WO2018137271A1

WO2018137271A1 - Discoloring smart label

Info

Publication number: WO2018137271A1
Application number: PCT/CN2017/075192
Authority: WO
Inventors: 张超; 田子健; 郭占云
Original assignee: 北京镧彩科技有限公司
Priority date: 2017-01-25
Filing date: 2017-02-28
Publication date: 2018-08-02
Also published as: CN107121214A; CN107121214B

Abstract

A smart label, for use in indicating the shelf life of a perishable product, comprising self-evolving discoloring indicator. The indicator comprises a metal nanomaterial, water-insoluble silver halide, a reducing agent, one or more cationic surfactants containing halide ions, water, and an optional acidity regulator. Extinction occurs in the metal nanomaterial within a wavelength range of 380 nm to 780 nm and elemental silver may epitaxially grow on the surface of the metal nanomaterial; the water-insoluble silver halide is selected from silver chloride, silver bromide, and silver iodide. The smart label may comprise an isolating and mixing device synchronize the start time of self-evolving discoloring reaction with the production time of a product. The smart label may comprise two or more self-evolving discoloring indicators having different specific components. Furthermore, a progress bar type smart label can be made by means of a particular arrangement order of a plurality of self-evolving discoloring indicators, so that the remaining shelf life of the product can be read more intuitively and accurately.

Description

Color change smart label

Technical field

The present invention relates to a smart label comprising a self-evolving color change indicator for indicating the shelf life of a perishable product.

Background technique

The safety of perishable products such as foods and medicines has always been the focus of attention. In order to prevent such products from being ingested or failing to achieve their desired effects due to microbial growth or deterioration of active ingredients, the time period for which the quality is qualified is usually indicated by indicating the shelf life (or expiration date, etc.). However, such shelf life (or expiration date, etc.) is usually estimated based on a number of oversimplified factors (including defined temperature, humidity, atmosphere, packaging, etc.), in practice often due to changes in storage conditions, especially temperature rise, The safety of food and medicine within the calibration period cannot be guaranteed. For example, foods or medicines that require cryopreservation may be subject to deterioration during the calibration period due to the inevitable experiencing of elevated temperatures during transportation, storage, and sale. Therefore, the shelf life (or expiration date) indicated on the product packaging at this stage is not sufficiently credible, and this problem may pose a huge threat to public health and safety.

In order to solve this problem, some techniques have been developed to truly record the temperature history experienced by the product, such as Time-Temperature Indicator (TTI). 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.

Due to the limitations of existing electronic and chemical TTIs, a new, uniform, inexpensive, and easy-to-use new TTI needs to be developed to track and record the temperature history of each individual product and will involve the product. Information about the quality status is presented directly to the consumer.

Summary of the invention

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.

In one aspect, the invention relates to a self-evolving color change indicator comprising the following components:

a) metallic nanomaterials,

b) water insoluble silver halide,

c) reducing agent,

d) one, two or more cationic surfactants containing halogen ions,

e) water, and,

f) optionally, an acidity regulator,

among them,

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, and

The water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide.

In a preferred embodiment of this aspect, the self-evolving color change indicator further comprises:

g) 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.

Preferably, when 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. Preferably, when 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. More preferably, 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. A water-soluble iodide such as potassium iodide, ammonium iodide or cetyltrimethylammonium iodide.

In another preferred embodiment of this aspect, 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. Preferably, 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. In another preferred embodiment of this aspect, the metal nanomaterial in the self-evolving color change indicator is a nanomaterial of a noble metal. Preferably, 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.

In another preferred embodiment of this aspect, 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. Preferably, the metal nanomaterial has a structure of nanorods. Preferably, 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.

In another preferred embodiment of this aspect, 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. Ammonium, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide,hexadecane Triethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethyl bromide Ammonium, octadecyltriethylammonium iodide, and the like. Preferably, the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride or cetyltrimethylammonium bromide.

In another preferred embodiment of this aspect, 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. Preferably, 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. More preferably, 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.

In another preferred embodiment of this aspect, the acidity modifier in the self-evolving color change indicator is a water soluble weak acid or a salt thereof. Preferably, 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.

In another preferred embodiment of this aspect, 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. Preferably, the antifreeze agent is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, and the like.

In another preferred embodiment of this aspect, 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. Preferably, the viscosity modifier is selected from the group consisting of carbomer, xanthan gum and the like.

In another preferred embodiment of this aspect, 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. Preferably, 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.

In another preferred embodiment of this aspect, 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.

In a more specific preferred embodiment of this aspect, the self-evolving color change indicator comprises the following components:

a) a gold nanorod having a diameter of less than 10 nm and an unlimited length,

b) silver chloride,

c) ascorbic acid,

d) cetyltrimethylammonium chloride,

e) water,

f) acetic acid, and,

g) cetyltrimethylammonium bromide,

Wherein the concentration of the cetyltrimethylammonium chloride in the indicator is not less than 0.01 mM.

In another aspect, the present invention is directed to a method of preparing a self-evolving color change indicator, the steps of which include:

1) thoroughly mixing a metal nanomaterial solution, a first cationic surfactant solution containing a first halogen ion, a reducing agent, and optionally an acidity adjuster to prepare a colloidal solution;

2) mixing a second cationic surfactant solution containing a second halogen ion with a soluble silver salt solution to form a silver halide suspension, and wherein the ratio of the amount of the halogen element to the silver element is greater than 1; or, The second cationic surfactant solution containing the second halogen ion is insoluble with water a suspension of silver halides to obtain a silver halide suspension;

3) mixing the above colloidal solution with a silver halide suspension and water to obtain a self-evolving color change indicator;

among them,

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

In a preferred embodiment of this aspect, 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. Or a variety of inhibitors. Preferably, when the inhibitor is a bromide-containing substance, the ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1. Preferably, when 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. More preferably, 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. A water-soluble iodide such as ammonium iodide or cetyltrimethylammonium iodide.

In another preferred embodiment of this aspect, the metal nanomaterial in the method of preparation is a nanomaterial of a noble metal. Preferably, 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. . More preferably, the metallic nanomaterial is a nanomaterial of gold.

In another preferred embodiment of this aspect, the metal nanomaterial in the preparation method has the following structure: nanospheres, nanorods, nanoplates, nanocage. Preferably, the metal nanomaterial has a structure of nanorods. Preferably, 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.

In another preferred embodiment of this aspect, the halogen ion-containing cationic surfactant in the preparation method is selected from the group consisting of cetyltrimethylammonium chloride and cetyltrimethylammonium bromide. Ten Hexacyclotrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide, cetyltriethylethyl Ammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethylammonium bromide, eighteen Alkyl triethyl ammonium iodide or the like. Preferably, the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride or cetyltrimethylammonium bromide.

In another preferred embodiment of this aspect, the reducing agent in the method of preparation is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof. Preferably, 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. More preferably, 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.

In another preferred embodiment of this aspect, the acidity regulator in the preparation method is a water-soluble weak acid or a salt thereof. Preferably, 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. More preferably, 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.

In another preferred embodiment of this aspect, 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. Preferably, the antifreeze agent is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, and the like.

In another preferred embodiment of this aspect, 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. Preferably, the viscosity modifier is selected from the group consisting of carbomer, xanthan gum and the like.

In another preferred embodiment of this aspect, 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. Preferably, 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.

In another preferred embodiment of this aspect, 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.

In still another aspect, the present invention is directed to a color change indicating method for a shelf life of a perishable product, comprising the steps of:

1) Measuring the variation of specific quality parameters of a perishable product at different temperatures over time, The time required for the product to deteriorate at the corresponding temperature;

2) The self-evolving color change indicator of any one of the technical solutions 1-30, wherein 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 are adjusted. One or more times, the time required for the perishable product to change from the initial color to the final color at the corresponding temperature is equal to the time required for the product to deteriorate;

3) According to the discoloration process of the perishable product, the corresponding relationship between the color of the solution and the degree of deterioration of the product is obtained, indicating the shelf life of the perishable product.

In a preferred embodiment of this aspect, 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 has the following advantages:

1. 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;

2. 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;

3. 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 Within the scope, 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);

4. 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;

5. 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 μg·mL ^-1 , and other auxiliary reagents are common additives. It is safe, non-toxic and low cost;

6. 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. Prior to mixing, 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.

Further, 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. In addition, 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. For example, 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.

DRAWINGS

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.

[Correct according to Rule 91 30.06.2017]
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.

Implementation

The self-evolving color change indicator and the preparation method thereof according to the present invention are described in detail below in conjunction with specific embodiments, and the purpose is to better understand the technical content of the public, rather than limiting the technical content. Modifications to the materials and methods of making the same, in the same or similar principles, are within the scope of the appended claims.

Self-evolving color change indicator

The self-evolving color change indicator of the present invention comprises the following components:

a) metallic nanomaterials,

b) water insoluble silver halide,

c) reducing agent,

d) one, two or more cationic surfactants containing halogen ions,

e) water, and,

f) optionally, an acidity regulator.

Further, in a preferred embodiment, 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.

Principle of invention

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.

Taking gold nanorods as an example, 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. As the silver shell thickens, the matte band of the longitudinal plasma element resonance gradually moves toward the short wave direction, thereby changing the color of the colloidal solution.

Nanomaterials and color changes

First, it should be noted that 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. An alloy of precious metals. In a preferred embodiment, gold nanomaterials are particularly preferred.

The shape of metal nanomaterials is also varied. In a particular embodiment, the metal nanomaterial has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocages, and mixtures of these nanostructures. In a preferred embodiment, 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:

When the elements are different: the same is a nanosphere with a diameter of 10 nm, the golden sphere is red, and the silver sphere is yellow;

When the sizes are different: 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;

When the shapes are different: 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.

As the silver shell gradually deposits on the metal nanostructures, the composition, size and shape of the metal nanomaterials change, so the color changes accordingly. Therefore, different metal nanostructures may have different color variations. E.g:

When a gold nanorod having a diameter of 10 nm and a length of 50 nm is used as a seed crystal, the color is sequentially red, orange, yellow, green, blue, purple, red, and orange as the silver shell grows;

When a palladium hexagonal nanoplate with a thickness of 2 nm and a side length of 40 nm is used as a seed crystal, the color is gray, green, blue, purple, and brown in accordance with the growth of the silver shell;

When a single crystal gold nanosphere having a diameter of 10 nm is used as a seed crystal, the color is sequentially red, orange, and yellow as the silver shell grows.

Thus, in a preferred embodiment, 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.

Silver source and surfactant

The silver compound to be reduced to elemental silver is another important component of the self-evolving color change indicator of the present invention. In theory, 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.

However, 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.

Thus, in addition to the direct use of water insoluble silver halide to formulate the self-evolving color change indicator of the present invention, water insoluble silver halide can also be formulated in situ. For example, 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.

From the above, 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 or cetyltrimethylammonium bromide. Further, it is particularly advantageous that the total concentration of the cationic surfactant in the indicator is not less than 0.01 mM.

reducing agent

Theoretically, the reducing agent is not particularly limited as long as the silver compound can be reduced to elemental silver. The present inventors have found that 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. 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.

Inhibitor

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. 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. When using substances containing iodide ions It is particularly preferable that 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.

Acidity regulator and kinetic regulation

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. In addition, 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. Examples of 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.

Other ingredients

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. Thus, 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.

Correlation technology between indicator color change process and metamorphic product deterioration process

Measure the time-dependent changes of specific quality parameters (such as the number of bacteria, the content of active ingredients, the content of harmful components, etc.) of perishable products at different temperatures (T ₁ , T ₂ ), and obtain the time required for product deterioration at the corresponding temperature. (t ₁ and t ₂ ). Adjusting the kinetic parameters of the color change reaction (such as metal nanomaterials, reducing agents, concentrations of weak acids, etc.), respectively, to the time required to change from the initial color to the final color at the corresponding temperature (t _{1 '} and t _{2 '} ) Equal to t ₁ and t ₂ . It can be seen that 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.

Color change indicator embodiment

Example 1

Self-evolving color change indicators were prepared using the following formulations and procedures.

formula:

Note 1: 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.

Note 2: 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.

operating:

1) Gold nanorod solution (standard concentration, 0.4000 g), cetyl group at a reaction temperature of 35 ° C Trimethylammonium chloride (0.100 M, 0.5000 g), cetyltrimethylammonium bromide (0.001 M, 0.4000 g), ascorbic acid (0.100 M, 0.1000 g) were thoroughly mixed to prepare a colloidal solution;

2) mixing equal amounts of cetyltrimethylammonium chloride (0.116 M) with silver nitrate (0.100 M) to form a silver halide suspension;

3) The above colloidal solution was mixed with a silver halide suspension (0.1350 g) and ultrapure water (3.4650 g) to obtain a self-evolving color change indicator.

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.

It can be seen from the spectral results that the self-evolving discoloration process of the solution is completed within 4 h at 35 ° C, and the extinction peak position is blue-shifted to about 558 nm at the end point.

Example 2

Using the same formulation and procedure as in Example 1, a self-developing color change indicator was formulated at a reaction temperature of 5 °C.

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.

From the spectral results, it is known that the self-evolving color change process of the self-evolving color change indicator is slowed down when the ambient temperature is lowered (from 35 ° C to 5 ° C) as compared with Example 1.

Example 3

A self-evolving color change indicator was prepared using the following formulation and the same procedure as in Example 1.

formula:

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.

From the spectral results, it was found that the self-evolving color change process of the self-evolving color change indicator was slowed down when the ascorbic acid concentration was lowered (the amount used was decreased from 0.1000 g to 0.0500 g) as compared with Example 1.

Example 4

formula:

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.

From the spectral results, it is known that when the concentration of cetyltrimethylammonium chloride is increased (the amount used is increased from 0.5000 g to 2.000 g), the self-evolving color change process of the self-evolving color change indicator is reduced as compared with Example 1. slow.

Example 5

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.

formula:

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.

From the spectral results, it was found that the self-evolving color change process of the self-evolving color change indicator was slowed down when the acidity adjuster was added as compared with Example 1.

Example 6

formula:

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.

From the results of the spectroscopy, compared with Example 1, when the amount of silver chloride added was decreased (from 0.1350 g to 0.0350 g), the self-evolving color change process of the self-evolving color change indicator was substantially completed within 1 h, and extinction at the end point. The peak position is blue shifted to around 660 nm.

Example 7

formula:

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.

From the spectral results shown in FIGS. 7A and 7B, it is known that 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. In particular, as the spectrum is blue shifted, 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. When the bromide ion inhibitor was added, 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). Thus, the bromide ion inhibitor slows down the discoloration process of the self-evolving color change indicator.

In addition, when no bromide ions were added, the extinction value of the self-evolving color change indicator increased, indicating that the color was lighter and darker (slow saturation), and the color of the solution obtained in Example 1 was not as bright as shown in Fig. 7C. From the transmission electron micrograph, when no bromide ions are added, silver is deposited on the side and both ends of the gold nanorods to obtain a symmetrical nanostructure (projected as a rectangle); when a proper amount of bromide ions is added, silver is in gold. There are almost no deposits on both ends of the nanorods, and almost only on one side, resulting in asymmetric nanostructures (projected as a boat), as shown in Figure 7D. Therefore, the addition of a bromide ion inhibitor also makes it easier and clearer to observe the color evolution of the self-developing color change indicator.

Example 8

formula:

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.

From the spectral results, it can be seen that when an appropriate amount of 1,2-propanediol (as an antifreeze) is added to the solution formulation, the solution can remain liquid at a temperature below 0 ° C and still have self-evolving discoloration properties.

Example 9

formula:

Note 1: The carbomer solution is mixed with carbomer powder and an appropriate amount of water to obtain a uniform transparent solution.

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.

As can be seen from the photograph, when carbomer (viscosity modifier) is added to the solution formulation, the sedimentation of the nanoparticles due to gravity can be effectively suppressed, and the colloidal solution system is more uniform.

Example 10

formula:

Note 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.

It can be seen from Fig. 10 that when an appropriate amount of agar is added to the solution formulation (as a gelling agent), the system is in a gel state and still has self-evolving discoloration properties.

Example 11

1) Measure the time-dependent changes of specific quality parameters (bacterial quantity, active ingredient content, and harmful component content) of perishable products at different temperatures, and obtain the time required for product deterioration at the corresponding temperature;

2) by adjusting the concentration of aqueous solution of surfactant containing chloride or bromide, aqueous solution of soluble ascorbate, soluble weak acid or weak acid salt solution and gold nanorod solution, so that the perishable product at the corresponding temperature is changed from red to green. Time is equal to the time required for product deterioration;

3) According to the discoloration process of the perishable product, the relationship between the color of the solution and the degree of deterioration of the product is obtained, indicating the shelf life of the perishable product, as shown in Fig. 11, the two are almost completely coincident.

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.

Smart Label Embodiment

The invention also relates to a smart label comprising a self-evolving color change indicator according to the invention.

Due to its own characteristics, self-developing color-changing indicators should not be in direct contact with products (especially for food products). On the other hand, 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.

In a preferred embodiment, 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. In particular, the smart label according to the invention comprises a joint through which the joint is combined with the packaging of the product.

For example, it 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. Illustratively, 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. And illustratively, 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. Acid resin, polyimide, polybenzimidazole, phenol-polyvinyl acetal, phenol-polyamide, phenol-epoxy resin, epoxy-polyamide, and the like. In other embodiments, 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.

In another more preferred embodiment, the self-evolving color change indicator is coated directly onto the outer package of the associated product to form an integrated package. For example, 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. In other embodiments, such as when the associated outer packaging surface is a material suitable for encapsulating a liquid, a self-evolving color changing indicator according to the present invention may be coated between the outer packaging surface and the additional film. It should be understood that 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.

A variety of technical advantages can be achieved with this integrated package. For example, it 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. In addition, 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. In addition, 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.

In one embodiment in accordance with the present invention, 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. Illustratively, 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. In an alternative embodiment, the concave portion can be disposed, for example, on an inwardly facing surface of the cap.

In another embodiment, 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. 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.

Smart tag embodiment with hybrid device

In another aspect, the invention also relates to a smart tag with a mixing device.

In actual industrial production, the production of self-evolving color-changing indicators and the production of products are often separated and unsynchronized. Since the self-evolving color-changing indicator has been self-configured, self-evolving reactions begin to occur, and products are often not produced simultaneously. The indication effect of the self-evolving color change indicator is weakened or becomes inaccurate when there is a significant time interval between the configuration time of the self-evolving color change indicator and the production time of the perishable product it intends to mark.

In order to solve the above problem, for example, 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. In a preferred embodiment, for example, 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.

In a particular embodiment, the mixing device is a removable wall that separates different components of the indicator. When it is intended to effect mixing of the different components, 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.

Preferably, 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.

Alternatively, 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. When it is intended to effect mixing of the different components, 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. Further preferably, the actuation portion can be a needle.

Those skilled in the art will appreciate that the 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.

In one embodiment, 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.

And alternatively, 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.

Illustratively, 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.

Those skilled in the art will appreciate that the preformed self-evolving color change indicator can include more components. For example, 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 .

Smart tag embodiment including multiple color change indicators

In another aspect, 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.

As described above, in practical applications, 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. In a particular perishable product, 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. Among them, 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

In addition, for some perishable products, 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. For example, the time required for a perishable product to change from the initial color to the final color at 25 ° C is 30 days. 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. Accordingly, the self-evolving reaction indicator is also less sensitive to the 15 °C environment. When the product has experienced 10 days after the completion of packaging at a lower temperature such as 15 ° C, 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.

For a particular user, the time elapsed at this low temperature is also an indicator of its concern. This can also be addressed by a smart tag that includes a variety of self-evolving color change indicators. For example, 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. For example, taking a product with a normal shelf life of 180 days at 15 ° C as an example (ie, its tracked quality parameter exceeds a certain level after 180 days at 15 ° C), 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. At this time, when the product is subjected to 10 days at 15 ° C after the completion of the packaging, 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.

There is also a case where for a particular perishable product, it may have been exposed to high temperatures since the factory, but the exposure time is short and the product is not deteriorated. However, such exposure may also be undesirable, for example due to the quality of cold chain transport. At this time, another 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. In particular, the second indicator changes color to a significant color difference to its original color after experiencing a threshold time at the target temperature. Illustratively, 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.

At this time, even if the label is exposed to a temperature higher than a specific temperature in a very short period of time, the second indicator has undergone a significant color change, indicating that the perishable product has been exposed to a temperature above a certain temperature. .

As described above, 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. The concentration and the concentration of the surfactant are achieved.

Progress bar smart tag embodiment

The invention also relates to a progress bar type smart tag.

In one embodiment, 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.

In particular, 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. In particular, 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.

And further, 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.

For example, in the embodiment shown in FIG. 13, 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. In particular, the first label segment of the label houses the first indicator and 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. Therein, 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. And in particular, 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.

Further, the 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. In this embodiment, 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. That is, at this time, 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.

Illustratively, in another embodiment, 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. Illustratively, 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.

Wherein 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. And in particular, 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 . And further, 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 . Illustratively, when the first indicator changes color to blue throughout the discoloration range, the third indicator changes color to red; and when the first indicator changes color to purple throughout the discoloration range, the second indicator also changes color To red. Figure 14 exemplarily shows the color changing process of the smart tag.

Those skilled in the art will appreciate that a greater number of indicators can similarly be placed in the smart tag, and the blue shift rate of the associated color change indicator is similarly adjusted to achieve a quality qualifying period for visually indicating the perishable product with a progress bar. Effect.

It will also be understood by those skilled in the art that the length of 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.

Smart tag embodiment with remaining shelf life days

The invention also relates to a smart tag with a number of days of remaining shelf life.

For the purpose of facilitating the prediction of the remaining quality qualification period of the perishable product, for example, 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.

In particular, in addition to the self-evolving color change indicator according to the present invention, 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.

For example, for a perishable product, the shelf life at 25 ° C is 16 days, the color change indicator used to indicate its color change range is green to red, and 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 . Regardless of the temperature and time experienced by the perishable product, it can be estimated that it has a shelf life of 8 days remaining when it is purple, or it can be estimated that it has a remaining shelf life of 4 days when it is purple. The user can intuitively feel the remaining shelf life of the perishable product by marking the remaining shelf life at the corresponding color. It should be noted that 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.

Although the invention is disclosed above in the foregoing embodiments, it is not intended to limit the invention. Those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the claims.

Claims

A smart label comprising a self-evolving color change indicator, wherein the self-evolving color change indicator comprises the following components:

a) metallic nanomaterials,

b) water insoluble silver halide,

c) reducing agent,

d) one, two or more cationic surfactants containing halogen ions,

e) water, and,

f) optionally, an acidity regulator,

among them,

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, and

The water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide.
A smart label according to claim 1 comprising a joint and by which the joint is combined with the packaging of the product.
The smart label of claim 2, the bond being bonded to the package of the product by an adhesive.
The smart label of claim 1 comprising a multilayer film and said self-evolving color change indicator is encapsulated between the multilayer films.
The smart label of claim 4 wherein at least one of said multilayer films is part of a package of product.
The smart label of claim 1 wherein the smart label includes a concave portion disposed on the bottle cap and a package portion for encapsulating the self-evolving color change indicator contained in the concave portion.
The smart label of any of claims 1-6, wherein the self-evolving color change indicator further comprises:

g) 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 smart label of any of claims 1-6, wherein the self-evolving color change indicator further comprises:

g) a substance containing a bromide ion, wherein the ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1.
The smart label of any of claims 1-6, wherein the self-evolving color change indicator further comprises:

g) an iodide-containing substance, wherein the ratio of the iodide ion to the metal atom constituting the metal nanomaterial is greater than 0.0005:1.
The smart label according to any one of claims 1 to 6, wherein the metal nanomaterial is a nano material of any one of gold, silver, platinum, and palladium, or any two of gold, silver, platinum, and palladium. Nanomaterials of any three or all four alloys.
A smart label according to any of claims 1-6, wherein the metal nanomaterial has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocage, etc., and mixtures of the above nanostructures.
The smart label according to any one of claims 1 to 6, wherein the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride and cetyltrimethyl bromide. Ammonium, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide, cetyl Triethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethylammonium bromide , octadecyltriethylammonium iodide, and the like.
The smart label according to any one of claims 1 to 6, wherein the water-insoluble silver halide is prepared from a solution of a cationic surfactant containing a halogen ion and a solution of a soluble silver salt, and wherein the halogen element and the silver element The ratio of the amount of substance is greater than one.
A smart label according to any one of claims 1 to 6 wherein the reducing agent is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof.
The self-evolving color change indicator according to any one of claims 1 to 6, wherein the acidity adjuster is a water-soluble weak acid or a salt thereof.
The smart label according to any one of claims 1 to 6, wherein 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 smart label according to any one of claims 1 to 6, wherein the self-evolving color change indicator further comprises a viscosity of 0.01% or more and 60% or less based on the total mass of the color change indicator. Conditioner.
The smart label according to any one of claims 1 to 6, wherein the self-evolving color change indicator further comprises a gelling agent of 0.01% or more and 10% or less based on the total mass of the color change indicator.
The smart label according to any one of claims 1 to 6, wherein the change can be achieved 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 for the initial color to change to the final color and the apparent activation energy of the color change process.
A smart label comprising a self-evolving color change indicator, wherein the self-evolving color change indicator comprises the following components:

a) metallic nanomaterials,

b) water insoluble silver halide,

c) reducing agent,

d) one, two or more cationic surfactants containing halogen ions,

e) water, and,

f) optionally, an acidity regulator,

among them,

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 one, two or more halogen ion-containing cationic surfactants are present in the indicator at a concentration of not less than 0.01 mM, and the water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide, and wherein

The smart tag includes a plurality of components that are separately housed and a mixing device, each of the plurality of components including one or more of the above-described components in the self-evolving color change indicator, and

Each of the plurality of components does not undergo a color change reaction by itself; and the plurality of components can be mixed by actuating the mixing device to obtain the self-evolving color change indicator.
The smart label of claim 20 wherein said mixing means comprises a removable wall separating said plurality of components.
A smart tag according to claim 20, wherein said removable wall comprises a magnetic portion that effects movement of said removable wall under magnetic force to effect said plurality of components the mix of.
A smart tag according to claim 20, wherein said mixing means comprises a spacer film separating said plurality of components and an actuation portion through which the spacer film can be punctured by actuating the actuator to achieve Mixing of multiple components.
The smart tag of claim 23 wherein said actuating portion is a needle.
A smart tag according to claim 24, wherein said actuating portion is actuated in one or more of a rotation, a press, a pull.
A smart tag according to claim 23, wherein said actuating portion comprises a magnetic portion that, under the action of a magnetic force, drives said actuating portion to puncture the spacer film to effect mixing of said plurality of components.
A smart tag according to claim 20, wherein said mixing means comprises a spacer film made of a hot-soluble substance separating said plurality of components, said spacer film being soluble after local heating.
A smart tag according to claim 20, wherein said mixing means comprises a spacer film made of a photodegradable substance separating said plurality of components, said spacer film being decomposable after partial illumination.
The smart tag of claim 20 wherein said smart tag comprises two components that are separately received.
A smart label according to claim 29, wherein one of said two components is a colloidal solution and the other of said two components is a silver halide suspension, wherein

The colloidal solution is formed by thoroughly mixing a metal nanomaterial solution, a first cationic surfactant solution containing one or more halogen ions, a reducing agent, and optionally an acidity regulator;

The silver halide suspension is formed by mixing a second cationic surfactant solution containing one or more halogen ions with a soluble silver salt solution, wherein the ratio of the amount of the halogen element to the silver element is greater than 1; It is formed by mixing a second cationic surfactant solution containing one or more halogen ions with a suspension of water-insoluble silver halide.
The smart label of any of claims 20-30, wherein the self-evolving color change indicator further comprises:

g) 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.
A smart tag according to any one of claims 20 to 30, wherein said self-evolving color change Indicators also include:

g) a substance containing a bromide ion, wherein the ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1.
The smart label of any of claims 20-30, wherein the self-evolving color change indicator further comprises:

g) an iodide-containing substance, wherein the ratio of the iodide ion to the metal atom constituting the metal nanomaterial is greater than 0.0005:1.
The smart label according to any one of claims 20 to 30, wherein the metal nanomaterial is a nano material of any one of gold, silver, platinum, and palladium, or any two of gold, silver, platinum, and palladium. Nanomaterials of any three or all four alloys.
A smart label according to any one of claims 20 to 30, wherein the metal nanomaterial has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocage, etc., and mixtures of the above nanostructures.
A smart label according to any one of claims 20 to 30, wherein the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride and cetyltrimethyl bromide. Ammonium, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide, cetyl Triethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethylammonium bromide , octadecyltriethylammonium iodide, and the like.
A smart label according to any one of claims 20 to 30, wherein the water-insoluble silver halide is prepared from a solution of a cationic surfactant containing a halogen ion and a solution of a soluble silver salt, and wherein the halogen element and the silver element The ratio of the amount of substance is greater than one.
A smart label according to any one of claims 20 to 30 wherein the reducing agent is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof.
The self-evolving color change indicator according to any one of claims 20 to 30, wherein the acidity adjuster is a water-soluble weak acid or a salt thereof.
The smart label according to any one of claims 20 to 30, wherein 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 smart label according to any one of claims 20 to 30, wherein the self-evolving color change indicator further comprises a viscosity of 0.01% or more and 60% or less based on the total mass of the color change indicator. Degree regulator.
The smart label according to any one of claims 20 to 30, wherein the self-evolving color change indicator further comprises a gelling agent of 0.01% or more and 10% or less based on the total mass of the color changing indicator.
The smart label according to any one of claims 20 to 30, wherein the change can be achieved 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 for the initial color to change to the final color and the apparent activation energy of the color change process.
A smart label comprising at least two self-evolving color change indicators, wherein each self-evolving color change indicator comprises the following components:

a) metallic nanomaterials,

b) water insoluble silver halide,

c) reducing agent,

d) one, two or more cationic surfactants containing halogen ions,

e) water, and,

f) optionally, an acidity regulator,

among them,

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, and

The water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide, and wherein

The specific components of the at least two self-evolving color change indicators are different from each other.
The smart label of claim 44, wherein each of said at least two self-evolving color change indicators indicates a product shelf life of the perishable product based on a particular quality parameter.
The smart label of claim 44 wherein said specific quality parameter is selected from the group consisting of: the number of flora, the amount of active ingredient, and the amount of harmful ingredients.
A smart tag according to claim 44, wherein said self-evolving color change indicator comprises a first indicator and a second indicator, wherein the first indicator indicates a shelf life of the product of the perishable product based on a particular quality parameter; Wherein the second indicator has a higher temperature than the target temperature The first indicator significantly accelerated the spectral blue shift rate.
A smart label according to claim 47, wherein said specific quality parameter is selected from the group consisting of: the number of flora, the amount of active ingredient, and the amount of harmful ingredients.
A smart tag according to claim 47, wherein said second indicator changes color to a color having a significant color difference from its original color after experiencing a threshold time at the target temperature.
A smart tag according to claim 49, wherein said target temperature is a cold chain transport temperature or 50 degrees Celsius.
The smart tag of claim 49 wherein said threshold time is half an hour.
The smart tag of claim 47 wherein the spectral blue shift rate of said second indicator at the target temperature is a particular multiple of the spectral blue shift rate of the first indicator at the target temperature.
A smart label according to any one of claims 45 to 52, wherein the self-evolving color change indicator indicates the shelf life of the perishable product based on a particular quality parameter by the following steps:

1) Measuring the variation of specific quality parameters of a perishable product at different temperatures with time, and obtaining the time required for product deterioration at the corresponding temperature;

2) providing the self-evolving color change indicator and adjusting one or more of a concentration of a metal nanomaterial, a concentration of a halogen ion, a concentration of an acidity adjuster, a concentration of a reducing agent, and a concentration of a surfactant, The time required for the perishable product to change from the initial color to the final color at the corresponding temperature is equal to the time required for the product to deteriorate;

3) According to the discoloration process of the perishable product, the corresponding relationship between the color of the solution and the degree of deterioration of the product is obtained, indicating the shelf life of the perishable product.
The smart label of any of claims 44-52, wherein the self-evolving color change indicator further comprises:

g) 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 smart label of any of claims 44-52, wherein the self-evolving color change indicator further comprises:

g) a substance containing a bromide ion, wherein the ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1.
A smart tag according to any of claims 44-52, wherein the self-evolving color change Indicators also include:

g) an iodide-containing substance, wherein the ratio of the iodide ion to the metal atom constituting the metal nanomaterial is greater than 0.0005:1.
The smart label according to any one of claims 44 to 52, wherein the metal nanomaterial is a nano material of any one of gold, silver, platinum, and palladium, or any two of gold, silver, platinum, and palladium. Nanomaterials of any three or all four alloys.
A smart label according to any of claims 44-52, wherein the metal nanomaterial has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocage, etc., and mixtures of the above nanostructures.
A smart label according to any one of claims 44 to 52, wherein the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride and cetyltrimethyl bromide. Ammonium, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium iodide, cetyl Triethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethylammonium bromide , octadecyltriethylammonium iodide, and the like.
A smart label according to any one of claims 44 to 52, wherein the water-insoluble silver halide is prepared from a cationic surfactant solution containing a halogen ion and a soluble silver salt solution, and wherein the halogen element and the silver element The ratio of the amount of substance is greater than one.
A smart label according to any one of claims 44 to 52 wherein the reducing agent is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof.
The self-evolving color change indicator according to any one of claims 44 to 52, wherein the acidity adjuster is a water-soluble weak acid or a salt thereof.
The smart label according to any one of claims 44 to 52, wherein 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 smart label according to any one of claims 44 to 52, wherein 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.
A smart label according to any one of claims 44 to 52, wherein the self-evolving color change indicator further comprises a gelling agent of 0.01% or more and 10% or less based on the total mass of the color changing indicator.
A smart label according to any one of claims 44 to 52, wherein the change can be achieved 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 for the initial color to change to the final color and the apparent activation energy of the color change process.
A progress bar smart tag comprising a plurality of label segments arranged in abutting order from a starting end to a distal end, wherein each label segment houses a self-evolving color changing indicator, and each of the self-evolving color changing indicators The agents all contain the following ingredients:

a) metallic nanomaterials,

b) water insoluble silver halide,

c) reducing agent,

d) one, two or more cationic surfactants containing halogen ions,

e) water, and,

f) optionally, an acidity regulator,

among them,

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, and

The water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide, and wherein

Each of the self-evolving color-changing indicators has the same color-changing range, but the spectral blue-shift rate of the self-evolving color-changing indicator accommodated in the label segment farther from the starting end is faster, and

A self-generating color changing agent disposed in a label segment at one end of which is disposed at the starting end is set to indicate a shelf life of the product of the perishable product based on a particular quality parameter.
A progress bar type smart tag according to claim 67, wherein the progress bar type smart tag is set to a time when the self-evolving color changing agent accommodated by each of the plurality of tag segments is discolored to a final color and based on The ratio of the product shelf life of the particular quality parameter is approximately equal to the ratio of the distance from the distal end to the end of the label segment near the starting end and the length of the smart tag.
A progress bar smart tag according to claim 67, wherein the progress bar smart tag is disposed on the background portion, the color of the background portion being substantially the final color of the color change range of the self-developing color change indicator.
A smart label according to claim 67, wherein said self-evolving color change indicator indicates a product shelf life of the perishable product based on a specific quality parameter by the following steps;

1) Measuring the variation of specific quality parameters of a perishable product at different temperatures with time, and obtaining the time required for product deterioration at the corresponding temperature;

2) providing the self-evolving color change indicator and adjusting one or more of a concentration of a metal nanomaterial, a concentration of a halogen ion, a concentration of an acidity adjuster, a concentration of a reducing agent, and a concentration of a surfactant, The time required for the perishable product to change from the initial color to the final color at the corresponding temperature is equal to the time required for the product to deteriorate;

3) According to the discoloration process of the perishable product, the corresponding relationship between the color of the solution and the degree of deterioration of the product is obtained, indicating the shelf life of the perishable product.
The smart label of any of claims 67-70, wherein the self-evolving color change indicator further comprises:

g) 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 smart label of any of claims 67-70, wherein the self-evolving color change indicator further comprises:

g) a substance containing a bromide ion, wherein the ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1.
The smart label of any of claims 67-70, wherein the self-evolving color change indicator further comprises:

g) an iodide-containing substance, wherein the ratio of the iodide ion to the metal atom constituting the metal nanomaterial is greater than 0.0005:1.
The smart label according to any one of claims 67 to 70, wherein the metal nanomaterial is a nano material of any one of gold, silver, platinum, and palladium, or any two of gold, silver, platinum, and palladium. Nanomaterials of any three or all four alloys.
A smart label according to any one of claims 67 to 70, wherein the metal nanomaterial has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocage, etc., and mixtures of the above nanostructures.
A smart label according to any one of claims 67 to 70, wherein the halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride and cetyltrimethyl bromide. Ammonium, cetyltrimethylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethyl bromide Ammonium, dodecyltrimethylammonium iodide, cetyltriethylammonium chloride, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyl Triethylammonium chloride, octadecyltriethylammonium bromide, octadecyltriethylammonium iodide, and the like.
A smart label according to any one of claims 67 to 70, wherein the water-insoluble silver halide is prepared from a solution of a cationic surfactant containing a halogen ion and a solution of a soluble silver salt, and wherein the halogen element and the silver element The ratio of the amount of substance is greater than one.
A smart label according to any one of claims 67 to 70 wherein the reducing agent is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof.
The self-evolving color change indicator according to any one of claims 67 to 70, wherein the acidity adjuster is a water-soluble weak acid or a salt thereof.
The smart label according to any one of claims 67 to 70, wherein 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 smart label according to any one of claims 67 to 70, wherein 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 smart label according to any one of claims 67 to 70, wherein the self-evolving color change indicator further comprises a gelling agent of 0.01% or more and 10% or less based on the total mass of the color change indicator.
The smart label according to any one of claims 67 to 70, wherein the change can be achieved 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 for the initial color to change to the final color and the apparent activation energy of the color change process.
A smart label comprising a self-evolving color change indicator and a color card, wherein the self-evolving color change indicator comprises the following components:

a) metallic nanomaterials,

b) water insoluble silver halide,

c) reducing agent,

d) one, two or more cationic surfactants containing halogen ions,

e) water, and,

f) optionally, an acidity regulator,

among them,

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, and

The water-insoluble silver halide is selected from the group consisting of silver chloride, silver bromide or silver iodide;

Setting the self-evolving color changing agent to indicate a product shelf life of the perishable product based on a specific quality parameter, and

The corresponding color in the color card is labeled with the time remaining for the shelf life of the product at the typical storage temperature of the perishable product.
A smart label according to claim 84, wherein said self-evolving color change indicator indicates a shelf life of a product of a perishable product based on a specific quality parameter by the following steps;

1) Measuring the variation of specific quality parameters of a perishable product at different temperatures with time, and obtaining the time required for product deterioration at the corresponding temperature;

2) providing the self-evolving color change indicator and adjusting one or more of a concentration of a metal nanomaterial, a concentration of a halogen ion, a concentration of an acidity adjuster, a concentration of a reducing agent, and a concentration of a surfactant, The time required for the perishable product to change from the initial color to the final color at the corresponding temperature is equal to the time required for the product to deteriorate;

3) According to the discoloration process of the perishable product, the corresponding relationship between the color of the solution and the degree of deterioration of the product is obtained, indicating the shelf life of the perishable product.
A smart tag according to claim 84 or 85, wherein said self-evolving color change indicator further comprises:

g) 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.
A smart tag according to claim 84 or 85, wherein said self-evolving color change indicator further comprises:

g) a substance containing a bromide ion, wherein the ratio of the bromide ion to the metal atom constituting the metal nanomaterial is greater than 0.005:1.
A smart tag according to claim 84 or 85, wherein said self-evolving color change indicator further comprises:

g) an iodide-containing substance, wherein the ratio of the iodide ion to the metal atom constituting the metal nanomaterial is greater than 0.0005:1.
The smart label according to claim 84 or 85, wherein the metal nanomaterial is a nano material of any one of gold, silver, platinum, and palladium, or any two of gold, silver, platinum, and palladium, and any three Or nanomaterials of all four alloys.
A smart label according to claim 84 or 85, wherein said metallic nanomaterial has a structure selected from the group consisting of nanospheres, nanorods, nanoplates, nanocage, etc., and mixtures of the above nanostructures.
A smart label according to claim 84 or 85, wherein said halogen ion-containing cationic surfactant is selected from the group consisting of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, and sixteen Alkyl trimethyl ammonium iodide, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium iodide, cetyl triethyl chloride Ammonium, cetyltriethylammonium bromide, cetyltriethylammonium iodide, octadecyltriethylammonium chloride, octadecyltriethylammonium bromide, octadecane Triethylammonium iodide and the like.
A smart label according to claim 84 or 85, wherein said water-insoluble silver halide is prepared from a cationic surfactant solution containing a halogen ion and a soluble silver salt solution, and wherein the amount of the halogen element and the silver element is The ratio is greater than 1.
A smart label according to claim 84 or 85 wherein said reducing agent is selected from the group consisting of ascorbic acid, isoascorbic acid or a derivative thereof.
The self-evolving color change indicator according to claim 84 or 85, wherein the acidity adjuster is a water-soluble weak acid or a salt thereof.
The smart label according to claim 84 or 85, wherein 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 smart label according to claim 84 or 85, wherein 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 smart label according to claim 84 or 85, wherein the self-evolving color change indicator further comprises a gelling agent of 0.01% or more and 10% or less based on the total mass of the color change indicator.
The smart label according to claim 84 or 85, wherein the change from the initial color can be achieved 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 for the final color and the process of color change Apparent activation energy.