Pyrolytic debinding glue, preparation method thereof and application thereof in electrolytic membrane cut pieces

Abstract

The present invention relates to the technical field of adhesives, and particularly to a thermal de-bonding glue, a preparation method thereof, and an application thereof in electrolytic membrane cut pieces. The thermal de-bonding glue comprises the following components in parts by weight: 90-95 parts of modified polyacrylic resin, 15-35 parts of tackifying resin, 1-3 parts of curing agent, and 80-85 parts of solvent. The present invention also provides a preparation method thereof. Compared with the prior art, the thermal de-bonding glue prepared by the present invention has the advantages of good thermal stability and no residual glue, and is suitable for application in electrolytic membrane cut pieces.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, and in particular to a pyrolytic adhesive, a preparation method and application thereof in electrolytic membrane cutting. Background Art

[0002] Pressure-sensitive adhesive is a widely used adhesive material. When pressure-sensitive adhesive is pasted to the surface of an object and pressure is applied, it will infiltrate the surface of the object and achieve strong adhesion through the interaction force between molecules. According to different usage requirements, the mechanical properties of pressure-sensitive adhesives are also different, among which peel force is a key indicator. The adhesion of the tape determines its application scenario: tapes with high adhesion are suitable for permanent bonding, while tapes with low peel force are suitable for temporary bonding, and a balance needs to be found between maintaining adhesion and easy removal. With the development of manufacturing technology, new processing technologies have put forward higher requirements on the performance of pressure-sensitive adhesives. Not only does the pressure-sensitive adhesive need to be firmly adhered to the substrate, but it is also required to be easily peeled off after use, or to provide remedies for incorrect operations during processing. Therefore, the viscosity-reducing viscoelastic film (also called viscosity-reducing pressure-sensitive adhesive, viscosity-reducing tape or debonding tape) came into being. This material is prepared by coating a viscosity-reducing viscoelastic on a polyester film, and the viscosity-reducing viscoelastic needs to add a switch that can respond to external stimuli (such as light, heat, pH value, solvent, etc.). In the initial state, the viscosity-reducing viscoelastic film has a high bonding strength, but its bonding strength decreases rapidly after responding to external stimuli. This material has a wide range of applications in many fields, such as medical wound dressings and the processing of ultra-thin and tiny devices.

[0003] The key to the development of debonding products is to have appropriate peeling force before stimulus response. In order to ensure that the tape does not fail during use, the peeling force before stimulus response is usually as high as possible. In order to better peel off the product, the peeling force after stimulus response is as low as possible. However, high peeling force before response and low peeling force after response are contradictory properties. It is easy to lose sight of one while focusing on the other in product design, which also increases the difficulty of product design. At present, UV response and thermal response are the main debonding products. UV irradiation is widely used because of its advantages such as low energy, simple operation and easy storage of products. Thermal response solves the defect that some application scenarios cannot be transparent. Thermal debonding includes thermal expansion debonding or thermal degradation debonding, shape memory or thermal phase change.

[0004] CN115093813A provides a heat-debonding adhesive, comprising 10 to 100 parts of an acrylic pressure-sensitive adhesive, 2 to 10 parts of a foaming agent, 0.1 to 5 parts of a curing agent, 0.1 to 4 parts of a polysiloxane, and 50 to 60 parts of a solvent. It also provides a heat-debonding protective film, which includes a substrate layer, a release layer, and a heat-debonding adhesive layer formed by the above heat-debonding adhesive. The heat-debonding adhesive provided by this invention has lubricity by introducing polysiloxane, thus effectively preventing residues from being left on the flexible circuit board during the process of removing the heat-debonding protective film. Moreover, after heating, the viscosity of the heat-debonding adhesive will be greatly reduced, enabling the heat-debonding protective film to be easily removed. Therefore, this invention solves the problems of low working efficiency and easy residue left on the circuit board during the process of removing the heat-debonding protective film adhered to the flexible circuit board.

[0005] CN118389098A discloses a heat-debonding polyacrylate pressure-sensitive adhesive and its preparation method. The heat-debonding polyacrylate pressure-sensitive adhesive is obtained by uniformly mixing a polyacrylate solution, a fluorine-modified acrylate rosin resin, composite foaming microspheres, and a crosslinking agent, and then coating and drying. By introducing fluorine-containing monomers into the tackifying resin and foaming microspheres, and utilizing the migration characteristics of fluorine-containing segments during the heating process, it is beneficial for the tackifying resin and foaming microspheres to migrate to the bonding surface, improving the heat-debonding efficiency and preventing the problem of residual adhesive during the heat-debonding process. At the same time, by controlling the dosage of fluorine-containing segments, the system is ensured to have good bonding performance, solving the problems of low efficiency and easy residual adhesive of the heat-debonding pressure-sensitive adhesive, and obtaining a heat-debonding polyacrylate pressure-sensitive adhesive with excellent performance.

[0006] The current heat-debonding protective film formed by adding an expansion foaming body to the pyrolysis station adhesive has a good use effect on circuit boards or electronic components, etc. At a certain temperature, the expansion foaming body in the heat-debonding glue foams and expands, reducing the viscosity of the glue, so that the protective film reaches an easy-to-peel degree. However, due to the presence of the foaming agent in this protective film, different degrees of residue will appear after peeling, and still need to be removed manually or with the assistance of machines, which is time-consuming and laborious. Summary of the Invention

[0007] In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to provide a heat-debonding glue, its preparation method, and its application in electrolytic membrane cut pieces.

[0008] Adding a thermally sensitive expansion material to the glue. After the glue is heated and the temperature rises, the thermally sensitive expansion material expands when heated, increasing in volume, thereby reducing the effective contact area with the object to be adhered, resulting in a decrease in the peel strength. However, as a nanomaterial, the thermal expansion additive is likely to remain on the surface of the substrate, leading to residual glue. In contrast to thermal expansion debonding, thermal degradation debonding reduces the modulus and molecular weight of the adhesive, resulting in a decrease in its bonding strength, without the participation of additives. Those that can be thermally degraded include polyperoxides, azo compounds, as well as carbamates, carbonates, acetals, acetal esters, and esters. High temperature causes thermal cleavage of covalent bonds, reducing the crosslinking density and thus resulting in debonding. As an ester bond that can be thermally cleaved, the thermal degradation ability decreases in order from tertiary ester to secondary ester to primary ester. However, when the thermally degradable glue is applied to electronic components, too low a thermal degradation temperature will instead cause the glue to debond at an inappropriate time. Therefore, the present invention provides a modified polyacrylate resin containing tert-butyl ester and tert-butoxycarbonyl. Among them, the tert-butyl ester has a relatively high thermal degradation ability, but the thermal degradation of tert-butoxycarbonyl requires a relatively higher temperature. Therefore, the obtained modified polyacrylate resin is not prone to debonding at a lower temperature, which avoids the glue from coming off and enables directional peeling.

[0009] To achieve the above object, the present invention provides a thermally degradable glue, comprising the following components in parts by weight: 90 - 95 parts of modified polyacrylate resin, 15 - 35 parts of tackifying resin, 1 - 3 parts of curing agent, and 80 - 85 parts of solvent.

[0010] The preparation method of the modified polyacrylate resin comprises the following steps:

[0011] X1. Add hydroxyethyl acrylate, di-tert-butyl dicarbonate, and 4-dimethylaminopyridine to toluene, stir at room temperature for 18 - 26 h, add chloroform for dilution, wash with dilute hydrochloric acid, and after liquid separation, the organic phase is dried, concentrated, and purified by column chromatography to obtain a modified monomer;

[0012] X2. Add the modified monomer, tert-butyl acrylate, isooctyl acrylate, and azobisisobutyronitrile to anisole, heat up for polymerization under an inert atmosphere, and after 2 - 4 h, purify by column chromatography to remove impurities and solvents to obtain the modified polyacrylate resin.

[0013] Further, the molar ratio of hydroxyethyl acrylate, di-tert-butyl dicarbonate, and 4-dimethylaminopyridine is 1:1 - 2:0.1 - 0.2.

[0014] Further, the molar ratio of the modified monomer, tert-butyl acrylate, isooctyl acrylate, and initiator is 5 - 9:5 - 9:4 - 10:0.1 - 0.2.

[0015] Further, the temperature range for the heating polymerization is 60 - 80 °C.

[0016] Further, the dosage of toluene is 0.5 to 2 times the total volume of hydroxyethyl acrylate, di-tert-butyl dicarbonate, and 4-dimethylaminopyridine.

[0017] Further, the dosage of chloroform is 2 to 6 times the volume of toluene.

[0018] Further, the dosage of anisole is 2 to 4 times the total volume of the modified monomer, tert-butyl acrylate, isooctyl acrylate, and azobisisobutyronitrile.

[0019] Further, the tackifying resin is one of terpene and its derivative resins, rosin and its derivative resins.

[0020] Further, the curing agent is one of isocyanate curing agents and epoxy curing agents.

[0021] Further, the solvent is one of ethyl acetate, toluene, or isopropanol.

[0022] A preparation method of a thermal de-tacking glue includes the following steps:

[0023] Mix the modified polyacrylic resin, tackifying resin, curing agent, and solvent evenly to obtain the thermal de-tacking glue.

[0024] The present invention also provides an application of the thermal de-tacking glue in electrolytic membrane cut pieces, specifically by coating the thermal de-tacking glue on the surface of aluminum foil.

[0025] Advantages of the present invention:

[0026] Compared with the prior art, the present invention provides a modified polyacrylate resin containing tert-butyl ester and tert-butoxycarbonyl. The thermal degradation ability of the tert-butyl ester is relatively high, but the thermal degradation of tert-butoxycarbonyl requires a relatively higher temperature. Therefore, the obtained modified polyacrylic resin is not easily de-tacked at a lower temperature, which avoids the debonding of the glue and enables directional peeling. Specific embodiments

[0027] Terpene resin, T-120, softening point ≥120, saponification value ≤1.5 mgKOH / g, iodine value 40 - 75, Shenzhen Yitian Chemical Co., Ltd.

[0028] Isocyanate curing agent, grade HB175 MP / X, NCO content 16% - 17%, BASF.

[0029] The present invention provides a thermal de-tacking glue prepared from a modified polyacrylic resin, a tackifying resin, a curing agent, and a solvent.

[0030] Modified polyacrylic resin is the matrix of adhesive and provides the main bonding performance. It plays the role of bearing and transmitting stress in adhesive and is a key component affecting the performance of adhesive.

[0031] Tackifying resins such as terpene resins or rosin and its derivative resins are used to increase the viscosity or adhesion of adhesives. These resins can improve the wettability and fluidity of adhesives, thereby improving their initial tack and bonding properties. Terpene resins are well soluble in various acrylic acids in solvent-based acrylic adhesives, and have significantly improved docking strength and cohesion.

[0032] Curing agents are substances that cause the polymers in the adhesive to undergo cross-linking reactions, thereby increasing the cohesion and heat resistance of the adhesive. Curing agents can be isocyanate or epoxy curing agents. Isocyanate curing agents react with hydroxyl groups or other active groups in the adhesive to form strong chemical bonds, thereby increasing the bonding strength and heat resistance of the adhesive. Epoxy curing agents react with epoxy groups to form a three-dimensional network structure, thereby increasing the cohesive strength of the adhesive. Solvents are used to adjust the viscosity and process properties of the adhesive, making it easier to apply and operate.

[0033] The above components work together to make the thermal debonding adhesive have good bonding properties. At the same time, it can be easily removed from the bonding surface by thermal debonding when necessary, making it suitable for specific industrial applications.

[0034] In the preparation of modified polyacrylic acid resin, hydroxyethyl acrylate is used as a reactive monomer, which contains hydroxyl and acrylic acid groups, and di-tert-butyl dicarbonate is used to react with hydroxyethyl acrylate to introduce additional functional groups to change the molecular structure of the resin and improve the performance of the resin. 4-Dimethylaminopyrrolidone is used as an auxiliary agent to promote the reaction between hydroxyethyl acrylate and di-tert-butyl dicarbonate and increase the reaction rate or selectivity.

[0035] Toluene as a solvent provides a homogeneous reaction medium, allowing the reactants to mix and react thoroughly. The volatility of toluene also facilitates the subsequent drying and concentration steps.

[0036] Chloroform is used as a diluent to reduce the viscosity of the reaction mixture, facilitating subsequent washing and separation steps.

[0037] Dilute hydrochloric acid is used to wash the organic phase to remove residual impurities and inorganic salts and improve the purity of the product.

[0038] Tert-butyl acrylate and isooctyl acrylate are used to copolymerize with modified monomers to form modified polyacrylic acid resins. They provide additional functional groups and different side chain structures, which affect the final properties of the resin, such as adhesion, flexibility, etc. Azobisisobutyronitrile is used as an initiator, which generates free radicals in the polymerization reaction, triggering the polymerization of acrylic acid monomers to form the polymer chain of the resin.

[0039] As a solvent for the polymerization reaction, anisole provides a homogeneous reaction medium and plays a role in controlling the reaction rate and the molecular weight of the polymer during the polymerization process. An inert atmosphere such as nitrogen or argon is used to exclude oxygen and other gases that may affect the polymerization reaction, preventing oxidation or degradation of the reaction system.

[0040] Through the synergistic effect of these components, the prepared modified polyacrylic resin has a specific chemical structure and functional groups, thereby endowing it with excellent adhesion and thermal de-adhesion properties, which are suitable for the production of thermal de-adhesion glue.

[0041] Example 1

[0042] A method for preparing a thermal de-adhesion glue, comprising the following steps, by weight:

[0043] Mix 90 parts of modified polyacrylic resin, 20 parts of terpene resin, 2 parts of isocyanate curing agent and 80 parts of ethyl acetate evenly to obtain the thermal de-adhesion glue.

[0044] The preparation method of the said modified polyacrylate resin, comprising the following steps, by weight:

[0045] X1. Add hydroxyethyl acrylate, di-tert-butyl dicarbonate and 4-dimethylaminopyridine in a molar ratio of 1:1:0.1 to toluene. The volume of toluene is the sum of the volumes of hydroxyethyl acrylate, di-tert-butyl dicarbonate and 4-dimethylaminopyridine. Stir at room temperature for 24 h, add chloroform with a volume 4 times that of toluene for dilution, wash with 0.1 mol / L dilute hydrochloric acid, and after liquid separation, the organic phase is dried, concentrated and purified by column chromatography to obtain a modified monomer;

[0046] X2. Add the modified monomer, tert-butyl acrylate, isooctyl acrylate and azobisisobutyronitrile in a molar ratio of 6:6:4:0.1 to anisole. The volume of anisole is 3 times the total volume of the modified monomer, tert-butyl acrylate, isooctyl acrylate and azobisisobutyronitrile. Polymerize at 60 °C under a nitrogen atmosphere for 3 h, and after column purification to remove impurities and solvents, obtain the modified polyacrylic resin.

[0047] Example 2

[0048] A method for preparing a thermal de-adhesion glue, comprising the following steps, by weight:

[0049] Mix 93 parts of modified polyacrylic resin, 20 parts of terpene resin, 2 parts of isocyanate curing agent and 80 parts of ethyl acetate evenly to obtain the thermal de-adhesion glue.

[0050] The preparation method of the said modified polyacrylate resin, comprising the following steps, by weight:

[0051] X1. Add hydroxyethyl acrylate, di-tert-butyl dicarbonate, and 4-dimethylaminopyridine to toluene at a molar ratio of 1:1:0.1. The volume of toluene is the sum of the volumes of hydroxyethyl acrylate, di-tert-butyl dicarbonate, and 4-dimethylaminopyridine. Stir at room temperature for 24 h, dilute with chloroform four times the volume of toluene, wash with 0.1 mol / L dilute hydrochloric acid, separate the layers, and dry, concentrate, and purify the organic phase by column chromatography to obtain the modified monomer;

[0052] X2. Add the modified monomer, tert-butyl acrylate, isooctyl acrylate, and azobisisobutyronitrile to anisole at a molar ratio of 6:6:4:0.1. The volume of anisole is three times the total volume of the modified monomer, tert-butyl acrylate, isooctyl acrylate, and azobisisobutyronitrile. Polymerize at 60 °C under a nitrogen atmosphere for 3 h, and then purify by column chromatography to remove impurities and solvents to obtain the modified polyacrylic acid resin.

[0053] Example 3

[0054] A preparation method of a thermal de-bonding glue, comprising the following steps, in parts by weight:

[0055] Mix 95 parts of the modified polyacrylic acid resin, 20 parts of terpene resin, 2 parts of isocyanate curing agent, and 80 parts of ethyl acetate evenly to obtain the thermal de-bonding glue.

[0056] The preparation method of the modified polyacrylate resin comprises the following steps, in parts by weight:

[0057] X1. Add hydroxyethyl acrylate, di-tert-butyl dicarbonate, and 4-dimethylaminopyridine to toluene at a molar ratio of 1:1:0.1. The volume of toluene is the sum of the volumes of hydroxyethyl acrylate, di-tert-butyl dicarbonate, and 4-dimethylaminopyridine. Stir at room temperature for 24 h, dilute with chloroform four times the volume of toluene, wash with 0.1 mol / L dilute hydrochloric acid, separate the layers, and dry, concentrate, and purify the organic phase by column chromatography to obtain the modified monomer;

[0058] X2. Add the modified monomer, tert-butyl acrylate, isooctyl acrylate, and azobisisobutyronitrile to anisole at a molar ratio of 6:6:4:0.1. The volume of anisole is three times the total volume of the modified monomer, tert-butyl acrylate, isooctyl acrylate, and azobisisobutyronitrile. Polymerize at 60 °C under a nitrogen atmosphere for 3 h, and then purify by column chromatography to remove impurities and solvents to obtain the modified polyacrylic acid resin.

[0059] Example 4

[0060] A preparation method of a thermal de-bonding glue, comprising the following steps, in parts by weight:

[0061] Mix 90 parts of modified polyacrylic resin, 15 parts of terpene resin, 2 parts of isocyanate curing agent and 80 parts of ethyl acetate evenly to obtain the thermal de-adhesive glue.

[0062] The preparation method of the modified polyacrylate resin includes the following steps, by weight:

[0063] X1. Add hydroxyethyl acrylate, di-tert-butyl dicarbonate and 4-dimethylaminopyridine to toluene at a molar ratio of 1:1:0.1. The volume of toluene is the sum of the volumes of hydroxyethyl acrylate, di-tert-butyl dicarbonate and 4-dimethylaminopyridine. Stir at room temperature for 24 h, add chloroform with a volume 4 times that of toluene for dilution, wash with 0.1 mol / L dilute hydrochloric acid, and after liquid separation, the organic phase is dried, concentrated and purified by column chromatography to obtain the modified monomer.

[0064] X2. Add the modified monomer, tert-butyl acrylate, isooctyl acrylate and azobisisobutyronitrile to anisole at a molar ratio of 6:6:4:0.1. The volume of anisole is 3 times the total volume of the modified monomer, tert-butyl acrylate, isooctyl acrylate and azobisisobutyronitrile. Polymerize at 60 °C under a nitrogen atmosphere for 3 h, and after column purification to remove impurities and solvents, obtain the modified polyacrylic resin.

[0065] Example 5

[0066] A preparation method of a thermal de-adhesive glue includes the following steps, by weight:

[0067] Mix 90 parts of modified polyacrylic resin, 25 parts of terpene resin, 2 parts of isocyanate curing agent and 80 parts of ethyl acetate evenly to obtain the thermal de-adhesive glue.

[0068] The preparation method of the modified polyacrylate resin includes the following steps, by weight:

[0069] X1. Add hydroxyethyl acrylate, di-tert-butyl dicarbonate and 4-dimethylaminopyridine to toluene at a molar ratio of 1:1:0.1. The volume of toluene is the sum of the volumes of hydroxyethyl acrylate, di-tert-butyl dicarbonate and 4-dimethylaminopyridine. Stir at room temperature for 24 h, add chloroform with a volume 4 times that of toluene for dilution, wash with 0.1 mol / L dilute hydrochloric acid, and after liquid separation, the organic phase is dried, concentrated and purified by column chromatography to obtain the modified monomer.

[0070] X2. Add the modified monomer, tert-butyl acrylate, isooctyl acrylate and azobisisobutyronitrile to anisole at a molar ratio of 6:6:4:0.1. The volume of anisole is 3 times the total volume of the modified monomer, tert-butyl acrylate, isooctyl acrylate and azobisisobutyronitrile. Polymerize at 60 °C under a nitrogen atmosphere for 3 h, and after column purification to remove impurities and solvents, obtain the modified polyacrylic resin.

[0071] Comparative Example 1

[0072] A preparation method of a thermal debinding glue, comprising the following steps, by weight:

[0073] Mix 90 parts of polyacrylic resin, 25 parts of terpene resin, 2 parts of isocyanate curing agent and 80 parts of ethyl acetate evenly to obtain the thermal debinding glue.

[0074] The preparation method of the polyacrylate resin comprises the following steps, by weight:

[0075] Add tert-butyl acrylate, isooctyl acrylate and azobisisobutyronitrile to anisole in a molar ratio of 12:4:0.1. The volume of anisole is 3 times the total volume of tert-butyl acrylate, isooctyl acrylate and azobisisobutyronitrile. Heat to 60 °C in a nitrogen atmosphere for polymerization. After 3 h, purify by column chromatography to remove impurities and solvents to obtain the modified polyacrylic resin.

[0076] Comparative Example 2

[0077] A preparation method of a thermal debinding glue, comprising the following steps, by weight:

[0078] Mix 90 parts of modified polyacrylic resin, 20 parts of terpene resin, 2 parts of isocyanate curing agent and 80 parts of ethyl acetate evenly to obtain the thermal debinding glue.

[0079] The preparation method of the modified polyacrylate resin comprises the following steps, by weight:

[0080] X1. Add hydroxyethyl acrylate, di-tert-butyl dicarbonate and 4-dimethylaminopyridine to toluene in a molar ratio of 1:1:0.1. The volume of toluene is the sum of the volumes of hydroxyethyl acrylate, di-tert-butyl dicarbonate and 4-dimethylaminopyridine. Stir at room temperature for 24 h. Dilute with chloroform with a volume 4 times that of toluene and wash with 0.1 mol / L dilute hydrochloric acid. After liquid separation, the organic phase is dried, concentrated and purified by column chromatography to obtain the modified monomer;

[0081] X2. Add the modified monomer, isooctyl acrylate and azobisisobutyronitrile to anisole in a molar ratio of 12:4:0.1. The volume of anisole is 3 times the total volume of the modified monomer, isooctyl acrylate and azobisisobutyronitrile. Heat to 60 °C in a nitrogen atmosphere for polymerization. After 3 h, purify by column chromatography to remove impurities and solvents to obtain the modified polyacrylic resin.

[0082] Test Example 1

[0083] The peel strength of the pyrolytically debonded glue prepared in the examples and control examples was tested before and after heat treatment. Referring to GB / T 2792-2014 "Test Method for Peel Strength of Adhesive Tapes", the 180° peel force of the glue before pyrolytic debonding and the 180° peel force after treatment at 80°C and 150°C were tested. The specific results are shown in Table 1.

[0084] Table 1 Test Results of Peel Force of Pyrolytically Debonded Glue

[0085] Experimental Scheme Peeling Force before Heat Treatment / N / 25 mm Peeling Force after Treatment at 80°C / N / 25 mm Peeling Force after Treatment at 150°C / N / 25 mm Example 1 10.12 7.12 0.46 Example 2 9.56 6.73 0.51 Example 3 9.67 6.80 0.47 Example 4 9.56 6.93 0.48 Example 5 9.66 6.89 0.58 Control Example 1 9.56 2.13 0.34 Control Example 2 9.47 7.89 5.76

[0086] As can be seen from Table 1, the pyrolytically debonded glue prepared by the present invention has good adhesiveness. After high-temperature treatment, the adhesiveness decreases to varying degrees. Compared with Control Example 1, the pyrolytic debonding of the glue prepared in the examples requires a higher temperature. The glue prepared in Control Example 1 can achieve pyrolytic debonding after heat treatment at 80°C. When electronic components are working, they may generate heat and reach a relatively high temperature. If the glue can achieve pyrolytic debonding at a lower temperature, there may be a risk of degumming. However, the adhesiveness of the glue prepared in Examples 1-5 does not decrease significantly after treatment at 80°C and still has good viscosity. This may be because the ester bond, as a thermally cleavable bond, has a decreasing thermal degradation ability from tertiary ester to secondary ester to primary ester. The modified polyacrylate in Example 1 contains tert-butyl ester and tert-butoxycarbonyl. The thermal degradation ability of tert-butyl ester is relatively high, but the thermal degradation of tert-butoxycarbonyl requires a relatively higher temperature. Therefore, the obtained modified polyacrylate resin is not easily debonded at a lower temperature. The polyacrylate in Control Example 1 only has tert-butyl ester as the thermal degradation group, and the modified polyacrylate in Control Example 2 only has tert-butoxycarbonyl as the thermal degradation group. Therefore, the glue in Control Example 1 will be debonded after treatment at 80°C, which also means that the glue may be debonded at a temperature lower than 80°C. The glue in Control Example 2 still has good adhesiveness and has not been debonded after treatment at 150°C, which means that the glue requires a higher pyrolytic debonding temperature and is not conducive to practical applications. Compared with Examples 2-5, the dosages of the modified polyacrylate and tackifying resin in Example 1 are different. As the basic components of the pyrolytically debonded glue, they provide the main adhesive properties. The tackifying resin is used to improve the viscosity of the glue and ensure good adhesion on different material surfaces. These resins improve the initial viscosity and peel force of the glue by forming a hydrogen bond network structure. When the dosages of the modified polyacrylate and tackifying resin are different, the adhesive performance of the glue is also different. From the data in Table 1, it can be seen that the adhesive performance of the glue in Example 1 is the best.

[0087] Test Example 2

[0088] The residual glue of the glue prepared in the examples and control examples was tested. The glue was pasted on the peeling board and torn off at a constant speed, and the area of the residual glue or residue was calculated and expressed as a percentage. The specific results are shown in Table 2.

[0089] Table 2 Residual Adhesive Property Test Results of Pyrolytic Debonding Glue

[0090] Experimental Scheme Area of Residual Adhesive or Residue / % Example 1 ＜1 Example 2 ＜1 Example 3 ＜1 Example 4 ＜1 Example 5 ＜1 Control Example 1 ＜1 Control Example 2 ＜1

[0091] When a thermally sensitive expansion material is added to the glue, after the temperature of the glue rises upon heating, the thermally sensitive expansion material expands upon heating and its volume increases, thereby reducing the effective contact area with the adhered object and causing the peel strength to decrease. However, as a nanomaterial, the thermal expansion additive is likely to remain on the surface of the substrate, resulting in residual glue. In contrast to thermal expansion debonding, thermal degradation debonding reduces the modulus and molecular weight of the adhesive, leading to a decrease in its bonding strength and does not require the participation of additives. Therefore, the probability of residual glue in the pyrolytic debonding glue prepared in the present invention is very low.

[0092] The preferred specific embodiments of the present invention have been described in detail above. It should be understood that those of ordinary skill in the art can make many modifications and variations based on the concept of the present invention without creative work. Therefore, all technical solutions that can be obtained by those skilled in the art in the technical field of the present invention based on the concept of the present invention through logical analysis, reasoning, or limited experiments on the basis of the prior art should fall within the protection scope determined by the claims.

Claims

1. A pyrolytic debinding glue, characterized in that, It comprises the following components in parts by weight: 90 - 95 parts of modified polyacrylic resin, 15 - 35 parts of tackifying resin, 1 - 3 parts of curing agent, and 80 - 85 parts of solvent; The preparation method of the said modified polyacrylate resin comprises the following steps: X1. Add hydroxyethyl acrylate, di - tert - butyl dicarbonate, and 4 - dimethylaminopyridine into toluene, stir at room temperature, dilute with chloroform, wash with dilute hydrochloric acid, separate the liquid, and purify the organic phase by drying, concentration, and column chromatography to obtain a modified monomer; X2. Add the modified monomer, tert - butyl acrylate, isooctyl acrylate, and azobisisobutyronitrile into anisole, heat up for polymerization under an inert atmosphere, and purify by column chromatography to remove impurities and solvents to obtain the modified polyacrylic resin.

2. The pyrolytic debinding glue according to claim 1, wherein Further, the molar ratio of hydroxyethyl acrylate, di - tert - butyl dicarbonate, and 4 - dimethylaminopyridine is 1:1 - 2:0.1 - 0.

2.

3. The pyrolytic debinding glue according to claim 1, wherein, Further, the molar ratio of the modified monomer, tert - butyl acrylate, isooctyl acrylate, and azobisisobutyronitrile is 5 - 9:5 - 9:4 - 10:0.1 - 0.

2.

4. The pyrolytic debinding glue according to claim 1, characterized in that, The temperature range for heating up for polymerization is 60 - 80 °C.

5. The pyrolytic debinding glue according to claim 1, wherein The tackifying resin is one of terpene and its derivative resins, rosin and its derivative resins.

6. The pyrolytic debinding glue according to claim 1, wherein, The curing agent is one of isocyanate - type curing agents, epoxy - type curing agents.

7. The pyrolytic debinding glue according to claim 1, characterized in that, The solvent is one of ethyl acetate, toluene, or isopropanol.

8. A method for preparing a pyrolytically debinding adhesive as described in any one of claims 1 to 7, characterized in that, It comprises the following steps: Mix 90 parts of modified polyacrylic resin, tackifying resin, curing agent, and solvent evenly to obtain the thermal de - tackifying glue.

9. The application of the thermal de - tackifying glue as described in claim 1 in electrolytic membrane cut pieces.