thermosensitive label, thermosensitive article, method for preparing a thermosensitive label and met

专利摘要:
THERMOSENSITIVE LABEL AND METHOD OF THERMOSENSITIVE LABEL AND METHOD OF PREPARATION AND USE FOR THE SAME. The present invention relates to a thermosensitive label to monitor the quality status of a thermosensitive article, a preparation method for the thermosensitive label and a thermosensitive article using the thermosensitive label. The thermosensitive label comprises two laminated layers physically separated, that is, a thermosensitive function layer (1) and an absorption indication function layer (2), in which a volatile dye layer (11) of the thermosensitive function layer ( 1) is sealed between a sealing film (13) and a first release layer, an insulation layer (23) of the absorption indication function layer (2) is covered by a second film and release layer, and the two laminated layers are separately stored and transported and are combined together respectively by removing the first release film layer and the second release film layer during use. The thermosensitive label can be stored and transported at normal temperature, which reduces the costs of using the thermosensitive label.
公开号:BR112015015159B1
申请号:R112015015159-0
申请日:2013-12-16
公开日:2020-11-10
发明作者:Zongwu Deng；Xiaofang Ying；Xiaoju Shi
申请人:Suzhou Qualimark Technology Co., Ltd；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to a thermosensitive label to monitor the quality status of a thermosensitive article, a method of preparing it and a method to monitor the quality status of a thermosensitive article using it. In particular, the present invention relates to the preparation of a thermosensitive label using a volatile dye. The thermosensitive label, by means of a color change of the adsorption material layer resulting from the volatilization of the volatile dye and then the adsorption of the volatile dye by the adsorption material layer, indicates whether a thermosensitive article has deteriorated or failed due to the influence of temperature or accumulated heat exposure. BACKGROUND TECHNIQUE
[002] Several articles or products are very sensitive to exposure to heat, like most vaccines (stored and transported, in general, between 2 ° C and 8 ° C), biological products, bioactive samples and some drugs and the like, as well as fresh foods such as fresh milk, dairy products, fresh meat, fresh fish and the like, need to be stored or transported at low temperature. For a long period of time, the main methods to ensure the safe use of these articles / products, especially drugs or food, included labeling with the period of validity, the quality guarantee period or the freshness preservation period. However, these methods generally cannot tell whether those drugs or foods that need to be stored and transported at a low temperature have been exposed to a temperature that exceeds safe storage and transport conditions for a long time and thus to excess heat. The safety and efficacy of various thermosensitive articles can best be guaranteed by using a simple and inexpensive method to accurately indicate whether thermosensitive articles, such as fresh food, vaccines, bioactive samples and the like that need to be stored at low temperature, deteriorate, fail or lose activity due to exposure to excess heat.
[003] In the 1990s, The World Health Organization (WHO) began to address the problem of vaccines that are exposed to heat during cold chain storage and transport, as this would lead to a decrease in the immune effect of vaccines, thereby reducing vaccine protection for children. Subsequently, WHO was called on to develop a label that is easy to use and inexpensive in order to accurately reflect the heat history of vaccines from the time they left the factory after manufacture, which are transported and stored to reach end users. The essential requirements for the label are shown as follows: 1. It can accurately indicate the vaccine exposed to excessive heat and, thus, restrict its use; 2. has a small volume and can be attached to a vial, ampoule, vaccine injector or similar; 3. it is stable and reliable throughout the process from production to actual use; and 4. it is suitable for low-cost mass production and satisfies the global demand for vaccines from the United Nations International Children's Fund (UNICEF).
[004] In 1996, the TempTime company (formally known as Lifelines) in the USA developed a label that can satisfy WHO requirements for the first time. The label is applied to polio vaccines produced by three vaccine manufacturers, namely GlaxoSmithKline, Sanofi-Pasteur and Novartis. The labels provided by Temptime are classified into three categories according to their functions. The first type is the Critical Temperature Indicator (CTI), which immediately changes the color once the temperature exceeds an adjusted value. The second one is the Critical Time and Temperature Indicator (CTTI), whose color change delays to a certain extent, that is, the label changes color after exposure to a temperature above the set value for several minutes or ten minutes. The third type is known as the Temperature and Time Indicator (TTI) which has a longer response time and where the temperature sensing material changes color after receiving a certain amount of heat. This type of label is a suitable label to indicate the vaccine's heat history.
[005] Currently, there are hundreds of patents related to these heat sensitive labels in the world. These patented technologies can be classified into mechanical type, chemical type, enzyme reaction type, microorganism type, polymer type, electronic type, diffusion type and the like, according to the product's operating principles. These technologies are mainly based on mechanical property, electrical property, diffusion property, bioenzyme reaction, polymerization and the like of functional materials. There are mainly three types of TTI labels that are well established and already commercialized: polymer type, enzyme reaction type and diffusion type.
[006] The polymer-type label is developed by the company TempTime in the USA and is based on the formation of a colored polymer as a result of solid state 1,4-addition polymerization of a substituted diacetylene derivative. The rate of polymerization increases as the temperature rises. The continuously formed polymer makes the color darker continuously, which, compared to the surrounding color, indicates whether the vaccines have been exposed to excess heat. It is necessary to filter and synthesize the appropriate polymeric monomer for this label. In addition, the label needs to be stored at -18 ° C or even lower after production, which obviously increases the cost of using the label.
[007] A recent enzyme reaction type indicator is essentially a type of pH indicator that indicates the heat history by measuring the color change caused by the change in pH value of the medium that is caused by the H + protons released from the enzyme hydrolysis catalyzed of lipid substrate. Enzymatic hydrolysis becomes faster as the temperature rises and, therefore, the rate of proton release also becomes faster. A typical type is a Vitsab ring indicator developed by a Swedish company.
[008] A more recent typical product of a diffusion type label is the 3M Monitoring Mark Indicator produced by the 3M company in the USA, based on the diffusion of a dye in a column, in which the temperature indicating the time range and the response time depends on the type of dyes. Another form of diffusion-type indicator can be prepared by coating a porous substrate with a material that has a specific melting point. The optical refraction indices of the substrate and the material are close together. When the coating material melts above a specific temperature and diffuses into the porous substrate, so that the air in the pores of the substrate escapes, the transmittance of the substrate increases and, thus, a color change can be achieved, showing the accumulated heat exposure.
[009] Currently, WHO classifies about twenty vaccines in 4 categories based on their thermal stability: the most unstable vaccines, unstable vaccines, stable vaccines and highly stable vaccines and therefore proposes the technical requirements for corresponding thermosensitive labels . The technical standards established in this way take into account the properties of indicator products in the prior art, but are not completely based on the thermal stability of vaccines per se. In fact, since each of about twenty vaccines that need cold chain storage and transport and are monitored throughout the process have different thermal stability, an ideal thermosensitive label should be an individualized thermosensitive label that adequately reflects thermal stability of the indicated product, that is, the rate of color change and the temperature effect of the same must keep as consistent as possible with the failure process of the indicated product.
[0010] Therefore, in the art, a thermosensitive label and a method to monitor the heat history of a thermosensitive article are still needed in order to monitor the storage and transport of a thermosensitive article in a convenient and accurate way to indicate whether an article thermosensitive fails or deteriorates. In particular, the thermosensitive label itself can be stored at room temperature before use. SUMMARY OF THE INVENTION
[0011] An objective of the present invention is to provide a thermosensitive label to monitor the quality status of a thermosensitive article that is used to monitor the heat history of a thermosensitive article and that indicates whether the thermosensitive article fails or deteriorates due to exposure excess heat. In addition, the thermosensitive label of the present invention can be stored at room temperature for a long time before use. In other words, the thermosensitive label of the present invention is not itself thermosensitive prior to use.
[0012] Another objective of the present invention is to provide a method for preparing a thermosensitive label to monitor the quality status of a thermosensitive article.
[0013] Yet another objective of the present invention is to provide a method for monitoring the quality status of a thermosensitive article.
[0014] For this purpose, the present invention provides a simple and effective thermosensitive label that can be used to monitor the accumulated heat exposure (ie, heat history) of a thermosensitive article and to alert you to exposure to excess heat during storage and transport of the thermosensitive article. When these labels are used to monitor the process of storing and transporting heat-sensitive articles, it can be seen if the accumulated heat exposure exceeds a pre-set limit. Furthermore, the thermosensitive label of the present invention is not sensitive to heat prior to use. In other words, the thermosensitive label of the present invention can be stored at room temperature or at an even higher temperature for a long time and thus can be transported and distributed conveniently.
[0015] first aspect of the present invention provides a thermosensitive label to monitor the quality status of a thermosensitive article comprising two laminated parts of a thermosensitive function layer and an adsorption indication function layer that are physically independent of each other before use. The thermosensitive function layer comprises: a sealing film; a first layer of substrate material in the sealing film, wherein the first layer of substrate material is preferably produced from white paper, copy paper or printing paper, more preferably fixed to the sealing film by aqueous adhesive; a layer of volatile dye formed on the first layer of substrate material, in which the difference between the energy of activation of the volatilization process of the volatile dye layer and that of the process of deterioration of the quality of the thermosensitive article is within a predetermined range and wherein the layer of volatile dye is preferably formed by coating or impregnating the first layer of substrate material with the volatile dye and a first layer of release film covering the layer of volatile dye, in which the sealing film and the first layer of release film are larger than the volatile dye layer in dimension and the volatile dye layer is sealed between the sealing film and the first release film layer. The adsorption indication function layer comprises: a second layer of substrate material that is produced from transparent material, preferably of polymer film; a reference indication layer that is located on top of the second layer of substrate material and has an observation window around which a reference color is present; a layer of adsorption material that is located under the second layer of substrate material and can absorb the dye from the volatile dye layer, in which the layer of adsorption material is superimposed or aligned with the observation window in the vertical direction and it is preferably larger than the observation window in dimension; an insulation layer produced from opaque material and located under the adsorption material layer, where the insulation layer is larger than the observation window in dimension, preferably greater than, or equal to the layer of volatile dye in dimension, more preferably, greater than, equal to or less than the layer of adsorption material in dimension and the volatile dye can diffuse through the insulation layer and a second layer of release film covering the insulation layer.
[0016] During use, the first release film layer and the second release film layer are peeled first, the insulation layer of the adsorption indication function layer is aligned with the volatile dye layer of the thermosensitive function; the adsorption material layer, the insulation layer and the volatile dye layer are sealed between the sealing film and the second layer of substrate material, and then the sealing film is adhered to a heat-sensitive article. Alternatively, the sealing film is first adhered to a heat-sensitive article, then the first release film layer and the second release film layer are peeled off, the insulation layer of the adsorption indication function layer is aligned to the volatile dye layer of the thermosensitive function layer and the adsorption material layer, the insulation layer and the volatile dye layer are sealed between the sealing film and the second layer of substrate material.
[0017] During use, the thermosensitive label of the present invention is applied to one or more regions of a thermosensitive article. During storage and transportation of the thermosensitive article, the volatile dye absorbs heat, volatilizes, diffuses through the insulation layer and then is adsorbed by the layer of adsorption material. The layer of adsorption material gradually becomes darker after adsorbing the colored volatile dye that can be observed through the observation window. The color depth of the adsorption material layer is positively correlated with the amount of the adsorbed dye, that is, the amount of the adsorbed dye is positively correlated with the amount of volatilization thereof and the amount of volatilization of the dye is positively correlated with the accumulated heat exposure (related to the degree of deterioration of the thermosensitive article). Selecting the type of dye according to a specific thermosensitive article that controls the rate of volatilization, diffusion and adsorption in combination with other methods enables the color response of the adsorption material layer caused by the adsorption of dye to respond to the change in activity of the thermosensitive article and thus can be readily determined whether the thermosensitive article is within the valid period or useful life simply by changing the color of the adsorption indication function layer.
[0018] Additionally, the thermosensitive label is not sensitive to exposure to heat before use, since the thermosensitive label of the present invention is presented as two laminated parts of a thermosensitive function layer and an adsorption indication function layer that are physically independent of each other before applying to a thermosensitive article and the volatile dye layer in the thermosensitive function layer of the present invention is sealed between the sealing film and the first release film layer before use. Therefore, the thermosensitive label of the present invention itself can be stored and transported at room temperature before use, without influencing the properties of the thermosensitive label of the present invention.
[0019] Again, the thermosensitive label of the present invention alone will not be influenced by the heat history of the thermosensitive label during storage and transportation before use, as the thermosensitive label can be immediately combined and applied before use. Thus, the thermosensitive label of the present invention can more accurately reflect the heat history of the thermosensitive article.
[0020] second aspect of the present invention refers to a thermosensitive article using the thermosensitive label of the present invention.
[0021] third aspect of the present invention relates to a method for preparing the thermosensitive label of the present invention.
[0022] fourth aspect of the present invention relates to a method for monitoring the thermosensitive article using the thermosensitive tag of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 is a diagram of the structure of the thermosensitive label, according to an embodiment of the present invention.
[0024] Figure 2 is a schematic diagram of the color change process of the thermosensitive label, according to a modality of the present invention during use.
[0025] Figure 3 is an effect diagram showing the color change of the thermosensitive label that is prepared using guaiazulene as the thermosensitive function material in example 1 of the present invention, over time during use.
[0026] Figure 4 shows the change in color difference ΔE * ab of the thermosensitive label that is prepared using guaiazulene as the thermosensitive function material in example 2 of the present invention, as a function of storage time t when the label thermosensitive is stored at different temperatures.
[0027] Figure 5 shows the activation energy of the color change process of the thermosensitive label that is prepared using guaiazulene as the thermosensitive function material in example 2 of the present invention, calculated with the color difference ΔE * ab = 40 as the end point of the color change.
[0028] Figure 6 shows the change in color difference ΔE * ab of the thermosensitive label that is prepared using guaiazulene as the thermosensitive function material and modifying the material and structure of the insulation layer in example 3 of the present invention, as a function of storage time t obtained at a constant temperature of 25 ° C.
[0029] Figure 7 shows the change in the color difference ΔE * ab of the thermosensitive label that is prepared using derivative of guaiaczulene substituted by R1 = COOCH3- as the thermosensitive function material in example 4 of the present invention, as a function of storage time t obtained at a constant temperature of 25 ° C.
[0030] Figure 8 shows the activation energy of the color change process of the thermosensitive label that is prepared using a guaiaczulene derivative of R1 = COOCH3 replaced as the thermosensitive function material in example 4 of the present invention, calculated with the color difference ΔE * ab = 40 as the end point of the color change.
[0031] Figure 9 shows the change in color difference of the thermosensitive label that is prepared using guaiazulene or derived guaiazulene substituted by R1 = COOCH3, COOCH (CH3) 2, COOC (CH3) 3, OR CHO as the material of thermosensitive function in example 5 of the present invention, as a function of time when the thermosensitive label is stored at 37 ° C.
[0032] Figure 10 shows the change in color difference ΔE * ab of the thermosensitive label that is prepared using guaiazulene as the thermosensitive function material and choosing five different adsorption materials in example 6 of the present invention, as a function of storage time t in the same temperature environment.
[0033] The terms and reference numbers used in the present invention are listed as follows:
[0034] thermosensitive function layer 1
[0035] adsorption indication function layer 2
[0036] first layer of substrate material 10
[0037] volatile dye layer 11
[0038] aqueous adhesive layer 12
[0039] sealing film 13
[0040] self-adhesive layer 14
[0041] 15 release film layer
[0042] transparent film substrate 20
[0043] adsorption indication area 21
[0044] layer of adsorption material 22
[0045] insulation layer 23
[0046] observation window 24
[0047] reference color 25 DETAILED DESCRIPTION OF THE MODALITIES
[0048] The first aspect of the present invention provides a thermosensitive label product for monitoring the accumulated heat exposure of a thermosensitive article and for warning of excess heat exposure thereof. This label comprises two laminated parts of a thermosensitive function layer and an adsorption indication function layer that are physically independent of each other before use, where:
[0049] the thermosensitive function layer comprises:
[0050] a sealing film;
[0051] a first layer of substrate material on the sealing film, wherein the first layer of substrate material is preferably produced from white paper, copy paper or printing paper, more preferably fixed to the sealing film by aqueous adhesive;
[0052] a layer of volatile dye formed in the first layer of substrate material, in which the difference between the activation energy of the volatilization process of the volatile dye layer and that of the quality deterioration process of the thermosensitive article is within a predetermined range and in which the layer of volatile dye is preferably formed by coating or impregnating the first layer of substrate material with the volatile dye; and
[0053] a first release film layer covering the volatile dye layer, wherein the sealing film and the first release film layer are larger than the dimension volatile dye layer and the volatile dye layer is sealed between the sealing film and the first release film layer,
[0054] and
[0055] the adsorption indication function layer comprises:
[0056] a second layer of substrate material which is produced from transparent material, preferably polymer film;
[0057] a reference indication layer that is located on top of the second layer of substrate material and has an observation window around which a reference color is present;
[0058] a layer of adsorption material that is located under the second layer of substrate material and can adsorb the dye from the volatile dye layer, in which the layer of adsorption material is superimposed or aligned with the observation window in vertical direction and is preferably larger than the observation window in dimension;
[0059] an insulation layer produced from opaque material and located under the adsorption material layer, in which the insulation layer is larger than the observation window in dimension, preferably greater than, or equal to the layer of volatile dye in dimension, more preferably, greater than, equal to or less than the layer of adsorption material in dimension and the volatile dye can diffuse through the insulation layer; and
[0060] a second layer of release film that covers the insulation layer.
[0061] During use, the first release film layer and the second release film layer are peeled off, the insulation layer of the adsorption indication function layer is aligned with the volatile dye layer of the thermosensitive function layer, the adsorption material layer, the insulation layer and the volatile dye layer are sealed between the sealing film and the second layer of substrate material, and then the sealing film is adhered to a heat-sensitive article. Alternatively, the sealing film is adhered to a thermosensitive article, then the first release film layer and the second release film layer are peeled off, the insulation layer of the adsorption indication function layer is aligned with the volatile dye of the thermosensitive function layer and the adsorption material layer, the insulation layer and the volatile dye layer are sealed between the sealing film and the second layer of substrate material.
[0062] During use, the volatile dye in the thermosensitive function layer will volatilize after exposure to heat (for example, at a desired disposal temperature, at a desired storage and / or transport temperature, if the disposal temperature rises unexpectedly, and at a desired disposal temperature for accelerated testing, for example, if the desired disposal temperature for accelerated testing is 25 ° C and / or 37 ° C). After diffusing through the insulation layer, the volatilized dye is irreversibly adsorbed by the adsorption material in the adsorption material layer. The color of the adsorption material layer becomes darker after adsorbing the volatilized dye (for example, the color in the adsorption indication area 21 of the adsorption material layer 22 shown in Figure 1 becomes darker), the which can be observed through the reference indication layer observation window. The color depth of the adsorption material layer is positively correlated with the amount of the adsorbed dye, whereas it is positively correlated with the accumulated heat exposure of the thermosensitive article.
[0063] Using the thermosensitive labels above according to the present invention, the accumulated heat exposure can be characterized by the color depth of the layer of material of visual adsorption and simply. In one mode, the color depth can be more characterized by the change in the color difference ΔE * ab. In one embodiment, the color change rate of the adsorption material layer can be characterized by the difference in the range of color variation divided by the time required to achieve the difference in range of color variation. In one embodiment, the change in the rate of color change over time follows the Arrhenius equation and can be characterized by the activation energy Ea obtained from that equation.
[0064] second aspect of the present invention provides a volatile dye, preferably a colored volatile dye, used to prepare the thermosensitive label. According to the present invention, the preferred volatile dye is guaiazulene of the following formula I or derivatives thereof:

[0065] where,
[0066] R1 includes, but is not limited to hydrogen, halogen, straight or branched C1-6 alkyl, straight or branched C1-6 alkoxy, straight or branched C1-6 alkyl hydroxy, -COR2, and -COOR2;
[0067] R2 is selected from hydrogen, straight or branched C1-6 alkyl (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, etc.), and straight or branched C1-6 alkylamine (such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, isopentylamine, neopentylamine, n- hexylamine and the like).
[0068] In one embodiment, R1 is selected from hydrogen, -COH, CH2OH, and -COOR2, and R2 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, and tert-butyl.
[0069] According to an embodiment of the present invention, the volatile dye layer may comprise the mixture of one or more (for example, two, three, or more than three) between guaiazulene or the derivatives thereof.
[0070] According to an embodiment of the present invention, the volatile dye layer can also comprise one or more volatilization aids which may be of various volatile materials which can regulate the volatilization rate of the dye and the temperature effect thereof. In a preferred embodiment, volatilization aids can be various volatile compounds which include, but are not limited to, linear or branched hydrocarbons or aromatic or cyclic hydrocarbons (which include, but are not limited to naphthalene and anthracene), various linear or branched alcohols or cyclic or aromatic alcohols (which include, but are not limited to, erythritol, lauryl alcohol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, stearyl alcohol, etc.), various linear or branched carboxylic acids or cyclic or aromatic carboxylic acids ( which include, but are not limited to, maleic acid, fumaric acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, adipic acid, sebacic acid, dodecanedioic acid, etc.), various amino acids (which include, but are not limited to, are limited to aminobenzoic acid, leucine, phenylalanine, etc.), various esters (which include, but are not limited to ethyl acetate, et c.), various sulfones (which include, but are not limited to diphenyl sulfone, diphenyl disulfone, dibenzyl sulfone, dibutyl sulfone, etc.). Volatilization aids can also be a variety of volatile natural substances (which include, but are not limited to naphthalene, camphor, etc.).
[0071] adsorption material used in the thermosensitive label of the present invention can be any material that can irreversibly adsorb the volatile dye. In one embodiment, the adsorption rate at which the adsorption material adsorbs the volatile dye is higher than the volatilization rate of the volatile dye. In one embodiment, the rate of adsorption at which the adsorption material adsorbs the volatile dye is much higher than the volatilization rate of the volatile dye. In one embodiment, the adsorption rate at which the adsorption material adsorbs the volatile dye is much higher than the volatilization rate of the volatile dye, so that the adsorption rate for the dye is substantial and merely related to the volatilization rate. of the dye. In one embodiment, the rate of adsorption at which the adsorption material adsorbs the volatile dye is much higher than the volatilization rate of the volatile dye, so that the apparent volatilization rate of the dye is influenced only by temperature (or heat) adsorbed), but not, for example, by the factor that is blocked by saturated steam / almost saturated steam due to its volatilization and the like. In one embodiment, the adsorption material includes, but is not limited to, self-adhesive oily or aqueous paper, commercial self-adhesive paper, self-adhesive tape and the like.
[0072] The material and structure of the insulation layer used in the thermosensitive label of the present invention are not limited, in particular, as long as the insulation layer has the following two functions: first, cover the color of the thermosensitive function layer, for which the insulation layer material is preferably a white opaque material; second, provide the diffusion path for the volatile dye to diffuse from the thermosensitive function layer to the adsorption material layer after volatilization, preferably with the diffusion rate regulation function at the same time. For example, the material of the insulation layer can be, but is not limited to plain white paper, copy paper, printing paper, self-adhesive label paper and the like. In one embodiment, white paper of 60 to 120 g / cm2 can be used as the insulation layer material. In one embodiment, white paper of 60 to 120 g / cm2 coated with a determined amount of self-adhesive that can irreversibly adsorb the volatile dye can be used as the insulation layer material. In one embodiment, two layers of white paper of 60 to 120 g / cm2 coated between them with a determined amount of self-adhesive that can irreversibly adsorb the volatile dye can be used as the material of the insulation layer. The change in structure can be reflected by the changes of several layers during the use of the label: in addition to the thermosensitive function layer of the label that presents the color of the volatile dye, the color of the volatile dye can appear only in the layer of adsorption material when white paper is used as the insulation layer. When white paper coated with adsorption material is used as the material of the insulation layer, the color of the volatile dye can appear both in the layer of adsorption material and in the insulation layer and, when a layer of paper insulation with layer double coated inside with a determined amount of adsorption material is used, the color of the volatile dye may appear both in the adsorption material layer and between the white papers of the insulation layer, so that the color change of the label temperature sensor of the present invention in use can be shown more effectively.
[0073] The present invention also provides the preparation process and storage methods for the thermosensitive label. In accordance with the method of the present invention, the preparation and storage of the thermosensitive label are divided into two independent parts for a thermosensitive function layer and an adsorption indication layer and includes two independent processes for preparing, respectively, two laminated parts of the thermosensitive function layer and the adsorption indication function layer.
[0074] According to the present invention, the process for preparing the thermosensitive function layer comprises: providing a sealing film; providing a first substrate material preferably produced from white paper, copy paper or printing paper on the sealing film and, more preferably, fixing the first substrate material to the sealing film with an aqueous adhesive; forming a layer of volatile dye in the first substrate material, preferably coating or impregnating the first substrate material with the volatile dye, in which the difference between the activation energy of the volatilization process of the volatile dye layer and that of the deterioration process quality of the thermosensitive article is within a predetermined range and covering the volatile dye layer with a first release film layer, where the sealing film and the first release film layer are larger than the dimension volatile dye layer and the volatile dye layer is sealed between the sealing film and the first release film layer, thus forming the thermosensitive layer.
[0075] In one embodiment, using a roll-to-roll production method, white paper of 60 to 120 g / cm2 is coated with a layer of aqueous adhesive that does not adsorb the thermosensitive function material and then it is attached to one side of the polymer film; before or after being fixed, the other side of the polymer film is coated with a self-adhesive layer that is used to affix the label to the heat-sensitive article in use, and the self-adhesive surface is protected with a release film before use. In one embodiment, using a roll-to-roll production method, the thermosensitive function material is coated on one side of the substrate's white paper by means of impregnation. The thermosensitive function material is dissolved in a suitable organic solvent (such as ethanol, acetone, diethyl ether, petroleum ether, ethyl acetate, etc.), with a preferred material concentration of 100 to 400 g / L and a movement speed preferred substrate material from 3 to 30 m / min when coated or impregnated. In one embodiment, the material coated with volatile dye is cut by the matrix into strips according to the size necessary for the label to be rolled up and then sealed for storage. In one embodiment, the substrate dimension of the thermosensitive function material cut by the die is 5 to 15 mm, preferably 8 to 12 mm. In one embodiment, the dimension of the polymer film cut by the matrix is 8 to 30 mm, preferably 10 to 20 mm.
[0076] According to the present invention, the process of making the adsorption indication function layer comprises: providing a second substrate material produced from a transparent material, preferably of a polymer film; forming a reference indication layer on the second substrate material, wherein the reference indication layer has an observation window around which a reference color is present; form a layer of adsorption material under the second substrate material, where the layer of adsorption material can adsorb the dye from the volatile dye layer, is superimposed or aligned with the observation window in the vertical direction and is preferably larger than the window dimension observation; form an insulation layer with an opaque material under the adsorption layer, where the insulation layer is larger than the observation window in dimension, preferably greater than, or equal to the volatile dye layer in dimension, more preferably, greater that, equal to or less than the layer of adsorption material in dimension, and the volatile dye can diffuse through the insulation layer and form a second release film under the insulation layer, in order to form the function layer of adsorption indication.
[0077] According to the present invention, the insulation layer, the adsorption material layer and the reference indication layer constitute another independent part of the label, known as the adsorption indication function layer. In one embodiment, a transparent self-adhesive that can irreversibly adsorb the volatile dye is used as the adsorption material. The self-adhesive is coated on the transparent polymer film as a plastic film and the surface of the self-adhesive can be protected with a release film before use. In one embodiment, a self-adhesive coated paper is used as the reference indication layer, where the color of the paper is used as the end point of the reference color and an observation window with a circular or rectangular shape or other geometric shape it is formed by cutting through the roll-to-roll matrix. In one embodiment, using a roll-to-roll production method, the reference indication layer is attached to one side of the second substrate material with no adsorption material applied. In one embodiment, using a roll-to-roll production method, the insulation layer required for the label size to be attached to the layer of adsorption material by cutting through the matrix and protected with a release film. In one embodiment, the adsorption indication function layer is cut by the matrix into strips according to the size required for the label, before being rolled up and then packed for storage. In one embodiment, the dimension of the observation window cut by the matrix is 3 to 10 mm, preferably 4 to 6 mm. In one embodiment, the size and shape of the insulation layer cut by the matrix are consistent with those of the volatile dye layer in the heat-sensitive function layer. In one embodiment, the dimension of the insulation layer cut by the matrix is larger than the volatile dye layer in the thermosensitive function layer. In one embodiment, the dimension of the adsorption indication function layer cut by the matrix is consistent with that of the thermosensitive function layer. In one embodiment, the dimension of the adsorption indication function layer cut by the matrix is greater than that of the thermosensitive function layer. In one embodiment, the dimension of the adsorption indication function layer cut by the matrix is smaller than that of the thermosensitive function layer.
[0078] sixth aspect of the present invention provides the method of using the thermosensitive label. In one embodiment, the thermosensitive function layer is transferred to a suitable position in the packaging container of the thermosensitive article, preferably by first peeling the release film under the thermosensitive function layer and then transferring the thermosensitive function layer. to a suitable position in the packaging container of the heat-sensitive article through the self-adhesive layer exposed at the bottom of the sealing film; then, the protective film release layer of the adsorption indication layer and the protective film release layer on top of the heat-sensitive function layer are peeled off, the insulation layer is aligned with the heat-sensitive function layer and those two parts are firmly fixed to each other and sealed with the self-adhesive layer of adsorption indication function. In one embodiment, the steps are as follows: first, peel the release film protection layer from the adsorption indication function layer and the release film protection layer on top of the thermosensitive function layer, align the insulation to the thermosensitive function layer and firmly fix and seal the two parts with the self-adhesive adsorption indication function layer, then peel off the release film at the bottom of the thermosensitive function layer and transfer the entire label to a suitable position in the packaging container of the heat-sensitive article with the self-adhesive layer exposed. Thus, in the case of monitoring the effect of exposure to accumulated heat or temperature in a thermosensitive article, for example, during storage and / or transportation, the volatile dye will not leak from the sealing system consisting of the sealing film and the second substrate material and by means of which all the volatilized dye produced under the change of temperature / exposure to heat will be substantially adsorbed on the adsorption material. According to the present invention, the color depth of the adsorption material layer can be observed or determined through the label observation window when the monitored thermosensitive article is not influenced by exposure to heat or temperature anymore, for example, after required storage and / or transportation. The color depth is positively correlated with the accumulated heat exposure of the thermosensitive article. Therefore, in one embodiment, the accumulated heat exposure of the thermosensitive article can be visually presented with the color of the adsorption material layer on the thermosensitive label of the present invention.
[0079] The present invention also provides the method for monitoring with the thermosensitive label of the present invention, including applying the thermosensitive label of the present invention to one or more regions of the thermosensitive article, observing the color of the adsorption material layer through the observation, as necessary, if the observed color is darker than the reference color, the thermosensitive article has failed and if the observed color is lighter than the reference color, it is indicated that the thermosensitive article has not failed.
[0080] In one embodiment, the method comprises the following steps:
[0081] supply a thermosensitive article, determine the period of time for which the thermosensitive article can last in order to maintain the valid quality state at the desired disposal temperature (for example, storage and / or transportation, or accelerated testing) (the period of time can refer to the longest period of time that the thermosensitive article can last, also known as the validity period, known as t1), determine the material of the thermosensitive function layer as well as the material of the adsorption indication layer and the structure of them to manufacture the thermosensitive label according to the time period (for example, selecting different dyes to obtain different volatilities or selecting different materials of the insulation layer to obtain different diffusion rates of the volatile dye or selecting adsorption materials different adsorption rates) and making the heat-sensitive function layer and layer of adsorption indication function of the thermosensitive label according to the method of the present invention.
[0082] According to the method of the present invention, align the thermosensitive function layer of the thermosensitive label to the adsorption indication layer of the thermosensitive label, seal and fix them firmly and measure the initial color difference in the window observation with a colorimeter (without volatilization and dye adsorption at that time, the initial color difference in the observation window can be expressed as CO). The label is placed in the desired arrangement (such as storage and / or transport or accelerated stability test) temperature (which can be expressed as T1 in the present invention) for storage, record the color difference in the observation window regularly. Plot a color difference curve as a function of time and obtain the color difference at the time of the storage validity period t1 of the thermosensitive article (the color difference in the observation window at that moment can be expressed as C1), and use as the reference color. The rate of change of color difference at this T1 temperature of disposition can be obtained by dividing the change in color difference (C1-C0) by the time necessary to achieve the change in color difference.
[0083] In one mode, store the thermosensitive label at different disposal temperatures and record a color difference in the observation window regularly. The color difference curve can be plotted as a function of time and the time required for staining in the observation window to reach the end point color difference at the elimination temperature can be obtained. The time is compared with the valid period of the thermosensitive article at that disposal temperature and under ideal conditions of disposal, those two periods of time should be as close as possible.
[0084] Divide the change in color difference (C1-C0) by the time t1 required to achieve the change in color difference at different elimination temperatures, to obtain the rate of change of color difference at different elimination temperatures T1. The rate of change of the color difference at a different elimination temperature is logged and the curve is plotted using this log value as ordered and the reciprocal of the elimination temperature (thermodynamic temperature) as abscissa. In principle, the activation energy of the thermosensitive label to reach the end point staining can be obtained based on the Arrhenius equation

[0085] where critical parameters such as activation energy E, velocity constant k, thermodynamic temperature T, etc. are included. In an ideal condition, the activation energy should be close to the activation energy of the thermally sensitive product to fail.
[0086] (v) Observe the coloring of the absorption layer through the observation window of the absorption indication function layer and compare it with the reference coloring to estimate the quality status of the thermosensitive article:
[0087] If the coloring in the observation window is lighter than the reference coloring, it is indicated that the thermosensitive article remains in an effective quality state;
[0088] If the coloring in the observation window is darker than the reference coloring, it is indicated that the thermosensitive article is not in an effective quality state;
[0089] The thermosensitive label of the present invention can be used to monitor a wide thermal stability range of thermosensitive articles. For example, this includes, but is not limited to, storing for 2 hours at 45 days, at 37 ° C, storing for 6 hours at 1 year at 25 ° C, with a corresponding activation energy of 60 to 100 kJ / mol. In one embodiment, guaiazulene is used as the volatile dye, a self-adhesive that irreversibly absorbs guaiazulene is used as the absorption material and white paper from 60 to 120 g / cm2, or paper coated with a certain amount of self-adhesive, or two layers of 60 to 120 g / cm2 paper coated between them with a certain amount of self-adhesive is used as the insulation layer. The produced thermosensitive label uses a color difference of 30 to 40 relative to plain white paper as an end point. When stored at 37 ° C, the time to reach the end point is between 1 and 30 hours and when stored at 25 ° C, the time to reach the end point is between 3 and 75 hours. In one embodiment, a guaiaczulene derivative substituted with R1 = COOCH3 is used as the volatile dye, a self-adhesive that irreversibly absorbs the guaiaczulene derivative is used as the absorption material and white paper from 60 to 120 g / cm2, or paper coated with a certain amount of self-adhesive, or two layers of 60 to 120 g / cm2 paper coated between them with a certain amount of self-adhesive is used as the insulation layer. The thermosensitive label produced in accordance with the present invention uses a color difference of 30 to 40 relative to plain white paper as an end point. When stored at 37 ° C, the time to reach the end point is between 2 and 35 days and when stored at 25 ° C, the time to reach the end point is between 6 and 80 days. In one embodiment, a guaiaczulene derivative substituted with R1 = COOC (CH3) 3 is used as the volatile dye, a self-adhesive that irreversibly absorbs the guaiaczulene derivative is used as the absorption material and 60 to 120 g white paper / cm2, or coated paper with about a self-adhesive amount, or two layers of 60 to 120 g / cm2 paper coated between them with a certain amount of self-adhesive is used as the insulation layer. The thermosensitive label produced in accordance with the present invention uses a color difference of 30 to 40 relative to plain white paper as an end point. When stored at 37 ° C, the time to reach the end point is between 1.5 and 30 days and when stored at 25 ° C, the time to reach the end point is between 5 and 60 days.
[0090] The objective of a modality of the present invention is to produce an individualized thermosensitive label of which the rate of color change and the temperature effect can adequately reflect the thermal stability of the indicated product. Such an individualized label can be designed for the specific storage requirements and characteristics of a certain type of heat-sensitive articles. In one embodiment, the objective can be achieved by selecting a volatile dye from which the volatilization rate and activation energy can adequately reflect the thermal stability of the indicated product, or other volatile opaque materials.
[0091] The purpose of one embodiment of the present invention is to produce a dye or material formulation by adding a volatilization aid to the selected volatile dye or other volatile opaque materials, to change the volatilization rate of the volatile materials and the effect of temperature, in such a way that this can accurately reflect the thermal stability of the indicated thermosensitive article.
[0092] The purpose of an embodiment of the present invention is to produce a thermosensitive label that can be stored at room temperature. The objective can be achieved by the following method, the two portions of the heat sensitive function layer and the absorption indication function layer are produced separately and stored and combined with each other during use; after the thermosensitive function layer is coated with the volatile dye, a release film that does not absorb the thermosensitive function material is used first to seal and protect the thermosensitive function layer; and the thermosensitive function layer and the absorption indication function layer are produced and stored separately, which in this way achieves ambient temperature preservation of these two functional portions.
[0093] In one embodiment of the present invention, a product is provided for monitoring accumulated heat exposure and warning of excessive heat exposure of a product needed to be stored and transported at low temperature (for example, the thermosensitive article of the present invention) during storage and transportation and is used to determine whether the thermosensitive article deteriorates / fails / loses activity due to exposure to excessive heat during cold storage and transportation. For the monitoring and alerting of a product, in the first aspect, based on the volatilization property of the material, the activation energy of the deterioration of the product quality due to heat exposure is represented quantitatively by the activation energy of the material volatilization process. ; in the second aspect, the volatile material used is a colored material; and in the third aspect, the absorption material layer, specifically the absorption indication area in the absorption material layer, is made of a material that can irreversibly absorb the colored volatile dye. Because the volatile material is absorbed by the absorption material layer after volatilization, which results in a significant color change in the absorption indication area, it can be determined as to whether the product remains valid or deteriorates / fails / loses activity.
[0094] In an embodiment of the present invention, thermosensitive function materials, that is, volatile dyes: guaiazulene and derivatives thereof, or a mixture of one or more of them, which are used to produce the volatile dye layer or the thermosensitive label described above are provided. The volatile material volatilizes after exposure to heat and the volatilization rate and its temperature effect can adequately reflect the rate of deterioration or failure of the indicated product and its temperature effect.
[0095] In an embodiment of the present invention, substrate materials used to produce the thermosensitive function layer of the thermosensitive label described above, such as plain paper, copy paper, printing paper and the like are provided.
[0096] In an embodiment of the present invention, materials used to produce the sealing film of the thermosensitive function layer of the thermosensitive label described above, such as polymer materials not permeable to volatile dye, are provided.
[0097] In an embodiment of the present invention, the absorption materials used to produce the layer of absorption material of the heat sensitive label described above, such as the various self-adhesives, are provided. Preferably, the absorption material absorbs a lot and irreversibly the thermosensitive function material (that is, the volatile dye) and the absorption rate is much higher than the volatilization rate of the thermosensitive function material, which ensures Thus, the apparent volatilization rate is influenced only by temperature.
[0098] In an embodiment of the present invention, the absorption materials used to produce the absorption material layer of the heat-sensitive label described above are provided, wherein the absorption material irreversibly absorbs the heat-sensitive material and the rate of change of coloring of the thermosensitive label and its temperature effect are regulated by selecting different absorption materials.
[0099] In an embodiment of the present invention, the production process and storage method of the thermosensitive label are provided, wherein both the thermosensitive function layer and the absorption indication function layer can be produced by the production processes such as such as roll to roll, die cut, fastening, etc. used in the production of traditional self-adhesives; and optimized material concentrations, the dimensions of each portion of the label, the speed of production and the like are provided, such that the thermosensitive label of the present invention can be produced cheaply, conveniently and mass.
[00100] In an embodiment of the present invention, the method of using the thermosensitive label is provided. The method is characterized in that the thermosensitive function layer and the absorption indication function layer are combined with each other during use and are effectively sealed to protect the functional portion of the thermosensitive label from being contaminated from the outside and to prevent volatile materials from contaminating the product or package after volatilization.
[00101] In an embodiment of the present invention, the test method of using the thermosensitive label is provided. The method is characterized in that the color difference in the label observation window is measured with a colorimeter to quantify the color change of the label, an appropriate end point of the color difference is selected to determine the response time and the rate of color change and the activation energy parameter of the thermosensitive label is determined with the Arrhenius equation. According to two parameters of the valid period and the activation energy of the thermosensitive article at a certain disposal temperature, the thermosensitive material and label structure applicable to the thermosensitive article are determined with the response time of the label and the activation energy of the obtained from the test results.
[00102] In an embodiment of the present invention, a method is provided to determine the reference color of the thermosensitive label. The method is characterized in that the label is stored at a desired disposal temperature and the color difference in the observation window is recorded regularly. A color difference curve as a function of time is plotted, the color difference of the thermosensitive label stored at the disposal temperature for the valid period t1 is obtained and used as the reference color and then the reference color is printed.
[00103] In an embodiment of the present invention, the application range of the thermosensitive label is provided, in which the indicated temperature range is between 0 ° C and 50 ° C, the indicated time range varies with temperature, with a range typical time of 2 hours to 45 days at 37 ° C, 6 hours to 1 year at 25 ° C, 1 day to 6 years at 5 ° C and the response activation energy is between 60 kJ / mol and 100 kJ / mol. EXAMPLES
[00104] The present invention will be described further by several types of examples below, but the scope of the present invention is not limited to them. It can be understood by those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. The present invention generally and / or specifically describes the material and the best method used in the test. Although many materials and methods of operation used to achieve the objectives of the present invention are known in the art, the present invention still describes them hereto as much as possible. EXAMPLES OF THE THERMOSENSITIVE LABEL
[00105] The present invention produced a thermosensitive label using the property of volatilization of materials and achieved the necessary effect of color change by a process of exposure, volatilization and absorption. The structure of an exemplary thermosensitive label designed by the inventor and the operating principle of it are shown in Figure 1 and Figure 2.
[00106] With reference to the cross-sectional view shown in Figure 1, the thermosensitive label of the present invention was described therein, which consisted of two portions: portion (a) was a thermosensitive function layer 1 and portion (b) it was an absorption indication function layer 2. These two portions were produced and stored separately and combined with each other and fixed to the surface of the thermosensitive article container or package to be monitored during use.
[00107] In the thermosensitive function layer 1, the layer of substrate material 10 was coated with a layer of aqueous adhesive 12 on the bottom face and then fixed on the sealing film 13. Since the sealing film 13 is not permeable to the dye , the diffusion of the dye down to contaminate the thermosensitive article can be prevented. The bottom face of the sealing film 13 was coated with a self-adhesive layer 14 and protected with a release film 15. The functional location at the top of the substrate material layer 10 was coated with a layer of colored volatile dye with volatilizing property. specific, thereby forming the thermosensitive layer 11 of the present invention. The volatilization rate of the volatile dye used and the temperature effect of it must be kept as consistent as possible with the rate of deterioration or failure of the indicated product and the temperature effect of the same. The thermosensitive function layer was dried and sealed for storage. The sealing property can ensure that the thermosensitive function layer can be stored and transported at room temperature.
[00108] In the absorption indication function layer 2, a thin transparent plastic film was used as the substrate material layer 20. A piece of self-adhesive paper was attached to the top face of the substrate film and the reference coloring 25 and the appropriate product information (for example, the type of thermosensitive article on which the label is applicable) or information on the use of the label (for example, information on how to operate when the label is used to determine whether the thermosensitive article failed or not) were printed on the self-adhesive paper before fixation and an observation window 24 of circular or rectangular shape or other geometric shapes was formed by die cutting. The bottom face of the substrate material layer 20 has been coated or impregnated with an absorption material layer that can effectively absorb the volatilized thermosensitive function dye, which thus forms the absorption material layer 22. In that For example, transparent high-adhesives that can irreversibly absorb volatile dye are used. In the position corresponding to the indication window, an insulating layer 23 of appropriate size was cut into a matrix and attached to the self-adhesive used as the absorption material. The volatile dye diffused through the insulation layer and was absorbed by the absorption layer after volatilization as a result of exposure to heat, so that the coloring of the absorption layer 21 becomes darker.
[00109] Figure 2 shows the process of changing the absorption indication function layer 21 relative to the reference coloring layer 25 when using the thermosensitive label of the present invention from a top view. It is illustrated that the present invention used the property of materials volatilization to produce the thermosensitive label and through the process of exposure to heat, volatilization and absorption, it achieved the color change of the indication portion of the label, which shows as to whether the heat-sensitive product that uses this label deteriorates or fails due to exposure to excessive heat.
[00110] During the combined use of the heat-sensitive label and the heat-sensitive article, the color depth of the reference coloring layer 25 has not changed, while the color depth of the absorption indication function layer has become darker as a result of the absorption. of the volatile dye by exposure to heat. The rate of color darkening was influenced by temperature. Even under a desired temperature provided for the thermosensitive article, the volatile dye layer 11 also volatilized to some extent. Accordingly, the coloring of the absorption layer slowly became darker. For example, for a drug with a valid period of 2 years for storage at 2 to 8 ° C, after that drug was stored strictly at 2 to 8 ° C for 2 years, the absorption layer 21 gradually became darker due to absorption of the slowly volatilized dye. At that time, the color of the absorption layer 21 was lighter than the reference color 25, which indicates that the drug was still qualified after storing at 2 to 8 ° C for two years. When the storage time continued, the absorption indication function layer 21 continued to darken due to the absorption of the volatilized dye. Subsequently, the coloring of the same was comparable to or darker than that of the reference coloring layer 25, which indicates that the drug has expired. This process is also a design modality of the material type of the volatile dye layer 11 and the color depth of the reference dye layer 25. An accelerated test modality is also described in this document. B. DETERMINATION OF THE COLORING OF THE REFERENCE COLORING LAYER OF THE THERMOSENSITIVE LABEL
[00111] After the thermosensitive label has been produced according to the structure shown in Figure 1, the change in color difference in the functional portion of the thermosensitive label, that is, the observation window, as a function of time was measured by a colorimeter under corresponding constant temperatures (for example, 5 ° C, 10 ° C, 25 ° C and / or 37 ° C, etc.) and the rate of color change of the thermosensitive label and its temperature effect was obtained.
[00112] The color change was digitized with a colorimeter. When the colorimeter is used to measure color change, a color space such as L * a * b * color space (also known as CIELAB color space) was first defined. In this coloring space, L * represents brightness; a * and b * are chromatic coordinates and represent the color directions; + a * represents the direction of red, -a * represents the direction of green, + b * represents the direction of yellow, -b * represents the direction of blue and the center is colorless. When the values of a * and b * increased and moved out of the center, the color saturation increased. In this coloring space, the color difference can be expressed as a single numerical value: ΔE * ab = [(ΔL *) 2+ (Δa *) 2+ (Δb *) 2] 05
[00113] where, ΔL * is the change in brightness, Δa * is the change along the geometric axis of red and green coloring and Δb * is the change of color along the geometric axis of yellow and blue coloring. Staining was quantified with a colorimeter such as Minolta CR-310 Chroma Meter, Colorlite Sph860 or similar, so that the color difference can be quantified. Then the color change of the produced thermosensitive label was evaluated and the color difference of an end point was determined. A white substrate such as A4 paper was used as a reference to measure the color difference. When the label was in use, the original color difference was observed through the observation window. The label was stored under the desired disposal temperature and the color difference in the observation window was recorded regularly. A curve describing the change in color difference over time was created and the color difference of the thermosensitive label stored at the disposal temperature for the valid period t1 was obtained and used as the reference color and then the reference color is printed . C. DESCRIPTION OF PRODUCTION AND APPLICATION OF THE THERMOSENSITIVE LABEL OF THE PRESENT INVENTION WITH SPECIFIC EXAMPLES EXAMPLE 1:
[00114] The thermosensitive function layer was prepared according to the method of the present invention with the use of guaiazulene (C15H18) as the thermosensitive functional material of the thermosensitive label, with the use of 60 g / cm2 white paper (offset paper of double-sided, Beijing Xinaopeng technology Co., LTD) as the substrate of the thermosensitive function material, with the use of polymer plastic film (PP) as the sealing film and with the use of a release film (PET release film , Suzhou Dawan plastics and electronics Co., LTD) commercially available. The absorption indication function layer was prepared according to the method of the present invention using a thin plastic film coated with a transparent self-adhesive (transparent piece of PET gum PF04, Shanghai Humai composite materials Co., LTD) as the substrate material layer and the absorption material layer of the absorption indication function layer, using 60 g / cm2 white paper as the insulation layer, using a commercially available release film and with the use of a self-adhesive paper as the material of the indication function layer. The thermosensitive function layer and the label absorption indication function layer were combined with each other by sealing and tightly fixing and the sealed sample was maintained at a constant temperature of 25 ° C. After resting for a while, the color of the thermosensitive label was observed and recorded. Figure 3 shows the color registration of the thermosensitive label, which was kept at a constant temperature of 25 ° C for 0 to 10 hours, in which the coloration of the absorption indication function layer became darker as the storage time changed. stretched. EXAMPLE 2:
[00115] Figure 4 shows the changes in color difference ΔE * ab as a function of time t at different temperatures obtained by storing the thermosensitive label produced in example 1 at 45 ° C, 37 ° C, 25 ° C and 5 ° C and recording the color difference in the observation window regularly with a colorimeter (Colorlite Sph860). The initial color difference was ΔE * ab = 4-5. By selecting the appropriate endpoint color difference, the time and rate of color change of the heat sensitive label were obtained. For example, when the end point color difference was ΔE * ab = 40, the time to reach the end point was 1.5, 3, 8, 77 hours at 45 ° C, 37 ° C, 25 ° C and 5 ° C respectively. The activation energy of the change process was then deduced with the Arrhenius equation and was about 56.4 kJ / mol (Figure 5), thus obtaining the parameters for characterizing the temperature effect during the process of changing the color of the thermosensitive label. EXAMPLE 3:
[00116] The thermosensitive labels of the present invention were produced in a similar manner to example 1, with the exception that the insulation layer material and structure were modified to regulate the color change rate of the thermosensitive label at temperatures different disposal methods. In particular, the thermosensitive labels were prepared according to the method of example 1 using guaiazulene as the thermosensitive material of the thermosensitive label and using 60 g / cm2 white paper (paper), double sided paper of 60 g / cm2 (paper + paper), white paper with a layer of 60 g / cm2 coated with a certain amount of self-adhesive (paper + adhesive), or white paper with two layers of 60 g / cm2 coated between them with a certain amount amount of self-adhesive (paper + adhesive + paper) respectively as the insulation layer. The thermosensitive function layer and the label absorption indication function layer were combined with each other by sealing and tightly fixing and the sealed sample was maintained at a constant temperature of 25 ° C. The color difference in the observation window was recorded regularly with a colorimeter and the changes obtained in the color difference ΔE * ab according to a time function t were shown in Figure 6: for heat-sensitive labels that use different insulation layers, the times to reach a specific end point were different. EXAMPLE 4:
[00117] The thermosensitive label of the present invention was produced in a similar manner to example 1, with the exception that the different thermosensitive material or combination thereof was used to regulate the rate of color change of the thermosensitive label and the energy of activation at different disposal temperatures. Figure 7 shows the changes in the color difference ΔE * ab as a function of time t at different temperatures obtained by the following steps: producing the thermosensitive label according to the method of example 1 by choosing the guaiazulene derivative substituted with R1 = COOCH3 as the heat-sensitive function material, combine the heat-sensitive function layer of the label with the absorption function layer of the label by tightly sealing and fixing, store at 55 ° C, 45 ° C, 37 ° C and 25 ° C and record the color difference in the observation window regularly with a colorimeter. The initial color difference of the label was ΔE * ab = 4-5. By selecting the appropriate endpoint color difference, the time and rate of color change of the heat sensitive label were obtained. For example, when the end point color difference was defined as ΔE * ab = 40, the time to reach the end point was 27, 65, 136, 421 hours at 55 ° C, 45 ° C, 37 ° C and 25 ° C respectively. Thus, the activation energy of the change process was deduced with the Arrhenius equation and was around 77 kJ / mol (Figure 8), thus obtaining the parameters for characterizing the temperature effect during the process of changing the color of the thermosensitive label. It can be seen that both the response time and activation energy of the thermosensitive label prepared with guaiaczulene derivative substituted by R1 = COOCH3 were different from those of the thermosensitive label prepared with guaiazulene. EXAMPLE 5:
[00118] Thermosensitive labels were produced in a similar way to example 1 using guaiazulene and guaiaczulene derivatives replaced by R1 = COOCH3, COOCH (CH3) 2, COOC (CHs) 3 and CHO respectively as the thermosensitive function material . From the changes in color difference as a function of time when stored at 37 ° C (Figure 9), it can be seen that, for labels with different thermosensitive materials, the times to reach the same end point color difference are many different. EXAMPLE 6:
[00119] The thermosensitive functional labels of the present invention were produced in a similar manner to example 1, with the exception that different absorption materials were used to regulate the rate of color change of the thermosensitive label and the activation energy of the same. Figure 10 showed a method with reference to the method of example 1. Thermosensitive labels were produced using guaiazulene as the thermosensitive function material and using five different absorption materials respectively. The rates of change in the color difference of the thermal-sensitive label absorption indication function layer as a function of time at the same room temperature were significantly different from each other.
[00120] The exemplary description and exemplary examples above will not limit the scope of protection of the present invention. Any technical solutions formed by identical alternation or equivalent substitution, or any thermosensitive label prepared with a different process or formulation according to the technical solution or concept of the present invention is within the scope of protection of the present invention.

权利要求:
Claims (15)
[0001]
1. Thermosensitive label to monitor the quality status of a thermosensitive article, especially dairy products, vaccines, biological products, bioactive samples, medicines, foods or drinks, comprising two laminated portions of a thermosensitive function layer (1) than a layer of adsorption indication function (2), which are physically independent of each other before use, characterized by the fact that the thermosensitive function layer (1) comprises: a sealing film (13); a first layer of substrate material (10) on the sealing film (13), wherein the first layer of substrate material (10) is preferably made of white paper, copy paper, or printing paper, more preferably attached to the film sealant (13) by aqueous adhesive; a layer of volatile dye (11) formed in the first layer of substrate material (10), in which the difference between the energy of activation of the volatilization process of the layer of volatile dye (11) and that of the process of deterioration of quality of the thermosensitive article is within a predetermined range, and in which the layer of volatile dye (11) is formed preferably by coating or impregnating the first layer of substrate material (10) with the volatile dye; and a first release film layer, which covers the volatile dye layer (11), wherein the sealing film (13) and the first release film layer are larger than the volatile dye layer (11) in dimension , and the volatile dye layer (11) is sealed between the sealing film (13) and the first release film layer, and the adsorption indication function layer (2) comprises: a second layer of substrate material, which is made of transparent material, preferably of polymer film; a reference indication layer, which is located above the second layer of substrate material and has an observation window (24) around which a reference coloring is present; a layer of adsorption material (22), which is located under the second layer of substrate material and is capable of absorbing the dye from the volatile dye layer (11), in which the layer of adsorption material (22) is superimposed or aligned with the observation window (24) in the vertical direction, and the layer of adsorption material (22) is preferably larger than the observation window (24) in the dimension; an insulation layer (23) made of opaque material and located under the layer of adsorption material (22), where the insulation layer (23) is larger than the observation window (24) in dimension, preferably larger or equal to the volatile dye layer (11) in the dimension, more preferably greater than, equal to or less than the adsorption material layer (22) in the dimension, and the volatile dye is able to diffuse through the insulation layer (23) ; and a second layer of release film, which covers the insulation layer (23).
[0002]
2. Thermosensitive label, according to claim 1, characterized by the fact that the layer of adsorption material (22) itself is made of a self-adhesive, preferably a transparent self-adhesive and more preferably an oily or aqueous self-adhesive, paper self-adhesive or self-adhesive tape.
[0003]
3. Thermosensitive label according to claim 1 or 2, characterized in that, during use, the first release film layer and the second release film layer are peeled off, the insulation layer (23) of the layer adsorption indication function (2) is aligned with the volatile dye layer (11) of the thermosensitive function layer (1), and the insulation layer (23) and the volatile dye layer (11) are sealed between the sealing film (13) and the second layer of substrate material; and then the sealing film (13) is adhered to the thermosensitive article; or, the sealing film (13) is adhered to the thermosensitive article, so the first release film layer and the second release film layer are peeled off, the insulation layer (23) of the adsorption indication function layer (2 ) is aligned with the volatile dye layer (11) of the thermosensitive function layer (1), and the insulation layer (23) and the volatile dye layer (11) are sealed between the sealing film (13) and the second layer of substrate material.
[0004]
4. Thermosensitive label according to any one of claims 1 to 3, characterized by the fact that the sealing film (13) is coated with a self-adhesive on the bottom face and the self-adhesive is covered by a third release film; during use, the third release film is peeled off, and then the sealing film (13) is adhered to the heat-sensitive article with the self-adhesive on the bottom face of the sealing film (13).
[0005]
5. Thermosensitive label according to any one of claims 1 to 4, characterized by the fact that the insulation layer (23) acts as a diffusion path for the dye that diffuses from the thermosensitive function layer (1) for the adsorption material layer (22) after volatilization and can regulate the diffusion rate of the volatile dye; the insulation layer (23) is preferably one layer or multiple layers, and an adsorption material that can absorb the dye can be coated between the multiple layers of the insulation layer (23); more preferably, the insulation layer (23) is made of opaque white material; and even more preferably, the insulation layer (23) is made of a material selected from white paper, copy paper, printing paper and self-adhesive label paper.
[0006]
6. Thermosensitive label according to any one of claims 1 to 5, characterized in that the color depth of the reference coloring around the observation window (24) of the reference indication layer is equal to the color depth of the layer of adsorption material (22) that absorbs the volatilized dye from the volatile dye layer (11) after the volatile dye layer (11) has been subjected to the same process as that in which the heat-sensitive article fails.
[0007]
7. Thermosensitive label according to any one of claims 1 to 6, characterized by the fact that the adsorption material can irreversibly absorb the volatilized dye from the volatile dye layer (11), and the adsorption rate at which the adsorption material absorbs the volatile dye is preferably much higher than the volatilization rate of the volatile dye.
[0008]
8. Thermosensitive label according to any one of claims 1 to 7, characterized by the fact that the activation energy of the volatilization process of the volatile dye layer (11) is 60 to 100 kJ / mol, and the difference between the activation energy of the volatilization process of the volatile dye layer (11) and that of the quality deterioration process of the thermosensitive article is preferably within the range of ± 10 kJ / mol, more preferably within the range of ± 5 kJ / mol .
[0009]
9. Thermosensitive label according to any one of claims 1 to 8, characterized by the fact that the volatile dye in the volatile dye layer (11) is at least one selected from azores, anthraquinone dyes, compounds of formula I and derivatives thereof, or a combination thereof, in which the compounds of formula I have the following general formula:
[0010]
10. Thermosensitive label according to any one of claims 1 to 9, characterized by the fact that the volatile dye layer (11) additionally comprises one or more volatilization aids, wherein the volatilization aid is one or more selected a from volatile compounds: linear alkanes, branched alkanes, cycloalkanes, or aromatic hydrocarbons, preferably including hexane, heptane, octane or the isomers thereof, cyclohexane, cycloheptane, cyclopentane, naphthalene, anthracene and the like; linear or branched or aromatic or cyclic alcohols, preferably including erythritol, lauryl alcohol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, stearyl alcohol and the like; linear or branched or aromatic or cyclic carboxylic acids, preferably including maleic acid, fumaric acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, adipic acid, sebacic acid, dodecanedioic acid and the like; amino acids, preferably including aminobenzoic acid, leucine, phenylalanine and the like; esters, preferably including ethyl acetate and the like; sulfones, preferably including diphenyl sulfone, diphenyl disulfone, dibenzyl sulfone, dibutyl sulfone and the like; and various volatile natural materials, preferably including naphthalene, camphor and the like.
[0011]
11. Thermosensitive article characterized by the fact that it comprises the thermosensitive label, as defined in any one of claims 1 to 10.
[0012]
12. Method for preparing the thermosensitive label to monitor the quality status of a thermosensitive article, as defined in any one of claims 1 to 10, characterized by the fact that the method comprises the following steps. providing a sealing film (13); providing a substrate material, preferably made of white paper, copy paper, or printing paper, in the sealing film (13) and more preferably, fixing the first substrate material to the sealing film (13) with an aqueous adhesive; form a layer of volatile dye (11) in the first substrate material, preferably by coating or impregnating the first substrate material with the volatile dye, in which the difference between the activation energy of the dye layer volatilization process volatile (11) and that of the quality deterioration process of the thermosensitive article is within a predetermined range; cover the volatile dye with a first release film layer, where the sealing film (13) and the first release film layer are larger than the volatile dye layer (11) in dimension, and the volatile dye layer (11) is sealed between the sealing film (13) and the first release film layer, thereby forming the thermosensitive function layer (1); and providing a second substrate material made of a transparent material, preferably a polymer film; forming a reference indication layer on the second substrate material, wherein the reference indication layer has an observation window (24) around which a reference coloring is present; form a layer of adsorption material (22) under the second substrate material, where the layer of adsorption material (22) can absorb the dye in the volatile dye layer (11), which is superimposed or aligned with the observation (24) in the vertical direction, preferably larger than the observation window (24) in the dimension; forming an insulation layer (23) with an opaque material under the adsorption material layer (22), wherein the insulation layer (23) is larger than the observation window (24) in dimension, preferably greater than or equal the volatile dye layer (11) in the dimension, more preferably greater than, equal to or less than the adsorption material layer (22) in the dimension, and the volatile dye is able to diffuse through the insulation layer (23); and forming a second release film under the insulation layer (23), so as to form an adsorption indication function layer (2).
[0013]
13. Method according to claim 12, further comprising the step of printing a reference coloring layer around the observation window (24) after forming the reference indication layer, characterized by the fact that the coloring layer The reference color is made of a non-volatile dye, and its color depth is equal to the color depth of the adsorption material layer (22) which absorbs the dye from the volatile dye layer (11) after the volatile dye layer. (11) have been subjected to the same process as that in which the thermosensitive article fails.
[0014]
14. Method according to claim 12 or 13, characterized by the fact that the reference coloring around the observation window (24) of the reference indication layer is determined by the following steps: 1) measuring the color difference initial in the observation window (24), that is, the initial color difference in the observation window (24) without volatilization and adsorption of the dye (CO), with a colorimeter; and 2) keep the label under a desired disposal condition, record the color difference in the observation window (24) regularly, plot a color difference curve as a function of time, obtain the color difference (C1) at the moment of the valid storage period of the thermosensitive label, and use the color obtained from the layer of adsorption material (22) observed through the observation window (24) when the color difference (C1) is observed as the reference color.
[0015]
15. Method for monitoring the quality status of a thermosensitive article, characterized by the fact that it comprises the following steps: applying the thermosensitive label, as defined in any of claims 1 to 10, or the thermosensitive label prepared according to the method , as defined in any one of claims 12 to 14, in one or more regions of the heat-sensitive article, and observe the coloring of the adsorption material layer (22) through the observation window (24) as necessary, if the coloring is the same or darker than the reference color, this indicates that the thermosensitive article fails; and if that coloring is lighter than the reference coloring, this indicates that the thermosensitive article does not fail.

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BR112015015159A2|2017-07-11|

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KR20150097751A|2015-08-26|

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法律状态:
2018-05-15| B25D| Requested change of name of applicant approved|Owner name: SUZHOU QUALIMARK TECHNOLOGY CO., LTD. (CN) |

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2018-06-05| B25G| Requested change of headquarter approved|Owner name: SUZHOU QUALIMARK TECHNOLOGY CO., LTD. (CN) |

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2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2020-04-14| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-09-15| B09A| Decision: intention to grant|

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2020-11-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/12/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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CN201210567490.4A|CN103903509B|2012-12-24|2012-12-24|Thermo-responsive label and its preparation and application|

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CN201210567490.4|2012-12-24|

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PCT/CN2013/089507|WO2014101679A1|2012-12-24|2013-12-16|Heat-sensitive label and preparation and use method therefor|

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