division Examples 1 to 9 Comparative Examples 1 to 7 CO ₂
(volume%) O ₂ (vol%) N ₂ (vol%) 10 5 Balance

10 10 Balance

20 5 Balance

20 10 Balance

30 5 Balance

30 10 Balance

100 - -

- 10 Balance

- - - -

-

As shown in Table 4 above, the foods contained in the packaging materials prepared according to Examples 1 to 6 of the present invention are superior to those of Comparative Examples 1 to 6 in which the chlorine dioxide gas is not contained in the packaging materials. Bacillus cereus ) Is rapidly decreased. Therefore, it was confirmed that the chlorine dioxide gas has excellent germicidal power against Bacillus cereus .

In addition, according to Example 7, the food contained in the packaging material containing only the chlorine dioxide gas and the carbon dioxide was superior to that of the Comparative Example 8 in which the packaging material containing no carbon dioxide gas (no chlorine dioxide gas) contained Bacillus cereus ) Is decreased. In addition, in Example 8 was contained in the casing of the oxygen, nitrogen and carbon dioxide without the presence of chlorine dioxide gas is Bacillus cereus (Bacillus Although the number of the stem of the cereus) were few in number is not, it was confirmed that even in Example 9 was immersed in the packaging material that exists only chlorine dioxide gas reduced the number of Bacillus cereus (Bacillus cereus).

It can be seen that the combination of chlorine dioxide gas and carbon dioxide shows better sterilizing power than the case of using oxygen or nitrogen instead of carbon dioxide.

Test Example  5.

25 g of the apple surface and 225 ml of sterilized physiological saline were put into a stomacher bag and shaken in a stomacher. After the stomachers were artificially contaminated with the strains on the surface of the apples, 0.1 ml of the dilution diluted by the decimal dilution method was taken and the number of bacteria was measured using standard flat plate method (KFDA) using Baird Parker Agar. After staining, the cells were cultured at 37 ° C for 24 hours and the number of colony forming units (CFU) was determined.

division Processing time (day) 0 One 6 11 14 Staphylococcus
( Staphylococcus aureus ) Example 1 5.60 + 0.03 ND ND ND ND Example 2 5.60 + 0.03 3.21 ± 0.01 ND ND ND Example 3 5.60 + 0.03 ND ND ND ND Example 7 5.99 + 0.07 3.94 + 0.02 ND ND ND Example 8 5.60 + 0.03 4.32 ± 0.01 2.75 + 0.02 1.38 + - 0.01 ND Example 9 5.60 + 0.03 4.59 + 0.03 3.59 ± 0.01 2.69 ± 0.02 ND Comparative Example 1 5.60 + 0.03 4.84 ± 0.02 5.32 ± 0.01 6.96 + 0.02 8.81 ± 0.03 Comparative Example 2 5.60 + 0.03 5.81 ± 0.01 7.98 + - 0.01 8.97 ± 0.01 10.91 + 0.02 Comparative Example 3 5.60 + 0.03 5.99 ± 0.02 8.17 ± 0.02 9.34 + 0.02 11.62 + - 0.01 Bacillus cereus
( Bacillus cereu s) Example 1 3.26 ± 0.05 ND 2.44 ± 0.08 3.87 ± 0.05 4.69 ± 0.06 Example 2 3.26 ± 0.05 ND 2.92 ± 0.03 3.99 + 0.07 5.01 + 0.08 Example 3 3.26 ± 0.05 ND 2.57 ± 0.06 3.92 ± 0.06 4.74 ± 0.05 Example 7 4.05 ± 0.08 ND 1.87 + 0.02 3.63 ± 0.058 4.81 ± 0.06 Example 8 3.26 ± 0.05 2.12 + 0.07 3.14 ± 0.05 4.19 + 0.06 5.09 ± 0.06 Example 9 3.26 ± 0.05 2.37 ± 0.08 3.39 ± 0.02 4.37 ± 0.05 5.17 ± 0.07 Comparative Example 1 3.26 ± 0.05 2.56 + 0.07 3.78 + 0.04 4.69 ± 0.07 5.88 + 0.03 Comparative Example 2 3.26 ± 0.05 3.58 + 0.04 4.96 ± 0.08 5.83 + 0.04 6.99 ± 0.09 Comparative Example 3 3.26 ± 0.05 3.74 ± 0.06 5.21 ± 0.07 6.06 ± 0.07 7.18 ± 0.05 Escherichia coli
( Escherichia coli O157: H7) Example 1 3.18 ± 0.10 ND ND ND ND Example 2 3.18 ± 0.10 ND ND ND ND Example 3 3.18 ± 0.10 ND ND ND ND Example 7 3.88 ± 0.08 1.02 + 0.09 ND ND ND Example 8 3.18 ± 0.10 2.06 ± 0.08 ND ND ND Example 9 3.18 ± 0.10 2.54 ± 0.05 0.81 + 0.06 ND ND Comparative Example 1 3.18 ± 0.10 3.17 ± 0.07 4.53 ± 0.09 5.27 ± 0.02 6.02 ± 0.09 Comparative Example 2 3.18 ± 0.10 3.21 ± 0.08 4.88 + 0.04 5.76 + - 0.10 6.98 + 0.04 Comparative Example 3 3.18 ± 0.10 3.72 ± 0.02 5.52 + 0.04 6.98 + 0.03 8.01 ± 0.05 Salmonella Enteritidis
( Salmonella enteritidis ) Example 1 4.33 + 0.02 ND ND ND ND Example 2 4.33 + 0.02 ND ND ND ND Example 3 4.33 + 0.02 ND ND ND ND Example 7 5.01 ± 0.05 1.47 ± 0.08 ND ND ND Example 8 4.33 + 0.02 3.07 ± 0.04 1.17 + 0.04 ND ND Example 9 4.33 + 0.02 3.39 ± 0.01 1.19 ± 0.02 ND ND Comparative Example 1 4.33 + 0.02 4.01 ± 0.05 4.96 + 0.07 5.83 + 0.04 7.19 + 0.06 Comparative Example 2 4.33 + 0.02 4.51 + 0.04 5.73 ± 0.08 6.61 + 0.09 7.99 + 0.04 Comparative Example 3 4.33 + 0.02 4.93 ± 0.06 6.11 + 0.06 7.04 ± 0.05 8.38 ± 0.05

* ND: Not detected

As shown in Table 5, it was confirmed that the foods contained in the packaging materials prepared according to Examples 1 to 3 and Examples 7 to 9 of the present invention had better sterilizing power than Comparative Examples 1 to 3.

Test Example  6.

6-1. Total phenol content (mg / g): Phenol content was measured according to the method of Kim et al. (1993). 100 μg of the sample, 2 μl of 2% Na ₂ CO ₃ and 100 μl of 50% Folin-Ciotalteau reagent were mixed, and the absorbance was measured at 750 nm after 30 minutes. The absorbance was measured using tannic acid as a standard Based on the calibration curve.

6-2. Color change: The color change of the apple surface was visually observed and classified in 1-5 steps. The first step is that the color is unchanged, and the color changes from step to step.

[Table 6] division Processing time (day) 0 One 6 11 14 Total phenol content
(mg / g) Example 1 1.57 1.56 1.52 1.49 1.46 Example 3 1.57 1.57 1.53 1.48 1.44 Example 5 1.57 1.56 1.51 1.48 1.45 Example 8 1.57 1.35 1.27 1.19 1.15 Example 9 1.57 1.34 1.27 1.20 1.14 Comparative Example 1 1.57 1.43 1.22 1.15 0.97 Comparative Example 3 1.57 1.38 1.17 0.94 0.81 Comparative Example 5 1.57 1.33 1.02 0.81 0.72 Color change Example 1 One One One One One Example 3 One One One One One Example 5 One One One One One Example 7 One One One One One Example 8 One One 2 2 2 Example 9 One One One 2 2 Comparative Example 1 One One 2 3 4 Comparative Example 3 One 2 3 3 4 Comparative Example 5 One 2 3 4 5

As shown in Table 6 above, the food contained in the packaging material prepared according to Examples 1, 3, 5, 8 and 9 of the present invention did not lower the total phenol content as compared with Comparative Examples 1, 3 and 5, Did not change.

Also, when the concentration of chlorine dioxide gas exceeds 5 ppm, the content of total phenol gradually decreases, and the color of food is changed.

Claims (25)

delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete (A) A chlorine dioxide aqueous solution having a pH of 3 including a sodium chlorite solution having a sodium chlorite concentration of 10000 ppm and a 0.1M universal buffer having a pH of 3 is absorbed by an acrylic polymer polymerized including an itaconic ester monomer, Introducing a polymer gel for releasing a chlorine dioxide gas into the polyethylene terephthalate packaging material continuously releasing 5 ppm of chlorine dioxide gas;
(B) introducing the food into the polyethylene terephthalate packaging material into which the chlorine dioxide gas-releasing polymer gel is introduced, and then replacing the food with a gas composed of oxygen, carbon dioxide, and nitrogen; And
(C) sealing the polyethylene terephthalate packaging material,
Wherein the gas displaced in step (B) is 5 vol% oxygen, 10-20 vol% carbon dioxide, and 75-85 vol% nitrogen. delete delete delete delete delete