WO2017159040A1 - Corps d'affichage d'historique de température, son procédé de fabrication et son procédé d'utilisation - Google Patents

Corps d'affichage d'historique de température, son procédé de fabrication et son procédé d'utilisation Download PDF

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Publication number
WO2017159040A1
WO2017159040A1 PCT/JP2017/002047 JP2017002047W WO2017159040A1 WO 2017159040 A1 WO2017159040 A1 WO 2017159040A1 JP 2017002047 W JP2017002047 W JP 2017002047W WO 2017159040 A1 WO2017159040 A1 WO 2017159040A1
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WIPO (PCT)
Prior art keywords
temperature
layer
display body
history display
color
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PCT/JP2017/002047
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English (en)
Japanese (ja)
Inventor
豊隆 湯浅
佐々木　洋
航平 會田
靖彦 多田
博之 香川
憲一 相馬
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株式会社 日立産機システム
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Publication of WO2017159040A1 publication Critical patent/WO2017159040A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/06—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using melting, freezing, or softening
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using changes in colour, translucency or reflectance

Definitions

  • the present invention relates to a temperature history display body that irreversibly displays a temperature history, a manufacturing method thereof, and a usage method thereof.
  • thermochromic markings that cause irreversible changes when deviating from the control temperature are being studied.
  • the color does not develop when the storage temperature of the product is lower than the set temperature, but the color develops when the temperature exceeds the set temperature, and the color remains developed even after cooling again. If a product deviates from the proper management temperature, its history remains.
  • this temperature history display body it is possible to grasp whether the temperature is managed at an appropriate temperature.
  • the temperature history display body is required to be stored at room temperature. If storage at room temperature is not possible, the temperature history display must be kept below the set temperature until the user attaches it to the product to be measured after the temperature history display is manufactured. Therefore, the temperature management of the temperature history display body becomes complicated.
  • Patent Document 1 discloses a temperature history including a temperature detecting layer containing a higher fatty acid metal salt that liquefies below a specific temperature, a color former layer, and a developer layer containing a developer and a heat melting component.
  • a display is disclosed.
  • the temperature detecting layer When placed in an environment below the critical temperature of the higher fatty acid metal salt, the temperature detecting layer is dissolved, and the developer layer and the color former layer are easily brought into contact with each other (“switch-on” state).
  • switch-on state
  • the temperature history display body is placed above the melting temperature of the hot-melt component in the developer layer, the hot-melt component containing the developer flows and comes into contact with and reacts with the color developing layer. It is described that color develops.
  • an ink-penetrating sheet adheres to a base sheet on which an indicator ink layer is partially attached, and at least the indicator ink layer is covered and peelable between the base sheet and the ink-penetrating sheet.
  • a temperature history indicator sheet having an intervening release sheet is disclosed. It is disclosed that the temperature history of the test object can be monitored by peeling off the release sheet.
  • the temperature history display body disclosed in Patent Document 2 can be operated at any timing by peeling off the release sheet. However, it is necessary to lift the ink-penetrating sheet once, peel off the release sheet, and then bond the ink-penetrating sheet onto the substrate. Although it is assumed that the temperature history display body is used in an existing production line for pharmaceuticals or foods, it is difficult to make it operable without reducing the line speed of the production line. Further, when the ink in the lower ink layer is diffused into the upper ink permeation layer, ink bleeding occurs, and it is difficult to maintain high-definition print information.
  • an object of the present invention is to provide a temperature history display body that can be stored at room temperature and can be easily operated at an arbitrary timing.
  • the temperature history display body melts when a predetermined temperature is exceeded, a base material, a color developing layer containing a color developing agent, a color developer for promoting color development or discoloration of the color developing agent.
  • the prevention layer and the color-developing layer are laminated in this order, and the side surface of the temperature-sensitive layer laminate is covered with a non-porous member, and the diffusion prevention layer is non-porous by an adhesive that peels below the freezing point of the temperature-sensitive agent. It is fixed to the member.
  • thermo history display body that can be stored at room temperature and can be easily operated at an arbitrary timing.
  • FIG. 2 is a cross-sectional view taken along the line AA ′ of the temperature history display body according to FIG. 1.
  • FIG. 3 is a BB ′ sectional view of the temperature history display body according to FIG. 2.
  • It is AA 'sectional view of the temperature history display body at the time of room temperature storage concerning one embodiment.
  • It is sectional drawing of the temperature history display body before detecting the deviation of the management temperature which concerns on one Embodiment.
  • It is a top view of the temperature history display body before detecting the deviation of the management temperature which concerns on one Embodiment.
  • It is sectional drawing of the temperature history display body after detecting the deviation of the management temperature which concerns on one Embodiment.
  • FIG. 1 shows a top view of a temperature history display body during room temperature storage according to an embodiment of the present invention.
  • 2 is a cross-sectional view taken along the line AA ′ of the temperature history display body according to FIG. 1
  • FIG. 3 is a cross-sectional view taken along the line BB ′.
  • the temperature history display body includes a base material 2, a temperature-sensitive layer 12, a diffusion prevention layer 6, and a coloring layer 7. On the base material 2, the temperature sensitive layer 12, the diffusion preventing layer 6, and the color developing layer 7 are laminated in this order.
  • An adhesive layer 1 is provided under the substrate 2.
  • the temperature-sensitive layer 12 includes a developer that promotes color development or discoloration of the color former and a temperature-sensitive agent that melts at a predetermined temperature or higher.
  • the temperature-sensitive layer is composed of a first layer 3 containing a developer and a second layer 4 laminated on the first layer 3 and containing the temperature-sensitive agent.
  • the second layer 4 plays a role of separating the color developing layer from the developer.
  • the side surface of the temperature sensitive layer is covered with a non-porous member 11.
  • the non-porous member covering the side surface of the temperature sensitive layer is integrated with the base material.
  • the non-porous member and the base material that cover the side surface of the temperature sensitive layer may not be integrated.
  • the diffusion preventing layer 6 plays a role of preventing the temperature-sensitive agent melted during storage at room temperature from diffusing into the coloring layer.
  • the diffusion preventing layer 6 is fixed to the non-porous member by the adhesive 5.
  • the pressure-sensitive adhesive 5 has a property of peeling below the freezing point of the temperature-sensitive agent.
  • the coloring layer is bonded to at least a part of the non-porous member that covers the side surface of the temperature-sensitive agent. Since the coloring layer is fixed to the non-porous member, it is possible to suppress the deviation of the coloring layer when the diffusion preventing layer is pulled out.
  • the diffusion preventing layer may be fixed to the non-porous member with an adhesive on one side (FIG. 4) or fixed on two sides. (FIG. 1).
  • FIG. 4 When the diffusion preventing layer and the non-porous member are bonded on one side as shown in FIG. 4, it is preferable that the coloring layer and the non-porous member are bonded on the other three sides. Further, when the diffusion preventing layer and the non-porous member are bonded at two sides as shown in FIG. 1, the coloring layer and the non-porous member are bonded at the other two sides as shown in FIG. Is preferred.
  • the temperature history display body according to FIG. 1 is cooled below the freezing point of the temperature-sensitive agent during use. After the second layer is solidified and pasted to the object to be measured via the adhesive layer 1, the diffusion preventing layer 6 is pulled out so that the temperature can be detected.
  • the temperature history display according to the present embodiment has a layer structure having a temperature-sensitive layer and a coloring layer, and there is a possibility that the coloring condition may change due to the contact interface of each layer being disturbed when the diffusion prevention layer is pulled out. Since the pressure-sensitive adhesive 5 peels below the freezing point of the temperature-sensitive agent, the diffusion preventing layer can be easily pulled out without exerting stress on each layer.
  • the temperature-sensitive agent a substance that melts at the upper limit of the temperature to be controlled is used.
  • the temperature-sensitive agent remains solid, so that the second layer suppresses the contact between the developer and the coloring layer, and the developer does not diffuse into the coloring layer. . Therefore, the color former does not develop or change color.
  • FIG. 7 is a sectional view showing a state after temperature deviation of the temperature history display body according to FIG. 2, and FIG. 8 is a top view thereof.
  • the temperature sensitive agent melts.
  • the developer diffuses through the second layer to the coloring layer, and the coloring agent and the developer react to develop or change color.
  • the color former 8 becomes a color former 9 that has developed or changed color. As described above, temperature deviation can be detected and displayed.
  • the temperature history display attached to the object to be measured controlled at an appropriate temperature can be used again by returning the diffusion prevention layer between the coloring layer and the temperature sensitive layer.
  • the coloring layer includes a coloring agent and a carrier that holds the coloring agent on the surface.
  • the color former a substance that is visually colorless or light-colored but changes its structure when touched with an acidic substance or a basic substance, and a substance that develops or changes color visually can be used.
  • a substance that is colorless or light-colored at a neutral pH of about 5 or more and less than 8 and that develops or changes color when the pH is less than about 5 is referred to as “a substance that develops color by touching an acidic material”.
  • a substance that develops or changes color at a pH of about 8 or more is referred to as a "substance that develops color by touching a basic material”.
  • the color former is weak in color and may have low visibility when it is in contact with an acidic or basic developer layer. In that case, moisture may coexist.
  • Some color formers improve color development by containing moisture. For example, phenolphthalein produces a very light pink color when water is not present together, but when it is slightly coexisted with water, it is well colored in pink.
  • a porous member having pores that can hold the color former can be used as the carrier for holding the color former. It is preferably continuous porous so that the developer can penetrate.
  • the material is required to be a material that does not denature even when the developer and color former are in contact with each other for a long time.
  • polyethylene, polypropylene, cellulose, and other polymers that are difficult to dissolve in ordinary organic solvents, and inorganic compounds such as silicon dioxide are suitable.
  • a material having excellent diffusibility in the thickness direction is preferable.
  • a material in which the color former and the developer are difficult to diffuse in the in-plane direction is preferable.
  • inkjet print paper and mat paper are preferable.
  • Ink jet print paper is filled with an inorganic substance such as talc or silica in the thickness direction of the paper surface. For this reason, since the liquid is more easily diffused in the thickness direction than in the in-plane direction, it is possible to suppress the bleeding of the print. Further, by adjusting the thickness of the printing paper, the time for contact between the developer and the color former can be adjusted, and the time from the deviation from the set temperature to the color development can be controlled.
  • the coloring layer preferably contains a polymer having an amino group.
  • the compound having an amino group is preferably a polymer having low crystallinity or an amorphous polymer.
  • a low-crystalline or amorphous polymer can form a color former layer in a substantially uniformly dispersed state after being mixed with the color former layer material.
  • the polymer having an amino group for example, polyethyleneimine, polyallylamine and the like are suitable.
  • the color former preferably further contains a conductive agent.
  • a conductive agent By including a conductive agent, printing can be performed with a charge control type ink jet printer. By printing the color former with an inkjet printer, it can be printed as characters, symbols, one-dimensional codes, two-dimensional codes, and the like. As a result, information other than the temperature information of the temperature history display body can be given. Furthermore, by using a two-dimensional code or the like, it is possible to convert the presence or absence of temperature deviation into data using a reading device.
  • a compound having a metal salt structure is preferable. Considering solubility in a solvent and corrosion of members, nitrate ions, perchlorate ions, and tetraphenylborate ions are preferable as the anions forming the metal salt structure compound.
  • the cation forming the compound having a metal salt structure lithium ion, sodium ion, ammonium ion, and tetramethylammonium ion are preferable.
  • the color former may contain a leveling agent for controlling the shape after the ink has landed on the substrate to be printed.
  • the coloring layer may be provided with a cord that does not change with temperature.
  • the code preferably has information such as a management temperature (melting point of the temperature-sensitive agent), the position, number, and type of the color former. For example, by providing a code having position information (relative position with respect to the code) of the color former, it is easy to read color data or the like with a reading device.
  • the temperature-sensitive layer includes a temperature-sensitive agent, a developer, and a carrier that holds these.
  • the temperature sensitive agent includes a first layer composed of a developer and a carrier impregnated with the developer, and a second layer composed of the temperature sensitive agent and the carrier impregnated with the temperature sensitive agent. It is preferable to include.
  • the first layer and the second layer will be described.
  • thermosensitive agent the substance which melt
  • a thermosensitive agent for example, for example, a long-chain hydrocarbon not containing an acidic group or a basic group, or a hydrocarbon having several branches is preferable.
  • an alcohol having a long-chain hydrocarbon chain or a branched hydrocarbon chain, a diol, a ketone, an amide having a long-chain hydrocarbon chain or a branched hydrocarbon chain, an ether, an ester, or the like can be used.
  • Examples of the hydrocarbon of a long chain, branched hydrocarbon chain, or cyclic hydrocarbon chain include cyclodecane (9 ° C.), dodecane, tetradecane (6 ° C.), hexadecane (17 ° C.), octadecane (28 ° C.), and the like.
  • the parentheses are melting points.
  • Examples of hydroxyl-terminated alcohols or diols include 1,4-butanediol (20 ° C.), 1-decanol (6 ° C.), 1-dodecanol (24 ° C.), 1,2-dodecane diol (58 ° C.), 2 -Tetradecanol (34 ° C) and the like.
  • Materials having a ketone structure include 2-decanone (3 ° C.), propiophenone (18 ° C.), butyrophenone (12 ° C.), isobutyrophenone (1 ° C.), hexanophenone (26 ° C.), octanophenone (22 ° C), decanophenone (35 ° C) and the like.
  • isopropyl palmitate isopropyl myristate, and pentadecane are preferable as the temperature sensitive agent.
  • the selection of the temperature-sensitive agent depends on the upper limit of the management set temperature of the product to be temperature controlled. For example, in the case of frozen foods such as meat, since the upper limit of the control set temperature is around ⁇ 16 ° C., a compound such as 1-octanol or 2-octanone having a melting point of ⁇ 16 ° C. may be used as the temperature sensitive agent. For frozen foods such as seafood, 3-octanone with a melting point of ⁇ 23 ° C. is a candidate. In the case of carbohydrate-based products, dodecane having a melting point of ⁇ 12 ° C. is a candidate for storage at a slightly higher temperature.
  • the product you want to control the temperature of is a pharmaceutical product that requires storage below 10 ° C, tetradecane with a melting point of 6 ° C, or 1-decanol, or 2-dodecane with a melting point of 3.5 ° C, hexadecane with a melting point of 17 ° C, or It is advisable to add 3-dodecanone having a melting point of 19 ° C. and 2-dodecanone having a melting point of 20 ° C. to adjust the melting point to approximately 10 ° C.
  • temperature-sensitive agents can be used alone, but a mixture of a compound having a higher melting point than that may be used. This is because by mixing a compound having a high melting point, the crystallinity is lowered and becomes amorphous, the temperature sensitive agent becomes dense, and the shielding property between the color former and the developer is improved. In particular, the amorphousness is increased by mixing compounds having similar structures. For example, by adding tetradecane having a melting point of 6 ° C. or hexadecane having a melting point of 17 ° C. to dodecane having a melting point of ⁇ 12 ° C., the temperature-sensitive layer becomes amorphous, and between the color former layer and the developer layer. This improves the shielding performance.
  • the temperature at which the temperature-sensitive layer containing a plurality of temperature-sensitive agents softens depends on the melting point and addition rate of the mixed materials. For example, when a material a having a high compatibility and a material a having a melting point of A ° C and a material b having a melting point of B ° C are mixed in an equal amount, the melting point is approximately between A and B. However, when the difference between the melting points of the two materials is large, specifically, when the temperature is 50 ° C. or higher, the temperature at which the temperature-sensitive layer softens or melts becomes substantially the same as the melting point of the lower melting material. Even when materials with low compatibility are used, the temperature at which the temperature-sensitive layer softens or melts is substantially the same as the melting point of the material with the lower melting point.
  • the temperature sensitive agent and the developer need to have low compatibility.
  • the temperature sensitive agent is a hydrophobic material
  • a hydrophilic material is used as the developer.
  • the compatibility is low, the temperature-sensitive agent and the developer are not mixed, so that the developer cannot diffuse into the color-forming layer after the temperature-sensitive agent has diffused into the color-forming layer.
  • the carrier impregnated with the temperature sensitive agent may be a porous member that does not hinder the diffusion of the developer into the coloring layer.
  • a porous member that does not hinder the diffusion of the developer into the coloring layer.
  • non-woven fabric composed of carbon fibers, glass fibers, metal fibers, or paper composed of cellulose fibers is desirable. It is also possible to use a silicon dioxide, polyethylene, or polypropylene powder by holding it with a binder having the same chemical structure to form a continuous porous body.
  • the temperature-sensitive agent used in the present invention is configured to melt and diffuse into the coloring layer when it deviates from the control temperature, and the colored ink may be swept away by the diffused temperature-sensitive agent.
  • the amount of the temperature sensitive agent held on the carrier used for the second layer is small.
  • the second layer solidified below the freezing point has no pinholes, and it is important to reliably prevent the developer from diffusing. For this reason, it is desirable that the diameter of the pores constituted by the fibers of the temperature-sensitive agent-impregnated carrier is small.
  • the pore median diameter of the carrier impregnated with the temperature-sensitive agent is preferably 11 ⁇ m or more and 18 ⁇ m or less when measured by a mercury intrusion method. By making the thickness 18 ⁇ m or less, pinhole formation can be suppressed. By setting the thickness to 11 ⁇ m or more, a desired diffusion rate can be obtained.
  • the developer is an acidic substance or a basic substance, and is selected according to the color former.
  • the acidic substance include a polymer having a carboxyl group or a sulfonic acid group.
  • polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, copolymer of styrene and polyacrylic acid copolymer of methyl acrylate and acrylic acid, copolymer of ethyl acrylate and acrylic acid, acrylic Copolymer of propyl acid and acrylic acid, copolymer of butyl acrylate and acrylic acid, copolymer of hexyl acrylate and acrylic acid, copolymer of octyl acrylate and acrylic acid, methyl methacrylate and acrylic acid Copolymer, Copolymer of ethyl methacrylate and acrylic acid, Copolymer of propyl methacrylate and acrylic acid, Copolymer of butyl methacrylate and
  • Examples of the basic substance include polymers having amino groups such as polyethyleneimine, polyallylamine, chitosan, polylysine, polyarginine, polyaniline and the like. What dissolved these in the alcohol-type solvent can be used as a color developer.
  • specific examples include diaminohexane, diaminooctane, diaminodecane, diaminododecane, etc., and those obtained by dissolving these in an alcohol solvent may be used as the developer. it can.
  • aliphatic monoamines specific examples include octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, etc., and those dissolved in alcoholic solvents should be used as the developer. Can do.
  • polymethacrylic acid, polystyrene sulfonic acid, a copolymer of styrene and polyacrylic acid, a copolymer of methyl acrylate and acrylic acid, a copolymer of ethyl acrylate and acrylic acid, Chitosan, polylysine, polyarginine and polyaniline are preferred, and polyacrylic acid, polyallylamine and polyethyleneimine are more preferred.
  • the developer and the color former react with each other by the liquid diffusion of the developer into the color development layer. Therefore, it is preferable to use the developer by dissolving it in a solvent such as water or ethanol.
  • a solvent such as water or ethanol.
  • the solvent to be used can be selected depending on the set management temperature. For example, it is preferable to use water as a solvent for temperature traceability in refrigerated storage.
  • the carrier impregnated with the developer may be a material that is a porous member and can hold a sufficient amount of developer for color development.
  • a material that is a porous member for example, in addition to natural fibers and organic chemical fibers, non-woven fabric composed of carbon fibers, glass fibers, metal fibers, or paper composed of cellulose fibers is desirable.
  • security of material becomes important. That is, it is an important selection criterion that it is harmless to the human body.
  • Any member that covers the side surfaces of the substrate and the temperature-sensitive layer may be a non-porous member.
  • an inexpensive film having high resistance to various organic solvents such as polyethylene is desirable.
  • Polyethylene terephthalate hereinafter abbreviated as PET
  • PET Polyethylene terephthalate
  • polypropylene, polystyrene, acrylic resin, polycarbonate, cyclic olefin resin, and the like can be used.
  • the base material preferably has an adhesive layer on the back surface.
  • the adhesive layer makes it easy to attach the temperature history display body to the management object.
  • the pressure-sensitive adhesive is not particularly limited as long as it has a property of peeling below the freezing point of the temperature-sensitive agent.
  • the adhesive force (N / mm) at the freezing point of the temperature-sensitive agent is preferably smaller than the adhesive force at a temperature 20 ° C. higher than the freezing point of the temperature-sensitive agent.
  • the adhesive force (N / mm) at the freezing point of the temperature-sensitive agent is preferably 1/10 or less of the adhesive force at a temperature 20 ° C. higher than the freezing point of the temperature-sensitive agent.
  • a temperature-sensitive adhesive tape having an adhesive layer containing methyl acrylate and an acrylate ester can be used as the adhesive.
  • This temperature-sensitive adhesive tape has a characteristic that it becomes 90% or less of the peel strength at the time of bonding by adhering the substrate and the adhesive tape and then cooling the adhesive temperature at 15 to 20 ° C.
  • the diffusion preventing layer is a polyimide tape and the base material is a PET tape. In this case, when the diffusion prevention layer is pulled out by cooling at 15 to 20 ° C. from the bonding temperature, the polyimide tape is peeled off from the temperature-sensitive adhesive tape, and the temperature-sensitive adhesive tape remains on the PET tape.
  • the diffusion preventing layer only needs to block the color developing layer and the temperature sensitive layer.
  • a glass plate a resin film such as polyethylene terephthalate (PET) or polytetrafluoroethylene (PTFE), a resin sheet, a resin tape, a rubber sheet, or the like can be used.
  • PET polyethylene terephthalate
  • PTFE polytetrafluoroethylene
  • a resin sheet a resin tape, a rubber sheet, or the like
  • a polyimide base material is particularly preferable.
  • a member having a higher friction coefficient than the diffusion preventing layer at the end of the diffusion preventing layer It is necessary for the temperature history display body to remove the diffusion prevention layer at the start of temperature detection. In order to remove the diffusion prevention layer at a high speed on the production line, a label peeling device or the like is used to pull out the diffusion prevention layer while holding a part of the diffusion prevention layer. For this reason, it is preferable that the edge part of a diffusion prevention layer has a high friction coefficient.
  • the thickness of the diffusion preventing layer is thin for the following reasons. That is, it is necessary to remove the diffusion preventing layer at the start of temperature detection, and to diffuse the temperature-sensitive agent and developer to the printing paper when the temperature deviates. For this reason, it is desirable that the gap between the coloring layer and the temperature-sensitive layer after removing the diffusion preventing layer is small, and a thin diffusion preventing layer is desirable.
  • strength is also necessary for extracting the diffusion layer in the production line, and the thickness of the diffusion prevention layer is preferably 5 ⁇ m or more and 10 ⁇ m or less in order to achieve both thinness and strength.
  • the method for producing a temperature history display body includes a temperature-sensitive layer forming step of forming a temperature-sensitive layer by cooling the temperature-sensitive agent to a freezing point or lower, a color-forming layer forming step of printing a color former on printing paper, A lamination step of laminating the base material, the temperature-sensitive layer, and the diffusion prevention layer; and a printing paper lamination step of laminating the printing paper on the diffusion prevention layer at room temperature after the lamination step.
  • the temperature history display body can be manufactured at room temperature except for the temperature-sensitive layer forming step and the laminating step.
  • the color forming layer forming step may be performed after the printing paper laminating step.
  • the temperature history display body can be used as follows, for example. A temperature history display body is attached to the temperature management object or its container, and the temperature history display body is brought into a temperature detectable state by pulling out the diffusion prevention layer. Then, it is determined whether or not the color layer is controlled at an appropriate temperature from the presence or absence of color change or color development.
  • FIG. 9 is a diagram showing an example of how to use the temperature history display.
  • a temperature history display body in which a color former is not printed on the color development layer is prepared.
  • a temperature history display 14 is attached to a container 13 of a temperature management object such as an ampule with a labeler.
  • a coloring agent is printed on the coloring layer by a printing device 15 such as an ink jet printer.
  • the temperature control object is put into a container under temperature control.
  • the diffusion preventing layer 6 is removed by the film removing device 17 or the like.
  • the ink was prepared by the following procedure. Bromophenol blue (Wako Pure Chemicals, 4g) is dissolved in ethanol (Wako Pure Chemicals, 240g), and lithium nitrate (Wako Pure Chemicals, 1.4g) is added as a conductive material, and contains a color former. Ink was used. Using this ink, printing is performed on the center of inkjet printer paper (thickness 0.3 mm, width 10 mm, length 20 mm), 5 x 10 mm with Hitachi Industrial Equipment's continuous inkjet printer, PX-R type, and the coloring layer Formed.
  • a 30% polyethyleneimine aqueous solution (average molecular weight: about 70,000, manufactured by Wako Pure Chemical Industries, 2 g) was diluted with 20 g of distilled water to prepare a developer solution.
  • a high-quality paper of 40 g / m 2 was cut into a width of 5 mm and a length of 10 mm, and impregnated with a developer solution to form a first layer. This was arrange
  • this tape was stored in a thermostatic bath set at 0 ° C. for 1 hour to solidify the temperature sensitive agent in the temperature sensitive layer.
  • Thermochromic confirmation experiment The above-mentioned temperature history display body was transferred to a thermostat set to 4 ° C., and the temperature history display body was attached to the curved surface of a pharmaceutical bottle that is a measurement object. Next, the diffusion prevention layer was pulled out, and the temperature detection of the temperature history display body was operated as shown in FIG. Although it stored at 4 degreeC for 24 hours by the thermostat, there was no change in the temperature history display body. Next, when the set temperature of the thermostat was set to 9 ° C., the temperature-sensitive agent began to melt, and after 30 minutes, as shown in FIG. 3, the developer diffused and contacted with the printing ink as the color former. Ink discoloration was confirmed.
  • a temperature history display was produced in the same manner as in Example 1 except that printing paper (inkjet printer paper) was laminated on the diffusion prevention layer, and ink containing a color former was printed.
  • a temperature history display body in which ink containing a color former was not printed on the color development layer was prepared.
  • This temperature history display body was stored in a thermostat set at 0 ° C. for 1 hour to solidify the temperature sensitive agent.
  • this temperature history display body was moved to a thermostat set to 4 ° C., and the temperature history display body was affixed to the curved surface of a pharmaceutical bottle that is a measurement object.
  • the printer head of the continuous ink jet printer described in Example 1 was placed in a thermostatic chamber, and ink containing a color former was printed on the printing paper constituting the color development layer.
  • thermochromic experiment was performed in the same manner as in Example 1 to confirm the discoloration of the ink.
  • the lot number and date of manufacture could be directly printed on the pharmaceutical bottle with colored ink.
  • Example 1 The temperature history display is the same as in Example 1 except that the diffusion preventive layer is affixed to the base material using a natural rubber-based adhesive tape (containing Pico Pale 100 (manufactured by Rika Kakyures)) as the adhesive. A body was prepared and a thermochromic confirmation experiment was conducted.
  • a natural rubber-based adhesive tape containing Pico Pale 100 (manufactured by Rika Kakyures)
  • the temperature history display body according to Comparative Example 1 uses the same temperature sensitive agent as in Example 1, when the temperature is 9 ° C. or higher, the coloring layer should be discolored. However, the color change of the ink was confirmed at 4 ° C. This is considered to be because the temperature-sensitive layer is damaged when the diffusion preventing layer is pulled out.
  • Bromothymol blue (Wako Pure Chemical, 6 g) is dissolved in ethanol (Wako Pure Chemical, 230 g) as an ink containing a color former, and lithium nitrate (Wako Pure Chemical, 1.5 g) is used as a conductive material.
  • a temperature history display was prepared in the same manner as in Example 1 except that the ink obtained by addition was used, and a thermochromic confirmation experiment was performed.
  • a temperature history display body was produced in the same manner as in Example 1 except that isopropyl palmitate (manufactured by Wako Pure Chemical Industries, Ltd., melting point: 12 ° C.) was used as the temperature sensitive agent. Further, a thermochromic confirmation experiment was conducted in the same manner as in Example 1 except that the set temperature was changed from 5 ° C. to 12 ° C. and the temperature at which the diffusion preventing layer was pulled out was 5 ° C.
  • the temperature history display body did not change up to the set temperature of 11 ° C., but when stored at 12 ° C., the ink started to change from colorless to blue after 9 minutes. Further, the color change of printing was completed after 18 minutes. Again, the set temperature was 4 ° C., but the print remained blue. Thereafter, the tape was taken out from the thermostat and analyzed, and as a result, it was confirmed that the temperature sensitive layer melted and diffused to the printing paper, and that the developer was in contact with the printing ink and colored.
  • the first layer containing the color developer, the second layer containing the temperature sensitive agent, the diffusion preventing layer with the temperature sensitive adhesive tape attached, and the color developing layer on which the color ink is printed are formed on the tape base material.
  • temperature detection starts by removing the diffusion prevention layer, and from the control temperature of the object to be measured. It was confirmed that the deviation of Moreover, it turned out that preset temperature can be adjusted by selecting the kind of thermosensitive agent to be used.
  • a tape (a non-slip tape manufactured by 3M Co., Ltd.) in which a silicone-based adhesive was applied to glass fiber reinforced silicone was affixed to the end portion 5 mm of the diffusion preventing layer, and a temperature history display was produced in the same manner as in Example 1.
  • a sectional view of the produced temperature history display body is shown in FIG. 10, and a top view is shown in FIG. 10 and 11, a non-slip tape 10 is provided at the end of the diffusion preventing layer 6.
  • SYMBOLS 1 Adhesion layer, 2 ... Base material, 3 ... 1st layer, 4 ... 2nd layer, 5 ... Adhesive, 6 ... Diffusion prevention layer, 7 ... Color development layer, 8 ... Color development agent, 9 ... Color development or discoloration Color developing agent, 10 ... Anti-slip tape, 11 ... Non-porous member, 12 ... Temperature sensitive layer, 13 ... Container, 14 ... Temperature history display, 15 ... Printing device, 16 ... Injection device, 17 ... Film removal device

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)

Abstract

L'objectif de la présente invention est de concevoir un corps d'affichage d'historique de température qui peut être stocké à température ambiante et qui peut être activé facilement à un moment défini arbitrairement. A cette fin, un corps de détection de température selon la présente invention comporte : un substrat ; une couche de formation de couleur comprenant un agent de formation de couleur ; une couche sensible à la température comprenant un agent de développement qui favorise la formation de la couleur de l'agent de formation de couleur ou un changement de couleur de celui-ci, et un agent sensible à la température qui fond lorsqu'une température prescrite est dépassée ; et une couche de prévention de diffusion qui est disposée entre la couche de formation de couleur et la couche sensible à la température et qui empêche la diffusion de l'agent de développement dans la couche de formation de couleur. La couche sensible à la température, la couche de prévention de diffusion et la couche de formation de couleur sont empilées dans cet ordre sur le substrat, une surface latérale de la couche sensible à la température est recouverte d'un élément non poreux, et la couche de prévention de diffusion est fixée à l'élément non poreux au moyen d'un agent adhésif qui se détache à une température inférieure ou égale à une température prescrite.
PCT/JP2017/002047 2016-03-15 2017-01-23 Corps d'affichage d'historique de température, son procédé de fabrication et son procédé d'utilisation WO2017159040A1 (fr)

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JP2016-050389 2016-03-15
JP2016050389A JP6511408B2 (ja) 2016-03-15 2016-03-15 温度履歴表示体、その製造方法、およびその使用方法

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US20200041359A1 (en) * 2017-04-17 2020-02-06 Hitachi Industrial Equipment Systems Co., Ltd. Temperature Detecting Material, Temperature Detecting Ink Using Same, Temperature Indicator, and Product Control System

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US10172734B2 (en) 2013-03-13 2019-01-08 DePuy Synthes Products, Inc. Capture tube mechanism for delivering and releasing a stent

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JPH11258369A (ja) * 1998-03-09 1999-09-24 Toyo Ink Mfg Co Ltd 時間または温度−時間積算値の表示材およびそれを用いた表示方法
JP2004077285A (ja) * 2002-08-19 2004-03-11 Oji Paper Co Ltd 温度管理用シートセット
JP2004257828A (ja) * 2003-02-25 2004-09-16 Kuromikku:Kk 示温装置

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JPS5243476A (en) * 1975-10-03 1977-04-05 Nippon Oil & Fats Co Ltd Temperature indicating material
JPH11258369A (ja) * 1998-03-09 1999-09-24 Toyo Ink Mfg Co Ltd 時間または温度−時間積算値の表示材およびそれを用いた表示方法
JP2004077285A (ja) * 2002-08-19 2004-03-11 Oji Paper Co Ltd 温度管理用シートセット
JP2004257828A (ja) * 2003-02-25 2004-09-16 Kuromikku:Kk 示温装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200041359A1 (en) * 2017-04-17 2020-02-06 Hitachi Industrial Equipment Systems Co., Ltd. Temperature Detecting Material, Temperature Detecting Ink Using Same, Temperature Indicator, and Product Control System
US11933677B2 (en) * 2017-04-17 2024-03-19 Hitachi Industrial Equipment Systems Co., Ltd. Temperature detecting material, temperature detecting ink using same, temperature indicator, and product control system

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