Title of Invention	TIME INDICATOR AND METHOD OF MANUFACTURING SAME .
Abstract	A time indicator comprising a first reservoir (13), a migration medium (11) and activating means for bringing liquid from the first reservoir (13) in contact with the migration medium (11) so that after activation the liquid migrates through the migration medium (11) producing a colour change therein. The activating means comprises a second reservoir (16) connected between the first reservoir (13) and the migration medium (11) whereby after activation the liquid travels relatively rapidly from the first reservoir (13) to the second reservoir (16) and then migrates relatively slowly along the length of the migration medium (11) over time.

Title of Invention

TIME INDICATOR AND METHOD OF MANUFACTURING SAME .

Abstract

A time indicator comprising a first reservoir (13), a migration medium (11) and activating means for bringing liquid from the first reservoir (13) in contact with the migration medium (11) so that after activation the liquid migrates through the migration medium (11) producing a colour change therein. The activating means comprises a second reservoir (16) connected between the first reservoir (13) and the migration medium (11) whereby after activation the liquid travels relatively rapidly from the first reservoir (13) to the second reservoir (16) and then migrates relatively slowly along the length of the migration medium (11) over time.

Full Text	TIME INDICATOR AND METHOD OP MANUFACTURING SAME Background to the Invention The present invention relates to an indicator for showing the product lifetime of the item to which said indicator is attached. More particularly the present invention relates to an indicator which, on activation by applying pressure, measures elapsed time and displays visual indications relating to the product lifetime of the item to which it is attached. The need to monitor the lifetime of food and drug products is well known, especially where such products deteriorate rapidly after manufacturing or opening. Milk- based products deteriorate rapidly from the time of manufacture, and many types of long-life products (such a canned produce) need to be disposed of within days of opening. Thus, a typical home environment needs a means of monitoring the freshness of the products in the refrigerator. In particular, in situations in which a can is opened or a foodstuff prepared but not consumed immediately in its entirety, the remains will often be placed in a container in the refrigerator. In the absence of a simple aid to show the consumer how long any such container has been in the refrigerator, the danger exists that said remains will deteriorate and pose a health risk. Alternatively, being unaware of how long this package has been in the refrigerator, ~ the over-cautious consumer may dispose of the contents before this becomes necessary. In either case, the need for a simple, inexpensive and reliable indicator or tag for such containers in the refrigerator is clear. A number of means to accomplish this objective are well known in the art. Co-pending application WO 01/26993, describes a cap containing an integral lifetime indicator where the first opening of the cap causes the activation of the lifetime indicator. However, this approach does not assist the consumer who is preparing a container of *left- overs" within the consumer's premises. Similarly, US patents 4,292,916; 5,053,339,- 5,446,705 and 5,633,835 describe colour changing devices for monitoring the shelf-life of perishable products. These devices are initiated by physically bringing into contact reactive layers so that a chemical reaction between them will start, and this action can only conveniently be performed at the time of initial manufacturing. While this approach ia suitable for monitoring the degradation of foodstuffs throughout the entire distribution chain, they are unsuitable for user activation and application within the home environment. Further prior art addresses issues associated with applying such devices during the manufacturing and packaging processes. US Patent 5,555,223 describes a process for attaching timing indicators to packaging, including the step of setting the timer's clock at the exact time of production. Thus the above prior art devices require special manufacturing steps at the product ion-end of the packaging and filling processes, rather than the end-user affixation and activation of a lifetime indicator at the time of use or of storage as envisaged in the current invention. Similarly, time-temperature indicators (TTIs) also address the task of monitoring the entire distribution chain, rather than providing an end-user solution. A number of liquid migration technologies are known in the art, but these typically rely either on the rapid wicking of paper and are thus good for time ranges in the minutes to hours range, or require complex fabrication of the migration media from materials such as gelatine or other gels in order to provide for slower migration, and are thus both complex and expensive to produce. Summary of the Invention According to the present invention, a time indicator comprises a first reservoir, a migration medium and activating means for bringing liquid from the first reservoir in contact with the migration medium so that after activation the liquid migrates through the migration medium producing a colour change therein, characterised in that the activating means comprises a second reservoir connected between the first reservoir and the migration medium whereby after activation the liquid travels relatively rapidly from the first reservoir to the second reservoir and then migrates relatively slowly along the length of the migration medium over time. As the liquid slowly migrates along the length of the migration medium, a visual indication of the time elapsed is given by the cumulative progress of the colour change. The time indicator may comprise indicia whereby the time elapsed. is measured by comparing the progress of the colour change along the migration medium with the indicia. The presence of the second reservoir allows for rapid dispersion of the liquid away from the first reservoir. This may reduce the risk of the device leaking when the liquid is forced out of the first reservoir. Furthermore, the accuracy of the measurement of elapsed time may also be improved since the measurement depends only on the nature of the migration medium and- liquid and is independent of the initial flow of the liquid from the first reservoir. The second reservoir may take the form of an internal cavity or chamber within the body of the time indicator, an inflatable pocket which inflates after activation or an absorption medium which absorbs the liquid after activation. The first and second reservoirs may be connected by a conduit which may include a material which allows rapid wieking of the liquid from the first reservoir to the second reservoir after activation. The first and second reservoirs may be located towards opposed ends of the migration medium or may be located towards the same end. The first reservoir may be housed within the second reservoir/ for example, the first reservoir may be in the form of a rupturable liquid capsule located within a cavity which, forms the second reservoir. Activating the time indicator causes the capsule to rupture releasing liquid into the cavity. The time indicator is preferably adapted, for example by appropriate selection of the properties of the liquid and the migration medium, so that the migration along the migration medium takes a predetermined time period. The time period may be between thirty minutes and six months, particularly in the days to weeks range. For example, for a time indicator for use with dairy products, the time period may be in the region of two to five days. Alternatively, for a time indicator for use with canned or bottled cooking sauces, the time period may be in the region of one to two weeks. Further examples include eye ointments or nasal sprays which may necessitate a time period of one month, filters, e.g. water filters, which may necessitate a time period of one to three months, cold meats or baby foods which may necessitate a time period of three to seven days or twenty-four to forty eight hours respectively. The activating means may be pressure activated, for example, applying pressure to the first reservoir may force liquid from the first reservoir into the second reservoir. The activating means may comprise a pressure-rupturable seal separating the first reservoir from the second reservoir and hence separating the first reservoir from the migration medium. The time indicator may comprise a base layer which may be formed with a dished portion for the first reservoir, a migration layer comprising the migration medium and an intermediate layer sandwiched between the base layer and the migration layer. Each layer and the migration medium may be sheet-like, for example, having the following characteristics, thin and flexible. The intermediate layer may be weakly adhered to the migration layer at one end of the migration medium whereby the second reservoir is formed between the upper and intermediate layers after activation. The second reservoir may in this way be an inflatable pocket. The time indicator may comprise an at least partially transparent layer mounted to the migration medium or migration layer. The at least partially transparent layer may be in the form of a partially transparent mask. The mask may comprise one or more transparent windows through which the colour change is visible. The transparent windows may act as indicia for measuring the progress of the colour change- One of the indicia may be arranged so that in conjunction with the second reservoir, it provides an indication that the device has been activated. For example, a first transparent window may be aligned above the second reservoir. The transparent windows may be defined by printing directly on the migration medium or migration layer which simplifies the manufacture of the time indicator. The migration medium or layer may be laminated to allow for printing thereon. The colour change may be from any other colour to red. The migration of the liquid may cause more than one, e.g. two or multiple, colour change in the migration medium. For example, the colour change may have an intermediate colour of yellow prior to the appearance of a red colour. The liquid may be coloured, whereby a visually observable colour change is produced in the migration medium by the migration of the liquid into pores in the migration medium. Alternatively, the liquid may contain a first reagent and the migration medium may contain a second reagent which reacts with said first reagent, thereby producing a colour change. The migration medium may be impregnated, doped or printed with the second reagent. The reaction system between said first and second reagent may be selected from the group comprising: chelation of a metal ion by a chelating agent, reaction of an acid/base with a pH indicator, reaction of an electron donor/acceptor with a redox indicator, and the enzymatic reaction between an enzyme and a substrate. The metal ions may be selected from the group consisting of zinc ions, copper ions, iron ions and calcium ions; chelating agents are selected from the group consisting of 1,10 phenanthroline, zincon, and 2,2'- biquioline (cupron) and PAR; acid/base reagents are selected from the group consisting of hydrochloric acid, citric acid, ascorbic acid, sodium hydroxide and sodium hydrogen phosphate; pH indicators are selected from the group consisting of bromothymol blue, methyl red and cresol red; electron donor/acceptors are selected from the group consisting of bleaching powder and vanadium salts,- and redox indicators are selected from the group consisting of n- phenylanthrancilic acid and bleachable dyes. The liquid may be a viscous liquid, such that the viscosity of said liquid controls the rate of liquid migration through the migration medium. The liquid may contain an oil and an oil-soluble dye or may contain water, a water-soluble dye and, in some cases, also a chemical to control the viscosity of said liquid. The mechanism for said migration may be diffusion or capillary action. The migration medium may be selected from the group consisting of polymeric micro-porous materials such as polyolefin plastics, cellulose-based materials including paper, sol-gels, and particle-filled Teflon. The migration medium may comprise a micro-porous polymeric material with a silica filler. The migration medium may be composed of a combination of the named porous materials, such as paper dipped in a sol-gel solution. The indicator may incorporate an adhesive backing for attachment to the products and packages to be stored. The indicator may comprise means defining a migration passage along the length of the migration medium. The defining means may be in the form of a seal. The migration passage reduces the amount of liquid which is required and reduces any accidental seepage of liquid from the indicator. According to a second aspect of the invention, there is provided a method of manufacturing a time indicator comprising providing a base layer formed with a dished portion for a liquid reservoir, an intermediate layer having an inlet and a migration layer comprising a migration medium; bonding the base layer to the intermediate layer with the inlet aligned with the dished portion; feeding liquid through the inlet into the dished portion to form a liquid reservoir; and partially bonding the migration layer to the intermediate layer whereby when the time indicator is activated liquid travels rapidly from the liquid reservoir to a chamber which is formed between the migration layer and the intermediate layer and then migrates slowly along the length of the migration medium over time. The intermediate layer preferably comprises a vent to allow air from the first reservoir to be vented as the first reservoir is filled with liquid during manufacture. Thus, the intermediate layer may be considered to act as a layer which facilitates filling. The method may comprise printing on part of the surface of the intermediate layer to resist bonding between the migration layer and the intermediate layer. In this way, a second reservoir in the form of an inflatable pocket may be formed after activation of the indicator. The pocket forms between the migration layer and the intermediate layer in the region of the part of the surface which resists bonding. The method may comprise defining a migration passage along the length of the migration medium, for example by forming a seal in the migration layer which defines the migration passage. The method may comprise bonding an at least partially transparent layer to the migration layer and may comprise defining indicia on the transparent layer whereby the time elapsed is measured by comparing the progress of the colour change along the migration medium with the indicia. Alternatively, the method may comprise printing indicia on the migration layer whereby the time elapsed is measured by comparing the progress of the colour change along the migration medium with the indicia. According to another aspect of the invention, there is provided a lifetime indicator device comprising a liquid reservoir containing a liquid with a dissolved red dye, a micro-porous medium composed of a polyolefin plastic with a primarily silica filler, a partially transparent mask placed above said micro-porous medium such that, on bringing the liquid in contact with said medium said liquid slowly diffuses through said medium yielding a colour change to red, where the front of said colour change slowly proceeds along said micro-porous medium and is viewed via a mask containing indicia that relate the progress of said front to the lifetime of the item to which the time indicator is attached. The invention will now be described in connection with certain embodiments with reference to the following illustrative figures so that it may be more fully understood. Brief Description of the Drawings Fig. 1A is an exploded plan view of the components of an indicator according to a first embodiment of the present invention; Figs. 1B and 1C are exploded cross-sections of the indicator of Pig. 1A before and after activation; Figs. 2A and 2B shows the details of a middle layer which may be used in the indicator of Fig 1; Fig. 3 shows an alternative indicator; Figs. 4A & 4B show an indicator in which the progress of the slow liquid-migration process over time is visible; Figs. 5A and 5B show exploded cross-sectional views of an alternative indicator before and after activation; Fig. 6 shows the slow liquid-migration process in the indicator of Figs. 5A and 5B over time. Detailed Description of the Drawings In the following figures similar numbers are used to designate similar parts. An exemplary time indicator (the device) according to the present invention is shown in Figs. 1A and 1B. The device comprises a base layer 10 containing a first liquid reservoir 13, a central layer 11 comprising a migration medium, and a partially transparent upper layer 12 which provides two windows 17,18 through which the progress of the liquid through the migration medium may be viewed. The base layer 10 constitutes a lower seal for the indicator as a whole. The base layer 10 comprises a dished portion 19 which forms a button and contains the first reservoir 13 which serves to drive the liquid-migration mechanism. The dished portion 19 may be thermoformed. The underside of said base layer 10 may be an adhesive surface serving to attach the indicator to the item being monitored. The upper surface of the base 10 is attached by strong adhesive to the central layer 11 except in two places: along a weak seal 14, and along a liquid conduit 15. The liquid conduit 15 has a first end connected to the seal 14 and a second end leading to a second reservoir in the form of an open section, or cavity 16 in the middle layer 11 which connects to the migration medium. Once assembled, the device is activated by compressing the dished portion 19 whereby the increased pressure on the liquid in the reservoir causes the weak seal 14 to rupture. The liquid flows rapidly down the liquid conduit 15 and up into the cavity 16 in the middle layer 11. Said middle layer 11 comprises a laminated package encapsulating a porous or micro-porous medium which acts as the migration medium. After entering the cavity 16, the liquid begins its slow- migration along said medium. The upper layer 12 comprises transparent windows 17, 18 (indicia) showing the progress of the said 3 low-migration process, thereby acting as a graphic mask. One window 18 is positioned above the cavity 16 in the middle layer 12 and a second window is positioned above the intended end-point. When the device is activated, the liquid flows into cavity 16 and a colour change is seen through the first window 18 which shows the device has been activated. A colour-change viewed at the second window 17 shows that the intended end-point (corresponding to the i lifetime of the item being monitored) has been reached. Referring now to Figs. 2A & 2B, there are seen two exemplary embodiments of the middle layer of the device, the middle layer being the slow liquid-migration component. In Pig. 2A, the middle layer 20 comprises a laminated strip 26 of a porous or micro-porous material which serves as the slow-migration medium for the liquid that arrives into the second reservoir or cavity 22 defined by the cut-out section of said medium. Said liquid migration is prevented from extending beyond the edges of the layer by a pressure heat seal 24 applied around the edges of the layer, said sealing operation essentially closing the pores of the micro-porous material. In an alternative embodiment shown in Fig. 2B, the middle layer 2 0 comprises an encapsulated strip 2 6 of a micro-porous material which serves as the slow-migration medium for the liquid that arrives into the cavity 22 cut into said medium. Said liquid-migration is prevented from extending beyond the strip 2 6 by the laminate-to-laminate bond in the surrounding margin 28. Referring now to Fig. 3, an alternative embodiment of the liquid release mechanism is shown. According to this embodiment a first reservoir in the form of a rupturable capsule 30 containing the liquid is placed within a second reservoir in the form of a cavity 32. Pressure exerted above and below said cavity 32 causes the release of the liquid into the cavity and hence the start of the liquid migration. In this embodiment, the lower layer of the device only serves to provide a lower seal, and thus the thermoformed reservoir and conduit of Fig. 1 are obviated. Referring now to Figs. 4A to 4F, the progress over time of the liquid-migration front in the migration medium is shown in Figs. 4A to 4C. The colour-change as viewed through the said partially transparent upper layer of the device is shown in Figs. 4D to 4F. Initially, as shown in Figs. 4A and 4D respectively, the liquid is contained within the cavity and a colour change is only visible in the first or start window 48. This shows that the device has been activated. As time progresses, as shown in Fig. 4B, the liquid starts to migrate out from the cavity and begins to colour the edges surrounding the cavity 42. As shown in Fig. 4E, no colour change is visible in the second or expire window. Over time the coloured area progressively and cumulatively expands lengthwise along the indicator by migrating down the migration medium 44. Finally, as shown in Fig. 4C, all or almost all of the migration medium has changed colour and as shown in Fig. 4F, a colour change is visible in the second window indicating that the product has expired. As will be clear to one skilled in the art, various types of graphic design may be employed for the expiry/lifetime end-point, including but not limited to various lines, curves, ellipses, rectangles or points. Similarly, indicia showing the progress of the liquid- migration front may also be employed, including but not limited to various arrows, curves, lines and points of different sizes. Furthermore, each embodiment, may be adapted to include numerous additional indicia to show the status of the time indicator. Such indicia (not shown) can include graphic symbols showing the gradual advance to said end-point. The starting colour seen through the windows may be the same as the background colour of the upper layer, and thus any colour change stands out clearly. The final colour may be red; a transition to red being readily understandable as a sign that the item being monitored should be disposed of. Figs. 5A and 5B show an alternative indicator comprising a base layer 50, an upper migration layer 56 comprising a migration medium and an intermediate layer 60 sandwiched between the upper layer 56 and the base layer 50. The upper migration layer 56 is laminated, i.e. covered on both surfaces by a laminate layer 51. The upper surface of the migration layer 56 is printed with indicia showing the start- point and the end-point, thus avoiding the need for a separate partially transparent upper layer for printing. Furthermore, the printing of the migration layer 56 may define transparent windows as in earlier embodiments. The base layer 50 is preferably made of PVC and is formed with a dished portion 52 which contains a first liquid reservoir 54. The intermediate layer is provided with a vent 65 and an inlet 64 which connects the liquid reservoir 54 to a small cavity 66 in the migration layer 56. The intermediate layer 60 is sealed to the migration layer 56 by a thermal adhesive applied to an upper surface of the intermediate layer 60 except in a print area 67 covering part of the lower surface of the migration layer 56. The print area 66 is printed with a material, e.g. paint, which forms a weak adhesive bond with the thermal adhesive which may be W60 and W60 pre-applied aliphatic polyester water-based urethane adhesives from Lmarr (Glen Ellen, CA, US). The device is activated by depressing the dished portion 52 which forces liquid from the reservoir 54 through inlet 64 into the cavity 66. The cavity 66 expands or inflates over the print area 67 to form a second reservoir in the form of an internal pocket 68 as shown in Fig. 5B. Once the pocket 68 is formed, the button or dished portion 52 remains in its depressed state. The liquid then begins to diffuse over time through the migration medium as described above. Figs. 6A to 6C show the device of Figs. 5A and 5B with a mechanism to channel the migration of the liquid into a narrow path through the migration medium. Heat and pressure is used to form a seal 70 which defines the narrow path. Fig. 6A shows the device before activation and thus no liquid is present in the cavity 66. Shortly after activation the cavity 66 is filled with liquid and liquid begins to diffuse into the migration medium as shown in Fig. 6B. Over time the liquid continues to advance along the migration medium along the narrow path defined by the seal 70 as shown in Fig. 6C The embodiment of Figs. 5A to 5B may be manufactured as follows: 1) A plastic PVC layer is thermoformed at 150 to 160°C to form a base layer 50 having a dished portion 52; 2) A second plastic layer having an inlet 64 and a vent 65 is glued to the base layer 50 to form an intermediate layer 60 with the inlet being aligned with the dished portion; 3) Liquid is fed through the inlet into the dished portion to form a first reservoir. As the liquid fills the reservoir, air is evacuated from the dished portion through the vent 65. The intermediate layer 60 may be considered to be a filling-facilitator layer and enables rapid manufacturing speeds to be achieved; 4) Adhesive is applied to the free surface of the intermediate layer 60; 5) A migration layer 56 comprising a migration medium is printed over part of its surface with a material, e.g. paint, which forme a weak bond with the adhesive on the intermediate layer; 6) The intermediate layer 60 and the migration layer 56 are bonded together at about 90°C, and 7) Optionally, heat (in the range 15O-200°C) and pressure are applied to the upper surface to melt the migration layer thereby forming a seal or partial seal which defines a narrow migration passage. 8) Optionally, the migration layer 56 may be printed with indicia or so as to define transparent windows to view start and end points of the migration. Alternatively, an additional partially transparent layer with such indicia may be bonded to the migration layer. In each of the embodiments the migration medium may be a porous material such as a micro-porous polymer, for instance a polyolefin plastic (with a primarily silica filler) such as Teslin® (PPG Industries, Inc., Pennsylvania, USA) or a polyethylene with a silica filler such as Artisyn ™ (Daramic Inc., Owensboro, KY, USA). The liquid used can be any viscous liquid with the appropriate (e.g. red) colouration, for example an edible oil such as corn oil containing an oil- soluble red-dye such as Oil Red EGN (Aldrich Chemical Company, Inc., USA). In this example, the rate of liquid migration is determined by the viscosity of the liquid and the thickness and density of the migration medium. Advantageously, the choice of an edible oil with a food dye ensures that the device will remain non-toxic, even in the event that it splits open. A further advantage of said oil/dye combination is that, as this liquid migrates along the migration medium, a two-stage colour-change front is produced as the underlying yellow colour of the oil precedes the appearance of the red colour. Thus a graduated colour change occurs, first to yellow as an intermediate colour, and then to red. Advantageously, said colour change sequence is intuitive to the consumer due to the familiarity of consumers with traffic lights which first turn yellow before becoming red. Similarly, a red colour is associated with danger and thus said combination provides an optimal colour change sequence for the device of the present invention. An alternative liquid/dye combination utilizes a water- soluble dye (e.g. a red food dye) in water, together with an additive, such as polyethylene glycol (PEG) , to control the viscosity of the resulting liquid and thus the rate of its migration. Additionally, a combination of dyes with differing retention times can be employed, so as to cause one colour (say yellow) to appear shortly before the final colour (say red) dominates. Alternatively, the migration medium may be a micro- porous doped sol-gel, the liquid may be a solution of a zinc salt such as zinc chloride, and the colour-changing reaction system may be a chelation reaction. As the zinc solution proceeds to migrate slowly through the doped sol-gel medium, it reacts with the dopant; in this case the chelating agent 4-(2-pyridylazo)resorcinol monosodium salt, hereinafter PAR, thereby yielding a colour change from yellow to red. In one embodiment, the support material for the doped sol-gel may be standard laser quality paper (80g/m2) paper which is cut into 1cm by 2.5cm strips and dip-coated with the PAR-doped sol-gel. The doped sol-gel liquid may be prepared by first adding a 5ml solution of tetraethoxysilane (TEOS) to a stirred solution consisting of 10ml ethanol, 1.6ml triply distilled water, 4 drops of concentrated (33%) hydrochloric acid (HCl) and 0.1g of PAR. After stirring for a further 5 minutes, 0.3g of a surfactant such as CTAB (hexadecyltrimethyl-ammonium bromide) is added and stirred until the solution becomes homogeneous. The solution is stirred for a further two hours. The paper may be dipped into this sol-gel liquid by holding the paper strip at one by a dipping machine; lowering it into the non-stirred solution and then withdrawing it at a rate of 0.08cm/sec. It is then left to dry at 50 °C in an oven for at least 24 hours to complete curing. In this example, the rate of liquid migration is determined by the pH during preparation of the sol-gel, which controls the resulting pore size. This choice of reaction system is especially advantageous because, even if the device were to split open, no dangerous chemicals would be released. Zinc solution is non-toxic (being an acceptable constituent of drinking water at levels up to 5mg/l) and the PAR remains entrapped as a dopant within the sol-gel matrix and therefore can not leach out. As is obvious to one skilled in the art, a number of alternative migration media and a number of alternative reaction mechanisms are feasible. A number of micro-porous media enable a slow-migration effect to be implemented; examples include Empore™ particle-filled Teflon (available from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota, USA), Other materials suitable for a migration media are cellulose-based materials such as paper where both capillary action and diffusion may contribute to the migration effect. A number of alternative chemical systems capable of producing a similar colour change to that of the above described embodiments are listed below: 1. To implement other chelation reactions, alternative chelating agents such as 1,10 phenanthroline, zincon, or 2,2'-biquioline (eupron) can be incorporated or doped into the porous medium while alternative liquid reagents that would migrate into the porous medium can include solutions of metal ions such as copper ions, iron ions and calcium ions. 2. To implement acid/base reaction systems, suitable pH indicators including bromothymol blue, methyl red, cresol red can be incorporated or doped into the migration medium, and suitable acid/base liquid reagents that would migrate into the migration medium can include the acids: hydrochloric acid, citric acid and ascorbic acid and the bases: sodium hydroxide and sodium hydrogen phosphate. 3. To implement redox reactions, redox indicators such as n- phenylanthrancilic acid or a bleachable dye can be incorporated or doped into the migration medium while alternative liquid reagents that would migrate into the migration medium can include solutions of bleaching powder or of vanadium salts. 4. To implement an enzymatic reaction, an enzyme such as a lipase can be incorporated or doped into the migration medium together with a pH indicator while a liquid substrate such as tricaproin would migrate into the migration medium. In one embodiment the reaction product of the enzymatic reaction of a lipase and tricaproin is caproic acid; said acid producing a colour shift in the pH indicator. The above chemical colour-change system can be implemented within the context of the present invention by ensuring that one of the chemical reagents is present in the migrating liquid, while the other is present in the migration medium. Means known in the art for placing a chemical within a migration medium include doping (as per the sol-gel description above); dipping and printing of the chemical into or on to said medium. As set out above, activation of each embodiment is by the simple application of pressure on a portion of said indicator, the invention has the advantage of being easy to use and may have foolproof operation. Furthermore, by basing the construction of the indictor on printable, sheet-like liquid migration media; fabrication may be performed using simple technologies such as printing, dipping, stamping and lamination. Thus, the time indicator may have a simple and inexpensive manufacture. For example off-the-ahelf media may be adapted to provide an indicator according to the invention. The time indicator of may also be suitable for attachment to containers or other items stored in the refrigerator or freezer and may use liquid which do not freeze, for example mixtures of propylene glycol and water at various concentrations or synthetic oils designed to operate at sub-zero conditions This may be particularly useful for the longer time frames, e.g. six months It will thus be seen that according to the present invention a simple and inexpensive time indicator for consumers is described. While the invention has been shown herein in what is presently conceived to be the most practical and preferred embodiments thereof, it will be apparent to those of ordinary skill in the art that many modifications may be made thereof within the scope of the invention, which scope is to be accorded the broadest interpretation of the appended claims so as to encompass all equivalent structures and devices. WE CLAIM: 1. A time indicator comprising a first reservoir, a migration medium and activating means for bringing liquid from the first reservoir in contact with the migration medium, the activating means comprising a second reservoir connected between the first reservoir and the migration medium whereby after activation the liquid travels relatively rapidly from the first reservoir to the second reservoir and then migrates relatively slowly along the length of the migration medium over time producing a colour change therein, characterised in that the second reservoir is in the form of an inflatable pocket which inflates after activation. 2. A time indicator as claimed in claim 1, wherein the first and second reservoirs are located towards opposed ends of the migration medium and are connected by a conduit. 3. A time indicator as claimed in claim 1 or claim 2, wherein the activation means comprises a pressure-rupturable seal between the first and second reservoirs. 4. A time indicator as claimed in any of the preceding claims, comprising a base layer formed with a dished portion for the first reservoir, a migration layer comprising the migration medium and an intermediate layer sandwiched between the base layer and the migration layer. 5. A time indicator as claimed in claim 4, wherein the intermediate layer is weakly adhered to the migration layer at one end of the migration medium whereby the second reservoir is formed between the migration and intermediate layers after activation. 6. A time indicator as claimed in any one of the preceding claims, comprising an at least partially transparent layer mounted to the migration medium. 7. A time indicator as claimed in any of the preceding claims, comprising indicia whereby the time elapsed is measured by comparing the progress of the colour change along the migration medium with the indicia. 8. A time indicator as claimed in claim 7, wherein the indicia are in the form of transparent windows through which the colour change is visible. 9. A time indicator as claimed in claim 7 or claim 8, wherein the indicia are defined by printing on the migration medium. 10. A time indicator as claimed in any of the preceding claims, wherein the properties of the liquid and the migration medium are selected so that migration along the migration medium takes a predetermined time period. 11. A time indicator as claimed in claim 10, wherein the time period is between thirty minutes and six months. 12. A time indicator as claimed in any of the preceding claims, wherein the liquid is a viscous liquid and the viscosity of the liquid controls the rate of liquid migration through the migration medium. 13. A time indicator as claimed in any of claims 10 to 12, wherein the liquid is selected from the group consisting of an oil mixed with an oil-soluble dye and water mixed with a water-soluble dye and a chemical to control its viscosity. 14. A time indicator as claimed in any of the preceding claims, wherein the migration medium is selected from the group consisting of polymeric micro-porous materials, cellulose-based materials, sol-gels, and particle-filled Teflon. 15. A time indicator as claimed in claim 14, wherein the migration medium comprises a micro-porous polymeric material with a silica filler. 16. A time indicator as claimed in any of the preceding claims, wherein the liquid is coloured, whereby a colour change is produced in the migration medium by the migration of the liquid along the migration medium. 17. A time indicator as claimed in any of claims 1 to 15, wherein the liquid contains a first reagent and the migration medium contains a second reagent which reacts with said first reagent, thereby producing the colour change. 18. A time indicator as claimed in claim 17, wherein the reaction system between said first and second reagent is selected from the group comprising: chelation of a metal ion by a chelating agent, reaction of an acid/base with a pH indicator, reaction of an electron donor/acceptor with a redox indicator, and the enzymatic reaction between an enzyme and a substrate. 19. A time.indicator as claimed in claim 18, wherein the metal ions are selected from the group consisting of zinc ions, copper ions, iron ions and calcium ions; chelating agents are selected from the group consisting of 1,10 phenanthroline, zincon, and 2,2'-biquioline (cupron) and PAR; acid/base reagents are selected from the group consisting of hydrochloric acid, citric acid, ascorbic acid, sodium hydroxide and sodium hydrogen phosphate; pH indicators are selected from the group consisting of bromothymol blue, methyl red and cresol red; electron donor/acceptors are selected from the group consisting of bleaching powder and vanadium salts; and redox indicators are selected from the group consisting of n-phenylanthrancilic acid and bleachable dyes. 20. A time indicator as claimed in any one of the preceding claims, wherein the colour change is to red. 21. A time indicator as claimed in any of the preceding claims, wherein migration of the liquid causes more than one colour change in the migration medium. 22. A time indicator as claimed in claim 21, wherein the colour changes first to yellow then to red. 23. A time indicator as claimed in any one of the preceding claims, comprising an adhesive backing. 24. A time indicator as claimed in any of the preceding claims, comprising means defining a migration passage along the length of the migration medium. 25. A method of manufacturing a time indicator comprising providing a base layer formed with a dished portion for a liquid reservoir, an intermediate layer having an inlet and a migration layer comprising a migration medium; bonding the base layer to the intermediate layer with the inlet aligned with the dished portion; feeding liquid through the inlet into the dished portion to form a first reservoir; and partially bonding the migration layer to the intermediate layer whereby a second reservoir in the form of an inflatable pocket is formed between the migration layer and the intermediate layer so that when the time indicator is activated liquid travels relatively rapidly from the first reservoir to inflate the second reservoir and then migrates relatively slowly along the length of the migration medium over time. 26. A method as claimed in claim 25, comprising printing on part of the surface of the intermediate layer to resist bonding between the migration layer and the intermediate layer whereby the inflatable pocket forms over the printed part. 27. A method as claimed in claim 25 or claim 26, comprising defining a migration passage along the length of the migration medium. 28. A method as claimed in claim 27, comprising forming a seal in the migration layer which defines the migration passage. 29. A method as claimed in any of claims 25 to 28, comprising bonding an at least partially transparent layer to the migration layer. 30. A method as claimed in claim 29, comprising defining indicia on the transparent layer whereby the time elapsed is measured by comparing the progress of the colour change along the migration medium with the indicia. 31. A method as claimed in any of claims 2 5 to 30, comprising printing indicia on the migration layer whereby the time elapsed is measured by comparing the progress of the colour change along the migration medium with the indicia. ----------------X------------- A time indicator comprising a first reservoir (13), a migration medium (11) and activating means for bringing liquid from the first reservoir (13) in contact with the migration medium (11) so that after activation the liquid migrates through the migration medium (11) producing a colour change therein. The activating means comprises a second reservoir (16) connected between the first reservoir (13) and the migration medium (11) whereby after activation the liquid travels relatively rapidly from the first reservoir (13) to the second reservoir (16) and then migrates relatively slowly along the length of the migration medium (11) over time.

Full Text

TIME INDICATOR AND METHOD OP MANUFACTURING SAME
Background to the Invention
The present invention relates to an indicator for
showing the product lifetime of the item to which said
indicator is attached. More particularly the present
invention relates to an indicator which, on activation by
applying pressure, measures elapsed time and displays visual
indications relating to the product lifetime of the item to
which it is attached.
The need to monitor the lifetime of food and drug
products is well known, especially where such products
deteriorate rapidly after manufacturing or opening. Milk-
based products deteriorate rapidly from the time of
manufacture, and many types of long-life products (such a
canned produce) need to be disposed of within days of
opening. Thus, a typical home environment needs a means of
monitoring the freshness of the products in the refrigerator.
In particular, in situations in which a can is opened or a
foodstuff prepared but not consumed immediately in its
entirety, the remains will often be placed in a container in
the refrigerator. In the absence of a simple aid to show the
consumer how long any such container has been in the
refrigerator, the danger exists that said remains will
deteriorate and pose a health risk. Alternatively, being
unaware of how long this package has been in the
refrigerator, ~ the over-cautious consumer may dispose of the
contents before this becomes necessary. In either case, the
need for a simple, inexpensive and reliable indicator or tag
for such containers in the refrigerator is clear.
A number of means to accomplish this objective are well
known in the art. Co-pending application WO 01/26993,
describes a cap containing an integral lifetime indicator
where the first opening of the cap causes the activation of
the lifetime indicator. However, this approach does not
assist the consumer who is preparing a container of *left-
overs" within the consumer's premises. Similarly, US patents
4,292,916; 5,053,339,- 5,446,705 and 5,633,835 describe colour
changing devices for monitoring the shelf-life of perishable
products. These devices are initiated by physically bringing
into contact reactive layers so that a chemical reaction
between them will start, and this action can only
conveniently be performed at the time of initial
manufacturing. While this approach ia suitable for
monitoring the degradation of foodstuffs throughout the
entire distribution chain, they are unsuitable for user
activation and application within the home environment.
Further prior art addresses issues associated with applying
such devices during the manufacturing and packaging
processes. US Patent 5,555,223 describes a process for
attaching timing indicators to packaging, including the step
of setting the timer's clock at the exact time of production.
Thus the above prior art devices require special
manufacturing steps at the product ion-end of the packaging
and filling processes, rather than the end-user affixation
and activation of a lifetime indicator at the time of use or
of storage as envisaged in the current invention. Similarly,
time-temperature indicators (TTIs) also address the task of
monitoring the entire distribution chain, rather than
providing an end-user solution. A number of liquid migration
technologies are known in the art, but these typically rely
either on the rapid wicking of paper and are thus good for
time ranges in the minutes to hours range, or require complex
fabrication of the migration media from materials such as
gelatine or other gels in order to provide for slower
migration, and are thus both complex and expensive to
produce.
Summary of the Invention
According to the present invention, a time indicator
comprises a first reservoir, a migration medium and
activating means for bringing liquid from the first reservoir
in contact with the migration medium so that after activation
the liquid migrates through the migration medium producing a
colour change therein, characterised in that the activating
means comprises a second reservoir connected between the
first reservoir and the migration medium whereby after
activation the liquid travels relatively rapidly from the
first reservoir to the second reservoir and then migrates
relatively slowly along the length of the migration medium
over time.
As the liquid slowly migrates along the length of the
migration medium, a visual indication of the time elapsed is
given by the cumulative progress of the colour change. The
time indicator may comprise indicia whereby the time elapsed.
is measured by comparing the progress of the colour change
along the migration medium with the indicia.
The presence of the second reservoir allows for rapid
dispersion of the liquid away from the first reservoir. This
may reduce the risk of the device leaking when the liquid is
forced out of the first reservoir. Furthermore, the accuracy
of the measurement of elapsed time may also be improved since
the measurement depends only on the nature of the migration
medium and- liquid and is independent of the initial flow of
the liquid from the first reservoir.
The second reservoir may take the form of an internal
cavity or chamber within the body of the time indicator, an
inflatable pocket which inflates after activation or an
absorption medium which absorbs the liquid after activation.
The first and second reservoirs may be connected by a conduit
which may include a material which allows rapid wieking of
the liquid from the first reservoir to the second reservoir
after activation. The first and second reservoirs may be
located towards opposed ends of the migration medium or may
be located towards the same end.
The first reservoir may be housed within the second
reservoir/ for example, the first reservoir may be in the
form of a rupturable liquid capsule located within a cavity
which, forms the second reservoir. Activating the time
indicator causes the capsule to rupture releasing liquid into
the cavity.
The time indicator is preferably adapted, for example by
appropriate selection of the properties of the liquid and the
migration medium, so that the migration along the migration
medium takes a predetermined time period. The time period may
be between thirty minutes and six months, particularly in the
days to weeks range. For example, for a time indicator for
use with dairy products, the time period may be in the region
of two to five days. Alternatively, for a time indicator for
use with canned or bottled cooking sauces, the time period
may be in the region of one to two weeks. Further examples
include eye ointments or nasal sprays which may necessitate a
time period of one month, filters, e.g. water filters, which
may necessitate a time period of one to three months, cold
meats or baby foods which may necessitate a time period of
three to seven days or twenty-four to forty eight hours
respectively.
The activating means may be pressure activated, for
example, applying pressure to the first reservoir may force
liquid from the first reservoir into the second reservoir.
The activating means may comprise a pressure-rupturable seal
separating the first reservoir from the second reservoir and
hence separating the first reservoir from the migration
medium.
The time indicator may comprise a base layer which may
be formed with a dished portion for the first reservoir, a
migration layer comprising the migration medium and an
intermediate layer sandwiched between the base layer and the
migration layer. Each layer and the migration medium may be
sheet-like, for example, having the following
characteristics, thin and flexible. The intermediate layer
may be weakly adhered to the migration layer at one end of
the migration medium whereby the second reservoir is formed
between the upper and intermediate layers after activation.
The second reservoir may in this way be an inflatable pocket.
The time indicator may comprise an at least partially
transparent layer mounted to the migration medium or
migration layer. The at least partially transparent layer may
be in the form of a partially transparent mask. The mask may
comprise one or more transparent windows through which the
colour change is visible. The transparent windows may act as
indicia for measuring the progress of the colour change- One
of the indicia may be arranged so that in conjunction with
the second reservoir, it provides an indication that the
device has been activated. For example, a first transparent
window may be aligned above the second reservoir. The
transparent windows may be defined by printing directly on
the migration medium or migration layer which simplifies the
manufacture of the time indicator. The migration medium or
layer may be laminated to allow for printing thereon.
The colour change may be from any other colour to red.
The migration of the liquid may cause more than one, e.g. two
or multiple, colour change in the migration medium. For
example, the colour change may have an intermediate colour of
yellow prior to the appearance of a red colour.
The liquid may be coloured, whereby a visually
observable colour change is produced in the migration medium
by the migration of the liquid into pores in the migration
medium. Alternatively, the liquid may contain a first reagent
and the migration medium may contain a second reagent which
reacts with said first reagent, thereby producing a colour
change. The migration medium may be impregnated, doped or
printed with the second reagent.
The reaction system between said first and second
reagent may be selected from the group comprising: chelation
of a metal ion by a chelating agent, reaction of an acid/base
with a pH indicator, reaction of an electron donor/acceptor
with a redox indicator, and the enzymatic reaction between an
enzyme and a substrate. The metal ions may be selected from
the group consisting of zinc ions, copper ions, iron ions and
calcium ions; chelating agents are selected from the group
consisting of 1,10 phenanthroline, zincon, and 2,2'-
biquioline (cupron) and PAR; acid/base reagents are selected
from the group consisting of hydrochloric acid, citric acid,
ascorbic acid, sodium hydroxide and sodium hydrogen
phosphate; pH indicators are selected from the group
consisting of bromothymol blue, methyl red and cresol red;
electron donor/acceptors are selected from the group
consisting of bleaching powder and vanadium salts,- and redox
indicators are selected from the group consisting of n-
phenylanthrancilic acid and bleachable dyes.
The liquid may be a viscous liquid, such that the
viscosity of said liquid controls the rate of liquid
migration through the migration medium. The liquid may
contain an oil and an oil-soluble dye or may contain water, a
water-soluble dye and, in some cases, also a chemical to
control the viscosity of said liquid.
The mechanism for said migration may be diffusion or
capillary action. The migration medium may be selected from
the group consisting of polymeric micro-porous materials such
as polyolefin plastics, cellulose-based materials including
paper, sol-gels, and particle-filled Teflon. The migration
medium may comprise a micro-porous polymeric material with a
silica filler. The migration medium may be composed of a
combination of the named porous materials, such as paper
dipped in a sol-gel solution.
The indicator may incorporate an adhesive backing for
attachment to the products and packages to be stored. The
indicator may comprise means defining a migration passage
along the length of the migration medium. The defining means
may be in the form of a seal. The migration passage reduces
the amount of liquid which is required and reduces any
accidental seepage of liquid from the indicator.
According to a second aspect of the invention, there is
provided a method of manufacturing a time indicator
comprising providing a base layer formed with a dished
portion for a liquid reservoir, an intermediate layer having
an inlet and a migration layer comprising a migration medium;
bonding the base layer to the intermediate layer with the
inlet aligned with the dished portion; feeding liquid through
the inlet into the dished portion to form a liquid reservoir;
and partially bonding the migration layer to the intermediate
layer whereby when the time indicator is activated liquid
travels rapidly from the liquid reservoir to a chamber which
is formed between the migration layer and the intermediate
layer and then migrates slowly along the length of the
migration medium over time.
The intermediate layer preferably comprises a vent to
allow air from the first reservoir to be vented as the first
reservoir is filled with liquid during manufacture. Thus, the
intermediate layer may be considered to act as a layer which
facilitates filling.
The method may comprise printing on part of the surface
of the intermediate layer to resist bonding between the
migration layer and the intermediate layer. In this way, a
second reservoir in the form of an inflatable pocket may be
formed after activation of the indicator. The pocket forms
between the migration layer and the intermediate layer in the
region of the part of the surface which resists bonding. The
method may comprise defining a migration passage along the
length of the migration medium, for example by forming a seal
in the migration layer which defines the migration passage.
The method may comprise bonding an at least partially
transparent layer to the migration layer and may comprise
defining indicia on the transparent layer whereby the time
elapsed is measured by comparing the progress of the colour
change along the migration medium with the indicia.
Alternatively, the method may comprise printing indicia on
the migration layer whereby the time elapsed is measured by
comparing the progress of the colour change along the
migration medium with the indicia.
According to another aspect of the invention, there is
provided a lifetime indicator device comprising a liquid
reservoir containing a liquid with a dissolved red dye, a
micro-porous medium composed of a polyolefin plastic with a
primarily silica filler, a partially transparent mask placed
above said micro-porous medium such that, on bringing the
liquid in contact with said medium said liquid slowly
diffuses through said medium yielding a colour change to red,
where the front of said colour change slowly proceeds along
said micro-porous medium and is viewed via a mask containing
indicia that relate the progress of said front to the
lifetime of the item to which the time indicator is attached.
The invention will now be described in connection with
certain embodiments with reference to the following
illustrative figures so that it may be more fully understood.

Brief Description of the Drawings
Fig. 1A is an exploded plan view of the components of an
indicator according to a first embodiment of the present
invention;
Figs. 1B and 1C are exploded cross-sections of the
indicator of Pig. 1A before and after activation;
Figs. 2A and 2B shows the details of a middle layer
which may be used in the indicator of Fig 1;
Fig. 3 shows an alternative indicator;
Figs. 4A & 4B show an indicator in which the progress of
the slow liquid-migration process over time is visible;
Figs. 5A and 5B show exploded cross-sectional views of
an alternative indicator before and after activation;
Fig. 6 shows the slow liquid-migration process in the
indicator of Figs. 5A and 5B over time.
Detailed Description of the Drawings

In the following figures similar numbers are used to
designate similar parts. An exemplary time indicator (the
device) according to the present invention is shown in Figs.
1A and 1B. The device comprises a base layer 10 containing a
first liquid reservoir 13, a central layer 11 comprising a
migration medium, and a partially transparent upper layer 12
which provides two windows 17,18 through which the progress
of the liquid through the migration medium may be viewed.
The base layer 10 constitutes a lower seal for the
indicator as a whole. The base layer 10 comprises a dished
portion 19 which forms a button and contains the first
reservoir 13 which serves to drive the liquid-migration
mechanism. The dished portion 19 may be thermoformed. The
underside of said base layer 10 may be an adhesive surface
serving to attach the indicator to the item being monitored.
The upper surface of the base 10 is attached by strong
adhesive to the central layer 11 except in two places: along
a weak seal 14, and along a liquid conduit 15. The liquid
conduit 15 has a first end connected to the seal 14 and a
second end leading to a second reservoir in the form of an
open section, or cavity 16 in the middle layer 11 which
connects to the migration medium.
Once assembled, the device is activated by compressing
the dished portion 19 whereby the increased pressure on the
liquid in the reservoir causes the weak seal 14 to rupture.
The liquid flows rapidly down the liquid conduit 15 and up
into the cavity 16 in the middle layer 11. Said middle layer
11 comprises a laminated package encapsulating a porous or
micro-porous medium which acts as the migration medium.
After entering the cavity 16, the liquid begins its slow-
migration along said medium.
The upper layer 12 comprises transparent windows 17, 18
(indicia) showing the progress of the said 3 low-migration
process, thereby acting as a graphic mask. One window 18 is
positioned above the cavity 16 in the middle layer 12 and a
second window is positioned above the intended end-point.
When the device is activated, the liquid flows into cavity 16
and a colour change is seen through the first window 18 which
shows the device has been activated. A colour-change viewed
at the second window 17 shows that the intended end-point
(corresponding to the i lifetime of the item being monitored)
has been reached.
Referring now to Figs. 2A & 2B, there are seen two
exemplary embodiments of the middle layer of the device, the
middle layer being the slow liquid-migration component. In
Pig. 2A, the middle layer 20 comprises a laminated strip 26
of a porous or micro-porous material which serves as the
slow-migration medium for the liquid that arrives into the
second reservoir or cavity 22 defined by the cut-out section
of said medium. Said liquid migration is prevented from
extending beyond the edges of the layer by a pressure heat
seal 24 applied around the edges of the layer, said sealing
operation essentially closing the pores of the micro-porous
material.
In an alternative embodiment shown in Fig. 2B, the
middle layer 2 0 comprises an encapsulated strip 2 6 of a
micro-porous material which serves as the slow-migration
medium for the liquid that arrives into the cavity 22 cut
into said medium. Said liquid-migration is prevented from
extending beyond the strip 2 6 by the laminate-to-laminate
bond in the surrounding margin 28.
Referring now to Fig. 3, an alternative embodiment of
the liquid release mechanism is shown. According to this
embodiment a first reservoir in the form of a rupturable
capsule 30 containing the liquid is placed within a second
reservoir in the form of a cavity 32. Pressure exerted above
and below said cavity 32 causes the release of the liquid
into the cavity and hence the start of the liquid migration.
In this embodiment, the lower layer of the device only serves
to provide a lower seal, and thus the thermoformed reservoir
and conduit of Fig. 1 are obviated.
Referring now to Figs. 4A to 4F, the progress over time
of the liquid-migration front in the migration medium is
shown in Figs. 4A to 4C. The colour-change as viewed through
the said partially transparent upper layer of the device is
shown in Figs. 4D to 4F. Initially, as shown in Figs. 4A and
4D respectively, the liquid is contained within the cavity
and a colour change is only visible in the first or start
window 48. This shows that the device has been activated.
As time progresses, as shown in Fig. 4B, the liquid
starts to migrate out from the cavity and begins to colour
the edges surrounding the cavity 42. As shown in Fig. 4E, no
colour change is visible in the second or expire window. Over
time the coloured area progressively and cumulatively expands
lengthwise along the indicator by migrating down the
migration medium 44. Finally, as shown in Fig. 4C, all or
almost all of the migration medium has changed colour and as
shown in Fig. 4F, a colour change is visible in the second
window indicating that the product has expired.
As will be clear to one skilled in the art, various
types of graphic design may be employed for the
expiry/lifetime end-point, including but not limited to
various lines, curves, ellipses, rectangles or points.
Similarly, indicia showing the progress of the liquid-
migration front may also be employed, including but not
limited to various arrows, curves, lines and points of
different sizes.
Furthermore, each embodiment, may be adapted to include
numerous additional indicia to show the status of the time
indicator. Such indicia (not shown) can include graphic
symbols showing the gradual advance to said end-point. The
starting colour seen through the windows may be the same as
the background colour of the upper layer, and thus any colour
change stands out clearly. The final colour may be red; a
transition to red being readily understandable as a sign that
the item being monitored should be disposed of.
Figs. 5A and 5B show an alternative indicator comprising
a base layer 50, an upper migration layer 56 comprising a
migration medium and an intermediate layer 60 sandwiched
between the upper layer 56 and the base layer 50. The upper
migration layer 56 is laminated, i.e. covered on both
surfaces by a laminate layer 51. The upper surface of the
migration layer 56 is printed with indicia showing the start-
point and the end-point, thus avoiding the need for a
separate partially transparent upper layer for printing.
Furthermore, the printing of the migration layer 56 may
define transparent windows as in earlier embodiments.
The base layer 50 is preferably made of PVC and is
formed with a dished portion 52 which contains a first liquid
reservoir 54. The intermediate layer is provided with a vent
65 and an inlet 64 which connects the liquid reservoir 54 to
a small cavity 66 in the migration layer 56. The intermediate
layer 60 is sealed to the migration layer 56 by a thermal
adhesive applied to an upper surface of the intermediate
layer 60 except in a print area 67 covering part of the lower
surface of the migration layer 56. The print area 66 is
printed with a material, e.g. paint, which forms a weak
adhesive bond with the thermal adhesive which may be W60 and
W60 pre-applied aliphatic polyester water-based urethane
adhesives from Lmarr (Glen Ellen, CA, US).
The device is activated by depressing the dished portion
52 which forces liquid from the reservoir 54 through inlet 64
into the cavity 66. The cavity 66 expands or inflates over
the print area 67 to form a second reservoir in the form of
an internal pocket 68 as shown in Fig. 5B. Once the pocket
68 is formed, the button or dished portion 52 remains in its
depressed state. The liquid then begins to diffuse over time
through the migration medium as described above.
Figs. 6A to 6C show the device of Figs. 5A and 5B with a
mechanism to channel the migration of the liquid into a
narrow path through the migration medium. Heat and pressure
is used to form a seal 70 which defines the narrow path. Fig.
6A shows the device before activation and thus no liquid is present in the cavity 66. Shortly after activation the
cavity 66 is filled with liquid and liquid begins to diffuse
into the migration medium as shown in Fig. 6B. Over time the
liquid continues to advance along the migration medium along
the narrow path defined by the seal 70 as shown in Fig. 6C
The embodiment of Figs. 5A to 5B may be manufactured as
follows:
1) A plastic PVC layer is thermoformed at 150 to 160°C to
form a base layer 50 having a dished portion 52;
2) A second plastic layer having an inlet 64 and a vent 65
is glued to the base layer 50 to form an intermediate
layer 60 with the inlet being aligned with the dished
portion;
3) Liquid is fed through the inlet into the dished portion
to form a first reservoir. As the liquid fills the
reservoir, air is evacuated from the dished portion
through the vent 65. The intermediate layer 60 may be
considered to be a filling-facilitator layer and enables
rapid manufacturing speeds to be achieved;
4) Adhesive is applied to the free surface of the
intermediate layer 60;
5) A migration layer 56 comprising a migration medium is
printed over part of its surface with a material, e.g.
paint, which forme a weak bond with the adhesive on the
intermediate layer;
6) The intermediate layer 60 and the migration layer 56 are
bonded together at about 90°C, and
7) Optionally, heat (in the range 15O-200°C) and pressure
are applied to the upper surface to melt the migration
layer thereby forming a seal or partial seal which
defines a narrow migration passage.
8) Optionally, the migration layer 56 may be printed with
indicia or so as to define transparent windows to view
start and end points of the migration. Alternatively, an
additional partially transparent layer with such indicia
may be bonded to the migration layer.
In each of the embodiments the migration medium may be a
porous material such as a micro-porous polymer, for instance
a polyolefin plastic (with a primarily silica filler) such as
Teslin® (PPG Industries, Inc., Pennsylvania, USA) or a
polyethylene with a silica filler such as Artisyn ™ (Daramic
Inc., Owensboro, KY, USA). The liquid used can be any
viscous liquid with the appropriate (e.g. red) colouration,
for example an edible oil such as corn oil containing an oil-
soluble red-dye such as Oil Red EGN (Aldrich Chemical
Company, Inc., USA). In this example, the rate of liquid
migration is determined by the viscosity of the liquid and
the thickness and density of the migration medium.
Advantageously, the choice of an edible oil with a food
dye ensures that the device will remain non-toxic, even in
the event that it splits open. A further advantage of said
oil/dye combination is that, as this liquid migrates along
the migration medium, a two-stage colour-change front is
produced as the underlying yellow colour of the oil precedes
the appearance of the red colour. Thus a graduated colour
change occurs, first to yellow as an intermediate colour, and
then to red. Advantageously, said colour change sequence is
intuitive to the consumer due to the familiarity of consumers
with traffic lights which first turn yellow before becoming
red. Similarly, a red colour is associated with danger and
thus said combination provides an optimal colour change
sequence for the device of the present invention.
An alternative liquid/dye combination utilizes a water-
soluble dye (e.g. a red food dye) in water, together with an
additive, such as polyethylene glycol (PEG) , to control the
viscosity of the resulting liquid and thus the rate of its
migration. Additionally, a combination of dyes with
differing retention times can be employed, so as to cause one
colour (say yellow) to appear shortly before the final colour
(say red) dominates.
Alternatively, the migration medium may be a micro-
porous doped sol-gel, the liquid may be a solution of a zinc
salt such as zinc chloride, and the colour-changing reaction
system may be a chelation reaction. As the zinc solution
proceeds to migrate slowly through the doped sol-gel medium,
it reacts with the dopant; in this case the chelating agent
4-(2-pyridylazo)resorcinol monosodium salt, hereinafter PAR,
thereby yielding a colour change from yellow to red.
In one embodiment, the support material for the doped
sol-gel may be standard laser quality paper (80g/m2) paper
which is cut into 1cm by 2.5cm strips and dip-coated with the
PAR-doped sol-gel. The doped sol-gel liquid may be prepared
by first adding a 5ml solution of tetraethoxysilane (TEOS) to
a stirred solution consisting of 10ml ethanol, 1.6ml triply
distilled water, 4 drops of concentrated (33%) hydrochloric
acid (HCl) and 0.1g of PAR. After stirring for a further 5
minutes, 0.3g of a surfactant such as CTAB
(hexadecyltrimethyl-ammonium bromide) is added and stirred
until the solution becomes homogeneous. The solution is
stirred for a further two hours. The paper may be dipped
into this sol-gel liquid by holding the paper strip at one by
a dipping machine; lowering it into the non-stirred solution
and then withdrawing it at a rate of 0.08cm/sec. It is then
left to dry at 50 °C in an oven for at least 24 hours to
complete curing.
In this example, the rate of liquid migration is
determined by the pH during preparation of the sol-gel, which
controls the resulting pore size. This choice of reaction
system is especially advantageous because, even if the device
were to split open, no dangerous chemicals would be released.
Zinc solution is non-toxic (being an acceptable constituent
of drinking water at levels up to 5mg/l) and the PAR remains
entrapped as a dopant within the sol-gel matrix and therefore
can not leach out.
As is obvious to one skilled in the art, a number of
alternative migration media and a number of alternative
reaction mechanisms are feasible. A number of micro-porous
media enable a slow-migration effect to be implemented;
examples include Empore™ particle-filled Teflon (available
from Minnesota Mining and Manufacturing Company, St. Paul,
Minnesota, USA), Other materials suitable for a migration
media are cellulose-based materials such as paper where both
capillary action and diffusion may contribute to the
migration effect.
A number of alternative chemical systems capable of
producing a similar colour change to that of the above
described embodiments are listed below:
1. To implement other chelation reactions, alternative
chelating agents such as 1,10 phenanthroline, zincon, or
2,2'-biquioline (eupron) can be incorporated or doped into
the porous medium while alternative liquid reagents that
would migrate into the porous medium can include solutions
of metal ions such as copper ions, iron ions and calcium
ions.
2. To implement acid/base reaction systems, suitable pH
indicators including bromothymol blue, methyl red, cresol
red can be incorporated or doped into the migration
medium, and suitable acid/base liquid reagents that would
migrate into the migration medium can include the acids:
hydrochloric acid, citric acid and ascorbic acid and the
bases: sodium hydroxide and sodium hydrogen phosphate.
3. To implement redox reactions, redox indicators such as n-
phenylanthrancilic acid or a bleachable dye can be
incorporated or doped into the migration medium while
alternative liquid reagents that would migrate into the
migration medium can include solutions of bleaching powder
or of vanadium salts.
4. To implement an enzymatic reaction, an enzyme such as a
lipase can be incorporated or doped into the migration
medium together with a pH indicator while a liquid
substrate such as tricaproin would migrate into the
migration medium. In one embodiment the reaction product
of the enzymatic reaction of a lipase and tricaproin is
caproic acid; said acid producing a colour shift in the pH
indicator.
The above chemical colour-change system can be
implemented within the context of the present invention by
ensuring that one of the chemical reagents is present in the
migrating liquid, while the other is present in the migration
medium. Means known in the art for placing a chemical within
a migration medium include doping (as per the sol-gel
description above); dipping and printing of the chemical into
or on to said medium.
As set out above, activation of each embodiment is by
the simple application of pressure on a portion of said
indicator, the invention has the advantage of being easy to
use and may have foolproof operation. Furthermore, by basing
the construction of the indictor on printable, sheet-like
liquid migration media; fabrication may be performed using
simple technologies such as printing, dipping, stamping and
lamination. Thus, the time indicator may have a simple and
inexpensive manufacture. For example off-the-ahelf media may
be adapted to provide an indicator according to the
invention. The time indicator of may also be suitable for
attachment to containers or other items stored in the
refrigerator or freezer and may use liquid which do not
freeze, for example mixtures of propylene glycol and water at
various concentrations or synthetic oils designed to operate
at sub-zero conditions
This may be particularly useful for the longer time
frames, e.g. six months
It will thus be seen that according to the present
invention a simple and inexpensive time indicator for
consumers is described. While the invention has been shown
herein in what is presently conceived to be the most
practical and preferred embodiments thereof, it will be
apparent to those of ordinary skill in the art that many
modifications may be made thereof within the scope of the
invention, which scope is to be accorded the broadest
interpretation of the appended claims so as to encompass all
equivalent structures and devices.
WE CLAIM:
1. A time indicator comprising a first reservoir, a migration
medium and activating means for bringing liquid from the first
reservoir in contact with the migration medium, the activating
means comprising a second reservoir connected between the first
reservoir and the migration medium whereby after activation the
liquid travels relatively rapidly from the first reservoir to the
second reservoir and then migrates relatively slowly along the
length of the migration medium over time producing a colour change
therein, characterised in that the second reservoir is in the form
of an inflatable pocket which inflates after activation.
2. A time indicator as claimed in claim 1, wherein the first and
second reservoirs are located towards opposed ends of the migration
medium and are connected by a conduit.
3. A time indicator as claimed in claim 1 or claim 2, wherein the
activation means comprises a pressure-rupturable seal between the
first and second reservoirs.
4. A time indicator as claimed in any of the preceding claims,
comprising a base layer formed with a dished portion for the first
reservoir, a migration layer comprising the migration medium and an
intermediate layer sandwiched between the base layer and the
migration layer.
5. A time indicator as claimed in claim 4, wherein the
intermediate layer is weakly adhered to the migration layer at one
end of the migration medium whereby the second reservoir is formed
between the migration and intermediate layers after activation.
6. A time indicator as claimed in any one of the preceding
claims, comprising an at least partially transparent layer mounted
to the migration medium.
7. A time indicator as claimed in any of the preceding claims,
comprising indicia whereby the time elapsed is measured by
comparing the progress of the colour change along the migration
medium with the indicia.
8. A time indicator as claimed in claim 7, wherein the indicia
are in the form of transparent windows through which the colour
change is visible.
9. A time indicator as claimed in claim 7 or claim 8, wherein the
indicia are defined by printing on the migration medium.
10. A time indicator as claimed in any of the preceding claims,
wherein the properties of the liquid and the migration medium are
selected so that migration along the migration medium takes a
predetermined time period.
11. A time indicator as claimed in claim 10, wherein the time
period is between thirty minutes and six months.
12. A time indicator as claimed in any of the preceding claims,
wherein the liquid is a viscous liquid and the viscosity of
the liquid controls the rate of liquid migration through the
migration medium.
13. A time indicator as claimed in any of claims 10 to 12, wherein
the liquid is selected from the group consisting of an oil mixed
with an oil-soluble dye and water mixed with a water-soluble dye
and a chemical to control its viscosity.
14. A time indicator as claimed in any of the preceding claims,
wherein the migration medium is selected from the group consisting
of polymeric micro-porous materials, cellulose-based materials,
sol-gels, and particle-filled Teflon.
15. A time indicator as claimed in claim 14, wherein the migration
medium comprises a micro-porous polymeric material with a silica
filler.
16. A time indicator as claimed in any of the preceding claims,
wherein the liquid is coloured, whereby a colour change is produced
in the migration medium by the migration of the liquid along the
migration medium.
17. A time indicator as claimed in any of claims 1 to 15, wherein
the liquid contains a first reagent and the migration medium
contains a second reagent which reacts with said first reagent,
thereby producing the colour change.
18. A time indicator as claimed in claim 17, wherein the reaction
system between said first and second reagent is selected from the
group comprising: chelation of a metal ion by a chelating agent,
reaction of an acid/base with a pH indicator, reaction of an
electron donor/acceptor with a redox indicator, and the enzymatic
reaction between an enzyme and a substrate.
19. A time.indicator as claimed in claim 18, wherein the metal
ions are selected from the group consisting of zinc ions, copper
ions, iron ions and calcium ions; chelating agents are selected
from the group consisting of 1,10 phenanthroline, zincon, and
2,2'-biquioline (cupron) and PAR; acid/base reagents are selected
from the group consisting of hydrochloric acid, citric acid,
ascorbic acid, sodium hydroxide and sodium hydrogen phosphate; pH
indicators are selected from the group consisting of bromothymol
blue, methyl red and cresol red; electron donor/acceptors are
selected from the group consisting of bleaching powder and
vanadium salts; and redox indicators are selected from the group
consisting of n-phenylanthrancilic acid and bleachable dyes.
20. A time indicator as claimed in any one of the preceding
claims, wherein the colour change is to red.
21. A time indicator as claimed in any of the preceding claims,
wherein migration of the liquid causes more than one colour change
in the migration medium.
22. A time indicator as claimed in claim 21, wherein the colour
changes first to yellow then to red.
23. A time indicator as claimed in any one of the preceding
claims, comprising an adhesive backing.
24. A time indicator as claimed in any of the preceding claims,
comprising means defining a migration passage along the length of
the migration medium.
25. A method of manufacturing a time indicator comprising
providing a base layer formed with a dished portion for a liquid
reservoir, an intermediate layer having an inlet and a migration
layer comprising a migration medium; bonding the base layer to the
intermediate layer with the inlet aligned with the dished portion;
feeding liquid through the inlet into the dished portion to form a
first reservoir; and partially bonding the migration layer to the
intermediate layer whereby a second reservoir in the form of an
inflatable pocket is formed between the migration layer and the
intermediate layer so that when the time indicator is activated
liquid travels relatively rapidly from the first reservoir to
inflate the second reservoir and then migrates relatively slowly
along the length of the migration medium over time.
26. A method as claimed in claim 25, comprising printing on part
of the surface of the intermediate layer to resist bonding between
the migration layer and the intermediate layer whereby the
inflatable pocket forms over the printed part.
27. A method as claimed in claim 25 or claim 26, comprising
defining a migration passage along the length of the migration
medium.
28. A method as claimed in claim 27, comprising forming a seal in
the migration layer which defines the migration passage.
29. A method as claimed in any of claims 25 to 28, comprising
bonding an at least partially transparent layer to the migration
layer.
30. A method as claimed in claim 29, comprising defining indicia
on the transparent layer whereby the time elapsed is measured by
comparing the progress of the colour change along the migration
medium with the indicia.
31. A method as claimed in any of claims 2 5 to 30, comprising
printing indicia on the migration layer whereby the time elapsed is
measured by comparing the progress of the colour change along the
migration medium with the indicia.
----------------X-------------
A time indicator comprising a first reservoir (13),
a migration medium (11) and activating means for bringing liquid
from the first reservoir (13) in contact with the migration medium
(11) so that after activation the liquid migrates through the migration
medium (11) producing a colour change therein. The activating
means comprises a second reservoir (16) connected between
the first reservoir (13) and the migration medium (11) whereby
after activation the liquid travels relatively rapidly from the first
reservoir (13) to the second reservoir (16) and then migrates relatively
slowly along the length of the migration medium (11) over
time.

Documents:

131-KOLNP-2004-CORRESPONDENCE.pdf

131-KOLNP-2004-FORM 27.pdf

131-KOLNP-2004-FORM-27.pdf

131-kolnp-2004-granted-abstract.pdf

131-kolnp-2004-granted-assignment.pdf

131-kolnp-2004-granted-claims.pdf

131-kolnp-2004-granted-correspondence.pdf

131-kolnp-2004-granted-description (complete).pdf

131-kolnp-2004-granted-drawings.pdf

131-kolnp-2004-granted-examination report.pdf

131-kolnp-2004-granted-form 1.pdf

131-kolnp-2004-granted-form 13.pdf

131-kolnp-2004-granted-form 18.pdf

131-kolnp-2004-granted-form 3.pdf

131-kolnp-2004-granted-form 5.pdf

131-kolnp-2004-granted-form 6.pdf

131-kolnp-2004-granted-gpa.pdf

131-kolnp-2004-granted-reply to examination report.pdf

131-kolnp-2004-granted-specification.pdf

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Patent Number

233688

Indian Patent Application Number

131/KOLNP/2004

PG Journal Number

14/2009

Publication Date

03-Apr-2009

Grant Date

01-Apr-2009

Date of Filing

14-Feb-2004

Name of Patentee

TIMESTRIP UK LIMITED

Applicant Address

FINSGATE, 5-7 CRANWOOD STREET, LONDON ECIV 9EE

Inventors:

#	Inventor's Name	Inventor's Address
1	FREEDMAN PAUL JOSEPH	C/O TIMESTRIP LIMITED EASTWAY ENTERPRISE CENTRE, 7 PAYNES PARK, HITCHIN, HERTS SG5 1EH
2	SOLOMON IAN MICHAEL	10 SHIOMO ZEMACH ZEMACH STREET, JERUSALEM
3	ISBITSKY REUBEN	C/O TIMESTRIP LIMITED EASTWAY ENTERPRISE CENTRE, 7 PAYNES PARK, HITCHIN, HERTS SG5 1EH
4	KAGAN MICHAEL LEON	8 GIDEON STREET, JERUSALEM
5	SCHRAGENHEIM ILAN	SIMTAT NANA, MOSHAV BNEY ZION, 60910

PCT International Classification Number

G04F 1/06,G04F 13/00

PCT International Application Number

PCT/GB2002/03137

PCT International Filing date

2002-07-09

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	0116878.0	2001-07-11	U.K.