dual function heat indicator

专利摘要:
DOUBLE FUNCTION HEAT INDICATOR The present invention generally relates to visual temperature history indicators, including temperature exposure indicators, cumulative time-temperature indicators, and cumulative double-peak time-temperature indicators. The dual function heat indicator (10, 30, 40, 50, 60, 70, 80) comprises a substrate (14, 42); a cumulative exposure indicator (34, 44) supported by the substrate (14) in a visible layered configuration, where the cumulative exposure indicator is configured to subject a change in optical appearance in response to cumulative heat exposure; and a peak exposure indicator (32, 52, 62, 72, 82) supported by the substrate (14) in a visible layered configuration, where the cumulative exposure indicator (34) and the peak exposure indicator (32 ) are functionally separate.
公开号:BR112014028058B1
申请号:R112014028058-4
申请日:2013-05-13
公开日:2021-01-05
发明作者:Thaddeus Prusik；Dawn E. Smith；Dene H. Taylor；Raquiba Hoque Arnold
申请人:Temptime Corporation；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present invention generally relates to visual temperature history indicators, including temperature exposure indicators, cumulative time-temperature indicators, and double peak and cumulative time-temperature indicators. BACKGROUND OF THE INVENTION
[002] Many commercial products are sensitive to heat and can lose their effectiveness or quality if they are subjected to excessive exposure to ambient heat before being used. Examples of heat-sensitive commercial products include certain pharmaceuticals, medical products, and foodstuffs as well as some industrial products. Consequently, the time-temperature indicators provided can monitor the cumulative ambient heat exposure of a host product and signal when a predetermined value that can correlate with a decline in the condition of the host product has been reached. The signal can be a color change, for example, a darkening of an indicator area, and can be generated by a heat trapping agent such as a diacetylene compound, or another technology, which integrates exposure to heat, as measured by temperature over time. Some examples of heat-sensitive diacetylene compounds, and time-temperature indicators that employ them, are described in U.S. Patent No. 8,067,483 to Prusik et al .; Patent Application Publication No. U.S. 2009/0131718 by Baughman et al .; and U.S. Patent Publication No. 2011/0086995 by Castillo Martinez et al. Other patents and patent publications that describe various time-temperature indicator technologies are cited elsewhere here.
[003] Some host products are also sensitive to short-term spikes, or heat exposure spikes that may not have enough cumulative heat value to cause an attached time-temperature indicator to signal that a heat exposure limit may have been hit. Some examples of these products are vaccines and other medical products that include a proteinaceous active ingredient.
[004] Consequently, there is a need for a dual function heat indicator that can effectively monitor exposure to cumulative ambient heat and exposure to peak ambient heat and provide a clear signal of possible exposure to excessive heat.
[005] Several proposals are known for indicators that can signal a previous exposure to temperatures that exceed a threshold. For example, US Patent Number 5,709,472, and its divisional patent, US Patent Number 6,042,264, by Prusik et al., Describe and claim a time-temperature indicator label to measure the length of time that a product was exposed to a temperature above a predetermined temperature. Also, U.S. Patent No. 7,517,146 to Smith et al. It describes an excess temperature indicator that can provide a visual indication of previous exposure of perishables, ripening products and other host products to an elevated temperature that exceeds a threshold temperature.
[006] Furthermore, U.S. Patent No. 5,057,434 to Prusik et al. ("Prusik et al. '434" here) refers to an improved time-temperature indicator device useful for monitoring the environmental exposure of products that are subject to progressive quality changes in response to these exposures. See, for example, column 1, lines 5-8 of Prusik et al. '434. As described, a cumulative time-temperature indicator and a limit indicator can be integrated into a single device. In addition, the device can develop color gradually and irreversibly as a function of time and temperature and monitor the actual condition of a perishable product more closely than a single indicator. See, for example, the summary of Prusik '434. The system's capabilities can be enhanced by a barrier layer that slows down the color development action. See, for example, column 9, lines 25-33. DESCRIPTION OF THE INVENTION
[007] Although the heat exposure indicators described in the background may be effective for their intended purposes, there is a need for a dual function heat indicator that can monitor cumulative ambient heat exposure and peak ambient heat exposure, and that has improved properties.
[008] Some commercial products are particularly sensitive to heat and have a small thermal capacity, so short spikes in excessive heat can be harmful. For example, vaccines are typically packaged in small bottles that include individual dosages and lose potency easily if their immunogenic proteins are subjected to excessive heat.
[009] Consequently, a dual-function heat indicator that can signal cumulative ambient heat exposure and exposure to a short-lived ambient heat spike could be useful for monitoring vaccines and other potentially harmful heat exposure products.
[010] An exemplary embodiment of the invention is a dual function heat indicator for monitoring exposure to cumulative ambient heat and exposure to peak ambient heat. The dual function heat indicator can include a substrate, a cumulative exposure indicator supported by the substrate and a peak exposure indicator supported by the substrate. The cumulative exposure indicator can be supported in a visible layer configuration, and can be color changeable in response to cumulative ambient heat exposure. The peak exposure indicator can also be supported by the substrate in a visible layered configuration.
[011] The peak exposure indicator can include a first reagent, a second reagent and a meltable solid. The first reagent can be chemically co-reacted with the second reagent to provide a color change and the melt solid can physically separate the first reagent from the second reagent. The color change chemical reaction can be induced in response to a peak exposure to ambient heat, which can be a peak that exceeds the melting point of the melt. For example, the melting of the meltable solid caused by the peak exposure to ambient heat can bring the first reagent into contact with the second reagent. This dual function heat indicator can indicate cumulative ambient heat exposure and / or peak ambient heat exposure by changing color. Some achievements can change color in response to any of the following: exposure to cumulative ambient heat that reaches a predetermined value; a peak ambient heat exposure event; a combination of the two events; and a combination of two partial events that can have a sufficient additive effect. The use of chemical reagents to provide a color change can allow the peak exposure indicator to respond quickly to a relatively short spike in exposure to ambient heat, and with the appropriate selection of reagents, with a strong color change.
[012] The dual function heat indicator can also include an active viewable area where the cumulative exposure indicator and the peak exposure indicator are viewable with the optical densities of the combined visualized indicators. Thus, the outputs of the cumulative exposure indicator and the peak exposure indicator can be integrated into a single display.
[013] In some exemplary embodiments, the peak exposure indicator can include a dual function heat indicator peak indicator layer and the first reagent and second reagent can be particulate and dispersed in the peak indicator layer. Including the first reagent and the second reagent, and optionally, the meltable solid in the same layer as the dual function heat indicator can help provide a quick response as a result of the proximity of the reagents.
[014] The cumulative exposure indicator can be transparent before changing color and can be configured on a first layer of the dual function heat indicator and the peak exposure indicator can be configured on a second layer of the heat indicator of dual function. The second layer can be arranged between the cumulative exposure indicator and the substrate, and the peak exposure indicator can be viewed through the cumulative exposure indicator when the last one is transparent.
[015] In another exemplary embodiment of the dual function heat indicator, the cumulative exposure indicator is configured in one layer and the peak exposure indicator is arranged in the same layer as the cumulative exposure indicator.
[016] In a further exemplary embodiment of the invention, a meltable colored material that has a small particle size and initially has a light color due to light scattering, and darkens on melting, can replace the first reagent and the second reagent. Alternatively, the material can reveal or obscure a background color by melting, resulting in a change in the visual appearance of an indicator.
[017] Another exemplary realization of the invention is a heat indicator to monitor exposure to ambient heat that exceeds a threshold temperature that employs an agglutinable particulate colored material that has a small particle size and initially has a light color due to light scattering, and that darkens in response to an event of exposure to ambient heat that exceeds the threshold temperature. A limit temperature can be a peak temperature, a freezing temperature or another suitable temperature.
[018] Another exemplary embodiment of the invention is a method of producing a dual function heat indicator to monitor cumulative ambient heat exposure and exposure to peak ambient heat. Optionally, the dual function heat indicator can be the exemplary embodiment previously described here. The method may include applying a liquid composition that includes a cumulative heat trap to a substrate. The cumulative heat trap can be color changeable in response to cumulative ambient heat exposure and can be transparent before changing color. In addition, the method may include drying the liquid composition on the substrate to provide a dry composition, without changing the color of the heat capture agent, and incorporating a peak exposure indicator composition into the liquid composition. The peak exposure indicator composition can include a first reagent, a second reagent and a melt solid.
[019] Drying can be conducted at a relatively low temperature, for example, a temperature below the melting point of the melt, such as a temperature below about 40 ° C or below about 30 ° C. Forced convection, control of air humidity or gas flow, and / or limiting the duration of drying can optionally be used to help dry and prevent the color change of the heat trapping agent. Other useful drying techniques that can be employed and that can be carried out at a suitably low temperature include radiation curing, for example, using ultraviolet light or electron beam energy.
[020] As an alternative to incorporating a peak exposure indicator composition into the liquid composition, the method may include sustaining a peak exposure indicator that includes a first reagent, a second reagent and a melt on the substrate, prior to applying the liquid composition, and applying the liquid composition on the peak exposure indicator on the substrate.
[021] In some exemplary embodiments of the method, the first reagent and the second reagent can be chemically co-reactive to provide a color change, the melt solid can physically separate the first reagent from the second reagent in the dry composition, or in substrate-supported peak exposure indicator, and / or the color change chemical reaction can be included in response to a peak exposure to ambient heat.
[022] Another exemplary embodiment may include applying the peak exposure indicator composition to a distinct area of the substrate before applying the liquid composition, and applying the liquid composition to the entire area of the peak exposure indicator. The substrate can support a coating of the peak exposure indicator composition and the coating can optionally extend over the entire area of the substrate.
[023] An alternative manufacturing method can have the cumulative and peak indicators prepared separately as described above, and then are combined by lamination.
[024] To practice some exemplary embodiments of the invention, the first reagent and the second reagent can be particulate and the liquid composition can include an aqueous dispersion of the first reagent, the second reagent and the melt solid.
[025] In an exemplary embodiment of the dual function heat indicator to monitor cumulative ambient heat exposure and peak ambient heat exposure, the dual function heat indicator can include a substrate, a cumulative exposure indicator supported by the substrate in a visible layered configuration, the cumulative exposure indicator is color changeable in response to cumulative ambient heat exposure, and a substrate-supported peak exposure indicator in a visible layered configuration, the peak exposure indicator can include a first reagent, a second reagent and a meltable solid, the first reagent is chemically liable to co-react with the second reagent to provide a color change, the melt solid physically separates the first reagent from the second reagent, and the chemical reaction of color change is induced in response to a peak temperature of exposure to ambient heat that exceeds the melting point that of the meltable solid in which the dual function heat indicator indicates at least one between cumulative exposure to ambient heat and exposure to peak ambient heat by changing color.
[026] Optionally, the exemplary realization of the dual function heat indicator can include an active viewable area in which the cumulative exposure indicator and the peak exposure indicator are visible in the active area with the optical densities of the visualized indicators combined. Furthermore, in the exemplary embodiment of the dual function heat indicator, the peak exposure indicator can include a peak indicator layer where the first reagent and the second reagent are particulate and dispersed.
[027] Alternatively, the exemplary realization of the dual function heat indicator may include a cumulative exposure indicator that can be transparent before changing color and is configured in a first layer while the peak exposure indicator is configured in a second layer, the second layer being arranged between the cumulative exposure indicator and the substrate and the peak exposure indicator is visible through the cumulative exposure indicator when it is transparent. In addition, optionally, in the exemplary realization of the dual function heat indicator the cumulative exposure indicator can be configured in one layer and the peak exposure indicator can be arranged in the same layer as the cumulative exposure indicator.
[028] Optionally in the exemplary realization of the dual function heat indicator, the substrate can be configured to be conformable with a host product which can allow the dual function heat indicator to be fixed to the host product, optionally, by supporting a layer pressure sensitive adhesive. In addition, optionally, in the exemplary embodiment of the dual function heat indicator, the first reagent and the second reagent can be solids and the melt solid can additionally include a thermal sensitizer to modify the melting point of the melt peak solid. In addition, the melt may include a binder. Alternatively, in the exemplary embodiment of the dual function heat indicator, the first reagent can include a color former and the second reagent may include a color developer and in which, optionally, the color former or the color developer, or both the color former as the color developer, are initially colorless.
[029] Optionally, in the exemplary realization of the dual function heat indicator, the color developer can be selected from a group consisting of an oil-soluble reducing agent, oxalic acid, phosphite ester, benzoic hydroxide ester, hydroidroquinone, a hydroquinone derivative such as dimethihydroquinone, di-tert-butyl hydroquinone, dialkylhydroquinone, 3-ethoxyphenol, 1,2-diethyl-3-hydroxybenzene, 1,3-diethyl-2-hydroxybenzene, 2,2'-methylenebis (3 , 4.6 trichlorophenol); primary and secondary amines fused or soluble in sensitizer that have low water solubility, for example, 4-butylaniline, phenol derivatives, organic acids, and acid clays, reactive acid hectorite clay, phenolic resins, phenol-acetylene resins , polyvalent metal salts of phenolic resins, modified phenolic alkyl resin including zinc, zinc salicylate, zinc salicylate resin, 4,4'-isopropylidenobisphenol (also known as bisphenol A), 1,7 -di (hydroxyphenylthio) -3, 5-dioxaeptane, 4-hydroxyethyl benzoate, 4-hydroxydimethyl phthalate, monobenzyl phthalate, bis- (4-hydroxy-2-methyl-5-ethylphenyl) sulfide, 4-hydroxy-4'-isopropoxyphenylsulfone, 4-hydroxyphenylbenzenesulfonate 4-hydroxybenzoyloxybenzylbenzoate, bis- (3-1-butyl-4-hydroxy-6-methylphenyl) sulfone, p-tert-butylphenol, or polymers based on bisphenol A.
[030] In addition, alternatively, in the exemplary realization of the dual function heat indicator, the color former can be selected from the group that includes 3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis ( p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) -phthalide, 3- (NN-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3-dimethylamino-5,7-dimethylfluoran, 3-diethylamino-7-methylfluoran, 3 - (2'-hydroxy-4'-dimethylaminophenyl) -3- (2 '[- methoxy-5'-chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy -5'-nitrophenyl-phthalide, 3- (2'-hydroxy-4'- diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalide, 3- (2'-methoxy-4'- dimethylaminophenyl) -3- (2'-hydroxy-4'-chloro-5'-methylphenyl) -phthalide, methylene blue benzoilleuco, malachite green lactone, N-2,4,5-trichlorophenilleuco auramine, 3-diethylamino-6-methyl- 7-chlorofluorane, 3,6-bis (diethyl mino) fluoran-Y— (4'-nitro) - anilinolactam, 3-diethylamino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane, 3-cyclohexylamino -6-chlorofluoran or 3-diethylamino-6,8-dimethylfluorane.
[031] In addition to the exemplary realization of the dual function heat indicator, the cumulative exposure indicator can include at least one thermally sensitive polymerizable diacetylene compound containing at least two conjugated acetylenic groups. In addition, the color change due to cumulative heat exposure can be irreversible and occur after a predetermined cumulative heat exposure. Optionally, the exemplary realization of the dual function heat indicator can include a freeze indicator in which the freeze indicator is supported by the substrate and where, optionally, the freeze indicator can be transparent before activation by exposure to a freezing temperature , can be held over the cumulative exposure indicator and the cumulative exposure indicator or can be viewed through the freeze indicator.
[032] Optionally in the exemplary realization of the dual function heat indicator, the substrate may include a printed reference surface. The substrate may be a synthetic sheet or film additionally comprised of polyethylene, polypropylene, polycarbonate, polyester, polyamide, polyurethane, polyvinyl chloride, polyvinylidene chloride, materials derived from cellulose, aluminum foil, paper or coated paper. Alternatively, the substrate can be transparent or white. Optionally in the exemplary embodiment, the substrate can be a transparent polyester film. In the exemplary realization of the dual function heat indicator, the peak indicator may include a prefabricated thermal paper or film that has a normal color change activation temperature of more than 60 ° C.
[033] The exemplary realization of the dual function heat indicator may include an activator applied to the prefabricated thermal paper or film configured to reduce the color change activation temperature of the prefabricated thermal paper or film to below 60 ° Ç. Optionally, the activator can be an organic solvent selected from the group consisting of heptadecanol, 4-methoxyphenol, pentadecanol, 2,4-di-tert-butyl phenol or benzophenone.
[034] Alternatively in the exemplary realization of the dual function indicator, the activator can be selected to have a melting point that is approximately equal to a desired predetermined peak ambient temperature limit which is indicated by the peak exposure indicator. The exemplary realization of the dual function heat indicator can optionally also include a barrier that separates the activator from the pre-made thermal paper or film, the barrier is configured to allow the activator to contact the thermal paper in response to a peak temperature of exposure to ambient heat higher than a predetermined peak temperature, but less than the normal activation temperature of the thermal paper. In addition, the barrier can be a meltable solid.
[035] Optionally, in the exemplary realization of the dual function heat indicator, the peak exposure indicator can have a response temperature selected from the group consisting of the range of about 30 ° C to about 50 ° C, in the range of about 40 ° C to about 60 ° C, in the range of about 30 ° C to about 40 ° C, in the range of about 40 ° C to about 50 ° C, in the range of 50 ° C to about 60 ° C, in the range of about 30 ° C to about 35 ° C, in the range of about 35 ° C to about 40 ° C, in the range of about 40 ° C to about 45 ° C, in the range of about 45 ° C to about 50 ° C, in the range of about 50 ° C to about 55 ° C, in the range of about 55 ° C to about 60 ° C, about 30 ° C, about 35 ° C, about 40 ° C, about 45 ° C, about 50 ° C, about 55 ° C, and about 60 ° C.
[036] In another exemplary embodiment of the dual function heat indicator to monitor cumulative ambient heat exposure and exposure to peak ambient heat, the dual function heat indicator includes a substrate, a cumulative exposure indicator supported by the substrate in a visible layer of the dual function heat indicator, the cumulative exposure indicator is color changeable in response to cumulative ambient heat exposure, and a peak exposure indicator supported by the substrate in another visible layer of the dual function heat indicator , the peak exposure indicator comprises a meltable colored particulate material, where the meltable colored particulate material has an average particle size that dyes the meltable colored particulate material with a light color, the light color being attributable to light scattering visible by the meltable colored material particles, where the melting of the melt colored particulate material f the peak exposure indicator changes its visual appearance, with the change in appearance being induced by a peak exposure to ambient heat that reaches a temperature that exceeds the melting point of the melt-colored particulate material, and in which the dual function heat indicator indicates exposure to cumulative ambient heat or exposure to peak ambient heat by changing color.
[037] Optionally, in the exemplary realization of the dual function heat indicator, the change in the appearance of the peak exposure indicator may be caused by the melting colored particulate material that darkens or it may be caused by the melting of the meltable particulate material that reveals a background or it may be caused by the melting of the molten particulate material that obscures a background. Alternatively, in the exemplary embodiment of the dual function heat indicator, the meltable particulate colored material includes a meltable solid and a dye dissolved in the meltable solid.
[038] In yet another exemplary embodiment, a heat event indicator for monitoring exposure to ambient heat at a temperature that exceeds a threshold temperature includes a substrate and an agglutinable particulate colored material supported by the substrate in which the agglutinable particulate colored material has an average particle size that dyes the bonded colored particulate material with a light color, the light color being attributable to the dispersion of visible light by the bonded colored material particles in which the coalescence of the bonded colored particulate material causes the colored material agglutinable particulate darkens, and the darkening is induced by an event of exposure to ambient heat that reaches a temperature that exceeds the limit temperature and in which the heat event indicator indicates the occurrence of the event of exposure to ambient heat by changing the color. Alternatively in this exemplary embodiment of the heat event indicator, the limit temperature can be a peak temperature and the bonded colored particulate material can be melt and melt in response to the event of exposure to ambient heat. Optionally, in the exemplary embodiment of the heat event indicator, the limit temperature can be a freezing temperature, the heat event indicator includes a dispersion of the particulate colored material that can be bonded in aqueous liquid medium, in which the dispersion is grouped and the material agglutinable particulate color adheres in response to the event of exposure to ambient heat.
[039] In addition, in another exemplary embodiment of the dual function heat indicator or heat event indicator, the host product and the dual function heat indicator or the heat event indicator can be associated to monitor the host product for exposure to heat; the host product, optionally, is a medical product comprising a heat-sensitive proteinaceous component.
[040] In yet another exemplary embodiment of the dual-function heat indicator, a method of producing a dual-function heat indicator to monitor cumulative ambient heat exposure and peak ambient heat exposure, optionally, a heat indicator Dual-function includes applying a liquid composition comprising a cumulative heat trap to a substrate, the cumulative heat trap being color changeable in response to cumulative ambient heat exposure and is transparent before changing color , and drying the liquid composition on the substrate to provide a dry composition, without changing the color of the heat capture agent, incorporating a peak exposure indicator composition into the liquid composition, the peak exposure indicator composition comprising a first reagent, a second reagent and a meltable solid, or sustain a peak exposure indicator comprising a first reagent and, a second reagent and a meltable solid on the substrate before applying the liquid composition and applying the liquid composition on the peak exposure indicator on the substrate where the first reagent and the second reagent are chemically amenable to co-reaction to provide a color change, the melt solid physically separates the first reagent from the second reagent in the dry composition or substrate-supported peak exposure indicator, and the color change chemical reaction is induced in response to a peak heat exposure environment. Optionally, exemplary realization of the dual function heat indicator fabrication method may include applying the peak exposure indicator composition to a distinct area of the substrate before applying the liquid composition and applying the liquid composition to the entire area of the heat indicator. peak exposure. Alternatively, the exemplary embodiment of the dual function heat indicator fabrication method may include the substrate that supports a coating of the peak exposure indicator composition, the coating optionally extending over the entire area of the substrate. Optionally, in the exemplary embodiment of the dual function heat indicator manufacturing method, the first reagent and the second reagent are particulate and the liquid composition includes an aqueous dispersion of the first reagent, the second reagent and the melt solid.
[041] In yet another exemplary embodiment, the method of treating a thermal substrate configured to respond to an ambient temperature above a first predetermined limit by changing the color, the method includes applying an activator to the thermal substrate, the activator is configured to cause the thermal substrate to change color at an ambient temperature above a second predetermined limit, the second predetermined limit is substantially less than the first predetermined limit. Optionally, in the exemplary embodiment, the method may include coating a printable surface of the thermal substrate with the activator where the activator includes a meltable solid. Alternatively, in the exemplary embodiment of the method, the thermal substrate can include a thermal coating that additionally includes a first reagent and a second reagent that are chemically amenable to co-reaction to provide a color change, where the color change is a reaction chemical that is induced in response to a peak temperature that exceeds the melting point of the activator. Optionally, in the exemplary embodiment of the method, the first reagent can include a color former and the second reagent comprises a color developer and where optionally, the color former or the color developer, or both the color former and the developer of color are initially colorless. The color developer can be selected from a group that includes an oil-soluble reducing agent, oxalic acid, phosphite ester, hydroxybenzoic acid ester, hydroidroquinone, a hydroquinone derivative such as dimethihydroquinone, di-tert-butyl hydroquinone, dialkylhydroquinone, 3-ethoxyphenol, 1,2-diethyl-3-hydroxybenzene, 1,3-diethyl-2-hydroxybenzene, 2,2'-methylenebis (3,4,6 trichlorophenol); primary and secondary amines fused or soluble in sensitizer that have low solubility in water, for example, 4-butylaniline, phenol derivatives, organic acids, and acid clays, reactive acid hectorite clay, phenolic resins, phenol-acetylene resins , polyvalent metal salts of phenolic resins, modified phenolic alkyl resin including zinc, zinc salicylate, zinc salicylate resin, 4,4'-isopropylidenobisphenol (also known as bisphenol A), 1,7 -di (hydroxyphenylthio) -3, 5-dioxaeptane, 4-hydroxyethyl benzoate, 4-hydroxydimethyl phthalate, monobenzyl phthalate, bis- (4-hydroxy-2-methyl-5-ethylphenyl) sulfide, 4-hydroxy-4'-isopropoxyphenylsulfone, 4-hydroxyphenylbenzenesulfonate 4-hydroxybenzoyloxybenzylbenzoate, bis- (3-1-butyl-4-hydroxy-6-methylphenyl) sulfone, p-tert-butylphenol, or polymers based on bisphenol A. The color former can be selected from a group that includes 3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethyl aminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p -dibutylaminophenyl) -phthalide, 3- (NN-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3-dimethylamino-5,7-dimethylfluoran, 3-diethylamino-7-methylfluoran, 3- ( 2'-hydroxy-4'-dimethylaminophenyl) -3- (2 '[- methoxy-5'-chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5 '-nitrophenyl-phthalide, 3- (2'-hydroxy-4'- diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalide, 3- (2'-methoxy-4'- dimethylaminophenyl) -3 - (2'-hydroxy-4'-chloro-5'-methylphenyl) -phthalide, methylene blue benzoilleuco, malachite green lactone, N-2,4,5-trichlorophenilleuco auramine, 3-diethylamino-6-methyl-7- chlorofluorane, 3,6-bis (diethylamino) fluoran-Y— (4'-nitro) - anilinolactam, 3-diethylamino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl -7-anilinofluorane, 3-cyclohexylamino-6-chlorofluoran or 3-diethylamino-6,8-dimethylfluorane. Optionally, in the exemplary implementation of the method, a barrier can be added that prevents direct contact between the activator and the thermal coating and in which the barrier is a meltable solid with a melting point of about the second limit temperature, where an ambient temperature above the second predetermined limit causes the barrier to fuse, activating the reaction between the first reagent and the second reagent to chemically co-react and provide a color change. Optionally, in the exemplary embodiment of the method, the melt solid is selected to have a melting point that is approximately the same as a desired predetermined peak ambient temperature limit which is indicated by the peak exposure indicator. Alternatively in the exemplary realization of the method, the thermal substrate can be prefabricated thermal paper or prefabricated thermal film. Optionally, in the exemplary embodiment of the method, the activator can be an organic solvent, preferably selected from a group that includes heptadecanol, 4-methoxyphenol, pentadecanol, 2,4-di-tert-butyl phenol or benzophenone, and more preferably the activator is benzophenone. Alternatively in the exemplary embodiment of the method, the ambient temperature above the second predetermined limit can cause the fusion of the activator that activates the reaction between the first reagent and the second reagent to chemically co-react and provide a color change.
[042] Still in an additional exemplary embodiment, a peak heat indicator includes a prefabricated thermal substrate normally configured to respond to an ambient temperature above a first predetermined limit by changing the color, and an activator applied to the thermal substrate and configured to interact with the prefabricated thermal substrate in such a way that the prefabricated substrate changes color to respond to an ambient temperature above a second predetermined limit by changing the color, the second predetermined limit being substantially lower than the first predetermined limit. Optionally in the exemplary embodiment of the peak heat indicator, the activator can include a meltable solid that has a melting point approximately equal to that of the second predetermined temperature, where an ambient temperature above the second predetermined limit causes the activator that activates the reaction to melt between the first reagent and the second reagent, causing them to chemically co-react and provide a color change. Alternatively in the exemplary embodiment of the peak indicator, the melt solid can be selected to have a melting point that is approximately equal to that of a desired predetermined peak ambient temperature limit which is indicated by the peak exposure indicator. Optionally in the exemplary embodiment of the peak indicator, the thermal substrate may include a thermal coating that further includes a first reagent and a second reagent that are chemically co-reactive to provide a color change in which the color change is a reaction chemical that is induced in response to a peak temperature that exceeds the melting point of the activator. Alternatively in the exemplary embodiment of the peak indicator, the first reagent comprises a color former and the second reagent comprises a color developer and in which optionally, the color former or the color developer, or both the color former and the developer of color are initially colorless. Optionally in the exemplary realization of the peak indicator, the color developer can be selected from a group that includes an oil-soluble reducing agent, oxalic acid, phosphite ester, hydroxybenzoic acid ester, hydroidroquinone, a hydroquinone derivative such as dimethihydroquinone , di-tert-butyl hydroquinone, dialkylhydroquinone, 3-ethoxyphenol, 1,2-diethyl-3-hydroxybenzene, 1,3-diethyl-2-hydroxybenzene, 2,2'-methylenebis (3,4,6 trichlorophenol); primary and secondary amines fused or soluble in solubilizers that have low water solubility, for example, 4-butylaniline, phenol derivatives, organic acids, acid clays, reactive acid hectorite clay, phenolic resins, phenol acetylene resins, polyvalent metal salts of phenolic resins, modified phenolic alkyl resin including zinc, zinc salicylate, zinc salicylate resin, 4,4'-isopropylidenobisphenol (also known as bisphenol A), 1,7 -di (hydroxyphenylthio) -3,5 -dioxaeptane, 4-hydroxyethyl benzoate, 4-hydroxydimethyl phthalate, monobenzyl phthalate, bis- (4-hydroxy-2-methyl-5-ethylphenyl) sulfide, 4-hydroxy-4'-isopropoxyphenylsulfone, 4-hydroxyphenylbenzenesulfonate - hydroxybenzoyloxybenzylbenzoate, bis- (3-1-butyl-4-hydroxy-6-methylphenyl) sulfone, p-tert-butylphenol, or polymers based on bisphenol A.
[043] Optionally in the exemplary realization of the peak indicator, the color former is selected from a group consisting of: 3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) ) -phthalide, 3- (NN-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3-dimethylamino-5,7-dimethylfluoran, 3-diethylamino-7-methylfluoran, 3- (2 ' -hydroxy-4'-dimethylaminophenyl) -3- (2 '[- methoxy-5'-chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'- nitrophenyl-phthalide, 3- (2'-hydroxy-4'-diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalide, 3- (2'-methoxy-4'-dimethylaminophenyl) -3- ( 2'-hydroxy-4'-chloro-5'-methylphenyl) -phthalide, methylene blue benzoilleuco, malachite green lactone, N-2,4,5-trichlorophenilleuco auramine, 3-diethylamino-6-methyl-7-chlorofluorane, 3,6-bis (diethylamino) fluoran-Y— (4'-nitro) -an ilinolactam, 3-diethylamino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane, 3-cyclohexylamino-6-chlorofluoran or 3-diethylamino-6,8- dimethylfluorane. Alternatively, in the exemplary embodiment of the peak indicator, the peak heat indication can also include a barrier configured to prevent direct contact between the activator and the thermal coating in which the barrier is a meltable solid. Optionally in the exemplary realization of the peak indicator, the thermal substrate is prefabricated thermal paper or prefabricated thermal film. Alternatively in the exemplary embodiment of the peak indicator, the activator is an organic solvent, preferably selected from the group that includes heptadecanol, 4-methoxyphenol, pentadecanol, 2,4-di-tert-butyl phenol or benzophenone, and more preferably benzophenone . BRIEF DESCRIPTION OF THE DRAWINGS
[044] Some exemplary apparatus embodiments of the invention, and exemplary procedures for making and using one or more exemplary embodiments, are described in detail here and by way of example, with reference to the attached drawings (which are not necessarily drawn to scale in any internal or external structures shown) and where similar reference characters designate similar elements across the various views.
[045] Figure 1 is a plan view of two exemplary dual-function heat indicators, according to an exemplary embodiment of the invention, arranged side by side on a support liner.
[046] Figure 1A is a plan view of two dual-function heat indicators with a printable margin according to the exemplary embodiment of the invention arranged side by side on a support liner.
[047] Figure 2 is a sectional view on line 2-2 of an exemplary embodiment of one of the exemplary dual function heat indicators shown in Figure 1.
[048] Figure 2A is a sectional view over line 2A-2A of an exemplary embodiment of one of the exemplary dual function heat indicators with a printable margin shown in Figure 1A.
[049] Figure 3 is a view similar to Figure 2 of another exemplary embodiment of the exemplary dual function heat indicator shown in Figure 1.
[050] Figure 4 is a view similar to Figure 2 of an additional exemplary embodiment of the exemplary dual function heat indicator shown in Figure 1.
[051] Figure 5 is a view similar to Figure 2 of an additional exemplary embodiment of the exemplary dual function heat indicator shown in Figure 1.
[052] Figure 6 is a view similar to Figure 2 of an additional exemplary embodiment of the exemplary dual function heat indicator shown in Figure 1.
[053] Figure 7 is a view similar to Figure 2 of an additional exemplary embodiment of the exemplary dual function heat indicator shown in Figure 1.
[054] Figure 8 is a view similar to Figure 2 of an additional exemplary embodiment of the exemplary dual function heat indicator shown in Figure 1.
[055] Figure 9 is a cross-sectional view of an exemplary manufactured dual-function heat indicator prototype discussed in Example 1 here.
[056] Figure 10 is a table, referring to Example 1 here, which shows the optical density measurements of the active region only in the cumulative indicator, the double indicator, and only the construction of thermal paper, at 90 ° C for several time intervals.
[057] Figure 11 is a table, with reference to Example 1 here, which shows the optical density measurements of the active region only in the cumulative indicator, the double indicator, and only the construction of thermal paper, at 80 ° C for several time intervals.
[058] Figure 12 is a table, with reference to Example 1 here, which shows the optical density measurements of the active region only in the cumulative indicator, the double indicator, and only the construction of thermal paper, at 50 ° C for several time intervals.
[059] Figure 13 is a table, with reference to Example 1 here, which shows the optical density measurements of the active region only in the cumulative indicator, the double indicator, and only the construction of thermal paper, at 37 ° C for several time intervals.
[060] Figure 14 is a table, with reference to Example 2 here, which shows the optical density measurements of the active region only in the cumulative indicator (similar to HEATmarker VVM14), the dual function heat indicator, and the peak indicator (DEGmarker 40), between 25-45 ° C.
[061] Figure 15 shows the test cards, with reference to Example 2 here, which shows the appearance of the cumulative indicator (similar to HEATmarker VVM14), the dual function heat indicator, and the peak indicator (DEGmarker 40) without heat and heated to 45 ° C.
[062] Figure 16 is a table, referring to Example 2, which shows the color appearance of the active region in comparison between the dual function heat indicator (VVM14-equivalent with DEGmarker 40) and the heat indicator dual function (VVM14-equivalent with DEGmarker 45).
[063] Figure 17 is a table, with respect to Example 4, which lists the sample, supplier, product, type, initial static sensitivity, and appearance of the active region of the samples after 40 min. at 43 ° C. DESCRIPTION OF ACCOMPLISHMENTS OF THE INVENTION
[064] Vaccines are a low-cost health intervention that can save millions of lives worldwide. However, there may be difficulties in protecting vaccine supplies from overheating during storage and distribution, particularly, but not exclusively, in low- and middle-income countries in warm climate regions. Unless a monitoring device is employed, a medical technician in the field, who wishes to administer a vaccine, has no way of distinguishing between vials containing still potent vaccine dosages from those that may have lost potency due to exposure to heat.
[065] The proteins that are generally the active constituents of vaccines are complex molecules that can have sophisticated three-dimensional conformations, whose presence is essential to obtain an effective immune response in a human individual to whom a vaccine is administered. Upon heating, proteins generally denature and quickly lose their three-dimensional conformation. Denaturation of a small portion of a vaccine dosage may be sufficient to compromise the potency of the dosage. Denaturation can occur slowly, as a result of a gradual build-up of low-level heat exposure, or quickly, as a result of a more intense peak of heat exposure. Similar considerations may apply to other immunogenic molecules, and complex biological products, whether natural or synthetic.
[066] Cumulative time-temperature indicators have generally been applied to vaccine vials to monitor historical cumulative heat exposures experienced by the vaccine and provide the medical technician, or other user, with a warning sign that the vaccine has experienced exposure to heat that may have affected its freshness and potency. As previously noted here, a cumulative time-temperature indicator may not respond effectively to a relatively short-term heat exposure peak that can also affect freshness or potency.
[067] Thus, a dual-function heat indicator that can signal cumulative ambient heat exposure and peak ambient heat exposure in a single device could be useful for monitoring heat exposure of heat-sensitive products like a vaccine, and for other purposes. Small, low-cost indicators could be additionally desired for application to typical single-dose vaccine vials that can have a capacity as small as 5 ml, and a mass cost, which can be below $ 0.25 per dosage in 2012, in some cases.
[068] The term "double", as used here, refers to at least two and may include more than two. The term "color" as used here includes achromatic visual appearances such as black, gray, and white, as well as chromatic appearances that have primary color tones, secondary color tones and / or other color tones, such as, without limitation, red, yellow, green, blue, purple, orange, brown and other tones. The terms "color change" and its grammatical variants are used to refer to changes in tone, intensity or clarity (or darkness) or other changes in visual appearance.
[069] The time-temperature indicator device described in Prusik et al. '434 can be used to signal a real rather than an apparent end to the life of the product, see, for example, the summary by Prusik et al. '434. The time-temperature indicator device may employ a composition that includes diacetylene monomer or other known time-temperature indicator, as a primary indicator of long-term storage of the product. See, for example, column 4, lines 23-238 by Prusik et al. '434. As described, the primary indicator is aided in color development by a secondary indicator that activates, for example, merges, at a predetermined temperature range. At temperatures above the melting point, the material becomes mobile and will diffuse through the layers and color to the indicator. See, for example, column 6, lines 26-29 by Prusik et al. '434. As the predetermined temperature range is reached, or exceeded, a change in color formation begins as a result of the dissolution of a dye composition. See, for example, column 6, lines 40-55 by Prusik et al. '434. Three examples of work described in Prusik et al. 434, Examples I-III, also employ a melt material and a dye that dissolves apparently to form the melt when melted.
[070] According to Prusik et al. '434, the secondary cues provided by the secondary indicator of the time-temperature indicator as described can be made to change rapidly. This system could be used, apparently, to detect the thawing of a frozen product, or the melting of a chocolate confectionery, according to Prusik et al. '434. See, for example, column 4, lines 50-52.
[071] The diffusion of a meltable material, and the dissolution of a dye, although apparently occurring rapidly in relation to the thawing of a frozen food product, or the melting of chocolate, can be unduly delayed when the potential denaturation of a protein needs to be monitored to indicate the likely condition of a vaccine or comparable product.
[072] Similar considerations may apply to vaccines administered to animals, other medical products that include proteinaceous active components, comparable biological products, and other products similarly sensitive to heat.
[073] Furthermore, the diffusion of a meltable material and the dissolution of a dye described in Prusik et al. '434 may require significant ambient heat energy input, which may delay the appearance of a color change after the onset of a peak exposure to excessive temperature.
[074] Consequently, there is a need for a dual function heat indicator that can monitor cumulative ambient heat exposure and a peak exposure to ambient heat in a single device and provide a rapid response to the onset of a peak heat exposure and a clear sign of possible overexposure to heat. If the peak exposure indicator component of a dual-function heat indicator responds very slowly to a peak heat exposure, an associated vaccine, or other heat-sensitive product, may denature and lose its potency, or otherwise. deteriorate before displaying a color change.
[075] A dual function heat indicator according to some exemplary embodiments of the invention can meet these needs by employing a meltable solid that physically separates a first reagent from a second reagent in which the first reagent is co-reactive with the second reagent to provide a color change, and the chemical reaction by color change is induced in response to a peak exposure to ambient heat. The chemical reaction by color change induced by the melting of the melt, as it responds to a peak of heat exposure that reaches a temperature that exceeds the melting point of the melt, can proceed quickly, providing a quick color change. The temperature above which this peak exposure indicator will respond can be predetermined by proper selection of the melt solid component or components, and the resulting melting point of the melt solid, and / or the glass transition temperature of the melt solid, if the latter is relevant. The component, or components of meltable solid, may, in some cases, include each or both the first reagent and the second reagent.
[076] A rapid color change, such as darkening at a distinct dark end point, can help ensure that peaks of heat exposure that are potentially harmful to an intended host product, for example, a vaccine, are appropriately indicated, for example, by the dark end point, and to reduce the risk that a peak of exposure to heat that can have enough heat energy to be harmful to the host product, for example, when denaturing proteins in a vaccine, will still not be able to activate the indicator cumulative exposure.
[077] A peak exposure indicator component of an exemplary dual function heat indicator embodiment of the invention can be correlated, or calibrated, to a host product that the dual function heat indicator is intended to monitor by selecting materials to set the melting point of the peak exposure indicator to not be higher than the excess temperature or limit temperatures that can be harmful to the host product. An example of a limit temperature is a temperature in the range of about 40 ° C to about 60 ° C, which may be suitable for monitoring a vaccine or other host product that includes an active protein or other sensitive biological material or the like. Other limit temperatures can also be used, for example, a limit temperature in the range of about 20 ° C to about 70 ° C, for these and other applications.
[078] The cumulative exposure indicator component of an exemplary dual-function heat indicator embodiment of the invention may be correlated with the heat response characteristics of an intended host product, to track continuous and / or sporadic lower level exposures to which an associated host product can be submitted. The cumulative exposure indicator can also provide a distinct color change, for example, darkening to a dark end point, at an appropriate predetermined cumulative heat value, to indicate the likely condition of the host product. In some exemplary embodiments of the invention, the cumulative exposure indicator may be a dark end point that is similar to the dark end point of the peak exposure indicator, if the last indicator has a dark end point. In these exemplary embodiments, the appearances of the two indicators can be visually combined in a single area to provide an integrated signal that can report two partial heat exposures as potentially representing an adverse heat exposure in combination. Cumulative exposure indicators, as described here, sometimes known as time-temperature indicators.
[079] The predetermined cumulative heat value can be selected in several ways, as known in the art, for example, to correspond with a probable imminent loss of effectiveness or quality of the host product. The cumulative exposure indicator can be configured to provide a desired end point by appropriate selection of a heat capture agent to include in the cumulative exposure indicator, as known in the art, or in another suitable manner.
[080] In addition, a cumulative exposure indicator used in an exemplary embodiment of the dual function heat indicator may appear colorless or slightly colored initially, that is, before heat activation. In some exemplary embodiments of the invention, the appearance of the cumulative exposure indicator can be transparent or translucent, at least initially, so that the appearance of the peak exposure indicator can be viewed or optically read through the cumulative exposure indicator. Thus, the initial appearance of the cumulative exposure indicator can largely be that of the substrate that supports the cumulative exposure indicator, for example, white. As the cumulative exposure indicator is subjected to thermal exposure, the active surface becomes progressively darker. However, the cumulative exposure indicator can maintain some transparency, possibly until the end point of the cumulative exposure indicator is reached.
[081] The term "transparent" is used here to include "translucent" and to refer to a material that can transmit some or all of the incident light, so that bodies, for example, colored surfaces, in addition to the material are visible, although they may diffuse, spread, or block some incident light, to a limited extent.
[082] The cumulative heat indicator can employ a heat capture agent that provides the transparent and subsequent browning appearances initially described. In some exemplary embodiments of the invention, the heat trapping agent may be present in particulate form, in admixture with particles of peak exposure indicator composition. In these exemplary embodiments, the heat trapping agent and the peak exposure indicator can contribute to the mixture with an initially transparent appearance and a dark appearance following exposure to heat.
[083] Except where the context indicates otherwise, the particulate materials employed in exemplary embodiments of the invention's dual-function heat indicator, or exemplary embodiments of the method, may have various particle sizes, as will be known or evident for an element versed in the technique, in the light of that description. For example, these particulate materials can have an average particle size of no more than about 10 μin, or from about 0.5 μin to about 5 μin. Some aspects of the exemplary embodiments of the invention employ materials that disperse light and may have different average particle sizes.
[084] The color change displayed by the peak exposure indicator may be irreversible and may occur after a peak exposure to predetermined ambient heat occurs. The response of the peak exposure indicator can be further increased, for example, by becoming faster, by employing the first and second particulate reagents and dispersing the first and second reagent particles in the same layer as an exemplary embodiment of the heat indicator of dual function. The meltable solid may partially or completely surround the particles of the first reagent or the particles of the second reagent or both types of particles, to provide physical separation between the two types of particles and prevent them from reacting prematurely. The particles of the first reagent can be intimately mixed with the particles of the second reagent and physically separated by a thin layer of the melt. The water insolubility of the first reagent, the second reagent and / or the melt material can be useful for manufacturing or other purposes.
[085] In addition, one or both the first reagent and the second reagent may be soluble in the melt. In addition, one between the first reagent and the second reagent can be dissolved or mixed with the solid material. In addition, the melt material can be a first melt material and a second melt material and can partially or completely involve a solution of the first reagent or the second reagent in the first melt material. One or more of these measures can be used to increase the response of the peak exposure indicator, or for other purposes. For example, these measures may allow the peak exposure indicator to respond quickly after activation by a peak exposure to ambient heat, with little, if any, delay in diffusing an active material or materials.
[086] In some exemplary embodiments of dual function heat indicators according to the exemplary embodiment of the invention, the first reagent and the second reagent can be solid. The meltable solid may include a thermal sensitizer to modify the melting point of the peak exposure indicator. The melt may include a binder, whether the melt or not includes a thermal sensitizer.
[087] For use with a host product that includes an active protein, and for other purposes, the peak exposure indicator can have a temperature response in the range of about 40 ° C to about 60 ° C. For this purpose, the peak exposure indicator can be melted at a temperature close to, or at, its response temperature or at a lower temperature, for example, up to 2 ° C lower. The melting points, or melting point range, of the meltable ingredients of the peak exposure indicator can be selected accordingly.
[088] A first reagent employed in an exemplary embodiment of the dual function heat indicator can be or can include a color former. A second reagent can be or can include a color developer. Optionally, the color former or the color developer, or both the color former and the color developer, can be initially colorless. The color former can develop the color as a result of reaction with the color developer.
[089] A cumulative exposure indicator employed in an exemplary embodiment of the dual-function heat indicator may include at least one thermally sensitive polymerizable diacetylene compound that includes at least two conjugated acetylenic groups, for example, a hexadiene bis (alkyl urea) compound .
[090] The color change displayed by the cumulative exposure indicator may be irreversible and may occur after exposure to predetermined cumulative ambient heat. The cumulative exposure indicator can employ various heat-trapping agents, for example, various polymerizable diacetylene compounds, or other heat-trapping agents, to vary the amount of heat exposure that causes a color change.
[091] The exemplary embodiments of the dual function heat indicator of the invention may exhibit a different color change after activation which provides a satisfactory contrast to the appearance of the dual function heat indicator before activation and an evident irreversible signal suggesting that exposure to adverse heat may have occurred, for example, a significant darkening of the indicator.
[092] The color change can be described in terms of changes in optical density. The optical density "OD" as used here is the log for base 10 of the inverse of reflected light from a sample. OD can be expressed by the formula ODA = logio (Io / I) where I is the light intensity at a specified wavelength À which is reflected by a sample and Io is the light intensity before entering the sample, where I is the light intensity at a specified wavelength À which is reflected by a sample and Io is the light intensity before entering the sample. Some exemplary embodiments of the dual function heat indicator may exhibit a 0.4 OD difference in optical density between appearances before activation and after activation of the indicator, providing a different color change and satisfactory contrast. Larger optical differences, for example, 0.5 OD or 0.6 OD, or greater, can also be displayed. Also, some exemplary embodiments of the dual function heat indicator may exhibit a difference in optical density of 0.2 OD or 0.3 OD between appearances before activation and after activation of the indicator, also providing a different color change. The color change can be provided by a color change of the cumulative exposure indicator or a color change of the peak exposure indicator or a combination of color changes of both indicators.
[093] An exemplary realization of the dual function heat indicator may include a visible active area for viewing the cumulative exposure indicator and / or the peak exposure indicator and may also include a colored reference area adjacent to the active area, this reference area can be colored to show the final appearance of the active area. The end point appearance can be an appearance like a dark appearance that indicates a likely condition of an associated host product, for example, that the host product has lost effectiveness or quality and should not be used.
[094] The exemplary embodiments of the dual function heat indicator of the invention can provide an irreversible, essentially permanent, or non-temporary record of an event or historical events of exposure to ambient heat.
[095] One or more other indicators, for example, a freeze indicator, can be combined with an exemplary embodiment of the invention's dual function heat indicator. The freezing indicator can be supported on a common substrate with the dual function heat indicator. For example, the freeze indicator can be transparent before activation by exposure to a freezing temperature and can be held over the dual function heat indicator, and the dual function heat indicator can be visible through the freeze indicator. This construction can provide a simple and compact indicator that can integrate responses to three different environmental inputs: freezing, cumulative heat, and a peak heat, in a single signal, for ease of understanding. Suitable freeze indicators and ways of sustaining a freeze indicator on a substrate with one or more other environmental condition indicators are described in U.S. Patent No. 7,490,575 to Taylor et al. Other suitable freezing indicators are described in Patent Nos. 7,891,310 to Taylor et al. and 8,122,844 by Smith et al.
[096] A substrate used in an exemplary embodiment of the dual-function heat indicator can be configured to conform to a host product, or to package a host product, for example, a vaccine vial containing a vaccine. The substrate can be flat to conform to a flat surface of the host product (or to a package containing the host product). Alternatively, the substrate can be curved in one dimension, or in two dimensions, to conform to a curved surface of the host product (or a package containing the host product), for example, the curved surface of a cylindrical vaccine bottle. . Also, a substrate can allow the dual function heat indicator to be attached to a host product, for example, by supporting a pressure sensitive adhesive layer. Adhesive fixation is an example of different ways in which the dual function heat indicator can be associated with a host product to monitor the host product for exposure to heat. Possible different ways of fixing include, for example, adhesion, bonding, connection, and joining, to the host product directly, or to a package containing the host product, or to a package, cardboard box, box or other container containing numerous items of host product. In addition, a dual-function heat indicator embedded in a label, or tag, can be inserted into a host product package, cardboard box or other container for one or more host product items.
[097] Some exemplary embodiments of the dual function heat indicator may employ a thermal paper, that is, a paper that supports a thermal coating, with the paper acting as a substrate and the thermal coating acting as a peak exposure indicator . The characteristics of the thermal coating can be selected, or modified, to provide a thermal paper that has peak exposure indicator characteristics that make the thermal paper suitable for use in an exemplary dual function heat indicator realization, in conjunction with a cumulative exposure indicator.
[098] An example of a thermal paper that can be used is a well-formed and lightweight soft paper that has a thermally responsive surface treatment or coating that includes color forming reagents. Some examples of suitable color-forming reagents consist of a leuco dye precursor as a first reagent, and a leuco dye developer as a second reagent. The precursor and developer of leuco dye can be solid particles. The color-forming reagents can be incorporated into a matrix that constitutes a meltable solid. The resulting matrix can be applied to a sheet of paper, or a continuous paper web, or other suitable substrate. For example, the matrix can be dispersed in a liquid medium and the resulting liquid dispersion can be coated on the substrate and dried. Drying can be carried out at a temperature of at least 2 ° C below the melting point of the matrix material to prevent melting of the matrix material, employing forced convection, low humidity, for example, a relative humidity below about 50 % or below about 40%, and / or an extended drying time. Through fusion, the matrix can allow the precursor and developer of leuco dyes to come together and develop the color.
[099] The thermally responsive coating can also include a thermal sensitizer. The thermal sensitizer can have a relatively low melting point so that the melting point of the thermally responsive coating does not exceed a desired threshold temperature for the host product. Also, the thermal sensitizer can be a solvent for one or both of the color-forming reagents so that after the thermal sensitizer melts, after exposure to heat, one or both of the color-forming reagents dissolve in the thermal sensitizer. The melting point of the solution resulting from the sensitizer and reagent may be below the melting point of the sensitizer, reducing the temperature response of the peak exposure indicator in some cases.
[0100] Additional optional ingredients of a thermal paper used in the practice of the exemplary embodiment of the invention include: stabilizers to increase image durability, referring to the color image generated by exposure to heat; fillers or pigments to extend and / or opacify the coating; binders to hold the coating components together and possibly separate, or help separate, the reactive components; lubricants to help the paper move steadily and smoothly over a printer or other manufacturing equipment; dispersants; antifoams; viscosity controllers; and / or anti-aesthetic agents. One or more of these optional additional ingredients can be used according to the requirements of a particular application. A thin transparent coating, for example, a polyurethane coating or other suitable synthetic polymer, can be applied over the thermal coating to add durability and improve writing ability, if desired.
[0101] In an exemplary method of making a suitable thermal paper, a leuco dye precursor or other color forming reagent can be mixed with a thermal sensitizer and ground to a suitable particle size. Optionally, the resulting particles can be encapsulated with a meltable capsule material that has a suitable melting point, for example, a polycondensed polymer such as a cross-linked amino formaldehyde resin, producing capsules or microcapsules of the color forming reagent. Separately, a color developer can also be mixed with the thermal sensitizer and can be added to the other coating ingredients, also as a solid at room temperature. The melting points of the thermal sensitizer (s) and the meltable capsule material can be selected according to the desired response temperature of the peak exposure indicator. If greater separation of the color reagents is desired, the color developer can also be encapsulated in the thermal sensitizer. The thermal sensitizer material used for the color developer, if any, may be the same as that used for the color forming reagent, or it may be a different, yet compatible, thermal sensitizer material.
[0102] Upon exposure to temperatures above a limit, the capsule material may soften and become permeable. If the thermal sensitizer also softens, or melts, the color-forming reagents can mix and react to provide a color change. In these exemplary embodiments of the invention, the thermal sensitizer and / or the capsule material can provide a physical separation between the color forming reagent and the color developer to prevent contact between the two color reagents. Physical separation can generally be maintained as long as the thermal paper is not exposed to temperatures above the threshold temperature, for example, during the manufacture of the thermal paper, the manufacture, storage, transportation, display and / or use of the dual heat indicator occupation.
[0103] The exemplary embodiments of the dual function heat indicator of the invention can be manufactured in several ways. An example of a manufacturing method includes preparing a peak exposure indicator composition for incorporation into the dual function heat indicator. The peak exposure indicator composition can be prepared by mixing a leuco dye precursor that is solid at room temperature with a thermal sensitizer that is also solid at room temperature. The mixed ingredients can be ground and then encapsulated with a suitable meltable capsule material, for example, a polycondensed polymer such as a cross-linked amino formaldehyde resin. A leuco dye developer can be included in the peak exposure indicator composition by mixing the leuco dye developer with a thermal sensitizing material, both materials are optionally solid particles at room temperature, and when adding the developer mixture to the peak exposure indicator.
[0104] Now with reference to Figures 1 and 2 of the attached drawings, the two exemplary embodiments of the dual function heat indicators shown, with reference 10 in Figures 1 and 2, can monitor cumulative ambient heat exposure and a peak of exposure to ambient heat in a single device. Multiple dual function heat indicators 10 can be incorporated as labels and can be supported on a liner 12 for quantity production. Various other dual function heat indicator configurations 10 are possible. Figure 1 shows a section of the liner 12 on which numerous dual function heat indicators 10 can be arranged in series, for mass production of dual function heat indicators, using printing industry technology, or industry technology packaging, or the like. These exemplary label designs can be produced at low cost in self-adhesive configurations and can be suitable for attaching to the outer surface of a mass-produced host product, or for packaging or a container for the host product.
[0105] Figure 2 is a cross-sectional view taken along imaginary line 2-2 in Figure 1 showing that the dual function heat indicator 10 can comprise a substrate 14, which supports an adhesive layer 16, which can be pressure sensitive, and which removably adheres the substrate 14 to the liner 12, so that the dual function heat indicator can be applied to a host product or a carton or carton. For this purpose, the liner 12 can be a self-adhesive liner that is coated with a low-energy surface material suitable for facilitating the removal of adhesive-coated substrate 14. The substrate 14 has a central active region, which supports a changing composition The color-changing composition 18 displays an active surface 20 arranged upwardly relative to substrate 14 for the optical reading externally of the dual function heat indicator 10. The active surface 20 displays the added responses of the pico and cumulative color change composition 18. A transparent or opaque reference material 22 can be configured in a ring that extends around the color change composition 18, or in another suitable configuration (not shown) next to or near the color-changing composition 18. Reference material 22 exhibits a static surface 24 arranged upwardly relative to substrate 14 for optical reading externally of the information dual function heat exchanger 10. Appearances of active surface 20 and static surface 24 can be optically read by a human observer or by a suitable image processing device, for example, a camera.
[0106] A transparent film 26 can superimpose the color changing composition 18 and the reference material 22 to provide protection against physical abrasion or misuse. The transparent film 26 can be attached to the color-changing composition 18 and the reference material 22 by a layer of adhesive (not shown), or in another suitable manner. The transparent film 26 may have printed symbols providing identification or instruction information, or other information regarding the dual function heat indicator and / or an associated host product. The transparent film 26 can be colored to filter the ambient light incident at wavelengths which can adversely affect the color changing composition 18 and can be substantially inert. For example, the transparent film 26 can be orange or red. Optionally, the transparent film 26 may include an ultraviolet filter material to filter, or block incident ultraviolet radiation. The transparent film 26 can be sufficiently transparent so that the active surface 20 and static surface 24 can be viewed and that the colors, or at least the optical densities on the active surface 20 and static surface 24, and changes in color or optical density in the active surface 20 and static surface 24, can be viewed and / or optically read.
[0107] Dual-function heat indicator 10, color-changing composition 18, and reference material 22 can have any desired shape. The shapes, considered independently, can be circular, square, rectangular, triangular, hexagonal, polygonal, elongated, circular, oval, elliptical, strip-shaped, another regular shape, an irregular shape, a shape that represents an image recognizable as a check mark, or other suitable format. As shown in Figure 1, for example, the dual function heat indicator 10 is circular, the reference material 22 occupies a smaller circle, and the color-changing composition 18 is configured as a square within the material circle. reference 22.
[0108] In the transverse dimension shown in Figure 2, the dual function heat indicator 10 has a layered structure. The relative shapes and dimensions of the various layers can be significantly varied. An exemplary embodiment of the dual function heat indicator 10 has thin laminar layers to provide a low profile device that can have a compact configuration and can be applied to small host products such as vaccine vials and the like.
[0109] The size of a dual function heat indicator such as dual function heat indicator 10 may vary according to the intended application, or for other purposes. Some exemplary embodiments of this dual function heat indicator may have a larger transverse dimension, which may be a dimension in the plane of Figure 1A, in the range of about 5 mm to about 30 mm, for example, from about 10 mm to about 15 mm. In that embodiment, the active surface 20 can have a larger cross-sectional dimension of about 1 mm to about 10 mm, for example, from about 2 mm to about 6 mm.
[0110] The color-changing composition 18 may include a heat trapping agent that functions as a cumulative heat indicator and a peak exposure indicator composition that functions as a peak exposure indicator. Suitable heat capture agents and peak exposure indicator compositions are described somewhere here. Thus, the color-changing composition 18 can change color in response to cumulative heat exposure and can also change color in response to peak heat exposure. In this way, the cumulative exposure indicator and the peak exposure indicator can be integrated into a single layer of dual function heat indicator 10.
[0111] The heat capture agent and peak exposure indicator composition can be configured on substrate 14 so that the appearances of their individual color responses on the active surface 20 are mixed in an additive manner, that is, so that any darkening of the cumulative exposure indicator is added to any darkening of the peak exposure indicator to provide an even darker appearance on the active surface 20. In terms of optical density, the individual optical densities of individual appearances are considered. The heat capture agent and the peak exposure indicator composition can be configured by mixing or combining particulates in several ways. For example, particles of the heat capture agent and particles of the peak exposure indicator composition can be dispersed in a common liquid carrier, the resulting dispersion can be dispersed over substrate 14, and the liquid carrier can then be evaporated, or the particulates can be applied to substrate 14 in a radiation curable coating, they can then be cured with the appropriate radiation.
[0112] Reference material 22 can assist an observer or visualization device to judge the state of color-changing composition 18 by having a similar appearance to the appearance of color-changing composition 18 that will develop after exposure to heat predetermined cumulative indicator of an end point.
[0113] In another exemplary embodiment as shown in Figure 1A, the dual function heat indicator 10 may have a substrate 14 with a printable substrate margin 14A on which printed symbols 28 can be printed. Figure 2A shows a cross-sectional view taken along imaginary line 2A-2A in Figure 1A. Figure 2A demonstrates that the printable margin of substrate 14A surrounds / is in an outer ring shape around color changing composition 18 and reference material 22. Otherwise, the dual function heat indicator 10 shown in Figure 1A and 2A can be very similar to that in Figure 1 and 2, as the dual function heat indicator in Figure 1A and 2A can also include a liner 12, a substrate 14, an adhesive layer 16, an active surface 20, a reference material 22, a static surface 24, and optionally, a transparent film 26. Thus, these components have the same numerical references in Figures 1A and 2A and are not further described here.
[0114] With reference to Figure 3, the dual function heat indicator shown, with reference 30 in Figure 3, is generally similar to the dual function heat indicator 10, with the difference that a cumulative exposure indicator and an indicator Peak exposure indicators are configured on separate individual layers instead of being integrated into a single layer of the device, as in the dual function heat indicator 10. The cumulative exposure indicator and the peak exposure indicator are prepared and separately printed. In plan view, dual function heat indicator 30 is similar to dual function heat indicator 10 so that no additional plan view of dual function heat indicator 30 is shown.
[0115] Depending on the dual function heat indicator 10, the dual function heat indicator 30 may include a liner 12, a substrate 14, an adhesive layer 16, an active surface 20, a reference material 22, a static surface 24, optionally, a transparent film 26 and, optionally, printed symbols 28 (not shown in cross section). Consequently, these components have the same numerical references in Figure 3 and are not further described here.
[0116] The dual function heat indicator 30 additionally includes a peak exposure indicator 32 sustained over a central region of the substrate 14, and a cumulative exposure indicator 34 covering the peak exposure indicator 32. The exposure indicator cumulative 34 can be initially transparent before exposure to heat so that the appearance of the peak exposure indicator 32 is optically readable or visible through the cumulative exposure indicator 34. Thus, the dual function heat indicator 30 combines the appearances of the cumulative exposure indicator and peak exposure indicator. With this configuration, an end point can be individually indicated by the cumulative exposure indicator, by the peak exposure indicator, or by a combination of a partial exposure of each indicator.
[0117] In an exemplary embodiment of the use of dual function heat indicator 30, in response to a brief exposure to a temperature above a predetermined peak temperature, the cumulative exposure indicator 34 remains essentially transparent and lighter than the surface reference 22. In the meantime, the active surface 20 of the combined cumulative explosive indicator 34 and the peak exposure indicator 32 darken rapidly reaching the end point of the dual function heat indicator 30. Darkening occurs as a result of the fusion of a matrix of wax, or other meltable solid, and the chemical reaction of the dye precursor with the dye developer, or other color-changing reagents.
[0118] The dual function heat indicator 30 can provide manufacturing or product benefits that derive from the separation of the heat capture agent employed in the cumulative exposure indicator 34 in one layer, if a heat capture agent is employed, while the color-forming reagents employed in the peak exposure indicator 32 are in another layer.
[0119] In an exemplary modified embodiment of the dual function heat indicator 30 (not shown), the peak exposure indicator 32 is arranged over the cumulative exposure indicator 34. In that case, the peak exposure indicator 32 can be transparent to allow the appearance of the cumulative exposure indicator 34 to be viewed, or optically read, on the active surface 20, while the cumulative exposure indicator 34 can now be transparent or opaque. The active surface 20 displays the added responses of the peak and cumulative components.
[0120] With reference to Figure 4, the dual function heat indicator shown, with the reference 40 in Figure 4, is also generally similar to the dual function heat indicator 10. According to the dual function heat indicator 30 in the realization As an example of Figure 3, the dual function heat indicator 40 differs from the dual function heat indicator 10 in that it has a cumulative exposure indicator and a peak exposure indicator that are configured in separate individual layers. However, unlike the example in Figure 3, in the dual function heat indicator 40, the peak exposure indicator is integrated into a single layer with a substrate.
[0121] Again, the dual function heat indicator 40 has a plan view similar to that of the dual function heat indicator 10 so that no additional plan view of the dual function heat indicator 40 is shown.
[0122] Depending on the dual function heat indicator 10, the dual function heat indicator 40 can include a liner 12, an adhesive layer 16, an active surface 20, a reference material 22, a static surface 24, optionally, a transparent film 26 and, optionally, printed symbols 28 (not shown in cross section). Consequently, these components have the same numerical references in Figure 4 and are not described further here.
[0123] The dual function heat indicator 40 additionally includes an active substrate 42 and a cumulative exposure indicator 44 supported on the active substrate 42. The active substrate 42 provides substrate functionality similar to that of the dual heat indicator substrate 14 function 10 and can be manufactured from similar substrate materials, for example, paper material or synthetic polymer. In addition, active substrate 42 includes a peak exposure indicator. The peak exposure indicator can be provided as a deposit of a peak exposure indicator composition, on the top surface of the active substrate 42. This deposit or coating is not referenced separately in Figure 4. As described in more detail elsewhere Here, the peak exposure indicator composition can include a first reagent and a second reagent. The second reagent can chemically co-react with the first reagent to provide a color change and the peak exposure indicator composition can be fused to induce the color change. In this exemplary embodiment of the dual function heat indicator, the peak exposure indicator incorporated in the active substrate 42 extends below the reference material 22. Consequently, the reference material 22 can be opaque, and can be devoid of transparency, so that the upper surface of the active substrate 42 is not visible through the reference material 22, since this view could be confusing when the active substrate 42 darkens as a result of a peak of heat exposure.
[0124] The cumulative exposure indicator 44 can be similar to the cumulative exposure indicator 34 in the exemplary embodiment of Figure 3 of a dual function heat indicator already described. Thus, the cumulative exposure indicator 44 can be initially transparent and the appearance of the peak exposure indicator applied to the top surface of the active substrate 42 can be optically readable or visible through the cumulative exposure indicator 44. Depending on the dual heat indicator function 30, the dual function heat indicator 40 combines the appearances of the cumulative exposure indicator and the peak exposure indicator. With the configuration of the dual function heat indicator 40 shown in Figure 4, an end point can also be indicated individually by the cumulative exposure indicator or by the peak exposure indicator, or by a combination of a partial exposure of each indicator.
[0125] The dual function heat indicator 40 illustrates an exemplary embodiment of the invention in which the active substrate 42 can be self-supporting prior to mounting on the dual function heat indicator 40 and can be supplied to a mass stock manufacturing point such as a sheet, strip or a continuous blanket of material. This ability can help the manufacturing process. Also, the deposition of the peak exposure indicator composition on the suitable substrate material can be carried out prior to the manufacture of dual function heat indicator 40, this can simplify the manufacturing process.
[0126] In a modified example embodiment of the dual function heat indicator 40 (not shown), the active substrate 42 is arranged over the cumulative exposure indicator 44. In that case, the active substrate 42 can be transparent to allow the appearance of the cumulative exposure indicator 44 is viewed, or optically read, on the active surface 20, while cumulative exposure indicator 44 can be transparent or opaque. In this modified exemplary embodiment, a layer of inactive substrate, such as substrate 14 shown in Figures 2 and 3, can also be employed between adhesive layer 16 and cumulative exposure indicator 44, as shown in Figure 4, to provide support.
[0127] Referring to Figure 5, the dual function heat indicator shown, with reference 50 in Figure 5, is also generally similar to the dual function heat indicator 10. As the dual function heat indicator 40 in carrying out As an example of Figure 4, the dual function heat indicator 50 differs from the dual function heat indicator 10 in that it has a cumulative exposure indicator and a peak exposure indicator that are configured in separate individual layers. Cumulative exposure indicator 44 and peak exposure indicator 52 are configured on separate layers. However, unlike the exemplary embodiment of Figure 4, in the dual function heat indicator 50, the peak exposure indicator can include three layers, that is, activator 54, color-changing composition 56, and barrier 58 Activator 54 can be a meltable solid which when liquid is a solvent for one or both of the co-reactants or it can be a reagent. Activators have been classified and it has been found that meltable activators can be selected with different effective temperatures so that thermal coatings with normally high thermal response temperatures and temperature dependent color development can be used for a family of peak indicators with a lower activation temperature suitable for the dual indicators in that description. Some activators include, but are not limited to, heptadecanol, 4-methoxyphenol, pentadecanol, 2,4-di-tert-butyl phenol or benzophenone. Various treatments of commercial or pre-made shelf paper can be used to reduce its activation temperature. The color change composition 56 can include a first reagent and a second reagent, which can chemically co-react to provide a color change. The color-changing composition 56 can be a layer or coating on the substrate 14. Barrier 58 can be a thin transparent coating on the color-changing composition surface 56 to prevent direct contact of the activator 54 in the solid state with the 56 color-changing composition and provide durability.
[0128] Depending on the dual function heat indicator 10, the dual function heat indicator 50 may include a liner 12, a substrate 14, an adhesive layer 16, an active surface 20, a reference material 22, a static surface 24, optionally, a transparent film 26 and, optionally, printed symbols (not shown) as shown in Figure 5. Consequently, these components have the same numerical references in Figure 4 and are not further described here.
[0129] In an additional exemplary embodiment of the dual function heat indicator 50, the dual function heat indicator 50 may omit cumulative exposure indicator 44 so that the peak exposure indicator 52 that includes activator 54, the color change composition 56, and barrier 58 is used as an independent peak indicator.
[0130] With reference to Figure 6, the dual function heat indicator shown, with the reference 60 in Figure 6, is also generally similar to the dual function heat indicator 10. As per the dual function heat indicator 40 in the realization As an example of Figure 4, the dual function heat indicator 60 differs from the dual function heat indicator 10 in that it has a cumulative exposure indicator and a peak exposure indicator that are configured in separate individual layers. Cumulative exposure indicator 44 and peak exposure indicator 62 are configured on separate layers. However, unlike the exemplary embodiment of Figure 4, in the dual function heat indicator 60, the peak exposure indicator may include three layers, i.e., reagent B 64, reagent A 66, and melt barrier 68. The reagent B 64 can be a layer that includes the co-reagents described above, or it can be a coating on the substrate 14. The additional reagent B 64 can be a mixture that includes binders. Reagent A 66 can be a layer that includes the complementary color generation co-reagent of reagent B 64. Additional reagent A 66 can be a mixture that includes binders. The melt barrier 68 can be a continuous layer of a melt solid that separates reagent A 66 and reagent B 64. Neither reagent A 66 nor reagent B 64 sounds capable of passing through barrier 68 while they are solid. Since the melt barrier 68 melts to form a liquid, reagent A 66 and reagent B 64 can co-react chemically to provide a color change.
[0131] Depending on the dual function heat indicator 10, the dual function heat indicator 60 may include a liner 12, a substrate 14, an adhesive layer 16, an active surface 20, a reference material 22, a static surface 24, optionally, a transparent film 26 and, optionally, printed symbols (not shown) as shown in Figure 6. Consequently, these components have the same numerical references in Figure 4 and are not further described here.
[0132] In an additional exemplary embodiment of the dual function heat indicator 60, the dual function heat indicator 60 may omit cumulative exposure indicator 44 so that the peak exposure indicator 62 which includes reagent B 64, reagent A 66, and melt barrier 68 is used as an independent peak indicator.
[0133] Referring to Figure 7, the dual function heat indicator shown, with reference 70 in Figure 7, is also generally similar to the dual function heat indicator 10. As per the dual function heat indicator 40 in carrying out As an example of Figure 4, the dual function heat indicator 70 differs from the dual function heat indicator 10 in that it has a cumulative exposure indicator and a peak exposure indicator that are configured in separate individual layers. Cumulative exposure indicator 44 and peak exposure indicator 72 are configured on separate layers. However, unlike the exemplary embodiment of Figure 4, in the dual function heat indicator 70, the peak exposure indicator can include two layers, that is, color layer 74 and opaque layer 76. Color layer 74 can have an intense color like black or red and can be configured as a layer on the substrate 14. The opaque layer 76 can be a meltable solid applied as a coating or paint on the color layer 74 or it can be small particles that disperse light making the opaque layer. Upon melting, the opaque 76 becomes transparent and the color layer 74 can be seen through it. The opaque layer 76 can be a wax.
[0134] Depending on the dual function heat indicator 10, the dual function heat indicator 70 may include a liner 12, a substrate 14, an adhesive layer 16, an active surface 20, a reference material 22, a static surface 24, optionally, a transparent film 26 and, optionally, printed symbols (not shown) as shown in Figure 7. Consequently, these components have the same numerical references in Figure 4 and are not further described here.
[0135] Still in an additional exemplary embodiment, the dual function heat indicator 80 to monitor cumulative ambient heat exposure and peak ambient heat exposure includes a substrate 14, a cumulative exposure indicator supported by the substrate in a visible layer 44, and a peak exposure indicator 82 which can include the melt-colored particulate material 84 supported by substrate 14 in another visible layer as shown in Figure 8. The dual function heat indicator 80 can further include a lining 12, a layer adhesive 16, an active surface 20, a reference material 22, a static surface 24, optionally, a transparent film 26 and, optionally, printed symbols (not shown). Cumulative exposure indicator 44 may be color changeable in response to cumulative ambient heat exposure, and peak exposure indicator 82 may include a meltable particulate colored material 84. In this exemplary embodiment, meltable particulate colored material 84 may have a average particle size that dyes the melt-colored particulate material 84 with a light color, the light color being attributable to the dispersion of visible light by the melt-colored particulate material 84. Optionally, the melt-colored particulate material 84 can include a melt solid and a dye dissolved in the meltable solid.
[0136] The melting of the melt-colored particulate material 84 may cause the melt-colored particulate material 84 to darken and the darkening may be irreversible so that the peak exposure indicator 82 provides an irreversible signal. Darkening can be induced by a peak exposure to ambient heat reaching a temperature that exceeds the melting point of the melt-colored particulate material 84. Thus, the dual function heat indicator 80 can indicate cumulative ambient heat exposure or exposure to peak ambient heat by changing the color.
[0137] Prior to activation, the melt-colored particulate material 84 can provide the peak exposure indicator 82 with a light color due to light scattering. When the melt-colored particulate material 84 softens or melts in response to the peak exposure to ambient heat, the small colored particles can agglutinate, join and / or melt, to provide one or more larger agglutinated masses or agglomerations that can exhibit the inherent color. colored material. The inherent color can be a dark or strongly colored appearance that the colored material exhibits in large quantities, for example, in a continuous film. The inherent color can also be opaque. The melt-colored particulate material 84 can obscure any background behind the melt-colored particulate material 84 in such a way that the background cannot be seen precisely through the melt-colored particulate material 84. When using a dye or other colorant, or when using a melt solid which has an inherent color, dark or strong colors, such as an intense red, or black, can be displayed so that the peak exposure indicator 82 displays satisfactory contrast between its appearances before and after activation, as described somewhere here .
[0138] The melt-colored particulate material 84 can provide a color change without significant migration of the melt-colored particulate material 84 or a melt component thereof. For example, the melt-colored particulate material 84 may remain immobile within a layer of the dual-function heat indicator 80. However, some small-scale migration of the melt-colored particulate material 84 may occur as the particles melt and clump together, or they come together, with adjacent particles, possibly forming a film, or coherent area or areas of colored material, or simply to form larger particles that are visible. In addition, the melt-colored particulate material 84 can provide a color change non-chemically, without reacting with a color developer or otherwise entering a chemical reaction.
[0139] Various meltable solids can be employed as a component of the meltable colored particulate material 84, as will be known or evident to an element skilled in the art, in light of this description, or will become known or evident in the future. Some examples of suitable melt solids include alkanes, alkyl esters, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, hexaneic acid, hexadecane and ethyl lactate, such as waxes, wax materials paraffin wax, microcrystalline wax, carnauba wax, beeswax, Chinese wax, gum wax, spermaceti, tallow, palm wax, soy wax, lanolin, wood fat, a wax polymer, a copolymer waxy, a polyolefin, polyethylene, polypropylene, a copolymer of ethylene-vinyl acetate, a copolymer of ethylene-acrylic acid and mixtures of two or more of the above wax materials. Some other materials useful as meltable solids in this aspect of the exemplary embodiment of the invention include the thermal sensitizers described here. A meltable solid that has a melting point corresponding to a desired peak temperature of the peak exposure indicator can be selected. The melt-colored particulate material 84 can be formulated without employing a solid side-chain crystallisable polymer, if desired. Some meltable solids can be selected according to how their glass transition temperatures relate to the desired limit temperature, if appropriate. Thus, the limit temperature of the peak exposure indicator can be varied by appropriate selection of the melt solid, with due allowance for the effect of the dye on the melting point of the melt solid, if any.
[0140] Additional exemplary embodiments of the invention may include protection from ultraviolet radiation, if desired. Ultraviolet radiation can interfere with the response of a dual-function heat indicator, in some cases, and can degrade a variety of materials. Ultraviolet protection can be provided in any one or more of several ways. For example, one or more ultraviolet filter materials can be included in the transparent film 26. In another exemplary embodiment, a visibly transparent ultraviolet filtration layer, such as a printed ultraviolet absorbent ink, can be placed directly on the active surface 20. This construction is described in U.S. Patent No. 7,682,830 to Prusik et al. An additional way to provide protection against ultraviolet radiation is the adhesive used to attach a transparent outer protective film, such as transparent film 26, if a transparent film and an adhesive are employed, to include one or more ultraviolet filters. This construction is described in Provisional Patent Application No. U.S. 61 / 611,319 to Smith et al. The ultraviolet protection measures described in Patent No. 7,682,830 and in Application No. 61 / 611,319 can be employed in an exemplary embodiment of the dual function heat indicator, as will be apparent to an element skilled in the art.
[0141] Various dyes or other optically different dyes or materials can be dissolved, or otherwise incorporated into a meltable solid employed in practicing the exemplary embodiment of the invention to provide the meltable solid with a different inherent appearance, as will be known or evident to a element versed in the technique, in the light of this description, will either become known or evident in the future. Examples of suitable dyes include Oil Black BS (C. I. Solvent Black 7 mixed with stearic acid, Orient Corporation of America, Kenilworth, New Jersey) and Oil Red O dye (Sigma-Aldrich, St. Louis, Missouri). Optionally, the dye or other optically different dye or material and / or the melt solid can be opaque so that the peak exposure indicator has an opaque appearance after activation. Some other optically different materials that can be employed include pigments, fluorescent materials, pearlizing materials, iridescent materials and mixtures of two or more optically different materials above.
[0142] An exemplary embodiment of a method of preparing a peak exposure indicator employing a meltable colored particulate material 84 configured in light scattering particles for inclusion in an exemplary embodiment of a dual function heat indicator will now be described. The method includes dissolving a relatively small amount of dye in a meltable solid formed from an organic material such as a wax, for example, from about 0.001 percent to about 1 percent by weight of the dye based on the weight of the melt colored material resulting. The meltable solid can be light in color, for example, white or pale yellow, and optionally, it can be transparent or translucent. Sufficient dye can be used to color the melt while avoiding an excess, for example, 0.02 weight percent Oil Black BS (CI Solvent Black 7 mixed with stearic acid), which is an intense black powder, can be dissolved in heneicosano. Heneicosane is a light or off-white linear C21 alkane that has a melting point of about 40 ° C which is available from Sigma-Aldrich (St. Louis, Missouri).
[0143] This method may also include preparing fine particles of the meltable colored material that has an average particle size that provides a light-colored appearance of the dyed wax can be prepared by any suitable size reduction procedure. Some examples of suitable size reduction procedures include emulsifying the meltable colored material at a temperature above its melting point, when the material is melted, then cooling the resulting emulsion, or precipitating the melted colored material in cold water, or otherwise. solvent, with vigorous mixing. Other suitable size reduction procedures will be known or evident to an element skilled in the art, in light of this description, or will become known or evident in the future. The sizing procedure can be performed to produce an average particle size in the range of about 50 nm to about 5 μin, in the range of about 100 nm to about 2 μin, in the range of about 200 nm to about 700 nm, or in the range of about 200 nm to about 350 nm. The parameters of the sizing procedure can be varied to provide a desired degree of light scattering, which optionally can be determined by the desired clarity of the melt-colored particulate material then prepared. The resulting particles can have an average particle size of at least about 50 nm, 10 nm, or 200 nm, and no more than about 350 nm, 700 nm, 2 μin or 5 μin.
[0144] The method may also include formulating a coating composition that incorporates the meltable colored particulate material and applying the coating composition to the substrate. Other ingredients such as thermal sensitizers, binders, pigments, lubricants, dispersants, defoaming agents, and the like, including the materials described here, optionally, can also be used in the coating composition. If used, these ingredients must have optical properties compatible with the intended optical performance of the peak exposure indicator.
[0145] The coating composition can be prepared by a method as described here to prepare a peak indicator composition except that the first reagent and the second reagent are omitted. Thus, the color-forming function of the first reagent and the second reagent can be replaced by the melt-colored particulate material. Using the previously described example of a black-dyed heneicosane wax, the dyed wax particles may be light in color, for example, whitish, due to light scattering, before activation of the peak exposure indicator. However, by melting the heneicosane wax in response to exposure to an ambient temperature at or above about 40 ° C, the melting point of the henesicosan wax, the inherent black color of the dyed wax particles becomes quickly evident. Immediately after melting, the small particles of dyed wax clump and cease the dispersion of light revealing their inherent color.
[0146] In a further aspect, the exemplary embodiment of the invention provides a heat event indicator to monitor exposure to ambient heat at a temperature that exceeds a threshold temperature. The heat event indicator may include a substrate and an aggregated particulate colored material supported by the substrate. The bonded colored particulate material may have an average particle size that dyes the bonded particulate indicator material with a light color, the light color being attributable to the dispersion of visible light by the particles of bonded colored material. The coalescence of the bonded colored particulate material can cause the material to darken, and darkening can be induced by an event of exposure to ambient heat that reaches a temperature that exceeds the limit temperature. Thus, the heat event indicator can indicate the occurrence of the event of exposure to ambient heat by changing the color.
[0147] In this heat event indicator, the limit temperature can be a peak temperature and the agglutinable particulate colored material can be meltable and can melt in response to the event of exposure to ambient heat. These heat event indicator achievements may be similar to a dual function heat indicator as described here in which the peak exposure indicator component of the dual function heat indicator employs a meltable, light scattering, particulate colored material and the cumulative exposure indicator is not present. The bondable colored particulate material may be similar to a meltable colored particulate material and may have an average particle size as described for the meltable colored particulate material. In addition, agglutinable particulate colored material can provide a color change in response to an appropriate heat event, without reacting with a color developer or other chemical reagent and without significant migration after melting. This heat event indicator can act as a peak exposure indicator.
[0148] Alternatively at a peak temperature, the limit temperature can be a freezing temperature, the heat event indicator can include a dispersion of the aggregated colored particulate material in an aqueous liquid medium, in which the dispersion groups and the colored material agglutinable particulate agglutinates in response to the event of exposure to ambient heat. This heat event indicator can include a transparent layer, a substrate, an adhesive layer, and a liner, as described here as one or more optional components.
[0149] Initially, the inherent color of the bonded colored particulate material can be masked by light scattering attributable to the average particle size of the bonded colored particulate material which gives the dispersed material a lighter appearance, for example, white, whitish or, in the case of a particulate colored material that is inherently black, pale gray, possibly. Also, the induced appearance of light scattering can be opaque. Freezing and / or thawing of the aqueous liquid medium can (m) induce coalescence causing the colored material particles to reveal their inherent color, which may be darker or more intense than the initial color. After freezing, the colored material can also obscure any background behind the colored material in such a way that the background cannot be precisely visualized through the colored material. As described for the meltable particulate colored material, the bondable particulate colored material can change color without employing a color developer or crystallized side-chain polymer or participating in a chemical reaction. This heat event indicator can act as a freeze indicator.
[0150] The dispersed agglutinable particulate colored material may have several components, as will be known or evident to an element skilled in the art, in light of this description, or will become known or evident in the future. In an exemplary embodiment, the colored material can include, or consist of, a dye, as described here, dissolved in a suitable hydrophobic liquid, such as an oil, and the oil can be dispersed in the aqueous liquid medium as appropriately sized droplets, providing a emulsion. Suitable oils and other useful features such an embodiment that indicates the freezing of the heat event indicator described herein are described in U.S. Patent US8430053B2 by Taylor et al.
[0151] In another exemplary embodiment, the colored material may include a finely divided pigment dispersed in the oil droplets, instead, or together with the dissolved dye. In a further example, pigment particles of an appropriate size to cause light scattering can provide the colored material and no oil or dye needs to be employed. MATERIALS
[0152] Various materials that can be employed in the practice of the exemplary embodiments of the invention detailed above will now be described. It will be known or evident to a person skilled in the art, in the light of that description, that other materials may also be suitable.
[0153] Lining. Suitable lining materials for dual-function heat indicator embodiments of the exemplary embodiment of the invention include various papers and synthetic polymeric materials, any of which can be coated to facilitate the removal of a dual-function heat indicator that has a coated substrate by adhesive of a liner. Other suitable lining materials will be known or apparent to an element skilled in the art. Some suitable papers include kraft paper, calendered kraft paper, varnish paper, and clay-coated paper. Some suitable synthetic polymeric materials include terephthalate, polypropylene and biaxially oriented polyolefins. Some suitable coating materials include polyvinyl alcohol, silicones, and other materials that have low surface energy.
[0154] Substrate. A substrate used in an exemplary embodiment of the dual function heat indicator can be manufactured from a variety of materials including printable or coated materials, for example, a sheet or film of synthetic plastic. Other suitable substrate materials will be known or apparent to an element skilled in the art. Suitable substrates can be flexible or rigid, transparent or opaque, optionally can be colored, and can be shaped like a blade, or similar to a sheet. White substrates can help contrast with a final appearance if the cumulative heat indicator and the peak exposure indicator are initially transparent. Also, when the indicators are initially transparent, distinctive signs, or a graphic, for example, a check mark, or other suitable human-readable or machine-readable evidence can be included on the substrate, and can be obscured after the indicator. dual-function heat switch to an end point appearance. For mass production, individual indicator substrates can be cut from sheets, strips, or continuous blankets. Some examples of such substrate materials include, without limitation, polyethylene, polypropylene, polycarbonate, polyester, polyamide, polyurethane, polyvinyl chloride, polyvinylidene chloride, materials derived from cellulose, aluminum foil, paper, coated paper, and a laminated structure that includes a layer or layers of any one or more of the above materials.
[0155] An additional example of a suitable substrate material is a dimensionally stable, flexible, white, opaque, corona-treated polyolefin film as supplied under the FASSON® PRIMAX® trademarks, product code 250, by Avery Dennison Corporation, Pasadena, California.
[0156] Optionally, in exemplary embodiments of the invention, where a substrate contacts an adhesive material, the substrate surface can be sealed or otherwise treated to inhibit the migration of the adhesive or adhesive components through the substrate material. Alternatively, or in addition, a substrate material or a layer of additional material, which resists such migration can be employed.
[0157] Cumulative exposure indicator. The cumulative exposure indicator employed in an exemplary embodiment of the dual function heat indicator can be or can include a heat trapping agent that can change the appearance in response to heat. The heat trap can darken with continued heat exposure, and the degree of darkening can provide a measure of cumulative heat exposure. Alternatively, the heat-trapping agent may exhibit another change in appearance, for example, whitening, a change in tone, or another optically readable indication. The heat trapping agent can include one or more heat sensitive compounds, some of which are described elsewhere here.
[0158] The cumulative exposure indicator can be manufactured by applying a suitable indicator ink that includes the heat-trapping agent to a substrate, then drying the indicator ink on the substrate, as described elsewhere here. The cumulative exposure indicator can include the dry ink residue and the substrate that supports the ink residue. The indicator paint may include a liquid vehicle; a film-forming agent dissolved in the liquid vehicle, an insoluble heat-trapping agent dispersed in the liquid vehicle and various optional ingredients, for example, one or more dispersants, anti-acid agents, colorants, preservatives, fragrances or other additives. An example of a suitable liquid carrier is an organic solvent such as isopropanol, or ethyl 3-ethoxypropionate. An example of a film-forming agent is nitrocellulose. Some examples of suitable indicator inks that can be employed in dual function heat indicator embodiments of the exemplary embodiment of the invention and its manufacture are described in U.S. Patent No. 8,067,483 and in the patent documents mentioned therein.
[0159] Some useful heat trapping agents can provide an irreversible indication of cumulative temperature exposure over time, and can provide a long-term record of heat exposure. The cumulative heat response of the heat trap may be such that the heat trap can monitor heat exposure as a temperature integral over time. In addition, the heat trapping agent may be sensitive to heat and may have useful indicator reactivity at ambient temperatures likely to be encountered by a monitored host product, for example, temperatures in the range of about 0 ° C to about 60 ° Ç.
[0160] The heat capture agent can include, or consist of, any one of a variety of chemical components. A useful exemplary embodiment of heat trapping agents includes one or more thermally sensitive diacetylene compounds, for example, an individual diacetylene compound or a co-crystallized mixture of two diacetylene compounds.
[0161] The diacetylene compound or compounds can be polymerized to provide a color change or other optically readable indication. Diacetylenic compounds useful in practicing the exemplary embodiment of the invention include polymerizable diacetylenic compounds that include at least two conjugated acetylenic groups, that is, groups having the formula -C = C- Some exemplary polymerizable diacetylenic compounds that can be used include compounds 2, 4-hexadiene-1,6-bis (alkylurea) substituted in which the alkyl group has from 1 to 20 carbon atoms, the previous diacetylene bis (alkylurea) compounds in which the alkyl substituents are linear, and co-crystallized mixtures of any two or more of the above bis (alkylurea) compounds. The two alkyl groups in any of the above diacetylene bis (alkylurea) compounds can be the same and the bis (alkylurea) compounds can be symmetrically substituted. Some particular examples of the above diacetylene bis (alkylurea) compounds include ethyl, propyl, butyl, octyl, dodecyl and octyl-substituted 2,4-hexadiene-1,6-bis (alkylurea) compounds, linear isomers of these compounds and co-crystallized mixtures of two or more linear isomers.
[0162] Some additional exemplary embodiments of useful diacetylene compounds that can be employed in exemplary embodiments of the dual function heat indicator are described in Patent Nos. U.S. 3,999,946; 4,189,399 and 4,384,980 to Patel; Patent Nos. U.S. 4,789,637 and 4,788,151 to Preziosi et al .; Patent Nos. U.S. 6,924,148; 7,019,171; 7,161,023; and 8,067,483 by Prusik, or Prusik et al .; Patent Application Publication No. U.S. 2009/0131718 by Baughman et al .; and Patent Application Publication No. U.S. 2011/0086995 by Castillo Martinez et al., among these documents the last three were previously cited here. Some useful heat trapping agents may include one or more diacetylene compounds and a reactivity enhancing adjuvant, for example, as described in US 8,067,483. Useful diacetylenic compounds are also described on page 36, line 10 to page 39, line 4 of Provisional Patent Application No. 61 / 611,319 filed on March 15, 2012.
[0163] Other chemicals and technologies that can be used as, or in, a heat capture agent for a cumulative exposure indicator component of an exemplary embodiment of a dual function heat indicator include: heat sensitive dyes that can be activated or deactivated by exposure to ultraviolet radiation to provide or tease the color; dyes that are activated to display color, or change color, by changes in pH, for example, as described in U.S. Patent No. 4,917,503 to Bhattacharjee; a reversibly photochromic compound, such as a compound that can be subjected to photoinduced staining by irradiation with light or ultraviolet radiation, followed by time and temperature-dependent discoloration, for example, a spiro-aromatic compound, some examples of which are described in the Publication of Patent Application No. US 2010/0034961 by Tenetov et al. ("US 2010/0034961"); and enzyme-based sensors as described in U.S. Patent No. 6,642,016 to Sjoholm, et al. or U.S. Patent No. 4,284,719 to Agerhem, et al.
[0164] Some additional exemplary embodiments of useful cumulative exposure indicators that can be employed to practice the exemplary embodiment of the invention are described in US Patent No. 5,622,137 to Lupton et al., US Patent No. 5,756,356 by Yanagi, et al., U.S. Patent No. 6,043,021 by Manico et al., and International Publication No. WO 99/39197 by Haarer et al. In addition, suitable cumulative exposure indicators that can be used to practice the exemplary realization of the invention will be known or evident to an element skilled in the art, in light of that description, or will become known or evident in the future. PICO EXPOSURE INDICATOR
[0165] The peak exposure indicator can be a meltable solid and can include a first reagent and a second reagent that are chemically amenable to co-reaction to provide a color change. In addition, the peak exposure indicator can be a reagent, it can include one or more reagents, it can separate the reagents, or it can be the agent that, through fusion, allows the reagents to react. Optionally, a thermal sensitizer can also be included. The first reagent and the second reagent can be present in the same layer as an exemplary embodiment of the dual function heat indicator. Alternatively, the first reagent and the second reagent may be present in layers other than an exemplary embodiment of the dual function heat indicator. The color change chemical reaction can be induced in response to a peak exposure to ambient heat and can be irreversible. Optionally, a single reagent can provide functionality indicating adequate peak exposure.
[0166] The peak exposure indicator can include additional ingredients that contribute to the useful functioning of an exemplary embodiment of the dual function heat indicator. Some examples of possible added ingredients, which can be used individually or in combination, include pigments, binders, lubricants, dispersants, defoaming agents, and other additives that can modify one or more characteristics of the peak exposure indicator, without impairing its performance, how it will be known or evident to an element skilled in the art, in light of this description, or it will become known or evident in the future. These additional ingredients, if present, can also be included in a single layer with the first reagent and the second reagent.
[0167] As an example, the first reagent can be a color precursor, or color former, and the second reagent can be a color developer. Many suitable color precursors and color developers are known and can be used individually or in combinations of two or more compatible compounds. Some suitable color forming reagents, which include some color precursors and color developers, are described in U.S. Patent No. 8,430,053 by Taylor et al., For example, in paragraphs [0199] to [0248]. Suitable color-forming reagents are also described in U.S. Patent No. 5,741,592 to Lewis et al. and in Patent Publication No. U.S. 2008/0233290 by Ward-Askey et al.
[0168] Some specific examples of useful color precursors include: specialty magenta 20, ODB-1 and ODB-2 (available from Emerald Hilton Davis, Cincinnati, Ohio); and PERG AS CRIPT® Red 16B (available from BASF, Charlotte, N.C.). Upon development, specialty magenta 20 and PERGASCRIPT® Red 16B produce an intense magenta color, and color precursors ODB-1 and ODB-2 become black.
[0169] Some additional examples of useful color precursors include: methylene blue benzoilleuco, malachite green lactone, N-2,4,5-trichlorophenilleuco auramine, additional compounds that are red when developed including 3-diethylamino-6-methyl-7 -chlorofluorane and 3,6- bis (diethylamino) fluoran-Y- (4'-nitro) -anilinolactam, additional compounds that are black when developed including 3-diethylamino-6-methyl-7-anilinofluorane and 3- (N-ethyl -N-isoamylamino) -6-methyl-7-anilinofluorane, and compounds that are orange when developed including 3-cyclohexylamino-6-chlorofluoran and 3-diethylamino-6,8-dimethylfluorane.
[0170] Still further examples of useful color precursors include: 3,3-bis (p-dimethylaminophenyl) -phthalide; 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone); 3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide; 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide; 3,3-bis (p-dibutylaminophenyl) -phthalide; 3- (N-N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane; 3-dimethylamino-5,7-dimethylfluoran; 3-diethylamino-7-methylfluoran; 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2 '[- methoxy-5'-chlorophenyl) phthalide; 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-nitrophenyl-phthalide; 3- (2'-hydroxy-4'-diethylaminophenyl) -3- (2'-methoxy -5'-methylphenyl) phthalide and 3- (2'-methoxy-4'-dimethylaminophenyl) -3- (2'-hydroxy-4'-chloro-5'-methylphenyl) -phthalide.
[0171] Some specific examples of useful color developers include oil-soluble reducing agents; oxalic acid, phosphite ester, hydroxybenzoic acid ester, hydroidroquinone, hydroquinone derivatives such as dimethihydroquinone, di-tert-butyl hydroquinone, other dialkylhydroquinones, and the like, 3-ethoxyphenol, 1,2-diethyl-3-hydroxybenzene, 1,3- diethyl-2-hydroxybenzene, 2,2'-methylenebis (3,4,6 trichlorophenol); primary and secondary amines fused or soluble in sensitizer that have low water solubility, for example, 4-butylaniline, phenol derivatives, organic acids, and acid clays, reactive acid hectorite clay FULACOLOR ™ XW (available from Rockwood Additives, Widnes, UK), phenolic resins, phenol-acetylene resins, polyvalent metal salts of phenolic resins, modified phenolic alkyl resin including zinc HRJ 2053 (available from SI Group, Schenectady, NY), zinc salicylate, salicylate resin zinc, 4,4'-isopropylidenobisphenol (also known as bisphenol A), 1,7 -di (hydroxyphenylthio) -3,5-dioxaeptane, 4-hydroxyethyl benzoate, 4-hydroxydimethyl phthalate, monobenzyl phthalate, bis- (4-hydroxy-2-methyl-5-ethylphenyl) sulfide, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxyphenylbenzenesulfonate, 4-hydroxybenzoyloxybenzylbenzoate, bis- (3-1- butyl-4-hydroxy-6-methylphenyl) sulfone , p-tert-butylphenol, or polymers based on bisphenol A. THERMAL SENSITIZERS
[0172] A thermal sensitizer can optionally be employed in an exemplary realization of the peak exposure indicator. A thermal sensitizer can be selected to have a melting point that causes the peak exposure indicator to at least start to melt at a desired response temperature, initiating the color change reaction.
[0173] The thermal sensitizer can be mixed with the first reagent and the second reagent and the resulting mixture can have a melting point that is equal to the desired response temperature or within about 2 ° C or about 5 ° C of desired response temperature of the peak exposure indicator. The mixture can be an intimate mixture of the ingredients in particulate form. Alternatively, the melting point of the thermal sensitizer can be equal to the desired response temperature or can be within about 2 ° C or about 5 ° C of the desired response temperature. When a thermal sensitizer is not used, at least one between the first reagent and the second reagent can have a melting point that is equal to the desired response temperature or is about 2 ° C or about 5 ° C of the response temperature desired.
[0174] The thermal sensitizer, if used, can help control the melting point of the peak exposure indicator, for example, by reducing the melting point and can initiate or accelerate the color-forming reaction.
[0175] Some materials useful as thermal sensitizers in the practice of the exemplary embodiment of the invention may include compounds fatty acid amide, acetamide, stearic acid amide, linolenic acid amide, lauric acid amide, myristic acid amide, methylol compounds, methylene -bis (stearamide), ethylene-bis (stearamide), p-hydroxybenzoic acid esters, methyl p-hydroxybenzoate, n-propyl p-hydroxybenzoate, isopropyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, diphenoxyethane, biphenyls aryl -substituted, alkyl-substituted biphenyls, p-benzyl biphenyl, phenyl toluidide, heptadecanol, 4-methoxyphenol, pentadecanol, 2,4-di-tert-butyl phenol, benzophenone, hydroxinaftoate diethyl terephthalate, alkyl alcohols, and diboxy oxide materials can be used individually or in combination. Useful heat sensitizers may optionally include a wax and / or a fatty acid.
[0176] Some materials useful as binders in the practice of the exemplary embodiment of the invention include starches, celluloses, natural and synthetic gelatins, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, vinyl chloride and vinyl chloride copolymers. , polybutylmethacrylate, and aqueous polystyrene emulsions. Two or more binding materials can be used. The binder, if used, can be water-insoluble, water-soluble or a mixture of one or more water-insoluble binding materials, and one or more water-soluble binding materials.
[0177] Some materials useful as pigments in the practice of the exemplary embodiment of the invention include calcium carbonate, silica, titanium dioxide, alumina, magnesia, talc, barium sulfate and aluminum stearate.
[0178] Some materials useful as lubricants in practicing the exemplary embodiment of the invention include flaxseed oil, tung oil, wax, paraffin, and polyethylene wax.
[0179] Other suitable materials will be known or evident for an element skilled in the art, in the light of this description, or will become known or evident in the future.
[0180] Dual-function exposure indicators according to the exemplary embodiment of the invention can be usefully used to monitor the condition of anyone among a wide range of heat-sensitive host products. Host products that can be monitored include, in addition to vaccines: temperature-sensitive health care products, for example, drugs, medications, pharmaceuticals, pharmaceuticals that incorporate a polypeptide, nucleic acid or cellular material, sensitive medical devices temperature, temperature sensitive prophylactics and the like; biological materials for industrial or therapeutic uses, for example, cultures, organs, and other parts of the human or animal body, blood, and perishable blood products; diagnostic devices, diagnostic kits containing c products, and perishable diagnostic ingredients; batteries, devices containing batteries, tools containing batteries; fresh or prepared foodstuffs, including fish, meat, dairy products, fruits, vegetables, bakery products, desserts, and the like; food service products, including restaurant food services; gourmet food products; perishable animal feed; cut and uncut flowers; plants; cosmetics, for example, cosmetics containing biological ingredients or other labile or perishable ingredients; beauty products; perishable industrial products; ink; solder; deadly ammunition and war materials; and fragile packaging and decontamination products.
[0181] A dual function exposure indicator according to the exemplary embodiment of the invention can be associated with a host product in a variety of ways, for example, by adhesion, bonding, connection, bonding or otherwise fixing on the dual-function exposure, or a label or tag incorporating the dual-function exposure indicator, to a desired host product, either directly to a host product, or to a package containing the host product, or to a packaging, carton cardboard, box or other container containing numerous items of host product. Also, the dual-function display indicator, label, or tag can be inserted into a package, cardboard box, or other host product container for one or more host product items. EXAMPLES EXAMPLE 1: MANUFACTURE OF DOUBLE-FUNCTION HEAT INDICATOR PROTOTYPES
[0182] The indicator prototypes were manufactured by laminating cumulative heat indicators type VVM14, printed on transparent film, on a commercially available thermal paper or prefabricated thermal paper. Cumulative heat indicators type VVM14 are prototypes of cumulative heat indicators formulated to respond in approximately 14 days at 37 ° C, and are intended to be similar to the commercially available HEATmarker VVM14, available from Temptime Corporation. VVM14 has a temperature response profile and is well manufactured to meet the requirements of the World Health Organization provided in PQS Performance Specification, Vaccine Vial Monitor WHO / PQS / E06 / IN05.2, 26 July 2011. It responds in 14 days at 37 ° C, in 90 days at 25 ° C, and> 3 years at 5 ° C. The indicator prototypes were manufactured on a Gallus 250 I printing machine. Two tests were carried out, the last one being to evaluate a thinner version of the transparent polyester film as an improvement. No set of prototypes was die cut in the Gallus press to avoid the cost of obtaining die tools, however, these were manually die cut to produce samples for demonstration. Tests have shown that the prototype process and construction are feasible. The prototypes were able to detect exposure to excessive heat and still monitor the cumulative effects of heat and time below the threshold.
[0183] The first test used DuPont Teijin Films ™ Melinex® 561, a 0.005-inch-thick transparent polyester film. This film is chemically treated on both sides to accept solvent-based inks and provide a clean cut when subjected to die cutting. The second prototype test used Transilwrap Company general purpose Oriented Polyester, a 0.00092 inch thick polyester film, the transparent polyester film was treated in one for solvent-based printing. Gotham Ink's "Gotham baseline lavender", a solvent-based flexo ink adjusted to obtain an exact color match with the indicator ink by adding adequate amounts of opaque white ink Gotham Series, magenta Gotham Series, and cyan Gotham Series was used to the reference ring ink. The "active" ink indicator was manufactured at home by dispersing a "KE" powder (2,4-hexadiene-1,6-bis (ethylurea) in a solvent-based nitrocellulose ink, according to the procedures described in US patent 8,067,483.The amount of KE in the ink and the amount of ink applied to the polyester film were selected to obtain a color match between the active temperature sensitive ink and the temperature insensitive reference ink after about 14 days at 37 ° C.
[0184] FLEXcon's laminate FLX055158 FLEXmount DFM-100 Clear V-224 150 Poly H-9 V-224 150 Poly H-9 was used. This laminate consists of a transparent polyester carrier film with both sides coated with a permanent pressure sensitive adhesive based on water. This was used to laminate the thermal paper on the printed transparent polyester film. The laminate was supplied with release liners on both sides, these are removed during prototype manufacturing. The initial screening showed that solvent-based adhesives can affect the ability of the thermal paper to darken, so the water-based adhesive was selected, as it did not show this effect. However, there may be suitable combinations of solvent-based adhesives with thermal paper that do not show this effect. The polyester carrier film and the two layers of adhesive add 0.003 mm to the thickness of the laminated structure. Each adhesive layer is 0.001 mm thick in a 0.001 mm PET carrier film. If an additional reduction in stiffness and thickness is required in the product, this laminating film could be replaced with an unsupported adhesive layer applied as a transfer tape product.
[0185] The thermal paper used is the Mactac DTR 9902 thermal label paper, which consists of high sensitivity direct scanable IR thermal paper finished with a high-adhesion permanent acrylic emulsion adhesive, supplied with a semi-blasted calendered kraft liner. The thickness of thermal paper is described as typically 0.0034 and the adhesive adds an additional 0.0007 to the thickness. The adhesive is designed for use in medical bottles and has an average peel resistance of 2.4 lbs / in. The adhesive was designed to adhere to metal, plastic and glass.
[0186] The manufacturing process consists of a first step through the Gallus press to form a laminate between the thermal paper and the double-sided adhesive laminating film. The thermal paper was placed on the unrolled roll with the active surface facing upwards. The handler and crown dryers were turned off and cold at this stage. If these are on, it could cause the thermal paper to darken. At the laminating station, the Flexmount DFM is assembled so that a liner is removed and the newly developed adhesive is placed in contact with the active surface of the thermal paper. The resulting laminated product is rewound so that it can be used in the laminating station in the second step.
[0187] The second step in the press consists of the transparent polyester film being unwound. In the first test, there was no need to be careful which side could be printed, as both sides were chemically treated to accept solvent ink. In the second test, however, the transparent polyester film had the chemically treated side only on the outer surface of the roll, so care was taken to mount the roll so that the outside could be printed.
[0188] To manufacture the cumulative indicator portion of the double indicator, the reference ring was printed on the transparent polyester film followed by two printed layers of the active ink.
[0189] The rollers made on the first pass through the press were mounted in the laminating station so that the self-adhesive liner on the other adhesive surface of the laminated film coated with double-sided adhesive is removed. The newly revealed adhesive came into contact with the cumulative indicator printed on the transparent polyester film. The entire laminate was inverted so that the transparent polyester film is on top. This configuration could then be ready to be die cut through the transparent polyester at the bottom in the self-adhesive liner of the thermal paper. Die cutting was not performed in these tests.
[0190] The results of the samples from the first prototype test using DuPont Teijin Films ™ Melinex® 561 can be seen in Figures 10 to 13. Three types of samples were obtained: the construction of a double indicator, only the thermal paper with the film of lamination and transparent film on top, and only the cumulative indicator portion of the double indicator (that is, the active and reference inks printed on the transparent film). Optical density measurements were performed using an X-Rite 504 Spectrodensitometer and cyan, magenta, yellow and black measurements were recorded. Only cyan optical density measurements are reported and have been used for performance analysis comparable to assessments of the active ink portion of the cumulative indicator. The reference ring has a cyan OD value of about 0.50, which is unaffected by exposure to temperature. The three types of sample were affected by temperature, and in each case the "end point" indicator for any given temperature can be represented by the amount of time that the indicator takes to reach an OD of around 0.50.
[0191] Ten samples from each phase were tested in isothermal water baths capable of controlling the temperature at + 0.1 ° C. The samples were assembled on white cardboard, then doubly sealed in aluminum and plastic bags and kept at varying temperatures during a series of specified time intervals, periodically remolding them from the baths to measure the change in DO over time. At higher temperatures, the samples were placed in two transparent plastic bags so that the response can be directly observed.
[0192] At 90 ° C, the indicator response was dominated by the thermal paper that darken within 1 second of immersion in the water bath. There was no change in the VVM14-like portion of the indicators in that time interval. End point, defined as when the absolute OD of cyan reaches 0.50, has not been reached for cumulative indicators until almost 40 minutes.
[0193] At 80 ° C the results are similar to those shown at 90 ° C except that the browning of thermal paper took a little longer, 10 seconds, and the maximum OD is slightly less. Cumulative indicators did not reach 0.5 OD until approximately 3 hours. In general, at temperatures of 50 ° C and below, thermal paper showed very little response and, therefore, the dual function heat indicator responded essentially as a cumulative indicator. EXAMPLE 2: DOUBLE-FUNCTION HEAT PROTOTYPE INDICATOR TO ILLUSTRATE THE EXEMPLIFICATIVE ACHIEVEMENT DEMONSTRATED IN FIGURE 7
[0194] Dual prototype heat indicators made by hand were made by laminating cumulative heat indicators type VVM14, printed on transparent film, in a commercially available or prefabricated limit indicator. The cumulative indicator component was made by printing a color-changing “active” diacetylene ink and a “static reference ink” on DuPont Teijin Films ™ Melinex® 561, a 0.005 inch thick transparent polyester film using a Gallus 250 I printing machine. The "active" ink was manufactured at home by dispersing "KE" powder (2,4-hexadiene-1,6-bis (ethylurea) in a solvent-based nitrocellulose ink, according to with the procedures described in US patent 8,067,483. The amount of KE in the ink and the amount of ink applied to the polyester film were selected to obtain a color match between the active temperature sensitive ink and the temperature insensitive reference ink after about 14 days at 37 ° C. The "reference" ink is Gotham Ink's "Gotham baseline lavender", a solvent based flexographic ink adjusted to obtain an exact color match with the indicator ink by adding suitable quantities opaque white ink Gotham Series, magenta, and cyan. This cumulative heat indicator was designed to have a similar appearance and time / temperature response to the Temptime's HEATmarker® VVM14 indicator.
[0195] Indicators type VVM14 that were printed on transparent film were placed on samples of Temptime's DEGmarker® 40 indicators and pasted on the edges on white cardboard (176 g / m2, 8.5 by 11 inches of Staples White Card Stock acid free code # 733350). Due to the fact that the active ink is almost transparent when printed on the transparent film, the gray central point of the DEGmarker 40 indicators could be easily seen through the active ink square of the VVM14 type indicators. For comparison, the VVM14 type indicators and the DEGmarker indicators were also included on the card.
[0196] The test card with the indicators was placed inside an oven (Boekel Scientific CCC1.4d thermal incubator), at 25 ° C, 35 ° C, 45 ° C and kept for 5 minutes at each temperature. Optical density (OD) was measured for the active part of each indicator after each 5-minute period using an X-rite 504 Spectrodensitometer and reported for cyan. There was no change in the indicators at 25 ° C and 35 ° C. At 45 ° C, the color change of the dual-function heat indicator and the DEGmarker indicator was rapid and visible and occurred within 2 minutes. The measured optical densities can be seen in Figure 14. Figure 15 shows the test card with the indicators without heating and heating to 45 ° C.
[0197] A second set of experiments was carried out where the dual function heat indicator prototypes were made and placed in transparent plastic bags sealed with heat so that they can be observed in increments of changes of 1 ° C in a bath of circulation water (Thermo Scientific AC 150 containing 60/40 water / propylene glycol). Each sample was placed in the bath at the specified temperature for 5 minutes. Observations were made at intervals of about 2 minutes analyzing the bath in the samples in the transparent plastic bags. OD measurements were not taken. One set of samples was made with DEGmarker 40 limit indicators, and another set was made in the same way with DEGmarker 45 limit indicators. The dual function heat indicator prototypes made with VVM14 and DEGmarker 40 or DEGmarker 45 provided responses within a degree or two between 40 ° C and 45 ° C respectively. When color changes are observed, they occur within 2 minutes of exposure. Since the DEGmarker response was observed through the VVM active ink “window” printed on transparent film when done in the dual function heat indicator construction, this construction could be used as a dual function heat indicator according to Figure 7. A comparison of the color appearance of the active region between the dual indicator prototypes made with VVM 14 and DEGmarker 40 or DEGmarker 45 at varying temperatures can be seen in Figure 16. The results show how effective the heat indicator prototypes are. Dual-function are at lower temperatures compared to just a cumulative indicator or peak indicator individually. EXAMPLE 3: DEMONSTRATION OF PEAK INDICATOR WITH FUSIBLE ACTIVATOR AT A TEMPERATURE ABOVE THE ACTIVATOR MELTING POINT AS ILLUSTRATED IN FIGURE 5
[0198] Ultratherm product number 004188 is a white direct thermal label paper from Wausau Paper, Wausau WI, with an initial thermal sensitivity of 75 ° C. Static sensitivity is a measure of the temperature at which the thermal layer reaction begins. The initial static thermal temperature is the temperature at which the thermal coating develops an optical density of 0.2 OD units. If thermal paper is used to provide the peak indicator component of a double indicator, then the initial static sensitivity temperature represents the lower end of the peak indicator response temperature range.
[0199] To demonstrate a peak indicator for use in a dual function heat indicator construction, a small amount of crystalline benzophenone powder (product B9300 from Sigma-Aldrich, St. Louis MO) was spread thinly over the Ultratherm 004188 printable surface. The melting point of benzophenone reported by the supplier is 48 to 49 ° C. This was placed in an oven at about 50 ° C. The coating developed a black color in less than 90 seconds where the crystals were. The rest of the paper remained white. The benzophenone appeared to have melted and penetrated the thermal coating in the black areas. The development of the paper by the activator occurred at a temperature much lower than the development temperature of the paper itself, and greater than the melting point of the meltable activator. EXAMPLE 4: PEAK INDICATOR WITH ACTIVATOR AND SUBSTRATE FUSIBLE AT A TEMPERATURE BELOW THE ACTIVATOR MELTING POINT.
[0200] Four direct thermal substrates were used for the next example of peak indicators for use in dual function heat indicator constructions. The thermal substrates were pairs of similar construction except that one in each pair was provided with a thin transparent protective coating to increase durability and scratch resistance. Activator samples with substrates were prepared in the same manner as in Example 3. Temperature exposure experiments were conducted by placing the test samples in plastic bags, drawing air out so that each side of the substrate is against the side of the bag, and then immerse it in a thermostatically controlled water bath (Neslab RTE 17 from ThermoElectron Corp.) at 43 ° C. The temperature was measured with a mercury thermometer with an accuracy of <0.1 ° C. The samples were observed periodically for color development and the test ended after 40 minutes. Figure 17 lists the samples, their static thermal sensitivities, as determined by the manufacturer, and the response to contact the activator.
[0201] In all cases, benzophenone crystals were visible, and there was no evidence of fusion. Also, when benzophenone was in direct contact with the mixture of materials that make up the thermal coating, color developed around the point of contact. The coated samples showed little or no development. Upon examination with a microscope, it was observed that the development points of the coated samples were generally associated with artifacts in the thermal coating, such as protruding fibers, which are well known as weak points of barrier coatings, and will be covered by very little coating, or none. While still intact, the coating appeared to act as a barrier between the activator and the thermal coating.
[0202] Example 5: Peak Indicator with Fusible Activator and Substrates with Protective Coating at a Temperature Below and Above the Melting Point
[0203] The two direct thermal substrates with protective coatings used in samples 113 and 115 in Example 4 were used in this example.
[0204] Activator samples with substrates were prepared in the same manner as in Example 3, and temperature exposure experiments were conducted in the same manner as in Example 4 except that the initial temperature is 35 ° C. The temperature was gradually increased over several hours. There was no development in these examples after 10 minutes at 44.0 ° C. The first sign of development was a single spot observed at 44.5 ° C in sample 113A after 10 minutes. After 20 minutes at 45.0 ° C, sample 115A also showed a single point of development. Development on both samples continued over a period of 10 minutes at 45.5 ° C. Extensive development was observed in sample 113A after a 10-minute stay at 46.0 ° C and for sample 115A after an additional 10 min. at 46.5 ° C. At this temperature, it was observed that the benzophenone crystals melted and developed in the adjacent region. Again, the development took place at temperatures much lower than the static sensitivity of the thermal substrate.
[0205] The melting point of benzophenone used for the examples above was determined separately on the device, but with the crystals between two glass microscope slides, again inside a polyethylene bag. The initial temperature is 45.0 ° C and temperature measurements are 0.1 ° C at approximately 3 minute intervals. The benzophenone was melted at 46.1 ° C.
[0206] In this example, the development of thermal composition occurred at temperatures much lower than the temperature of static sensitivity of the thermal substrates, but also similarly close to the melting point of the meltable activator, even though the thermal substrates have different thermal sensitivities. The difference between the temperature where development was prevented by the transparent barrier coating and where it occurred quickly is no more than two degrees. This exemplary realization of a coated thermal substrate and a meltable activator demonstrated a specific response temperature, stability at temperatures lower than, but close to the response temperature, and rapid visual response from a small temperature transition through the response temperature. INCORPORATED DESCRIPTIONS
[0207] The entire description of each US patent, each US patent application, each international patent publication, each foreign patent publication, any other publication, and each unpublished patent application identified in this specification is hereby incorporated by reference, in its entirety, for all purposes. It may appear that there is a conflict between the meaning of a term used in describing the exemplary embodiment of the invention in that specification and the use of the term in the material incorporated by reference of another document, the meaning of the term as used here is intended to prevail. Any reference to an "exemplary embodiment of the invention" in any incorporated description will be understood to refer to the exemplary embodiment of the invention described, or claimed, in the incorporated description. ABOUT DESCRIPTION
[0208] The detailed description here will be read in light of and in combination with the background descriptions of the exemplary embodiment of the invention and the brief summary of the exemplary embodiment of the invention where information regarding the written description of the exemplary embodiment of the invention, the best way to practicing the exemplary embodiment of the invention, or describing modifications, alternatives or other useful embodiments of the exemplary embodiment of the invention can also be explicitly presented, or implied, as will be evident to an element skilled in the art.
[0209] The terms "include", "own", "own", and "contain", and their various grammatical forms, will be understood as not limited and not because they exclude additional steps, elements or unmentioned steps of the method.
[0210] Throughout the description, when compositions, instruments, devices, appliances, systems or processes are described having, including, or comprising specific components or elements, or in the case of processes, specific steps, it will be contemplated that compositions, instruments, devices , apparatus, systems or processes according to the present exemplary embodiment of the invention can also consist essentially, or consist, of the mentioned components, elements or steps.
[0211] In this application, when an element or component is said to be included and / or selected from a list or group of elements or components cited, it should be understood that the element or component can be any of the elements or components cited , or can be selected from a group consisting of two or more elements or components mentioned.
[0212] The use of the singular form here is intended to include the plural form (and vice versa) except where the context indicates otherwise.
[0213] Also, when the term "about", "approximate", "approximately" or a similar term is used before a quantitative value, the specific quantitative value itself will be understood to be included, and to be explicitly quoted, except where the description specifically expresses the opposite.
[0214] Regarding the processes, it will be understood that the order of steps or the order to perform certain actions is irrelevant since the process described remains operable. In addition, two or more steps or actions can be carried out simultaneously, except where the context indicates otherwise. In addition, any proportions mentioned here will be understood as proportions by weight, based on the weight of the relative composition, except where the context indicates otherwise. Also, except where the context indicates otherwise, or suggests otherwise, any methods according to the exemplary embodiment of the invention that are described here, or one or more steps of the methods, can be practiced at an ambient temperature in the range of about 20 ° C to about 25 ° C.
[0215] The description of the background of the exemplary embodiment of the invention here may include perceptions, discoveries, understandings or descriptions, or associations of descriptions, which were not known in the prior art relative to the present exemplary embodiment of the invention, but which are provided by the exemplary embodiment of the invention, and will be considered elements of the exemplary embodiment of the invention. Some contributions to the exemplary realization of the invention can be specifically pointed out as attributable to the exemplary realization of the invention, and other contributions to the exemplary realization of the invention will be evident from its context. Simply because a document has been cited in that application, no admission that is made in the field of the document, this may be very different from that of the exemplary embodiment of the invention, is analogous to the field or fields of the present exemplary embodiment of the invention.
[0216] The description of the exemplary embodiment of the invention here will be understood to include combinations of the various elements of the exemplary embodiment of the invention, and of its described or suggested alternatives, including described, indicated or suggested alternatives in any one or more of the various methods, products , compositions, systems, devices, instruments, aspects, achievements, examples described in the specification or drawings, if any, and to include any other written or illustrated combination or group of elements of the exemplary realization of the invention or the possible practice of the exemplary realization of the invention, except for groups or combinations of elements that are incompatible, or contrary to the purposes of the exemplary realization of the invention, as will, or will become, evident to an element skilled in the art. Furthermore, the embodiments of the exemplary embodiment of the invention may have any configuration in accordance with the exemplary embodiment of the invention that is described here, or is shown in any attached drawing, and may employ any compatible materials of the useful materials or structures described herein.
[0217] Scope of Exemplary Realization of the Invention. The present exemplary embodiment of the invention includes the examples and embodiments described here and other specific forms of the exemplary embodiment of the invention that incorporate the spirit or essential features of the exemplary embodiment of the invention or the respective examples or embodiments described. The foregoing examples and embodiments are in all respects intended to be illustrative of the exemplary embodiment of the invention described here. It will be understood that many and several modifications of the exemplary embodiment of the invention, or of an example or embodiment of the exemplary embodiment of the invention described here, will become evident to the elements versed in the relative technique, or may become evident as the technique develops, in the light of the previous description. Such modifications are contemplated to be within the spirit and scope of the exemplary embodiment of the invention or exemplary embodiments of the invention described here.

权利要求:
Claims (13)
[0001]
1. DUAL FUNCTION INDICATOR (30, 50, 60, 80) to monitor cumulative ambient heat exposure and peak ambient heat exposure, the dual function heat indicator (30, 50, 60, 80) being characterized by comprising: a substrate (14); a cumulative exposure indicator (34, 44) supported by the substrate (14) in a visible layered configuration of the dual function heat indicator (30, 50, 60, 80), where the cumulative exposure indicator is configured to submit a change in optical appearance in response to exposure to cumulative ambient heat; and a peak exposure indicator (32, 52, 62, 82), in which peak exposure indicator (32, 52, 62, 82): (a) comprises a prefabricated thermal paper or film that has a temperature activation of normal color change of more than 60 ° C; (b) is supported by the substrate (14) in a configuration in other visible layers of the dual function heat indicator (30, 50, 60, 80), where the peak exposure indicator (32, 52, 62, 82) comprises: (b1) a first reagent, a second reagent and a meltable solid, the first reagent is chemically liable to co-react with the second reagent to provide a color change, the melt solid physically separates the first reagent from the second reagent, and the color change chemical reaction is induced in response to a peak temperature of exposure to ambient heat that exceeds the melting point of the melt; or (b2) a meltable colored particulate material; wherein the fusible colored particulate material has an average particle size that dyes the fusible colored particulate material with a light color, the light color being attributable to the dispersion of visible light by the fusible colored material particles; where the melting of the meltable colored particulate material causes the peak exposure indicator to change its visual appearance, with the change in appearance being induced by a peak exposure to ambient heat that reaches a temperature that exceeds the melting point of the fusible colored particulate material; and wherein the appearance of the peak exposure indicator (32, 52, 62, 82) is viewed or optically read through the cumulative exposure indicator (34, 44) prior to exposure to heat; where the dual function heat indicator (30, 50, 60, 80) indicates exposure to cumulative ambient heat or exposure to peak ambient heat through color change.
[0002]
2. HEAT INDICATOR (30, 50, 60, 80), according to claim 1, characterized in that the first reagent and second reagent are particulate and are dispersed in a peak indicator layer.
[0003]
HEAT INDICATOR (30, 50, 60, 80) according to any one of claims 1 to 2, characterized in that the first reagent and second reagent are solid and the melt solid additionally comprises a thermal sensitizer to modify the melting point peak melt solid.
[0004]
HEAT INDICATOR (30, 50, 60) according to any one of claims 1 to 3, characterized in that the first reagent comprises a color former and the second reagent comprises a color developer and in which, optionally, the former of color or the color developer, or both the color former and the color developer, are initially colorless.
[0005]
HEAT INDICATOR (30, 50, 60, 80) according to any one of claims 1 to 4, characterized in that the melt comprises a binder.
[0006]
6. HEAT INDICATOR (30, 50, 60, 80), according to claim 1, characterized by the change in the appearance of the peak exposure indicator (32, 52, 62, 82) being caused by the melting of the melt particulate material that reveals or obscures a background.
[0007]
7. HEAT INDICATOR (30, 50, 60, 80), according to claim 1, characterized by the change in the appearance of the peak exposure indicator (32, 52, 62, 82) being caused by the melt colored particulate material that it gets dark.
[0008]
HEAT INDICATOR (30, 50, 60, 80) according to any one of claims 1 and 6 to 7, characterized in that the meltable particulate colored material comprises a meltable solid and a dye dissolved in the meltable solid.
[0009]
9. HEAT INDICATOR (30, 50, 60, 80), according to any one of claims 1 to 8, characterized in that the substrate is configured to be compatible with a host product and allows the dual function heat indicator to be fixable in the host product, optionally, supporting a pressure sensitive adhesive layer.
[0010]
10. HEAT INDICATOR (30, 50, 60, 80) according to any one of claims 1 to 9, characterized in that the cumulative exposure indicator (34, 44) comprises at least one thermally sensitive polymerizable diacetylene compound containing at least two conjugated acetylenic groups.
[0011]
11. HEAT INDICATOR (30, 50, 60, 80), according to claim 1, characterized in that it additionally comprises an activator applied to the prefabricated paper or thermal film configured to reduce the color change activation temperature of the paper or pre-fabricated thermal film below 60 ° C.
[0012]
12. HEAT INDICATOR (30, 50, 60, 80), according to claim 11, characterized in that the activator is selected from a group consisting of heptadecanol, 4-methoxyphenol, pentadecanol, 2,4-di-tert - butyl phenol or benzophenone.
[0013]
HEAT INDICATOR (30, 50, 60, 80) according to any one of claims 1 to 12, characterized in that it comprises a reference surface printed on the substrate (14).

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同族专利:

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公开号 | 公开日

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CN104428644B|2017-11-03|

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AU2013259063A1|2014-11-13|

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DK2847563T3|2019-11-04|

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BR112014028058A2|2017-07-18|

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RU2014150045A|2016-07-10|

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KR20150032830A|2015-03-30|

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WO2013170273A2|2013-11-14|

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JP2015520850A|2015-07-23|

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AU2013259063B2|2016-11-10|

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MX370922B|2020-01-09|

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BR112014028058A8|2019-01-29|

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EP2847563A2|2015-03-18|

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HK1203607A1|2015-10-30|

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US20140044609A1|2014-02-13|

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US20180321159A1|2018-11-08|

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MX2014013755A|2015-09-07|

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WO2013170273A3|2014-01-30|

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ZA201408169B|2015-12-23|

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EP2847563B1|2019-07-31|

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US10514340B2|2019-12-24|

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EP3620767A1|2020-03-11|

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US20160069812A1|2016-03-10|

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EP2847563A4|2015-09-30|

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US10031086B2|2018-07-24|

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CA2871439A1|2013-11-14|

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US20160313253A1|2016-10-27|

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KR102071093B1|2020-01-29|

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IN2014DN08883A|2015-05-22|

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CN104428644A|2015-03-18|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US8067A|1851-04-29|Horseshoe |

---

US483A|1837-11-25|Improvement in spring-saddles |

---

US434A|1837-10-20|Method of attaching glass kbtobs to metallic sockets |

---

US5057A|1847-04-10|chambers |

---

US3247006A|1960-10-12|1966-04-19|Oxford Paper Co|Pressure sensitive record sheet, method of making and composition therefor|

---

US3999946A|1976-02-23|1976-12-28|Allied Chemical Corporation|Time-temperature history indicators|

---

US4189399A|1977-07-19|1980-02-19|Allied Chemical Corporation|Co-crystallized acetylenic compounds|

---

US4384980A|1977-07-19|1983-05-24|Allied Corporation|Co-crystallized acetylenic compounds|

---

US4228126A|1977-11-25|1980-10-14|Allied Chemical Corporation|Diacetylene time-temperature indicators|

---

US4389217A|1979-05-11|1983-06-21|Allied Corporation|Integrated time-temperature or radiation-dosage history recording device|

---

SE414509B|1979-05-17|1980-08-04|Kockums Chem|POWDER-SUBSTRATE COMPOSITION WHICH DOES NOT INCLUDE HYDROPHOBIC ENZYME SUBSTATE ADSORBED TO A PARTICULAR CONSERVATOR WITHOUT USING THE COMPOSITION IN TIME-TEMPERATURE TYPE ENZYMATIC INDICATOR DEVICE|

---

US4299880A|1979-11-15|1981-11-10|Minnesota Mining And Manufacturing Company|Demand and timed renewing imaging media|

---

JPS57144793A|1981-03-05|1982-09-07|Ricoh Co Ltd|Heatsensitive recording material|

---

US4428321A|1981-11-16|1984-01-31|Minnesota Mining And Manufacturing Co.|Thermally-activated time-temperature indicator|

---

US4753188A|1982-05-24|1988-06-28|Mdt Corporation|Heat history indicator|

---

US4917503A|1985-12-02|1990-04-17|Lifelines Technology, Inc.|Photoactivatable leuco base time-temperature indicator|

---

US4789637A|1986-09-29|1988-12-06|Lifelines Technology, Inc.|Acid complexed acetylenic compounds useful as environmental indicating materials|

---

US4788151A|1986-09-29|1988-11-29|Lifelines Technology, Inc.|Metal complexed acetylenic compounds useful as environmental indicating materials|

---

US5057434A|1989-08-29|1991-10-15|Lifelines Technology, Inc.|Multifunctional time-temperature indicator|

---

US5622137A|1994-03-24|1997-04-22|Trans World Services|Temperature sensors|

---

US5756356A|1995-03-31|1998-05-26|Toyo Ink Manufacturing Co., Ltd.|Method of indicating time or temperature-time accumulated value as color change, and materials therefor|

---

US6042264A|1995-10-23|2000-03-28|Lifelines Technology, Inc.|Time-temperature indicator device and method of manufacture|

---

US5709472A|1995-10-23|1998-01-20|Lifelines Technology, Inc.|Time-temperature indicator device and method of manufacture|

---

US6410896B2|1995-10-27|2002-06-25|Medical Indicators, Inc.|Shielding method for microwave heating of infant formula to a safe and uniform temperature|

---

US5741592A|1995-12-20|1998-04-21|Ncr Corporation|Microsencapsulated system for thermal paper|

---

US5822280A|1996-05-06|1998-10-13|Temtec, Inc.|Long term rapid color changing time indicator employing dye absorbing layer|

---

JPH11140339A|1997-11-12|1999-05-25|Oji Paper Co Ltd|Irreversibly temperature-indicating material|

---

US6043021A|1997-12-09|2000-03-28|Eastman Kodak Company|Packaged photographic product containing time and temperature integrating indicator device, and process for monitoring thermal exposure of photographic material|

---

DE19803208C2|1998-01-28|2003-04-30|Dietrich Haarer|Substrate for packaging or attaching to products and methods for quality determination|

---

US6509296B1|1998-02-27|2003-01-21|Eastman Kodak Company|Thermographic imaging elements and processes for their use|

---

US6060426A|1998-06-30|2000-05-09|Ncr Corporation|Thermal paper with security features|

---

RU2131117C1|1998-09-15|1999-05-27|Общество с ограниченной ответственностью "Фирма ВИПС-МЕД"|Temperature and time sterilization indicator and process of its manufacture|

---

US6524000B1|1999-04-30|2003-02-25|Ncr Corporation|Time-temperature indicators activated with direct thermal printing and methods for their production|

---

JP2003507724A|1999-08-24|2003-02-25|コーニンクレッカフィリップスエレクトロニクスエヌヴィ|Substrate provided with layer of thermochromic oxide|

---

SE9903617D0|1999-10-05|1999-10-05|Se Interengineering Ab|Device and method for determining the status of a product|

---

US6544925B1|2000-03-02|2003-04-08|Lifelines Technology, Inc.|Activatable time-temperature indicator system|

---

US6602594B2|2000-04-25|2003-08-05|Nichiyu Giken Kogyo Co., Ltd.|Irreversible heat-sensitive composition|

---

JP2004028915A|2002-06-27|2004-01-29|Fuji Seal Inc|Temperature history managing label|

---

US7682830B2|2003-06-10|2010-03-23|Temptime Corporation|Product shelf life monitoring systems|

---

US6924148B2|2003-07-02|2005-08-02|Temptime Corporation|Reactivity control in substituted diacetylenic monomer shelf life monitoring systems|

---

GB0322907D0|2003-09-30|2003-10-29|Arjo Wiggins Ltd|Improvements in thermal paper|

---

US7139226B2|2004-02-25|2006-11-21|Brady Worldwide, Inc.|Long term rapid color changing time indicator|

---

JP4789083B2|2004-07-15|2011-10-05|株式会社ジークエスト|Temperature sensitive seal|

---

US7161023B2|2004-07-28|2007-01-09|Temptime Corporation|Morphology control of substituted diacetylenic monomers for shelf life monitoring systems|

---

US7442237B1|2004-09-16|2008-10-28|The United States Of America As Represented By The Secretary Of The Army|Multi-agent end-of-service-life indicator for respirator filters|

---

US7019171B1|2004-12-02|2006-03-28|Temptime Corporation|Particle size control for acetylenic agents useful in condition monitoring systems|

---

US20060247967A1|2005-05-02|2006-11-02|Thaddeus Prusik|Method of marketing maturing consumable products and products useful therein|

---

US20090050049A1|2005-07-27|2009-02-26|Vincent Craig|Time-temperature indicators|

---

GB2430257A|2005-09-16|2007-03-21|Sun Chemical Ltd|Bar code having a time-temperature indicator|

---

US7571695B2|2006-11-06|2009-08-11|Temptime Corporation|Freeze indicators, flexible freeze indicators and manufacturing methods|

---

JP5050249B2|2005-11-08|2012-10-17|テンプタイムコーポレーション|Combined temperature exposure indicator|

---

FI20065238A|2006-04-18|2007-10-19|Upm Raflatac Oy|Method and indicator for monitoring termination of a predetermined temperature dependent time period|

---

US8067483B2|2006-06-29|2011-11-29|Temptime Corporation|Adjuvant-mediated reactivity enhancement of polymerizable diacetylenic materials|

---

US7517146B2|2006-08-30|2009-04-14|Temptime Corporation|Color-retaining excess-temperature exposure indicator|

---

CN101611115A|2007-01-11|2009-12-23|弗雷什波因特控股有限公司|Photostabilised time temperature indicator|

---

JP5110900B2|2007-02-20|2012-12-26|日油技研工業株式会社|Temperature control indicator for cooking|

---

US8269042B2|2007-10-30|2012-09-18|Temptime Corporation|Crystallized diacetylenic indicator compounds and methods of preparing the compounds|

---

US8911861B2|2008-12-11|2014-12-16|Landec Corporation|Thermochromic indicator|

---

DK2414420T3|2009-03-31|2015-09-28|Temptime Corp|Cocrystallizable DIACETYLENMONOMERSAMMENSÆTNINGER, CRYSTAL PHASES AND MIXTURES AND SIMILAR PRACTICES|

---

US20100264640A1|2009-04-17|2010-10-21|Lane T Randall|Device for obcuring printed indicia and method of use|

---

CN102844649B|2009-08-31|2014-04-02|泰坦公司|Freeze indicators with controlled temperature response|

---

CN101900685A|2010-06-12|2010-12-01|北京联合大学|Method for manufacturing microbial time-temperature indicator card|

---

US8671871B2|2010-09-29|2014-03-18|Temptime Corporation|Temperature-activated time-temperature indicator|

---

US8430053B2|2010-09-30|2013-04-30|Temptime Corporation|Color-changing emulsions for freeze indicators|

---

US20120174853A1|2011-01-06|2012-07-12|Robert Wilson|Temperature Sensing Food Stuff Label|

---

WO2013138637A1|2012-03-15|2013-09-19|Temptime Corporation|Robust, ultraviolet-protected ambient condition history indicator and method of making same|US10260956B2|2012-06-15|2019-04-16|Freshpoint Quality Assurance Ltd.|Time and/or temperature sensitive devices and methods of use thereof|

---

CN104583741B|2012-08-16|2017-10-31|泰坦公司|Using the freeze indicators and its manufacture method of light scattering|

---

JP2014163798A|2013-02-25|2014-09-08|Fujifilm Corp|Ultraviolet sensitive sheet, ultraviolet sensitive set, and ultraviolet sensitive method|

---

JP6177706B2|2013-02-25|2017-08-09|富士フイルム株式会社|Ultraviolet sensing sheet, manufacturing method thereof, and ultraviolet sensing method|

---

WO2014150723A1|2013-03-15|2014-09-25|Ccl Label, Inc.|Thin conductors, connectors, articles using such, and related methods|

---

US9841381B2|2013-10-10|2017-12-12|Mcmaster University|Temperature change indicator and methods of making the same|

---

US9902861B2|2014-06-21|2018-02-27|Klt Technologies|Single color reversible temperature indicator|

---

JP5889985B1|2014-09-12|2016-03-22|日清食品ホールディングス株式会社|Thermal history change type indicator|

---

US10184840B2|2015-01-07|2019-01-22|The Boeing Company|Portable device for quantifying thermochromatic coating signatures|

---

US10352777B2|2015-01-07|2019-07-16|The Boeing Company|Systems and methods for monitoring temperatures of batteries|

---

US20170343425A1|2015-01-14|2017-11-30|Ayoub ALZUMAYA|Indicator for the quality of a product|

---

JP6383694B2|2015-03-30|2018-08-29|株式会社日立産機システム|Temperature history display body and manufacturing method thereof|

---

WO2016195675A1|2015-06-03|2016-12-08|Bemis Company, Inc.|Package for indicating heat-seal condition|

---

US10908031B1|2015-10-16|2021-02-02|Prasidiux, Llc|Stimulus indicating device employing the swelling action of polymer gels|

---

US10067011B2|2016-02-23|2018-09-04|International Business Machines Corporation|Pressure indicator films for high temperature applications|

---

US10024792B2|2016-08-08|2018-07-17|The Boeing Company|Removable chromatic witness assembly, system, and method to monitor thermal events and impact events on a composite structure|

---

GB2550987B|2016-10-19|2018-09-05|Seven Star Wraps Ltd|Wrapping|

---

BR112019010835A2|2016-12-02|2019-10-01|Bemis Co Inc|packaging to indicate thermal seal condition|

---

US20210095129A1|2017-03-29|2021-04-01|3M Innovative Properties Company|Thermal indicator, thermal indicating composition and thermal indicating structure|

---

CN111051207A|2017-04-20|2020-04-21|沃拉蒂莱分析公司|System and method for tracking chemical and odor exposure|

---

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---

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---

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---

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---

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---

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法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2020-02-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-10-20| B09A| Decision: intention to grant|

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2021-01-05| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261645889P| true| 2012-05-11|2012-05-11|

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US61/645,889|2012-05-11|

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PCT/US2013/040824|WO2013170273A2|2012-05-11|2013-05-13|Dual-function heat indicator and method of manufacture|

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