High-temperature-resistant epoxy resin adhesive as well as preparation method and application thereof

Abstract

The invention discloses a high-temperature-resistant epoxy resin adhesive as well as a preparation method and application thereof, the high-temperature-resistant epoxy resin adhesive comprises a component A and a component B. The component A comprises the following raw materials in parts by weight: 50-60 parts of epoxy resin; 5 to 15 parts of a toughening agent; 0.1 to 0.3 part of a dispersant; 0.1 to 0.3 part of a coupling agent; 0.05 to 0.15 part of a defoaming agent; 0.5 to 2 parts of a thixotropic agent; 20 to 50 parts of filler; the epoxy resin is composed of trifunctional epoxy resin, tetrafunctional epoxy resin and organosilicon modified epoxy resin; the component B comprises the following raw materials in parts by weight: 18-30 parts of a curing agent; 0.1 to 0.3 part of a dispersant; 0.1 to 0.3 part of a coupling agent; 0.05 to 0.2 part of a defoaming agent; 0.5 to 2 parts of a thixotropic agent; and 70-80 parts of a filler. The high-temperature-resistant epoxy resin adhesive can meet the long-term 250 DEG C high-temperature-resistant requirement, and can be applied as a high-temperature-resistant electronic component bonding material.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives, and in particular relates to a high temperature resistant epoxy resin adhesive and a preparation method and application thereof. Background Art

[0002] With the rapid development of science and technology, the use scenarios of some products are becoming more and more stringent. For example, hot air blowers are used at high temperatures of 250°C for a long time, and their fan ports and some components need to be bonded and fixed with epoxy resin adhesives. However, at present, epoxy resin adhesives on the market have the disadvantages of being brittle and having poor heat resistance. Even if there are related modified high-temperature resistant epoxy resin adhesives, they are only resistant to high temperatures in the short term and cannot meet the needs of some current high-tech products. Therefore, it is necessary to study epoxy resin adhesives that can withstand long-term temperatures of 250°C. Secondly, under the requirements of high temperature resistance and low curing shrinkage, there is also the problem of uneven mixing of AB two-component epoxy adhesives. Summary of the invention

[0003] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention provides a high temperature resistant epoxy resin adhesive and a preparation method and application thereof, which can meet the long-term high temperature resistance requirement of 250°C and can be used as a high temperature resistant electronic component bonding material.

[0004] The above technical objectives of the present invention are achieved through the following technical solutions:

[0005] A high temperature resistant epoxy resin adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 50-60 parts of epoxy resin; 5-15 parts of toughening agent; 0.1-0.3 parts of dispersant; 0.1-0.3 parts of coupling agent; 0.05-0.15 parts of defoaming agent; 0.5-2 parts of thixotropic agent; 20-50 parts of filler; the epoxy resin is composed of a trifunctional epoxy resin, a tetrafunctional epoxy resin and a silicone-modified epoxy resin; the component B comprises the following raw materials in parts by weight: 18-30 parts of curing agent; 0.1-0.3 parts of dispersant; 0.1-0.3 parts of coupling agent; 0.05-0.2 parts of defoaming agent; 0.5-2 parts of thixotropic agent; and 70-80 parts of filler.

[0006] In some embodiments of the present invention, the epoxy resin is composed of trifunctional epoxy resin TT310, tetrafunctional epoxy resin TT410 and silicone-modified epoxy resin BYW-471 in a weight ratio of (4-7):(21-24):(25-29).

[0007] In some embodiments of the present invention, the toughening agent is a core-shell structure toughening agent.

[0008] In some embodiments of the present invention, the toughening agent is at least one of Dow toughening agent TWS-2672 and Kaneka toughening agent MX-154.

[0009] In some embodiments of the present invention, the toughening agent is Dow toughening agent TWS-2672.

[0010] In some embodiments of the present invention, the dispersant is at least one of BYK-9010 and BYK-9011.

[0011] In some embodiments of the present invention, the coupling agent is at least one of KH-560 and KH-550.

[0012] In some embodiments of the present invention, the defoaming agent is BYK-530.

[0013] In some embodiments of the present invention, the component A further comprises 0.1-0.3 parts of an antioxidant, and the antioxidant is at least one of phthalocyanine blue and cerium oxide.

[0014] In some embodiments of the present invention, the antioxidant is phthalocyanine blue.

[0015] In some embodiments of the present invention, the thixotropic agent is white carbon black.

[0016] In some embodiments of the present invention, the thixotropic agent is white carbon black with a model number of TS-720.

[0017] In some embodiments of the present invention, the B component further comprises 0.01-0.04 parts of a pigment, and the pigment is carbon black.

[0018] In some embodiments of the present invention, the filler is silicon powder.

[0019] In some embodiments of the present invention, the filler is a mixture of 800 mesh silicon micropowder and 1000 mesh silicon micropowder.

[0020] In some embodiments of the present invention, the filler in component A is a mixture of 800 mesh silicon powder and 1000 mesh silicon powder in a weight ratio of (18-23):(14-18).

[0021] In some embodiments of the present invention, the filler in the B component is a mixture of 800 mesh silicon powder and 1000 mesh silicon powder in a weight ratio of (39-42): (33-36).

[0022] In some embodiments of the present invention, the model of the 800-mesh silicon micropowder is DC1180, and the model of the 1000-mesh silicon micropowder is DC1130.

[0023] In some embodiments of the present invention, the silicon micropowder needs to be surface treated before use. The specific operation is: silicon micropowder, methyl orthosilicate and water are mixed in a weight ratio of (400-600):1:1, stirred and then dried to obtain the treated silicon micropowder.

[0024] In some embodiments of the present invention, the temperature of the drying after stirring in the surface treatment is 80-120°C.

[0025] In some embodiments of the present invention, the surface treatment is performed by mixing methyl orthosilicate with water and then adding the mixture dropwise to the silicon powder.

[0026] In some embodiments of the present invention, the curing agent is composed of 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and diethyltoluenediamine in a weight ratio of (8-10): (10-20).

[0027] A method for preparing the high temperature resistant epoxy resin adhesive as described above comprises the following steps:

[0028] (1) First, the epoxy resin and toughening agent in the formula amount are stirred and dispersed after heating, cooled to room temperature, mixed with the dispersant, coupling agent, defoaming agent, thixotropic agent and filler in the formula amount, and dispersed to obtain component A;

[0029] (2) Mixing the formulated amount of curing agent, dispersant, coupling agent, defoaming agent, thixotropic agent and filler, and dispersing to obtain component B;

[0030] (3) Mixing the component A and the component B to obtain an epoxy resin adhesive.

[0031] In some embodiments of the present invention, the temperature after heating in step (1) is 80-150°C.

[0032] As mentioned above, high temperature resistant epoxy resin adhesive is used as bonding material for electronic components.

[0033] The beneficial effects of the present invention are as follows: the high temperature resistant epoxy resin adhesive of the present invention uses trifunctional epoxy resin, tetrafunctional epoxy resin and organosilicon modified epoxy resin for compounding, which is beneficial to reduce the curing shrinkage rate of the adhesive and improve the temperature resistance; at the same time, the present invention uses a specific core-shell structure powder toughening agent, which can significantly improve the flexibility of the adhesive and has little effect on the glass transition temperature of the adhesive; the specific alicyclic diamine and aromatic amine curing agents are selected, and the obtained cured product has good mechanical properties and thermal stability; in addition, in the present invention, the surface modification of the filler enhances the bonding strength of the adhesive to the substrate and the dispersibility of the powder in the colloid, thereby improving the high temperature resistance of the epoxy resin adhesive; the selection of a suitable antioxidant can reduce the cracking phenomenon of the epoxy resin adhesive. The raw materials of the present invention cooperate with each other, and the prepared epoxy resin adhesive can withstand a high temperature of 250°C for a long time, and maintains good shear strength and heat aging resistance at high temperature, has good bonding performance to various substrates, and can be used as a bonding material for high temperature resistant electronic components. DETAILED DESCRIPTION

[0034] The present invention will be further described below in conjunction with specific embodiments.

[0035] Embodiment 1:

[0036] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 10 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0037] Among them, the epoxy resin is a trifunctional epoxy resin TT310, a tetrafunctional epoxy resin TT410, and a silicone-modified epoxy resin BYW-471 in a weight ratio of 12:32:10. The manufacturer of the silicone-modified epoxy resin BYW-471 is Zhongshan Boyuwen Electronics Co., Ltd.; the toughening agent is MX-154; the dispersant is byk-9010; the coupling agent is KH-560; the defoaming agent is byk-530; and the thixotropic agent is white carbon black TS-720; the filler is a silicon micropowder component with different mesh sizes, the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 need to be surface treated before use, the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then drop into the reactor, after high-speed stirring for 2h, dry at 100°C to obtain the treated silicon micropowder;

[0038] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0039] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is BYK-9011; coupling agent is KH-550; defoaming agent is BYK-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface-treated silica powder, the treatment method is the same as component A, and the weight ratio of silica powder DC1180 to DC1130 is 40:35.5.

[0040] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0041] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0042] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0043] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0044] Embodiment 2:

[0045] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 10 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0046] The epoxy resin is a trifunctional epoxy resin TT310, a tetrafunctional epoxy resin TT410, and an organosilicon-modified epoxy resin BYW-471 in a weight ratio of 6:26:22; the toughening agent is MX-154; the dispersant is BYK-9010; the coupling agent is KH-560; the defoaming agent is BYK-530; the thixotropic agent is white carbon black TS-720; the filler is a silicon micropowder component of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then dropwise add into the reactor, and after high-speed stirring for 2h, dry at 100°C to obtain the treated silicon micropowder;

[0047] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0048] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A, and the weight ratio of silica powder DC1180 to DC1130 is 40:35.5;

[0049] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0050] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0051] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0052] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0053] Embodiment 3:

[0054] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 10 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0055] The epoxy resin is composed of trifunctional epoxy resin TT310, tetrafunctional epoxy resin TT410 and organosilicon modified epoxy resin BYW-471 in a weight ratio of 5:22:27; the toughening agent is MX-154; the dispersant is BYK-9010; the coupling agent is KH-560; the defoaming agent is BYK-530; the thixotropic agent is white carbon black TS-720; the filler is silicon micropowder components of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then dropwise add into the reactor, and dry at 100°C after high-speed stirring for 2h to obtain the treated silicon micropowder;

[0056] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0057] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A, and the weight ratio of silica powder DC1180 to DC1130 is 40:35.5;

[0058] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0059] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0060] (2) mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0061] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0062] Embodiment 4:

[0063] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 12 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0064] The epoxy resin is a trifunctional epoxy resin TT310, a tetrafunctional epoxy resin TT410, and an organosilicon-modified epoxy resin BYW-471 in a weight ratio of 5:22:27; the toughening agent is a core-shell rubber structure powder TWS-2672; the dispersant is BYK-9010; the coupling agent is KH-560; the defoaming agent is BYK-530; the thixotropic agent is white carbon black TS-720; the filler is a silicon micropowder component of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then dropwise add into the reactor, and after high-speed stirring for 2h, dry at 100°C to obtain the treated silicon micropowder;

[0065] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0066] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A, and the weight ratio of silica powder DC1180 to DC1130 is 40:35.5;

[0067] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0068] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0069] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0070] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0071] Embodiment 5:

[0072] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 12 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; antioxidant: 0.2 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0073] The epoxy resin is a trifunctional epoxy resin TT310, a tetrafunctional epoxy resin TT410, and an organosilicon-modified epoxy resin BYW-471 in a weight ratio of 5:22:27; the toughening agent is a core-shell rubber structure powder TWS-2672; the dispersant is byk-9010; the coupling agent is KH-560; the defoaming agent is byk-530; the antioxidant is cerium oxide; the thixotropic agent is white carbon black TS-720; the filler is a silicon micropowder component of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then dropwise add them into the reactor, and after high-speed stirring for 2h, dry them at 100°C to obtain the treated silicon micropowder;

[0074] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0075] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A, and the weight ratio of silica powder DC1180 to DC1130 is 40:35.5;

[0076] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0077] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, antioxidant, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0078] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0079] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0080] Embodiment 6:

[0081] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 12 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; antioxidant: 0.2 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0082] The epoxy resin is composed of trifunctional epoxy resin TT310, tetrafunctional epoxy resin TT410 and organosilicon modified epoxy resin BYW-471 in a weight ratio of 5:22:27; the toughening agent is core-shell rubber structure powder TWS-2672; the dispersant is byk-9010; the coupling agent is KH-560; the defoaming agent is byk-530; the antioxidant is phthalocyanine blue; the thixotropic agent is white carbon black TS-720; the filler is silicon micropowder components of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 is placed in a reactor, 1g of methyl orthosilicate is mixed with 1g of water and then added dropwise into the reactor, and after high-speed stirring for 2h, it is dried at 100°C to obtain the treated silicon micropowder;

[0083] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0084] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A, and the weight ratio of silica powder DC1180 to DC1130 is 40:35.5;

[0085] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0086] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, antioxidant, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0087] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0088] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0089] Embodiment 7:

[0090] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 12 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; antioxidant: 0.2 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0091] The epoxy resin is composed of trifunctional epoxy resin TT310, tetrafunctional epoxy resin TT410 and organosilicon modified epoxy resin BYW-471 in a weight ratio of 5:22:27; the toughening agent is core-shell rubber structure powder TWS-2672; the dispersant is byk-9010; the coupling agent is KH-560; the defoaming agent is byk-530; the antioxidant is phthalocyanine blue; the thixotropic agent is white carbon black TS-720; the filler is silicon micropowder components of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 do not need to be surface treated before use;

[0092] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0093] Wherein, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is not surface treated, and the weight ratio of silica powder DC1180 to DC1130 is 40:35.5;

[0094] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0095] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, antioxidant, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0096] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0097] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0098] Embodiment 8:

[0099] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A contains the following raw materials in parts by weight: epoxy resin: 50 parts; toughening agent: 5 parts; dispersant: 0.1 parts; coupling agent: 0.1 parts; defoaming agent: 0.05 parts; antioxidant: 0.1 parts; thixotropic agent: 0.5 parts; filler: 32 parts;

[0100] The epoxy resin is a trifunctional epoxy resin TT310, a tetrafunctional epoxy resin TT410, and an organosilicon-modified epoxy resin BYW-471 in a weight ratio of 4:21:25; the toughening agent is a core-shell rubber structure powder TWS-2672; the dispersant is byk-9010; the coupling agent is KH-560; the defoaming agent is byk-530; the antioxidant is phthalocyanine blue; the thixotropic agent is white carbon black TS-720; the filler is a silicon micropowder component of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 18:14, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then dropwise add into the reactor, and after high-speed stirring for 2h, dry at 100°C to obtain the treated silicon micropowder;

[0101] Component B contains the following raw materials by weight: curing agent 1: 8 parts; curing agent 2: 10 parts; dispersant: 0.1 parts; coupling agent: 0.1 parts; defoaming agent: 0.05 parts; thixotropic agent: 0.5 parts; pigment: 0.01 parts; filler: 72 parts;

[0102] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A, and the weight ratio of silica powder DC1180 to DC1130 is 39:33;

[0103] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0104] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, antioxidant, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0105] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0106] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0107] Embodiment 9:

[0108] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 60 parts; toughening agent: 15 parts; dispersant: 0.3 parts; coupling agent: 0.3 parts; defoaming agent: 0.15 parts; antioxidant: 0.3 parts; thixotropic agent: 2 parts; filler: 41 parts;

[0109] The epoxy resin is a trifunctional epoxy resin TT310, a tetrafunctional epoxy resin TT410, and an organosilicon-modified epoxy resin BYW-471 in a weight ratio of 7:24:29; the toughening agent is a core-shell rubber structure powder TWS-2672; the dispersant is BYK-9010; the coupling agent is KH-560; the defoaming agent is BYK-530; the antioxidant is phthalocyanine blue; the thixotropic agent is white carbon black TS-720; the filler is a silicon micropowder component of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 23:18, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then dropwise add into the reactor, and after high-speed stirring for 2h, dry at 100°C to obtain the treated silicon micropowder;

[0110] Component B contains the following raw materials by weight: curing agent 1: 10 parts; curing agent 2: 20 parts; dispersant: 0.3 parts; coupling agent: 0.3 parts; defoaming agent: 0.2 parts; thixotropic agent: 2 parts; pigment: 0.04 parts; filler: 78 parts;

[0111] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A, and the weight ratio of silica powder DC1180 to DC1130 is 42:36;

[0112] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0113] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, antioxidant, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0114] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0115] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0116] Comparative Example 1:

[0117] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 10 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0118] The epoxy resin is composed of trifunctional epoxy resin TT310 and tetrafunctional epoxy resin TT410 in a weight ratio of 11:43; the toughening agent is MX-154; the dispersant is byk-9010; the coupling agent is KH-560; the defoaming agent is byk-530; the thixotropic agent is white carbon black TS-720; the filler is silicon micropowder components of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then dropwise add into the reactor, and after high-speed stirring for 2h, dry at 100°C to obtain the treated silicon micropowder;

[0119] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0120] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A; the weight ratio of silica powder DC1180 to DC1130 is 40:35.5;

[0121] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0122] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0123] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0124] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0125] Comparative Example 2:

[0126] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 10 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0127] The epoxy resin is composed of tetrafunctional epoxy resin TT410 and silicone modified epoxy resin BYW-471 in a weight ratio of 43:11; the toughening agent is MX-154; the dispersant is BYK-9010; the coupling agent is KH-560; the defoaming agent is BYK-530; the thixotropic agent is white carbon black TS-720; the filler is silicon micropowder components of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then dropwise add into the reactor, and after high-speed stirring for 2h, dry at 100°C to obtain the treated silicon micropowder;

[0128] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0129] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A; the weight ratio of silica powder DC1180 to DC1130 is 40:35.5;

[0130] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0131] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0132] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0133] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0134] Comparative Example 3:

[0135] A high temperature resistant epoxy resin adhesive, composed of component A and component B: component A comprises the following raw materials in parts by weight: epoxy resin: 54 parts; toughening agent: 10 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 part; filler: 35.5 parts;

[0136] The epoxy resin is composed of trifunctional epoxy resin TT310 and silicone modified epoxy resin BYW-471 in a weight ratio of 11:43; the toughening agent is MX-154; the dispersant is BYK-9010; the coupling agent is KH-560; the defoaming agent is BYK-530; the thixotropic agent is white carbon black TS-720; the filler is silicon micropowder components of different mesh sizes, and the weight ratio of silicon micropowder DC1180 to DC1130 is 20:15.5, wherein DC1180 and DC1130 need to be surface treated before use, and the specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then dropwise add into the reactor, and after high-speed stirring for 2h, dry at 100°C to obtain the treated silicon micropowder;

[0137] Component B contains the following raw materials in parts by weight: curing agent 1: 9.1 parts; curing agent 2: 14.4 parts; dispersant: 0.2 parts; coupling agent: 0.2 parts; defoaming agent: 0.1 parts; thixotropic agent: 1 parts; pigment: 0.02 parts; filler: 75.5 parts;

[0138] Among them, curing agent 1 is 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane; curing agent 2 is diethyltoluenediamine; dispersant is byk-9011; coupling agent is KH-550; defoamer is byk-530; thixotropic agent is white carbon black TS-720; pigment is carbon black; filler is surface treated silica powder, the treatment method is the same as component A; the weight ratio of silica powder DC1180 to DC1130 is 40:35.5;

[0139] The preparation method of the above-mentioned high temperature resistant epoxy adhesive comprises the following steps:

[0140] (1) First, the epoxy resin and toughening agent in the formula amount are rapidly stirred and dispersed at 100° C. for 1 hour, then cooled to room temperature, mixed with the dispersant, coupling agent, defoamer, thixotropic agent and filler in the formula amount, and dispersed at high speed to obtain component A;

[0141] (2) Mixing the formulated amount of curing agent 1, curing agent 2, dispersant, coupling agent, defoaming agent, thixotropic agent, pigment and filler, and dispersing at high speed to obtain component B;

[0142] (3) Component A and component B are uniformly mixed in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0143] Test example:

[0144] The properties of the epoxy resin adhesives prepared in Examples 1-9 of the present invention and Comparative Examples 1-3 were tested.

[0145] Sample preparation: 1. Mix component A and component B, stir evenly and degas under vacuum for 10 minutes, then apply the mixed epoxy resin adhesive on the aluminum sheet, build a shear specimen, and then put it in an oven to cure it under the curing conditions of 120℃ / 2h+150℃ / 1h+180℃ / 1h. 2. Apply a layer of epoxy resin adhesive of about 2mm on the aluminum sheet, with a coating area of ​​25mm×80mm, and then put it in an oven to cure it under the curing conditions of 120℃ / 2h+150℃ / 1h+180℃ / 1h to obtain a specimen for testing the cracking of the adhesive surface. The aluminum sheet mentioned in the sample is 1 series aluminum with a size of 25mm×100mm.

[0146] Test method:

[0147] 1. Shear strength: Test the shear strength at room temperature and 200°C respectively;

[0148] 2. Heat aging resistance: Put the cured shear specimens and the specimens with cracks on the surface of the adhesive into a 250℃ oven for aging for 350 hours, take them out, and measure the shear strength at room temperature. The shear strength is tested according to GB7124-86, and the cracking of the aluminum sheet surface film is observed. The method for determining the surface cracking grade is as follows: measure the crack width with a vernier caliper, and record the number of cracks in the aluminum sheet surface film area of ​​25mm×80mm. Cracking level 1: crack width is 0.05mm~0.1mm, and the number of cracks is 0~5; cracking level 2: crack width is 0.1mm~0.15mm, and the number of cracks is 5~10; cracking level 3: crack width is 0.15mm~0.25mm, and the number of cracks is 10~15; cracking level 4: crack width is 0.20mm~0.30mm, and the number of cracks is 10~20. The glue falls off and powders, which also belongs to cracking level 4.

[0149] 3. Glass transition temperature Tg test, the test equipment model is TMA / SDTA2+ (Mettler), the test standard is GB / T 19466.2-2004, generally, the higher the Tg point temperature, the better the high temperature resistance; thermal gravimetric analysis, using thermal analysis instrument TG209F3 (Netzsch, Germany), air atmosphere, from 25°C to 800°C, record the temperature when 5% weight loss, generally the higher the temperature, the better the temperature resistance.

[0150] The experimental results are shown in Table 1.

[0151] Table 1: Epoxy resin adhesive performance test results

[0152]

[0153] As can be seen from Table 1, the shear strength of the epoxy resin adhesive of the present invention at room temperature can reach 8.2 MPa or more, and can reach a maximum of 13.2 MPa; the shear strength at 200°C can reach 4.5 MPa or more, and can reach a maximum of 8.4 MPa; the shear strength after aging in a 250°C oven for 350 hours can reach 2.2 MPa or more, and can reach a maximum of 6.2 MPa; the glass transition temperature Tg can reach 162°C or more, and can reach a maximum of 182°C; the temperature of thermal weight loss of 5% can reach 316°C or more, and can reach a maximum of 377°C.

[0154] In addition, by comparing Comparative Examples 1-3 and Example 1, it can be seen that when the epoxy resin contains only two of the trifunctional epoxy resin TT310, the tetrafunctional epoxy resin TT410 and the silicone-modified epoxy resin BYW-471 under the premise that other formula ratios remain unchanged and the total amount of epoxy resin remains unchanged, the bonding strength and high temperature resistance of the epoxy resin adhesive will decrease, indicating that the trifunctional epoxy resin TT310, the tetrafunctional epoxy resin TT410 and the silicone-modified epoxy resin BYW-471 in the present invention can synergistically improve the bonding strength and high temperature resistance of the epoxy resin adhesive; by comparing Example 2 with Example 1, it can be seen that when other formula ratios remain unchanged, the ratios of the three epoxy resins are adjusted, and the addition amount of the silicone-modified epoxy resin BYW-471 is increased, which is beneficial to improving the epoxy resin adhesive. The bonding strength and high temperature resistance of the epoxy resin adhesive are shown in Table 1. By comparing Example 4 with Example 3, it can be seen that the toughening agent TWS-2672 is more conducive to improving the high temperature resistance of the epoxy resin adhesive than the toughening agent MX-154. By comparing Example 5 with Example 4, it can be seen that when component A contains an antioxidant, the high temperature resistance of the epoxy resin adhesive is more excellent, and the surface cracking grade can reach level 2. By comparing Example 6 with Example 5, it can be seen that the antioxidant phthalocyanine blue is more conducive to improving the high temperature resistance of the epoxy resin adhesive than the antioxidant cerium oxide, and can significantly increase the surface crack resistance of the epoxy resin adhesive. By comparing Example 7 with Example 6, it can be seen that when the silicon powder in component A and component B of the epoxy resin adhesive is not subjected to a specific surface treatment, the high temperature resistance of the epoxy resin adhesive obtained will be significantly reduced.

[0155] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A high temperature resistant epoxy resin adhesive, characterized in that: It comprises component A and component B, wherein component A comprises the following raw materials in parts by weight: Epoxy resin: 50-60 parts; Toughening agent: 5-15 parts; Dispersant: 0.1-0.3 parts; Coupling agent: 0.1-0.3 parts; Defoaming agent: 0.05-0.15 parts; Thixotropic agent: 0.5-2 parts; Filler: 20-50 parts; The epoxy resin is composed of trifunctional epoxy resin, tetrafunctional epoxy resin and organosilicon-modified epoxy resin; The B component comprises the following raw materials in parts by weight: Curing agent: 18-30 parts; Dispersant: 0.1-0.3 parts; Coupling agent: 0.1-0.3 parts; Defoaming agent: 0.05-0.2 parts; Thixotropic agent: 0.5-2 parts; Filler: 70-80 parts.

2. A high temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The epoxy resin is composed of trifunctional epoxy resin TT310, tetrafunctional epoxy resin TT410 and silicone modified epoxy resin BYW-471 in a weight ratio of (4-7):(21-24):(25-29).

3. The high temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The toughening agent is a core-shell structure toughening agent.

4. The high temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The component A also includes 0.1-0.3 parts of an antioxidant, and the antioxidant is at least one of phthalocyanine blue and cerium oxide.

5. The high temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The filler is silicon powder.

6. A high temperature resistant epoxy resin adhesive according to claim 5, characterized in that: The silicon micropowder needs to be surface treated before use. The specific operation is: silicon micropowder, methyl orthosilicate and water are mixed in a weight ratio of (400-600):1:1, stirred and then dried to obtain the treated silicon micropowder.

7. A high temperature resistant epoxy resin adhesive according to claim 6, characterized in that: The mixing method in the surface treatment is to first mix methyl orthosilicate with water and then dropwise add the mixture into the silicon micropowder.

8. The high temperature resistant epoxy resin adhesive according to claim 1, characterized in that: The curing agent is composed of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and diethyltoluenediamine in a weight ratio of (8-10): (10-20).

9. A method for preparing the high temperature resistant epoxy resin adhesive according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) First, the epoxy resin and toughening agent in the formula amount are stirred and dispersed after heating, cooled to room temperature, mixed with the dispersant, coupling agent, defoaming agent, thixotropic agent and filler in the formula amount, and dispersed to obtain component A; (2) Mixing the formulated amount of curing agent, dispersant, coupling agent, defoaming agent, thixotropic agent and filler, and dispersing to obtain component B; (3) Mixing the component A and the component B to obtain an epoxy resin adhesive.

10. Use of the high temperature resistant epoxy resin adhesive according to any one of claims 1 to 8 as a bonding material for electronic components.

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