JP2009227306A - Method for storing article having low water activity - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent oxidization of an article having a low water activity which cannot be fully prevented from oxidization by usual deoxidation packaging because of the suspended oxygen absorption capability of a deoxidizer. <P>SOLUTION: The method for storing an article having a low water activity stores an article whose water activity is 0.40 or below using a deoxidizer containing glycerin, alkaline substance, a phenol, a quinone, a transition metal or its compound, and water. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for preserving an article having a water activity of 0.40 or less to which deoxygenated packaging is applied.

  In this specification, “deoxygenation” means that the oxygen concentration in a sealed environment is 0.1% or less, and “deoxygenation agent” is for the purpose of realizing a deoxygenation state. It means things such as drugs and materials used. Further, “deoxygenating” is synonymous with “having a function as an oxygen scavenger”. Furthermore, “oxygen absorption” means that drugs, materials, and the like take up oxygen in the environment regardless of the reached oxygen concentration. Furthermore, “deoxygenation packaging” means packaging an article for the purpose of deoxidizing the package.

  Currently, packaging technology using oxygen scavengers is widely applied as a food preservation method in Japan. Deoxygenation packaging technology is caused by the presence of oxygen by using an oxygen scavenger in a packaging container that encloses food to be stored, or by packaging it with a packaging material that has a deoxygenating function and keeping it anaerobic. It is a technology that prevents food quality deterioration and harm caused by microorganisms. According to this technique, it is possible to maintain good quality of food.

  The oxygen scavenger is usually used enclosed in a breathable sachet. In general, an oxygen absorber mainly composed of iron powder is used as an oxygen scavenger, and an oxygen absorber based on an organic material that is not sensitive to metal detectors is used as an oxygen scavenger (an organic material such as glycerin). (See Patent Documents 1 and 2) However, since general oxygen scavengers undergo an oxidation reaction in the presence of moisture, oxygen scavengers are used when oxygen scavengers are used in low-moisture foods such as dried foods or in combination with desiccants. In this case, the moisture in the oxygen scavenger composition is transferred to the food or desiccant, and the oxygen scavenging performance is stopped.

  From the above circumstances, an oxygen scavenger that retains oxygen scavenging performance even when used in low-moisture foods is desired, and Patent Document 3 discloses an oxygen scavenger composed of iron powder, a phenol compound, and the like. Yes. According to the present invention, even in the case where a dry food is stored for a long period of time, it is excellent in durability under use conditions accompanying moisture transfer in the oxygen absorbent, and can exhibit stable deoxygenation performance. However, the present invention has not been put into practical use.

  Patent Document 4 discloses an oxygen scavenger composed of catechol and activated carbon, having a low moisture content in the oxygen scavenger and suitable for storing dried food. However, catechol is designated as a Class 1 Designated Chemical Substance by the Law on Promotion of Improvement in Management and the like (PRTR Law) for grasping the amount of specified chemical substances released into the environment.

  Patent Document 5 discloses an oxygen scavenger that does not require moisture for oxygen absorption using an unsaturated fatty acid compound or a chain hydrocarbon polymer having an unsaturated group as an oxygen absorber. The oxygen scavenger according to the present invention has been put into practical use and is used for storage of metal parts and electronic parts. However, since it is expensive compared with general oxygen scavengers, it is not suitable for food applications.

JP-A-3-10664 JP 2003-79354 A JP-A-5-168842 JP 2000-050849 A Japanese Patent Laid-Open No. 4-029741

  In the present invention, when an article having a water activity of 0.40 or less or an article having a water activity of 0.40 or less in combination with a desiccant is deoxygenated and packaged, the package is kept in a deoxygenated state, and the food is kept for a long time. Is to provide a way to save.

As a result of intensive investigations for the above purpose, the present inventors have carried out deoxygenation packaging using a deoxygenating agent containing glycerin as a main ingredient, thereby deoxidizing the package containing articles having a water activity of 0.40 or less. The present invention has been found to be able to be maintained, and the present invention has been completed.
That is, the present invention stores an article having a water activity of 0.40 or less in an oxygen scavenger containing glycerin, an alkaline substance, phenols or quinones, a transition metal or a compound thereof, and water. This is a method for storing an article.

  In the preservation method of the present invention, the alkaline substance is a hardly water-soluble solid, and the hardly water-soluble solid is loaded with at least glycerin, phenols or quinones, a transition metal or a compound thereof, and water. The phenol is preferably catechol or 5-methylresorcin.

  Moreover, in the preservation | save method of this invention, a desiccant can also be used together and it is preferable to use together the desiccant which has quicklime as a main ingredient.

  According to the present invention, it is possible to absorb oxygen without stopping the oxygen absorbing ability of the oxygen scavenger even in a system in which moisture in the oxygen scavenger composition is easily transferred to an article to be stored or a desiccant. is there.

  Since water is essential for the oxidation of metals such as iron and ascorbic acid, it is possible to store hygroscopic articles in a deoxygenated state using a deoxygenating agent mainly composed of these components, and a desiccant. It has been considered difficult to store articles in a deoxygenated state in combination. However, the present inventors may use an oxygen scavenger consisting of glycerin, alkaline substances, phenols or quinones, transition metals or compounds thereof, and water in combination with hygroscopic articles and desiccants. The present inventors have newly found that the oxygen absorption reaction proceeds and that the inside of the packaging bag containing the article to be stored can be deoxygenated.

  The oxygen scavenger of the present invention is preferably used by being supported on a carrier material (poorly water-soluble solid, sheet, etc.), and water is added to and mixed with each of the components as necessary. Used as tablets, sheets, etc. The glycerin used for the main agent may be a commercially available product, or may contain impurities such as water that do not interfere with the deoxygenation reaction.

  Phenols or quinones act as initiators for the reaction, and are characterized by an increase in the amount of oxygen absorbed by addition of a small amount to the main component glycerin. Examples of phenols include catechol, resorcin, hydroquinone, pyrogal, gallic acid, and tannin. Examples of quinones include benzoquinone, naphthoquinone, phenanthraquinone, and diphenoquinone. Among them, polyhydric phenols having a hydroxyl group substituted at the meta position or para position are excellent in increasing oxygen absorption. The blending amount of phenols or quinones is preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of glycerin. Further, the blending amount of the polyhydric phenol having a hydroxyl group substituted at the meta position or para position is preferably 0.01 to 5 parts by weight, particularly 0.1 to 1 part by weight based on 100 parts by weight of glycerin. preferable. Even if the blending amount is larger than the above range, the contribution to the increase in the oxygen absorption amount of glycerin commensurate with the increase in the composition amount is not brought about, resulting in poor economic efficiency.

  Examples of polyphenols having a hydroxyl group substituted at the meta position or para position include 5-methylresorcin, hydroquinone, methylhydroquinone, 2,3-dimethylhydroquinone, tert-butylhydroquinone, methoxyhydroquinone, resorcin, 1, 2,4-trihydroxybenzene and phloroglucinol can be exemplified, and among them, 5-methylresorcin is preferable. Moreover, you may mix and use each as needed, and may combine one and other phenols other than the above.

  The transition metal or a compound thereof serves as a catalyst for the reaction of glycerin, which is the main agent. As the transition metal, iron, cobalt, nickel, copper, zinc and manganese are preferable, and copper, manganese and nickel are more preferable. Examples of transition metal compounds include transition metal halides, sulfates, nitrates, phosphates, carbonates, oxides, hydroxides, organic acid salts and other double salts, and chelate compounds. Preferred specific examples include: Examples include cuprous chloride, cupric chloride, cupric sulfate, cupric hydroxide, cuprous oxide, cupric oxide, manganese chloride, manganese nitrate, manganese carbonate, manganese metal, and nickel chloride. I can do it. These transition metal compounds are added in combination of one or more as required, and act as a catalyst for the composition of the present invention, and the blending amount is preferably 1 to 20 parts per 100 parts of glycerin. 5 to 10 parts is particularly preferred.

  Alkaline substances are substances that act alkaline with water or dissolve in water to exhibit alkalinity, and are alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, tertiary phosphates, Diphosphates and the like are preferable, and hydroxides of alkali metals and alkaline earth metals are particularly preferable. Specifically, for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, tribasic sodium phosphate, dibasic sodium phosphate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, tribasic potassium phosphate, dibasic phosphate Potassium, calcium hydroxide, magnesium hydroxide and the like are preferable. Among these, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like are particularly preferable. The amount of the alkaline substance to be mixed with glycerin is preferably 10 to 2000 parts by weight, more preferably 30 to 1000 parts by weight with respect to 100 parts by weight of glycerin. When the mixing amount of the alkaline substance is smaller than the above range, the oxygen absorption amount as the composition is small, which is not preferable. When the mixing amount of the alkaline substance is larger than the above range, the oxygen absorption amount per unit weight becomes small. It is necessary to enlarge the packaging material for packaging the composition. For example, when the article to be stored is a food, the filling of the food packaging body is inadequate and the appearance is not preferable.

  The poorly water-soluble solid is a solid that is insoluble or hardly soluble in water and serves as a carrier here. Specific examples of poorly water-soluble solids include slaked lime, activated carbon, zeolite, perlite, diatomaceous earth, activated clay, silica, kaolin, talc, pentonite, activated alumina, gypsum, silica alumina, calcium silicate, magnesium oxide, graphite, Examples thereof include powder or granular materials such as carbon black, aluminum hydroxide, and iron oxide. The poorly water-soluble solid is used alone or in combination of two or more as required. By blending a poorly water-soluble solid, the contact area of the liquid component in the composition with oxygen can be increased, the oxygen absorption rate or oxygen absorption amount can be increased, and the composition can be handled easily. . In addition, it is preferable to use an alkaline substance for the poorly water-soluble solid because the volume can be kept small and the amount of oxygen absorbed per unit weight becomes large. The amount of the poorly water-soluble solid is appropriately selected in relation to other components, and is not particularly limited, but is preferably 0.1 to 10,000 parts by weight, particularly preferably 1 to 1000 parts by weight with respect to 100 parts by weight of glycerin.

  Since water is essential for the progress of the oxygen absorption reaction, the progress of the oxygen absorption reaction can be adjusted by the amount of addition. The amount of water added in this case is not particularly limited, but is preferably adjusted to 70% by weight or less of the entire composition, and preferably 50% by weight or less. If the amount of water added is more than the above range, the composition becomes pasty and the contact area with oxygen of the composition becomes small.

  In the present invention, the mixing method of each component described above is not particularly limited. However, when the component is a liquid and a powder, any method can be used as long as each component can be uniformly mixed. After impregnating the solution with the liquid, a method of adding the powder so as to be dusted can be employed.

  Each said component is normally accommodated in a breathable packaging material, and is set as a package. As the packaging method, for example, each component is mixed and then wrapped in a small bag sealed by a heat seal at the peripheral edge of the breathable packaging material by a packing machine to form an oxygen scavenger packaging bag. This oxygen scavenger packaging bag can be stored in a non-breathable packaging material together with the article to be preserved, or stored in an airtight container together with the article to be preserved and sealed.

  Examples of articles having a water activity of 0.40 or less stored in the present invention include foods, rice crackers such as rice crackers, confectionery such as cookies and pie, seeds such as peanuts, tea leaves, dried vegetables, Examples include freeze-dried foods.

The water activity is a scale indicating the free water content in an article, and is represented by a number from 0 to 1, with 0 for an article without moisture and 1 for pure water. That is, the water activity is defined as Aw as the water activity of an article, P is the water vapor pressure in the space after the article is sealed, P is the relative humidity in the space, RH (%), and the pure water vapor pressure is If P ₀ ,
Aw = P / P ₀ = RH / 100
Is defined.

In the present invention, food is sealed together with an oxygen scavenger in a non-breathable packaging material. In the present invention, the material of the packaging material is not particularly limited, but it is desirable that the oxygen permeability generally used for deoxidized packaging is 20 cm ³ / (m ² · day · atm) or less. In addition, when the food to be stored is cookies, rice crackers, freeze-dried foods, etc., a desiccant may be enclosed in the package for the purpose of preventing deterioration due to moisture during storage.

  Although there is no restriction | limiting in particular in the desiccant used for this invention, The thing containing a silica gel, quicklime, a calcium chloride processed product, and a silica alumina gel is used preferably. Of these, a desiccant containing quicklime is particularly preferably used.

  Next, the present invention will be described in more detail with reference to examples.

Example 1
100 parts by weight of glycerin, 6 parts by weight of manganese chloride tetrahydrate, 0.6 parts by weight of catechol, and 65 parts by weight of water are mixed to make a solution. This solution is impregnated with 412 parts by weight of granular slaked lime, and a granular oxygen absorbent is added. Obtained. An oxygen absorbent packaging bag A was prepared by sealing 2.0 g of the obtained oxygen absorbent in a small bag (45 mm × 50 mm) laminated with a polyethylene film having a hole formed on the inner surface of paper, and then sealing by heat sealing.
About 10 g of commercially available cookies (water activity is 0.32) were sealed in a barrier nylon film (biaxially oriented polypropylene / polyethylene / nylon / polyethylene / linear low density polyethylene) together with the oxygen absorbent packaging bag A.
The sealed bag was stored at 35 ° C., and the oxygen gas concentration in the bag was opened by gas chromatography every 10 days for 40 days, and the cookies were subjected to sensory evaluation. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, the same test was performed except that AGELESS Z-30PT (deoxygenating agent mainly composed of iron powder manufactured by Mitsubishi Gas Chemical Co., Ltd., for 30 ml of oxygen) was used instead of the oxygen absorbent packaging bag A. did. The results are shown in Table 1.

Table 1
Storage days Test item Example 1 Comparative example 1
Day 10 Oxygen concentration (%) 0.01 or less 0.02
Cookie flavor Good Good
Day 20 Oxygen concentration (%) 0.01 or less 0.07
Cookie flavor Good Good
Day 30 Oxygen concentration (%) 0.01 or less 1.55
Cookie flavor is good
Day 40 Oxygen concentration (%) 0.01 or less 2.84
Cookie flavor is good

(Example 2)
100 parts by weight of glycerin, 6 parts by weight of manganese chloride tetrahydrate, 0.6 parts by weight of 5-methylresorcin, and 65 parts by weight of water are mixed to form a solution, and 412 parts by weight of granular slaked lime is impregnated into this solution. An absorbent was obtained. 8.0 g of the obtained oxygen absorbent was sealed in a small bag (60 mm × 75 mm) laminated with a polyethylene film having a hole formed on the inner surface of paper, and then sealed by heat sealing to obtain an oxygen absorbent packaging bag B.
About 200 g of commercially available fried rice crackers (water activity is 0.1 or less) with the above-mentioned oxygen absorbent packaging bag B and a desiccant for food made by Sakamoto Lime Industry Co., Ltd. Sealed in nylon / polyethylene film.
The sealed bag was stored at 25 ° C., and the oxygen gas concentration in the bag was opened by gas chromatography every month for 6 months, and the sensory evaluation of the fried rice cracker was performed. The results are shown in Table 2.

(Comparative Example 2)
In Example 2, the same test was carried out except that AGELESS ZP-200 (deoxygenating agent mainly composed of iron powder manufactured by Mitsubishi Gas Chemical Co., Ltd., for 200 ml of oxygen) was used in place of the oxygen absorbent packaging bag B. did. The results are shown in Table 2.

Table 2
Storage days Test item Example 2 Comparative example 2
1 month Oxygen concentration (%) 0.01 or less 0.01 or less
Rice cracker flavor Good Good
2 months Oxygen concentration (%) 0.01 or less 0.09
Rice cracker flavor Good Good
3 months Oxygen concentration (%) 0.01 or less 0.20
Rice cracker flavor Good Slightly reduced
4 months Oxygen concentration (%) 0.01 or less 0.29
Rice cracker flavor Good Slightly reduced
5 months Oxygen concentration (%) 0.01 or less 0.35
Rice cracker flavor Good Slightly reduced
6 months Oxygen concentration (%) 0.01 or less 0.38
Rice cracker flavor Good Decrease

According to the present invention, when deoxidizing and packaging an article having a water activity of 0.40 or less, the moisture in the oxygen scavenger composition is transferred to an article to be stored or a desiccant, and the oxygen scavenging performance is not stopped. It has become possible to maintain the body in a deoxygenated state for a long time. This makes it possible to prevent oxidation of articles having a water activity of 0.40 or less over a long period of time.

Claims (4)

A method for storing an article comprising storing an article having a water activity of 0.40 or less in a deoxygenating agent containing glycerin, an alkaline substance, phenols or quinones, a transition metal or a compound thereof, and water. . The method for storing an article according to claim 1, wherein the phenol is catechol or 5-methylresorcin. The method for storing an article according to claim 1 or 2, wherein a desiccant is used in combination. The method for preserving an article according to claim 3, wherein the desiccant is a desiccant containing quicklime.