CN107745559B - Thermal indicator, container and application - Google Patents

Thermal indicator, container and application Download PDF

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Publication number
CN107745559B
CN107745559B CN201710854201.1A CN201710854201A CN107745559B CN 107745559 B CN107745559 B CN 107745559B CN 201710854201 A CN201710854201 A CN 201710854201A CN 107745559 B CN107745559 B CN 107745559B
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layer
volatile
adhesive
base
base layer
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CN107745559A (en
Inventor
刘永生
郭欣
刘文恒
熊梅英
张雪翼
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Shenzhen Nine Stars Printing and Packaging Group Co Ltd
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Shenzhen Nine Stars Printing and Packaging Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/064—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/12—Means for the attachment of smaller articles
    • B65D23/14—Means for the attachment of smaller articles of tags, labels, cards, coupons, decorations or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
    • B65D25/20—External fittings
    • B65D25/205—Means for the attachment of labels, cards, coupons or the like
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity

Abstract

The invention relates to a thermosensitive indicating device, a containing device and application. A temperature sensitive indicating device comprising: a base layer; the substrate layer is hermetically connected with the substrate layer to form a containing body capable of blocking gas, and the substrate layer is made of a transparent material; the volatile layer is printed on the surface, close to the base material layer, of the base layer and is contained in the containing body, and the volatile layer contains volatile dye; the isolation layer covers the surface of one side of the volatilization layer, which is far away from the substrate layer, and the isolation layer is opaque and has air permeability; and the bonding adsorption layer is positioned between the base layer and the base material layer and covers the surface of the isolation layer, the base layer is bonded and hermetically connected with the base layer through the bonding adsorption layer to form a containing body, and the material of the bonding adsorption layer is selected from at least one of acrylic resin, pressure-sensitive adhesive, polyurethane and UV (ultraviolet) adhesive. The thermosensitive indicating device is simple in structure and beneficial to miniaturization.

Description

Thermal indicator, container and application
Technical Field
The invention relates to a thermosensitive indicating device, a containing device and application.
Background
The perishable products such as food, beverage, blood, vaccine, meat food and the like need to be stored under a specific temperature environment, if the storage environment temperature exceeds a specified temperature, the perishable products will deteriorate rapidly, and consumers will bring damages to human bodies after using the perishable products, and serious people even die. Therefore, it is necessary to provide an indicator device that can continuously change color in a temperature-sensitive manner to determine the cumulative amount of heat applied to the product to be tested by the degree of color change, and thus determine whether the perishable product is defective.
The conventional thermosensitive time indicating device comprises a substrate layer, an indicating layer and a protective layer, wherein the indicating layer and the protective layer are formed on the surface of the substrate layer, the indicating layer is contained in a containing space formed by the substrate layer and the protective layer, the protective layer is provided with a vent hole, and the indicating layer can react with external gas when the vent hole is opened. The through hole is sealed by a seal, and the heat-sensitive time indicating device is activated by peeling the seal when in use.
However, the provision of the through hole in the protective layer and the provision of the peelable sealing member, and the provision of the sealing member to completely seal the through hole, results in a complicated structure of the heat-sensitive time indicator device; in use, the sealing member needs to be peeled off by hand, so that the sealing member cannot be too small for convenient operation, which is disadvantageous to miniaturization of the heat-sensitive time indicator.
Disclosure of Invention
Accordingly, there is a need for a heat-sensitive time indicator, a storage device and an application that are simple in structure and advantageous for miniaturization.
A temperature sensitive indicating device comprising:
a base layer;
the substrate layer is hermetically connected with the base layer to form a containing body capable of blocking gas, and the substrate layer is made of a transparent material;
the volatile layer is printed on the surface, close to the base material layer, of the base layer and contained in the containing body, the volatile layer contains volatile dye, the volatile dye is selected from at least one of compound I, derivatives of the compound I, azo dyes, anthraquinone dyes, pyrethrin, transfluthrin, enynthrin, permethrin, prallethrin, tefluthrin, prallethrin and N, N-diethyl-m-toluamide, and the structural formula of the compound I is as follows:
Figure BDA0001413269000000021
wherein R is1Is hydrogen, halogen, CH2OH, C1-C6 straight chain or branched chain alkyl, C1-C6 straight chain or branched chain alkoxy, COR2Or COOR2，R2Hydrogen, C1-C6 linear alkyl, C1-C6 branched alkyl, C1-C6 linear alkyl amino or C1-C6 branched alkyl amino;
the isolation layer covers one side surface of the volatilization layer, which is far away from the substrate layer, and is opaque and has air permeability; and
and the bonding adsorption layer is positioned between the base layer and the base material layer and covers the surface of the isolation layer, the base layer is bonded and hermetically connected with the base layer through the bonding adsorption layer to form the accommodating body, and the material of the bonding adsorption layer is selected from at least one of acrylic resin, pressure-sensitive adhesive and polyurethane.
According to the thermosensitive indicating device, the volatile dye in the volatile layer is almost non-volatile at low temperature, and is heated and volatilized when the temperature rises, the bonding and adsorbing layer is attached to the surface of the isolating layer and displays the color of the isolating layer, the material of the bonding and adsorbing layer not only can be bonded with the substrate layer and the substrate layer, but also can be used for adsorbing the volatile dye to change the color, the volatile dye penetrates through the isolating layer and is adsorbed by the bonding and adsorbing layer, the color of the bonding and adsorbing layer is gradually changed after adsorbing the volatile dye, and the color is increased along with the continuous volatilization of the volatile dye, so that the heating condition can be judged according to the color change of the; the thermosensitive indicating device only needs to be stored at low temperature, has a simple structure and is beneficial to miniaturization design.
In one embodiment, the compound I is guaiazulene.
In one embodiment, the azo dye is selected from at least one of Sudan red, 4-aminobiphenyl, 4-chloro-2-methylaniline, 4-chloroaniline, benzidine and 2, 6-dimethylaniline; and/or
The anthraquinone dye is selected from at least one of emodin, chrysophanol, madder, rubiadin and chrysophanol anthrone.
In one embodiment, the volatile layer further comprises a binder selected from at least one of acrylic resin, polyvinyl butyral, nitrocellulose, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, water-soluble resin, and water-dispersible resin.
In one embodiment, the volatilization layer further comprises an auxiliary agent, and the auxiliary agent is at least one selected from volatilization auxiliary agents and slow release auxiliary agents.
In one embodiment, the volatilization auxiliary agent is selected from at least one of alkane, aromatic hydrocarbon, alcohol, carboxylic acid, amino acid, ester, sulfone and camphor; and/or
The slow release auxiliary agent is at least one of chitosan, cyclodextrin and acrylic resin.
In one embodiment, the material of the isolation layer is selected from at least one of ink, paper, and opaque, breathable film.
In one embodiment, the adhesive layer is arranged between the volatilization layer and the isolation layer.
A containing device comprises a container and the thermosensitive indicating device attached to the container.
The thermosensitive indicating device is applied to the fields of vaccines, blood products and milk.
Drawings
FIG. 1 is a schematic structural diagram of an accommodating apparatus according to an embodiment;
FIG. 2 is a schematic structural diagram of a heat-sensitive indicating device of the receiving device of FIG. 1;
FIG. 3 is a schematic view of the temperature sensitive indicating device of FIG. 3 in another state;
FIG. 4 is a schematic structural view of the receiving device of FIG. 1 in another state;
fig. 5 is a schematic structural view of a heat-sensitive indicating device according to another embodiment.
Detailed Description
The temperature-sensitive indicating device, the housing device, and the application will be described in further detail with reference to the embodiments.
Referring to fig. 1, a receiving device 10 of an embodiment includes a thermal indicating device 100 and a receiving container 200.
In the illustrated embodiment, the container 200 is an ampoule bottle. The container 200 includes a bottle 210 and a cover 230. The temperature sensitive indicating device 100 is attached to the surface of the vial 210. Of course, in other embodiments, the temperature-sensitive indicating device 100 may also be attached to the surface of the cover 230. In other embodiments, the container 200 is not limited to an ampoule bottle, but may be other types of packaging bottles, packaging boxes or packaging bags, and the temperature-sensitive indicating device 100 may be attached to the container 200 by other means, such as housing.
Referring to fig. 2, a heat-sensitive indicating device 100 of an embodiment includes a substrate layer 110, a volatilization layer 120, an isolation layer 130, a bonding adsorption layer 150, a substrate layer 160, a reference layer 170, an adhesive layer 180, and a release layer 190.
The base layer 110 is made of Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), or a composite material having a surface compounded with the above materials. The composite material can be common PET/aluminum foil/heat-sealing PET composite material ("/" stands for lamination, the same is applied below), common PP/aluminum foil/heat-sealing CPP composite material, LDPE/aluminum foil/PP composite material and HDPE/aluminum foil/PET composite material. Wherein CPP represents unstretched polypropylene. In one embodiment, the substrate layer 110 is provided as a non-transparent material by printing or compounding an opaque material. Of course, the material of the base layer 110 is not limited to the above materials, and other materials having good air tightness may be used as the material of the base layer 110.
The volatilization layer 120 is formed on one surface of the substrate layer 110. In the illustrated embodiment, the volatilization layer 120 is printed in the middle of the side of the substrate layer 110. The volatile layer 120 is printed with a volatile ink. The thickness of the volatilization layer 120 is 0.01mm to 1 mm.
The volatile ink has a property of being volatilized after absorbing heat. In one embodiment, the volatile ink comprises the following components in parts by mass:
1-50 parts of volatile dye;
20-60 parts of a binder;
30-70 parts of a solvent; and
1-10 parts of assistant.
The solvent is at least one selected from water, ethanol, acetone, ethyl acetate, isopropanol, n-propanol, etc. And volatilizing the solvent after printing to form a volatilizing layer 120, wherein the volatilizing layer 120 contains 1-50 parts of volatile dye, 20-60 parts of binder and 1-5 parts of auxiliary agent.
The volatile dye is at least one selected from the group consisting of compound I, a derivative of compound I, an azo dye, an anthraquinone dye, pyrethrin, transfluthrin, empenthrin, permethrin, prallethrin, tefluthrin, prallethrin and N, N-diethyl-m-toluamide. Preferably, the volatile dye is 10 parts to 30 parts.
The structural formula of the compound I is as follows:
Figure BDA0001413269000000051
wherein R is1Is hydrogen, halogen, CH2OH, C1-C6 straight chain or branched chain alkyl, C1-C6 straight chain or branched chain alkoxy, COR2Or COOR2，R2Is hydrogen, C1-C6 straight chain alkyl, C1-C6 branched chain alkyl, C1-C6 straight chain alkyl amino or C1-C6 branched chain alkyl amino.
Preferably, R2Is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, sec-butylamino, tert-butylamino, n-pentylaminoAn amino group, an isopentylamino group, a neopentyl amino group, or a n-hexylamino group.
Preferably, R1Is hydrogen, -COH, -CH2OH、COOR2。
Preferably, compound I is guaiazulene.
Preferably, the azo dye is at least one selected from the group consisting of sudan red, 4-aminobiphenyl, 4-chloro-2-methylaniline, 4-chloroaniline, benzidine and 2, 6-dimethylaniline.
Preferably, the anthraquinone dye is at least one selected from emodin, chrysophanol, madder, rubicin, quinizarin and chrysophanol anthrone.
The binder provides tack to the volatile ink. The binder is at least one selected from acrylic resin, polyvinyl butyral, nitrocellulose, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, water-soluble resin and water-dispersible resin. Preferably, the water-soluble resin is at least one selected from the group consisting of maleic acid resin, shellac, maleic acid resin-modified shellac, urethane and aqueous amino resin. The water dispersible resin is at least one selected from polyisocyanate and water-based phenolic resin. Preferably, the binder is 30 to 40 parts.
The auxiliary agent is at least one of a volatile auxiliary agent and a slow release auxiliary agent. Of course, in other embodiments, the adjuvants may also include defoamers, stabilizers, dispersants, preservatives, leveling agents, slip agents, crosslinking agents.
In one embodiment, the volatilization aid is selected from at least one of alkanes, aromatics, alcohols, carboxylic acids, amino acids, esters, sulfones, and camphor. Preferably, the alkane is selected from at least one of linear alkanes, branched alkanes, and cyclic alkanes, and more preferably, the alkane is selected from at least one of hexane, heptane, octane, isomers thereof, cyclohexane, cycloheptane, and cyclopentane. Preferably, the aromatic hydrocarbon is at least one selected from naphthalene and anthracene. Preferably, the alcohol is at least one selected from the group consisting of a linear alcohol, a branched alcohol, an aromatic alcohol and a cyclic alcohol, and more preferably, the alcohol is at least one selected from the group consisting of a erythritol, a lauryl alcohol, a tridecyl alcohol, a tetradecyl alcohol, a pentadecyl alcohol, a palmityl alcohol, a heptadecyl alcohol and a stearyl alcohol. The carboxylic acid is selected from at least one of linear carboxylic acid, branched carboxylic acid, aromatic carboxylic acid, and cyclic carboxylic acid, and more preferably, the carboxylic acid is selected from at least one of maleic acid, fumaric acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, adipic acid, sebacic acid, and dodecanedioic acid. The amino acid is selected from at least one of aminobenzoic acid, leucine and phenylalanine. The ester is at least one selected from ethyl acetate, isoamyl acetate, methyl benzoate, methyl salicylate and glyceride. The sulfone is at least one selected from diphenyl sulfone, diphenyl disulfone, dibenzyl sulfone, and dibutyl sulfone. Preferably, the volatilization auxiliary agent is 3 to 7 parts.
In one embodiment, the slow release auxiliary agent is at least one selected from chitosan, cyclodextrin and acrylic resin. The slow release auxiliary agent is 3-7 parts.
Of course, it should be noted that the binder and the auxiliary agent may be omitted according to the printing requirements or the process.
The isolation layer 130 is stacked on a surface of the volatilization layer 120 away from the substrate layer 110. The barrier layer 130 is opaque and has breathability. In one embodiment, the material of the isolation layer 130 is selected from at least one of ink, paper, and opaque, breathable film. The opaque breathable film is a Polyethylene (PE) film or a biaxially oriented polypropylene (BOPP) film. In order to have a good display effect, the isolation layer 130 has a stable color, and preferably, the isolation layer 130 is white. Preferably, the isolation layer 130 is printed with white ink. The thickness of the isolation layer 130 is 0.01mm to 1 mm.
The adhesive adsorption layer 150 covers the surface of the isolation layer 130 and the substrate layer 110 not covered by the volatilization layer 120. The adhesive adsorption layer 150 has good adhesive and adsorption capabilities, and can adsorb volatile dyes volatilized from the volatile layer 120. The material of the adhesive adsorption layer 150 is at least one selected from acrylic resin, pressure-sensitive adhesive and polyurethane, preferably acrylic resin, the main absorption peak of the acrylic resin to light is outside the solar spectrum range, and the light resistance of the volatile dye with poor light resistance is greatly enhanced after entering the acrylic resin. Preferably, the acrylic resin is at least one selected from the group consisting of polymethacrylic acid, polymethacrylate, polybutylmethacrylate, polyacrylamide, and polyacrylonitrile. The pressure-sensitive adhesive is at least one of resin pressure-sensitive adhesive and rubber pressure-sensitive adhesive. The polyurethane is at least one of an adhesive containing urethane groups (-NHCOO-) in a molecular chain and an adhesive containing isocyanate groups (-NCO) in a molecular chain. Preferably, the thickness of the adhesive adsorption layer 150 is 0.01mm to 1 mm.
The base layer 160 is laminated on the surface of the adhesive adsorption layer 150, and is hermetically connected to the base layer 110 through the adhesive adsorption layer 150 to form a container capable of blocking gas, and the volatilization layer 120 is contained in the container. The base material layer 160 has good transparency and good air-tightness so that the color of the adhesive adsorption layer 150 can be observed through the base material layer 160. The substrate layer 160 also serves as a load bearing for the printed reference layer 170. The base material layer 160 is made of Polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), or a composite transparent material having a surface compounded with the above materials. The composite transparent material can be a common PET/heat-seal PET composite material, a common PP/heat-seal CPP composite material, an LDPE/PP composite material and an HDPE/PET composite material. Of course, the material of the base layer 160 is not limited to the above-described material, and any other material having good transparency and air-tightness may be used as the material of the base layer 160.
The reference layer 170 is formed on the surface of the substrate layer 160 remote from the bonded sorbent layer 150. In the illustrated embodiment, the reference layer 170 is printed from a conventional ink. The reference layer 170 is formed with a hollow window (not shown) corresponding to the volatilization layer 120, so that the color of the adhesive adsorption layer 150 absorbing the volatile dye volatilized by the volatilization layer 120 can be observed. The reference layer 170 is used to provide a reference color having at least two fixed colors for comparison with the color of the adhesive absorbent layer 150, so that the user can clearly know whether the color of the adhesive absorbent layer 150 is in the initial color (just before use) or in the final color (the reaction time is longest, and exceeds the expiration date of the product), and it is preferable that the reference layer 170 further includes a neutral color so that the consumer can judge the use time of the product by comparing the colors. The reference layer 170 has a thickness of 0.01mm to 1 mm.
The adhesive layer 180 is formed on the surface of the substrate layer 110 away from the volatile layer 120. The adhesive layer 180 is used to adhere the temperature sensitive indicating device 100 to the surface of another article. The material of the adhesive layer 180 is at least one selected from acrylic resin, polyurethane, and pressure sensitive adhesive. The thickness of the adhesive layer 180 is 0.1mm to 1 mm.
The peeling layer 190 is adhered to the surface of the adhesive layer 180. Preferably, the peeling layer 190 is cellophane or paper coated with silicone oil, so that the peeling layer 190 can be peeled from the surface of the adhesive layer 180. The thickness of the peeling layer 190 is 0.1mm to 2 mm.
The receiving device 10 can be used for receiving articles with high requirements on storage temperature, such as vaccines, when the articles are stored at low temperature, the volatile dye in the volatilization layer 120 is not volatilized basically, the adhesive adsorption layer 150 is transparent and does not change color, the color of the isolation layer 130 is shown, when the temperature rises, the volatile dye begins to volatilize, the volatile dye penetrates through the air-permeable isolation layer 130 and is absorbed by the adhesive adsorption layer 150, as shown in fig. 3, the color of the adhesive adsorption layer 150 gradually changes after absorbing the volatile dye and continuously deepens along with the rise of the temperature and the lengthening of the time, the color change period is adjusted to be matched with the deterioration period of the articles, as shown in fig. 4, whether the articles are deteriorated due to excessive heating can be judged by observing the color of the adhesive adsorption layer 150 of the thermosensitive indicating device 100 attached to the surface of the receiving device 200. The temperature sensitive indicator 100 of the container 10 can be stored only at low temperature, and has a simple structure and is advantageous for miniaturization.
The heat-sensitive indicating device 100 can be applied to the fields of vaccines, blood products and milk. For example, the heat-sensitive indicator 100 may be attached to an ampoule bottle and the vaccine may be contained in the ampoule bottle.
Referring to fig. 5, a thermal indicating device 300 according to another embodiment has substantially the same structure as the thermal indicating device 100, and the difference is that: an adhesive layer 340 is also disposed between the isolation layer 330 and the volatile layer 320 and the substrate layer 310.
In the illustrated embodiment, the isolation layer 330 covers the surface of the volatilization layer 320 and the surface of the substrate layer 310 close to the volatilization layer 320. The isolation layer 330 is adhered to the volatilization layer 320 and the base layer 310 by an adhesive layer 340. The material of the adhesive layer 340 is at least one selected from polyvinyl alcohol water-based glue, vinyl acetate water-based glue, and phenolic water-based glue.
The adhesive adsorption layer 350 is laminated on the surface of the isolation layer 330.
In the thermosensitive indicating device 300, the isolation layer 330 covers the surface of the volatilization layer 320 and the surface of the substrate layer 310 close to the volatilization layer 320, so that the overall color of the thermosensitive indicating device 300 is more uniform, and the preparation difficulty is reduced. By providing the adhesive layer 340 between the isolation layer 330 and the volatilization layer 320, when the isolation layer 330 is paper or an opaque breathable film, the stability between the two can be increased, preventing the isolation layer 330 from being displaced.
The following description will be given with reference to specific examples.
Example 1
The structure of the heat-sensitive time indicator of example 1 is shown in fig. 2, and includes a base layer 110, a volatilization layer 120, a separation layer 130, a bonding adsorption layer 150, a base material layer 160, a reference layer 170, an adhesive layer 180, and a release layer 190.
The base layer 110 is made of PET and has a thickness of 0.15 mm.
The volatile layer 120 is prepared by printing with a volatile ink, which comprises, by mass, 20 parts of the volatile dye guaiazulene, 40 parts of maleic acid, 50 parts of an aqueous solvent, and 5 parts of a volatile auxiliary agent lauric acid. The volatile layer 120 comprises 20 parts by mass of volatile dye guaiazulene, 40 parts by mass of maleic acid binder and 5 parts by mass of a volatile auxiliary agent lauric acid. The thickness of the volatilization layer 120 was 0.2 mm.
The material of the isolation layer 130 is aqueous white ink with a thickness of 0.05 mm.
The material of the adhesive adsorption layer 150 is polymethacrylic acid, and the thickness is 0.1 mm.
The base material layer 160 is made of a PET film and has a thickness of 0.15 mm.
The reference layer 170 has a thickness of 0.02mm and includes three colors of light blue, medium blue, and dark blue, which provide the starting color, the intermediate color, and the end color of the indicating composition, respectively.
The adhesive layer 180 is made of pressure sensitive adhesive and has a thickness of 0.1 mm.
The material of the peeling layer 190 is cellophane, and the thickness is 0.2 mm. Placing the thermosensitive time indicating device in an environment at 0 ℃ for 360 days, wherein the color of the bonding adsorption layer 150 is changed from light blue to dark blue; placing the temperature-sensitive time indicator in an environment at 5 ℃ for 180 days, wherein the color of the bonding adsorption layer 150 is changed from light blue to dark blue; the temperature-sensitive time indicator is placed in an environment at 10 ℃ and kept for 50 days, and the color of the adhesive adsorption layer 150 is changed from light blue to dark blue; the temperature-sensitive time indicator was placed in an environment at 30 c for 5 days, and the adhesive adsorption layer 150 changed in color from light blue to dark blue.
Example 2
The structure of the heat-sensitive time indicator of example 2 is shown in fig. 5, and includes a substrate layer 310, a volatilization layer 320, an isolation layer 330, a bonding layer 340, a bonding adsorption layer 350, a substrate layer 360, a reference layer 370, an adhesive layer 380, and a release layer 390.
The base layer 310 is made of PET and has a thickness of 0.18 mm.
The volatile layer 320 is prepared by printing with volatile ink, the volatile ink comprises, by mass, 30 parts of volatile dye guaiazulene, 45 parts of aqueous polyurethane, 50 parts of aqueous solvent and 5 parts of slow release aid β cyclodextrin, the volatile layer 320 comprises, by mass, 30 parts of volatile dye guaiazulene, 45 parts of aqueous polyurethane binder and 5 parts of slow release aid cyclodextrin, and the thickness of the volatile layer 120 is 0.2 mm.
The material of the isolation layer 330 is 60g of coated paper, and the thickness is 0.05 mm.
The material of tie coat 340 is polyvinyl alcohol water-based glue, and thickness is 0.01 mm.
The material of the bonding adsorption layer 350 is polymethacrylic acid, and the thickness is 0.1 mm.
The material of substrate layer 360 is the PET film, and thickness is 0.15 mm.
Reference layer 370 has a thickness of 0.01mm and includes three colors of light blue, medium blue, and dark blue, which provide the starting color, the intermediate color, and the end color of the indicating composition, respectively.
The adhesive layer 380 is made of pressure sensitive adhesive and has a thickness of 0.1 mm.
The material of the peeling layer 390 is cellophane with a thickness of 0.2 mm. Placing the thermosensitive time indicator in an environment at 0 ℃ for 600 days, wherein the color of the bonding adsorption layer 350 is changed from light blue to dark blue; placing the temperature-sensitive time indicator in an environment at 5 ℃ for 300 days, wherein the color of the bonding adsorption layer 350 is changed from light blue to dark blue; the temperature-sensitive time indicator is placed in an environment at 10 ℃ for 120 days, and the color of the bonding adsorption layer 350 is changed from light blue to dark blue; the temperature-sensitive time indicator was placed in an environment at 30 c for 15 days and the adhesive absorption layer 350 changed from light blue to dark blue in color.
Example 3
The present example has the same structure as example 1, but differs in the thermal ink composition, and includes a base layer 110, a volatilization layer 120, a separator 130, a bonding adsorption layer 150, a base layer 160, a reference layer 170, an adhesive layer 180, and a release layer 190, as shown in fig. 2.
The base layer 110 is made of PET and has a thickness of 0.15 mm.
The volatile layer 120 is prepared by printing with a volatile ink, which comprises, by mass, 50 parts of a volatile dye guaiazulene ethyl derivative, 40 parts of a water-based polyurethane, 50 parts of a water solvent, and 10 parts of a volatile auxiliary naphthalene. The volatile layer 120 comprises 50 parts by mass of a volatile dye guaiazulene ethyl derivative, 40 parts by mass of a water-based polyurethane adhesive and 10 parts by mass of a volatile auxiliary agent naphthalene. The thickness of the volatilization layer 120 was 0.2 mm.
The material of the isolation layer 130 is aqueous white ink with a thickness of 0.05 mm.
The material of the adhesive adsorption layer 150 is polymethacrylic acid, and the thickness is 0.1 mm.
The base material layer 160 is made of a PET film and has a thickness of 0.15 mm.
The reference layer 170 has a thickness of 0.02mm and includes three colors of light blue, medium blue, and dark blue, which provide the starting color, the intermediate color, and the end color of the indicating composition, respectively.
The adhesive layer 180 is made of pressure sensitive adhesive and has a thickness of 0.1 mm.
The material of the peeling layer 190 is cellophane, and the thickness is 0.2 mm. Placing the thermosensitive time indicator in an environment at 0 ℃ for 250 days, wherein the color of the bonding adsorption layer 150 is changed from light blue to dark blue; placing the temperature-sensitive time indicator in an environment at 5 ℃ for 120 days, wherein the color of the bonding adsorption layer 150 is changed from light blue to dark blue; the temperature-sensitive time indicator is placed in an environment at 10 ℃ and kept for 30 days, and the color of the adhesive adsorption layer 150 is changed from light blue to dark blue; the temperature-sensitive time indicator was placed in an environment at 30 c for 3 days, and the adhesive adsorption layer 150 changed in color from light blue to dark blue.
Example 4
The structure of this embodiment is the same as that of embodiment 2, except that the thermal ink composition is different, and as shown in fig. 5, the thermal ink composition includes a base layer 310, a volatilization layer 320, a separation layer 330, an adhesive layer 340, an adhesive adsorption layer 350, a base layer 360, a reference layer 370, and an adhesive layer 380 (and a release layer 390).
The base layer 310 is made of PET and has a thickness of 0.18 mm.
The volatile layer 320 is prepared by printing with a volatile ink, which comprises, by mass, 10 parts of a volatile dye guaiazulene methyl derivative, 45 parts of a maleic acid resin, 50 parts of an aqueous solvent, and 5 parts of a slow release auxiliary agent chitosan (chitosan). The volatile layer 320 comprises, by mass, 10 parts of a volatile dye guaiazulene methyl derivative, 45 parts of a maleic acid resin binder, and 5 parts of a slow release aid chitosan. The thickness of the volatilization layer 120 was 0.2 mm.
The material of the isolation layer 330 is 60g of coated paper, and the thickness is 0.05 mm.
The material of tie coat 340 is polyvinyl alcohol water-based glue, and thickness is 0.01 mm.
The material of the bonding adsorption layer 350 is polymethacrylic acid, and the thickness is 0.1 mm.
The material of substrate layer 360 is the PET film, and thickness is 0.15 mm.
Reference layer 370 has a thickness of 0.01mm and includes three colors of light blue, medium blue, and dark blue, which provide the starting color, the intermediate color, and the end color of the indicating composition, respectively.
The adhesive layer 380 is made of pressure sensitive adhesive and has a thickness of 0.1 mm.
The material of the peeling layer 390 is cellophane with a thickness of 0.2 mm. Placing the thermosensitive time indicator in an environment at 0 ℃ for 700 days, wherein the color of the bonding adsorption layer 350 is changed from light blue to dark blue; placing the thermosensitive time indicating device in an environment at 5 ℃ for 350 days, wherein the color of the bonding adsorption layer 350 is changed from light blue to dark blue; the temperature-sensitive time indicator is placed in an environment at 10 ℃ and kept for 150 days, and the color of the bonding adsorption layer 350 is changed from light blue to dark blue; the temperature-sensitive time indicator was placed in an environment at 30 c for 20 days and the adhesive absorption layer 350 changed from light blue to dark blue in color.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. A temperature sensitive indicator device for storage at cryogenic temperatures, comprising:
a base layer;
the substrate layer is hermetically connected with the base layer to form a containing body capable of blocking gas, and the substrate layer is made of a transparent material;
the volatile layer is printed on the surface, close to the base material layer, of the base layer and contained in the containing body, the volatile layer contains volatile dye, the volatile dye is selected from at least one of compound I, derivatives of the compound I, azo dyes, anthraquinone dyes, pyrethrin, transfluthrin, enynthrin, permethrin, prallethrin, tefluthrin, prallethrin and N, N-diethyl-m-toluamide, and the structural formula of the compound I is as follows:
Figure FDA0002364113150000011
wherein R is1Is hydrogen, halogen, CH2OH, C1-C6 straight chain or branched chain alkyl, C1-C6 straight chain or branched chain alkoxy, COR2Or COOR2，R2Hydrogen, C1-C6 linear alkyl, C1-C6 branched alkyl, C1-C6 linear alkyl amino or C1-C6 branched alkyl amino;
the isolation layer covers the surface of one side, away from the substrate layer, of the volatilization layer, is opaque and has air permeability, and the material of the isolation layer is selected from at least one of ink, paper and an opaque and breathable film; and
the adhesive adsorption layer is positioned between the base layer and the base material layer and covers the surface of the isolation layer, the base layer is bonded and hermetically connected with the base layer through the adhesive adsorption layer to form the accommodating body, and the material of the adhesive adsorption layer is selected from at least one of acrylic resin, pressure-sensitive adhesive and polyurethane;
the base layer is laminated on the surface of the adhesive adsorption layer, and is hermetically connected with the base layer through the adhesive adsorption layer to form a container capable of blocking gas.
2. A temperature-sensitive indicator device according to claim 1, wherein compound I is guaiazulene.
3. A thermal indicating device according to claim 1 wherein said azo-based dye is selected from at least one of sudan red, 4-aminobiphenyl, 4-chloro-2-methylaniline, 4-chloroaniline, benzidine and 2, 6-dimethylaniline; and/or
The anthraquinone dye is selected from at least one of emodin, chrysophanol, madder, rubiadin and chrysophanol anthrone.
4. A thermal indicator according to claim 1 wherein the volatile layer further comprises a binder selected from at least one of acrylic resins, polyvinyl butyral, nitrocellulose, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, water soluble resins and water dispersible resins.
5. A thermal indicator according to claim 1 wherein the volatilisation layer further comprises an aid selected from at least one of a volatilisation aid and a slow release aid.
6. A thermal indicator device according to claim 5 wherein the volatilization aid is selected from at least one of an alkane, an aromatic hydrocarbon, an alcohol, a carboxylic acid, an amino acid, an ester, a sulfone, and camphor; and/or
The slow release auxiliary agent is at least one of chitosan, cyclodextrin and acrylic resin.
7. A thermal indicator according to claim 1 further comprising an adhesive layer disposed between the volatilisation layer and the barrier layer.
8. A storage device comprising a storage container and the thermal indicator according to any one of claims 1 to 7 attached to the storage container.
9. Use of a heat sensitive indicator device according to any of claims 1 to 7 in the field of vaccines, blood products, milk.
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