JPH05168842A - Oxygen adsorbent - Google Patents

Abstract

PURPOSE:To obtain a deoxidizing agent having excellent durability and stable deoxidizing performance even under such a condition that water moves into the oxygen adsorbent. CONSTITUTION:The oxygen adsorbent consists of iron powder, a phenol compd., metal, halide, active carbon, water, and water holding agent. This oxygen adsorbent is packed in an air-passable packaging material to obtain a deoxidizing agent. This deoxidizing agent shows extremely excellent initial deoxidization performance and little deterioration even for long-term storage under severe conditions that water moves into the oxygen adsorbent used for dry foods, dry foods and desiccant, food with high water content, acid foods, etc.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an oxygen absorbent,
More specifically, it is an oxygen absorbent composed of iron powder and phenolic compounds as essential components, which are the main parts of the conventional iron-based oxygen scavenger and organic oxygen scavenger.

[0002]

2. Description of the Related Art An oxygen scavenger is a composition having a property of absorbing oxygen, and is usually used by being enclosed in a breathable pouch. Generally, an oxygen absorber utilizing oxidation of metal powder such as iron powder is used as a deoxidizer. The packaging material (hereinafter referred to as "packaging material") that constitutes the breathable sachet enclosing the oxygen scavenger includes, for example, a packaging material in which paper and a perforated polyethylene film are laminated, a perforated plastic film, paper and a perforated film. Packaging material with polyethylene film laminated and bonded,
Packaging materials using non-woven fabrics or microporous membranes are used.

[0003]

As a problem in food preservation technology using an oxygen absorber, the oxygen absorber is used in foods such as dry foods, high-moisture foods, acidic foods, oil-processed foods, and alcohol-containing foods. Since the usage conditions tend to be harsh over a wide variety of application fields such as use, the moisture contained in the oxygen absorbent composition migrates to the dry food and impairs the deoxidization performance,
Even if deoxidized in the early stage, it cannot absorb oxygen flowing from the outside and cannot be deoxygenated, resulting in poor deoxidation, making it difficult to store for a long period of time. Since it migrates to the composition, stains are generated on the surface of the packaging material and the appearance is impaired, oil of food permeates the packaging material, the air permeability of the packaging material is impaired, and the deoxidizing performance is impaired. Be done. Due to such drawbacks, it is the current situation that the material and structure of the packaging material are changed according to the situation of using the oxygen absorber.

In particular, conventional deoxidants undergo an oxidative reaction in the presence of water, so that when they are used together with a dried food or a desiccant in a dried food, the initial deoxidized state is incomplete. However, since the external oxygen slightly flows through the barrier packaging material during storage, the deoxidized state during storage for a long time is incomplete.

Further, even if an organic oxygen scavenger that does not require the inclusion of water in the oxidation reaction is used in a system in which no water is present, the oxidation reaction is significantly reduced and it takes a long time to deoxidize. The deoxidized state was incomplete or impractical, and its effect was insufficient. Even if the material and structure of the packaging material are devised, such drawbacks have not been solved yet, and there are many unsatisfactory points in commercial oxygen absorbers.

The present invention has a wide variety of application fields such as use in foods such as dry foods, high-moisture foods, acidic foods, oil-processed foods and alcohol-containing foods, and the water content of the high-moisture foods is transferred to the oxygen absorbent composition. Yes, stains occur on the surface of the packaging material, oil of food permeates the packaging material, even if the use conditions tend to be severe, such as migration of water into the oxygen absorbent composition in the dry food, especially, An object of the present invention is to provide an oxygen absorbent that exhibits stable deoxidizing performance even when used in a dry food in combination with a dry food or a drying agent and has excellent durability.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that iron powder (A), phenol compound (B), metal halide (C), activated carbon (D)
An oxygen absorbent containing water, water (E) and a water retention agent (F) has an excellent initial deoxidizing performance, and the deoxidizing performance when the deoxidizing agent is used for food and stored for a long period of time. The present invention has been completed with the finding that since there is no deterioration, it is possible to reliably remove oxygen flowing from the outer bag during storage and maintain a completely deoxidized state.

The present invention relates to iron powder (A), phenol compound
(B), metal halide (C), activated carbon (D), water
An oxygen absorbent comprising (E) and a water retention agent (F). Hereinafter, the present invention will be described in detail.

In the present invention, as the iron powder (A), reduced iron powder, electrolytic iron powder, atomized iron powder or ground iron powder can be used, and there is no particular limitation, and the particle size is usually 50 mesh or less. Especially, those having 100 mesh or less are preferably used. Iron powder can be used even if it contains impurities as long as it does not interfere with the purpose of oxygen absorption. If necessary, metal powder such as copper powder and zinc powder may be used alone or in combination in place of iron powder, but iron powder is generally used.

In the present invention, the phenol compound (B)
Is a polyvalent hydroxyl group-containing aromatic compound having an antioxidant function selected from the group consisting of phenol, catechol, pyrogallol, cresol, gallic acid, resorcin and hydroquinone. The phenol compound (B) is used in an amount of 1 to 50 parts by weight, preferably 3 to 25 parts by weight, based on 100 parts by weight of iron powder.

In the invention, the metal halide (C) is an alkali metal such as sodium, potassium or lithium, an alkaline earth metal such as calcium or magnesium, or copper, zinc, aluminum, tin, manganese, iron, cobalt, nickel. And a metal halide (C) consisting of one kind of metal selected from the group consisting of, and one kind of halogen selected from a halogen atom such as chlorine, bromine and iodine. As a specific metal halide, sodium chloride, potassium chloride, magnesium chloride, potassium chloride, magnesium chloride, potassium bromide and the like are generally used. The amount of the metal halide (C) used is 0.05 to 50 parts, preferably 0.5 to 25 parts with respect to 100 parts by weight of iron powder.
Parts by weight.

In the present invention, the activated carbon (D) includes activated carbon produced from raw materials such as plant-based wood, sawdust, coconut shell, pulp waste liquid, mineral-based coal, petroleum, coke and petroleum pitch. Be done. Activated carbon (D) contributes as an accelerator for the oxidation reaction of iron powder (A) with phenolic compounds (B), so other carbon substances such as graphite, carbon black, charcoal can be used in addition to activated carbon. However, it is preferable to use activated carbon in consideration of the promoting action. Activated carbon
The amount of (D) used is iron powder (A) and phenol compound (B)
The total amount is 5 to 80 parts by weight, preferably 10 to 50 parts by weight.

In the present invention, the water retention agent (F) may be calcined vermiculite, kieselguhr, perlite, zeolite, activated clay, bentonite, kaolin, wood powder, activated carbon, cellulose, etc. Powdered to granular calcined vermiculite and zeolites, which are also simply called hirucite, are preferred. The water retention agent (F) is used in an amount of 30 to 200 parts by weight, preferably 60 to 130 parts by weight, based on 100 parts by weight of water (E).

In the present invention, the amount of water (E) used is 2.5 to 50 parts by weight, preferably 5 to 50 parts by weight, based on the iron powder (A).
25 parts by weight. In addition to the components (A) to (E) described above, additives of other components may be added, if necessary. Further, the oxygen absorbent of the present invention is blended and mixed by a mixer such as a kneader, a Nauter mixer, a roll mill, a gear compounder.

The oxygen absorbent obtained in this manner is treated with a Gurley type air-permeable packing material having an air permeability in the range of 1 to 10,000 seconds / 100 ml, for example, a non-woven fabric, a microporous membrane, or a water resistant material. Laminated perforated plastic film made of polyethylene, ethylene vinyl acetate copolymer, ionomer resin, etc. as a seal layer inside the laminated film of oil-resistant processed paper and perforated plastic laminated film and water- and oil-resistant processed paper Alternatively, it is used as an oxygen scavenger by filling it in a bag made of a lamininate film or the like formed into a large number of streaks or fine meshes by extrusion laminating of resin, printing method, coating method, or the like. The oxygen scavenger is stored in an oxygen-barrier outer bag in a hermetically sealed and deaerated package, and is unsealed at the time of use to be sealed in an oxygen-barrier food package before use.

[0016]

The present invention relates to iron powder (A), phenol compound
(B), metal halide (C), activated carbon (D), water (E)
And an oxygen absorbent containing a water retention agent (F). Iron powder and a phenol compound, which are the main components of the conventional iron-based deoxidizer and organic-based oxygen absorber and are directly involved in the oxygen absorption reaction. Composed of essential ingredients.

Iron-based oxygen scavengers that are currently the mainstream of oxygen scavengers are at least iron powder, metal halides, activated carbon,
Each type of oxygen scavenger is prepared by adjusting the oxygen scavenging rate with water as an essential component in consideration of these compounding compositions and the air permeability of the breathable packaging material. Since water is involved in the deoxidation reaction, the content of water in the iron-based oxygen scavenger decreases, and if it falls below a certain amount, not only does the deoxidation reaction decrease, but it also stops at all and becomes impossible to deoxidize. Become.

When a commercially available oxygen scavenger is used in a dry food or a dry food in combination with a desiccant, the oxygen scavenging rate is extremely reduced and the oxygen is not completely deoxidized, or the oxygen is initially deoxidized. However, the moisture in the oxygen scavenger is lost during long-term storage, the minute amount of oxygen passing through the packaging bag cannot be removed, and the deoxidized state in the packaging system becomes incomplete, resulting in The effect of the oxygen scavenger is lost due to the oxidation of the food, and the original role of the oxygen scavenger cannot be fulfilled.

On the other hand, the organic oxygen scavenger generally has a composition containing water, but the oxygen scavenging rate is slower than that of the iron oxygen scavenger, and it is limited to the slow-acting type. Further, in this system, the deoxygenation reaction proceeds even when there is no water at all, but it tends to be extremely reduced as compared with the composition containing water, and in many cases it is not completely deoxygenated.

Since the organic oxygen scavenger generally has a slow oxygen scavenging rate, it is used for special purposes where the deterioration of foods such as dry foods is slow and the migration of water from the oxygen scavenger is disliked. is the current situation. However, in such a system, the initial deoxygenation is insufficient and the deoxidized state does not become perfect even after long-term storage. Can't exert.

In order to make up for such a drawback, even if a breathable packaging material having an air permeability for packaging the oxygen absorbent is devised, since the packaging material originally has an air permeability, the oxygen absorbent through the packaging material is The drainage of water can not be overwhelmed.

Differently from the organic oxygen scavenger, the initial oxygen scavenging rate can be adjusted and the oxygen scavenging rate can be adjusted by differently mixing the phenolic compound (B) with the compounding composition containing iron powder (A) as a main component. A type of oxygen scavenger can be supplied. In addition, this oxygen scavenger makes full use of the high oxygen scavenging rate, which is a characteristic of iron-based oxygen scavengers, to completely deoxidize the inside of the packaging system at the beginning of use, so it is a product with rapid deterioration. Can be used in the same manner as conventional iron-based oxygen scavengers.

Even if the oxygen absorber is used in a packaging system in which a dry food or a desiccant is present and water is completely lost to stop the oxidation reaction of iron, the oxygen absorber is properly blended with the oxygen absorber. The oxidation reaction of the phenol compound (B) progresses regardless of the presence or absence of water, except for the oxidation reaction rate. Therefore, the phenol compound (B) reacts with the oxygen gradually flowing from the outer bag during long-term storage and completely reacts within the packaging system. Can be deoxidized.

Therefore, in the present invention, the oxygen absorbent is used as an oxygen scavenger by filling a bag made of a breathable packaging material having a Gurley type air permeability of 1 to 10,000 seconds / 100 ml. The oxygen scavenger has stable oxygen scavenging performance even when used under special and harsh conditions that cannot be used not only with the iron-based oxygen scavenger as described above, but also with the iron-based oxygen absorber. It can exhibit stable performance comparable to that of an oxygen agent.

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to these examples. [1] Preparation of sample and comparative sample

Samples 1 to 15 NaCl or KCl, water, calcined vermiculite or zeolite, and activated carbon were mixed in the proportions shown in Table 1, to which a predetermined amount of iron powder and phenol compounds shown in Table 1 were added and mixed. And oxygen absorbers were prepared.

Comparative Sample-1, 2 NaCl, water, calcined vermiculite, and activated carbon were mixed at the ratio shown in Table 1, and a predetermined amount of iron powder shown in Table 1 was added and mixed to prepare an oxygen absorbent. ..

Comparative Sample-3 Phenolic compounds and activated carbon were mixed at the ratio shown in Table 1 to prepare an oxygen absorbent.

Comparative Sample-4 Phenolic compounds, activated carbon, and water were mixed in the proportions shown in Table 1 to prepare an oxygen absorbent.

Comparative sample-5 Phenolic compounds, activated carbon, NaCl and water were mixed at the ratio shown in Table 1 to prepare an oxygen absorbent. Sample-1 above
-15 and comparative samples-1 to 5 are shown in Table 1.

[0030]

[Table 101]

[0031]

[Table 102]

[2] Preparation of oxygen scavenger 3 g of the oxygen absorber prepared in the above [1] was used as a perforated PET.
/ PE Laminated film and water- and oil-resistant processed paper Laminated film made of extrusion-laminated polyethylene resin as a sealing layer inside a laminated film Gurley type Air permeability 1500-4000 seconds / 100ml 50 x 5 packaging materials
Each oxygen absorber was prepared by filling and sealing a bag made to a size of 0 mm.

[3] Deoxidizing performance test Each of these deoxidizing agents and 500 ml of air were put in a bag of oxygen barrier packaging material (KON / PE, 15 × 30 cm), sealed, and allowed to stand at 25 ° C. The oxygen concentration was measured every hour and the time until the oxygen concentration became zero was obtained. A similar test was conducted under the condition that the relative humidity in the packaging system was kept at 10% RH or less by using a necessary amount of desiccant together. The number of samples is 10 in each example.
Went in point.

Next, the sample used for the deoxidation performance test was stored at 25 ° C., and after 6 months, the oxygen concentration in the packaging system was measured to confirm the degree of deoxidation in the system. .. The measurement results are shown in Table 2.

[0035]

[Table 201]

[0036]

[Table 202]

[4] Various oxygen scavenger characteristics tests The oxygen absorbers and oxygen scavengers samples (Examples) and comparative samples (Comparative examples) prepared in the above [1] and [2] were tested for fluidity, The workability, bag-making property, and durability were measured. The measurement results are shown in Table 2 above.

[0038]

INDUSTRIAL APPLICABILITY The present invention provides a dry food, an oxygen absorber prepared by packaging an oxygen absorbent in a breathable packaging material, a combination system of a dry food and a desiccant, a high-moisture food, an acidic food, an oil-processed food, Even when used in severe applications such as alcohol-containing foods under various conditions, it suppresses contamination by rust, stains, and adhesion to packaging materials, and has extremely stable deoxidizing performance without deterioration of deoxidizer for a long period of time. Have. Therefore, it is a preservative that can be used in applications where it is difficult to use an oxygen absorber, especially in dry foods and applications in which water in the oxygen absorber is lost, such as when used in combination with a dry food. Since it can be used in a wide range as, it is extremely significant in the industry including the food field.

Front Page Continuation (72) Inventor Yoichi Yamakawa 2-2-1 Otemachi, Chiyoda-ku, Tokyo Inside Nippon Soda Co., Ltd.

Claims (3)

[Claims] 1. Oxygen absorption comprising iron powder (A), phenol compound (B), metal halide (C), activated carbon (D), water (E) and water retention agent (F). Agent. 2. A phenol compound (B) is phenol,
The oxygen absorbent according to claim 1, which is at least one kind of a polyvalent hydroxyl group-containing aromatic compound selected from the group consisting of catechol, pyrogallol, cresol, gallic acid, hydroquinone and resorcin. 3. A phenol compound (B) is an iron powder (A).
The oxygen absorbent according to claim 1 or 2, wherein the content is 1 to 50 parts by weight based on 100 parts by weight.