JP2007307451A - Oxygen scavenger composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxygen scavenger composition which controls the amount of carbon dioxide generated and absorbed to preserve an article in a deoxygenated state under a particular carbon dioxide concentration without affecting the carbon dioxide concentration. <P>SOLUTION: The oxygen scavenger is prepared by mixing a substance obtained by immersing a porous material (c) with an unsaturated fatty acid or chain hydrocarbon polymer (a) and a catalyst (b), a hydroxide (d) of an alkaline earth metal, a moisture imparting agent (e) and a deodorant (f). The oxygen scavenger is comprised of 0.1-0.5 pts.wt. of the catalyst (b), 50-300 pts.wt. of the porous material (c), 0.3-10 pts.wt. of the hydroxide of the alkaline earth metal (d), 30-100 pts.wt. of the moisture imparting agent and 10-100 pts.wt. of the deodorant per 100 pts.wt. of the unsaturated fatty acid or chain hydrocarbon polymer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel oxygen scavenger in which the generation amount and absorption amount of carbon dioxide gas are adjusted. For example, an oxygen scavenger that requires substantially no carbon dioxide from the oxygen scavenger under atmospheric composition and that the oxygen scavenger does not substantially absorb carbon dioxide at a carbon dioxide concentration of 10%. Used for Note that “substantially” means, for example, that the amount of carbon dioxide generated from the oxygen scavenger is 1 ml / g or less under the atmospheric composition, and the amount of carbon dioxide absorbed by the oxygen absorber under a carbon dioxide concentration of 10%. It means here that it is less than 5ml / g.

Conventionally, in order to prevent oxidation of foods and pharmaceuticals, improve storage stability, and the like, these objects are sealed in a container together with an oxygen scavenger, and the inside of the sealed container is made oxygen-free. Some objects require an oxygen scavenger that does not substantially absorb and generate carbon dioxide.
For example, in Patent Documents 1 to 3, sodium bicarbonate injection as an antacid, acidosis treatment, etc. is sealed with a gas barrier film to avoid pH fluctuation of the chemical solution, and iron-based or ascorbic acid-based deoxygenation The invention used with the agent is disclosed.

  However, these oxygen scavengers not only absorb oxygen but also involve a reaction that absorbs or generates carbon dioxide. For example, an iron-based oxygen scavenger absorbs carbon dioxide because iron reacts not only with oxygen but also with carbon dioxide to form an iron carbonate compound. When the oxygen scavenger absorbs carbon dioxide, carbon dioxide is released from the chemical solution, so that there is a problem that the pH of the chemical solution necessary for maintaining the medicinal effect cannot be maintained. Moreover, since the reaction between iron and carbon dioxide gas inhibits the reaction between iron and oxygen, there is a problem in that the oxygen absorbing performance of the oxygen scavenger is lowered.

  On the other hand, ascorbic acid-based oxygen scavengers generate carbon dioxide that is about 50% to 95% of the amount of oxygen absorbed along with oxygen absorption, and the generated carbon dioxide dissolves in the chemical solution, so it is necessary to maintain its efficacy. However, there was a problem that the pH of various chemical solutions could not be maintained.

  Carbon dioxide has a bacteriostatic and insecticidal action, suppresses the generation of aerobic bacteria, fungi, and insects, and is effective in preventing spoilage and insect damage. It is known that the carbon dioxide concentration is 30%, it has a temporary effect, and if it exceeds 50%, mold can be prevented. For example, fresh meat, wiener sausage, Japanese / Western confectionery, semi-fresh confectionery, beans, cereals and the like use carbon dioxide-substituted sealed packaging, and an oxygen scavenger may be used in combination. In this case, since it is necessary to maintain a specific carbon dioxide gas concentration in the sealed container, there has been a problem that it is difficult to use an oxygen scavenger that absorbs or releases carbon dioxide.

Patent Documents 4, 5 and 6 disclose inventions relating to oxygen scavengers using an unsaturated fatty acid compound or a chain hydrocarbon polymer having an unsaturated group as an oxidation reactant. Since these oxidation reactants generate some carbon dioxide with oxygen absorption, the amount of generated carbon dioxide and the amount of carbon dioxide cannot be adjusted unless a means for absorbing carbon dioxide is applied. The concentration could not be kept substantially constant.
JP-A-5-04675 JP 2001-192069 A JP-A-8-164185 Japanese Patent Laid-Open No. 4-029741 JP 2003-128151 A JP-A-8-282737

  The present invention substantially generates carbon dioxide under atmospheric composition for storage of articles in a gas composition coexisting with oxygen and carbon dioxide for deoxygenation preservation independent of the concentration of carbon dioxide in the sealed container and the object. And an oxygen scavenger that does not substantially absorb carbon dioxide in the presence of a high concentration of carbon dioxide.

As a result of intensive investigations based on unsaturated fatty acid-based oxygen scavengers for the above purpose, the inventors of the present invention did not substantially generate carbon dioxide under atmospheric composition, and carbon dioxide in the presence of high-concentration carbon dioxide. The inventors have found a substance that does not substantially absorb gas and have completed the present invention.
That is, the present invention comprises (a) an unsaturated fatty acid compound or a chain hydrocarbon polymer having an unsaturated group and (b) a catalyst impregnated in (c) a porous body, (d) an alkaline earth metal water. It comprises a mixture of an oxide, (e) a moisture donor and (f) a deodorant, and (a) 100 parts by weight of an unsaturated fatty acid compound or a chain hydrocarbon polymer having an unsaturated group, ) 0.01-0.5 parts by weight of catalyst, (c) 50-300 parts by weight of porous material, (d) 0.3-10 parts by weight of alkaline earth metal hydroxide, (e) 30-100 parts by weight of water donor Part (f) is a deoxygenating agent whose deodorizing agent is 10 to 100 parts by weight.

  In the present invention, it is preferable that the amount of carbon dioxide generated under the atmospheric composition is 1 ml / g or less, and the amount of carbon dioxide absorbed when the carbon dioxide concentration is 10% is 5 ml / g or less. Further, (c) the porous body and (e) the porous body of the moisture donor are preferably diatomaceous earth, and (d) an oxygen scavenger in which the alkaline earth metal hydroxide is slaked lime.

  Since this oxygen scavenger is not substantially involved in the change in carbon dioxide concentration, it can be stored stably for a long period of time even for foods, pharmaceuticals and other items that require storage under a specific carbon dioxide concentration. It became.

  The proportion of each component of the oxygen scavenger in the present invention is such that (a) 100 parts by weight of an unsaturated fatty acid compound or a chain hydrocarbon polymer having an unsaturated group (hereinafter referred to as an oxidation reactant) is (b) a catalyst. 0.01 to 0.5 parts by weight, preferably 0.01 to 0.1 parts by weight, (c) 50 to 300 parts by weight of porous material, preferably 100 to 250 parts by weight, and (d) 0.3 to 10 parts by weight of alkaline earth metal hydroxide. Parts by weight, preferably 0.5 to 7 parts by weight, (e) 30 to 100 parts by weight of water donor, preferably 50 to 80 parts by weight, (f) 10 to 100 parts by weight of deodorant, preferably 10 to 80 parts by weight Part. The usage amount of each component is optimized according to the initial oxygen amount during hermetic packaging and the oxygen permeation amount of the packaging material.

    (b) When the amount of the catalyst is small, the oxygen absorption performance is lowered. When the amount is large, the oxygen absorption rate is excessively increased, and oxygen is absorbed when handled in the air, so that the oxygen absorption performance is lowered. (e) When the porous body is small, (a) the oxygen-reactive substance cannot be impregnated, and the oxygen absorption performance is lowered. (d) When the alkaline earth metal hydroxide is low, (a) carbon dioxide gas generated by the oxidation reaction of the oxidation reactant cannot be absorbed, and the carbon dioxide concentration in the container under atmospheric composition When the amount of carbon dioxide increases, carbon dioxide is excessively absorbed, so that the concentration of carbon dioxide in the container decreases. (e) When the moisture donor is small, (d) the carbon dioxide absorption performance of the alkaline earth metal hydroxide decreases, and when it is large, the volume of the oxygen scavenger increases and the cost increases. (f) When there are few deodorizers, odorous gas such as carboxylic acid produced as a by-product in the oxygen absorption reaction cannot be absorbed and the odor becomes strong, and when there are many deodorizers, the amount of carbon dioxide absorption increases and the concentration of carbon dioxide in the container decreases. To do.

  The oxidation reaction material of the oxygen scavenger in the present invention is (a) an unsaturated fatty acid compound or a chain hydrocarbon polymer having an unsaturated group. These are not necessarily a single substance, and may be a mixture of two or more. Moreover, these may have a substituent.

  As unsaturated fatty acid compounds, fatty acids obtained from linoleic acid, linolenic acid, arachidonic acid, parinaric acid, dimer acid, vegetable oil, animal oil, that is, linseed oil fatty acid, soybean oil fatty acid, tung oil fatty acid, coconut oil fatty acid, sesame oil fatty acid, cottonseed oil fatty acid Rapeseed oil fatty acid, tall oil fatty acid, and oils and metal salts containing these esters can be used.

  As a chain hydrocarbon polymer having an unsaturated group, liquid butadiene oligomer, liquid isoprene oligomer, squalene, liquid acetylene oligomer, liquid pentadiene oligomer, liquid oligoester acrylate, liquid butene oligomer, liquid BR, liquid SBR, liquid NBR, Liquid chloroprene oligomer, liquid sulfide oligomer, liquid isobutylene oligomer, liquid butyl rubber, liquid cyclopentadiene petroleum resin, liquid oligostyrene, liquid hydroxy polyolefin oligomer, liquid alkyd resin, liquid unsaturated polyester resin, natural rubber, etc. Polymers can be used.

  As the catalyst (b) for promoting the oxidation reaction of the oxidation reactant in the present invention, at least one selected from Cu, Fe, Co, Ni, Cr, Mn, Pb, Zn and a compound group thereof can be used. For example, inorganic salts such as sulfates, chloride salts, nitrates, fatty acid salts such as linseed oil, soybean oil, rapeseed oil, tall oil fatty acids, organic salts such as naphthenates, octylates, rosinates, metal salts of acetylacetone, Alkyl metal compounds and the like can be used. Among these Cu, Fe, Co, Ni, Cr, Mn, Pb, Zn, and compounds thereof, Fe, Co, Mn, and Zn salts are preferable from the viewpoint of oxidation reaction promoting performance and safety.

In the present invention, (a) the unsaturated fatty acid compound or the chain hydrocarbon polymer having an unsaturated group and (b) the catalyst are preferably used by impregnating (c) the porous body.
(c) When a material with a relatively large amount of carbon dioxide adsorption / desorption, such as natural zeolite, is used as the porous body, the carbon dioxide concentration in the container is stable because the carbon dioxide is physically adsorbed / desorbed due to temperature changes. do not do. On the other hand, in the case of a porous body that does not adsorb or desorb carbon dioxide gas or has very little, there is no change in the carbon dioxide gas concentration in the container due to temperature change, and oxygen is not dependent on the carbon dioxide gas concentration in the container. Could be absorbed.

  In the present invention, white carbon, calcium silicate, colloidal silica, vermiculite, diatomaceous earth, or the like can be used as the porous body that does not absorb and desorb carbon dioxide gas. Among these, diatomaceous earth is preferable because it is inexpensive and has a high impregnation rate of the oxidation reaction substance.

The (a) unsaturated fatty acid compound or the chain hydrocarbon polymer having an unsaturated group used in the present invention generates a little carbon dioxide with oxygen absorption. For this reason, (d) carbon dioxide generated slightly by the alkaline earth metal hydroxide is absorbed.
As substances that absorb carbon dioxide, generally known are synthetic zeolites such as quick lime, slaked lime, iron, activated carbon and molecular sieves, and natural zeolites such as mordenite and erionite. Although the oxygen concentration and the carbon dioxide concentration in the sealed container vary depending on the object, the carbon dioxide absorbing component needs to absorb a certain amount of carbon dioxide gas without depending on the carbon dioxide concentration in the container. As a result, a substance of a physical adsorption system such as zeolite whose carbon dioxide absorption depends on the concentration of carbon dioxide is not suitable for the present invention, and an alkaline earth metal hydroxide that absorbs carbon dioxide by a chemical reaction is used. Among these, slaked lime having a high carbon dioxide absorption rate is preferable.

  However, (d) Alkaline earth metal hydroxides need water to absorb carbon dioxide, and water with a relative humidity of 70% or more is necessary when replenishing moisture from the atmosphere. confirmed. Therefore, as a result of investigating a method for absorbing a certain amount of carbon dioxide gas without depending on the water activity of the article to be applied and the relative humidity in the atmosphere, (e) mixing a water donating agent such as a porous body impregnated with water Thus, a method that does not depend on the applied article was found.

  As the porous body in the case of using a porous body in which water is retained (impregnated) as the (e) moisture donor of the present invention, the porous body does not physically adsorb carbon dioxide, and is a preferred embodiment described above (a) The same porous material (c) used for impregnation with the oxidation reaction product is preferred. It can be easily packaged by a machine by aligning the particle diameters of the oxygen absorbent and the moisture donor and mixing them uniformly.

  (E) In the case of a moisture donor, the ratio of each component is (d) 100 to 100 parts by weight of an alkaline earth metal hydroxide, while the porous body is 600 to 6000 parts by weight of water. Is 300 to 4000 parts by weight.

  As the (f) deodorant in the present invention, it can be selected from activated carbon, activated carbon fiber, molecular sea carbon, bone charcoal, etc., and 5 ml of carbon dioxide absorption at 25 ° C. and 1/10 atmospheric pressure (0.1 atm). / g or less is preferable. When the carbon dioxide absorption is greater than 5 ml / g, the carbon dioxide absorption increases and the carbon dioxide concentration in the container decreases.

  The oxygen absorber used in the present invention can be filled and packaged with a breathable packaging material and used as an oxygen absorber package. The breathable packaging material used at that time is not particularly limited as long as it is a packaging material used for an oxygen scavenger, but quickly absorbs oxygen and absorbs carbon dioxide gas generated accordingly, In order to keep the gas composition constant, a packaging material having as high a breathability as possible is preferable.

  The container in which the present invention is used is made of a packaging material having oxygen barrier properties. Packaging materials include films laminated with metal foils such as aluminum foil, films laminated with films deposited with silicon oxide, aluminum oxide, etc., gas barrier films such as films laminated with barrier nylon films and K-coated nylon films, and HDPE , PP, PET, polyvinyl alcohol, ethylene vinyl alcohol copolymer, ethylene vinyl acetate copolymer, vinylidene chloride polymer, K coat resin, silicon oxide vapor deposition resin, aluminum oxide vapor deposition resin or aluminum vapor deposition resin Can be used.

  Specific examples of the present invention are shown below, and the present invention will be described in more detail. In addition, this invention is not limited to an Example.

Example 1
A liquid mixture consisting of 50 g of paulownia oil (unsaturated fatty acid content 95 wt%) and 1.25 g of tall oil fatty acid Mn (Mn concentration 4%) is added to 100 g of diatomaceous earth, stirred and mixed, and 37 g of granular activated carbon is added and mixed to make it fluid. A certain granular material A was obtained.
Next, the fluid granular material B obtained by impregnating 60 g of water with 100 g of the same kind of diatomaceous earth as described above was obtained.
Finally, 100 g of powder A was mixed uniformly with 15 g of powder B and 1.8 g of fine powder of slaked lime to obtain powder C.

Filled a small bag (outer dimension: 25mm x 55mm, inner dimension 25mm x 38mm) with a polyethylene film laminated with 1.9g of powder C on the inner surface of the paper, heat-sealed the hole, and oxygen scavenger packaging Got the body.
This oxygen scavenger package is enclosed in an aluminum foil laminate bag (120 mm x 150 mm) with 280 ml of mixed gas adjusted to 10% carbon dioxide and 18.5% oxygen, and the opening is heat sealed and sealed, and a packaging bag for storage Got. This packaging bag was stored in a 25 ° C. environment.

Table 1 shows the results of measuring the gas concentration in the storage packaging bag by gas chromatography at the start of storage (initial) and after 5 days.
After 5 days, it was confirmed that the substance was in a substantially oxygen-free state (the substance is in a state where the oxygen concentration is 0.1% or less). The carbon dioxide absorption is shown in Table 1.

Examples 2 and 3
Example 1 was the same as Example 1 except that it was stored in a 25 ° C. environment at 5 ° C. and a 40 ° C. environment.

Comparative Examples 1, 2, 3
A storage packaging bag was obtained in the same manner as in Example 1 except that the diatomaceous earth used in the granular material of Example 1 was changed to natural zeolite. Comparative Examples 2 and 3 were the same as Example 1 except that the samples were stored in a 25 ° C. environment in the same manner as in Examples 2 and 3 except that they were stored in a 5 ° C. and 40 ° C. environment.

  After 5 days, the gas concentration in the storage packaging is as shown in Table 1. The carbon dioxide absorption of this product was 3.1 to 4.2 ml, but the comparative product absorbed 15.8 to 17.8 ml and a large amount of carbon dioxide. Was.

[Table 1]
Example Comparative Example
1 2 3 1 2 3
Storage temperature (℃) 25 5 40 25 5 40
Initial gas mixture volume (ml) 280 ← ← ← ← ←
Initial oxygen (%) 18.90 18.45. 18.04 18.99 18.71 17.99
Carbon dioxide (%) 9.74 10.50 9.21 10.26 10.11 10.91
Oxygen (ml) 52.9 51.7 50.5 53.2 52.4 50.4
Carbon dioxide (ml) 27.3 29.4 25.8 28.7 28.3 30.5
After 5 days Oxygen concentration (%) 0.07 0.03 0.03 0.07 0.02 0.05
Carbon dioxide concentration (%) 10.67 11.22 10.00 5.68 5.01 6.90
Oxygen absorption (ml) 52.8 51.6 50.4 53.0 52.3 50.3
Carbon dioxide absorption (ml) 3.4 4.2 3.1 16.8 17.8 15.8

Examples 4 and 5
Using the same storage packaging bag as in Example 1, in Example 4, the gas concentration in the storage packaging bag was measured at the start of storage (initial) and after 2 days, and in Example 5 at the start of storage (initial) and after 6 days. It was measured by gas chromatography. The results are shown in Table 2.

Comparative Examples 4 and 5
As in Examples 4 and 5, except that the powder C1.9g used in Examples 4 and 5 was changed to a mixture of 0.8g of iron powder and 0.6g of water donating agent, which is equivalent to the amount of oxygen absorbed. did. The results are shown in Table 2.

The product of the present invention was substantially oxygen-free on the second day, but oxygen remained in the comparative product (substantially oxygen-free means an oxygen concentration of 0.1% or less).
In addition, the carbon dioxide gas concentration of the present invention was stable at about 5 ml on both the second and sixth days, but the comparative product absorbs a large amount of carbon dioxide, 26-32 ml, and the amount of carbon dioxide gas absorbed over time. It was confirmed that the change was made.

[Table 2]
Example Comparative Example
4 5 4 5
Storage temperature (℃) 25 ← ← ←
Initial gas mixture (ml) 280 ← ← ←
Initial oxygen (%) 18.07 18.07 18.06 18.06
Carbon dioxide (%) 11.67 11.67 11.70 11.70
Oxygen (ml) 50.6 50.6 50.6 50.6
Carbon dioxide (ml) 32.7 32.7 32.8 32.8
After saving (number of days to save) 2 days 6 days 2 days 6 days
Oxygen concentration (%) 0.04 0.04 5.22 0.03
Carbon dioxide concentration (%) 12.43 12.43 3.05 0.25
Oxygen absorption (ml) 50.5 50.5 39.4 50.5
Carbon dioxide absorption (ml) 4.8 4.8 26.2 32.3

Example 6
The same as Example 1 except that the mixed gas 280 ml used for the oxygen scavenger package was changed to 250 ml of air. The results are shown in Table 3.

Comparative Example 6
Example 6 was the same as Example 6 except that the powder granules obtained by removing 0.25 g of the water donor powder granules B from the powder granules C 1.9 g used in Example 6 were changed to 1.65 g.

  After 5 days, the product of the present invention had a carbon dioxide absorption of 0.1 ml and a carbon dioxide concentration of 0.0%, but the amount of carbon dioxide generation in Comparative Example 6 was 1.9 ml and the carbon dioxide concentration was 0.9%, and there was no water donor. Was confirmed to generate carbon dioxide under atmospheric composition.

[Table 3]
Example Comparative Example
6 6
Storage temperature (℃) 25 25
Initial gas mixture volume (ml) 250 ←
Initial oxygen (%) 20.90 20.09
Carbon dioxide (%) 0.03 0.03
Oxygen (ml) 52.3 53.2
Carbon dioxide (ml) 0.1 0.1
After 5 days Oxygen concentration (%) 0.02 0.03
Carbon dioxide concentration (%) 0.0 0.9
Oxygen absorption (ml) 52.2 52.2
Carbon dioxide absorption (ml) 0.1 -1.9

  According to the present invention, when storing an article in an atmosphere coexisting with oxygen and carbon dioxide, oxygen can be absorbed without affecting the concentration of carbon dioxide and the article can be stored in an oxygen-free state. As a result, foods, health foods, pharmaceuticals, etc. can be stored for a long time in a deoxygenated state under a specific carbon dioxide concentration.

Claims (5)

(a) an unsaturated fatty acid compound or a chain hydrocarbon polymer having an unsaturated group and (b) a catalyst impregnated in (c) a porous body, (d) an alkaline earth metal hydroxide, (e) It consists of a mixture of a moisture donor and (f) a deodorant, and (b) catalyst is 0.01 to 0.5 to 100 parts by weight of (a) unsaturated fatty acid compound or chain hydrocarbon polymer having an unsaturated group. Parts by weight, (c) 50-300 parts by weight of porous material, (d) 0.3-10 parts by weight of alkaline earth metal hydroxide, (e) 30-100 parts by weight of moisture donor, (f) deodorizing An oxygen scavenger in which the agent is 10 to 100 parts by weight. The oxygen scavenger according to claim 1, wherein the amount of carbon dioxide generated under atmospheric composition is 1 ml / g or less, and the amount of carbon dioxide absorbed under a carbon dioxide concentration of 10% is 5 ml / g or less. 2. The oxygen scavenger according to claim 1, wherein (e) the water donor is a porous body impregnated with water. 4. The oxygen scavenger according to claim 1 or 3, wherein the porous material is diatomaceous earth. 2. The oxygen absorber according to claim 1, wherein the alkaline earth metal hydroxide is slaked lime.