JPH05209871A - Oxygen sensing agent - Google Patents

Abstract

PURPOSE:To obtain sensing agent which can exhibit stable function even in a dry state and which is almost free from influence of light. CONSTITUTION:Oxygen sensing agent includes organic compound with three or more carbons having a primary amine group and a hydroxyl group or compound of the organic compound and organic or inorganic acid, and/or a substance where the organic acid and organic or inorganic acid coexist, in addition to thiazine and/or indigo pigment. Since the oxygen sensing agent is almost free from influence of light and exhibits stable function in a system for preserving a product in a non-oxygen and dry state, it is optimum as oxygen sensing agent for preservation of a product sensitive to humid, for example, preservation of dry food, corrosion protection of metal, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is for knowing whether or not the system is anoxic in the storage of food, the storage of metal products and parts such as electronic materials and electronic products containing metals, and the storage of other articles. Related to oxygen detectors. In this specification,
The term "oxygen detecting agent" refers to an oxygen detecting agent composition, but sometimes includes a tablet containing the oxygen detecting agent composition or a film or sheet coated with the oxygen detecting agent composition, and is collectively referred to as "oxygen detecting agent". I have to say. Further, the "oxygen detecting agent" may be referred to as "detecting agent".

[0002]

2. Description of the Related Art Conventionally, an oxygen detecting agent containing a reducing substance such as glucose has been used as an agent for detecting anoxic conditions.
It is proposed in Japanese Patent Laid-Open No. 3-120493. However, this detecting agent requires water in order to exert the oxygen detecting function, and the oxygen detecting function is not sufficiently exerted when used in a dry system. Further, as a countermeasure against this, even if water is added to the detection agent composition in advance, since the water moves to a preservative such as a dry food or a desiccant, not only the detection function is changed but also the object to be preserved. May cause dry food to become damp. As oxygen detecting agents that have improved these drawbacks, JP-A-61-144568 and JP-A-62-12853 propose oxygen detecting agents containing an organic acid salt of a thiazine dye and ethanolamine as essential components. .. However, when the detection agent is irradiated with light, it may have a color tone indicating anoxic state even in the state where a trace amount of oxygen exists in the system. As described above, the conventional oxygen detecting agents have the drawback that the oxygen detecting function does not sufficiently function in a dry state and the function becomes unstable under the influence of light.

[0003]

The object of the present invention is to solve the above-mentioned drawbacks of the conventional oxygen detecting agents, to allow the oxygen detecting agent to exhibit its sufficient function even in a dry state, and to have a stable function even under irradiation of light. Is to be able to demonstrate.

[0004]

The present invention is directed to an organic compound having a primary amine group and a hydroxyl group and having 3 or more carbon atoms, or a compound of the organic compound and an organic acid or an inorganic acid, and / or
Alternatively, the present invention relates to an oxygen detecting agent characterized by containing an organic compound and an organic acid or an inorganic acid together and containing a thiazine-based and / or indigo-based dye.

The organic compound having a primary amine group and a hydroxyl group and having 3 or more carbon atoms (hereinafter sometimes referred to as a main agent) used in the present invention is for discoloring a dye in an oxygen-free state. The amine group and the hydroxyl group are functional groups that have the function of changing the color of the dye in anoxic state, and the organic compound may have other functional groups. That is,
In the present invention, there is no particular limitation as long as it is an organic compound having a primary amine group and a hydroxyl group and having 3 or more carbon atoms,
Usually, a low molecular weight compound having 3 or more carbon atoms is used, but an oligomer or polymer having more carbon atoms can also be used if necessary.

When the organic compound having a primary amine group and a hydroxyl group has 2 or less carbon atoms, it is highly volatile and volatilizes during storage to deteriorate the function or cause an odor problem. Further, even if an inorganic acid or an organic acid is made to coexist to reduce the volatility, the function is unstable and it is often practically inconvenient.

Specific examples of the organic compound having a primary amine group and a hydroxyl group and having 3 or more carbon atoms used in the present invention include 3-amino-1,2-propanediol, 3-amino-1-propanol and 3-amino-1-propanol. Amino-2-propanol, 4-amino-1-butanol, 4-amino-3-butanol, 5-amino-1-pentanol, 5-amino-4-pentanol, 6-amino-1-hexanol,
6-amino-5-hexanol, glucosamine, aminophenol, aminonaphthol, 4-amino-1,2-
Organic compounds such as butanediol may be mentioned. further,
Even in an organic compound having a primary amine group and a hydroxyl group and having 3 or more carbon atoms, an amino alcohol in which the carbon to which the primary amine group is bonded and the carbon to which the hydroxyl group is bonded are adjacent to each other is more preferable.

The above-mentioned organic compound having a primary amine group and a hydroxyl group and having 3 or more carbon atoms and an inorganic acid or a compound of an organic acid and / or the organic compound and an organic acid or a substance in which the inorganic acid coexists are the organic compound and the inorganic compound. A compound such as a salt with an acid or an organic acid, an adduct of the organic compound with an inorganic acid or an organic acid, or a compound in which the organic compound and the inorganic acid or an organic acid coexist without being combined. In these systems, volatilization of the composition is small and odor is not generated, which is preferable. The inorganic acid used for this is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, silicic acid or the like, and is not particularly limited. Organic acids include fatty acids and sulfonic acids, and are not particularly limited. The organic compound having a primary amine group and a hydroxyl group and having 3 or more carbon atoms, or an inorganic acid or a compound with an organic acid may be used alone or as a mixture of two or more kinds. In addition, other inorganic or organic compounds may be mixed.

The dye used in the present invention is a dye whose color tone in the presence of oxygen in the presence of an electron donor changes to colorless or another color tone in the absence of oxygen. This dye is a thiazine-based dye and / or an indigo-based dye, and the thiazine-based dye and the indigo-based dye are represented by the following chemical formulas 1 and 2, respectively.

[Chemical 1]

[Chemical 2]

Examples of the thiazine dyes include lout violet, azure C, azure B, methylene blue, and thionine blue having a thiazine nucleus, and, like neomethylene blue and brilliant alizarin blue, a --OH group as a side chain on the skeletal carbon. And those to which —SO ₃ H and the like are bound are also included. Further, as the indigo dye, indico, indigo carmine, bromoindigo R and the like are used. Further, in order to make the discolored state of the thiazine-based dye clear, the detection agent of the present invention may contain other dyes which do not discolor depending on the presence or absence of oxygen.

In the present invention, the shape of the oxygen sensing agent is not particularly limited, but the preferred shape for placing the oxygen sensing agent together with the oxygen scavenger and the object to be stored in the closed system is a tablet, a film or a film. Examples include a shape printed on a sheet such as paper or non-woven fabric.

In order to maintain the strength of the tablet,
Inorganic fillers including silicates and the like, organic fillers such as polymers are included, and stearates, which are lubricants, and main agents are supported on the fillers. A tablet is produced by molding a composition comprising a main agent and the above substances, and a conventional method can be applied to the tablet production method.

When the oxygen sensing agent is in the form of printing, the oxygen sensing agent composition contains ethyl cellulose, polyvinyl alcohol, a binder such as starch, and the like for maintaining the adhesiveness of the main agent and the dye, and calcium carbonate, titanium oxide. , Barium sulfate and other pigments are added. Furthermore, a polyhydric alcohol such as glycerin or polyethylene glycol is added to water and / or an organic solvent together with the main agent and the dye, if necessary, during the production. A liquid printing composition comprising these components is applied to a film or sheet and dried to form a detection agent. In this case, the printing on the film or sheet surface may be partial or full.

Further, in the case of a printing form, in addition to printing on a film or sheet, it can be printed on a packaging material such as a storage object or a deoxidizer as a printing object, a packaging container or a packaging bag. .. When printing on a packaging material, it is desirable to print an oxygen sensing agent on the inside of a transparent oxygen-barrier packaging base material and further laminate an oxygen-permeable material. Of course, instead of directly printing, the oxygen sensing agent printed on the film or sheet may be used. For example, a packaging bag made of a composite film in which an oxygen detecting agent is arranged between a transparent oxygen barrier film and an oxygen permeable film is preferably used.

The oxygen barrier packaging base material has an oxygen permeability of 1
It is preferably 000 ml / m ² · 24 hr · atm or less, and the oxygen permeable material preferably has an oxygen permeability of 1000 ml / m ² · 24 hr · atm or more. As the oxygen barrier film, a film coated with vinylidene chloride or a film deposited with silicon oxide is used. As the oxygen permeable film, polyethylene, silicone resin, polypropylene, vinyl acetate-
Non-porous or perforated films such as polyethylene copolymers can be mentioned.

The oxygen detector of the present invention may be packaged in an oxygen permeable film. This form is a preferred form in which the oxygen detection agent does not come into direct contact with the object to be stored through the film and does not contaminate the object to be stored.
Further, the color change rate of the oxygen detecting agent can be adjusted by adjusting the oxygen diffusion rate of the film. As the specific examples of the oxygen permeable film used for packaging, those mentioned above can be used, and the oxygen permeability is 1000 ml / m ² · 24hr · atm.
The above is preferable.

[0017]

EXAMPLES The present invention will be specifically described with reference to examples.
The present invention is not limited to this embodiment. Examples 1 to 32 ( Production of Oxygen Sensing Agent Composition) Each of the materials shown in Tables 1 and 2 was added to ethanol, dissolved and dispersed by high-speed stirring (homomixer), and uniformly dispersed liquid oxygen was detected. An agent composition was produced.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

The substances indicated by abbreviations in Table 1, Table 2, Table 3 and Table 4 are substances having the following names. [Main agent] (3 or more -NH ₂ carbon atoms, an organic compound having an -OH group) APD: 3- amino-1,2-propanediol AP1N: 3- amino-1-propanol AP2N: 3- Amino-2- Propanol AB1N: 4-amino-1-butanol AB3N: 4-amino-3-butanol APE1N: 5-amino-1-pentanol APE4N: 5-amino-4-pentanol AH1N: 6-amino-1-hexanol AH5N: 6-amino-5-hexanol GCA: glucosamine APH: aminophenol AN: aminonaphthol ABD: 4-amino-1,2-butanediol [acidic substance] OL: oleic acid LA: lauric acid HCl: hydrochloric acid [dye] MB: Methylene blue TI: Thionine AC: Azure C NMB: Ne Omethylene Blue BAAB: Brilliant Alizarin Blue RVO: Laut Violet ACD: Acid Red IC: Indicocarmine [Binder] EC: Ethylcellulose PVA: Polyvinyl alcohol [Polyhydric alcohol] GC: Glycerin TME: Trimethylolethane PEG: Polyethylene glycol

Examples 33 to 66 (Printing on Substrate) The sensing agent composition produced in Examples 1 to 32 was applied to each substrate of neutral paper, film or non-woven fabric shown in Table 5 with a Mayer bar, It was dried with hot air at 100 ° C. for 45 seconds.

[Table 5]

[Table 6]

Examples 67 to 93 (Functions of Oxygen Sensing Agent) Oxygen sensing agents (paper form) produced in Examples 33 to 59.
A test piece cut into 20 x 20 mm was made into a KON / PE bag (size 150) with an oxygen scavenger and an air volume of 250 ml.
Fluorescent lamp (40 mm)
It was stored under the condition of an ambient temperature of 25 ° C. under the light irradiation of w). Tables 7 and 8 show changes with time of the oxygen concentration in the system, the humidity and the color tone of the detection agent at this time. As the oxygen scavenger used in this example, 10 g of granular activated carbon was impregnated with a mixture of 0.5 g of iron linoleate and 3 g of soybean oil, and 15 g of silica gel (A type) was used.
Together with this, it is a package (size 60 × 90 mm) packaged in a breathable packaging material of paper / open-pore polyethylene.

Comparative Example 1 5 g of glucose, 0.2 g of methylene blue (MB) and 0.2 g of acid red (ACD) were sequentially added to 45 g of a 50% aqueous ethanol solution and stirred at high speed to form a uniform solution. 35 g of magnesium oxide and 8 g of magnesium stearate were further added and mixed uniformly, and the mixture was dried at 80 ° C. for 35 minutes to prepare a bulk detection agent powder. Next, this bulk powder has a diameter of 7 mm and a depth of 10 mm.
Put in a box and press with a load of 300 kg to give tablets (diameter 7
mm × thickness of about 4 mm). The function of the obtained tablet-shaped detecting agent was confirmed by the same method as in Examples 67 to 93. The results are shown in Table 8.

Comparative Example 2 A paper-like detector was prepared in the same manner as in Example 33, except that triethanolamine was used instead of 3-amino-1,2-propanediol, and the same method as in Examples 67 to 93 was used. The discoloration status of the detection agent was confirmed. The results are shown in Table 8.

[Table 7]

[Table 8] Oxygen Sensing Agent Test (1) (Table 7
followed by)

As is apparent from Tables 7 and 8, the detection agents of Examples 33 to 59 according to the present invention were "oxygen-free" BR after 24 hours under anoxic conditions under light irradiation and drying,
It showed BRR or R, and then kept R for one month. On the other hand, the detection agent of Comparative Example 1 was once "oxygen-free" B
R and R, but after 1 month (under dry condition), it returned to "aerobic color" BBR despite being anoxic. In addition, in the detection agent of Comparative Example 2, although the oxygen concentration was 3.5% and oxygen was present under light irradiation,
"Oxygen-free color" R was shown.

Examples 94 to 100 (Function of Sensing Agent) Two sensing agents ( paper- like) prepared in Examples 60 to 66 were used.
Cut into 0 x 20 mm and make a bag made of silicon oxide vapor-deposited composite film (size 150 x with deoxidizer and air volume of 250 ml).
It was sealed at 200 mm) and attached to a glass window irradiated with sunlight at a room temperature of 25 ° C. for storage. Table 9 shows changes with time in the oxygen concentration in the system, the humidity, and the color tone of the detection agent at this time. Table 9 shows the changes with time in the oxygen concentration in the system, the humidity, and the color tone of the detection agent at this time. The oxygen scavenger used in this example was obtained by impregnating 10 g of granular activated carbon with a mixture of 0.5 g of iron linoleate and 3 g of soybean oil and packaging together with 15 g of quicklime in a breathable packaging material of paper / open polyethylene ( Size 90 × 1
20 mm).

COMPARATIVE EXAMPLE 3 The function of the detecting agent was the same as that of Examples 94 to 100, but the same tablet-type detecting agent containing glucose as the main ingredient confirmed in Comparative Example 1 was used.

COMPARATIVE EXAMPLE 4 The same paper-like detecting agent of triethanolamine as the main agent whose function was confirmed in Comparative Example 2 was examined in the same manner as in Examples 94 to 100 to confirm the discoloration state of the detecting agent. The results of Comparative Example 3 and Comparative Example 4 are shown in Table 9.

[Table 9]

Example 101 On the opposite side of the coating of a stretched nylon film (15 μm) coated with vinylidene chloride (thickness: 2 μm), the oxygen-sensing agent composition containing the aminopropadiol base agent prepared in Example 1 was formed into a circle with a diameter of 5 mm. Gravure printing was performed at a coating amount of 3 g / m ² and then dried at 100 ° C. for 45 seconds. Then, a 5 wt% isocyanate adhesive dissolved in ethyl acetate was applied (3 g / m ² ) to the printed surface of this film printed with the oxygen detector composition (3 g / m ² ), and heat-treated at 95 ° C. for 24 seconds, and then the polyethylene film ( 55 μm) was laminated to prepare a film for printing a detection agent. A bag (150 × 200 mm) was prepared using the laminated film in which the detecting agent was printed in a circle in this manner, and the oxygen absorber and 250 ml of air were sealed in this bag, and the function of the detecting agent was performed in the same manner as in Example 67. I did a test.
The confirmation of the oxygen detection function was based on the discoloration status of the detection agent printed on the inner surface of the bag. The results are shown in Table 10. The discoloration speed of this detection agent is slightly slower than that of Example 67, which is a paper-shaped detection agent having the same main agent, but there is no problem in practical use.

[Table 10] The color tone display of the detection agent conforms to the display of Note 1 in Table 9.

Example 102 2 g of aminopropadiol (APD), oleic acid (O
L) 8 g, methylene blue (MB) 0.2 g and glycerin (GC) 8 g are sequentially added to ethanol 52 g,
High speed stirring resulted in a uniform solution. To this solution, 500 g of silicon oxide, which is a white filler, and 8 g of magnesium stearate were further added and uniformly mixed, and the mixture was dried to prepare a bulk detection agent powder. Place the bulk powder of the oxygen detector obtained in this way into a box with a diameter of 7 mm and a depth of 10 mm.
It was pressed with a load of 00 Kg and formed into tablets (diameter 7 mm x thickness about 4 mm). The obtained tablet-shaped oxygen sensing agent was confirmed to function in the same manner as in Example 67,
The oxygen detection function similar to that of Example 67 of the paper-like oxygen detection agent containing the same APD as the main agent was observed.

Examples 103 to 105 (Function of Sensing Agent, Effect of Light Irradiation) A test piece obtained by cutting the paper-like acid detecting agent of the APD main agent produced in Example 47 into 20 mm × 20 mm square was deoxidized. The composition and the desiccant were attached together inside a vinylidene chloride-coated stretched nylon composite film bag (250 × 300 mm), and 250 ml of air was sealed and sealed. This sample is 25 ℃
Stored in a place with different light intensity. Table 1 shows changes in the oxygen concentration, humidity, and color tone of the detection agent in the system during this test.
Shown in 1. The oxygen scavenger used in this example is the same as the oxygen scavenger used in Example 67. The desiccant is a package (size 75 × 100 mm) in which 20 g of silica gel (A type) is packaged in a paper / open-hole polyethylene packaging material.

Comparative Examples 5 to 7 The tablet-like detection agent having the same glucose base as that used in Comparative Example 1 was used to measure the dye change of the detection agent in the same manner as in Examples 103 to 105. The results are shown in Table 11.

Comparative Examples 8 to 10 The same paper-like detection agent containing triethanolamine as the main agent used in Comparative Example 2 was used to measure the color tone change of the detection agent in the same manner as in Examples 103 to 105. The results are shown in Table 11.

[Table 11]

As shown in Table 11, the APD-based paper-like oxygen detecting agent prepared in Example 47 was 50 to 3%.
It shows “anoxic color” BR, BRR or R under anoxic condition after 24 hours under irradiation of light of 500 lux, and 1
"Oxygen-free color" was maintained even after months passed. On the other hand, although the color of the detection agent of Comparative Example 1 did not change depending on the illuminance, it still returned to the “aerobic color” BBR after 1 month under drying. Further, the detection agent of Comparative Example 2 has a slow color change under the condition of low illuminance (after 24 hours,
BBR at an oxygen concentration of 0.0%) and hypersensitivity in a place where the illuminance is strong. Even though the oxygen concentration was 1.5%, BR under the irradiation of 750 lux and R under the irradiation of 3500 lux and R were "oxygen-free".

Example 106 The paper-like detection agent, which is the APD main agent, produced in Example 47 was cut into 15 mm × 15 mm, and a polyethylene film having a thickness of 30 μm (size 35 × 35 mm, oxygen permeability 350) was cut.
0 ml / m ² · 24 hr · atm). This oxygen detection agent is used together with a deoxidizer, a desiccant, and an air amount of 250 ml to form a vinylidene chloride-coated stretched nylon composite film bag (250 x
300 mm) and sealed. Store this sample at 25 ℃,
Table 12 shows the oxygen concentration and humidity in the system and the change in color tone of the oxygen detection agent. The oxygen scavenger used in this example is the same as in Example 6.
It is the same as the oxygen scavenger used in 7.

[Table 12] The color tone display of the detection agent conforms to the display of Note 1 in Table 9.

The discoloration rate of the sensing agent packaged with the oxygen permeable film tested in Example 106 was slightly slower than the result of Example 67 in the case where the same sensing agent was not packaged, but it was practically used. There is no problem above.

[0035]

The oxygen detecting agent of the present invention is a detecting agent which exhibits a stable function even in a dry state and is hardly affected by light. In addition, the oxygen detection agent of the present invention can be easily printed on paper or film, and can be formed into tablets. In addition to this, it is also possible to print on a tape or sheet for use, and a wide variety of practical use forms can be adopted. It is extremely important to constantly check the presence or absence of oxygen in a system for storing an article in anoxic state, and the oxygen detection agent of the present invention is excellent in the oxygen detection function particularly in a storage environment under dry conditions and / or exposure conditions. , To show its true value. Therefore, the oxygen detection agent of the present invention is a storage condition of metals and semiconductors under which drying conditions are indispensable, rust prevention of metals, storage of dried foods, and storage state under light irradiation, for example, storage in a store showcase. Ideal for detecting oxygen below.

Claims (1)

[Claims] 1. An organic compound having a primary amine group and a hydroxyl group and having 3 or more carbon atoms, or a compound of the organic compound and an organic acid or an inorganic acid, and / or a substance in which the organic compound and the organic acid or the inorganic acid coexist. An oxygen detecting agent characterized by containing a thiazine-based and / or indigo-based dye.