CN103578350A

CN103578350A - Chemical intelligent tag component and preparation method for chemical intelligent tag component

Info

Publication number: CN103578350A
Application number: CN201310234052.0A
Authority: CN
Inventors: 万祥龙
Original assignee: Anhui University of Science and Technology
Current assignee: Anhui University of Science and Technology
Priority date: 2013-06-13
Filing date: 2013-06-13
Publication date: 2014-02-12
Anticipated expiration: 2033-06-13
Also published as: CN103578350B

Abstract

The invention discloses a chemical intelligent tag component and a preparation method for the chemical intelligent tag component. The chemical intelligent tag component comprises a tag (1) and a dispersant (2), wherein the tag consists of a substrate layer (11), a dispersion layer (12) which is closely overlaid on the surface of the substrate layer, and an outer shell (13); the dispersant is added from one side of the dispersion layer when the tag is activated. The preparation method for the chemical intelligent tag component disclosed by the invention is simple and is low in cost; food quality can be monitored effectively.

Description

A kind of chemical intelligent label assembly and preparation method thereof

Technical field

The present invention relates to Time-temperature pointing technology field, particularly relate to a kind of chemical intelligent label assembly and preparation method thereof.

Background technology

The shelf-life of food is under the storage requirement that indicates at label of prepackaged food, keeps the time limit of quality.Within this time limit, product is suitable for selling completely, and keeps the peculiar quality that needn't illustrate or illustrate in label.By effective period of food quality, consumer can understand the quality condition of purchased product, and manufacturer can specify correct circulating pathway and sales mode.

Food is polynary, an active complex system, the microbial growth relevant with food quality, enzyme reaction, materialization variation etc. all may occur at one time, and more extraneous conditions also can affect the carrying out of these reactions as temperature, humidity, especially temperature is most important on the impact of shelf-life.The existing judgement Main Basis that whether can also eat food is the shelf-life of the upper printing of packing, but in the whole accumulating stage, temperature has immeasurability, the date of therefore printing is the quality condition of reactor product really, such as there being some food that need to refrigerate not use the chill car of regulation in transportation, will cause food to go bad within the maintenance phase of packaging for foodstuff, the pregnant woman's miscarriage and the food poisoning that cause thus happened occasionally in recent years, Zhe Gei China food-safety problem has proposed stern challenge, the modern society taking place frequently in various food quality problems, we more should focus on food-safety problem, improve the quality of living.

Time-temperature indicator (Time-Temperature Indicator, TTI) the simple device that be a kind of that be easy to measure or observe and time, temperature variation is relevant, it changes reflection food whole process or the residing temperature conditions of part, the temperature changing process of monitored food experience can be indicated, and then rotten scope and the remaining shelf life of food may be estimated according to temperature changing process.The irreversible change of the aspects such as that its reaction principle has is machinery, chemistry, galvanochemistry, enzyme reaction, microorganism, this variation and temperature correlation, and be continuous accumulation, the result of variation finally reflects as change color with visible materialization phenomenon conventionally.

TTI device just put forward before more than 40 year, and be applied to need on the biological products vaccine of refrigeration, the application on food, starts from last century end, mainly for those to the more sensitive refrigeration of temperature, frozen food, as fresh milk, frozen fish, meat, seafood products etc.The TTI that business is used in the world at present mainly contains three classes: the 3M Monitor Mark of first kind Shi3M company, it is a kind of TTI that utilizes diffusion principle, depend on the color reaction that chemical substance wherein occurs in the process of diffusive migration, by coloured fatty acid ester, the diffusion length on the good porous refill of water absorptivity records temperature over time as response, when storage temperature is during lower than the fusing point of ester matter, indicator does not respond; When storage temperature is during higher than the fusing point of ester matter, indicator starts response, and the Applicable temperature scope of diffused indicator is relevant with the type of selected ester matter; Equations of The Second Kind is the Vist ab Check Point of VITSAB company, thereby the principle of this TTI is enzymatic hydrolysis to occur under controlled condition based on a kind of lipid substrates make pH reduction cause that the color of acid base indicator changes, temperature is higher, the speed of the proton that enzymatic lipid substrate hydrolysis discharges is faster, and its change color is along with larger variation also occurs in the prolongation of time; The 3rd class is the Fresh Check of LifeLines Technology company, its principle is chemical polymerization, form coloured polymkeric substance, by utilizing, form the change color producing after opaque colored polymkeric substance after colourless alkynes class monomer solid phase-polymerization and record temperature variation, polyreaction is along with temperature raises and accelerates, thereby cause indicator color to deepen sooner, this time-temperature indicator is necessary freezing before use, in order to avoid reacting activation.

The indication of above type has respectively different limitation.As the time-temperature indicator for response type, need to encapsulate gas or liquid on the one hand, need to do to separate with lipid film, when temperature surpasses after the fusing point of lipid film, chemical reaction is carried out in two kinds of materials mixing again.On the one hand the impact of the temperature before lipid film does not have breakage can not record, its two, once reaction, its boundary reacting completely is difficult for defining.Generally comparatively suitable as a kind of indicator that can not surpass certain temperature, the combined influence of reflecting time and temperature comprehensively.Product for the 3M company of diffused, it is the factor of generalized time and temperature well, but because water in solution and pigment the different segregation phenomenons that cause of rate of propagation can occur on porous paper when the diffusion, consequently color diffuse interface is not neat, unintelligible, fuzzy.

Although TTI can improve the quality of food, reduce food waste, give consumer more real quality guarantee, but to this day,, because the reason of economy, feasibility and practicality is subject to certain restrictions, only have indicator product few in number to put into commercial market.As very promising shelf-life predictor, people are to the research of TTI and apply in the ascendantly, constantly have new patent to occur.For example:

The patent No. is that the utility model patent of 200720032925.x discloses a kind of temperature-time indication label, this label comprises the storage pond of splendid attire diffusion liquid and is loaded with the label base plate of diffusion layer, wherein, in diffusion liquid, can contain pigment, dyestuff or the material that can react with diffusion layer, diffusion liquid is isolated from the outside by sealing or spacer, after removing isolation, label is activated, now, diffusion liquid spreads to diffusion layer by capillary line, its diffusion length is by determining environment temperature and diffusion time, being suitable for goods is storing, monitoring in transportation, but this indicating label production process is very complicated.

The patent No. is that 200910227305.5 patent of invention discloses a kind of diffused time-temperature indicator and indicating card and preparation method thereof, this time-temperature indication card adopts the potpourri of gaultherolin and γ-hexalactone as diffusate, add again colorant and be fully mixed and made into indicator, and then ultralow temperature processes and to make its formation solidify state, the indicator after solidifying is contacted and makes indicating card with dispersive medium.When environment temperature is during higher than indicator fusing point, indicator melts and is " activated ", and then will spread along dispersive medium, just can know course and the remaining shelf life of the Contact Temperature of food by diffusion length.The time-temperature indication card of this invention, can change the proportioning between gaultherolin and γ-hexalactone, realizes the critical temperature of regulation and control indicator between-3～-15 ℃, to adapt to the needs of different frozen food.But this indicating card can only be for the Time-temperature indication of frozen food, and preparation section is complicated, and consumer is difficult to intuitively read the information that wherein recorded.

Summary of the invention

The object of the invention is the technical matters existing in existing effective period of food quality indicating label, a kind of chemical intelligent label, label assembly and preparation method thereof are provided, this principle of change color that chemical intelligent label assembly of the present invention utilizes the diffusion of electrolyte solution in polymkeric substance and chemical doping to cause polymkeric substance realizes the monitoring to food quality, chemical intelligent label prepared by the present invention, preparation section is simple, with low cost, containing time-temperature indicator function, can be for the quality monitoring of normal temperature and frozen food or medicine.

For realizing object of the present invention, the chemical intelligent label that one aspect of the present invention provides a kind of integral body to be rectangle, comprises basalis, diffusion layer, shell and time scale scale, wherein:

Described basalis is by insulating and transparent material forms; Described diffusion layer and time scale scale are arranged on the surface of described basalis; Described shell is by described basalis and diffusion layer sealing; The starting point of described time scale scale is corresponding with the position on a top of diffusion layer.

Wherein, described basalis is selected from polyethylene terephthalate (PET), tygon (PE), polypropylene (PP), polybutylene terephthalate (PBT) plastics or polycarbonate (PC) plastics, is preferably PET.

Particularly, the length of described basalis is 30-50mm; Width is 2-20mm; Thickness is 0.01-0.02mm; The length of diffusion layer 12 is 30-50mm, and thickness is 0.01-0.1mm, width 2-20mm.

Wherein, described diffusion layer is the membraneous material being comprised of the first polymkeric substance and the second polymkeric substance, and wherein, described the first polymkeric substance is selected a kind of in salt state polyaniline, polypyrrole or PEDOT; The second polymkeric substance is selected a kind of in polyvinyl alcohol (PVA), hydroxyethyl cellulose, branching starch, shitosan.

Particularly, described the first polymkeric substance is selected salt state polyaniline; The second polymkeric substance is selected polyvinyl alcohol (PVA).

Especially, the mass ratio of described the first polymkeric substance and the second polymkeric substance is 1-10:1, is preferably 1-2:1.

Especially, described the first polymkeric substance is selected conducting polymer; Described the second polymkeric substance is selected water-soluble polymers.

Wherein, described diffusion layer and time scale scale be arranged on described basalis the same side surface or described diffusion layer be arranged on the surface of described basalis one side, the surface that time scale scale is arranged on described basalis opposite side.

Wherein, described shell is selected transparent transparent thermoplastic material or UV glue.

Particularly, described transparent thermoplastic material is selected from tygon, polypropylene, Polyvinylchloride, polystyrene, polyoxymethylene, poly-carbonic acid junket, a kind of in polyamide, acrylic acid.

Especially, described shell and described basalis, diffusion layer fit tightly.

The present invention provides a kind of preparation method of above-mentioned chemical intelligent label on the other hand, comprises as follows step in sequence:

1) conductive polymer solution and water-soluble polymer solution are mixed, make conduction-water-soluble polymers mixed solution;

2) conduction-water-soluble polymers mixed solution is coated on to the surface of described basalis one side, is then dried processing, form described diffusion layer, then cut into the label sample of corresponding size;

3) opposite side of the basalis of the label sample after cutting is printed described time scale scale, and the starting point of described time scale scale is consistent with one end of diffusion layer, makes exposed label;

4) with thermoplastic or UV glue, exposed label is sealed, the thermoplastic or the UV glue that are wrapped in exposed label outside form described shell, obtain.

Wherein, described conducting polymer is selected one or more in polyaniline, polypyrrole, poly-3,4-ethylene dioxythiophene, is preferably polyaniline; Described water-soluble polymers is selected base cellulose, branching starch, and one or more in shitosan, polyvinyl alcohol (PVA), are preferably polyvinyl alcohol (PVA).

Particularly, the solid content of described conductive polymer solution, water-soluble polymer solution is respectively 5-20%.

Wherein, the conducting polymer in described conductive polymer solution and the mass ratio of water-soluble polymers are 1-10:1, are preferably 1-2:1.

Particularly, the polyaniline in described polyaniline solutions and the mass ratio of the polyvinyl alcohol (PVA) in poly-vinyl alcohol solution are 1-10:1, are preferably 1-2:1.

Wherein, step 2) described in, dry processing is that the base layer material that has been coated with polymer solution is placed in to exsiccator, in relative humidity, is less than 20%, and temperature is dry 12-24 hour under the condition of 15-30 ℃, obtains polymkeric substance dry film, makes diffusion layer; Thermoplastic described in step 4) is selected from tygon, polypropylene, Polyvinylchloride, polystyrene, polyoxymethylene, poly-carbonic acid junket, a kind of in polyamide, acrylic acid.

Particularly, the mode that adopts dip-coating or spin coating is the surface at described basalis by polyaniline-polyvinyl alcohol solution coat.

Further aspect of the present invention provides a kind of intelligent label assembly that comprises above-mentioned functional label and diffusant.

Wherein, described diffusant is selected NaOH solution, KOH solution, Ca (OH) ₂solution, ammoniacal liquor.

Particularly, the concentration of described NaOH solution is 0.001-1mol/L, is preferably 0.1mol/L; The concentration of described KOH solution is 0.001-1mol/L.

Another aspect of the invention provides a kind of using method of above-mentioned intelligent label assembly, comprises that the starting point that described diffusant is joined to time scale scale in described intelligent label is to corresponding diffusion layer.

Wherein, adopt syringe to puncture the shell of described intelligent label, described diffusant is joined to corresponding diffusion layer.

The chemical intelligent label that the present invention provides a kind of integral body to be rectangle on the other hand, comprises basalis, diffusion layer, shell, time scale scale and diffusant carrier, wherein:

Described basalis is by insulating and transparent material forms; Described diffusion layer, diffusant carrier and time scale scale are arranged on the surface of basalis, and described diffusion layer, diffusant carrier are positioned at the same side of basalis; Described shell is by described basalis, diffusion layer and the sealing of diffusant carrier; Described diffusant carrier is arranged along the length direction of diffusion layer, is positioned at a top of diffusion layer, and combines closely with diffusion layer; The starting point of described time scale scale is corresponding with the position on the top that diffusion layer and diffusant carrier join.

Wherein, described diffusant carrier is selected nonwoven fabrics, hydrophilic polymer or kapillary.

Particularly, described diffusant carrier lengths is 5-20mm, and thickness is 0.05-0.5mm, width 5-15mm.

Wherein, described diffusion layer, diffusant carrier and time scale scale are arranged on described basalis the same side surface or described diffusion layer, diffusant carrier are arranged on the surface of described basalis one side, the surface that time scale scale is arranged on described basalis opposite side.

Wherein, described shell and described basalis, diffusion layer, diffusant carrier fit tightly.

Further aspect of the present invention provides a kind of preparation method of above-mentioned chemical intelligent label, comprises as follows step in sequence:

2) in basalis one side, arrange after boundary belt, conduction-water-soluble polymers mixed solution is coated on to a side of the basalis that is provided with boundary belt, dry, form described diffusion layer, make just base of intelligent label;

3) cut just base of intelligent label, the label sample of making corresponding size, wherein the boundary belt of intelligent label sample is positioned at one end of label sample, removes boundary belt, form protection trough, the size of described protection trough is consistent with described diffusant carrier size;

4) opposite side of the basalis (11) of the label sample after cutting is printed described time scale scale (3) or time scale scale (3) is affixed on to the opposite side of basalis (11), the starting point of described time scale scale (3) is consistent with one end of diffusion layer (12), makes exposed label;

5) diffusant carrier is placed in the protection trough of exposed label; with thermoplastic or UV glue, exposed label and diffusant carrier are sealed; the thermoplastic or the UV glue that are wrapped in exposed label and diffusant carrier outside form described shell (13), obtain.

Further aspect of the present invention provides a kind of intelligent label assembly that comprises above-mentioned intelligent label and diffusant.

Another aspect of the invention provides a kind of using method of above-mentioned intelligent label assembly, comprises described diffusant is joined in described intelligent label on diffusant carrier.

Wherein, adopt syringe to puncture the shell of described intelligent label, described diffusant is joined on described diffusant carrier.

The chemical intelligent label that further aspect of the present invention provides a kind of integral body to be rectangle, comprises seal and the time scale scale of basalis, diffusion layer, shell, diffusant inlet, sealing diffusant inlet, wherein:

Described basalis is by insulating and transparent material forms; Described diffusion layer and time scale scale are arranged on described basalis surface; Described shell is by described basalis and diffusion layer sealing; The starting point of described time scale scale is corresponding with the position on a top of diffusion layer; Described diffusant inlet is opened on shell, and its position is corresponding with the starting point of described time scale scale.

Wherein, described shell and described basalis, diffusion layer fit tightly.

Particularly, described diffusant inlet is opened on the shell of described diffusion layer one side of sealing.

2) conduction-water-soluble polymers mixed solution is coated on to the surface of described basalis one side, is then dried processing, then cut into the label sample of corresponding size;

4) with thermoplastic or UV glue, exposed label is sealed, the thermoplastic or the UV glue that are wrapped in exposed label outside form described shell;

5) in the one end that seals the shell of diffusion layer one side, corresponding to the start position of described time scale scale, offer described diffusant inlet, then with seal, sealed, obtain.

Wherein, described diffusant joins on the corresponding diffusion layer of the starting point of the time scale scale in described intelligent label by diffusant main-inlet.

The chemical intelligent label that another aspect of the invention provides a kind of integral body to be rectangle, comprises seal, time scale scale and the diffusant carrier of basalis, diffusion layer, shell, diffusant inlet, sealing diffusant inlet, wherein:

Described basalis is by insulating and transparent material forms; Described diffusion layer, diffusant carrier and time scale scale are arranged on the surface of basalis, and described diffusion layer, diffusant carrier are positioned at the same side of basalis; Described shell is by described basalis, diffusion layer and the sealing of diffusant carrier; Described diffusant carrier is arranged along the length direction of diffusion layer, is positioned at a top of diffusion layer, and combines closely with diffusion layer; The position on the top that the starting point of described time scale scale is joined with diffusant carrier with diffusion layer is corresponding; Described diffusant inlet is opened on shell, and the position of its setting is corresponding with the starting point of described time scale scale.

Particularly, the length of described basalis is 30-50mm; Width is 2-20mm; Thickness 0.01-0.02mm; The length of diffusion layer 12 is 30-50mm, and thickness is 0.01-0.1mm, width 2-20mm.

Particularly, described shell and described basalis, diffusion layer, diffusant carrier fit tightly.

Especially, described diffusant inlet is opened on the shell of the described diffusion layer of sealing, diffusant carrier one side.

5) diffusant carrier is placed in the protection trough of exposed label, with thermoplastic or UV glue, exposed label and diffusant carrier are sealed, the thermoplastic or the UV glue that are wrapped in exposed label and diffusant carrier outside form described shell (13);

6) in one end of described shell (13), corresponding to the start position of described time scale scale (3), offer described diffusant inlet (15), then use seal (16) to be sealed, obtain.

Another aspect of the invention provides a kind of chemical intelligent label assembly, comprises chemical intelligent label and diffusant as mentioned above, and wherein said diffusant is selected the alkaline solution that concentration is 0.001-1mol/L.

Wherein, described alkaline solution is selected NaOH solution, KOH solution, Ca (OH) ₂the alkaline electrolyte solution such as solution, ammoniacal liquor, preferably NaOH solution.

Particularly, select the NaOH solution that concentration is 0.1mol/L.

Diffusant is dripped to the one end (i.e. one end corresponding with time scale scale starting point) at diffusion layer, diffusant spreads in diffusion layer, because diffusion layer is aqueous salt state polyaniline mixed film, after the doping of itself and diffusant, there is change color, according to the distance of diffusant movement in diffusion layer and the variation of color, indicate the temperature variation experiencing and the time of product to be instructed, the quality of visual indication product to be instructed and shelf-life.

In chemical intelligent label of the present invention, the mass ratio of the first polymkeric substance and the second polymkeric substance is to determine according to the shelf-life of product to be instructed, that is to say, according to the shelf-life of product to be instructed, regulate the mass ratio of the first polymkeric substance and the second polymkeric substance, and then regulate the rate of diffusion of described diffusant on diffusion layer, thereby diffusant is diffused into the required time of the other end equated with the shelf-life of product to be instructed from one end of diffusion layer.

Tool of the present invention has the following advantages:

1, the chemical tags that prepared by the present invention only consists of one layer of polymeric dry film, and preparation technology is simple, and cost is low.

2, after the chemical tags that prepared by the present invention is activated, the migratory behaviour of diffusant in polymkeric substance dry film meets the rule of molecular reaction diffusion, the length of the diffusion length of diffusant can, in order to indicate the length of diffusion time, can be indicated the shelf-life of product to be identified by the distance of diffusant diffusion in label.

3, the chemical intelligent label that prepared by the present invention is indicated the shelf-life of different food products or medicine by controlling the ratio of polyaniline and aqueous polymer, simple, convenient, effective.

4, the steady change course that the chemical intelligent label that prepared by the present invention can not only be followed the tracks of and record product experiences, and can also indicate intuitively quality and the quality guarantee period of product by the variation of color, the residue shelf time of product to be instructed reflected intuitively.

5, in the present invention, the rate of propagation of diffusant in diffusion layer can regulate by the proportion of composing of first, second polymkeric substance in diffusion layer, the diffusion time of diffusant in diffusion layer can be to the scope of several months or several years, to regulate for several minutes, has practical application widely.

Accompanying drawing explanation

Fig. 1 is the diagrammatic cross-section of the chemical intelligent label of the embodiment of the present invention 1;

Fig. 2 is the front schematic view of the chemical intelligent label of the embodiment of the present invention 1;

Fig. 3 is the diagrammatic cross-section after the chemical intelligent label of the embodiment of the present invention 1 is activated;

Fig. 4 is the diagrammatic cross-section of the chemical intelligent label of the embodiment of the present invention 2;

Fig. 5 is the diagrammatic cross-section of the chemical intelligent label of the embodiment of the present invention 4;

Fig. 6 is the front schematic view of the chemical intelligent label of the embodiment of the present invention 4;

Fig. 7 is the diagrammatic cross-section after the chemical intelligent label of the embodiment of the present invention 4 is activated;

Fig. 8 is the diagrammatic cross-section of the chemical intelligent label of the embodiment of the present invention 5;

Fig. 9 is the diagrammatic cross-section of the embodiment of the present invention 7 chemical intelligent labels;

Figure 10 is the front schematic view of the chemical intelligent label of the embodiment of the present invention 7;

Figure 11 is the diagrammatic cross-section after the chemical intelligent label of the embodiment of the present invention 7 is activated;

Figure 12 is the diagrammatic cross-section of the embodiment of the present invention 10 chemical intelligent labels;

Figure 13 is the front schematic view of the chemical intelligent label of the embodiment of the present invention 10;

Figure 14 is the diagrammatic cross-section after the chemical intelligent label of the embodiment of the present invention 10 is activated;

Figure 15 is to time-temperature accumulation effect record diagram after test example 1 of the present invention activates chemical intelligent label.

Figure 16 is the schematic diagram of the chemical intelligent label assembly of test example 1 of the present invention application on the shelf-life at indication milk.

Reference numeral: 1, label; 11, basalis; 12, diffusion layer; 13, shell; 14, diffuse interface; 15, diffusant inlet; 16, seal; 2, diffusant; 3, time scale scale; 31, time scale scale starting point; 4, outer packaging bag; 5, diffusant carrier.

Embodiment

Below in conjunction with specific embodiment, further describe the present invention, advantage and disadvantage of the present invention will be more clear along with description.But these embodiment are only exemplary, scope of the present invention are not formed to any restriction.It will be understood by those skilled in the art that lower without departing from the spirit and scope of the present invention and can the details of technical solution of the present invention and form be modified or be replaced, but these modifications and replacement all fall within the scope of protection of the present invention.

Embodiment 1

One, chemical intelligent label

As shown in Figure 1, 2, chemical intelligent label 1 integral body of the present invention is rectangular build, and the basalis 11 being comprised of insulating material, the diffusion layer 12 that is arranged on basalis 11 surfaces, shell 13, time scale scale 3 form.Wherein:

A side at basalis 11 indicates time scale scale 3; Described diffusion layer 12 is positioned at the opposite side of described basalis 11, and combines closely with basalis 11, and the combine size at position of diffusion layer 12 and basalis 11 equates; The starting point 31 of time scale scale 3 is corresponding with the apical position of diffusion layer 12;

Described shell 13 is positioned at the outside of described diffusion layer 12 and basalis 11, fit tightly with surrounding, the lower surface of surrounding, upper surface and the basalis 11 of diffusion layer 12, be wrapped in the outside of described diffusion layer 12 and basalis 11, by diffusion layer 12 and basalis 11 sealings.

Basalis 11, diffusion layer 12 are rectangular build, and the length of basalis 11 is 30-50mm, and width is 2-20mm, and thickness is 0.01-0.02mm; The length of diffusion layer 12 is 30-50mm, and thickness is 0.01-0.1mm, width 2-20mm.In the embodiment of the present invention, the length of basalis 11 is chosen as 25mm, and width is 15mm, and thickness is 0.02mm; The length of diffusion layer 12 is 25mm, and thickness is 0.02mm, width 15mm.Basalis in the present embodiment 11 is selected polyethylene terephthalates (PET), and other are all applicable to the present invention as tygon (PE), polypropylene (PP), polybutylene terephthalate (PBT) plastics or polycarbonate (PC) plastics.

Diffusion layer described in the present invention 12 is polyaniline, polypyrrole, poly-3,4-ethylene dioxythiophene, or selects polyaniline-polyvinyl alcohol potpourri, and wherein the mass ratio of polyaniline and polyvinyl alcohol (PVA) is 1-10:1, is preferably 1-2:1.Diffusion layer described in the present invention 12 is except selecting polyaniline-polyvinyl alcohol potpourri, and other water-soluble polymerss are as hydroxyethyl cellulose, branching starch, and shitosan etc. all can mix with polyaniline use.Except selecting polyaniline, other conducting polymers are used as polypyrrole, poly-3,4-ethylene dioxythiophene also can replace polyaniline.

The potpourri that diffusion layer 12 in the embodiment of the present invention selects the polyaniline-polyvinyl alcohol that is 1:1 by mass ratio to form.Shell described in the present invention 13 is selected thermoplasticss, ultraviolet light or the photocuring glue of filming.

Two, chemical intelligent label assembly

Chemical intelligent label assembly of the present invention is comprised of intelligent label 1 and diffusant 2, when intelligent label is used, with the syringe that diffusant 2 is housed, sealing diffusion layer one side the shell 13 corresponding with time scale scale starting point place pierced through and inject diffusant, diffusant is in the interior diffusion of diffusion layer 12, the distance that diffusant moves in diffusion layer, the variation of color, indicate the temperature variation experiencing and the time of product to be instructed, the quality of visual indication product to be instructed and shelf-life.

Dripped the chemical intelligent label assembly of diffusant, the chemical intelligent label cut-open view after activating as shown in Figure 3.

The diffusant 2 using in intelligent label assembly of the present invention is selected the NaOH solution that concentration is 0.1mol/L, other concentration are that the NaOH solution of 0.001-1mol/L is also applicable to the present invention, and other are as KOH solution (concentration is 0.001-1mol/L), Ca (OH) ₂the alkaline electrolyte solutions such as solution, ammoniacal liquor (mass percent concentration is 0.05%-1%) are all applicable to the present invention.

Three, prepare chemical intelligent label

3.1 is 10% by solids content, and polyaniline aqueous solution joins in polyvinyl alcohol water solution same volume, that solids content is 10%, stir, mix, the green polyaniline-polyvinyl alcohol solution that the solids content that makes polyaniline is 5%, standby, wherein, the mass ratio of polyaniline and polyvinyl alcohol (PVA) is 1:1.

The solids content of the polyaniline aqueous solution in the present embodiment is 10%, and the polyaniline aqueous solution that other solids contents are 5-20% is also applicable to the present invention; The solids content of polyvinyl alcohol water solution is 10%, and the polyvinyl alcohol water solution that other solids contents are 5-20% is also applicable to the present invention.

The present invention utilizes the diffusion of electrolyte solution in polymkeric substance and chemical doping reaction occurs and causes that the principle of change color carries out time, temperature monitoring to product to be instructed, wherein, electrolyte solution in polymkeric substance diffusion length with diffusion time and temperature variation, can the reaction time, temperature accumulative effect; Meanwhile, utilize electrolyte solution and conducting polymer generation doping reaction to cause that conducting polymer change color indicates the distance of the movement of diffuse interface.Can there is the material of change color in other, as polypyrrole, poly-3,4-ethylene dioxythiophene (PEDOT) etc. is all applicable to the present invention by acidity or alkaline electrolyte doping.

It is to accelerate the rate of propagation of diffusant (being alkaline solution) in diffusion layer that the present invention adds the object of water-soluble polymers in conducting polymer (as polyaniline, polypyrrole, poly-3,4-ethylene dioxythiophene).In the embodiment of the present invention, selecting the potpourri dry film of polyvinyl alcohol (PVA) and polyaniline is diffusion layer, adds polyvinyl alcohol (PVA) to accelerate the rate of propagation of NaOH solution in diffusion layer in polyaniline.The present invention is except adding in polyaniline solutions poly-vinyl alcohol solution, other water-soluble polymer solutions, and as hydroxy ethyl fiber cellulose solution, branching starch solution, chitosan solution etc. are all applicable to the present invention.

Polyaniline in diffusion layer and the mass ratio of polyvinyl alcohol (PVA) regulate according to the time length of the shelf-life of product to be instructed, if the long shelf-life of product to be instructed, the mass ratio of increase polyaniline and polyvinyl alcohol (PVA); The shelf-life of product to be instructed is short, reduces the mass ratio of polyaniline and polyvinyl alcohol (PVA).Regulate the mass ratio of polyaniline and polyvinyl alcohol (PVA), adjust the rate of propagation of diffusant, make diffusant from one end of diffusion layer, be diffused into the needed time of the other end and equate with the shelf-life of product to be instructed.

3.2 adopt spin coating instrument (Shenyang Si Le company) that green polyaniline-polyvinyl alcohol solution is coated on to polyethylene terephthalate (PET) base material one side in the mode of spin coating, then (relative humidity is less than 20% the PET base material that has been coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 ℃) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET basalis, make diffusion layer 12, the thickness of wherein controlling diffusion layer 12 is 20 ± 0.2 μ m, make just base of intelligent label,

In the present invention by coating method by polyaniline-polyvinyl alcohol solution coat the surface at described basalis 11, in the dry process that forms polyaniline-polyvinyl alcohol rete, at exsiccator inner drying time >=8h, wherein the relative humidity in exsiccator is less than 20%, baking temperature is 15-30 ℃.

The base material using in the embodiment of the present invention (PET) is of a size of: length 50mm, width 40mm.The base material of other sizes is also applicable to the present invention.

3.3 by intelligent label just base (being coated with the PET matrix material of polyaniline-polyvinyl alcohol film) to cut into 25mm(long) * 15mm(is wide) and sample, obtain intelligent label sample;

3.4 according to diffusant the rate of propagation on diffusion layer, at the back side of basalis 11, the one side that is not coated with polyaniline-polyvinyl alcohol is printed the time scale scale 3 of the time that represents, the reference shelf-life as product to be instructed, makes exposed label;

3.5 are placed in exposed label on plastic packaging machine, with thermoplastic, exposed intelligent label is encapsulated in to thermoplastics inside, be about to exposed label and be wrapped in thermoplastics inside, obtain intelligent label 1, the thermoplastics that is wrapped in exposed label outside is the shell 13 of intelligent label 1.

The present invention except with thermoplastic by the whole plastic packagings of exposed label thermoplastic inside, can also be with thermoplastic by the whole plastic packagings of other parts except basalis 11, forming thermoplastics is that shell 13 seals other parts that fit tightly a side except diffusion layer 12 and basalis 11.

The present invention, except adopting thermoplastics to carry out plastic packaging label, can also adopt ultraviolet cured adhesive (or UV glue) to seal label, for example, purchased from the UV glue of Shenzhen Gu Tuo Electron Material Co., Ltd.

Four, chemical intelligent label using method

4.1 are affixed on chemical intelligent label 1 on the outer packaging bag of product to be instructed, and label substrate layer 11 is close to the surface of the outer packaging bag of product to be instructed;

4.2 use syringes are drawn the NaOH solution (being diffusant 2) that concentration is 0.1mol/L, then with the start position place of syringe corresponding time scale scale 3 in chemical intelligent label 1, the shell of intelligent label 1 13 is pierced through, then NaOH solution is injected on the diffusion layer 12 of intelligent label;

4.3 use fluid sealants will be injected the position sealing that device pierces through on shell 13.

NaOH solution spreads along green polyaniline-polyvinyl alcohol dry film (being diffusion layer 12), the Polyaniline Doped of green salt state after NaOH, become blue polyaniline in eigenstate, shown in (I):

Diffusion agent N aOH solution spreads in polyaniline-polyvinyl alcohol dry film (being diffusion layer 12), diffusion layer becomes blueness by green, in diffusion layer 12, form the diffuse interface 14 of a blue-green, as shown in Figure 3, As time goes on, the other end that NaOH solution is diffused to by one end of label 1 gradually, the diffuse interface 14 of blue-green is constantly mobile along polyaniline-polyvinyl alcohol dry film (diffusion layer 12), so, the distance that the diffuse interface 14 of blue-green moves is just set up and is contacted with the time, thus reactor product quality and shelf-life intuitively.

Embodiment 2

One, chemical intelligent label

Except the shell 13 of chemical intelligent label 1 is positioned at the outside of described diffusion layer 12, only fit tightly with surrounding, the upper surface of diffusion layer 12, be wrapped in the outside of described diffusion layer 12, outside diffusion layer 12 sealings, all the other are identical with embodiment 1, as shown in Figure 4.

In the embodiment of the present invention, the size of basalis 11, except the size with diffusion layer 12 is identical, can also be greater than the size of diffusion layer 12.

Two, chemical intelligent label assembly

Identical with embodiment 1

Three, prepare chemical intelligent label

Except with thermoplastic, the surrounding of the diffusion layer of exposed intelligent label 12, upper surface being carried out plastic packaging on plastic packaging machine, all the other are identical with embodiment 1.

Four, chemical intelligent label using method

Identical with embodiment 1

Embodiment 3

One, chemical intelligent label

Except the time scale scale 3 of chemical intelligent label 1 is positioned at the same side of basalis 11 with diffusion layer 12, all the other are identical with embodiment 1.

Two, chemical intelligent label assembly

Identical with embodiment 1

Three, prepare chemical intelligent label

3.1 is 10% by solids content, and polyaniline aqueous solution joins in polyvinyl alcohol water solution same volume, that solids content is 10%, stir, mix, the green polyaniline-polyvinyl alcohol solution that the solids content that makes polyaniline is 5%, standby, wherein, the volume ratio of polyaniline aqueous solution and polyvinyl alcohol water solution is 1:1.

3.2 according to diffusant the rate of propagation on diffusion layer, in a side of basalis 11, print the time scale scale 3 of the time that represents;

3.3 adopt spin coating instrument (Shenyang Si Le company) that green polyaniline-polyvinyl alcohol solution coat has been printed to time scale scale 3 one sides at basalis 11, then (relative humidity is less than 20% the PET basalis that has been coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 ℃) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET basalis, make diffusion layer 12, the thickness of wherein controlling diffusion layer 12 is 20 ± 0.2 μ m, makes just base of intelligent label;

3.4 by intelligent label just base (being coated with the PET matrix material of polyaniline-polyvinyl alcohol film) to cut into 25mm(long) * 15mm(is wide) and sample be placed on plastic packaging machine, with thermoplastic, the first base of intelligent label is encapsulated in to thermoplastics inside, be about to the first base of intelligent label and be wrapped in thermoplastics inside, obtain intelligent label 1, the thermoplastics that is wrapped in the first base of intelligent label outside is the shell 13 of intelligent label 1.

Four, chemical intelligent label using method

Identical with embodiment 1.

Embodiment 4

One, chemical intelligent label

As shown in Figure 5,6, chemical intelligent label 1 integral body of the present invention is rectangular build, seal 16, the time scale scale 3 of the basalis 11 being comprised of insulating material, the diffusion layer 12 that is arranged on basalis 11 surfaces, shell 13, diffusant inlet 15, sealing diffusant inlet 15 form, wherein:

A side at basalis 13 indicates time scale scale 3, at its opposite side, is diffusion layer 12, and diffusion layer 12 is combined closely with basalis 11, and the combine size at position of diffusion layer 12 and basalis 11 equates; The starting point 31 of time scale scale 3 is corresponding with the apical position of diffusion layer 12;

Shell 13 is positioned at the outside of described diffusion layer 12 and basalis 11, fits tightly with surrounding, the lower surface of surrounding, upper surface and the basalis 11 of diffusion layer 12, is wrapped in the outside of described diffusion layer 12 and basalis 11, by diffusion layer 12 and basalis 11 sealings;

On shell 13, offer diffusant inlet 15, diffusant inlet 15 is positioned at the end of a side of diffusion layer 12, the position of its setting to corresponding, when intelligent label activates, starts timing from the starting point of time scale scale 3 with the starting point of described time scale scale 3;

Seal 16 is for sealing diffusant inlet 15, and its size adapts with size of diffusant inlet 15.

During intelligent label 1 un-activation, seal 16 is closed diffusant inlet 15, when intelligent label being affixed on the outer packaging bag that indicates product, remove seal 16, open diffusant inlet 15, splash into diffusant, activate intelligent label (as shown in Figure 7), then with seal 16, again diffusant inlet 15 is sealed.

In the present embodiment, the size of basalis 11, diffusion layer 12 is identical with embodiment 1.The material that basalis 11, diffusion layer 12, shell 13 are used is identical with embodiment 1.

Two, chemical intelligent label assembly

Chemical intelligent label assembly of the present invention is comprised of intelligent label 1 and diffusant 2, when intelligent label is used, the seal of label 1 16 is removed, open diffusant inlet 15, expose diffusion layer 12, then diffusant 2 is dripped on diffusion layer 12, and then with seal 16, diffusant inlet 15 is sealed.Diffusant spreads in diffusion layer, and the variation according to diffusant in the mobile distance of diffusion layer and color indicates the temperature variation experiencing and the time of product to be instructed, the quality of visual indication product to be instructed and shelf-life.

Dripped diffusant 2 chemical intelligent label assembly afterwards, the chemical intelligent label cut-open view after activating as shown in Figure 7.

Three, prepare chemical intelligent label

3.1 is 10% by solids content, and polyaniline aqueous solution joins in polyvinyl alcohol water solution same volume, that solids content is 10%, stir, mix, the green polyaniline-polyvinyl alcohol solution that the solids content that makes polyaniline is 5%, standby, wherein, the mass ratio of polyaniline and polyvinyl alcohol (PVA) is 1:1;

3.2 adopt spreader (Tianjin essence section tech, 200 μ m) by green polyaniline-polyvinyl alcohol solution coat in polyethylene terephthalate (PET) basalis 11 1 sides, then (relative humidity is less than 20% the PET basalis that has been coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 ℃) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET basalis, make diffusion layer 12, wherein the thickness of diffusion layer 12 is 20 ± 0.2 μ m, makes just base of intelligent label;

3.5 are placed in exposed label on plastic packaging machine, with thermoplastic, exposed intelligent label are encapsulated in to thermoplastics inside, are about to exposed label and are wrapped in thermoplastics inside, and the thermoplastics that is wrapped in exposed label outside is the shell 13 of intelligent label 1;

One end of 3.6 shells 13 in sealing diffusion layer one side, offers diffusant inlet 15 corresponding to the start position of the time scale scale 3 on basalis 11, then with seal 16, is sealed, and obtains.

In the present invention, seal 16 is selected adhesive waterproof tape, chance water cure glue (as moral jail scholar's 201 glue) or UV glue.

The present invention, except adopting thermoplastics to carry out plastic packaging label, can also adopt UV glue to claim again UV glue (Shenzhen Gu Tuo Electron Material Co., Ltd) to seal label.

Four, chemical intelligent label using method

4.2 open the seal 16 on intelligent label 1, open diffusant inlet 15, expose the diffusion layer 12 of intelligent label;

The 4.3 NaOH solution (being diffusant 2) that are 0.01mol/L by concentration, drop on diffusion layer 12 from the diffusant inlet 15 of opening, then with seal 16 by 15 sealings of diffusant inlet.

Diffusion agent N aOH solution, in the middle diffusion of label 1, as shown in Figure 7, reacts quality and the shelf-life of product to be indicated according to the distance of diffusion.

Embodiment 5

One, chemical intelligent label

Except the shell 13 of chemical intelligent label 1 is positioned at the outside of described diffusion layer 12, only fit tightly with surrounding, the upper surface of diffusion layer 12, be wrapped in the outside of described diffusion layer 12, outside diffusion layer 12 sealings, all the other are identical with embodiment 4, as shown in Figure 8.

Two, chemical intelligent label assembly

Identical with embodiment 4

Three, prepare chemical intelligent label

Except with thermoplastic, the surrounding of the diffusion layer of exposed intelligent label 12, upper surface being carried out plastic packaging on plastic packaging machine, all the other are identical with embodiment 4.

Four, chemical intelligent label using method

Identical with embodiment 4

Embodiment 6

One, chemical intelligent label

Two, chemical intelligent label assembly

Identical with embodiment 1

Three, prepare chemical intelligent label

3.3 adopt spreader that green polyaniline-polyvinyl alcohol solution coat has been printed to time scale scale 3 one sides at basalis 11, then (relative humidity is less than 20% the PET basalis that has been coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 ℃) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET basalis, make diffusion layer 12, wherein the thickness of diffusion layer 12 is 20 ± 0.2 μ m, makes just base of intelligent label;

3.4 by intelligent label just base (being coated with the PET matrix material of polyaniline-polyvinyl alcohol film) to cut into 25mm(long) * 15mm(is wide) and sample be placed on plastic packaging machine, with thermoplastic, exposed intelligent label is encapsulated in to thermoplastics inside, be about to exposed label and be wrapped in thermoplastics inside, obtain intelligent label 1, the thermoplastics that is wrapped in exposed label outside is the shell 13 of intelligent label 1.

One end of 3.5 shells 13 in sealing diffusion layer one side, offers diffusant inlet 15 corresponding to the position of the time scale scale starting point 31 on basalis, then with seal 16, is sealed, and obtains.

Four, chemical intelligent label using method

Identical with embodiment 4.

Embodiment 7

One, chemical intelligent label

As shown in Fig. 9,10, chemical intelligent label 1 integral body of the present invention is rectangular build, and the basalis 11 being comprised of insulating material, the diffusion layer 12 that is arranged on basalis 11 surfaces, shell 13, time scale scale 3, diffusant carrier 5 form.Wherein:

A side at basalis 11 indicates time scale scale 3; Described diffusion layer 12 is positioned at the opposite side of described basalis 11, and combines closely with basalis 11; Diffusant carrier 5 is positioned at the same side of basalis 11 with diffusion layer 12, and combines closely each other; Diffusant carrier 5 is arranged along the length direction of diffusion layer 12, is positioned at the top of diffusion layer 12; The length sum of diffusant carrier 5 and diffusion layer 12 and basalis 11 equal in length, the width of diffusant carrier 5, diffusion layer 12 equates with the width of basalis 11; The starting point 31 of time scale scale 3 is corresponding with the apical position of diffusion layer 12;

Described shell 13 is positioned at the outside of described diffusion layer 12, diffusant carrier 5 and basalis 11, is closely wrapped in the outside of diffusion layer 12, diffusant carrier 5 and basalis 11, by diffusion layer 12, diffusant carrier 5 and basalis 11 sealings.

Basalis 11, diffusion layer 12 are rectangular build, and the length of basalis 11 is 30-50mm, and width is 2-20mm, and thickness is 0.01-0.02mm; The length 30-50mm of diffusion layer 12, thickness 0.01-0.1mm, width 2-20mm.

In the embodiment of the present invention, the length of basalis 11 is chosen as 30mm, and width is 15mm, and thickness is 0.015mm; The length of diffusion layer 12 is 25mm, and thickness is 0.02mm, width 15mm; The length of diffusant carrier is 5mm, width 15mm, thickness 0.02mm.The selected material of basalis 11 in the embodiment of the present invention, diffusion layer 12 is identical with embodiment 1; Diffusant carrier 5 is selected nonwoven fabrics chip, and the material that other can storage solutions is all applicable to the present invention as hydrophilic polymer, kapillary etc.

Two, chemical intelligent label assembly

Chemical intelligent label assembly of the present invention is comprised of intelligent label 1 and diffusant 2, when intelligent label is used, with the syringe that diffusant 2 is housed, the shell 13 of diffusant carrier 5 correspondences is pierced through, then diffusant 2 is injected on diffusant carrier 5, because diffusant carrier 5 is positioned at the top of diffusion layer 12 and combines closely with diffusion layer 12, therefore be adsorbed on diffusant in diffusant carrier 5 in the interior diffusion of diffusion layer 12, indicate the temperature variation experiencing and the time of product to be instructed, the quality of visual indication product to be instructed and shelf-life.

Dripped the chemical intelligent label assembly after diffusant 2, the chemical intelligent label cut-open view after activating as shown in figure 11.

Three, prepare chemical intelligent label

3.2 first in PET base material one end, along its Width, sticking width is 7mm protective tapes, then adopt spin coating instrument that green polyaniline-polyvinyl alcohol solution coat is being posted on polyethylene terephthalate (PET) base material of protective tapes one side, then (relative humidity is less than 20% the base material after coating to be put into exsiccator, temperature is 15-30 ℃) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET base material, make diffusion layer 12, the thickness of wherein controlling diffusion layer 12 is 20 ± 0.2 μ m, make just base of intelligent label,

The base material using in the embodiment of the present invention (PET) is of a size of: length 50mm, width 40mm.

3.3 cut just base (being coated with the PET matrix material of polyaniline-polyvinyl alcohol film) of intelligent label, making the base material length after cutting is 30mm, width is 15mm, and wherein, protective tapes is positioned at one end of base material, diffusion layer and protective tapes are arranged along the length direction of base material, the length of diffusion layer is 25mm, and the length of protective tapes is 5mm, removes protective tapes, form protection trough, obtain intelligent label sample;

3.4 according to diffusant the rate of propagation on diffusion layer, opposite side surface at basalis 11, the one side that is not coated with polyaniline-polyvinyl alcohol is printed the time scale scale 3 of the time that represents, wherein, the starting point of time scale scale 3 is consistent with the starting point of diffusion layer 12, also consistent with the terminal of protection trough, the reference shelf-life as product to be instructed, make exposed label;

3.5 are placed in exposed label on plastic packaging machine; and diffusant carrier 5 nonwoven fabrics are placed in protection trough; with thermoplastic by exposed label with to be placed in the protection trough of exposed label diffusant carrier package inner at thermoplastics; be about to exposed label and diffusant carrier is wrapped in thermoplastics inside, the thermoplastics that is wrapped in exposed label and diffusant carrier outside is the shell 13 of intelligent label 1.

Four, chemical intelligent label using method

4.2 use syringes are drawn the NaOH solution (being diffusant 2) that concentration is 0.1mol/L, then with the position of syringe corresponding diffusant carrier 5 in chemical intelligent label 1, the shell of intelligent label 1 13 is pierced through, then NaOH solution is injected on the diffusant carrier 5 of intelligent label;

Diffusion agent N aOH solution, in the middle diffusion of label 1, as shown in figure 11, reacts quality and the shelf-life of product to be indicated according to the distance of diffusion.

Embodiment 8

One, chemical intelligent label

Except the shell 13 of chemical intelligent label 1 is positioned at the outside of described diffusion layer 12, diffusant carrier 5, only fit tightly with diffusion layer 12, the surrounding of diffusant carrier 5, upper surface, be wrapped in the outside of described diffusion layer 12, diffusant carrier 5, outside diffusion layer 12 and diffusant carrier 5 are sealed, all the other are identical with embodiment 7, as shown in figure 12.

Two, chemical intelligent label assembly

Identical with embodiment 7

Three, prepare chemical intelligent label

Except with thermoplastic, the surrounding of the diffusion layer of exposed intelligent label 12, diffusant carrier 5, upper surface being carried out plastic packaging on plastic packaging machine, all the other are identical with embodiment 7.

Four, chemical intelligent label using method

Identical with embodiment 7.

Embodiment 9

One, chemical intelligent label

Except the time scale scale 3 of chemical intelligent label 1 is positioned at the same side of basalis 11 with diffusion layer 12, all the other are identical with embodiment 7.

Two, chemical intelligent label assembly

Identical with embodiment 7

Three, prepare chemical intelligent label

3.1 is 10% by solids content, and polyaniline aqueous solution joins in polyvinyl alcohol water solution same volume, that solids content is 10%, stir, mix, the green polyaniline-polyvinyl alcohol solution that the solids content that makes polyaniline is 5%, standby, wherein, the mass ratio of polyaniline water and polyvinyl alcohol (PVA) is 1:1;

3.2 one end at PET base material, along its Width, to stick width be 7mm protective tapes;

3.3 according to diffusant the rate of propagation on diffusion layer, along base material length direction, the protective tapes of take is starting point along one end of base material length direction, in a side of posting the base material of protective tapes, prints the time scale scale 3 of the time that represents;

3.4 adopt spin coating instrument that green polyaniline-polyvinyl alcohol solution coat has been printed to time scale scale 3 one sides at base material, then (relative humidity is less than 20% the PET basalis that has been coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 ℃) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET basalis, make diffusion layer 12, the thickness of wherein controlling diffusion layer 12 is 20 ± 0.2 μ m, makes just base of intelligent label;

3.5 cut just base (being coated with the PET matrix material of polyaniline-polyvinyl alcohol film) of intelligent label, making the base material length after cutting is 30mm, width is 15mm, and wherein, protective tapes is positioned at one end of base material, diffusion layer and protective tapes are arranged along the length direction of base material, the length of diffusion layer is 25mm, and the length of protective tapes is 5mm, removes protective tapes, form protection trough, obtain exposed label;

3.6 are placed in exposed label on plastic packaging machine; and diffusant carrier 5 nonwoven fabrics are placed in protection trough; with thermoplastic by exposed label with to be placed in the protection trough of exposed label diffusant carrier package inner at thermoplastics; be about to exposed label and diffusant carrier is wrapped in thermoplastics inside, the thermoplastics that is wrapped in exposed label and diffusant carrier outside is the shell 13 of intelligent label 1.

Four, chemical intelligent label using method

Identical with embodiment 1.

Embodiment 10

One, chemical intelligent label

As shown in Figure 12,13, chemical intelligent label 1 integral body of the present invention is rectangular build, seal 16, time scale scale 3, the diffusant carrier 5 of the basalis 11 being comprised of insulating material, the diffusion layer 12 that is arranged on basalis 11 surfaces, shell 13, diffusant inlet 15, sealing diffusant inlet 15 form, wherein:

A side at basalis 13 indicates time scale scale 3, at its opposite side, be diffusion layer 12 and diffusant carrier 5, diffusion layer 12, diffusant carrier 5 are combined closely with basalis 11, and diffusant carrier 5 is arranged along the length direction of diffusion layer 12, is positioned at the top of diffusion layer 12; The length sum of diffusant carrier 5 and diffusion layer 12 and basalis 11 equal in length, the width of diffusant carrier 5, diffusion layer 12 equates with the width of basalis 11; The starting point 31 of time scale scale 3 is corresponding with the apical position of diffusion layer 12;

Described shell 13 is positioned at the outside of described diffusion layer 12, diffusant carrier 5 and basalis 11, is closely wrapped in the outside of diffusion layer 12, diffusant carrier 5 and basalis 11, by diffusion layer 12, diffusant carrier 5 and basalis 11 sealings;

On shell 13, offer diffusant inlet 15, diffusant inlet 15 is positioned at one end of diffusion layer 12, and the position of its setting is consistent with the position of described diffusant carrier 5;

During intelligent label 1 un-activation, seal 16 is closed diffusant inlet 15, when intelligent label being affixed on the outer packaging bag that indicates product, remove seal 16, open diffusant inlet 15, splash into diffusant, activate intelligent label (as shown in figure 14), then with seal 16, again diffusant inlet 15 is sealed.

In the present embodiment, the size of basalis 11, diffusion layer 12, diffusant carrier 5 is identical with embodiment 7.The material that basalis 11, diffusion layer 12, shell 13, diffusant carrier 5 are used is identical with embodiment 7.

Two, chemical intelligent label assembly

Chemical intelligent label assembly of the present invention is comprised of intelligent label 1 and diffusant 2, when intelligent label is used, the seal of label 1 16 is removed, open diffusant inlet 15, expose diffusant carrier 5, then diffusant 2 is dripped on diffusant carrier 5, and then with seal 16, diffusant inlet 15 is sealed.Because diffusant carrier 5 is positioned at the top of diffusion layer 12 and combines closely with diffusion layer 12, therefore be adsorbed on diffusant in diffusant carrier 5 in the interior diffusion of diffusion layer 12, indicate the temperature variation experiencing and the time of product to be instructed, the quality of visual indication product to be instructed and shelf-life.

Dripped diffusant 2 chemical intelligent label assembly afterwards, the chemical intelligent label cut-open view after activating as shown in figure 14.

Three, prepare chemical intelligent label

3.1 is 10% by solids content, and polyaniline aqueous solution joins in polyvinyl alcohol water solution same volume, that solids content is 10%, stir, mix, the green polyaniline-polyvinyl alcohol solution that the solids content that makes polyaniline is 5%, standby, wherein, the mass ratio of polyaniline and polyvinyl alcohol (PVA) is 1:1);

3.2 first in one end of PET base material, along its Width, to stick width be 7mm protective tapes; Then adopt spin coating instrument by green polyaniline-polyvinyl alcohol solution coat on polyethylene terephthalate (PET) base material, then (relative humidity is less than 20% the PET basalis that has been coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 ℃) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET basalis, make diffusion layer 12, the thickness of wherein controlling diffusion layer 12 is 20 ± 0.2 μ m, makes just base of intelligent label;

3.3 cut just base of intelligent label, making the base material length after cutting is 30mm, width is 15mm, and wherein, protective tapes is positioned at one end of base material, diffusion layer and protective tapes are arranged along the length direction of base material, the length of diffusion layer is 25mm, and the length of protective tapes is 5mm, removes protective tapes, form protection trough, obtain intelligent label sample;

3.4 according to diffusant the rate of propagation on diffusion layer, opposite side at basalis 11, the one side that is not coated with polyaniline-polyvinyl alcohol is printed the time scale scale 3 of the time that represents, wherein, the starting point of time scale scale 3 is consistent with the starting point of diffusion layer 12, also consistent with the terminal of protection trough, the reference shelf-life as product to be instructed, make exposed label;

3.5 are placed in exposed label on plastic packaging machine, and diffusant carrier 5 nonwoven fabrics are placed in protection trough, with thermoplastic by exposed intelligent label with to be placed in the protection trough of exposed label diffusant carrier package inner at thermoplastics, be about to exposed label and diffusant carrier is wrapped in thermoplastics inside, the thermoplastics that is wrapped in exposed label and diffusant carrier outside is the shell 13 of intelligent label 1;

Diffusant inlet 15 is offered in the position of the diffusant carrier 5 on the corresponding basalis 11 in 3.6 one end at shell 13, then uses seal (UV glue) 16 to be sealed, and obtains.

Four, chemical intelligent label using method

4.2 open the seal 16 on intelligent label 1, open diffusant inlet 15, expose the diffusant carrier 5 of intelligent label;

The 4.3 NaOH solution (being diffusant 2) that are 0.01mol/L by concentration, drop on diffusant carrier 5 from the diffusant inlet 15 of opening, then with seal 16 by 15 sealings of diffusant inlet.

Diffusion agent N aOH solution, in the middle diffusion of label 1, as shown in figure 14, reacts quality and the shelf-life of product to be indicated according to the distance of diffusion.

Embodiment 11

One, chemical intelligent label

Except the shell 13 of chemical intelligent label 1 is positioned at the outside of described diffusion layer 12, diffusant carrier 5, only fit tightly with diffusion layer 12, the surrounding of diffusant carrier 5, upper surface, be wrapped in the outside of described diffusion layer 12, diffusant carrier 5,

outside diffusion layer

12,5 sealings of diffusant carrier, all the other are identical with embodiment 10, as shown in figure 15.

Two, chemical intelligent label assembly

Identical with embodiment 10.

Three, prepare chemical intelligent label

Except with thermoplastic, the surrounding of the diffusion layer of exposed intelligent label 12, diffusant carrier 5, upper surface being carried out plastic packaging on plastic packaging machine, all the other are identical with embodiment 10.

Four, chemical intelligent label using method

Identical with embodiment 10

Embodiment 12

One, chemical intelligent label

Except the time scale scale 3 of chemical intelligent label 1 is positioned at the same side of basalis 11 with diffusion layer 12, all the other are identical with embodiment 10.

Two, chemical intelligent label assembly

Identical with embodiment 10

Three, prepare chemical intelligent label

3.4 adopt spin coating instrument that green polyaniline-polyvinyl alcohol solution coat has been printed to time scale scale 3 one sides at PET base material, then (relative humidity is less than 20% the base material after coating to be put into exsiccator, temperature is 15-30 ℃) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET basalis, make diffusion layer 12, the thickness of wherein controlling diffusion layer 12 is 20 ± 0.2 μ m, makes just base of intelligent label;

3.6 are placed in exposed label on plastic packaging machine, and diffusant carrier 5 nonwoven fabrics are placed in protection trough, with thermoplastic by exposed label with to be placed in the protection trough of exposed label diffusant carrier package inner at thermoplastics, be about to exposed label and diffusant carrier is wrapped in thermoplastics inside, the thermoplastics that is wrapped in exposed label and diffusant carrier outside is the shell 13 of intelligent label 1;

Diffusant inlet is offered in the position of 3.7 diffusant carriers 5 on the shell 13 corresponding basalises 11 in one end, then with seal sealing, obtains.

Four, chemical intelligent label using method

Identical with embodiment 10.

Record case to time-temperature after test example 1 chemical intelligent label of the present invention activates

After in the NaOH solution that is 0.1mol/L by concentration (being diffusant 2) inhalation syringe, with syringe along the length direction perpendicular to intelligent label 1 pierce through the embodiment of the present invention 1 preparation the shell 3 of chemical intelligent label, perforation position is positioned at the top of intelligent label 1, it is the top of diffusion layer 12, this position is consistent with the start position of time scale scale 3, in intelligent label 1, inject diffusion agent N aOH solution, activate intelligent label of the present invention, then perforation position is sealed, then intelligent label 1 is placed in successively at 23 ± 2 ℃ standing 10 hours, at 5 ± 2 ℃ standing 40 hours, at 23 ± 2 ℃ standing 60 hours again, and record is along with Time-temperature changes, the distance of the movement of blue-green diffuse interface 14 in chemistry intelligent label, draw under different temperatures, the time-distance graph that blue-green diffuse interface 14 moves, as shown in figure 15.

As can be seen from Figure 15, after chemical intelligent label is activated, in temperature, be under the condition of 23 ± 2 ℃, diffuse interface 14 has moved 4mm in the 10h starting, and translational speed is 0.4mm/h; In temperature, be that under 5 ± 2 ℃ of conditions, diffuse interface 14 has moved 2mm in 40h subsequently, translational speed is 0.05mm/h; In temperature, be that under the condition of 23 ± 2 ℃, diffuse interface 14 has moved 3.5mm in follow-up 60h, translational speed is 0.058mm/h.

Experimental result shows, intelligent label prepared by the present invention is under condition of different temperatures, and rate of propagation is different, and under higher temperature conditions, rate of propagation is fast, and under lower temperature conditions, rate of propagation is slow.The movement law of polyaniline moving boundary meets the theory that molecule spreads under different temperatures, illustrate that this label is effective, can be by the length of polyaniline translational speed and displacement in the present invention and the shelf-life of product to be indicated, term of validity etc. to combining, in order to indicate the quality time limit of product.

Chemical intelligent label assembly prepared by test example 2 the present invention is the application on the shelf-life at indication boxed milk

At room temperature the shelf-life of (20～25 ℃) is 100h to fresh boxed milk

1) the chemical intelligent label 1 of embodiment 1 preparation is affixed on the external packing box 4 of boxed milk, the basalis 11 of label is close to the surface of milk external packing box;

2) the NaOH solution (being diffusant 2) that is 0.1mol/L by syringe absorption concentration is in syringe, then with syringe, the starting point of the time scale scale 3 of intelligent label 1 31 position shells 13 are pierced through, and the NaOH solution of about 0.5mL (being diffusant 2) is injected on the diffusion layer 12 of intelligent label 1, activate intelligent label 1;

3) with fluid sealant, the position sealing that device pierces through will be injected on shell 13;

4) boxed milk that posts intelligent label is placed on successively to temperature for being placed in lower 10 hours, 7 ℃ temperature of lower 15 hours, 22 ℃ temperature of lower 25 hours, 5.5 ℃ temperature of 22 ℃ of temperature lower 10 hours, observe the change in location of the blue-green diffuse interface 14 of diffusion layer 12 on chemical intelligent label 1, record is along with Time-temperature changes, the distance of the movement of blue-green diffuse interface 14 in chemistry intelligent label, draw under different temperatures, the time-distance graph that blue-green diffuse interface 14 moves, as shown in figure 16.

When blue-green diffuse interface 14 exists, take blue-green diffuse interface as separatrix, the blue region on diffusion layer 12 represents the time that boxed milk lives through, green area represents the remaining shelf life of boxed milk; When diffusion layer 12 all becomes blueness, show that milk has passed through the shelf-life, no longer fresh, do not advise eating.

As can be seen from Figure 16, after chemical intelligent label is activated, in temperature, be under 22 ℃ of conditions, blue-green diffuse interface 14 has moved 7mm in the 25h starting; Under 5.5 ℃ of conditions, blue-green diffuse interface 14 has moved 0.8mm in 15h; Again being placed in temperature is that under 22 ℃ of conditions, blue-green diffuse interface 14 has moved 1mm in 10h; In temperature, be under 7 ℃ of conditions, blue-green diffuse interface 14 has moved 0.5mm in follow-up 10h, under high temperature, blue-green interface movement is fast, under low temperature, blue-green interface movement is slow, along with the variation of time, the displacement at blue-green interface 14 is constantly increasing (as shown in figure 16), and very visual indication goes out the remaining shelf life of boxed milk.

Claims

1. a chemical intelligent label (1), integral body is rectangle, and it is characterized in that, comprises basalis (11), diffusion layer (12), shell (13) and time scale scale (3), wherein:

Described basalis (11) is by insulating and transparent material forms; Described diffusion layer (12) and time scale scale (3) are arranged on the surface of described basalis;

Described shell (13) is by described basalis (11) and diffusion layer (12) sealing;

The starting point of described time scale scale (3) is corresponding with the position on a top of diffusion layer (12).

2. a chemical intelligent label (1), integral body is rectangle, and it is characterized in that, comprises basalis (11), diffusion layer (12), shell (13), time scale scale (3), diffusant carrier (5), wherein:

Described basalis (11) is by insulating and transparent material forms; Described diffusion layer (12), diffusant carrier (5) and time scale scale (3) are arranged on the surface of basalis, and described diffusion layer (12), diffusant carrier (5) are positioned at the same side of basalis (11);

Described shell (13) is by described basalis (11), diffusion layer (12) and diffusant carrier (5) sealing;

Described diffusant carrier (5) is arranged along the length direction of diffusion layer (12), is positioned at a top of diffusion layer (12);

The starting point of described time scale scale (3) is corresponding with the position on the top that diffusion layer (12) and diffusant carrier (5) join.

3. a chemical intelligent label (1), integral body is rectangle, it is characterized in that, comprise seal (16) and the time scale scale (3) of basalis (11), diffusion layer (12), shell (13), diffusant inlet (15), sealing diffusant inlet (15), wherein:

Described basalis (11) is by insulating and transparent material forms; Described diffusion layer (12) and time scale scale (3) are arranged on described basalis surface;

The starting point of described time scale scale (3) is corresponding with the position on a top of diffusion layer (12);

It is upper that described diffusant inlet (15) is opened in shell (13), and its position is corresponding with the starting point of described time scale scale (3).

4. a chemical intelligent label (1), integral body is rectangle, it is characterized in that, the seal (16), time scale scale (3) and the diffusant carrier (5) that comprise basalis (11), diffusion layer (12), shell (13), diffusant inlet (15), sealing diffusant inlet (15), wherein:

The starting point of described time scale scale (3) is corresponding with the position on the top that diffusion layer (12) and diffusant carrier (5) join;

It is upper that described diffusant inlet (15) is opened in shell (13), and the position of its setting is corresponding with the starting point of described time scale scale (3).

5. a chemical intelligent label assembly, it is characterized in that comprising as arbitrary in claim 1-4 as described in chemical intelligent label (1) and diffusant (2), wherein said diffusant (2) is selected the alkaline solution that concentration is 0.001-1mol/L.

6. a using method for intelligent label assembly as claimed in claim 5, is characterized in that, described diffusant is joined to corresponding the locating on diffusion layer (12) of start position of the time scale scale (3) in described intelligent label (1).

7. the preparation method of chemical intelligent label as claimed in claim 1, is characterized in that comprising as follows step in sequence:

2) conduction-water-soluble polymers mixed solution is coated on to the surface of described basalis (11) one sides, is then dried, form described diffusion layer (12), then cut into the label sample of corresponding size;

3) opposite side of the basalis (11) of the label sample after cutting is printed described time scale scale (3) or time scale scale (3) is affixed on to the opposite side of basalis (11), the starting point of described time scale scale (3) is consistent with one end of diffusion layer (12), makes exposed label;

4) with thermoplastic or UV glue, exposed label is sealed, the thermoplastic or the UV glue that are wrapped in exposed label outside form described shell (13), obtain.

8. the preparation method of chemical intelligent label as claimed in claim 2, is characterized in that comprising as follows step in sequence:

9. the preparation method of chemical intelligent label as claimed in claim 3, is characterized in that comprising as follows step in sequence:

1) polyaniline solutions and poly-vinyl alcohol solution are mixed, make polyaniline-polyvinyl alcohol solution;

2) surface in described basalis (11) by polyaniline-polyvinyl alcohol solution coat, is then dried, and then cuts into the label sample of corresponding size;

3) opposite side of the basalis (11) of the label sample after cutting is printed described time scale scale (3), and the starting point of described time scale scale (3) is consistent with one end of diffusion layer (12), makes exposed label;

4) with thermoplastic or UV glue, exposed label is sealed, the thermoplastic or the UV glue that are wrapped in exposed label outside form described shell (13);

5) in one end of described shell (13), corresponding to the start position of described time scale scale (3), offer described diffusant inlet (15), then use seal (16) to be sealed, obtain.

10. the preparation method of chemical intelligent label as claimed in claim 4, is characterized in that comprising as follows step in sequence: