WO2015075996A1 - 熱履歴表示材 - Google Patents

熱履歴表示材 Download PDF

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Publication number
WO2015075996A1
WO2015075996A1 PCT/JP2014/073492 JP2014073492W WO2015075996A1 WO 2015075996 A1 WO2015075996 A1 WO 2015075996A1 JP 2014073492 W JP2014073492 W JP 2014073492W WO 2015075996 A1 WO2015075996 A1 WO 2015075996A1
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WIPO (PCT)
Prior art keywords
layer
history display
heat history
group
coating layer
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Ceased
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PCT/JP2014/073492
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English (en)
French (fr)
Japanese (ja)
Inventor
戸川　惠一朗
西田　光生
辻井　康人
直士 中島
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Toyobo Co Ltd
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Toyobo Co Ltd
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Publication of WO2015075996A1 publication Critical patent/WO2015075996A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • 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
    • G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K3/00—Thermometers giving results other than momentary value of temperature
    • G01K3/02—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values
    • G01K3/04—Thermometers giving results other than momentary value of temperature giving means values; giving integrated values in respect of time

Definitions

  • the present invention relates to a heat history display material for displaying a heat history experienced by an article, and more specifically, includes a heat history display layer containing a predetermined dye, and changes in hue of the heat history display layer.
  • the present invention relates to a heat history display material capable of displaying a heat history experienced by an article.
  • a temperature indicating material whose hue changes with temperature changes is attached to the article, and the temperature change experienced by the article is indicated.
  • a technique for grasping from a hue change of a material is conventionally known [for example, JP 07-049656 A (Patent Document 1)].
  • the structure of the conventional temperature indicating material was extremely complicated.
  • the temperature change experienced can be displayed, the thermal history is not displayed, ie, the hue change based on the experienced temperature and the history of the time placed under that temperature (temperature-time history). It wasn't something to do.
  • Patent Document 2 discloses a polymer comprising a polymer and a dye fixed in a specific molecular dispersion state in the polymer. A temperature time history display comprising the composition is described. When this temperature / time history display body is held at a temperature equal to or higher than a specific temperature for a certain period of time, the color changes to a hue different from the initial hue.
  • thermal history display material such as a temperature / time history display body can be suitably applied to an application in which the thermal history (temperature-time history) of an article is displayed by changing its hue by sticking to a certain article. Somewhere, it is required that the heat history of the article can be accurately displayed.
  • an object of the present invention is to provide a heat history display material capable of accurately displaying the heat history (temperature-time history) of an article by changing the hue.
  • the present invention provides the following heat history display material.
  • a first coating layer A thermal history display layer in which an associative fluorescent dye having different fluorescence wavelengths in an excimer state and a monomer state is fixed in a specific molecular dispersion state;
  • a second coating layer in this order, The heat history display layer is a layer that changes color to a hue different from the initial hue when held for a certain period of time at a temperature equal to or higher than a specific temperature,
  • the thermal history display material whose thermal conductivity in 25 degreeC of a said 1st coating layer is 1 * 10 ⁇ 4 > W / m ⁇ 2 > K or less.
  • the first covering layer is disposed on the heat history display layer so as to cover one main surface of the heat history display layer;
  • the third covering layer is a layer having a through hole penetrating in the thickness direction,
  • the fluorescent dye has the following formula:
  • each R independently represents hydrogen, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyl group, a hydroxyalkyl group, a halogen group, a phenylene vinylene group or a cyano group.
  • Each R 1 independently represents hydrogen, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyl group, a hydroxyalkyl group, a halogen group, a phenylene vinylene group or a cyano group;
  • Each R 2 independently represents hydrogen, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyl group, a hydroxyalkyl group, a halogen group, a phenylene vinylene group or a cyano group.
  • the heat history display material according to any one of [1] to [9], which is an oligophenylene vinylene compound represented by the formula:
  • the heat history display material (label) of the present invention includes a heat history display layer that irreversibly discolors to a hue different from the initial hue when held for a certain period of time at a temperature equal to or higher than a specific temperature.
  • the thermal history (temperature-time history) experienced by can be accurately displayed by the hue change of the thermal history display layer.
  • the thermal history of the article that is, the history of elapsed time above a specific temperature (whether it has been held for a certain period of time at a temperature above a specific temperature) can be accurately and easily determined by the hue change of the heat history display layer.
  • the thermal history display material of the present invention can stably and accurately display the thermal history of the article regardless of (or approximately) the environmental temperature where the article to which it is attached is placed. This is extremely advantageous.
  • FIG. 2 It is sectional drawing which shows typically one Embodiment of the heat history display material which concerns on this invention. It is a top view which shows typically the 3rd coating layer used for the heat history display material shown by FIG. 2 is a cross-sectional view schematically showing a heat history display material produced in Example 1.
  • FIG. 2 is a cross-sectional view schematically showing a heat history display material produced in Example 1.
  • FIG. 1 is a cross-sectional view schematically showing an embodiment of a heat history display material according to the present invention.
  • the heat history display material 1 shown in FIG. 1 contains a first coating layer 10; a fluorescent dye, and is irreversibly changed to a hue different from the initial hue when held for a certain time at a temperature higher than a specific temperature.
  • the heat history display layer 20 that changes color to the second coating layer 40 is included in this order.
  • the third coating layer 30 is disposed so as to cover the side surface of the heat history display layer 20, and the third coating layer 40 is laminated on the surface opposite to the heat history display layer 20 in the second coating layer 40.
  • the adhesive resin layer 50 is further provided.
  • the thermal history display material 1 is used by being attached to an article whose thermal history is to be detected so that the first coating layer 10 is the outermost surface, specifically, a third adhesive resin layer. 50 is used by sticking to the article.
  • Thermal history display layer 20 is a layer in which a predetermined fluorescent dye is fixed in a specific molecular dispersion state. It has the property of irreversibly changing to a hue different from the hue. In order to express such properties, in the present invention, associative fluorescent dyes having different fluorescence wavelengths in the excimer state and the monomer state are used as the fluorescent dye.
  • the associative fluorescent dye has a different hue depending on its molecular dispersion state. Even when the thermal history display layer 20 is formed using the fluorescent dye in a specific molecular dispersion state, the thermal history display is performed. The specific molecular dispersion state can be maintained in the layer 20. When the heat history display material 1 containing such a fluorescent dye is held at a specific temperature or more for a predetermined time or more, the molecular dispersion state of the fluorescent dye molecules contained in the heat history display layer 20 changes, and as a result, fluorescence The hue of the dye (and hence the heat history display layer 20) changes.
  • Associative fluorescent dyes having different fluorescence wavelengths in the excimer state and the monomer state are usually the same when the fluorescent dye molecules are close to each other and when one of them absorbs light and enters an excited state, the other ground state molecule and excimer (Excited aggregate) is formed, and excimer emission on the longer wavelength side than monomer emission is exhibited.
  • the “excimer state” is a state in which a plurality of fluorescent dye molecules are associated with or close to each other, and light emission by a single fluorescent dye molecule is caused by energy transfer between the molecules when the fluorescent dye molecules are associated with or in close proximity to each other. It means a state that causes light emission (excimer light emission) at a longer wavelength than (monomer light emission).
  • the “monomer state” means that since the fluorescent dye molecules are separated from each other than the excimer state, energy transfer between the fluorescent dye molecules does not occur, and light emission (monomer light emission) of the fluorescent dye molecules at that time is simply It means a state corresponding to light emission when one excited molecule returns to the ground state.
  • the boundary between the transition between the monomer state and the excimer state is continuous. Therefore, in the transition from the monomer state to the excimer state or the transition from the excimer state to the monomer state, the fluorescent dye molecule partially passes through the state in which the monomer state and the excimer state are mixed. Appears to change continuously (or stepwise).
  • the hue of the heat history display layer 20 changes color continuously (or stepwise) according to the heat history (temperature-time history)
  • a more detailed heat history of the article to which the heat history display material 1 is attached is obtained. It is preferable in that it can be known.
  • the fluorescent dye used in the present invention has both excimer emission and monomer emission in the visible region. Accordingly, the heat history display layer 20 can be imparted with a property of changing to a hue different from the initial hue when held at a temperature equal to or higher than a specific temperature for a certain period of time.
  • the difference in maximum fluorescence wavelength between excimer emission and monomer emission of the fluorescent dye is preferably greater than 100 nm. More preferably, it is 120 nm or more, and most preferably 150 nm or more. If the difference in maximum fluorescence wavelength is 100 nm or less, the hue change when held at a temperature above a specific temperature for a certain period of time is small, and it may be difficult to visually identify the hue change.
  • the fluorescent dye is preferably capable of emitting fluorescence when excited by light in the visible region.
  • the hue of the heat history display layer 20 can be easily visually identified under a normal environment where the article is placed (under illumination or sunlight).
  • the wavelength of visible light that can be absorbed by the fluorescent dye in the monomer state and the absorbance at that wavelength, and the wavelength of visible light that can be absorbed by the fluorescent dye in the excimer state and the absorbance at that wavelength may be the same, or at least Some may be different.
  • oligophenylene vinylene compounds that are relatively noticeable in hue change and easy to visually confirm.
  • each R independently represents hydrogen, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyl group, a hydroxyalkyl group, a halogen group, a phenylene vinylene group, or a cyano group.
  • R 1 independently represents hydrogen, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyl group, a hydroxyalkyl group, a halogen group, a phenylene vinylene group or a cyano group
  • R 2 each independently And hydrogen, an alkyl group having 1 to 36 carbon atoms, an alkoxy group having 1 to 36 carbon atoms, a hydroxyl group, a hydroxyalkyl group, a halogen group, a phenylene vinylene group or a cyano group.
  • R is preferably hydrogen or a hydroxyl group, more preferably hydrogen.
  • R 1 is preferably an alkoxy group having 1 to 36 carbon atoms, and more preferably an alkoxy group having 15 to 36 carbon atoms.
  • R 2 is preferably an alkoxy group having 1 to 36 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms.
  • the heat history display layer 20 is preferably a layer containing a binder resin together with a fluorescent dye.
  • the fluorescent dye is dispersed and fixed in the binder resin in the heat history display layer 20.
  • the binder resin is selected so that it has translucency and can uniformly dissolve and disperse the fluorescent dye.
  • the binder resin is preferably a resin whose physical properties reversibly change with heating and cooling, and is preferably a solvent-soluble resin or a thermoplastic resin from the viewpoint of processability and the like.
  • the glass transition temperature of the binder resin is preferably 50 ° C. or higher from the viewpoint of processability and the like.
  • binder resins include polyolefin resins (polyethylene, polypropylene, etc.); cycloolefin resins; polyester resins (polyethylene terephthalate (PET), copolymer of PET and 1,4-cyclohexanedimethanol ( PETG), polybutylene terephthalate, polyethylene naphthalate, etc.); polycarbonate resin; polyimide resin; polyamideimide resin; polyetherimide resin; polyurethane resin; polyvinyl resin (polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoro) Ride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl acetate, polyvinyl alcohol, poly-2-vinylpyridine, polyvinyl butyral, etc.); polystyrene Fat; Polyamide resin (nylon 6, nylon 6.6, nylon 12, nylon 4.6, etc.); polyacrylonitrile resin; acrylic resin (polyrene Fat; Poly
  • Biodegradable polymers such as gelatin, cellulose, polylactic acid, polycaprolactone, modified polyvinyl alcohol, and casein, and hydrocarbon compounds such as paraffin can also be used.
  • polyesters it is preferable to use polyesters, and it is particularly preferable to use PET and PETG.
  • the binder resin and the fluorescent dye preferably have appropriate compatibility (affinity).
  • “Moderate compatibility (affinity)” means that when the binder resin and the fluorescent dye fixed in a specific molecular dispersion state in the binder resin are held at a temperature equal to or higher than a specific temperature for a predetermined time or longer, It is compatible to such a degree that it irreversibly changes to a hue different from the hue of.
  • both are kept separated in the produced heat history display layer 20, and can be kept at a temperature above a specific temperature for a certain period of time. This state is maintained. In this case, since the fluorescent dye molecules are always close to each other, the monomer state cannot be expressed either before or after being held at a temperature equal to or higher than a specific temperature for a predetermined time or longer.
  • the fluorescent dye when the compatibility between the binder resin and the fluorescent dye is too high, the fluorescent dye is completely dissolved in the binder resin, so that depending on the content of the fluorescent dye in the heat history display layer 20, the specific temperature or more is exceeded.
  • the fluorescent dye molecules are separated and dispersed before and after being held at a temperature of a certain time or longer, and the excimer state cannot be expressed.
  • An example of a combination of a binder resin and a fluorescent dye having appropriate compatibility is a polyester resin (particularly PET, PETG) or polystyrene as a binder resin and an alkoxy having 15 to 36 carbon atoms as R 1 as a fluorescent dye. And a combination with an oligophenylene vinylene compound represented by the above formula wherein R 2 is an alkoxy group having 1 to 3 carbon atoms.
  • the content of the fluorescent dye in the heat history display layer 20 is preferably 0.01 to 10% by weight, more preferably 0.1 to 8% by weight, based on 100% by weight of the binder resin. More preferably, it is 5 to 5% by weight. In such a range, the content of the fluorescent dye is such that when the fluorescent dye is held at a temperature higher than a specific temperature for a certain period of time, the binder resin and the fluorescent dye are changed in color to a hue different from the initial hue. It is desirable to adjust according to compatibility.
  • the molecules of the fluorescent dye in the heat history display layer 20 are initially dispersed and fixed in a monomer state. In this case, when the heat history display material is exposed to a specific temperature or more for a predetermined time or more, the dispersed state of the fluorescent dye molecules shifts to the excimer state, and the hue of the fluorescent dye changes.
  • the “specific temperature” is preferably a temperature equal to or higher than the glass transition temperature of the heat history display layer 20. Below the glass transition temperature, the fluorescent dye molecules are constrained by the binder resin in a sufficiently spaced and dispersed state, and the dispersion state does not change, but when the glass transition temperature is exceeded, the polymer chains of the binder resin are entangled. As it becomes loose, the movement of the polymer chain increases, this restriction is released, the fluorescent dye molecule becomes movable, an excimer (excited aggregate) is formed, and the hue starts to change (red shift).
  • the concentration of the excimer (excited aggregate) increases to such a level that it can be clearly distinguished from the hue in the monomer state.
  • Fluorescent dye molecules that have been unconstrained have a large amount of movement at higher temperatures. Therefore, the higher the specific temperature, the more the excimer (excited aggregate) concentration can be clearly distinguished from the hue in the monomer state. The time until it becomes high enough to change is shortened.
  • the design of the heat history display material (that is, how much heat history causes the hue change) is desired. be able to.
  • the fluorescent dye is mixed and dispersed in the molten binder resin, and water or the like is used during molding. Also, there is a method of solidifying by dispersing rapidly.
  • the temperature at which the fluorescent dye is mixed and dispersed in the binder resin is usually a temperature equal to or higher than the glass transition temperature of the binder resin, preferably from the glass transition temperature (K) to the glass transition temperature (K) ⁇ 2.0. More preferably, it is between glass transition temperature (K) ⁇ 1.1 and glass transition temperature (K) ⁇ 1.7.
  • the heat history display layer 20 is not limited to the above-described one in which the fluorescent dye is dispersed and fixed in the binder resin in the monomer state by melt blending, and the fluorescent dye is in the monomer state in the binder resin by other manufacturing methods.
  • the fluorescent dye and the binder resin may be uniformly mixed by a solution blend in which the fluorescent dye and the binder resin are dissolved in a solvent.
  • the heat history display layer 20 can be obtained by performing the drying process which removes a solvent.
  • the heat history display layer 20 may be formed by chemically bonding (covalently bonding) a fluorescent dye to a binder resin.
  • a chemical bond type thermal history display layer 20 the hue change rate can be delayed and the possibility that the fluorescent dye bleeds out from the thermal history display layer 20 during use can be eliminated. it can.
  • the chemical bond type heat history display layer 20 tends to require a larger amount of fluorescent dye than the heat history display layer 20 by melt blending in order to cause a hue change, within the above range, It is desirable to increase the content.
  • a reactive substituent capable of reacting with the binder resin is introduced into the fluorescent dye.
  • the reactive substituent include a hydroxyl group, an amino group, a carboxyl group, an acrylic acid group, an acrylate group, an isocyanate group, an epoxy group, cyanate esters, and benzoxazines, and preferably a hydroxyl group.
  • the fluorescent dye is an oligophenylene vinylene compound represented by the above formula
  • a reactive functional group is introduced into one or more substituents of R, R 1 and R 2 , or R, R 1 , Any one or more of R 2 may be a reactive substituent.
  • the binding position of the fluorescent dye in the binder resin is not particularly limited, and the fluorescent dye may be bound to the polymer main chain of the binder resin, or the fluorescent side chain may be fluorescent to control the association of the fluorescent dye.
  • a dye may be bound.
  • the kind of the binder resin in the chemical bond type is not particularly limited as long as it has a substituent capable of chemically bonding with the fluorescent dye, and can be selected from those exemplified above. Further, when a branched polymer, hyperbranch, dendrimer, cross-linked polymer or the like is used as the binder resin, the mobility of the chemically bonded fluorescent dye is increased, so that the threshold of hue change can be clarified.
  • the heat history display layer 20 can contain additives in addition to fluorescent dyes and binder resins.
  • the additive include an organic, inorganic or organometallic toner, and a fluorescent brightening agent. By containing one or more of these, the hue change of the heat history display layer 20 can be further clarified.
  • Specific examples of other additives include polymers other than binder resins, antistatic agents, antifoaming agents, dyeability improvers, dyes other than the above fluorescent dyes, pigments, matting agents, stabilizers, antioxidants, ultraviolet rays Contains inhibitor.
  • antioxidants aromatic amines, phenols, and other antioxidants can be used.
  • stabilizers phosphoric acid and phosphoric acid esters are used, as well as sulfur and amines. Stabilizers can be used.
  • the heat history display layer 20 can be in the form of a film or fiber, and is preferably in the form of a film.
  • the thickness of the film-like heat history display layer 20 is not particularly limited, but is usually about 10 to 200 ⁇ m. Further, the heat history display layer 20 may be a compact having a suitable size by solidifying fine objects such as particles and fine pieces.
  • the 1st coating layer 10 is a layer arrange
  • the first covering layer 10 includes a translucent resin layer 11 and a first adhesive resin layer 12 laminated on the surface on the heat history display layer 20 side.
  • the 1st adhesive resin layer 12 is a layer for sticking the translucent resin layer 11 to the heat history display layer 20 (and 3rd coating layer 30 mentioned later).
  • the surface on the first coating layer 10 side of the heat history display material 1 is the surface on the side that is the outermost surface when the heat history display material 1 is attached to an article (on the side opposite to the surface to be attached). It is a surface on the side for visually recognizing whether or not a hue change has occurred in the heat history display layer 20. Therefore, the first coating layer 10 includes the translucent resin layer 11. The first adhesive resin layer 12 also has translucency.
  • the thermal conductivity of the first cover layer 10 is 1 ⁇ 10 4 W / m 2 K or less at 25 ° C., preferably 0.8 ⁇ 10 4 W / m 2 K or less. Regardless of the environmental temperature at which the article to which the heat history display material 1 is adhered is placed by disposing the first covering layer 10 having thermal conductivity within such a range on the outermost surface of the heat history display material 1. Regardless of (or approximately), the heat history of the article can be stably and accurately displayed by the hue change of the heat history display layer 20.
  • the thermal conductivity of the first coating layer 10 at 25 ° C. exceeds 1 ⁇ 10 4 W / m 2 K, it is affected by the environmental temperature, and the timing of the hue change differs depending on the environmental temperature. The function as a heat history display material will be impaired.
  • the timing of the hue change can be made constant, and the thermal history of the article can be displayed stably and accurately. Can do.
  • the thermal conductivity is a physical property value specific to the material constituting the layer. The larger the value, the larger the amount of heat that moves, and the easier the heat is transferred. On the other hand, the amount of heat transferred (easy heat transfer) is inversely proportional to the layer thickness.
  • the thermal conductivity in the present invention indicates the ease of transmission of net heat taking into account the thermal conductivity and the layer thickness.
  • the thermal conductivity can be obtained by a laser flash method as shown in the section of [Example] described later.
  • the layer thickness in the above formula is the total thickness of the multilayer structure when it has a multilayer structure like the first coating layer 10.
  • the resin constituting the translucent resin layer 11 is not particularly limited as long as it is a resin that has translucency and can realize the thermal conductivity in the above range when the first coating layer 10 is used.
  • Polyester resin polyethylene terephthalate (PET), copolymer of PET and 1,4-cyclohexanedimethanol (PETG), polybutylene terephthalate, polyethylene naphthalate, etc.
  • acrylic resin polyacrylic acid resin, polyacrylic resin Polyacrylate resins such as methyl methacrylate, polymethacrylate and polybutyl acrylate); polystyrene resins; polyamide resins (nylon 6, nylon 6.6, nylon 12, nylon 4.6, etc.); polyolefin resins (polyethylene, polypropylene) Etc.); Vinyl halide resin (polyvinyl chloride) , Polyvinylidene chloride, polyvinyl fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene); can be exemp
  • a coating agent capable of reducing the thermal conductivity may be applied to at least one of the main surfaces of the translucent resin layer 11.
  • the thickness of the translucent resin layer 11 is not particularly limited as long as it is a thickness capable of realizing the above range of thermal conductivity when the first coating layer 10 is used, but is preferably about 10 to 300 ⁇ m.
  • the thickness of the translucent resin layer 11 is smaller than 10 ⁇ m, the protective function of the heat history display layer 20 tends to be insufficient, and an ultraviolet absorber is added to the translucent resin layer 11 to absorb ultraviolet rays. In the case of imparting, the ultraviolet absorptivity tends to be insufficient.
  • the thickness of the translucent resin layer 11 exceeds 300 ⁇ m, the handleability when using the heat history display material for labeling or the like may be lacking.
  • the first adhesive resin layer 12 can be a pressure-sensitive adhesive layer composed of an acrylic, silicone-based, urethane-based, rubber-based or other pressure-sensitive adhesive, and is an adhesive layer composed of an adhesive. You can also.
  • the thickness of the first adhesive resin layer 12 is usually about 0.05 to 10 ⁇ m.
  • the surface on the first coating layer 10 side in the heat history display material 1 is a surface on the side for visually confirming whether or not a hue change has occurred in the heat history display layer 20. Therefore, the haze of the first coating layer 10 is preferably 40% or less, and more preferably 30% or less. The haze is measured by a method according to JIS K 7136.
  • the 2nd coating layer 40 is a layer arrange
  • the second coating layer 40 is attached with the heat history display material 1 from such an eluent in preparation for a situation where a part of the components of the heat history display layer 20 is eluted by heat. It also plays a role of protecting worn articles.
  • the second covering layer 40 is composed of a high thermal conductivity layer 41 and a second adhesive resin layer 42 laminated on the surface on the heat history display layer 20 side.
  • the second adhesive resin layer 42 is a layer for attaching the high thermal conductivity layer 41 to the heat history display layer 20 (and a third covering layer 30 described later).
  • the thermal conductivity of the second coating layer 40 is preferably 2 ⁇ 10 6 W / m 2 K or more at 25 ° C., and more preferably 3 ⁇ 10 6 W / m 2 K or more. Assuming that the first covering layer 10 described above has a predetermined thermoelectric layer property by disposing the second covering layer 40 having thermal conductivity within such a range on the surface to be adhered to the article. Regardless of (or approximately) the environmental temperature at which the article to which the heat history display material 1 is stuck is placed, the heat history of the article is more stable and more accurate by the hue change of the heat history display layer 20. Can be displayed.
  • the heat conductivity here is also defined by the above formula.
  • the layer thickness is the total thickness of the multilayer structure in the case of a multilayer structure like the second coating layer 40.
  • the material constituting the high thermal conductivity layer 41 is preferably a material that can realize the thermal conductivity in the above range when the second coating layer 40 is used.
  • high heat conductivity such as aluminum, tin, stainless steel, copper, etc. Mention may be made of metals of conductivity.
  • the thickness of the high thermal conductivity layer 41 is preferably a thickness that can realize the thermal conductivity in the above range when the second coating layer 40 is formed, and is not affected by the environmental temperature, for example, an article (for example, a heat It is preferable that the temperature is about 1 to 100 ⁇ m so that the temperature of the contents in the container to which the history display material is attached can be displayed more accurately.
  • the configuration, material, and thickness of the second adhesive resin layer 42 can be the same as those of the first adhesive resin layer 12.
  • An additive that improves the thermal conductivity of the second coating layer 40, such as metal powder, may be added to the second adhesive resin layer 42.
  • the second coating layer 40 is a second adhesive for adhering the high thermal conductivity layer 41 to the heat history display layer 20 (and a third coating layer 30 described later).
  • the present invention is not limited to such an embodiment.
  • the second coating layer 40 is composed of only the high thermal conductivity layer 41, and an adhesive resin layer is provided on the third coating layer 30 side to be described later. And the second coating layer 40 may be bonded.
  • the third covering layer 30 is a layer for covering and protecting all the sides of the heat history display layer 20.
  • it also plays a role of ensuring an appropriate rigidity of the heat history display material 1 as a label application to be attached to an article.
  • all the surfaces of the heat history display layer 20 are covered (sealed) with a plurality of coating layers. The function of stably and accurately displaying the heat history of the article by changing the hue is preferable for ensuring long-term sustainability.
  • a layer that penetrates in the thickness direction and has a through-hole 31 having the same shape as that of the heat history display layer 20 in the approximate center is used as the third covering layer 30.
  • the shape of the through hole 31 is not particularly limited, and may be a shape corresponding to the outer shape of the heat history display layer 20.
  • the material constituting the third coating layer 30 can be selected, for example, from the thermoplastic resins exemplified above for the translucent resin layer 11, but the thermal conductivity of the third coating layer 30 is the first. It is advantageous to make it higher than one coating layer 10 in order to accurately display the thermal history of the article.
  • the thickness of the third cover layer 30 can be the same as or approximately the same as the thickness of the heat history display layer 20.
  • the third coating layer 30 can be omitted.
  • the first covering layer 10 and the second covering layer 40 over the entire side.
  • at least one of the first adhesive resin layer 12 of the first coating layer 10 and the second adhesive resin layer 42 of the second coating layer 40 may be omitted.
  • the 3rd adhesive resin layer 50 is a layer provided arbitrarily as needed, and is a layer for sticking the heat history display material 1 to articles
  • the configuration, material, and thickness of the third adhesive resin layer 50 can be the same as those of the first adhesive resin layer 12.
  • An additive that improves thermal conductivity, such as metal powder, may be added to the third adhesive resin layer 50.
  • the heat history display material of the present invention may include a support layer laminated on the outer surface of the third adhesive resin layer 50 in order to increase its rigidity.
  • the support layer can be, for example, a film made of a thermoplastic resin selected from those exemplified above as the resin constituting the translucent resin layer 11.
  • a fourth adhesive resin layer for adhering the heat history display material 1 to an article can be further laminated on the outer surface thereof.
  • an adhesive resin layer (the third adhesive resin layer 50 or the fourth adhesive resin layer) is laminated on the outermost surface of the heat history display material 1 that is attached to the article.
  • this adhesiveness It is preferable to laminate a release layer for protecting the surface of the adhesive resin layer on the outer surface of the resin layer.
  • This release layer is usually laminated until sticking to an article and peeled off when sticking.
  • a release paper or the like can be used in addition to the polyester resin film and the polyolefin resin film.
  • the product can be attached to the product regardless of (or approximately) the environmental temperature at which the product and the heat history display material are placed. Can be accurately and easily determined based on a hue change of the heat history display layer. Moreover, since the heat history display material of this invention has a simple structure, it can be manufactured easily and advantageously in terms of manufacturing cost.
  • ⁇ Measurement condition ⁇ Measuring device: “TC7000 type” manufactured by ULVAC-RIKO, ⁇ Laser pulse width: 0.4 ms ⁇ Laser pulse energy: 10 J / pulse or more, Laser wavelength: 1.06 ⁇ m (Nd glass laser) ⁇ Laser beam diameter: 10 ⁇ , ⁇ Temperature measurement method: infrared sensor (thermal diffusivity measurement), thermocouple (specific heat measurement), -Measurement temperature: 25 ° C ⁇ Measurement atmosphere: in vacuum.
  • the glass transition temperature of the obtained copolyester resin was 78 ° C., and the reduced viscosity was 0.7.
  • the obtained copolyester resin was remelted, and then a C18RG dye (oligophenylene vinylene) in which R is hydrogen, R 1 is an octadecyloxy group (C 18 H 37 O—), and R 2 is a methoxy group in the above formula.
  • Compound was added to the obtained copolymer polyester resin by 1.3 wt% and melt blended for 10 minutes to obtain a polymer composition in which the fluorescent dye was uniformly dispersed in the copolymer polyester resin. .
  • the obtained polymer composition was heated and pressed at 230 ° C., and then rapidly cooled with cold water to obtain a thermal history display layer 20 (column shape having a diameter of about 2 cm) having a thickness of 50 ⁇ m.
  • the heat history display layer 20 was yellow.
  • first coating layer A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m is prepared, and an acrylic adhesive (“SK Dyne 701” manufactured by Soken Chemical Co., Ltd.) is dried on one surface thereof. It was applied with a gravure roll coater so that the subsequent thickness was about 1.5 ⁇ m, and dried at 60 ° C. for 10 seconds. Subsequently, release paper was bonded to the outer surface of the pressure-sensitive adhesive layer, and then cut into a size of 3 cm in length and 3 cm in width to obtain a first coating layer having a pressure-sensitive adhesive layer.
  • the obtained first covering layer (laminated body of PET film and pressure-sensitive adhesive layer) had a thermal conductivity of 3.1 ⁇ 10 3 W / m 2 K.
  • Second coating layer 40 a tin foil having a thickness of 25 ⁇ m was prepared, and an acrylic pressure-sensitive adhesive (“SK Dyne 701” manufactured by Soken Chemical Co., Ltd.) was applied to one surface thereof.
  • the pressure-sensitive adhesive layer 50 was formed by applying with a gravure roll coater so that the thickness after drying was about 1.5 ⁇ m and drying at 60 ° C. for 10 seconds.
  • the thermal conductivity of the tin foil as the second coating layer 40 was 2.36 ⁇ 10 6 W / m 2 K.
  • the release paper 51 was bonded to the outer surface of the pressure-sensitive adhesive layer 50, it was cut into a size of 3 cm in length and 3 cm in width to produce a second coating layer 40 having the pressure-sensitive adhesive layer 50.
  • a 50 ⁇ m-thick void-containing polyester film (“Chrisper K7911” manufactured by Toyobo Co., Ltd.) is prepared, and an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd.) is provided on one surface thereof.
  • “SK Dyne 701”] was applied with a gravure roll coater so that the thickness after drying was about 1.5 ⁇ m, and dried at 60 ° C. for 10 seconds to form an adhesive layer 32.
  • the third covering layer 30 made of the base material 33 having the pressure-sensitive adhesive layer 32 was produced by cutting into a size of 3 cm in length and 3 cm in width so as to be located in the area.
  • first covering layer A 25 ⁇ m thick biaxially stretched PET film is prepared, and an acrylic pressure-sensitive adhesive (“SK Dyne 701” manufactured by Soken Chemical Co., Ltd.) is dried on one side. It was applied with a gravure roll coater so as to be about 1.5 ⁇ m, and dried at 60 ° C. for 10 seconds. Subsequently, release paper was bonded to the outer surface of the pressure-sensitive adhesive layer, and then cut into a size of 3 cm in length and 3 cm in width to obtain a first coating layer having a pressure-sensitive adhesive layer. The obtained first coating layer (laminated body of PET film and pressure-sensitive adhesive layer) had a thermal conductivity of 1.2 ⁇ 10 4 W / m 2 K.
  • the heat history display material was attached to the trunk of the sake can (Kita Sangyo's Tokuhmusume “Ibanban”) through the outermost adhesive layer.
  • This sake can is an aluminum can with a heating function.
  • the liquor can with the heat history display material adhered was placed in each environment at temperatures of ⁇ 20 ° C. and 40 ° C., the bottom of the can was pressed to start heating, and the hue change of the heat history display material was visually observed.
  • the heat history display material of Example 1 changed from an initial yellow color to an orange color in about 5 minutes after the start of heating in any environment of ⁇ 20 ° C. and 40 ° C.
  • the heat history display material of Comparative Example 1 in the environment of ⁇ 20 ° C., it took about 10 minutes after the start of heating to change the color from the initial yellow to orange, while in the environment of 40 ° C. Below, about 3 minutes after the start of heating, the initial yellow color changed to orange, and the time until the color change varied.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)
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CN108949098A (zh) * 2018-06-21 2018-12-07 安徽扬帆充气游乐设备制造有限公司 一种高性能高粘合力pvc充气艇用胶黏剂
CN111087578A (zh) * 2019-12-31 2020-05-01 湖州师范学院 一种双稳态电致荧光变色聚合物材料及其制备方法和应用

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KR101843854B1 (ko) * 2016-10-31 2018-03-30 한국생산기술연구원 온도감응소재를 포함한 온도감응필름, 이의 제조방법 및 이를 이용한 온도감응패치 및 패치형 온도계

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JP2004115719A (ja) * 2002-09-27 2004-04-15 Sk Kaken Co Ltd 熱可逆性発消色粉粒体
JP2009300986A (ja) * 2008-05-13 2009-12-24 Toyobo Co Ltd 温度時間経歴を表示する流通履歴表示ラベル
WO2011125837A1 (ja) * 2010-03-31 2011-10-13 日油技研工業株式会社 温度管理インジケータ及びそれが付された構造物

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JP2004115719A (ja) * 2002-09-27 2004-04-15 Sk Kaken Co Ltd 熱可逆性発消色粉粒体
JP2009300986A (ja) * 2008-05-13 2009-12-24 Toyobo Co Ltd 温度時間経歴を表示する流通履歴表示ラベル
WO2011125837A1 (ja) * 2010-03-31 2011-10-13 日油技研工業株式会社 温度管理インジケータ及びそれが付された構造物

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Publication number Priority date Publication date Assignee Title
CN108949098A (zh) * 2018-06-21 2018-12-07 安徽扬帆充气游乐设备制造有限公司 一种高性能高粘合力pvc充气艇用胶黏剂
CN111087578A (zh) * 2019-12-31 2020-05-01 湖州师范学院 一种双稳态电致荧光变色聚合物材料及其制备方法和应用
CN111087578B (zh) * 2019-12-31 2022-04-05 湖州师范学院 一种双稳态电致荧光变色聚合物材料及其制备方法和应用

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