CN103578350B

CN103578350B - A kind of chemical intelligent label assembly and preparation method thereof

Info

Publication number: CN103578350B
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: 2016-01-06
Anticipated expiration: 2033-06-13
Also published as: CN103578350A

Abstract

The invention discloses a kind of chemical intelligent label assembly and preparation method thereof, described chemical intelligent label assembly comprises label (1) and diffusant (2), wherein said label is made up of basalis (11), the diffusion layer (12) being closely superimposed upon substrate surface, shell (13), and described diffusant adds from the side of diffusion layer when activating label.The preparation method of chemical intelligent label of the present invention is simple, and cost is low, can effectively monitor food quality.

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

Under the storage requirement that shelf-life of food, to be prepackaged food indicated at label, keep the time limit of quality.Within this time limit, product is suitable for selling completely, and keeps the peculiar quality that need not illustrate in label or illustrate.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 change etc. all may occur at one time, and more extraneous conditions such as temperature, humidity also can affect the carrying out of these reactions, especially the impact of temperature on the shelf-life is most important.The existing judgement Main Basis that whether can also eat food is the shelf-life of the upper printing of packaging, but in the whole accumulating stage, temperature has immeasurability, the date of therefore printing can not the quality condition of reactor product really, need the food of refrigeration in transportation, do not use the chill car of regulation than if any some, food will be caused to go bad within the maintenance phase of packaging for foodstuff, the pregnant woman's miscarriage caused thus and food poisoning happened occasionally in recent years, this proposes stern challenge to China's food-safety problem, in the modern society that various food quality problem takes place frequently, we more should focus on food-safety problem, improve the quality of living.

Time-temperature indicator (Time-TemperatureIndicator, TTI) be a kind of that be easy to measure or observe with time, simple device that temperature variation is relevant, its change reflection food whole process or the temperature conditions residing for 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.Its reaction principle have machinery, chemistry, galvanochemistry, enzyme reaction, the aspect such as microorganism irreversible change, this change and temperature correlation, and be accumulation continuously, the result of change is finally usual to be reflected as color changes with visible materialization phenomenon.

TTI device just put forward before more than 40 year, and be applied on the biological products vaccine that need refrigerate, 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 of business mainly contains three classes in the world at present: the first kind is the 3MMonitorMark of 3M company, it is a kind of TTI utilizing diffusion principle, depend on the color reaction that chemical substance wherein occurs in the process of diffusive migration, namely be responsively worth by the diffusion length of coloured fatty acid ester on the porous refill that water absorptivity is excellent and record temperature over time, when the fusing point of storage temperature lower than ester matter, indicator does not respond; When the fusing point of storage temperature higher than ester matter, indicator then 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 VistabCheckPoint of VITSAB company, the principle of this TTI based on a kind of lipid substrates, enzymatic hydrolysis occurs under controlled conditions to make pH reduce thus cause the color of acid base indicator to change, temperature is higher, the speed of the proton of enzymatic lipid substrate hydrolysis release is faster, and its color changes along with change greatly also occurs in the prolongation of time; The FreshCheck of the 3rd Lei Shi LifeLinesTechnology company, its principle is chemical polymerization, form coloured polymkeric substance, temperature variation is recorded by the color change produced after forming opaque colored polymkeric substance after utilizing colourless alkynes class monomer solid phase-polymerization, polyreaction raises along with temperature and accelerates, thus causing indicator color to deepen sooner, this time-temperature indicator is necessary freezing before use, in order to avoid reacting activation.

The instruction of above type has different limitation respectively.As the time-temperature indicator for response type, need encapsulation gas or liquid on the one hand, need to do to separate with lipid film, after temperature exceedes the fusing point of lipid film, two kinds of material mixing carry out chemical reaction again.Temperature impact on the one hand before lipid film does not have breakage can not record, its two, once reaction, its boundary reacted completely not easily defines.Generally comparatively suitable as a kind of indicator that can not exceed certain temperature, can not the combined influence of reflecting time and temperature comprehensively.For the product of the 3M company of diffused, it can the factor of well generalized time and temperature, but can there occurs the different and segregation phenomenon caused of rate of propagation when spreading due to water in solution and pigment on porous paper, and 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, the Study and appliance of people to TTI is in the ascendant, constantly has new patent to occur.Such as:

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, pigment can be contained in diffusion liquid, 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 is spread to diffusion layer by capillary line, its diffusion length was determined by environment temperature and diffusion time, be suitable for goods in storage, monitoring in transportation, but this indicating label production process is very complicated.

The patent No. be 200910227305.5 patent of invention disclose 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 colorant again and be fully mixed and made into indicator, and then super low temperature makes it be formed to solidify state, the indicator after solidifying is contacted with dispersive medium and makes indicating card.When environment temperature is higher than indicator fusing point, namely indicator thawing is " activated ", and then will spread along dispersive medium, and just can be known 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, and realization regulates and controls the critical temperature of indicator between-3 ~-15 DEG C, to adapt to the needs of different frozen food.But this indicating card can only be used for the Time-temperature instruction of frozen food, and preparation section is complicated, and consumer is difficult to wherein the recorded information of reading directly perceived.

Summary of the invention

The object of the invention is the technical matters for existing in existing effective period of food quality indicating label, a kind of chemical intelligent label, label assembly and preparation method thereof are provided, chemical intelligent label assembly of the present invention utilizes electrolyte solution diffusion in the polymer and chemical doping to cause the color of polymkeric substance to change this principle to realize monitoring to food quality, chemical intelligent label prepared by the present invention, preparation section is simple, with low cost, containing time-temperature indicator function, may be used 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 entirety to be rectangle, comprises basalis, diffusion layer, shell and time scale scale, wherein:

Described basalis is by insulate 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 be made up of the first polymkeric substance and the second polymkeric substance, wherein, and the one in described first polymeric oxidizer salt state polyaniline, polypyrrole or PEDOT; One in second polymeric oxidizer polyvinyl alcohol (PVA), hydroxyethyl cellulose, branched starch, shitosan.

Particularly, described first polymeric oxidizer salt state polyaniline; Second polymeric oxidizer polyvinyl alcohol (PVA).

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

Especially, described first polymeric oxidizer conducting polymer; Described second polymeric oxidizer water-soluble polymers.

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

Wherein, described shell selects transparent transparent thermoplastic material or UV glue.

Particularly, described transparent thermoplastic material is selected from tygon, polypropylene, Polyvinylchloride, polystyrene, polyoxymethylene, poly-carbonic acid junket, the one 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 the step that following order is carried out:

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

2) conduction-water-soluble polymers mixed solution is coated on the surface of described basalis side, then carries out drying process, 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 prints described time scale scale, and the starting point of described time scale scale is consistent with one end of diffusion layer, obtained exposed label;

4) with thermoplastic or UV glue by exposed evident seal, be wrapped in thermoplastic outside exposed label or UV glue forms described shell, obtain final product.

Wherein, described conducting polymer select in polyaniline, polypyrrole, poly-3,4-ethylene dioxythiophene one or more, be preferably polyaniline; Described water-soluble polymers selects base cellulose, branched starch, one or more in shitosan, polyvinyl alcohol (PVA), is 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 mass ratio of the polyaniline in described polyaniline solutions and the polyvinyl alcohol (PVA) in poly-vinyl alcohol solution is 1-10:1, is preferably 1-2:1.

Wherein, step 2) described in dry process be that the base layer material being coated with polymer solution is placed in exsiccator, be less than 20% in relative humidity, temperature is dry 12-24 hour under the condition of 15-30 DEG C, obtains polymkeric substance dry film, i.e. obtained diffusion layer; Thermoplastic described in step 4) is selected from tygon, polypropylene, Polyvinylchloride, polystyrene, polyoxymethylene, poly-carbonic acid junket, the one in polyamide, acrylic acid.

Particularly, the mode of dip-coating or spin coating is adopted polyaniline-polyvinyl alcohol solution to be coated on the surface of described basalis.

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

Wherein, described diffusant selects 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 the diffusion layer of starting point to correspondence described diffusant being joined time scale scale in described intelligent label.

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

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

Described basalis is by insulate 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 basalis, diffusion layer and diffusant carrier seal by described shell; Described diffusant carrier arranges 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 diffusant carrier connects with diffusion layer.

Wherein, described diffusant carrier selects 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, the surface that described diffusion layer, diffusant carrier and time scale scale are arranged on the surface of described basalis the same side or described diffusion layer, diffusant carrier is arranged on described basalis side, time scale scale are arranged on the surface of 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 the step that following order is carried out:

2) after basalis side arranges boundary belt, conduction-water-soluble polymers mixed solution is coated on the side of the basalis being provided with boundary belt, dry, form described diffusion layer, obtained intelligent label just base;

3) intelligent label just base is cut, make the label sample of corresponding size, wherein the boundary belt of intelligent label sample is positioned at one end of label sample, removing 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 prints described time scale scale (3) or time scale scale (3) is affixed on the opposite side of basalis (11), the starting point of described time scale scale (3) is consistent with one end of diffusion layer (12), obtained 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 vector outside form described shell (13), to obtain final product.

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

Another aspect of the invention provides a kind of using method of above-mentioned intelligent label assembly, comprises and to be joined by described diffusant 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 entirety to be rectangle, comprises basalis, diffusion layer, shell, diffusant inlet, the seal closing diffusant inlet and time scale scale, wherein:

Described basalis is by insulate and transparent material forms; Described diffusion layer and time scale scale are arranged on described substrate 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 be opened in seal described diffusion layer side shell on.

2) conduction-water-soluble polymers mixed solution is coated on the surface of described basalis side, then carries out drying process, then cut into the label sample of corresponding size;

4) with thermoplastic or UV glue by exposed evident seal, be wrapped in thermoplastic outside exposed label or UV glue forms described shell;

5) one end of the shell in sealing diffusion layer side, the start position corresponding to described time scale scale offers described diffusant inlet, is then closed with seal, to obtain final product.

Wherein, described diffusant is joined 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 entirety to be rectangle, comprises basalis, diffusion layer, shell, diffusant inlet, the seal closing diffusant inlet, time scale scale and diffusant carrier, wherein:

Described basalis is by insulate 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 basalis, diffusion layer and diffusant carrier seal by described shell; Described diffusant carrier arranges 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 diffusant carrier connects with diffusion layer; Described diffusant inlet is opened on shell, and its position arranged 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 side.

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

6) in one end of described shell (13), the start position corresponding to described time scale scale (3) offers described diffusant inlet (15), then uses seal (16) to be closed, to obtain final product.

Another aspect of the invention provides a kind of chemical intelligent label assembly, comprises chemical intelligent label described above and diffusant, and wherein said diffusant selects concentration to be the alkaline solution of 0.001-1mol/L.

Wherein, described alkaline solution selects NaOH solution, KOH solution, Ca (OH) ₂the alkaline electrolyte solution such as solution, ammoniacal liquor, preferred NaOH solution.

Particularly, concentration is selected to be the NaOH solution of 0.1mol/L.

Diffusant is dripped in one end (namely corresponding with time scale scale starting point one end) of diffusion layer, diffusant spreads in diffusion layer, because diffusion layer is aqueous salt state polyaniline mixed film, after itself and diffusant adulterate, generation color changes, according to the change of diffusant Distance geometry color of movement in diffusion layer, indicate the temperature variation experienced 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 determines according to the shelf-life of product to be instructed, that is, 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, thus the time be diffused into needed for the other end from one end of diffusion layer by diffusant is equal with the shelf-life of product to be instructed.

Tool of the present invention has the following advantages:

1, the chemical tags that prepared by the present invention is only made up 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 in order to indicate the length of diffusion time, can indicate 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 indicates the shelf-life of different food products or medicine by the ratio controlling polyaniline and aqueous polymer, simple, convenient, effective.

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

5, in the present invention, the rate of propagation of diffusant in diffusion layer can be regulated by the proportion of composing of first, second polymkeric substance in diffusion layer, diffusant can be regulate to the scope of several months or several years for several minutes the diffusion time in diffusion layer, 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 chemical intelligent label of the embodiment of the present invention 7;

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 chemical intelligent label of the embodiment of the present invention 10;

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 figure after chemical intelligent label activates by test example 1 of the present invention.

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

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

Further describe the present invention below in conjunction with specific embodiment, advantage and disadvantage of the present invention will be more clear along with description.But these embodiments are only exemplary, do not form any restriction to scope of the present invention.It will be understood by those skilled in the art that and can modify to the details of technical solution of the present invention and form or replace down without departing from the spirit and scope of the present invention, but these amendments 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 entirety of the present invention is in cuboid-type, and the basalis 11 be made up of insulating material, the diffusion layer 12 being arranged on basalis 11 surface, shell 13, time scale scale 3 form.Wherein:

Time scale scale 3 is indicated in the side of basalis 11; 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 is equal; 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 the surrounding of the surrounding of diffusion layer 12, upper surface and basalis 11, lower surface, be wrapped in the outside of described diffusion layer 12 and basalis 11, diffusion layer 12 and basalis 11 are sealed.

Basalis 11, diffusion layer 12 are in cuboid-type, 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 11 in the present embodiment selects polyethylene terephthalate (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 12 described in the present invention 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 12 described in the present invention is except selecting polyaniline-polyvinyl alcohol potpourri, and other water-soluble polymerss are as hydroxyethyl cellulose, branched starch, and shitosan etc. all can be used in combination with polyaniline.Except selecting polyaniline, other conducting polymers such as polypyrrole, poly-3,4-ethylene dioxythiophene also can replace polyaniline to use.

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

Two, chemical intelligent label assembly

Chemical intelligent label assembly of the present invention is made up of intelligent label 1 and diffusant 2, when intelligent label uses, with be equipped with diffusant 2 syringe will sealing diffusion layer side and the shell 13 corresponding with time scale scale starting point place pierce through and inject diffusant, diffusant spreads in diffusion layer 12, diffusant is the distance of movement, the change of color in diffusion layer, indicate the temperature variation experienced 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 namely activating as shown in Figure 3.

The NaOH solution that the diffusant 2 used in intelligent label assembly of the present invention selects concentration to be 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, preparative chemistry intelligent label

3.1 by solids content be 10% polyaniline aqueous solution join same volume, solids content is in the polyvinyl alcohol water solution of 10%, stir, mix, the solids content of obtained polyaniline is the green polyaniline-polyvinyl alcohol solution of 5%, for subsequent use, 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 other solids contents are that the polyaniline aqueous solution of 5-20% is also applicable to the present invention; The solids content of polyvinyl alcohol water solution is 10%, and other solids contents are that the polyvinyl alcohol water solution of 5-20% is also applicable to the present invention.

The present invention utilizes electrolyte solution diffusion in the polymer and chemical doping occurs and reacts the principle causing color to change and carry out time, temperature monitoring to product to be instructed, wherein, electrolyte solution in the polymer diffusion length with diffusion time and temperature variation, can the reaction time, temperature build effect; Meanwhile, electrolyte solution and conducting polymer generation doping reaction is utilized to cause conducting polymer color to change the distance of the movement indicating diffuse interface.Can there is the material of color change in other, as polypyrrole, poly-3,4-ethylene dioxythiophene (PEDOT) etc. are all applicable to the present invention by acid or alkaline electrolyte doping.

The object that the present invention adds water-soluble polymers in conducting polymer (as polyaniline, polypyrrole, poly-3,4-ethylene dioxythiophene) accelerates diffusant (i.e. alkaline solution) rate of propagation in diffusion layer.The potpourri dry film selecting polyvinyl alcohol (PVA) and polyaniline in the embodiment of the present invention is diffusion layer, adds polyvinyl alcohol (PVA) and accelerate the rate of propagation of NaOH solution in diffusion layer in polyaniline.The present invention except adding except poly-vinyl alcohol solution in polyaniline solutions, and other water-soluble polymer solutions, as hydroxyethyl cellulose solution, branched 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, increase the mass ratio of 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), the rate of propagation of adjustment diffusant, the time that diffusant is diffused into required for the other end from one end of diffusion layer is equal 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 polyethylene terephthalate (PET) base material side in the mode of spin coating, then (relative humidity is less than 20% the PET base material being coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 DEG C) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET base layer, i.e. obtained diffusion layer 12, the thickness wherein controlling diffusion layer 12 is 20 ± 0.2 μm, obtained intelligent label just base,

By coating method, polyaniline-polyvinyl alcohol solution is coated on the surface of described basalis 11 in the present invention, dry formed in the process of polyaniline-polyvinyl alcohol rete exsiccator inner drying time >=8h, the relative humidity wherein in exsiccator is less than 20%, baking temperature is 15-30 DEG C.

The base material (PET) used in the embodiment of the present invention 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 namely 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 the rate of propagation of diffusant on diffusion layer, and at the back side of basalis 11, the one side not namely being coated with polyaniline-polyvinyl alcohol prints the time scale scale 3 of the time that represents, as the reference shelf-life of product to be instructed, and obtained exposed label;

Exposed label is placed on plastic packaging machine by 3.5, with thermoplastic, exposed intelligent label is encapsulated in thermoplastics inside, be wrapped in thermoplastics inside by exposed label, obtain intelligent label 1, the thermoplastics being wrapped in exposed label outside is the shell 13 of intelligent label 1.

The present invention except with thermoplastic by whole for exposed label plastic packaging except thermoplastic inside, can also with thermoplastic by the whole plastic packaging of other parts except basalis 11, form thermoplastics and shell 13 and seal except diffusion layer 12 and basalis 11 fit tightly other parts of side.

The present invention carries out except plastic packaging except adopting thermoplastics to label, and ultraviolet cured adhesive (or UV glue) can also be adopted to seal label, such as, purchased from the UV glue of Gu Tuo Electron Material Co., Ltd of Shenzhen.

Four, chemical intelligent label using method

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

4.2 draw with syringe the NaOH solution (i.e. 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 13 of intelligent label 1 is pierced through, then NaOH solution is injected on the diffusion layer 12 of intelligent label;

4.3 shell 13 will be injected the position sealing that device pierces through with fluid sealant.

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

Diffusion agent N aOH solution is diffusion in polyaniline-polyvinyl alcohol dry film (i.e. diffusion layer 12), diffusion layer becomes blue by green, the diffuse interface 14 of a blue-green is formed in diffusion layer 12, 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 of diffuse interface 14 movement of blue-green is just set up with the time and is contacted, thus reactor product quality and shelf-life intuitively.

Embodiment 2

One, chemical intelligent label

Shell 13 except chemical intelligent label 1 is positioned at the outside of described diffusion layer 12, and only fit tightly with the surrounding of diffusion layer 12, upper surface, be wrapped in the outside of described diffusion layer 12, outside being sealed by diffusion layer 12, 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 is except identical with the size of diffusion layer 12, can also be greater than the size of diffusion layer 12.

Two, chemical intelligent label assembly

Identical with embodiment 1

Three, preparative chemistry intelligent label

Except being undertaken except plastic packaging with thermoplastic by the surrounding of the diffusion layer 12 of exposed intelligent label, upper surface 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 except 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, preparative chemistry intelligent label

3.1 by solids content be 10% polyaniline aqueous solution join same volume, solids content is in the polyvinyl alcohol water solution of 10%, stir, mix, the solids content of obtained polyaniline is the green polyaniline-polyvinyl alcohol solution of 5%, for subsequent use, wherein, the volume ratio of polyaniline aqueous solution and polyvinyl alcohol water solution is 1:1.

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

3.3 adopt spin coating instrument (Shenyang Si Le company) that green polyaniline-polyvinyl alcohol solution is coated on basalis 11 have printed time scale scale 3 side, then (relative humidity is less than 20% the PET base layer being coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 DEG C) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET base layer, i.e. obtained diffusion layer 12, the thickness wherein controlling diffusion layer 12 is 20 ± 0.2 μm, obtained intelligent label just base;

3.4 by intelligent label just base (being namely 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, first for intelligent label base is encapsulated in thermoplastics inside, thermoplastics inside is wrapped in by the first base of intelligent label, obtain intelligent label 1, the thermoplastics being wrapped in the first base outside of intelligent label 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 entirety of the present invention is in cuboid-type, the basalis 11 be made up of insulating material, the diffusion layer 12 being arranged on basalis 11 surface, shell 13, diffusant inlet 15, the seal 16 of sealing diffusant inlet 15, time scale scale 3 form, wherein:

Indicating time scale scale 3 in the side of basalis 13, is diffusion layer 12 at its opposite side, and diffusion layer 12 and basalis 11 are combined closely, and the combine size at position of diffusion layer 12 and basalis 11 is equal; 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, be wrapped in the outside of described diffusion layer 12 and basalis 11, diffusion layer 12 and basalis 11 sealed with the surrounding of the surrounding of diffusion layer 12, upper surface and basalis 11, lower surface;

Shell 13 is offered diffusant inlet 15, diffusant inlet 15 is positioned at the end of the side of diffusion layer 12, its position arranged and the starting point of described time scale scale 3 to corresponding, when intelligent label activates, timing from the starting point of time scale scale 3;

Seal 16 is for closing diffusant inlet 15, and the size of its size and diffusant inlet 15 adapts.

During intelligent label 1 un-activation, diffusant inlet 15 is closed by seal 16, when intelligent label being affixed on the outer packaging bag indicating product, removing seal 16, open diffusant inlet 15, instillation diffusant, activates intelligent label (as shown in Figure 7), is then again closed by diffusant inlet 15 with seal 16.

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 use is identical with embodiment 1.

Two, chemical intelligent label assembly

Chemical intelligent label assembly of the present invention is made up of intelligent label 1 and diffusant 2, when intelligent label uses, the seal 16 of label 1 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 closed.Diffusant spreads in diffusion layer, according to the change of diffusant in the mobile Distance geometry color of diffusion layer, indicates the temperature variation experienced 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 namely activating as shown in Figure 7.

Three, preparative chemistry intelligent label

3.1 by solids content be 10% polyaniline aqueous solution join same volume, solids content is in the polyvinyl alcohol water solution of 10%, stir, mix, the solids content of obtained polyaniline is the green polyaniline-polyvinyl alcohol solution of 5%, for subsequent use, wherein, the mass ratio of polyaniline and polyvinyl alcohol (PVA) is 1:1;

3.2 adopt spreader (Tianjin essence section tech, 200 μm) green polyaniline-polyvinyl alcohol solution is coated on polyethylene terephthalate (PET) basalis 11 side, then (relative humidity is less than 20% the PET base layer being coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 DEG C) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET base layer, i.e. obtained diffusion layer 12, wherein the thickness of diffusion layer 12 is 20 ± 0.2 μm, obtained intelligent label just base,

Exposed label is placed on plastic packaging machine by 3.5, with thermoplastic, exposed intelligent label is encapsulated in thermoplastics inside, is wrapped in thermoplastics inside by exposed label, and the thermoplastics being wrapped in exposed label outside is the shell 13 of intelligent label 1;

3.6 in one end of the shell 13 of sealing diffusion layer side, and the start position corresponding to the time scale scale 3 on basalis 11 offers diffusant inlet 15, is then closed with seal 16, to obtain final product.

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

The present invention carries out except plastic packaging except adopting thermoplastics to label, and UV glue can also be adopted to seal label also known as UV glue (Gu Tuo Electron Material Co., Ltd of Shenzhen).

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;

Concentration is the NaOH solution (i.e. diffusant 2) of 0.01mol/L by 4.3, drops on diffusion layer 12, then closed by diffusant inlet 15 with seal 16 from the diffusant inlet 15 opened.

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

Embodiment 5

One, chemical intelligent label

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

Two, chemical intelligent label assembly

Identical with embodiment 4

Three, preparative chemistry intelligent label

Except being undertaken except plastic packaging with thermoplastic by the surrounding of the diffusion layer 12 of exposed intelligent label, upper surface 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, preparative chemistry intelligent label

3.3 adopt spreader that green polyaniline-polyvinyl alcohol solution is coated on basalis 11 have printed time scale scale 3 side, then (relative humidity is less than 20% the PET base layer being coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 DEG C) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET base layer, i.e. obtained diffusion layer 12, wherein the thickness of diffusion layer 12 is 20 ± 0.2 μm, obtained intelligent label just base;

3.4 by intelligent label just base (being namely 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 thermoplastics inside, thermoplastics inside is wrapped in by exposed label, obtain intelligent label 1, the thermoplastics being wrapped in exposed label outside is the shell 13 of intelligent label 1.

3.5 in one end of the shell 13 of sealing diffusion layer side, and diffusant inlet 15 is offered in the position corresponding to the time scale scale starting point 31 on basalis, is then closed with seal 16, to obtain final product.

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 entirety of the present invention is in cuboid-type, and the basalis 11 be made up of insulating material, the diffusion layer 12 being arranged on basalis 11 surface, shell 13, time scale scale 3, diffusant carrier 5 form.Wherein:

Time scale scale 3 is indicated in the side of basalis 11; Described diffusion layer 12 is positioned at the opposite side of described basalis 11, and combines closely with basalis 11; Diffusant carrier 5 and diffusion layer 12 are positioned at the same side of basalis 11, and combine closely each other; Diffusant carrier 5 arranges along the length direction of diffusion layer 12, is positioned at the top of diffusion layer 12; Diffusant carrier 5 is equal with the length of basalis 11 with the length sum of diffusion layer 12, and the width of diffusant carrier 5, diffusion layer 12 is equal 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, diffusion layer 12, diffusant carrier 5 is sealed with basalis 11.

Basalis 11, diffusion layer 12 are in cuboid-type, 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.Basalis 11 in the embodiment of the present invention, the material selected by diffusion layer 12 are identical with embodiment 1; Diffusant carrier 5 selects nonwoven fabrics chip, and other material such as hydrophilic polymer, the kapillary etc. of storage solutions all can be applicable to the present invention.

Two, chemical intelligent label assembly

Chemical intelligent label assembly of the present invention is made up of intelligent label 1 and diffusant 2, when intelligent label uses, with the syringe that diffusant 2 is housed, the shell 13 of diffusant carrier 5 correspondence is pierced through, then diffusant 2 is injected on diffusant carrier 5, be positioned at the top of diffusion layer 12 due to diffusant carrier 5 and combine closely with diffusion layer 12, therefore the diffusant be adsorbed in diffusant carrier 5 spreads in diffusion layer 12, indicate the temperature variation experienced 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 namely activating as shown in figure 11.

Three, preparative chemistry intelligent label

3.2 first in PET base material one end, sticking width along its Width is 7mm protective tapes, then on polyethylene terephthalate (PET) base material adopting spin coating instrument to be coated on by green polyaniline-polyvinyl alcohol solution to post protective tapes side, then (relative humidity is less than 20% the base material after coating to be put into exsiccator, temperature is 15-30 DEG C) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green in PET base material, i.e. obtained diffusion layer 12, the thickness wherein controlling diffusion layer 12 is 20 ± 0.2 μm, obtained intelligent label just base,

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

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

3.4 according to the rate of propagation of diffusant on diffusion layer, on the opposite side surface of basalis 11, namely the one side not being coated with polyaniline-polyvinyl alcohol prints 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 namely consistent with the terminal of protection trough, as the reference shelf-life of product to be instructed, obtained exposed label;

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

Four, chemical intelligent label using method

4.2 draw with syringe the NaOH solution (i.e. 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 13 of intelligent label 1 is pierced through, then NaOH solution is injected on the diffusant carrier 5 of intelligent label;

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

Embodiment 8

One, chemical intelligent label

Shell 13 except 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, preparative chemistry intelligent label

Except being undertaken except plastic packaging with thermoplastic by the surrounding of the diffusion layer 12 of exposed intelligent label, diffusant carrier 5, upper surface 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 except 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, preparative chemistry intelligent label

3.1 by solids content be 10% polyaniline aqueous solution join same volume, solids content is in the polyvinyl alcohol water solution of 10%, stir, mix, the solids content of obtained polyaniline is the green polyaniline-polyvinyl alcohol solution of 5%, for subsequent use, wherein, the mass ratio of polyaniline water and polyvinyl alcohol (PVA) is 1:1;

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

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

3.4 adopt spin coating instrument that green polyaniline-polyvinyl alcohol solution is coated on base material have printed time scale scale 3 side, then (relative humidity is less than 20% the PET base layer being coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 DEG C) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET base layer, i.e. obtained diffusion layer 12, the thickness wherein controlling diffusion layer 12 is 20 ± 0.2 μm, obtained intelligent label just base;

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

Exposed label is placed on plastic packaging machine by 3.6; and diffusant carrier 5 nonwoven fabrics is placed in protection trough; with thermoplastic by exposed label and be placed on exposed label protection trough in diffusant carrier package inner at thermoplastics; be wrapped in thermoplastics inside by exposed label and diffusant carrier, the thermoplastics being 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 entirety of the present invention is in cuboid-type, the basalis 11 be made up of insulating material, the diffusion layer 12 being arranged on basalis 11 surface, shell 13, diffusant inlet 15, the seal 16 of sealing diffusant inlet 15, time scale scale 3, diffusant carrier 5 form, wherein:

Time scale scale 3 is indicated in the side of basalis 13, be diffusion layer 12 and diffusant carrier 5 at its opposite side, diffusion layer 12, diffusant carrier 5 are combined closely with basalis 11, and diffusant carrier 5 arranges along the length direction of diffusion layer 12, is positioned at the top of diffusion layer 12; Diffusant carrier 5 is equal with the length of basalis 11 with the length sum of diffusion layer 12, and the width of diffusant carrier 5, diffusion layer 12 is equal 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, diffusion layer 12, diffusant carrier 5 is sealed with basalis 11;

Shell 13 is offered diffusant inlet 15, and diffusant inlet 15 is positioned at one end of diffusion layer 12, and its position arranged is consistent with the position of described diffusant carrier 5;

During intelligent label 1 un-activation, diffusant inlet 15 is closed by seal 16, when intelligent label being affixed on the outer packaging bag indicating product, removing seal 16, open diffusant inlet 15, instillation diffusant, activates intelligent label (as shown in figure 14), is then again closed by diffusant inlet 15 with seal 16.

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 use is identical with embodiment 7.

Two, chemical intelligent label assembly

Chemical intelligent label assembly of the present invention is made up of intelligent label 1 and diffusant 2, when intelligent label uses, the seal 16 of label 1 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 closed.Be positioned at the top of diffusion layer 12 due to diffusant carrier 5 and combine closely with diffusion layer 12, therefore the diffusant be adsorbed in diffusant carrier 5 spreads in diffusion layer 12, indicate the temperature variation experienced 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 namely activating as shown in figure 14.

Three, preparative chemistry intelligent label

3.1 by solids content be 10% polyaniline aqueous solution join same volume, solids content is in the polyvinyl alcohol water solution of 10%, stir, mix, the solids content of obtained polyaniline is the green polyaniline-polyvinyl alcohol solution of 5%, for subsequent use, wherein, the mass ratio of polyaniline and polyvinyl alcohol (PVA) is 1:1);

3.2 first in one end of PET base material, to stick width along its Width be 7mm protective tapes; Then spin coating instrument is adopted to be coated on polyethylene terephthalate (PET) base material by green polyaniline-polyvinyl alcohol solution, then (relative humidity is less than 20% the PET base layer being coated with polyaniline-polyvinyl alcohol mixed solution to be put into exsiccator, temperature is 15-30 DEG C) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET base layer, i.e. obtained diffusion layer 12, the thickness wherein controlling diffusion layer 12 is 20 ± 0.2 μm, obtained intelligent label just base;

3.3 cut intelligent label just base, the length substrate after cutting is made to be 30mm, width is 15mm, and wherein, protective tapes is positioned at one end of base material, diffusion layer and protective tapes arrange along the length direction of base material, the length of diffusion layer is 25mm, and the length of protective tapes is 5mm, removing protective tapes, form protection trough, obtain intelligent label sample;

3.4 according to the rate of propagation of diffusant on diffusion layer, at the opposite side of basalis 11, namely the one side not being coated with polyaniline-polyvinyl alcohol prints 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 namely consistent with the terminal of protection trough, as the reference shelf-life of product to be instructed, obtained exposed label;

Exposed label is placed on plastic packaging machine by 3.5, and diffusant carrier 5 nonwoven fabrics is placed in protection trough, with thermoplastic by exposed intelligent label and be placed on exposed label protection trough in diffusant carrier package inner at thermoplastics, be wrapped in thermoplastics inside by exposed label and diffusant carrier, the thermoplastics being 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 3.6 diffusant carriers 5 on the corresponding basalis 11 in one end of shell 13, then uses seal (UV glue) 16 to be closed, to obtain final product.

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;

Concentration is the NaOH solution (i.e. diffusant 2) of 0.01mol/L by 4.3, drops on diffusant carrier 5, then closed by diffusant inlet 15 with seal 16 from the diffusant inlet 15 opened.

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

Embodiment 11

One, chemical intelligent label

Shell 13 except 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, diffusant carrier 5 are sealed, all the other are identical with embodiment 10, as shown in figure 15.

Two, chemical intelligent label assembly

Identical with embodiment 10.

Three, preparative chemistry intelligent label

Except being undertaken except plastic packaging with thermoplastic by the surrounding of the diffusion layer 12 of exposed intelligent label, diffusant carrier 5, upper surface 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 except 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, preparative chemistry intelligent label

3.4 adopt spin coating instrument that green polyaniline-polyvinyl alcohol solution is coated on PET base material have printed time scale scale 3 side, then (relative humidity is less than 20% the base material after coating to be put into exsiccator, temperature is 15-30 DEG C) in dry 12-24 hour, polyaniline-polyvinyl alcohol forms the polyaniline-polyvinyl alcohol potpourri dry film of one deck green on PET base layer, i.e. obtained diffusion layer 12, the thickness wherein controlling diffusion layer 12 is 20 ± 0.2 μm, obtained intelligent label just base;

Exposed label is placed on plastic packaging machine by 3.6, and diffusant carrier 5 nonwoven fabrics is placed in protection trough, with thermoplastic by exposed label and be placed on exposed label protection trough in diffusant carrier package inner at thermoplastics, be wrapped in thermoplastics inside by exposed label and diffusant carrier, the thermoplastics being 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 corresponding basalis 11 in shell 13 one end, then closes with seal, to obtain final product.

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

By concentration be 0.1mol/L NaOH solution (i.e. diffusant 2) inhalation syringe in after, with syringe along the length direction perpendicular to intelligent label 1 pierce through prepared by the embodiment of the present invention 1 the shell 3 of chemical intelligent label, perforation position is positioned at the top of intelligent label 1, the i.e. top of diffusion layer 12, this position is consistent with the start position of time scale scale 3, diffusion agent N aOH solution is injected in intelligent label 1, activate intelligent label of the present invention, then perforation position is sealed, then 10 hours are left standstill at intelligent label 1 being placed in 23 ± 2 DEG C successively, 40 hours are left standstill at 5 ± 2 DEG C, 60 hours are left standstill again at 23 ± 2 DEG C, and record is along with Time-temperature change, the distance of the movement of blue-green diffuse interface 14 in chemistry intelligent label, under drawing different temperatures, the time-distance graph of blue-green diffuse interface 14 movement, as shown in figure 15.

As can be seen from Figure 15, after chemical intelligent label is activated, be under the condition of 23 ± 2 DEG C in temperature, diffuse interface 14 moves 4mm in the 10h started, and translational speed is 0.4mm/h; Under temperature is 5 ± 2 DEG C of conditions, diffuse interface 14 moves 2mm in 40h subsequently, and translational speed is 0.05mm/h; Be that under the condition of 23 ± 2 DEG C, diffuse interface 14 moves 3.5mm in follow-up 60h in temperature, 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 at different temperatures, illustrate that this label is effective, can by the length of polyaniline translational speed and displacement in the present invention with wait that the shelf-life, the term of validity etc. that indicate product are to combining, in order to indicate the quality time limit of product.

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

The shelf-life of fresh boxed milk at room temperature (20 ~ 25 DEG C) is 100h

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

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

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

4) boxed milk posting intelligent label is placed on successively temperature for being placed in 22 DEG C of temperature lower 25 hours, 5.5 DEG C temperature lower 15 hours, 22 DEG C temperature lower 10 hours, 7 DEG C 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 along with Time-temperature change, the distance of the movement of blue-green diffuse interface 14 in chemistry intelligent label, under drawing different temperatures, the time-distance graph of blue-green diffuse interface 14 movement, as shown in figure 16.

When blue-green diffuse interface 14 exists, with blue-green diffuse interface for separatrix, the blue region on diffusion layer 12 represents the time that boxed milk lives through, and green area represents the remaining shelf life of boxed milk; When diffusion layer 12 all becomes blueness, show that milk have 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, under temperature is 22 DEG C of conditions, blue-green diffuse interface 14 moves 7mm in the 25h started; Under 5.5 DEG C of conditions, blue-green diffuse interface 14 moves 0.8mm in 15h; Again being placed in temperature is that under 22 DEG C of conditions, blue-green diffuse interface 14 moves 1mm in 10h; Under temperature is 7 DEG C of conditions, blue-green diffuse interface 14 moves 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 change 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 preparation method for chemical intelligent label, is characterized in that comprising following step of sequentially carrying out:

2) conduction-water-soluble polymers mixed solution is coated on the surface of basalis (11) side, then carries out drying, form diffusion layer (12), then cut into the label sample of corresponding size;

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

4) with thermoplastic or UV glue by exposed evident seal, be wrapped in thermoplastic outside exposed label or UV glue forms shell (13), obtain final product;

Wherein said chemical intelligent label entirety is rectangle, comprise basalis (11), diffusion layer (12), shell (13) and time scale scale (3), described basalis (11) is by insulate 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 preparation method for chemical intelligent label, is characterized in that comprising following step of sequentially carrying out:

2) after basalis side arranges boundary belt, conduction-water-soluble polymers mixed solution is coated on the side of the basalis being provided with boundary belt, dry, form diffusion layer, obtained intelligent label just base;

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

4) opposite side time-write interval graduated scale (3) of the basalis (11) of the label sample after cutting or time scale scale (3) is affixed on the opposite side of basalis (11), the starting point of described time scale scale (3) is consistent with one end of diffusion layer (12), obtained 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 vector outside form shell (13), to obtain final product;

Wherein said chemical intelligent label entirety is rectangle, comprise basalis (11), diffusion layer (12), shell (13), time scale scale (3), diffusant carrier (5), wherein: described basalis (11) is by insulate 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 basalis (11), diffusion layer (12) and diffusant carrier (5) seal by described shell (13); Described diffusant carrier (5) arranges 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 diffusant carrier (5) connects with diffusion layer (12).

3. a preparation method for chemical intelligent label, is characterized in that comprising following step of sequentially carrying out:

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

2) polyaniline-polyvinyl alcohol solution is coated on the surface of basalis (11), then carries out drying, then cut into the label sample of corresponding size;

3) opposite side time-write interval graduated scale (3) of the basalis (11) of the label sample after cutting, the starting point of described time scale scale (3) is consistent with one end of diffusion layer (12), obtained exposed label;

4) with thermoplastic or UV glue by exposed evident seal, be wrapped in thermoplastic outside exposed label or UV glue forms shell (13);

5) in one end of described shell (13), the start position corresponding to described time scale scale (3) offers diffusant inlet (15), then uses seal (16) to be closed, to obtain final product;

Wherein said chemical intelligent label entirety is rectangle, comprise basalis (11), diffusion layer (12), shell (13), diffusant inlet (15), close the seal (16) of diffusant inlet (15) and time scale scale (3), wherein: described basalis (11) is by insulate and transparent material forms; Described diffusion layer (12) and time scale scale (3) are arranged on described substrate surface; 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); Described diffusant inlet (15) is opened on shell (13), and its position is corresponding with the starting point of described time scale scale (3).

4. a preparation method for chemical intelligent label, is characterized in that comprising following step of sequentially carrying out:

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

6) in one end of described shell (13), the start position corresponding to described time scale scale (3) offers diffusant inlet (15), then uses seal (16) to be closed, to obtain final product;

Wherein said chemical intelligent label entirety is rectangle, comprise basalis (11), diffusion layer (12), shell (13), diffusant inlet (15), close the seal (16) of diffusant inlet (15), time scale scale (3) and diffusant carrier (5), wherein: described basalis (11) is by insulate 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 basalis (11), diffusion layer (12) and diffusant carrier (5) seal by described shell (13); Described diffusant carrier (5) arranges 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 diffusant carrier (5) connects with diffusion layer (12); Described diffusant inlet (15) is opened on shell (13), and its position arranged is corresponding with the starting point of described time scale scale (3).