JP2017177013A - Deoxidizer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic deoxidizer composition having a large amount of oxygen absorption per unit volume.SOLUTION: A deoxidizer composition comprises a granule that comprises an α layer comprising a glycerol, a metal salt, water and a porous carrier and a β layer comprising an alkaline material, where the granule forms a layered structure in the order of α layer and β layer from the inside of the granule to the outside.SELECTED DRAWING: None

Description

  The present invention relates to an oxygen scavenger composition.

  For example, sachet-shaped oxygen absorbers used in the past are mainly glycerin, ascorbic acid, ersorbic acid, gallic acid using iron-based oxygen absorbers and organic substances that chemically react with oxygen. It can be broadly divided into organic oxygen scavengers using acids and the like. Since organic oxygen absorbers do not react with metal detectors, they are mainly used for foods that cannot be used with iron oxygen absorbers such as hams and sausages that use metal detectors to inspect metal foreign objects in foods. It is done.

  Organic substances used for organic oxygen scavengers often react chemically with oxygen in an alkaline aqueous solution. For this reason, organic oxygen scavengers are usually used in the form of powders obtained by impregnating a porous carrier (porous carrier) such as activated carbon with an alkaline aqueous solution in which an organic substance that reacts with oxygen is dissolved in water together with an alkaline substance. It is done.

  On the other hand, since iron-based oxygen absorbers use iron powder without using a carrier, the ratio of iron is large as a substance that chemically reacts with oxygen in the oxygen absorber. However, since the organic oxygen scavenger uses a carrier, the proportion of organic substances that chemically react with oxygen in the oxygen scavenger is lower than the proportion of iron in the iron oxygen scavenger. . In addition, since the porous carrier usually has a low bulk density, the oxygen absorption amount per volume of the organic oxygen scavenger is about a fraction of that of the iron oxygen absorber. Therefore, in order to make the performance of the organic oxygen scavenger comparable to that of the iron oxygen scavenger, it is necessary to increase the absolute value of the organic oxygen scavenger volume. The volume of the oxygen agent becomes large. Therefore, methods for increasing the amount of oxygen absorbed per volume of the organic oxygen scavenger have been studied so far.

  For example, Patent Document 1 discloses an oxygen scavenger composition comprising a granular material that is pressure-molded containing an oxygen-absorbing substance, water, and a swelling agent. The method proposed in Patent Document 1 is a method of increasing the amount of oxygen absorbed per volume of the oxygen scavenger composition by reducing the volume of the oxygen scavenger composition by pressure molding.

International Publication No. 2007/046449

  However, the oxygen scavenger composition as described in Patent Document 1 impairs oxygen permeability when pressure-molded. In order to ensure air permeability, a swelling agent that absorbs moisture and swells may be included in the oxygen absorber composition, but the volume of the oxygen absorber composition increases by the volume of the swelling agent. In addition, the volume of the oxygen scavenger composition when the sachet is made becomes large.

  Then, an object of this invention is to provide the organic type oxygen absorber composition with a high oxygen absorption amount per unit volume.

  As a result of studies conducted by the present inventors to solve the above-described problems of the prior art, a powder having an α layer containing glycerol, a metal salt, water, and a porous carrier, and a β layer containing an alkaline substance. The oxygen scavenger composition in which the granular material forms a layer structure in the order of α layer and β layer from the inside to the outside of the granular material has a high oxygen absorption per unit volume. As a result, they have reached the present invention. That is, the present invention is as follows.

[1]
Including an α layer containing a glycerin, a metal salt, water, and a porous carrier, and a β layer containing an alkaline substance,
The granular material forms a layer structure in the order of the α layer and the β layer from the inside to the outside of the granular material,
Oxygen scavenger composition.
[2]
The mass ratio of the total amount of the α layer to the total amount of the β layer is 1.0 or more and 3.0 or less.
The oxygen scavenger composition according to [1].
[3]
The α layer contains 20% by mass or more and 50% by mass or less of the glycerin with respect to the total amount of the α layer, and contains 10% by mass or more and 30% by mass or less of the porous carrier.
The oxygen scavenger composition according to [1] or [2].

  According to the oxygen scavenger composition of the present invention, the oxygen absorption amount per unit volume can be increased.

FIG. 3 is a graph showing the particle size distribution of the oxygen scavenger composition of Example 1. 2 is a cross-sectional photograph of the oxygen scavenger composition of Example 1.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.

[Oxygen scavenger composition]
The oxygen scavenger composition of the present embodiment includes an α layer (hereinafter also simply referred to as “α layer”) containing glycerins, a metal salt, water, and a porous carrier, an alkaline substance, and optionally porous. And a granular material having a β layer (hereinafter also simply referred to as a “β layer”) containing a functional carrier. Moreover, the said granular material forms the layer structure in order of (alpha) layer and (beta) layer toward the outer side from this granular material. The oxygen scavenger composition of this embodiment has a high oxygen absorption per unit volume. This factor is inferred as follows (however, the factor is not limited to this). The oxygen scavenger composition of the present embodiment is mainly compared with the conventional granule containing glycerin because the granule forms a layer structure in the order of α layer containing glycerin and β layer. Thus, the bulk density is increased and the amount of oxygen absorbed per unit volume is increased due to suppression of variations in the shape and average particle diameter of the powder. In addition, the oxygen scavenger composition of the present embodiment can increase the oxygen absorption amount without requiring pressure molding or substantially containing an expanding agent, and further improves fluidity. Excellent. Here, “substantially contains” means that the content of the swelling agent is 0.1% by mass or more with respect to the total amount (100% by mass) of the oxygen scavenger composition.

  Here, “a layer structure in the order of α layer and β layer” means a structure in which an α layer is formed inside the void of the β layer. Therefore, not only the structure in which the surface of the α layer is covered with the β layer, but also a structure in which the α layer is filled in part of the voids of the three-dimensional network structure of the β layer is included. Therefore, “a layer structure in the order of α layer and β layer” in this specification includes a granular material in which the boundary between the α layer and the β layer is not exactly clear. Moreover, the granular material of this embodiment may further have layers other than the α layer and the β layer. Furthermore, the oxygen scavenger composition of the present embodiment only needs to contain a powder body that forms “a layer structure in the order of α layer and β layer”, and “a layer structure in the order of α layer and β layer”. It may further contain a powder or granule that does not form. Needless to say, the oxygen scavenger composition of the present embodiment may be an oxygen scavenger composition composed only of powder particles forming a “layer structure in the order of α layer and β layer”.

  Although the shape of the granular material of this embodiment is not specifically limited, For example, a spherical shape, an ellipse shape, and a cylinder are mentioned, A spherical shape is preferable from the tendency which is excellent in a filling property, and a bulk density becomes higher.

  The average particle diameter of the oxygen scavenger composition is preferably 10 μm or more and 5000 μm or less, and more preferably 100 μm or more and 2000 μm or less from the viewpoint of maintaining the fluidity of the oxygen scavenger composition when filling a pouch with a packaging machine. is there. In order to obtain an oxygen scavenger composition having an average particle diameter in the above range, for example, sieving may be performed using a sieve having openings of 100 μm and 2000 μm. The average particle size can be measured by, for example, a commercially available laser diffraction / scattering particle size distribution measuring device (LA-960 manufactured by Horiba, Ltd.).

  The mass ratio of the total mass of the α layer to the total mass of the β layer (α layer / β layer) is preferably 0.5 or more and 5.0 or less, and in order to increase the oxygen absorption amount per unit volume, More preferably, it is 1.0 or more and 3.0 or less. When the mass ratio of the α layer / β layer is within such a range, the amount of the alkaline substance contained in the β layer in contact with the glycerins contained in the α layer can be ensured to be a predetermined amount or more. The oxygen absorption amount tends to be further improved due to the fact that the action with the substance is not inhibited.

The bulk density of the oxygen scavenger composition is not particularly limited, but is preferably 0.5 g / cm ³ or more, more preferably 0.6 g / cm ³ or more, and even more preferably 0.7 g / cm ³ or more. It is. When the bulk density is 0.5 g / cm ³ or more, the oxygen absorption amount per volume tends to be more excellent. In order to obtain an oxygen scavenger composition having a bulk density in the above range, for example, a target bulk density may be selected using a specific gravity classifier (such as a high speed aspirator manufactured by Tokyo Flour Mill Co., Ltd.). The bulk density is measured by the method described in Examples described later.

[Α layer]
The α layer of this embodiment is a layer containing glycerins, metal salts, water, and a porous carrier. Although there is no particular limitation in order to obtain a granular material having a layer structure in the order of α layer and β layer from the inside to the outside, for example, for a droplet made of a raw material of the α layer having viscosity Then, it is only necessary to attach a granular material made of the raw material of the β layer to the surface of the droplet. As a result, a granular material having an α layer and a β layer outside the α layer is formed.

<Glycerins>
Glycerols of this embodiment, glycerin skeleton _{(-O-CH 2 CH (O} -) - CH 2 -O-) means a compound having a. As the glycerins, those generally available such as glycerin can be used without particular limitation, and glycerin is preferable. Glycerins can be used alone or in combination of two or more as required.

  The α layer preferably contains 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 50% by mass or less of glycerin with respect to the total amount (100% by mass) of the α layer. When the content of glycerin is in such a range, the viscosity and fluidity of the raw material of the α layer are maintained, and the oxygen absorption amount of the obtained oxygen scavenger composition tends to increase.

<Metal salt>
The metal salt of this embodiment has a function of catalyzing an oxidation reaction of glycerol.

  The metal salt is not particularly limited, and examples thereof include transition metal halides, sulfates, nitrates, phosphates, carbonates, oxides, hydroxides, organic acid salts, other double salts, and chelate compounds. Can be mentioned. The type of the transition metal is not particularly limited, but is preferably iron, cobalt, nickel, copper, zinc, and manganese. Among these, iron, copper, and manganese are more preferable, and manganese is more preferable because of its high reaction rate.

  Preferred specific examples of the metal salt include ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, cuprous chloride, cupric chloride, cupric sulfate, cupric hydroxide, Examples include copper citrate, copper tartrate, manganese chloride, manganese bromide, manganese acetate, and manganese hydroxide, manganese chloride is more preferable, and manganese chloride tetrahydrate is more preferable.

  The metal salt mentioned above can be used individually by 1 type or in combination of 2 or more types as needed. Further, these metal salts can be easily obtained as commercial products.

  The content of the metal salt is preferably 1.0 part by mass or more and 30 parts by mass or less, and more preferably 1.0 part by mass or more and 5 parts by mass or less with respect to the mass of glycerol (100 parts by mass) contained in the α layer. 0.0 parts by mass or less. When the content of the metal salt is in such a range, the oxidation reaction of glycerol tends to be promoted.

<Porous carrier>
The porous carrier of the present embodiment is not particularly limited as long as it is a carrier having a porous shape. Here, the porous means a state having a large number of pores on the surface and inside that can be confirmed by an electron microscope.

The porous carrier is preferably a silica. Silicas mean silicon dioxide (SiO ₂ ) as a main component. By using silicas, the viscosity of the raw material of the α layer can be maintained and the fluidity of the α layer can be controlled.

  Although it does not specifically limit as silicas used for this embodiment, For example, hydrophobic silica, wet silica, dry silica, silica gel, diatomaceous earth, acid clay, activated clay, perlite, kaolin, talc, and bentonite are mentioned.

  The porous carrier mentioned above can be used alone or in combination of two or more as required. Moreover, these porous carriers can be easily obtained as commercial products.

  The α layer preferably contains a porous carrier in an amount of from 5.0% by mass to 50% by mass, and more preferably from 10% by mass to 30% by mass with respect to the total amount (100% by mass) of the α layer. When the content of the porous carrier is in such a range, the viscosity and fluidity of the raw material of the α layer tend to be ensured.

<Water>
The water of this embodiment can use well-known water, such as a pure water, without limitation.

  The mass ratio (mass ratio of glycerol, metal salt, and water: silica) of the total mass of glycerols, metal salts, and water contained in the α layer to the mass of silicas is preferably 1: 9 to It is the range of 1: 3, More preferably, it is the range of 1: 7 to 1: 4. When the mass ratio is within such a range, the viscosity and fluidity of the raw material of the α layer are appropriately maintained. It is easy to form, and the β layer of the granular material is easily formed outside the α layer, and the effects of the present invention tend to be expressed more reliably.

[Β layer]
The β layer is a layer containing an alkaline substance and, if necessary, a porous carrier. The β layer is formed outside the α layer.

<Alkaline substances>
The alkaline substance of the present embodiment is not particularly limited as long as it is a substance that acts with water or dissolves in water and exhibits alkalinity.

  As the alkaline substance, alkali metal and alkaline earth metal hydroxides, carbonates, hydrogen carbonates, tertiary phosphates, and secondary phosphates are preferred for reasons of safety in oral toxicity. And alkaline earth metal hydroxides are more preferred. Of these, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide are more preferable.

  The alkaline substance mentioned above can be used individually by 1 type or in combination of 2 or more types as needed. In addition, these alkaline substances can be easily obtained as commercial products.

  The β layer contains an alkaline substance with respect to the total mass (100% by mass) of the β layer, preferably 90% by mass or more and 100% by mass or less, and more preferably 95 from the viewpoint of increasing the contact area with the glycerol. Including from 100% by mass to 100% by mass.

<Porous carrier>
The kind of the porous carrier of this embodiment can be the same as the porous carrier used for the α layer described above, and is preferably silica.

  The β layer contains a porous carrier, preferably 0% by mass or more and 10% by mass or less, with respect to the total mass (100% by mass) of the β layer. 1 mass% or more and 5.0 mass% or less are included. By containing a porous carrier, the fluidity of the powder tends to be improved, and when the content of the porous carrier is 10% by mass or less, the porous carrier is removed from the powder. It tends to suppress the generation of dust.

[Method for producing oxygen scavenger composition]
An example of a method for producing the oxygen scavenger composition of the present embodiment is shown below. First, the above metal salt is dissolved in water to prepare an aqueous metal salt solution. The prepared metal salt aqueous solution, glycerin, and porous carrier are mixed to prepare a liquid that is a raw material for the α layer. Next, the raw material for the β layer of the alkaline substance and silica is put into the mixing apparatus, and the liquid that is the raw material for the α layer is dropped while mixing on the raw material for the β layer of the alkaline substance (and the porous carrier), A granular material having a β layer formed outside the α layer is prepared. Here, the dropping time of the liquid which is the raw material of the α layer is preferably about several seconds to several minutes. Although it does not specifically limit as a mixing apparatus to be used, For example, a vertical granulator (made by Paulec Co., Ltd.), a high speed mixer (made by Earth Technica Co., Ltd.), and an Akira machine company make granulator are mentioned.

  Hereinafter, the present embodiment will be described in more detail using examples and comparative examples. However, the present embodiment can be appropriately changed as long as the effects of the present invention are exhibited. In the examples and comparative examples, “parts” and “%” mean mass parts and mass% unless otherwise specified.

[Average particle size]
The average particle size of the oxygen scavenger composition was measured with a laser diffraction / scattering particle size distribution measuring device (LA-960 manufactured by Horiba, Ltd.). 1 is a graph showing the particle size distribution of the oxygen scavenger composition of Example 1. FIG.

[Cross-section photo]
The cross-sectional photograph of the oxygen scavenger composition was cut with a cutter to produce a cross-section and taken with a digital microscope (VHX-2000 manufactured by Keyence Corporation). 2 is a cross-sectional photograph of the oxygen scavenger composition of Example 1. FIG.

Example 1
Manganese chloride tetrahydrate 56 parts (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 643 parts of water to obtain an aqueous manganese chloride solution. 699 parts of the obtained aqueous manganese chloride solution, 2087 parts of 85% glycerin (manufactured by Wako Pure Chemical Industries, Ltd.) and 900 parts of silica (Carplex # made by DSL. Japan) are mixed, and the viscosity which is the raw material of the α layer is mixed A liquid was obtained.

  Next, 1900 parts of calcium hydroxide (manufactured by Chichibu Industry Co., Ltd., powdered slaked lime) was charged into a high speed mixer (SPG20L manufactured by Earth Technica Co., Ltd.). Then, the liquid which is the raw material of the obtained α layer was put on the powdered slaked lime and mixed at 200 rpm. Further, 27 parts of hydrophobic silica (SS-30P manufactured by Tosoh Silica Co., Ltd.) was added, mixed at 60 rpm, and an oxygen scavenger composition comprising spherical powder particles whose outer layer was covered with the β layer. Got. The average particle diameter of the obtained oxygen scavenger composition was 1.0 mm (FIG. 1). Moreover, the obtained granular material had a structure which has (alpha) layer in the center part, and has (beta) layer in the outer side (FIG. 2).

[Bulk density]
The bulk density (g / cm ³ ) of the obtained oxygen scavenger composition was measured according to JIS Z 8901. The obtained results are shown in Table 1.

[Oxygen absorption]
The oxygen absorption amount of the obtained oxygen scavenger composition was measured as follows. 1.0 g of the obtained oxygen scavenger composition was put into a gas barrier bag (size: 250 × 400 mm) of a nylon / polyethylene laminate film, and sealed with 3000 mL of air. After holding this bag at 25 ° C. for 7 days, the oxygen concentration in the bag was measured, and the oxygen absorption amount (mL) was calculated. The obtained oxygen absorption amount was divided by the volume (mL) of the oxygen scavenger composition to calculate the oxygen absorption amount (mL / mL) per unit volume. The obtained results are shown in Table 1.

[Liquidity]
The fluidity (seconds) of the obtained oxygen scavenger composition was measured by putting 100 ml of the oxygen scavenger composition into the funnel used in JIS Z 8901 and measuring the time until the whole amount dropped from the funnel. The obtained results are shown in Table 1.

(Comparative Example 1)
An oxygen scavenger composition was produced in the same manner as in Example 1 except that 900 parts of silica used in Example 1 were not used. The obtained oxygen scavenger composition does not include a granular material having a structure in which an α layer and a β layer are formed on the outside of the α layer. It contained a granular material infiltrated with the liquid as a raw material and not excellent in fluidity. The oxygen absorbing amount, bulk density, and fluidity of the obtained oxygen scavenger composition were measured in the same manner as in Example 1. The obtained results are shown in Table 1.

  As is clear from Table 1, the oxygen scavenger composition of Example 1 has a higher bulk density and an oxygen absorption amount per unit volume (mL / mL) than the oxygen scavenger composition of Comparative Example 1. It was at least confirmed to be high and excellent in fluidity.

(Examples 2 to 4)
From the mass of 56 parts of manganese chloride tetrahydrate used in the α layer, 2087 parts of 85% glycerin, 643 parts of water and 900 parts of silica and 1900 parts of calcium hydroxide used in the β layer in Example 1, In Example 2, 1330 parts of calcium hydroxide, in Example 3, 56 parts of manganese chloride tetrahydrate and 2505 parts of 85% glycerin used in the 85% glycerin α layer, in Example 4, 52 parts of manganese chloride tetrahydrate, 85% An oxygen scavenger composition was produced in the same manner as in Example 1 except that the mass was changed to 1927 parts of glycerin, 594 parts of water, and 1115 parts of silica. Moreover, the bulk density and oxygen absorption amount of the obtained oxygen scavenger composition were measured in the same manner as in Example 1. The obtained results are shown in Table 2.

  As is clear from Tables 2 and 1, the oxygen scavenger compositions of Examples 2 to 4 each have a higher bulk density than the oxygen scavenger composition of Comparative Example 1, and oxygen absorption per unit volume. At least a high amount (mL / mL) was confirmed.

  If the oxygen scavenger composition according to the present invention is used, the oxygen scavenger composition using glycerin that has high oxygen absorption per unit volume without being pressure-molded or substantially containing a swelling agent. Can manufacture things. Moreover, if the oxygen scavenger composition is used, an oxygen scavenger having the same performance or more can be produced with a smaller sachet than a conventional oxygen scavenger composition.

Claims (3)

Including an α layer containing a glycerin, a metal salt, water, and a porous carrier, and a β layer containing an alkaline substance,
The granular material forms a layer structure in the order of the α layer and the β layer from the inside to the outside of the granular material,
Oxygen scavenger composition. The mass ratio of the total amount of the α layer to the total amount of the β layer is 1.0 or more and 3.0 or less.
The oxygen scavenger composition according to claim 1. The α layer contains 20% by mass or more and 50% by mass or less of the glycerin with respect to the total amount of the α layer, and contains 10% by mass or more and 30% by mass or less of the porous carrier.
The oxygen scavenger composition according to claim 1 or 2.