High-performance bio-based acrylate adhesive, preparation method thereof and adhesive tape

Abstract

The invention discloses a high-performance bio-based acrylate adhesive, a preparation method thereof and an adhesive tape. The high-performance bio-based acrylate adhesive comprises the following raw material components in parts by weight: 10-97 parts of a bio-derived acrylate monomer, 3-5 parts of acrylic acid, 90-100 parts of a solvent and 0.1-0.4 part of an initiator. According to the invention, biomass raw materials are utilized to replace traditional monomers, the use amount of fossil resources such as petroleum is reduced, the adhesive tape meets the requirements of green environmental protection and sustainable development, and the adhesive tape prepared by the invention has the advantages of high viscosity, high retention, warping resistance, easiness in degradation, environmental friendliness and the like, and has a very good application prospect.

Description

Technical Field

[0001] The invention relates to the field of bio-based adhesive materials, and in particular to a high-performance bio-based acrylate adhesive, a preparation method thereof and an adhesive tape. Background Art

[0002] In recent years, environmental issues such as global warming have attracted great attention from people, who hope to reduce dependence on fossil resources such as petroleum, and also reduce the use of fossil resources and other materials in the adhesive field. In addition, petrochemical-derived acrylic pressure-sensitive adhesives have slow biodegradation and are difficult to degrade by direct disposal or landfill. The environmental problems caused by non-degradable waste adhesive products are becoming increasingly serious. Therefore, the development of environmentally friendly and degradable acrylic pressure-sensitive adhesives has become an urgent need.

[0003] The production of bio-based acrylate monomers is generally based on the catalytic esterification reaction of alcohols extracted from plants and acrylic acid, wherein the source of bio-based alcohols is generally natural products such as vegetable oils and borneol. Such raw materials are abundant in source and highly renewable, which is in line with the sustainable development strategy. Moreover, bio-based tapes have better performance than traditional tapes, so it is of great significance to produce a high-performance bio-based acrylate tape. Patent CN 117567967 A discloses a bio-based acrylate adhesive, tape and preparation method thereof, and the bio-based acrylic adhesive layer is also used. Although it has good peeling force on various substrates, it is similar to some acrylic bio-based tapes currently on the market, generally has good adhesion, but poor anti-warping performance, or good warping performance does not take into account the retention, initial adhesion and other properties. Therefore, the development of a high-performance acrylic bio-based tape with excellent anti-warping performance, high viscosity and easy degradability is a problem that needs to be solved urgently. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a high-performance bio-based acrylate adhesive, a preparation method thereof and an adhesive tape in view of the deficiencies in the above-mentioned prior art.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is: In the first aspect of the present invention, a high-performance bio-based acrylate adhesive is provided, comprising the following raw material components in parts by weight: 10 parts to 97 parts of bio-sourced acrylate-based monomers, 3 parts to 5 parts of acrylic acid, 90 parts to 100 parts of solvents, and 0.1 to 0.4 parts of initiators.

[0006] Preferably, the bio-sourced acrylate-based monomer is selected from at least one of n-heptyl acrylate, isobornyl acrylate, butyl acrylate, and 2-octyl acrylate.

[0007] Preferably, the initiator includes initiator AIBN and initiator HTP-65W.

[0008] Preferably, the solvent is ethyl acetate.

[0009] A second aspect of the present invention provides a method for preparing the high-performance bio-based acrylate adhesive as described above, comprising the following steps:

[0010] The bio-sourced acrylate monomer and acrylic acid are mixed to obtain a monomer mixture; the solvent and part of the monomer mixture are mixed, and when the temperature is raised to 35-45°C, nitrogen is introduced for 15-60 minutes, and part of the initiator is added at 60-65°C. After reacting at this temperature for 0.5-3 hours, the remaining monomer mixture is added dropwise for 0.5-3 hours, and the reaction is continued for 15-60 minutes after the addition is completed; the temperature is raised to 68-75°C, the remaining initiator is added, and the reaction is continued at this temperature for 2-8 hours to obtain the high-performance bio-based acrylate adhesive.

[0011] Preferably, the method for preparing the high-performance bio-based acrylate adhesive comprises the following steps:

[0012] The bio-sourced acrylate monomer and acrylic acid are mixed to obtain a monomer mixture; the solvent and part of the monomer mixture are mixed and placed in a four-necked flask equipped with a stirrer, a condenser and a nitrogen tube, and a water bath is turned on for heating. When the temperature rises to 40°C, nitrogen is introduced at a flow rate of 100 mL / min. After the nitrogen is introduced for 30 minutes, initiator AIBN is added at 63°C, and the nitrogen flow rate is reduced to 30 mL / min. After reacting at this temperature for 1.5 hours, the remaining monomer mixture is added dropwise for 1.5 hours. After the addition is completed, the reaction is continued for 0.5 hours; the temperature is raised to 70°C, and the initiator HTP-65W is added. The reaction is continued at this temperature for 4 hours to obtain the high-performance bio-based acrylate adhesive.

[0013] A third aspect of the present invention provides a high-performance bio-based acrylate tape, which is prepared by the following method:

[0014] S1. By weight, 100 parts of the high-performance bio-based acrylate adhesive described above, 30 parts to 55 parts of tackifying resin KE-311, 7 parts to 15 parts of tackifying resin 6108, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a buffer layer glue solution;

[0015] S2. By weight, 100 parts of the high-performance bio-based acrylate adhesive described above, 30 parts to 55 parts of tackifying resin KE-311, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a back coating adhesive solution;

[0016] S3, coating the buffer layer glue on the surface of the PET substrate, baking and curing to form a buffer layer, and obtaining a semi-finished product;

[0017] S4, coating the back coating adhesive on the back of the semi-finished PET substrate, baking and curing to form a back coating adhesive layer, and laminating a release film on the back coating adhesive layer to obtain the high-performance bio-based acrylate tape.

[0018] Preferably, the curing agent is a mixture of an isocyanate curing agent and an epoxy curing agent.

[0019] Preferably, the mass ratio of the isocyanate curing agent to the epoxy curing agent is 15:1-60:1.

[0020] Preferably, the high-performance bio-based acrylate tape is prepared by the following method:

[0021] S1. By weight, 100 parts of the high-performance bio-based acrylate adhesive described above, 30 parts to 55 parts of tackifying resin KE-311, 7 parts to 15 parts of tackifying resin 6108, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a buffer layer glue solution;

[0022] S2. By weight, 100 parts of the high-performance bio-based acrylate adhesive described above, 30 parts to 55 parts of tackifying resin KE-311, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a back coating adhesive solution;

[0023] S3, coating the buffer layer glue on the surface of the PET substrate, baking at 120° C. for 5 min, forming a buffer layer with a thickness of 90 μm, and obtaining a semi-finished product;

[0024] S4, coating the back coating adhesive on the back of the semi-finished PET substrate, baking at 120° C. for 5 min to form a back coating adhesive layer with a thickness of 90 μm, and laminating a release film on the back coating adhesive layer to obtain the high-performance bio-based acrylate tape.

[0025] The beneficial effects of the present invention are:

[0026] The present invention provides a high-performance bio-based acrylate adhesive, a preparation method thereof and an adhesive tape. The present invention utilizes biomass raw materials to replace traditional monomers, thereby reducing the use of fossil resources such as petroleum, and meeting the requirements of green environmental protection and sustainable development. The adhesive tape prepared by the present invention has the advantages of high viscosity, high holding power, anti-warping, easy degradation, environmental friendliness, etc., and has good application prospects. DETAILED DESCRIPTION

[0027] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.

[0028] It should be understood that the terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or more other elements or combinations thereof.

[0029] The test methods used in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples are all commercially available unless otherwise specified. In the following examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if the manufacturer is not specified, are all conventional products that can be purchased commercially.

[0030] The invention provides a high-performance bio-based acrylate adhesive, which comprises the following raw material components in parts by weight: 10-97 parts of bio-source acrylate-based monomers, 3-5 parts of acrylic acid, 90-100 parts of solvents, and 0.1-0.4 parts of initiators.

[0031] Among them, acrylic acid is a carboxyl-containing monomer. By using this carboxyl-containing polar group monomer, the cohesive force of the adhesive and the retention performance can be effectively improved. If the acid value is too high, the polarity will be too large and there will be too many cross-linkable groups, resulting in the adhesive layer being too hard, poor wetting of the adhered object, and easy occurrence of jump points, which affects the adhesion.

[0032] In a preferred embodiment, the bio-sourced acrylate monomer is selected from at least one of n-heptyl acrylate, isobornyl acrylate, butyl acrylate, and 2-octyl acrylate. Although the side chain groups of these monomers have different structural units from petrochemical products, they have similar properties to petroleum-based monomers, and thus can replace traditional petroleum-based monomers to reduce the consumption of petroleum resources.

[0033] In a preferred embodiment, the initiator includes initiator AIBN and initiator HTP-65W.

[0034] In a preferred embodiment, the solvent is ethyl acetate.

[0035] The present invention also provides a method for preparing the above high-performance bio-based acrylate adhesive, comprising the following steps:

[0036] The bio-sourced acrylate monomer and acrylic acid are mixed to obtain a monomer mixture; the solvent and part of the monomer mixture are mixed, and when the temperature is raised to 35-45°C, nitrogen is introduced for 15-60 minutes, and part of the initiator is added at 60-65°C. After reacting at this temperature for 0.5-3 hours, the remaining monomer mixture is added dropwise for 0.5-3 hours. After the addition is completed, the reaction is continued for 15-60 minutes; the temperature is raised to 68-75°C, the remaining initiator is added, and the reaction is continued at this temperature for 2-8 hours to obtain a high-performance bio-based acrylate adhesive.

[0037] In a preferred embodiment, the method for preparing a high-performance bio-based acrylate adhesive comprises the following steps:

[0038] The bio-sourced acrylate monomer and acrylic acid are mixed to obtain a monomer mixture; the solvent and part of the monomer mixture are mixed and placed in a four-necked flask equipped with a stirrer, a condenser and a nitrogen tube, and a water bath is turned on for heating. When the temperature rises to 40°C, nitrogen is introduced at a flow rate of 100 mL / min. After the nitrogen is introduced for 30 minutes, initiator AIBN is added at 63°C, and the nitrogen flow rate is reduced to 30 mL / min. After reacting at this temperature for 1.5 hours, the remaining monomer mixture is added dropwise for 1.5 hours. After the addition is completed, the reaction is continued for 0.5 hours; the temperature is raised to 70°C, and the initiator HTP-65W is added. The reaction is continued at this temperature for 4 hours to obtain a high-performance bio-based acrylate adhesive.

[0039] The present invention also provides a high-performance bio-based acrylate tape, which is prepared by the following method:

[0040] S1. By weight, 100 parts of the high-performance bio-based acrylate adhesive of any one of claims 1 to 4, 30 parts to 55 parts of tackifying resin KE-311, 7 parts to 15 parts of tackifying resin 6108, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a buffer layer glue solution;

[0041] S2. By weight, 100 parts of the high-performance bio-based acrylate adhesive of any one of claims 1 to 4, 30 parts to 55 parts of tackifying resin KE-311, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a back coating adhesive solution;

[0042] S3, coating the buffer layer glue on the surface of the PET substrate, baking and curing to form a buffer layer, and obtaining a semi-finished product;

[0043] S4, coating the back coating adhesive on the back of the semi-finished PET substrate, baking and curing to form a back coating adhesive layer, and laminating a release film on the back coating adhesive layer to obtain a high-performance bio-based acrylate tape.

[0044] In a preferred embodiment, the curing agent is a mixture of an isocyanate curing agent and an epoxy curing agent.

[0045] In a preferred embodiment, the mass ratio of the isocyanate curing agent to the epoxy curing agent is 15:1-60:1.

[0046] In a preferred embodiment, the high-performance bio-based acrylate tape is prepared by the following method:

[0047] S1. By weight, 100 parts of the high-performance bio-based acrylate adhesive of any one of claims 1 to 4, 30 parts to 55 parts of tackifying resin KE-311, 7 parts to 15 parts of tackifying resin 6108, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a buffer layer glue solution;

[0048] S2. By weight, 100 parts of the high-performance bio-based acrylate adhesive of any one of claims 1 to 4, 30 parts to 55 parts of tackifying resin KE-311, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a back coating adhesive solution;

[0049] S3, coating the buffer layer glue on the surface of the PET substrate, baking at 120° C. for 5 min, forming a buffer layer with a thickness of 90 μm, and obtaining a semi-finished product;

[0050] S4. Apply the back coating adhesive on the back of the semi-finished PET substrate, bake at 120° C. for 5 minutes to form a back coating adhesive layer with a thickness of 90 μm, and attach a release film to the back coating adhesive layer to obtain a high-performance bio-based acrylate tape.

[0051] Tackifying resin KE-311 and tackifying resin 6108 can help improve adhesive properties (eg, peel strength).

[0052] In the present invention, free radical polymerization is adopted to synthesize acrylic glue, which can improve the adhesion of the adhesive layer to the substrate, and improve the adhesion and cohesion of the adhesive layer. The addition of a curing agent can appropriately increase the crosslinking density of the product and improve the cohesion of the product. The tackifying resin can further improve the adhesion of the product.

[0053] The above is the overall concept of the present invention, and detailed embodiments and comparative examples are provided below on the basis of the overall concept of the present invention to further illustrate the present invention.

[0054] The main raw materials and their sources in the following examples and comparative examples are as follows:

[0055]

[0056] Synthesis Example Preparation of five different acrylic adhesives

[0057] Synthesis example one

[0058] Weigh 97 parts of 2-octyl acrylate and 3 parts of acrylic acid, place 30wt% of the monomer and 90 parts of ethyl acetate in a four-necked flask equipped with a stirrer, a condenser and a nitrogen tube, turn on the water bath heating, and when the temperature rises to 40°C, introduce nitrogen at a flow rate of 100ml / min. After introducing nitrogen for 30 minutes, add 0.1 parts of initiator AIBN at 63°C, and reduce the nitrogen flow rate to 30ml / min. After reacting at this temperature for 1.5 hours, start dripping the remaining 70wt% of the monomer, and the dripping time is 1.5 hours. After dripping, continue to react for 0.5 hours. Heat to 70°C, add 0.1 parts of high-temperature initiator HTP-65W, and continue to react at this temperature for 4 hours to obtain an acrylate adhesive.

[0059] Synthesis Example 2

[0060] Weigh 95 parts of n-heptyl acrylate and 5 parts of acrylic acid, place 30wt% of the monomer and 90 parts of ethyl acetate in a four-necked flask equipped with a stirrer, a condenser and a nitrogen tube, turn on the water bath heating, and when the temperature rises to 40°C, introduce nitrogen at a flow rate of 100ml / min. After introducing nitrogen for 30 minutes, add 0.1 parts of initiator AIBN at 63°C, and reduce the nitrogen flow rate to 30ml / min. After reacting at this temperature for 1.5 hours, start to drip the remaining 70wt% of the monomer, and the dripping time is 1.5 hours. After dripping, continue to react for 0.5 hours. Heat to 70°C, add 0.1 parts of high-temperature initiator HTP-65W, and continue to react at this temperature for 4 hours to obtain an acrylate adhesive.

[0061] Synthesis Example 3

[0062] Weigh 67 parts of n-heptyl acrylate, 20 parts of 2-octyl acrylate, 10 parts of isobornyl acrylate and 3 parts of acrylic acid, place 30wt% of the monomers and 90 parts of ethyl acetate in a four-necked flask equipped with a stirrer, a condenser and a nitrogen tube, turn on the water bath heating, and when the temperature rises to 40°C, introduce nitrogen at a flow rate of 100ml / min. After introducing nitrogen for 30min, add 0.1 parts of initiator AIBN at 63°C, and reduce the nitrogen flow rate to 30ml / min. After reacting at this temperature for 1.5h, start dripping the remaining 70wt% of the monomers, and the dripping time is 1.5h. After dripping, continue to react for 0.5h. Heat to 70°C, add 0.1 parts of high-temperature initiator HTP-65W, and continue to react at this temperature for 4h to obtain an acrylate adhesive.

[0063] Synthesis Example 4

[0064] Weigh 67 parts of butyl acrylate, 20 parts of 2-octyl acrylate, 10 parts of isobornyl acrylate and 3 parts of acrylic acid, place 30wt% of the monomers and 90 parts of ethyl acetate in a four-necked flask equipped with a stirrer, a condenser and a nitrogen tube, turn on the water bath heating, and when the temperature rises to 40°C, introduce nitrogen at a flow rate of 100ml / min. After introducing nitrogen for 30min, add 0.1 parts of initiator AIBN at 63°C, and reduce the nitrogen flow rate to 30ml / min. After reacting at this temperature for 1.5h, start dripping the remaining 70wt% of the monomers, and the dripping time is 1.5h. After dripping, continue to react for 0.5h. Heat to 70°C, add 0.1 parts of high-temperature initiator HTP-65W, and continue to react at this temperature for 4h to obtain an acrylate adhesive.

[0065] Synthesis Example 5

[0066] Weigh 67 parts of isooctyl acrylate, 20 parts of 2-octyl acrylate, 10 parts of isobornyl acrylate and 3 parts of acrylic acid, place 30wt% of the monomers and 90 parts of ethyl acetate in a four-necked flask equipped with a stirrer, a condenser and a nitrogen tube, turn on the water bath heating, and when the temperature rises to 40°C, introduce nitrogen at a flow rate of 100ml / min. After introducing nitrogen for 30min, add 0.1 parts of initiator AIBN at 63°C, and reduce the nitrogen flow rate to 30ml / min. After reacting at this temperature for 1.5h, start dripping the remaining 70wt% of the monomers, and the dripping time is 1.5h. After dripping, continue to react for 0.5h. Heat to 70°C and continue to react at this temperature for 4h to obtain an acrylate adhesive.

[0067] The composition and molecular weight information of the above five acrylic adhesives are shown in Table 1:

[0068] Table 1

[0069]

[0070] It can be seen from the above table:

[0071] In synthesis examples 1-4, the dropwise addition synthesis process is used and the high temperature initiator HTP-65W is added later, so that the molecular weight of the synthetic glue is larger and the molecular weight distribution is narrower. In addition, a large amount of bio-based monomers are used to replace traditional monomers, and the bio-based content of the glue is higher.

[0072] In Synthesis Example 5, although the dropping method was used for synthesis, only AIBN was used as the initiator, which resulted in a smaller molecular weight of the synthetic glue and a wider molecular weight distribution. In addition, a large amount of petroleum-based monomer, isooctyl acrylate, was used, which did not meet the requirements of sustainable development.

[0073] Embodiment 1

[0074] A high-performance bio-based acrylic tape is prepared by the following method:

[0075] S1. By weight, 100 parts of the acrylic adhesive of Synthesis Example 1, 40 parts of tackifying resin KE-311, 10 parts of tackifying resin 6108, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a buffer layer glue solution;

[0076] S2. By weight, 100 parts of the acrylic adhesive of Synthesis Example 1, 40 parts of tackifying resin KE-311, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a back coating adhesive solution;

[0077] S3, coating the buffer layer glue on the surface of the transparent PET substrate, baking at 120° C. for 5 min, forming a buffer layer with a thickness of 90 μm, and obtaining a semi-finished product;

[0078] S4. Apply the back coating adhesive on the back of the semi-finished transparent PET substrate, bake at 120° C. for 5 minutes to form a back coating adhesive layer with a thickness of 90 μm, and adhere a 50 μm release film on the back coating adhesive layer to obtain a high-performance bio-based acrylate tape.

[0079] Embodiment 2

[0080] A high-performance bio-based acrylic tape is prepared by the following method:

[0081] S1. By weight, 100 parts of the acrylic adhesive of Synthesis Example 2, 40 parts of tackifying resin KE-311, 10 parts of tackifying resin 6108, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a buffer layer glue solution;

[0082] S2. By weight, 100 parts of the acrylic adhesive of Synthesis Example 1, 40 parts of tackifying resin KE-311, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a back coating adhesive solution;

[0083] S3, coating the buffer layer glue on the surface of the transparent PET substrate, baking at 120° C. for 5 min, forming a buffer layer with a thickness of 90 μm, and obtaining a semi-finished product;

[0084] S4. Apply the back coating adhesive on the back of the semi-finished transparent PET substrate, bake at 120° C. for 5 minutes to form a back coating adhesive layer with a thickness of 90 μm, and adhere a 50 μm release film on the back coating adhesive layer to obtain a high-performance bio-based acrylate tape.

[0085] Embodiment 3

[0086] A high-performance bio-based acrylic tape is prepared by the following method:

[0087] S1. By weight, 100 parts of the acrylic adhesive of Synthesis Example 3, 40 parts of tackifying resin KE-311, 10 parts of tackifying resin 6108, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a buffer layer glue solution;

[0088] S2. By weight, 100 parts of the acrylic adhesive of Synthesis Example 1, 40 parts of tackifying resin KE-311, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a back coating adhesive solution;

[0089] S3, coating the buffer layer glue on the surface of the transparent PET substrate, baking at 120° C. for 5 min, forming a buffer layer with a thickness of 90 μm, and obtaining a semi-finished product;

[0090] S4. Apply the back coating adhesive on the back of the semi-finished transparent PET substrate, bake at 120° C. for 5 minutes to form a back coating adhesive layer with a thickness of 90 μm, and adhere a 50 μm release film on the back coating adhesive layer to obtain a high-performance bio-based acrylate tape.

[0091] Embodiment 4

[0092] A high-performance bio-based acrylic tape is prepared by the following method:

[0093] S1. By weight, 100 parts of the acrylic adhesive of Synthesis Example 4, 40 parts of tackifying resin KE-311, 10 parts of tackifying resin 6108, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a buffer layer glue solution;

[0094] S2. By weight, 100 parts of the acrylic adhesive of Synthesis Example 1, 40 parts of tackifying resin KE-311, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a back coating adhesive solution;

[0095] S3, coating the buffer layer glue on the surface of the transparent PET substrate, baking at 120° C. for 5 min, forming a buffer layer with a thickness of 90 μm, and obtaining a semi-finished product;

[0096] S4. Apply the back coating adhesive on the back of the semi-finished transparent PET substrate, bake at 120° C. for 5 minutes to form a back coating adhesive layer with a thickness of 90 μm, and adhere a 50 μm release film on the back coating adhesive layer to obtain a high-performance bio-based acrylate tape.

[0097] Comparative Example 1

[0098] A high-performance bio-based acrylic tape is prepared by the following method:

[0099] S1. By weight, 100 parts of the acrylic adhesive of Synthesis Example 5, 40 parts of tackifying resin KE-311, 10 parts of tackifying resin 6108, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a buffer layer glue solution;

[0100] S2. By weight, 100 parts of the acrylic adhesive of Synthesis Example 1, 40 parts of tackifying resin KE-311, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a back coating adhesive solution;

[0101] S3, coating the buffer layer glue on the surface of the transparent PET substrate, baking at 120° C. for 5 min, forming a buffer layer with a thickness of 90 μm, and obtaining a semi-finished product;

[0102] S4. Apply the back coating adhesive on the back of the semi-finished transparent PET substrate, bake at 120° C. for 5 minutes to form a back coating adhesive layer with a thickness of 90 μm, and adhere a 50 μm release film on the back coating adhesive layer to obtain a high-performance bio-based acrylate tape.

[0103] Comparative Example 2

[0104] A high-performance bio-based acrylic tape is prepared by the following method:

[0105] S1. By weight, 100 parts of the acrylic adhesive of Synthesis Example 4, 40 parts of tackifying resin TP2040, 10 parts of tackifying resin 6108, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a buffer layer glue solution;

[0106] S2. By weight, 100 parts of the acrylic adhesive of Synthesis Example 1, 40 parts of tackifying resin TP2040, 1.5 parts of isocyanate crosslinking agent (TDI), and 0.05 parts of epoxy curing agent (SUPERCX 7) were mixed evenly to obtain a back coating adhesive solution;

[0107] S3, coating the buffer layer glue on the surface of the transparent PET substrate, baking at 120° C. for 5 min, forming a buffer layer with a thickness of 90 μm, and obtaining a semi-finished product;

[0108] S4. Apply the back coating adhesive on the back of the semi-finished transparent PET substrate, bake at 120° C. for 5 minutes to form a back coating adhesive layer with a thickness of 90 μm, and adhere a 50 μm release film on the back coating adhesive layer to obtain a high-performance bio-based acrylate tape.

[0109] The adhesive tapes prepared in the examples and comparative examples were subjected to the following performance tests:

[0110] 180° peeling force test method: stick one side of the 25mm wide tape on a standard steel plate, roll it back and forth with a 2kg roller twice (600mm / min), place it at room temperature (23±2℃, relative humidity 50%) for 20 minutes, then use a universal tensile testing machine to perform 180° peeling at 300mm / min, test three times, and take the average value;

[0111] Nameplate anti-rebound test method: make a 150mm long and 20mm wide strip of tape, stick it on the surface of a standard aluminum plate (specification: 150mm*20mm*0.5mm), roll it back and forth with a 4kg roller twice (10m / min), place it at room temperature (23±2℃, relative humidity 50%) for 24h, then place it in a 50℃, 95%RH test environment, measure the warping height (mm) at both ends after 15min, 30min, 1h, 2h, 4h, 24h, and 48h, and the warping height (mm) = left height + right height.

[0112] 0-5mm: very good, 6-15mm: good, 16-25mm: average, 26-40mm: poor.

[0113] The test results are shown in Table 2 below:

[0114] Table 2

[0115] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative Example 1 Comparative Example 2 thickness 205 205 205 205 205 205 180° peel strength--SUS 4290 3923 4163 3708 2732 3838 180° Peel Strength-PP 4279 3950 4120 3729 2750 3850 180° Peel Strength-Al 3120 2846 3012 2601 1264 2091 Retention 232 183 198 131 224 179 Rolling ball initial adhesion 32# 28# 30# 28 20# 28# Dynamic shear 1.9 1.7 1.8 1.7 1.2 1.6 Anti-rebound ability 0 3 2 4 32 18

[0116] The test data show that:

[0117] The various tests of Examples 1-4 show that their performance is relatively excellent;

[0118] Comparative Example 1 has obvious performance degradation due to the difference in monomer types and low bio-based content;

[0119] Although Comparative Example 2 used monomers with a high bio-based content, one of the tackifying resins was replaced (tackifying resin KE-311 was replaced with tackifying resin TP2040), resulting in a significant decrease in various performances.

[0120] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. A high-performance bio-based acrylic adhesive, characterized in that: The invention comprises the following raw material components in parts by weight: 10-97 parts of biologically derived acrylate monomers, 3-5 parts of acrylic acid, 90-100 parts of solvents, and 0.1-0.4 parts of initiators.

2. The high-performance bio-based acrylate adhesive according to claim 1, characterized in that: The biologically derived acrylate monomer is selected from at least one of n-heptyl acrylate, isobornyl acrylate, butyl acrylate and 2-octyl acrylate.

3. The high-performance bio-based acrylate adhesive according to claim 1, characterized in that: The initiators include initiator AIBN and initiator HTP-65W.

4. The high-performance bio-based acrylate adhesive according to claim 1, characterized in that: The solvent is ethyl acetate.

5. A method for preparing a high-performance bio-based acrylate adhesive as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: The bio-sourced acrylate monomer and acrylic acid are mixed to obtain a monomer mixture; the solvent and part of the monomer mixture are mixed, and when the temperature is raised to 35-45°C, nitrogen is introduced for 15-60 minutes, and part of the initiator is added at 60-65°C. After reacting at this temperature for 0.5-3 hours, the remaining monomer mixture is added dropwise for 0.5-3 hours, and the reaction is continued for 15-60 minutes after the addition is completed; the temperature is raised to 68-75°C, the remaining initiator is added, and the reaction is continued at this temperature for 2-8 hours to obtain the high-performance bio-based acrylate adhesive.

6. The method for preparing a high-performance bio-based acrylate adhesive according to claim 5, characterized in that: The following steps are involved: The bio-sourced acrylate monomer and acrylic acid are mixed to obtain a monomer mixture; the solvent and part of the monomer mixture are mixed and placed in a four-necked flask equipped with a stirrer, a condenser and a nitrogen tube, and a water bath is turned on for heating. When the temperature rises to 40°C, nitrogen is introduced at a flow rate of 100 mL / min. After the nitrogen is introduced for 30 minutes, initiator AIBN is added at 63°C, and the nitrogen flow rate is reduced to 30 mL / min. After reacting at this temperature for 1.5 hours, the remaining monomer mixture is added dropwise for 1.5 hours. After the addition is completed, the reaction is continued for 0.5 hours; the temperature is raised to 70°C, and the initiator HTP-65W is added. The reaction is continued at this temperature for 4 hours to obtain the high-performance bio-based acrylate adhesive.

7. A high-performance bio-based acrylic tape, characterized in that: It is prepared by the following method: S1. By weight, 100 parts of the high-performance bio-based acrylate adhesive according to any one of claims 1 to 4, 30 parts to 55 parts of tackifying resin KE-311, 7 parts to 15 parts of tackifying resin 6108, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a buffer layer glue solution; S2. By weight, 100 parts of the high-performance bio-based acrylate adhesive according to any one of claims 1 to 4, 30 parts to 55 parts of tackifying resin KE-311, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a back coating adhesive solution; S3, coating the buffer layer glue on the surface of the PET substrate, baking and curing to form a buffer layer, and obtaining a semi-finished product; S4, coating the back coating adhesive on the back of the semi-finished PET substrate, baking and curing to form a back coating adhesive layer, and laminating a release film on the back coating adhesive layer to obtain the high-performance bio-based acrylate tape.

8. The high-performance bio-based acrylic tape according to claim 7, characterized in that: The curing agent is a mixture of isocyanate curing agent and epoxy curing agent.

9. The high-performance bio-based acrylic tape according to claim 8, characterized in that: The mass ratio of the isocyanate curing agent to the epoxy curing agent is 15:1-60:

1.

10. The high-performance bio-based acrylic tape according to claim 7, characterized in that: It is prepared by the following method: S1. By weight, 100 parts of the high-performance bio-based acrylate adhesive according to any one of claims 1 to 4, 30 parts to 55 parts of tackifying resin KE-311, 7 parts to 15 parts of tackifying resin 6108, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a buffer layer glue solution; S2. By weight, 100 parts of the high-performance bio-based acrylate adhesive according to any one of claims 1 to 4, 30 parts to 55 parts of tackifying resin KE-311, and 0.75 parts to 3 parts of curing agent are mixed evenly to obtain a back coating adhesive solution; S3, coating the buffer layer glue on the surface of the PET substrate, baking at 120° C. for 5 min, forming a buffer layer with a thickness of 90 μm, and obtaining a semi-finished product; S4, coating the back coating adhesive on the back of the semi-finished PET substrate, baking at 120° C. for 5 min to form a back coating adhesive layer with a thickness of 90 μm, and laminating a release film on the back coating adhesive layer to obtain the high-performance bio-based acrylate tape.

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