KR820001107B1 - Oxygen indicator - Google Patents

Abstract

An indicator of O, esp. for use in food packaged with an inert gas or vacuum packed, contains compds. I (-Y+ = is -O+ =, -S+=, or N+-Z (Z = H, alkyl); R1-R10 = H, alkyl, alkoxy; X = halogen) or II (M = alkali material), alk. material, and reducing agent. Thus, 100 parts Mg(OH)2, 0.055 part methylene blue and 3.3 parts H2O were mixed until the color was uniform. The powder was mixed rapidly with 10 parts FeSO47H2O and tabletted. When the tablet (or the blue powder) was introduced into an O-contg. atm(0.1% 0) the color changed to white. Removal of the O caused a return to the blue color.

Description

Oxygen detector

The present invention relates to an oxygen detecting agent. In more detail, it is composed of reducing substances such as pigments, alkaline substances and ferrous compounds, subdithionate salts, or reducing sugars as essential components, and when oxygen is present in the atmosphere. If not, the present invention relates to an oxygen detecting agent which can visually determine the presence or absence of oxygen by changing its color tone, that is, by reversible color change.

It is caustic that has such a function. Aqueous solutions of glucose and methylene blue are known and used for microbiology. This is because blue methylene blue becomes colorless in the absence of oxygen and becomes blue again by invasion of oxygen. As a result, the presence of oxygen is indicated by the color change of blue ← → colorless.

However, since the detection agent is an aqueous solution, it is difficult to handle, and it is impossible to use it in a system in which there is a substance which dislikes water or a substance which is considered to be contaminated by water. . Moreover, because of its instability, it has a drawback of insufficient storage stability. In other words, since glucose is not only oxidized but also decomposes at room temperature even without oxygen, this detector needed to be stored in a cool dark place where it was not exposed to light. Furthermore, this detection agent has a drawback that the discoloration area is insensitive to oxygen concentration of about 0.5%, and has a drawback that is difficult to use in a system where trace amount of oxygen is a problem.

MEANS TO SOLVE THE PROBLEM The present inventors reached | attained this invention, as a result of earnestly examining in order to overcome the fault mentioned above and to develop a solid detection agent.

That is, this invention, (a) General formula (1)

Food,

Or formula (2)

Food,

[M represents an alkali metal]

Indigo carmine pigment | dye represented by (b) hydroxide or oxide of alkaline earth metal; Aluminum hydroxide; Phosphates, carbonates or organic acid salts of ammonia alkali or alkaline earth metals; ammonia; Or an oxygen detecting agent comprising an alkaline substance composed of one or more kinds of amines, and (c) a reducing substance composed of one or more of dithionite, ferrous compounds or reducing sugars. .

In the general formula (1), the alkyl group and the alkoxy group generally have 1 to 4 carbon atoms, and the aryl group includes, for example, a phenyl group and toluyl group.

As a dye represented by General formula (1), it is methylene blue (C.I. Basic Blue 9), for example.

Etc. Pigments are also used in the form of double salts, such as double salts of methylene blue, exemplified by methylene blue-FZ, -SG, -BH, -FZH and the like. The amount of the dye used is not particularly limited as long as it is an amount to impart a function as a detecting agent, but is preferably 0.001-10 parts by weight, particularly 0.01-1 part by weight, based on 100 parts by weight of the entire detection agent. In the present invention, the alkaline substance includes hydroxides or oxides of alkaline earth metals such as calcium hydroxide, magnesium hydroxide, calcium oxide, and magnesium oxide; Aluminum hydroxide thereon; Basic salts of inorganic weak acids exemplified by phosphoric acid, carbonic acid and the like; Alkali earth metal hydroxides, alkaline earth metal oxides or aluminum hydroxides, especially magnesium hydroxide, are preferred in consideration of basic salts of organic acids, ammonia and amines, among which long-term storage stability, coloration of pigments, and ease of solidification of the detection agent. Do.

The amount of alkaline substances used is sufficient to add the necessary amount to maintain the pH of the detector to the alkali side, and there is no special limitation, but when alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide are used as alkaline substances Since it functions as a support | carrier, these detection agents can be made solid without using a support | carrier by using these in large quantities.

In the present invention, the dithionate is a substance represented by the general formula M × S ₂ O ₄ (wherein M is a positive atom or a positive atom group, and the valence of M is Z and Zx = 2). As hydrosulfite. Sodium dithionate (Na ₂ S ₂ O ₄ ) and zinc dithionate are common, and sodium dithionate is preferably used.

Examples of the ferrous compound include inorganic salts exemplified by ferrous sulfate, ferrous chloride, ferrous sulfate ammonium, and the like; Organic acid salts exemplified by ferrous hydroxide, ferrous lactate, or the like; Sulfides and the like, and inorganic salts and sulfides are preferable. Among these, inorganic salts, such as ferrous sulfate, ferrous chloride, and ferrous ammonium ammonium, are preferable in view of availability of the detecting agent and the like.

In the present invention, reducing sugars are monosaccharides exemplified as D-mannose, D-glucose, D-fractose, D-erythrose, D-arabinose, and the like, and a certain number of monosaccharide molecules exemplified by maltose, lactose and the like. Refers to reducing small saccharides (glucose) by glucoside linkage. Among them, D-glucose and D-fructose are preferred in consideration of availability and reducing power.

The amount of these reducing substances is not particularly limited as long as the detection agent functions, but it is uneconomical to use a large amount. 0.1-90 weight part, especially 1-50 weight part is preferable with respect to 100 weight part of detection agents.

In order for the oxygen detecting agent of the present invention to function, it is necessary to contain water or an alcohol compound. Therefore, it is necessary that water vapor is present in the system in which the detection agent is used or that the detection agent contains water or an alcohol compound. Various types of systems are considered as the case where water vapor is present in the system in which the detection agent is used. For example, the detection agent is placed in a system such as food containing a lot of moisture.

Since the oxygen stopper of the present invention does not interfere with its function even in the form of an aqueous solution or a slurry, the amount of water used may be adjusted according to the conditions of use without particular limitation, but the solid state is preferable in consideration of practical aspects such as ease of handling. In the case of making it into a solid state, the range of 0.1-20 weight part is preferable with respect to 100 weight part of whole detection agents normally. As water, you may use the crystallized water of compound increase. Examples of the compound having crystal water include inorganic compounds such as metal oxides, hydroxides, sulfides, halides, sulfates, nitrates, borates, phosphates, carbonates and silicates; Or organic acid salts; Various complex salts thereon; There are compounds in which water molecules bind in crystal structures such as double salts.

Representative examples of the compound having crystal water include sodium carbonate 10H ₂ O and sodium sulfate 10H ₂ O. The compound having crystal water may be used alone or in combination. The amount of the compound used depends on the content of the crystal water and is selected according to the amount of water used above.

In the present invention, the alcohol compound has a free alcoholic hydroxyl group, and although some alcohols and derivatives thereof are contained, a liquid compound having low volatility is preferable. Specifically, for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, cyclohexanol, glycerin, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, triethylene And various alcohols or derivatives thereof exemplified by glycol, polyethylene glycol, dipropylene glycol, methyl cellosolve, butyl cellosolve, ethyl cellosolve, benzyl alcohol, monoethanolamine, diethanolamine triethanolamine and the like. Among them, polyhydric alcohols or derivatives thereof exemplified by glycerin, ethylene glycol, propylene glycol, and the like having low volatility are preferably used. An alcohol compound is used individually or in combination of 2 or more types, or can also be used together with water.

Although the usage-amount is based on the kind, Usually, 0.1-50 weight part with respect to 100 weight part of whole detection agents, and 1-20 weight part is preferable when it is solid.

In the case where water vapor is present in the system in which the detection agent is used, the detection agent does not necessarily need to contain water or an alcohol compound, but is preferably included in consideration of the reaction rate of the detection agent. In consideration of reaction speed and price, water is more preferable than alcohol compound. When high boiling point alcohol compound and water are used together, the alcohol compound is important for holding the water.

The detection agent of the present invention does not depend on the type and amount of components intrinsically functional or not, and depending on the purpose of use and the conditions of use, the excess of water or alcohol compounds, the excess of alkaline substances, the excess of reducing substances, etc. It can be adjusted to, but in consideration of stability and handleability, it is preferable to adjust to a solid shape.

In the case of solidifying, the powder may be used as it is, but it may be molded into a tablet or the like by mechanical means. At this time, you may add a binder, a mold release agent, etc. In order to solidify the detection agent, it is preferable to carry the above-mentioned components on a neutral or alkaline carrier. Examples of these carriers include metal hydroxides exemplified by calcium hydroxide, magnesium hydroxide, aluminum hydroxide and the like; Metal oxides exemplified by calcium oxide, magnesium oxide, aluminum oxide, titanium dioxide, silica gel, silica-alumina gel, synthetic zeolite, natural zeolite, kaolin, granular clay, etc .; Inorganic acid salts exemplified by alkaline earth metal salts such as calcium sulfate, magnesium silicate, magnesium chloride, calcium phosphate, barium carbonate, magnesium carbonate and the like; Organic acid salts exemplified by magnesium stearate, calcium hydroxide, calcium tartarate, calcium malate, calcium benzoate and the like; Cellulosic materials such as ion exchange resins, cellulose, paper, cloth, and other organic polymer compounds. These carriers are then used in amounts required as carriers.

In the present invention, the preparation of the detection agent is not particularly limited, and for example, a dye, an alkaline substance and a reducing substance, raw materials such as water or an alcohol compound, and optionally other additives, if necessary, are usually prepared by mixing using mechanical means. do.

Although the detection agent of this invention has a function enough also in a liquid state, solid is preferable in consideration of stability and handleability.

The detecting agent of the present invention is added with a colorant such as a dye, an alkaline substance, a reducing substance, a filler which does not interfere with function in some cases, a pigment which does not change color under aerobic or anaerobic conditions, a dye, and other additives.

The color of the detecting agent of the present invention differs depending on its components. In addition, the use of color regulators indicate the color controlled by it.

The detection agent of the present invention can be used in combination with a vacuum packaging method, a nitrogen seed-work method, a deoxygenation method, and the like used for preservation of produced foods and processed foods, and for the prevention of oxidation of organic chemicals and metals, etc. You can check it. Therefore, the difficulty of the above-described method due to incomplete degassing and air leakage due to poor sealing of the container can be prevented.

Since the detecting agent of the present invention can be obtained as a solid, its application range is very large. That is, if it is solid, it is used suitably also in the system in which the handleability is excellent and the substance which dislikes water and the substance by which water contamination is considered exists.

Moreover, since the detection agent of this invention is excellent in stability, it does not need to store in a cool dark place, and has the advantage that long-term storage is possible. In other words, long-term preservation is possible in the air for more than several months and under anaerobic conditions for more than one year.

In addition, the detection agent of the present invention has a big advantage that the discoloration area is sensitive to the oxygen concentration of about 0.1%, and thus is suitably used for anaerobic preservation management of foods and the like.

Hereinafter, the present invention will be described in detail with reference to the following Examples.

Example 1

0.055 parts by weight of methylene blue and 3.3 parts by weight of water were added to 100 parts of magnesium hydroxide, and the mixture was shaken and mixed so that the magnesium hydroxide was uniformly colored.

10 parts by weight of ferrous sulfate (FeSO _4. 7H ₂ O) powder was quickly mixed with this colored (blue) powder to obtain a mixed powder, and a part of it was purified.

When the obtained blue powder and tablets were left in a nitrogen atmosphere (oxygen concentration 0.1%), both the powder and the tablets turned white. Then, when oxygen was injected, both of them turned blue again.

Example 2

Of ferrous sulfate (FeSO _4. 7H ₂ O) that the amount of powder (量) 50 parts by weight, except were conducted in the same manner as in Example 1. As a result, the same result as in Example 1 was obtained.

Example 3

0.055 parts by weight of methylene blue and 3.3 parts by weight of water were added to 100 parts by weight of calcium hydroxide, followed by shaking and mixing so that the calcium hydroxide was uniformly colored.

30 parts by weight of ferrous sulfate (FeSO _4. 7H ₂ O) powder was quickly mixed with this colored (blue) powder to obtain a mixed powder, and a portion thereof was refined.

The blue powder and the tablet thus obtained were subjected to functional confirmation in the same manner as in Example 1, whereby the same results as in Example 1 were obtained.

Example 4

100 parts by weight of calcium hydroxide, 10 parts by weight of ferrous sulfate (FeSO _4. 7H ₂ O), 0.05 parts by weight of methylene blue, 3.3 parts by weight of water, 0.015 parts by weight of edible red No. 106 (acid red) was adjusted in the same manner as in Example 1. did.

The obtained blue-purple powder and tablets turned red when left in a nitrogen atmosphere (oxygen concentration 0.1%). Then, when oxygen was injected, it became blue purple again.

Example 5

As shown in Table 1, the type of alkaline substance, ferrous compound, pigment, water, or alcoholic acid combination was changed, and the component ratio (parts by weight), the adjustment method, and the performance test method were the same as in Example 1.

The results are shown in Table 1.

TABLE 1

Example 6

An oxygen detecting agent was obtained by mixing 3 parts by weight of 85% hydro sulfite (trade name: Super Light PB-200, Mitsubishi Gas Chemical Co., Ltd.), 12 parts by weight of slaked lime, 0.005 parts by weight of methylene blue and 0.2 parts of water.

This detector turned white when left under nitrogen atmosphere (oxygen concentration 0.06%). It then developed blue when oxygen was injected into it.

Example 7

The composition was the same as in Example 6 except that the composition ratio of the detecting agent and the type of alkali were changed and activated carbon was added. The detector changed color at an oxygen concentration of 0.1% or less. The results are shown in Table 2.

TABLE 2

Example 8

It carried out similarly to Example 6 except having used the compound which has crystal water instead of water. The results are shown in Table 3.

TABLE 3

Example 9

Oxygen concentration detector obtained by adding 12 parts by weight of dry calcium hydroxide, 3 parts by weight of 85% sodium dithionate, 0.8 parts by weight of granular activated carbon, and 0.5 parts by weight of methylene blue to 0.5 parts of ethylene glycol was preserved in a nitrogen atmosphere. It changed from white to white. The O ₂ concentration at that time was 0.08%. When oxygen was injected again, it immediately returned to color.

Example 10

It carried out similarly to Example 9 except having changed the kind of alkaline substance or the kind of alcohol. The results are shown in Table 4.

TABLE 4

Example 11

It carried out similarly to Example 6 except having changed the kind of pigment | dye or alkaline substance. The results are shown in Table 5.

TABLE 5

* The structural formula of the pigment is as follows.

Capri Blue

Example 12

An oxygen detecting agent was obtained in the same manner as in Example 6 except that 0.2 part of water was not mixed. 2 g of the obtained detection agent was placed in a 100 cc container, and then 5 cc of water was deposited in 1 g of cotton wool in this container, and then, when left under a nitrogen atmosphere (oxygen concentration 0.06%), the color turned white. It then developed blue when oxygen was injected into it.

Example 13

10 parts by weight of magnesium hydroxide, 0.1 parts by weight of D-glucose, 0.005 parts by weight of methylene blue and 0.2 parts by weight of water

The blue detection agent was prepared and turned white when left in a nitrogen atmosphere (oxygen concentration of 0.1%). It then turned blue again when oxygen was injected.

Example 14

It carried out similarly to Example 13 except having replaced the kind of alkaline earth metal and sugar. The results are shown in Table 6.

TABLE 6

Example 15

An alcohol compound was used instead of water, and the kind of alkaline earth metal was changed to carry out the same experiment as in Example 13. The results are shown in Table 7.

TABLE 7

Example 16

10 parts by weight of magnesium hydroxide, 0.1 parts by weight of glucose, 0.005 parts by weight of methylene blue and 0.2 parts by weight of water were mixed to prepare a detection agent. The obtained detection agent was left in air for one month, and immediately turned white in an anaerobic atmosphere.

For comparison, when the detection agent mixed with 0.1 parts by weight of sodium hydroxide, 0.1 parts by weight of glucose, 0.005 parts by weight of methylene blue and 10 parts by weight of water was left in the air for one week, the detector after standing was not all white in an anaerobic atmosphere. .

Example 17

It carried out similarly to Example 13 except having changed the kind of pigment | dye and alkaline-earth metal. The results are shown in Table 8.

TABLE 8

※ The structural formula of the pigment is as follows.

Example 18

An oxygen detecting agent was obtained in the same manner as in Example 13 except that 0.2 part of the mole was not mixed. 2 g of the obtained detection agent was placed in a 100 cc container. Furthermore, when 5 cc of water was deposited in 1 g of cotton wool in this container, it was turned white when left under a nitrogen atmosphere (oxygen concentration 0.06%). It then developed blue when oxygen was injected into it.

[Comparative Example]

For comparison, an aqueous solution obtained by mixing 0.1 part by weight of sodium hydroxide, 0.1 part by weight of glucose, 0.005 part by weight of methylene blue and 10 parts by weight of water was left in air for 1 week. The aqueous solution after standing was not white at all even if placed in an anaerobic atmosphere.

Claims (1)

As described above in the text, a dye, an alkali earth metal hydroxide or an oxide represented by the following general formula (1) or the following general formula (2); Aluminum hydroxide; Phosphates, carbonates or organic acid salts of ammonia, alkali or alkaline earth metals; ammonia; Or an oxygen detecting agent composed of one or more alkaline substances of amine and one or more reducing substances of dithionite, ferrous compound or reducing sugars. .