JP2008185446A - Temperature history management device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a temperature history management device which can be directly attached to an object to be inspected along the shape thereof, has a built-in power source which is reusable by the charging, and can be used under the environment of sub-zero temperature. <P>SOLUTION: This temperature history management device has at least a temperature sensor 13 and the power source. An inorganic radical battery is built in the temperature history management device as the power source. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a temperature history management device for storing and managing a temperature history during transportation or storage of food, beverages, fresh flowers, blood products, medicines, precision instruments and the like.

  In recent years, temperature histories of logistics products such as food, beverages, medicines, and precision instruments are stored, and temperature management during transportation or storage has been performed. Patent Documents 1 and 2 disclose an apparatus that manages such a temperature history during physical distribution. In addition, it is also required to grasp the temperature change when an object to be detected is placed in a place where temperature management is not thorough such as outdoors due to loading from a warehouse to a transport truck.

  In particular, in recent years, construction of product management systems using RFID (Radio Frequency Identification) tags has progressed. For example, in the distribution field of fresh food such as meat and seafood, RFID tags are attached to food or packaging, the temperature of the container in which the fresh food is transported is measured and stored in the RFID tag, and the fresh food is stored based on the stored results. It is proposed to manage. Patent Document 3 discloses a reader / writer (read / write) device that includes a temperature sensor and writes temperature information measured by the temperature sensor to an RFID tag.

An RFID tag has a basic structure including an exterior body, an IC module and an antenna incorporated in the exterior body, and some have an internal power supply (see, for example, Patent Document 4). As described above, an RFID tag with a built-in power supply has an advantage that information transmission (several tens of meters) can be performed over a long distance compared to an RFIC tag without a built-in power supply. As such a power source, a thin lithium coin battery that is a primary battery, a lithium ion secondary battery that is a rechargeable battery (secondary battery), a nickel-hydrogen secondary battery, a lead storage battery, and the like have been considered.
JP 2004-108703 A Utility Model Registration No. 3069949 JP 2006-23963 A JP 2002-304996 A Japanese Patent No. 3687736 JP 2002-304996 A

  When accurate temperature management is performed on a distribution product, it is assumed that a temperature history management device is directly attached to each distribution product. In this case, it is conceivable to incorporate a power supply in the temperature history management device in terms of recovery of the device and remounting to another physical distribution product. However, the above-described thin lithium coin battery, lithium ion secondary battery, nickel metal hydride secondary battery, etc. require a thickness of 1 mm or more and cannot be bent firmly. Therefore, the temperature history management device incorporating these batteries has a limit in thinning, and even if it is thinned, it cannot be bent. Therefore, when these batteries are built in, it is difficult to directly attach the temperature history management device to a logistics product having a curved surface such as irregularities. In that case, the temperature history management device must be attached to the transport container or storage container, or the temperature history of the container and the entire warehouse must be measured, and the temperature history of the logistics product cannot be measured accurately. In addition, when the exterior of the apparatus is molded in conformity with the surface shape for direct attachment to a physical distribution product or its container, the outer shape of the apparatus is uneven, making it difficult to organize or hold.

  In addition, when a primary battery is used as a power source of the temperature history management device, it cannot be charged and reused, and therefore it must be disposable or replaced.

  Further, the batteries listed above have poor low temperature characteristics. For example, the current required for driving cannot be obtained in a minus temperature environment. Therefore, in the case of refrigerated or frozen logistics products such as foods, beverages, fresh flowers, blood products, medicines, and precision instruments that require temperature control, it has been difficult to use the battery in the temperature history management device.

  If it is assumed that an RFID tag is used for the temperature history management device itself, not only when power is supplied by electromagnetic waves from the reader / writer device, but also the temperature of the item that the RFID tag itself changes with time must be measured. I must. Therefore, an RFID tag used for the temperature history management device further requires a temperature sensor and a power source. Further, when it is desired to output the measured temperature history information to an external device far away, an RFID tag with a built-in power supply is required. However, the above-described battery considered as a power source for RFID tags has the problems described so far. Therefore, the conventional RFID tag with a built-in battery cannot be used for a temperature history management device that is directly attached to a logistics product having various shapes.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a temperature history management device that can be directly attached to an object to be detected because it is thin and soft and incorporates a power source that can be reused by charging and that can be used even in a minus temperature environment.

  A temperature history management apparatus according to the present invention is a temperature history management apparatus having at least a temperature sensor and a power source, which is attached to an object to be detected for temperature history and is used even in a minus temperature environment, wherein the power source is an organic radical. A battery is used.

  The temperature history management device of the present invention is characterized in that the thickness is 1 mm or less.

  The organic radical battery used in the present invention is a battery using an oxidation-reduction reaction of an organic radical compound that is an active material. Patent Document 5 discloses an organic radical battery using a radical compound such as a nitroxide radical compound, an aryloxy radical compound, and a polymer compound having a specific aminotriazine structure as a positive electrode material. In a battery using an oxidation-reduction reaction of an organic radical compound described in Patent Document 6, a positive electrode in which a nitroxyl polymer and carbon (conducting agent) are mixed is used.

  By using such an organic radical battery, it is possible to provide a power supply for a temperature history management device that can be thinned to 0.4 mm or less, can be bent, and can be recharged. Organic radical batteries can also be used in negative temperature environments, and are optimal power sources for measuring and managing temperature history.

  According to the present invention, it is possible to provide a temperature history management device that can be used even in a minus temperature environment and that is directly attached to a physical distribution product to detect temperature. The temperature history management device can be used repeatedly because the power source is a secondary battery.

  Next, a preferred embodiment of the present invention will be described with reference to the drawings.

[1] Temperature history management device (RFID tag)
FIG. 1A is a plan view of the temperature history management device of the present embodiment. 1B is a cross-sectional view taken along line AB in FIG. 1A, and FIG. 1C is a cross-sectional view taken along line CD in FIG. 1A. FIG. 1D is a cross-sectional view taken along line EF in FIG. 1A.

  The temperature history management device of the present embodiment includes an organic radical battery 1, an IC module 2 driven by this, a temperature sensor 13, temperature information output means 14, and an RFID tag including an antenna 3. In FIG. 1A, a display device is shown as the temperature information output means 14.

  This RFID tag has a structure in which an overlay 9a, a core sheet 8a, a core sheet 8b, and an overlay 9b are stacked in this order and bonded together.

  The overlay 9b as the uppermost layer is a transparent plastic film having a thickness of about 0.1 mm made of a resin such as PVC, ABS, or PET-G. The charging terminal 7 for the organic radical battery 1 is exposed on the overlay 9b.

  The core sheet 8b, which is the lower layer of the overlay 9b, is a plastic sheet having a thickness of 0.25 to 0.35 mm made of a resin such as PVC, ABS, or PET-G. In the core sheet 8b, a through hole 6 for connecting the charging terminal 7 to the wiring of the organic radical battery 1 is formed.

  The core sheet 8a, which is the lower layer of the core sheet 8b, is a plastic sheet having a thickness of 0.25 to 0.35 mm made of resin such as PVC, ABS, PET-G, and the temperature sensor 13 and temperature information output. The means 14, the organic radical battery 1, the IC module 2, the antenna 3, and the like are arranged and connected to each other by a wiring 15. Thereby, the IC module 2 is driven by the organic radical battery 1 and performs temperature measurement, temperature history storage, communication, and the like using the temperature sensor 14, the temperature information output means 15 and the antenna 3. The antenna 3 is provided as a planar coil antenna connected to the IC module 2. Although the temperature sensor 13 is covered by the core sheet 8b, the temperature information output means 14 is exposed from a hole provided in the overlay 9b (FIGS. 1C and 1D).

  The overlay 9a as the lowermost layer is a transparent plastic film having a thickness of about 0.1 mm made of a resin such as PVC, ABS, or PET-G.

  2A is a cross-sectional view of the sealing layer 100 in which the organic radical battery 1 is incorporated, and FIG. 2B is a view of the sealing layer 100 as viewed from below. In the sealing layer 100, the outer peripheral portion 102 on the back surface is adhesive. The organic radical battery 1 is housed in a battery cover 101, and a tab 11 made of metal or carbon protrudes from the organic radical battery 1. The tab 11 is electrically connected to each electrode of the battery 1.

  Such a sealing layer 100 can be bonded to the core sheet 8b by the portion 102 having the adhesiveness on the outer periphery of the back surface thereof. When the sealing layer 100 is attached, the tab 11 of the battery 1 overlaps the terminal 12 of the IC module 2 as shown in FIG. 1B. Thereby, the battery 1 is electrically connected to the IC module 2. In addition, the overlay 9b and the core sheet 8b are provided with openings through which the tab 11 and the battery 1 enter when the sealing layer 100 is bonded.

The battery 1 can be replaced by removing the seal layer 100. In this case, a silicon (SiO _x ; x = 1 to 2) layer or silicon nitride having a thickness of about 30 to 200 nm is formed on the space where the battery is installed and the surface of the seal layer 100 facing the battery 1 in order to improve waterproofness. A (SiO _x N; x = 0.5 to 1.5) layer is preferably formed by vapor deposition or the like.

  In the present embodiment, the organic radical battery 1 can be replaced, but a configuration in which the battery 1 is fixed on the core sheet 8a and covered with the overlay 9b without using the seal layer 100 and the battery cover 101 is also conceivable.

  As described above, the shape of the temperature history management device including the temperature sensor and the organic radical battery is not limited to the illustrated shape, and can take various shapes. For example, various shapes such as a seal shape, a card shape, a coin shape, a sheet shape, or a bag shape or a box shape by incorporating a seal shape or a sheet shape device can be taken.

  An example of an IC module in an RFID tag applied to the temperature history management device of this embodiment will be described. FIG. 3 is a conceptual diagram of this IC module. The IC module 2 includes a memory 2a (ROM, RAM), a control microprocessor 2b, a modulator 2c, a command 2d, a clock 2e, and a front end 2f. The electric power supplied from the organic radical battery 1 to the IC module 2 is used for temperature detection by the temperature sensor 13, storage of the detected temperature data in the memory 2a, display of temperature history or data transmission.

[2] Temperature sensor As the temperature sensor 13 used in the temperature history management device of the present embodiment, a contact type thermocouple, a resistance temperature detector, a thermistor, a bimetal, a non-contact type radiation thermometer, or the like can be used. In the present invention, since the temperature history management device is directly attached to the object to be detected, it is desirable to use a contact-type temperature sensor.

[3] Means for Outputting Temperature Information As the temperature information output means 14 used in the present embodiment, means for transmitting information to a computer by wireless communication such as high-frequency wireless communication or optical communication can be considered. Alternatively, a display device such as a liquid crystal display, an organic or inorganic EL display, or an electrophoretic display may be used. Further, the temperature information may be output by a method in which the storage medium such as a memory card is taken out from the apparatus. Alternatively, the temperature information may be output by connecting the computer and the temperature history management device with a cable or printing them out.

  In particular, it is desirable to use the output by wireless communication in order to make use of the effect that the temperature history management device can be made thin.

[4] Means for issuing an alarm Further, the temperature history management device according to the present embodiment may include means for issuing an alarm when the temperature information exceeds a predetermined threshold. As this alarm means, light, sound, or the like transmitted to a computer by wireless communication can be used. In addition, when the temperature information exceeds a predetermined threshold value, the temperature setting can be changed by communicating with a temperature control device of a container or a warehouse.

[6] Organic Radical Battery Next, an organic radical battery used in the temperature history management device of this embodiment will be described. FIG. 4 is a perspective view of an organic radical battery, and FIG. 5 is an exploded perspective view showing an internal configuration of the organic radical battery.

  The organic radical battery is a thin organic radical battery having a thickness of 0.7 mm or less. The basic structure of a thin organic radical battery is a laminate in which a radical positive electrode 202 using a stable radical compound as a positive electrode active material, a separator 203 made of porous polypropylene, cellulose or the like, and a negative electrode 204 made of metallic lithium or the like are laminated in this order. is there. This laminated body is sealed with the electrolytic solution penetrating the separator 203 and sandwiched between the exterior films 201 from both sides. Further, the positive electrode 202 and the negative electrode 204 are connected to a positive electrode lead 205 and a negative electrode lead 206, respectively, and are configured such that electric power can be taken out through these leads. As the exterior film 201, an aluminum laminate film having a low water vapor permeability is used.

  Hereinafter, each component of the organic radical battery used in the present invention will be described.

(1) Radical positive electrode As a positive electrode active material in the radical positive electrode 202, a nitroxide radical represented by the following formula (1) in the reduced state and an oxoammonium (nitroxide cation) represented by the following formula (2) in the oxidized state as partial structures The nitroxide radical polymer contained therein can be used.

  When an organic radical battery is used as a primary battery, charge is transferred between a nitroxide radical group represented by the following formula (1) and an oxoammonium group represented by the following formula (2) at the time of discharging. It is considered a thing. In addition, when used as a secondary battery, during charge / discharge, charge is transferred reversibly between a nitroxide radical group represented by the following formula (1) and an oxoammonium group represented by the following formula (2). It is thought that Here, the nitroxide radical group represents a substituent in which the oxygen atom constituting the nitroxide group formed by bonding an oxygen atom and a nitrogen atom has an unpaired electron. In this nitroxide radical group, unpaired electrons (radicals) on oxygen are stabilized by the electron withdrawing property of the nitrogen atom.

  By using such a nitroxide radical polymer, a battery having a high energy density can be stably operated.

  Examples of typical structures of the nitroxide radical polymer are shown in the following formulas (3) to (7).

  These radical polymers represented by the formulas (3) to (7) are used as positive electrode active materials in the reduced state, the nitroxide radicals represented by the above formulas (3) to (7), and the oxidized state in the following formula (8). It is an oxoammonium (nitroxide cation) represented by (12). And it is thought that the charge is transferred between the nitroxide radicals of the above formulas (3) to (7) and the oxoammonium of the following formulas (8) to (12) when the battery is operated.

  In addition, the weight average molecular weight of these nitroxide radical polymers is preferably 500 or more, and more preferably 5000 or more. This is because when the weight average molecular weight is 500 or more, it becomes difficult to dissolve in the battery electrolyte, and when the molecular weight is 5000 or more, it becomes almost insoluble. The polymer of the polymer may be any of a chain, a branch, and a network. Moreover, the structure which bridge | crosslinked with the crosslinking agent may be sufficient.

  Moreover, although these nitroxide radical polymers can be used independently, you may use it in combination of 2 or more types. Moreover, you may use in combination with another active material.

  Moreover, when forming an electrode using a nitroxide radical polymer, a conductivity-imparting agent can be mixed for the purpose of reducing impedance. Examples of the material for the conductivity-imparting agent include carbonaceous fine particles such as graphite, carbon black, and acetylene black, and conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polyacene.

  In addition, a binder can be used in order to strengthen the bond between the nitroxide radical polymer and the conductivity-imparting agent. Examples of such binders include polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene / butadiene copolymer rubber, polypropylene, and polyethylene. Resin binders such as polyimide and various polyurethanes.

  The radical positive electrode 202 is formed by forming a nitroxide radical polymer as the above positive electrode active material on a positive electrode current collector. Examples of the positive electrode current collector include nickel, aluminum, copper, gold, silver, an aluminum alloy, stainless steel, and carbon. It is possible to use a foil or a flat plate made of or the like. In particular, in order to facilitate the folding of the battery, it is preferable to produce a positive electrode in which a gel-like nitroxide radical polymer is formed on a foil-like current collector material.

(2) Negative electrode As the active material in the negative electrode 204, lithium metal or a lithium alloy can be used. Examples of the lithium alloy include a LiAl alloy, a LiAg alloy, a LiPb alloy, a LiSi alloy, a Li—Bi—Pb—Sn—Cd alloy, and a Li—Ga—In alloy. These shapes are not particularly limited, and may be, for example, a thin film, a powdered product, a fiber, or a flake. These negative electrode active materials can be used alone or in combination.

  The negative electrode 204 is formed by forming the above active material on a current collector. As the current collector, the same material as that of the current collector constituting the positive electrode can be used. Of course, the active material and the current collector are selected as materials and thicknesses that facilitate battery folding.

  In addition, a binder can be used to strengthen the connection between the constituent materials of the negative electrode 204. Examples of such binders include polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene / butadiene copolymer rubber, polypropylene, and polyethylene. , Polyimide, partially carboxylated cellulose, various polyurethanes and the like.

(3) Separator A separator 203 such as a porous film made of polyethylene, polypropylene, or the like, a cellulose film, or a nonwoven fabric can be used so that the radical positive electrode 202 and the negative electrode 204 do not come into contact with each other.

(4) Electrolyte The battery 1 shown in FIG. 5 has a separator 203 into which an electrolytic solution has permeated.

The electrolytic solution of the separator 203 performs charge carrier transport between both electrodes of the negative electrode 204 and the positive electrode 202, and generally has an ionic conductivity of 10 ⁻⁵ to 10 ⁻¹ S / cm at 20 ° C. Is preferred. As the electrolytic solution, for example, an electrolytic solution in which an electrolyte salt is dissolved in a solvent can be used.

Examples of the electrolyte salt include LiPF ₆ , LiClO ₄ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , LiC (C ₂ F ₅ SO ₂ ) _{3 and the} like.

  Examples of the solvent for dissolving such electrolyte salt include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, tetrahydrofuran, dioxolane, sulfolane, dimethylformamide, dimethylacetamide, and N-methyl-2. -An organic solvent such as pyrrolidone can be used. These solvents can be used alone or in admixture of two or more.

  Further, the battery may have a solid electrolyte instead of the separator 203. Examples of the solid electrolyte include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-ethylene copolymer, vinylidene fluoride-monofluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer Polymers, vinylidene fluoride-tetrafluoroethylene copolymers, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymers, etc., vinylidene fluoride polymers, acrylonitrile-methyl methacrylate copolymers, acrylonitrile-methyl Acrylate copolymer, acrylonitrile-ethyl methacrylate copolymer, acrylonitrile-ethyl acrylate copolymer, acrylonitrile-methacrylic acid copolymer, acrylonitrile-acrylic acid copolymer, acryloni Lil - vinyl acetate copolymer, acrylonitrile-based polymer, further polyethylene oxide, ethylene oxide - propylene oxide copolymers, and polymers of these acrylates body or methacrylate body thereof. As these solid electrolytes, those obtained by adding an electrolyte solution to the above polymer substance to form a gel, or those in the above polymer substance state can be used as they are. In order to easily bend the battery, it is desirable to use a gel electrolyte.

  For example, when the organic radical battery is used in a negative temperature environment, it is preferable to use an electrolyte having a low solidification temperature and a high dielectric constant. In general, an electrolytic solution having a high dielectric constant has a high viscosity, and the electrical conductivity decreases because the viscosity further increases in a minus temperature environment. For this reason, conventional secondary batteries often use a mixture of an electrolyte solution having a high dielectric constant and an electrolyte solution having a low viscosity but a low dielectric constant. On the other hand, in the case of an organic radical battery, high low temperature characteristics can be seen even when a highly viscous electrolyte is used alone. The reason for this is not clear, but it is likely that the positive electrode of the radical battery gels with the electrolyte solution, which accelerates the ion diffusion in the active material associated with the charge / discharge reaction, which compensates for the high viscosity. It is guessed.

  Therefore, the organic radical battery used when the temperature history management device of the present invention is used in a minus temperature environment, a solvent having a dielectric constant of 20 or more, such as propylene carbonate, butylene carbonate, γ-butyrolactone, alone or It is desirable to mix and use with other solvents at a ratio of 50% or more by weight.

(5) Battery Shape The shape of the organic radical battery used in the present invention is not limited to the sheet type shown in FIG. In addition to the sheet-type battery shape, a cylindrical shape, a square shape, a coin shape, and the like can be given. Such a battery is produced by sealing the electrode laminate or wound body such as the positive electrode, the negative electrode, the electrolyte, and the separator described above with a metal case, a resin case, a metal foil, a laminate film, or the like. However, from the viewpoint of facilitating thinning, the battery shape is preferably a sheet type sealed with a laminate film. As the laminate film, a synthetic resin film alone, a laminate of a metal foil such as an aluminum foil and a synthetic resin film, or a synthetic resin film deposited with an oxide such as SiO ₂ can be used.

(Radical polymer synthesis example)
A synthesis example of the radical polymer represented by the above formula (5) is shown below.

  First, a monomer (2,2,6,6-tetramethylpiperidine-4-vinyloxy-1-oxyl) was synthesized. The synthesis of this monomer was carried out using a method in which an alcohol having a corresponding radical and vinyl acetate were heated to reflux in the presence of an iridium catalyst. Specifically, according to the method described in Journal of The American Society (Journal of The American Society, 124, 1590-1591 (2002), Yasutaka Ishii) and JP-A-2003-73321, Synthesized.

  Next, this 2,2,6,6-tetramethylpiperidine-4-vinyloxy-1-oxyl (monomer) was polymerized by a reaction represented by the following formula (13). The specific method is shown below.

  Under an argon atmosphere, 10.0 g (50.4 mmol) of 2,2,6,6-tetramethylpiperidine-4-vinyloxy-1-oxyl (monomer) synthesized as described above was placed in a 200 mL three-necked round bottom flask. , 100 mL of dichloromethane was added and cooled to -78 ° C. Furthermore, after adding 280 mg (2 mmol) of boron trifluoride-diethyl ether complex to make it uniform, the mixture was reacted at −78 ° C. for 20 hours. After completion of the reaction, the reaction mixture was returned to room temperature, and the resulting solid was filtered, washed several times with methanol, and vacuum dried to obtain a radical polymer represented by formula (5) as a red solid (yield) 70%).

When the IR spectrum of the obtained radical polymer was measured, peaks 966 and 674 (cm ⁻¹ ) derived from the vinyl group observed in the case of the above monomer disappeared. Further, the obtained radical polymer was insoluble in an organic solvent or the like. The spin density of the radical polymer determined by ESR spectrum was 3.05 × 10 ²¹ spin / g. This almost coincided with the spin concentration when it was assumed that all radical groups in the polymer were not deactivated by polymerization and existed as radicals.

(Example of manufacturing organic radical battery)
Next, an example of manufacturing an organic radical battery will be described.

  1.68 g of a finely divided radical polymer represented by formula (5), 0.6 g of carbon powder (Ketjenbrak EC300J; manufactured by Lion), and 96 mg of carboxymethyl cellulose (CMC: HB-9; manufactured by Nippon Zeon Co., Ltd.) Then, 24 mg of polytetrafluoroethylene (PTFE: F-104; manufactured by Daikin) and 7.2 mL of water were stirred with a homogenizer to prepare a uniform slurry. This slurry was applied on an aluminum foil (thickness 20 μm: positive electrode current collector) with an electrode production coater, and further dried at 80 ° C. for 3 minutes to form a radical positive electrode layer having a thickness of 50 μm.

  Next, the radical positive electrode thus obtained was punched into a square of 20 × 20 mm. A nickel lead having a length of 3 cm and a width of 0.5 mm was welded to the aluminum foil surface of the positive electrode. Moreover, after bonding lithium foil (thickness 30 micrometers) on copper foil (negative electrode electrical power collector), it punched in the square of 20x20 mm, and formed the negative electrode. A nickel lead having a length of 3 cm and a width of 0.5 mm was welded to the copper foil surface of the negative electrode.

  Next, a radical positive electrode, a porous polypropylene separator (25 × 25 mm square), and a negative electrode were laminated in this order so that the slurry of the radical positive electrode and the lithium layer of the negative electrode were opposed to each other, thereby producing a pair of electrodes with nickel leads. .

Thereafter, two sheets of aluminum laminate film (40 mm length × 40 mm width × 0.76 mm thickness) that can be heat-sealed are heat-sealed to form a bag, and the above-mentioned is produced as described above. A pair of electrodes with nickel leads was inserted. Further, an electrolytic solution [a mixed solution of ethylene carbonate (EC) / diethyl carbonate (DEC) containing 1.0 mol / L LiPF ₆ electrolyte salt (mixing ratio EC: DEC = 3: 7)] in an aluminum laminate case. 0.5cc. At this time, the end of the nickel lead of the electrode with the nickel lead was placed 1 cm outside the aluminum laminate case, and one side of the aluminum laminate case that was not welded was thermally fused. As a result, the electrode and the electrolyte were completely sealed in the aluminum laminate case.

  As described above, an organic radical battery (length 40 mm × width 40 mm × thickness 0.4 mm) was produced. The battery was charged at 100 mA for 30 seconds and then discharged at a constant current of 0.1 mA. As a result, discharging was performed at an average voltage of 3.5 V for 5 hours (energy amount: 1.8 mWh).

  Hereinafter, a temperature history management device according to the present invention will be described with reference to the drawings. However, the present invention is not limited to the following examples unless it exceeds the gist.

(Example 1)
FIG. 6 is a conceptual diagram of the temperature history management device according to the first embodiment of the present invention. As shown in the figure, this apparatus 301 includes a temperature sensor 302, an information processing unit 303 that processes temperature information detected by the temperature sensor 302, and a high-frequency wireless that transmits data processed by the information processing unit 303 to the outside. A transmission unit 304 is provided, and an organic radical battery 305 is used as a power source for the temperature sensor 302, the information processing unit 303, and the high-frequency wireless transmission unit 304.

  This temperature history management device 301 is formed in a card shape and a thickness of 0.7 mm using a flexible material. Further, even when a temperature history management device in which the organic radical battery 302 is accommodated within this thickness is used to transport an object to be detected in a container whose room temperature is set to −20 ° C., the organic radical battery has a current of 25 mA, It was possible to transmit a 300 MHz high frequency radio for 20 m by supplying a pulse current of 1 msec.

  Moreover, since it is a card-like temperature history management device containing a bendable organic radical battery, it can be mounted directly on the object to be detected and its container following the irregularities of its outer shape. As a result, it is possible to measure the exact temperature of the object to be detected. In addition, since it is not necessary to mold the exterior of the temperature history management device in advance according to the object to be detected and the curved shape of the container, it is easy to carry and organize after using the device.

  1A to 1D, the IC module 2 serves as the information processing unit 303, and the temperature information output unit 14 serves as the high-frequency wireless transmission unit 304.

  A usage method and an operation example in this case will be described.

  A temperature history management device 301 for a card-like RFID tag is directly attached to an object to be detected in a container room under a minus temperature environment. When an activation signal or a measurement start signal is input to the information processing unit 303 of the temperature history management device 301 using electromagnetic waves, the temperature history management device 301 is activated, and the temperature measurement of an object to be detected during storage or transportation is a temperature. Start with sensor 302. The measured temperature information is sequentially stored in the information processing unit 303. Thereafter, when a temperature history read signal is input to the temperature history management device 301 using electromagnetic waves, the radio frequency wireless transmission unit 304 wirelessly transmits the temperature history data stored so far in the information processing unit 303 to the outside. Alternatively, the high-frequency wireless transmission unit 304 may wirelessly transmit the temperature data temporarily stored in the information processing unit 303 to the outside simultaneously with storing the measured object temperature.

  After the storage period ends or after transportation, the temperature history management device 301 is removed from the object to be detected and collected. The collected organic radical battery 302 of the temperature history management device 301 is recharged. Thereby, it can reuse for another to-be-detected object.

(Example 2)
FIG. 7 is a conceptual diagram of the temperature history management device according to the second embodiment of the present invention. As shown in the figure, the apparatus 401 includes a temperature sensor 402, an information processing unit 403 that processes temperature information detected by the temperature sensor 402, and a liquid crystal display 404 that displays data processed by the information processing unit 403. The organic radical battery 405 is used as a power source for the temperature sensor 402, the information processing unit 403, and the liquid crystal display 404.

  The temperature history management device 401 is formed into a sheet shape and a thickness of 1 mm using a flexible material.

  Since the temperature history management device 401 of the present embodiment uses a bendable organic radical battery, it can be mounted on the object to be detected and its container directly following the irregularities of its outer shape. As a result, it is possible to measure the exact temperature of the object to be detected. In addition, since it is not necessary to mold the exterior of the temperature history management device in advance according to the object to be detected and the curved shape of the container, it is easy to carry and organize after using the device. Of course, the liquid crystal display 404 of this example is flexible.

  1A to 1D, the IC module 2 serves as the information processing unit 403, and the temperature information output unit 14 serves as the liquid crystal display 404.

  A usage method and an operation example in this case will be described.

  A temperature history management device 401 for a sheet-like RFID tag is directly attached to an object to be detected in a warehouse under a minus temperature environment. When an activation signal or a measurement start signal is input to the information processing unit 403 of the temperature history management device 401 using electromagnetic waves, the temperature history management device 401 is activated, and the temperature sensor 402 is used to measure the temperature of an object to be detected. Start with. The measured temperature information is sequentially stored in the information processing unit 403. Thereafter, when a temperature history read signal is input to the temperature history management device 401 using electromagnetic waves, the temperature history data stored so far in the information processing unit 403 is displayed on the liquid crystal display 404. Alternatively, the temperature data temporarily stored in the information processing unit 403 may be displayed on the liquid crystal display 404 simultaneously with the storage of the measured object temperature. If the temperature history cannot be displayed at a time because the size of the liquid crystal display 404 is small, the temperature data may be displayed continuously in time series.

  At the time of delivery when the state where the temperature history management of the detected object is necessary ends, the sheet-like temperature history management device 401 is removed from the detected object and collected. The recovered organic radical battery 402 of the temperature history management device 401 is recharged. Thereby, it can utilize again for another to-be-detected object.

(Example 3)
FIG. 8 is a conceptual diagram of the temperature history management device according to the third embodiment of the present invention. As shown in the figure, the apparatus 501 includes a temperature sensor 502, an information processing unit 503 that processes temperature information detected by the temperature sensor 502, and an electrophoretic display that displays data processed by the information processing unit 503. (Electrophoretic Display (EPD)) 504, and an organic radical battery 505 is used as a power source for the temperature sensor 502, the information processing unit 503, and the electrophoretic display 504.

  The temperature history management device 501 is formed into a sheet shape and a thickness of 0.9 mm using a flexible material.

  Since the temperature history management device 501 of the present embodiment uses a bendable organic radical battery, it can be attached to the object to be detected and its container directly following the irregularities of its outer shape. As a result, it is possible to measure the exact temperature of the object to be detected. Moreover, since it is not necessary to shape the exterior of the temperature history management device in advance according to the object to be detected and the curved shape of the container, it is easy to carry and organize after using the device. Of course, the electrophoretic display 504 of this example is flexible electronic paper.

  1A to 1D, the IC module 2 serves as the information processing unit 503, and the temperature information output unit 14 serves as the electrophoretic display 504. The usage method and operation example in this case are the same as those in the second embodiment. However, in FIG. 8, as an example of the electrophoretic display 504, a change in temperature with time is displayed as a line graph.

Example 4
FIG. 9 is a conceptual diagram of a temperature history management device according to Embodiment 4 of the present invention. As shown in the figure, the apparatus 601 includes a temperature sensor 602, an information processing unit 603 that processes temperature information detected by the temperature sensor 602, and data processed by the information processing unit 603 has exceeded a predetermined threshold. An alarm generation unit 604 that sounds an alarm sound in case, and an alarm generation unit 505 that generates an alarm by emitting light. An organic radical battery 606 is used as a power source for the temperature sensor 602, the information processing unit 603, and the alarm generation units 604 and 605.

  The temperature history management device 601 is formed in a card shape and a thickness of 0.8 mm using a flexible material.

  Since the temperature history management device 601 of the present embodiment uses a bendable organic radical battery, it can be attached to the object to be detected and its container directly following the irregularities of its outer shape. As a result, it is possible to measure the exact temperature of the object to be detected. In addition, since it is not necessary to mold the exterior of the temperature history management device in advance according to the object to be detected and the curved shape of the container, it is easy to carry and organize after using the device.

  1A to 1D, the IC module 2 serves as the information processing unit 603, and alarm generation units 604 and 605 are provided instead of the temperature information output unit 14.

  A usage method and an operation example in this case will be described.

  A card-type RFID tag temperature history management device 601 is directly attached to an object to be detected in a container under a minus temperature environment. When a detection signal or a measurement start signal is input to the information processing unit 603 of the temperature history management device 601 using electromagnetic waves when the detected object is transported from the production factory to the store using this container, the temperature history management device 601 is started. Then, temperature measurement of the object to be detected during transportation is started using the temperature sensor 602. The measured temperature information is sequentially stored in the information processing unit 603. The information processing unit 603 compares the stored temperature data with a predetermined threshold value, and generates an alarm sound or light using the alarm generation units 604 and 605 when the data exceeds the predetermined threshold value.

  When the detected object is delivered to a store where the temperature history management of the detected object is finished, the card-like temperature history management device 601 is removed from the detected object and collected. The recovered organic radical battery 602 of the temperature history management device 601 is recharged when returning to the factory. Thereby, when conveying the next to-be-detected object, it can utilize again.

(Comparative Example 1)
A temperature history management device was produced in the same manner as in Example 1 except that a coin-type lithium primary battery having a volume equivalent to that of the organic radical battery 305 was used for the organic radical battery 305 in FIG. When used to transport an object to be detected in a container whose room temperature is set to −20 ° C., the coin-type lithium primary battery cannot flow a pulse current of 25 mA for 1 msec as in the first embodiment. Was impossible. Further, since the coin-type lithium primary battery is hard and cannot be bent, the temperature history management device incorporating the coin-type lithium primary battery cannot be deformed along the outer shape of the object to be detected. Therefore, it cannot be directly attached to the object to be detected, and in order to attach it, it has been necessary to form it in accordance with the outer shape of the object to be detected.

(Comparative Example 2)
A temperature history management device was produced in the same manner as in Example 1 except that a manganese primary battery having a volume equivalent to that of the organic radical battery 305 was used for the organic radical battery 305 in FIG. When used to transport an object to be detected in a container whose room temperature is set to −20 ° C., the manganese primary battery cannot flow a pulse current that flows 25 mA for 1 msec as in Example 1, and high-frequency wireless transmission is not possible. It was possible. Further, since the manganese primary battery is also hard and cannot be bent, the temperature history management device incorporating the manganese primary battery cannot be deformed along the outer shape of the object to be detected. Therefore, it cannot be directly attached to the object to be detected, and in order to attach it, it has been necessary to form it in accordance with the outer shape of the object to be detected.

(Comparative Example 3)
A temperature history management device was produced in the same manner as in Example 3 except that a nickel metal hydride battery was used for the organic radical battery 505 in FIG. The nickel-metal hydride battery has a thickness of about 6 mm and is hard and cannot be bent. Therefore, the temperature history management device incorporating this is thick and cannot be deformed along the outer shape of the object to be detected. As a result, it cannot be directly attached to the object to be detected, and in order to attach it, it has been necessary to form the object in accordance with the outer shape of the object to be detected. Furthermore, since the temperature history management device is thick, irregularities are formed when it is mounted on the outer shape of the detected object, making it difficult to organize the detected object in the warehouse.

It is a top view of the temperature history management apparatus by one Embodiment of this invention. It is sectional drawing in the AB line of FIG. 1A. It is sectional drawing in the CD line of FIG. 1A. It is sectional drawing in the EF line | wire of FIG. 1A. It is sectional drawing of the sealing layer which has an organic radical battery inside. It is the figure which looked at the seal layer shown in Drawing 2A from the lower part. It is a conceptual diagram of the IC module inside the RFID tag applied to the temperature history management device according to the embodiment of the present invention. It is a perspective view of a thin organic radical battery applicable to the present invention. It is a disassembled perspective view which shows the structure of the organic radical battery of FIG. It is the top view which showed typically the card-like temperature log | history management apparatus which concerns on Example 1 of this invention. It is the top view which showed typically the sheet-like temperature history management apparatus which concerns on Example 2 of this invention. It is the top view which showed typically the sheet-like temperature log | history management apparatus which concerns on Example 3 of this invention. It is the top view which showed typically the sheet-like temperature log | history management apparatus which concerns on Example 4 of this invention.

Explanation of symbols

1 Organic radical battery 2 IC module 2a Memory (ROM, RAM)
2b Microprocessor for control 2c Modulator 2d Command 2e Clock 2f Front end 3 Antenna 6 Through hole 7 Charging terminal 8a, 8b Core sheet 9a, 9b Overlay 11 Tab 12 Terminal 13 Temperature sensor 14 Temperature information output means 15 Wiring 100 Seal layer DESCRIPTION OF SYMBOLS 101 Battery cover 102 Adhesive part 201 Exterior film 202 Radical positive electrode 203 Separator 204 Negative electrode 205 Positive electrode lead 206 Negative electrode lead 301 Card-like temperature history management apparatus 302 Temperature sensor 303 Information processing part 304 High-frequency wireless transmission part 305 Organic radical battery 401 Sheet-like temperature history management device 402 Temperature sensor 403 Information processing unit 404 Liquid crystal display 405 Organic radical battery 501 Seal-like temperature history management device 502 Temperature Capacitors 503 information processing unit 504 electrophoretic display 505 organic radical battery 601 card-like temperature history management unit 602 temperature sensor 603 information processing unit 604 warning generation unit (sound)
605 Alarm generator (light)
606 Organic radical battery

Claims (9)

  A temperature history management device having at least a temperature sensor and a power source, which is attached to an object to be detected for temperature history and used even in a minus temperature environment, and using an organic radical battery as the power source.   The temperature history management device according to claim 1 whose thickness is 1 mm or less.   The temperature history management apparatus according to claim 1, further comprising means for outputting temperature information detected by the temperature sensor.   The temperature history management device according to any one of claims 1 to 3, further comprising means for issuing an alarm when temperature information measured by the temperature sensor exceeds a predetermined threshold value. An exterior body,
A temperature sensor installed in the exterior body, an information processing unit that processes temperature information detected by the temperature sensor, an output unit that outputs data processed by the information processing unit to the outside, and a power source that drives them Prepared,
The temperature history management device according to claim 1, wherein the power source is an organic radical battery. The exterior body has a thickness of 1 mm or less,
The temperature history management device according to claim 5, wherein at least the information processing unit and the organic radical battery are provided in the exterior body.   7. The temperature history management apparatus according to claim 5, wherein the output unit is a wireless transmission unit that transmits data processed by the information processing unit to the outside.   7. The temperature history management apparatus according to claim 5, wherein the output means is display means for displaying data processed by the information processing unit to the outside.   7. The output means according to claim 5 or 6, wherein the output means is an alarm generation means for alarming outside at least one of sound and light when data processed by the information processing unit exceeds a predetermined threshold. The temperature history management device described.

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