CN109410738A - A kind of thermo-responsive label, preparation method and application method - Google Patents

A kind of thermo-responsive label, preparation method and application method Download PDF

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Publication number
CN109410738A
CN109410738A CN201710702278.7A CN201710702278A CN109410738A CN 109410738 A CN109410738 A CN 109410738A CN 201710702278 A CN201710702278 A CN 201710702278A CN 109410738 A CN109410738 A CN 109410738A
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Prior art keywords
layer
thermo
responsive
volatile dye
label
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Chinese (zh)
Inventor
邓宗武
史小菊
英晓芳
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Priority to CN201710702278.7A priority Critical patent/CN109410738A/en
Publication of CN109410738A publication Critical patent/CN109410738A/en
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    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31D—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER, NOT PROVIDED FOR IN SUBCLASSES B31B OR B31C
    • B31D1/00—Multiple-step processes for making flat articles ; Making flat articles
    • B31D1/02—Multiple-step processes for making flat articles ; Making flat articles the articles being labels or tags
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F2003/0257—Multilayer

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Laminated Bodies (AREA)

Abstract

The embodiment of the invention provides a kind of thermo-responsive label, preparation method and application methods, the thermo-responsive label is used to monitor the quality state of thermo-responsive article, including physically indicating two laminate portions of functional layer in mutually independent temperature-sensitive functional layer and absorption before use, wherein the temperature-sensitive functional layer includes: sealing film, the first substrate material layer, volatile dye layer, the first release film layer；The absorption instruction functional layer includes: the second substrate material layer, function marker, sorbing material layer, separation layer and the second release film layer；The volatile dye is ferrocene or derivatives thereof；The label can select different sublimable dyes to make according to the thermal stability of monitored article, can more effectively monitor thermo-responsive article, and the label can store under room temperature.The invention further relates to the preparation methods and application method of the thermo-responsive label.

Description

A kind of thermo-responsive label, preparation method and application method
Technical field
The present invention relates to thermo-responsive article monitoring technical fields, more particularly to a kind of thermo-responsive label, preparation method And application method.
Background technique
Some pairs of temperature very sensitive article or product need to store or transport at low temperature, such as most of vaccine, life Tetramune, bioactivity sample and a part of drug etc., and such as fresh milk, dairy produce, fresh meat, fresh fish fresh food etc..It is long Since phase, mark validity period, shelf-life or freshness date guarantee that these goods/products especially drug or food safety uses Main method, but these methods can not often reflect whether are drug that those need to store and transport under cryogenic or food Exposure too long time at a temperature of being more than safety in transportation and storage.Various thermo-responsive article examples are accurately indicated using the method for cheap and simple Such as need whether the fresh food, vaccine (mostly between 2 DEG C~8 DEG C), bioactivity sample of low-temperature storage are storing or transporting Go bad, fail or inactivate because of being more than safety in transportation and storage temperature during defeated, can better ensure that it uses safe and use Effect.
Patel etc. discloses a kind of color-changing device for time-temperature instruction of sandwich structure in US5053339, The device include one containing activation component activation adhesive tape layer, one containing indicate component indicator tape layer, one it is non-must The barrier layer being located between activation adhesive tape layer and indicator tape layer needed.By each funtion part of the time temperature indicator device After assembling according to the method that the patent provides, after activating the activation component in adhesive tape layer heated, meeting (is spread or is migrated across non- Required barrier layer) enter in indicator tape layer and point reacts with key group, and lead to the variation of marker color.For reality The color change of existing instruction device, the patent to the selection principle and strategy of functional material are found with each of color change The chemical reaction of kind various kinds.
Patent CN 201110178976.4 also utilizes sandwich indicator structure, discloses a kind of utilization dye sublimation-expansion Scattered-adsorption process realizes the time temperature indicator device of color change, the mistake for the realization color change which uses Journey is simpler, more conducively the mass production of product, and the batch precision of product is easier to control, but the technical solution is based on sight The color of temperature-sensitive functional layer excess dye is examined to judge that it monitors the remaining validity period of product, there are two deficiencies, first is that observation It needs to tear when the color of excess dye to damage the indicator, second is that the technical solution needs strictly to apply in quantitatively temperature-sensitive functional layer The amount of deposited dyestuff increases the difficulty of controlling of production process.
Patent CN 201210567490.4 further overcomes the two deficiencies, by using transparent windows, can not damage Bad indicator realizes continuous observation color change process, while can also be with to the quantitative requirement of the dyestuff applied in temperature-sensitive functional layer Substantially relax, reduce requirements for the production process, be more suitable for the purposes of indicator, and is conducive to the quality control of indicator production System.The patent in implementation process, core technology first is that selecting temperature-sensitive function of the suitable dyestuff as thermo-responsive label Material, the patent provides a Plant Extracts blue oil hydrocarbon (a kind of natural azulene derivatives) and its a series of derivatives as heat The temperature-sensitive functional material of sensitive tags.But it finds in the specific implementation process, by the distillation by provided temperature-sensitive functional material The limitation of speed is only used for validity period (corresponding temperature-sensitive 4~20 days at 37 DEG C using the thermo-responsive label that these materials make The rate of sublimation of functional material).
The sublimable dye that above-mentioned patent uses belongs to Azulene analog derivative series, and what on the one hand thermo-responsive label was applicable in has Effect phase range nevertheless suffers from limitation, on the other hand still has wind in material safety and availability using single a series of material Danger, based on the thermo-responsive label of different materials series exploitation it is possible to prevente effectively from this two risks.
Summary of the invention
The embodiment of the present invention is designed to provide a kind of thermo-responsive label based on ferrocene or derivatives thereof, its preparation Method and application method, wherein volatile dye of the ferrocene or derivatives thereof as thermo-responsive label；Specific technical solution is such as Under:
Present invention firstly provides a kind of thermo-responsive labels, including the temperature-sensitive functional layer and absorption instruction function being bonded each other Layer, wherein
The temperature-sensitive functional layer includes:
Film is sealed, the sealing film is preferably by polyethylene, polyvinyl chloride, polypropylene, polystyrene, poly terephthalic acid second Diol ester or PET leaching membrane paper are made；
The first substrate material layer on the sealing film, first substrate material layer is preferably by blank sheet of paper, copy paper, print Brush paper or PET leaching membrane paper are made, and are more preferably fitted on the sealing film by water-base cement；
Volatile dye layer is formed on first substrate material layer, containing volatile dye, the volatility Dye coating is preferably coated or impregnated with by the property of will volatilize dyestuff and is formed and in first substrate material layer；
And
The absorption indicates that functional layer includes:
Second substrate material layer, is made of clear material, and is preferably made of polymer film；
Function marker is located on second substrate material layer and has watch window, in the observation window Reference color is preferably provided with around mouthful；
Sorbing material layer is located under second substrate material layer and can adsorb in the volatile dye layer Dyestuff, wherein the sorbing material layer in vertical direction with the watch window is overlapping or Chong Die, the preferably described adsorption material The size of the bed of material is greater than the size of the watch window；
Separation layer is made of opaque material and is located under the sorbing material layer, the size of the separation layer Greater than the size of the watch window, the size of the preferably greater than or equal to described volatile dye layer, more preferably greater than, be equal to or Less than the size of the sorbing material layer, the volatile dye can diffuse through the separation layer；Wherein,
The volatile dye layer of the temperature-sensitive functional layer and the separation layer of the absorption instruction functional layer are bonded opposite to each other；
The volatile dye is ferrocene shown in formula I or derivatives thereof；
Wherein:
R1、R2、R3One of represent hydrogen, halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 straight chain or Branched alkyl, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4Selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 Linear or branched alkyl group amine, other two represent hydrogen；
Or
R1、R2It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 straight chain or branch Alkyl group, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4It is straight selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 Chain or branched alkyl amine, R3Represent hydrogen；
Or
R1、R3It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 straight chain or branch Alkyl group, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4It is straight selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 Chain or branched alkyl amine, R2Represent hydrogen.
Preferably, the temperature-sensitive functional layer further includes the first release film layer, is covered on the volatile dye layer, Described in the size of sealing film and first release film layer be greater than the size of the volatile dye layer and by the volatilization Property dye coating is sealed between the sealing film and first release film layer；
Preferably, the absorption instruction functional layer further includes the second release film layer for covering the separation layer；
Preferably, the temperature-sensitive functional layer and absorption instruction functional layer are physically independent before the use.
Preferably, the sorbing material layer is formed itself by adhesive sticker, is preferably formed by transparent non-setting adhesive, more preferably oily Property or aqueous adhesive sticker, self-adhesive paper or adhesive sticker adhesive tape.
Preferably, adhesive sticker is coated under the sealing film and the adhesive sticker is covered by third release film layer；
It when in use then will be described using the adhesive sticker under the sealing film by removing the third release film layer Sealing film is covered on the thermo-responsive article.
Preferably, the separation layer as after described ferrocene or derivatives thereof volatilization from the temperature-sensitive functional layer to described The diffusion admittance of sorbing material layer and the diffusion velocity that the ferrocene can be regulated and controled or derivatives thereof；It is preferred that the separation layer It is single-layer or multi-layer, and the adsorption material for adsorbing described ferrocene or derivatives thereof can be applied between the multi-layer isolation layer Material；The more preferable separation layer is formed by White-opalescent material；Even more preferably from by being selected from blank sheet of paper, copy paper, printing paper, not doing The material of glue label paper is formed.
Preferably, depth Yu the volatility dye of reference color of the function marker around the watch window The sorbing material layer is because adsorbing from the volatility after bed of material experience disposes identical process with the thermo-responsive article failure Ferrocene to volatilize in dye coating or derivatives thereof and obtain color depth it is identical.
Preferably, the corresponding color difference Δ E* of reference colorab=35-55.
Preferably, the adsorbent material can irreversibly adsorb the dye evaporated from the volatile dye layer The speed of material, the preferably described adsorbent material absorption volatile dye is much larger than the evaporation rate of volatile dye.
The present invention also provides a kind of methods for preparing above-mentioned thermo-responsive label comprising following steps:
Sealing film is provided, the sealing film is preferably by polyethylene, polyvinyl chloride, polypropylene, polystyrene, poly- terephthaldehyde Sour glycol ester or PET leaching membrane paper are made；
The first substrate material is provided on the sealing film, first substrate material layer is preferably by blank sheet of paper, copy paper, print Brush paper or PET leaching membrane paper are made, more preferably by the way that first substrate material is fitted on the sealing film using water-base cement；
Volatile dye layer is formed on the first substrate material, the volatile dye layer contains volatile dye, preferably It is coated or impregnated on first substrate material and is formed by the property of will volatilize dyestuff；
And
The second substrate material layer formed by transparent material, preferably the second substrate material made of polymer film are provided；
Function marker is formed in second substrate material layer, there is the function marker watch window preferably to exist There is reference color around the watch window；
Sorbing material layer is formed under second substrate material layer, the sorbing material layer can adsorb the volatility Volatile dye in dye coating, and the sorbing material layer is overlapping or Chong Die with the watch window in vertical direction, The size of the sorbing material layer is preferably greater than the size of the watch window；
Separation layer is formed by opaque material under the sorbing material layer, the size of the separation layer is greater than the observation The size of window, the size of the preferably greater than or equal to described volatile dye layer more preferably greater than, are equal to or less than the absorption The size of material layer, the separation layer can diffuse through the volatile dye；
The volatile dye is ferrocene shown in formula I or derivatives thereof；
Wherein:
R1、R2、R3One of represent hydrogen, halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 straight chain or Branched alkyl, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4Selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 Linear or branched alkyl group amine, other two represent hydrogen；
Or
R1、R2It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 straight chain or branch Alkyl group, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4It is straight selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 Chain or branched alkyl amine, R3Represent hydrogen；
Or
R1、R3It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 straight chain or branch Alkyl group, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4It is straight selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 Chain or branched alkyl amine, R2Represent hydrogen.
Preferably, cover the first release film on the volatile dye layer, wherein the sealing film and described first from The size of type film layer is greater than the size of the volatile dye layer and the volatile dye layer is sealed in the sealing film Between first release film layer, to form temperature-sensitive functional layer.
Preferably, the second release film is covered under the separation layer, adsorbs instruction functional layer to be formed.
The present invention also provides a kind of methods of quality state for monitoring thermo-responsive article, comprising the following steps:
On one or more regions on the thermo-responsive article using any one of aforementioned thermo-responsive label or The thermo-responsive label according to prepared by method above-mentioned, the face of the sorbing material layer is observed when required by watch window Color, if the color is identical as reference color or than reference color depth, the thermo-responsive article is no longer valid；If the color It is more shallow than reference color, then show that the thermo-responsive article not yet fails.
A kind of thermo-responsive label, preparation method and application method provided in an embodiment of the present invention, in a creative way with two Volatile dye of the luxuriant iron or derivatives thereof as thermo-responsive label；The type for enriching thermo-responsive label extends thermo-responsive The application range of label.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with It obtains other drawings based on these drawings.
Fig. 1 is the thermo-responsive label construction schematic diagram of one embodiment of the invention.
Fig. 2 is that the embodiment of the present invention 2 uses ferrocene derivatives (1=CHO, R2、R3=H) it is distillation volatile dye system The thermo-responsive label made color difference Δ E*ab at 55 DEG C, 45 DEG C, 37 DEG C, 25 DEG C is changed over time.
Fig. 3 is that the embodiment of the present invention 3 uses ferrocene derivatives (R not of the same race1=COCH3, CHO or COPh, R2、R3=H) For distillation volatile dye production thermo-responsive label at 55 DEG C color difference Δ E*ab change over time.
Fig. 4 is in the embodiment of the present invention 4 using ferrocene derivatives (R not of the same race1=COCH3Or CHO, R2、R3=H) system The activation energy for the thermo-responsive label made.
Fig. 5 is that the embodiment of the present invention 5 uses different-thickness (60g/m2、100g/m2、2*60g/m2、60+100g/m2、2* 100g/m2) the color difference Δ E*ab of thermo-responsive label of separation layer production changes over time.
The some terms and its appended drawing reference that the present invention uses are summarized as follows:
1 12 second substrate material layer of water-base cement of temperature-sensitive functional layer, 20 watch window 24
Absorption instruction functional layer 2 seals absorption instruction 21 reference color 25 of area of film 13
First substrate material layer, 10 adhesive sticker, 14 sorbing material layer 22
11 third release film layer of volatile dye layer, 15 separation layer 23
Specific embodiment
First aspect present invention provides a kind of, thermo-responsive label product, which includes that temperature-sensitive functional layer and absorption refer to Show functional layer, wherein
The temperature-sensitive functional layer includes:
Film is sealed, the sealing film is preferably by polyethylene, polyvinyl chloride, polypropylene, polystyrene, poly terephthalic acid second Diol ester or PET leaching membrane paper are made；
It is described sealing film on the first substrate material layer, first substrate material layer preferably by blank sheet of paper, copy paper or Printing paper is made, and is more preferably fitted on the sealing film by water-base cement；
Volatile dye layer is formed on first substrate material layer, and the volatile dye layer preferably passes through The property of will volatilize dyestuff is coated or impregnated in first substrate material layer and is formed；
The absorption indicates that functional layer includes:
Second substrate material layer, is made of clear material, and is preferably made of polymer film；
Function marker is located on second substrate material layer and has watch window, in the observation window Reference color is preferably provided with around mouthful；
Sorbing material layer is located under second substrate material layer and can adsorb in the volatile dye layer Dyestuff, wherein the sorbing material layer is overlapping or Chong Die with the watch window in vertical direction, preferably its size is greater than The size of the watch window；
Separation layer is made of opaque material and is located under the sorbing material layer, the size of the separation layer Greater than the size of the watch window, the size of the preferably greater than or equal to described volatile dye layer, more preferably greater than, be equal to or Less than the size of the sorbing material layer, and the separation layer can diffuse through the volatile dye；
The volatile dye layer of the temperature-sensitive functional layer and the separation layer of the absorption instruction functional layer are bonded opposite to each other；
The volatile dye is ferrocene shown in formula I or derivatives thereof；
Wherein:
R1、R2、R3One of represent hydrogen, halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 straight chain or Branched alkyl, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4Selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 Linear or branched alkyl group amine, other two represent hydrogen；
Or
R1、R2It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 straight chain or branch Alkyl group, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4It is straight selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 Chain or branched alkyl amine, R3Represent hydrogen；
Or
R1、R3It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 straight chain or branch Alkyl group, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4It is straight selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 Chain or branched alkyl amine, R2Represent hydrogen.
In a kind of specific embodiment of the invention, the temperature-sensitive functional layer and absorption instruction functional layer are before the use It is physically independent；The temperature-sensitive functional layer further includes the first release film layer, is covered on the volatile dye layer, Described in the size of sealing film and first release film layer be greater than the size of the volatile dye layer and by the volatilization Property dye coating is sealed between the sealing film and first release film layer；The absorption instruction functional layer further includes covering institute State the second release film layer of separation layer.When using thermo-responsive label provided by the invention, the first release film layer and second is removed The separation layer of the absorption instruction functional layer is directed at the volatile dye layer of the temperature-sensitive functional layer, will adsorbed by release film layer Material layer, separation layer and volatile dye layer are enclosed between the sealing film and second substrate material layer；Then by institute Sealing film is stated to be covered on the thermo-responsive article；Alternatively, the sealing film is covered on the thermo-responsive article, then shell From the first release film layer and the second release film layer, the separation layer of the absorption instruction functional layer is directed at the temperature-sensitive functional layer Sorbing material layer, separation layer and volatile dye layer are enclosed in the sealing film and second substrate by volatile dye layer Between material layer.
When in use, ferrocene in the temperature-sensitive functional layer or derivatives thereof is under certain condition (such as at expectation Under the temperature conditions set, such as under the temperature conditions of desired storage and/or transport, for example, it is surprisingly raised disposing temperature In the case of, it such as under the desired disposition temperature conditions of accelerated test, such as in the desired disposition temperature of accelerated test is 25 DEG C And/or in the case where 37 DEG C) can volatilize.After ferrocene of volatilization or derivatives thereof diffuses through separation layer, by the adsorption material Adsorbent material in the bed of material irreversibly adsorbs, and the rear color of ferrocene of sorbing material layer absorption volatilization or derivatives thereof gradually becomes Deep (such as darkening in the absorption instruction area 21 in sorbing material layer 22 shown in Fig. 1), can be indicated by function The watch window observation of layer.The color depth of sorbing material layer and the being positively correlated property of adsorbance of dyestuff, and the latter with it is thermo-responsive The thermal history of article is (related to the degradation of thermo-responsive article) related.
By the thermo-responsive label using aforementioned present invention, the thermal history for monitoring thermo-responsive article can use adsorbent material The color depth of layer intuitively and easily characterizes.In one embodiment, which can further use color difference, example As the variation of Δ E*ab characterizes.Term " color difference " refers to the umerical color with colorimeter measurement.For example, using L*a* The b* colour space (also known as CIELAB color space), in this colour space, L* represents brightness；A* and b* is chromaticity coordinate, is indicated Color direction；+ a* indicates red direction, and-a* indicates green direction, and+b* indicates yellow direction, and-b* indicates blue direction, center It is colourless.When a* and b* value increases and removes from center, color saturation increases.Colour difference meter is widely used in precise measurement color difference.? In this colour space, color difference can indicate that calculation formula is as follows with single value, Δ E*ab:
Δ E*ab=[(Δ L*)2+ (Δ a*)2+ (Δ b*)2]0.5
In one embodiment, sorbing material layer rate of color change can be by the chromatic aberration range that sets divided by reaching Time representation needed for the chromatic aberration range.In one embodiment, rate of color change variation with temperature is obeyed Arrhenius equation can obtain activation energy by the equation.
The adsorbent material that thermo-responsive label of the present invention uses can be it is any can irreversibly adsorb it is described two cyclopentadienyl The material of iron or derivatives thereof.In one embodiment, the speed of adsorbent material absorption ferrocene or derivatives thereof Greater than the evaporation rate of ferrocene or derivatives thereof.In one embodiment, the described adsorbent material absorption ferrocene or its Evaporation rate of the speed of derivative much larger than ferrocene or derivatives thereof.In one embodiment, the adsorbent material Evaporation rate of the speed much larger than ferrocene or derivatives thereof for adsorbing ferrocene or derivatives thereof, so that the speed that dyestuff is adsorbed Degree is substantially only related with the evaporation rate of ferrocene or derivatives thereof.In one embodiment, the adsorbent material is inhaled The speed of attached ferrocene or derivatives thereof is much larger than the evaporation rate of ferrocene or derivatives thereof, so that ferrocene or derivatives thereof Apparent evaporation rate be only influenced by temperature, without by for example because of saturation/nearly saturated vapor institute caused by after itself volatilization The influence of the factors such as obstruction.In one embodiment, the adsorbent material include but is not limited to oiliness or aqueous adhesive sticker, Business self-adhesive paper and adhesive sticker adhesive tape etc..In one embodiment, the adsorbent material includes but is not limited to Ai Lidan The AP104 of Unisem, AT20, HP104, S692N adhesive etc..
The insolated layer materials and structure that thermo-responsive label of the invention uses are not particularly limited, as long as the separation layer has There is the function of following two aspects, is to cover the color of temperature-sensitive functional layer, therefore the insolated layer materials are preferably first The material of White-opalescent；Next, which is to provide after ferrocene or derivatives thereof volatilization, is diffused into sorbing material layer from temperature-sensitive functional layer Diffusion admittance, be preferably able to play a part of simultaneously to regulate and control diffusion velocity.For example, the insolated layer materials can be but not limited to Common blank sheet of paper, copy paper, printing paper, sticky label paper, wood-free paper or art paper etc..In one embodiment, it uses 60-120g/m2Wood-free paper as insolated layer materials.In one embodiment, using 60-120g/m2Art paper be used as every Layer material.In one embodiment, using be coated with it is a certain amount of can ferrocene described in Irreversible Adsorption or derivatives thereof The 60-120g/m of adhesive sticker2Blank sheet of paper as insolated layer materials.In one embodiment, using two layers of 60-120g/m2It is white The double-deck blank sheet of paper of the adhesive sticker of ferrocene described in a certain amount of energy Irreversible Adsorption or derivatives thereof is coated among paper as isolation Layer material.The variation of this structure can reflect in the variation of each layer from label use process: in addition to the temperature-sensitive function of label Ergosphere is presented outside the color of ferrocene or derivatives thereof, and only sorbing material layer can be in when using blank sheet of paper as the label of separation layer The color of existing ferrocene or derivatives thereof.Use when being coated with the blank sheet of paper of adsorbent material as insolated layer materials, sorbing material layer The color of ferrocene or derivatives thereof can all be presented with separation layer；Using applied among double-deck blank sheet of paper a certain amount of adsorbent material every When absciss layer, the color of ferrocene or derivatives thereof is all presented between sorbing material layer and the blank sheet of paper of separation layer, so can more have Effect ground shows the color change of thermo-responsive label of the invention when in use.
The present invention also provides the production technologies and storing mode of the thermo-responsive label.According to the method for the present invention, institute The production and storage for the thermo-responsive label stated are divided into temperature-sensitive functional layer and absorption instruction two independent parts of functional layer, including phase The mutually independent process for preparing temperature-sensitive functional layer and absorption instruction two laminate portions of functional layer respectively.
According to the present invention, the preparation process of the temperature-sensitive functional layer include: provide sealing film, the sealing film preferably by Polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyethylene terephthalate or PET leaching membrane paper are made；Described close The first substrate material is provided in sealer, preferably the first substrate material made of blank sheet of paper, copy paper or PET leaching membrane paper, more preferably By the way that first substrate material is fitted on the sealing film using water-base cement；Volatility is formed on the first substrate material Dye coating is preferably formed by being coated or impregnated with ferrocene or derivatives thereof on first substrate material；Described The first release film is covered on volatile dye layer, wherein the size of the sealing film and first release film layer is greater than described wave Hair property dye coating size and the volatile dye layer is sealed between the sealing film and first release film layer, To form temperature-sensitive functional layer.
In one embodiment, by roll-to-roll production method, by 60-120g/m2Blank sheet of paper (the first substrate material Layer) water-base cement of ferrocene or derivatives thereof is not adsorbed in one layer of coating, then fits to thin polymer film (sealing film), such as poly- second On film made of alkene, polyvinyl chloride, polypropylene, polystyrene, polyethylene terephthalate etc.；Thin polymer film it is another One layer of adhesive sticker is applied before or after blank sheet of paper is bonded on one side, by the adhesive sticker label pasted when for using described in On thermo-responsive article, protected using preceding adhesive sticker face third release film.In one embodiment, pass through roll-to-roll life Ferrocene or derivatives thereof is coated to blank sheet of paper another side by the method impregnated by production mode, can be by ferrocene or derivatives thereof It is dissolved in suitable organic solvent (such as ethyl alcohol, acetone, ether, petroleum ether, ethyl acetate), it is preferred when being impregnated or coated Material concentration is 100-200g/L, and preferred substrate material traveling speed is 3-30m/ minutes.In one embodiment, it will apply It applies after covering the first release film on the volatile dye layer of ferrocene or derivatives thereof, winds and according to the size of labeling requirement It is die cut slitting, then sealed package storage.In one embodiment, the size of the blank sheet of paper of cross cutting is 5-15mm, the size of optimization It is 8-12mm.In one embodiment, the thin polymer film size of cross cutting is 8-30mm, and the size of optimization is 10-20mm.
According to the present invention, the manufacturing process of the described absorption instruction functional layer includes: for providing and being formed by transparent material Two substrate materials, preferably by polymer film (polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyethylene terephthalate Film made of ester etc.) made of the second substrate material；Function marker, the function are formed on second substrate material Marker has watch window and in the preferred embodiment, can have reference color around the watch window； Sorbing material layer is formed under second substrate material, the sorbing material layer can adsorb in the volatile dye layer Ferrocene or derivatives thereof, and the sorbing material layer is overlapping or Chong Die with the watch window in vertical direction, preferably Its size is greater than the size of the watch window；Separation layer is formed by opaque material under the sorbing material layer, it is described every Size of the size of absciss layer greater than the watch window, the size of the preferably greater than or equal to described volatile dye layer, more preferably Greater than, equal to or less than the sorbing material layer size, the separation layer can diffuse through ferrocene or derivatives thereof；With The second release film is covered under the separation layer, adsorbs instruction functional layer to be formed.
According to the present invention, separation layer, sorbing material layer, function marker constitute another independent sector of label, referred to as Absorption instruction functional layer.In one embodiment, adsorbent material uses ferrocene described in energy Irreversible Adsorption or derivatives thereof Transparent non-setting adhesive, adhesive sticker coated in transparent thin polymer film for example polyethylene, polyvinyl chloride, polypropylene, polystyrene, On film made of polyethylene terephthalate etc., protected using preceding adhesive sticker face with release film.In an embodiment In, for function marker using the paper of coating adhesive sticker, the color of paper is the color with reference to terminal, is formed and is justified by roll-to-roll cross cutting Shape is rectangular or the watch window of other geometries.In one embodiment, by roll-to-roll production method, by function Marker fits to the one side for not applying adsorbent material of the second substrate material.In one embodiment, by roll-to-roll The separation layer cross cutting that label sizes require is fitted on sorbing material layer, and is protected with the second release film by production method.One In a embodiment, slitting, then packing and storing will be die cut according to the size of labeling requirement after absorption instruction functional layer winding.One In a embodiment, the size of the watch window of cross cutting is 3-10mm, and the size of optimization is 4-6mm.In one embodiment, The separation layer size and shape of cross cutting are consistent with the size of volatile dye layer in temperature-sensitive functional layer.In an embodiment In, the separation layer size of cross cutting is greater than the size of the volatile dye layer in temperature-sensitive functional layer.In one embodiment, it is die cut Absorption instruction functional layer size it is consistent with temperature-sensitive functional layer size.In one embodiment, the absorption of cross cutting indicates function Layer size is greater than temperature-sensitive functional layer size.In one embodiment, the absorption instruction functional layer size of cross cutting is less than temperature-sensitive function Ergosphere size.
The present invention also provides the application methods of the thermo-responsive label.In one embodiment, by temperature-sensitive functional layer The suitable position of the packing container of the thermo-responsive article is pasted, temperature-sensitive functional layer lower part is preferably located at by removing first Third release film layer, then temperature-sensitive functional layer is pasted by the adhesive sticker being located under sealing film that is exposed described The suitable position of the packing container of thermo-responsive article；Then the second release film layer and temperature-sensitive functional layer of absorption marker are removed again The first release film layer, separation layer and temperature-sensitive functional layer are aligned, are adjacent to two parts using the adhesive sticker of absorption marker close Envelope.In one embodiment, the second release film layer of first removing absorption marker and first release at the top of temperature-sensitive functional layer Separation layer and temperature-sensitive functional layer are aligned, two parts are adjacent to sealing using the adhesive sticker of sorbing material layer by film layer；Again by temperature-sensitive The third release film layer removing of the protection non-drying glue layer of functional layer bottom, then utilizes exposed non-drying glue layer that will entirely mark Label paste the suitable position of the packing container of the thermo-responsive article.As a result, in the feelings for monitoring thermo-responsive article thermal history Under condition, such as in storage and/or transportational process, volatile dye ferrocene or derivatives thereof is in by the sealing film and second Without escaping in the enclosed system that substrate material is constituted, so that the ferrocene or derivatives thereof of volatilization is substantially completely adsorbed to In the adsorbent material.According to the present invention, terminate for example in the thermo-responsive article of monitoring in the storage and/or fortune by needing After defeated process, the color depth of sorbing material layer can be observed or measured by the watch window of label.The depth of color with It is positively correlated between the thermal history (related to the degradation of thermo-responsive article) of the thermo-responsive article.Therefore, in a reality It applies in scheme, the degradation of the thermo-responsive article can be by the color of the sorbing material layer of thermo-responsive label of the invention Lai straight See ground characterization.
The present invention also provides the methods being monitored using thermo-responsive label of the invention, including on thermo-responsive article One or more regions on apply thermo-responsive label of the invention, observe the adsorption material when required by watch window The color of the bed of material, if the color, than reference color depth, the thermo-responsive article is no longer valid；If the color ratio refers to face Color is shallow, then shows that the thermo-responsive article not yet fails.
In one embodiment, method includes the following steps:
(i) provide a thermo-responsive article, determine the thermo-responsive article its expectation disposition (such as storage and/or transport, or Person's Accelerated stability test) at a temperature of keep effective quality state institute can duration (can refer to institute's energy in the present invention Lasting maximum duration, also referred to as validity period can be indicated with t1), and the method according to the invention makes thermo-responsive label Temperature-sensitive functional layer and absorption instruction functional layer.
(ii) the method according to the invention seals the temperature-sensitive functional layer of thermo-responsive label and absorption instruction functional layer alignment Be adjacent to, with the starting color difference of colorimeter measurement watch window (volatilize and adsorb without dyestuff at this time, the priming color of watch window/ Color difference can be expressed as C0).Label is placed in expectation disposition (such as storage and/or transport or Accelerated stability test) At a temperature of (can be indicated in the present invention with T1) store, the color difference of time recording watch window.It changes with time song as color difference Line, (color/color difference of watch window can indicate the color difference for finding under thermo-responsive time object storing validity period t1 at this time For C1), using it as reference color.The variation (C1-C0) of color difference is obtained divided by the time needed for realizing the chromatic aberration The rate of chromatic aberration under disposition temperature T1.
(iii) in one embodiment, the thermo-responsive label is stored at a temperature of different disposition, time recording is seen Examine the color difference of window.Make color difference versus time curve, finds watch window color at a temperature of the disposition and reach home color The difference required time compares the validity period of the time and the thermo-responsive article at a temperature of disposition, ideally, two A time should be as close possible to.
(iv) by the variation of color difference (C1-C0) divided by the time needed for realizing the chromatic aberration at a temperature of different disposition T1 obtains the rate of chromatic aberration under different disposition temperature T1.The logarithm of chromatic aberration rate at a temperature of taking the difference to dispose, Make ordinate with the logarithm, the inverse of disposition temperature (thermodynamic temperature) is made curve as abscissa, is based in principle Arrhenius equationIt, can including key parameters such as activation energy, rate constants k, thermodynamic temperature T To obtain activation energy (the namely work of the volatilization process of volatile dye layer that the thermo-responsive label reaches the terminal colour Change energy).Ideally, which should be close with the failure activation energy of the thermo-responsive product.In an embodiment In, the activation energy of the quality comparison process of the activation energy of the volatilization process of the volatile dye layer and the thermo-responsive article Difference is within the scope of ± 10kJ/mol, more preferably within the scope of ± 5kJ/mol.
(v) from the watch window of absorption marker adsorption layer color, and compared with reference color, judge institute State the quality state of thermo-responsive article:
If the color for adsorbing marker is more shallow than reference color, show that the thermo-responsive article is maintained at effective quality shape State；
If the color for adsorbing marker is identical as reference color or than reference color depth, shows the thermo-responsive article Beyond effective quality state.
The purpose of one embodiment of the invention is the thermo-responsive label that production can save at normal temperature, can be by such as Lower method is realized: the temperature-sensitive functional layer and absorption instruction functional layer two parts of thermo-responsive label make storage respectively, and when use closes Two be one.After ferrocene of temperature-sensitive functional layer or derivatives thereof coating, first with to volatile dye used without suction-operated from Type film is sealed.Temperature-sensitive functional layer and absorption marker make storage respectively, realize being stored at room temperature for two funtion parts.
In one embodiment of the invention, the volatile dye layer for making above-mentioned thermo-responsive label is provided Ferrocene or derivatives thereof.It volatilizees after ferrocene or derivatives thereof heat absorption, the speed and its temperature effect of volatilization can make temperature-sensitive Sense label sufficiently reflects the speed and its temperature effect that indicated product is rotten or fails.
It should be noted that ferrocene employed in the present invention or derivatives thereof, can pass through phase in the prior art Preparation method is closed to prepare, for the preparation method of ferrocene or derivatives thereof, the present invention is herein without limiting.
In one embodiment of the invention, of the temperature-sensitive functional layer for making above-mentioned thermo-responsive label is provided One substrate material, for example, common blank sheet of paper, copy paper, printing paper or PET leaching membrane paper etc..
In one embodiment of the invention, the close of the temperature-sensitive functional layer for making above-mentioned thermo-responsive label is provided The material of sealer, the polymer material of for example, impermeable volatile dye: polyethylene, polyvinyl chloride, polypropylene, polyphenyl second Alkene, polyethylene terephthalate or PET leaching membrane paper etc..
In one embodiment of the invention, the suction of the sorbing material layer for making above-mentioned thermo-responsive label is provided Enclosure material: being, for example, various adhesive stickers.It is preferred that the adsorbent material has strong irreversible absorption to make ferrocene or derivatives thereof With adsorption rate guarantees ferrocene or derivatives thereof apparent evaporation rate much larger than the evaporation rate of ferrocene or derivatives thereof Only it is affected by temperature.
In one embodiment of the invention, the suction of the sorbing material layer for making above-mentioned thermo-responsive label is provided Enclosure material, wherein adsorbent material has Irreversible Adsorption effect to ferrocene or derivatives thereof, by selecting different adsorbent materials Regulate and control the color change and its temperature effect of thermo-responsive label.
In one embodiment of the invention, the production technology and storage method of the thermo-responsive label are provided, heat Roll-to-roll coating, cross cutting, the fitting etc. that quick functional layer and absorption instruction functional layer can be used using traditional adhesive sticker production Production method, and provide the material concentration of optimization, the size of label each section, speed of production etc., so that heat of the invention Sensitive tags being capable of inexpensively and advantageously batch micro operations.
In one embodiment of the invention, the application method of the thermo-responsive label is provided, it is characterised in that: heat Quick functional layer and absorption marker are combined into one when in use, are bonded and effectively seal each other, protect the function of thermo-responsive label Can position not by outside contamination, while polluted product or its packaging after the volatilization that avoids ferrocene or derivatives thereof.
In one embodiment of the invention, the test method of the thermo-responsive label is provided, is measured using color difference The color difference of the watch window of label is measured to quantify the color change of label, chooses color difference terminal Δ E* appropriateab=35-55, really Response time and the color change for calibrating label, the Activation parameters of thermo-responsive label are determined using Arrhenius equation.Inventor By the study found that it is preferred that in Δ E*ab=35-55 is within the scope of this, using estimating practical color difference and have terminal color difference Reference color when, it is relatively accurate.ΔE*abSince color is too deep or excessively shallow when excessive or too small, all it is unfavorable for observation judgement, therefore It is improper.
In one embodiment of the invention, the determination method of the reference color of the thermo-responsive label is provided, it will Label stores at a temperature of disposing as expectation, the color difference of time recording watch window.Make color difference versus time curve, looks for The color difference under time validity period t1 is stored at a temperature of the disposition to the thermo-responsive article, using it as reference color, print The reference color of brush label.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Firstly, the structure of thermo-responsive label provided by illustrating the present invention and its determination of reference color.
The present invention makes thermo-responsive label using the volatilization property of ferrocene or derivatives thereof, passes through heated-volatilization-suction Attached process realizes required color change effect.A kind of structure such as Fig. 1 of illustrative thermo-responsive label of the present inventor's design It is shown.
Sectional view shown in Figure 1 consists of two parts wherein depicting a kind of thermo-responsive label of the invention, (a) Part is temperature-sensitive functional layer 1, is partially (b) absorption instruction functional layer 2, and two parts make storage respectively, and when use is combined into one, Paste the container or surface of package of thermo-responsive article to be monitored.
In temperature-sensitive functional layer 1, one layer of water-base cement 12 is applied below the first substrate material layer 10, then fit to sealing film On 13, due to sealing impermeable ferrocene of film 13 or derivatives thereof so preventing ferrocene or derivatives thereof downward diffusion pollution Thermo-responsive article.One layer of adhesive sticker 14 is applied below sealing film 13 again, and is protected with third release film layer 15.In the first substrate Functional part above material layer 10 applies one layer of ferrocene or derivatives thereof, forms the volatile dye layer 11 in the present invention. It is sealed after the production of temperature-sensitive functional layer 1 is dry, sealing performance guarantees that temperature-sensitive functional layer can be stored and be transported at room temperature.
In absorption instruction functional layer 2, the second substrate material layer 20 uses transparent plastic film, pastes in the upper surface of substrate film Close self-adhesive paper be used as function marker, be bonded before self-adhesive paper printing reference color 25 and product information appropriate (such as be somebody's turn to do The applicable thermo-responsive type of goods of label) or label use information (such as needing whether to judge thermo-responsive article using label The information how operated when failure), and pass through the watch window 24 of the round rectangular or other geometries of cross cutting formation.? Below two substrate material layers 20, printing or coated one layer of adsorbent material that can effectively adsorb ferrocene or derivatives thereof, shape At sorbing material layer 22.In the present embodiment using the transparent non-setting adhesive of energy Irreversible Adsorption ferrocene or derivatives thereof.Right The separation layer 23 of suitable dimension in indication window position, should be die cut and be directly attached on the adhesive sticker as adsorbent material.Two Separation layer is diffused through after the heated volatilization of luxuriant iron or derivatives thereof and is adsorbed material layer absorption, adsorbs sorbing material layer especially The color in the absorption instruction area 21 in material layer constantly deepens.
The color of the reference color of thermo-responsive label can be determined using following methods:
Chromatism measurement is using white substrate such as A4 paper as reference, when label enables, measures starting color difference by watch window. It is stored at a temperature of label is disposed as expectation, the color difference of time recording watch window.Make color difference versus time curve, It finds the thermo-responsive article and stores color difference under the time validity period t1 at a temperature of disposition, using it as reference color, The reference color of printed label.
Embodiment 1: the preparation of the thermo-responsive label using ferrocene or derivatives thereof as volatile dye
Use ferrocene or derivatives thereof as the volatile dye of thermo-responsive label, with 60g/m2PET leaching membrane paper make For the first substrate material layer, using polymer (polypropylene) plastic foil as sealing film, and (PET is release using commercial release film Film, Suzhou Da Wan plastic electronic Co., Ltd) it is used as the first release film layer, temperature-sensitive function is prepared according to the method provided by the invention Layer.To be coated with the plastics (poly- third of transparent non-setting adhesive (PET gum slide PF04, Shanghai Hu Mai composite material Co., Ltd) Alkene) second substrate material layer and sorbing material layer of the film as absorption instruction functional layer, with 80g/m2Wood-free paper be used as every Absciss layer, and use commercial release film as the second release film layer, layer material is indicated using self-adhesive paper as function, according to this hair Bright method preparation absorption instruction functional layer.Prepared thermo-responsive label can be as shown in Figure 1.
Embodiment 2: with ferrocene derivatives (R1=CHO, R2、R3=H) as volatile dye production thermo-responsive label Color response at 55 DEG C, 45 DEG C, 37 DEG C and 25 DEG C
With ferrocene derivatives (1=CHO, R2、R3=H) it is used as volatile dye, with 80g/m2Wood-free paper as isolation Layer, makes two components of thermo-responsive label as described in Example 1.By the temperature-sensitive functional layer of thermo-responsive label and absorption instruction Functional layer is combined into one sealing and is adjacent to, and the sample of sealing is placed under 55 DEG C, 45 DEG C, 37 DEG C and 25 DEG C constant temperatures.It places special After fixing time, the color of thermo-responsive label is observed and recorded.Fig. 2 is thermo-responsive label in 55 DEG C, 45 DEG C, 37 DEG C and 25 DEG C constant temperature items The color record placed under part, from figure 2 it can be seen that Δ E*ab is continuously increased with the extension of storage time, and temperature is got over Height is increased speed faster；That is, the color of absorption marker is constantly deepened with the extension of storage time, and temperature is got over It is faster to deepen speed for height.
Embodiment 3: with ferrocene derivatives (R not of the same race1=COCH3, CHO or COPh, R2、R3=H) it is contaminated as volatility Expect thermo-responsive label color response test at 55 DEG C of production
With ferrocene derivatives (R not of the same race1=COCH3, CHO or COPh, R2、R3=H) it is used as volatile dye, by real The method for applying example 1 makes two components of thermo-responsive label.By the temperature-sensitive functional layer of thermo-responsive label and absorption instruction laminated two It is adjacent to for a sealing, the sample of sealing is placed in 55 DEG C of waters bath with thermostatic control and is placed, each specific time uses Colorlite Sph860 color difference meter measurement records the color difference Δ E*ab of the watch window of thermo-responsive label, as a result as shown in Figure 3.It can from Fig. 3 To find out, R1When=COCH or CHO, with the extension of storage time, Δ E*ab increases sharply, and R1The ferrocene of=COPh spreads out It is biological then relative increase is slower.
Embodiment 4: with ferrocene derivatives (R not of the same race1=COCH3Or CHO, R2、R3=H) it is used as volatile dye system The thermo-responsive label activation energy made calculates
With ferrocene derivatives (R not of the same race1=COCH3Or CHO, R2、R3=H) it is used as volatile dye, by embodiment 1 Method make two components of thermo-responsive label.The temperature-sensitive functional layer of thermo-responsive label and absorption marker are combined into one close Sealing label is tight, and the sample of sealing is placed in 55 DEG C, 45 DEG C, 37 DEG C and 25 DEG C waters bath with thermostatic control and is placed, and each specific time is used Colorlite Sph860 measurement records the color difference of the watch window of thermo-responsive label, as a result as shown in figure 4, at 55 DEG C, 45 DEG C, 37 DEG C and 25 DEG C of waters bath with thermostatic control measure the variation of display window color difference Δ E*ab t at any time at a temperature of placing, further according to Arrhenius equationThe activation energy for obtaining the thermo-responsive label is respectively 86kJ/mol and 76kJ/mol.
Embodiment 5: thick with the color difference of the thermo-responsive label of different-thickness separation layer production-time response-insolated layer materials Degree influences.
Thermo-responsive label, ferrocene derivatives (R are made in the method for embodiment 11=CHO, R2、R3=H), difference It is using different-thickness (60g/m2、100g/m2、2*60g/m2、60+100g/m2、2*100g/m2) wood-free paper as isolation Layer, to regulate and control the thermo-responsive label color pace of change.By the temperature-sensitive functional layer of thermo-responsive label and absorption instruction laminated two It is adjacent to for a sealing, the sample of sealing is placed in 40 DEG C of waters bath with thermostatic control and is placed, each specific time uses Colorlite Sph860 measurement records the color difference of the display window of thermo-responsive label.Fig. 5 is measured at a temperature of 40 DEG C of waters bath with thermostatic control are placed The variation of the watch window color difference Δ E*ab of the thermo-responsive label of different-thickness separation layer t at any time.As can be seen from Figure 5 same At a temperature of one, label chromatic aberration rate increases with separation layer thickness and is slowed down, so as to micro- by adjusting separation layer thickness Adjust the label speed of response.
As can be seen that the present invention is used as prepared by volatile dye using ferrocene or derivatives thereof from above-described embodiment Thermo-responsive label, can be adapted for the thermo-responsive article that the shelf-life at 37 DEG C is 5 hours or so and activation energy is 76kJ/mol, Or the shelf-life is 30 hours or so at 37 DEG C and activation energy is thermo-responsive article of 86kJ/mol etc..
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all Any modification, equivalent replacement, improvement and so within the spirit and principles in the present invention, are all contained in protection scope of the present invention It is interior.

Claims (11)

1. a kind of thermo-responsive label, including the temperature-sensitive functional layer and absorption instruction functional layer being bonded each other, wherein
The temperature-sensitive functional layer includes:
Film is sealed, the sealing film is preferably by polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyethylene terephthalate Ester or PET leaching membrane paper are made；
The first substrate material layer on the sealing film, first substrate material layer is preferably by blank sheet of paper, copy paper, printing paper Or PET leaching membrane paper is made, and is more preferably fitted on the sealing film by water-base cement；
Volatile dye layer is formed on first substrate material layer, containing volatile dye, the volatile dye Layer is preferably coated or impregnated with by the property of will volatilize dyestuff to be formed and in first substrate material layer；
And
The absorption indicates that functional layer includes:
Second substrate material layer, is made of clear material, and is preferably made of polymer film；
Function marker is located on second substrate material layer and has watch window, in the watch window Surrounding is preferably provided with reference color；
Sorbing material layer is located under second substrate material layer and can adsorb the dye in the volatile dye layer Material, wherein the sorbing material layer overlaps in vertical direction with the watch window or Chong Die, the preferably described sorbing material layer Size be greater than the watch window size；
Separation layer is made of opaque material and is located under the sorbing material layer, and the size of the separation layer is greater than The size of the watch window, the size of the preferably greater than or equal to described volatile dye layer, more preferably greater than, is equal to or less than The size of the sorbing material layer, the volatile dye can diffuse through the separation layer；Wherein,
The volatile dye layer of the temperature-sensitive functional layer and the separation layer of the absorption instruction functional layer are bonded opposite to each other；
The volatile dye is ferrocene shown in formula I or derivatives thereof；
Wherein:
R1、R2、R3One of represent hydrogen, halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 linear chain or branched chain Alkyl, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4Selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 straight chain Or branched alkyl amine, other two represent hydrogen；
Or
R1、R2It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 linear chain or branched chain alkane Base, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4Selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 straight chain or Branched alkyl amine, R3Represent hydrogen；
Or
R1、R3It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 linear chain or branched chain alkane Base, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4Selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 straight chain or Branched alkyl amine, R2Represent hydrogen.
2. thermo-responsive label according to claim 1 covers wherein the temperature-sensitive functional layer further includes the first release film layer It covers on the volatile dye layer, wherein the size of the sealing film and first release film layer is contaminated greater than the volatility The size of the bed of material and the volatile dye layer is sealed between the sealing film and first release film layer；
The absorption instruction functional layer further includes the second release film layer for covering the separation layer；
The temperature-sensitive functional layer and absorption instruction functional layer are physically independent before the use.
3. thermo-responsive label as described in claim 1, wherein the sorbing material layer is formed itself by adhesive sticker, preferably by saturating Bright adhesive sticker is formed, more preferably oiliness or aqueous adhesive sticker, self-adhesive paper or adhesive sticker adhesive tape.
4. thermo-responsive label as described in claim 1, wherein being coated with adhesive sticker and the adhesive sticker under the sealing film It is covered by third release film layer；
Then utilize the adhesive sticker sealed under film by the sealing by removing the third release film layer when in use Film is covered on the thermo-responsive article.
5. thermo-responsive label as described in claim 1, wherein after the separation layer volatilizees as described ferrocene or derivatives thereof From the temperature-sensitive functional layer to the diffusion admittance of the sorbing material layer and the ferrocene can be regulated and controled or derivatives thereof Diffusion velocity；It is preferred that the separation layer is single-layer or multi-layer, and absorption described two can be applied between the multi-layer isolation layer The adsorbent material of luxuriant iron or derivatives thereof；The more preferable separation layer is formed by White-opalescent material；Even more preferably from by being selected from Blank sheet of paper, copy paper, printing paper, sticky label paper material formed.
6. thermo-responsive label as described in claim 1, wherein reference face of the function marker around the watch window The adsorption material after identical process is disposed in the depth of color and volatile dye layer experience and the thermo-responsive article failure The color depth that the bed of material is obtained because adsorbing the ferrocene or derivatives thereof to volatilize from the volatile dye layer is identical.
7. the thermo-responsive label as described in any one of claim 1-6, the wherein corresponding color difference Δ E* of reference colorab=35-55.
8. thermo-responsive label as described in claim 1, wherein the adsorbent material can be adsorbed irreversibly from the volatility The speed of the dyestuff evaporated in dye coating, the preferably described adsorbent material absorption volatile dye is much larger than volatile dye Evaporation rate.
9. a kind of method for the thermo-responsive label for preparing any one such as claim 1-8 comprising following steps:
Sealing film is provided, the sealing film is preferably by polyethylene, polyvinyl chloride, polypropylene, polystyrene, poly terephthalic acid second Diol ester or PET leaching membrane paper are made；
The first substrate material is provided on the sealing film, first substrate material layer is preferably by blank sheet of paper, copy paper, printing paper Or PET leaching membrane paper is made, more preferably by the way that first substrate material is fitted on the sealing film using water-base cement；
Volatile dye layer is formed on the first substrate material, the volatile dye layer contains volatile dye, preferably passes through The property of will volatilize dyestuff is coated or impregnated on first substrate material and is formed；
And
The second substrate material layer formed by transparent material, preferably the second substrate material made of polymer film are provided；
Function marker is formed in second substrate material layer, the function marker has watch window preferably described There is reference color around watch window；
Sorbing material layer is formed under second substrate material layer, the sorbing material layer can adsorb the volatile dye Volatile dye in layer, and the sorbing material layer is overlapping or Chong Die with the watch window in vertical direction, it is described The size of sorbing material layer is preferably greater than the size of the watch window；
Separation layer is formed by opaque material under the sorbing material layer, the size of the separation layer is greater than the watch window Size, the size of the preferably greater than or equal to described volatile dye layer, more preferably greater than, be equal to or less than the adsorbent material The size of layer, the separation layer can diffuse through the volatile dye；
The volatile dye is ferrocene shown in formula I or derivatives thereof；
Wherein:
R1、R2、R3One of represent hydrogen, halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 linear chain or branched chain Alkyl, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4Selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 straight chain Or branched alkyl amine, other two represent hydrogen；
Or
R1、R2It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 linear chain or branched chain alkane Base, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4Selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 straight chain or Branched alkyl amine, R3Represent hydrogen；
Or
R1、R3It is independently represented each other halogen, vinyl, alkynyl, nitro, cyano, amido, phenyl, C1-C6 linear chain or branched chain alkane Base, C1-C6 linear chain or branched chain alcohol ,-COR ,-COOR4；R4Selected from hydrogen, phenyl, C1-C6 linear or branched alkyl group, C1-C6 straight chain or Branched alkyl amine, R2Represent hydrogen.
10. according to the method described in claim 9, its further include: cover the first release film on the volatile dye layer, Described in the size of sealing film and first release film layer be greater than the size of the volatile dye layer and by the volatilization Property dye coating is sealed between the sealing film and first release film layer, to form temperature-sensitive functional layer；
The second release film is covered under the separation layer, adsorbs instruction functional layer to be formed.
11. a kind of method for the quality state for monitoring thermo-responsive article, comprising the following steps:
Using according to the described in any item heat of claims 1-7 on one or more regions on the thermo-responsive article Thermo-responsive label, sees when required by watch window prepared by sensitive tags or the method according to claim 11 Examine the color of the sorbing material layer, if the color it is identical as reference color or than reference color depth, the thermo-responsive object Product are no longer valid；If the color is more shallow than reference color, show that the thermo-responsive article not yet fails.
CN201710702278.7A 2017-08-16 2017-08-16 A kind of thermo-responsive label, preparation method and application method Pending CN109410738A (en)

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