JPS6017393B2 - Oxygen indicator ink composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to oxygen indicator ink compositions.

Oxygen absorbers are effective in maintaining the quality of various foods, preventing mold, and preventing pests, so several types are already on the market. However, with conventional oxygen scavengers, it is often difficult to distinguish between those that have oxygen absorption capacity and those that have lost oxygen absorption capacity, leading to quality accidents due to unknowing use of substances that have already lost oxygen absorption capacity. There is a danger. Therefore, a method of visually determining the oxygen absorbing ability of an oxygen scavenger is desired. In response to these demands, various oxygen indicators made into tablets have been proposed (Japanese Unexamined Patent Application Publication No. 1983-1999).
Publication No. 1120493, etc.). However, in the case of tablets, holes must be made in the bag in which they are packaged and they must be sealed together with an oxygen absorber, which poses problems with filling capacity, and the indicators used are expensive. be. Furthermore, an oxygen indicator that combines methylene blue with a strong reducing agent such as hydrosulfite or ascorbic acid has been developed (Tsubaki Publication No. 54-482). This indicator has the advantage that it can be used by impregnating filter paper or gauze, or by printing it with a water-soluble resin binder, but when used in combination with a strong reducing agent such as methylene blue and hydrosulfite, The reduction potential of the reducing agent is extremely low, and although the reducing ability is strong, the reducing agent is consumed quickly in an atmosphere where oxygen exists, and the indicator ability is lost in a short period of time during storage. When reducing sulfur compounds such as sulfur compounds are used, they give off a foul odor peculiar to sulfur, which is not preferable in terms of use. Furthermore, since a water-soluble resin binder is used during printing, the indicator film formed has poor water resistance and cannot withstand long-term storage.Also, since water is used as a solvent, drying during the printing process is slow, resulting in extremely low work efficiency. There are drawbacks. The present invention has been made in view of the above points, and an object of the present invention is to provide an oxygen indicator ink composition that can be used for a long period of time.

The present inventors have discovered that thiazine dyes, indigoid dyes, thioindigoid dyes, and sulfur dyes change color significantly in the presence of oxygen and in deoxygenated conditions (oxygen concentration 0.1% or less) in the coexistence of reducing sugars and alkaline substances. and that this coexistence system maintains its indicator ability for a long time even when left in the presence of oxygen, unlike when hydrosulfite or ascorbic acid is used. They discovered that it was possible to make ink by dissolving or dispersing it in water, and completed the present invention.

That is, the present invention provides an oxygen indicator ink characterized in that at least one member of the group consisting of thiazine dyes, indigoid dyes, thioindigoid dyes, and sulfur dyes, reducing sugars, and alkaline substances are dissolved or dispersed in a resin solution. The composition is summarized.

The present invention will be explained in detail below.

In the present invention, the following dyes are used.

'11 Thiazine dyes having as a basic structure: for example, methylene purulent, etc.'
21 Indigoid dyes having as a basic structure; for example, potassium indigo sulfonate, etc. Thioindigoid dyes having a 3' basic structure: Mikethrene Brilliant Pink R, etc. sulfur dyes having C.I. 1. Sulfua: “Blue 7th order,
As reducing spears, D-maltose, D-glucose,
Monosaccharides such as D-fructose, D-esasulose, and O-arabinose; reducing oligosaccharides consisting of glycosidic bonds of a certain number of monosaccharide molecules such as maltose and lactose are used, and the amount used is 1 part of the above dye ( It is preferably 1 to 10 dollars per weight (hereinafter parts and % are based on weight).

Next, the alkaline substance may be any substance that has a pH of 8 or higher when it comes into contact with water, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, calcium hydroxide, calcium carbonate, sodium hydrogen carbonate, Hydroxides, carboxylates, and various salts such as potassium hydrogen carbonate, calcium hydrogen carbonate, magnesium hydroxide, sodium acetate, potassium acetate, potassium sodium tartrate, and potassium 2-ethylhexanoate are used.

The amount used is preferably 1 to 10 parts per part of the above dye. Examples of resin solutions for dissolving or dispersing the three-component oxygen sensing material include cellulose derivatives such as ethyl cellulose, ethyl hydroxyethyl cellulose, and cellulose acetyl propionate, butyral resin, polyester resin, acrylic resin, and polyether resin. , polyamide resin, petroleum resin, various hard resins, etc., preferably aromatic resins such as toluene and xylene, ester resins such as ethyl acetate and butyl acetate, ketone resins such as methyl ethyl ketone and methyl isobutyl ketone, methanol, and ethanol. , alcohols such as inpropyl alcohol, and those dissolved in organic solvents such as ethylene glycol monoethers or glycols such as ethylene glycol are used.

It is preferable that 5 to 2 parts of the resin be dissolved in 100 parts of the solvent. The ink composition of the present invention has the above-mentioned resin solution 1.
0 contact, the oxygen sensing material consisting of the above three-component system was
~4 Obtained by dissolving or dispersing the base.
The method for dissolving or dispersing this is to mix all the ingredients and form a bran using a general method such as a sand mill, a pole mill, a roll mill, or an atraitor, but in order to maintain its performance as an indicator for a long time, the ink should be sealed in a sealed state. It is desirable to Incidentally, it is effective to add about 5% of glycerin to the ink composition of the present invention, based on the total amount, in order to hasten the discoloration of the indicator. In addition, various additives and active agents such as /ionic surfactants may be added to the ink composition of the present invention.

Furthermore, by separately adding a pigment that is not reduced within the composition system to the ink composition of the present invention, the respective colors in the presence and absence of oxygen can be adjusted to easily distinguishable colors. I can do it.

Such pigments include, for example, Chromophthal Magenta G, Chromophthal Red G, and Gurmanuntocarmine H.
Examples include monoazo pigments and condensed azo pigments such as F4 and permanent carmine FBB, which can be added in an amount of about 0.1 to 5% based on the entire ink composition. The ink composition of the present invention configured as described above can be applied to the surface of any base material such as paper, plastic film, metal foil, etc. by a printing method such as gravure printing, offset printing, letterpress printing, or screen printing, or by a coating method. After application, an oxygen indicator film can be formed by drying.

It is desirable that the coating is applied for about 1 to 10 days per day (when dry). Furthermore, the ink composition of the present invention can be printed on air-permeable packaging materials for packaging oxygen absorbers, and can also be printed on packaging materials for packaging foods and the like. As is clear from the above description, the ink composition of the present invention has excellent printability, and the film formed after printing can be used as an oxygen indicator for a long period of time, making it possible to determine the oxygen absorbing ability of the oxygen scavenger. , it is possible to determine the deoxidization state of the part in which the deoxidizer is sealed.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 An oxygen sensing material consisting of 0.05 part of methylene blue, 0.1 part of glucose, and a cape of magnesium hydroxide was mixed with cellulose acetate propionate (manufactured by Eastman Co., Ltd., C.A.
．． P) The ink composition of the present invention was prepared by mixing 3 parts of a varnish consisting of 12% inpropyl alcohol, 44% inpropyl alcohol, and 44% ethyl acetate into 7 parts of the varnish and kneading it in a sand mill for 1 hour. did.

Using the obtained ink composition, a gravure plate with a plate depth of 80 mm was printed on high-quality paper (manufactured by Sanyo Kokusaku Pulp Co., Ltd., OR, 60 evenings/end).
When gravure printing was performed on the paper, a dark-toned print with a methylene blue color was obtained. When this printed matter was sealed together with an oxygen absorber (Ageless F manufactured by Mitsubishi Gas Chemical Co., Ltd.) in a bag made of a laminated film of propylene film (23〃) coated with polyvinylidene chloride and polyethylene (40A), it held for about 1 time. The methylene blue color became lighter, indicating that the oxygen inside the bag was absorbed by the oxygen scavenger and the bag became deoxidized. On the other hand, those left in the air remain dark blue, and those left in the air for 30 days at room temperature become dark blue and become almost colorless when sealed together with the above oxygen scavenger. It was confirmed that the performance as an indicator had not deteriorated.
Examples 2 to 26 The same procedure as in Example 1 was carried out except that the following components were used as the oxygen sensing material, and the following color changes were obtained.

The numerical values in the table below indicate the amount of each component mixed in parts by weight. Comparative Example An oxygen detecting agent consisting of 0.05 part of methylene blue and 0.05 part of sodium hydrosulfite (Na2S204) was formed into an ink and printed in exactly the same manner as in Example 1, and then a performance test was conducted.

Claims (1)

[Scope of Claims] 1. An oxygen indicator characterized in that at least one member of the group consisting of thiazine dyes, indigoid dyes, thioindigoid dyes, and sulfur dyes, reducing sugars, and alkaline substances are dissolved or dispersed in a resin solution. Ink composition. 2. The composition according to item 1 above, further comprising glycerin.