JP2022185384A - Deoxidant with antibacterial - Google Patents

Abstract

To provide a deoxidant that imparts a space antibacterial to a deoxidant, dose not damage property of an article contacting with flavor of a food product, and heightens storability of a content, in particular, a deoxidant that maintains the antibacterial property not only in a distribution process but also after a commercial product is opened in a home of a consumer.SOLUTION: A deoxidant that is powder containing a plurality of composite particles containing granules which are antioxidant imparted with antibacterial properties and contain an antibacterial agent selected from the group consisting of an oxygen-absorbing composition and an aldehyde compound having a molecular weight of 200 or less, and hydrophilic inorganic particles formed by adhering by forming a layer of a thickness of 1 mm or less on a surface of the granules, the oxygen-absorbing composition contains a liquid agent containing an oxygen absorbing substance, an alkali compound, and a transition metal compound.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an oxygen absorber having antibacterial properties.

It is known to use oxygen scavengers to prevent oxidation of the contents. In particular, for long-term preservation of food, an oxygen scavenger is often enclosed in food packaging containers. Oxygen scavengers prevent the growth of aerobic bacteria and fungi in packaging containers during the distribution process and suppress the deterioration of food, acting as so-called antibacterial and antifungal effects.

In a food packaging container, after the consumer has opened the packaging, oxygen enters the container and the food deteriorates. Therefore, in order to maintain the antibacterial and antifungal properties after opening, it is effective to use a combination of an oxygen absorber and an antibacterial agent.

Prior Document 1 reports an ethanol vapor-dispersing oxygen absorber in which an ethanol vapor-dispersing function is added to the oxygen absorber. However, there is a risk that the flavor of the food will be spoiled, for example, the odor peculiar to ethanol will be imparted to the food, or the odor peculiar to ethanol will come out when the package is opened.

Japanese Patent No. 6420619

A main object of the present invention is to provide a granular oxygen absorber which is endowed with antibacterial and bactericidal properties and which enhances the preservability of the contents. In particular, the aim is to maintain the antibacterial properties not only during the distribution process but also after the consumer has opened the product at home.

The present invention provides an oxygen absorber obtained by mixing and granulating a plurality of components, wherein the oxygen absorber is coated with hydrophilic fine particles, the thickness of the coating layer is 1 mm or less, and the oxygen absorber is is composed of a porous support carrying an oxygen-absorbing substance, an alkaline compound, a transition metal compound, and an antibacterial agent, wherein the antibacterial agent is an aldehyde compound having a molecular weight of 200 or less.

Further, the aldehyde compound is supported by a binder.

Also, the binder is characterized by having amphipathic properties.

Also, the binder is characterized by comprising any one of polyvinylpyrrolidone, hydroxypropylcellulose, and hydroxypropylmethylcellulose.

Also, the antimicrobial agent is characterized in that it is selected from the group consisting of (E)-2-hexenal, hexanal, cinnamaldehyde, citral, and decanal.

Further, it is characterized in that the amount of the antibacterial agent added is 0.01 to 20.0% by mass to impart antibacterial properties.

Further, it is characterized in that the amount of the antibacterial agent added is 0.1 to 5.0% by mass to impart antibacterial properties.

The present invention makes it possible to maintain the antibacterial properties not only during the distribution process but also after the packaging bag is opened. By using an antibacterial agent selected from the group consisting of aldehyde compounds having a molecular weight of 200 or less, the inventors have found that even after the packaging bag is opened, these antibacterial agents provide good antibacterial properties in the packaging bag even after resealing. I found that I can get the sex.

Schematic diagram of oxygen scavenger with antibacterial property. A photograph showing the state of the medium at the end of culture.

Several embodiments of the invention are described in detail below. However, the present invention is not limited to the following embodiments.

As shown in FIG. 1, the antibacterial oxygen absorber 100 according to one embodiment includes a porous carrier, an oxygen-absorbing composition carried on the carrier, and a powder containing an antibacterial agent. and hydrophilic inorganic fine particles 20 adhering to the surface of the granules 10 . The number of composite particles contained in the oxygen absorber according to the present embodiment may be, for example, 10 or more and 10000 or less per 1 g of the oxygen absorber.

The mass of each composite particle constituting the powder of the oxygen absorber 100 may be 0.3 mg or more, or 0.5 mg or more, and may be 10.0 mg or less, or 7.0 mg or less per composite particle. There may be. Such finer composite particles tend to provide higher oxygen absorption capacity.

The support constituting the granules 10 may be porous particles capable of supporting the oxygen-absorbing composition. Usually, the oxygen-absorbing substance is supported on the carrier by impregnating the carrier with the oxygen-absorbing composition. The support is for example selected from activated carbon, zeolite particles, bentonite particles, activated alumina particles, activated clay, calcium silicate particles and diatomaceous earth.

The oxygen-absorbing composition contains a liquid formulation containing an oxygen-absorbing substance, an alkaline compound, and a transition metal compound.

The liquid agent containing the oxygen-absorbing substance may be an oxygen-absorbing substance that is liquid at room temperature (eg, 5 to 35° C.) or a solution containing a liquid or solid oxygen-absorbing substance. The oxygen-absorbing substance is the main ingredient of the oxygen-absorbing composition and is a substance that absorbs oxygen. The oxygen absorbing material may be, for example, a compound that consumes and absorbs oxygen by itself oxidizing. In this embodiment, an oxygen-absorbing substance that is liquid at room temperature or dissolved in a solvent can be used.

Such oxygen-absorbing substances are, for example, one or more compounds selected from the group consisting of glycerin, 1,2-glycol, and sugar alcohols. Specific examples of 1,2-glycols include ethylene glycol and propylene glycol. Specific examples of sugar alcohols include erythritol, arabitol, xylitol, adonitol, mannitol, and sorbitol. When the liquid agent is a solution of an oxygen absorbing substance, examples of solvents in which the oxygen absorbing substance dissolves include water; methanol, ethanol, 1-propanol, i2-propanol, 1-butanol, 2-butanol, 2-methyl-1 - lower aliphatic alcohols such as propanol, 2-methyl-2-propanol and 2-methyl-2-butanol; glycols such as ethylene glycol, propylene glycol and trimethylene glycol; and phenol. These oxygen-absorbing substances can be used singly or in combination.

The amount of the oxygen-absorbing substance is usually 80 to 200 parts by weight, and may be 100 to 180 parts by weight, per 100 parts by weight of the carrier. When the amount of the oxygen-absorbing substance is within these ranges, it tends to be easy to obtain an oxygen scavenger having an appropriate oxygen-absorbing capacity.

Oxygen absorbing materials may require water for the reaction to absorb oxygen. Therefore, even if the oxygen-absorbing substance itself is liquid at room temperature, water can be added to the liquid agent as required. The amount of water added as necessary is usually 0 to 80 parts by mass, and may be 20 to 60 parts by mass, per 100 parts by mass of the oxygen-absorbing substance. The amount of water is usually 0 to 90 parts by weight, and may be 20 to 70 parts by weight, with respect to 100 parts by weight of the carrier.

An alkaline compound is a compound that forms an alkaline aqueous solution when dissolved in water. When the oxygen-absorbing substance has a hydroxyl group, the hydroxyl group is ionized by the alkaline compound, thereby activating the oxygen absorption reaction. In the state of the oxygen-absorbing composition, part of the alkaline compound is often dissolved in the liquid agent containing the oxygen-absorbing substance.

The alkaline compound may be an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate, tertiary phosphate, or secondary phosphate. Alkaline compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, radium hydroxide, lithium carbonate, sodium carbonate, selected from the group consisting of calcium carbonate, magnesium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, lithium hydrogen carbonate, tribasic sodium phosphate, tribasic potassium phosphate, dibasic sodium phosphate, and dibasic potassium phosphate It may be one or more compounds that are

The amount of the alkaline compound is usually 100 to 300 parts by weight, and may be 150 to 250 parts by weight, per 100 parts by weight of the carrier. When the amount of the oxygen-absorbing substance is within these ranges, it tends to be easy to obtain an oxygen scavenger having an appropriate oxygen-absorbing capacity.

A transition metal compound is a compound containing a transition metal element, and is added to promote the oxygen absorption reaction of the oxygen absorbing substance. The transition metal compound is often dissolved in a liquid agent containing an oxygen-absorbing substance in the state of the oxygen-absorbing composition. Specific examples of transition metal elements include iron, cobalt, nickel, copper, zinc, and manganese. The transition metal compound can be, for example, a transition metal halide, sulfate, nitrate, phosphate, carbonate, organic acid salt, oxide, hydroxide, or chelate compound. The transition metal compound may be a double salt containing a transition metal element. Transition metal compounds include copper(I) chloride, copper(II) chloride, copper(II) sulfate, copper(II) hydroxide, copper(I) oxide, copper(II) oxide, manganese chloride, manganese nitrate, manganese carbonate , and nickel chloride.

The amount of the transition metal compound is usually 10 to 70 parts by mass, and may be 30 to 50 parts by mass, per 100 parts by mass of the support. When the amount of the transition metal compound is within these ranges, it tends to be easy to obtain an oxygen scavenger having a suitable oxygen absorption capacity.

The oxygen-absorbing composition may further contain other substances as necessary. Other substances include, for example, catechol compounds. The amount of other substances is usually about 30 parts by mass or less with respect to 100 parts by mass of the carrier.

The antimicrobial agent is an aldehyde compound having a molecular weight of 200 or less, preferably 60 or more and 200 or less, more preferably 90 or more and 200 or less. Non-limiting examples of aldehyde compounds that can be used include (E)-2-hexenal (molecular weight 98.14), hexanal (molecular weight 100.16), benzaldehyde (molecular weight 106.12), octanal (molecular weight 128.21 ), cinnamaldehyde (molecular weight 132.16), anisaldehyde (molecular weight 136.15), piperonal (molecular weight 150.13), perillaldehyde (molecular weight 150.22), vanillin (molecular weight 152.15), citral (3,7 -dimethyl-2,6-octadienal) (molecular weight 152.23), citronellal (molecular weight 154.25), decanal (molecular weight 156.27), and hydroxycitronellal (molecular weight 172.26). Preferred aldehyde compounds include (E)-2-hexenal, hexanal, cinnamaldehyde, citral, and decanal.

The antibacterial drug is preferably supported on a binder in order to impart sustained release properties. By carrying the antibacterial agent described above in a binder, the release rate can be reduced at low temperatures, and the sustained release rate can be increased when the oxygen scavenger absorbs oxygen and generates heat. Gum arabic, polyvinyl alcohol, sodium alginate, gelatin, cellulose, carboxymethyl cellulose, methyl cellulose, polyvinylpyrrolidone, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, polyvinyl butyral, ethyl cellulose and the like can be used as binders. Among them, amphipathic polyvinylpyrrolidone, hydroxypropylcellulose, and hydroxypropylmethylcellulose can be preferably used.

The concentration of the antibacterial agent added is preferably 1 to 20%. If it is less than 1%, the amount of the agent cannot be volatilized sufficiently to exhibit antibacterial properties, and if it is 20% or more, the effect of increasing the amount of the agent. can not be obtained, and there is a possibility that the problem of deterioration of granulation properties, such as a decrease in the strength of the granules, may occur.

The particle diameter (maximum width) of the granules 10 before adhesion of the inorganic fine particles is not particularly limited, but may be, for example, 0.3 to 8.0 mm, or 0.3 mm or more and less than 5 mm.

The granules 10 composed of the carrier, the oxygen-absorbing composition, and the antibacterial agent are obtained by granulating a mixture containing the carrier, the oxygen-absorbing composition, and the components constituting the antibacterial agent. can be done. Each component constituting the oxygen-absorbing composition may be mixed together or separately. The mixer for mixing is not particularly limited, and may be, for example, a container rotating mixer such as a cylindrical or V-shaped mixer, or a ribbon type, horizontal screw type, paddle type, or planetary motion type. It may be a container fixed type mixer such as. Granulation can be carried out, for example, by an extrusion granulation method using a screen having predetermined apertures.

The hydrophilic inorganic fine particles 20 are water-insoluble particles containing a hydrophilic inorganic substance as a main component. The hydrophilic inorganic fine particles 20 usually contain 50% by mass or more of the hydrophilic inorganic substance based on the total mass. Examples of hydrophilic inorganic substances include hydrophilic silicon dioxide, calcium silicate hydrate, magnesium oxide, and aluminum silicate.

The ability of the hydrophilic inorganic fine particles 20 to easily absorb the oxygen-absorbing composition can contribute to improving the oxygen absorption capacity of the oxygen absorber. The extent to which the hydrophilic inorganic fine particles absorb the oxygen-absorbing composition can be evaluated by the liquid absorption amount of the hydrophilic inorganic fine particles 20 . The liquid absorption amount is measured by a method of causing the powder of the hydrophilic inorganic fine particles 20 to absorb a liquid agent containing an oxygen-absorbing substance constituting the oxygen-absorbing composition and a test liquid composed of a transition metal compound. The test liquid for measuring the liquid absorption amount contains the liquid agent containing the oxygen-absorbing substance and the transition metal compound in the same mass ratio as that in the oxygen-absorbing composition. When the amount of liquid absorption measured by this method (the mass of the test liquid absorbed by the hydrophilic inorganic fine particles 20 per 1 g) is 2.0 g/g or more, there is a tendency that a high oxygen absorption capacity can be obtained. . From the same point of view, the liquid absorption amount may be 2.5 g/g or more, or 3.0 g/g or more. Although the upper limit of the liquid absorption amount is not particularly limited, it may be, for example, 20 g/g or less.

The hydrophilic inorganic fine particles 20 having the average particle diameter, pore volume, specific surface area, and liquid absorption amount exemplified above can be produced by a normal method, and can be obtained by appropriately selecting from commercially available products. can also

The oxygen absorber is prepared by mixing a plurality of hydrophilic inorganic fine particles 20 with a plurality of granules 10 containing a support, an oxygen-absorbing composition, and an antibacterial agent. can be obtained by a method comprising a step of adhering hydrophilic inorganic fine particles 20 to the surface of the By forming a mixed powder in which the granules 10 powder and the hydrophilic inorganic fine particles 20 are mixed as a whole, a plurality of hydrophilic inorganic fine particles adhere to the surfaces of the individual granules. For example, by mixing the granules 10 and the hydrophilic inorganic fine particles 20 and shaking the resulting mixture, the hydrophilic inorganic fine particles 20 can be adhered to the granules 10 .

The hydrophilic inorganic fine particles 20 adhered to the granules 10 by the method of mixing powders as described above form a relatively thin layer. , for example tablets with an outer shell obtained by tableting. Specifically, the hydrophilic inorganic fine particles 20 adhering to the surface of the granule 10 can form a layer with a thickness of 1 mm or less, or 0.7 mm or less. The fact that the layer of the hydrophilic inorganic fine particles 20 is thin indicates that the material (oxygen-absorbing substance, alkaline compound or It can also be confirmed by detecting an element contained in the transition metal compound). Generally, in the case of the oxygen absorber according to the present embodiment, at least one element contained in the material constituting the granules 10 has a concentration of 0.05 atomic % or more, or 0.1 atomic % or more. often detected. On the other hand, when an outer shell portion having a certain thickness that encloses the granules 10 is formed by tableting, the elements of the material constituting the granules 10 are not substantially detected by EDX analysis. .

An oxygen scavenging package according to one embodiment can be mainly composed of the oxygen scavenging agent according to the above embodiment and an air-permeable packaging material containing this oxygen scavenging agent. The air-permeable wrapping material can be appropriately selected from those commonly used in the technical field. Specific examples of air-permeable packaging materials include bags made of a base material made of perforated plastic film, nonwoven fabric, microporous film, paper, or a combination thereof. This oxygen absorber package can be housed in, for example, various food packaging containers and used for the purpose of maintaining the freshness of food.

A food package according to one embodiment includes the above oxygen absorber package and a food packaging container in which the oxygen absorber package is enclosed. The food packaging container can be appropriately selected from those commonly used in the field of food packaging, and a sealable container is suitable. Food packaging containers include bags, deep drawn packages, tray packages, stretch packages and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to these examples.

[Example 1]
The raw materials shown in Table 1, i.e., activated carbon, an oxygen-absorbing composition containing an oxygen-absorbing substance, an alkaline compound, and a transition metal salt, and a binder on which an antibacterial agent is previously supported by pre-mixing, are uniformly mixed in a sealed state to form a mixture. got The obtained mixture was granulated by an extrusion granulator equipped with a screen having a screen hole diameter of 1.0 mmφ and a porosity of 22.6% to obtain granular granules 10 . Next, hydrophilic silicon dioxide was coated as the hydrophilic inorganic fine particles 20 to obtain the oxygen absorber 100 imparted with antibacterial properties. A schematic is presented in FIG.

[Example 2]
An oxygen absorber 100 imparted with antibacterial properties was obtained in the same manner as in Example 1, except that the amount of the antibacterial agent added was changed to 0.1.

[Example 3]
An oxygen absorber 100 imparted with antibacterial properties was obtained in the same manner as in Example 1, except that the amount of the antibacterial agent added was changed to 5.0.

[Example 4]
An oxygen absorber 100 imparted with antibacterial properties was obtained in the same manner as in Example 1 except that the antibacterial agent was citral.

[Example 5]
An antibacterial oxygen absorber 100 was obtained in the same manner as in Example 1 except that the amount of the antibacterial agent added was 20.0.

[Example 6]
An antibacterial deoxidant 100 was obtained in the same manner as in Example except that the binder was hydroxypropylmethylcellulose.

[Example 7]
An antibacterial deoxidant 100 was obtained in the same manner as in Example except that the binder was polyvinylpyrrolidone.

[Example 8]
An oxygen absorber 100 imparted with antibacterial properties was obtained in the same manner as in Example 1, except that the amount of the antibacterial agent added was 0.01.

[Example 9]
An antibacterial deoxidant 100 was obtained in the same manner as in Example 1 except that no binder was added.

[Example 10]
An antibacterial oxygen absorber 100 was obtained in the same manner as in Example 1 except that the binder was polyvinyl butyral.

[Comparative Example 1]
An oxygen scavenger was obtained in the same manner as in Example 1 except that no antibacterial agent was added.

(Filling of granules)
3.0 g of the oxygen scavengers prepared in Examples 1 to 10 and Comparative Example 1 were made of polyethylene terephthalate/polyethylene/paper/polyethylene/, and were formed by a laminate having through-holes in a size of 60 mm x 60 mm. It was filled in the package of

(storage test)
An oxygen-impermeable film of polyethylene terephthalate having a thickness of 12 μm deposited with aluminum oxide was laminated to a polyethylene film having a thickness of 30 μm using a urethane adhesive to form a heat-sealable layer. Next, a pouch having internal dimensions of 10 cm×25 cm was obtained with the heat-sealable layers facing each other. Next, a potato dextrose medium was prepared in a circular Petri dish with a diameter of 5 cm, and a bacterial solution containing Aspergillus niger at a concentration of 1.0×10 ² cfu/ml was applied. was housed in a pouch together with a sachet of

After culturing the medium housed in the pouch at 10° C. for one week, the pouch was opened. After maintaining the unsealed state for about 2 hours, the unsealed portion was heat-sealed again and cultured at 10° C. for 1 week. After culturing, the pouch was opened, kept open for about 2 hours, resealed, and further cultured at 10°C for 1 week.

The state of the medium at the end of each culture was evaluated as the antifungal property. Level 1 when growth of Aspergillus niger is not visually observed, level 2 when growth is slightly observed visually, and level when growth is visually observed but judged to be insufficient 3. Level 4 was given when the growth was visually recognized sufficiently and the growth was determined to be sufficient. Visual observations of levels 1 to 4 are shown in FIG.

Table 2 shows the antifungal evaluation results of Examples 1 to 10 and Comparative Examples. When the petri dishes were opened after one week, no fungal growth was observed in any of the petri dishes. On the other hand, in the system to which the antibacterial agent was added, the antifungal property was observed even after two weeks (after resealing), whereas the growth of mold was observed in the comparative example in which the antibacterial agent was not added. Further, when stored for 3 weeks, no antibacterial properties were exhibited in the case where no binder was used, the case where the amount of the antibacterial agent was added was 0.01 parts by mass, and the binder was polyvinyl butyral. From the above, it was confirmed that when an antibacterial drug was carried in an amphipathic binder, hydroxypropylcellulose, hydroxypropylmethylcellulose, or polyvinylpyrrolidone, the drug was gradually released even after opening, and the antibacterial activity was maintained for a long time. .

10 Granules 20 Hydrophilic inorganic fine particles 100 Oxygen absorber with antibacterial properties

Claims (7)

An oxygen absorber obtained by mixing and granulating a plurality of ingredients,
The oxygen scavenger is coated with hydrophilic fine particles,
The thickness of the coating layer is 1 mm or less,
The oxygen scavenger comprises a porous support carrying an oxygen-absorbing substance, an alkaline compound, a transition metal compound, and an antibacterial agent,
An oxygen scavenger having antibacterial properties, wherein the antibacterial agent is an aldehyde compound having a molecular weight of 200 or less. 2. The oxygen scavenger having antibacterial properties according to claim 1, wherein said aldehyde compound is supported on a binder. 3. The oxygen scavenger having antibacterial properties according to claim 1 or 2, wherein said binder has amphipathic properties. 4. The oxygen absorber having antibacterial properties according to any one of claims 1 to 3, wherein the binder comprises any one of polyvinylpyrrolidone, hydroxypropylcellulose and hydroxypropylmethylcellulose. Having antibacterial properties according to any one of claims 1 to 4, wherein the antibacterial agent is selected from the group consisting of (E)-2-hexenal, hexanal, cinnamaldehyde, citral, and decanal. An oxygen scavenger characterized by: 6. The antibacterial oxygen absorber according to any one of claims 1 to 5, wherein the amount of the antibacterial agent added is 0.01 to 20.0% by mass. 7. The oxygen absorber having antibacterial properties according to any one of claims 1 to 6, wherein the amount of the antibacterial agent added is 0.1 to 5.0% by mass.

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