A high temperature resistant epoxy resin adhesive and its preparation method and application

Abstract

The invention discloses a high-temperature resistant epoxy resin adhesive and a preparation method and application thereof. The high-temperature resistant epoxy resin adhesive includes a component A and a component B. The component A includes 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; and 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 includes 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. This high-temperature resistant epoxy resin adhesive can meet the long-term high-temperature resistance requirements of 250°C and can be used as a bonding material for high-temperature resistant electronic components.

Description

Technical Field

[0001] The present 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 blower ports and some components need to be bonded and fixed with epoxy resin adhesives. However, at present, the 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, a preparation method, and applications thereof. The high-temperature resistant epoxy resin adhesive can meet the requirement of long-term high-temperature resistance of 250°C and can be used as a bonding material for high-temperature resistant electronic components.

[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. 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; and 20-50 parts of filler. The epoxy resin comprises a trifunctional epoxy resin, a tetrafunctional epoxy resin, and a silicone-modified epoxy resin. 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 component B 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 component B 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, and 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 a 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 a trifunctional epoxy resin, a tetrafunctional epoxy resin and a silicone-modified epoxy resin as the adhesive material for compounding, which is beneficial to reducing the adhesive curing shrinkage rate and improving 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 resulting cured product has good mechanical properties and thermal stability; in addition, in the present invention, the filler is surface modified to enhance 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 epoxy resin adhesive prepared can withstand high temperatures of 250°C for a long time, and maintain good shear strength and heat aging resistance at high temperatures. It has good bonding properties to various substrates and can be used as a high-temperature resistant electronic component bonding material. DETAILED DESCRIPTION

[0034] The present invention will be further described below with reference to specific embodiments.

[0035] Example 1:

[0036] 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: 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 silica powder component of different mesh sizes, and the weight ratio of silica powder DC1180 to DC1130 is 20:15.5. 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 add dropwise to the reactor, stir at high speed for 2h, and then dry at 100°C to obtain the treated silica powder;

[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 mixed evenly in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0044] Example 2:

[0045] 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: 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] 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 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. The specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then add dropwise into the reactor, stir at high speed for 2h, and then 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; 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;

[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 mixed evenly in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0053] Example 3:

[0054] 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: 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] 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 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 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. The specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then add dropwise into the reactor, stir at high speed for 2h, and then dry at 100°C 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; 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;

[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 prepare component B;

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

[0062] Example 4:

[0063] 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: 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] 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 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. The specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate and 1g water and then add dropwise into the reactor, stir at high speed for 2h, and then 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; 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;

[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 mixed evenly in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0071] Example 5:

[0072] 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: 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] 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 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. The specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate and 1g water and then add dropwise into the reactor, stir at high speed for 2h, and then dry 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; 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;

[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 mixed evenly in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0080] Example 6:

[0081] 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: 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] 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 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 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 20:15.5. DC1180 and DC1130 need to be surface treated before use. The specific operation process is to put 500g Put DC1180 or DC1130 into the reactor, mix 1g of methyl orthosilicate with 1g of water and add dropwise into the reactor, stir at high speed for 2h and then dry at 100℃ to obtain the treated silicon powder;

[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; 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;

[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 mixed evenly in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0089] Example 7:

[0090] 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: 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 silicone 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. DC1180 and DC1130 do not require surface treatment 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] 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 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 mixed evenly in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0098] Example 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] 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 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. The specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate and 1g water and then add dropwise into the reactor, stir at high speed for 2h, and then 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; 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 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 mixed evenly in a weight ratio of 1:1 to obtain an epoxy resin adhesive.

[0107] Example 9:

[0108] A high-temperature resistant epoxy resin adhesive is composed of component A and component B: component A contains 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] 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 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. The specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate and 1g water and then add dropwise into the reactor, stir at high speed for 2h, and then dry at 100°C to obtain the treated silicon micropowder;

[0110] Component B contains the following raw materials in parts 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; 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 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 mixed evenly 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 contains 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] Among them, the epoxy resin is a trifunctional epoxy resin TT310 and a 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 a silicon micropowder component of different mesh sizes, and the weight ratio of silicon micropowder DC1180 and 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 add dropwise into the reactor, stir at high speed for 2h, and then 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; 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; 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 mixed evenly 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 contains 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] Among them, the epoxy resin is a tetrafunctional epoxy resin TT410 and a 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 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. The specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then add dropwise into the reactor, stir at high speed for 2h, and then 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; 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; 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 mixed evenly 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 contains 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] Among them, the epoxy resin is a trifunctional epoxy resin TT310 and a 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 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. The specific operation process is to put 500g DC1180 or DC1130 into a reactor, mix 1g methyl orthosilicate with 1g water and then add dropwise into the reactor, stir at high speed for 2h, and then 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; 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; 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 mixed evenly 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] Specimen Preparation: 1. Mix components A and B, stir thoroughly, and degas under vacuum for 10 minutes. Then, apply the mixed epoxy resin adhesive to an aluminum sheet, construct shear strips, and place in an oven for curing at 120°C / 2h + 150°C / 1h + 180°C / 1h. 2. Apply a layer of epoxy resin adhesive approximately 2mm thick to an aluminum sheet measuring 25mm x 80mm. Place in an oven for curing at 120°C / 2h + 150°C / 1h + 180°C / 1h to produce a strip to test for adhesive surface cracking. The aluminum sheet used in the test is 1-series aluminum, measuring 25mm x 100mm.

[0146] Test method:

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

[0148] 2. Heat Aging Resistance: Cured shear specimens and specimens tested for adhesive surface cracking were placed in a 250°C oven for aging for 350 hours. Shear strength was then measured at room temperature in accordance with GB7124-86. The cracking of the aluminum sheet's surface film was observed. The surface cracking grade was determined as follows: crack width was measured with a vernier caliper, and the number of cracks within a 25 mm x 80 mm area of ​​the aluminum sheet's surface film was recorded. 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 falling off and powdering also belongs to cracking level 4.

[0149] 3. Glass transition temperature (Tg) test: The test equipment model is TMA / SDTA2+ (Mettler), and the test standard is GB / T 19466.2-2004. Generally, the higher the Tg point temperature, the better the high-temperature resistance. Thermogravimetric analysis: Using thermal analyzer TG209F3 (Netzsch, Germany), in an air atmosphere, the temperature is raised from 25°C to 800°C, and the temperature at 5% weight loss is recorded. Generally, the higher the temperature, the better the heat 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 5% thermal weight loss 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 other formula ratios remain unchanged and the total amount of epoxy resin remains unchanged, 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, 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 the other formula ratios remain unchanged, adjusting the ratio of the three epoxy resins and increasing the addition amount of the silicone modified epoxy resin BYW-471 are beneficial to improving the epoxy resin adhesive. The results show that the bonding strength and high temperature resistance of the epoxy resin adhesive are better than those of the MX-154 toughening agent in Example 4; when component A contains an antioxidant, the high temperature resistance of the epoxy resin adhesive is better, and the surface cracking grade can reach level 2; when component A contains an antioxidant, 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 cracking resistance of the epoxy resin adhesive; when component A and component B of the epoxy resin adhesive are not subjected to specific surface treatment, the high temperature resistance of the epoxy resin adhesive 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 considered as equivalent replacement methods and are included in the scope of protection 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; the toughening agent is a core-shell structure toughening agent; the A component also includes 0.1-0.3 parts of an antioxidant, and the antioxidant is at least one of phthalocyanine blue and cerium oxide; the filler is silicon micropowder; the silicon micropowder needs to be surface-treated before use, and 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; the curing agent is composed of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and diethyltoluenediamine in a weight ratio of (8-10):(10-20).

2. The 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 mixing method in the surface treatment is to first mix methyl orthosilicate with water and then dropwise add the mixture into the silicon micropowder.

4. A method for preparing the high temperature resistant epoxy resin adhesive according to any one of claims 1 to 3, 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, and mixed with the dispersant, coupling agent, defoaming agent, thixotropic agent and filler in the formula amount to disperse 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) Component A and component B are mixed to obtain an epoxy resin adhesive.

5. Use of the high temperature resistant epoxy resin adhesive according to any one of claims 1 to 3 as a bonding material for electronic components.

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