Preparation method of novel electro-stripping pressure-sensitive adhesive coating liquid

Abstract

The invention discloses a preparation method of a novel electro-stripping pressure-sensitive adhesive coating liquid, which comprises the following steps: by taking a mixed liquid of a non-water-soluble monomer and a non-water-soluble ionic liquid as a dispersion phase, dispersing the dispersion phase in continuous-phase water under the action of an emulsifier, carrying out emulsion polymerization on the components of the dispersion phase under the action of an initiator to prepare ionic microspheres, and drying the ionic microspheres to obtain the electro-stripping pressure-sensitive adhesive coating liquid. And uniformly mixing the ionic microspheres, the water-based pressure-sensitive adhesive emulsion, the filler and the auxiliary agent to obtain the novel electro-stripping pressure-sensitive adhesive coating liquid. The novel electro-stripping pressure-sensitive adhesive coating liquid prepared by the invention solves the problem that the existing ion pressure-sensitive adhesive coating liquid is not environment-friendly due to the fact that a large amount of organic solvents are used in the synthesis process, and the problems of ionic liquid leakage and moisture absorption after bonding are solved.

Description

Technical Field

[0001] This invention belongs to the field of advanced materials preparation technology. More specifically, this invention relates to a method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid. Background Technology

[0002] Pressure-sensitive adhesives (PSAs) are widely used in consumer electronics, automotive, home appliances, and photovoltaic industries due to their efficient application process. With the circular economy becoming mainstream, there is an urgent need for efficient peeling and disassembly of PSA bonds. Ionic PSAs, prepared by introducing ionic liquids into polymers, can effectively achieve electro-exfoliation of PSA bonds through interfacial electrochemical reactions under energization. However, existing ionic PSA coating solutions are mainly prepared by directly blending polymers with ionic liquids or by directly copolymerizing ionic liquid monomers with acrylate monomers. These existing technologies have two main problems: First, they use large amounts of organic solvents, which are not only costly but also environmentally unfriendly, hindering long-term sustainable development in this field. Second, after bonding, existing ionic PSAs may experience leakage of the internal ionic liquid during service life and are also prone to absorbing moisture from the air, significantly affecting their lifespan. Summary of the Invention

[0003] One object of the present invention is to solve at least the above-mentioned problems and / or defects, and to provide at least the advantages described below.

[0004] To achieve these and other advantages according to the present invention, the present invention provides a method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid, comprising: using a mixture of a non-water-soluble monomer and a non-water-soluble ionic liquid as a dispersed phase, dispersing the dispersed phase in a continuous phase of water under the action of an emulsifier, performing emulsion polymerization between the components of the dispersed phase under the action of an initiator to prepare ionic microspheres, and then mixing the ionic microspheres with an aqueous pressure-sensitive adhesive emulsion uniformly to obtain the novel electro-exfoliating pressure-sensitive adhesive coating liquid.

[0005] Preferably, the non-water-soluble monomer refers to an olefin monomer with a solubility in water of less than 1 g / 100 mL at room temperature and containing a double bond capable of undergoing free radical polymerization, specifically including: soft monomers, hard monomers, functional monomers, and crosslinking monomers.

[0006] Preferably, the soft monomer in the non-water-soluble monomer refers to an olefin monomer with a glass transition temperature below 0 ˚C in the homopolymer, and is further an acrylate monomer, specifically including one or more of the following: hydroxyethyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, tetrahydrofuran acrylate, lauryl acrylate, and lauryl methacrylate. The mass fraction of the soft monomer is 0-50 wt% of the non-water-soluble monomer.

[0007] Preferably, the hard monomer of the non-water-soluble monomer refers to an olefin monomer whose homopolymer has a glass transition temperature higher than 0 ˚C, specifically including one or more of the following: methyl methacrylate, styrene, ethyl methacrylate, n-butyl methacrylate, n-isobutyl methacrylate, acryloylmorpholine, tetrahydrofuran methacrylate, norbornene, isobornene methacrylate, cyclohexyl methacrylate, and 2-hydroxypropyl methacrylate; The hard monomer accounts for 0 to 70 wt% of the non-water-soluble monomer.

[0008] Preferably, the functional monomer of the non-water-soluble monomer refers to a soft olefin monomer or a hard olefin monomer whose molecular structure contains a weakly coordinating monomer with ions, and the functional monomer can be used as a soft mononuclear hard monomer; the functional monomer specifically includes one or more of the following: methoxyethyl acrylate, methoxyethyl methacrylate, methyl polyethylene glycol monomethyl ether acrylate with a molecular weight of less than 200 g / mol, polyethylene glycol monomethyl ether acrylate with a molecular weight of less than 200 g / mol, perfluoropropyl vinyl ether, perfluoropolyether acrylate with a molecular weight of less than 400 g / mol, perfluoromethyl vinyl ether, perfluorobutyl acrylate, perfluorooctyl acrylate, perfluorohexylethyl acrylate, trifluoromethylstyrene, pentafluorostyrene, trifluoroethyl methacrylate, butyl hexafluoroacrylate, and dodecafluoroheptyl methacrylate; The functional monomer accounts for 20-60 wt% of the non-water-soluble monomer.

[0009] Preferably, the crosslinking monomer of the non-water-soluble monomer refers to an olefin monomer containing two or more free radical polymerizable double bonds, specifically including: divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentanediol diacrylate, 1,6-hexanediol diacrylate, bisphenol A dimethacrylate, and butylene dimethacrylate, or one or more of these. The mass fraction of the crosslinking monomer is 0-5 wt% of all water-insoluble monomers.

[0010] Preferably, the non-water-soluble ionic liquid refers to a room-temperature molten salt with a solubility in water of less than 1 g / 100 mL at room temperature and capable of dissociating into anions and cations, specifically including one or more of imidazole ionic liquids, pyridine ionic liquids, pyrrole ionic liquids, thiazole ionic liquids, and quaternary ammonium salt ionic liquids. The mass fraction of the non-water-soluble ionic liquid is 20-50 wt% of the non-water-soluble monomer.

[0011] Preferably, the emulsifier includes ionic emulsifiers and nonionic emulsifiers, specifically including: long-chain alkyl sulfates with more than 12 carbon atoms, long-chain alkyl sulfonates with more than 12 carbon atoms, long-chain alkylbenzene sulfonates with more than 12 carbon atoms, long-chain alkyl carboxylates with more than 12 carbon atoms, long-chain alkyl ammonium salts with more than 12 carbon atoms, and one or more of polyoxyethylene octylphenol ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenol ether, sodium dioctyl sulfosuccinate, glyceryl monostearate, Tween series, and Span series; The emulsifier accounts for 4 to 10 wt% of the dispersed phase.

[0012] Preferably, the initiator comprises a single initiation system or a redox initiation system; The single-initiator system specifically includes one or more of potassium persulfate, ammonium persulfate, sodium persulfate, and azobisisobutyramidine hydrochloride; The redox initiators include one or more of the following: persulfate and sulfite, persulfate and bisulfite, persulfate and thiosulfate, persulfate and aliphatic amine, persulfate and aliphatic diamine, and hydrogen peroxide and ferrous sulfate. The initiation system comprises 0.5–2 wt% of the insoluble monomers. The initiator can be added in one go, in batches, or continuously dripped. The oil-to-water ratio of the emulsion polymerization is 1:1 to 1:10; Before emulsion polymerization, the dispersed phase is slowly added to the continuous phase water, accompanied by mechanical stirring and / or ultrasound. The ion microspheres have a diameter of 10~350 nm, a particle size distribution of 0.01~0.5, and a solid content of 20%~50%.

[0013] Preferably, the aqueous pressure-sensitive adhesive latex refers to a pressure-sensitive adhesive latex prepared by conventional emulsion polymerization, including: aqueous acrylic pressure-sensitive adhesive latex or pressure-sensitive adhesive latex prepared by emulsification process, specifically including: one or more of aqueous acrylic pressure-sensitive adhesive latex, aqueous rubber-based pressure-sensitive adhesive latex, and aqueous polyurethane pressure-sensitive adhesive latex; the glass transition temperature of the aqueous pressure-sensitive adhesive latex after thorough drying is below -20 ˚C; The novel electro-exfoliating pressure-sensitive adhesive coating liquid is prepared by adding fillers, which specifically include one or more of the following: calcium carbonate, silica, titanium dioxide, zinc oxide, talc, nanocellulose, hydroxyapatite, montmorillonite, kaolin, graphene, and graphite powder; there is no particular limitation on the amount of filler used, and it is added according to the actual situation. The preparation process of the novel electro-exfoliating pressure-sensitive adhesive coating liquid also includes additives. These additives are used to improve the process and performance of the novel electro-exfoliating pressure-sensitive adhesive coating liquid, including one or more of the following: plasticizers, thickeners, tackifiers, antioxidants, curing agents, anti-oxidants, ultraviolet absorbers, preservatives, lubricants, pH adjusters, defoamers, and antifungal agents. The thickeners include polyacrylic acid thickeners, polyacrylamide thickeners, and cellulose ether thickeners. The tackifiers include polyethylene glycol tackifiers and sorbitol tackifiers; the antioxidants include emulsion-type hindered phenolic antioxidants, rosin ester antioxidants, and zinc dithiocarbamate antioxidants; the pH adjusters include inorganic bases, organic amines, carbonates, and bicarbonates; the UV absorbers include water-dispersible emulsified triazine UV absorbers and water-dispersible emulsified benzotriazole UV absorbers; there is no particular limitation on the amount of filler additives used, which are added according to the actual situation. After the ion-sensitive pressure adhesive coating solution is dried, the mass fraction of the ion microspheres is 20-80 wt%. The ion-sensitive adhesive prepared by the ion-sensitive adhesive coating solution has an ionic conductivity greater than 1×10⁻⁶. -6 S / m; Electro-exfoliation of the novel electro-exfoliating pressure-sensitive adhesive coating liquid refers to the process where, after the novel electro-exfoliating pressure-sensitive adhesive coating liquid is applied to the substrate and cured to obtain pressure-sensitive adhesive, a DC voltage greater than 10 V is applied to both ends of the pressure-sensitive adhesive bonded to the substrate, and the energizing time is 1~10 min, resulting in a reduction of the peeling force of the pressure-sensitive adhesive bond of more than 70%.

[0014] This invention offers at least the following advantages: The novel electro-exfoliating pressure-sensitive adhesive coating solution prepared by this invention solves the environmentally unfriendly problem of the extensive use of organic solvents in the synthesis of existing ionic pressure-sensitive adhesive coating solutions. This invention is the first to prepare ionic microspheres from non-water-soluble monomers and non-water-soluble ionic liquids, and then blends these ionic microspheres with an aqueous pressure-sensitive adhesive emulsion to obtain the novel electro-exfoliating pressure-sensitive adhesive coating solution, thus solving the problems of ionic liquid leakage and moisture absorption after bonding. Simultaneously, it greatly improves the current problem of pressure-sensitive adhesives being unable to peel off as needed after effective bonding, achieving peeling off as needed after applying a safe voltage, and solving the problems of disassembly, recycling, and reuse of special components in flexible electronics.

[0015] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached Figure Description

[0016] Figure 1 The 90° peel curves of the novel electro-exfoliating pressure-sensitive adhesive coating liquid prepared in Example 1 after curing are shown in the following figures: no energization and 90V energization for 5 minutes. Figure 2 The 90° peel curves of the novel electro-exfoliating pressure-sensitive adhesive coating liquid prepared in Example 2 after curing are shown in the following figures: no energization and energized at 60V for 5 minutes. Figure 3 The 90° peel curves of the novel electro-exfoliating pressure-sensitive adhesive coating liquid prepared in Example 3 after curing are shown in the following figures: no energization and 90V energization for 5 minutes. Figure 4 The 90° peel curves of the novel electro-exfoliating pressure-sensitive adhesive coating liquid prepared in Example 5 after curing are shown in the following figures: no power applied and 30V power applied for 5 minutes. Figure 5 The 90° peel curves of the novel electro-exfoliating pressure-sensitive adhesive coating liquid prepared in Example 1 after curing are shown in the following figures: no energization and 50V energization for 5 minutes. Figure 6 The change in 90° peel force of the novel electro-exfoliating pressure-sensitive adhesive coating liquid prepared in Example 1 after curing at 55 °C / 95%RH for different times. Detailed Implementation

[0017] The present invention will now be described in further detail with reference to the accompanying drawings, so that those skilled in the art can implement it based on the description.

[0018] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof. Example 1: A method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid, comprising: By weight, 60 parts of methyl methacrylate (hard monomer), 40 parts of methoxyethyl acrylate (soft monomer, functional monomer), 60 parts of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt (water-insoluble ionic liquid), and 5 parts of 1,6-hexanediol diacrylate (crosslinking monomer) were mixed thoroughly to prepare the dispersed phase. 4 parts of sodium dodecyl sulfate were dissolved in 600 parts of deionized water to prepare the continuous phase. 2 parts of ammonium persulfate were dissolved in 100 parts of deionized water and mixed thoroughly to prepare the initiator solution. Under a nitrogen atmosphere at room temperature and a stirring speed of 600 r / min, the dispersed phase was slowly added to the continuous phase, and mechanical stirring was continued for 15 min. The reaction system was heated to 70 ˚C, and the initiator solution was slowly added dropwise to the reaction system. The reaction was then stirred for 5 h before being discharged to obtain ionic microspheres. The ion microspheres prepared in this embodiment have a diameter of approximately 120 nm and a particle size distribution of 0.095.

[0019] 50 parts of ionic microspheres with a solid content of 20% were mixed with 50 parts of Desay 3089 aqueous polyacrylate pressure-sensitive adhesive latex with a solid content of 38% (glass transition temperature of about -25 ˚C), and 5 parts of sodium polyacrylate (thickener) were added to obtain a novel electro-exfoliating pressure-sensitive adhesive coating solution.

[0020] The prepared novel electro-exfoliating pressure-sensitive adhesive coating solution was coated onto a 0.01 mm thick stainless steel film, with the adhesive layer thickness controlled at 0.1 mm. After drying, it was bonded to the stainless steel. Figure 1 As shown, the 90˚ peel force is 1240 N / m when no power is applied; after applying a 90 V DC voltage for 5 minutes, the 90˚ peel force decreases to 50 N / m.

[0021] like Figure 6 As shown, the novel electro-exfoliating pressure-sensitive adhesive coating solution prepared in this embodiment exhibits a stable 90° peel force within a 384-hour aging period under 55 °C / 95%RH conditions. This indicates that the novel electro-exfoliating pressure-sensitive adhesive coating solution still has an extremely long service life under high humidity conditions, solving the problem of moisture absorption affecting the service life of ion pressure-sensitive adhesives.

[0022] Example 2: A method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid, comprising: By weight, 50 parts styrene (hard monomer), 45 parts methoxyethyl methacrylate (functional monomer), 5 parts hydroxyethyl acrylate (soft monomer), 70 parts 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt (water-insoluble ionic liquid), and 5 parts 1,6-hexanediol diacrylate (crosslinking monomer) were mixed thoroughly to prepare the dispersed phase. 4 parts sodium hexadecyl sulfate were dissolved in 500 parts deionized water to prepare the continuous phase. 3 parts potassium persulfate were dissolved in 100 parts deionized water and mixed thoroughly to prepare the initiator solution. Under a dry argon atmosphere at room temperature, the dispersed phase was slowly added to the continuous phase, and mechanical stirring was continued for 30 min. The reaction system was then heated to 75 ˚C, and the initiator solution was slowly added dropwise to the reaction system. After stirring for 5 h, the product was discharged to obtain ionic microspheres.

[0023] The ion microspheres prepared in this embodiment have a diameter of approximately 169 nm and a particle size distribution of 0.125.

[0024] 70 parts of ion microspheres with a solid content of 30% were mixed with 60 parts of Aquolin-type aqueous polyurethane pressure-sensitive adhesive latex with a solid content of 50% (glass transition temperature of approximately -23 ˚C) to obtain a novel electro-exfoliating pressure-sensitive adhesive coating solution.

[0025] The novel electro-exfoliating pressure-sensitive adhesive coating solution was applied to a 0.01 mm thick stainless steel film, with the adhesive layer thickness controlled at 0.1 mm. After drying, it was bonded to the stainless steel. Figure 2 As shown, the 90˚ peel force is 1090 N / m when no power is applied; after applying a 60 V DC voltage at both ends for 5 minutes, the 90˚ peel force decreases to 200 N / m.

[0026] Example 3: A method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid, comprising: By weight, 40 parts of ethyl methacrylate (hard monomer), 20 parts of polyethylene glycol monomethyl ether acrylate (functional monomer) with a molecular weight lower than 200 g / mol, 40 parts of isooctyl methacrylate (soft monomer), 60 parts of 1-octyl-3-methylimidazolium hexafluorophosphate (water-insoluble ionic liquid), and 6 parts of 1,3-propanediol diacrylate (crosslinking monomer) were mixed thoroughly to prepare a dispersed phase. 6 parts of sodium dodecylbenzenesulfonate were dissolved in 600 parts of deionized water to prepare a continuous phase. 5 parts of sodium persulfate were dissolved in 80 parts of deionized water and mixed thoroughly to prepare an initiator solution. A small portion of the initiator solution was mixed with the continuous phase. Under a nitrogen atmosphere, the dispersed phase was slowly added dropwise to the mixture of the initiator solution and the continuous phase. The mixture was heated to 75 ˚C and stirred for 1 h. The remaining initiator solvent was then slowly added dropwise, and the reaction was continued for 10 h to obtain ionic microspheres.

[0027] The ion microspheres prepared in this embodiment have a diameter of approximately 154 nm and a particle size distribution of 0.084.

[0028] 70 parts of ionic microspheres with a solid content of 26% were mixed with 50 parts of HANKINS S750 water-based rubber pressure-sensitive adhesive latex with a solid content of 35% (glass transition temperature of about -40 ˚C), and 3 parts of D-sorbitol (tackifier) ​​were added to obtain a novel electro-exfoliating pressure-sensitive adhesive coating solution.

[0029] A novel electro-exfoliating pressure-sensitive adhesive coating solution was applied to a 0.01 mm thick stainless steel film, with the adhesive layer thickness controlled at 0.1 mm. After drying, it was bonded to the stainless steel. Figure 3 As shown, the 90˚ peel force is 950 N / m when no power is applied; after applying a 90 V DC voltage to both ends for 5 minutes, the 90˚ peel force decreases to 10 N / m.

[0030] Example 4: A method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid, comprising: By weight, 50 parts of n-butyl methacrylate (hard monomer), 30 parts of methyl polyethylene glycol monomethyl ether acrylate (functional monomer, hard monomer) with a molecular weight of less than 200 g / mol, 20 parts of methoxyethyl acrylate (functional monomer, soft monomer), 70 parts of 1-butyl-3-methylimidazolium hexafluorophosphate (water-insoluble ionic liquid), and 5 parts of 1,6-ethylene glycol diacrylate (crosslinking monomer) were mixed thoroughly to prepare the dispersed phase. 7 parts of hexadecyltrimethylammonium bromide were dissolved in 600 parts of deionized water to prepare the continuous phase. 6 parts of ammonium persulfate were dissolved in 100 parts of deionized water and mixed thoroughly to prepare the initiator solution. Under a nitrogen atmosphere at room temperature and a stirring speed of 800 r / min, the dispersed phase was slowly added to the continuous phase, and mechanical stirring was continued for 1.5 h. The reaction system was heated to 80 ˚C, and the initiator solution was added dropwise to the reaction system in two portions. The reaction was then continued with stirring for 6 h before being discharged to obtain ionic microspheres. The ion microspheres prepared in this embodiment have a diameter of approximately 132 nm and a particle size distribution of 0.075.

[0031] 60 parts of ionic microspheres with a solid content of 22% were mixed with 50 parts of Desay 3089 aqueous polyacrylate pressure-sensitive adhesive latex with a solid content of 38% (glass transition temperature of approximately -27 ˚C), and 3 parts of sodium carboxymethyl cellulose (thickener) were added to obtain a novel electro-exfoliating pressure-sensitive adhesive coating solution.

[0032] like Figure 4As shown, the prepared novel electro-exfoliating pressure-sensitive adhesive coating liquid was coated onto a 0.01 mm thick stainless steel film, with the adhesive layer thickness controlled at 0.1 mm. After drying, it was bonded to the stainless steel. Figure 5 As shown, the 90˚ peel force is 780 N / m when no power is applied; after applying a 30 V DC voltage at both ends for 5 minutes, the 90˚ peel force decreases to 75 N / m.

[0033] Example 5: A method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid, comprising: By weight, 50 parts of methyl methacrylate (hard monomer), 10 parts of butyl hexafluoroacrylate (functional monomer), 40 parts of methoxyethyl acrylate (soft monomer), 60 parts of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt (water-insoluble ionic liquid), and 6 parts of 1,6-ethylene glycol diacrylate (crosslinking monomer) were mixed thoroughly to prepare the dispersed phase. 1 part of hexadecyltrimethylammonium bromide and 5 parts of sodium dodecyl sulfate were dissolved in 600 parts of deionized water to prepare the continuous phase. 6 parts of ammonium persulfate and sodium sulfite were dissolved in 150 parts of deionized water and mixed thoroughly to prepare the initiator solution. Under an argon atmosphere at room temperature and with uniform stirring, the dispersed phase was slowly added dropwise to the continuous phase. The droplets were uniformly dispersed using a homogenizer, and the mixture was stirred for 50 min. The reaction system was then heated to 75 ˚C, and the initiator solution was slowly added dropwise over 40 min. The reaction was then continued with stirring for 10 h before being discharged to obtain ionic microspheres.

[0034] The ion microspheres prepared in this embodiment have a diameter of approximately 186 nm and a particle size dispersion of 0.099.

[0035] 50 parts of ionic microspheres with a solid content of 25% were mixed with 50 parts of HANKINS S750 aqueous rubber pressure-sensitive latex with a solid content of 38% (glass transition temperature of about -30 ˚C), and 2 parts of hydroxyethyl cellulose (thickener) were added to obtain a novel electro-exfoliating pressure-sensitive adhesive coating solution.

[0036] The prepared novel electro-exfoliating pressure-sensitive adhesive coating solution was coated onto a 0.01 mm thick stainless steel film, with the adhesive layer thickness controlled at 0.1 mm. After drying, it was bonded to the stainless steel. Figure 5 As shown, the 90˚ peel force is 890 N / m when no power is applied; after applying a 50 V DC voltage at both ends for 5 minutes, the 90˚ peel force decreases to 200 N / m.

[0037] Example 6: A method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid, comprising: By weight, 50 parts of methoxyethyl methacrylate (functional monomer, hard monomer), 10 parts of perfluoropropyl vinyl ether (functional monomer), 40 parts of ethyl acrylate (soft monomer), 60 parts of 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt (water-insoluble ionic liquid), and 6 parts of dibutyl methacrylate (crosslinking monomer) were mixed thoroughly to prepare the dispersed phase. 5 parts of glyceryl monostearate were dissolved in 500 parts of deionized water to prepare the continuous phase. 6 parts of potassium persulfate were dissolved in 100 parts of deionized water and mixed thoroughly to prepare the initiator solution. The dispersed phase and the continuous phase were added to a pre-emulsification vessel and stirred for 30 min to form a stable monomer pre-emulsion. The mixture was heated to 70 ˚C under a nitrogen atmosphere, and the initiator solution was added dropwise in three portions. After reacting for 7 h, ionic microspheres were obtained.

[0038] 70 parts of ion microspheres with a solid content of 25% were mixed with 50 parts of Henkel LA3141 aqueous polyacrylate pressure-sensitive adhesive latex with a solid content of 58% (glass transition temperature of approximately -33 ˚C) to obtain a novel electro-exfoliating pressure-sensitive adhesive coating solution.

[0039] Example 7: A method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid, comprising: By weight, 60 parts of isobutyl methacrylate (hard monomer), 10 parts of isooctyl acrylate (soft monomer), 5 parts of perfluorobutyl acrylate (functional monomer), 25 parts of methoxyethyl methacrylate (functional monomer), 60 parts of 1-butylpyridine hexafluorophosphate (water-insoluble ionic liquid), and 7 parts of diethylene glycol dimethacrylate (crosslinking monomer) were mixed thoroughly to prepare the dispersed phase. 7 parts of sodium dioctyl sulfosuccinate were dissolved in 600 parts of deionized water to prepare the continuous phase. 8 parts of potassium persulfate were dissolved in 100 parts of deionized water and mixed thoroughly to prepare the initiator solution. Under a helium atmosphere at room temperature, the dispersed phase was slowly added dropwise to the continuous phase while maintaining the temperature and stirring for 2 hours. The temperature was then raised to 75 ˚C, and the initiator was added dropwise all at once. After reacting for another 12 hours, ionic microspheres were obtained.

[0040] 50 parts of ion microspheres with a solid content of 15% were mixed with 50 parts of Aquolin-type aqueous polyurethane pressure-sensitive adhesive latex with a solid content of 50% (glass transition temperature of about -22 ˚C), and 5 parts of sodium polyacrylate (thickener) were added to obtain a novel electro-exfoliating pressure-sensitive adhesive coating solution.

[0041] The number of devices and processing scale described herein are for the purpose of simplifying the description of the invention. Applications, modifications, and variations of the invention will be readily apparent to those skilled in the art.

[0042] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. A method for preparing a novel electro-exfoliating pressure-sensitive adhesive coating liquid, characterized in that, include: Using a mixture of non-water-soluble monomers and non-water-soluble ionic liquids as the dispersed phase, the dispersed phase is dispersed in the continuous phase of water under the action of an emulsifier. Under the action of an initiator, the components of the dispersed phase undergo emulsion polymerization to prepare ionic microspheres. Then, the ionic microspheres are mixed evenly with an aqueous pressure-sensitive adhesive emulsion to obtain a novel electro-exfoliating pressure-sensitive adhesive coating solution.

2. The preparation method of the novel electro-exfoliating pressure-sensitive adhesive coating liquid as described in claim 1, characterized in that, The non-water-soluble monomers refer to olefin monomers that have a solubility in water of less than 1 g / 100 mL at room temperature and contain double bonds that can undergo free radical polymerization. Specifically, they include soft monomers, hard monomers, functional monomers, and crosslinking monomers.

3. The preparation method of the novel electro-exfoliating pressure-sensitive adhesive coating liquid as described in claim 2, characterized in that, The soft monomers in the non-water-soluble monomers refer to olefin monomers with a glass transition temperature below 0 ˚C in the homopolymer, and are further classified as acrylate monomers, specifically including one or more of the following: hydroxyethyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, tetrahydrofuran acrylate, lauryl acrylate, and lauryl methacrylate. The mass fraction of the soft monomer is 0-50 wt% of the non-water-soluble monomer.

4. The preparation method of the novel electro-exfoliating pressure-sensitive adhesive coating liquid as described in claim 2, characterized in that, The hard monomers of the non-water-soluble monomers refer to olefin monomers whose homopolymers have a glass transition temperature higher than 0 ˚C, specifically including one or more of the following: methyl methacrylate, styrene, ethyl methacrylate, n-butyl methacrylate, n-isobutyl methacrylate, acryloylmorpholine, tetrahydrofuran methacrylate, norbornene, isobornene methacrylate, cyclohexyl methacrylate, and 2-hydroxypropyl methacrylate. The hard monomer accounts for 0 to 70 wt% of the non-water-soluble monomer.

5. The preparation method of the novel electro-exfoliating pressure-sensitive adhesive coating liquid as described in claim 2, characterized in that, The non-water-soluble monomers refer to soft or hard olefin monomers whose molecular structure contains weak coordination with ions. These functional monomers can be used as soft mononuclear hard monomers. Specifically, the functional monomers include one or more of the following: methoxyethyl acrylate, methoxyethyl methacrylate, methyl polyethylene glycol monomethyl ether acrylate with a molecular weight of less than 200 g / mol, polyethylene glycol monomethyl ether acrylate with a molecular weight of less than 200 g / mol, perfluoropropyl vinyl ether, perfluoropolyether acrylate with a molecular weight of less than 400 g / mol, perfluoromethyl vinyl ether, perfluorobutyl acrylate, perfluorooctyl acrylate, perfluorohexylethyl acrylate, trifluoromethylstyrene, pentafluorostyrene, trifluoroethyl methacrylate, butyl hexafluoroacrylate, and dodecafluoroheptyl methacrylate. The functional monomer accounts for 20-60 wt% of the non-water-soluble monomer.

6. The preparation method of the novel electro-exfoliating pressure-sensitive adhesive coating liquid as described in claim 2, characterized in that, The crosslinking monomer of the non-water-soluble monomer refers to an olefin monomer containing two or more free radical polymerizable double bonds, specifically including: divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentanediol diacrylate, 1,6-hexanediol diacrylate, bisphenol A dimethacrylate, and butylene dimethacrylate, or one or more of these. The mass fraction of the crosslinking monomer is 0-5 wt% of all water-insoluble monomers.

7. The preparation method of the novel electro-exfoliating pressure-sensitive adhesive coating liquid as described in claim 1, characterized in that, The non-water-soluble ionic liquid refers to a room-temperature molten salt with a solubility in water of less than 1 g / 100 mL at room temperature and capable of dissociating into anions and cations. Specifically, it includes one or more of the following: imidazole ionic liquids, pyridine ionic liquids, pyrrole ionic liquids, thiazole ionic liquids, and quaternary ammonium salt ionic liquids. The mass fraction of the non-water-soluble ionic liquid is 20-50 wt% of the non-water-soluble monomer.

8. The preparation method of the novel electro-exfoliating pressure-sensitive adhesive coating liquid as described in claim 1, characterized in that, The emulsifiers include ionic emulsifiers and nonionic emulsifiers, specifically including: long-chain alkyl sulfates with more than 12 carbon atoms, long-chain alkyl sulfonates with more than 12 carbon atoms, long-chain alkylbenzene sulfonates with more than 12 carbon atoms, long-chain alkyl carboxylates with more than 12 carbon atoms, long-chain alkyl ammonium salts with more than 12 carbon atoms, and one or more of polyoxyethylene octylphenol ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenol ether, sodium dioctyl sulfosuccinate, glyceryl monostearate, Tween series, and Span series; The emulsifier accounts for 4 to 10 wt% of the dispersed phase.

9. The preparation method of the novel electro-exfoliating pressure-sensitive adhesive coating liquid as described in claim 1, characterized in that, The initiator includes a single initiation system or a redox initiation system; The single-initiator system specifically includes one or more of potassium persulfate, ammonium persulfate, sodium persulfate, and azobisisobutyramidine hydrochloride; The redox initiators include one or more of the following: persulfate and sulfite, persulfate and bisulfite, persulfate and thiosulfate, persulfate and aliphatic amine, persulfate and aliphatic diamine, and hydrogen peroxide and ferrous sulfate. The initiation system comprises 0.5–2 wt% of the insoluble monomers. The initiator can be added in one go, in batches, or continuously dripped. The oil-to-water ratio of the emulsion polymerization is 1:1 to 1:10; Before emulsion polymerization, the dispersed phase is slowly added to the continuous phase water, accompanied by mechanical stirring and / or ultrasound. The ion microspheres have a diameter of 10~350nm, a particle size distribution of 0.01~0.5, and a solid content of 20%~50%.

10. The preparation method of the novel electro-exfoliating pressure-sensitive adhesive coating liquid as described in claim 1, characterized in that, The aqueous pressure-sensitive adhesive latex refers to a pressure-sensitive adhesive latex prepared by conventional emulsion polymerization, including: aqueous acrylic pressure-sensitive adhesive latex or pressure-sensitive adhesive latex prepared by emulsification process, specifically including: one or more of aqueous acrylic pressure-sensitive adhesive latex, aqueous rubber pressure-sensitive adhesive latex, and aqueous polyurethane pressure-sensitive adhesive latex; the glass transition temperature of the aqueous pressure-sensitive adhesive latex after thorough drying is below -20˚C. The novel electro-exfoliating pressure-sensitive adhesive coating liquid is also prepared by adding fillers, which specifically include one or more of the following: calcium carbonate, silicon dioxide, titanium dioxide, zinc oxide, talc, nanocellulose, hydroxyapatite, montmorillonite, kaolin, graphene, and graphite powder. The preparation process of the novel electro-exfoliating pressure-sensitive adhesive coating liquid also includes additives. These additives are used to improve the process and performance of the novel electro-exfoliating pressure-sensitive adhesive coating liquid, including one or more of the following: plasticizers, thickeners, tackifiers, antioxidants, curing agents, antioxidants, ultraviolet absorbers, preservatives, lubricants, pH adjusters, defoamers, and mildew inhibitors. Specifically, the thickeners include polyacrylic acid thickeners, polyacrylamide thickeners, and cellulose ether thickeners; the tackifiers include polyethylene glycol tackifiers and sorbitol tackifiers; the antioxidants include emulsion-type hindered phenolic antioxidants, rosin ester antioxidants, and zinc dithiocarbamate antioxidants; the pH adjusters include inorganic bases, organic amines, carbonates, and bicarbonates; and the ultraviolet absorbers include water-dispersible emulsified triazine ultraviolet absorbers and water-dispersible emulsified benzotriazole ultraviolet absorbers. After the ion-sensitive pressure adhesive coating solution is dried, the mass fraction of the ion microspheres is 20-80 wt%. The ion-sensitive adhesive prepared by the ion-sensitive adhesive coating solution has an ionic conductivity greater than 1×10⁻⁶. -6 S / m; Electro-exfoliation of the novel electro-exfoliating pressure-sensitive adhesive coating liquid refers to the process where, after the novel electro-exfoliating pressure-sensitive adhesive coating liquid is applied to the substrate and cured to obtain pressure-sensitive adhesive, a DC voltage greater than 10V is applied to both ends of the pressure-sensitive adhesive bonded to the substrate, and the energizing time is 1~10 min, resulting in a reduction of the peeling force of the pressure-sensitive adhesive bond by more than 70%.

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