WO2015045799A1 - 熱履歴表示材 - Google Patents

熱履歴表示材 Download PDF

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Publication number
WO2015045799A1
WO2015045799A1 PCT/JP2014/073489 JP2014073489W WO2015045799A1 WO 2015045799 A1 WO2015045799 A1 WO 2015045799A1 JP 2014073489 W JP2014073489 W JP 2014073489W WO 2015045799 A1 WO2015045799 A1 WO 2015045799A1
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Prior art keywords
history display
heat history
layer
group
resin layer
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PCT/JP2014/073489
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English (en)
French (fr)
Japanese (ja)
Inventor
西田　光生
戸川　惠一朗
春彦 成澤
辻井　康人
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東洋紡株式会社
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Publication of WO2015045799A1 publication Critical patent/WO2015045799A1/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
    • G01K11/12—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
    • G01K11/16—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 of organic 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems

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.
  • Patent Document 1 Japanese Patent Laid-Open No. 07-049656.
  • the structure of the conventional temperature indicating material was extremely complicated.
  • the temperature change experienced can be displayed, it does not display the thermal history, that is, the hue change based on the experienced temperature and the history of time spent under that temperature (temperature-time history). It wasn't something to do.
  • Patent Document 2 Japanese Patent Laid-Open No. 2009-299013
  • Patent Document 3 Japanese Patent Laid-Open No. 2009-300986
  • Patent Document 4 Japanese Patent Laid-Open No. 2009-298470.
  • Patent Publication describes a temperature time history display body including a polymer composition comprising a polymer and a dye fixed in a specific molecular dispersion state in the polymer.
  • the 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 is irreversibly changed to a hue different from the initial hue.
  • JP 07-049656 A JP 2009-299013 A JP 2009-3000986 A JP 2009-298470 A
  • 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.
  • the inventors of the present invention may not cause the above-described irreversible discoloration as described above when exposed to ultraviolet rays, and the temperature / time history display body does not function normally as a heat history display material. I found out that there was a fear.
  • an object of the present invention is to provide a heat history display material that can accurately display the heat history (temperature-time history) of an article by hue change even when exposed to ultraviolet rays.
  • the present invention provides the following heat history display material.
  • 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 heat history display material comprising an outer resin layer having ultraviolet absorptivity on at least one surface side of the heat history display layer.
  • the heat history display material according to any one of [1] to [3], further including a base material.
  • the substrate has a through-hole penetrating in the thickness direction, The heat history display layer according to [4], wherein the heat history display layer is embedded in the through hole.
  • 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 [8], which is an oligophenylene vinylene compound represented by the formula:
  • a heat history display material with a release layer comprising the heat history display material according to [7] and a release layer laminated on the surface of the adhesive resin layer opposite to the outer resin layer.
  • 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 heat history display material of the present invention comprises an outer resin layer made of a resin having ultraviolet absorptivity, so that it is left for a long period of time under an ultraviolet ray (for example, outdoors, fluorescent lamps, LEDs, incandescent bulbs). Even if it is), the thermal history (temperature-time history) of the article can be accurately displayed by the hue change.
  • an ultraviolet ray for example, outdoors, fluorescent lamps, LEDs, incandescent bulbs.
  • FIG. 1 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 base material used for the heat history display material shown by FIG.
  • 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 an outer resin layer 10; a fluorescent dye, and irreversibly discolors to a hue different from the initial hue when held for a certain period of time at a temperature above a specific temperature.
  • the heat history display layer 20; the organic thin film layer 40 is included in this order.
  • the base material 30 is arrange
  • 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 containing such a fluorescent dye is held at a specific temperature or higher for a predetermined time or longer, the molecular dispersion state of the fluorescent dye molecules contained in the heat history display layer 20 changes, and as a result, the fluorescent dye Therefore, the hue of 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 in close proximity to each other, and light emission by a single fluorescent dye molecule is caused by energy transfer between 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 a state in which the monomer state and the excimer state are mixed. Appears to change continuously (or step by step).
  • 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 is attached is known. It is preferable in that it can be performed.
  • 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.
  • Fluorescent dyes preferably used that can be excited by visible light and emit fluorescence in the visible region in both the monomer state and the excimer state are oligophenylene vinylene compounds.
  • oligophenylene vinylene compounds that are relatively noticeable in hue change and easy to visually confirm, 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.
  • 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 the initial state when the binder resin and the fluorescent dye fixed in a specific molecular dispersion state in the binder resin are held at a temperature higher than a specific temperature for a certain period of time. 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.
  • R 1 or R 2 is the number of carbon atoms as the fluorescent dye.
  • examples thereof include oligophenylene vinylene compounds represented by the above formula, which are 15 to 36 alkoxy groups.
  • the binder resin having appropriate compatibility is preferably a polyester resin.
  • the acid value of the binder resin (polyester resin or the like) is preferably 0.5 to 45 eq / 1t, more preferably 1 to 35 eq / 1t, and most preferably 1 to 30 eq / 1t.
  • the acid value contained in the polyester resin exceeds 45 eq / 1t, it is irreversibly changed to a hue different from the initial hue even when held at a temperature above a specific temperature for a certain period of time when exposed to ultraviolet rays. It will not discolor and will not function as a heat history display material. If the acid value is less than 0.5 eq / 1t, the cost increases during production, which tends to be impractical.
  • an acid value can be measured by the titration using potassium hydroxide like the below-mentioned Example, for example.
  • Examples of the method for adjusting the acid value to 0.5 to 45 eq / 1t include a method for adjusting a glycol / dicarboxylic acid molar ratio during polyester synthesis and a method for lowering the thermal history during removal.
  • the molar ratio of glycol / dicarboxylic acid is preferably 2.10 to 1.60, more preferably 2.05 to 1.65, and most preferably 2.00. ⁇ 1.70.
  • glycol / dicarboxylic acid molar ratio is less than 1.6, the acid value tends to be high, and if the glycol / dicarboxylic acid molar ratio exceeds 2.1, the production cost increases, so that it tends to be impractical.
  • the heat history display material of the present invention When the heat history display material of the present invention is exposed to ultraviolet rays by constituting the outer resin layer with a resin having ultraviolet absorptivity (for example, left outdoors under a fluorescent lamp, LED, incandescent bulb for a long time).
  • a resin having ultraviolet absorptivity for example, left outdoors under a fluorescent lamp, LED, incandescent bulb for a long time.
  • the thermal history temperature-time history
  • the display accuracy of the thermal history (temperature-time history) can be further increased.
  • the effect of controlling the acid value of the binder resin is considered to be effective when all the ultraviolet rays cannot be absorbed even if the outer resin layer is given ultraviolet absorption characteristics.
  • the content of the fluorescent dye in the heat history display layer 20 is preferably 0.01 to 10% by weight, more preferably 0.5 to 5% by weight with respect to 100% by weight of the binder resin.
  • the dye content is within such a range that when the dye in the polymer composition is held for a certain period of time at a temperature above a specific temperature, the polymer and the polymer are changed to a hue different from the initial hue. It is desirable to adjust according to the compatibility of the dye.
  • 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 made 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 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 including 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, and antioxidants. .
  • 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 outer resin layer 10 is a layer disposed on one main surface (upper surface in FIG. 1) of the heat history display layer 20. By disposing the outer resin layer 10 on one main surface of the heat history display layer 20, the main surface can be covered and protected from ultraviolet rays.
  • the outer resin layer 10 is composed of a translucent resin layer 11 and an adhesive resin layer 12 laminated on the surface on the heat history display layer 20 side.
  • the adhesive resin layer 12 is a layer for adhering the outer resin layer 10 to the heat history display layer 20 (and a base material 30 described later).
  • the surface on the outer resin layer 10 side in the heat history display material 1 is the surface on the outermost surface when the heat history display material 1 is attached to an article (surface 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, it is preferable that the outer resin layer 10 has translucency. That is, it is preferable that the translucent resin layer 11 and the adhesive resin layer 12 have translucency.
  • the outer side resin layer 10 has ultraviolet absorptivity.
  • the ultraviolet transmittance of the outer resin layer 10 is preferably 1.01 to 5%, more preferably 0.05 to 3%.
  • the outer resin layer 10 having ultraviolet absorptivity the hue of the heat history display layer 20 is changed regardless of (or approximately) the amount of ultraviolet light irradiated on the article to which the heat history display material 1 is adhered.
  • the thermal history of the article can be displayed stably and accurately.
  • the ultraviolet transmittance can be determined by, for example, the Lambert Bale method.
  • at least one of the translucent resin layer 11 and the adhesive resin layer 12 constituting the outer resin layer 10 only needs to have ultraviolet absorptivity.
  • the resin constituting the translucent resin layer 11 having ultraviolet absorptivity is not particularly limited as long as it has ultraviolet absorptivity.
  • thermoplastic resin examples include polyester resins (polyethylene terephthalate (PET), copolymers of PET and 1,4-cyclohexanedimethanol (PETG), polybutylene terephthalate, polyethylene naphthalate, etc.); acrylic resins; Polystyrene resin (polyamide resin (nylon 6, nylon 6.6, nylon 12, nylon 4.6, etc.)); polyolefin resin (polyethylene, polypropylene, etc.); vinyl halide resin (polyvinyl chloride, polyvinylidene chloride, Polyvinyl fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene); cellulose resin; polycarbonate resin; polyacrylonitrile resin.
  • polyester resins polyethylene terephthalate (PET), copolymers of PET and 1,4-cyclohexanedimethanol (PETG), polybutylene terephthalate, polyethylene naphthalate, etc.
  • acrylic resins examples include Polysty
  • preferable resins include polyester resins and cellulose resins, and particularly preferable resins include polyethylene terephthalate, polybutylene terephthalate, polynaphthalene terephthalate, and polycarbonate.
  • the translucent resin layer 11 is preferably a film-like member obtained by uniaxially or biaxially stretching these resins.
  • the ultraviolet absorber is not particularly limited, and for example, any of the ultraviolet absorbers for thermoplastic resins such as naphthalene series, benzophenone series, benzotriazole series and salicylic acid ester series can be used.
  • examples of such ultraviolet absorbers include polyethylene naphthalene, naphthalene dicarboxylic acid copolyester, 2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′- Examples thereof include dihydroxy-4-methoxybenzophenone, 2-hydroxyphenylbenzotriazole, and phenyl salicylate.
  • polyethylene naphthalene and naphthalene dicarboxylic acid copolyester are preferably used, and polyethylene naphthalene is more preferably used from the viewpoints of heat resistance and water resistance.
  • these ultraviolet absorbers can be used individually or in combination of 2 or more types,
  • stabilizers, such as antioxidant and a hindered amine may be used together.
  • the blending amount of the ultraviolet absorber in the translucent resin layer 11 is preferably about 0.01 to 20% by weight based on the total weight of the translucent resin layer 11.
  • a resin having ultraviolet absorptivity itself may be used as the resin constituting the translucent resin layer 11, instead of kneading or applying the ultraviolet absorber.
  • a resin having ultraviolet absorptivity per se include polyethylene naphthalate (PEN) and polyester containing anthracene dicarboxylic acid, pyrene dicarboxylic acid or naphthacene dicarboxylic acid as a dicarboxylic acid component.
  • the translucent resin layer 11 preferably has a predetermined translucency so that the color change of the internal heat history display layer can be visually confirmed.
  • a metal foil may be included as part of the translucent resin layer 11.
  • the thickness of the translucent resin layer 11 can be arbitrarily set, but is usually preferably about 10 to 200 ⁇ m. When the thickness of the translucent resin layer 11 is less than 10 ⁇ m, the ultraviolet absorptivity becomes insufficient. On the other hand, when it is thicker than 200 ⁇ m, the discoloration of the dye that has received the heat history is lowered, and it becomes difficult to accurately display the heat history and the time elapsed by the product.
  • the adhesive resin layer 12 can be a pressure-sensitive adhesive layer composed of an acrylic, silicone-based, urethane-based or rubber-based pressure-sensitive adhesive, or can be an adhesive layer composed of an adhesive.
  • the adhesive resin layer 12 may be provided with ultraviolet absorptivity.
  • the above-described ultraviolet absorber is kneaded into the resin constituting the adhesive resin layer 12, or the resin itself has ultraviolet absorptivity. May be used.
  • the thickness of the adhesive resin layer 12 is usually about 0.05 to 5 ⁇ m.
  • the outer resin layer 10 is attached to one surface of the heat history display layer 20 (the surface that is the outermost surface when the heat history display material 1 is attached to an article (attachment).
  • the surface on the side opposite to the surface to be applied)) is provided only on the side, but the surface on the side to be attached to the article of the heat history display layer 20 may be irradiated with ultraviolet rays (for example, heat
  • ultraviolet rays for example, heat
  • the article to which the history display material 1 is attached is an ultraviolet transmissive resin container or the like, it is preferable to provide an outer resin layer on the side of the heat history display layer 20 attached to the article.
  • an outer resin layer may be provided instead of the organic thin film layer 40 (omitting the organic thin film layer 40), and between the organic thin film layer 40 and the heat history display layer 20 or the heat of the organic thin film layer 40.
  • An outer resin layer may be provided on the side opposite to the history display layer 20 (aside from the organic thin film layer 40). Further, the outer resin layer may be provided so as to seal the entire predetermined portion including the heat history display layer 20.
  • the outer resin layer 10 is provided on the outermost surface of the heat history display material 1, but is not necessarily provided on the outermost surface.
  • An outer resin layer may be provided as an arbitrary layer between the heat history display layer 20.
  • the outer resin layer 10 is provided so as to cover not only the heat history display layer 20 but also one surface of the substrate 30, but the outer resin layer is at least a heat history display layer. 20 need only be provided so as to cover 20, and need not necessarily be provided so as to cover the base material 30.
  • Organic thin film layer 40 is a layer disposed on the other main surface (the lower surface in FIG. 1) of the thermal history display layer 20. By disposing the organic thin film layer 40 on the other main surface of the heat history display layer 20, the main surface can be covered and protected. In addition, the organic thin film layer 40 protects an article having a heat history display material attached thereto from such an eluate in preparation for a situation in which a part of the components of the heat history display layer 20 is eluted by heat. Also plays a role.
  • the material constituting the organic thin film layer 40 is not particularly limited, and examples thereof include polyethylene terephthalate, polyethylene, polypropylene, and polylactic acid.
  • the base material 30 is a layer for covering and protecting all the sides of the heat history display layer 20. In addition to the outer resin layer 10 and the like, it also plays a role of securing an appropriate rigidity of the heat history display material 1 as a label used for sticking to an article. As in the embodiment shown in FIG. 1, 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 32 having the same shape as that of the heat history display layer 20 at the center is used as the base material 30.
  • the shape of the through-hole 32 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 base material 30 can be selected, for example, from the thermoplastic resins exemplified above for the outer resin layer 10, but selecting a material having ultraviolet absorptivity increases the thermal history of the article. This is advantageous for accurate display.
  • the thickness of the base material 30 can be the same as or approximately the same as the thickness of the heat history display layer 20.
  • an adhesive resin layer 31 is laminated on the surface of the base material 30 on the organic thin film layer 40 side.
  • the adhesive resin layer 31 is a layer for attaching the base material 30 to the organic thin film layer 40.
  • the configuration, material, and thickness of the adhesive resin layer 31 can be the same as those of the adhesive resin layer 12.
  • the base material 30 can be omitted.
  • the base material 30 in order to cover (seal) all the surfaces of the heat history display layer 20, it is preferable to join all sides (all end portions) of the outer resin layer 10 and the organic thin film layer 40.
  • at least one of the adhesive resin layer 12 of the outer resin layer 10 and the adhesive resin layer 31 of the base material 30 may be omitted.
  • the adhesive resin layer 50 is a layer that is optionally provided as necessary, and is a layer for adhering the heat history display material 1 to an article.
  • the adhesive resin layer 50 is provided on the outermost surface of the heat history display layer 20 opposite to the outer resin layer 10. By providing the adhesive resin layer 50, the heat history display material 1 can be used as a seal-type label.
  • the configuration, material, and thickness of the adhesive resin layer 50 can be the same as those of the adhesive resin layer 12.
  • the heat history display material of the present invention can include a support layer laminated on the outer surface of the adhesive resin layer 50 in order to increase its rigidity.
  • a material of the support layer for example, a thermoplastic resin exemplified as a material constituting the outer resin layer 10 can be used.
  • an adhesive resin layer for adhering the heat history display material 1 to an article may be further laminated on the outer surface (the outermost surface of the heat history display layer opposite to the outer resin layer). it can.
  • an adhesive resin layer adheresive resin layer 50 or another adhesive resin layer
  • the outer surface of the adhesive resin layer it is preferable to laminate a peelable layer (peeling layer) for protecting the surface of the adhesive 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 heat history display material (label) of the present invention by sticking this to an article, the article is not less than a specific temperature regardless of (or approximately) the amount of ultraviolet irradiation to the article. It is possible to accurately and easily determine whether or not the temperature has been maintained for a certain time or more by the 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.
  • the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
  • the solution viscosity of the polyester resin reduced viscosity ⁇ sp / c (dl / g)
  • the composition ratio of the polyester resin the glass transition temperature of the polyester resin
  • the acid value of the polyester resin the weather resistance test was performed according to the following method.
  • the weather resistance test was performed using an accelerated weather resistance tester QUV (manufactured by Q-Panel). In addition, after being held at 35 ° C. for 2 hours while being irradiated with UV, a test of 100 cycles was carried out with a total of 10 hours of tests held at 30 ° C. for 8 hours under humidity conditions where UV irradiation was not performed and dew condensation was taken as one cycle. .
  • QUV accelerated weather resistance tester
  • Example 1 According to the following procedure, the heat history display material having the configuration shown in FIG. 1 was produced.
  • thermal history display layer A In a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a distillation tube, ethylene glycol and propylene glycol as glycol components, terephthalic acid as dicarboxylic acid components, and a molar ratio of glycol component / dicarboxylic acid component of 2.0. Furthermore, 0.3 mol part of triethylamine is charged with respect to 200 mol parts of the monomer component (total of glycol component and dicarboxylic acid component), and 250 ° C. in a nitrogen atmosphere and 2 atm for 5 hours. The esterification reaction was carried out while gradually elevating the temperature until the distilled water was removed from the system.
  • the glass transition temperature of the copolyester resin (binder resin) A was 78 ° C., the reduced viscosity was 0.7, and the acid value was 21 eq / 1t.
  • 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 copolymerized polyester resin by 1.3% by weight and melt blended for 10 minutes to obtain a polymer composition in which the dye was uniformly dispersed in the copolymerized polyester resin.
  • the obtained polymer composition was heated and pressed at 230 ° C., and then rapidly cooled with cold water to obtain a cylindrical heat history display layer 20 (heat history display layer A) having a thickness of 50 ⁇ m and a diameter of about 2 cm.
  • the heat history display layer A was yellow.
  • outer resin layer A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m containing 0.3% by weight of an ultraviolet absorber [“ADEKA STAB LA36” manufactured by ADEKA Co., Ltd.] is prepared as the translucent resin layer 11.
  • An acrylic pressure-sensitive adhesive (“SK Dyne 701” manufactured by Soken Chemical Co., Ltd.) was applied on a gravure roll coater so that the thickness after drying was about 1.5 ⁇ m, and dried at 60 ° C. for 10 seconds. Layer 12 was formed.
  • release paper was bonded to the outer surface of the pressure-sensitive adhesive layer, and then cut out into a size of 3 cm in length and 3 cm in width to produce an outer resin layer 10 (outer resin layer A) having a pressure-sensitive adhesive layer.
  • the outer side resin layer A has ultraviolet absorptivity by blending an ultraviolet absorber (ultraviolet transmittance: 0.01%).
  • base material 30 As the base material 30, a 50 ⁇ m-thick void-containing polyester film (“Chrisper K7911” manufactured by Toyobo Co., Ltd.) was prepared, and an acrylic pressure-sensitive adhesive [manufactured by Soken Chemical Co., Ltd. 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 31. Next, after attaching release paper to the outer surface of the pressure-sensitive adhesive layer 31, a through-hole having a diameter of about 2 cm that penetrates the base material 30, the pressure-sensitive adhesive layer 31 and the release paper in the thickness direction is provided. The base material 30 which cut out to the size of 3 cm long x 3 cm wide so that it may be located, and has the adhesive layer 31 was produced.
  • organic thin film layer 40 an acrylic pressure-sensitive adhesive was prepared on a biaxially stretched PET film having a thickness of 50 ⁇ m, and an acrylic pressure-sensitive adhesive [manufactured by Soken Chemical Co., Ltd. “SK Dyne” was prepared. 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 50. Next, 51 release papers were bonded to the outer surface of the pressure-sensitive adhesive layer 50, and then cut into a size of 3 cm in length ⁇ 3 cm in width to produce an organic thin film layer 40 having the pressure-sensitive adhesive layer 50.
  • the heat history display layer 20 was overlapped with the ends thereof and attached to the heat history display layer 20 and the substrate 30.
  • the heat history display material (Example 1) which contains the adhesive resin layer (adhesive layer) 50 in the outermost surface on the opposite side to the outer side resin layer 10 of the heat history display layer 20 was obtained.
  • Example 2 A heat history display material (Example 2) was obtained in the same manner as in Example 1 except that the following outer resin layer B was used instead of the outer resin layer A.
  • Outside resin layer B A biaxially stretched PET film having a thickness of 50 ⁇ m containing 3% by weight of polyethylene naphthalate (PEN) resin is prepared as the translucent resin layer 11, and an acrylic pressure-sensitive adhesive [manufactured by Soken Chemical Co., Ltd. “ 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 12. Subsequently, release paper was bonded to the outer surface of the pressure-sensitive adhesive layer 12, and then cut into a size of 3 cm in length and 3 cm in width to produce an outer resin layer 10 (outer resin layer B) having the pressure-sensitive adhesive layer 12. In addition, this outer side resin layer B has ultraviolet absorptivity by mix
  • Example 3 A heat history display material (Example 3) was produced in the same manner as in Example 1 except that the following outer resin layer C was used instead of the outer resin layer A.
  • Outside resin layer C A biaxially stretched PEN film having a thickness of 50 ⁇ m is prepared as the translucent resin layer 11, and an acrylic adhesive (“SK Dyne 701” manufactured by Soken Chemical Co., Ltd.) is dried on one side thereof to a thickness of about 1
  • the pressure-sensitive adhesive layer 12 was formed by coating with a gravure roll coater to a thickness of 5 ⁇ m and drying at 60 ° C. for 10 seconds. Subsequently, release paper was bonded to the outer surface of the pressure-sensitive adhesive layer 12, and then cut into a size of 3 cm in length and 3 cm in width to produce an outer resin layer 10 (outer resin layer C) having the pressure-sensitive adhesive layer 12. Since the outer resin layer C is a PEN film, it has ultraviolet absorptivity (ultraviolet transmittance: 0.05%).
  • Example 4 A heat history display material (Example 4) was produced in the same manner as in Example 1 except that the following heat history display layer B was used instead of the heat history display layer A.
  • the glass transition temperature of the copolyester resin (binder resin) B was 78 ° C., the reduced viscosity was 0.7, and the acid value was 42 eq / 1t.
  • the heat history display layer B was obtained in the same manner as the heat history display layer A by using the copolyester resin B.
  • Example 1 A heat history display material (Comparative Example 1) was produced in the same manner as in Example 1 except that the following outer resin layer D was used instead of the outer resin layer A.
  • Outside resin layer D A biaxially stretched PET film having a thickness of 50 ⁇ m is prepared as the translucent resin layer 11, and an acrylic pressure-sensitive adhesive (“SK Dyne 701” manufactured by Soken Chemical Co., Ltd.) is dried on one side thereof to a thickness of about 1
  • the pressure-sensitive adhesive layer 12 was formed by coating with a gravure roll coater to a thickness of 5 ⁇ m and drying at 60 ° C. for 10 seconds. Subsequently, release paper was bonded to the outer surface of the pressure-sensitive adhesive layer 12, and then cut out into a size of 3 cm in length and 3 cm in width to produce an outer resin layer 10 (outer resin layer D) having the pressure-sensitive adhesive layer 12.
  • the outer side resin layer D is a PET film, it has substantially no ultraviolet absorptivity (ultraviolet transmittance: 75.6%).

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Theoretical Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
PCT/JP2014/073489 2013-09-27 2014-09-05 熱履歴表示材 WO2015045799A1 (ja)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2010261728A (ja) * 2009-04-30 2010-11-18 Pilot Ink Co Ltd 封入式可逆熱変色性表示体及びその製造方法
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2010261728A (ja) * 2009-04-30 2010-11-18 Pilot Ink Co Ltd 封入式可逆熱変色性表示体及びその製造方法
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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