Oxygen indicator adapted for printing or coating and oxygen-indicating device

• US 4,349,509 A
• Filed: 06/27/1980
• Issued: 09/14/1982
• Est. Priority Date: 07/03/1979
• Status: Expired due to Term

• Current Assignee: Mitsubishi Gas Chemical Company Incorporated (Mitsubishi Electric Corporation)
• Original Assignee: Mitsubishi Gas Chemical Company Incorporated (Mitsubishi Electric Corporation)
• Inventors: Yoshikawa, Yoshio, Nawata, Takanari, Kondo, Yukio, Goto, Mikio
• Primary Examiner(s): EVANS, JOSEPH
• Application Number:
  US06/163,870
• Time in Patent Office: 809 Days
• Field of Search: 252/408, 422/56, 422/57, 23/932, 426/87
• US Class Current: 422/426
• CPC Class Codes: C09B 7/02 Bis-indole indigos
• CPC Class Codes: G01N 31/225 for oxygen, e.g. including dissolved oxygen
• CPC Class Codes: G01N 33/02 Food
• CPC Class Codes: Y10T 436/207497 Molecular oxygen

Abstract

An oxygen indicator adapted for printing or coating which comprises (a) at least one reducing agent, (b) a dyestuff causing color change when it is reduced with the reducing agent, (c) at least one thickening agent and (d) at least one solvent and a sheet-like oxygen indicator in which a composition comprising the above four components (a)-(d) is coated or printed on a substrate are disclosed.

Claims

1. An oxygen indicator adapted for printing which comprises

(a) at least one reducing agent selected from the group consisting of mixtures of at least one alkaline substance and dithionites, ferrous compounds, reducing saccharides or mixtures thereof;

ascorbic acid;

erysorbic acid or a salt thereof;

stannous salts;

hydroxyamine;

hydrazine;

keto-carboxylic acids;

sulfoxylates;

alkali metal sulfides and boron hydrides;

(b) a dyestuff which has a color in an atmosphere containing oxygen and a different color in a non-oxygen containing atmosphere when it is reduced with said reducing agent;

(c) at least one thickening agent selected from the group consisting of sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl-cellulose, sodium alginate, polyvinyl alcohol, gum arabic powder, gum tragacanth, dextrin and casein in an amount of 0.05-10% by weight on the basis of (a), (b), (c) and (d); and

(d) at least one solvent selected from the group consisting of water, alcohols, and mixtures thereof.

3. The oxygen indicator as defined in claim 1 wherein the reducing agent is selected from mixtures of at least one alkaline substance and dithionites, ferrous compounds, reducing saccharides and mixtures thereof.

4. The oxygen indicator as defined in claim 3 wherein the alkaline substance is selected from hydroxides or weak acid salts of alkali metals or alkaline earth metals.

5. The oxygen indicator as defined in claim 1 wherein the dyestuff is represented by the formula ##STR4## wherein --Y⁺ ═

is selected from the group consisting of --O⁺ ═

, --S⁺═ and

##STR5## wherein Z is selected from the group consisting of hydrogen, an alkyl group having 1-4 carbon atoms and an aryl group having 6-7 carbon atoms;

each of R₁ -R₆ is independently selected from the group consisting of hydrogen, an alkyl group having 1-4 carbon atoms, an alkoxy group having 1-4 carbon atoms and a nitro group;

each of R₇ -R₁₀ is independently selected from the group consisting of hydrogen and an alkyl group having 1-4 carbon atoms; and

X is halogen.

6. The oxygen indicator as defined in claim 1 wherein the dyestuff is represented by the formula ##STR6## wherein M is an alkali metal.

7. The oxygen indicator as defined in claim 1, characterized in that it further contains at least one surfactant.

8. The oxygen indicator as defined in claim 7 wherein the surfactant is selected from the group consisting of alkylsulfates, alkylnaphthalenesulfonates, naphthalenesulfonic acid-formalin condensates, polyoxyethylene alkylsulfates, polyoxyethylenealkylether, polyoxyethylene alkylphenolethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, alkylamino acid, quaternary ammonium salts and mixtures thereof.

9. The oxygen indicator as defined in claim 1, characterized in that it further contains at least one neutral or alkaline compound which is slightly soluble in water.

10. The oxygen indicator as defined in claim 9 wherein the compound which is slightly soluble in water is selected from the group consisting of BaSO₄, CaCO₃, MgCO₃, Mg(OH)₂ and Ca(OH)₂.

11. The oxygen indicator as defined in claim 1, characterized in that it further contains an inert dyestuff not causing color change through reacting with other components in the indicator.

2. A sheet-like oxygen indicator comprising a sheet selected from the group consisting of cellulosic sheets and plastic sheets and a composition coated or printed thereon which comprises

(a) at least one reducing agent selected from the group consisting of mixtures of at least one alkaline substance and dithionites, ferrous compounds, reducing saccharides or mixtures thereof;

ascorbic acid;

erysorbic acid or a salt thereof;

stannous salts;

hydroxyamine, hydrazine;

keto-carboxylic acids;

sulfoxylates;

alkali metal sulfides and boron hydrides;

(b) a dyestuff which has a color in an atmosphere containing oxygen and a different color in a non-oxygen containing atmosphere when it is reduced with said reducing agent;

(c) at least one water soluble polymeric compound in an amount of 0.05 to 10% by weight on the basis of weight of the total composition selected from the group consisting of sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, sodium alginate, polyvinyl alcohol, gum arabic powder, gum tragacanth, dextrin and casein; and

(d) at least one solvent selected from the group consisting of water, alcohols, and mixtures thereof.

12. The sheet like oxygen indicator as defined in claim 2 wherein the reducing agent is selected from mixtures of at least one alkaline substances and dithionites, ferrous compounds, reducing saccharides or mixtures thereof.

13. The sheet like oxygen indicator as defined in claim 12 wherein the alkaline substance is selected from hydroxides or weak acid salts of alkali metals or alkaline earth metals.

14. The sheet like oxygen indicator as defined in claim 12 or 13, characterized by adsorbing or adhering the alkaline substance onto or to the sheet, and then printing or coating the dyestuff, dithionites, reducing saccharides or ferrous compounds and solvent.

15. The sheet like oxygen indicator as defined in claim 2 wherein the dyestuff is represented by the formula ##STR7## wherein --Y³⁰ ═

is selected from the group consisting of --O⁺ ═

, --S⁺ ═ and

##STR8## wherein Z is selected from the group consisting of hydrogen, an alkyl group having 1-4 carbon atoms and an aryl group having 6-7 carbon atoms;

each of R₁ -R₆ is independently selected from the group consisting of hydrogen, an alkyl group having 1-4 carbon atoms, an alkoxy group having 1-4 carbon atoms and a nitro group;

each of R₇ -R₁₀ is independently selected from the group consisting of hydrogen and an alkyl group having 1-4 carbon atoms; and

X is halogen.

16. The sheet like oxygen indicator as defined in claim 2 wherein the dyestuff is the one represented by the formula ##STR9## wherein M is alkali metal.

17. The sheet like oxygen indicator as defined in claim 2, characterized in that it further contains at least one surfactant.

18. The sheet like indicator as defined in claim 17 wherein the surfactant is selected from the group consisting of alkylsulfates, alkylnaphthalenesulfonates, naphthalenesulfonic acid-formalin condensates, polyoxyethylene alkylsulfates, polyoxyethylenealkylether, polyoxyethylene alkylphenolethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, alkylamino acid, quaternary ammonium salts and mixtures thereof.

19. The sheet like oxygen indicator as defined in claim 2 characterized in that it further contains at least one neutral or alkaline compound which is slight soluble in water.

20. The sheet like oxygen indicator as defined in claim 19 wherein the compound which is slightly soluble in water is selected from the group consisting of BaSO₄, CaCO₃, MgCO₃, Mg(OH)₂ and Ca(OH)₂.

21. The sheet like oxygen indicator as defined in claim 2, characterized in that it further contains an inert dyestuff which does not cause color change through reaction with other components in the indicator.