JPH0326100B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an oxygen absorber used for oxygen-free storage of foods, furs, clothing, etc. More specifically, the present invention relates to an oxygen scavenger whose main components are hydrides (hereinafter referred to as HAQs) of anthraquinones (hereinafter referred to as AQ) or their tautomers and acidic substances. BACKGROUND ART Conventionally, in order to extend the shelf life of foods, etc., a method has been implemented in which the foods, etc. are placed in a sealed container, and an oxygen absorber is further sealed therein to remove oxygen from the air within the sealed container. Oxygen scavengers used in this method include those made by adding calcium hydroxide and activated carbon to hydrosulfite and further adding water, those made by adding metal halides, carriers, and water to metal powder such as iron, and others. ,
Hydroquinone, gallic acid, catechol, glucose,
Products containing lignin, erythorbic acid, BHT, BHA, or ascorbic acid as main components for oxygen removal have been proposed. has an adverse effect such as generating foul-smelling sulfur dioxide gas and leaving a residual odor on the object to be stored. There are drawbacks such as strong ones. As a result of intensive research into the development of oxygen scavengers that do not have these drawbacks, the present inventors discovered 1, 4, 4a, 9a-
Tetrahydroanthraquinone (hereinafter, Tetrahydro is TH, Tetrahydroanthraquinone is THAQ)
We have completed the present invention by discovering that HAQs such as (abbreviated as ) are extremely effective as oxygen scavengers and that acidic substances promote this action. In the present invention, the HAQs used as the main component of the oxygen scavenger may be substituted HAQs in which the hydrogen groups at positions 1 to 8 of the AQ skeleton are substituted with other substituents,
Of course, unsubstituted HAQs may also be used. Other substituents include, for example, alkyl groups such as methyl, ethyl, propyl, and butyl; halogen groups such as chloro and bromo; alkoxy groups such as methoxy, ethoxy, propoxy, and bitoxy; endoalkylene such as endomethylene and endoethylene; Examples include acyloxy groups such as acetoxy; other hydroxy, amino, nitro, and cyano groups. Regarding the hydrogenated position of the AQ skeleton in HAQs, it is necessary that at least one of the unsaturated bonds is saturated, but in particular 1,
It is preferable that at least one of the unsaturated bonds related to 4, 4a, 5, 8, 8a, 9, 9a, 10, and 10a is saturated, and furthermore, at least one of the unsaturated bonds related to 4a, 8a, 9a, and 10a is saturated. Preferably, one or more of them is saturated. For example, 1, 4, 4a, 9a−
THAQs, 1,4-dihydroanthrahydroquinone (hereinafter, dihydro is DH, anthrahydroquinone is AHQ, dihydroanthrahydroquinone is
abbreviated as DHAHQ), 1, 2, 3, 4
-THAHQs, 1,4-DHAQs, 1,2,3,
4,4a,9a-hexahydroanthraquinones,
1,2,3,4-THAHQs, 1,2,3,4,
4a, 9a-hexahydro AHQs, AHQs, 1,
4,4a,5,8,8a,9a,10a-octahydro
AQs, 1,4,4a,5,8,9a-hexahydro
AHQs, 1,4,5,8-THAQs, above
Quinhydrones include AQs and AHQs. In particular, HAQs that can be produced industrially at low cost include 1,4,4a,9a-THAQs, 1,4-
DHAHQ is preferred, especially 1,4,4a,9a-
THAQs are preferred. 1, 4, 4a, 9a−THAQ
Examples include 1,4,4a,9a-THAQ;
Examples include 2-methyl-, 2,3-dimethyl-, and 2-chloro-substituted 1,4,4a,9a-THAQ. In practice, it may be a mixture of two or more of the HAQs described above. Further, it is preferable to use fine powder for HAQ to improve contact with oxygen. The above HAQs can be easily produced according to conventional methods. For example, 1,4,4a,
5,8,8a,9a,10a-octahydro AQs or 1,4,4a,9a-THAQs are produced, and then the above compounds are easily produced according to known methods such as isomerization, hydrogenation, and oxidation. can do. Tautomers of HAQs include, for example, 9-hydroxyanthrones, 1,2,3,
4,4a,9a-1, which is represented by hexahydro AHQs
Tautomers such as 2,3,4,4a,9a-hexahydro-10-hydroxyanthrones can be mentioned. In the present invention, when using HAQ as an oxygen scavenger, rather than using HAQ alone,
It is extremely effective to use HAQs as a main component and to add or mix an acidic substance, a carrier, and an aqueous medium and/or an organic solvent to rapidly absorb oxygen in the atmosphere. The reaction of HAQs to absorb oxygen is the following 1, 4,
As shown in the examples of 4a and 9a-THAQ, this is thought to be due to the reaction between hydrogen and oxygen that saturated the AQ skeleton. THAQ+1/2O ₂ =DHAQ+H ₂ O (1) DHAQ+1/2O ₂ =AQ+H ₂ O (2) (However, THAQ: 1, 4, 4a, 9a−THAQ,
DHAQ: 1,4-DHAQ) The reaction (1) proceeds relatively easily, but the reaction (2) tends to be relatively slower than the reaction (1). Acidic substances include inorganic acids, organic acids, acid salts,
Examples include salts of strong and weak acids and other acidic substances. For example, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid; carboxylic acids such as phthalic acid, benzoic acid, malic acid, tartaric acid, citric acid, succinic acid, fumaric acid, maleic acid, malic acid, acetic acid, propionic acid, and benzenesulfonic acid. , p-toluenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, and other sulfonic acids; acid salts of the above inorganic or organic acids, such as sodium sulfate, potassium sulfate, sodium phthalate, etc.; ferrous chloride Salts of strong and weak acids such as , ferric chloride, ammonium chloride, nickel chloride, calcium chloride, aluminum chloride, cuprous chloride, cupric chloride, ferrous sulfate, ferric sulfate, ammonium sulfate, alum; acidic Examples include acidic substances such as ion exchange resins, acidic zeolites, and acid clay. The amount of these acidic substances used should be more than the catalytic amount,
Usually 0.0001 to 10 times the weight of HAQs, preferably 0.001 to 5.0 times, more preferably 0.01 to 5.0 times the weight
Selected from 2.0 times the weight. In the present invention, by using a carrier
It is extremely effective in increasing the contact area between HAQs, etc. and oxygen, and reducing the amount of acidic substances and media used. Examples of carriers include activated carbon, silica,
Porous carriers such as silica gel, silica alumina, zeolite, and diatomaceous earth; other examples include pulp, soybean protein, popcorn powder, polyurethane, sawdust, and defatted bran. In particular, a porous carrier, preferably activated carbon, is effective in effectively exhibiting the oxygen scavenging ability of HAQs. The amount of carrier used varies depending on the type of carrier, but is generally at least 0.01 times the weight of HAQ, usually 0.1
The weight ratio is at least 10 times by weight, preferably at least 0.2 times by weight and at most 8 times by weight, and more preferably at least 0.3 times by weight and at most 5 times by weight. When the amount of carrier decreases, the oxygen scavenger tends to decrease when the amount of medium used, such as an aqueous medium, is relatively small. If the amount of carrier used is too large, the capacity per unit volume as an oxygen scavenger will decrease. In the present invention, the main component of the oxygen absorber is
In order to effectively utilize the oxygen scavenger such as HAQ, it is preferable to simultaneously contain a medium such as an aqueous medium and/or an organic solvent. Water is usually used as the aqueous medium, but salts or water-soluble organic solvents may also be dissolved therein. Alternatively, it may be moisture contained in a carrier or atmosphere, or moisture absorbed from objects such as foods, or it may be in the form of water of crystallization of the above acidic substances and other salts. Examples of compounds having water of crystallization include alum, Na ₂ SO ₄ .10H ₂ O, and the like. The amount of the aqueous medium to be used is usually 3 times or less, preferably 2 times or less and 0.0001 times or more by weight, and more preferably 1 time or more and 0.001 times or more by weight of the HAQ as water. The organic solvent is preferably one that can dissolve HAQs as much as possible, such as monohydric or polyhydric alcohols such as ethanol, propanol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, trimethylolethane, methyl ethyl ketone, etc. , ketones such as methyl butyl ketone, esters such as ethyl acetate, and hydrocarbons such as benzene, toluene, and xylene, preferably water-soluble solvents, and more preferably alcohols. Organic solvents can be used alone as a medium, but alcohols can be used together with an aqueous medium. The amount to be used is the same as that for the aqueous medium, but when added to the aqueous medium, it may be added in an amount of 0.001 times or more, preferably 0.05 times or more by weight, relative to the aqueous medium. The presence of organic solvents such as alcohols, even in extremely small amounts, dissolves HAQs one by one and diffuses onto the surface of the carrier to improve contact with air, thereby dissolving HAQs and oxygen. It is presumed that this will further promote the reaction. In addition, to promote the oxygen scavenging ability of HAQs,
Acidic acid using 1,4-naphthoquinone sulfonate, metal phthalocyanine compound (sodium cobalt phthalocyanine sulfonate, etc.), iron salt (iron chloride, etc.), copper salt (copper chloride, etc.), iron oxide, redox catalyst of copper oxide as a promoter. Can be used with substances. The oxygen scavenger of the present invention can be easily produced by sequentially mixing HAQs or their tautomers, an acidic substance, an aqueous medium and/or an organic solvent, and a carrier. , HAQ type medium, acidic substance and medium are separately mixed with a predetermined amount of carrier, and if necessary, the mixture is compressed into tablets, granulated, or as a powder and applied to one or both sides of a sheet with adhesive or adhesive. An oxygen permeable bag, such as a perforated polyethylene film, is fixed by a known fixing method such as hammering, and then covered with a laminated paper bag, a perforated plastic film made of polypropylene, polybutadiene, polyester, polyvinyl chloride, cellophane, etc., or a laminate film thereof. It can be used wrapped or stored in a perforated container. When storing these encapsulants for a long period of time, it is preferable to cover them with a film that can block air.If the storage film is removed when used as an oxygen scavenger, the oxygen in the atmosphere can be easily removed. can do. In order to make the powder sticky, a water-soluble polymer compound may be added as a binder. Examples of the compound include sodium alginate,
Examples include CMC, hydroxymethyl cellulose, ethyl cellulose, propyl cellulose, starch, and polyvinyl alcohol. Hereinafter, it will be explained in detail using examples. Example 1 1, 4, 4a, 9a- as main ingredient of oxygen scavenger
HAQ containing 84% THAQ, 14.4% 1,4-DHAQ
(Main ingredient) 10g, acidic substance, carrier, and medium are mixed in the proportions shown in Table 1, and the mixture is placed in a 4-liter glass container containing air at room temperature (approximately 20 to 25°C).
The amount of oxygen absorbed was measured using an oxygen meter. The results are shown in Table 1. In addition, Table 1 shows the main ingredients.
Converted to 1.0g unit and displayed.

【table】

[Table] Example 2 The same procedure as in Example 1 was carried out except that the acidic substance and medium were used as shown in Table 1. The results are shown in Table 2.

[Table] Example 3 In Example 1, 1,4-
The same results as in Example 1 were obtained except that DHAHQ was used.

Claims (1)

[Scope of Claims] 1. An oxygen scavenger characterized by containing an anthraquinone hydride or its tautomer and an acidic substance. 2. The anthraquinone hydride has an anthraquinone skeleton of at least 1, 4, 4a, 5, 8, 8a,
The oxygen scavenger according to claim 1, which is a hydrogenated anthraquinone in which one or more of the unsaturated bonds at positions 9, 9a, 10, and 10a is saturated. 3. The oxygen scavenger according to claim 2, wherein the hydrogenated anthraquinones are substituted or unsubstituted 1,4,4a,9a-tetrahydroanthraquinones. 4. The oxygen scavenger according to claim 2, wherein the hydrogenated anthraquinones are substituted or unsubstituted 1,4-dihydroanthrahydroquinones. 5. An oxygen scavenger containing an anthraquinone hydride or its tautomer, an acidic substance, a carrier, and an aqueous medium and/or an organic solvent.