Time watch or depletion indicator for removable substances

• US 4,248,597 A
• Filed: 12/12/1978
• Issued: 02/03/1981
• Est. Priority Date: 12/12/1978
• Status: Expired due to Term

• Current Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Original Assignee: Akzona Incorporated (Nouryon BV)
• Inventors: McNeely, Gerald W.
• Primary Examiner(s): Marcus, Michael S.
• Application Number:
  US05/968,871
• Time in Patent Office: 784 Days
• Field of Search: 422/58, 422/55-57, 422/59, 422/119, 422/60, 422/61, 23/230 R, 116/206
• US Class Current: 116/206
• CPC Class Codes: G01N 31/22 using chemical indicators G01N31/02 takes precedence
• CPC Class Codes: G07C 1/00 Registering, indicating or recording the time of events or elapsed time, e.g. time-recorders for work people registering or indicating the working of machines or vehicles G07C3/00, G07C5/00
• CPC Class Codes: Y10S 252/962 Temperature or thermal history

Abstract

A novel depletion indicator (time watch) for removable substances containing acid or basic groups is disclosed, together with a novel method of use therefor. The removable substance of a predetermined concentration comes into contact with a suitable pH color indicator that can change color at a predetermined pH range within a much larger measurable pH range, which color change occurs as the concentration of the removable substance diminishes by passing through a permeable film containing both the removable substance and the pH color indicator.The color change occurs at a predetermined time, e.g., the same time that the active ingredient has diminished to the point it is determined to be inactive.

Claims

1. A device for indicating the depletion of a removable substance by observing a color change, said device comprising:

(a) a permeable film; and

(b) a porous matrix containing a mixture consisting essentially of (1) a predetermined amount of a removable substance (I) containing acidic or basic groups and (II) capable of diffusing through said permeable film (a) and (2) a pH color indicator that undergoes a color change at a predetermined pH range without a chemical reaction with (I) without a broader pH range, said broader pH range bounded by a first pH measurable at said predetermined amount corresponding to when said removable substance commences to diffuse through said permeable film (a) and a second pH measurable after said removable substance has diffused through said permeable film and said color has occurred, said permeable film (a) containing said porous matrix (b).

2. The device of claim 1 wherein said porous matrix is selected from the group consisting of cellulose, polystyrene, a tetrafluoroethylene polymer, and polyester.

3. The device of claim 1 wherein said removable substance is a pesticide.

4. The device of claim 1 wherein said removable substance is an insecticide.

5. The device of claim 1 wherein said pH color indicator is selected from the group consisting of methyl red, chlorophenol red, ethyl red, malachite green, and phenol red.

6. The device of claim 1 wherein said pH color indicator is selected from the group consisting of o-cresolphthalein, thymolphthalein, alizarin yellow and phenolphthalein.

7. The device of claim 1 wherein said permeable film is selected form the group consisting of polypropylene, polyethylene, polyvinylchloride, polycarbonate, polyester, and polyamide.

8. The device of claim 1 wherein said removable substance is ethylenediamine and said pH color indicator is phenolphthalein.

9. The device of claim 1 wherein said removable substance is 2,2-dichlorovinyl dimethyl phosphate and said pH color indicator is chlorophenol red.

10. The device of claim 1 wherein said removable substance is hydrochloric acid and said pH color indicator is methyl red.

11. The device of claim 1 wherein said permeable film is polypropylene.

12. The device of claim 1 wherein said permeable film is polyvinylchloride.

13. The device of claim 1 wherein said removable substance is dimethyl phosphite and said pH color indicator is chlorophenol red.

14. The device of claim 1 wherein said removable substance is hydrochloric acid and said pH color indicator is malachite green.

15. The device of claim 1 wherein said pH color indicator and said removable substance are initially present in a ratio of the former to the latter of about 1 g/10² ml to about 1 g/10⁶ ml.

16. The device of claim 1, wherein an impermeable crushable pouch is within the permeable film, which pouch also contains the matrix.

17. The device of claim 1 further comprising

an impermeable crushable pouch containing said porous matrix (b), said impermeable crushable pouch within said permeable film (a).

18. The device of claim 1 further comprising a color painted on said permeable film in an area adjacent said porous matrix (a) and having a color corresponding to that of said pH color indicator (2) after it has changed color.

19. The device of claim 18 further comprising a second color painted on said permeable film in the area adjacent said porous matrix (a) and having a color corresponding to that of said pH color indicator (2) after it has started but not yet completed its color change.

20. A time watch for determining when a predetermined period of time has elapsed by observing a color change, comprising:

(a) a permeable film;

(b) a porous matrix containing a mixture consisting essentially of (1) a controlled release substance having acidic or basic groups diffusable through said permeable film (a); and

(2) a suitable pH color indicator that undergoes a color change without a chemical reaction with said controlled release substance (1) and in a predetermined pH range within a broader pH range bounded by;

(aa) a pH of (a) (1) measurable before any migration of (b)(1) from the porous matrix and before any color change has occurred; and

(bb) a pH of (a)(2) measurable after migration of (b)(1) from the porous matrix and after the color change has occurred;

(c) an impermeable crushable pouch containing an acid or base having acidic or a basic groups with the proviso that if the controlled release substance of (b)(1) is an acid, the crushable pouch contains a base and if the controlled release substance is a base, the pouch contains an acid; and

with a second proviso that said pouch and porous matrix are separated by said permeable film through which (b)(1) is diffusable; and

(d) a transparent impermeable container containing (a), (b) and (c) by which the porous matrix can be observed.

30. A method for determining when a predetermined period of time has elapsed, comprising:

gently crushing the time watch of one of claims 20, 21 or 22 and crushable pouch therein.

21. A device for indicating the depletion of a controlled release substance by observing a color change comprising:

(A) a mixture consisting essentially of;

(1) a controlled release substance containing acid or basic groups;

(2) a suitable pH color indicator that undergoes a color change without a chemical reaction with said controlled release substance and at a pH within a pH range bounded by a first pH measured as the concentration of said controlled release substance starts to diminish in said device and a second pH measured after said controlled release substance has completely diminished; and

(B) a permeable film containing said mixture, said film characterized by having the ability to pass said controlled release substance therethrough.

22. A time watch for determining when a predetermined period of time has elapsed by observing a color change, said time watch comprising:

(a) a permeable film;

(b) an impermeable crushable pouch containing a controlled release substance having acidic or basic groups and diffusable through said permeable film (a);

(c) a porous matrix containing a mixture consisting essentially of (1) an acid or a base and (2) a suitable pH color indicator that undergoes a color change without a chemical reaction with said controlled release substance and at a predetermined pH range within a broader pH range, said broader pH range bounded by (aa) a pH measurable before said controlled release substance initially contacts (c)(1) with the proviso that if the groups of said controlled release substance are acidic, then (c)(1) is a base and if the groups of said controlled release are basic, then (c)(1) is an acid and (bb) a second pH measurable after said controlled release substance has intimately contacted and has completely neutralized (c)(1) and said pH color indicator has completely changed color;

said permeable film (a) separating said impermeable crushable pouch (b) and said porous matrix (c); and

(d) a transparent impermeable container containing (a), (b), and (c) permitting said porous matrix (c) to be observed.

23. The device of claim 22 wherein the pH color indicator is thymol blue and the release substance is hydrochloric acid.

24. A time watch for determining when a predetermined period of time has elapsed by observing a color change, said time watch comprising:

(a) a permeable film;

(b) a porous matrix containing a mixture consisting essentially of (1) a predetermined amount of a removable substance containing acidic or basic groups and capable of diffusing through said permeable film and (2) a suitable pH color indicator that undergoes a color change without a chemical reaction with said removable substances, and at a predetermined pH range within a broader pH range, said broader pH range being bounded by a first pH measurable at said predetermined amount when said removable substance commences to diffuse through said permeable film and a second pH measurable after said removable substance has diffused through said permeable film and the color change has occurred;

(c) an impermeable crushable pouch covering said permeable film and said porous matrix, with the proviso that said impermeable crushable pouch and said porous matrix are separated by said permeable film; and

(d) a transparent impermeable container containing (a), (b), and (c) permitting said porous matrix (b) to be observed.

25. A method for indicating the depletion of a controlled release substance having a known period of effectiveness after activation of said controlled release substance, by a color change, said method comprising:

(a) activating the release of a removable substance through a permeable film, said removable substance being placed in a porous matrix containing a mixture consisting essentially of said removable substance and a suitable pH indicator, said removable substance being present in a predetermined amount, and capable of diffusing through said permeable film, and containing acidic or basic groups, said suitable pH color indicator capable of undergoing a color change without a chemical reaction with the removable substance and at a predetermined pH range within a broader pH range, said broader pH range being bounded by a pH measurable at said predetermined amount when said removable substance commences to diffuse through said permeable film and a second pH measurable after said removable substance has diffused through said permeable film and the color change has occurred, and

(b) noting said color change.

26. The method of claim 25 wherein activation is accomplished by

tearing an impermeable pouch containing the removable substance in the same concentration as within said permeable film and porous matrix, which pouch is detachable from said permeable film.

27. The method of claim 25 wherein the removable substance is different from the controlled release substance and is non-toxic.

28. The method of claim 25 wherein the controlled release substance is a pesticide or insecticide in an animal collar.

29. The method of claim 28 wherein the activation set occurs substantially simultaneously with the activation of the animal collar.