Electrolytic adhesive, preparation method thereof and electrolytic adhesive tape

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to an electrolytic adhesive, a preparation method thereof and an electrolytic adhesive tape. The electrolytic adhesive comprises the following raw material components in parts by weight: 100 parts of an adhesive main body, 2-10 parts of an auxiliary agent and 300 parts of a solvent, the adhesive main body contains an anion-based acrylate copolymer and cations. According to the electrolytic adhesive disclosed by the invention, the anion-based acrylate copolymer and the imidazolium cations are added into the adhesive main body, so that additional addition of ionic liquid is avoided, migration of the ionic liquid in a high-temperature and high-humidity environment is prevented, and the weather resistance and the moisture resistance of the electrolytic adhesive are improved. The storage performance of the electrolytic adhesive in the high-temperature and high-humidity environment is improved, and the reduction amplitude of the adhesive force before electrification is small after the electrolytic adhesive is subjected to the high-temperature and high-humidity condition.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives, and in particular relates to an electrolytic adhesive and a preparation method thereof, and an electrolytic adhesive tape. Background Art

[0002] In modern industrial production and daily life, electrolytic adhesives and electrolytic adhesive tapes are widely used in the 3C electronics field due to their unique electrical response peeling properties. These materials can achieve fast and clean peeling after applying voltage, which provides great convenience for equipment maintenance, replacement and assembly. However, traditional electrolytic adhesives often rely on the addition of ionic liquids to enhance their electrolytic performance and peeling effect, which to some extent limits their application scope and use environment.

[0003] Although ionic liquids play an important role in improving the conductivity and peelability of electrolytic adhesives, their stability in high temperature and high humidity environments has become an urgent problem to be solved. Under high temperature and high humidity conditions, ionic liquids are prone to migration, resulting in a significant decrease in the weather resistance and moisture resistance of electrolytic adhesives, which in turn affects their bonding performance and electrolytic peeling effect. In addition, the migration of ionic liquids may also cause electrochemical corrosion inside the material, posing a potential threat to the long-term reliability and safety of the equipment. Summary of the invention

[0004] The purpose of the present invention is to provide an electrolytic adhesive and a preparation method thereof, and an electrolytic adhesive tape.

[0005] The first aspect of the present invention provides an electrolytic adhesive, which comprises the following raw material components by weight: 100 parts of an adhesive main body, 2 to 10 parts of an auxiliary agent and 300 parts of a solvent;

[0006] The adhesive body contains anionic acrylate copolymer and cationic acrylate copolymer.

[0007] In one embodiment of the present application, the anion is a conjugate base of an acidic substance.

[0008] In one embodiment of the present application, the anion is one of a carboxyl anion, a sulfonic acid anion or a phosphonic acid anion.

[0009] In one embodiment of the present application, the cation includes one of a nitrogen-containing onium cation, a sulfur-containing onium cation, or a phosphorus-containing onium cation.

[0010] In one embodiment of the present application, the cation includes one of an imidazolium cation, an ammonium cation or a pyridinium cation.

[0011] In one embodiment of the present application, the auxiliary agent is polyethylene glycol 200, and the solvent is ethyl acetate.

[0012] In one embodiment of the present application, the raw materials for preparing the adhesive body include: raw materials for preparing copolymers and bicarbonate of imidazolium;

[0013] The raw materials for preparing the copolymer include, by weight: 280 parts of short-chain (meth) alkyl acrylate monomer, 30 parts of long-chain (meth) alkyl acrylate monomer, 60 parts of acrylic acid polyether bond ester monomer, 41 parts of acidic vinyl monomer, 465 parts of ethyl acetate, and 1.4 parts of initiator; wherein

[0014] The number of moles of the acidic vinyl monomer units and the imidazolium bicarbonate salt in the copolymer is equal.

[0015] In one embodiment of the present application, short-chain (meth) alkyl acrylate monomers can improve flexibility, enhance adhesion, and absorb fracture energy; long-chain (meth) alkyl acrylate monomers can improve cohesive strength, increase operating temperature, and enhance wear resistance; acrylic acid polyether bond ester monomers can improve fluidity and coating properties, enhance adhesion, and adjust the glass transition temperature; acidic vinyl monomers can enhance adhesion, improve cohesive strength, and impart special reaction characteristics.

[0016] In one embodiment of the present application, the carbon number of the alkyl group of the short-chain (meth) alkyl acrylate monomer is 1 to 6, such as butyl acrylate; the carbon number of the alkyl group of the long-chain (meth) alkyl acrylate monomer is at least 7, such as isooctyl methacrylate; the number of ether bonds in the acrylic acid polyether ester monomer is at least 2, such as diethylene glycol ethyl ether acrylate; the acidic groups in the acidic vinyl monomer include carboxyl, sulfonic acid, and phosphonic acid, such as acrylic acid, vinyl sulfonic acid, and vinyl phosphonic acid.

[0017] Accordingly, a second aspect of the present invention provides a method for preparing the electrolytic adhesive as described above, comprising:

[0018] Dissolve the required monomers and initiators in ethyl acetate according to given mass fractions to carry out polymerization reaction;

[0019] After the polymerization reaction is completed, adding imidazolium bicarbonate to the polymer solution, keeping the molar numbers of imidazolium bicarbonate and acidic vinyl monomer consistent;

[0020] After the neutralization reaction is completed, the adhesive body is obtained;

[0021] Weigh 100 parts of adhesive main body, 5 parts of polyethylene glycol 200, and 300 parts of ethyl acetate, mix them evenly and centrifuge to degas to obtain electrolytic adhesive.

[0022] In one embodiment of the present application, a method for preparing an electrolytic adhesive comprises the following steps:

[0023] 280 parts of short-chain (meth) alkyl acrylate monomer, 30 parts of long-chain (meth) alkyl acrylate monomer, 60 parts of acrylic acid polyether bond ester monomer, 41 parts of acidic vinyl monomer and 320 parts of ethyl acetate were weighed, mixed and added into a reactor; then, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65° C.; then, 0.6 parts of azobisisobutyronitrile was weighed, dissolved in 15 parts of ethyl acetate, and then the solution was added into the reactor, and the reaction was maintained at 65° C. for 4 hours; then, 0.8 parts of azobisisobutyronitrile was weighed again, dissolved in 130 parts of ethyl acetate, and added dropwise to the reaction system, and the addition was completed within 20 minutes; during this period, the reaction temperature was raised to 78° C., and reflux reaction was carried out for 3 hours; finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature, the entire polymerization process was completed, and a copolymer was obtained;

[0024] Weighing the imidazolium bicarbonate so that the molar numbers of the acidic vinyl monomer unit and the imidazolium bicarbonate in the copolymer are equal; adding the imidazolium bicarbonate to the copolymer solution, and continuously stirring until no bubbles are generated; after the neutralization reaction is completed, an adhesive body is obtained;

[0025] Weigh 100 parts of adhesive main body, 5 parts of polyethylene glycol 200, and 300 parts of ethyl acetate, mix them evenly and centrifuge to degas to obtain electrolytic adhesive.

[0026] Accordingly, a third aspect of the present invention provides an electrolytic adhesive tape, comprising: a release film, a common adhesive, a conductive substrate, an electrolytic adhesive and a release film arranged in sequence from top to bottom;

[0027] The electrolytic adhesive is the electrolytic adhesive as described above.

[0028] In one embodiment of the present application, the common adhesive is a pressure-sensitive adhesive;

[0029] The conductive substrate is aluminized PET or an aluminum foil PET composite film.

[0030] In one embodiment of the present application, the thickness of the electrolytic adhesive tape is 10 μm to 300 μm.

[0031] In one embodiment of the present application, a release film, a common adhesive, a conductive substrate, an electrolytic adhesive, and a release film are bonded together to obtain an electrolytic adhesive tape.

[0032] The beneficial effects of the present invention are:

[0033] Different from the prior art, the electrolytic adhesive provided by the present application avoids the additional addition of ionic liquids by adding anionic acrylate copolymers and imidazolium cations to the adhesive body, preventing the migration of ionic liquids in high temperature and high humidity environments, thereby improving the weather resistance and moisture resistance of the electrolytic adhesive. It performs well in improving the storage performance of the electrolytic adhesive in high temperature and high humidity environments, and after experiencing high temperature and high humidity conditions, the decrease in its adhesion before power-on is small.

[0034] In addition, the existing electrolytic adhesives need to be additionally added with ionic liquids. In a high temperature and high humidity environment, the above ionic liquids are prone to migration, thereby reducing the high temperature and high humidity storage performance of the electrolytic adhesive, and the adhesion before power is greatly reduced.

[0035] Other features and advantages of the present invention will be described in the following description, and partly become apparent from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention are realized and obtained by the structures particularly pointed out in the description and the drawings.

[0036] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, preferred embodiments are given below and described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0038] Figure 1 is a schematic structural diagram of an anionic acrylate copolymer according to one embodiment of the present invention;

[0039] Figure 2 2 is a schematic diagram of the structure of an ionic liquid according to an embodiment of the present invention and as a comparative example;

[0040] Figure 3 is a schematic diagram of a finished product of an electrolytic adhesive tape according to an embodiment of the present invention;

[0041] Figure 4 is a schematic diagram of an electrolytic adhesive tape during electrolytic bonding according to one embodiment of the present invention;

[0042] Figure 5 Test data table of the electrolytic adhesive tapes of the embodiments and comparative examples. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0044] The present application provides an electrolytic adhesive and a preparation method thereof, and an electrolytic adhesive tape, which are described in detail below. It should be noted that the description order of the following embodiments does not limit the preferred order of the embodiments of the present application. In the following embodiments, the description of each embodiment has its own emphasis. For parts that are not described in detail in a certain embodiment, please refer to the relevant description of other embodiments.

[0045] See also Figure 3 The electrolytic adhesive tape includes: a release film 1, a common adhesive, a conductive substrate, an electrolytic adhesive and a release film 2 which are arranged in sequence from top to bottom.

[0046] The common adhesive may be a pressure-sensitive adhesive. The pressure-sensitive adhesive may be an acrylic polymer. The conductive substrate may be an aluminized PET or an aluminum foil PET composite film, or may be other substrates with conductive functions. The thickness of the electrolytic adhesive tape is 10 μm to 300 μm.

[0047] The electrolytic adhesive and electrolytic adhesive tape of the present invention will be described in detail below in conjunction with specific embodiments.

[0048] Example 1

[0049] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 41g of acrylic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed and dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C, and reflux reaction was carried out for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer C-0.1.

[0050] Accurately weigh 98 g of 1-ethyl-3-methylimidazole bicarbonate (M1) so that the molar number of the acrylic acid monomer unit in the polymer is equal to that of M1. Add M1 to the copolymer solution and continue stirring until no bubbles are generated. After the neutralization reaction is completed, the adhesive main body, anionic acrylate copolymer C-0.1-M1, is obtained.

[0051] Weigh 100 g of C-0.1-M1, 5 g of polyethylene glycol 200, and 300 g of ethyl acetate, mix them evenly, and centrifuge to degas, so as to obtain the electrolytic adhesive of the present invention.

[0052] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0053] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the conductive substrate to obtain the electrolytic adhesive tape.

[0054] Example 2

[0055] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 41g of vinyl sulfonic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed, dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C, and reflux reaction was carried out for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer S-0.1.

[0056] Accurately weigh 73 g of 1-ethyl-3-methylimidazole bicarbonate (M1) so that the molar number of the vinyl sulfonic acid monomer unit in the polymer is equal to that of M1. Add M1 to the copolymer solution and continue stirring until no bubbles are generated. After the neutralization reaction is completed, the adhesive main body, anionic acrylate copolymer S-0.1-M1, is obtained.

[0057] Weigh 100 g of S-0.1-M1, 5 g of polyethylene glycol 200, and 300 g of ethyl acetate, mix them evenly, and centrifuge to degas, so as to obtain the electrolytic adhesive of the present invention.

[0058] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0059] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the aluminum foil to obtain the electrolytic adhesive tape.

[0060] Example 3

[0061] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 41g of vinyl phosphonic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed and dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C and refluxed for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer P-0.1.

[0062] Weigh 118 g of 1-ethyl-3-methylimidazole bicarbonate (M1) accurately, so that the molar ratio of the vinylphosphonic acid monomer unit and M1 in the polymer is 1:2, because vinylphosphonic acid has two acidic active hydrogens. Add M1 to the copolymer solution and continue stirring until no bubbles are generated. After the neutralization reaction is completed, the adhesive body, anionic acrylate copolymer P-0.1-M1, is obtained.

[0063] Weigh 100 g of P-0.1-M1, 5 g of polyethylene glycol 200, and 300 g of ethyl acetate, mix them evenly, and centrifuge to degas, so as to obtain the electrolytic adhesive of the present invention.

[0064] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0065] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the aluminum foil to obtain the electrolytic adhesive tape.

[0066] Example 4

[0067] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 41g of acrylic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed and dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C, and reflux reaction was carried out for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer C-0.1.

[0068] Weigh 114 g of 1-butyl-3-methylimidazole bicarbonate (M2) accurately so that the molar number of the acrylic acid monomer unit in the polymer is equal to that of M2. Add M2 to the copolymer solution and continue stirring until no bubbles are generated. After the neutralization reaction is completed, the adhesive main body, anionic acrylate copolymer C-0.1-M2, is obtained.

[0069] Weigh 100 g of C-0.1-M2, 5 g of polyethylene glycol 200, and 300 g of ethyl acetate, mix them evenly, and centrifuge to degas, so as to obtain the electrolytic adhesive of the present invention.

[0070] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0071] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the aluminum foil to obtain the electrolytic adhesive tape.

[0072] Example 5

[0073] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 41g of acrylic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed and dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C, and reflux reaction was carried out for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer C-0.1.

[0074] Accurately weigh 95 g of 1,3-dimethylimidazole bicarbonate (M3) so that the molar number of the acrylic acid monomer unit in the polymer is equal to that of M3. Add M3 to the copolymer solution and continue stirring until no bubbles are generated. After the neutralization reaction is completed, the adhesive main body, anionic acrylate copolymer C-0.1-M3, is obtained.

[0075] Weigh 100 g of C-0.1-M3, 5 g of polyethylene glycol 200, and 300 g of ethyl acetate, mix them evenly, and centrifuge to degas, so as to obtain the electrolytic adhesive of the present invention.

[0076] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0077] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the aluminum foil to obtain the electrolytic adhesive tape.

[0078] Example 6

[0079] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 8g of acrylic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed and dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C, and reflux reaction was carried out for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer C-0.02.

[0080] Accurately weigh 19 g of 1-ethyl-3-methylimidazole bicarbonate (M1) so that the molar number of the acrylic acid monomer unit in the polymer is equal to that of M1. Add M1 to the copolymer solution and continue stirring until no bubbles are generated. After the neutralization reaction is completed, the adhesive main body, anionic acrylate copolymer C-0.02-M1, is obtained.

[0081] Weigh 100 g of C-0.02-M1, 5 g of polyethylene glycol 200, and 300 g of ethyl acetate, mix them evenly, and centrifuge to degas, so as to obtain the electrolytic adhesive of the present invention.

[0082] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0083] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the aluminum foil to obtain the electrolytic adhesive tape.

[0084] Example 7

[0085] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 19g of acrylic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed and dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C, and reflux reaction was carried out for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer C-0.05.

[0086] Weigh 45 g of 1-ethyl-3-methylimidazole bicarbonate (M1) accurately so that the molar number of the acrylic acid monomer unit in the polymer is equal to that of M1. Add M1 to the copolymer solution and continue stirring until no bubbles are generated. After the neutralization reaction is completed, the adhesive main body, anionic acrylate copolymer C-0.05-M1, is obtained.

[0087] Weigh 100 g of C-0.05-M1, 5 g of polyethylene glycol 200, and 300 g of ethyl acetate, mix them evenly, and centrifuge to degas, so as to obtain the electrolytic adhesive of the present invention.

[0088] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0089] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the aluminum foil to obtain the electrolytic adhesive tape.

[0090] Example 8

[0091] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 65g of acrylic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed and dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C, and reflux reaction was carried out for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer C-0.15.

[0092] Weigh 115 g of 1-ethyl-3-methylimidazole bicarbonate (M1) accurately so that the molar number of the acrylic acid monomer unit in the polymer is equal to that of M1. Add M1 to the copolymer solution and continue stirring until no bubbles are generated. After the neutralization reaction is completed, the adhesive main body, anionic acrylate copolymer C-0.15-M1, is obtained.

[0093] Weigh 100 g of C-0.15-M1, 5 g of polyethylene glycol 200, and 300 g of ethyl acetate, mix them evenly, and centrifuge to degas, so as to obtain the electrolytic adhesive of the present invention.

[0094] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0095] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the aluminum foil to obtain the electrolytic adhesive tape.

[0096] Comparative Example 1

[0097] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 41g of acrylic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed and dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C, and reflux reaction was carried out for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer C-0.1.

[0098] Weigh 100 g C-0.15, 5 g polyethylene glycol 200, and 300 g ethyl acetate, mix them evenly, and centrifuge to degas to obtain an electrolytic adhesive.

[0099] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0100] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the aluminum foil to obtain the electrolytic adhesive tape.

[0101] Comparative Example 2

[0102] First, accurately weigh 280g of butyl acrylate, 30g of isooctyl methacrylate, 60g of diethylene glycol ethyl ether acrylate and 41g of acrylic acid as monomers, and 320g of ethyl acetate as solvent, mix them evenly and add them to the reactor. Subsequently, nitrogen was introduced for 1 hour to exclude oxygen, and the reaction system was heated to 65°C. Next, 0.6g of azobisisobutyronitrile (AIBN) was weighed and dissolved in 15g of ethyl acetate, and then the solution was added to the reactor and kept reacting at 65°C for 4 hours. After that, 0.8g of AIBN was weighed again, dissolved in 130g of ethyl acetate, and added dropwise to the reaction system to ensure that the addition was completed within 20 minutes. During this period, the reaction temperature was raised to 78°C, and reflux reaction was carried out for 3 hours. Finally, after the polymerization reaction was completed, the reaction system was cooled to room temperature to complete the entire polymerization process to obtain copolymer C-0.1.

[0103] Weigh 100g C-0.1, 27g 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl imide) (TFSI-M1), 5g polyethylene glycol 200, and 300g ethyl acetate, mix them evenly, and centrifuge to degas to obtain the electrolytic adhesive of the present invention, wherein the mass of trifluoromethanesulfonyl imide is 10g.

[0104] The electrolytic adhesive was coated on the release surface of a release film, placed in a 120° C. oven, dried, and attached to the release surface of another release film, and placed in a 50° C. oven for aging for 2 days to obtain an electrolytic adhesive film.

[0105] The electrolytic adhesive film is respectively bonded to one side of the conductive substrate and the release surface of the release film 1, and the common adhesive with the release film 2 is bonded to the other side of the aluminum foil to obtain the electrolytic adhesive tape.

[0106] The following performance tests were performed on the electrolytic adhesives obtained in Examples 1 to 8 and Comparative Examples 1 to 2:

[0107] Peel force before power on at room temperature [g / 25mm]: The sample size of the electrolytic adhesive film is 25mm×100mm, the thickness is 25μm, and the back of the test surface is covered with a 50μm thick aluminum foil. The sample is pasted on a stainless steel plate with a pasting area of ​​25mm×25mm. Use a 2kg pressure roller to roll back and forth 3 times at a speed of 120mm / s. The environment is placed at room temperature and ambient humidity. After 30 minutes, test the 180° peel force on a tensile machine.

[0108] Peel force after power on at room temperature [g / 25mm]: The sample size of the electrolytic adhesive film is 25mm×100mm, the thickness is 25μm, and the back of the test surface is covered with an aluminum foil with a thickness of 50μm. The sample is pasted on a stainless steel plate with a pasting area of ​​25mm×25mm. Use a 2kg roller to roll back and forth 3 times at a speed of 120mm / s, and place it in an environment with room temperature and ambient humidity. After 30 minutes, connect the positive pole of the DC power supply to the conductive substrate, and the negative pole to the stainless steel plate. Power on with a DC voltage of 15V for 20s. After the power-on ends, quickly test the 180° peel force on the tensile machine.

[0109] Peel force recovery rate [%]: After the above-mentioned peel force test at room temperature after power on, the electrolytic adhesive film is peeled off from the stainless steel plate, and then applied to the stainless steel plate again, and rolled back and forth 3 times with a 2kg roller at a speed of 120mm / s, and placed in an environment with room temperature and humidity. After 30 minutes, the 180° peel force at room temperature is tested again on the tensile machine, and the result is divided by the above-mentioned peel force at room temperature after power on.

[0110] Peel force before power on at high temperature [g / 25mm]: The sample size of the electrolytic adhesive film is 25mm×100mm, the thickness is 25μm, and the back of the test surface is covered with a 50μm thick aluminum foil. The sample is pasted on a stainless steel plate with a pasting area of ​​25mm×25mm. Use a 2kg pressure roller to roll back and forth 3 times at a speed of 120mm / s, and place it in an environment of 70℃ and ambient humidity. After 72 hours, test the 180° peel force on a tensile machine.

[0111] Peel force after power on at high temperature [g / 25mm]: The sample size of the electrolytic adhesive film is 25mm×100mm, the thickness is 25μm, and the back of the test surface is covered with an aluminum foil with a thickness of 50μm. The sample is pasted on a stainless steel plate with a pasting area of ​​25mm×25mm. Use a 2kg roller to roll back and forth 3 times at a speed of 120mm / s, and place it in an environment of 70℃ and ambient humidity. After 72 hours, connect the positive pole of the DC power supply to the conductive substrate, and the negative pole to the stainless steel plate. Power on with a DC voltage of 15V for 20s. After the power-on ends, quickly test the 180° peel force on the tensile machine.

[0112] Peel force before power on under high temperature and high humidity [g / 25mm]: The sample size of the electrolytic adhesive film is 25mm×100mm, the thickness is 25μm, the back of the test surface is covered with 50μm thick aluminum foil, and the sample is pasted on a stainless steel plate with a pasting area of ​​25mm×25mm. Use a 2kg pressure roller to roll back and forth 3 times at a speed of 120mm / s, and place it in an environment of 85℃ and 85% humidity. After 72 hours, test the 180° peel force on a tensile machine.

[0113] Peel force after power on under high temperature and high humidity [g / 25mm]: The sample size of the electrolytic adhesive film is 25mm×100mm, the thickness is 25μm, the back of the test surface is covered with an aluminum foil with a thickness of 50μm, and the sample is pasted on a stainless steel plate with a pasting area of ​​25mm×25mm. Use a 2kg roller to roll back and forth 3 times at a speed of 120mm / s, and place it in an environment of 85℃ and 85% humidity. After 72 hours, connect the positive pole of the DC power supply to the conductive substrate, and the negative pole to the stainless steel plate, and power on with a DC voltage of 15V for 20s. After the power-on ends, quickly test the 180° peel force on the tensile machine.

[0114] High temperature holding power [mm]: The sample size of the electrolytic adhesive film is 25mm×100mm, the thickness is 25μm, and the back of the test surface is covered with 25μm thick PET. The sample is pasted on the stainless steel plate, and the covering area is 25mm×25mm. Use a 2kg roller to roll back and forth 3 times at a speed of 120mm / s and let it stand for 30 minutes. Fix the end of the sample, hang a 1kg weight, place it in an environment of 70℃, and observe whether the sample falls off the test stainless steel plate after 24 hours. If the sample falls off the stainless steel plate during this period, record the time from placement to falling off [h]. If the sample does not fall off the stainless steel plate during this period, but slips, record the slip distance [mm].

[0115] Get as Figure 5 The test data are shown in the table.

[0116] It can be seen from Examples 1 to 5 that the electrolytic adhesive of the present invention has good peeling force before power is applied at room temperature, and the peeling force is greatly reduced after power is applied, and there is almost no residue on the surface of the substrate, achieving a good electrolytic bonding effect. The peeling force recovery rate is above 70%, indicating that after one bonding, the electrolytic adhesive still has a high peeling force and good recovery. The above results show that the electrolytic adhesive of the present invention has good electrolytic bonding effect and recovery at room temperature.

[0117] After the electrolytic adhesive was placed at 70°C and ambient humidity for 72 hours, the drop in peel force before power-on was less than 20%. After being placed at 85°C and 85% humidity for 72 hours, the drop in peel force before power-on was less than 25%. In terms of high-temperature retention, the electrolytic adhesive did not fall off the stainless steel plate, only slipped, and the slip distance was less than 5mm. At the same time, under the above two environments, the peel force of the electrolytic adhesive after power-on is still very low, and there is almost no residue on the surface of the substrate, achieving a good electrolytic bonding effect. The above results show that the electrolytic adhesive of the present invention has a small drop in adhesion before power-on under high temperature and high humidity environments, and has a good electrolytic bonding effect after power-on.

[0118] Furthermore, the electrolytic adhesive of the present invention exhibits good electrolytic adhesive properties for three acidic vinyl monomers and three imidazolium cations, and does not show significant performance degradation under high temperature and high humidity, and has high universality.

[0119] It can be seen from Examples 6 to 8 that as the mass fraction of the acidic vinyl monomer in the copolymer decreases, the peeling force of the electrolytic adhesive increases and the electrolytic adhesive effect decreases. At the same time, under high temperature and high humidity environment, the reduction in the peeling force of the electrolytic adhesive increases. When the mass fraction of the acidic vinyl monomer in the copolymer increases to 15%, the peeling force of the electrolytic adhesive is greatly reduced and cannot meet the performance requirements. The above results show that in the electrolytic adhesive of the present invention, the optimal mass fraction of the acidic vinyl monomer in the copolymer is 10%.

[0120] Comparative Example 1 shows that when imidazolium cations are not added, the difference in peeling force of the electrolytic adhesive before and after power-on at room temperature is very small, and there is no electrolytic bonding effect. Comparative Example 2 shows that when ionic liquids with small molecule anions are added, the peeling force of the electrolytic adhesive before power-on under high temperature and high humidity environment decreases by nearly 90% compared with that under room temperature environment, which is difficult to meet the performance requirements.

[0121] In summary, the embodiments of the present invention avoid the additional addition of ionic liquids by adding anionic acrylate copolymers and imidazolium cations to the adhesive body, preventing the migration of ionic liquids in high temperature and high humidity environments, thereby improving the weather resistance and moisture resistance of the electrolytic adhesive. Compared with the existing patented ionic liquids, the electrolytic adhesive performs well in improving the storage performance in high temperature and high humidity environments, and after experiencing high temperature and high humidity conditions, the decrease in its adhesion before power-on is relatively small.

[0122] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. An electrolytic adhesive, characterized in that: The raw material components include, by weight: 100 parts of adhesive main body, 2 to 10 parts of auxiliary agent and 300 parts of solvent; The adhesive body contains anionic acrylate copolymer and cationic acrylate copolymer.

2. The electrolytic adhesive according to claim 1, characterized in that: The anion is the conjugate base of the acidic substance.

3. The electrolytic adhesive according to claim 1, characterized in that: The anion is one of a carboxyl anion, a sulfonic acid anion or a phosphonic acid anion.

4. The electrolytic adhesive according to claim 1, characterized in that: The cation includes one of a nitrogen-containing onium cation, a sulfur-containing onium cation, or a phosphorus-containing onium cation.

5. The electrolytic adhesive according to claim 1, characterized in that: The cation includes one of an imidazolium cation, an ammonium cation or a pyridinium cation.

6. The electrolytic adhesive according to claim 1, characterized in that: The raw materials for preparing the adhesive body include: raw materials for preparing copolymers and imidazolium bicarbonate; The raw materials for preparing the copolymer include, by weight: 280 parts of short-chain (meth) alkyl acrylate monomer, 30 parts of long-chain (meth) alkyl acrylate monomer, 60 parts of acrylic acid polyether bond ester monomer, 41 parts of acidic vinyl monomer, 465 parts of ethyl acetate, and 1.4 parts of initiator; wherein The number of moles of the acidic vinyl monomer units and the imidazolium bicarbonate salt in the copolymer is equal.

7. A method for preparing an electrolytic adhesive as claimed in any one of claims 1 to 6, characterized in that: include Dissolve the required monomers and initiators in ethyl acetate according to given mass fractions to carry out polymerization reaction; After the polymerization reaction is completed, adding imidazolium bicarbonate to the polymer solution, keeping the molar numbers of imidazolium bicarbonate and acidic vinyl monomer consistent; After the neutralization reaction is completed, the adhesive body is obtained; Weigh 100 parts of adhesive main body, 5 parts of polyethylene glycol 200, and 300 parts of ethyl acetate, mix them evenly and centrifuge to degas to obtain electrolytic adhesive.

8. An electrolytic adhesive tape, characterized in that: include: The release film, common adhesive, conductive substrate, electrolytic adhesive and release film are arranged in sequence from top to bottom; The electrolytic adhesive is the electrolytic adhesive as described in any one of claims 1-6.

9. The electrolytic adhesive tape according to claim 8, characterized in that: The common adhesive is a pressure-sensitive adhesive; The conductive substrate is aluminized PET or an aluminum foil PET composite film.

10. The electrolytic adhesive tape according to claim 8, characterized in that: The thickness of the electrolytic adhesive tape is 10 μm to 300 μm.

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