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CN110927151A - Quality guarantee state indicator and preparation method thereof - Google Patents

Quality guarantee state indicator and preparation method thereof Download PDF

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Publication number
CN110927151A
CN110927151A CN201911229004.6A CN201911229004A CN110927151A CN 110927151 A CN110927151 A CN 110927151A CN 201911229004 A CN201911229004 A CN 201911229004A CN 110927151 A CN110927151 A CN 110927151A
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indicator
adhesive
membrane
film
porous substrate
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滕超
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Lu'anyi New Material Technology Co Ltd
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Lu'anyi New Material Technology Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour

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Abstract

The invention relates to the technical field of high-barrier packaging, in particular to a quality guarantee state indicator and a preparation method thereof. The quality guarantee state indicator comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer, a protective membrane and a pressure-sensitive adhesive layer which are sequentially contacted; the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive; the porous substrate is made of expanded polytetrafluoroethylene. The protective film and the pressure-sensitive adhesive layer may be replaced with a second permeable film. When carbon dioxide, oxygen and steam exist in the environment where the quality guarantee state indicator is located, the carbon dioxide, the oxygen and the steam can reach the composite indicating layer through the first transparent film, and the composite indicating layer effectively indicates the entering condition of the carbon dioxide, the oxygen and the steam through color change.

Description

Quality guarantee state indicator and preparation method thereof
Technical Field
The invention relates to the technical field of high-barrier packaging, in particular to a quality guarantee state indicator and a preparation method thereof.
Background
In the fields of food, medicine, precision instruments and the like, high barrier packaging is required to isolate the entry of gases such as carbon dioxide, oxygen, water vapor and the like in the environment as far as possible. The high-barrier package is usually made of a multilayer composite high-barrier film solution, generally comprises base resin, barrier resin and a binder, and has excellent mechanical properties and can meet the requirements of printing, coloring, heat sealing, bonding and the like by compounding the advantages of various materials; of course, the most important is to prevent deterioration, putrefaction or adverse effects from the environment. However, when the package is impacted, squeezed or otherwise subjected to external forces, the high barrier film may be damaged, resulting in the high barrier package losing its barrier effect without the knowledge of the customer. How to detect when the high-barrier package loses the barrier effect is a problem to be solved urgently in the field of high-barrier packages.
Patent CN1318531C prints a water-soluble oil film on a liquid transfer substrate, and when water vapor passes through the water-soluble oil film, the printed pattern of the water-soluble oil film becomes blurred, so that the entry of water vapor can be detected. However, in the packaging of medicines and foods, the scheme has the problems that a water-soluble oil film pollutes the packaged objects, and the sensitivity of the liquid transmission substrate layer to the moisture entering cannot meet the requirement.
Patent CN102782474B proposes pigments and plastics with functions of indicating oxygen, carbon dioxide and other gases, which can indicate oxygen, carbon dioxide and other gases sensitively, and can be used in packages of food, medicine and the like, but the patent does not indicate a specific scheme how to use the indicator.
Patent CN104974380A proposes a film for indicating carbon dioxide in medical treatment and a preparation method thereof, which visually observes the existence of carbon dioxide through color, but the carbon dioxide concentration value is required to be more than 2%, which is not suitable for the high-barrier packaging requirement in many occasions.
Patent CN107179314A has prepared a sticker of instruction carbon dioxide, its structure is indicator + non-setting adhesive sticker, mainly used for detecting when enclosing in containing carbon dioxide gas replacement device, because the gas atmosphere change that causes when sealed the problem, not be used for in the packing thing, the application range has certain limitation.
Therefore, the development of a quality guarantee state indicator which is suitable for high-barrier packaging, can effectively indicate that carbon dioxide, oxygen or water vapor and other gases invade in a packaged object, has a simple structure and is low in production cost is a technical problem to be solved urgently in the field of high-barrier packaging.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a quality guarantee status indicator and a method for manufacturing the same, which can effectively indicate that carbon dioxide, oxygen or water vapor or other gases invade into a packaged object.
The invention provides a quality guarantee state indicator, which comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer, a protective membrane and a pressure-sensitive adhesive layer which are contacted in sequence;
the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive;
the porous substrate is made of expanded polytetrafluoroethylene;
or
The quality guarantee state indicator comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer and a second permeable membrane which are sequentially contacted;
the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive;
the porous substrate is made of expanded polytetrafluoroethylene.
Preferably, the carbon dioxide indicator includes a carbon dioxide-sensitive reactive dye, a basic substance, and a solvent;
the carbon dioxide sensitive reactive dye comprises one or more of m-cresol purple, thymolphthalein, o-cresol phthalein, acryloyl fluorescein, β -methylumbelliferyl snore, bromothymolphthalein blue, cresol red, hexadecyl trimethyl ammonium hydroxide, neutral red, phenol red, rhodamine 6G, sulforhodamine 101, lily blue and thymolphthalein blue, wherein the alkaline substance comprises sodium hydroxide, potassium hydroxide or calcium hydroxide;
the oxygen indicator comprises an oxygen-sensitive reactive dye and a solvent;
the oxygen sensitive active dye comprises one or more of methylene blue, azure B, Nile blue, terpyridyl ruthenium, ruthenium perchlorate, octaethyl porphyrin ketone platinum and proflavine;
the moisture indicator comprises a water-soluble ink.
Preferably, the adhesive in the adhesive layer comprises one or more of a polyester adhesive and a polyurethane adhesive.
Preferably, the protective film comprises one or more of a polyethylene film, a polypropylene film, a polystyrene film, a polyvinyl chloride film, a polyvinylidene chloride film, a polyethylene terephthalate film and a nylon film;
the pressure-sensitive adhesive layer comprises one or more of rubber pressure-sensitive adhesive, polyacrylate pressure-sensitive adhesive and organic silicon pressure-sensitive adhesive.
Preferably, the first transparent film comprises one or more of a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polystyrene film, a polyvinyl chloride film, a polyvinylidene chloride film, a polyethylene terephthalate film and a nylon film.
Preferably, the second permeable membrane comprises one or more of a polyethylene membrane, a polytetrafluoroethylene membrane, a polypropylene membrane, a polystyrene membrane, a polyvinyl chloride membrane, a polyvinylidene chloride membrane, a polyethylene terephthalate membrane and a nylon membrane.
The invention also provides a preparation method of the quality guarantee state indicator, which comprises the following steps:
A1) coating a mixed reagent of an adhesive and an indicator on the surface of the first permeable membrane, and carrying out dry compounding on the coated first permeable membrane and the porous substrate to obtain a first composite membrane; the porous substrate is made of expanded polytetrafluoroethylene;
B1) coating an adhesive on the porous substrate of the first compound film, and carrying out dry compounding on the coated porous substrate and a protective film to obtain a second compound film;
C1) coating a pressure-sensitive adhesive on the protective film of the second compound film, and drying to obtain a quality guarantee state indicator;
or
A2) Coating a mixed reagent of an adhesive and an indicator on the surface of the first permeable membrane, and carrying out dry compounding on the coated first permeable membrane and the porous substrate to obtain a first composite membrane; the porous substrate is made of expanded polytetrafluoroethylene;
B2) and coating an adhesive on the porous substrate of the first compound film, and performing dry compounding on the coated porous substrate and the second permeable film to obtain the quality guarantee state indicator.
Preferably, the first and second liquid crystal materials are,
in the step a1), the step b,
the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h;
after the dry compounding, the method further comprises the following steps: cooling, compacting, rolling and curing;
in the step B1), the step B,
the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h;
after the dry compounding, the method further comprises the following steps: cooling, compacting, rolling and curing.
Preferably, the first and second liquid crystal materials are,
in the step a2), the step b,
the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h;
after the dry compounding, the method further comprises the following steps: cooling, compacting, rolling and curing;
in the step B2), the step B,
the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h;
after the dry compounding, the method further comprises the following steps: cooling, compacting, rolling and curing.
The invention provides a quality guarantee state indicator, which comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer, a protective membrane and a pressure-sensitive adhesive layer which are contacted in sequence; the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive; the porous substrate is made of expanded polytetrafluoroethylene;
or
The quality guarantee state indicator comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer and a second permeable membrane which are sequentially contacted; the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive; the porous substrate is made of expanded polytetrafluoroethylene.
When the environment of quality guarantee state indicator is in carbon dioxide, oxygen and steam, carbon dioxide, oxygen and steam can reach the compound indicator layer through first penetrating membrane, and the compound indicator layer can be through discolouring, the entering condition of instruction carbon dioxide, oxygen and steam. Therefore, the quality guarantee state indicator provided by the invention can effectively indicate that the gas such as carbon dioxide, oxygen or water vapor enters the packaged object.
The substrate layer used by the invention is of an expanded polytetrafluoroethylene (ePTFE) structure, compared with the common substrates such as a starch grafted acrylate porous substrate, a starch grafted acrylamide porous substrate, a high-substitution degree crosslinked carboxymethyl cellulose porous substrate and the like, the expanded polytetrafluoroethylene (ePTFE) is more resistant to high temperature, ageing and chemical stability, and the substrate layer can not cause indicator deterioration due to hydrolysis, so that the service life of the indicator is ensured, the moisture permeability is excellent, and the high efficiency and accurate indication work of the indicator is ensured.
The experimental result shows that the carbon dioxide in the packaging environment passes through 2cm3/(cm30.1mm 24h), oxygen passage 2cm3/(cm30.1mm 24h) or passage of water vapor 2 g/(m)224h), the shelf life indicator may turn blue.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a quality guarantee status indicator according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a quality guarantee status indicator according to another embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a quality guarantee state indicator, which comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer, a protective membrane and a pressure-sensitive adhesive layer which are contacted in sequence;
the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive.
The shelf life indicator is constructed as shown in fig. 1. Fig. 1 is a schematic structural diagram of a quality guarantee status indicator according to an embodiment of the present invention. Wherein, 1 is a first permeable membrane, 2 is a composite indicating layer, 3 is a porous substrate, 4 is an adhesive layer, 5 is a protective membrane, and 6 is a pressure-sensitive adhesive layer.
The shelf life indicator provided by the present invention comprises a first permeable membrane 1. In an embodiment of the present invention, the first permeable membrane allows only carbon dioxide, oxygen and water vapor to pass through. The liquid or macromolecular substance is unable to pass through the first permeable membrane. Therefore, the quality guarantee state indicator can ensure that carbon dioxide, oxygen or water vapor in the high-barrier package can quickly enter the quality guarantee state indicator, and chemical substances such as color developing agents in the indicator are prevented from permeating out to pollute packaged substances. In certain embodiments of the present invention, the first permeable membrane meets food grade requirements. In certain embodiments of the present invention, the first transparent permeable film is a first transparent permeable film. The first transparent film comprises one or more of a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polystyrene film, a polyvinyl chloride film, a polyvinylidene chloride film, a polyethylene terephthalate film and a nylon film. In some embodiments of the present invention, when the first permeable film is a multi-layer film, the arrangement order of the layers in the multi-layer film is not particularly limited. In certain embodiments of the present invention, when the first permeable film is a composite film of a plurality of films, the films of the composite film may be bonded by an adhesive that is in contact with the adhesive of the composite indicator layer.
In some embodiments of the present invention, the first permeable membrane has a thickness of 35 to 200 μm.
The shelf life indicator provided by the invention also comprises a composite indicating layer 2. In the invention, the components of the composite indicating layer comprise an adhesive and an indicator.
The indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator.
In certain embodiments of the present invention, the carbon dioxide indicator comprises a carbon dioxide sensitive reactive dye, a basic substance, and a solvent.
The method for preparing the carbon dioxide indicator is not particularly limited, and in certain embodiments of the present invention, the carbon dioxide indicator is prepared by mixing a carbon dioxide-sensitive reactive dye, a basic substance and a solvent. Wherein the alkaline substance is common inorganic alkali, the addition amount of the alkaline substance is only required to ensure that the pH value of the carbon dioxide indicator is not less than 8.5, and the addition amount of the solvent is only required to ensure that the concentration of the indicator is 0.1-1 wt%.
In certain embodiments of the present invention, the oxygen indicator comprises an oxygen-sensitive reactive dye and a solvent. In certain embodiments of the present invention, the oxygen-sensitive reactive dye comprises one or more of methylene blue, azure B, nile blue, ruthenium terpyridyl, ruthenium perchlorate, platinum octaethylporphyrinone, and proflavin. In certain embodiments of the present invention, the solvent in the oxygen indicator comprises glycerol, ethylene glycol or diethylene glycol. In certain embodiments of the present invention, the mass ratio of the oxygen-sensitive reactive dye to the solvent is 1: 10 to 50.
In certain embodiments of the present invention, the moisture indicator comprises a water-soluble ink. In certain embodiments, the moisture indicator comprises HP Ink jetcard 51649a blue printing oil Ink, HIDACID AZURE bluedusless 20DA2228 blue dye powder from b.f. goodrich, or FASTUSOL Red 43LN from BASF.
The adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive. The adhesive in the composite indicating layer plays a role in fixing the indicator.
In certain embodiments of the invention, the polyester-based adhesive is selected from one or more of Henkel Plastic Padding, hot melt polyester adhesive technomert 6208S, and saturated polyester schrader PS 6009.
In certain embodiments of the present invention, the polyurethane-based adhesive is preferably a one-component polyurethane adhesive and/or a two-component polyurethane adhesive; the single-component polyurethane adhesive is preferably a solvent-free polyurethane adhesive or an alcohol-soluble polyurethane adhesive; the solvent-free polyurethane adhesive is preferably UR7505, UR7506, UR8150, UR7330, Henkel Liofol UR7740 or UR7750 produced by Beijing chemical research institute; the alcohol solvent type polyurethane adhesive is preferably selected from U-7750, H-100, and UF2870 or UF9985E of New Oriental group Huaguang resin Co. The two-component polyurethane adhesive preferably comprises a component A and a component B; the component A preferably comprises polyester polyol, polyether polyol or polyol with the carbon chain length of less than 12, and the component B preferably comprises polyurethane prepolymer. The polyurethane prepolymer is prepared by reacting aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate. In certain embodiments of the present invention, the A component of the two-part polyurethane adhesive is preferably Henkel3100, Japan TOYOBO TU-02C01, or TU-02 FC; the B component is preferably Hardener N3300 or M9.
The invention has no special limit on the proportion of the adhesive and the indicator, and the proportion is subject to the satisfaction of the respective performance requirements.
The thickness of the composite indicating layer is not particularly limited, and can be selected according to actual conditions.
The shelf life indicator provided by the present invention further comprises a porous substrate 3. The porous substrate is an indicator carrier.
In some embodiments of the present invention, the porous substrate is expanded polytetrafluoroethylene (ePTFE). In certain embodiments of the invention, the porous substrate is GORE-TEX & reg or WINDSTOPPER & reg, manufactured by GORE corporation.
In some embodiments of the present invention, the porous substrate has a thickness of 100 to 500. mu.m.
The shelf life indicator provided by the invention further comprises an adhesive layer 4. The adhesive layer is used for bonding the porous substrate and the protective film.
In some embodiments of the present invention, the adhesive in the adhesive layer comprises one or more of a polyester adhesive and a polyurethane adhesive.
In certain embodiments of the invention, the polyester-based adhesive is selected from one or more of Henkel Plastic Padding, hot melt polyester adhesive technomert 6208S, and saturated polyester schrader PS 6009.
In certain embodiments of the present invention, the polyurethane-based adhesive is preferably a one-component polyurethane adhesive and/or a two-component polyurethane adhesive; the single-component polyurethane adhesive is preferably a solvent-free polyurethane adhesive or an alcohol-soluble polyurethane adhesive; the solvent-free polyurethane adhesive is preferably UR7505, UR7506, UR8150, UR7330, Henkel Liofol UR7740 or UR7750 produced by Beijing chemical research institute; the alcohol solvent type polyurethane adhesive is preferably selected from U-7750, H-100, and UF2870 or UF9985E of New Oriental group Huaguang resin Co. The two-component polyurethane adhesive preferably comprises a component A and a component B; the component A preferably comprises polyester polyol, polyether polyol or polyol with the carbon chain length of less than 12, and the component B preferably comprises polyurethane prepolymer. The polyurethane prepolymer is prepared by reacting aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate. In certain embodiments of the present invention, the A component of the two-part polyurethane adhesive is preferably Henkel3100, Japan TOYOBO TU-02C01, or TU-02 FC; the B component is preferably Hardener N3300 or M9.
The quality guarantee state indicator further comprises a protective film 5. The protective film is used for protecting the indicator from leakage or pollution by the external environment.
In certain embodiments of the present invention, the protective film comprises one or more of a polyethylene film, a polypropylene film, a polystyrene film, a polyvinyl chloride film, a polyvinylidene chloride film, a polyethylene terephthalate film, and a nylon film.
In some embodiments of the present invention, the thickness of the protective film is 35 to 90 μm.
The shelf life indicator provided by the invention further comprises a pressure sensitive adhesive layer 6.
In certain embodiments of the present invention, the composition of the pressure sensitive adhesive layer comprises one of a rubber-based pressure sensitive adhesive, a polyacrylate-based pressure sensitive adhesive, and a silicone-based pressure sensitive adhesive. In certain embodiments, the composition of the pressure sensitive adhesive layer is Henkel LOCTITE DURO-TAK UV4000, Henkel AQUENCE PS454A or Henkel TECHNOMIT PS MT 56.
The quality guarantee state indicator is a label type quality guarantee state indicator. In certain embodiments of the present invention, the shelf-life indicator further comprises a release film. The release film is compounded on the pressure-sensitive adhesive layer and used for protecting the pressure-sensitive adhesive layer. When the quality guarantee state indicator is used, the release film can be taken off, and the pressure-sensitive adhesive layer of the quality guarantee state indicator is pasted in a packaging bag to be detected, so that the quality guarantee state indicator is fixed. The material and thickness of the release film are not particularly limited in the present invention, and the release film known to those skilled in the art may be used. In some embodiments of the present invention, the release film may be a PET release film of dongxin composite material limited, Dongguan city, a PE release film of Changzhou spring adhesive product technology limited, or a PET fluoroplastic release film of Shenzhen Yichuan thin film limited.
The label type quality guarantee state indicator provided by the invention is suitable for quality guarantee state detection of the transparent sealing bag.
In some embodiments of the present invention, the protective film and the pressure sensitive adhesive layer may be replaced with a second permeable film. Specifically, the quality guarantee state indicator comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer and a second permeable membrane which are sequentially contacted;
the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive.
The structure is shown in fig. 2. Fig. 2 is a schematic structural diagram of a quality guarantee status indicator according to another embodiment of the present invention. Wherein, 1 is a first permeable membrane, 2 is a composite indicating layer, 3 is a porous substrate, 4 is an adhesive layer, and 7 is a second permeable membrane.
The first transparent film 1, the composite indicating layer 2, the porous substrate 3, and the adhesive layer 4 are the same as those described above, and are not described herein again.
In an embodiment of the invention, the second permeable membrane allows only carbon dioxide, oxygen and water vapor to pass through. Liquid or macromolecular substances cannot pass through the second permeable membrane. Therefore, the quality guarantee state indicator can ensure that carbon dioxide, oxygen or water vapor in the high-barrier package can quickly enter the quality guarantee state indicator, and chemical substances such as color developing agents in the indicator are prevented from permeating out to pollute packaged substances. In certain embodiments of the invention, the second permeable membrane meets food grade requirements. In certain embodiments of the present invention, the second permeable film is a second transparent permeable film. The second permeable membrane comprises one or more of a polyethylene membrane, a polytetrafluoroethylene membrane, a polypropylene membrane, a polystyrene membrane, a polyvinyl chloride membrane, a polyvinylidene chloride membrane, a polyethylene terephthalate membrane and a nylon membrane. In some embodiments of the present invention, when the second permeable film is a multi-layer film, the arrangement order of the layers in the multi-layer film is not particularly limited. In certain embodiments of the present invention, when the second permeable membrane is a composite membrane of multiple layers of membranes, the layers of the composite membrane may be bonded by an adhesive that is in contact with the adhesive in the composite indicator layer.
In some embodiments of the present invention, the second permeable membrane has a thickness of 35 to 100 μm.
The quality guarantee state indicator shown in fig. 2 can be directly made into a sealed packaging bag, and whether gas such as carbon dioxide, oxygen or water vapor invades in the packaged object can be detected directly through the packaging bag.
The invention provides a quality guarantee state indicator, which comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer, a protective membrane and a pressure-sensitive adhesive layer which are contacted in sequence; the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive. When the environment of quality guarantee state indicator is in carbon dioxide, oxygen and steam, carbon dioxide, oxygen and steam can reach the compound indicator layer through first penetrating membrane, and the compound indicator layer can be through discolouring, the entering condition of instruction carbon dioxide, oxygen and steam. Therefore, the quality guarantee state indicator provided by the invention can effectively indicate that the gas such as carbon dioxide, oxygen or water vapor enters the packaged object. Meanwhile, the outer layer film of the quality guarantee state indicator can prevent chemical substances such as color developing agents and the like in the indicator from permeating to pollute packaged substances, can be in direct contact with packaged objects such as food, medicines or precise instruments and the like, cannot pollute the packaged objects, and is high in safety. And the quality guarantee state indicator has simple and convenient use method, intuition and easy operation.
The present invention also provides a method for preparing the quality guarantee status indicator, comprising the following steps:
A1) coating a mixed reagent of an adhesive and an indicator on the surface of the first permeable membrane, and carrying out dry compounding on the coated first permeable membrane and the porous substrate to obtain a first composite membrane;
B1) coating an adhesive on the porous substrate of the first compound film, and carrying out dry compounding on the coated porous substrate and a protective film to obtain a second compound film;
C1) and coating a pressure-sensitive adhesive on the protective film of the second compound film, and drying to obtain the quality guarantee state indicator.
In the preparation method, the components and thicknesses of the first permeable membrane, the porous substrate and the protective membrane are the same as above, and are not described again. The thicknesses of the layer groups are the same as above, and are not described in detail here.
In certain embodiments of the present invention, step a1), the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator, and a moisture indicator.
In certain embodiments of the present invention, the carbon dioxide indicator comprises a carbon dioxide sensitive reactive dye, a basic substance, and a solvent.
The method for preparing the carbon dioxide indicator is not particularly limited, and in certain embodiments of the present invention, the carbon dioxide indicator is prepared by mixing a carbon dioxide-sensitive reactive dye, a basic substance and a solvent. Wherein the alkaline substance is common inorganic alkali, the addition amount of the alkaline substance is only required to ensure that the pH value of the carbon dioxide indicator is not less than 8.5, and the addition amount of the solvent is only required to ensure that the concentration of the indicator is 0.1-1 wt%.
In certain embodiments of the present invention, the oxygen indicator comprises an oxygen-sensitive reactive dye and a solvent. In certain embodiments of the present invention, the oxygen-sensitive reactive dye comprises one or more of methylene blue, azure B, nile blue, ruthenium terpyridyl, ruthenium perchlorate, platinum octaethylporphyrinone, and proflavin. In certain embodiments of the present invention, the solvent in the oxygen indicator comprises glycerol, ethylene glycol or diethylene glycol. In certain embodiments of the present invention, the mass ratio of the oxygen-sensitive reactive dye to the solvent is 1: 10 to 50.
In certain embodiments of the present invention, the moisture indicator comprises a water-soluble ink. In certain embodiments, the moisture indicator comprises HP Ink jetcard 51649a blue printing oil Ink, HIDACID AZURE bluedusless 20DA2228 blue dye powder from b.f. goodrich, or FASTUSOL Red 43LN from BASF.
In certain embodiments of the present invention, step a1), the adhesive comprises one or more of a polyester-based adhesive and a polyurethane adhesive. The adhesive serves to secure the indicator.
In certain embodiments of the invention, the polyester-based adhesive is selected from one or more of Henkel Plastic Padding, hot melt polyester adhesive technomert 6208S, and saturated polyester schrader PS 6009.
In certain embodiments of the present invention, the polyurethane-based adhesive is preferably a one-component polyurethane adhesive and/or a two-component polyurethane adhesive; the single-component polyurethane adhesive is preferably a solvent-free polyurethane adhesive or an alcohol-soluble polyurethane adhesive; the solvent-free polyurethane adhesive is preferably UR7505, UR7506, UR8150, UR7330, Henkel Liofol UR7740 or UR7750 produced by Beijing chemical research institute; the alcohol solvent type polyurethane adhesive is preferably selected from U-7750, H-100, and UF2870 or UF9985E of New Oriental group Huaguang resin Co. The two-component polyurethane adhesive preferably comprises a component A and a component B; the component A preferably comprises polyester polyol, polyether polyol or polyol with the carbon chain length of less than 12, and the component B preferably comprises polyurethane prepolymer. The polyurethane prepolymer is prepared by reacting aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate. In certain embodiments of the present invention, the A component of the two-part polyurethane adhesive is preferably Henkel3100, Japan TOYOBO TU-02C01, or TU-02 FC; the B component is preferably Hardener N3300 or M9.
The invention has no special limit on the proportion of the adhesive and the indicator in the step A1), so as to meet the respective performance requirements. In some embodiments of the invention, the coating amount of the adhesive is 2.5-4.5 g/m2. The preparation method of the mixed reagent of the adhesive and the indicator is not particularly limited, and the adhesive and the indicator can be directly and uniformly mixed.
In certain embodiments of the present invention, in step A1), the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃; in certain embodiments, the drying temperature of the drying tunnel in the dry compounding is 10 ℃, 20 ℃, 30 ℃ or 45 ℃. In certain embodiments of the present invention, in step a1), the drying time of the drying tunnel in the dry compounding is 1-24 hours; in certain embodiments, the drying time of the drying tunnel in the dry compounding is 24h, 18h, 15h or 3 h.
In certain embodiments of the present invention, the dry-compounding the completely coated first permeable membrane with the porous substrate in step a1) comprises:
and drying the coated first permeable membrane at 10-45 ℃ in a drying tunnel, then melting the coated mixed reagent in a heating state, and attaching the mixed reagent to a porous substrate.
In some embodiments of the present invention, step a1), after the dry-compounding, further includes: cooling, compacting, rolling and curing. The method and parameters for cooling, compacting, rolling and curing in the dry compounding are not particularly limited in the present invention, and those known to those skilled in the art can be used.
In certain embodiments of the present invention, step a1), the dry compounding is performed in a dry compound machine.
In certain embodiments of the present invention, step B1), the adhesive comprises one or more of a polyester-based adhesive and a polyurethane adhesive. In certain embodiments of the present invention, the coating amount of the adhesive in the step B1) is 2.5 to 4.5g/m2。
In certain embodiments of the invention, the polyester-based adhesive is selected from one or more of Henkel Plastic Padding, hot melt polyester adhesive technomert 6208S, and saturated polyester schrader PS 6009.
In certain embodiments of the present invention, the polyurethane-based adhesive is preferably a one-component polyurethane adhesive and/or a two-component polyurethane adhesive; the single-component polyurethane adhesive is preferably a solvent-free polyurethane adhesive or an alcohol-soluble polyurethane adhesive; the solvent-free polyurethane adhesive is preferably UR7505, UR7506, UR8150, UR7330, Henkel Liofol UR7740 or UR7750 produced by Beijing chemical research institute; the alcohol solvent type polyurethane adhesive is preferably selected from U-7750, H-100, and UF2870 or UF9985E of New Oriental group Huaguang resin Co. The two-component polyurethane adhesive preferably comprises a component A and a component B; the component A preferably comprises polyester polyol, polyether polyol or polyol with the carbon chain length of less than 12, and the component B preferably comprises polyurethane prepolymer. The polyurethane prepolymer is prepared by reacting aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate. In certain embodiments of the present invention, the A component of the two-part polyurethane adhesive is preferably Henkel3100, Japan TOYOBO TU-02C01, or TU-02 FC; the B component is preferably Hardener N3300 or M9.
In certain embodiments of the present invention, in the step B1), the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃; in certain embodiments, the drying temperature of the drying tunnel in the dry compounding is 10 ℃, 20 ℃, 30 ℃ or 45 ℃. In certain embodiments of the present invention, in step B1), the drying time of the drying tunnel in the dry compounding is 1-24 hours; in certain embodiments, the drying time of the drying tunnel in the dry compounding is 24h, 18h, 15h or 3 h.
In certain embodiments of the present invention, the dry-compounding of the completely coated porous substrate with the protective film in step B1) comprises:
drying the coated porous substrate in a drying tunnel at 10-45 ℃, then melting the coated adhesive in a heating state, and attaching the adhesive to a protective film.
In some embodiments of the present invention, step B1), after the dry-compounding, further includes: cooling, compacting, rolling and curing. The method and parameters for cooling, compacting, rolling and curing in the dry compounding are not particularly limited in the present invention, and those known to those skilled in the art can be used.
In certain embodiments of the present invention, step B1), the dry compounding is performed in a dry compound machine.
In certain embodiments of the present invention, in step C1), the pressure-sensitive adhesive comprises one or more of a rubber-based pressure-sensitive adhesive, a polyacrylate-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive. In certain embodiments, the composition of the pressure sensitive adhesive layer is Henkel LOCTITE DURO-TAK UV4000, Henkel AQUENCE PS454A, or Henkel TECHNOMETL PSMT 56.
In some embodiments of the invention, the coating amount of the pressure-sensitive adhesive is 2.5-4.5 g/m2。
In step C1), the method and parameters of drying are not limited in the present invention, and those known to those skilled in the art can be used.
In some embodiments of the present invention, in step C1), after the drying, the method further includes: and bonding the dried pressure sensitive adhesive layer with a release film, and coiling to obtain the quality guarantee state indicator.
The material and thickness of the release film are the same as above, and are not described again here.
The quality guarantee state indicator prepared by the method is a label type quality guarantee state indicator. When the quality guarantee state indicator is used, the release film can be taken off, and the pressure-sensitive adhesive layer of the quality guarantee state indicator is pasted in a packaging bag needing to be detected, so that the quality guarantee state indicator is fixed, and then the packaging bag is sealed.
The present invention also provides a method for preparing the quality guarantee status indicator, comprising the following steps:
A2) coating a mixed reagent of an adhesive and an indicator on the surface of the first permeable membrane, and carrying out dry compounding on the coated first permeable membrane and the porous substrate to obtain a first composite membrane;
B2) and coating an adhesive on the porous substrate of the first compound film, and performing dry compounding on the coated porous substrate and the second permeable film to obtain the quality guarantee state indicator.
In the preparation method, the components and thicknesses of the first permeable membrane, the porous substrate and the second permeable membrane are the same as above, and are not described again. The thicknesses of the layer groups are the same as above, and are not described in detail here.
In certain embodiments of the present invention, step a2), the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator, and a moisture indicator.
In certain embodiments of the present invention, the carbon dioxide indicator comprises a carbon dioxide sensitive reactive dye, a basic substance, and a solvent.
The method for preparing the carbon dioxide indicator is not particularly limited, and in certain embodiments of the present invention, the carbon dioxide indicator is prepared by mixing a carbon dioxide-sensitive reactive dye, a basic substance and a solvent. Wherein the alkaline substance is common inorganic base, the addition amount of the alkaline substance is enough to ensure that the pH value of the carbon dioxide indicator is more than 9, and the addition amount of the solvent is enough to ensure that the concentration of the indicator is 0.1-1 wt%.
In certain embodiments of the present invention, the oxygen indicator comprises an oxygen-sensitive reactive dye and a solvent. In certain embodiments of the present invention, the oxygen-sensitive reactive dye comprises one or more of methylene blue, azure B, nile blue, ruthenium terpyridyl, ruthenium perchlorate, platinum octaethylporphyrinone, and proflavin. In certain embodiments of the present invention, the solvent in the oxygen indicator comprises glycerol, ethylene glycol or diethylene glycol. In certain embodiments of the present invention, the mass ratio of the oxygen-sensitive reactive dye to the solvent is 1: 10 to 50.
In certain embodiments of the present invention, the moisture indicator comprises a water-soluble ink. In certain embodiments, the moisture indicator comprises HP Ink jetcard 51649a blue printing oil Ink, HIDACID AZURE bluedusless 20DA2228 blue dye powder from b.f. goodrich, or FASTUSOL Red 43LN from BASF.
In certain embodiments of the present invention, step a2), the adhesive comprises one or more of a polyester-based adhesive and a polyurethane adhesive. The adhesive serves to secure the indicator.
In certain embodiments of the invention, the polyester-based adhesive is selected from one or more of Henkel Plastic Padding, hot melt polyester adhesive technomert 6208S, and saturated polyester schrader PS 6009.
In certain embodiments of the present invention, the polyurethane-based adhesive is preferably a one-component polyurethane adhesive and/or a two-component polyurethane adhesive; the single-component polyurethane adhesive is preferably a solvent-free polyurethane adhesive or an alcohol-soluble polyurethane adhesive; the solvent-free polyurethane adhesive is preferably UR7505, UR7506, UR8150, UR7330, Henkel Liofol UR7740 or UR7750 produced by Beijing chemical research institute; the alcohol solvent type polyurethane adhesive is preferably selected from U-7750, H-100, and UF2870 or UF9985E of New Oriental group Huaguang resin Co. The two-component polyurethane adhesive preferably comprises a component A and a component B; the component A preferably comprises polyester polyol, polyether polyol or polyol with the carbon chain length of less than 12, and the component B preferably comprises polyurethane prepolymer. The polyurethane prepolymer is prepared by reacting aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate. In certain embodiments of the present invention, the A component of the two-part polyurethane adhesive is preferably Henkel3100, Japan TOYOBO TU-02C01, or TU-02 FC; the B component is preferably Hardener N3300 or M9.
The invention has no special limit on the proportion of the adhesive and the indicator in the step A2), so as to meet the respective performance requirements. In some embodiments of the invention, the coating amount of the adhesive is 2.5-4.5 g/m2. The preparation method of the mixed reagent of the adhesive and the indicator is not particularly limited, and the adhesive and the indicator can be directly and uniformly mixed.
In some embodiments of the invention, in the step A2), the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h.
In certain embodiments of the present invention, the dry-compounding the completely coated first permeable membrane with the porous substrate in step a2) comprises:
and drying the coated first permeable membrane at 10-45 ℃ in a drying tunnel, then melting the coated mixed reagent in a heating state, and attaching the mixed reagent to a porous substrate.
In some embodiments of the present invention, step a2), after the dry-compounding, further includes: cooling, compacting, rolling and curing. The method and parameters for cooling, compacting, rolling and curing in the dry compounding are not particularly limited in the present invention, and those known to those skilled in the art can be used.
In certain embodiments of the present invention, step a2), the dry compounding is performed in a dry compound machine.
In certain embodiments of the present invention, step B2), the adhesive comprises one or more of a polyester-based adhesive and a polyurethane adhesive. In certain embodiments of the present invention, the coating amount of the adhesive in the step B2) is 2.5 to 4.5g/m2。
In certain embodiments of the invention, the polyester-based adhesive is selected from one or more of Henkel Plastic Padding, hot melt polyester adhesive technomert 6208S, and saturated polyester schrader PS 6009.
In certain embodiments of the present invention, the polyurethane-based adhesive is preferably a one-component polyurethane adhesive and/or a two-component polyurethane adhesive; the single-component polyurethane adhesive is preferably a solvent-free polyurethane adhesive or an alcohol-soluble polyurethane adhesive; the solvent-free polyurethane adhesive is preferably UR7505, UR7506, UR8150, UR7330, Henkel Liofol UR7740 or UR7750 produced by Beijing chemical research institute; the alcohol solvent type polyurethane adhesive is preferably selected from U-7750, H-100, and UF2870 or UF9985E of New Oriental group Huaguang resin Co. The two-component polyurethane adhesive preferably comprises a component A and a component B; the component A preferably comprises polyester polyol, polyether polyol or polyol with the carbon chain length of less than 12, and the component B preferably comprises polyurethane prepolymer. The polyurethane prepolymer is prepared by reacting aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate. In certain embodiments of the present invention, the A component of the two-part polyurethane adhesive is preferably Henkel3100, Japan TOYOBO TU-02C01, or TU-02 FC; the B component is preferably Hardener N3300 or M9.
In some embodiments of the invention, in the step B2), the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h.
In certain embodiments of the present invention, the dry-compounding of the fully coated porous substrate with the second permeable membrane in step B2) comprises:
drying the coated porous substrate in a drying tunnel at 10-45 ℃, then melting the coated adhesive in a heating state, and attaching the adhesive to a second permeable membrane
In some embodiments of the present invention, step B2), after the dry-compounding, further includes: cooling, compacting, rolling and curing. The method and parameters for cooling, compacting, rolling and curing in the dry compounding are not particularly limited in the present invention, and those known to those skilled in the art can be used.
In certain embodiments of the present invention, step B2), the dry compounding is performed in a dry compound machine.
The quality guarantee state indicator prepared by the method can be directly made into a sealed packaging bag, and whether carbon dioxide, oxygen or water vapor and other gases invade the packaged object can be detected directly through the packaging bag.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
The preparation method of the quality guarantee state indicator provided by the invention is simple to operate, high in efficiency and low in pollution.
The experimental result shows that the carbon dioxide in the packaging environment passes through 2cm3/(cm30.1mm 24h), oxygen passage 2cm3/(cm30.1mm 24h) or passage of water vapor 2 g/(m)224h), the shelf life indicator may turn blue.
In order to further illustrate the present invention, a quality guarantee status indicator and a method for manufacturing the same according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
Placing polytetrafluoroethylene film (ePTFE, 100 μm) at a position of dry lamination machine, and coating polyurethane adhesive (Henkel3100, coating amount of adhesive is 3 g/m)2) And a carbon dioxide indicator (the reactive dye is thymolphthalein, the alkaline substance is potassium hydroxide, the solvent is glycerol, the pH value of the carbon dioxide indicator is 8.5, and the concentration of the carbon dioxide indicator is 1 wt%), drying the coated first permeable membrane in a drying tunnel at 10 ℃ for 24 hours, then melting the coated mixed reagent in a heating state, attaching the molten mixed reagent to a porous substrate (a starch grafted acrylamide porous substrate, 230 mu m) placed on a second dry compound machine, cooling, compacting, rolling and curing to form a first compound membrane;
then, the first composite film was placed at a position where a dry lamination machine was placed, and a polyurethane adhesive (Henkel3100, the amount of the adhesive applied was 3 g/m) was applied to the porous substrate of the first composite film2) Drying the coated porous substrate in a drying tunnel at 10 ℃ for 24h, then melting the coated adhesive in a heating state, attaching the adhesive to a protective film (polyethylene film, 50 mu m) placed on a second dry compounding machine, cooling, compacting, rolling and curing to form a second composite film;
coating a pressure-sensitive adhesive Henkel LOCTITE DURO-TAKUV 4000 on the protective film of the second composite film (the coating amount of the pressure-sensitive adhesive is 2.3 g/m)2) After drying, the dried pressure sensitive adhesive layer was bonded to a release film (PET release film from dongxin composites ltd, Dongguan) and rolled to obtain a quality guarantee state indicator.
Example 2
A composite film (180 μm) obtained by bonding a polytetrafluoroethylene film (ePTFE) and a polyethylene film (PE) was placed in a position where a dry lamination machine was placed, and a polyurethane adhesive (Henkel3100 was applied to the surface thereof in an amount of 3g/m2) And an oxygen indicator (methylene blue, the solvent is glycerol, and the mass ratio of the methylene blue to the glycerol is 1: 50) the mixed reagent of (a) and (b),drying the coated first permeable membrane in a drying tunnel at 10 ℃ for 24 hours, then melting the coated mixed reagent in a heating state, attaching the melted mixed reagent to a porous substrate (a starch grafted acrylamide porous substrate, 230 microns) placed in a second dry compound machine, cooling, compacting, rolling and curing to form a first compound membrane;
then, the first composite film was placed at a position where a dry lamination machine was placed, and a polyurethane adhesive (Henkel3100, the amount of the adhesive applied was 3 g/m) was applied to the porous substrate of the first composite film2) Drying the coated porous substrate in a drying tunnel at 10 ℃ for 24h, then melting the coated adhesive in a heating state, attaching the adhesive to a protective film (polyethylene film, 50 mu m) placed on a second dry compounding machine, cooling, compacting, rolling and curing to form a second composite film;
coating polyacrylate pressure sensitive adhesive Henkel AQUENCE PS454A (coating amount of pressure sensitive adhesive is 2.3 g/m) on the protective film of the second composite film2) And after drying, bonding the dried pressure-sensitive adhesive layer with a release film (PE release film of Changzhou spring adhesive product science and technology Co., Ltd.) to obtain a quality guarantee state indicator.
Example 3
Placing a composite film (180 μm) obtained by bonding a polytetrafluoroethylene film (ePTFE) and a low density polyethylene film (LDPE) at a position of a dry lamination machine, and coating polyurethane adhesive (Henkel 3100) on the surface thereof in an amount of 3g/m2) And a mixed reagent of a water vapor indicator (HP Ink jetcard 51649a blue printing oil Ink), drying the coated first permeable membrane for 24 hours at 10 ℃, then melting the coated mixed reagent in a heating state, attaching the melted mixed reagent to a porous substrate (230 mu m starch grafted acrylamide porous substrate) placed on a second dry compound machine, cooling, compacting, rolling and curing to form a first compound membrane;
then, the first composite film was placed at a position where a dry lamination machine was placed, and a polyurethane adhesive (Henkel3100, the amount of the adhesive applied was 3 g/m) was applied to the porous substrate of the first composite film2) Drying the coated porous substrate in a drying tunnel at 10 ℃ for 24 hours,then, the coated adhesive is melted in a heating state and is attached to a protective film (polyethylene film, 50 μm) placed on a second dry compound machine, and after cooling, pressing, rolling and curing, a second compound film is formed;
coating polyacrylate pressure-sensitive adhesive Henkel TECHNOMETT PSMT56 (the coating amount of the pressure-sensitive adhesive is 2.3 g/m) on the protective film of the second compound film2) And after drying, bonding the dried pressure sensitive adhesive layer with a release film (PET fluoroplastic release film of Shenzhen Yichuan film Co., Ltd.) to obtain a coil, thereby obtaining the quality guarantee state indicator.
Example 4
Placing polytetrafluoroethylene membrane (ePTFE, 100 μm) at the first position of dry lamination machine, coating polyurethane adhesive (Henkel Liofol UR7740/UR7750, coating adhesive amount is 2.5g/m2) And a carbon dioxide indicator (the reactive dye is m-cresol purple, the alkaline substance is sodium hydroxide, the solvent is diethylene glycol, the pH value of the carbon dioxide indicator is 8.5, and the concentration of the carbon dioxide indicator is 1 wt%), drying the coated first permeable membrane at 20 ℃ for 18h in a drying tunnel, then melting the coated mixed reagent in a heating state, attaching the molten mixed reagent to a porous substrate (a crosslinked carboxymethyl cellulose grafted acrylamide porous substrate, 230 mu m) placed in a second dry compounding machine, cooling, compacting, rolling and curing to form a first composite membrane;
then the first compound film is placed at the first position of the dry compound machine, polyurethane adhesive (Henkel Liofol UR7740/UR7750, the coating amount of the adhesive is 2.5g/m2) Drying the coated porous substrate in a drying tunnel at 20 ℃ for 18h, then melting the coated adhesive in a heating state, attaching the adhesive to a protective film (polyethylene terephthalate film, 85 microns) placed on a second dry compounding machine, cooling, pressing, rolling and curing to form a second compound film;
coating a rubber pressure sensitive adhesive Henkel TECHNOMET PS MT56 (the coating amount of the pressure sensitive adhesive is 2.3 g/m) on the protective film of the second compound film2) And after drying, the dried pressure sensitive adhesive layer and the release film (Shenzhen Yichuan)PET fluoroplastic release film of film limited) and rolled to obtain the quality guarantee state indicator.
Example 5
Placing a composite film obtained by bonding polytetrafluoroethylene (ePTFE, 100 μm) film and High Density Polyethylene (HDPE) film at a position of dry lamination machine, coating polyurethane adhesive (Henkel Liofol UR7740/UR7750 with coating amount of 2.5g/m2) And an oxygen indicator (Nile blue, the solvent is diethylene glycol, and the mass ratio of the Nile blue to the diethylene glycol is 1: 20) drying the coated first permeable membrane for 18 hours at the temperature of 20 ℃, then melting the coated mixed reagent in a heating state, attaching the melted mixed reagent to a porous substrate (crosslinked carboxymethyl cellulose grafted acrylamide porous substrate, 240 microns) placed in a second dry compound machine, cooling, compacting, rolling and curing to form a first compound membrane;
then the first compound film is placed at the first position of the dry compound machine, polyurethane adhesive (Henkel Liofol UR7740/UR7750, the coating amount of the adhesive is 2.5g/m2) Drying the coated porous substrate in a drying tunnel at 20 ℃ for 18h, then melting the coated adhesive in a heating state, attaching the adhesive to a protective film (polyethylene terephthalate film, 85 microns) placed on a second dry compounding machine, cooling, pressing, rolling and curing to form a second compound film;
a rubber-based pressure sensitive adhesive Henkel AQUENCE PS454A (coating amount of pressure sensitive adhesive is 2.3 g/m) was coated on the protective film of the second film2) And after drying, bonding the dried pressure-sensitive adhesive layer with a release film (PE release film of Changzhou spring adhesive product science and technology Co., Ltd.) to obtain a quality guarantee state indicator.
Example 6
Placing a composite membrane (200 μm) obtained by bonding polytetrafluoroethylene membrane (ePTFE) and polypropylene membrane (PP) at a position of dry lamination machine, coating polyurethane adhesive (Henkel Liofol UR7740/UR7750 with coating amount of 2.5g/m2) And a water vapor indicator (HIDACID AZURE Bluedusless 20DA2228 blue, B.F. Goodrich)Color dye powder), drying the coated first permeable membrane in a drying tunnel for 18h at 20 ℃, then melting the coated mixed reagent in a heating state, attaching the melted mixed reagent to a porous substrate (crosslinked hydroxyethyl cellulose grafted acrylamide porous substrate, 240 mu m) placed on a second dry compound machine, cooling, compacting, rolling and curing to form a first compound membrane;
then the first compound film is placed at the first position of the dry compound machine, polyurethane adhesive (Henkel Liofol UR7740/UR7750, the coating amount of the adhesive is 2.5g/m2) Drying the coated porous substrate in a drying tunnel at 20 ℃ for 18h, then melting the coated adhesive in a heating state, attaching the adhesive to a protective film (polyethylene terephthalate film, 85 microns) placed on a second dry compounding machine, cooling, pressing, rolling and curing to form a second compound film;
coating a rubber pressure-sensitive adhesive Henkel LOCTITE DURO-TAK UV4000 on the protective film of the second compound film (the coating amount of the pressure-sensitive adhesive is 2.3 g/m)2) After drying, the dried pressure sensitive adhesive layer was bonded to a release film (PET release film from dongxin composites ltd, Dongguan) and rolled to obtain a quality guarantee state indicator.
Example 7
A composite film (200 μm) obtained by bonding a polytetrafluoroethylene film (ePTFE) and an biaxially oriented polypropylene film (OPP) was placed in a position where a dry lamination machine was placed, and a polyurethane adhesive (Sumitock 802, the amount of the adhesive applied was 2.5 g/m) was applied to the surface thereof2) And a carbon dioxide indicator (the reactive dye is thymolphthalein, the alkaline substance is potassium hydroxide, the solvent is glycerol, the pH value of the carbon dioxide indicator is 8.5, and the concentration of the carbon dioxide indicator is 1 wt%), drying the coated first permeable membrane at 30 ℃ for 15h in a drying tunnel, then melting the coated mixed reagent in a heating state, attaching the molten mixed reagent to a porous substrate (a cross-linked hydroxyethyl cellulose grafted acrylamide porous substrate, 230 mu m) placed on a second dry compound machine, cooling, compacting, rolling and curing to form a first compound membrane;
then will beA first composite film was placed at a position where a dry lamination machine was placed, and a polyurethane adhesive (Sumitock 802, amount of adhesive applied was 2.5 g/m) was applied on a porous substrate of the first composite film2) Drying the coated porous substrate in a drying tunnel at 30 ℃ for 15h, then melting the coated adhesive in a heating state, attaching the adhesive to a second permeable membrane (polytetrafluoroethylene membrane, 100 microns) placed on a dry compounding machine, cooling, compacting, rolling and curing to obtain the quality guarantee state indicator.
Example 8
A polytetrafluoroethylene film (ePTFE, 100 μm) was placed in a dry lamination machine, and a polyurethane adhesive (Sumitock 802, amount of adhesive applied was 2.5 g/m) was applied to the surface thereof2) And an oxygen indicator (methylene blue, the solvent is glycerol, and the mass ratio of the methylene blue to the glycerol is 1: 50) drying the coated first permeable membrane for 15 hours at 30 ℃, then melting the coated mixed reagent in a heating state, attaching the melted mixed reagent to a porous substrate (crosslinked hydroxyethyl cellulose grafted acrylamide porous substrate, 230 microns) placed in a second dry compound machine, cooling, pressing, rolling and curing to form a first compound membrane;
then, the first composite film was placed at a position where a dry lamination machine was placed, and a polyurethane adhesive (Sumitock 802, amount of adhesive applied was 2.5 g/m) was applied on the porous substrate of the first composite film2) Drying the coated porous substrate in a drying tunnel at 30 ℃ for 15h, then melting the coated adhesive in a heating state, attaching the adhesive to a second permeable membrane (polytetrafluoroethylene membrane, 100 microns) placed on a dry compounding machine, cooling, compacting, rolling and curing to obtain the quality guarantee state indicator.
Example 9
A polytetrafluoroethylene film (ePTFE, 100 μm) was placed in a dry lamination machine, and a polyurethane adhesive (Sumitock 802, amount of adhesive applied was 2.5 g/m) was applied to the surface thereof2) And a water vapor indicator (HP Ink jetcard 51649a blue printing oil Ink), drying the completely coated first permeable membrane at 30 ℃ for 15h, and heatingMelting the coated mixed reagent, attaching the melted mixed reagent to a porous substrate (crosslinked hydroxyethyl cellulose grafted acrylamide porous substrate, 230 microns) placed on a second dry compound machine, cooling, compacting, rolling and curing to form a first compound film;
then, the first composite film was placed at a position where a dry lamination machine was placed, and a polyurethane adhesive (Sumitock 802, amount of adhesive applied was 2.5 g/m) was applied on the porous substrate of the first composite film2) Drying the coated porous substrate in a drying tunnel at 30 ℃ for 15h, then melting the coated adhesive in a heating state, attaching the adhesive to a second permeable membrane (polytetrafluoroethylene membrane, 100 microns) placed on a dry compounding machine, cooling, compacting, rolling and curing to obtain the quality guarantee state indicator.
Example 10
Placing a polytetrafluoroethylene film (ePTFE, 100 μm) at a position where a dry lamination machine was placed, and coating a polyurethane adhesive (Henkel Plastic coating, coating amount of adhesive was 2.5 g/m)2) And a carbon dioxide indicator (the reactive dye is m-cresol purple, the alkaline substance is sodium hydroxide, the solvent is diethylene glycol, the pH value of the carbon dioxide indicator is 8.5, and the concentration of the carbon dioxide indicator is 1 wt%), drying the coated first permeable membrane at 45 ℃ for 3 hours in a drying tunnel, then melting the coated mixed reagent in a heating state, attaching the molten mixed reagent to a porous substrate (a crosslinked carboxymethyl cellulose grafted acrylamide porous substrate, 230 mu m) placed in a second dry compounding machine, cooling, compacting, rolling and curing to form a first composite membrane;
then the first composite film is placed at the first position of a dry type compound machine, and polyurethane adhesive (UR 7505 produced by Beijing chemical research institute with the adhesive coating amount of 2.5 g/m) is coated on the porous substrate of the first composite film2) Drying the coated porous substrate in a drying tunnel at 45 ℃ for 3h, then melting the coated adhesive in a heating state, attaching the adhesive to a second permeable film (polyethylene terephthalate film, 85 microns) placed on a dry compounding machine, cooling, compacting, rolling and curing to obtain the quality guarantee state indicator.
Example 11
Placing a composite film (200 μm) obtained by bonding polytetrafluoroethylene film (ePTFE) and high density polyethylene film (HDPE) at a position where a dry lamination machine is placed, and coating polyurethane adhesive (UR 7505 produced by Beijing chemical research institute with adhesive coating amount of 2.5 g/m) on the surface2) And an oxygen indicator (Nile blue, the solvent is diethylene glycol, and the mass ratio of the Nile blue to the diethylene glycol is 1: 30) drying the coated first permeable membrane in a drying tunnel at 45 ℃ for 3 hours, then melting the coated mixed reagent in a heating state, attaching the melted mixed reagent to a porous substrate (crosslinked carboxymethyl cellulose grafted acrylamide porous substrate, 230 microns) placed in a second dry compound machine, cooling, pressing, rolling and curing to form a first compound membrane;
then the first composite film is placed at the first position of a dry type compound machine, and polyurethane adhesive (UR 7505 produced by Beijing chemical research institute with the adhesive coating amount of 2.5 g/m) is coated on the porous substrate of the first composite film2) Drying the coated porous substrate in a drying tunnel at 45 ℃ for 3h, then melting the coated adhesive in a heating state, attaching the adhesive to a second permeable film (polyethylene terephthalate film, 85 microns) placed on a dry compounding machine, cooling, compacting, rolling and curing to obtain the quality guarantee state indicator.
Example 12
Placing a composite membrane (180 μm) prepared by bonding polytetrafluoroethylene membrane (ePTFE) and polypropylene membrane (PP) at a position where a dry lamination machine is placed, and coating polyurethane adhesive (UR 7505 produced by Beijing chemical research institute with adhesive coating amount of 2.5 g/m) on the surface2) And a water vapor indicator (HIDACID AZURE BlueDUstless20DA2228 blue dye powder of B.F. Goodrich), drying the coated first permeable membrane at 45 ℃ for 3h, then melting the coated mixed reagent in a heating state, attaching the melted mixed reagent to a porous substrate (crosslinked hydroxyethyl cellulose grafted acrylamide porous substrate, 230 μm) placed in a second dry compound machine, cooling, pressing, rolling and curing to form a first compound membrane;
then will beThe first composite film was placed at a position where a dry type laminating machine was placed, and a polyurethane adhesive (UR 7505 manufactured by Beijing chemical research institute, coating amount of adhesive was 2.5 g/m) was coated on the porous substrate of the first composite film2) Drying the coated porous substrate in a drying tunnel at 45 ℃ for 3h, then melting the coated adhesive in a heating state, attaching the adhesive to a second permeable film (polyethylene terephthalate film, 85 microns) placed on a dry compounding machine, cooling, compacting, rolling and curing to obtain the quality guarantee state indicator.
Example 13
The release film is removed from the label type quality guarantee state indicator prepared in the embodiments 1-6, and the pressure sensitive adhesive layer of the quality guarantee state indicator is adhered in a packaging bag to be detected, so that the quality guarantee state indicator is fixed. The detection steps are as follows: placing the quality guarantee state indicator in a high-barrier seal, vacuumizing, replacing with nitrogen (99.999%) to protect the atmosphere, and introducing carbon dioxide 2cm into the vent3/(cm30.1mm 24h) or oxygen 2cm3/(cm30.1mm 24h) water vapor 2 g/(m)224h), the color change of the shelf life indicator is observed. Specific detection results are shown in table 1.
The quality guarantee state indicator prepared in the above examples 7-12 can be directly made into a sealed package bag. Specific detection results are shown in table 1.
TABLE 1 quality assurance status test results for quality assurance status indicators prepared in examples 1-12
Figure BDA0002303038840000251
As can be seen from Table 1, the carbon dioxide passes 2cm3/(cm30.1mm 24h), the quality status indicator can turn blue, oxygen passes 2cm3/(cm30.1mm 24h), the quality status indicator can turn blue, and moisture passes through 2 g/(m)224h), the shelf life indicator may turn blue.
The experimental results show that the carbon dioxide in the packaging environmentPassing by 2cm3/(cm30.1mm 24h), oxygen passage 2cm3/(cm30.1mm 24h) or passage of water vapor 2 g/(m)224h), the shelf life indicator may turn blue.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A quality guarantee state indicator comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer, a protective membrane and a pressure-sensitive adhesive layer which are contacted in sequence;
the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive;
the porous substrate is made of expanded polytetrafluoroethylene;
or
The quality guarantee state indicator comprises a first permeable membrane, a composite indicating layer, a porous substrate, an adhesive layer and a second permeable membrane which are sequentially contacted;
the components of the composite indicating layer comprise an adhesive and an indicator; the indicator comprises one or more of a carbon dioxide indicator, an oxygen indicator and a water vapor indicator; the adhesive in the composite indicating layer comprises one or more of polyester adhesive and polyurethane adhesive;
the porous substrate is made of expanded polytetrafluoroethylene.
2. The shelf-life indicator according to claim 1, wherein said carbon dioxide indicator comprises a carbon dioxide sensitive reactive dye, a basic substance and a solvent;
the carbon dioxide sensitive reactive dye comprises one or more of m-cresol purple, thymolphthalein, o-cresol phthalein, acryloyl fluorescein, β -methylumbelliferyl snore, bromothymolphthalein blue, cresol red, hexadecyl trimethyl ammonium hydroxide, neutral red, phenol red, rhodamine 6G, sulforhodamine 101, lily blue and thymolphthalein blue, wherein the alkaline substance comprises sodium hydroxide, potassium hydroxide or calcium hydroxide;
the oxygen indicator comprises an oxygen-sensitive reactive dye and a solvent;
the oxygen sensitive active dye comprises one or more of methylene blue, azure B, Nile blue, terpyridyl ruthenium, ruthenium perchlorate, octaethyl porphyrin ketone platinum and proflavine;
the moisture indicator comprises a water-soluble ink.
3. Quality status indicator according to claim 1, wherein the adhesive in the adhesive layer comprises one or more of a polyester-based adhesive and a polyurethane adhesive.
4. The shelf-life indicator according to claim 1, wherein said protective film comprises one or more of a polyethylene film, a polypropylene film, a polystyrene film, a polyvinyl chloride film, a polyvinylidene chloride film, a polyethylene terephthalate film, and a nylon film;
the pressure-sensitive adhesive layer comprises one or more of rubber pressure-sensitive adhesive, polyacrylate pressure-sensitive adhesive and organic silicon pressure-sensitive adhesive.
5. The shelf-life indicator of claim 1, wherein said first permeable membrane comprises one or more of a polyethylene membrane, a polytetrafluoroethylene membrane, a polypropylene membrane, a polystyrene membrane, a polyvinyl chloride membrane, a polyvinylidene chloride membrane, a polyethylene terephthalate membrane, and a nylon membrane.
6. The shelf-life indicator of claim 1, wherein said second permeable membrane comprises one or more of a polyethylene membrane, a polytetrafluoroethylene membrane, a polypropylene membrane, a polystyrene membrane, a polyvinyl chloride membrane, a polyvinylidene chloride membrane, a polyethylene terephthalate membrane, and a nylon membrane.
7. A method of making a shelf-life indicator comprising the steps of:
A1) coating a mixed reagent of an adhesive and an indicator on the surface of the first permeable membrane, and carrying out dry compounding on the coated first permeable membrane and the porous substrate to obtain a first composite membrane; the porous substrate is made of expanded polytetrafluoroethylene;
B1) coating an adhesive on the porous substrate of the first compound film, and carrying out dry compounding on the coated porous substrate and a protective film to obtain a second compound film;
C1) coating a pressure-sensitive adhesive on the protective film of the second compound film, and drying to obtain a quality guarantee state indicator;
or
A2) Coating a mixed reagent of an adhesive and an indicator on the surface of the first permeable membrane, and carrying out dry compounding on the coated first permeable membrane and the porous substrate to obtain a first composite membrane; the porous substrate is made of expanded polytetrafluoroethylene;
B2) and coating an adhesive on the porous substrate of the first compound film, and performing dry compounding on the coated porous substrate and the second permeable film to obtain the quality guarantee state indicator.
8. The production method according to claim 7,
in the step a1), the step b,
the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h;
after the dry compounding, the method further comprises the following steps: cooling, compacting, rolling and curing;
in the step B1), the step B,
the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h;
after the dry compounding, the method further comprises the following steps: cooling, compacting, rolling and curing.
9. The production method according to claim 7,
in the step a2), the step b,
the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h;
after the dry compounding, the method further comprises the following steps: cooling, compacting, rolling and curing;
in the step B2), the step B,
the drying temperature of the drying tunnel in the dry compounding is 10-45 ℃, and the drying time of the drying tunnel is 1-24 h;
after the dry compounding, the method further comprises the following steps: cooling, compacting, rolling and curing.
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