High-temperature-resistant acid-base-resistant flexible electronic tag and manufacturing process thereof

Abstract

The invention discloses a high-temperature-resistant, acid-resistant and alkali-resistant flexible electronic tag and a manufacturing process thereof, and belongs to the technical field of flexible electronic tags, and the manufacturing process of the electronic tag comprises the following steps: S1, mixing polyether-ether-ketone and polyimide, then carrying out melt blending, then adding alumina ceramic nanofibers, and carrying out hot press molding and surface treatment to obtain a high-temperature-resistant, acid-resistant and alkali-resistant flexible electronic tag; a composite base material layer is obtained; s2, mixing ethylene glycol, polyvinylpyrrolidone, hydroxyethyl cellulose, silver nanowires, TiN nanosheets and poly (3, 4-ethylenedioxythiophene)-polystyrolsulfon acid to obtain composite slurry, and then spraying and curing the composite slurry on the surface of the composite base material layer to obtain an anti-corrosion conductive layer; and S3, mixing a hexamethylene diisocyanate tripolymer, Silquest A-1170 and hydroxyl silicone oil, then adding a microencapsulation repairing agent into the mixture to form a prepolymer, and spraying and curing the prepolymer to the surface of the corrosion-resistant conductive layer to obtain the high-temperature-resistant acid-base-resistant flexible electronic tag.

Description

Technical Field

[0001] The present invention relates to the field of electronic tag technology, and specifically to a flexible electronic tag and its preparation process suitable for environments with extremely high temperatures (>200°C), strong acids (such as concentrated sulfuric acid and hydrochloric acid), and strong bases (such as sodium hydroxide solution). The flexible electronic tag is suitable for scenarios such as chemical equipment monitoring, medical high-temperature sterilization, and semiconductor production. Background Art

[0002] Existing flexible electronic tags often use a silicone substrate combined with a metal nanowire conductive layer (such as CN103473594B). This utilizes the silicone's ductility to achieve stretchability, but its temperature resistance is insufficient (silicone's temperature resistance is less than 150°C). Furthermore, in strong acidic and alkaline environments, the substrate swells and the metal corrodes, leading to signal failure. For example, applications such as monitoring high-temperature acidic and alkaline environments in chemical reactors and tracking high-temperature sterilization of medical devices urgently require electronic tags that are both heat-resistant, corrosion-resistant, and flexible.

[0003] Existing technology, CN103473594B, uses a silicone substrate and silver nanowire antennas. While stretchable, the substrate easily softens and deforms at high temperatures (for example, the tensile strength of silicone decreases by >50% at temperatures above 180°C), and the resistivity of the silver nanowires increases by >200% within 48 hours in concentrated hydrochloric acid. Furthermore, the interfacial bonding between the silicone substrate and the metal nanowires is weak, and repeated stretching can easily cause the conductive layer to break.

[0004] With the increasing demand for extreme environment monitoring in industrial intelligence, it is urgent to develop a flexible electronic tag with a high-temperature resistant substrate, a corrosion-resistant conductive layer and a stable interface. Summary of the Invention

[0005] The purpose of the present invention is to provide a high-temperature resistant and acid-alkali resistant flexible electronic tag and its manufacturing process to solve the technical problems of substrate softening, conductive layer corrosion and interface peeling of existing flexible electronic tags mentioned in the background technology in high temperature and acid-alkali environment.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A manufacturing process for a high-temperature resistant, acid- and alkali-resistant flexible electronic tag comprises the following steps: S1. Mixing polyetheretherketone and polyimide, heating to 320° C. and melt-blending for 40 to 45 minutes, adding 1 wt % of alumina ceramic nanofibers, and blending at a constant temperature for 15 to 20 minutes, followed by hot pressing and surface treatment to obtain a composite substrate layer; S2, mixing ethylene glycol, polyvinyl pyrrolidone, hydroxyethyl cellulose and silver nanowires, shearing for 30 minutes, then heating to 35-40°C, adding TiN nanosheets thereto, ultrasonically treating for 10 minutes, stirring for 1 hour, then adding poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid thereto, stirring for 1 hour to obtain a composite slurry, and then spraying the composite slurry on the surface of the composite substrate layer, and after three-stage curing, obtaining a corrosion-resistant conductive layer; S3. After mixing hexamethylene diisocyanate trimer, Silquest A-1170 aminosilane coupling agent, and hydroxy silicone oil, add 4-5 wt% of microencapsulated repair agent, and then add ethyl acetate to dilute to a solid content of 30%. Stir at 60°C for 4 hours to form a prepolymer. Spray the prepolymer onto the surface of the corrosion-resistant conductive layer and cure at 80°C for 1 hour to obtain a high-temperature resistant, acid- and alkali-resistant flexible electronic tag.

[0007] Furthermore, the polyetheretherketone and polyimide described in S1 are mixed in a weight ratio of 7:3.

[0008] Furthermore, the surface treatment process described in S1 is as follows: a bionic honeycomb microstructure is formed by using laser microtexturing technology; the wavelength of the laser is set to 1064nm, and the power density of the laser is set to 10J / cm 2 The pore size of the bionic honeycomb microstructure is 100 μm, and the depth of the bionic honeycomb microstructure is 50 μm.

[0009] Furthermore, the usage ratio of ethylene glycol, polyvinyl pyrrolidone, polyvinyl pyrrolidone, silver nanowires, TiN nanosheets, and poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid in S2 is 65-70 g: 4-5 g: 4-5 g: 27-30 g: 3-5 g: 2.5-3.0 g.

[0010] Furthermore, the three-stage curing in S2 is as follows: first, UV curing for 30 seconds, then heating to 80-85°C for pre-curing for 10-15 minutes, and finally heating to 180-185°C for final curing for 20-30 minutes; the wavelength of the UV curing is 365nm, and the intensity is 50mW / cm 2 .

[0011] Furthermore, the hexamethylene diisocyanate trimer, Silquest A-1170 aminosilane coupling agent, and hydroxy silicone oil described in S3 are mixed in a molar ratio of 1:0.5 to 1:2.

[0012] Furthermore, the microencapsulated repair agent in S3 is prepared by the following steps: A1. Mix vinyltrimethoxysilane, deionized water, and sodium lauryl sulfate, and then shear emulsify in a water bath at 40-50°C for 10-20 minutes to form a stable emulsion. A2. Mix urea with 37% formaldehyde by mass, adjust the pH to 8.0-8.5, and heat to 70°C and stir for 1 hour to obtain a prepolymer solution. A3. Add the prepolymer solution dropwise to the stable emulsion at a volume ratio of 1:1 with stirring, adjust the pH to 4.0-4.5, raise the temperature to 60-70°C, and react for 3 hours. After the reaction, adjust the pH to neutral, cool to 25°C, separate, wash, dry, and sieve through 500 mesh to obtain a microencapsulated repair agent.

[0013] Furthermore, the vinyltrimethoxysilane, deionized water and sodium lauryl sulfate described in A1 are mixed in a mass ratio of 1:5:0.2.

[0014] Furthermore, the urea described in A2 is mixed with formaldehyde having a mass fraction of 37% at a mass ratio of 0.4 to 0.5:1.

[0015] Furthermore, the high temperature resistant, acid and alkali resistant flexible electronic tag is manufactured by the above manufacturing process.

[0016] Beneficial effects of the present invention: The present invention provides a high-temperature, acid- and alkali-resistant flexible electronic tag and its manufacturing process. Through the collaborative innovation of a composite substrate layer, a corrosion-resistant conductive layer, and an acid- and alkali-resistant protective layer, the present invention significantly improves the comprehensive performance of the flexible electronic tag in extreme high-temperature, strong acid and strong alkali environments. A specific analysis is as follows: First, in the composite substrate layer, the present invention uses a polyetheretherketone (PEEK) / polyimide (PI) blend: a 7:3 weight ratio blend, combined with PEEK's high melting point (343°C) and PI's high decomposition temperature (550°C), significantly raising the composite substrate's glass transition temperature and inhibiting high-temperature softening. Simultaneously, alumina ceramic nanofiber reinforcement: 1wt% of the nanofibers inhibits creep of the composite substrate through mechanical interlocking, increasing the high-temperature dimensional stability of the flexible electronic tag by more than three times (reducing the deformation rate from 3.5% to 0.7%).

[0017] The present invention then utilizes laser microtexturing technology within the composite substrate layer to create a honeycomb structure with a pore size of 100 μm and a depth of 50 μm. This increases the contact area between the corrosion-resistant conductive layer and the composite substrate layer, significantly enhancing the interfacial bonding strength through a mechanical interlocking effect. Furthermore, a comparison of peel strength reveals that the present invention significantly improves the peel strength (3.6 N / mm) compared to existing silicone substrates, resolving the issue of the conductive layer peeling caused by repeated bending of flexible electronic tags.

[0018] Secondly, in the corrosion-resistant conductive layer, the present invention utilizes the passivation effect of TiN nanosheets: their chemical inertness inhibits oxidation of the silver nanowires, reducing the breakage of the conductive path caused by acid / alkali corrosion. Simultaneously, the gap filling effect of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid fills the gaps between the silver nanowires and the TiN, blocking the penetration path of the corrosive medium, thereby reducing the resistance change rate of the flexible electronic tag in acid / alkali environments by 76% to 82%.

[0019] Again, in the composite substrate layer and the acid- and alkali-resistant protective layer, the present invention disperses stress through a bionic structure: the honeycomb microstructure reduces local crack expansion through stress dispersion. At the same time, the microcapsule repair agent actively repairs: during the bending process, the microcapsules rupture and release the silicone repair agent to fill tiny cracks, ultimately significantly improving the durability of the corrosion-resistant conductive layer.

[0020] Finally, in the acid- and alkali-resistant protective layer, the silicone repair agent in the microcapsules prepared by the present invention is released under acid, alkali or mechanical stress, and reacts with the aminosilane in the acid- and alkali-resistant protective layer to form a SiO2-Si-O-Si network, thereby closing the crack path and inhibiting the penetration of the corrosive medium.

[0021] In summary, this invention solves the industry challenges of flexible electronic tag substrate softening, conductive corrosion, and interface peeling in high-temperature, acidic, and alkaline environments through multi-level collaborative design. Test data fully verifies its creativity, practicality, and industrial application value. DETAILED DESCRIPTION

[0022] Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is obvious that described embodiment is only a part of embodiment of the present invention, rather than whole embodiment. Based on the embodiment in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise all fall within the scope of protection of the present invention. Raw materials, reagents or devices used in the following examples, unless otherwise specified, can be obtained from conventional commercial sources, or can be obtained by existing known methods.

[0023] Example 1 Design of high temperature resistant, acid and alkali resistant flexible electronic tags: 1. Composite substrate layer: (1) Composition of the substrate layer: Polyetheretherketone (PEEK, particle size 20 μm, melting point 343 °C) and polyimide (PI, decomposition temperature 550 °C) were mixed in a weight ratio of 7:3, placed at 320 °C for melt blending for 40 min, and then 1 wt% of alumina ceramic nanofibers (diameter 50 nm, length 10 μm) were added as a reinforcement phase and blended at a constant temperature for 15 min. After completion, a composite substrate with a thickness of 400 ± 10 μm was prepared by hot pressing. Among them, PEEK provides high temperature resistance and PI provides flexibility. After the two are blended, the glass transition temperature of the composite substrate is increased, thereby improving the high temperature resistance of the composite substrate. At the same time, the introduction of alumina ceramic nanofibers can improve the mechanical strength of the composite substrate.

[0024] (2) Interface enhancement: A bionic honeycomb microstructure is formed on the surface of the composite substrate by laser microtexturing technology to enhance the bonding strength with the conductive layer. The laser wavelength is set to 1064 nm and the laser power density is set to 10 J / cm 2 , the pore size of the bionic honeycomb microstructure is 100 μm and the depth is 50 μm, and finally a composite substrate layer is obtained.

[0025] 2. Anti-corrosion conductive layer: (1) Conductive material: Weigh 65 g of ethylene glycol (purity ≥ 99.5%, viscosity 16.5 mPa·s), 4 g of polyvinyl pyrrolidone (PVP, K30 type, molecular weight 40,000) and 1 g of hydroxyethyl cellulose (HEC, viscosity 4000 mPa·s) and add them to a planetary mixer. Stir at a low speed of 500 rpm for 10 min to fully dissolve PVP / HEC. Then add 27 g of silver nanowires (diameter 80 nm, length 50 μm, purity 99.9%), start high-speed shearing (2000 rpm, 30 min), and then control the temperature at 35 °C. Then add 3 g of TiN nanosheets (thickness 2 nm). After the addition is complete, Ultrasonic treatment (frequency 40kHz, power 300W, time 10min) was performed. After the treatment, stirring was continued at 1500rpm for 1h, and then 2.5g of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS, solid content 1.3wt% aqueous solution) was added as an interfacial binder. Stirring was continued for 1h to obtain a composite slurry. The composite slurry was then sprayed on the surface of the composite substrate layer by inkjet printing to form an antenna line (line width 400±10μm), that is, a corrosion-resistant conductive structure was formed, wherein the chemical inertness of the TiN nanosheets inhibited silver oxidation, and the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid was used to fill the nano gap.

[0026] (2) Gradient curing process: The corrosion-resistant conductive structure prepared above is further cured in three stages. First, it is cured by ultraviolet light (wavelength 365nm, intensity 50mW / cm2 , time 30s), then heated to 80℃ for pre-curing 10min, and finally heated to 180℃ for final curing 20min to finally obtain a corrosion-resistant conductive layer.

[0027] 3. Acid and alkali resistant protective layer: (1) Preparation of microencapsulated repair agent: A1. Preparation of core material emulsion: Vinyltrimethoxysilane (purity ≥98%, Aladdin reagent), deionized water, and sodium dodecyl sulfate (SDS) were mixed in a mass ratio of 1:5:0.2 and emulsified at high speed (10,000 rpm for 10 minutes) in a 40°C water bath to form a stable emulsion. A2. Preparation of urea-formaldehyde prepolymer: Urea (analytical grade, purity ≥99.5%, Sinopharm Group) was mixed with 37% formaldehyde at a mass ratio of 0.4:1. The pH of the mixture was then adjusted to 8.0 with 10% sodium hydroxide solution. After adjustment, the mixture was heated to 70°C and stirred for 1 hour to obtain a colorless, transparent prepolymer solution. A3. In-situ coating reaction: The prepolymer solution was added dropwise to the stable emulsion at a volume ratio of 1:1 with stirring, and the pH of the reaction system was adjusted to 4.0 with 10% by mass of citric acid (analytical grade). After completion, the system was heated to 60°C and reacted for 3 hours to promote the cross-linking and curing of the urea-formaldehyde resin on the surface of the silicone droplets. After completion, the pH of the system was adjusted to neutral with sodium hydroxide. After adjustment, the system was cooled to 25°C and centrifuged (speed 8000 rpm, time 5 min), and then washed with deionized water. The solid components were collected and vacuum dried (60°C, 8 hours), and then passed through a 500-mesh sieve to obtain a microencapsulated repair agent.

[0028] (2) Hexamethylene diisocyanate trimer (HDI, Covestro Desmodur N3600), Silquest A-1170 aminosilane coupling agent (Maitu), and hydroxy silicone oil (hydroxyl content 10wt%, viscosity 1000mPa·s (25℃)) were mixed in a molar ratio of 1:0.5:2, and then 4wt% of microencapsulated repair agent was added thereto. Ethyl acetate was added to dilute the mixture to a solid content of 30%, and the mixture was stirred at 60℃ for 4h to form a prepolymer. The prepolymer was sprayed onto the surface of the corrosion-resistant conductive layer and cured at 80℃ for 1h to form an acid- and alkali-resistant protective layer with a thickness of 450μm. Finally, a high-temperature resistant and acid- and alkali-resistant flexible electronic tag was obtained.

[0029] Example 2 Design of high temperature resistant, acid and alkali resistant flexible electronic tags: 1. Composite substrate layer: (1) Composition of the substrate layer: Polyetheretherketone (PEEK, particle size 20 μm, melting point 343 °C) and polyimide (PI, decomposition temperature 550 °C) were mixed in a weight ratio of 7:3, placed at 320 °C for melt blending for 45 min, and then 1 wt% of alumina ceramic nanofibers (diameter 50 nm, length 10 μm) were added as a reinforcement phase and blended at a constant temperature for 20 min. After completion, a composite substrate with a thickness of 400 ± 10 μm was prepared by hot pressing. Among them, PEEK provides high temperature resistance and PI provides flexibility. After the two are blended, the glass transition temperature of the composite substrate is increased, thereby improving the high temperature resistance of the composite substrate. At the same time, the introduction of alumina ceramic nanofibers can improve the mechanical strength of the composite substrate.

[0030] (2) Interface enhancement: A bionic honeycomb microstructure is formed on the surface of the composite substrate by laser microtexturing technology to enhance the bonding strength with the conductive layer. The laser wavelength is set to 1064 nm and the laser power density is set to 10 J / cm 2 , the pore size of the bionic honeycomb microstructure is 100 μm and the depth is 50 μm, and finally a composite substrate layer is obtained.

[0031] 2. Anti-corrosion conductive layer: (1) Conductive material: 68 g of ethylene glycol (purity ≥ 99.5%, viscosity 16.5 mPa·s), 4.5 g of polyvinyl pyrrolidone (PVP, K30 type, molecular weight 40,000) and 1 g of hydroxyethyl cellulose (HEC, viscosity 4000 mPa·s) were weighed and added to a planetary mixer. The mixture was stirred at a low speed of 500 rpm for 10 min to fully dissolve the PVP / HEC. Then, 30 g of silver nanowires (diameter 80 nm, length 50 μm, purity 99.9%) were added. High-speed shearing was started (2000 rpm, 30 min). The temperature was then controlled at 40 °C. 5 g of TiN nanosheets (thickness 2 nm) were added. After the addition was complete, , and subjected to ultrasonic treatment (frequency 40 kHz, power 300 W, time 10 min). After treatment, stirring was continued at 2000 rpm for 1 hour, and then 2.8 g of poly (3,4-ethylenedioxythiophene) - polystyrene sulfonic acid (PEDOT:PSS, solid content 1.3 wt% aqueous solution) was added thereto as an interfacial binder, and stirring was continued for 1 hour to obtain a composite slurry. The composite slurry was then sprayed on the surface of the composite substrate layer by inkjet printing to form an antenna line (line width 400 ± 10 μm), that is, a corrosion-resistant conductive structure was formed, wherein the chemical inertness of the TiN nanosheets inhibited silver oxidation, and the poly (3,4-ethylenedioxythiophene) - polystyrene sulfonic acid was used to fill the nano gap.

[0032] (2) Gradient curing process: The corrosion-resistant conductive structure prepared above is further cured in three stages. First, it is cured by ultraviolet light (wavelength 365nm, intensity 50mW / cm2 , time 30s), then heated to 80℃ for pre-curing 15min, and finally heated to 180℃ for final curing 30min, finally obtaining a corrosion-resistant conductive layer.

[0033] 3. Acid and alkali resistant protective layer: (1) Preparation of microencapsulated repair agent: A1. Preparation of core material emulsion: Vinyltrimethoxysilane (purity ≥98%, Aladdin reagent), deionized water, and sodium dodecyl sulfate (SDS) were mixed in a mass ratio of 1:5:0.2 and emulsified at high shear speed (12,000 rpm, 20 min) in a 45°C water bath to form a stable emulsion. A2. Preparation of urea-formaldehyde prepolymer: Urea (analytical grade, purity ≥99.5%, Sinopharm Group) was mixed with 37% formaldehyde at a mass ratio of 0.5:1. The pH of the mixture was then adjusted to 8.0 with 10% sodium hydroxide solution. After adjustment, the mixture was heated to 70°C and stirred for 1 hour to obtain a colorless, transparent prepolymer solution. A3. In-situ coating reaction: The prepolymer solution was added dropwise to the stable emulsion at a volume ratio of 1:1 with stirring, and the pH of the reaction system was adjusted to 4.0 with 10% by mass of citric acid (analytical grade). After completion, the system was heated to 65°C and reacted for 3 hours to promote the cross-linking and curing of the urea-formaldehyde resin on the surface of the silicone droplets. After completion, the pH of the system was adjusted to neutral with sodium hydroxide. After adjustment, the system was cooled to 25°C and centrifuged (speed 10,000 rpm, time 5 min), and then washed with deionized water. The solid components were collected and vacuum dried (60°C, 8 hours), and then passed through a 500-mesh sieve to obtain a microencapsulated repair agent.

[0034] (2) Hexamethylene diisocyanate trimer (HDI, Covestro Desmodur N3600), Silquest A-1170 aminosilane coupling agent (Maitu), and hydroxy silicone oil (hydroxyl content 10wt%, viscosity 1000mPa·s (25℃)) were mixed in a molar ratio of 1:1:2, and then 5wt% of microencapsulated repair agent was added thereto. Ethyl acetate was added to dilute the mixture to a solid content of 30%, and the mixture was stirred at 60℃ for 4h to form a prepolymer. The prepolymer was sprayed onto the surface of the corrosion-resistant conductive layer and cured at 80℃ for 1h to form an acid- and alkali-resistant protective layer with a thickness of 450μm. Finally, a high-temperature resistant and acid- and alkali-resistant flexible electronic tag was obtained.

[0035] Example 3 Design of high temperature resistant, acid and alkali resistant flexible electronic tags: 1. Composite substrate layer: (1) Composition of the substrate layer: Polyetheretherketone (PEEK, particle size 20 μm, melting point 343 °C) and polyimide (PI, decomposition temperature 550 °C) were mixed in a weight ratio of 7:3, placed at 320 °C for melt blending for 45 min, and then 1 wt% of alumina ceramic nanofibers (diameter 50 nm, length 10 μm) were added as a reinforcement phase and blended at a constant temperature for 20 min. After completion, a composite substrate with a thickness of 400 ± 10 μm was prepared by hot pressing. Among them, PEEK provides high temperature resistance and PI provides flexibility. After the two are blended, the glass transition temperature of the composite substrate is increased, thereby improving the high temperature resistance of the composite substrate. At the same time, the introduction of alumina ceramic nanofibers can improve the mechanical strength of the composite substrate.

[0036] (2) Interface enhancement: A bionic honeycomb microstructure is formed on the surface of the composite substrate by laser microtexturing technology to enhance the bonding strength with the conductive layer. The laser wavelength is set to 1064 nm and the laser power density is set to 10 J / cm 2 , the pore size of the bionic honeycomb microstructure is 100 μm and the depth is 50 μm, and finally a composite substrate layer is obtained.

[0037] 2. Anti-corrosion conductive layer: (1) Conductive material: Weigh 70 g of ethylene glycol (purity ≥ 99.5%, viscosity 16.5 mPa·s), 5 g of polyvinyl pyrrolidone (PVP, K30 type, molecular weight 40,000) and 1 g of hydroxyethyl cellulose (HEC, viscosity 4000 mPa·s) and add them to a planetary mixer. Stir at a low speed of 500 rpm for 10 min to fully dissolve PVP / HEC. Then add 30 g of silver nanowires (diameter 80 nm, length 50 μm, purity 99.9%), start high-speed shearing (2000 rpm, 30 min), and then control the temperature at 40 °C. Then add 5 g of TiN nanosheets (thickness 2 nm). After the addition is complete, Ultrasonic treatment (frequency 40kHz, power 300W, time 10min) was performed. After the treatment, stirring was continued at 2000rpm for 1h, and then 3.0g of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS, solid content 1.3wt% aqueous solution) was added as an interfacial binder. Stirring was continued for 1h to obtain a composite slurry. The composite slurry was then sprayed on the surface of the composite substrate layer by inkjet printing to form an antenna line (line width 400±10μm), that is, a corrosion-resistant conductive structure was formed, wherein the chemical inertness of the TiN nanosheets inhibited silver oxidation, and the poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid was used to fill the nano gap.

[0038] (2) Gradient curing process: The corrosion-resistant conductive structure prepared above is further cured in three stages. First, it is cured by ultraviolet light (wavelength 365nm, intensity 50mW / cm2 , time 30s), then heated to 85℃ for pre-curing 15min, and finally heated to 185℃ for final curing 30min to finally obtain a corrosion-resistant conductive layer.

[0039] 3. Acid and alkali resistant protective layer: (1) Preparation of microencapsulated repair agent: A1. Preparation of core material emulsion: Vinyltrimethoxysilane (purity ≥98%, Aladdin reagent), deionized water, and sodium dodecyl sulfate (SDS) were mixed in a mass ratio of 1:5:0.2 and emulsified at high speed (12,000 rpm for 20 minutes) in a 50°C water bath to form a stable emulsion. A2. Preparation of urea-formaldehyde prepolymer: Urea (analytical grade, purity ≥99.5%, Sinopharm Group) was mixed with 37% formaldehyde at a mass ratio of 0.5:1. The pH of the mixture was then adjusted to 8.5 with 10% sodium hydroxide solution. After adjustment, the mixture was heated to 70°C and stirred for 1 hour to obtain a colorless, transparent prepolymer solution. A3. In-situ coating reaction: The prepolymer solution was added dropwise to the stable emulsion at a volume ratio of 1:1 with stirring, and the pH of the reaction system was adjusted to 4.5 with 10% by mass of citric acid (analytical grade). After completion, the system was heated to 70°C and reacted for 3 hours to promote the cross-linking and curing of the urea-formaldehyde resin on the surface of the silicone droplets. After completion, the pH of the system was adjusted to neutral with sodium hydroxide. After adjustment, the system was cooled to 25°C and centrifuged (speed 10,000 rpm, time 5 min), and then washed with deionized water. The solid components were collected and vacuum dried (60°C, 8 hours), and then passed through a 500-mesh sieve to obtain a microencapsulated repair agent.

[0040] (2) Hexamethylene diisocyanate trimer (HDI, Covestro Desmodur N3600), Silquest A-1170 aminosilane coupling agent (Maitu), and hydroxy silicone oil (hydroxyl content 10wt%, viscosity 1000mPa·s (25℃)) were mixed in a molar ratio of 1:1:2, and then 5wt% of microencapsulated repair agent was added thereto. Ethyl acetate was added to dilute the mixture to a solid content of 30%, and the mixture was stirred at 60℃ for 4h to form a prepolymer. The prepolymer was sprayed onto the surface of the corrosion-resistant conductive layer and cured at 80℃ for 1h to form an acid- and alkali-resistant protective layer with a thickness of 450μm. Finally, a high-temperature resistant and acid- and alkali-resistant flexible electronic tag was obtained.

[0041] Comparative Example 1 Comparative Example 1 is the control group of Example 2. 1 wt% of the alumina ceramic nanofibers (50 nm in diameter, 10 μm in length) in the composite substrate layer of Example 2 are removed, and the remaining raw materials, raw material amounts and manufacturing methods remain the same as in Example 2, and finally a high-temperature resistant, acid- and alkali-resistant flexible electronic tag is obtained.

[0042] Comparative Example 2 Comparative Example 2 is the control group of Example 2. The interface enhancement process of the composite substrate in Example 2 is removed, that is, the process of forming a bionic honeycomb microstructure by laser microtexturing technology is removed. The remaining raw materials, raw material amounts and manufacturing methods remain the same as in Example 2, and finally a high-temperature resistant and acid- and alkali-resistant flexible electronic tag is obtained.

[0043] Comparative Example 3 Comparative Example 3 is the control group of Example 2. The raw material poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS, solid content 1.3wt% aqueous solution) in the anti-corrosion conductive layer in Example 2 is removed, and the remaining raw materials, raw material amounts and manufacturing processes are kept consistent with Example 2, and finally a high-temperature resistant and acid- and alkali-resistant flexible electronic tag is obtained.

[0044] Comparative Example 4 Comparative Example 4 is the control group of Example 2. The raw material microencapsulated repair agent in the acid and alkali resistant protective layer in Example 2 is removed, and the remaining raw materials, raw material amounts and manufacturing process are kept consistent with Example 2, and finally a high-temperature resistant and acid-alkali resistant flexible electronic tag is obtained.

[0045] The performance tests were conducted on the high temperature resistant, acid and alkali resistant flexible electronic tags manufactured in Examples 1 to 3 and Comparative Examples 1 to 4. The performance test process is as follows, and the test results are shown in Table 1: (1) High temperature stability test: The high temperature resistant and acid-base resistant flexible electronic tag samples were placed in a 250°C oven for constant temperature treatment for 24 hours, and the deformation rate (dimensional change, %) and resistance change rate (ΔR / R0, %) were measured.

[0046] (2) Strong acid / alkali environment tolerance test: The high-temperature resistant and acid-alkali resistant flexible electronic tag samples were immersed in 60wt% H2SO4 (80℃) and 10wt% NaOH (60℃) solutions respectively, and the resistance change rate was measured after 48 hours.

[0047] (3) Interface adhesion test: The adhesion between the corrosion-resistant conductive layer and the composite substrate layer was evaluated according to the ASTM D3359 100-grid method (grades 0 to 5B, with 5B being the best), and the peel strength (N / mm) was measured.

[0048] (4) Bending cycle durability test: The high-temperature resistant and acid- and alkali-resistant flexible electronic tag sample was fixed on a bending tester (radius 5 mm, frequency 1 Hz), and the resistance change rate after 500 bends was recorded.

[0049] Table 1 Test results

[0050] As can be seen from Table 1: (1) High temperature stability (deformation rate and ΔR / R0): Example: Deformation rate <1%, ΔR / R0 <1.5% (alumina nanofibers inhibit creep, PEEK / PI blending increases Tg).

[0051] Comparative Example 1: deformation rate 3.5% (no nanofiber reinforcement, substrate softening significantly at high temperature).

[0052] (2) Strong acid / base tolerance (ΔR / R0 in H2SO4 / NaOH): Example: ΔR / R0<15% (TiN passivated silver nanowires, PEDOT filled gaps).

[0053] Comparative Example 3: ΔR / R0>47% (no PEDOT, corrosion medium penetration accelerates silver oxidation).

[0054] Comparative Example 4: ΔR / R0=18% (no microcapsule repair, crack expansion leads to aggravated corrosion).

[0055] (3) Interface bonding strength (grid strength and peel strength): Example: 5B grade, peel strength>3.0 N / mm (laser microtexturing mechanical interlocking).

[0056] Comparative Example 2: 2B grade, peel strength 1.1 N / mm (no surface structure, insufficient bonding strength).

[0057] (4) Bending cycle durability (500 times ΔR / R0): Example: ΔR / R0<8% (microcapsules repair cracks, bionic structure disperses stress).

[0058] Comparative Example 2: ΔR / R0=23.5% (interface peeling causes the conductive layer to break).

[0059] Comparative Example 4: ΔR / R0=18.4% (no self-repairing function, microcracks accumulated).

[0060] It should be noted that, in this document, terms such as "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0061] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A manufacturing process for a high temperature resistant, acid and alkali resistant flexible electronic tag, characterized in that: The following steps are involved: S1. Mixing polyetheretherketone and polyimide, heating to 320° C. and melt-blending for 40 to 45 minutes, adding 1 wt % of alumina ceramic nanofibers, and blending at a constant temperature for 15 to 20 minutes, followed by hot pressing and surface treatment to obtain a composite substrate layer; S2, mixing ethylene glycol, polyvinyl pyrrolidone, hydroxyethyl cellulose and silver nanowires, shearing for 30 minutes, then heating to 35-40°C, adding TiN nanosheets thereto, ultrasonically treating for 10 minutes, stirring for 1 hour, then adding poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid thereto, stirring for 1 hour to obtain a composite slurry, and then spraying the composite slurry on the surface of the composite substrate layer, and after three-stage curing, obtaining a corrosion-resistant conductive layer; S3. After mixing hexamethylene diisocyanate trimer, Silquest A-1170 aminosilane coupling agent, and hydroxy silicone oil, add 4-5 wt% of microencapsulated repair agent, and then add ethyl acetate to dilute to a solid content of 30%. Stir at 60°C for 4 hours to form a prepolymer. Spray the prepolymer onto the surface of the corrosion-resistant conductive layer and cure at 80°C for 1 hour to obtain a high-temperature resistant, acid- and alkali-resistant flexible electronic tag.

2. The manufacturing process of a high temperature resistant, acid and alkali resistant flexible electronic tag according to claim 1, characterized in that: The polyetheretherketone and polyimide described in S1 are mixed in a weight ratio of 7:

3.

3. The manufacturing process of a high temperature resistant, acid and alkali resistant flexible electronic tag according to claim 1, characterized in that: The surface treatment process described in S1 is to form a bionic honeycomb microstructure using laser microtexturing technology; the wavelength of the laser is set to 1064nm, and the power density of the laser is set to 10J / cm 2 The pore size of the bionic honeycomb microstructure is 100 μm, and the depth of the bionic honeycomb microstructure is 50 μm.

4. The manufacturing process of a high temperature resistant, acid and alkali resistant flexible electronic tag according to claim 1, characterized in that: The usage ratio of ethylene glycol, polyvinyl pyrrolidone, polyvinyl pyrrolidone, silver nanowires, TiN nanosheets, and poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid in S2 is 65-70g:4-5g:4-5g:27-30g:3-5g:2.5-3.0g.

5. The manufacturing process of a high temperature resistant, acid and alkali resistant flexible electronic tag according to claim 1, characterized in that: The three-stage curing in S2 is: first, UV curing for 30 seconds, then heating to 80-85°C for pre-curing for 10-15 minutes, and finally heating to 180-185°C for final curing for 20-30 minutes; the wavelength of the UV curing is 365nm, and the intensity is 50mW / cm 2 .

6. The manufacturing process of a high temperature resistant, acid and alkali resistant flexible electronic tag according to claim 1, characterized in that: The hexamethylene diisocyanate trimer, Silquest A-1170 aminosilane coupling agent, and hydroxy silicone oil described in S3 are mixed in a molar ratio of 1:0.5 to 1:

2.

7. The manufacturing process of a high temperature resistant, acid and alkali resistant flexible electronic tag according to claim 1, characterized in that: The microencapsulated repair agent in S3 is prepared by the following steps: A1. Mix vinyltrimethoxysilane, deionized water, and sodium lauryl sulfate, and then shear emulsify in a water bath at 40-50°C for 10-20 minutes to form a stable emulsion. A2. Mix urea with 37% formaldehyde by mass, adjust the pH to 8.0-8.5, and heat to 70°C and stir for 1 hour to obtain a prepolymer solution. A3. Add the prepolymer solution dropwise to the stable emulsion at a volume ratio of 1:1 with stirring, adjust the pH to 4.0-4.5, raise the temperature to 60-70°C, and react for 3 hours. After the reaction, adjust the pH to neutral, cool to 25°C, separate, wash, dry, and sieve through 500 mesh to obtain a microencapsulated repair agent.

8. The manufacturing process of a high temperature resistant, acid and alkali resistant flexible electronic tag according to claim 7, characterized in that: The vinyltrimethoxysilane, deionized water and sodium lauryl sulfate described in A1 were mixed in a mass ratio of 1:5:0.

2.

9. The manufacturing process of a high temperature resistant, acid and alkali resistant flexible electronic tag according to claim 7, characterized in that: The urea described in A2 is mixed with formaldehyde having a mass fraction of 37% in a mass ratio of 0.4 to 0.5:

1.

10. A high temperature resistant and acid and alkali resistant flexible electronic tag, characterized in that: The invention is manufactured by the manufacturing process according to any one of claims 1 to 9.

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