TIME TEMPERATURE INDICATOR LABEL

Abstract

A time-temperature integrating (TTi) indicator label comprises an initiator reservoir and a target reservoir, said initiator reservoir containing a pH modification system and said target reservoir comprising a pH responsive indicator. The pH responsive indicator may be photo-initiated. There is also provided a time-temperature indicator label comprising first and second reservoirs separated by a hydrogel valve, said valve allowing passage of an acid from said first reservoir to said second reservoir when the hydrogel valve is activated.

Claims

1. A time-temperature integrating (TTi) indicator label comprises an initiator reservoir and a target reservoir, said initiator reservoir containing a photoinitiated pH modification system and said target reservoir comprising a pH responsive indicator, wherein the label further comprises a third reservoir comprising a temperature-dependent timing mechanism comprising at least one of a diol, a polyol, a water-soluble polymer, and a gel.

2. A label according to claim 1, wherein the diol is selected from methylene glycol, ethylene glycol, propylene glycol, butylene glycol, longer-chain alkylene glycols, and derivatives thereof.

3. A label according to claim 1, wherein the polyol is selected from glycerol, hydroxyethyl cellulose, hydroxypropyl cellulose, polyethylene glycol, and derivatives thereof.

4. A label according to claim 1, wherein the water-soluble polymer is selected from polyacrylic acid, polyvinylpyrrolidone, polyacrylamide, a polysaccharide, a polypeptide, and derivatives thereof.

5. A label according to claim 4, wherein the polysaccharide is selected from agar, agarose, agaropectin, cellulose, and derivatives thereof.

6. A label according to claim 1, wherein the third reservoir comprises a diol and a polyol, preferably propylene glycol and glycerol.

7. A label according to claim 6 wherein the percentage of propylene glycol to glycerol in the timing mechanism is from 100% propylene glycol and 0% glycerol to 0% propylene glycol and 100% glycerol.

8. A label according to claim 1, wherein the gel is a cured aqueous solution of N-isopropyl acrylamide, Polyethylene (glycol) Diacrylate, sodium acrylate and a photoinitiator.

9. A label according to claim 1, wherein the gel/hydrogel is a cured polyol-based solution of N-isopropyl acrylamide, Polyethylene (glycol) Diacrylate, sodium acrylate and a photoinitiator.

10. A label according to any preceding claim, wherein said pH modification system comprises an acid generation system.

11. A label according to any preceding claim, further characterised in that said initiator and target reservoirs are separate portions of the same physical reservoir.

12. A label according to any preceding claim, wherein said initiator and target reservoirs are physically separate, distinct reservoirs.

13. A label according to any of claims 10 to 12, further characterised in that said acid generation system comprises a photo-initiated acid generation system.

14. A label according to claim 13, further characterised in that said photo-initiated acid generation system comprises a photo acid generator (PAG).

15. A label according to claim 14, wherein said PAG comprises an onium salt, an arylketosulphinate, an o-nitrobenzyl ester, a napthoquinone diazide, or an oximinosulphonate.

16. A label according to any preceding claim, further characterised in that said initiator reservoir is at least partially filled with a hydrogel polymer.

17. A label according to claim 16, further characterised in that said acid generation system is entrained within a matrix formed by said hydrogel polymer.

18. A label according to either of claim 16 or 17, further characterised in that said acid generation system comprises an acid entrained within said hydrogel polymer, said hydrogel polymer being a photosensitive hydrogel polymer, such that on exposure to light said hydrogel polymer de-swells effecting release of said acid into said initiator reservoir.

19. A label according to any of claims 1 to 18, wherein the initiator reservoir comprises a PAG, a solvent, and, optionally, a photosensitiser.

20. A label according to any preceding claim, further characterised in that at least a portion of said initiator reservoir is arranged such that it can be exposed to light.

21. A label according to claim 20, wherein said arrangement to allow exposure to light is achieved via the provision of a peelable/removable, substantially light impermeable upper layer of said label.

22. A label according to any preceding claim, further characterised in that at least a portion of said target reservoir is visible from outwith said label to allow visual inspection thereof.

23. A label according to any preceding claim, said reservoirs being arranged in series, initiator to accumulator to target reservoir.

24. A label according to claim 23, wherein said initiator and accumulator reservoirs are separated by a stimuli-responsive hydrogel polymer plug.

25. A label according to claim 23, wherein said accumulator and target reservoirs are separated by a stimuli-responsive hydrogel polymer plug.

26. A label according to claim 23, wherein said initiator and accumulator reservoirs are separated by a first stimuli-responsive hydrogel polymer plug, and said accumulator and target reservoirs are separated by a second stimuli-responsive hydrogel polymer plug.

27. A label according to claim 26, wherein said first stimuli-responsive hydrogel polymer plug and said second stimuli-responsive hydrogel polymer plug comprise different hydrogel polymers.

28. A label according to claim 26 or 27, further characterised in that said first stimuli-responsive hydrogel polymer plug and said second stimuli-responsive hydrogel polymer plug are both responsive to the same stimulus.

29. A label according to claim 26 or 27, wherein said first stimuli-responsive hydrogel polymer plug and said second stimuli-responsive hydrogel polymer plug are both responsive to different levels of the same stimulus.

30. A label according to any of claims 24 to 29, wherein said stimuli-responsive hydrogel polymer plugs comprise pH responsive hydrogel polymers.

31. A label according to claim 26 or 27, further characterised in that said first stimuli-responsive hydrogel polymer plug and said second stimuli-responsive hydrogel polymer plug are responsive to different stimuli.

32. A label according to any of claims 1 to 31, further characterised in that said accumulator reservoir is (at least partially) filled with a further hydrogel polymer and or a high viscosity medium.

33. A time-temperature indicator label according to any preceding claim comprising an initiator reservoir, an accumulator reservoir and a target reservoir arranged in series, said reservoirs each being separated by a pH responsive hydrogel polymer plug, said initiator reservoir containing a PAG, said initiator reservoir further being provided with a substantially light impermeable, peelable cover such that it can be selectively exposed to light, said accumulator reservoir further containing a hydrogel polymer matrix or a high viscosity medium; said target reservoir further containing a pH indicator compound; such that upon removal of said peelable layer said PAG is exposed to light, said PAG reacts to generate hydrogen ions, said hydrogen ions then causing the de-swelling of the first pH responsive hydrogel polymer plug, allowing ingress of said hydrogen ions into said accumulator reservoir, the contents of said accumulator reservoir hence becoming gradually more acidic as the hydrogen ions diffuses in from said initiator reservoir; subsequently, as the level of hydrogen ions in said accumulator reservoir accumulates to a sufficient level said hydrogen ions causes the de-swelling of said second pH responsive hydrogel polymer plug, thereby allowing ingress of said hydrogen ions into said target reservoir wherein said hydrogen ions interacts with said pH indicator compound to effect a colour change, said colour change being observable by the user through a viewing pane incorporated into said target reservoir.

34. A time-temperature indicator label according to any of claims 1 to 32 comprising two or more initiator reservoirs, each connected to a separate accumulator reservoir, said connections each being blocked by separate, pH responsive hydrogel plugs, said separate accumulator reservoirs each being connected, via a further two separate pH responsive hydrogel plugs, to said target reservoir, said initiator reservoirs each containing a PAG, said initiator reservoirs further being provided with a substantially light impermeable, peelable cover such that they can be selectively exposed to light, said accumulator reservoirs each further containing a hydrogel polymer matrix or high viscosity medium; said target reservoir further containing a pH indicator compound; such that upon removal of said peelable layer said silver chloride or PAG is exposed to light, said PAG reacts to form hydrogen ions, said hydrogen ions then causing the de-swelling of the first pH responsive hydrogel polymer plugs, allowing ingress of said hydrogen ions into said accumulator reservoirs, the contents of said accumulator reservoir hence becoming gradually more acidic as the hydrogen ions diffuses in from said initiator reservoirs; over time, diffusion of hydrogen ions causes the pH of the accumulator reservoirs to drop to such a level that the said second hydrogel plugs de-swell, thereby providing a fluid connection between said accumulator reservoirs and said target reservoir, wherein said hydrogen ions interacts with said pH indicator compound to effect a colour change, said colour change being observable by the user through a viewing pane incorporated into said target reservoir.

35. A label according to claim 34, further characterised in that said first and second accumulator reservoirs cause the de-swelling of said plugs separating them from said target reservoir at disparate points in time, such that the contents of said first accumulator reservoir diffuse into said target reservoir earlier than the contents of said second accumulator reservoir, such that two distinct colour changes are effected.

36. A label according to claim 35, wherein said time differential is achieved through the provision of different hydrogel polymer materials for the pH responsive hydrogel plugs.

37. A label according to claim 35, wherein said time differential is achieved through the generation of different levels of acidity in said respective initiator reservoirs.

38. A label according to claim 35, wherein said time differential is achieved through the provision of different hydrogel polymer materials or high viscosity media within said two or more accumulator reservoirs.

39. A label according to claim 35, wherein said time differential is achieved through variation in the relative sizes of said two or more accumulator reservoirs.

40. A label according to claim 35, wherein said time differential is achieved through a combination of one or more of the provision of different hydrogel polymer materials for the pH responsive hydrogel plugs, the generation of different levels of acidity in said respective initiator reservoirs, the provision of different hydrogel polymer materials or high viscosity media within said two or more accumulator reservoirs and variation in the relative sizes of said two or more accumulator reservoirs.

41. A label according to any preceding claim, further comprises a three layer, laminar construction comprising a base layer, an intermediate layer and a top layer.

42. A label according to claim 41 further characterised in that said base layer and top layer are substantially unitary, unbroken polymer films.

43. A label according to either of claims 41 and 42, characterised in that said reservoirs are formed by die-cutting and removal of portions of said intermediate layer prior to lamination.

44. A label according to any of claims 41 to 43, further comprising a peelable strip preventing the inadvertent ingress of light to said initiator reservoir(s).

45. A label according to any preceding claim, further characterised in that said target reservoir further contains one or more pH reactive inks arranged to enhance the colour change of said acid responsive indicator.

46. A label according to any of claims 1 to 45, further characterised in that said target reservoir further contains one or more pH reactive inks, said one or more pH reactive inks fulfilling the role of said acid responsive indicator.

47. A label according to either of claims 45 and 46, wherein said pH reactive inks are entrapped within a polymer matrix contained within said target reservoir.

48. A label according to claim 47, wherein said polymer matrix comprises a UV cured polymer matrix.

49. A label according to any preceding claim, further characterised in that said stimuli-responsive hydrogel polymers are selected from the group comprising poly (vinyl alcohol)/poly (acrylic acid) [PVA/PAA]; poly (methacrylic acid) [PMAA] and 2-(dimethylamino) ethylmethacrylate/N-vinyl pyrrolidone [DNAEMA/NVP].

50. A label according to any preceding claim, wherein photo-initiated acid generation system comprises a photosensitiser.

51. A label according to claim 50, wherein the photosensitiser is perylene.

52. A label according to claim 51, wherein the perylene is included in an amount of from around 0.5 wt % to around 5 wt %, preferably around 1 wt %.

53. A time-temperature indicator label comprising first and second reservoirs separated by a hydrogel valve, said valve allowing passage of an acid from said first reservoir to said second reservoir when the hydrogel valve is activated, the label further comprising a temperature-dependent timing mechanism comprising at least one of a diol, a polyol, a water-soluble polymer and a gel.

54. A label according to claim 53, wherein the polyol is selected from glycerol, hydroxyethyl cellulose, hydroxypropyl cellulose, polyethylene glycol, and derivatives thereof.

55. A label according to claim 53, wherein the diol is selected from methylene glycol, ethylene glycol, propylene glycol, butylene glycol, and derivatives thereof.

56. A label according to claim 53, wherein the water-soluble polymer is selected from polyacrylic acid, polyvinylpyrrolidone, polyacrylamide, polysaccharide, polypeptide, and derivatives thereof.

57. A label according to claim 56, wherein the polysaccharide is selected from agarose, agaropectin, cellulose, and derivatives thereof.

58. A label according to any of claims 53 to 57, wherein the temperature-dependent timing mechanism comprises a diol and a polyol, preferably glycerol and propylene glycol, preferably wherein the percentage of propylene glycol to glycerol in the timing mechanism is from 100% propylene glycol and 0% glycerol to 0% propylene glycol and 100% glycerol.

59. A label according to any of claims 53 to 58, wherein the hydrogel valve is opened by exposure to light and/or heat.

60. A label according to any of claims 53 to 57, wherein the hydrogel valve is opened by exposure to light.

61. A label according to any of claims 53 to 58, wherein the first reservoir comprises an acidic solution.

62. A label according to claim 60, wherein the hydrogel comprising the hydrogel valve shrinks or de-swells on exposure to light and allows the acidic solution to pass into the second reservoir.

63. A label according to any of claims 53 to 62 further comprising a third reservoir, preferably wherein the third reservoir comprises the temperature-dependent timing mechanism.

64. A label according to claim 63, wherein the third reservoir is separated from the second reservoir by a stimuli-reactive hydrogel plug.

65. A label according to claim 64, wherein the stimuli reactive hydrogel plug is pH reactive and shrinks or de-swells at a predetermined pH.

66. A label according to any of claims 63 to 65, wherein the third reservoir comprises a pH responsive indicator.

67. A time-temperature indicator label substantially as hereinbefore described with reference to the claims and description.

Description

[0111] Embodiments of the invention will now be described by way of example and with reference to the accompanying schematic drawings wherein:

[0112] FIG. 1 is a schematic plan view of a label in accordance with the first and second aspects of the present invention;

[0113] FIG. 2 is a schematic cross section of a label in accordance with the first aspect of the present invention:

[0114] FIG. 3 is a schematic plan view of a body layer of a label in accordance with the first and second aspects of the present invention;

[0115] FIG. 4 is a schematic plan view of a label in accordance with the first aspect of present invention;

[0116] FIGS. 5 to 9 are schematic plan views of a label in accordance with the first aspect of present invention showing the timing mechanism in action from when the label is first activated through a first colour change and finally to a second colour change;

[0117] FIGS. 10a to 10d are photographs of an exemplary label in accordance with the first aspect of the present invention showing the progress of the timing mechanism;

[0118] FIG. 11 is a schematic representation of a label in accordance with the first aspect of the present invention:

[0119] FIG. 12 is a graph showing the distance acid had diffused through a hydrogel versus time at 5 C., room temperature (around 21 C.), and at 40 C.

[0120] FIG. 1 shows a schematic depiction of a time temperature integrating (TTi) indicator label 1 according to the first and second aspects of the present invention. The label 1 comprises transparent activation windows 2 and transparent viewing window 3. The transparent activation windows 2 overlie at least a portion of the photoinitiated pH modification system and/or the pH or light sensitive hydrogel plug. The transparent viewing window 3 allows the user to view the colour of the pH responsive indicator contained within the label 1. It will be appreciated that the activation windows 2 and the viewing window 3 may be of any suitable shape and size. It will also be appreciated that there may be any number of activation windows 2, including there being only a single activation window. Similarly, there may be any number of viewing windows 3. The activation window 2 and the viewing window 3 may overlap or be the same window.

[0121] Referring to FIG. 1, the label 1 is shown in plan form and the top layer 4 is shown as being blank. At least a portion of the top layer 4 is preferably transparent to allow light to activate the timing mechanism, namely the pH modification system and/or the pH or light sensitive hydrogel plug. However, it will be appreciated that portions of the top layer 4 may be opaque and/or the surface of the top layer 4 may be printed with decorations and/or information. The area of the top layer 4 above the photoinitiated hydrogel valve and/or photoinitiated pH modification system may not be entirely transparent, but is sufficiently transparent to allow sufficient light to pass through to activate the hydrogel valve and/or the pH modification system, and to allow the user to view the colour of the pH responsive indicator.

[0122] FIG. 2 is a cross sectional view of the structure of label 1 (not to scale). Label 1 comprises a release liner 5. The release liner 5 may be calendered paper, such as glassine, or a polymer film, such as a polyolefin film. The release liner 5 may comprise polyethylene terephthalate or any other suitable polymer. The release liner 5 may be coated with silicone. Where the release liner 5 comprises calendered paper, it is preferably around 30 to around 80 microns thick, and where the release liner comprises a polymer film, it is preferably around 10 to 20 microns thick. However, it will be appreciated that where reference is made to the thickness of any particular layer, that the skilled person would recognise that any suitable thickness could be used. The release liner 5 allows the label to be transported and fed through the label applicator machinery, and is removed prior to the label application. The release liner 5 covers an adhesive layer 6. The adhesive 6 is preferably a pressure sensitive adhesive. The adhesive layer 6 allows the label 1 to be affixed to packaging. The adhesive layer 6 is attached to the base layer 7.

[0123] The base layer 7 is preferably a polymer film. The base layer 7 is preferably white to allow the colour of the pH responsive indicator to be seen clearly by the consumer, but any colour could be used which allows the consumer to readily determine the colour of the pH responsive indicator. Preferably, the base layer 7 is an uninterrupted film. The base layer 7 may comprise polypropylene. The base layer may be around 50 to around 120 microns thick. The base layer is preferably an uninterrupted film. A pH sensitive colour changing ink 9 is printed onto the base layer 7. The pH sensitive colour changing ink 9 changes colour in response to changes in pH and provides the visual indication to the consumer of the status of the product to which the label 1 is applied.

[0124] The label 1 also comprises a body layer 8. The body layer 8 is preferably laminated onto the base layer 7 and serves to define the reservoirs of the label 1. The body layer 8 includes cut-outs which create cavities which may be filled with hydrogels, PAGS, high viscosity media, and/or buffer solution, as appropriate. The body layer 8 may be die cut. The body layer 8 may be self-adhesive. The body layer 8 may comprise polypropylene. The body layer may be around 50 to around 120 microns thick.

[0125] A buffer solution may be located in viewing cavity/target reservoir 10. The buffer solution is preferably colourless and serves to maintain the pH sensitive colour changing ink 9 at a constant pH until the label 1 is activated. The buffer solution preferably does not strongly resist changes in pH.

[0126] A photoinitiated pH modification system and/or pH or temperature sensitive hydrogel plug is located in the activation cavity/initiator reservoir 11 and or between the initiator reservoir 11 and the accumulator reservoir 16 respectively. It will be appreciated that the base layer 7 and body layer 8 may be printed using 3D printing techniques or tactile printing processes such that no die cutting is required. 3D digital printing and high volume rotary screen deposition may be used to form the base layer 7 and body layer 8. As such, the base layer 7 and the body layer 8 may be unitary.

[0127] The label 1 also comprises a top layer 4. The top layer 4 is preferably a polymeric film. The top layer 4 may comprise polypropylene or any other suitable polymer. The top layer 4 may be around 50 to around 75 microns thick. Preferably, the top layer 4 is an uninterrupted film, meaning that it comprises no cuts, perforations, recesses, or similar. The top layer 4 is preferably laminated onto the upper surface of the body layer 8. The top layer 4 may be printed with a pattern or information 13. The top layer 4 is preferably transparent such that at least a portion of the transparent area of the top layer 4 overlies at least a portion of the viewing cavity/target reservoir 10 and the activation cavity/initiator reservoir 11. The label 1 optionally comprises a peel-off layer 12. The peel-off layer 12 is preferably substantially impermeable to light. The peel-off layer 12 is preferably a filmic material, and may comprise polypropylene or any other suitable polymer. The peel-off layer 12 may be a metallic film. The peel-off layer 12 may be a metallised clear polymer film, which may comprise non-metallised areas which allow the consumer to view the viewing window/target reservoir. The peel-off layer 12 may be around 50 to around 75 microns thick. The peel-off layer 12 is preferably uninterrupted. The peel-off layer 12 may comprise inherently light impermeable material, or may be printed with one or more layers of light impermeable ink. The peel-off layer 12 may be laminated onto the surface of the top layer 4. The peel-off layer 12 is readily removable from the top layer 4 to allow the label 1 to be activated.

[0128] FIG. 3 is an exemplary plan view of the die cut areas of the body layer 8. The die cut areas form a continuous cavity. It will be appreciated that any suitable shape could be used and that the invention is not limited by the particular configuration shown. The viewing cavity/target reservoir 10 and activation cavity/initiator reservoir 11 are shown in plan view. The viewing cavity/target reservoir 10 and activation cavities/initiator reservoir 11 may be of any suitable shape. The activation cavity 11 defines the first/initiator reservoir and the viewing cavity 10 defines the second/target reservoir. Also shown are the areas in which hydrogel plugs or valves 14a, 14b, 15a, and 15b are located in the assembled label 1. The hydrogel plugs or valves 14a, 14b, 15a, and 15b create five discrete reservoirs or cavities in the label 1 which may be filled. In the present embodiment, the hydrogel plugs 14a, 14b, 15a, and 15b create two initiator reservoirs 11a, 11b, two accumulator reservoirs 16a, 16b, and a single target reservoir 10. It will be appreciated that other embodiments may have different numbers of such reservoirs. Accumulator reservoirs 16a and 16b are described in more detail in respect of FIG. 4. According to the first aspect of the present invention, the initiator reservoirs 11 comprise the pH modification system, which may comprise a PAG, solvent, and optionally a photosensitiser. In another embodiment, the initiator reservoir(s) 11 comprise an acidic solution which is allowed to pass into the accumulator reservoir(s) 16 when a photo-sensitive valve separating the initiator reservoir(s) 11 from the accumulator reservoir(s) is exposed to light.

[0129] FIG. 4 shows a label 1 comprising a photoinitiated acid generation system in the initiator reservoir 11b. Adjacent to the photoinitiated acid generation system in the initiator reservoir 11b is a first hydrogel plug or valve 14b. The first hydrogel plug or valve 14b is pH sensitive and, prior to activation, serves as a separator between the acid generation system in the initiator reservoir 11b and the high viscosity medium in accumulator reservoir 16b. Once the PAG system in the initiator reservoir 11b has been activated, the first hydrogel plug or valve 14b de-swells or otherwise collapses to allow hydrogen ions to diffuse into the accumulator reservoir 16b. Contained within the accumulator reservoir 16b is a high viscosity medium which regulates the rate of diffusion of the hydrogen ions through the accumulator reservoir 16b. The rate of diffusion is controlled by the chemical composition, viscosity, and/or temperature of the high viscosity medium. Preferably the viscosity is in the range of from about 20 to about 7500 centipoise (at 20 C.). Preferably, the viscosity of the high viscosity medium in accumulator reservoir 16b is higher than that of the high viscosity medium in accumulator reservoir 16a. The pH of the high viscosity medium in accumulator reservoir 16b is preferably around 5.5 to around 7.0 prior to the activation of the label 1. The label 1 also comprises a second hydrogel plug or valve 15b. The second hydrogel plug or valve 15b separates the accumulator reservoir 16b from the target reservoir 10. Once the pH in the accumulator reservoir 16b drops of a predetermined level, the second hydrogel plug or valve 15b de-swells or otherwise collapses, thereby allowing hydrogen ions to pass into the target reservoir 10 and lower the pH. The drop in pH results in a visible colour change. The other side of the label 1 has a similar structure and similar features are given the same numbers, but with different letters. The other side of the label 1 operates in the same way, but the high viscosity medium in the accumulator reservoir 16a is different to that in accumulator reservoir 16b, which results in a different rate of diffusion of hydrogen ions along the reservoirs. Since the hydrogel plugs 15a and 15b are induced to de-swell at different times, this results in two colour changes at different times.

[0130] FIGS. 5 to 9 shows how the label 1 functions once it has been exposed to light. Exposing the PAG in the initiator reservoirs 11a, 11b to light causes the PAG to generate hydrogen ions, which lower the pH adjacent the hydrogel plugs 14a, 14b. The PAGs in the initiator reservoirs 11a, 11b may be the same or different. The PAGs may be included in the same or in different concentrations. In FIG. 5, the PAGs in the initiator reservoirs 11a, 11b have been activated by exposure to light and the decrease in pH caused by the generation of acidic species has caused the hydrogel plugs 14a, 14b to collapse. The collapse of the hydrogel plugs 14a, 14b results in them acting as a valve and allowing the hydrogen ions which have been generated by the PAG to pass into the respective accumulator reservoirs 16a, 16b. The PAGs can lower the pH to around 0 to around 2.0. The hydrogel plugs 14a, 14b may de-swell by around 40% at the predetermined pH.

[0131] FIG. 6 shows the diffusion of the hydrogen ions through each of the accumulator reservoirs 16a, 16b. The hydrogen ions have diffused further along accumulator reservoir 16 a compared to accumulator reservoir 16b. This is due to the different high viscosity media used in the reservoirs.

[0132] FIG. 7 shows the hydrogen ions having diffused along the accumulator reservoir 16a and reached hydrogel plug 15a. Hydrogel plug 15a is configured to deswell at a predetermined pH, such as around 4.5, and the concentration of ions in accumulator reservoir 16a continues to increase until the pH of the media adjacent the hydrogel plug 15a falls to the predetermined pH.

[0133] As shown in FIG. 8, once the pH adjacent the hydrogel plug 15a falls to the predetermined level, the hydrogel plug 15a de-swells and the hydrogen ions are able to rapidly pass into the target reservoir 10. The pH in the target reservoir 10 locally falls on account of the influx of hydrogen ions and this results in a colour change in the pH sensitive colour changing ink. The drop in pH in the target reservoir 10 is not sufficient to activate the second hydrogel plug 15b, which is configured to de-swell at a lower pH, such as, for example, around 2.5.

[0134] FIG. 9 shows the case where further time has passed and the hydrogen ions in the accumulator reservoir 16b have diffused towards hydrogel plug 15b and caused it to de-swell. Since hydrogel plug 15b is configured to de-swell at a pH which is lower than the pH required to de-swell hydrogel plug 15a, when hydrogel plug 15b de-swells, the concentration of hydrogen ions which pass into the target reservoir 10 is greater and causes a further drop in pH in the target reservoir 10. This further drop on pH causes a second colour change in the pH sensitive colour changing ink. The second colour change may be from amber to red to indicate that the product is no longer suitable for use.

[0135] FIGS. 10a to 10d show the progress of the colour change of an exemplary label 1. FIG. 10a shows the label 1 prior to activation, and the remaining figures show the progress of the colour change as the hydrogel plugs 15a, and 15b de-swell and allow the pH in the target reservoir to drop. FIG. 10b shows a front of colour change originating from the lower portion of the central window and FIG. 10c shows the colour change extending almost to the top of the central window. FIG. 10d shows the completed colour change

[0136] FIG. 11 shows a schematic representation of the functioning of the label according to the first aspect of the present invention. The label 1 comprises a first reservoir, also known as an initiator reservoir 11, comprising a pH modification system. In the illustrated embodiment, the pH modification system comprises a photo-acid generator 17. The PAG 17 is depicted as separate from the initiator reservoir 11, but this is for the sake of an example and it will be appreciated that the PAG 17 may be dispersed within the initiator reservoir 11 and does not have to be a separate layer. The label 1 further comprises a first hydrogel plug 14 which separates the initiator reservoir 11 from a second reservoir 16, which may be referred to as an accumulator reservoir. In addition, the label further comprises a second hydrogel plug 15 which separates the accumulator reservoir 16 from a third reservoir 10, which may be referred to as a target reservoir 10. It will be appreciated that certain embodiments do not comprise a separate accumulator reservoir 16. The target reservoir 10 comprises a pH responsive indicator which changes colour in response to changes in pH.

[0137] The label 1 may also comprise a light impermeable layer or barrier 12 to substantially block light from activating the photo acid generator 17. It will be appreciated that the light impermeable layer 12 is a removable feature of the label, which may be removed by the user or when the label is applied to a package.

[0138] In use, the light impermeable layer or barrier 12 is removed to expose the PAG 17 to light. On exposure to light, the PAG 17 generates hydrogen ions in the initiator reservoir 11. The increase in concentration of the hydrogen ions results in a drop in pH, for example from around 6.0 to around 4.5. When the pH in the initiator reservoir 11 drops to a predetermined level, the first hydrogel plug 14 de-swells to allow the hydrogen ions from the initiator reservoir 11 to pass into the second reservoir 16. Due to the increased concentration of hydrogen ions in the initiator reservoir 11 compared to the second reservoir 16, the hydrogen ions pass down the concentration gradient and into the second reservoir 16. As such, by altering the composition of the accumulator reservoir 16, it is possible to control the rate of diffusion of the hydrogen ions through the accumulator reservoir 16. The hydrogen ions are able to pass along the accumulator reservoir 16 until they reach the second hydrogel plug 15. The rate of diffusion of the hydrogen ions through the second plug 15 is very low or preferably substantially zero, which allows the concentration of hydrogen ions in the area adjacent the second plug 15 to increase, thereby lowering the pH. Once the pH has fallen to a predetermined level, for example around 4.5, the second plug 15 de-swells to allow the hydrogen ions from the accumulator reservoir 16 to pass into the target reservoir 10. The influx of hydrogen ions into the target reservoir 10 causes a drop in pH in the target reservoir 10. The pH responsive indicator in the target reservoir 10 changes colour in response to the drop in pH. The colour of the target reservoir 10 is visible to the user and the change in colour in the target reservoir 10 provides a visual indication that the label 1 has been activated for a first predetermined period of time. Preferably, the colour changes from green to orange or amber. Having the concentration of hydrogen ions accumulate near to the target reservoir 10 and then having the second hydrogel plug 15 collapse at a predetermined pH results in a rapid influx of hydrogen ions into the target reservoir 10 and a rapid change in colour. In the event that there was no plug or barrier between the accumulator reservoir 16 and the target reservoir 10, the change in pH of the target reservoir 10 would be more gradual and would drop slowly as the hydrogen ions diffused through the accumulator reservoir 16. This would lead to a gradual change in the colour of the target reservoir 10 and the user would have a much less clearly defined indication of the passage of time. In this way, it will be appreciated that the sequential collapse of the hydrogel plugs allows for the accumulation of hydrogen ions such that when the hydrogel plugs de-swell, there is a large concentration gradient of hydrogen ions from one side of the plug to the other, so that there is rapid diffusion of hydrogen ions into the next reservoir. The rate of diffusion of the hydrogen ions is controlled by the composition of the accumulator reservoir 16. The accumulator reservoir 1 may contain a high viscosity medium, such as a composition comprising, in any combination, one or more of carboxymethyl cellulose, hydroxyethyl cellulose, carbopol, and/or surfynol 465 in water. It will be appreciated that in some embodiments, there is not a valve or plug between different reservoirs and the timing mechanism is controlled by the rate of diffusion through a reservoir intermediate the initiation reservoir and the target reservoir. Therefore, in an embodiment, the label comprises an initiator reservoir, a target reservoir, and an intermediate portion or reservoir, wherein the intermediate portion or reservoir comprises a temperature-dependent timing mechanism. The timing mechanism is preferably based on the rate of diffusion of a species, such as an acid, through the reservoir.

[0139] The label 1 may comprise one or more initiator reservoirs and/or one or more accumulator reservoirs. Where there is more than one accumulator reservoir, the properties of one of the accumulator reservoirs may be altered to make the rate of diffusion along the reservoir slower. This may be achieved in any suitable way, such as, for example, increasing the length of the accumulator reservoir, altering the cross sectional area of the accumulator reservoir, providing a choke in the accumulator reservoir, or altering the material or materials contained within the accumulator reservoir. Having two accumulator reservoirs allows there to be two influxes of hydrogen ions into the target reservoir and two separate rapid drops in pH. This allows there to be more than one colour change in the reservoir. The second colour change may be from orange or amber to red. The second colour change may indicate that the product to which the label is applied is no longer fit for consumption. Thus, the time period for the first colour change to occur is dependent on the rate at which hydrogen ions are able to pass along a first accumulator reservoir, and the time period for the second colour change is dependent on the rate at which the hydrogen ions are able to pass along a second accumulator reservoir. In other embodiments, the hydrogen ions may pass along the two accumulator reservoirs at the same rate, but one reservoir may be longer than the other.

[0140] FIG. 12 is a graph showing the distance an acid had travelled along the medium versus time at 5 C. (lowermost two lines), room temperature (around 21 C.) (middle two lines), and at 40 C. (highest line). The acid used was 1M HCl and the gel used was cured from a solution of glycerol (40 wt %), propylene glycol (40 wt %) and water (20 wt %). It can be clearly seen that the rate of diffusion is increased at higher temperatures all else being equal.

[0141] FIG. 13 is a table showing the distance an acid had travelled in various media as a function of time at different temperatures. Each of the compositions investigated increased rates of diffusion at higher temperatures. The HVMT was 0.5% w/w hydroxyethyl cellulose in water. VG/PG/H.sub.2O 40/40/20 represents a mixture of (vegetable) glycerol, propylene glycol and water in the ratio 40:40:20 by volume. PG represents propylene glycol by itself and VG/PG 50/50 represents a 50:50 mixture by volume of (vegetable) glycerol and propylene glycol. As with the graph shown in FIG. 12, the acid source was 1M HCl.

[0142] These results indicate that the difference in the rate of diffusion at various temperatures is greatest for glycerol, propylene glycol, and mixtures thereof. As such, glycerol, propylene glycol, and mixtures therefore show the highest variation of rates of diffusion of the materials tested and are therefore eminently suitable to be used in a temperature-dependent timing mechanism.

EXAMPLES

[0143] Photoinitiated Acid Generators

[0144] Examples of the photoinitiated pH modification system have been fabricated and tested. The results of the tests demonstrate the suitability of photo acid generators to generate hydrogen ions following exposure to light and thereby alter the pH of a system.

Example 1

[0145] A 50% w/w solution of the triarylsulphonium salts

##STR00005##

in propylene carbonate was prepared an exposed to light to generate acid. The solution comprised 1% by weight perylene. The solution was then brought into contact with an aqueous based, high viscosity medium (HVMT) comprising an admixture of carboxymethyl cellulose and carbopol and the pH of the HVMT was measured over time to track the migration of the hydrogen ions through the HVMT from the PAG solution.

[0146] In the first experiment 3:1 PAG:HVMT (w %/w %) was used. The solution was exposed to light for 24 hours. The pH of the HVMT began at 5.9 and after one hour in contact with the PAG solution, the pH had fallen to 4.0. At 24 hours, the pH had fallen to 2.3, and the pH ultimately fell to 1.8 after six days.

[0147] In a second experiment 6:1 PAG:HVMT (w %/w %) was used. The solution was exposed to light for 144 hours. The pH of the HVMT began at 5.3 and had fallen to 2.1 after 24 hours in contact with the PAG solution. The pH ultimately fell to 1.8 after 2 days.

Example 2

[0148] A solution of 1 wt % Irgacure PAG 290 in benzyl alcohol was prepared. The solution contained 1 wt % perylene with respect to benzyl alcohol. The initial pH was 4.5 and had fallen to 1.4 24 hours after activation. To this solution 35 wt % of water was added after 24 hours and the pH of the water was measured to be 4.4

Example 3

[0149] A solution of 1 wt % Speedcure 938 in ethanol was prepared. The solution contained 1 wt % perylene. The initial pH was measured to be 5.5, and this fell to one 24 hours after activation. To this solution, 35 wt % of water was added after 24 hours and the pH of the water was measured to be 2.6.

[0150] A solution of 20 wt % Speedcure 938 in ethanol was prepared. The solution contained 1 wt % perylene. The initial pH was measured to be 5, and this fell to 0.15 24 hours after activation. To this solution, 35 wt % of water was added after 24 hours and the pH of the water was measured to be 1.6.

Example 4

[0151] In a similar way to Example 1, a 10% w/w solution of Di-phenyl iodonium hexafluorophosphate with 1% w/w perylene was prepared in benzyl alcohol. The solution was activated by exposure to light and then subsequently brought into contact with an aqueous based, high viscosity medium (HVMT) comprising an admixture of carboxymethyl cellulose and carbopol and the pH of the HVMT was measured over time to track the migration of the hydrogen ions through the HVMT from the PAG solution.

TABLE-US-00002 Time PAG solution exposed to PAG:HVMT pH at pH after pH after light (wt %/wt %) t = 0 1 hour 24 hours Final pH 24 hours 3:1 5.0 3.4 1.8 1.5 after 2 days 144 hours 3:1 5.2 1.5 0.5 144 hours 1:1 5.0 2.1 0.8 1 hour 2:1 5.0 4.2 2.7 1.7 after 2 days

Example 5

[0152] A 1% w/w solution of Irgacure 103 with 1% w/w perylene was prepared in ethanol. The initial pH of the solution was 6.5, which dropped to 0.6 24 hours after exposure to light. To this solution, 35 wt % of water was added after 24 hours and the pH of the water was measured to be 2.6.

[0153] A 1% w/w solution of Irgacure 103 with 1% w/w perylene was prepared in benzyl alcohol. The initial pH of the solution was 6.2, which dropped to 0.3 24 hours after exposure to light. To this solution, 50 wt % of water was added after 24 hours and the pH of the water was measured to be 3.4

[0154] A 10% w/w solution of Irgacure 103 without perylene was prepared in ethanol. The pH of the solution was 2.5 four hours after exposure to light, which dropped to 0 24 hours after exposure to light. To this solution, 75 wt % of water was added after 24 hours and the pH of the water was measured to be 3.6.

[0155] It is apparent from this example that the use of a photosensitiser is not a strict requirement and that suitable PAGs may be used that do not require a photosensitiser.

Example 6

[0156] A 1% w/w solution of Irgacure 121 with 1% w/w perylene was prepared in benzyl alcohol. The initial pH of the solution was 4.0, which dropped to 0.1 24 hours after exposure to light. To this solution, 50 wt % of water was added after 24 hours and the pH of the water was measured to be 3.6.

[0157] A 1% w/w solution of Irgacure 121 with 1% w/w perylene was prepared in benzyl alcohol. The initial pH of the solution was 4.0, which dropped to 0.1 24 hours after exposure to light. To this solution, 50 wt % of water was added after 24 hours and the pH of the water was measured to be 3.6.

[0158] It can be clearly seen from each of the Examples that it is possible to generate large drops in pH by exposing PAGs to light, and that the hydrogen ions generated are able to diffuse through hydrogels and cause a drop in the pH of the hydrogels. Thus, it is possible to use photoinitiated acid generators to start the timing mechanism of a time-temperature integrating indicator label. Although a photosensitiser may be used in conjunction with the PAG, it is possible to generate hydrogen ions from PAGs without the use of a photosensitiser.

[0159] pH Reactive Hydrogels

[0160] In order to demonstrate the ability of hydrogels to de-swell in response to drops in pH, a number of exemplary hydrogels were investigated.

Example 7

[0161] The first hydrogels studied comprised polymers of carboxyethyl acrylate using a polyethylene diacrylate (PEGDA) cross-linking agent. The Q values represent the relative swelling due to adsorption of water (numbers greater than one) or shrinking due to expulsion of water (numbers less than one).

TABLE-US-00003 Sample % PEGDA (w/w) % Water (w/w) Q (pH 6.5) Q (pH 3) 1 1 0 5.7 0.99 2 1 30 3.7 0.7 3 1 50 3.1 0.57 4 5 0 1.23 1.00 5 5 10 1.7 0.78 6 5 30 1.15 0.65

[0162] 1. 100 wt % (99% mol BCEA and 1% mol PEGDA);

[0163] 2. 70 wt % (99% mol BCEA and 1% mol PEGDA) and 30 wt % water;

[0164] 3. 50 wt % (99% mol BCEA and 1% mol PEGDA) and 50 wt % water;

[0165] 4. 100 wt % (95% mol BCEA and 5% mol PEGDA);

[0166] 5. 90 wt % (95% mol BCEA and 5% mol PEGDA) and 10 wt % water; and

[0167] 6. 70 wt % (95% mol BCEA and 5% mol PEGDA) and 30 wt % water.

[0168] As can be seen, the hydrogels formed with some water already included, namely polymerised with water present, were less prone to absorbing additional water. It should be noted that each sample shrunk when exposed to a lower pH. As such, it can be seen that a plug made from such hydrogel compositions could serve as a valve when exposed to drops in pH.

Example 8

[0169] A second type of hydrogels comprising polymers of acrylic acid and N,N-methylenebisacrylamide as the cross-linking agent were studied. Analogous hydrogels comprising sodium acrylate (SA) can be formed.

TABLE-US-00004 Q(pH 5.7) Q(pH 5.7) Q (pH 2.10) SA:PEGDA 20% Speedcure 1% TST/OTf 0.1M citric (% mole) 938 in ethanol in water acid 99:1 0.55 1.5 1.6 95:5 0.65 3.7 1.9 90:10 0.68 6.1 3.0 (2h) 1.0

Example 9

[0170] A hydrogel formed via the co-polymerisation of sodium acrylate 30 wt % and 2-(2-ethoxyethoxy-ethyl acrylate (EOEOEA) 70 wt %, using PEGDA as the cross-linking agent in the amount of 1 wt % provide a Q value of greater than 8.0 at pH 6.75. The Q value was 1.83 in 1% Speedcure 938 in ethanol at pH 6.3, and the Q value was 1.40 in 50 wt % triarylsulphonium salts in propylene carbonate.

[0171] Where the amount of PEGDA was increased to 5 wt %, the same monomer mix produced a hydrogel with a Q value of 2.6 at pH 6.75 and a Q value of 1.25 in 50 wt % triarylsulphonium salts in propylene carbonate.

[0172] Similar suppression of Q values can be obtained through the addition of sodium chloride to the HVMT and the degree of swelling of the hydrogel can be reduced from greater than 8 to around 1.5. The hydrogels show volume transition from water (ph 5.5) to acidic aqueous solutions acidified with a PAG solution (10 wt % Igracure 103 in benzyl alcohol). As such, it is clear that the acid produced by the PAG can lead to a shrinkage of the hydrogels.

Example 10Diffusion at 40 C.

[0173] In order to demonstrate the application of the present invention, samples were prepared comprising two hydrogel plugs comprising 40/40/20 (vegetable) glycerol/propylene glycol/water with the space in between the plugs comprising different mixtures of (vegetable) glycerol (VG) and propylene glycol (PG). The different mixture were: 100% VG/0% PG, 75% VG/25% PG, 50% VG/50% PG, and 25% VG/75% PG. In order to track the progress of the acid through the system, a pH responsive indicator was incorporated into the medium. It will be appreciated that it is only necessary for the target reservoir to comprise the pH responsive indicator in the present invention.

[0174] FIGS. 14a to h show the progress of the acid along the samples at t=0, 1, 2, 4, 6, 24, 26, and 29 hours respectively at 40 C. In each figure the topmost sample comprises 100% VG. The middle sample comprises 75% VG/25% PG, and the lowermost sample comprises 25% VG/75% PG.

[0175] A very rapid collapse of the first hydrogel plug is observed at this elevated temperature in the samples with the highest glycerol content as demonstrated by the colour change of the viscous medium. In the two samples with the highest glycerol content, the acid has diffused to the second plug and caused it to collapse after 24 hours. The sample comprising 100% glycerol has run to completion after 29 hours. The diffusion of acid in the other two samples was not complete at 29 hours, but was continuing. As such, the rate at which the acid is able to diffuse through the medium can be controlled by altering the composition of the medium through which the acid diffuses.

Example 11Diffusion at Room Temperature

[0176] FIGS. 15a to e show the progress of the acid along the samples at t=0, 2, 19, 43, and 77 hours. The medium chosen for this experiment was a 50/50 (by volume) mixture of (vegetable) glycerol and propylene glycol.

[0177] The time taken for the first hydrogel plug to collapse was around four hours, which is longer than at 40 C. Diffusion through the medium then progressed at a lower rate than that seen at 40 C. with collapse of the second hydrogel plug beginning at around 77 hours.

[0178] FIGS. 16a to f show the progress of the acid along the samples at t=0, 2, 4, 6, 24, and 29 hours respectively. It appears that the first hydrogel plug in the 75/25 sample did not fully seal the capillary tube and that the acid was able to pass around the side of the plug rather than causing the plug to collapse. As with the 50/50 sample, the rate of diffusion through the media at room temperature was less than that at 40 C. As such, where the label is exposed to increased temperatures, the rate at which the colour change occurs is increased, which reflects the increased rate of spoilage of the product to which the label is attached.

Example 12Diffusion at 5 C.

[0179] FIGS. 17a to e show the progress of the acid along the 50/50 VG/PG sample at t=0, 2, 19, 43, and 77 hours, and FIGS. 18a to f show the progress of the acid along the 100/0, 75/25, and 25/75 VG/PG samples at t=0, 2, 4, 6, 24, and 29 hours.

[0180] As with Examples 10 and 11, the rate of diffusion in the high VG samples was highest and the rate of diffusion decreased with an increase in the amount of PG in the sample. In addition, the rate of diffusion along the sample was lower than in the samples held at room temperature and at 40 C.

[0181] The present invention provide for a reliable time-temperature integrating (TTi) indicator label that may be initiated by exposure to light. The use of a photoinitiated timing mechanism avoids the disadvantages of the activation means of the prior art.