A non-benzene high-temperature-resistant, impact-resistant and easy-to-exhaust adhesive tape

Abstract

The present invention relates to the technical field of adhesive tapes, and discloses a non-benzene adhesive tape that is resistant to high temperature and impact and easy to exhaust. 3 ~10 4 2-Ethylhexyl acrylate monomer, terpene resin, and low-molecular-weight aliphatic hydrocarbon resin are added to the butyl acrylate adhesive, and a formula is selected to stabilize the peeling force of the glue at 500-800 gf / in, thereby avoiding the problems of poor high-temperature resistance and impact resistance caused by excessive molecular weight. Nickel-plated carbon fiber powder modified with boric acid is added to improve the high-temperature resistance of the colloid. Boric acid can also condense with terminal hydroxyl polydimethylsiloxane to further enhance the impact resistance of the colloid. The organic functional groups contained in the silane coupling agent have good compatibility with the glue, which is beneficial to improving the stability of the colloid. The coating thickness of the adhesive layer is controlled to 13-15 μm, and a W20 mesh release film is used to ensure that the resulting tape has good air permeability and impact resistance.

Description

Technical Field

[0001] The invention relates to the technical field of adhesive tapes and discloses a non-benzenized, high-temperature, impact-resistant and easy-to-degas adhesive tape. Background Art

[0002] In recent years, adhesive tape has become ubiquitous in our daily lives. It is an indispensable material in industrial manufacturing and electronic assembly. With the development of industrial technology and the improvement of economic levels, the requirements for adhesive tape performance are becoming increasingly higher. In the context of promoting environmental protection, people demand products that are benzene-free. Benzene-free adhesive tapes are harmless to the environment and human health. However, existing benzene-free adhesive tapes have limited applications and cannot meet the needs of manufacturing high-temperature and explosion-proof film tapes.

[0003] The purpose of explosion-proof film tape is to prevent people from being injured by flying glass fragments caused by external impact, and extremely high impact resistance is required for the tape. However, the benzene-free tape prepared by existing technology has an increased molecular weight of the material and an excessively high cohesive performance of the adhesive layer, resulting in the tape's impact resistance and high-temperature resistance being deteriorated when subjected to damage modes such as falling and shearing, as well as high-temperature bonding processes. At the same time, conventional tapes are prone to blistering during the high-temperature lamination process. The bubbles in the final product do not disappear and are accompanied by wrinkles, which greatly reduces the quality and service life of the tape.

[0004] Therefore, it is of great significance to provide a benzene-free tape with good high temperature resistance, good impact resistance and good exhaust performance. Summary of the Invention

[0005] The object of the present invention is to provide a non-benzenized high-temperature-resistant, impact-resistant and easy-to-degas adhesive tape to solve the problems raised in the above background technology.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] A non-benzene adhesive tape that is resistant to high temperatures, impacts, and degassing easily, wherein the preparation method of the adhesive tape comprises the following steps:

[0008] S1: adding epoxy resin and curing accelerator to the non-benzene adhesive and mixing them evenly to obtain non-benzene glue;

[0009] S2: After the substrate is corona-discharged, a non-benzened glue is coated to a thickness of 13 to 15 μm, a grid release film is covered on the surface of the non-benzened glue, and the adhesive tape is obtained by aging.

[0010] More optimally, the peeling force of the non-benzenized glue is 500-800 gf / in; the model of the grid release film is W20 (the specification of the grid grid of the release surface is 20 μm*20 μm).

[0011] More optimally, the non-benzened glue comprises the following raw materials: 100 parts by mass of non-benzened adhesive, 2.5 to 3.5 parts of epoxy resin, and 1.7 to 2.5 parts of curing accelerator.

[0012] More optimally, the preparation of the non-benzenized adhesive comprises the following steps:

[0013] S1: Mix the adhesive, heptane, and initiator, raise the temperature to 60-70°C, stir, and react for 8-15 minutes, then dropwise add a small molecule monomer and N,N-methylenebisacrylamide, react for 8-20 minutes, and quickly cool to room temperature to obtain a modified adhesive;

[0014] S2: Add tackifying resin and heptane to the modified adhesive, stir, and react for 4 to 9 hours, adding solvent every 1 to 2 hours to ensure that the amount of solvent does not decrease; after the reaction is completed, when the residual heat of the reaction is ≥40°C, add modified nickel-plated carbon fiber powder and toughening agent, wait until the temperature drops to room temperature, and let it stand for 1 to 3 hours to obtain a non-benzened adhesive.

[0015] More optimally, the small molecule monomer is 2-ethylhexyl acrylate monomer; the adhesive is a monomer with a molecular weight of 10 3 ~10 4 The butyl acrylate adhesive; the tackifying resin includes terpene resin and aliphatic hydrocarbon resin.

[0016] More optimally, the non-benzened adhesive includes the following raw materials: by weight, 30 to 50 parts of adhesive, 210 to 290 parts of heptane, 0.1 to 0.2 parts of initiator, 6 to 10 parts of small molecule monomer, 0.3 to 0.5 parts of N,N-methylenebisacrylamide, 0.7 to 1.3 parts of terpene resin, 0.2 to 0.5 parts of aliphatic hydrocarbon resin, 3 to 5 parts of modified nickel-plated carbon fiber powder, and 0.3 to 0.5 parts of toughening agent.

[0017] More optimally, the preparation of the modified nickel-plated carbon fiber powder includes the following steps: taking nickel-plated carbon fiber powder, adding ethanol aqueous solution, ultrasonically dispersing, adding silane coupling agent and boric acid, heating to 70-80°C, stirring for 1-2 hours, filtering and drying to obtain modified nickel-plated carbon fiber powder.

[0018] More optimally, the modified nickel-plated carbon fiber powder includes the following raw materials: by weight, 0.75-0.9 parts of nickel-plated carbon fiber powder, 8-15 parts of ethanol aqueous solution, 0.5-2 parts of silane coupling agent, and 3-6 parts of boric acid.

[0019] More optimally, the silane coupling agent is an aminosilane coupling agent.

[0020] More optimally, the preparation method of the non-benzene glue is as follows: adding epoxy resin, curing accelerator, and terminal hydroxyl polydimethylsiloxane to the non-benzene adhesive in parts by weight, and mixing them evenly to obtain the non-benzene glue.

[0021] More optimally, the non-benzene glue comprises the following raw materials: by weight, 100 parts of non-benzene adhesive, 2.5-3.5 parts of epoxy resin, 1.7-2.5 parts of curing accelerator, and 8-12 parts of terminal hydroxy polydimethylsiloxane.

[0022] Compared with the prior art, the present invention has the following beneficial effects: (1) the molecular weight of 10 3 ~10 4 The benzene-free butyl acrylate adhesive is mainly used, and is modified with 2-ethylhexyl acrylate monomer and N,N-methylenebisacrylamide. The bisacrylamide reacts with free radicals to cross-link small molecular groups with large molecular weight groups, increasing the complexity and disorder of the structure. After the reaction, the temperature is quickly lowered to avoid cross-linking of molecular chains to form large molecular groups. A benzene-free modified adhesive is obtained with stable peeling force. As a result, the adhesive has high temperature stability due to the preparation of the adhesive with stable viscosity.

[0023] (2) Using a modified adhesive prepared with benzene-free butyl acrylate adhesive as the main component, and mixing it with terpene resin and low molecular weight aliphatic hydrocarbon resin to form a glue with stable viscosity at high temperature (at 300°C, the peel force is stable at 500-800 gf / in), avoiding the problems of poor high temperature resistance and poor impact resistance caused by excessive molecular weight;

[0024] (3) Using a silane coupling agent to connect boric acid and nickel-plated carbon fiber powder, both the nickel-plated carbon fiber powder and the boric acid can improve the high-temperature resistance of the colloid. Boric acid can also condense with the hydroxy-terminated polydimethylsiloxane added in the subsequent step to further improve the impact resistance of the colloid. The silane coupling agent contains organic functional groups and has good compatibility with the glue, which is conducive to improving the stability of the colloid.

[0025] (4) Using W20 type mesh release film to solve the problem of bubbles generated during high temperature process, so that the produced tape has good air permeability;

[0026] (5) Control the thickness of the adhesive layer between 13 and 15 μm to ensure that the impact resistance and chemical resistance of the tape are greater than 0.5J. DETAILED DESCRIPTION

[0027] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0028] In the following examples, the raw materials are: butyl acrylate adhesive (Tesca), boric acid (CAS: 98-80-6), ethanol aqueous solution (ethanol content: 50%, the rest is water), silane coupling agent (model: KH-791), heptane (CAS: 142-82-5, Tianjin Kemeiou), azobisisobutyronitrile (Aladdin), 2-ethylhexyl acrylate (CAS: 103-11-7, Tesca), N,N-methylenebisacrylamide (CAS: 110-26-9, Aladdin), terpene resin (model KT100, Wuhan Kanos Technology Co., Ltd.), aliphatic hydrocarbon resin (model: Escorez1315, ExxonMobil) , nickel-plated carbon fiber powder (model: 800-1000 mesh, Dongguan Juona New Materials Co., Ltd.), isobornyl acrylate (CAS: 5888-33-5, Sigma-Aldrich Trading Co., Ltd.), hydroxy-terminated polydimethylsiloxane (Sigma-Aldrich Trading Co., Ltd.), epoxy resin (model: T31, Eric Technology), titanium acetylacetonate (CAS: 14024-64-7, TCI), oleic acid (CAS: 112-80-1, Aladdin); cleaning agent (model ESM1030M, Eastman hydrocarbon cleaning fluid); artificial sebum (model: KM1-1700-0700, Beijing Zhongxi Huada Technology Co., Ltd.);

[0029] The following parts are by mass;

[0030] Example 1: S1: Take 40 parts of butyl acrylate, raise the temperature to 45°C, quickly add 100 parts of heptane at a rate of 1.5 L / min, stir at a rate of 200 r / min for 15 minutes, add 0.1 parts of initiator, raise the temperature to 65°C, reduce the stirring speed to 20 r / min, react for 10 minutes, add 8 parts of 2-ethylhexyl acrylate monomer dropwise at a rate of 1.5 L / 10 minutes, raise the temperature to 65°C, add 0.4 parts of N,N-methylenebisacrylamide, react for 10 minutes, and quickly cool to room temperature to obtain a modified adhesive;

[0031] S2: Add 0.75 parts of terpene resin, 0.25 parts of Escorez 1315 low molecular weight aliphatic hydrocarbon resin, and 130 parts of heptane to the modified adhesive, reduce the stirring speed to 10 r / min, and reflux under condensation for 6 hours. Add the solvent every 1 hour to ensure that the amount of heptane does not decrease. After the reaction is completed, increase the stirring speed to 200 r / min. When the residual heat of the reaction is ≥40°C, add 0.8 parts of nickel-plated carbon fiber powder, stir for 30 minutes, add 0.4 parts of toughening agent, wait until the temperature drops to room temperature, and let it stand for 2 hours to obtain a non-benzened adhesive.

[0032] S3: Take 100 parts of non-benzened adhesive, add 3 parts of epoxy resin and 1.7 parts of curing accelerator, and stir for 20 minutes to obtain non-benzened glue.

[0033] Example 2: S1: Take 30 parts of butyl acrylate, raise the temperature to 45°C, quickly add 150 parts of heptane at a rate of 1.5 L / min, stir at a rate of 200 r / min for 15 minutes, add 0.2 parts of initiator, raise the temperature to 65°C, reduce the stirring speed to 20 r / min, react for 10 minutes, add 10 parts of 2-ethylhexyl acrylate monomer dropwise at a rate of 1.5 L / 10 minutes, raise the temperature to 65°C, add 0.5 parts of N,N-methylenebisacrylamide, react for 10 minutes, and quickly cool to room temperature to obtain a modified adhesive;

[0034] S2: Add 0.75 parts of terpene resin, 0.25 parts of Escorez 1315 low molecular weight aliphatic hydrocarbon resin, and 140 parts of heptane to the modified adhesive, reduce the stirring speed to 10 r / min, and reflux under condensation for 6 hours. Add solvent every 1 hour to ensure that the amount of heptane does not decrease. After the reaction is completed, increase the stirring speed to 200 r / min, add 0.9 parts of nickel-plated carbon fiber powder when the residual heat of the reaction is 40°C, stir for 30 minutes, add 0.5 parts of toughening agent, wait until the temperature drops to room temperature, and let it stand for 2 hours to obtain a non-benzened adhesive.

[0035] S3: Take 100 parts of non-benzened adhesive, add 3.5 parts of epoxy resin and 2.5 parts of curing accelerator, and stir for 20 minutes to obtain non-benzened glue.

[0036] Example 3: S1: Take 50 parts of butyl acrylate, raise the temperature to 45°C, quickly add 100 parts of heptane at a rate of 1.5 L / min, stir at 200 r / min for 15 minutes, add 0.1 parts of initiator, raise the temperature to 65°C, reduce the stirring speed to 20 r / min, react for 10 minutes, add 6 parts of 2-ethylhexyl acrylate monomer dropwise at a rate of 1.5 L / 10 minutes, raise the temperature to 65°C, add 0.4 parts of N,N-methylenebisacrylamide, react for 10 minutes, and quickly cool to room temperature to obtain a modified adhesive;

[0037] S2: Add 0.75 parts of terpene resin, 0.25 parts of Escorez 1315 low molecular weight aliphatic hydrocarbon resin, and 130 parts of heptane to the modified adhesive, reduce the stirring speed to 10 r / min, and reflux under condensation for 6 hours. Add solvent every 1 hour to ensure that the amount of heptane does not decrease. After the reaction is completed, increase the stirring speed to 200 r / min, add 0.75 parts of nickel-plated carbon fiber powder when the residual heat of the reaction is 40°C, stir for 30 minutes, add 0.4 parts of toughening agent, wait until the temperature drops to room temperature, and let it stand for 2 hours to obtain a non-benzened adhesive.

[0038] S3: Take 100 parts of non-benzened adhesive, add 2.5 parts of epoxy resin and 2 parts of curing accelerator, and stir for 20 minutes to obtain non-benzened glue.

[0039] Example 4: S1: Take 40 parts of butyl acrylate, raise the temperature to 45°C, quickly add 100 parts of heptane at a rate of 1.5 L / min, stir at 200 r / min for 15 minutes, add 0.1 parts of initiator, raise the temperature to 65°C, reduce the stirring speed to 20 r / min, react for 10 minutes, add 8 parts of 2-ethylhexyl acrylate monomer dropwise at a rate of 1.5 L / 10 minutes, raise the temperature to 65°C, add 0.4 parts of N,N-methylenebisacrylamide, react for 10 minutes, and quickly cool to room temperature to obtain a modified adhesive;

[0040] S2: Take 0.8 parts of nickel-plated carbon fiber powder and 10 parts of ethanol, ultrasonically disperse for 5-15 minutes, add 1 part of silane coupling agent and 4 parts of boric acid, heat to 70-80°C, stir for 1-2 hours, filter and dry to obtain modified nickel-plated carbon fiber powder;

[0041] S3: Add 0.75 parts of terpene resin, 0.25 parts of Escorez 1315 low molecular weight aliphatic hydrocarbon resin, and 130 parts of heptane to the modified adhesive, reduce the stirring speed to 10 r / min, and reflux under condensation for 6 hours. Add the solvent every 1 hour to ensure that the amount of heptane does not decrease. After the reaction is completed, increase the stirring speed to 200 r / min, add 3 parts of modified nickel-plated carbon fiber powder when the residual heat of the reaction is 40°C, stir for 30 minutes, add 0.4 parts of toughening agent, wait until the temperature drops to room temperature, and let it stand for 2 hours to obtain a non-benzened adhesive.

[0042] S4: Take 100 parts of non-benzene adhesive, add 3 parts of epoxy resin, 1.7 parts of curing accelerator, and 10 parts of terminal hydroxyl polydimethylsiloxane, and stir for 20 minutes to obtain non-benzene glue.

[0043] Experiment: (1) Take a non-benzene adhesive, add different amounts of epoxy resin, titanium acetylacetonate, and end-hydroxy polydimethylsiloxane, use a 15μm polyimide substrate, control the adhesive layer to 15μm, and test the viscosity (peel force) of the obtained non-benzene adhesive after being placed at room temperature for 20 minutes. The addition amount of epoxy resin, titanium acetylacetonate, and end-hydroxy polydimethylsiloxane and the source of the non-benzene adhesive are shown in Table 1:

[0044] Table 1:

[0045]

[0046] If the peeling force of the adhesive layer is too high, the bonding strength between the adhesive surface and the process surface will be too high, which will hinder the exhaust performance of the tape during high temperature processes;

[0047] The peeling force of the adhesives in schemes 6 to 10 was between 500 and 800 gf / in. The more effective schemes 6, 7, 9, and 10 were selected and tested for peeling force at 300°C for different time periods. Three strips were measured in each time period and the average value was taken to test the initial adhesion. The results are shown in Table 2:

[0048] Table 2:

[0049]

[0050] Based on the above data, Solution 10 has a stable high-temperature peel strength and viscosity of 500-800 gf / in and the highest initial adhesion, making it the best solution.

[0051] (2) Design of grid release film: During the high-temperature process, gas is stored between the uneven process surface and the tape, which expands during high-temperature curing and pushes up the tape to form bubbles. This requires the tape to have good air permeability. To evaluate the exhaust performance of this type of tape, it is necessary to monitor the number of bubbles generated per square decimeter of the release film after 10 minutes on a 300°C hot press and after 30 minutes at room temperature, and observe its appearance.

[0052] Implementation plan: Take the glue prepared in Scheme 6, apply it on the corona surface of the substrate with a coating thickness of 15 μm, cover it with a release film, and age it in an oven at 70°C for 18 hours to obtain a tape.

[0053] See Table 3 for the selected release film models:

[0054] Table 3:

[0055]

[0056] The bonding process surfaces of the W20 and W45 grid release films have larger exhaust channels and faster gas leakage rates, and there is no visible change in appearance after lamination. Based on the above test data and cost considerations, the W20 grid release film was selected for the design of this product.

[0057] (3) Implementation schemes a-g: Take the glue prepared in Implementation scheme 6, apply it to the corona surface of the substrate, cover it with W20 mesh release film, and oven age it at 70°C for 18 hours; the specific coating thickness is shown in Table 4;

[0058] Implementation scheme h: Take the glue of Implementation scheme 10, apply it to the corona surface of the substrate, cover it with W20 mesh release film, and cure it in an oven at 70℃ for 18 hours; the specific coating thickness is shown in Table 4;

[0059] Table 4:

[0060] Implementation Plan a b c d e f g h Glue thickness / μm 9 10 11 12 13 14 15 15 Impact resistance / J 0.31 0.39 0.45 0.53 0.59 0.63 0.66 0.72 Peel force / gf / in 510.3 570.9 612.7 645.6 703.9 745.1 751.9 793.2

[0061] It can be seen that when the thickness of the adhesive layer is ≥12μm, the impact resistance can meet the requirement of >0.5J. In solution h, the addition of modified nickel-plated carbon fiber powder and hydroxyl-terminated polydimethylsiloxane increases the impact resistance of the resulting tape, and the peel force is between 500-800gf / in, which meets the requirements.

[0062] The tapes of schemes d to h were selected and laminated to the process surface. They were placed in oleic acid, hand soap, detergent, and artificial sebum, respectively, and soaked for 3 days. The impact resistance was then tested. The results are shown in Table 6.

[0063] Table 6:

[0064]

[0065] As can be seen from the above table, the tape has good chemical resistance and impact resistance. When the coating thickness is ≥13μm, it can meet the impact resistance requirement of >0.5J, and solution h has the best effect.

[0066] In summary, the present invention provides a benzene-free adhesive tape with good high temperature resistance, good impact resistance and good exhaust performance.

[0067] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0068] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A non-benzenized, high-temperature, impact-resistant, and easily degassable adhesive tape, characterized by: The preparation method of the adhesive tape comprises the following steps: S1: adding epoxy resin and curing accelerator to the non-benzenized adhesive, mixing them evenly, and obtaining the non-benzenized glue; S2: After the substrate is corona-discharged, a non-benzened glue is coated to a thickness of 13 to 15 μm, a grid release film is covered on the surface of the non-benzened glue, and the adhesive tape is obtained by aging. The peeling force of the non-benzenized glue is 500-800 gf / in; the model of the grid release film is W20; The non-benzene glue comprises the following raw materials: 100 parts by mass of non-benzene adhesive, 2.5 to 3.5 parts of epoxy resin, and 1.7 to 2.5 parts of curing accelerator; The preparation of the non-benzenized adhesive comprises the following steps: S1: mixing an adhesive, heptane, and an initiator, raising the temperature to 60-70° C., stirring, reacting for 8-15 minutes, dropwise adding a small molecule monomer, adding N,N-methylenebisacrylamide, reacting for 8-20 minutes, and rapidly cooling to room temperature to obtain a modified adhesive; S2: Add tackifying resin and heptane to the modified adhesive, stir, and react for 4 to 9 hours, adding heptane every 1 to 2 hours; After the reaction is completed, when the residual heat of the reaction is ≥40°C, add nickel-plated carbon fiber powder and toughening agent, wait until the temperature drops to room temperature, and let it stand for 1 to 3 hours to obtain a non-benzenized adhesive; The small molecule monomer is 2-ethylhexyl acrylate monomer; the adhesive is a monomer with a molecular weight of 10 3 ~10 4 The butyl acrylate adhesive; the tackifying resin includes terpene resin and aliphatic hydrocarbon resin.

2. The non-benzenized, high-temperature, impact-resistant, and easily degassable adhesive tape according to claim 1, characterized in that: The non-benzene adhesive includes the following raw materials: by weight, 30 to 50 parts of adhesive, 210 to 290 parts of heptane, 0.1 to 0.2 parts of initiator, 6 to 10 parts of small molecule monomer, 0.3 to 0.5 parts of N,N-methylenebisacrylamide, 0.7 to 1.3 parts of terpene resin, 0.2 to 0.5 parts of aliphatic hydrocarbon resin, 0.75 to 0.9 parts of nickel-plated carbon fiber powder, and 0.3 to 0.5 parts of toughening agent.

3. The non-benzenized, high-temperature, impact-resistant, and easily degassable adhesive tape according to claim 1, characterized in that: The nickel-plated carbon fiber powder is pretreated with boric acid. The specific process is: taking the nickel-plated carbon fiber powder, adding ethanol aqueous solution, ultrasonically dispersing, adding silane coupling agent and boric acid, heating to 70-80° C., stirring for 1-2 hours, filtering and drying to obtain modified nickel-plated carbon fiber powder.

4. The non-benzenized, high-temperature, impact-resistant, and easily degassable adhesive tape according to claim 3, characterized in that: The modified nickel-plated carbon fiber powder comprises the following raw materials: by weight, 0.75-0.9 parts of nickel-plated carbon fiber powder, 8-15 parts of ethanol aqueous solution, 0.5-2 parts of silane coupling agent, and 3-6 parts of boric acid.

5. The non-benzenized, high-temperature, impact-resistant, and easily degassable adhesive tape according to claim 3, characterized in that: The preparation method of the non-benzene glue comprises the following steps: adding epoxy resin, curing accelerator and hydroxyl-terminated polydimethylsiloxane to a non-benzene adhesive in parts by weight, and mixing the mixture evenly to obtain the non-benzene glue.

6. The non-benzenized, high-temperature, impact-resistant, and easily degassable adhesive tape according to claim 5, characterized in that: The non-benzene glue comprises the following raw materials: by weight, 100 parts of non-benzene adhesive, 2.5-3.5 parts of epoxy resin, 1.7-2.5 parts of curing accelerator, and 8-12 parts of terminal hydroxyl polydimethylsiloxane.

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