JPH0938486A - Oxygen absorber and its package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low-cost disoxidant having safety in food sanitation and excellent in practicality by solving the problem of low oxygen absorbing performance of the conventional glycerol-base disoxidant and considerably enhancing the oxygen absorbing performance. SOLUTION: A granular disoxidant compsn. is composed of glycerol, t- butylhydroquinone, a transition metal or its compd., an alkaline substance, a slightly water-soluble solid and water. The compsn. is housed in a gas permeable packing material having regulated gas permeability to obtain the objective disoxidant packed body.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inexpensive and safe oxygen scavenger containing glycerin as a main ingredient and a package thereof. The term "oxygen scavenger" is mainly used herein to mean "composition having oxygen scavenging effect" (oxygen scavenger composition), but "package of composition having oxygen scavenging effect" (oxygen scavenger package) ) May also be used in the meaning of.

[0002]

2. Description of the Related Art There is a method of using an oxygen scavenger as a storage technology for foods and the like. This method is to make an oxygen absorber coexist in an article to be stored in a gas-barrier sealed bag or a sealed container (hereinafter, simply referred to as a sealed container). The oxygen in the sealed system is absorbed by the oxygen absorber, This is a method of suppressing the deterioration of quality due to oxidation and the growth of bacteria and microorganisms by keeping the storage atmosphere substantially oxygen-free. This method is widely used to maintain the quality of articles whose quality is changed by the presence of oxygen. As the oxygen scavenger, an oxygen scavenger mainly containing iron powder has been conventionally used in view of its oxygen absorption capacity, easiness of handling, safety, cost and the like. However, packaged foods that use oxygen scavengers often undergo a product inspection with a metal detector to check for the inclusion of metallic foreign substances after sealing in the packaging process. Due to the sensitivity of the metal detector, the metal detector could not be used to inspect a packaged food containing an oxygen scavenger containing iron powder as a main ingredient.

From the above circumstances, there is a demand for an oxygen scavenger containing an organic substance as a main component which is not sensitive to a metal detector other than the oxygen scavenger of the iron powder main component. The deoxidizing agent containing ascorbic acid as the main agent shown in Sho-51-136845 and the oxygen absorbing agent containing phenols as the main agent shown in JP-B No. 61-39098 are mentioned. However, ascorbic acid-based agents have a problem of high cost because ascorbic acid is expensive. In addition, the phenol-based compounds have problems in safety such as accidental ingestion. On the other hand, the applicant of the present invention has filed Japanese Patent Application Laid-Open Nos. 3-8441 and 3-
10663 and Japanese Patent Laid-Open No. 3-10664 have developed a deoxidizer containing a sugar or a polyhydric alcohol as a main component. Among them, it was found that the deoxidizer containing glycerin as a main component, which is disclosed in JP-A-3-10664, is excellent in safety, oxygen absorption capacity and cost. However, the oxygen absorbers containing glycerin as the main component still have a problem that the oxygen absorption amount is lower than that of the iron-based oxygen absorbers, and the cost of the product becomes high.

[0004]

The object of the present invention is to solve the above-mentioned problems of the oxygen absorber having glycerin as a main component,
An object of the present invention is to provide an oxygen scavenger that is inexpensive, safe for food hygiene, and that is not detected even by a metal detector that is excellent in practicability by significantly improving oxygen absorption performance.

[0005]

Means for Solving the Problems The present inventors have focused on phenols, which are one component of an oxygen absorber composition, in order to improve the oxygen absorption performance of conventional oxygen absorbers containing glycerin as a main component. As a result of diligent studies, it was surprisingly found that t-butylhydroquinone has an excellent radical-forming ability and acts as an excellent initiator for the deoxygenation reaction of the main component, and the present invention has been completed. That is, the present invention is characterized by using t-butylhydroquinone as a phenol in an oxygen scavenger containing glycerin as a main component and containing a phenol as a means for solving the problems.

In the present invention, it is considered that t-butylhydroquinone is particularly excellent in radical forming ability and acts as an excellent initiator, whereby the oxygen absorption rate is significantly improved and the oxygen absorption amount is increased. Generally, in a deoxidant containing glycerin as the main agent and containing phenols, the phenol itself is easily oxidized and easily becomes a radical, so that the main agent, glycerin, undergoes hydrogen abstraction to react with oxygen. It can be considered that it plays the role of an agent. However, various compounds exemplified as phenols in conventional oxygen absorbers based on glycerin have low radical-generating ability as an initiator. Therefore, oxygen absorbers using these phenols are
The oxygen absorption capacity was not always satisfactory. Hereinafter, the present invention will be described in detail.

The oxygen scavenger of the present invention is composed of a transition metal or its compound, an alkaline substance, a poorly water-soluble solid and water in addition to glycerin and t-butylhydroquinone which are the main components, and is a granular oxygen scavenger comprising the above composition. It is an agent.
The glycerin used as the main agent may be one that is usually commercially available, or may contain impurities such as water. Further, as glycerin, a mixture of glycerin may be used as long as the object of the present invention can be achieved.

As described above, t-butylhydroquinone acts as an initiator of the reaction, and even if it is added in a small amount to the main ingredient glycerin, it can bring about an increase in oxygen absorption. The blending amount of t-butylhydroquinone is 1
It is 5 parts by weight or more, preferably 10 to 30 parts by weight, more preferably 10 to 15 parts by weight with respect to 00 parts by weight. When the blending amount of t-butylhydroquinone with respect to glycerin which is the main ingredient is small, the effect is not sufficient and the oxygen absorption amount is low,
Further, even if the blending amount is increased beyond the above range, the oxygen absorption amount does not increase and reaches a ceiling, so it is not a good idea in terms of cost to increase it further. Further, from the viewpoint of safety and health of the oxygen absorber, it is not preferable that the amount of t-butylhydroquinone is large.

The transition metal or the compound thereof functions as a catalyst for the reaction of the main agent. As the transition metal, iron,
Cobalt, nickel, copper, zinc, manganese are preferred,
Copper, manganese and nickel are more preferable. As the transition metal compound, a transition metal halide, sulfate, nitrate, phosphate, carbonate, oxide, hydroxide, organic acid salt,
Other double salts, chelate compounds and the like can be mentioned, and preferable specific examples thereof include cuprous chloride, cupric chloride, cupric sulfate,
Examples thereof include cupric hydroxide, cuprous oxide, cupric oxide, manganese chloride, manganese nitrate, manganese carbonate, metal manganese and nickel chloride. The compounding amount of the transition metal compound is preferably 1 part by weight or more, more preferably 5 to 30 parts by weight, based on 100 parts by weight of glycerin. When the blending amount of the transition metal compound is small, a sufficient catalytic effect cannot be obtained and the oxygen absorption amount is low, and even when the blending amount exceeds the above blending amount, the oxygen absorption amount reaches a ceiling, which is not preferable in terms of cost and safety and health. .

The alkaline substance refers to a substance which exhibits alkalinity by acting with or dissolving in water and having a pH of about 9-14. As the alkaline substance, hydroxides of alkaline earth metals are preferable, and calcium hydroxide is particularly preferable. The amount of the alkaline substance compounded is preferably 10 parts by weight or more, and more preferably 50 to 200 parts by weight, based on 100 parts by weight of glycerin. If the blending amount of the alkaline substance is small, the reaction does not proceed sufficiently and the oxygen absorption amount is small. Further, even if the blending amount exceeds the above range, the effect does not increase, and only the total amount of the oxygen scavenger is increased, which is not a good idea.

The sparingly water-soluble solid is a solid insoluble or sparingly soluble in water, and serves as a carrier here. Specific examples of the poorly water-soluble solid include granular materials such as activated carbon, perlite, diatomaceous earth, and activated clay. Among them, diatomaceous earth having a large water absorption amount per volume is preferable. The amount of the poorly water-soluble solid may be an amount capable of supporting the oxygen absorber composition, and the amount can be appropriately selected within the range of 20 to 50% by weight based on the oxygen absorber composition. .

In the present invention, as a method for producing an oxygen scavenger, the above oxygen scavenger composition can be made into a granular product, and the obtained granular composition exhibits desired performance as an oxygen scavenger. If possible, the manufacturing method is not necessarily limited. As a method for producing an oxygen scavenger, for example, a solution of glycerin, t-butylhydroquinone, a transition metal or a compound thereof and water is impregnated into a poorly water-soluble granular solid, and a powdered alkaline substance is mixed and coated. A granular oxygen scavenger can be manufactured. In this case, each component of the solution does not necessarily have to be a solution of all the components at once and impregnated into the carrier, but the components may be appropriately combined to form a solution, and the components may be sequentially impregnated. Alternatively, a method in which a granular alkaline substance is selected as the poorly water-soluble solid and the alkaline substance is impregnated with a solution of each of the above components may be used.

Further, in the present invention, the above-mentioned granular oxygen absorber composition is usually housed in a breathable packaging material to form an oxygen absorber package. The breathable packaging material preferably has a Gurley type air permeability of 20,000 s / 100 ml or less as the air permeability, and particularly, a Gurley type air permeability of 8,000 to 20,000 s /
100 ml is preferably used. If the air permeability of the breathable packaging material is higher than the above range, the escape of water in the oxygen scavenger composition becomes large, which causes a shortage of water necessary for the oxygen absorption reaction, resulting in a decrease in oxygen absorption. Of course, if the air permeability of the breathable packaging material is too small, the oxygen absorption rate will be slowed down, which is not preferable, and in order to efficiently exhibit the oxygen absorption performance of the oxygen scavenger of the present invention, the permeability of the breathable packaging material should be reduced. It is important that the temper is in the above range. As the breathable packaging material, a packaging material known as a breathable packaging material for an oxygen scavenger, for example, a perforated plastic film, a non-woven fabric, a microporous film, paper or the like alone or a composite breathable material having this as a base material. Packaging materials can be used. In addition, in order to obtain appropriate air permeability, for example, a perforated plastic film such as polyolefin may be laminated on the air-permeable packaging material of the base material to adjust the aperture ratio of the laminated perforated film. .

The oxygen scavenger of the present invention is used as a oxygen scavenger package for preservation of articles such as food by sealing in a gas barrier packaging bag or container together with articles to be preserved such as food. be able to.

[0015]

【Example】

Example 1 100 parts by weight of glycerin, manganese chloride tetrahydrate 4.5
Parts by weight, 8.8 parts by weight of t-butylhydroquinone and 76 parts by weight of water to form a solution, and 141 parts by weight of granular diatomaceous earth (average particle size 1.5 mm, apparent density 0.32) is mixed with this solution. The solution was impregnated, and 100 parts by weight of powdered slaked lime was added to the obtained granular material and mixed sufficiently to uniformly coat the surface to obtain a granular oxygen absorber. Next, 2 g of the obtained granular oxygen scavenger was made using a laminated film of perforated polyester film / perforated polyethylene film (Gurley air permeability 10,000 s / 100 ml) whose air permeability was adjusted (55 mm in length) × 45 mm) and the opening was heat-sealed to obtain an oxygen absorber package.
A gas barrier bag of nylon / polyethylene laminate film (length 300 mm x width 2)
20 mm), filled with 1250 ml of air and sealed. The sealed bag of the oxygen absorber package in which air was enclosed was kept at room temperature, and the oxygen concentration in the bag was measured. The oxygen absorption amount for 48 hours (2 days) is shown in Table 1. With respect to the granular oxygen scavenger obtained above, changes in radical generation with time were traced using ESR, and the results are shown in FIG.

Comparative Example 1-7 The same composition as in Example 1 was used except that t-butylhydroquinone in the oxygen scavenger composition of Example 1 was changed to t-butylhydroquinone described below, and granular deoxidation was carried out in the same manner as in Example 1. An oxygen agent composition was obtained and the oxygen absorption performance was measured. The results are also shown in Table 1. Comparative Example 1; Catechol Comparative Example 2; t-Butylcatechol Comparative Example 3; Hydroquinone Comparative Example 4; Resorcinol Comparative Example 5; Pyrogallol Comparative Example 6; Gallic Acid For comparison, the granular oxygen absorber of Comparative Example 1 was also used. The change with time of the radical generation amount is shown in FIG.

[0017]

[Table 1] Note: Oxygen absorption is shown for 48 hours.

[0018]

EFFECTS OF THE INVENTION In the oxygen scavenger containing glycerin as the main component, the conventional phenols were used, however, the amount of radicals generated was small as a reaction initiator, and the effect was not always sufficient. The t-butylhydroquinone of No. 2 shows an excellent action as a reaction initiator because a large amount of radicals are generated. By using t-butylhydroquinone, the oxygen scavenger of the present invention has a significantly improved oxygen absorption ability. However, the oxygen absorption amount increases. As a result, it is possible to reduce the amount of the oxygen absorber composition including glycerin which is the main ingredient, and to make the oxygen absorber compact, and it is possible to significantly reduce the cost.

[Brief description of drawings]

FIG. 1 shows the change over time in the radical production amount of a deoxidizing composition.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Hasegawa 6-1 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi Gas Chemical Co., Ltd. Tokyo Research Laboratory

Claims (3)

[Claims] 1. An oxygen scavenger which is mainly composed of glycerin and contains t-butylhydroquinone. 2. An oxygen scavenger package in which the oxygen scavenger according to claim 1 is housed in a breathable packaging material having a controlled air permeability. 3. The oxygen scavenger package according to claim 2, wherein the breathable packaging material according to claim 2 has a Gurley type air permeability of 8,000 to 20,000 s / 100 ml.