Bi-component acrylic epoxy adhesive as well as preparation method and application thereof

Abstract

The invention belongs to the field of automobile flanging adhesives, and relates to a bi-component acrylic epoxy adhesive as well as a preparation method and application thereof. The bi-component acrylic epoxy adhesive comprises a component A and a component B. The component A contains an acrylate monomer, polyurethane acrylate resin, double-bond silane modified glass beads, manganese dioxide, an amine curing agent, an optional first toughening agent, an optional first thixotropic agent and an optional first pigment. And the component B contains epoxy resin, epoxy silane modified glass beads, hydrogen peroxide, a free radical initiator, an optional second toughening agent, an optional second thixotropic agent and an optional second pigment. According to the invention, through the synergistic effect of two dimensions of reduction of the body strength of the adhesive and improvement of the bonding force, the adhesive realizes complete cohesive failure.

Description

Technical Field

[0001] The invention belongs to the field of automobile hemming adhesives, and in particular relates to a two-component acrylic epoxy adhesive and a preparation method and application thereof. Background Art

[0002] Automobile hemming glue is a kind of glue widely used in the automobile production process, mainly used for bonding the hemming parts of automobile sheet metal parts (such as inner and outer door panels, engine hood, trunk lid, etc.). With the intelligentization of automobiles, automobile sheet metal parts can not only strengthen the structure, seal the body, improve the safety performance of the body collision and extend the life of the body after being bonded with hemming glue, but also reduce the body pit problem caused by welding and ensure the smoothness and beauty of the body by using adhesive instead of welding.

[0003] At present, there are two main systems of automotive hemming adhesive: one is a single-component epoxy system, and the other is a two-component acrylic epoxy system. The single-component epoxy system is usually a heat-curing system, which must be cured at high temperature. During the transportation process after the hemming, the hemming adhesive is not cured, which causes displacement and cannot keep the inner and outer panels relatively fixed. The two-component acrylic epoxy system can be cured at room temperature, has good pre-curing performance, and helps prevent the inner and outer panels from moving. When the automotive hemming adhesive is applied to the hemming part of the automotive sheet metal, the corresponding failure form is cohesive failure or interface failure. Among them, when the peel failure occurs in the adhesive itself, it indicates that the bonding strength between the adhesive and the bonded material is greater than the strength of the adhesive itself, which is called cohesive failure. When the peel failure occurs at the bonding interface, it indicates that the bonding strength between the adhesive and the bonded material is less than the strength of the adhesive itself, which is called interface failure. The existing two-component acrylic epoxy system is prone to interface failure, while the required failure form of automotive adhesives requires complete cohesive failure. Summary of the invention

[0004] The invention aims to provide a two-component acrylic epoxy adhesive whose failure form is cohesive failure, and a preparation method and application thereof.

[0005] Specifically, the two-component acrylic epoxy adhesive provided by the present invention comprises component A and component B, wherein component A contains acrylate monomers, polyurethane acrylate resin, double-bond silane-modified glass microspheres, manganese dioxide and amine curing agent, and optionally a first toughening agent, a first thixotropic agent and a first pigment, and component B contains epoxy resin, epoxy silane-modified glass microspheres, hydrogen peroxide and a free radical initiator, and optionally a second toughening agent, a second thixotropic agent and a second pigment.

[0006] The preparation method of the two-component acrylic epoxy adhesive provided by the invention comprises: uniformly mixing various raw materials in component A to obtain component A; and uniformly mixing various raw materials in component B to obtain component B.

[0007] The invention also provides application of the two-component acrylic epoxy adhesive as automobile hemming adhesive.

[0008] The key of the present invention is: on the one hand, manganese dioxide is added to component A and hydrogen peroxide is added to component B, so that when components A and B are mixed, manganese dioxide reacts with hydrogen peroxide to produce oxygen, and oxygen can act as an oxygen inhibitor in the reaction process of acrylate monomers and polyurethane acrylate resins with free radical initiators, thereby controlling the degree of polymerization of polyacrylates and reducing the bulk strength of the adhesive; on the other hand, adding double-bond silane-modified glass microbeads to component A and epoxy silane-modified glass microbeads to component B can increase the adhesion between the adhesive and the substrate, thereby better achieving the purpose of cohesive force destruction. That is, the present invention synergizes from two dimensions of reduced adhesive bulk strength and increased adhesion, so that the adhesive achieves complete cohesive failure. DETAILED DESCRIPTION

[0009] The two-component acrylic epoxy adhesive provided by the present invention comprises component A and component B. The volume ratio of component A to component B is preferably (3-5):1, such as 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 4.8:1, 5:1 or any value therebetween.

[0010] In the present invention, the component A contains acrylate monomers, polyurethane acrylate resins, double bond silane modified glass microspheres, manganese dioxide and amine curing agents, and optional first toughening agents, first thixotropic agents and first pigments. Wherein, based on the total weight of the component A, the content of the acrylate monomers is preferably 40-70%, such as 40%, 45%, 50%, 55%, 60%, 65%, 70% or any value therebetween; the content of the polyurethane acrylate resin is preferably 10-30%, such as 10%, 15%, 20%, 25%, 30% or any value therebetween; the content of the double bond silane modified glass microspheres is preferably 1-10%, such as 1%, 2%, 4%, 6%, 8%, 10% or any value therebetween; the content of the manganese dioxide is preferably 0.01-0.5%, such as 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 0.10%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19%, 0.20%, 0.21%, 0.22%, 0.23%, 0.24%, 0.25%, 0.26%, 0.27%, 0.28%, 0.29%, 0.30%, 0.31%, 0.32%, 0.33%, 0.34%, 0.36%, 0.37%, 0.38%, 0.39%, 0.40%, 0.41%, 0.42%, 0.43%, 0. .5% or any value therebetween; the content of the amine curing agent is preferably 0.1-1%, such as 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1% or any value therebetween; the content of the first toughening agent is preferably 10-30%, such as 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30% or any value therebetween; the content of the first thixotropic agent is preferably 1-10%, such as 1%, 2%, 4%, 6%, 8%, 10% or any value therebetween; the content of the first pigment is preferably 0.1-1%, such as 0.1%, 0.2%, 0.4%, 0.6%, 0.8%, 1% or any value therebetween.

[0011] In the present invention, the B component contains epoxy resin, epoxysilane-modified glass microspheres, hydrogen peroxide and a free radical initiator, and optionally a second toughening agent, a second thixotropic agent and a second pigment. Wherein, based on the total weight of the B component, the content of the epoxy resin is preferably 30-60%, such as 30%, 35%, 40%, 45%, 50%, 55%, 60% or any value therebetween; the content of the epoxysilane-modified glass microspheres is preferably 1-10%, such as 1%, 2%, 4%, 6%, 8%, 10% or any value therebetween; the hydrogen peroxide is preferably used in the form of a hydrogen peroxide solution with a concentration of 5-35wt%, and the specific concentration of the hydrogen peroxide solution can be, for example, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60 ... t% or any value therebetween; the content of the free radical initiator is preferably 1-10%, such as 1%, 2%, 4%, 6%, 8%, 10% or any value therebetween; the content of the second toughening agent is preferably 10-30%, such as 10%, 15%, 20%, 25%, 30% or any value therebetween; the content of the second thixotropic agent is preferably 1-10%, such as 1%, 2%, 4%, 6%, 8%, 10% or any value therebetween; the content of the second pigment is preferably 0.1-1%, such as 0.1%, 0.2%, 0.4%, 0.6%, 0.8%1% or any value therebetween.

[0012] In the present invention, the acrylate monomer and polyurethane acrylate resin in component A undergo a polymerization reaction with the free radical initiator in component B, and the initial strength can reach above 10 MPa. After that, high-temperature curing causes the epoxy resin in component B to undergo a secondary reaction with the amine curing agent in component A, and the final strength can reach above 15 MPa.

[0013] In the present invention, the double bond silane modified glass microspheres can be various existing glass microspheres with double bond silanes on the surface, which can be obtained by commercial purchase or prepared according to various existing methods. Preferably, they are obtained by coupling double bond silanes with glass microspheres. Among them, the double bond silanes can be listed as at least one of 3-(methacryloyloxy)propyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane and vinylmethyldimethoxysilane. The mass ratio of the double bond silane to the glass microspheres is preferably (0.5-5):100, such as 0.5:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, 4.5:100, 5:100 or any value therebetween. The coupling reaction conditions preferably include a temperature of 110°C to 130°C, such as 110°C, 115°C, 120°C, 125°C, 130°C or any value therebetween; and a time of 1h to 5h, such as 1h, 2h, 3h, 4h, 5h or any value therebetween.

[0014] In the present invention, the epoxysilane-modified glass microspheres can be various existing glass microspheres with epoxysilane bonded to the surface, which can be commercially available or prepared according to various existing methods. Preferably, they are obtained by coupling epoxysilane with glass microspheres. The epoxysilane can be exemplified by at least one of 3-glycidyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidylpropyltriethoxysilane, 3-glycidylpropylmethyldiethoxysilane and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane. The mass ratio of the epoxy silane to the glass microspheres is preferably (0.5-5):100, such as 0.5:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, 4.5:100, 5:100 or any value therebetween. The conditions for the coupling reaction preferably include a temperature of 110°C to 130°C, such as 110°C, 115°C, 120°C, 125°C, 130°C or any value therebetween; and a time of 1h to 5h, such as 1h, 2h, 3h, 4h, 5h or any value therebetween.

[0015] In the present invention, the acrylic acid ester monomer can be an ester compound of various existing acrylic acid and its homologues, and specific examples thereof include but are not limited to at least one of methacrylic acid phosphate, acrylic acid ester monomer, methacrylic acid ester monomer, etc. Among them, the methacrylic acid phosphate can be listed as at least one of 2-hydroxyethyl methacrylic acid phosphate, 2-hydroxymethyl methacrylic acid phosphate or a mixture thereof with phosphoric acid. The acrylic acid ester monomer can be listed as at least one of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobornyl acrylate, etc. The methacrylic acid ester monomer can be listed as at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, etc. The acrylic acid ester monomer preferably contains methacrylic acid phosphate and acrylic acid ester monomer and / or methacrylic acid ester monomer at the same time. The mass ratio of the content of the methacrylic acid phosphate to the total content of the acrylate monomer and the methacrylic acid ester monomer is preferably (1-25):100, such as 1:100, 2:100, 5:100, 8:100, 10:100, 12:100, 15:100, 18:100, 20:100, 22:100, 25:100 or any value therebetween. The inventors of the present invention have found that by compounding the methacrylic acid phosphate with the acrylate monomer and / or the methacrylic acid ester monomer in a mass ratio of (1-25):100 as an acrylate monomer, the resulting adhesive has a more excellent bonding force.

[0016] In the present invention, the amine curing agent can be selected from at least one of aliphatic amines, aromatic amines, and alicyclic amines. Among them, the aliphatic amines can be exemplified by ethylenediamine and / or diethylenetriamine. The aromatic amines can be exemplified by m-phenylenediamine and / or p-phenylenediamine. The alicyclic amines can be exemplified by at least one of triethylenediamine, diethylenetriamine, and hexamethylenetetramine.

[0017] In the present invention, the free radical initiator can be an existing substance that can initiate the polymerization of unsaturated monomers, for example, it can be an azo initiator and / or a peroxide initiator. Wherein, specific examples of the azo initiator include, but are not limited to: at least one of dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azodicarbonamide, azobisisopropylimidazoline hydrochloride, azoisobutylcyanoformamide, azobiscyclohexylcarbonitrile, azobiscyanovaleric acid, azobisisopropylimidazoline, azobisisobutyronitrile, azobisisovaleronitrile and azobisisoheptylonitrile. Specific examples of the peroxide initiator include, but are not limited to: at least one of hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, benzoyl peroxide, diisopropyl peroxide and tert-butyl benzoyl peroxide.

[0018] In the present invention, the first toughening agent and the second toughening agent can be various existing substances that can increase the flexibility of the adhesive, without particular limitation. For example, they can be at least one of rubber toughening agents, thermoplastic elastomer toughening agents, low molecular weight polyamide toughening agents, etc. In a preferred embodiment, the first toughening agent is a rubber toughening agent, and the second toughening agent is a core-shell structured epoxy toughening agent. The rubber toughening agent used in component A is mainly acrylic monomers, which can dissolve the rubber toughening agent well and provide certain strength. The core-shell structured epoxy toughening agent used in component B can dissolve better in epoxy resin and does not require heating. Among them, the rubber toughening agent can be exemplified by at least one of liquid polysulfide rubber, liquid polybutadiene rubber, nitrile rubber, ethylene-propylene rubber, and styrene-butadiene rubber. The core-shell structured epoxy toughening agent is preferably selected from at least one of MX-150, MX-153, MX-154 of Nippon Kayaku Co., Ltd. and YT-3156 of Fujian Jinghan Co., Ltd.

[0019] In the present invention, the first thixotropic agent and the second thixotropic agent can be various existing substances that can endow the adhesive with thixotropic properties, and they can be independently selected from at least one of fumed silica, organic bentonite, hydrogenated castor oil, and polyamide wax, preferably fumed silica.

[0020] In the present invention, the first pigment and the second pigment can be various existing substances that can endow the adhesive with color, and they can be independently selected from at least one of carbon black, copper manganese black, iron chromium black, ultramarine blue, phthalocyanine blue, iron blue, permanent red, phthalocyanine green, and iron green.

[0021] In the present invention, the terms "first" and "second" are mainly used to distinguish the same material introduced at different positions for the convenience of description, without any other special meaning.

[0022] The preparation method of the two-component acrylic epoxy adhesive provided by the present invention includes: mixing the raw materials in component A evenly to obtain component A; mixing the raw materials in component B evenly to obtain component B.

[0023] The present invention has no particular limitation on the way of mixing the raw materials for preparing component A, and they can be mixed in any order. Preferably, the mixing is achieved in the following way: adding acrylate monomers and / or methacrylate monomers and optionally the first toughening agent into a double planetary hybrid reactor and stirring and mixing evenly, then adding polyurethane acrylate resin, amine curing agent, and manganese dioxide and stirring and mixing evenly, optionally adding the first pigment and stirring and mixing evenly, then adding the first thixotropic agent and stirring and mixing evenly, and then adding double bond silane-modified glass beads and methacrylic acid phosphate and stirring and mixing evenly to obtain component A.

[0024] The present invention has no particular limitation on the method for uniformly mixing the raw materials for preparing component B, and the raw materials can be mixed in any order, preferably in the following manner: adding the epoxy resin and the optional second toughening agent into a double planetary hybrid reactor and stirring evenly, optionally adding the second thixotropic agent and the second pigment and stirring evenly, then adding the free radical initiator and hydrogen peroxide and stirring evenly, and then adding the epoxy silane-modified glass microspheres and stirring evenly to obtain component B.

[0025] The invention also provides application of the two-component acrylic epoxy adhesive as automobile hemming adhesive.

[0026] The present invention will be described in detail below by way of examples. The examples of the embodiments are intended to explain the present invention and should not be construed as limiting the present invention. If no specific techniques or conditions are specified in the embodiments, the techniques or conditions described in the literature in this area or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0027] In the following examples and comparative examples, polyurethane acrylate resin was purchased from Changxing Company, Taiwan, China, with a brand name of DR-U299; SBS rubber toughener was purchased from Kraton, USA, with a brand name of D1153; SIS rubber toughener was purchased from Kraton, USA, with a brand name of D1113; core-shell epoxy toughener was purchased from Kaneka, Japan, with a brand name of MX-154; bisphenol A type epoxy resin was purchased from KUKDO, South Korea, with a brand name of YD-128, and an epoxy equivalent of 184-190 g / eq; bisphenol F type epoxy resin was purchased from Mitsubishi Chemical Corporation, with a brand name of 806, and an epoxy equivalent of 160 g / eq; epoxy resin (isosorbide diglycidyl ether) was purchased from DENACOL GSR-101 of Nagase ChemteX, Japan, with an epoxy equivalent of 129 g / eq; and fumed silica was AEROSIL R202 of Evonik.

[0028] Preparation Example 1

[0029] 0.5 g of 3-(methacryloyloxy)propyltrimethoxysilane and 100 g of 60-mesh glass microspheres were placed in a vacuum degassing mixer and dispersed at high speed for 5 minutes. The mixture was then removed and aged at 120° C. for 2 hours. After cooling, double-bond silane-modified glass microspheres were obtained, which were recorded as SW-1.

[0030] Preparation Example 2

[0031] 5 g of 3-(methacryloyloxy)propyltrimethoxysilane and 100 g of 60-mesh glass microspheres were placed in a vacuum degassing mixer and dispersed at high speed for 5 minutes. The mixture was then removed and aged at 120° C. for 2 hours. After cooling, double-bond silane-modified glass microspheres were obtained, which were recorded as SW-2.

[0032] Preparation Example 3

[0033] 0.5 g of 3-glycidyloxypropyltrimethoxysilane and 100 g of 60-mesh glass microspheres were placed in a vacuum degassing mixer and dispersed at high speed for 5 minutes, then removed and aged at 120° C. for 2 hours. After cooling, epoxy silane-modified glass microspheres were obtained, which were recorded as HW-1.

[0034] Preparation Example 4

[0035] 5 g of 3-glycidyloxypropyltrimethoxysilane and 100 g of 60-mesh glass microspheres were placed in a vacuum degassing mixer and dispersed at high speed for 5 minutes, then removed and aged at 120° C. for 2 hours. After cooling, epoxy silane-modified glass microspheres were obtained, which were recorded as HW-2.

[0036] Example 1 Two-component acrylic epoxy adhesive and preparation method thereof

[0037] The two-component acrylic epoxy adhesive provided in this embodiment includes component A and component B.

[0038] Preparation of component A: Add 40g of isobornyl methacrylate and 30g of rubber toughening agent into a double planetary hybrid reactor and stir to mix evenly, then add 10g of polyurethane acrylate resin, 0.2g of ethylenediamine and 0.05g of manganese dioxide and stir to mix evenly, then add 2g of fumed silica and stir to mix evenly, then add 7.75g of double bond silane-modified glass microspheres SW-1 and 10g of methyl methacrylate phosphate (KAYAMER PM-2 from Nippon Chemical Company) and stir to mix evenly to obtain component A.

[0039] Preparation of component B: Add 60g of bisphenol A epoxy resin and 10g of core-shell epoxy toughening agent into a double planetary hybrid reactor and stir evenly, add 9g of fumed silica and 1g of carbon black and stir evenly, then add 9g of benzoyl peroxide and 1g of hydrogen peroxide and stir evenly, then add 10g of epoxy silane-modified glass microspheres HW-1 and stir evenly to obtain component B.

[0040] Example 2 Two-component acrylic epoxy adhesive and preparation method thereof

[0041] The two-component acrylic epoxy adhesive provided in this embodiment includes component A and component B.

[0042] Preparation of component A: Add 60g of methyl methacrylate and 15g of rubber toughening agent into a double planetary hybrid reactor and stir to mix evenly, then add 10g of polyurethane acrylate resin, 0.8g of diethylenetriamine and 0.2g of manganese dioxide and stir to mix evenly, then add 1g of fumed silica and stir to mix evenly, then add 5g of double bond silane-modified glass microspheres SW-2 and 8g of methyl methacrylate phosphate (Harcryl 1228, Advanced Chemical Company, USA) and stir to mix evenly to obtain component A.

[0043] Preparation of component B: Add 36.5g of bisphenol F epoxy resin and 30g of core-shell epoxy toughening agent into a double planetary hybrid reactor and stir evenly, add 10g of fumed silica and 0.5g of carbon black and stir evenly, then add 10g of benzoyl peroxide and 5g of hydrogen peroxide and stir evenly, then add 8g of epoxy silane-modified glass microspheres HW-2 and stir evenly to obtain component B.

[0044] Example 3 Two-component acrylic epoxy adhesive and preparation method thereof

[0045] The two-component acrylic epoxy adhesive provided in this embodiment includes component A and component B.

[0046] Preparation of component A: Add 50g of methacrylic acid and 10g of rubber toughening agent into a double planetary hybrid reactor and stir to mix evenly, then add 30g of polyurethane acrylate resin, 0.5g of triethylenediamine and 0.5g of manganese dioxide and stir to mix evenly, then add 6g of fumed silica and stir to mix evenly, then add 2g of double bond silane-modified glass microspheres SW-1 and 1g of methacrylate phosphate (Harcryl 1228M, Advanced Chemical Company, USA) and stir to mix evenly to obtain component A.

[0047] Preparation of component B: Add 40g of isosorbide diglycidyl ether and 28g of core-shell structure epoxy toughening agent into a double planetary hybrid reactor and stir evenly, add 8g of fumed silica and 0.1g of carbon black and stir evenly, then add 3.9g of benzoyl peroxide and 10g of hydrogen peroxide and stir evenly, then add 10g of epoxy silane-modified glass microspheres HW-2 and stir evenly to obtain component B.

[0048] Example 4 Two-component acrylic epoxy adhesive and preparation method thereof

[0049] The two-component acrylic epoxy adhesive provided in this embodiment includes component A and component B.

[0050] Preparation of component A: Add 50g of tetrahydrofurfuryl methacrylate, 10g of isobornyl acrylate and 15g of rubber toughening agent into a double planetary hybrid reactor and stir to mix evenly, then add 10g of polyurethane acrylate resin, 0.8g of diethylenetriamine and 0.2g of manganese dioxide and stir to mix evenly, then add 1g of fumed silica and stir to mix evenly, then add 5g of double bond silane-modified glass microspheres SW-2 and 8g of methyl methacrylate phosphate (Harcryl1228M, Advanced Chemical Company, USA) and stir to mix evenly to obtain component A.

[0051] Preparation of component B: Add 36.5g of bisphenol A epoxy resin and 30g of core-shell epoxy toughening agent into a double planetary hybrid reactor and stir evenly, add 10g of fumed silica and 0.5g of carbon black and stir evenly, then add 10g of benzoyl peroxide and 5g of hydrogen peroxide and stir evenly, then add 8g of epoxy silane-modified glass microspheres HW-2 and stir evenly to obtain component B.

[0052] Example 5 Two-component acrylic epoxy adhesive and preparation method thereof

[0053] A two-component acrylic epoxy adhesive was prepared according to the method of Example 1, except that methacrylate phosphate was replaced by isobornyl methacrylate in the same weight portion, and the other conditions were the same as in Example 1 to obtain a two-component acrylic epoxy adhesive.

[0054] Comparative Example 1

[0055] A two-component acrylic epoxy adhesive was prepared according to the method of Example 1, except that the manganese dioxide in component A was replaced by titanium dioxide in the same weight portion, and the other conditions were the same as in Example 1 to obtain a reference two-component acrylic epoxy adhesive.

[0056] Comparative Example 2

[0057] A two-component acrylic epoxy adhesive was prepared according to the method of Example 1, except that no manganese dioxide was added to component A and no hydrogen peroxide was added to component B. The other conditions were the same as in Example 1, to obtain a reference two-component acrylic epoxy adhesive.

[0058] Comparative Example 3

[0059] A two-component acrylic epoxy adhesive was prepared according to the method of Example 1, except that the double-bond silane-modified glass microspheres SW-1 in component A were replaced by the same weight of unmodified glass microspheres, and the epoxy silane-modified glass microspheres HW-1 in component B were replaced by the same weight of unmodified glass microspheres, and the other conditions were the same as in Example 1 to obtain a reference two-component acrylic epoxy adhesive.

[0060] Test Case

[0061] (1) Peel strength test: According to ASTM D1876, the A component and the B component of the two-component acrylic epoxy adhesive obtained in each embodiment and comparative example were mixed evenly at a volume ratio of 4:1 and then applied to the substrate (aluminum plate). The two substrates were bonded to an area of ​​25×229×(0.25±0.3) mm. The adhesive was placed at room temperature for 1 hour, then heated and cured at 170°C for 20 minutes, and then taken out and cooled to obtain a sample. The obtained sample was tested for 180° peel strength using a tensile testing machine at a tensile rate of 200 mm / min. The results are shown in Table 1.

[0062] (2) Shear force test: According to ASTM D1002, component A and component B of the two-component acrylic epoxy adhesive obtained in each example and comparative example were mixed evenly at a volume ratio of 4:1 and then applied to the substrate (aluminum plate). The two substrates were bonded to a bonding area of ​​25.4×12.7×(0.25±0.3) mm. The adhesive was placed at room temperature for 1 hour, then heated and cured at 170°C for 20 minutes, and then taken out and cooled to obtain a sample. The obtained sample was tested for shear force using a tensile testing machine at a tensile rate of 10 mm / min. The results are shown in Table 1.

[0063] Table 1

[0064] project Peel force (N / mm) Destruction form Shear force (MPa) Destruction form Example 1 6.9 CF 18.8 CF Example 2 6.3 CF 18.2 CF Example 3 6.2 CF 19.3 CF Example 4 6.2 CF 19.1 CF Example 5 4.9 Partial CF 14.3 Partial CF Comparative Example 1 6.8 AF 18.9 AF Comparative Example 2 7.2 AF 19.5 AF Comparative Example 3 4.4 AF 14.2 AF

[0065] Note: CF is cohesive failure and AF is interfacial failure.

[0066] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and intent of the present invention.

Claims

1. A two-component acrylic epoxy adhesive, characterized in that: The two-component acrylic epoxy adhesive comprises a component A and a component B, wherein the component A contains an acrylate monomer, a polyurethane acrylate resin, double-bond silane-modified glass microspheres, manganese dioxide and an amine curing agent, and optionally a first toughening agent, a first thixotropic agent and a first pigment, and the component B contains an epoxy resin, epoxysilane-modified glass microspheres, hydrogen peroxide and a free radical initiator, and optionally a second toughening agent, a second thixotropic agent and a second pigment.

2. The two-component acrylic epoxy adhesive according to claim 1, characterized in that: Based on the total weight of the component A, the content of the acrylate monomer is 40-70%, the content of the polyurethane acrylate resin is 10-30%, the content of the double-bond silane-modified glass microspheres is 1-10%, the content of the manganese dioxide is 0.01-0.5%, the content of the amine curing agent is 0.1-1%, the content of the first toughening agent is 10-30%, the content of the first thixotropic agent is 1-10%, and the content of the first pigment is 0.1-1%.

3. The two-component acrylic epoxy adhesive according to claim 1, characterized in that: Based on the total weight of the B component, the content of the epoxy resin is 30-60%, the content of the epoxysilane-modified glass microspheres is 1-10%, the content of the hydrogen peroxide is 1-10%, the content of the free radical initiator is 1-10%, the content of the second toughening agent is 10-30%, the content of the second thixotropic agent is 1-10%, and the content of the second pigment is 0.1-1%.

4. The two-component acrylic epoxy adhesive according to claim 1, characterized in that: The volume ratio of component A to component B is (3-5):

1.

5. The two-component acrylic epoxy adhesive according to claim 1, characterized in that: The double-bond silane-modified glass microspheres are obtained by coupling double-bond silane with glass microspheres; Preferably, the double bond silane is selected from at least one of 3-(methacryloyloxy)propyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane and vinylmethyldimethoxysilane; The mass ratio of the double bond silane to the glass microspheres is (0.5-5):100; The coupling reaction conditions include a temperature of 110° C. to 130° C. and a time of 1 h to 5 h.

6. The two-component acrylic epoxy adhesive according to claim 1, characterized in that: The epoxysilane-modified glass microspheres are obtained by coupling epoxysilane with glass microspheres; Preferably, the epoxysilane is selected from at least one of 3-glycidyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidylpropyltriethoxysilane, 3-glycidylpropylmethyldiethoxysilane and β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; The mass ratio of the epoxy silane to the glass microspheres is (0.5-5):100; The coupling reaction conditions include a temperature of 110° C. to 130° C. and a time of 1 h to 5 h.

7. The two-component acrylic epoxy adhesive according to claim 1, characterized in that: The acrylic acid ester monomers contain methacrylic acid phosphate and acrylic acid ester monomers and / or methacrylic acid ester monomers; Preferably, the mass ratio of the content of the methacrylic acid phosphate to the total content of the acrylate monomer and the methacrylate monomer is (1-25):

100.

8. The two-component acrylic epoxy adhesive according to claim 1, characterized in that: The first toughening agent is a rubber toughening agent, and the second toughening agent is a core-shell structure epoxy toughening agent; The first thixotropic agent and the second thixotropic agent are both fumed silica; The first pigment and the second pigment are each independently at least one of carbon black, copper manganese black, iron chrome black, ultramarine, phthalocyanine blue, iron blue, permanent red, phthalocyanine green and iron green.

9. The method for preparing the two-component acrylic epoxy adhesive according to any one of claims 1 to 8, characterized in that: The method comprises: uniformly mixing various raw materials in component A to obtain component A; and uniformly mixing various raw materials in component B to obtain component B.

10. Use of the two-component acrylic epoxy adhesive according to any one of claims 1 to 8 as an automobile hem adhesive.