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WO2018137271A1 - Étiquette intelligente à décoloration - Google Patents

Étiquette intelligente à décoloration Download PDF

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Publication number
WO2018137271A1
WO2018137271A1 PCT/CN2017/075192 CN2017075192W WO2018137271A1 WO 2018137271 A1 WO2018137271 A1 WO 2018137271A1 CN 2017075192 W CN2017075192 W CN 2017075192W WO 2018137271 A1 WO2018137271 A1 WO 2018137271A1
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WO
WIPO (PCT)
Prior art keywords
self
color change
evolving
smart label
change indicator
Prior art date
Application number
PCT/CN2017/075192
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English (en)
Chinese (zh)
Inventor
张超
田子健
郭占云
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北京镧彩科技有限公司
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Publication of WO2018137271A1 publication Critical patent/WO2018137271A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/12—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
    • G01K11/14—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 inorganic materials
    • 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
    • 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

Definitions

  • the present invention relates to a smart label comprising a self-evolving color change indicator for indicating the shelf life of a perishable product.
  • shelf life or expiration date, etc.
  • oversimplified factors including defined temperature, humidity, atmosphere, packaging, etc.
  • TTI Time-Temperature Indicator
  • One major type of TTI is an electronic based data logger and a radio frequency identification chip. They can track and record the temperature changes experienced by the product, but these techniques are often costly and difficult to fully cover the entire process of the product “from producer to consumer”, and it is difficult for consumers to visually read the information recorded therein.
  • Another type of TTI is based on physicochemical reactions such as dye diffusion, enzymatic hydrolysis and polymerization. However, such TTIs often limit their use due to their large size, single color change, poor kinetic range, and high cost.
  • the present invention develops a novel TTI that can be used to track, simulate, and indicate the metamorphic process of a perishable product, as well as the cumulative effect of temperature over time during cold chain logistics.
  • the self-evolving color change indicator of the invention is extremely sensitive to the surface plasmon resonance of the shape and composition of the binary metal nanocrystal, and has an unprecedented wide range of kinetic adjustability, thereby deteriorating bacterial growth or active ingredients in the perishable product.
  • the dynamics are matched to visualize product quality changes to consumers.
  • the self-evolving color change indicator used in the invention has the advantages of rich color change, small volume, low cost and no toxicity. Moreover, its kinetic range is large and easy to adjust, covering the metamorphic kinetic parameters of most perishable products.
  • the invention relates to a self-evolving color change indicator comprising the following components:
  • the metal nanomaterial has extinction in a wavelength range of 380 nm to 780 nm and an elemental silver can be epitaxially grown on the surface thereof.
  • the halogen ion is selected from the group consisting of chloride ion, bromide ion and iodide ion.
  • the concentration of the one, two or more halogen-containing cationic surfactants in the indicator is not less than 0.01 mM
  • the water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide.
  • the self-evolving color change indicator further comprises:
  • a bromide-containing substance one or more of a bromide-containing substance, an iodide-containing substance, a sulfur ion-containing substance, a sulfur-hydrogen ion-containing substance, a mercaptan, and a thioether.
  • the self-evolving color change indicator further comprises a bromide ion-containing substance
  • a ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1.
  • the self-evolving color change indicator further comprises a substance containing an iodide ion, wherein the iodide ion and the metal constituting the metal nanomaterial The ratio of atoms is greater than 0.0005:1.
  • the bromide ion-containing substance or the iodide-containing substance is selected from the group consisting of water-soluble bromide such as sodium bromide, potassium bromide, ammonium bromide, cetyltrimethylammonium bromide, or sodium iodide.
  • water-soluble bromide such as sodium bromide, potassium bromide, ammonium bromide, cetyltrimethylammonium bromide, or sodium iodide.
  • a water-soluble iodide such as potassium iodide, ammonium iodide or cetyltrimethylammonium iodide.
  • the water-insoluble silver halide in the self-evolving color change indicator is prepared from a halogen ion-containing cationic surfactant solution and a soluble silver salt solution, and wherein the halogen element and the silver element The ratio of the amount of matter is greater than one.
  • the soluble silver salt is selected from the group consisting of water-soluble silver salts such as silver nitrate, silver acetate, silver trifluoroacetate, silver perchlorate, and silver fluoroborate.
  • the metal nanomaterial in the self-evolving color change indicator is a nanomaterial of a noble metal.
  • the metal nanomaterial is a nano material of any one of gold, silver, platinum, palladium, or an alloy of any two of gold, silver, platinum, palladium, any three or all of four alloys. More preferably, the metallic nanomaterial is a nanomaterial of gold.
  • the metal nanomaterial in the self-evolving color change indicator has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocages, and the like, and mixtures of the above nanostructures.
  • the metal nanomaterial has a structure of nanorods.
  • the metal nanomaterial has a structure of nanorods having a diameter of less than 20 nm and an unlimited length. More preferably, the metal nanomaterial has a structure of nanorods having a diameter of less than 10 nm and an unlimited length.
  • the halogen ion-containing cationic surfactant in the self-evolving color change indicator is selected from the group consisting of cetyltrimethylammonium chloride and cetyltrimethyl bromide.
  • the reducing agent in the self-evolving color change indicator is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof.
  • the reducing agent is selected from the group consisting of (iso)ascorbic acid or a water-soluble salt thereof, a halogenated (iso)ascorbic acid, and a water-soluble salt thereof.
  • the reducing agent is selected from the group consisting of water-soluble salts such as (iso)ascorbic acid, (iso)ascorbate, (iso)ascorbate, (iso)ammonium ascorbate, (iso)calcium ascorbate.
  • the acidity modifier in the self-evolving color change indicator is a water soluble weak acid or a salt thereof.
  • the acidity adjusting agent is selected from the group consisting of water-soluble salts such as formic acid, acetic acid, lactic acid, citric acid, oxalic acid, gluconic acid and sodium, potassium, ammonium, calcium salts thereof.
  • the self-evolving color change indicator further comprises an antifreeze agent of 1% or more and 60% or less based on the total mass of the color change indicator.
  • the antifreeze agent is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, and the like.
  • the self-evolving color change indicator further comprises a viscosity modifier greater than or equal to 0.01% and less than or equal to 60% based on the total mass of the color change indicator.
  • the viscosity modifier is selected from the group consisting of carbomer, xanthan gum and the like.
  • the self-evolving color change indicator further comprises a gelling agent in an amount of 0.01% or more and 10% or less based on the total mass of the color changing indicator.
  • the gelling agent is a water soluble gelling agent. More preferably, the gelling agent is selected from the group consisting of agar, gelatin, agarose, gum arabic, calcium alginate, carrageenan and the like.
  • the self-evolving color change indicator achieves a change by adjusting the concentration of the metal nanomaterial, the concentration of the halogen ion, the concentration of the acidity adjuster, the concentration of the reducing agent, and the concentration of the surfactant. The time required to change from the initial color to the final color and the apparent activation energy of the color change process.
  • the self-evolving color change indicator comprises the following components:
  • a gold nanorod having a diameter of less than 10 nm and an unlimited length
  • concentration of the cetyltrimethylammonium chloride in the indicator is not less than 0.01 mM.
  • the present invention is directed to a method of preparing a self-evolving color change indicator, the steps of which include:
  • the metal nanomaterial has extinction in a wavelength range of 380 nm to 780 nm and an elemental silver can be epitaxially grown on the surface thereof.
  • the first cationic surfactant containing the first halogen ion and the second cationic surfactant containing the second halogen ion may be the same or different, and their total concentration in the indicator is not less than 0.01 mM,
  • the first halogen and the second halogen may be the same or different and are independently selected from the group consisting of chloride ion, bromide ion, and iodide ion, and
  • the water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide.
  • the preparation method further comprises adding one of a bromide ion-containing substance, an iodide ion-containing substance, a sulfur ion-containing substance, a sulfur-hydrogen ion-containing substance, a mercaptan, and a thioether.
  • a bromide ion-containing substance an iodide ion-containing substance
  • a sulfur ion-containing substance a sulfur-hydrogen ion-containing substance
  • a mercaptan a thioether.
  • the ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1.
  • the inhibitor is an iodide-containing substance
  • the ratio of the iodide ion to the metal atom constituting the metal nanomaterial is greater than 0.0005:1.
  • the bromide ion or iodide ion-containing substance is selected from the group consisting of water-soluble bromide such as sodium bromide, potassium bromide, ammonium bromide, cetyltrimethylammonium bromide, or sodium iodide or potassium iodide.
  • water-soluble bromide such as sodium bromide, potassium bromide, ammonium bromide, cetyltrimethylammonium bromide, or sodium iodide or potassium iodide.
  • a water-soluble iodide such as ammonium iodide or cetyltrimethylammonium iodide.
  • the metal nanomaterial in the method of preparation is a nanomaterial of a noble metal.
  • the metal nanomaterial is a nano material of any one of gold, silver, platinum, and palladium, or an alloy of any two, any three, or all four of gold, silver, platinum, and palladium.
  • the metallic nanomaterial is a nanomaterial of gold.
  • the metal nanomaterial in the preparation method has the following structure: nanospheres, nanorods, nanoplates, nanocage.
  • the metal nanomaterial has a structure of nanorods.
  • the metal nanomaterial has a structure of nanorods having a diameter of less than 20 nm and an unlimited length. More preferably, the metal nanomaterial has a structure of nanorods having a diameter of less than 10 nm and an unlimited length.
  • the halogen ion-containing cationic surfactant in the preparation method is selected from the group consisting of cetyltrimethylammonium chloride and cetyltrimethylammonium bromide.
  • the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethyl
  • the reducing agent in the method of preparation is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof.
  • the reducing agent is selected from the group consisting of (iso)ascorbic acid or a water-soluble salt thereof, a halogenated (iso)ascorbic acid, and a water-soluble salt thereof.
  • the reducing agent is selected from the group consisting of water-soluble salts such as (iso)ascorbic acid, (iso)ascorbate, (iso)ascorbate, (iso)ammonium ascorbate, (iso)calcium ascorbate.
  • the acidity regulator in the preparation method is a water-soluble weak acid or a salt thereof.
  • the acidity adjusting agent is selected from the group consisting of water-soluble salts such as formic acid, acetic acid, lactic acid, citric acid, oxalic acid, gluconic acid and sodium, potassium, ammonium, calcium salts thereof.
  • the soluble silver salt is selected from the group consisting of water-soluble silver salts such as silver nitrate, silver acetate, silver trifluoroacetate, silver perchlorate, and silver fluoroborate.
  • the preparation method further comprises an antifreeze agent of 1% or more and 60% or less based on the total mass of the color change indicator.
  • the antifreeze agent is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, and the like.
  • the preparation method further comprises a viscosity modifier greater than or equal to 0.01% and less than or equal to 60% based on the total mass of the color change indicator.
  • the viscosity modifier is selected from the group consisting of carbomer, xanthan gum and the like.
  • the preparation method further comprises a gelling agent in an amount of 0.01% or more and 10% or less based on the total mass of the color changing indicator.
  • the gelling agent is a water soluble gelling agent. More preferably, the gelling agent is selected from the group consisting of agar, gelatin, agarose, gum arabic, calcium alginate, carrageenan and the like.
  • the preparation method achieves the change by initially adjusting the concentration of the metal nanomaterial, the concentration of the halogen ion, the concentration of the acidity regulator, the concentration of the reducing agent, and the concentration of the surfactant. The time it takes for the color to change to the final color.
  • the present invention is directed to a color change indicating method for a shelf life of a perishable product, comprising the steps of:
  • the color change indicating method is characterized in that the specific quality parameter of the deteriorated product is: the number of the flora, the content of the active ingredient, and the content of the harmful component.
  • the self-evolving color change indicator of the present invention can track and record the temperature change history experienced by the perishable product, simulate the deterioration process of the product to be indicated, and visually indicate the product quality and shelf life by color;
  • the self-evolving color change indicator of the present invention exhibits a resolvable color change during the color change process, which can achieve rich color changes such as red, orange, yellow, green, blue, purple, red, and orange;
  • the rate of discoloration of the self-evolving color change indicator of the present invention can be adjusted such that the time elapsed from the initial color to the final color at a specific temperature (e.g., room temperature (25 ° C) is from several minutes to several months
  • a specific temperature e.g., room temperature (25 ° C) is from several minutes to several months
  • the same self-evolving color change indicator can exhibit different time from the initial color to the final color at different temperatures (significantly slower than room temperature at low temperatures);
  • the self-evolving color change indicator of the present invention may be in a solution state or in a hydrogel state, which is convenient for different practical needs;
  • the self-evolving color change indicator of the present invention has a low dosage, and the color change can be distinguished by the naked eye as a lower limit, wherein the amount of gold and silver reagent is less than 10 ⁇ g ⁇ mL -1 , and other auxiliary reagents are common additives. It is safe, non-toxic and low cost;
  • the preparation process of the self-evolving color change indicator according to the present invention is completely carried out in an aqueous phase environment, and does not require harsh conditions such as high temperature and high pressure, and the preparation process is safe and simple, and can be prepared by the manufacturer during the packaging of food and medicine.
  • the invention also relates to a smart label comprising the above self-evolving color change indicator, which ensures accurate indication of the product shelf life without affecting the quality of the product itself.
  • the self-developing color change indicator can be packaged or sealed with a transparent, non-adsorbing material. If the label is attached directly to the outer packaging of the product, or the self-evolving color indicator is directly coated on the outer packaging of the product to form an integrated In the package, the smart label can also be placed in the recess of the product or the bottom of the bottle.
  • the invention also relates to a smart tag with a mixing device.
  • the pre-formed self-evolving color change indicator does not undergo a color change reaction. After mixing, the color change reaction begins to achieve as much synchronization as possible with the production of the product.
  • the self-evolving color change indicator components that will react may be separately contained in the different components.
  • the smart tag includes a mixing device that, by actuating the mixing device, allows mixing of the components of the indicator contained in the prefabricated label to effect activation of the smart tag.
  • the present invention also relates to achieving a more accurate indication of the shelf life of a product by a combination of self-evolving color change indicators having different dynamic properties.
  • the different kinds of self-evolving color change indicators in the smart tag have different spectral blue shift rates at a particular temperature, and then different times from the initial color change to the final color, with different sensitivities for different specific temperatures.
  • the kinetics of different metamorphic parameters of the product can be simulated by different self-evolving color-changing indicators to comprehensively evaluate the shelf life of the product.
  • the present invention also relates to a progress bar type smart tag that adjusts the blue shift rate of the associated color change indicator to achieve an effect of visually indicating the quality of the perishable product with a progress bar.
  • the smart tag can include a plurality of self-evolving color-changing indicators having different spectral blue-shift rates, which are sequentially adjacent in order to gradually increase in time from the initial color change to the final color.
  • the present invention also relates to a smart label for indicating the remaining shelf life of a perishable product, for example, the color in the discoloration range of the color-changing indicator according to the present invention and the time required for the perishable product to deteriorate at its usual temperature
  • the ground mark can roughly estimate the time remaining for the perishable product to deteriorate.
  • Figure 1 The process of discoloration of the self-evolving color change indicator of Example 1 in a constant temperature environment of 35 °C.
  • Figure 2 Discoloration process of the self-evolving color change indicator of Example 2 in a constant temperature environment of 5 ° C, which shows that the self-evolving color change process of the self-evolving color change indicator is slowed down when the ambient temperature is lowered.
  • Figure 3 The discoloration process of the self-evolving color change indicator of Example 3 in a constant temperature environment at 35 ° C, which shows that the self-evolving color change process of the self-evolving color change indicator is slowed down when the concentration of the reducing agent is lowered.
  • Figure 4 The discoloration process of the self-evolving color change indicator of Example 4 in a constant temperature environment of 35 ° C, which shows that the self-evolving color change process of the self-evolving color change indicator is slowed down when the surfactant concentration is increased.
  • Figure 5 Discoloration process of the self-evolving color change indicator of Example 5 in a constant temperature environment at 35 ° C, which shows that the self-evolving color change process of the self-evolving color change indicator is slowed down when the acidity adjuster is added.
  • Figure 6 The color change process of the self-evolving color change indicator of Example 6 in a constant temperature environment of 35 ° C, which indicates that the self-evolving color change process of the self-evolving color change indicator cannot reach the final color when the amount of silver halide added is insufficient.
  • Figure 7 The discoloration process of the self-evolving color change indicator of Example 7 in a constant temperature environment at 35 ° C, which shows the effect of no addition of an inhibitor on the self-evolving color change process of the self-evolving color change indicator, specifically in the spectral blue shift rate Slow down, the indicator color is lighter and darker, and the saturation is low.
  • Figure 8 The color change process of the self-evolving color change indicator of Example 8 in a constant temperature environment of -5 ° C, which indicates that the aqueous self-evolving color change indicator can work normally below zero after the addition of the antifreeze.
  • Figure 9 is a diagram showing the discoloration process of the self-evolving color change indicator of Example 9 in a constant temperature environment of 35 ° C, which shows that after the addition of the viscosity modifier, the sedimentation of the nanoparticles due to gravity can be effectively suppressed, and the colloidal solution system is more uniform. .
  • Figure 10 Detailed color change process of the self-evolving color change indicator of Example 10 in a constant temperature environment at 25 ° C, wherein the gelling agent renders the system in a gel state.
  • Figure 11 is a graphical representation of the color change of the self-evolving color change indicator of the present invention as a function of microbial multiplication at temperatures of 35 ° C and 5 ° C.
  • Figure 12 Self-evolving color change indicator housed in a concave portion provided on the outer surface of the product bottle cap.
  • Figure 13A Initial state of a smart strip of progress bar having the composition of two self-evolving color change indicators, wherein both the first indicator and the second indicator are green.
  • Figure 13B The smart tag of Figure 13A undergoes a change over time, with the first indicator turning blue-green and the second indicator turning blue.
  • Figure 13C The smart tag of Figure 13B continues to undergo a change over time, with the first indicator turning blue and the second indicator turning purple.
  • Figure 13D The smart tag of Figure 14C continues to undergo a change over time, wherein the second indicator turns red, the same color as the background portion, the first indicator turns purple, and the complete color bar changes to only half The length corresponds to the quality qualified period remaining in the perishable product.
  • Figure 13E is a color comparison table for explaining the color of different portions in Figures 13A, 13B, 13C, and 13D.
  • Figure 14A Initial state of a smart strip with a progress bar consisting of three self-evolving color change indicators.
  • Figure 14B The smart tag of Figure 14A undergoes a change over time.
  • Figure 14C The smart tag of Figure 14B continues to undergo a change over time.
  • Figure 14D The smart tag of Figure 14C continues to undergo changes over time.
  • Figure 14E The smart tag of Figure 14D continues to undergo changes over time.
  • the self-evolving color change indicator of the present invention comprises the following components:
  • the self-evolving color change indicator of the present invention further comprises one or more of the following components: an inhibitor, an antifreeze, a viscosity modifier, and a gel former.
  • the invention is based on the principle that the reduction reaction of silver halide produces elemental silver which is deposited on the metal nanomaterial (as a seed crystal) and gradually changes the color of the metal nanomaterial as the thickness of the deposited layer increases.
  • the silver halide when the silver halide is gradually reduced to elemental silver with time, the silver is continuously epitaxially grown on the gold nanorods to form a silver shell-wrapped gold core.
  • the matte band of the longitudinal plasma element resonance gradually moves toward the short wave direction, thereby changing the color of the colloidal solution.
  • the metal nanomaterial is not particularly limited as long as it has extinction in a wavelength range of 380 nm to 780 nm and elemental silver can be epitaxially grown on the surface thereof.
  • a typical metal nanomaterial satisfying this condition is a noble metal nanomaterial, including but not limited to gold, silver, platinum, palladium, etc., two, three, four or more may also be used.
  • gold nanomaterials are particularly preferred.
  • metal nanomaterials The shape of metal nanomaterials is also varied.
  • the metal nanomaterial has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocages, and mixtures of these nanostructures.
  • the metal nanomaterial has the structure of a nanorod.
  • the initial color of metal nanomaterials is related to factors such as compositional elements, size, and shape. E.g:
  • the same is a nanosphere with a diameter of 10 nm, the golden sphere is red, and the silver sphere is yellow;
  • the same is a gold nanosphere, the color is red when the diameter is 10 nm, and the color is purple when the diameter is 50 nm;
  • the same is a gold nanorod with a diameter of 10 nm, which is blue when the aspect ratio is 2:1, and orange-red when the aspect ratio is 5:1.
  • the color is sequentially red, orange, yellow, green, blue, purple, red, and orange as the silver shell grows;
  • the color is gray, green, blue, purple, and brown in accordance with the growth of the silver shell;
  • the color is sequentially red, orange, and yellow as the silver shell grows.
  • gold nanorods having a diameter of less than 20 nm, especially 10 nm are preferably used, the change in color change of which can be changed sequentially from red, orange, yellow, green, blue, purple, red, and orange.
  • the silver compound to be reduced to elemental silver is another important component of the self-evolving color change indicator of the present invention.
  • all silver compounds which can be reduced to elemental silver by a reducing agent can be used for this purpose, for example, water-soluble silver salts and water-insoluble silver halides.
  • the water-soluble silver salt includes, but is not limited to, silver nitrate, silver acetate, silver perchlorate, silver fluoride, silver trifluoroacetate, silver fluoroborate, and the like; the water-insoluble silver halide may be selected from silver chloride and bromine. Silver or silver iodide.
  • the inventors have surprisingly found that the use of insoluble silver halide in the self-evolving color change indicator of the present invention can achieve an excellent effect of higher repeatability because if a soluble silver salt is used, the system Both the halide ion and the reducing agent react with the silver ion, and the two compete to make the concentration of the silver ion in the system unstable, thereby making the repeatability of the discoloration process worse. This competitive reaction is avoided when water insoluble silver halide is used.
  • water insoluble silver halide can also be formulated in situ.
  • a water-soluble silver salt is preferentially reacted with a cationic surfactant containing a halogen ion (chloride ion, bromide ion or iodide ion) to form a suspension (in which the ratio of the amount of the halogen element to the silver element is greater than 1, to ensure All silver ions are converted to precipitates, and then a reducing agent is added.
  • a cationic surfactant containing a halogen ion (chloride ion, bromide ion or iodide ion) to form a suspension (in which the ratio of the amount of the halogen element to the silver element is greater than 1, to ensure All silver ions are converted to precipitates, and then a reducing agent is added.
  • the surfactant is preferably a cationic surfactant, and more preferably a halogen ion-containing cationic surfactant including, but not limited to, cetyltrimethylammonium chloride, cetyltrimethyl Ammonium methyl bromide, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide, Cetyltriethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethyl Ammonium bromide, octadecyltriethylammonium iodide, and the like. Particular preference is given to cetyltrimethylammonium chloride
  • the reducing agent is not particularly limited as long as the silver compound can be reduced to elemental silver.
  • ascorbic acid, isoascorbic acid or a derivative thereof can well achieve the object of the present invention, for example, (iso)ascorbic acid or a water-soluble salt thereof, halogenated (iso)ascorbic acid or a water-soluble salt thereof.
  • halogenated (iso)ascorbic acid or a water-soluble salt thereof Specifically, but not limited to, (iso) ascorbic acid, (iso) sodium ascorbate or (iso) potassium ascorbate, (iso) ammonium ascorbate, (iso) calcium ascorbate and other water-soluble salts.
  • the present inventors have found that if silver is made long only in the diameter direction of the nanorods and not long in the longitudinal direction, a richer color change is obtained, and the color is bright and the saturation is high.
  • the present inventors have unexpectedly found that the following inhibitors having strong affinity with the surface of the metal nanomaterial can achieve this purpose: a substance containing bromide ions, a substance containing iodide ions, a substance containing sulfur ions, and a sulfur-containing hydrogen. Ionic materials, mercaptans and thioethers.
  • a substance containing a bromide ion When a substance containing a bromide ion is used, a ratio of a bromide ion to a metal atom constituting the metal nanomaterial of more than 0.005:1 is particularly preferable.
  • the ratio of the iodide ion to the metal atom constituting the metal nanomaterial is more than 0.0005:1.
  • the bromide-containing substance or the iodide-containing substance is selected from the group consisting of water-soluble bromide such as sodium bromide, potassium bromide, ammonium bromide, cetyltrimethylammonium bromide, or sodium iodide or potassium iodide.
  • a water-soluble iodide such as ammonium iodide or cetyltrimethylammonium iodide.
  • the kinetics of the self-evolving color change indicator of the present invention can be varied in various ways, such as the concentration of the metal nanomaterial, the concentration of the halide ions, the concentration of the reducing agent, the concentration of the surfactant, and the like.
  • the kinetics of the self-evolving color change indicator can be adjusted most simply by the addition of an acidity regulator.
  • the acidity regulator is a water-soluble weak acid or a salt thereof, such as an organic weak acid or an inorganic weak acid.
  • acidity regulators include, but are not limited to, water-soluble salts of formic acid, acetic acid, lactic acid, citric acid, oxalic acid, and gluconic acid, and sodium, potassium, ammonium, calcium, and the like.
  • the self-evolving color change indicator of the present invention may also contain one or more other ingredients to further improve its physicochemical properties for practical needs.
  • these other ingredients include antifreeze, viscosity modifiers or gelling agents.
  • Antifreeze can lower the freezing point of the system, allowing it to work below 0 degrees Celsius.
  • An antifreeze agent of 1% or more and 60% or less based on the total mass of the color change indicator is particularly preferable.
  • Examples of antifreeze agents include, but are not limited to, ethylene glycol, propylene glycol, glycerol, and the like.
  • the viscosity modifier can increase the viscosity of the system and avoid uneven distribution of components in the system caused by the precipitation of silver halide.
  • the self-evolving color change indicator of the present invention is more uniform in color after the addition of the viscosity modifier.
  • a viscosity modifier which is 0.01% or more and 60% or less based on the total mass of the color change indicator is particularly preferable.
  • examples of viscosity modifiers include, but are not limited to, carbomer and xanthan gum.
  • the gelling agent can achieve two purposes: on the one hand, similar to the viscosity modifier, inhibiting the unevenness due to the sedimentation of the silver chloride; on the other hand, the color changing system can be changed from a liquid state to a solid state, which may be advantageous for subsequent processing.
  • a gelling agent having a total mass of 0.01% or more and 10% or less based on the total mass of the color changing indicator is particularly preferred.
  • Preferred gelling agents are water soluble gelling agents. Examples of gelling agents include, but are not limited to, agar, gelatin, agarose, gum arabic, calcium alginate, carrageenan, and the like.
  • the color of the solution has a one-to-one correspondence with the degree of deterioration of the product, that is, the color of the solution can indicate the quality of the product: when the solution is in the original color, it means that the product is far from the expiration standard; when the solution is in the middle color , indicating that the product has a shelf life of more than half; when the solution is in the final color, the product has expired.
  • the degree of blue shift of the maximum extinction peak position of the solution (or other color-related parameters, such as color coordinates, etc.) is plotted on the horizontal axis, and the product quality parameter is plotted on the vertical axis to obtain the indicator color change process and the metamorphic product deterioration process. Correlation function curves at different temperatures.
  • Self-evolving color change indicators were prepared using the following formulations and procedures.
  • the standard concentration of gold nanorod solution is prepared by dispersing gold nanorods in cetyltrimethylammonium chloride solution (0.010M) with extinction peaks at 508 nm and 825 nm, of which optical density at 508 nm. It is 10.000 cm -1 and the optical density at 825 nm is 44.000 cm -1 . The same below.
  • a standard concentration of silver chloride suspension is obtained by mixing an equal mass of a solution of cetyltrimethylammonium chloride (concentration: 0.116 M) and silver nitrate (concentration of 0.100 M). The same below.
  • the prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in FIGS. 1A and 1B.
  • the prepared self-evolving color change indicator was placed in a constant temperature environment of 5 ° C, and its extinction spectrum was measured every 24 hours, and the results are shown in FIGS. 2A and 2B.
  • a self-evolving color change indicator was prepared using the following formulation and the same procedure as in Example 1.
  • the prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in FIGS. 3A and 3B.
  • a self-evolving color change indicator was prepared using the following formulation and the same procedure as in Example 1.
  • the prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in FIGS. 4A and 4B.
  • a self-evolving color change indicator was prepared using the following formulation and the same procedure as Example 1 except that acetic acid was added in step 1.
  • the prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in Figs. 5A and 5B.
  • a self-evolving color change indicator was prepared using the following formulation and the same procedure as in Example 1.
  • the prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in Figs. 6A and 6B.
  • a self-evolving color change indicator was prepared using the following formulation and the same procedure as in Example 1.
  • the prepared self-evolving color change indicator was placed in a constant temperature environment of 35 ° C, and its extinction spectrum was measured every 1.0 h, and the results are shown in FIGS. 7A to 7D.
  • the self-evolving color change process of the self-evolving color change indicator also changes when bromide ions (inhibitors) are not added, as shown in the spectral blue shift. The rate is slowed down.
  • the self-evolving color change indicator formulated using the gold nanorod solution of Example 1 or 7 will exhibit the following color changes: red, orange, yellow, green, blue, purple, red, orange.
  • the self-evolving color change indicator of Example 1 changed from orange red to blue green to red again at 2 h and 4 h; when the bromide inhibitor was not added, the case of Example 7 At 2h and 4h, the self-evolving color-changing indicator changed from orange-red to light-green to blue-gray (see Figure 7C for details).
  • the bromide ion inhibitor slows down the discoloration process of the self-evolving color change indicator.
  • a self-evolving color change indicator was prepared using the following formulation and the same procedure as in Example 1.
  • the prepared self-evolving color change indicator was placed in a constant temperature environment of -5 ° C, and its extinction spectrum was measured every 7 days. The results are shown in FIG.
  • a self-evolving color change indicator was prepared using the following formulation and the same procedure as in Example 1.
  • the prepared self-evolving color change indicator was placed in an environment of 35 ° C, and after 5 hours, a red solution was obtained, and an appropriate amount of the red solution was transferred to a cuvette. At the same time, the self-evolving color change indicator obtained in Example 1 was allowed to stand for 48 hours, and then the red solution was transferred to another cuvette. The result is shown in Figure 9.
  • a self-evolving color change indicator was prepared using the following formulation and the same procedure as in Example 1.
  • the agar solution is heated by mixing agar powder with an appropriate amount of water to obtain a uniform transparent solution. Since the solution may form a gel after cooling, it must be mixed with other component solutions evenly, and the obtained solution is rapidly cooled to 5 About °C, to be used after forming a gel.
  • the prepared self-evolving color change indicator was cut into small pieces, placed in a 25 ° C environment, and its color was recorded over time, and the results are shown in FIG. Figure 10 shows the color change process of the self-evolving color change indicator within 12 hours. Specifically, the starting color (red) from the 12 o'clock direction gradually changes from the 1 o'clock direction color to the 11 o'clock direction color, in order: red, orange, yellow, green, green, blue Green, blue, blue-violet, purple, magenta, red, red.
  • the color change indicating technology of the present invention utilizes the sensitivity of chemical reaction kinetics to temperature to simulate the temperature dependence of the metamorphic product deterioration process. By adjusting the amount of reagents, it is possible to simulate the deterioration process of a perishable product and indicate the quality and shelf life of the product.
  • the color change indicator described in the application of the invention has the characteristics of clear color contrast, simple operation, low cost and high safety, and can be used for tracking and recording the temperature change experienced by the product during transportation, storage and sales, and simulating the deterioration process of the product. The product quality and shelf life are visually indicated by the color change of the indicator itself.
  • the invention also relates to a smart label comprising a self-evolving color change indicator according to the invention.
  • self-developing color-changing indicators should not be in direct contact with products (especially for food products).
  • products especially for food products.
  • the self-evolving color-changing indicator in order to ensure that the self-evolving color-changing indicator can accurately reflect the cumulative effect of temperature and time experienced by the product, it is also necessary.
  • the self-evolving color change indicator is tightly bonded to the product. Therefore, a suitable combination method is critical to ensure that product quality is not affected by self-evolving color change indicators and accurately simulate temperature time cumulative effects.
  • the invention adopts the transparent non-adsorbing material to package or seal the self-evolving color change indicator to realize the purpose of combining the self-developing color change indicator with the product without direct contact, and further, the indicator color change reaction can be obviously observed. Effect.
  • the transparent non-adsorbing packaging material is preferably selected from the group consisting of polypropylene, polyethylene or polyterephthalic acid materials.
  • the self-developing color change indicator is packaged in the form of a label using a transparent, non-adsorptive material, and the indicator label is attached directly to the outer package of the product by labeling.
  • the smart label according to the invention comprises a joint through which the joint is combined with the packaging of the product.
  • the label can be set on the product packaging that was originally used to indicate the shelf life of the product. Further, the label can be made into a profiled label to achieve the aesthetics of the package.
  • the label can be attached in a variety of ways, such as by bonding the label's bond to the product package with an adhesive.
  • the adhesive may be of a type known to those skilled in the art to be suitable for the application.
  • the adhesive may be selected from thermoplastic adhesives such as cellulose esters, vinyl polymers (polyvinyl acetate, polyvinyl alcohol, perchloroethylene, polyisobutylene, etc.), polyesters, polyethers , polyamide, polyacrylate, a-cyanoacrylate, polyvinyl acetal, ethylene-vinyl acetate copolymer, and the like.
  • the adhesive may also be selected from thermosetting adhesives such as epoxy resins, phenolic resins, urea-formaldehyde resins, melamine-formaldehyde resins, silicone resins, furan resins, unsaturated polyesters, and propylene.
  • thermosetting adhesives such as epoxy resins, phenolic resins, urea-formaldehyde resins, melamine-formaldehyde resins, silicone resins, furan resins, unsaturated polyesters, and propylene.
  • Acid resin polyimide, polybenzimidazole, phenol-polyvinyl acetal, phenol-polyamide, phenol-epoxy resin, epoxy-polyamide, and the like.
  • the adhesive may also be selected from synthetic rubber type adhesives and rubber resin type adhesives such as neoprene, styrene butadiene rubber, butyl rubber, sodium butadiene rubber, isoprene rubber, and poly Sulfur rubber, urethane rubber, chlorosulfonated polyethylene elastomer, silicone rubber, etc.; and, phenolic-butyronitrile rubber, phenolic-chloroprene rubber, phenolic-polyurethane rubber, epoxy-nitrile rubber, epoxy-polysulfide rubber Wait. Since the label is adhered to the outer packaging of the product, in order to prevent the peeling problem that may occur during transportation, the selected adhesive should have a good adhesive effect.
  • synthetic rubber type adhesives and rubber resin type adhesives such as neoprene, styrene butadiene rubber, butyl rubber, sodium butadiene rubber, isoprene rubber, and poly Sulfur rubber, urethane rubber, chlor
  • the self-evolving color change indicator is coated directly onto the outer package of the associated product to form an integrated package.
  • a smart label in accordance with the present invention comprises a multilayer film, and a self-evolving color change indicator according to the present invention is coated between different layers of film on the surface of the associated outer package.
  • a self-evolving color changing indicator according to the present invention may be coated between the outer packaging surface and the additional film.
  • the film material used to encapsulate the self-evolving color change indicator is, for example, transparent or translucent, and has suitable strength to facilitate viewing of the color change effect of the indicator.
  • this integrated package can effectively prevent the self-evolving color-changing indicator from falling off from the outer packaging of the product due to various reasons during transportation.
  • the packaging method can effectively prevent the bad merchant from artificially tearing off the smart label of the product packaging that has passed the shelf life or near the shelf life.
  • the self-evolving color-changing indicator is packaged into a separate label by transparent non-adsorbing material, which usually requires an additional cutting and sealing step, and then adheres to the product packaging, which is relatively complicated and costly. Therefore, the use of integrated packaging can also achieve economic and convenient effects.
  • a self-evolving color change indicator can be exemplarily housed in a concave portion provided on a bottle cap for certain products having a bottle cap.
  • the bottle cap may, for example, be molded to have a concave portion provided on its outward surface, as shown in Figure 12, in which the self-evolving color change indicator according to the present invention is filled and not transparent
  • the packaged portion of the adsorbed packaging material seals it therein.
  • the concave portion can be disposed, for example, on an inwardly facing surface of the cap.
  • the self-evolving color change indicator can also be filled into a recess located outside the bottom of the bottle and sealed therein by a transparent, non-adsorbing packaging material.
  • a transparent, non-adsorbing packaging material such as a transparent, non-adsorbing packaging material.
  • Such a groove can be provided, for example, in a conventional beverage bottle or container for effects such as aesthetics, so that it is not necessary to additionally customize the container for setting the self-evolving color change indicator.
  • the invention also relates to a smart tag with a mixing device.
  • the interval between the configuration of the self-evolving color change indicator and the production time of the associated perishable product can be shortened as much as possible.
  • a self-evolving color change indicator configuration device can be placed in the packaging line. But such a disadvantage is the additional cost of retrofitting.
  • Another way is to provide a prefabricated self-evolving color change indicator label in which the components of the self-evolving color change indicator according to the present invention that are relatively stable and do not undergo a self-discoloration reaction are grouped.
  • the self-evolving color change indicator label for example, further includes a mixing device by which the components of the indicator separately contained in the prefabricated label can be mixed to form a self-evolving color change indicator according to the present invention.
  • the mixing device is a removable wall that separates different components of the indicator.
  • the removable wall can be moved or removed such that the different components are thoroughly mixed to form a self-evolving color change indicator in accordance with the present invention.
  • the removable wall may, for example, comprise a magnetic portion that can be moved or removed by magnetic attraction or repulsive force between the magnet outside the label and the magnetic portion to effect mixing of the different components.
  • the mixing device includes a spacer film and an actuation portion that separate different components of the indicator, and the actuation portion is capable of piercing the spacer film.
  • the spacer film can be puncture by actuating the actuation portion, thereby allowing the different components to be thoroughly mixed to form a self-evolving color change indicator in accordance with the present invention.
  • the actuation portion can be a needle.
  • actuation portion can have other shapes and configurations, and actuation of the actuation portion can be accomplished, for example, by rotation, compression, pulling, and the like.
  • the actuation portion may, for example, comprise a magnetic portion, and the aforementioned actuation is achieved by magnetic attraction or repulsive force between the magnet outside the label and the magnetic portion of the actuation portion.
  • the mixing device is, for example, an interval made of a hot soluble substance or a photodegradable substance membrane.
  • the spacer film can be melted or decomposed, for example by heating or by light, to effect mixing of the different components of the indicator.
  • one component of the prefabricated self-evolving color change indicator comprises one of a colloidal solution and a silver halide suspension mentioned in the preparation method of the self-evolving color change indicator according to the present invention, and the other The other of the foregoing is included in the composition.
  • the preformed self-evolving color change indicator can include more components.
  • it comprises three components, wherein the first component comprises a metal nanomaterial solution, the second component comprises a component other than the metal nanomaterial solution in the colloidal solution, and the third component comprises a silver halide suspension .
  • the invention also relates to a smart tag comprising a plurality of self-evolving color change indicators.
  • the smart tag consists of at least two self-evolving color-changing indicators that have different compositions and therefore different chemical kinetic properties. That is, the different kinds of self-evolving color change indicators in the smart tag have different spectral blue shift rates at a particular temperature, and then the time required to change from the initial color to the final color is different.
  • the color change indicating method according to the present invention is realized by adjusting the composition of the indicator such that the color change thereof and the specific quality parameter of the perishable product change with time.
  • different quality parameters are of greater importance, and they vary over time at a particular temperature.
  • This problem can be solved by using different types of self-evolving color change indicators to track different quality parameters of the same perishable product over time.
  • the method of tracking each quality parameter is the same as the step of the color change indicating method described earlier. In this way, the situation in which the specific quality parameters of the product change over time can be more fully reflected.
  • the quality parameters such as the number of bacteria, the content of active ingredients, and the content of harmful ingredients
  • the deterioration rate of the product varies greatly under different temperature conditions, and a single self-evolving color change indicator may have the defect of insufficient sensitivity to reaction at certain temperatures.
  • the time required for a perishable product to change from the initial color to the final color at 25 ° C is 30 days.
  • the self-evolving reaction indicator In order to simulate the deterioration of the product, it is necessary to set the self-evolving reaction indicator to have a metamorphic reaction with the product. The same kinetics.
  • the perishable product has low sensitivity to 15°C environment, that is, the product deteriorates slowly in the environment of 15°C, and the shelf life of the product can be extended to For example 180 days.
  • the self-evolving reaction indicator is also less sensitive to the 15 °C environment.
  • the color change of the self-evolving reaction indicator is not obvious, so it is difficult for the consumer to understand that the product has experienced the low temperature by the change of the color of the indicator. The time, even if the specific quality parameter of the perishable product being tracked at this time did not change significantly over time.
  • the time elapsed at this low temperature is also an indicator of its concern.
  • a smart tag that includes a variety of self-evolving color change indicators.
  • one of the self-evolving color change indicators normally tracks specific quality parameters of the associated perishable product at different temperatures, such as by the method of color change as previously described.
  • the time experienced for the product at low temperatures can be indicated by an additional color change indicator that provides a significant increase in the spectral blue shift rate at this low temperature.
  • a self-evolving color change indicator may be additionally provided ( The second indicator), which has a blue shift rate at 15 °C, is six times the self-evolving color indicator (first indicator) that normally tracks the quality parameters of the product.
  • the discoloration of the first indicator is less obvious, and the second indicator is significantly higher in color shift due to its blue shift rate, and can prompt the easy
  • the deteriorated product has been subjected to a period of time at 15 ° C since it was shipped from the factory.
  • a self-evolving color change indicator having different chemical kinetic properties is additionally attached to the label by a self-evolving color change indicator (first indicator) that normally tracks the specific quality parameter of the perishable product (No.
  • the second indicator is such that the second indicator has an extremely high spectral blue shift rate at temperatures above the target temperature.
  • the second indicator changes color to a significant color difference to its original color after experiencing a threshold time at the target temperature.
  • the target temperature is a cold chain transport temperature or 50 degrees Celsius; the threshold time is half an hour; and the second indicator changes from green to red.
  • the second indicator has undergone a significant color change, indicating that the perishable product has been exposed to a temperature above a certain temperature.
  • the modulation of the spectral blue shift rate of different kinds of color change indicators can be adjusted, for example, by adjusting the concentration of the metal nanomaterial, the concentration of the halogen ions, the concentration of the acidity regulator, and the reducing agent.
  • concentration and the concentration of the surfactant are achieved.
  • the invention also relates to a progress bar type smart tag.
  • the smart label according to the present invention is provided with a plurality of color-changing indicators, which have different spectral blue-shift rates, for example, and the specific shape and arrangement can be used to indicate the product in the form of an intuitive progress bar. The effect of quality qualified period.
  • the progress bar smart tag according to the present invention includes a plurality of label segments arranged in abutting order from the starting end to the distal end, wherein each label segment houses a self-evolving color changing indicator according to the present invention, wherein each A self-evolving color change indicator has the same range of discoloration, but the spectral blue shift rate of the self-evolving color change indicator contained in the label segment farther from the start end is faster.
  • the self-evolving color changing agent accommodated in the label segment at one end of which is disposed at the starting end is set to indicate the shelf life of the product of the perishable product based on a particular quality parameter.
  • the progress bar smart tag is configured such that the ratio of the time when the self-evolving color changing agent accommodated by each of the plurality of label segments is changed to the final color and the product shelf life based on the specific quality parameter substantially corresponds to The ratio of the distance from the far end to the end of the label segment near the start end and the total length of the smart tag.
  • the smart tag according to the present invention includes two tag segments disposed adjacent to the start end and the far end, each accommodating a self-evolving color change indicator, and each Self-evolving color change indicators are set to range from green to red.
  • the first label segment of the label houses the first indicator
  • the second label segment of the label houses the second indicator.
  • the first label segment is aligned adjacent to the second label segment and both have the same shape.
  • the first indicator tracks a particular quality parameter of the associated perishable product, such as by a color change indicating method in accordance with the present invention.
  • the second indicator is provided for at a specific temperature T and the color change indicator associated with the first indication 1, T 2 spectrum the blue shift rate is twice the first indicator.
  • This can be achieved, for example, by adjusting the concentration of the metal nanomaterial, the concentration of the halogen ion, the concentration of the acidity regulator, the concentration of the reducing agent, and the concentration of the surfactant.
  • first label segment and the second label segment are both disposed on the background portion, the background portion having a final color of a color change range of the first indicator and the second indicator.
  • the background portion is red.
  • Fig. 13A shows the initial state of the smart tag in which both the first indicator and the second indicator are green. For example, after a period of time at a particular temperature T 1 , T 2 , the first indicator turns blue-green, and the second indicator turns blue because its blue shift rate is twice that of the first indicator.
  • Figure 13B shows.
  • Figure 13C shows the smart tag after a period of time has elapsed, when the first indicator turns blue and the second indicator turns purple.
  • Figure 13D shows the smart label when the second indicator turns red, when the first indicator is purple. Since the color of the background portion is also red, the intuitive feeling at this time is that the complete color bar as shown in FIG. 12A changes to only half the length. This corresponds to the quality qualified period remaining in the perishable product.
  • the ratio of the time when the self-evolving color change indicator contained in the second label segment is changed to the final color and the product shelf life is approximately 1/2, and the distance from the distal end to the end of the second label segment near the start end is The ratio to the total length of the smart tag is also 1/2, which is equal.
  • a smart tag in accordance with the present invention includes three tag segments, a first tag segment, a second tag segment, and a third tag segment.
  • the three label segments have the same shape and are arranged in series. Similar to the previous embodiment, the three label segments correspondingly receive the first indicator, the second indicator, and the third indicator.
  • the first indicator tracks a particular quality parameter of the associated perishable product, such as by a color change indicating method in accordance with the present invention.
  • the second indicator is arranged such that the spectral blue shift rate is faster than the first indicator at a particular temperature T 1 , T 2 .
  • the third indicator is set such that the spectral blue shift rate is faster than the second indicator at a particular temperature T 1 , T 2 .
  • the first indicator changes color to blue throughout the discoloration range
  • the third indicator changes color to red
  • the second indicator also changes color To red.
  • Figure 14 exemplarily shows the color changing process of the smart tag.
  • each label segment may be inconsistent as long as it satisfies the time at which the self-developing color changing agent accommodated by each of the plurality of label segments is discolored to the final color and based on the specific quality parameter.
  • the ratio of the shelf life of the product is approximately equal to the ratio of the distance from the far end to the end of the tag segment near the start end and the total length of the smart tag, so that the technical effect of the shelf life can be visually indicated by the progress bar.
  • the invention also relates to a smart tag with a number of days of remaining shelf life.
  • the color in the color change range of the color change indicator according to the present invention and the time at which the color of the perishable product is normally required to be discolored to the color may correspond.
  • the ground mark can roughly estimate the time remaining for the perishable product to deteriorate.
  • the smart label further includes a color card on which the number of days of the remaining shelf life corresponding to the color is marked, the number of days marked based on the perishable product
  • the storage temperature is usually obtained by, for example, a prior experiment.
  • the shelf life at 25 ° C is 16 days
  • the color change indicator used to indicate its color change range is green to red
  • the color change indicator sequentially changes color to green - blue - purple - purple - Red, which exemplarily takes 4 days from green to blue at 25 ° C, 8 days from green to purple, 12 days from green to purple, and 16 days from green to red .
  • the user can intuitively feel the remaining shelf life of the perishable product by marking the remaining shelf life at the corresponding color.
  • the perishable product may thereafter be exposed to a temperature higher than 25 ° C or lower, and the quality qualified period may be correspondingly shorter or longer than the estimated time.

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Abstract

L'invention concerne une étiquette intelligente, destinée à être utilisée pour indiquer la durée de conservation d'un produit périssable, qui comprend un indicateur à décoloration auto-évolutive. L'indicateur comprend un nanomatériau métallique, un halogénure d'argent insoluble dans l'eau, un agent réducteur, un ou plusieurs tensioactifs cationiques contenant des ions halogénures, de l'eau et un régulateur d'acidité facultatif. Une extinction se produit dans le nanomatériau métallique dans une plage de longueurs d'onde allant de 380 nm à 780 nm et l'argent élémentaire peut croître de manière épitaxiale sur la surface du nanomatériau métallique; l'halogénure d'argent insoluble dans l'eau est choisi parmi le chlorure d'argent, le bromure d'argent et l'iodure d'argent. L'étiquette intelligente peut comprendre un dispositif d'isolation et de mélange qui synchronise le temps de début d'une réaction de décoloration auto-évolutive avec le temps de production d'un produit. L'étiquette intelligente peut comprendre deux indicateurs à décoloration auto-évolutive ou plus, ayant différents constituants spécifiques. En outre, une étiquette intelligente de type à barre de progression peut être réalisée au moyen d'un ordre d'agencement particulier d'une pluralité d'indicateurs à décoloration auto-évolutive, de telle sorte que la durée de conservation restante du produit peut être lue de manière plus intuitive et précise.
PCT/CN2017/075192 2017-01-25 2017-02-28 Étiquette intelligente à décoloration WO2018137271A1 (fr)

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CN113532683B (zh) * 2021-07-09 2022-06-03 江南大学 一种基于聚二乙炔脂质体的时间温度指示剂的制备方法
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