• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Temperature-activatable temperature indicator which contains a substrate and an indicator material which is carried on the substrate. The indicator material includes a mixture of a crystalline polymer with side chains and conductive particles, and it provides an electrical indication of exposure to elevated temperatures.
    公开号:BE1027234B1
    申请号:E20205330
    申请日:2020-05-13
    公开日:2021-07-26
    发明作者:Thaddeus Prusik；Thi N Do；Ravi Bhatia；Mohannad Abdo；Brian Huffman
    申请人:Temptime Corp；
    IPC主号:
    专利说明:

    [0001] The present disclosure relates to the field of temperature indicators. In particular, some embodiments include temperature-activatable temperature indicators that are electrically readable. STATE OF THE ART
    [0002] Many vaccines, active pharmaceutical ingredients, food and other products are temperature-sensitive or perishable and can lose quality over time, the speed being influenced by the temperature of the product, which is closely correlated with the prevailing ambient temperature, that is, with the Temperature in the immediate vicinity of the product. Time-temperature indicators are known which provide a simple visual indication of the past heat exposure to the receiving product, e.g., the cumulative heat exposure or its peak value. An indicator which is provided in the vicinity of the product packaging or on the same experiences temperature effects over time which are similar to those which the product itself experiences. The visual indication can be used to show whether a product may have lost quality or freshness. Some time-temperature indicators are capable of integrating the temperature related exposure of various conditions in a predictable and quantitative manner over time, and they can be used to monitor the cumulative thermal exposure to indicate the practical shelf life of perishable ingestible products , or for other purposes.
    [0003] Known time-temperature indicators can provide a color change to a predetermined end point in order to indicate possible loss of quality, or freshness, of the receiving product. The change in color may be indicated on a convenient label, or the like, for visual reading, for example visually by a human viewer or by an electronic device such as a bar code reader or cellular phone. The color change can be chromatic or achromatic, or it can be provided by some other visually detectable change in optical parameters. The setting of the parameters of the temperature-dependent response of the time-temperature indicator over time can make it possible for them to be correlated with a decay feature of the receiving product in such a way that the color change expediently takes place in coordination with the likely condition of the receiving product.
    [0004] Some known time-temperature indicators use diacetylene-like monomer compounds which polymerize in response to environmental conditions, such as the effects of temperature, to provide a color change. See, for example, published US patent applications No. 2009/0131718; 2011/0086995; and 2008/0004372; and U.S. Patent Nos. 4,789,637; 4,788,151; 5,254,473; 5,053,339; 5,045,283; 4,189,399; 4,384,980; and 3,999,946.
    [0005] Some other time-temperature indicators use a diffusion technique, such as in US Pat. Nos. 6,741,523; 6,614,728; and 5,667,303; and published US patent application No. 2003/0053377.
    [0006] Furthermore, with certain perishable products, such as vaccines and sensitive drugs, as well as with some food and other products, including some industrial products, the quality or safety can be impaired by a relatively brief exposure to a temperature which is a predetermined threshold value exceeds. Various proposals are known for monitoring such temperature effects, including those in US Pat. Nos. 7,517,146; 5,709,472; and 6,042,264.
    [0007] There is, however, a need for improved temperature indicators that can be read without the need for a visually detectable change in optical parameters. SUMMARY
    [0008] The present disclosure relates to temperature-activated temperature indicators in which the electrical conductivity is used to provide an indication of the action of elevated temperatures, which can be a reversible or an irreversible indication. In some embodiments, the indicator is a small, flexible, inexpensive temperature event recorder that can be easily fabricated, such as printing, and that is suitable for attaching to small objects such as vaccine bottles. For example, the indicator can be able to be printed directly on product labels or packaging.
    [0009] Some embodiments of the present invention include a temperature-activatable temperature indicator that includes a substrate and an indicator material that is carried on the substrate. The indicator material contains a mixture of a crystalline polymer with side chains and conductive particles.
    [0010] Some embodiments of the present invention include a temperature activatable temperature indicator that includes a substrate, a first layer supported on the substrate, and a second layer comprising a crystalline polymer with side chains. The first
    [0011] According to some embodiments, a perishable female product includes a temperature indicator according to the present disclosure, the temperature indicator being in connection with the female product to monitor the effect of the respective prevailing ambient temperature on the female product.
    [0012] Some embodiments of the present invention include a method of making a temperature activatable temperature indicator comprising: melting a crystalline polymer having side chains, adding conductive particles to form a mixture, and applying the mixture to a substrate.
    [0013] These and other property features are disclosed in more detail in the accompanying figures and the detailed description below. BRIEF DESCRIPTION OF THE DRAWINGS
    [0014] 1A is a schematic view of an example of a temperature indicator, according to an example embodiment of the disclosure.
    [0015] 1B is a schematic view of another example of a temperature indicator, according to an example embodiment of the disclosure.
    [0016] Figure 2 is a graph showing the temperature-viscosity curves for the three temperature indicator materials in accordance with the present invention.
    [0017] Fig. 3A is an example of a perishable receiving product in conjunction with a temperature indicator to monitor the effect of the prevailing ambient temperature on the receiving product, wherein the temperature indicator is electrically connected to the antenna of an RFID tag.
    [0018] Fig. 3B is an example of a perishable receiving product in conjunction with a temperature indicator to monitor the effect of the prevailing room temperature on the receiving product, wherein the temperature indicator is electrically connected to the chip of an RFID tag. DETAILED DESCRIPTION
    [0019] The present invention relates to temperature indicators which can be activated and which are constructed from a substrate and an indicator material which is supported on the substrate. The indicator material can be applied in layers or printed or otherwise adhered to the substrate. The disclosed temperature indicators provide an indication of the action of elevated temperatures, in particular an electrical indication of the action of elevated temperatures. The temperature indicators provide a record, in some cases an irreversible record, of specific temperature events that have acted on the indicator (and thus on any product to which it is attached). In some cases, a perishable female product includes a temperature indicator in accordance with the present disclosure, the temperature indicator being in conjunction with the female product to monitor the exposure of the female product to the prevailing ambient temperature.
    [0020] The substrate can be made of various materials, such as a polymer film, cardboard or fabric, or similar materials. The substrate may include a pressure sensitive adhesive to adhere the temperature indicator to a receiving product, package, or container. If so desired, the adhesive can be protected with a peelable protective film, which is removed prior to attachment.
    [0021] The indicator material is designed such that it experiences a change in conductivity in response to the action of a temperature which is above a temperature threshold value on the indicator material. In some cases, the change in conductivity occurs almost immediately or after a relatively short period of time for the temperature, which is above the temperature threshold value, to act on the indicator material. In such cases, the change in conductivity may occur after the temperature above the temperature threshold has been exposed to the indicator material for about 30 seconds or less, such as about 25 seconds or less, about 20 seconds or less, about 15 seconds Seconds or less, about 10 seconds or less, about 5 seconds or less, or about 2 seconds or less. In some cases, the change in conductivity occurs after a relatively longer period of time of exposure to the temperature, which is above the temperature threshold, on the indicator material. In such cases, the change in conductivity occurs after the temperature above the temperature threshold has been exposed to the indicator material for about 1 minute to about 48 hours, such as about 1 minute to about 2 minutes, about 2 minutes to about For 5 minutes, about 5 minutes to about 10 minutes, about 10 minutes to about 30 minutes, about 30 minutes to about 1 hour, about 1 hour to about 90 minutes, about 1 hour to about 2 hours, about For 2 hours to about 5 hours, about 5 hours to about 10 hours, about 10 hours to about 24 hours, about 24 hours to about 36 hours, or about 24 hours to about 48 hours.
    [0022] In response to the action of the temperature, which is above the temperature threshold, the indicator material can have a change in conductivity starting from a first conductivity before the action of the temperature, which is above the temperature threshold, to a second conductivity after the action Temperature that is above the temperature threshold. In some cases the first conductivity is higher than the second conductivity. In some cases the second conductivity is higher than the first conductivity.
    [0023] The change in the conductivity of the indicator material can be a change starting from a conductive state to an insulating state, or a change starting from an insulating state to a conductive state. In some cases, the indicator material may be conductive prior to exposure to the temperature above the temperature threshold, after which it is insulating after exposure to the temperature above the temperature threshold. In some cases, the indicator material may be insulating prior to exposure to the temperature above the temperature threshold, whereupon it is conductive after exposure to the temperature above the temperature threshold. Whether a material is conductive or insulating can be determined by determining the sheet resistance of the material. Typically, the sheet resistance of a suitable conductive material will be about 100 ohms / square or less, such as about 70 ohms / square or less, about 50 ohms / square or less, about 30 ohms / square or less, about 20 ohms / square or less , or about 10 ohms / square or less. Typically, the sheet resistance of an insulating material will be about 100,000 ohms / square or more, such as about
    [0024] This change in conductivity can be irreversible or reversible. In the event of an irreversible change in conductivity, the change in conductivity remains when the temperature, which is above the temperature threshold, no longer acts on the indicator material.
    [0025] The indicator material includes conductive particles. In some cases, the indicator material is in a first layer and a crystalline polymer with side chains is in a second layer, with the first layer sandwiched between the substrate and the second layer.
    [0026] In some cases, the indicator material includes a crystalline side chain polymer (SCC) and conductive particles. In some cases, the side chain crystalline polymer and conductive particles coexist in a single layer in the form of a mixture that may be uniform. In some cases, the conductive particles are dispersed or dissolved in the crystalline polymer with side chains, or they are partially or completely encapsulated by the crystalline polymer with side chains. The conductive particles can be distributed in the crystalline polymer with side chains in a substantially homogeneous or innomogeneous manner. In some cases the indicator material will be in the form of a single-layer thin film which is supported on the substrate. In some cases, the thin film is less than about 5 mils in thickness (one mil of an inch being 0.001 inches, 25.4 micrometers), such as about 1 mil to about 4 mils inches, about 2 mils to about 3 mils, or about 3 mils. 1A shows an embodiment of a temperature indicator 10 in a schematic view. The indicator 10 includes a substrate 12. The substrate serves as a carrier for a layer which contains a mixture of conductive particles 14 and a crystalline polymer 16 with side chains.
    [0027] 1B shows another embodiment of a temperature indicator 20 in a schematic view. The indicator 20 contains a substrate 12. The substrate serves as a carrier for a layer which contains conductive particles 14 and a matrix material 18. Suitable matrix materials include binders, surfactants, coating additives, and solvents, among others. The temperature indicator 20 further includes a layer that contains a crystalline polymer with side chains 16. As in Fig.
    [0028] The crystalline polymer with side chains and the conductive particles can be present in the indicator material in various weight ratios. In some cases the weight ratio of crystalline polymer with side chains to conductive particles in the indicator material is about 50:50 to about 20:80, about 45:55 to about 20:80, about 40:60 to about 20:80, about 35: 65 to about 20:80, about 30:70 to about 20:80, about 25:75 to about 20:80, about 40:60 to about 25:75, about 35:65 to about 25:75, about 30: 70 to about 25:75, about 40:60 to about 30:70, about 35:65 to about 30:70, about 30:70, about 35:65, about 40:60, about 45:55, or about 50: 50. In some cases the weight ratio of crystalline polymer with side chains to conductive particles in the indicator material is about 1: 1.2 to about 1: 4, such as about 1: 1.3 to about 1: 3, about 1: 1.3 to about 1: 2.5, about 1: 1.4 to about 1: 2.4, about 1: 1.5 to about 1: 2.3, about 1: 1.6 to about 1: 2.4, about 1: 1.7 to about 1: 2.5, about 1: 1.8 to about 1: 2.6, about 1: 1.9 to about 1: 2.7, about 1: 2 to about 1: 2 , 6, about 1: 2.1 to about 1: 2.5, about 1: 2.2 to about 1: 2.4, or about 1: 2.3
    [0029] Advantageously, the crystalline polymer with side chains can provide a relatively abrupt transition from the solid state to the liquid state. An abrupt transition can be useful in relating the properties of the temperature response of the polymer to those of the recipient product in such a way as to facilitate the monitoring of the temperature effect on the recipient product. The melting range of the crystalline polymer with side chains generally indicates how abrupt the transition from the solid state to the liquid state occurs. In some cases, a relatively narrow melting range may be useful, for example a melting range of about 10 ° C, about 5 ° C, about 2 ° C, about 1 ° C, or about 0.5 °. The side chain crystalline polymers can also have a relatively low melting temperature, such as from about 55 ° C to about 65 ° C, about 45 ° C to about 55 ° C, about 35 ° C to about 45 ° C, about 25 ° C to about 35 ° C, about 65 ° C or less, about 60 ° C or less, about 55 ° C or less, about 50 ° C or less, about 45 ° C or less, about 40 ° C or less, about 35 ° C or less, about 30 ° C or less, or about 25 ° C or less.
    [0030] Without wanting to explain this theory to be binding, it is assumed that the crystalline polymer with side chains, after a temperature threshold has acted on it for a sufficiently long period of time, melts and in this way separates the conductive particles from one another or rearranges them in such a way that the indicator material experiences a change in conductivity.
    [0031] In the present document, the terms "melting temperature" or "melting point" are used in such a way that they refer to the temperature at which a material per degree Celsius shows the highest heat absorption per unit when the determination is made by means of dynamic differential calorimetry. Above its melting temperature the material can exhibit liquid properties and below its melting temperature the material can exhibit solid properties.
    [0032] In the present document, the term "melting temperature range" is used in such a way that it refers to the temperature range from the temperature at which the melting process begins to the melting temperature of a material.
    [0033] In the present document, the term "temperature of onset of melting" is used to refer to the temperature at which the fusible material begins to show an increase in unit-related heat absorption per degree Celsius when determined by means of dynamic Differential calorimetry takes place. The material may be solid below its melting point temperature.
    [0034] The crystalline polymer with side chains may have a melting temperature which approaches the temperature threshold of the temperature indicator. For example, the temperature threshold can be about 55 ° C to about 65 ° C, about 45 ° C to about 55 ° C, about 35 ° C to about 45 ° C, about 25 ° C to about 35 ° C, about 65 ° C, or less, about 60 ° C or less, about 55 ° C or less, about 50 ° C or less, about 45 ° C or less, about 40 ° C or less, about 35 ° C or less, about 30 ° C or less , or about 25 ° C or less.
    [0035] Suitable crystalline polymers with side chains include polymers and copolymers of methacrylates and acrylates that have straight chain aliphatic side chains that are capable of becoming crystalline at a temperature of interest, for example at a temperature in the range of about 25 ° C up to about 65 ° C. The side chains can have at least 10 carbon atoms, for example from about 10 to about 30 carbon atoms, such as about 10 to 30 carbon atoms, 10 to 24 carbon atoms, 10 to 22 carbon atoms, 10 to 20 carbon atoms, 12 to 18 carbon atoms, 14 to 16 carbon atoms, 14 up to 18 carbon atoms, 16 to 18 carbon atoms, 12 to 16 carbon atoms or 14 to 16 carbon atoms. Some examples of such polymers include poly (alkyl methacrylates) such as poly (hexadecyl methacrylate) or poly (octadecyl methacrylate), poly (alkyl acrylates) such as poly (tetradecyl acrylate), poly (hexadecyl acrylate), or poly (dodecyl acrylate), copolymers such as a copolymer from
    [0036] The properties of the crystalline polymer with side chains can be adjusted by introducing cross-links into the polymer structure by adding one or more cross-linking agents in the polymerization process. For example, a bifunctional acrylic or methacrylic ester, or other suitable compound, such as a hexanediol dicrylate, can be added in the polymerization process in such a way that they serve as a crosslinking agent and result in a crosslinked polymer product. For example, the crystalline polymer can be cross-linked with side chains in order to improve the maintenance of the changed conductivity, i.e. to extend the period of time over which a temperature below the temperature threshold can act on the indicator material before the changed conductivity ceases to exist. In some cases, a relatively low density of crosslinks, for example from about 0.01 to about 0.09 intermolecular crosslinks per polymer chain, or weight average molecular weight, can be used.
    [0037] In the present document, the term "molecular weight" is used in such a way that it relates to a weight average molecular weight, unless it is a number average molecular weight resulting from the context. The side chain crystalline polymers can have a molecular weight of at least about 1,000 Da, such as at least about 1,500 Da, at least about 2,000 Da, or at least about 5,000 Da. In some cases, the side chain crystalline polymer has a molecular weight in the range of about 2,000 Da to about 300,000 Da, such as about 3,000 Da to about 300,000 Da, about 5,000 Da to about 250,000 Da, about 10,000 Da to about
    [0038] In general, a crystalline polymer with side chains of higher molecular weight can have a higher viscosity when it is in the liquid state at a temperature near its melting point than the corresponding crystalline polymer with side chains of lower molecular weight. Thus, the property characteristics of the crystalline polymer with side chains can be further adjusted by varying the molecular weight of the crystalline polymer with side chains.
    [0039] The conductive particles can include any suitable conductive material. In some cases, the conductive particles can include copper, silver, gold, aluminum, or a mixture or combination of one or more of the foregoing. The conductive particles can have various sizes and shapes. In some cases, the conductive particles have an average particle size, which can be a volume equivalent sphere diameter, of about 500 nm to about 1000 µm, such as about 500 nm to about 100 µm, about 500 nm to about 50 µm, about 500 nm to about 10 µm, about 500 nm to about 5 µm, about 500 nm to about 1 µm, about 1 µm to about 2 µm, about 2 µm to about 3 µm, about 3 µm to about 4 µm, about 4 µm to about 5 µm, about 1 µm to about 1000 µm, about 10 µm to about 500 µm, about 20 µm to about 200 µm, about 25 µm to about 100 µm, about 30 µm to about 50 µm, or about 40 µm. In some cases, the conductive particles have a spherical shape. In some cases, the conductive particles are in the form of flakes, which may further be characterized by an aspect ratio of flake thickness to flake diameter, for example about 1:50 to about 1: 1000, about 1:50 to about 1: 500 or about 1 : 100: to about 1: 250.
    [0040] The properties of the indicator material can be adjusted by adding a binder and / or one or more further additives. Suitable binders include, but are not limited to, starches, celluloses, natural and synthetic gelatins, methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, polymethacrylate, polyurethane, epoxy resins, copolymers of vinyl acrylate and vinyl methacrylate, and vinyl acrylate, aqueous emulsion Polystyrene. The useful additives also include, inter alia, rheology modifiers, surfactants, wetting agents or lubricants.
    [0041] In accordance with the present invention, methods of manufacturing a temperature indicator are also disclosed. The methods include melting a crystalline polymer having side chains as described herein, adding conductive particles as described herein to form a mixture, and applying the mixture to a substrate as described herein.
    [0042] Furthermore, switchable RFID labels are disclosed which comprise an indicator material according to the present description. In some cases, a switchable RFID tag includes an antenna and a switch that is electrically connected to the antenna. In some cases, a switchable RFID tag includes a chip and a switch that is electrically connected to the chip. In some cases, the switch includes an indicator material, the indicator material including a mixture of a crystalline polymer with side chains and conductive particles as described herein. In some cases, the switch includes an indicator material and a crystalline polymer with side chains, the indicator material including conductive particles. In some cases, the switchable RFID tag also includes an integrated circuit that is electrically connected to the antenna.
    [0043] 3A shows an embodiment of a perishable ingestive product 30 in conjunction with a temperature indicator 24 to monitor the effect of the respective room temperature on the ingestive product. In one embodiment, the perishable absorbent product is a vaccine contained in a sample vial. The temperature indicator 24 can be electrically connected to an antenna 22 of an RFID tag, which can furthermore contain a chip.
    [0044] 3B shows an embodiment of a perishable female product 30 in connection with a temperature indicator 24 in order to monitor the effect of the respective prevailing ambient temperature on the female product. In one embodiment, the perishable ingestive product is a vaccine contained in a sample vial. The temperature indicator 24 can be electrically connected to a chip 26 of an RFID tag, which can furthermore contain an antenna 22.
    [0045] Ink formulations with various ratios of crystalline polymer with side chains (SCC) to conductive Cu / Ag particles (40 µm particle size) were prepared and the physical properties of the formulations were investigated. The SCC polymer contains an acrylate polymer main chain with C14 and C16 side chain groups, which has a molecular weight of 5,000 to 7,000 Da. The formulations were prepared by melting the SCC polymer, adding the conductive particles, and mixing to obtain a mixture of the SCC polymer and conductive particles. Formulations with weight ratios of the SCC polymer to conductive particles of 30:70, 40:60 and 50:50 were prepared. The melting onset temperature, the melting peak temperature and the Bingham viscosity in cps at 25 ° C were measured and the values are shown in Table 1.
    [0046] The Bingham viscosity of the formulations was also measured at various temperatures, and the results are shown in FIG. The results show that the viscosity decreases with increasing temperature. The results also show that formulation 1 (30:70 SCC polymer: conductive particles) has a higher viscosity over a temperature range than formulation 2 (40:60 SCC polymer: conductive particles), which in turn has a higher viscosity than the Formulation 3 (50:50 SCC polymer: conductive particles). Example 2
    [0047] The formulations according to Example 1 were applied in layers to substrates made of polyethylene terephthalate (PET) using a thin-film applicator of the Gardco bird type at 35 ° C. and at 50 ° C. The wet film thickness of the applied thin layer was approximately 3 mils. The thin films were allowed to solidify at room temperature (an ambient temperature of -20 ° C). The sheet resistance of the applied thin layers was measured at room temperature. The samples were then placed on a warm plate at different temperatures. The films were then removed from the warm plate and allowed to cool and resolidify for approximately 15 minutes. Afterwards, measurements of the surface resistance were carried out in order to investigate the influence of temperature on the conductivity of the SCC polymer. The values of the surface resistance are listed in Table 2. Table 2 sample | Formulation | Original terms | Resistance No. Sheet Resistance | increased after the (ohm / square) temperature | Effect of the increased temperature and the subsequent resolidification (ohms / square) 1A formulation | 8.3 5 min. At> 1,000,000 1: 40 ° C 30:70 SCC-
    [0048] The results show that the resistance of the thin layer which comprises the formulation 1 increases significantly after heating, so that the originally conductive thin layer becomes practically non-conductive after heating. After the heated samples were allowed to cool to room temperature for 48 hours, the respective resistances of Samples 1A, 1B and 1C were measured to find that they had returned to their original values as they were before the heating. The results also show that the resistance of the thin layer comprising formulation 2 increases significantly after heating to 40 ° C., so that the originally conductive thin layer becomes practically non-conductive after heating. When the originally conductive thin film containing Formulation 2 was heated to 35 ° C, 30 ° or 25 °, the resistance of the thin film also increased, but to a lesser extent, namely by about 50 times, by about 20 times or around 2 times. After the heated samples were allowed to cool to room temperature for 48 hours, the respective resistances of Samples 2A, 2B, 2C and 2D were measured to find that they had returned to their original values as they were before the heating. The results also show that the resistance of the thin film comprising Formulation 3, which was originally non-conductive, remains essentially non-conductive after heating. Example 3
    [0049] An irreversible temperature indicator is made by melting the SCC polymer, conductive particles such as Cu / Ag particles (particle size 40 µm) and a binder such as epoxy (for solvent-based systems) or water-reducible epoxy (for water-based systems ) and mixing takes place to form a mixture of SCC polymer, conductive particles and binder. Formulations are produced with weight ratios of SCC polymer to conductive particles which are, for example, 30:70, 40:60 and 50:50.
    [0050] Furthermore, an irreversible temperature indicator is produced by melting a cross-linked SCC polymer, adding conductive particles such as Cu / Ag particles (particle size 40 µm) and mixing it to form a mixture of cross-linked SCC polymer and conductive Particles to form. Formulations are produced with weight ratios of crosslinked SCC polymer to conductive particles which are, for example, 30:70, 40:60 and 50:50.
    [0051] Furthermore, an irreversible temperature indicator is produced by using an SCC polymer with a molecular weight of at least approximately
    [0052] The formulations are applied in layers at 35 ° C and 50 ° C using a thin film applicator of the Gardco bird type. The wet film thickness of the applied thin layer is approximately 3 mils. Inches. The thin layers are allowed to solidify at room temperature (-20 ° C). The sheet resistance of the applied thin layers is measured at room temperature, it being found that the thin layers are conductive. The samples are then placed on a warm plate at different temperatures. The films are then removed from the warm plate, whereupon they are allowed to cool and resolidify. Afterwards, measurements of the surface resistance are carried out in order to investigate the influence of temperature on the conductivity of the thin films.
    [0053] The sheet resistance values show that the resistance of the thin layers increases significantly after heating, so that the originally conductive thin layers become practically non-conductive after heating. After allowing the heated samples to cool to room temperature for 48 hours, the resistance is measured and it is determined that it remains non-conductive.
    [0054] An irreversible temperature indicator is produced by forming a base layer which contains about 90% by weight of conductive particles (flake-like) such as Cu / Ag particles (particle size 40 µm) and about 10% by weight of binder such as such as epoxy binders. A topcoat is then added containing about 25% by weight of conductive particles (spherical / spherical shape), about 75% by weight of a mixture of an SCC polymer and an alkane such as heneicosane (a C21 alkane). The surface resistance of the indicator is measured before melting and it is found to be> 1,000,000 ohms / square (i.e. the indicator is practically non-conductive). The indicator is then heated and it is found that the sheet resistance is <100 ohms / square (i.e. the originally non-conductive indicator becomes conductive after heating).
    [0055] These and other embodiments are expressly incorporated by the author of the present disclosure.
    [0056] Unless otherwise stated, all numerical values, the amounts of ingredients, properties such as the molecular weight, reaction conditions and so on, as used in the description and the claims, are to be interpreted in such a way that they are always accompanied by the term "approximately" are modified. Unless otherwise stated, the numerical characteristics as given in the present description and the appended claims are approximate values that depend on which of the desired properties are to be achieved by the embodiments of the present disclosure , can vary. Without this constituting an attempt to limit the application of the teaching of the equivalent equivalents to the scope of protection of the claims, each of the numerical parameters should furthermore at least be interpreted in such a way that the number of specified significant digits is taken into account and common rounding procedures are used become. Regardless of the fact that the numerical value ranges and characteristic values which define the broad scope of protection of the present disclosure are approximate values, the numerical values which are specified in the specific
    [0057] The terms "a", "an", "the" and similar reference words, when used in connection with the description of embodiments of the present disclosure (in particular in connection with the following claims), are such to be understood that they cover both the singular and the plural, unless otherwise stated in the present document or the context clearly speaks against it. In the present case, the specification of value ranges is only used as an abbreviated method for naming each value that falls within this range individually and separately. Unless otherwise stated in the present document, each individual value is part of the explanations as if it were mentioned individually here. All of the methods described here can be carried out in any order, unless otherwise stated in the present document or this is otherwise clearly prohibited in the context of the context. The use of any or all examples, or exemplary expressions (eg, "such as") in this document is only used to better explain the embodiments of the present disclosure and is not intended to limit the scope of the present disclosure. The language in the description is in no way should it be construed as indicating a non-claimed element which would be indispensable for implementing the embodiments of the present disclosure.
    [0058] Groupings of optionally used elements or embodiments according to the present disclosure are not intended as
    [0059] [0059] Certain embodiments of the invention are described herein, including the best mode known to the inventor of practicing the embodiments of the present disclosure. It is understood that variants of these described embodiments will be apparent to those of ordinary skill in the art upon reading the above description. The inventor expects those skilled in the art to make appropriate use of such variations, and it is the inventor's intention that the embodiments of the present disclosure be implemented in a manner other than that specifically described herein. Accordingly, the present disclosure includes all modifications and equivalent implementations of the subject matter, as it is mentioned in the appended claims, insofar as this is permissible under applicable law. In addition, the present disclosure covers any combination of the elements described above in all possible variants thereof, unless otherwise stated in the present document or the context otherwise clearly speaks against it.
    [0060] Specific embodiments of the invention disclosed herein may be further restricted in the claims by using the terms consisting of or consisting essentially of. When the transitional term "consisting of" in the
    [0061] To the extent that patents and printed publications are referred to in the course of the present disclosure, each of these literature references and printed publications is also incorporated into the present document individually and in its entirety by reference.
    [0062] Finally, it should be understood that the presently disclosed embodiments are illustrative of the principles of the present invention. Other modifications that may be used are within the scope of the present disclosure. Thus, by way of example, but not by way of limitation, alternative configurations of the embodiments of the present invention may be employed in accordance with the present teachings. Accordingly, the present disclosure is not limited to exactly what is shown and described.
    权利要求:
    Claims (1)
    [1]
    EXPECTATIONS
    A temperature activatable temperature indicator comprising: a substrate; and an indicator material which is carried on the substrate, wherein the indicator material comprises a mixture of a crystalline polymer with side chains and conductive particles.
    2. A temperature activatable temperature indicator comprising: a substrate; an indicator material carried on the substrate, the indicator material comprising conductive particles; and a crystalline polymer with side chains; wherein the indicator material is in a first layer and the crystalline polymer with side chains is in a second layer, the first layer being disposed between the substrate and the second layer.
    3. Temperature indicator according to claim 1 or 2, wherein the indicator material experiences a change in conductivity in response to the action of a temperature which is above a temperature threshold value.
    4. Temperature indicator according to claim 3, wherein the indicator material retains the changed conductivity after a subsequent exposure to a temperature which is below the temperature threshold value.
    5. Temperature indicator according to claim 3, wherein the indicator material does not retain the changed conductivity after a subsequent exposure to a temperature which is below the temperature threshold value.
    6. The temperature indicator according to any one of claims 3 to 5, wherein the indicator material has a first conductivity prior to exposure to the temperature which is above the temperature threshold value, and after exposure to the temperature which is above the temperature threshold value,
    has a second conductivity, the first conductivity being higher than the second conductivity.
    7. A temperature indicator according to any one of claims 3 to 5, wherein the indicator material has a first conductivity prior to exposure to the temperature above the temperature threshold and a second conductivity after exposure to the temperature above the temperature threshold, wherein the second conductivity is higher than the first conductivity.
    8. The temperature indicator of any one of claims 3 to 5, wherein the indicator material is conductive prior to exposure to the temperature above the temperature threshold and is insulating after exposure to the temperature above the temperature threshold.
    9. The temperature indicator of any one of claims 3 to 5, wherein the indicator material is insulating prior to exposure to the temperature above the temperature threshold and is conductive after exposure to the temperature above the temperature threshold.
    10. The temperature indicator of any one of claims 3 to 9, wherein the change in conductivity occurs after the temperature above the temperature threshold has been applied for about 30 seconds or less, such as about 20 seconds or less, about 15 seconds long or less, about 10 seconds or less, about 5 seconds or less, or about 2 seconds or less.
    11. The temperature indicator of any one of claims 3 to 9, wherein the change in conductivity occurs after the temperature above the temperature threshold has been applied for about 1 minute to about 48 hours, such as about 1 minute to about 2 minutes , about 2 minutes to about 5 minutes, about 5 minutes to about 10 minutes, about 10 minutes to about 30
    For about 30 minutes to about 1 hour, about 1 hour to about 2 hours, about 2 hours to about 5 hours, about 5 hours to about 10 hours, about 10 hours to about 24 hours, about 24 minutes Hours to about 36 hours, or about 24 hours to about 48 hours.
    12. A temperature indicator according to any one of the preceding claims, wherein the crystalline polymer with side chains has a molecular weight of at least about 1,000 Da.
    13. The temperature indicator of any one of the preceding claims, wherein the crystalline polymer with side chains has a molecular weight in the range of about 2,000 Da to about 300,000 Da, such as about 3,000 Da to about 300,000 Da, about 5,000 Da to about 250,000 Da, about 10,000 Da to about 200,000 Da, about 15,000 Da to about
    150,000 Da, about 20,000 Da to about 120,000 Da, about 30,000 Da to about 100,000 Da, about 50,000 Da to about 80,000 Da, about 2,000 Da to about 20,000 Da, about 3,000 Da to about
    15,000 Da, about 4,000 Da to about 10,000 Da, about 4,000 Da to about 5,000 Da, about 5,000 Da to about 6,000 Da, about 6,000 Da to about 7,000 Da, about 7,000 Da to about 8,000 Da, about
    8,000 Da to about 9,000 Da, about 9,000 Da to about 10,000 Da, about 2,000 Da to about 10,000 Da, about 10,000 Da to about
    20,000 Da, about 20,000 Da to about 30,000 Da, about 30,000 Da to about 50,000 Da, about 50,000 Da to about 100,000 Da, about 100,000 Da to about 150,000 Da, about 150,000 Da to about 200,000 Da, about 200,000 Da to about 250,000 Da , or about 250,000 Da to about 300,000 Da.
    14. Temperature indicator according to any one of the preceding claims, wherein the crystalline polymer with side chains comprises a methacrylate polymer, a methacrylate copolymer, an acrylate polymer or an acrylate copolymer of a monomer unit which has a crystallizable linear aliphatic side chain with at least 10 carbon atoms, such as with 10 to 30
    Carbon atoms, 10 to 24 carbon atoms, 10 to 22 carbon atoms, 10 to 20 carbon atoms, 12 to 18 carbon atoms, 14 to 16 carbon atoms, 14 to 18 carbon atoms, 16 to 18 carbon atoms, 12 to 16 carbon atoms, or 14 to 16 carbon atoms.
    15. A temperature indicator according to any one of the preceding claims, wherein the crystalline polymer with side chains is selected from the group consisting of the following: a poly (alkyl methacrylate), a poly (tetradecyl acrylate), a poly (hexadecyl methacrylate), a poly (octadecyl methacrylate) , a poly (alkyl acrylate), a poly (hexadecyl acrylate), poly (dodecyl acrylate), a copolymer of hexadecyl acrylate and octadecyl methacrylate, a poly (hexyl-cododecyl acrylate), a copolymer of tetradecyl acrylate and octadecyl acrylate, a copolymer of hexadecyl acrylate and octadecyl methacrylate and octadecyl methacrylate Copolymer of tetradecyl acrylate and hexadecyl acrylate.
    16. The temperature indicator of any one of the preceding claims, wherein the conductive particles comprise copper, silver, gold, aluminum, or combinations thereof.
    17. A temperature indicator according to any one of claims 1 or 3 to 16, wherein the weight ratio of the crystalline polymer with side chains to the conductive particles in the indicator material is about 1: 1.2 to about 1: 4, such as about 1: 1.3 to about 1: 3, about 1: 1.3 to about 1: 2.5, about 1: 1.4 to about 1: 2.4, about 1: 1.5 to about 1: 2.3, about 1: 1.6 to about 1: 2.4, about 1: 1.7 to about 1: 2.5, about 1: 1.8 to about 1: 2.6, about 1: 1.9 to about 1: 2 , 7, about 1: 2 to about 1: 2.6, about 1: 2.1 to about 1: 2.5, about 1: 2.2 to about 1: 2.4, or about 1: 2.3 .
    18. The temperature indicator of any one of the preceding claims, wherein the conductive particles have an average particle size of about 500 nm to about 1000 µm, such as about 500 nm to about 100 µm, about 500 nm to about 50 µm, about 500 nm to about 10 µm ,
    about 500 nm to about 5 µm, about 500 nm to about 1 µm, about 1 µm to about 2 µm, about 2 µm to about 3 µm, about 3 µm to about 4 µm, about 4 µm to about 5 µm, about 1 µm µm to about 1000 µm, about 10 µm to about 500 µm, about 20 µm to about 200 µm, about 25 µm to about 100 µm, about 30 µm to about 50 µm, or about 40 µm.
    19. A temperature indicator according to any one of the preceding claims, wherein the conductive particles are spherical in shape.
    20. A temperature indicator according to any one of claims 1 to 18, wherein the conductive particles are in the form of flakes.
    21. A temperature indicator according to any one of the preceding claims, wherein the indicator material further comprises a binder.
    22. A temperature indicator according to any one of the preceding claims, wherein the crystalline polymer is cross-linked with side chains.
    23. Temperature indicator according to any one of the preceding claims, wherein the indicator material is present as a single-layer thin layer.
    24. The temperature indicator of claim 23, wherein the thin layer has a thickness of less than about 5 mils, such as about 1 mil to about 4 mils, about 2 mils to about 3 mils. Inches or about 3 mils.
    25. Perishable ingestive product which includes the temperature indicator according to any one of the preceding claims, wherein the temperature indicator is in connection with the absorbent product to monitor the effect of the respective prevailing ambient temperature on the absorbent product.
    26. A method of making a temperature indicator comprising: melting a crystalline polymer having side chains, adding conductive particles to form a mixture, and applying the mixture to a substrate.
    27. A switchable RFID tag comprising: an antenna and a switch electrically connected to the antenna, the switch comprising an indicator material, the indicator material comprising a mixture of a crystalline polymer with side chains and conductive particles.
    28. The switchable RFID tag of claim 27, further comprising an integrated circuit electrically connected to the antenna.
    29. A switchable RFID tag comprising: a chip and a switch electrically connected to the chip, the switch comprising an indicator material, the indicator material comprising a mixture of a crystalline polymer with side chains and conductive particles.
    30. The switchable RFID tag of claim 29, further comprising an antenna and an integrated circuit electrically connected to the antenna.
    31. A switchable RFID tag comprising: an antenna and a switch electrically connected to the antenna, the switch comprising an indicator material and a crystalline polymer having side chains, the indicator material comprising conductive particles.
    32. The switchable RFID tag of claim 31, further comprising an integrated circuit electrically connected to the antenna.
    33. A switchable RFID tag comprising: a chip and a switch electrically connected to the chip, the switch comprising an indicator material and a crystalline polymer with side chains, the indicator material comprising conductive particles.
    34. The switchable RFID tag of claim 33, further comprising an antenna and an integrated circuit electrically connected to the antenna.
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    同族专利:
    公开号 | 公开日
    BE1027234A1|2020-11-20|
    CN114026399A|2022-02-08|
    GB2597184A|2022-01-19|
    DE112020002393T5|2022-02-17|
    WO2020231921A1|2020-11-19|
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    法律状态:
    2021-08-18| FG| Patent granted|Effective date: 20210726 |
    优先权:
    申请号 | 申请日 | 专利标题
    US201962847018P| true| 2019-05-13|2019-05-13|
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