High-toughness high-adhesion epoxy resin adhesive and preparation method thereof

Abstract

The invention discloses a high-toughness and high-adhesion epoxy resin adhesive and a preparation method thereof, and relates to an epoxy resin adhesive and a preparation method thereof. The invention aims to solve the problems of high brittleness, low adhesion to metal materials such as steel, titanium alloy and nickel alloy and poor strength of the existing epoxy adhesive. The high-toughness and high-adhesion epoxy resin adhesive comprises a component A and a component B, the component A comprises the following components in parts by mass: epoxy resin, phosphate acrylate oligomer toughened epoxy resin, core-shell particle toughened epoxy resin and epoxy phosphate; and the component B comprises the following components in parts by mass: a polyamide curing agent, an alicyclic amine curing agent and a phosphate esterification curing agent. According to the invention, the phosphate esterification acrylate oligomer toughened epoxy resin and the core-shell particle type toughening agent are used for synergistic toughening, so that the toughness of the epoxy adhesive is greatly improved; the adhesive force of the epoxy adhesive to various metal materials is improved, and the high-toughness and high-adhesive-force epoxy resin adhesive is prepared.

Description

Technical Field

[0001] The present invention relates to an epoxy resin adhesive and a preparation method thereof. Background Art

[0002] Epoxy resin is a thermosetting polymer material, which is widely used in the fields of electronics, coatings, automobiles, aerospace, etc. due to its advantages such as low price, chemical corrosion resistance, and good mechanical strength. Since epoxy resin has a high crosslinking density after curing, it has brittleness, which limits its application in high-tech fields such as composite materials, electronics and electrical appliances. In addition, the bonding effect of epoxy resin on some low surface energy metals such as steel, titanium alloy, and nickel alloy is not good. To improve the bonding performance of epoxy resin to these special metals, special treatment of the metal surface is often required. Common methods include phosphoric acid anodization, chromic acid anodization, etc., to improve the interfacial bonding condition between epoxy resin and metal, thereby improving the bonding effect, but at the same time increasing the complexity and cost of the process. Although these treatment methods can increase the surface roughness of the metal by using the principle of chemical etching, thereby improving the bonding strength, however, along with the dissolution phenomenon of the metal during the chemical etching process and the continuous increase of the surface roughness, the fatigue strength of the metal is reduced. More critically, in the actual application process of these traditional chemical treatment methods, a series of intractable environmental problems are derived, such as the proper treatment of toxic chemicals and the effective treatment of a large amount of wastewater.

[0003] Patent CN117659918A prepared a moisture and heat resistant epoxy reinforcing adhesive by reacting epoxy resin with phosphoric anhydride to obtain phosphate / epoxy resin, and used liquid nitrile rubber toughener to toughen epoxy resin. The toughening means is single and fails to toughen epoxy resin from multiple angles; Patent CN 118879250 B prepared an adhesive for aramid paper and PI film composite materials by using a mixed solution of bisphenol A epoxy resin and a polymer hydroxyacrylic resin modified with a phosphate monomer and a liquid anhydride. Although the adhesion was increased by the phosphate, the toughness of the epoxy resin was not increased, and the peel strength of the prepared adhesive was low; In Patent CN119773278A, the metal needs to be treated by plasma electrolytic oxidation before the resin is bonded to the metal. The process is complex and the electrolyte used poses a threat to the environment. Patent CN103980847A provides a preparation method and use of a self-curing polyacrylate-epoxy resin adhesive, but the shear and peel strength of the prepared product is low. None of the above patents have carried out bonding tests on difficult-to-bond metals such as steel, titanium, and nickel, and it is impossible to show whether the bonding to these metals can be improved. Summary of the Invention

[0004] The object of the present invention is to solve the problems of large brittleness of existing epoxy adhesives and low adhesive force and poor strength in bonding metal materials such as steel, titanium alloy, and nickel alloy, and to provide a high-toughness and high-adhesion epoxy resin adhesive and its preparation method.

[0005] A high-toughness and high-adhesion epoxy resin adhesive comprises a component A and a component B;

[0006] The component A comprises, by mass parts: 50 parts to 100 parts of epoxy resin, 30 parts to 60 parts of phosphoric acid esterified acrylate oligomer toughened epoxy resin, 10 parts to 30 parts of core-shell particle toughened epoxy resin, and 1 part to 3 parts of epoxy phosphate;

[0007] The component B comprises, by mass parts: 10 parts to 30 parts of polyamide curing agent, 5 parts to 15 parts of alicyclic amine curing agent, and 10 parts to 20 parts of phosphoric acid esterified curing agent.

[0008] A preparation method of a high-toughness and high-adhesion epoxy resin adhesive is specifically completed according to the following steps:

[0009] 1. Weigh 50 parts to 100 parts of epoxy resin, 30 parts to 60 parts of phosphoric acid esterified acrylate oligomer toughened epoxy resin, 10 parts to 30 parts of core-shell particle toughened epoxy resin, 1 part to 3 parts of epoxy phosphate, 10 parts to 30 parts of polyamide curing agent, 5 parts to 15 parts of alicyclic amine curing agent, and 10 parts to 20 parts of phosphoric acid esterified curing agent by mass parts;

[0010] 2. Stir and mix evenly 50 parts to 100 parts of epoxy resin, 30 parts to 60 parts of phosphoric acid esterified acrylate oligomer toughened epoxy resin, 10 parts to 30 parts of core-shell particle toughened epoxy resin, and 1 part to 3 parts of epoxy phosphate at room temperature to obtain the component A;

[0011] 3. Stir and mix evenly 10 parts to 30 parts of polyamide curing agent, 5 parts to 15 parts of alicyclic amine curing agent, and 10 parts to 20 parts of phosphoric acid esterified curing agent at room temperature to obtain the component B;

[0012] 4. Stir and mix evenly the component A obtained in step 2 and the component B obtained in step 3 at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive.

[0013] The principle of the present invention:

[0014] Phosphate compounds can chelate with metals to form complexes and improve the adhesive's bonding properties to metals. Phosphate compounds are often added to epoxy adhesives in small amounts in the form of additives. The addition has limited effect on the improvement of the bonding properties, and excessive addition will affect other properties of the adhesive. The present invention introduces phosphate substances from three perspectives: toughening agent, curing agent, and additive, including: (1) using conventional soft and hard acrylate monomers as the basic raw materials and acrylate phosphate esters as functional monomers, a phosphated acrylate oligomer toughened epoxy resin is prepared by a synthetic reaction; (2) utilizing the characteristic that epoxy phosphates can react with amine compounds, the epoxy phosphates are used to modify epoxy curing agents to prepare phosphated curing agents; (3) adding a certain amount of epoxy phosphates as an additive in the form of direct addition. Under the premise of increasing the content of phosphate substances in the adhesive, the other properties of the adhesive are not affected while greatly improving the bonding strength to difficult-to-bond metals. The present invention also adds core-shell particles in the preparation process of the epoxy resin adhesive, which synergistically toughens the epoxy resin toughened by the phosphated acrylate oligomer, improves the toughness of the adhesive, and finally prepares an epoxy resin adhesive with high toughness and high adhesion.

[0015] Compared with the prior art, the present invention has the following advantages:

[0016] 1. The present invention utilizes the characteristics that phosphate ester can chelate with metal to form complexes and improve the bonding performance of adhesives to difficult-to-bond metals. Phosphate ester substances are introduced from three perspectives: toughening agent, curing agent and auxiliary agent. More phosphate ester groups are introduced into the adhesive system, which effectively improves the bonding strength of the adhesive to the metal.

[0017] 2. The epoxy resin is toughened by using core-shell particles and phosphated acrylate oligomers. The core-shell toughening agent is generally composed of a soft core and a hard shell. The shell structure has good compatibility with the epoxy resin matrix while dispersing and protecting the core material. The core structure plays a key role in inducing shear deformation of the polymer matrix when it is stressed, thereby absorbing impact energy and improving toughness. The synthetic phosphated acrylate oligomer toughened epoxy resin will form shear yield in the deformable area, concentrating the stress on the matrix around it. Under the action of external stress, many deformation zones will appear, thus producing a toughening effect. This synergistic toughening mechanism can significantly improve the toughness of epoxy resin compared to the single toughening using core-shell particles or rubber-type toughening agents.

[0018] 3. During the synthesis of the toughened epoxy resin with phosphoric acid esterified acrylate oligomer, a reinforcing agent is used. The reinforcing agent contains two double bonds and has a certain internal cross-linking function, which can increase the strength and toughness of the toughening agent, and the toughening effect of the toughening agent is also enhanced. The reinforcing agent also contains epoxy groups, which can improve the compatibility with epoxy resin. This characteristic enables the phosphoric acid esterified acrylate oligomer to be evenly dispersed in the epoxy resin matrix and participate in the curing reaction during the curing process, further enhancing the toughening effect.

[0019] 4. The toughened epoxy resin with phosphoric acid esterified acrylate oligomer is prepared by a one-step method without using organic solvents. On the one hand, it eliminates the emission of volatile organic compounds and avoids environmental pollution. On the other hand, it reduces the post-treatment steps such as solvent evaporation, simplifies the synthesis process, and has a lower cost. This sustainable development concept that combines environmental benefits and economic benefits meets the requirements of green development. Specific Embodiments

[0020] The following describes the specific embodiments of the present invention in detail, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments.

[0021] Specific Embodiment 1: This embodiment is a preparation method of a high-toughness and high-adhesion epoxy resin adhesive, which is specifically completed according to the following steps:

[0022] I. Weigh 50 to 100 parts by mass of epoxy resin, 30 to 60 parts by mass of toughened epoxy resin with phosphoric acid esterified acrylate oligomer, 10 to 30 parts by mass of core-shell particle toughened epoxy resin, 1 to 3 parts by mass of epoxy phosphate, 10 to 30 parts by mass of polyamide curing agent, 5 to 15 parts by mass of alicyclic amine curing agent, and 10 to 20 parts by mass of phosphoric acid esterified curing agent;

[0023] II. Stir and mix evenly 50 to 100 parts by mass of epoxy resin, 30 to 60 parts by mass of toughened epoxy resin with phosphoric acid esterified acrylate oligomer, 10 to 30 parts by mass of core-shell particle toughened epoxy resin, and 1 to 3 parts by mass of epoxy phosphate at room temperature to obtain Component A;

[0024] III. Stir and mix evenly 10 to 30 parts by mass of polyamide curing agent, 5 to 15 parts by mass of alicyclic amine curing agent, and 10 to 20 parts by mass of phosphoric acid esterified curing agent at room temperature to obtain Component B;

[0025] IV. Stir and mix the component A obtained in Step 2 and the component B obtained in Step 3 evenly at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive. Specific Embodiment 2: The difference between this embodiment and Specific Embodiment 1 is that the epoxy resin is one or more of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic epoxy resin, biphenyl epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, and aliphatic epoxy resin. Other steps are the same as those in Specific Embodiment 1.

[0026] Specific Embodiment 3: The difference between this embodiment and one of Specific Embodiments 1 or 2 is that the phosphoric acid esterified acrylate oligomer toughened epoxy resin is prepared from 50 parts to 70 parts of acrylate soft monomers, 10 parts to 20 parts of acrylate hard monomers, 2 parts to 5 parts of acrylate phosphate, 3 parts to 5 parts of reactive enhancer, 1 part to 3 parts of initiator, and 65 parts to 100 parts of liquid epoxy resin; the preparation method is: mix 50 parts to 70 parts of acrylate soft monomers, 10 parts to 20 parts of acrylate hard monomers, 2 parts to 5 parts of acrylate phosphate, 3 parts to 5 parts of reactive enhancer, 1 part to 3 parts of initiator, and 65 parts to 100 parts of liquid epoxy resin evenly, and carry out a stirring reaction for 2 h to 4 h under the conditions of 80 °C to 100 °C and a stirring speed of 200 r / min to 500 r / min. Other steps are the same as those in Specific Embodiment 1 or 2.

[0027] Specific Embodiment 4: The difference between this embodiment and one of Specific Embodiments 1 to 3 is that the acrylate soft monomer is one or more of butyl acrylate, isooctyl acrylate, ethyl acrylate, and n-octyl acrylate; the acrylate hard monomer is one or more of methyl methacrylate, styrene, vinyl acetate, ethyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, acrylonitrile, glycidyl methacrylate, glycidyl acrylate, acrylic acid, and methacrylic acid. Other steps are the same as those in Specific Embodiments 1 to 3.

[0028] Specific Embodiment 5: The difference between this embodiment and one of Specific Embodiments 1 to 4 is that the acrylate phosphate is one or more of 2-hydroxyethyl methacrylate phosphate, acidic polyfunctional acrylate phosphate, and alkyl acrylate phosphate; the reactive enhancer is diallyl bisphenol A diglycidyl ether; the initiator is benzoyl peroxide or azobisisobutyronitrile; the liquid epoxy resin is one or more of E51, E44, and E54. Other steps are the same as those in Specific Embodiments 1 to 4.

[0029] Embodiment Six: The difference between this embodiment and any one of Embodiments One to Five is that the core-shell particle toughened epoxy resin is one or more of MX125, MX153, MX154, and MX257; the epoxy phosphate is one or more of LY-73, LY-75, YM-1007, 801, VOK-903, and LRD-4A. Other steps are the same as those in Embodiments One to Five.

[0030] MX125, MX153, MX154, and MX257 described in this embodiment are purchased from Shanghai Kayin Chemical Co., Ltd.

[0031] LY-73, LY-75, and YM-1007 described in this embodiment are purchased from Jining Fangyu Chemical Co., Ltd.; 801 is purchased from Qingdao Shengshi New Materials Co., Ltd.; VOK-903 is purchased from Guangzhou Situlong Chemical Co., Ltd.; LRD-4A is purchased from Nanxiong Santuo Chemical Industry Co., Ltd.

[0032] Embodiment Seven: The difference between this embodiment and any one of Embodiments One to Six is that the polyamide curing agent is one or more of V115, V125, V140, 200#, and 300#; the alicyclic amine curing agent is one or more of isophorone diamine, 4,4'-diaminodicyclohexylmethane, dicyclohexylamine, and 3,3'-dimethyl-4,4'-diaminomethylcyclohexylmethane. Other steps are the same as those in Embodiments One to Six.

[0033] V115, V125, and V140 described in this embodiment are purchased from Jining Tangyi Chemical Co., Ltd.; 200# and 300# are purchased from Suzhou Hengsite Industry Co., Ltd.

[0034] Embodiment Eight: The difference between this embodiment and any one of Embodiments One to Seven is that the phosphoric acid esterified curing agent is prepared from 20 parts to 40 parts of fatty amine and 2 parts to 10 parts of epoxy phosphate; the preparation method is: mixing 20 parts to 40 parts of fatty amine and 2 parts to 10 parts of epoxy phosphate evenly, and stirring and reacting at 80°C to 120°C and a stirring speed of 200 r / min to 500 r / min for 3 h to 6 h. Other steps are the same as those in Embodiments One to Seven.

[0035] Embodiment 9: The difference between this embodiment and any one of Embodiments 1 to 8 is that the fatty amine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, and hexamethylenediamine; the epoxy phosphate ester is one of LY-73, LY-75, YM-1007, 801, VOK-903, or LRD-4A. Other steps are the same as those in Embodiments 1 to 8.

[0036] In this embodiment, LY-73, LY-75, and YM-1007 were purchased from Jining Fangyu Chemical Co., Ltd.; 801 was purchased from Qingdao Shengshi New Materials Co., Ltd.; VOK-903 was purchased from Guangzhou Situlong Chemical Co., Ltd.; and LRD-4A was purchased from Nanhong Santuo Chemical Industry Co., Ltd.

[0037] The following examples are used to verify the beneficial effects of the present invention:

[0038] Example 1: A high-toughness and high-adhesion epoxy resin adhesive, including component A and component B, and the preparation method is specifically completed according to the following steps:

[0039] I. Preparation of phosphoric acid esterified acrylate oligomer toughened epoxy resin:

[0040] ①. Weigh 50 parts of butyl acrylate, 10 parts of acrylonitrile, 2 parts of 2-hydroxyethyl methacrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of dibenzoyl peroxide, and 65 parts of liquid epoxy resin E51 by weight;

[0041] ②. Mix the weighed 50 parts of butyl acrylate, 10 parts of acrylonitrile, 2 parts of 2-hydroxyethyl methacrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of dibenzoyl peroxide, and 65 parts of liquid epoxy resin E51 evenly, and stir and react at 80°C and a stirring speed of 200 r / min for 2 h to obtain phosphoric acid esterified acrylate oligomer toughened epoxy resin;

[0042] II. Preparation of phosphoric acid esterified curing agent:

[0043] ①. Weigh 20 parts of ethylenediamine and 2 parts of 801 epoxy phosphate ester by weight;

[0044] ②. Mix the weighed 20 parts of ethylenediamine and 2 parts of 801 epoxy phosphate ester evenly, and stir and react at 80°C and a stirring speed of 200 r / min for 3 h to obtain a phosphoric acid esterified curing agent;

[0045] III. Preparation of high-toughness and high-adhesion epoxy resin adhesive:

[0046] ①. Weigh 80 parts by mass of E51 epoxy resin, 30 parts of toughened epoxy resin with phosphoric acid esterified acrylate oligomer, 10 parts of toughened epoxy resin with MX154 core-shell particles, 1 part of 801 epoxy phosphate, 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane and 10 parts of phosphoric acid esterified curing agent;

[0047] ②. Stir and mix evenly the weighed 80 parts of E51 epoxy resin, 30 parts of toughened epoxy resin with phosphoric acid esterified acrylate oligomer, 10 parts of toughened epoxy resin with MX154 core-shell particles and 1 part of 801 epoxy phosphate at room temperature to obtain Component A;

[0048] ③. Stir and mix evenly the weighed 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane and 10 parts of phosphoric acid esterified curing agent at room temperature to obtain Component B;

[0049] ④. Stir and mix evenly Component A obtained in step ② and Component B obtained in step ③ at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive.

[0050] The 801 epoxy phosphate described in Example 1 was purchased from Qingdao Shengshi New Materials Co., Ltd.;

[0051] The toughened epoxy resin with MX154 core-shell particles described in Example 1 was purchased from Shanghai Kayin Chemical Co., Ltd.;

[0052] The V140 polyamide curing agent described in Example 1 was purchased from Jining Tangyi Chemical Co., Ltd.

[0053] Example 2: A high-toughness and high-adhesion epoxy resin adhesive, including Component A and Component B, and the preparation method is specifically completed according to the following steps:

[0054] I. Preparation of toughened epoxy resin with phosphoric acid esterified acrylate oligomer:

[0055] ①. Weigh 60 parts by weight of n-octyl acrylate, 15 parts of isobutyl methacrylate, 2 parts of alkyl acrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 2 parts of dibenzoyl peroxide and 80 parts of liquid epoxy resin E54;

[0056] ②. Mix evenly the weighed 60 parts of n-octyl acrylate, 15 parts of isobutyl methacrylate, 2 parts of alkyl acrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 2 parts of dibenzoyl peroxide and 80 parts of liquid epoxy resin E54, and stir and react at 80 °C and a stirring speed of 200 r / min for 2 h to obtain toughened epoxy resin with phosphoric acid esterified acrylate oligomer;

[0057] II. Preparation of phosphoric acid esterified curing agent:

[0058] ①. Weigh 30 parts of tetraethylenepentamine and 5 parts of VOK-903 epoxy phosphate by weight;

[0059] ②. Mix the weighed 30 parts of tetraethylenepentamine and 5 parts of VOK-903 epoxy phosphate evenly, and stir and react at 80 °C and a stirring speed of 200 r / min for 3 h to obtain a phosphoric acid esterified curing agent;

[0060] III. Preparation of a high-toughness and high-adhesion epoxy resin adhesive:

[0061] ①. Weigh 90 parts of E54 epoxy resin, 40 parts of phosphoric acid esterified acrylate oligomer toughened epoxy resin, 15 parts of MX125 core-shell particle toughened epoxy resin, 1 part of VOK-903 epoxy phosphate, 15 parts of V115 polyamide curing agent, 10 parts of isophorone diamine curing agent and 10 parts of phosphoric acid esterified curing agent by mass;

[0062] ②. Mix the weighed 90 parts of E54 epoxy resin, 40 parts of phosphoric acid esterified acrylate oligomer toughened epoxy resin, 15 parts of MX125 core-shell particle toughened epoxy resin, and 1 part of VOK-903 epoxy phosphate evenly by stirring at room temperature to obtain Component A;

[0063] ③. Mix the weighed 15 parts of V115 polyamide curing agent, 10 parts of isophorone diamine curing agent and 10 parts of phosphoric acid esterified curing agent evenly by stirring at room temperature to obtain Component B;

[0064] ④. Mix Component A obtained in step ② and Component B obtained in step ③ evenly by stirring at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive.

[0065] The VOK-903 epoxy phosphate described in Example 2 was purchased from Guangzhou Situlong Chemical Co., Ltd.;

[0066] The MX125 core-shell particle toughened epoxy resin described in Example 2 was purchased from Shanghai Kayin Chemical Co., Ltd.;

[0067] The V115 polyamide curing agent described in Example 2 was purchased from Jining Tangyi Chemical Co., Ltd.

[0068] Example 3: A high-toughness and high-adhesion epoxy resin adhesive, including Component A and Component B, and the preparation method is specifically completed according to the following steps:

[0069] I. Preparation of phosphoric acid esterified acrylate oligomer toughened epoxy resin:

[0070] ①. Weigh 70 parts by weight of isooctyl acrylate, 20 parts of glycidyl acrylate, 2 parts of acidic polyfunctional acrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 2 parts of dibenzoyl peroxide, and 80 parts of liquid epoxy resin E44;

[0071] ②. Mix the weighed 70 parts of isooctyl acrylate, 20 parts of glycidyl acrylate, 2 parts of acidic polyfunctional acrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 2 parts of dibenzoyl peroxide, and 80 parts of liquid epoxy resin E44 evenly, and stir and react at 80 °C and a stirring speed of 200 r / min for 2 h to obtain a phosphate - esterified acrylate oligomer toughened epoxy resin;

[0072] II. Preparation of phosphate - esterified curing agent:

[0073] ①. Weigh 40 parts by weight of hexamethylenediamine and 5 parts of VOK - 903 epoxy phosphate;

[0074] ②. Mix the weighed 40 parts of hexamethylenediamine and 5 parts of VOK - 903 epoxy phosphate evenly, and stir and react at 80 °C and a stirring speed of 200 r / min for 3 h to obtain a phosphate - esterified curing agent;

[0075] III. Preparation of high - toughness and high - adhesion epoxy resin adhesive:

[0076] ①. Weigh 100 parts by mass of E44 epoxy resin, 40 parts of phosphate - esterified acrylate oligomer toughened epoxy resin, 20 parts of MX153 core - shell particle toughened epoxy resin, 1 part of VOK - 903 epoxy phosphate, 20 parts of V115 polyamide curing agent, 15 parts of 4,4’ - diaminodicyclohexylmethane curing agent, and 15 parts of phosphate - esterified curing agent;

[0077] ②. Mix the weighed 100 parts of E44 epoxy resin, 40 parts of phosphate - esterified acrylate oligomer toughened epoxy resin, 20 parts of MX153 core - shell particle toughened epoxy resin, and 1 part of VOK - 903 epoxy phosphate evenly by stirring at room temperature to obtain component A;

[0078] ③. Mix the weighed 20 parts of V115 polyamide curing agent, 15 parts of 4,4’ - diaminodicyclohexylmethane curing agent, and 15 parts of phosphate - esterified curing agent evenly by stirring at room temperature to obtain component B;

[0079] ④. Mix the component A obtained in step ② and the component B obtained in step ③ evenly by stirring at room temperature to obtain a high - toughness and high - adhesion epoxy resin adhesive.

[0080] The VOK - 903 epoxy phosphate described in Example 3 was purchased from Guangzhou Situlong Chemical Co., Ltd.

[0081] The MX153 core-shell particle toughened epoxy resin described in Example 3 was purchased from Shanghai Kayin Chemical Co., Ltd.

[0082] The V115 polyamide curing agent described in Example 3 was purchased from Jining Tangyi Chemical Co., Ltd.

[0083] The model of the acidic polyfunctional acrylate phosphate described in Example 3 is PM3060, which was purchased from Guangzhou Jingde Chemical Materials Co., Ltd.

[0084] Comparative Example 1: In Step 1, prepare an unphosphorylated acrylate oligomer toughened epoxy resin, that is, do not add 2-hydroxyethyl methacrylate phosphate; omit the use of 1 part of 801 epoxy phosphate in Component A; use unphosphorylated ethylenediamine in Component B; the preparation method is as follows:

[0085] I. Prepare an unphosphorylated acrylate oligomer toughened epoxy resin:

[0086] ①. Weigh 50 parts of butyl acrylate, 10 parts of acrylonitrile, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of dibenzoyl peroxide, and 65 parts of liquid epoxy resin E51 by weight.

[0087] ②. Mix the weighed 50 parts of butyl acrylate, 10 parts of acrylonitrile, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of dibenzoyl peroxide, and 65 parts of liquid epoxy resin E51 evenly, and stir and react at 80 °C and a stirring speed of 200 r / min for 2 h to obtain an unphosphorylated acrylate oligomer toughened epoxy resin.

[0088] II. Prepare a high-toughness and high-adhesion epoxy resin adhesive:

[0089] ①. Weigh 80 parts of E51 epoxy resin, 30 parts of unphosphorylated acrylate oligomer toughened epoxy resin, 10 parts of MX154 core-shell particle toughened epoxy resin, 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of ethylenediamine by mass.

[0090] ②. Mix the weighed 80 parts of E51 epoxy resin, 30 parts of unphosphorylated acrylate oligomer toughened epoxy resin, and 10 parts of MX154 core-shell particle toughened epoxy resin evenly by stirring at room temperature to obtain Component A.

[0091] ③. Mix the weighed 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of ethylenediamine evenly by stirring at room temperature to obtain Component B.

[0092] ④. Mix the Component A obtained in Step ② and the Component B obtained in Step ③ evenly by stirring at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive.

[0093] Comparative Example 2: The difference between this example and Example 1 is as follows: In Step 1 for preparing the unphosphorylated acrylate oligomer toughened epoxy resin, 2-hydroxyethyl methacrylate phosphate is not added; in Component B, unphosphorylated ethylenediamine is used. The preparation method is as follows:

[0094] I. Preparation of unphosphorylated acrylate oligomer toughened epoxy resin:

[0095] ① Weigh 50 parts by weight of butyl acrylate, 10 parts of acrylonitrile, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of dibenzoyl peroxide, and 65 parts of liquid epoxy resin E51.

[0096] ② Mix the weighed 50 parts of butyl acrylate, 10 parts of acrylonitrile, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of dibenzoyl peroxide, and 65 parts of liquid epoxy resin E51 evenly, and stir and react at 80 °C and a stirring speed of 200 r / min for 2 h to obtain the unphosphorylated acrylate oligomer toughened epoxy resin.

[0097] II. Preparation of high-toughness and high-adhesion epoxy resin adhesive:

[0098] ① Weigh 80 parts by mass of E51 epoxy resin, 30 parts of unphosphorylated acrylate oligomer toughened epoxy resin, 10 parts of MX154 core-shell particle toughened epoxy resin, 1 part of 801 epoxy phosphate, 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of ethylenediamine.

[0099] ② Mix the weighed 80 parts of E51 epoxy resin, 30 parts of unphosphorylated acrylate oligomer toughened epoxy resin, 10 parts of MX154 core-shell particle toughened epoxy resin, and 1 part of 801 epoxy phosphate evenly by stirring at room temperature to obtain Component A.

[0100] ③ Mix the weighed 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of ethylenediamine evenly by stirring at room temperature to obtain Component B.

[0101] ④ Mix the Component A obtained in Step ② and the Component B obtained in Step ③ evenly by stirring at room temperature to obtain the high-toughness and high-adhesion epoxy resin adhesive.

[0102] Comparative Example 3: The difference between this example and Example 1 is as follows: In Step 1 for preparing the unphosphorylated acrylate oligomer toughened epoxy resin, 2-hydroxyethyl methacrylate phosphate is not added. The preparation method is as follows:

[0103] I. Preparation of unphosphorylated acrylate oligomer toughened epoxy resin:

[0104] ①. Weigh 50 parts by weight of butyl acrylate, 10 parts of acrylonitrile, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of dibenzoyl peroxide, and 65 parts of liquid epoxy resin E51;

[0105] ②. Mix the weighed 50 parts of butyl acrylate, 10 parts of acrylonitrile, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of dibenzoyl peroxide, and 65 parts of liquid epoxy resin E51 evenly, and stir and react for 2 h under the conditions of 80 °C and a stirring speed of 200 r / min to obtain a non-phosphorylated acrylate oligomer toughened epoxy resin;

[0106] II. Preparation of phosphorylated curing agent:

[0107] ①. Weigh 20 parts of ethylenediamine and 2 parts of 801 epoxy phosphate by weight;

[0108] ②. Mix the weighed 20 parts of ethylenediamine and 2 parts of 801 epoxy phosphate evenly, and stir and react for 3 h at 80 °C and a stirring speed of 200 r / min to obtain a phosphorylated curing agent;

[0109] III. Preparation of high-toughness and high-adhesion epoxy resin adhesive:

[0110] ①. Weigh 80 parts of E51 epoxy resin, 30 parts of non-phosphorylated acrylate oligomer toughened epoxy resin, 10 parts of MX154 core-shell particle toughened epoxy resin, 1 part of 801 epoxy phosphate, 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of phosphorylated curing agent by mass;

[0111] ②. Mix the weighed 80 parts of E51 epoxy resin, 30 parts of non-phosphorylated acrylate oligomer toughened epoxy resin, 10 parts of MX154 core-shell particle toughened epoxy resin, and 1 part of 801 epoxy phosphate evenly by stirring at room temperature to obtain component A;

[0112] ③. Mix the weighed 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of phosphorylated curing agent evenly by stirring at room temperature to obtain component B;

[0113] ④. Mix the component A obtained in step ② and the component B obtained in step ③ evenly by stirring at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive.

[0114] Comparative Example 4: The difference between this example and Example 1 is that unphosphorylated ethylenediamine is used in component B; the preparation method is as follows:

[0115] I. Preparation of phosphorylated acrylate oligomer toughened epoxy resin:

[0116] ①. Weigh 50 parts by weight of butyl acrylate, 10 parts of acrylonitrile, 2 parts of 2-hydroxyethyl methacrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of benzoyl peroxide, and 65 parts of liquid epoxy resin E51;

[0117] ②. Mix the weighed 50 parts of butyl acrylate, 10 parts of acrylonitrile, 2 parts of 2-hydroxyethyl methacrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of benzoyl peroxide, and 65 parts of liquid epoxy resin E51 evenly, and stir and react at 80 °C and a stirring speed of 200 r / min for 2 h to obtain a phosphate esterified acrylate oligomer toughened epoxy resin;

[0118] II. Preparation of a high-toughness and high-adhesion epoxy resin adhesive:

[0119] ①. Weigh 80 parts by mass of E51 epoxy resin, 30 parts of phosphate esterified acrylate oligomer toughened epoxy resin, 10 parts of MX154 core-shell particle toughened epoxy resin, 1 part of 801 epoxy phosphate, 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of ethylenediamine;

[0120] ②. Stir and mix evenly the weighed 80 parts of E51 epoxy resin, 30 parts of phosphate esterified acrylate oligomer toughened epoxy resin, 10 parts of MX154 core-shell particle toughened epoxy resin, and 1 part of 801 epoxy phosphate at room temperature to obtain Component A;

[0121] ③. Stir and mix evenly the weighed 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of ethylenediamine at room temperature to obtain Component B;

[0122] ④. Stir and mix evenly Component A obtained in step ② and Component B obtained in step ③ at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive.

[0123] Comparative Example 5: The difference between this example and Example 1 is that when preparing the phosphate esterified acrylate oligomer toughened epoxy resin in step one, diallyl bisphenol A diglycidyl ether is not added. The preparation method is as follows:

[0124] ①. Weigh 50 parts by weight of butyl acrylate, 10 parts of acrylonitrile, 2 parts of 2-hydroxyethyl methacrylate phosphate, 1 part of benzoyl peroxide, and 65 parts of liquid epoxy resin E51;

[0125] ②. Weigh 50 parts of butyl acrylate, 10 parts of acrylonitrile, 2 parts of 2-hydroxyethyl methacrylate phosphate, 1 part of benzoyl peroxide, and 65 parts of liquid epoxy resin E51, mix them evenly, and stir and react for 2 h at 80 °C and a stirring speed of 200 r / min to obtain a phosphate esterified acrylate oligomer toughened epoxy resin;

[0126] II. Preparation of phosphate esterified curing agent:

[0127] ①. Weigh 20 parts of ethylenediamine and 2 parts of 801 epoxy phosphate by weight;

[0128] ②. Mix the weighed 20 parts of ethylenediamine and 2 parts of 801 epoxy phosphate evenly, and stir and react at 80 °C and a stirring speed of 200 r / min for 3 h to obtain a phosphate esterified curing agent;

[0129] III. Preparation of high-toughness and high-adhesion epoxy resin adhesive:

[0130] ①. Weigh 80 parts of E51 epoxy resin, 30 parts of phosphate esterified acrylate oligomer toughened epoxy resin, 10 parts of MX154 core-shell particle toughened epoxy resin, 1 part of 801 epoxy phosphate, 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of phosphate esterified curing agent by mass;

[0131] ②. Mix the weighed 80 parts of E51 epoxy resin, 30 parts of phosphate esterified acrylate oligomer toughened epoxy resin, 10 parts of MX154 core-shell particle toughened epoxy resin, and 1 part of 801 epoxy phosphate evenly by stirring at room temperature to obtain Component A;

[0132] ③. Mix the weighed 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane, and 10 parts of phosphate esterified curing agent evenly by stirring at room temperature to obtain Component B;

[0133] ④. Mix Component A obtained in step ② and Component B obtained in step ③ evenly by stirring at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive.

[0134] Comparative Example 6: The difference between this example and Example 1 is that MX154 core-shell particle toughened epoxy resin is not added to Component A. The preparation method is as follows:

[0135] I. Preparation of phosphate esterified acrylate oligomer toughened epoxy resin:

[0136] ①. Weigh 50 parts of butyl acrylate, 10 parts of acrylonitrile, 2 parts of 2-hydroxyethyl methacrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of benzoyl peroxide, and 65 parts of liquid epoxy resin E51 by weight;

[0137] ②. Weigh 50 parts of butyl acrylate, 10 parts of acrylonitrile, 2 parts of 2-hydroxyethyl methacrylate phosphate, 3 parts of diallyl bisphenol A diglycidyl ether, 1 part of benzoyl peroxide and 65 parts of liquid epoxy resin E51, mix them evenly, and stir and react for 2 h at 80 °C with a stirring speed of 200 r / min to obtain a phosphate esterified acrylate oligomer toughened epoxy resin;

[0138] II. Preparation of phosphate esterified curing agent:

[0139] ①. Weigh 20 parts of ethylenediamine and 2 parts of 801 epoxy phosphate by weight;

[0140] ②. Mix the weighed 20 parts of ethylenediamine and 2 parts of 801 epoxy phosphate evenly, and stir and react at 80 °C with a stirring speed of 200 r / min for 3 h to obtain a phosphate esterified curing agent;

[0141] III. Preparation of high-toughness and high-adhesion epoxy resin adhesive:

[0142] ①. Weigh 80 parts of E51 epoxy resin, 30 parts of phosphate esterified acrylate oligomer toughened epoxy resin, 1 part of 801 epoxy phosphate, 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane and 10 parts of phosphate esterified curing agent by mass;

[0143] ②. Mix the weighed 80 parts of E51 epoxy resin, 30 parts of phosphate esterified acrylate oligomer toughened epoxy resin and 1 part of 801 epoxy phosphate evenly by stirring at room temperature to obtain component A;

[0144] ③. Mix the weighed 10 parts of V140 polyamide curing agent, 5 parts of 1,4-diaminocyclohexane and 10 parts of phosphate esterified curing agent evenly by stirring at room temperature to obtain component B;

[0145] ④. Mix component A obtained in step ② and component B obtained in step ③ evenly by stirring at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive.

[0146] Next, the high-toughness and high-adhesion epoxy resin adhesives prepared in Examples 1 to 3 and the epoxy resin adhesives in Comparative Examples 1 to 6 will be subjected to the following performance tests:

[0147] Refer to GB / T 7124-2008 for the shear strength test of the adhesive on different metal substrates at 25 °C, and refer to GB / T7122-1996 for the peel strength test of the adhesive on an aluminum substrate at 25 °C; among them, the aluminum test pieces are all subjected to phosphoric acid anodizing treatment with reference to HB / Z197-1991. The results are shown in Table 1.

[0148] Table 1

[0149]

[0150]

[0151] As can be seen from Table 1, the epoxy resin adhesives prepared in Examples 1 to 3 have high shear and peel strengths. At 25°C, the shear strengths on aluminum, steel, and titanium substrates all exceed 30 MPa, the shear strengths on nickel substrates all exceed 20 MPa, and the peel strengths all exceed 8.5 kN / m.

[0152] Combined with the performance analysis of Comparative Examples 1 to 6 and Example 1, the specific results are as follows:

[0153] (1) Combining the technical solutions of Comparative Example 1 and Example 1, it can be seen from the data in the table that the adhesive system has high toughness and strength. Without introducing phosphate ester substances, the peel strength of the adhesive in Comparative Example 1 when bonding aluminum alloy is greater than 7 kN / m, and the shear strength is greater than 30 MPa, but the bonding strengths to difficult-to-bond materials such as steel, titanium, and nickel test pieces are significantly lower. The adhesive prepared in Example 1 modified by multi-angle phosphoric acid esterification can improve the adhesion to metal materials, which is very effective for difficult-to-bond materials such as steel, titanium, nickel, etc., and also has a certain degree of improvement in the bonding to phosphoric acid anodized aluminum test pieces.

[0154] (2) Combining the technical solutions of Comparative Examples 1, 2 and Example 1, it can be seen from the data in the table that only adding a small amount of epoxy phosphate to the system can only limitedly improve the bonding performance to difficult-to-bond metal materials, which is significantly different from the effect obtained by the present technical solution. This shows that only by adding epoxy phosphate cannot significantly improve the bonding performance to difficult-to-bond metal materials.

[0155] (3) Combining the technical solutions of Comparative Examples 1, 2, 3 and Example 1, it can be seen from the data in the table that the adhesive prepared in Comparative Example 3 with epoxy phosphate added to the system and a phosphoric acid esterification curing agent used has a slight increase in the shear strengths on aluminum, steel, and titanium substrates and the aluminum peel strength compared with Comparative Example 2, and a large increase in the shear strength on nickel substrates, indicating that the phosphoric acid esterification curing agent can further improve the adhesion of the adhesive on the basis of epoxy phosphate, but there is still an obvious gap from the effect obtained in Example 1.

[0156] (4) By combining the technical solutions of Comparative Examples 1, 2, 3, 4 and Example 1, it can be seen from the data in the table that for the adhesive prepared in Comparative Example 4 with the addition of epoxy phosphate and phosphated acrylate oligomer to the system, the shear strength of aluminum, steel, and titanium substrates has been improved to a certain extent, and the shear strength of nickel substrate has been greatly improved, and the effect is better than that of Comparative Example 3. This indicates that the phosphated acrylate oligomer has a better ability to improve adhesion than the phosphated curing agent, and the best effect is achieved in Example 1 with the addition of all three substances.

[0157] (5) By combining the technical solutions of Comparative Example 5 and Example 1, it can be seen from the data in the table that since a reactive enhancer is added in Example 1, internal crosslinking of the phosphated oligomer occurs, and the strength and toughness of the toughener are improved. Compared with Comparative Example 5, the shear strength of aluminum, steel, titanium, and nickel substrates and the aluminum peel strength have been improved to a certain extent. This indicates that adding a reactive enhancer to the system can improve the strength and toughness of the toughener and further enhance the toughening effect of the toughener.

[0158] (6) By combining the technical solutions of Comparative Example 6 and Example 1, it can be seen from the data in the table that compared with Example 1, the adhesive prepared in Comparative Example 6 does not introduce core-shell particles, and its peel strength has decreased significantly, while the shear strength is relatively less affected. This indicates that the addition of core-shell particles can synergistically toughen with the phosphated acrylate oligomer to effectively improve the toughness of the system.

Claims

1. A high-toughness and high-adhesion epoxy resin adhesive, characterized in that The epoxy resin adhesive comprises component A and component B; Component A, by mass parts, comprises: 50 parts to 100 parts of epoxy resin, 30 parts to 60 parts of phosphate esterified acrylate oligomer toughened epoxy resin, 10 parts to 30 parts of core-shell particle toughened epoxy resin, and 1 part to 3 parts of epoxy phosphate; Component B, by mass parts, comprises: 10 parts to 30 parts of polyamide curing agent, 5 parts to 15 parts of alicyclic amine curing agent, and 10 parts to 20 parts of phosphate esterified curing agent.

2. The high-toughness and high-adhesion epoxy resin adhesive according to claim 1, characterized in that The epoxy resin is one or more of bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic epoxy resin, biphenyl type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and aliphatic epoxy resin.

3. The high-toughness and high-adhesion epoxy resin adhesive according to claim 1, wherein The phosphate esterified acrylate oligomer toughened epoxy resin is prepared from 50 parts to 70 parts of acrylate soft monomer, 10 parts to 20 parts of acrylate hard monomer, 2 parts to 5 parts of acrylate phosphate ester, 3 parts to 5 parts of reactive enhancer, 1 part to 3 parts of initiator, and 65 parts to 100 parts of liquid epoxy resin; the preparation method is: mixing 50 parts to 70 parts of acrylate soft monomer, 10 parts to 20 parts of acrylate hard monomer, 2 parts to 5 parts of acrylate phosphate ester, 3 parts to 5 parts of reactive enhancer, 1 part to 3 parts of initiator, and 65 parts to 100 parts of liquid epoxy resin evenly, and carrying out stirring reaction for 2 h to 4 h under the conditions of 80 °C to 100 °C and a stirring speed of 200 r / min to 500 r / min.

4. The high-toughness and high-adhesion epoxy resin adhesive according to claim 3, wherein The acrylate soft monomer is one or more of butyl acrylate, isooctyl acrylate, ethyl acrylate, and n-octyl acrylate; the acrylate hard monomer is one or more of methyl methacrylate, styrene, vinyl acetate, ethyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, acrylonitrile, glycidyl methacrylate, glycidyl acrylate, acrylic acid, and methacrylic acid.

5. The high-toughness and high-adhesion epoxy resin adhesive according to claim 3, wherein The acrylate phosphate ester is one or more of 2-hydroxyethyl methacrylate phosphate ester, acidic polyfunctional acrylate phosphate ester, and alkyl acrylate phosphate ester; the reactive enhancer is diallyl bisphenol A diglycidyl ether; the initiator is benzoyl peroxide or azobisisobutyronitrile; the liquid epoxy resin is one or more of E51, E44, and E54.

6. The high-toughness and high-adhesion epoxy resin adhesive according to claim 1, characterized in that The core-shell particle toughened epoxy resin is one or more of MX125, MX153, MX154, and MX257; the epoxy phosphate is one or more of LY-73, LY-75, YM-1007, 801, VOK-903, and LRD-4A.

7. The high-toughness and high-adhesion epoxy resin adhesive according to claim 1, characterized in that The polyamide curing agent is one or more of V115, V125, V140, 200# and 300#; the alicyclic amine curing agent is one or more of isophorone diamine, 4,4`-diaminodicyclohexylmethane, 1,4-diaminocyclohexane and 3,3`-dimethyl-4,4`-diaminomethylcyclohexylmethane.

8. The high-toughness and high-adhesion epoxy resin adhesive according to claim 1, wherein The phosphoric acid esterified curing agent is prepared from 20 parts to 40 parts of fatty amine and 2 parts to 10 parts of epoxy phosphoric acid ester; the preparation method is: mixing 20 parts to 40 parts of fatty amine and 2 parts to 10 parts of epoxy phosphoric acid ester evenly, and carrying out stirring reaction at 80°C to 120°C and a stirring speed of 200 r / min to 500 r / min for 3 h to 6 h.

9. The high-toughness and high-adhesion epoxy resin adhesive according to claim 1, characterized in that The fatty amine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine and hexamethylenediamine; the epoxy phosphoric acid ester is LY-73, LY-75, YM-1007, 801, VOK-903 or LRD-4A.

10. The preparation method of the high-toughness and high-adhesion epoxy resin adhesive according to claim 1, characterized in that The specific preparation method is completed according to the following steps:

1. Weigh 50 parts to 100 parts of epoxy resin, 30 parts to 60 parts of phosphoric acid esterified acrylate oligomer toughened epoxy resin, 10 parts to 30 parts of core-shell particle toughened epoxy resin, 1 part to 3 parts of epoxy phosphoric acid ester, 10 parts to 30 parts of polyamide curing agent, 5 parts to 15 parts of alicyclic amine curing agent and 10 parts to 20 parts of phosphoric acid esterified curing agent by mass fraction; 2. Stir and mix evenly 50 parts to 100 parts of epoxy resin, 30 parts to 60 parts of phosphoric acid esterified acrylate oligomer toughened epoxy resin, 10 parts to 30 parts of core-shell particle toughened epoxy resin and 1 part to 3 parts of epoxy phosphoric acid ester at room temperature to obtain component A; 3. Stir and mix evenly 10 parts to 30 parts of polyamide curing agent, 5 parts to 15 parts of alicyclic amine curing agent and 10 parts to 20 parts of phosphoric acid esterified curing agent at room temperature to obtain component B; 4. Stir and mix evenly the component A obtained in step 2 and the component B obtained in step 3 at room temperature to obtain a high-toughness and high-adhesion epoxy resin adhesive.

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