WO2014101679A1 - 热敏感标签及其制备和使用方法 - Google Patents

热敏感标签及其制备和使用方法 Download PDF

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Publication number
WO2014101679A1
WO2014101679A1 PCT/CN2013/089507 CN2013089507W WO2014101679A1 WO 2014101679 A1 WO2014101679 A1 WO 2014101679A1 CN 2013089507 W CN2013089507 W CN 2013089507W WO 2014101679 A1 WO2014101679 A1 WO 2014101679A1
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WIPO (PCT)
Prior art keywords
layer
heat sensitive
heat
dye
volatile
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PCT/CN2013/089507
Other languages
English (en)
French (fr)
Inventor
邓宗武
英晓芳
史小菊
Original Assignee
苏州华实材料技术服务有限公司
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Application filed by 苏州华实材料技术服务有限公司 filed Critical 苏州华实材料技术服务有限公司
Priority to EP13869238.9A priority Critical patent/EP2937850B1/en
Priority to US14/651,077 priority patent/US9744742B2/en
Priority to JP2015549963A priority patent/JP6387014B2/ja
Priority to BR112015015159-0A priority patent/BR112015015159B1/pt
Priority to KR1020157019544A priority patent/KR101741612B1/ko
Publication of WO2014101679A1 publication Critical patent/WO2014101679A1/zh

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/12—Coating on the layer surface on paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00—Labels, badges
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
    • 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
    • G09F2003/0257—Multilayer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor

Definitions

  • the present invention relates to a heat sensitive label for monitoring the quality status of a heat sensitive article, a method for preparing the same, and a method for monitoring the quality condition of the heat sensitive article.
  • the present invention relates to the use of volatile dyes for the manufacture of heat-sensitive labels, by the color change of the layer of adsorbent material caused by the adsorption of the volatile material after the volatile dye is volatilized, to indicate whether the heat-sensitive article is affected by temperature or Deteriorating or failing at a certain temperature for a long time. Background technique
  • Some items or products that are very sensitive to temperature need to be stored or transported at low temperatures, such as most vaccines, biological products, biologically active samples and some medicines, as well as fresh foods such as fresh milk, dairy products, fresh meat, fresh fish, etc. .
  • the expiration date, shelf life or shelf life is the main method to ensure the safe use of these goods/products, especially drugs or foods, but these methods often fail to reflect whether drugs or foods that need to be stored and transported at low temperatures are safe. Excessive exposure time at storage and storage temperatures.
  • TempTime (formerly Lifelines) in the United States first developed a label that met the requirements of the WHO and applied it to polio vaccines produced by three vaccine manufacturers, GlaxoSmithKline, Sanofi-Pasteur and Novartis.
  • the tags supplied by Temptime are mainly used according to the functions used. Class.
  • the first type is the Critical Temperature Indicator (CTI), which changes color as soon as the temperature exceeds the set value.
  • CTTI Critical Temperature-Time Indicator
  • the response time of the third type of tag needs to be longer. It is called the Time-Temperature Indicator (TTI). It is the temperature-sensitive material that changes color after receiving a certain amount of heat. This type of tag is suitable for indicating the thermal history of the vaccine. s Mark.
  • the polymer type was developed by TempTime Corporation of the United States and is based on the substitution of a substituted diacetylene derivative by solid state 1, 4-addition polymerization to form a colored polymer. The rate of the polymerization increases with increasing temperature, and the resulting polymer continues to darken the color, indicating whether the vaccine is overheated by contrast with the surrounding color.
  • This type of label needs to be screened to synthesize a suitable polymerized monomer, and the label needs to be stored at -18 ° C or even lower after the label is produced, which significantly increases the cost of label use.
  • the early enzyme-reactive indicator is essentially a type of pH indicator that releases protons H+ by measuring the hydrolysis of the enzyme-catalyzed lipid substrate, causing the pH of the medium to change, causing a change in color, indicating temperature or heat history. .
  • the enzymatic hydrolysis reaction increases with increasing temperature, and the release rate of protons is therefore accelerated.
  • Representative is the Vitsab ring indicator developed by a Swedish company.
  • a representative product of the earlier diffusion-type heat-sensitive label is the 3M Monitor Mark indicator produced by 3M Company of the United States. It is based on the diffusion of dye on the string, and the temperature indication range and response period depend on the type of dye.
  • Another form of diffusion type indicator is to apply a material having a specific melting point to a porous substrate, the refractive indices of which are close to each other. When the coated material melts above a specific temperature and diffuses into the porous substrate, the light in the pores of the matrix is removed, and the transmittance of the substrate is increased, so that a change in color can also be achieved, indicating a heating process.
  • the ideal heat-sensitive label should be a personalized heat-sensitive label that fully reflects the thermal stability of the indicated product, ie the speed of color change and its temperature effect are as consistent as possible with the indicated product failure process. .
  • the heat sensitive label of the present invention can be stored at room temperature for a long time before use, that is, the heat sensitive label of the present invention is not itself thermally sensitive prior to use.
  • Another object of the present invention is to provide a method for preparing a heat sensitive label for monitoring the quality status of a heat sensitive article.
  • the present invention provides a simple and effective heat sensitive label that can be used to monitor the cumulative heat received by heat sensitive items (i.e., thermal history) and to alert for excessive heat.
  • heat sensitive items i.e., thermal history
  • this type of label can be used to know whether the accumulated heat is beyond the range that people expect to control.
  • the heat sensitive label of the present invention is insensitive to heat prior to use, that is, the heat sensitive label of the present invention can be stored for a long time at normal temperature or even higher temperatures, and thus can be conveniently transported and distributed. .
  • a first aspect of the present invention provides a heat sensitive label for monitoring the quality condition of a heat sensitive article, comprising two laminated portions of a thermally functional layer and an adsorption indicating functional layer that are physically independent from each other prior to use.
  • the heat sensitive functional layer includes: a sealing film; a first substrate material layer on the sealing film, the first substrate material layer is preferably made of white paper, copy paper, or printing paper, more preferably a water-based adhesive is attached to the sealing film; a volatile dye layer formed on the first substrate material layer, an activation energy of the volatile dye layer and a quality of the heat sensitive article The difference in activation energy of the varying process is within a predetermined range, and the volatile dye layer is preferably formed by coating or impregnating a volatile dye on the first substrate material layer; and the first release film layer, Covering the volatile dye layer, wherein the size of the sealing film and the first release film layer is larger than the size of the volatile dye layer and sealing the volatile dye layer on the sealing film And between the first release film layer.
  • the adsorption indicating functional layer comprises: a second substrate material layer, which is transparent Made of a material, preferably made of a polymer film; a functional indicator layer over the second substrate material layer and having a viewing window with a reference color around the viewing window; a layer of adsorbent material located Under the second substrate material layer and capable of adsorbing dyes in the volatile dye layer, wherein the adsorbent material layer overlaps or overlaps with the observation window in a vertical direction, preferably having a size larger than the observation a size of the window; an isolation layer made of an opaque material and located below the layer of adsorbent material, the size of the spacer layer being greater than the size of the viewing window, preferably greater than or equal to the size of the volatile dye layer, More preferably, it is larger than, equal to or smaller than the size of the layer of adsorbent material, and the spacer layer is capable of diffusing through the volatile dye; and a second release film layer, the second release film layer covering the isolation layer .
  • the heat sensitive label of the present invention is applied to one or more regions of the heat sensitive article.
  • the volatile dye absorbs heat and volatilizes and diffuses through the barrier layer to be adsorbed by the adsorbent layer.
  • the color of the adsorbent layer gradually becomes darker and can be observed through the observation window.
  • the color depth of the adsorbent layer is positively correlated with the amount of dye adsorbed, that is, the amount of dye adsorbed is positively correlated with the amount of dye, and the amount of dye is related to the thermal history it experiences (related to the degree of deterioration of heat sensitive items). ) is positively correlated.
  • Selecting the type of dye for a specific heat sensitive article and combining other methods to regulate the rate of volatilization, diffusion, and adsorption of the dye can cause the color change response of the adsorbent layer due to the adsorption of the dye to correspond to the activity change of the heat sensitive article, thereby It is easy to determine whether the heat sensitive article is in the expiration date or shelf life simply by the color change of the adsorption layer.
  • the heat-sensitive label of the present invention is physically independent of each other, two laminated portions of the heat-sensitive functional layer and the adsorption indicating functional layer before being applied to the heat-sensitive article, and in the heat-sensitive functional layer of the present invention
  • the volatile dye layer is sealed between the sealing film and the first release film layer prior to use, so the heat sensitive label of the present invention is insensitive to heat prior to use. Therefore, the heat-sensitive label of the present invention can be stored and transported at a normal temperature by itself without being affected without affecting the performance of the heat-sensitive label of the present invention.
  • the present invention since the heat sensitive label of the present invention can be combined and applied immediately before use, the present invention
  • the heat sensitive label itself is not affected by the thermal history of the heat sensitive label during storage and shipping prior to use, whereby the heat sensitive label of the present invention more accurately reflects the thermal history experienced by the heat sensitive item.
  • a second aspect of the invention relates to a heat sensitive article to which the heat sensitive label of the invention is applied.
  • a third aspect of the invention relates to a method of making a heat sensitive label of the invention.
  • a fourth aspect of the invention relates to a method of monitoring a heat sensitive article using the heat sensitive label of the present invention.
  • FIG. 1 is a schematic structural view of a heat sensitive label in accordance with an embodiment of the present invention.
  • FIG. 2 is a schematic illustration of the process of color change of a heat sensitive label during use in accordance with an embodiment of the present invention.
  • Fig. 3 is a view showing the effect of color change with time during use of a heat-sensitive label manufactured by using a blue oil hydrocarbon as a heat-sensitive functional material in Example 1 of the present invention.
  • Fig. 4 is a view showing the change of the label color difference AE*ab with the storage time t when the heat sensitive label manufactured by using the blue oil hydrocarbon as the heat sensitive functional material in Example 2 of the present invention is stored at different temperatures.
  • Figure 6 shows the color difference AE*ab obtained with the heat sensitive material of the heat sensitive label made of the blue oil hydrocarbon as the heat sensitive label and changing the material of the spacer layer and its structure at a constant temperature of 25 ° C in the embodiment 3 of the present invention.
  • the change in storage time t The change in storage time t.
  • Fig. 10 shows a sixth embodiment of the present invention in which a blue oil hydrocarbon is used as a heat-sensitive functional material, and five different adsorbing materials are used to produce a heat-sensitive label, and the color difference AE*ab changes with storage time t under the same temperature environment.
  • Thermal functional layer 1 Water-based adhesive layer 12 Transparent film substrate 20 Observation window 24, adsorption indication function layer 2 Sealing film 13 Adsorption indication area 21 Reference color 25 First substrate material layer 10 Adhesive layer 14 Adsorbent material layer 22
  • a first aspect of the present invention provides a heat sensitive label product for monitoring the cumulative heat received by a heat sensitive article and for alerting it to excessive heat, the label comprising two layers of a heat sensitive functional layer and an adsorption indicating functional layer that are physically independent from each other prior to use. Layer part, where
  • the thermal functional layer includes:
  • the first substrate material layer is preferably made of white paper, copy paper, or printing paper, more preferably attached to the sealing film by an aqueous glue;
  • the volatile dye layer is preferably formed by coating or impregnating a volatile dye on the first substrate material layer;
  • a size of the sealing film and the first release film layer is larger than a size of the volatile dye layer and the volatile dye is a layer is sealed between the sealing film and the first release film layer
  • the adsorption indicating functional layer includes:
  • a second substrate material layer made of a transparent material, preferably made of a polymer film; a functional indicator layer over the second substrate material layer and having a viewing window around the viewing window With reference color;
  • a layer of adsorbent material underlying the second layer of substrate material and capable of adsorbing a dye in the layer of volatile dye, wherein the layer of adsorbent material overlaps or overlaps the viewing window in a vertical direction, Preferably, the size thereof is larger than the size of the observation window;
  • a barrier layer made of an opaque material and located below the layer of adsorbent material, the spacer layer having a size greater than a dimension of the viewing window, preferably greater than or equal to a size of the volatile dye layer, more preferably greater than, Is equal to or smaller than the size of the layer of adsorbent material, and the separator is capable of diffusing through the volatile dye;
  • the first release film layer and the second release film layer are peeled off, the isolation layer of the adsorption indicating functional layer is aligned with the volatile dye layer of the heat sensitive functional layer, and the adsorption material layer and the isolation layer are And a volatile dye layer is enclosed between the sealing film and the second substrate material layer; then the sealing film is attached to the heat sensitive article; or the sealing film is attached to the On the heat sensitive article, then peeling off the first release film layer and the second release film layer, aligning the isolation layer of the adsorption indicating functional layer with the volatile dye layer of the heat sensitive functional layer, and adsorbing the material layer And a barrier layer and a volatile dye layer are enclosed between the sealing film and the second substrate material layer.
  • the volatile dye in the heat sensitive functional layer is heated under conditions (eg, at a temperature that is desired to be disposed of, such as at a desired storage and/or transport temperature, such as an unexpected rise in treatment temperature)
  • a temperature that is desired to be disposed of such as at a desired storage and/or transport temperature, such as an unexpected rise in treatment temperature
  • the desired treatment temperature of the accelerated test is 25 ° C and/or 37 ° C, it volatilizes.
  • the adsorbent material in the adsorbent material layer is irreversibly adsorbed, and the color of the adsorbent material layer is gradually deepened after adsorbing the volatilized dye (for example, the adsorption in the adsorbent material layer 22 shown in FIG. 1).
  • the color in the indication area 21 becomes darker, which can be observed by referring to the observation window of the indication layer.
  • the color depth of the adsorbent layer is positively correlated with the amount of dye adsorbed, which in turn is positively correlated with the heat absorbed by the heat sensitive article.
  • the cumulative thermal history of the thermally sensitive article being monitored can be visually and simply characterized by the color depth of the layer of adsorbent material.
  • the color depth can be further characterized by a change in color difference AE* ab .
  • the rate of color change of the layer of adsorbent material can be characterized by the time range over which the set of color differences is varied divided by the time required to reach the range of color difference variations.
  • the rate of color change as a function of temperature obeys the Arrhenius equation and can be characterized by the activation energy E a obtained from the equation.
  • a second aspect of the invention provides a volatile dye, preferably a colored volatile dye, for use in making the heat sensitive label.
  • a volatile dye is a blue oil hydrocarbon of the formula I or a derivative thereof:
  • Rl includes, but is not limited to, hydrogen, halogen, d- 6 straight or branched fluorenyl, d- 6 straight or branched decyloxy, d- 6 straight or branched fluorenyl hydroxy, -COR2, -COOR2;
  • R2 is selected from hydrogen, d- 6 straight or branched fluorenyl (eg methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and the like), d_ 6 straight-chain or branched-chain alkyl group (e.g.
  • the R 1 is selected from the group consisting of hydrogen, —COH, CH 2 OH, —COOR 2
  • R 2 is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Tert-butyl.
  • the volatile dye layer may comprise a mixture of one or more (e.g., two, three, or more) of a blue oil hydrocarbon or a derivative thereof.
  • the volatile dye layer may further include one or more volatile auxiliary agents, and the volatile auxiliary agent may be a volatile substance capable of regulating the volatilization speed of the dye and its temperature effect.
  • the volatile auxiliary may be various volatile compounds including, but not limited to, linear or branched or cyclic hydrocarbons or aromatic hydrocarbons (including but not limited to naphthalene, anthracene), various linear chains.
  • Or branched or aromatic or cyclic alcohols including but not limited to butanol, lauryl alcohol, tridecyl alcohol, tetradecanol, pentadecyl alcohol, stearyl alcohol, heptadecyl alcohol, stearyl alcohol, etc.
  • various linear chains Or branched or aromatic or cyclic carboxylic acids including but not limited to maleic acid, fumaric acid, lauric acid, tridecanoic acid, myristic acid, hexadecanoic acid, palmitic acid, fatty acid, azelaic acid, ten Diterpenic acid, etc.
  • various amino acids including but not limited to aminobenzoic acid, leucine, phenylalanine, etc.
  • various ester compounds including but not limited to ethyl acetate, etc.
  • various sulfones Including but not limited to diphenyl sulfone, diphenyl disulfone, dibenzyl sulf
  • the adsorbent material used in the heat sensitive label of the present invention may be any material capable of irreversibly adsorbing the volatile dye.
  • the adsorbent material adsorbs the volatile dye at a greater rate than the volatile dye.
  • the adsorbent material adsorbs the volatile dye at a much faster rate than the volatile dye.
  • the adsorbent material adsorbs the volatile dye much faster than the volatile dye, so that the dye is adsorbed at a rate substantially only with the dye. The rate of volatilization is related.
  • the adsorbent material adsorbs the volatile dye much faster than the volatile dye, so that the apparent volatilization rate of the dye is only affected by the temperature (or absorbed heat), and is not affected by, for example, The effect of saturated/near-saturated vapors generated by self-evaporation and other factors.
  • the adsorbent material includes, but is not limited to, an oily or aqueous adhesive, a commercial adhesive tape, and a self-adhesive tape.
  • the material and structure of the spacer used in the heat-sensitive label of the present invention are not particularly limited as long as the spacer layer has the following two functions: first, the color of the heat-sensitive functional layer is covered, and therefore the material of the spacer layer is preferably It is a white opaque material; the second is to provide a diffusion channel from the heat-sensitive functional layer to the adsorbent layer after the dye is volatilized, and it is preferable to simultaneously control the diffusion speed.
  • the spacer material may be, but not limited to, ordinary white paper, copy paper, printing paper, sticker paper, or the like. In one embodiment, 60-120 g /cm 2 of white paper is used as the separator material.
  • a white paper coated with a quantity of 60-120 g /cm 2 capable of irreversibly adsorbing the volatile dye is used as the separator material.
  • a two-layer 60-120 g /cm 2 white paper is used to coat a double layer of white paper capable of irreversibly adsorbing the volatile dye as a release layer material.
  • both the adsorbent layer and the separator layer exhibit the color of the volatile dye; when a double layer of white paper is used to coat a certain amount of the adsorbent material, the adsorbent layer and The color of the volatile dye is present between the white sheets of the barrier layer, so that the color change of the heat sensitive label of the present invention in use can be more effectively exhibited.
  • the invention also provides a production process and storage method of the heat sensitive label.
  • the production and storage of the heat-sensitive label are divided into two independent parts of a heat-sensitive functional layer and an adsorption indicating functional layer, including two independent heat-sensitive functional layers and an adsorption indicating functional layer.
  • the process of laminating parts are divided into two independent parts of a heat-sensitive functional layer and an adsorption indicating functional layer, including two independent heat-sensitive functional layers and an adsorption indicating functional layer.
  • the preparation process of the heat-sensitive functional layer includes: providing a sealing film, providing a first substrate material on the sealing film, preferably a first lining made of white paper, copy paper, or printing paper a base material, more preferably by attaching the first substrate material to the sealing film by using an aqueous glue; forming a volatile dye layer on the first substrate material, preferably by coating or impregnating the volatile dye Forming on the first substrate material, a difference between an activation energy of a volatilization process of the volatile dye layer and an activation energy of a quality change process of the heat sensitive article is within a predetermined range; on the volatile dye layer Covering the first release film, wherein the size of the sealing film and the first release film layer is larger than the size of the volatile dye layer and the volatile dye layer is Sealed between the sealing film and the first release film layer to form a heat sensitive functional layer.
  • 60-120 g / cm 2 of white paper is coated with a layer of water-based glue that does not adsorb the heat-sensitive functional material by roll-to-roll production, and then attached to the polymer film;
  • the other side of the polymer film is coated with a layer of self-adhesive before or after the white paper is attached, and the label is pasted onto the heat-sensitive article by the adhesive when used, and the adhesive surface is used before use. Release film protection.
  • the heat-sensitive functional material is applied to the white paper side of the substrate by a method of impregnation in a roll-to-roll production manner, and the heat-sensitive functional material is dissolved in a suitable organic solvent (eg, In ethanol, acetone, diethyl ether, petroleum ether, ethyl acetate, etc., the preferred material concentration during dipping or coating is 200-400 g /L, and the preferred substrate material travel speed is 3-30 m/min.
  • the volatile dye-coated material is wound and then cut into strips according to the dimensions required by the label and then sealed for storage.
  • the die cut heat sensitive functional material substrate has a size of 5-15 mm and an optimized size of 8-12 mm. In one embodiment, the die cut polymer film size is 8-30 mm and the optimized size is 10-20 mm.
  • the manufacturing process of the adsorption indicating functional layer includes: providing a second substrate material formed of a transparent material, preferably a second substrate material made of a polymer film; and the second substrate material Forming a functional indicating layer thereon, the functional indicating layer having a viewing window and having a reference color around the viewing window; forming an adsorbent layer under the second substrate material, the adsorbing material layer capable of adsorbing the volatilization a dye in the dye layer, and the layer of adsorbent overlaps or overlaps the viewing window in a vertical direction, preferably having a size larger than the size of the viewing window; forming an isolation from the opaque material under the layer of adsorbent material a layer having a size larger than a size of the observation window, preferably greater than or equal to a size of the volatile dye layer, more preferably greater than, equal to, or smaller than a size of the adsorbent layer, the spacer layer being capable of diffusing Passing the volatile
  • the barrier layer, the layer of adsorbent material, and the functional indicator layer form another separate portion of the label, referred to as the adsorption indicating functional layer.
  • the adsorbent material is a transparent adhesive that can irreversibly adsorb the volatile dye, and the adhesive is coated on a transparent polymer film such as a plastic film, and the self-adhesive surface is protected by a release film before use.
  • the functional indicator layer uses a self-adhesive coated paper, the color of which is the color of the reference end point, and is formed by roll-to-roll die-cutting to form a circular or square or other geometric viewing window.
  • the functional indicator layer is applied to the side of the second substrate material to which the adsorbent material is not applied by roll-to-roll production.
  • the liner of the desired size of the label is die cut onto the layer of adsorbent material by roll-to-roll production and protected with a release film.
  • the adsorption indicating functional layer is wound and then cut into strips according to the size required by the label, and then packaged and stored.
  • the die cut viewing window is 3-10 mm in size and the optimized size is 4-6 mm.
  • the size and shape of the die cut barrier layer is consistent with the size of the volatile dye layer in the heat sensitive functional layer.
  • the size of the die cut spacer layer is greater than the size of the volatile dye layer in the heat sensitive functional layer. In one embodiment, the die cut adsorption indicates that the functional layer size is consistent with the thermal functional layer size. In one embodiment, the die cut adsorption indicates that the functional layer size is greater than the thermal functional layer size. In one embodiment, the die cut adsorption indicates that the functional layer size is less than the thermal functional layer size.
  • a sixth aspect of the invention provides a method of using the heat sensitive label.
  • the heat sensitive functional layer is affixed to a suitable location of the packaging container of the heat sensitive article, preferably by first peeling off the release film located in the lower portion of the heat sensitive functional layer, and then passing through the exposed sealing film.
  • the lower self-adhesive layer adheres the heat-sensitive functional layer to a suitable position of the packaging container of the heat-sensitive article; and then peels off the release film protective layer of the adsorption indicating layer and the release film protective layer on the top of the heat-sensitive functional layer Align the barrier layer with the thermal functional layer and seal the two parts tightly with the adhesive of the adsorption indicator layer.
  • the release film protective layer of the adsorption indicating layer and the top release film protective layer of the heat sensitive functional layer are first peeled off, and the isolation layer and the heat sensitive functional layer are aligned, and the adhesive of the adsorption indicating layer is utilized.
  • the two parts are tightly sealed; the release film of the protective self-adhesive layer at the bottom of the heat-sensitive functional layer is peeled off, and then the entire label is pasted into the packaging container of the heat-sensitive article by using the generated self-adhesive layer. position.
  • the volatile dye is in a closed system composed of the sealing film and the second substrate material without The dye is released so that the dye volatilized by the heat/temperature change is substantially completely adsorbed into the adsorbent material.
  • the color depth of the layer of adsorbent material can be observed or determined by the viewing window of the label after the monitoring of the heat sensitive article is terminated by heat or temperature, for example after a desired storage and/or transport process.
  • the cumulative thermal history of the heat sensitive article can be visually characterized by the color of the layer of adsorbent material of the heat sensitive label of the present invention.
  • the present invention also provides a method of monitoring using the heat sensitive label of the present invention, comprising applying the heat sensitive label of the present invention to one or more regions on a heat sensitive article, viewing the adsorbent material through an observation window as needed.
  • the color of the layer if the color is darker than the reference color, the heat sensitive item has failed; if the color is lighter than the reference color, it indicates that the heat sensitive item has not expired.
  • the method comprises the steps of:
  • the material of the heat sensitive functional layer of the heat sensitive label and the adsorption indicating functional layer material and its structure (for example, by selecting different volatile dyes to obtain different volatility, or by selecting different barrier materials to obtain volatile dyes)
  • the different diffusion rate, or by selecting different adsorbent materials to obtain different adsorption rates, the heat sensitive functional layer and the adsorption indicating functional layer of the heat sensitive label are produced in accordance with the method of the present invention.
  • the heat sensitive functional layer of the heat sensitive label and the adsorption indicating functional layer are aligned and sealed, and the initial color difference of the observation window is measured by a color difference meter (at this time, no dye volatilization and adsorption, observation window)
  • the initial color/color difference can be expressed as co).
  • the label is stored at a temperature (indicated by T1 in the present invention) at a desired disposal (e.g., storage and/or transport, or stability acceleration test), and the color difference of the observation window is periodically recorded.
  • the color difference of the heat sensitive item stored in the validity period tl (the color/color difference of the observation window can be expressed as Cl), and use it as the reference color.
  • the rate of change in color difference (C1-C0) is divided by the time required to achieve the change in color difference to obtain the rate at which the color difference changes at the treatment temperature T1.
  • the heat sensitive label is stored at different treatment temperatures and the color difference of the viewing window is recorded periodically. Calculating the color difference curve with time, finding the time required for the color of the observation window to reach the end color difference at the treatment temperature, and comparing the time with the validity period of the heat sensitive article at the treatment temperature, ideally, two times It should be as close as possible.
  • the line in principle, is based on the Arrhenius equation 2'303 T , which includes key parameters such as activation energy E , rate constant k, thermodynamic temperature T, etc., and the activation energy of the heat sensitive label reaching the end point color can be obtained. Ideally, the activation energy should be close to the failure activation energy of the heat sensitive product.
  • the color of the adsorption indicating layer is lighter than the reference color, it indicates that the heat sensitive article remains in an effective quality state
  • the heat sensitive label of the present invention is capable of monitoring the range of thermal stability of a wide range of heat sensitive articles. For example, including, but not limited to, storage at 37 ° C for 2 hours - 45 days, storage at 25 ° C for 6 hours - 1 year, corresponding activation energy range of 60-100 kJ / mol.
  • the volatile dye uses a blue oil hydrocarbon
  • the adsorbent material uses an irreversible adsorbent of a blue oil hydrocarbon
  • the separator is coated with a white paper or a white paper of 60-120 g /cm 2 .
  • a quantity of self-adhesive or two layers of 60-120 g / cm 2 of white paper is coated with a certain amount of adhesive.
  • the heat-sensitive label produced has an end point of 30-40 with respect to ordinary white paper, and the storage reaches the end point at 37 ° C for 1-30 hours, and the time to reach the end point at 25 ° C is 3- Between 75 hours.
  • the adsorbent material uses a self-adhesive that irreversibly adsorbs the blue oil hydrocarbon derivative
  • the separator uses 60-120 g / A certain amount of adhesive is applied between cm 2 of white paper or white paper with a certain amount of adhesive or two layers of 60-120 g/cm 2 of white paper.
  • the heat-sensitive label manufactured in accordance with the present invention has an ink color difference of 30-40 with respect to ordinary white paper as an end point, and the storage time at 37 ° C reaches the end point between 2 and 35 days, and the time to reach the end point at 25 ° C is Between 6-80 days.
  • the adsorbent material uses a self-adhesive for irreversibly adsorbing the blue oil hydrocarbon derivative
  • the separator is used 60
  • a certain amount of self-adhesive is applied between -120 g /cm 2 of white paper or white paper with a certain amount of adhesive or two layers of 60-120 g / cm 2 of white paper.
  • the heat-sensitive label manufactured according to the present invention has an ink color difference of 30-40 with respect to ordinary white paper as an end point, and the storage reaches the end point at 37 ° C for 1.5-30 days, and the time to reach the end point at 25 ° C Between 5 and 60 days. It is an object of one embodiment of the present invention to produce a personalized heat sensitive label having a color change speed and temperature effect sufficient to reflect the thermal stability of the indicated product, which can be tailored to the specific storage requirements of a particular type of heat sensitive item and Features to design. In one embodiment, this can be accomplished by screening for volatile dyes or other volatile opaque materials that exhibit a rate of volatilization and an activation energy that adequately reflects the thermal stability of the indicated product.
  • the purpose of one embodiment of the present invention is to produce a heat sensitive label that can be stored at room temperature, which can be realized by the following methods:
  • the heat sensitive functional layer of the heat sensitive label and the adsorption indicating functional layer are separately prepared and stored, and the two are combined into one. .
  • the thermal functional layer and the adsorption indicating layer are separately stored and implemented to realize two functions. Part of the preservation at room temperature.
  • a monitoring and early warning product for accumulating thermal history of a cryogenic storage product (for example, the heat sensitive article of the present invention) during storage and transportation, for determining whether the heat sensitive work item is Deterioration/failure/deactivation due to excessive heat during cold chain storage and transportation.
  • the activation energy in the volatilization process of the material is used to quantitatively express the activation energy of the product due to the thermal history;
  • the volatile material used in the second aspect is Colored material;
  • the adsorbent material layer is made of a material capable of irreversibly adsorbing the colored volatile dye, especially the adsorption indicating zone in the adsorbent material layer. Since the volatile material is adsorbed by the adsorbed material layer after being volatilized by heat, the color of the adsorption indicating zone changes significantly, and it is determined whether the commodity is still effective or has deteriorated/inactivated/inactivated.
  • thermosensitive functional material for producing a volatile dye layer of the above heat sensitive label, namely a volatile dye: a blue oil hydrocarbon and a derivative thereof, or one or more thereof Kind of mixture.
  • the volatile material volatilizes after it absorbs heat, and its volatilization speed and its temperature effect enable the thermal label to fully reflect the speed of deterioration or failure of the indicated product and its temperature effect.
  • a substrate material for making a heat sensitive functional layer of the above heat sensitive label is provided, such as plain white paper, copy paper, printing paper, and the like.
  • a material for a sealing film for making a heat sensitive functional layer of the above heat sensitive label is provided, such as a polymeric material that is impermeable to volatile dyes.
  • an adsorbent material for making a layer of adsorbent material for the heat sensitive label described above is provided: for example, a variety of stickers.
  • the adsorbent material has a strong irreversible adsorption effect on the heat sensitive material (i.e., volatile dye), and the adsorption speed is much higher than that of the heat sensitive functional material, and the apparent volatilization speed of the heat sensitive functional material is only affected by the temperature.
  • an adsorbent material for making a layer of an adsorbent material of the above heat sensitive label, wherein the adsorbent material has an irreversible adsorption effect on the heat sensitive material, and the color change of the heat sensitive label is regulated by selecting different adsorbing materials. Speed and its temperature effect.
  • a production process and a storage method of the heat-sensitive label are provided, and both the heat-sensitive functional layer and the adsorption indicating functional layer can adopt roll-to-roll coating and die-cutting used in conventional self-adhesive production.
  • Production methods such as lamination, and providing optimized material concentration, size of each part of the label, production speed, etc., enable the heat sensitive label of the present invention to be mass-produced inexpensively and conveniently.
  • a method of using the heat sensitive label characterized in that: the heat sensitive functional layer and the adsorption indicating layer are combined in one use and effectively sealed to protect the heat sensitive label.
  • the functional parts are free from external pollution, while avoiding contamination of the product or its packaging after volatile materials are volatilized.
  • a test method for the heat sensitive label characterized in that: the color difference of the observation window of the label is measured by a color difference meter to quantify the color change of the label, and an appropriate color difference end point is selected to determine the response of the label.
  • Time and color change rate using the Arrhenius equation to determine the activation energy parameters of the heat sensitive label.
  • the heat sensitive material and the label structure of the heat sensitive article are determined by the response time of the label obtained by the test result and the activation energy thereof.
  • a method of determining a reference color of the heat sensitive label characterized in that: the label is stored at a temperature at which the treatment is desired, and the color difference of the observation window is periodically recorded. The color difference curve with time is found, and the color difference of the heat sensitive article stored at the treatment temperature for the expiration date tl is found as a reference color, and the reference color of the label is printed.
  • a range of applications of the heat sensitive label wherein the indicated temperature range is between 0 and 50 ° C, the indicated time range varies with temperature, and the typical time range is The activation energy of the response is between 60-100 kJ/mol between 2 hours and 45 days at 37 °C, between 6 hours and 1 year at 25 °C, and between 1 and 6 years at 5 °C. between.
  • A an example of a heat sensitive tag
  • the invention utilizes the volatile matter of the substance to make a heat sensitive label, and achieves the desired color change effect by a heat-volatilization-adsorption process.
  • the structure of an exemplary heat sensitive label designed by the inventors and its working principle are shown in Figs. 1 and 2.
  • a heat sensitive label of the present invention is depicted, which is composed of two parts, (a) a part of the heat sensitive functional layer 1, and (b) a part of the adsorption indicating functional layer 2, two parts. Separately make the storage, when used, combine them into one, and paste them onto the container or packaging surface of the heat sensitive items to be monitored.
  • a layer of aqueous glue 12 is applied on the underside of the substrate material layer 10, and then bonded to the seal.
  • the sealing film 13 since the sealing film 13 is impermeable to the dye, the dye is prevented from diffusing downward to contaminate the heat sensitive article.
  • a layer of self-adhesive 14 is applied to the underside of the sealing film 13 and protected by a release film 15.
  • a functional layer on the substrate material layer 10 is coated with a colored volatile dye having a specific volatility as a heat-sensitive functional material to form the heat-sensitive functional layer 11 in the present invention.
  • the rate of volatilization of the volatile dye used and its temperature effect are as consistent as possible with the indicated product deterioration or failure rate and its temperature effect.
  • the heat-sensitive functional layer is sealed and stored after drying, and the sealing performance ensures that the heat-sensitive functional layer can be stored and transported at room temperature.
  • the substrate material layer 20 is made of a transparent plastic film, and a self-adhesive paper is attached on the surface of the substrate film, and the reference color 25 and appropriate product information are printed on the front self-adhesive paper (for example, The type of heat sensitive item to which the label applies) or label usage information (eg, information on how to operate if the label is used to determine if the heat sensitive item has failed) and form a circular or square or other geometric viewing window 24 by die cutting.
  • an adsorbent material which can effectively adsorb volatile heat-sensitive functional dyes is printed or coated to form an adsorbent material layer 22.
  • a transparent adhesive capable of irreversibly adsorbing a volatile dye is used in this embodiment.
  • An isolation layer 23 of a suitable size is die-cut at a portion corresponding to the indication window and directly attached to the sticker as an adsorbent material.
  • the volatile dye is diffused by heat and diffused through the separation layer and adsorbed by the adsorption layer, so that the color of the adsorption layer is deepened 21 .
  • FIG. 2 shows the change process of the adsorption indicating layer 21 relative to the reference color layer 25 during use of the heat sensitive label of the present invention from a top view, illustrating that the present invention utilizes the volatile energy of the material to make a heat sensitive label, which is heated to be volatilized.
  • An adsorption process that changes the color of the indicator portion of the label to indicate whether the product using the heat-sensitive label has deteriorated or failed due to excessive heat.
  • the color depth of the reference color layer 25 is constant, and the color depth of the adsorption indicating area 21 of the adsorbed material layer is deepened by the adsorption of the heat volatilized dye.
  • the speed of deepening is affected by temperature. Even at the temperature expected by the heat sensitive article, the volatile dye layer 11 is volatilized to some extent, and the color of the adsorbed layer is gradually deepened. For example, for a drug with a storage period of 2-8 °C for 2 years, the drug is strictly stored at 2-8 ° C for 2 years, and the adsorption layer 21 will gradually become deeper due to the adsorption of the slowly volatilized dye.
  • the reference color layer 25 is somewhat lighter, indicating that the drug is still acceptable after 2 years of storage at 2-8 °C. After the storage time continues to increase, the adsorption indicating layer 21 will continue to darken by continuing to adsorb the volatilized dye, and thereafter its color will be substantially closer or deeper than the reference color layer 25, indicating that the drug has passed the expiration date.
  • This process is also an embodiment of designing the material type of the volatile dye layer 11 and the color depth of the reference color layer 25. This article also describes the implementation of the acceleration method. B. Color determination of the reference color layer of the heat sensitive label
  • Color changes can be digitized using a colorimeter.
  • a colorimeter When using a colorimeter to measure color changes, first define a color space such as L*a*b* color space (also known as CIELAB color space).
  • L* represents brightness
  • a* and b* are chromaticity coordinates, indicating color direction
  • +a* means red direction
  • -a* means green direction
  • +b* means yellow direction
  • -b* means In the blue direction
  • the center is colorless.
  • the values of a* and b* increase and move out of the center, the color saturation increases.
  • the color difference can be represented by a single value:
  • AE*ab [ (AL*) 2 + (Aa*) 2 + (Ab*) 2 5 where is the change in brightness, ⁇ * is the change along the red-green color axis, and Ab* is the yellow-blue color The change of the axis.
  • a colorimeter such as Minolta CR-310 Chroma Meter Colorlite Sph860
  • the color difference can be quantified, the color-changing function of the produced heat-sensitive label can be evaluated, and the end point chromatic aberration can be determined.
  • the chromatic aberration measurement is based on a white substrate such as A4 paper, and when the label is activated, the initial chromatic aberration is measured through the observation window.
  • the label is stored at the temperature at which it is desired to be disposed, and the color difference of the observation window is periodically recorded. A curve of color difference over time is obtained, and the color difference of the heat sensitive article stored at the treatment temperature for a period of validity tl is found, which is used as a reference color to print the reference color of the label.
  • a plastic film coated with a transparent adhesive (PET adhesive transparent sheet PF04, Shanghai Humai Composite Material Co., Ltd.) was used as a substrate material layer and an adsorbent layer for the adsorption indicating functional layer, and was white at 60 g / cm 2 .
  • the paper is used as a release layer, and a commercial release film is used, and a self-adhesive paper is used as a functional indicator layer material, and an adsorption indicating functional layer is prepared according to the method of the present invention.
  • the thermal functional layer of the label and the adsorption indicator layer are combined to form a tight seal, and the sealed sample is placed under a constant temperature of 25 ° C. After a certain period of time, observe the color of the heat sensitive label.
  • Figure 3 is a heat sensitive label placed at a constant temperature of 25 ° C 0-10 small When the color is recorded, the color of the adsorption indicating layer is deepened as the storage time is extended.
  • Example 1 Example 1:
  • Example 4 is a heat sensitive label prepared in Example 1 stored at 45 ° C, 37 ° C, 25 ° C and 5 ° C, using a color difference meter (Colorlite Sph860) to record the color difference of the observation window, at different temperatures
  • the color difference AE* ab changes with time t.
  • the starting color difference AE* ab 4-5, by selecting the appropriate end point chromatic aberration, the color change time and speed of the heat sensitive label can be obtained.
  • the heat sensitive functional label of the present invention was fabricated in a manner similar to that of Example 1, except that the spacer material and its structure were modified to control the rate of color change of the heat sensitive label at different treatment temperatures.
  • blue oil hydrocarbon is used as the heat sensitive material of the heat sensitive label
  • the separation layer is respectively 60 g / cm 2 white paper (paper), double layer 60 g / cm 2 white paper (paper + paper), single layer 60 g /cm 2 white paper coated with a certain amount of self-adhesive (paper + glue), double layer 60 g / cm 2 white paper between a certain amount of stickers (paper + glue + paper), according to the method of Example Make a heat-sensitive label, combine the thermal functional layer of the label and the adsorption indicator layer into a tight seal.
  • the heat sensitive functional label of the present invention is manufactured in a manner similar to that of Embodiment 1, except that different heat sensitive materials or combinations thereof are selected to control the color change speed of the heat sensitive label at different treatment temperatures and activation energy.
  • Store at 55 ° C, 45 ° C, 37 ° C, and 25 ° C. Record the color difference of the observation window with a color difference meter to obtain the color difference AE* ab at different temperatures as a function of time t.
  • AE* ab 4- 5.
  • the color change time and speed of the heat sensitive label can be obtained by selecting the appropriate endpoint color difference. End point color
  • the time to reach the end point at 55 ° C, 45 ° C, 37 ° C, and 25 ° C is 27 hours, 65 hours, 136 hours, and 421 hours, respectively.
  • Example 5
  • the heat sensitive functional label of the present invention was fabricated in a manner similar to that of Example 1, except that different adsorbent materials were selected to regulate the color change speed of the heat sensitive label and its temperature effect.
  • 10 is a method according to the first embodiment, in which a blue oil hydrocarbon is used as a heat-sensitive functional material, and five different adsorbing materials are selected to produce a heat-sensitive label, and the color difference of the adsorption indicating layer of the heat-sensitive label changes with time under the same temperature environment. Shows a significant difference.

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Abstract

一种用于监测热敏感物品的品质状态的热敏感标签，热敏感标签的制备方法以及使用所述热敏感标签的热敏感物品。该热敏感标签包括两个物理上分离的叠层，即热敏功能层（1）和吸附指示功能层（2），其中热敏功能层（1）的挥发性染料层（11）被密封在密封膜（13）和第一离型膜层之间，吸附指示功能层（2）的隔离层（23）被第二离型膜层覆盖，所述两个叠层分别储运，在使用时分别剥离第一离型膜层和第二离型膜层组合在一起，因此该热敏感标签可以在常温下储运，降低了热敏感标签的使用成本。

Description

热敏感标签及其制备和使用方法 技术领域
本发明涉及监测热敏感物品品质状态的热敏感标签、 其制备方法及用其监测热 敏感物品品质状态的方法。 具体地说， 本发明涉及利用挥发性染料制作热敏感标 签， 通过挥发性染料挥发后被吸附材料层吸附而导致的吸附材料层的颜色变化， 来 显示热敏感物品是否因受温度的影响或在某一温度下经受过长时间而变质或失效。 背景技术
一些对温度非常敏感的物品或产品需要在低温下储存或运输， 如大部分疫苗、 生物制品、 生物活性样品和一部分药品等， 以及如鲜奶、 奶制品、 鲜肉、 鲜鱼等新 鲜食品等。 长期以来， 标注有效期、 保质期或保鲜期是保证这些物品 /产品特别是药 品或食品安全使用的主要方法， 但这些方法往往无法反映那些需要在低温条件下储 存和运输的药品或食品是否在超过安全储运温度下暴露过长的时间。 采用简单廉价 的方法准确指示各种热敏感物品例如需要低温储存的新鲜食品、 疫苗 (多在 2V〜8V 之间)、 生物活性样品等是否在储存或运输过程中因为超过安全储运温度而变质、 失 效或失活， 可以更好地保证其使用安全和使用。
二十世纪九十年代， 世界卫生组织 (WHO)开始关注疫苗在冷链储运过程中受热 过度问题， 因为这会导致疫苗的免疫效果下降， 从而降低疫苗对儿童的保护作用。 随后， WHO 呼吁开发一种使用方便、 成本低廉的标签， 以准确反映疫苗从制造出 厂后经运输和储存到达终端用户过程中的热历史。 对该标签的基本要求如下： 1、 能 准确指示从而限制使用受热过度的疫苗； 2、 体积小， 能粘贴到疫苗瓶、 安瓿瓶、 注 射器等之上； 3、 从生产到实际使用的整个过程中稳定可靠； 4、 适合规模生产、 成 本低廉、 能满足联合国儿童基金会 (UNICEF)全球疫苗需求。
1996年， 美国一家名为 TempTime 的公司 (前身为 Lifelines)首先开发出能满足 WHO要求的标签， 并应用于 GlaxoSmithKline、 Sanofi-Pasteur和 Novartis三家疫 苗制造商生产的小儿麻痹症疫苗。 Temptime公司供应的标签按照使用功能主要有三 类。 第一类是临界温度指示器 (Critical Temperature Indicator, CTI), 这类标签在 温度一旦超过设定值就立即变色。 第二类是所谓临界热敏感标签 (Critical Temperature-Time Indicator, CTTI), 这种标签的变色速度有所延迟， 暴露在设定 的温度以上数分钟或数十分钟后变色。 第三类标签的响应时间需要更长一些， 称为 热敏感标签 (Time-Temperature Indicator, TTI), 是感温材料接受特定量的热量后才 变色， 这类标签才是适合指示疫苗的热历史的标签。
目前， 国际上有关这种热敏感标签的专利已经有上百个。 这些专利技术按照产 品的工作原理， 可以分为机械型、 化学型、 酶反应型、 微生物型， 聚合物型、 电子 化学型和扩散型等。 这些技术主要是基于材料的机械性质、 电性质、 扩散性质、 生 物酶反应、 聚合反应等， 比较成熟并已商品化的 ΤΤΙ标签主要有三类： 聚合物型、 酶反应型和扩散型。
聚合物型是由美国 TempTime 公司开发的， 主要是基于取代丁二炔衍生物通过 固态 1， 4-加成聚合反应， 生成有颜色的聚合物。 该聚合反应的速率随温度的升高而 加快， 不断生成的聚合物使颜色不断加深， 通过与周边颜色对比， 可以指示疫苗是 否受热过度。 这种标签需要筛选合成合适的聚合单体， 且标签制成后需要在 -18°C甚 至更低的温度下保存， 这明显增加了标签的使用成本。
早期的酶反应型指示器实质上是一类 pH值指示器， 它通过测量酶催化的脂类 底物水解释放质子 H+， 导致介质的 pH值改变， 从而引起颜色的变化， 指示温度或 受热历史。 酶促水解反应随温度升高而加快， 质子的释放速率也因此加快。 具有代 表性的是瑞典一家公司研制的 Vitsab环形指示器。
更早期的扩散型热敏感标签的代表性产品是美国 3M 公司生产的 3M Monitor Mark牌指示器， 它是基于染料在细绳上的扩散， 温度指示范围和响应期取决于染料 的类型。 另一种形式的扩散型指示器是将特定熔点的材料涂布到多孔基质上， 二者 的光折射率接近。 当涂布的材料在特定的温度以上熔化并扩散到多孔基质中， 排出 基质孔中的空气后， 基质的透光率增加， 因而也可实现颜色的变化， 显示受热过 程。
目前， WHO 将近二十种疫苗按照其热稳定性能分为 4类： 最不稳定疫苗、 不 稳定疫苗、 稳定疫苗和高稳定性疫苗， 并据此提出对相应的热敏感标签的产品技术 要求。 据此制定的技术标准考虑了现有指示器产品的性能， 并非完全以疫苗本身的 热稳定性能为依据。 事实上， 在需要冷链储运并全程监测的近二十种疫苗中， 每种 疫苗的热稳定性是不相同的， 理想的热敏感标签应该是充分反映所指示产品热稳定 性能的个性化热敏感标签， 即颜色变化的速度及其温度效应与所指示的产品失效过 程尽量一致。
为此， 本领域仍然需要可用于监测热敏感物品热历史的热敏感标签和方法， 以 方便地用于热敏感物品的储运监测， 并且能够准确指示热敏感物品是否已经失效或 变质， 尤其是在使用之前热敏感标签自身能够常温保存。 发明内容
本发明的一个目的是提供一种用于监测热敏感物品品质状态的热敏感标签， 将 其用于监测热敏感物品储运过程的热历史， 并指示热敏感物品是否因温度影响已经 失效或变质。 另外， 本发明的热敏感标签在使用之前能够在常温下长时间保存， 也 就是说， 本发明的热敏感标签在使用之前自身并不是热敏感的。
本发明的另一个目的是提供一种用于制备监测热敏感物品品质状态的热敏感标 签的方法。
本发明的再一个目的是提供一种用于监测热敏感物品品质状态的方法。
为此， 本发明提供了一种简单、 有效的可用于监测热敏感物品累计受热量 （即 热历史） 并预警受热过度的热敏感标签。 这种标签用于热敏感物品的储运过程监测 时， 可以知晓其累计受热量是否超出人们期待控制的范围。 另外， 本发明的热敏感 标签在使用之前对热不敏感， 也就是说， 本发明的热敏感标签能够在常温下或甚至 更高的温度下长时间储存， 并由此能够便利地运输、 分销。
本发明第一方面提供了一种用于监测热敏感物品的品质状态的热敏感标签， 包 括使用之前物理上呈相互独立的热敏功能层和吸附指示功能层两个叠层部分。 所述 热敏功能层包括： 密封膜； 在所述密封膜上的第一衬底材料层， 所述第一衬底材料 层优选由白纸、 复印纸、 或印刷纸制成， 更优选通过水性胶贴合在所述密封膜上； 挥发性染料层， 其形成于所述第一衬底材料层之上， 所述挥发性染料层的挥发过程 的活化能与所述热敏感物品的品质变化过程的活化能的差值在预定范围内， 所述挥 发性染料层优选通过将挥发性染料涂覆或浸渍在所述第一衬底材料层上而形成； 和 第一离型膜层， 其覆盖在所述挥发性染料层上， 其中所述密封膜和所述第一离型膜 层的尺寸大于所述挥发性染料层的尺寸并且将所述挥发性染料层密封在所述密封膜 和所述第一离型膜层之间。 所述吸附指示功能层包括： 第二衬底材料层， 其由透明 材料制成， 优选由聚合物膜制成； 功能指示层， 其位于所述第二衬底材料层之上并 且具有观察窗口， 在所述观察窗口的周围具有参考颜色； 吸附材料层， 其位于所述 第二衬底材料层之下并且能够吸附所述挥发性染料层中的染料， 其中所述吸附材料 层在垂直方向上与所述观察窗口交叠或重叠， 优选其尺寸大于所述观察窗口的尺 寸； 隔离层， 其由不透明材料制成并且位于所述吸附材料层之下， 所述隔离层的尺 寸大于所述观察窗口的尺寸， 优选大于或等于所述挥发性染料层的尺寸， 更优选大 于、 等于或小于所述吸附材料层的尺寸， 并且所述隔离层能够扩散通过所述挥发性 染料； 和第二离型膜层， 所述第二离型膜层覆盖所述隔离层。
在使用时， 首先剥离第一离型膜层和第二离型膜层， 将所述吸附指示功能层的 隔离层对准所述热敏功能层的挥发性染料层， 将吸附材料层、 隔离层和挥发性染料 层封闭在所述密封膜和所述第二衬底材料层之间； 然后将所述密封膜贴覆在所述热 敏感物品上； 或者， 首先将所述密封膜贴覆在所述热敏感物品上， 然后剥离第一离 型膜层和第二离型膜层， 将所述吸附指示功能层的隔离层对准所述热敏功能层的挥 发性染料层， 将吸附材料层、 隔离层和挥发性染料层封闭在所述密封膜和所述第二 衬底材料层之间。
在使用时， 将本发明的热敏感标签应用到热敏感物品的一个或更多个区域中。 在该热敏感物品的储运过程中， 挥发性染料吸收热量挥发并扩散穿过隔离层被吸附 材料层吸附， 吸附材料层吸附挥发性有色染料后颜色逐渐变深， 并可以通过观察窗 观测。 吸附材料层的颜色深度与其吸附的染料量呈正相关性， 也就是说染料吸附量 与染料的挥发量呈正相关性， 而染料的挥发量与其所经历的热历史 (与热敏感物品的 劣化程度相关)呈正相关性。 针对具体的热敏感物品来选择染料的种类并结合其它方 法调控染料的挥发、 扩散和吸附的速度， 能够使得吸附材料层因吸附染料而产生变 色响应与热敏感物品的活性变化相对应， 由此可以简单地通过吸附层颜色变化而容 易地确定热敏感物品是否处于有效期或货架期内。
另外， 由于本发明的热敏感标签在应用到热敏感物品之前呈物理上相互独立的 热敏功能层和吸附指示功能层两个叠层部分， 并且在本发明的热敏功能层中的所述 挥发性染料层在使用之前被密封在所述密封膜和所述第一离型膜层之间， 所以本发 明的热敏感标签在使用之前对热是不敏感的。 因此， 本发明的热敏感标签在使用之 前自身能够在常温下储存并运输， 而不会影响本发明的热敏感标签的性能。
再次， 由于本发明的热敏感标签能够在使用之前即刻组合应用， 所以本发明的 热敏感标签自身不会受到热敏感标签在使用之前的储存和运输过程中的热历史的影 响， 由此本发明的热敏感标签能够更准确地反映热敏感物品所经历的热历史。
本发明的第二方面涉及应用了本发明的热敏感标签的热敏感物品。
本发明的第三方面涉及制备本发明的热敏感标签的方法。
本发明的第四方面涉及利用本发明的热敏感标签监测热敏感物品的方法。 附图说明
图 1是根据本发明的一个具体实施方案的热敏感标签的结构示意图。
图 2 是根据本发明的一个具体实施方案的热敏感标签在使用过程中颜色变化的 过程的示意图。
图 3是本发明实施例 1 中采用蓝油烃作为热敏功能材料制造的热敏感标签在使 用过程中颜色随时间变化的效果图。
图 4示出本发明实施例 2中采用蓝油烃作为热敏功能材料制造的热敏感标签在 不同温度下储存时标签色差 AE*ab随储存时间 t的变化。
图 5示出本发明实施例 2中采用蓝油烃作为热敏功能材料制作的热敏感标签以 色差 AE*ab =40作为变色的终点求得的变色过程的活化能。
图 6示出了本发明实施例 3 中以蓝油烃作为热敏感标签的热敏材料并且改变隔 离层材料及其结构制作的热敏感标签在 25°C恒温条件下得到的色差 AE*ab 随储存时 间 t的变化。
图 7示出本发明实施例 4中采用 Rl=COOCH3取代的蓝油烃衍生物作为热敏功 能材料制作的热敏感标签在不同温度下储存得到的色差 AE*ab 随储存时间 t 的变 化。
图 8示出本发明实施例 4中采用 Rl=COOCH3取代的蓝油烃衍生物作为热敏功 能材料制作热敏感标签以色差 AE*ab =40 作为变色的终点求得的变色过程的活化 能。
图 9 示出本发明实施例 5 选用蓝油烃、 Rl=COOCH3、 COOCH(CH3)2、 COOC(CH3)3 、 CHO 取代的蓝油烃衍生物作为热敏功能材料制作热敏感标签在 37°C下储存时色差随时间的变化。
图 10是本发明实施例 6以蓝油烃为热敏功能材料， 选用五种不同的吸附材料制 作热敏感标签， 在相同温度环境下色差 AE*ab随储存时间 t的变化。 本发明使用的一些术语及其附 标记汇总如下：
热敏功能层 1 水性胶层 12 透明膜衬底 20 观察窗口 24， 吸附指示功能层 2 密封膜 13 吸附指示区 21 参考颜色 25 第一衬底材料层 10 不干胶层 14 吸附材料层 22
挥发性染料层 11 离型膜层 15 隔离层 23
具体实施方式
本发明第一方面提供了一种监测热敏感物品累计受热量并预警其受热过度的热 敏感标签产品， 该标签包括使用之前物理上呈相互独立的热敏功能层和吸附指示功 能层两个叠层部分， 其中
所述热敏功能层包括：
密封膜；
在所述密封膜上的第一衬底材料层， 所述第一衬底材料层优选由白纸、 复印纸、 或印刷纸制成， 更优选通过水性胶贴合在所述密封膜上；
挥发性染料层， 其形成于所述第一衬底材料层之上， 所述挥发性染料层 的挥发过程的活化能与所述热敏感物品的品质变化过程的活化能的差值在预定范围 内， 所述挥发性染料层优选通过将挥发性染料涂覆或浸渍在所述第一衬底材料层上 而形成； 和
第一离型膜层， 其覆盖在所述挥发性染料层上， 其中所述密封膜和所述 第一离型膜层的尺寸大于所述挥发性染料层的尺寸并且将所述挥发性染料层密封在 所述密封膜和所述第一离型膜层之间，
和
所述吸附指示功能层包括：
第二衬底材料层， 其由透明材料制成， 优选由聚合物膜制成； 功能指示层， 其位于所述第二衬底材料层之上并且具有观察窗口， 在所 述观察窗口的周围具有参考颜色；
吸附材料层， 其位于所述第二衬底材料层之下并且能够吸附所述挥发性 染料层中的染料， 其中所述吸附材料层在垂直方向上与所述观察窗口交叠或重叠， 优选其尺寸大于所述观察窗口的尺寸；
隔离层， 其由不透明材料制成并且位于所述吸附材料层之下， 所述隔离 层的尺寸大于所述观察窗口的尺寸， 优选大于或等于所述挥发性染料层的尺寸， 更 优选大于、 等于或小于所述吸附材料层的尺寸， 并且所述隔离层能够扩散通过所述 挥发性染料； 和
第二离型膜层， 所述第二离型膜层覆盖所述隔离层。
在使用时， 剥离第一离型膜层和第二离型膜层， 将所述吸附指示功能层的隔离 层对准所述热敏功能层的挥发性染料层， 将吸附材料层、 隔离层和挥发性染料层封 闭在所述密封膜和所述第二衬底材料层之间； 然后将所述密封膜贴覆在所述热敏感 物品上； 或者， 将所述密封膜贴覆在所述热敏感物品上， 然后剥离第一离型膜层和 第二离型膜层， 将所述吸附指示功能层的隔离层对准所述热敏功能层的挥发性染料 层， 将吸附材料层、 隔离层和挥发性染料层封闭在所述密封膜和所述第二衬底材料 层之间。
在使用时， 所述热敏功能层中的挥发性染料在受热条件下 (例如在期望处置的温 度情况下， 例如在期望的贮藏和 /或运输的温度情况下， 例如在处置温度意外升高的 情况下， 例如在加速试验期望的处置温度情况下， 例如在加速试验期望的处置温度 为 25°C和 /或 37°C的情况下)会挥发。 挥发的染料扩散通过隔离层后， 被所述吸附材 料层中的吸附材料不可逆地吸附， 吸附材料层吸附挥发的染料后颜色逐渐变深 （例 如图 1中所示的吸附材料层 22中的吸附指示区 21中的颜色变深） ， 可以通过参考 指示层的观察窗口观测。 吸附材料层的颜色深度与染料的吸附量呈正相关性， 后者 又与热敏感物品所吸收的热量呈正相关性。
通过利用上述根据本发明的热敏感标签， 所监测热敏感物品的累计热历史能够 用吸附材料层的颜色深度直观地并且简便地表征。 在一个实施方案中， 该颜色深度 可进一步用色差 AE*ab的变化表征。 在一个实施方案中， 吸附材料层颜色变化速率可 由设定的色差变化范围除以达到所述色差变化范围所需的时间表征。 在一个实施方 案中， 颜色变化速率随温度的变化服从 Arrhenius 方程， 可以用由该方程得到的活 化能 Ea表征。
本发明第二方面提供了制作所述热敏感标签使用的挥发性染料， 优选为有色挥 发性染料。 根据本发明， 优选的挥发性染料是下式 I的蓝油烃或其衍生物：
Figure imgf000010_0001
其中，
Rl包括但不限于氢、 卤素、 d_6直链或支链垸基、 d_6直链或支链垸氧基、 d_6 直链或支链垸基羟基、 -COR2、 -COOR2;
R2选自氢、 d_6直链或支链垸基 (例如甲基、 乙基、 正丙基、 异丙基、 正丁基、 仲丁基、 叔丁基、 正戊基、 异戊基、 新戊基、 正己基等)、 d_6直链或支链垸基胺基 (例如甲基胺基、 乙基胺基、 正丙基胺基、 异丙基胺基、 正丁基胺基、 仲丁基胺基、 叔丁基胺基、 正戊基胺基、 异戊基胺基、 新戊基胺基、 正己基胺基等)。
在一个实施方案中， 所述 R1 选自氢、 -COH、 CH2OH、 -COOR2, R2 选自 氢、 甲基、 乙基、 正丙基、 异丙基、 正丁基、 仲丁基、 叔丁基。
根据本发明的一个实施方案， 所述挥发性染料层可以包含蓝油烃或其衍生物的 一种或更多种 （例如两种、 三种、 或三种以上） 的混合物。
根据本发明的一个实施方案， 所述的挥发性染料层中还可以包括一种或多种挥 发助剂， 所述挥发助剂可以是各种可调控染料挥发速度及其温度效应的易挥发物 质。 在一个优选实施方案中， 所述挥发助剂可以是各种易挥发化合物， 包括但不限 于直链或支链或环垸烃或芳香烃 (包括但不限于萘、 蒽)， 各种直链或支链或芳香或环 醇 (包括但不限于丁四醇、 月桂醇、 十三醇、 十四醇、 十五醇、 软脂醇、 十七醇、 硬 脂醇等)， 各种直链或支链或芳香或环链羧酸 (包括但不限于马来酸、 富马酸、 月桂 酸、 十三垸酸、 豆蔻酸、 十五垸酸、 棕榈酸、 肥酸、 癸二酸、 十二垸二酸等)， 各种 氨基酸 (包括但不限于氨基苯甲酸、 亮氨酸、 苯丙氨酸等)， 各种酯类化合物 （包括但 不限于乙酸乙酯等） ， 各种砜 (包括但不限于二苯基砜、 二苯基二砜、 二苄基砜、 二 丁基砜等)， 也可以是各种易挥发天然物质 （包括但不限于萘、 樟脑等） 。
本发明的所述热敏感标签使用的吸附材料可以是任何能够不可逆地吸附所述挥 发性染料的材料。 在一个实施方案中， 所述的吸附材料吸附挥发性染料的速度大于 挥发性染料的挥发速度。 在一个实施方案中， 所述的吸附材料吸附挥发性染料的速 度远大于挥发性染料的挥发速度。 在一个实施方案中， 所述的吸附材料吸附挥发性 染料的速度远大于挥发性染料的挥发速度， 使得染料被吸附的速度基本上只与染料 的挥发速度有关。 在一个实施方案中， 所述的吸附材料吸附挥发性染料的速度远大 于挥发性染料的挥发速度， 使得染料的表观挥发速度只受温度 (或吸收的热量)的影 响， 而不受例如因自身挥发后所产生的饱和 /近饱和蒸气所阻碍等因素的影响。 在一 个实施方案中， 所述的吸附材料包括但不限于油性或水性不干胶、 商业不干胶纸及 不干胶胶带等。
本发明的热敏感标签使用的隔离层材料及结构不做具体限制， 只要所述隔离层 具有如下两个方面的功能即可， 首先是遮盖热敏功能层的颜色， 因此所述隔离层材 料优选是白色不透明的材料； 其次是提供染料挥发后从热敏功能层扩散到吸附材料 层的扩散通道， 优选能够同时起调控扩散速度的作用。 例如， 所述隔离层材料可以 是但不限于普通的白纸、 复印纸、 印刷纸、 不干胶标签纸等。 在一个实施方案中， 采用 60-120g/cm2的白纸作为隔离层材料。 在一个实施方案中， 采用涂敷了一定量能 不可逆吸附所述挥发性染料的不干胶的 60-120g/cm2的白纸作为隔离层材料。 在一个 实施方案中， 采用两层 60-120g/cm2的白纸中间涂敷了一定量能不可逆吸附所述挥发 性染料的不干胶的双层白纸作为隔离层材料。 这种结构的变化可以从标签使用过程 中各层的变化反映出来： 除了标签的热敏功能层呈现挥发性染料的颜色外， 使用白 纸作为隔离层的标签时只有吸附材料层能呈现挥发性染料的颜色。 使用涂敷了吸附 材料的白纸作为隔离层材料时， 吸附材料层和隔离层都会呈现挥发性染料的颜色； 使用双层白纸中间涂敷一定量吸附材料的隔离层时， 吸附材料层和隔离层的白纸之 间都呈现挥发性染料的颜色， 如此能够更有效地显现本发明的热敏感标签在使用时 的颜色变化。
本发明还提供了所述热敏感标签的生产工艺和储存方式。 根据本发明的方法， 所述的热敏感标签的生产和储存分为热敏功能层和吸附指示功能层两个独立的部 分， 包括相互独立的分别制备热敏功能层和吸附指示功能层两个叠层部分的过程。
根据本发明， 所述的热敏功能层的制备过程包括： 提供密封膜， 在所述密封膜 上提供第一衬底材料， 优选由白纸、 复印纸、 或印刷纸制成的第一衬底材料， 更优 选通过利用水性胶将所述第一衬底材料贴合在所述密封膜上； 在第一衬底材料上形 成挥发性染料层， 优选通过将挥发性染料涂覆或浸渍在所述第一衬底材料上来形 成， 所述挥发性染料层的挥发过程的活化能与所述热敏感物品品质变化过程的活化 能的差值在预定范围内； 在所述挥发性染料层上覆盖第一离型膜， 其中所述密封膜 和所述第一离型膜层的尺寸大于所述挥发性染料层的尺寸并且将所述挥发性染料层 密封在所述密封膜和所述第一离型膜层之间， 从而形成热敏功能层。
在一个实施方案中， 通过卷对卷的生产方式， 将 60-120g/cm2的白纸涂敷一层不 吸附所述热敏功能材料的水性胶， 再贴合到聚合物薄膜上； 聚合物薄膜的另一面在 白纸贴合之前或之后涂敷一层不干胶， 用于使用时通过该不干胶将标签粘贴到所述 热敏感物品上， 在使用前不干胶面用离型膜保护。 在一个实施方案中， 通过卷对卷 的生产方式将所述的热敏功能材料通过浸渍的方法涂敷到所述衬底的白纸一面， 将 热敏功能材料溶解在合适的有机溶剂 （如乙醇、 丙酮、 乙醚、 石油醚、 乙酸乙酯 等） 中， 浸渍或涂敷时优选的材料浓度是 200-400g/L， 优选的衬底材料走行速度是 3-30m/分钟。 在一个实施方案中， 将涂敷上挥发性染料的材料收卷后按照标签要求 的尺寸模切分条， 再密封包装储存。 在一个实施方案中， 模切的热敏功能材料衬底 的尺寸是 5-15 mm, 优化的尺寸是 8-12 mm。 在一个实施方案中， 模切的聚合物薄 膜尺寸是 8-30 mm， 优化的尺寸是 10-20 mm。
根据本发明， 所述的吸附指示功能层的制造过程包括： 提供由透明材料形成的 第二衬底材料， 优选由聚合物膜制成的第二衬底材料； 在所述第二衬底材料上形成 功能指示层， 所述功能指示层具有观察窗口并且在所述观察窗口的周围具有参考颜 色； 在所述第二衬底材料下形成吸附材料层， 所述吸附材料层能够吸附所述挥发性 染料层中的染料， 并且所述吸附材料层在垂直方向上与所述观察窗口交叠或重叠， 优选其尺寸大于所述观察窗口的尺寸； 在所述吸附材料层下由不透明材料形成隔离 层， 所述隔离层的尺寸大于所述观察窗口的尺寸， 优选大于或等于所述挥发性染料 层的尺寸， 更优选大于、 等于或小于所述吸附材料层的尺寸， 所述隔离层能够扩散 通过所述挥发性染料； 和在所述隔离层下覆盖第二离型膜， 以形成吸附指示功能 层。
根据本发明， 隔离层、 吸附材料层、 功能指示层构成标签的另一个独立部分， 称为吸附指示功能层。 在一个实施方案中， 吸附材料使用能不可逆吸附所述挥发性 染料的透明不干胶， 不干胶涂敷在透明的聚合物薄膜例如塑料薄膜上， 使用前不干 胶面用离型膜保护。 在一个实施方案中， 功能指示层使用涂敷不干胶的纸， 纸的颜 色为参考终点的颜色， 通过卷对卷模切形成圆形或方形或其它几何形状的观察窗 口。 在一个实施方案中， 通过卷对卷的生产方式， 将功能指示层贴合到第二衬底材 料的未施加吸附材料的一面。 在一个实施方案中， 通过卷对卷的生产方式， 将标签 尺寸要求的隔离层模切贴合到吸附材料层上， 并用离型膜保护。 在一个实施方案 中， 将吸附指示功能层收卷后按照标签要求的尺寸模切分条， 再包装储存。 在一个 实施方案中， 模切的观察窗口的尺寸是 3-10 mm, 优化的尺寸是 4-6 mm。 在一个实 施方案中， 模切的隔离层尺寸和形状与热敏功能层中的挥发性染料层的尺寸一致。 在一个实施方案中， 模切的隔离层尺寸大于热敏功能层中的挥发性染料层的尺寸。 在一个实施方案中， 模切的吸附指示功能层尺寸与热敏功能层尺寸一致。 在一个实 施方案中， 模切的吸附指示功能层尺寸大于热敏功能层尺寸。 在一个实施方案中， 模切的吸附指示功能层尺寸小于热敏功能层尺寸。
本发明第六方面提供了所述热敏感标签的使用方法。 在一个实施方案中， 将热 敏功能层粘贴到所述的热敏感物品的包装容器的合适位置， 优选通过首先剥离位于 热敏功能层下部的离型膜， 然后通过所暴露出的位于密封膜下的不干胶层将热敏功 能层粘贴到所述的热敏感物品的包装容器的合适位置； 然后再剥离吸附指示层的离 型膜保护层和热敏功能层顶部的离型膜保护层， 将隔离层和热敏功能层对准， 利用 吸附指示层的不干胶将两部分贴紧密封。 在一个实施方案中， 先剥离吸附指示层的 离型膜保护层和热敏功能层的顶部离型膜保护层， 将隔离层和热敏功能层对准， 利 用吸附指示层的不干胶将两部分贴紧密封； 再将热敏功能层底部的保护不干胶层的 离型膜剥离， 然后利用所出的不干胶层将整个标签粘贴到所述的热敏感物品的包装 容器的合适位置。 由此， 在监测热敏感物品受热量或者受温度影响程度的情况下， 例如贮藏和 /或运输过程中， 挥发性染料处于由所述密封膜和第二衬底材料构成的密 闭体系中而不外逸， 从而因遇热量 /温度变化而挥发的染料基本上完全被吸附到所述 吸附材料中。 根据本发明， 在所述监测热敏感物品结束受热量或者受温度影响时， 例如在经过需要的贮藏和 /或运输过程之后， 可以通过标签的观察窗口观察或测定吸 附材料层的颜色深度。 颜色的深度与所述热敏感物品的累计热历史之间呈正相关。 因此， 在一个实施方案中， 所述热敏感物品的累计热历史可由本发明的热敏感标签 的吸附材料层的颜色来直观地表征。
本发明还提供了利用本发明的热敏感标签进行监测的方法， 包括在热敏感物品 上的一个或更多个区域上应用本发明的热敏感标签， 在需要时通过观察窗口观察所 述吸附材料层的颜色， 如果该颜色比所述参考颜色深， 则所述热敏感物品已经失 效； 如果该颜色比所述参考颜色浅， 则表明所述热敏感物品尚未失效。
在一个实施方案中， 该方法包括以下步骤：
(i)提供一热敏感物品， 确定该热敏感物品在其期望处置 (例如贮藏和 /或运输， 或 者稳定性加速试验)的温度下保持有效品质状态所能持续的时间 (在本发明中可以指所 能持续的最长时间， 亦可称为有效期， 可以 tl表示)， 并据此确定制作所述热敏感标 签的热敏功能层的材料和吸附指示功能层材料及其结构 （例如通过选择不同的挥发 性染料来获得不同的挥发性， 或者通过选择不同的隔离层材料来获得挥发性染料的 不同的扩散通过速率， 或者通过选择不同的吸附材料来获得不同的吸附速率） ， 按 照本发明的方法制作热敏感标签的热敏功能层和吸附指示功能层。
(ii)按照本发明的方法将热敏感标签的热敏功能层和吸附指示功能层对准密封贴 紧， 用色差计测量观察窗口的起始色差 (此时无染料挥发和吸附， 观察窗口的初始颜 色 /色差可以表示为 co)。 将标签置于期望处置 (例如贮藏和 /或运输， 或者稳定性加速 试验)的温度下 (在本发明中可以 T1表示)储存， 定时记录观察窗口的色差。 作色差随 时间的变化曲线， 找到所述热敏感物品储存有效期 tl时间下的色差 (此时观察窗口的 颜色 /色差可以表示为 Cl)， 将之作为参考颜色。 将色差的变化 （C1-C0) 除以实现 所述色差变化所需的时间得到该处置温度 T1下色差变化的速率。
(iii)在一个实施方案中， 在不同的处置温度下储存所述热敏感标签， 定时记录观 察窗口的色差。 作色差随时间的变化曲线， 找到所述处置温度下观察窗口颜色到达 终点色差所需的时间， 将该时间与所述热敏感物品在该处置温度下的有效期对比， 理想情况下， 两个时间应该尽可能接近。
(iv)将色差的变化 （C1-C0 ) 除以不同处置温度下实现所述色差变化所需的时间 tl, 得到不同处置温度 T1下色差变化的速率。 取所述不同处置温度下色差变化速率 的对数， 以该对数值作纵坐标， 所述处置温度 （热力学温度） 的倒数作横坐标作曲 log k =— ― H- log A
线， 原理上基于 Arrhenius方程 2'303 T ， 其中包括活化能 E、 速率常数 k、 热力学温度 T 等关键参数， 可以得到所述热敏感标签到达所述终点颜 色的活化能。 理想情况下， 该活化能应该与所述热敏感产品的失效活化能接近。
(V)从吸附指示层的观察窗口观察吸附层的颜色， 并与参考颜色进行对比， 判断 所述热敏感物品的品质状态：
如果吸附指示层的颜色比参考颜色浅， 则表明所述热敏感物品保持在有效品质 状态；
如果吸附指示层的颜色与参考颜色相同或比参考颜色深， 则表明所述热敏感物 品超出有效品质状态。 本发明的热敏感标签能够监测宽泛的热敏感物品的热稳定性范围。 例如， 包括 但不限于， 在 37°C下储存有效期 2小时 - 45天， 25°C下储存有效期 6小时 - 1年， 对应的活化能范围为 60-100 kJ/mol。 在一个实施方案中， 所述挥发性染料使用蓝油 烃、 所述吸附材料使用不可逆吸附蓝油烃的不干胶、 隔离层使用 60-120g/cm2的白纸 或白纸涂敷一定量的不干胶或两层 60-120g/cm2的白纸之间涂敷一定量的不干胶。 所 制造的热敏感标签以相对于普通白纸的色差 30-40作为终点， 在 37°C下储存到达终 点的时间在 1-30小时之间， 在 25°C下到达终点的时间在 3-75小时之间。 在一个实 施方案中， 所述挥发性染料使用 Rl=COOCH3取代的蓝油烃衍生物、 所述吸附材料 使用不可逆吸附该蓝油烃衍生物的不干胶、 隔离层使用 60-120g/cm2的白纸或白纸涂 敷一定量的不干胶或两层 60-120g/cm2的白纸之间涂敷一定量的不干胶。 按照本发明 制造的热敏感标签以相对于普通白纸的色差 30-40作为终点， 在 37°C下储存到达终 点的时间在 2-35天之间， 在 25°C下到达终点的时间在 6-80天之间。 在一个实施方 案中， 所述挥发性染料使用 Rl=COOC ( CH3) 3取代的蓝油烃衍生物、 所述吸附材 料使用不可逆吸附该蓝油烃衍生物的不干胶、 隔离层使用 60-120g/cm2的白纸或白纸 涂敷一定量的不干胶或两层 60-120g/cm2的白纸之间涂敷一定量的不干胶。 按照本发 明制造的热敏感标签， 以相对于普通白纸的色差 30-40作为终点， 在 37°C下储存到 达终点的时间在 1.5-30天之间， 在 25°C下到达终点的时间在 5-60天之间。 本发明一个实施方案的目的是制作变色速度及其温度效应能充分反映所指示产 品热稳定性能的个性化热敏感标签， 这种个性化标签可以针对某一种类的热敏感物 品的具体贮藏要求和特性来设计。 在一个实施方案中可以通过筛选挥发速度及其活 化能充分反映所指示产品热稳定性能的挥发性染料或其他挥发性不透明材料来实 现。
本发明一个实施方案的目的是可以通过在所选择的挥发性染料或其它挥发性不 透明材料中添加挥发助剂， 制成染料或材料配方， 改变挥发性材料的挥发速度及其 温度效应， 使之精确地反映所指示热敏感物品的热稳定性。
本发明一个实施方案的目的是制作可以在常温下保存的热敏感标签， 可以通过 如下方法实现： 热敏感标签的热敏功能层和吸附指示功能层两部分分别制作储藏， 使用时合二为一。 热敏功能层的挥发性染料涂敷后， 先用对所用热敏功能材料无吸 附作用的离型膜密封保存。 热敏功能层与吸附指示层分别制作储存， 实现两个功能 部分的常温保存。
在本发明的一个实施方案中， 提供了一种低温储运产品 (例如本发明所述热敏感 物品)在储运过程中的累计热历史的监测和预警产品， 用于判定热敏功物品是否在冷 链储运过程中因受热过度而变质 /失效 /失活。 对于该监测和预警产品， 第一方面中基 于材料的挥发性质， 利用材料挥发过程中的活化能来定量表现产品的因热历史而品 质变化的活化能； 第二方面中采用的挥发性材料是有色材料； 第三方面中用能不可 逆吸附有色挥发性染料的材料制作吸附材料层， 尤其是吸附材料层中的吸附指示 区。 由于挥发性材料受热挥发后被吸附材料层吸附， 导致吸附指示区的颜色发生显 著变化， 判定商品是否依然有效或已变质 /失效 /失活。
在本发明的一个实施方案中， 提供了用于制作上述热敏感标签的挥发性染料层 的热敏功能材料， 即挥发性染料： 蓝油烃及其系列衍生物、 或其一种或更多种的混 合物。 挥发性材料吸热后挥发， 其挥发的速度及其温度效应能使热敏标签充分反映 所指示产品变质或失效的速度及其温度效应。
在本发明的一个实施方案中， 提供了用于制作上述热敏感标签的热敏功能层的 衬底材料， 例如为普通的白纸、 复印纸、 印刷纸等。
在本发明的一个实施方案中， 提供了用于制作上述热敏感标签的热敏功能层的 密封膜的材料， 例如为不可渗透挥发性染料的聚合物材料。
在本发明的一个实施方案中， 提供了用于制作上述热敏感标签的吸附材料层的 吸附材料： 例如为各种不干胶。 优选所述吸附材料对热敏能够材料 （即挥发性染 料） 有强不可逆的吸附作用， 吸附速度远大于热敏功能材料的挥发速度， 保证热敏 功能材料表观挥发速度只受温度影响。
在本发明的一个实施方案中， 提供了用于制作上述热敏感标签的吸附材料层的 吸附材料， 其中吸附材料对热敏材料有不可逆吸附作用， 通过选用不同的吸附材料 调控热敏感标签的变色速度及其温度效应。
在本发明的一个实施方案中， 提供了所述热敏感标签的生产工艺和储存方法， 热敏功能层和吸附指示功能层均可以采用传统不干胶生产采用的卷对卷涂敷、 模 切、 贴合等生产方式， 并且提供了优化的材料浓度、 标签各部分的尺寸、 生产速度 等， 使得本发明的热敏感标签能够廉价地并且便利地批量制造。
在本发明的一个实施方案中， 提供了所述热敏感标签的使用方法， 其特征在 于： 热敏功能层和吸附指示层在使用时合二为一并且有效密封， 保护热敏感标签的 功能部位不受外界污染， 同时避免挥发性材料挥发后污染产品或其包装。
在本发明的一个实施方案中， 提供了所述热敏感标签的测试方法， 其特征在 于： 利用色差计测量标签的观察窗口的色差以量化标签的颜色变化， 选取适当的色 差终点确定标签的响应时间和变色速度， 利用 Arrhenius 方程确定热敏感标签的活 化能参数。 根据热敏感物品在特定处置温度下的有效时间及其活化能两个关键参 数， 利用测试结果得到的标签的响应时间及其活化能确定适用该热敏感物品的热敏 材料及标签结构。
在本发明的一个实施方案中， 提供了所述热敏感标签的参考颜色的确定方法， 其特征在于： 将标签至于期望处置的温度下储存， 定时记录观察窗口的色差。 作色 差随时间的变化曲线， 找到所述热敏感物品在所述处置温度下储存有效期 tl 时间下 的色差， 将之作为参考颜色， 印刷标签的参考颜色。
在本发明的一个实施方案中， 提供了所述热敏感标签的应用范围， 其中其指示 的温度范围在 0-50 °C之间， 其指示的时间范围随温度而异， 典型的时间范围是 37°C 下在 2小时 -45天之间， 25°C下在 6小时 -1年之间， 5°C下 1天 -6年之间， 响应的活 化能在 60-100 kJ/mol之间。 实施例
通过下面的各种类型的实施例可以对本发明进行进一步的描述， 然而， 本发明 的范围并不限于下述实施例。 本领域的专业人员能够理解， 在不背离本发明的精神 和范围的前提下， 可以对本发明进行各种变化和修饰。 本发明对试验中所使用到的 材料以及试验方法进行一般性和 /或具体的描述。 虽然为实现本发明目的所使用的许 多材料和操作方法是本领域公知的， 但是本发明仍然在此作尽可能详细描述。
A、 热敏感标签的实例
本发明利用物质的挥发性质制作热敏感标签， 通过受热一挥发一吸附过程， 实 现所需的颜色变化效果。 本发明人设计的一种示例性的热敏感标签的结构及其工作 原理示于图 1和图 2中。
参见图 1 所示截面图， 其中描绘了本发明的一种热敏感标签， 其由两部分组 成， （a) 部分是热敏功能层 1， (b) 部分是吸附指示功能层 2， 两部分分别制作储 藏， 使用时合二为一， 粘贴到待监测的热敏感物品的容器或包装表面。
在热敏功能层 1 中， 衬底材料层 10 的下面涂敷一层水性胶 12， 再贴合到密封 膜 13上， 由于密封膜 13不可透过染料所以阻止染料向下扩散污染热敏感物品。 密 封膜 13的下面再涂敷一层不干胶 14， 并用离型膜 15保护。 在衬底材料层 10上面的 功能部位涂敷一层具有特定挥发性能的有色挥发性染料作为热敏功能材料， 形成本 发明中的热敏功能层 11。 所用挥发性染料挥发的速度及其温度效应与所指示的产品 变质或失效的速度及其温度效应尽量一致。 热敏功能层制作干燥后密封保存， 密封 性能保证热敏功能层可以在室温下储存和运输。
在吸附指示功能层 2中， 衬底材料层 20使用透明塑料薄膜， 在衬底膜的上面贴 合不干胶纸， 贴合前不干胶纸印刷参考颜色 25和适当的产品信息 (例如该标签适用 的热敏感物品种类)或标签使用信息 (例如在需要利用标签判断热敏感物品是否失效时 如何操作的信息)， 并通过模切形成圆形或方形或其它几何形状的观察窗口 24。 在衬 底材料层 20 的下面， 印刷或涂渍一层可以有效吸附挥发的热敏功能染料的吸附材 料， 形成吸附材料层 22。 在本实施例中使用能不可逆吸附挥发性染料的透明不干 胶。 在对应于指示窗口部位， 模切合适尺寸的隔离层 23并直接贴合到作为吸附材料 的不干胶上。 挥发性染料受热挥发后扩散通过隔离层被吸附层吸附， 使吸附层的颜 色不断变深 21。
图 2示出了从俯视的角度观察本发明热敏感标签在使用过程中吸附指示层 21相 对于参考颜色层 25的变化过程， 说明本发明利用材料的挥发性能制作热敏感标签， 通过受热一挥发一吸附过程， 实现标签指示部位颜色的变化， 显示使用该热敏感标 签的产品是否因受热过度而变质或失效。
在热敏感标签与热敏感物品组合使用过程中， 参考颜色层 25的颜色深度不变， 而吸附材料层的吸附指示区 21的颜色深度会因吸附受热挥发的染料而变深。 变深的 速度受温度的影响。 即使是在热敏感物品规定期望的温度下， 挥发性染料层 11亦有 一定程度的挥发， 吸附层的颜色也相应缓慢变深。 例如对于 2-8°C贮藏效期 2年的药 品， 该药品严格在 2-8°C贮藏 2年后， 吸附层 21会因吸附缓慢挥发的染料而渐渐变 深， 此时其颜色会比参考颜色层 25浅一些， 表明该药品在 2-8°C贮藏 2年后仍然是 合格的。 贮藏时间继续延长后， 吸附指示层 21 会因继续吸附挥发的染料而继续变 深， 此后其颜色会比参考颜色层 25基本接近或更深， 表明药品已过有效期。 这个过 程亦是设计挥发性染料层 11 的材料种类以及参考颜色层 25 的颜色深度的一种实施 方案。 本文还介绍了加速方式的实施方案。 B、 热敏感标签的参考颜色层的颜色确定
根据图 1 所示的结构制作原型热敏感标签后， 在相应的恒温条件下 (例如 5°C、 10°C、 25°C和 /或 37°C等)， 使用比色计测量热敏感标签的功能部位即观察窗口的色 差随时间的变化， 可以得到热敏感标签的变色速度及其温度效应。
使用比色计可以将颜色的变化数字化。 使用比色计测量颜色变化时， 先定义一 个色空间如 L*a*b*色空间 (亦称为 CIELAB色空间）。 在这个色空间中， L*代表亮 度； a*和 b*是色度坐标， 表示色彩方向； +a*表示红色方向， -a*表示绿色方向， +b*表示黄色方向， -b*表示蓝色方向， 中心无色。 当 a*和 b*值增加并从中心移出 时， 色饱和度增加。 在这个色空间中， 色差可以用单一的数值表示：
AE*ab = [ (AL*)2 + (Aa*)2 + (Ab*)2 5 其中， 为亮度的变化， Δίΐ*为沿红色 -绿色色轴的变化， Ab*为沿黄色-蓝色色 轴的变化。 使用如 Minolta CR-310 Chroma Meter Colorlite Sph860等比色计定量 化色彩， 就可以定量化色差， 对制作的热敏感标签的变色功能进行评价并确定终点 色差。 色差测量以白色衬底如 A4纸作为参考， 标签启用时， 通过观察窗口测量起始 色差。 将标签至于期望处置的温度下储存， 定时记录观察窗口的色差。 作色差随时 间的变化曲线， 找到所述热敏感物品在所述处置温度下储存有效期 tl 时间下的色 差， 将之作为参考颜色， 印刷标签的参考颜色。
C、 以具体实例说明本发明热敏感标签的制作和应用
实施例 1:
使用蓝油烃 （C15H18) 作为热敏感标签的热敏功能材料， 以 60g/cm2的白纸 （双 胶纸， 北京鑫奥鹏科技有限公司） 作为热敏功能层的衬底， 以聚合物 （PP) 塑料膜 作为密封膜， 并且使用商用离型膜 （PET 离型膜， 苏州达万塑胶电子有限公司） ， 按照本发明的方法制备热敏功能层。 以涂覆了透明不干胶 （PET背胶透明片 PF04， 上海虎迈复合材料有限公司） 的塑料薄膜作为吸附指示功能层的衬底材料层和吸附 材料层， 以 60g/cm2的白纸作为隔离层， 并且使用商用离型膜， 以不干胶纸作为功 能指示层材料， 根据本发明的方法制备吸附指示功能层。 将标签的热敏功能层和吸 附指示层合二为一密封贴紧， 将密封的样品置于 25°C恒温条件下。 放置特定时间 后， 观察记录热敏感标签的颜色。 图 3是热敏感标签在 25°C恒温条件下放置 0-10小 时的颜色记录， 吸附指示层的颜色随着储存时间的延长不断变深。 实施例 1:
图 4是将实施例 1制作的热敏感标签放在 45°C、 37°C、 25°C和 5°C下储存， 利 用色差计 （Colorlite Sph860) 定时记录观察窗口的色差， 得到不同温度下色差 AE*ab 随时间 t 的变化。 起点色差 AE*ab=4-5， 通过选取适当的终点色差， 可以得到该热敏 感标签的变色时间和速度。 如终点色差定为 AE*ab=40 时， 在 45°C、 37°C、 25°C和 5°C下到达终点的时间分别为 1.5小时、 3小时、 8小时、 77小时， 再由 Arrhenius 方程可以推导出其变化过程对应的活化能， 活化能约为 56.4 kJ/mol (图 5)， 从而得到 热敏感标签变色过程温度效应的表征参数。 实施例 3:
以与实施例 1 类似的方式制造本发明的热敏感功能标签， 不同之处在于改变隔 离层材料及其结构， 以调控所述热敏感标签在不同处置温度下的颜色变化速度。 具 体地， 以蓝油烃作为热敏感标签的热敏材料， 隔离层分别采用 60g/cm2 白纸 (纸） 、 双层 60g/cm2白纸 （纸 +纸） 、 单层 60g/cm2白纸涂一定量的不干胶 （纸 + 胶） 、 双层 60g/cm2白纸之间涂一定量的不干胶 （纸 +胶 +纸） ， 按照实施例 1 的方 法制作热敏感标签， 将标签的热敏功能层和吸附指示层合二为一密封贴紧， 将密封 的样品置于 25°C恒温条件下， 利用色差计定时记录观察窗口的色差， 得到的色差 AE*ab随时间 t的变化如图 6所示： 使用不同隔离层的热敏感标签到达特定的终点的 时间不同。 实施例 4:
以与实施例 1 类似的方式制造本发明的热敏感功能标签， 不同之处在于通过选 用不同的热敏材料或其组合， 以调控所述热敏感标签在不同处置温度下的颜色变化 速度及其活化能。 图 7 是选用 Rl=COOCH3取代的蓝油烃衍生物作为热敏功能材 料， 按照实施例 1 的方法制作热敏感标签， 将标签的热敏功能层和吸附指示层合二 为一密封贴紧， 在 55°C、 45°C、 37°C、 和 25 °C下储存， 利用色差计定时记录观察窗 口的色差， 得到不同温度下的色差 AE*ab随时间 t的变化， 标签的起点色差 AE*ab=4- 5。 通过选取适当的终点色差， 可以得到该热敏感标签的变色时间和速度。 如终点色 差定为 AE*ab=40时， 在 55°C、 45°C、 37°C、 和 25°C下到达终点的时间分别为 27小 时、 65小时、 136小时、 和 421小时， 由此再由 Arrhenius 方程可以推导出其变化 过程对应的活化能， 活化能约为 77.0 kJ/mol (图 8)， 从而得到热敏感标签变色过程温 度效应的表征参数。 可以看到， 用 Rl=COOCH3取代的蓝油烃衍生物制作的热敏感 标签， 其响应时间和活化能都不同于用蓝油烃制作的热敏感标签。 实施例 5:
以与实施例 1类似的方式， 分别选用蓝油烃、 Rl=COOCH3、 COOCH(CH3)2、 COOC(CH3)3、 CHO 取代的蓝油烃衍生物作为热敏功能材料制作的热敏感标签， 在 37°C下储存时色差随时间的变化 （图 9 ) ， 可以看到到达相同色差终点时不同热敏 材料的标签需要的时间不同。 实施例 6:
以与实施例 1 类似的方式制造本发明的热敏感功能标签， 不同之处在于通过选 用不同的吸附材料以调控热敏感标签的变色速度及其温度效应。 图 10是参考实施例 1 的方法， 以蓝油烃为热敏功能材料， 选用五种不同的吸附材料制作热敏感标签， 在相同温度环境下热敏感标签的吸附指示层色差随时间的变化速度呈现显著的不 同。
上述示例性的描述和示例性实施例对本发明的保护范围不构成任何限制。 凡采 用等同变换或者等效替换而形成的技术方案， 或者使用不同的工艺或配方， 按照本 发明的技术方案或构想制备的热敏感标签， 均落在本发明权利保护范围之内。

Claims

权 利 要 求 书
1、 一种用于监测热敏感物品的品质状态的热敏感标签， 包括使用之前物理上 呈相互独立的热敏功能层和吸附指示功能层两个叠层部分， 其中
所述热敏功能层包括：
密封膜；
在所述密封膜上的第一衬底材料层， 所述第一衬底材料层优选由白纸、 复印纸、 或印刷纸制成， 更优选通过水性胶贴合在所述密封膜上；
挥发性染料层， 其形成于所述第一衬底材料层之上， 所述挥发性染料层 的挥发过程的活化能与所述热敏感物品的品质变化过程的活化能的差值在预定范围 内， 所述挥发性染料层优选通过将挥发性染料涂覆或浸渍在所述第一衬底材料层上 而形成； 和
第一离型膜层， 其覆盖在所述挥发性染料层上， 其中所述密封膜和所述 第一离型膜层的尺寸大于所述挥发性染料层的尺寸并且将所述挥发性染料层密封在 所述密封膜和所述第一离型膜层之间，
以及
所述吸附指示功能层包括：
第二衬底材料层， 其由透明材料制成， 优选由聚合物膜制成； 功能指示层， 其位于所述第二衬底材料层之上并且具有观察窗口， 在所 述观察窗口的周围具有参考颜色；
吸附材料层， 其位于所述第二衬底材料层之下并且能够吸附所述挥发性 染料层中的染料， 其中所述吸附材料层在垂直方向上与所述观察窗口交叠或重叠， 优选所述吸附材料层的尺寸大于所述观察窗口的尺寸；
隔离层， 其由不透明材料制成并且位于所述吸附材料层之下， 所述隔离 层的尺寸大于所述观察窗口的尺寸， 优选大于或等于所述挥发性染料层的尺寸， 更 优选大于、 等于或小于所述吸附材料层的尺寸， 所述挥发性染料能够扩散通过所述 隔离层； 和
第二离型膜层， 所述第二离型膜层覆盖所述隔离层。
2. 权利要求 1 的热敏感标签， 其中所述吸附材料层自身由不干胶形成， 优选由 透明不干胶形成， 更优选为油性或水性不干胶、 不干胶纸或不干胶胶带。
3. 权利要求 1或 2的热敏感标签， 其中， 在使用时， 剥离第一离型膜层和第二 离型膜层， 将所述吸附指示功能层的隔离层对准所述热敏功能层的挥发性染料层， 将隔离层和挥发性染料层封闭在所述密封膜和所述第二衬底材料层之间； 然后将所 述密封膜贴覆在所述热敏感物品上；
或者：
将所述密封膜贴覆在所述热敏感物品上， 然后剥离第一离型膜层和第二离型膜 层， 将所述吸附指示功能层的隔离层对准所述热敏功能层的挥发性染料层， 将隔离 层和挥发性染料层封闭在所述密封膜和所述第二衬底材料层之间。
4. 权利要求 1 - 3 的任一项的热敏感标签， 其中所述密封膜之下涂覆有不干 胶并且所述不干胶被第三离型膜覆盖，
在使用时通过剥离所述第三离型膜然后利用所述密封膜之下的不干胶将所述密 封膜贴覆在所述热敏感物品上。
5. 权利要求 1 - 4 的任一项的热敏感标签， 其中， 所述隔离层作为染料挥发 后从所述热敏功能层到所述吸附材料层的扩散通道并且能够调控所挥发染料的扩散 速度； 优选所述隔离层是单层或多层， 并且所述多层隔离层之间可以涂敷吸附所述 染料的吸附材料； 更优选所述隔离层由白色不透明材料形成； 还更优选由选自白 纸、 复印纸、 印刷纸、 不干胶标签纸的材料形成。
6. 权利要求 1 - 5 的任一项的热敏感标签， 其中所述功能指示层的在所述观 察窗口周围的参考颜色的深度与所述挥发性染料层经历与所述热敏感物品失效处置 相同的过程后所述吸附材料层因吸附从所述挥发性染料层中挥发的染料而获得的颜 色深度相同。
7. 权利要求 1 - 6的任一项的热敏感标签， 其中， 所述吸附材料能够不可逆地 吸附从所述挥发性染料层中挥发出来的染料， 优选所述的吸附材料吸附挥发性染料 的速度远大于挥发性染料的挥发速度。
8. 权利要求 1 - 7的任一项的热敏感标签， 其中所述热敏感物品选自奶制品、 疫苗、 生物制品、 生物活性样品、 药品、 食品或饮品。
9. 权利要求 1 - 8的任一项的热敏感标签， 其中所述挥发性染料层的挥发过程 的活化能为 60 - 100 kj/mol , 优选所述挥发性染料的挥发过程的活化能与所述热敏 感物品的品质变化过程的活化能的差值在 ±10 kj/mol 范围内， 更优选在 ±5 kj/mol 范围内。
10. 权利要求 1 - 9 的任一项的热敏感标签， 其中所述挥发性染料层中的挥发 性染料选自偶氮类染料、 蒽醌类染料、 式 I 化合物及其衍生物中的至少一种或其组 合， 其中式 I化合物具有如下通 ：
Figure imgf000024_0001
其中，
R1 选自氢、 卤素、 直链或支链垸基、 d-6直链或支链垸氧基、 -C0R2、 - C00R2, 优选选自氢、 -COH、 CH2OH、 -COOR2;
R2 选自氢、 d-6直链或支链垸基、 d-6直链或支链垸基胺基， 优选选自甲基、 乙 基、 正丙基、 异丙基、 正丁基、 仲丁基、 叔丁基、 正戊基、 异戊基、 新戊基、 正己 基、 甲基胺基、 乙基胺基、 正丙基胺基、 异丙基胺基、 正丁基胺基、 仲丁基胺基、 叔丁基胺基、 正戊基胺基、 异戊基胺基、 新戊基胺基、 正己基胺基， 更优选选自 氢、 甲基、 乙基、 正丙基、 异丙基、 正丁基、 仲丁基、 叔丁基。
11. 权利要求 1 - 10的任一项的热敏感标签， 其中所述的挥发性染料层中还包 括一种或更多种挥发助剂， 所述挥发助剂选自以下易挥发化合物的一种或更多种： 直链垸烃、 支链垸烃、 环垸烃或芳香烃， 优选包括己垸、 庚垸、 辛垸或其异构 体、 环己垸、 环庚垸、 环戊垸、 萘、 蒽等；
直链或支链或芳香或环醇， 优选包括丁四醇、 月桂醇、 十三醇、 十四醇、 十五 醇、 软脂醇、 十七醇、 硬脂醇等；
直链或支链或芳香或环链羧酸， 优选包括马来酸、 富马酸、 月桂酸、 十三垸 酸、 豆蔻酸、 十五垸酸、 棕榈酸、 肥酸、 癸二酸、 十二垸二酸等；
氨基酸， 优选包括氨基苯甲酸、 亮氨酸、 苯丙氨酸等；
酯， 优选包括乙酸乙酯等；
砜， 优选包括二苯基砜、 二苯基二砜、 二苄基砜、 二丁基砜等；
以及各种易挥发天然物质， 优选包括萘、 樟脑等。
12. 一种使用了权利要求 1 - 11的任一项的热敏感标签的热敏感物品。
13. 一种制备如权利要求 1到 11任一项的监测热敏感物品品质状态的热敏感标 签的方法， 其包括以下步骤：
提供密封膜，
在所述密封膜上提供第一衬底材料， 优选由白纸、 复印纸、 或印刷纸制成的第 一衬底材料， 更优选通过利用水性胶将所述第一衬底材料贴合在所述密封膜上； 在第一衬底材料上形成挥发性染料层， 优选通过将挥发性染料涂覆或浸渍在所 述第一衬底材料上来形成， 所述挥发性染料层的挥发过程的活化能与所述热敏感物 品品质变化过程的活化能的差值在预定范围内；
在所述挥发性染料层上覆盖第一离型膜， 其中所述密封膜和所述第一离型膜层 的尺寸大于所述挥发性染料层的尺寸并且将所述挥发性染料层密封在所述密封膜和 所述第一离型膜层之间， 从而形成热敏功能层；
以及
提供由透明材料形成的第二衬底材料， 优选由聚合物膜制成的第二衬底材料； 在所述第二衬底材料上形成功能指示层， 所述功能指示层具有观察窗口并且在 所述观察窗口的周围具有参考颜色；
在所述第二衬底材料下形成吸附材料层， 所述吸附材料层能够吸附所述挥发性 染料层中的染料， 并且所述吸附材料层在垂直方向上与所述观察窗口交叠或重叠， 所述吸附材料层的尺寸优选大于所述观察窗口的尺寸； 在所述吸附材料层下由不透明材料形成隔离层， 所述隔离层的尺寸大于所述观 察窗口的尺寸， 优选大于或等于所述挥发性染料层的尺寸， 更优选大于、 等于或小 于所述吸附材料层的尺寸， 所述隔离层能够扩散通过所述挥发性染料； 和
在所述隔离层下覆盖第二离型膜， 以形成吸附指示功能层。
14. 权利要求 13的方法， 其进一步包括在形成所述功能指示层之后， 在所述观 察窗口周围涂覆参考颜色层的步骤， 所述参考颜色层用非挥发性染料制成， 并且其 颜色深度与所述挥发性染料层经历与所述热敏感物品失效处置相同的过程后所述吸 附材料层因吸附所述挥发性染料层的染料而获得的颜色深度相同。
15. 权利要求 13或 14 的方法， 其中通过如下步骤来确定所述功能指示层的观 察窗口周围的参考颜色：
( 1 ) 用色差计测量观察窗口的起始色差， 即无染料挥发和吸附时观察窗口的初 始色差 （CO) ; 和
( 2 ) 将所述标签置于期望处置的条件下， 定时记录观察窗口的色差， 作色差随 时间的变化曲线， 找到所述热敏感物品储存有效期时间下的色差 (Cl)， 将在观察到 色差 (C1)时通过所述观察窗口看到的所述吸附材料层的颜色作为参考颜色。
16.一种监测热敏感物品的品质状态的方法， 包括以下步骤：
在所述热敏感物品上的一个或更多个区域上应用根据权利要求书 1 - 11 任一 项所述的热敏感标签或者根据权利要求 13 - 15 任一项的方法所制备的热敏感标 签，
在需要时通过观察窗口观察所述吸附材料层的颜色， 如果该颜色与所述参考颜 色相同或比所述参考颜色深， 则所述热敏感物品已经失效； 如果该颜色比所述参考 颜色浅， 则表明所述热敏感物品尚未失效。
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