JPH038441A - Deoxidant - Google Patents

Abstract

PURPOSE:To obtain a deoxidant undetectable with a metal detector by preparing a compsn. consisting of sugaralcohol, an alkaline substance and phenols or quinones. CONSTITUTION:100 pts.wt. 4-6C sugaralcohol such as erythritol, arabitol or sorbitol is mixed with about >=10 pts.wt. alkaline substance such as sodium hydroxide or calcium hydroxide reacting with water and assuming alkalinity. A small amt. of mono-, di- or polyhydric phenols or o- or p-quinones having catalytic action and increasing the rate of oxygen absorption is further added to the mixture. A transition metal compd., a slightly water soluble solid and water may be added as required. They are uniformly mixed and enclosed in a gas permeable packing material. The resulting packed deoxidant and food, etc., are enclosed in a gas impermeable packing material and this material is hermetically sealed. Since the deoxidant is not detected with a metal detector, foreign matter in the food can be detected with the metal detector.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxygen scavenger. More specifically, the present invention relates to a novel oxygen scavenger whose main ingredient is a sugar alcohol.

In this specification, the term "oxygen scavenger" is mainly used to mean a "composition that has an oxygen scavenging effect" (oxygen scavenger composition), but it also refers to a "package of a composition that has an oxygen scavenging effect" (oxygen scavenger composition). It is also sometimes used to mean an oxygen agent package.

[Conventional technology]

Oxygen absorbers are used as a preservation technique for foods, etc.
This is a gas-barrier sealed bag or container (hereinafter referred to as
Sometimes simply called a sealed container or container. ) By placing food, etc. and an oxygen scavenger inside the sealed system to create a substantially oxygen-free condition, it suppresses the oxidation of foods, etc. and the growth and proliferation of bacteria and mold. Used for preservation.

Conventionally, oxygen scavengers based on iron powder have been used for reasons such as their oxygen absorption ability, ease of handling, safety, and cost.

By the way, in the case of packaged foods, for example, after the food is sealed in a packaging bag, it is passed through a metal detector to check for foreign matter contamination.

However, since oxygen absorbers based on iron powder are naturally detected by metal detectors, metal detectors cannot be applied to packaged foods that contain oxygen absorbers.

[Problem to be solved by the invention]

In view of the above-mentioned problems of the prior art, an object of the present invention is to provide an oxygen scavenger that will not be detected even when applied to a metal detector.

[Means to solve the problem]

A means to solve the above problems is to use a composition of oxygen scavenger consisting of (1) sugar alcohol, (2) alkaline substance, and (2) phenols or quinones. This means is an improvement on the oxygen scavenger consisting of a sugar alcohol and an alkaline substance previously proposed by the present inventors.

Embodiments of the solution include a composition consisting of (1) a sugar alcohol, (2) an alkaline substance, and (2) a phenol or quinone, and a composition in which other components are added to the above composition as necessary. (1) sugar alcohol,
Oxygen scavenger consisting of alkaline substances and phenols,
(2) Oxygen scavenger consisting of sugar alcohol, alkaline substance, phenol and water; (3) Oxygen scavenger consisting of sugar alcohol, alkaline substance, phenol and transition metal compound; (4) Sugar alcohol, alkaline substance, phenol. , an oxygen scavenger consisting of a transition metal compound and water;
(5) an oxygen scavenger consisting of a glycoalcoholic alkaline substance, phenols and a poorly water-soluble solid; (6) an oxygen scavenger consisting of a glycoalcoholic alkaline substance, a phenol, a poorly water-soluble solid and water; (7) a sugar alcohol; (8) an oxygen scavenger consisting of an alkaline substance, phenols, a transition metal compound, and a poorly water-soluble solid; (8) an oxygen scavenger consisting of a sugar alcohol, an alkaline substance, a phenol, a transition metal compound, a poorly water-soluble solid, and water; 9) Oxygen scavenger consisting of sugar alcohol alkaline substances and quinones, αO sugar alcohol scavenger consisting of alkaline substances, quinones and water, 01) Consisting of sugar alcohols, alkaline substances, quinones and transition metal compounds Oxygen scavenger, alpha-sugar alcohol, alkaline substance, quinones, transition metal compound, and water-based oxygen scavenger, alpha-sugar alcohol, alkaline substance, quinone, and poorly water-soluble solid oxygen scavenger, alpha-sugar alcohol, Oxygen scavenger consisting of alkaline substances, quinones, poorly water-soluble solids, and water, α$
Sugar alconope Oxygen scavenger consisting of alkaline substances, quinones, transition metal compounds and poorly water-soluble solids, 00 sugar alcohols, alkaline substances, quinones, transition metal compounds,
Examples include oxygen scavengers made of poorly water-soluble solids and water.

In the above solution, the sugar alcohol may be a commercially available sugar alcohol, may contain impurities such as water, or may be a mixture. Examples of the sugar alcohol include sugar alcohols having 4 carbon atoms, sugar alcohols having 5 carbon atoms, and sugar alcohols having 6 carbon atoms. More specifically, examples include sugar alcohols with 4 carbon atoms such as erythritol, sugar alcohols with 5 carbon atoms such as arabitol, xylitonopeadonitol, and sugar alcohols with 6 carbon atoms such as mannitonopesorbitol and dulcitol. However, xylitol, mannitol, sorbitol, etc. are preferable, and sorbitol is particularly preferable.

Furthermore, the alkaline substance is a substance that exhibits alkalinity by acting with water or by dissolving in water.

Preferred are alkali metal or alkaline earth metal hydroxides, carbonates, hydrogen carbonates, tertiary phosphates, diphosphates, etc., and particularly preferred are alkali metal and alkaline earth metal hydroxides. . Specifically, for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium triphosphate, sodium diphosphate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium triphosphate,
Potassium diphosphate, calcium hydroxide, magnesium hydroxide, etc. are preferred. Among these, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. are particularly preferred. The alkaline substances can be used alone or in combination of two or more. The amount of alkaline substance mixed with sugar alcohol is 100 parts (parts by weight, hereinafter the same).

) is preferably 10 parts or more, more preferably 30 to 1.000 parts.

If the amount of the alkaline substance mixed is less than the above range, the amount of oxygen absorbed by the composition will be small (which is undesirable), and if the amount of the alkaline substance mixed is more than the above range, the amount of oxygen absorbed per unit weight will be small. Therefore, the packaging material for packaging the composition needs to be large, which leads to problems in loading the food package and is also unfavorable in terms of appearance.

Phenols exhibit a catalytic effect in the above solutions and can lead to an increase in the rate of oxygen absorption even when added in small amounts. As phenols, -valent phenols,
Examples include polyhydric phenols having a valence of two or more. The -hydric phenols may be substituted phenols or aromatic derivatives having other substituents on the aromatic nucleus, as long as they have one hydroxyl group directly connected to the aromatic nucleus in one molecule. The dihydric phenols may be substituted phenols or aromatic derivatives having other substituents on the aromatic nucleus, as long as they have at least two hydroxyl groups directly connected to the aromatic nucleus.

In addition, in this specification, a substance having a plurality of aromatic nuclei in one molecule and a plurality of hydroxyl groups directly connected to the aromatic nucleus, even if a single aromatic nucleus has only a single hydroxyl group. Included in polyhydric phenols.

Of course, the phenols may also be phenol salts (phenolates) in which the hydrogen of the hydroxyl group is substituted with a metal or the like. Among these phenols, polyhydric phenols having a valence of two or more are preferred in terms of their catalytic action. More specifically, catechol, resorcinol, hydroquinone, pyrogallol, naphthohydroquinone, phloroglucin, gallic acid, tannin 1. Examples include polyhydric phenols such as tannic acid, dihydroxyphenylphenol, and derivatives thereof. Among these, polyhydric phenols such as catechonoperesorcin, hydroquinone, pyrogallic acid, tannin, and tannic acid are preferred in terms of their catalytic effect on oxygen absorption rate, ease of availability, and the like.

In the solution described above, quinones can be used instead of phenols. Like phenols, quinones also exhibit a catalytic effect in the above-mentioned solution, and can lead to an increase in the rate of oxygen absorption even when added in small amounts. As the quinones, 〇-quinones, p-quinones, etc. can be used.

As long as it has a quinone structure, it may be a derivative having a substituent on the quinone nucleus. More specifically, examples include benzoquinone, naphthoquinone, phenanthraquinone, diphenoquinone, and quinones made of derivatives thereof. Among these, benzoquinone, diphenoquinone, etc. are preferred.

Phenols or quinones may be used alone or in combination of two or more. Further, phenols and quinones may be used in combination. The amount of phenols or quinones mixed with sugar alcohol is not particularly limited, but is preferably 1 part or more, particularly preferably 5 parts or more, per 100 parts of sugar alcohol.

If the blending amount is less than the above range, the catalytic effect of the phenols or quinones will be small. Furthermore, the upper limit of the amount of phenols or quinones mixed with sugar alcohol is not particularly limited, and it is possible to mix more than a catalytic amount of phenols or quinones, but 5,000 parts or less per 100 parts of sugar alcohol. It is preferably 1.000 parts or less, particularly preferably 1.000 parts or less. Even if the blending amount of phenols or quinones is increased beyond the above range, the sugar alcohol will not contribute to an increase in the amount of oxygen absorption commensurate with the increase in the amount of the composition,
It becomes uneconomical.

Examples of transition metal compounds include transition metal halides, sulfates, nitrates, phosphates, carbonates, oxides, hydroxides,
Examples include organic acid salts, other double salts, and chelate compounds. Transition metals include iron, cobalt, nickel, copper,
Zinc, manganese, etc. are used, and copper, iron, manganese, etc. are preferred. Preferred specific examples of transition metal compounds include ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, cuprous chloride, cupric chloride, cupric sulfate, cupric hydroxide, Examples include copper citrate, cuprous tartrate, cupric tartrate, manganese chloride, and the like. These transition metal compounds are added singly or in combination of two or more as necessary, and act as a catalyst for the composition of the present invention, and the amount thereof is preferably 1 part or more per 100 parts of sugar alcohol. Particularly preferred is 5 parts or more.

Slightly water-soluble solids are solid substances that are insoluble or sparingly soluble in water, and specifically include activated carbon, zeolite, perlite, diatomaceous earth, activated clay, silica, kaolin, talc, bentonite, activated alumina, gypsum, and silica. Examples include powders or granules of alumina, calcium silicate, magnesium oxide, graphite, carbon black, aluminum hydroxide, iron oxide, and the like. The poorly water-soluble solids may be used alone or in combination of two or more, if necessary. By incorporating a poorly water-soluble solid, it is possible to increase the oxygen absorption rate or the amount of oxygen absorption, and to simplify the handling of the composition.

Furthermore, by incorporating a poorly water-soluble solid, the contact area of the liquid component in the composition with oxygen can be increased. The blending amount of the poorly water-soluble solid is appropriately selected in relation to other components, and is not particularly limited, but is 0.1 to 10% of glycerin 100B.
．． 000 parts is preferred, and 1 to 1.000 parts is particularly preferred.

In the case where water is not added in the solution described above, the water necessary for the reaction is supplied by water that evaporates from the object to be preserved such as food. When water is added to the oxygen scavenger composition, the oxygen absorption reaction proceeds without depending on water from foods, etc., so it is possible to adjust the progress of the oxygen absorption reaction by adjusting the amount added. The amount of water added in this case is not particularly limited, but is desirably adjusted to 70% by weight or less, more preferably 50% by weight or less based on the total composition. If the amount of water added is larger than the above range, the composition becomes pasty, and the contact area of the composition with oxygen becomes small, which is not preferable.

In the present invention, there are no particular restrictions on the method of mixing the above-mentioned components, but if the components are liquid and powder, any method that can uniformly mix each component may be used, and if granules are used as the component, for example, A method may be adopted in which the liquid is impregnated into the granular material and then the powder is added so as to be sprinkled thereon. Each of the above components is usually housed in an air-permeable packaging material to form a package. As for the packaging method, for example, after mixing each component, it can be wrapped in a pouch sealed by heat-sealing the periphery of an air-permeable packaging material using a backing machine to form an oxygen absorber package.

This oxygen absorber package can be used to preserve foods, etc. by storing the oxygen absorber package together with foods, etc. in an air-impermeable packaging material and sealing it, or by storing it together with foods, etc. in an airtight container and sealing it.

[Effect]

When the oxygen absorber of the present invention does not contain water in its composition, it can be applied to foods with a relatively high moisture content, and the oxygen absorber of the present invention can be of a type that absorbs oxygen by incorporating moisture that evaporates from the food into the composition. I can do it. Since sugar alcohols are hygroscopic, they perform a good deoxidizing function in an atmosphere with a high rate of water evaporation. In this case, the advantage is that it is easy to handle until it is sealed together with food. Furthermore, if water is added to the composition, it can be used as an oxygen absorber that removes oxygen regardless of the water content of the food.

〔Example〕

Examples 1 to 9 After mixing each oxygen scavenger component shown in Table 1, a small bag (
It was housed in a size of 5Qmm in length and 80mm in width to form an oxygen absorber package. This oxygen scavenger package was placed in a bag made of polyvinylidene chloride coated stretched nylon and polyethylene laminated together with 1°,000 rd of air, and after being sealed, it was left in an atmosphere at 25°C. After 3 days, the oxygen concentration in the bag was measured and the amount of oxygen absorbed was determined. The results are shown in Table 1.

For Examples 1.3.5.7 and 9, absorbent cotton impregnated with water was sealed together and the relative humidity was measured at 100°C. It was carried out under %.

Comparative Example 1 The same procedure as in Example 1 was carried out except that catechol was not used as the oxygen scavenger component.

The amount of oxygen absorbed at this time was 3 ml.

Example 10 2 g of erythritol, 3.3 g of calcium hydroxide, 0.7 g of 2°6-di-t-butyl-p-cresol, and 0.7 g of copper sulfate.

The same procedure as in Example 1 was carried out except that 2 g of silica powder, 0.7 g of activated carbon, and 2 g of water were mixed and used as an oxygen scavenger.

Two days later, when I measured the oxygen concentration inside the bag, it was 0.
．． It was less than 1%. The amount of oxygen absorbed at this time was 206-.

Example 11 Same as Example 1 except that 2 g of xylitol, 3.3 g of calcium hydroxide, 0.7 g of catechol, 0.7 g of copper sulfate, 2 g of silica powder, 0.7 g of activated carbon and 2 g of water were mixed and used as an oxygen scavenger. operated on.

Two days later, when I measured the oxygen concentration inside the bag, it was 0.
．． It was less than 1%. The amount of oxygen absorbed at this time was 206-.

Example 12 2 g of sorbitol, 3.3 g of calcium hydroxide, 0.7 g of tannic acid (Tannic acid CL manufactured by Fuji Chemical Industry ■).

The same procedure as in Example 1 was carried out except that 0.7 g of copper sulfate, 2 g of silica powder, 0.7 g of activated carbon and 2 g of water were mixed and used as an oxygen scavenger.

Two days later, when I measured the oxygen concentration inside the bag, it was 0.
．． It was less than 1%. The amount of oxygen absorbed at this time is 206 m1
Met.

Example 13 After raising 400 adult brown elephants in 1 kg of brown rice for one week, the adults were removed. The remaining brown rice was divided into 40 g portions and used for the following samples.

40 g of brown rice as a sample and the oxygen absorber package of Example 11,
Placed in a bag made of polyvinylidene chloride coated stretched nylon and polyethylene laminated and the air volume inside the bag is 1.000.
It was sealed so that -. 10 identical specimens were prepared and 20
It was stored in a constant temperature room. After storing it for 20 days, it was opened and placed indoors at 25°C, and the number of brown elephants emerging from the sample brown rice was recorded.

As a control, the same test as above was conducted except that the oxygen absorber package was not enclosed in the bag. In this case, the number of brown elephants emerging was taken as 100%.

The results are shown in Table 2.

Table 2 Example 14 Ten 15g steamed buns and the oxygen absorber package of Example 12 were placed in a bag made by laminating polyvinylidene chloride coated stretched nylon and polyethylene, and the air content in the bag was 1.0.
00-, and stored hermetically at 20°C. One week later, the oxygen concentration and carbon dioxide concentration in the bag were measured, and the properties of the manju were observed.

As a control, the same test as above was conducted except that the oxygen absorber package was not enclosed in the bag.

The results are shown in Table 3.

It can be applied to a wide range of items to be preserved, such as preventing fading and preventing rust.

Claims (5)

[Claims] (1) Oxygen scavenger consisting of sugar alcohol, alkaline substance, and phenols or quinones. (2) Claim 1 in which the phenols are monohydric phenols.
Oxygen scavenger described in. (3) Claim 1 wherein the phenols are polyhydric phenols.
Oxygen scavenger described in. (4) An oxygen absorber package comprising the oxygen absorber according to any one of claims 1 to 3 housed in an air-permeable packaging material. (5) A food package obtained by storing the oxygen absorber package according to claim 4 and a food in an air-impermeable packaging material or an airtight container and sealing or sealing the package.