High-toughness damp-heat-resistant ultraviolet light and heat dual-curing organic silicon adhesive and preparation method thereof

Abstract

The invention discloses a high-toughness damp-heat-resistant ultraviolet light and heat dual-curing organic silicon adhesive and a preparation method thereof. The ultraviolet light and heat dual-curing organic silicon adhesive comprises dual-curing alkenyl-terminated resin, hydrogen-containing silicone oil, a dual-curing catalyst, a stabilizer and an auxiliary agent, the dual-curing alkenyl-terminated resin has a structure as shown in a formula (I): # imgabs0 #, R1 is an alicyclic group, R2 is C3-C5 alkyl, and n is a positive integer of 20-60; the hydrogen content of the hydrogen-containing silicone oil is 0.1 to 2.5 wt%; the dual-curing catalyst is a metal platinum catalyst; the stabilizer is an alkynol compound or a maleate compound; the molar ratio of hydrogen in the hydrogen-containing silicone oil to vinyl in the dual-curing alkenyl-terminated resin is 1-1.5. According to the present invention, the double-curing vinyl-terminated resin and the double-curing catalyst are contained, such that the ultraviolet light and heat double-curing can be achieved, the reasonable matching of the components can achieve the excellent damp-heat resistance and the excellent cold-hot impact resistance, and the high practical application value is provided.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, and in particular to a high-toughness, moisture-heat-resistant, ultraviolet-light and heat-resistant dual-curing organic silicone adhesive and a preparation method thereof. Background Art

[0002] Organosilicon compounds refer to compounds containing Si-C bonds, in which silicon atoms are connected to them through carbon atoms of organic groups, that is, at least one organic group is connected to silicon atoms to form organosilicon compounds. Organosilicon polymers refer to polymers containing elemental silicon in the main chain and organic groups connected to silicon atoms. Polyorganosiloxanes with repeated Si-O-Si bonds as the main chain and organic groups connected to silicon atoms are the main representatives and structural forms of organosilicon polymers. Polysiloxanes are a new type of polymer, and there are a large number of active groups at the ends of the main chain. Due to the long bond length of the Si-O bond, the large bond angle, and the extremely flexible structural characteristics of the Si-O main chain, it has a series of excellent properties that other materials cannot match. It can not only withstand high temperatures but also withstand low temperatures. Therefore, it can be used in a wide temperature range and has good weather resistance, corrosion resistance, electrical insulation, ozone resistance, hydrophobicity, flame retardancy, physiological inertness and other properties. Compared with traditional linear polymers, polysiloxanes have the characteristics of low viscosity, no chain entanglement, and good solubility due to their special branched structure, a large number of end groups, and the resulting low viscosity, no chain entanglement, and good solubility. Therefore, silicone polymer materials have been widely used in various aspects of the national economy, such as aerospace, electronics and electrical, chemical machinery, medical and health care, etc. However, silicone resins are usually cured by moisture curing or heat curing. However, the slow curing speed of moisture curing, high energy consumption and long time of heat curing limit the application of silicone resins.

[0003] UV curing technology is highly efficient, pollution-free, energy-saving, and simple. It is an environmentally friendly green technology that is becoming increasingly popular in the electronics industry. Photocuring adhesives are single-component adhesives that can even have a shelf life of more than one year at room temperature as long as they are kept in a dark place. Once exposed to ultraviolet light, they can be cured within a few seconds. They have a fast curing speed and high yield, making them particularly suitable for the production line assembly process of electronic products. However, traditional UV-curing silicones have disadvantages such as low hardness and poor adhesion to the substrate. There are also problems such as incomplete curing in shadowed areas and limited curing depth. In addition, the substrate is generally required to be a transparent material, which limits the application of photocuring silicone materials.

[0004] In electronic assembly, initial adhesion can ensure that components are quickly positioned and fixed. Adhesives with higher initial adhesion can significantly improve production efficiency. Moisture and heat resistance can adapt electronic devices to operate normally in harsh environments such as outdoor humidity and high temperature, ensuring the quality and reliability of electronic equipment. With the development of the electronics industry, its performance requirements are also continuously improving.

[0005] Therefore, in order to overcome the defects of the current UV or heat-cured organic silicone adhesives, it is still an urgent problem to develop a UV and heat-cured organic silicone adhesive with fast positioning, high toughness and moisture and heat resistance. Summary of the invention

[0006] To solve the above problems, the present invention provides a high-toughness, moisture-heat-resistant UV-light and heat-resistant dual-curing organic silicone adhesive and a preparation method thereof, and also provides a preparation method of a dual-curing terminal olefin resin, which overcomes the inherent disadvantages of single curing; by changing the type of the main resin and using different components in combination, the existing technology can overcome the inability to simultaneously achieve high toughness, moisture-heat resistance, and rapid positioning of electronic components.

[0007] In order to solve the above problems, the present invention provides a high-toughness, moisture-heat-resistant, ultraviolet and heat-resistant dual-curing organic silicone adhesive, comprising a dual-curing terminal olefin resin, hydrogen-containing silicone oil, a dual-curing catalyst, a stabilizer and an auxiliary agent;

[0008] The dual-cured terminal olefin resin is prepared from alicyclic diisocyanate monomers, terminal olefin alcohols and dual-terminal hydroxyl hydrogenated polybutadiene, and has a structure as shown in formula (I):

[0009]

[0010] Among them, R 1 is an alicyclic group, R 2 is a C3-C5 alkyl group, and n is a positive integer of 20-60;

[0011] The hydrogen content of the hydrogen-containing silicone oil is 0.1-2.5wt%, preferably 1-2wt%, and more preferably 1.55-1.66wt%.

[0012] The dual-cure catalyst is a metal platinum catalyst;

[0013] The stabilizer is an acetylenic alcohol compound or a maleate compound;

[0014] The molar ratio of hydrogen in the hydrogen-containing silicone oil to vinyl in the dual-cured terminal olefin resin is between 1 and 1.5, such as 1, 1.1, 1.2, 1.3, 1.4, 1.5 or any value therebetween; preferably between 1.3 and 1.5, more preferably 1.4.

[0015] In the present invention, the number average molecular weight of the dual-cured terminal olefin resin is 2000 to 4000, preferably 2000 to 3000;

[0016] In the present invention, the UV and heat dual-curing organic silicone adhesive comprises the following components in parts by weight: 60 to 100 parts of dual-curing terminal olefin resin, such as 60, 65, 70, 75, 80, 85, 90, 95, 100 parts or any value therebetween; 5 to 10 parts of hydrogen-containing silicone oil, such as 5, 6, 7, 8, 9, 10 parts or any value therebetween; catalyst (2 to 10) × 10 -6 Quantity, such as (2, 3, 4, 5, 6, 7, 8, 9, 10) × 10 -6 parts or any value therebetween; stabilizer (20-200)×10 -6 copies, such as (20, 40, 80, 120, 140, 180, 200) × 10 - parts or any value therebetween; 1 to 6 parts of auxiliary agent, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts or any value therebetween,

[0017] In the present invention, the preparation method of the dual-cured terminal olefin resin is:

[0018] S1. Mix the diisocyanate monomer, the first catalyst, the antioxidant and the polymerization inhibitor under light-proof conditions, and add terminal olefin alcohol dropwise at 40-50° C. When the NCO content in the reaction reaches 50% of the initial theoretical value, an intermediate product 1 is obtained;

[0019] S2. In a light-proof condition, the double-terminal hydroxyl hydrogenated polybutadiene and the second catalyst are mixed, the temperature is raised to 60-80° C., the intermediate product 1 is added dropwise, and the reaction is carried out until the NCO mass content reaches 0.1%, thereby obtaining the dual-cured terminal olefin resin.

[0020] In the present invention, in step S1, the molar ratio of the diisocyanate monomer to the terminal alkenyl alcohol is 0.9-1.1, such as 0.9, 0.95, 1, 1.15, 1.1 or any value therebetween;

[0021] In step S2, the molar ratio of the intermediate product 1 to the dihydroxy-terminated hydrogenated polybutadiene is 1.8-2.2, such as 1.8, 1.85, 1.9, 1.95, 2, 2.05, 2.1, 2.15, 2.2 or any value therebetween.

[0022] In the present invention, the first and second catalysts are respectively selected from one or more of organic tin, organic bismuth, organic zinc, organic cobalt and organic base catalysts.

[0023] In the present invention, the alicyclic diisocyanate monomer is selected from one or more of cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1-isocyanato-2-diisocyanatomethylcyclopentane, isophorone diisocyanate, bis-(4-isocyanatocyclohexyl)-methane, 2,4-dicyclohexylmethane diisocyanate, 1,3- or 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methylcyclohexyl)-methane, 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, and 2,4- or 2,6-hexahydrotoluene diisocyanate.

[0024] In the present invention, the number average molecular weight of the double-terminal hydroxyl hydrogenated polybutadiene is between 1000 and 3500.

[0025] In the present invention, the terminal alkenyl alcohol is a C3-C5 alkyl group having an olefinic bond at one end and a hydroxyl group at the other end, preferably 3-butene-1-ol and 4-pentene-1-ol.

[0026] In the present invention, the metal platinum catalyst is selected from any one or more of acetylacetonate platinum, trimethylmethylcyclopentadiene platinum, cis-dichlorotri(butylphosphine)platinum, cis-dichlorobis(dimethylphenylphosphine)platinum, tetrakis(1-phenyl-3-hexyltriazene)platinum, platinum / oxalate complex and β-dicarbonylplatinum, and acetylacetonate platinum or trimethylmethylcyclopentadiene platinum is preferred in the present invention.

[0027] In the present invention, the auxiliary agent is selected from one or more of a diluent, an antioxidant, an adhesion promoter, a coupling agent, a defoamer, a leveling agent, a wetting agent, a leveling agent, a toughening agent, a flame retardant, a pigment and a filler.

[0028] On the other hand, the present invention also provides a method for preparing a high-toughness, moisture-heat-resistant UV and heat dual-curing organic silicone adhesive, comprising the following steps: mixing the dual-curing terminal olefin resin, hydrogen-containing silicone oil, dual-curing catalyst, stabilizer and auxiliary agent, stirring for 1 to 5 hours under vacuum conditions of -0.005MPa to -0.2MPa and temperature of 20 to 40°C to obtain a UV and heat dual-curing organic silicone adhesive.

[0029] Beneficial effects of the present invention:

[0030] The present invention provides a high-toughness, moisture-heat-resistant UV and heat dual-curing organic silicone adhesive, comprising a dual-curing terminal olefin-based resin and a dual-curing catalyst, which can achieve dual curing. On the one hand, it can quickly have initial bonding strength when irradiated with ultraviolet light, and can achieve preliminary positioning of electronic components; when heated and cured, it can achieve deep post-curing and shadow area curing, shorten the heating and curing time, reduce energy consumption, and achieve a greater final strength. Using the prepared dual-curing terminal olefin-based resin as the main resin of the UV and heat dual-curing organic silicone adhesive, with suitable hydrogen-containing silicone oil, catalyst, stabilizer, silane coupling agent, and additives, it can also achieve excellent moisture and heat resistance, cold and heat shock resistance, and has high practical application value.

[0031] The present invention also prepares a dual-cured terminal olefin resin. The oligomer contains more isomeric groups in its molecular chain by introducing hydrogenated polybutadiene. The microscopic molecular chain spatial structure of the dual-cured terminal olefin resin as the main resin has the property of not being easily affected by the outside world when cured, so that it has excellent moisture and heat resistance; at the same time, the polymer main chain skeleton formed is a carbon-carbon chemical bond, which reduces the internal rotation steric hindrance in the dual-cured terminal olefin resin molecule. In addition, the alicyclic diisocyanate monomer in the oligomer makes the structure contain urethane bonds and alicyclic structures, which provides the oligomer with higher bonding strength and good flexibility.

[0032] The olefinic bonds of the dual-cure terminal olefinic resin of the present invention can be rapidly cross-linked by ultraviolet light irradiation under the action of a dual-cure catalyst, and can also undergo addition reaction with the silicon-hydrogen bonds at both ends of the hydrogen-containing silicone oil molecules under heating conditions, thereby forming an organic silicone adhesive with a relatively high cross-linking density, providing excellent moisture and heat resistance performance guarantee for electronic equipment and components.

[0033] The dual-cured terminal olefin resin prepared by the present invention is an oligomer with high toughness and moisture and heat resistance, which provides more possibilities for further developing more photothermal dual-cured organic silicone adhesives. DETAILED DESCRIPTION

[0034] The present invention is further described below in conjunction with specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0035] The raw materials and sources used in the following examples and comparative examples are as follows:

[0036] Dibutyltin dilaurate (DBTDL), selected from McLean, brand name DBTDL; isophorone diisocyanate (IPDI), selected from Wanhua Chemical, brand name IPDI; dicyclohexylmethane diisocyanate (HMDI), selected from Wanhua Chemical, brand: HMDI; 3-butene-1-ol, selected from Titan, brand name Adamas; 4-pentene-1-ol, selected from Titan, brand name Adamas; 2,6-di-tert-butyl-4-methylphenol, selected from Shanghai Ronghe Chemical; hydroquinone, selected from Eastman, brand name HQ; double-terminated hydroxyl hydrogenated polybutadiene, selected from Japan Soda, brand names NISSO-PB GI-1000 and NISSO-PB GI-2000; polymethyl hydrogen siloxane, selected from Dow, brand name XIAMETER TM MHX 1107; platinum diacetylacetonate, selected from Nantong Genesee, brand name Genesee UT 500; ethynyl cyclohexanol, selected from BASF of Germany; silane coupling agent, selected from Momentive of the United States, brand name SilquestA-187; fumed silica, selected from Wacker of Germany, brand name H18; antioxidant, selected from BASF of Germany, brand name 1010; Karstedt catalyst, selected from Shanghai Myrrel.

[0037] Preparation Example 1

[0038] (1) In a three-necked flask with a thermometer, 100 g of IPDI, 0.132 g of catalyst DBTDL, 0.132 g of di-tert-butyl-4-methylphenol and 0.05 g of hydroquinone were added dropwise at 40° C. The NCO group concentration was continuously monitored during the reaction. When it reached 50% of the initial theoretical value, the intermediate product IPDI-butenol was obtained.

[0039] (2) Under light-proof conditions, 100 g of double-terminated hydroxyl hydrogenated polybutadiene (NISSO-PB GI-1000) and 0.1 g of catalyst DBTDL were added to a three-necked flask with a thermometer, the temperature was raised and maintained at 60° C., 38 g of the intermediate product IPDI-butenol in step 1 was added dropwise, and the NCO content was tested every 30 minutes. When the NCO mass content was 0.1%, heating was stopped to obtain the final dual-cured terminal olefin resin A.

[0040] Preparation Example 2

[0041] (1) In a three-necked flask equipped with a thermometer, 100 g of HMDI, 0.132 g of catalyst DBTDL, 0.132 g of di-tert-butyl-4-methylphenol and 0.05 g of hydroquinone were added dropwise at 40° C. The NCO group concentration was continuously monitored during the reaction. When it reached 50% of the initial theoretical value, the intermediate product HMDI-pentenol was obtained.

[0042] (2) Under light-proof conditions, 100 g of double-terminated hydroxyl hydrogenated polybutadiene (NISSO-PB GI-2000) and 0.1 g of catalyst DBTDL were added to a three-necked flask with a thermometer, the temperature was raised and maintained at 60° C., 36.4 g of the intermediate product IPDI-pentenol in step 1 was added dropwise, and the NCO content was tested every 30 minutes. When the NCO mass content was 0.1%, heating was stopped to obtain the final dual-cured terminal olefin resin B.

[0043] Example 1

[0044] 82 parts of the obtained dual-cured terminal olefin resin A, 6.8 parts of polymethyl hydrogen siloxane, 8×10 -6 60 x 10 ethynyl cyclohexanol -6 0.2 parts of silane coupling agent, 0.2 parts of auxiliary agents (0.2 parts of antioxidant, 3 parts of fumed silica) were added into the reaction kettle, and stirred for 5 hours under the conditions of vacuum degree -0.2MPa and temperature 40°C to obtain a high-toughness, moisture-heat-resistant, ultraviolet and heat-resistant dual-curing organic silicone adhesive.

[0045] Example 2

[0046] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0047] 61 parts of dual-cured terminal olefin resin A and 3.7 parts of polymethyl hydrogen siloxane, and other steps remain unchanged.

[0048] Example 3

[0049] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0050] 74 parts of dual-cure terminal olefin resin A and 4.1 parts of polymethyl hydrogen siloxane, and other steps remain unchanged.

[0051] Example 4

[0052] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0053] 92 parts of dual-cure terminal olefin resin A and 5.2 parts of polymethyl hydrogen siloxane, and other steps remain unchanged.

[0054] Example 5

[0055] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0056] 101 parts of dual-cured terminal olefin resin A and 6 parts of polymethyl hydrogen siloxane, and the other steps remain unchanged.

[0057] Example 6

[0058] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0059] 7.3 parts of polymethyl hydrogen siloxane, and other steps remain unchanged.

[0060] Example 7

[0061] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0062] 6 parts of polymethyl hydrogen siloxane, and other steps remain unchanged.

[0063] Example 8

[0064] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0065] 8.3 parts of polymethyl hydrogen siloxane, and other steps remain unchanged.

[0066] Example 9

[0067] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0068] 3.9 parts of polymethyl hydrogen siloxane, and other steps remain unchanged.

[0069] Example 10

[0070] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0071] 82 parts of dual-cure terminal olefin resin B and 5.2 parts of polymethyl hydrogen siloxane, and other steps remain unchanged.

[0072] Embodiment 11

[0073] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0074] 61 parts of dual-cured terminal olefin resin B and 3.9 parts of polymethyl hydrogen siloxane, and the other steps remain unchanged.

[0075] Example 12

[0076] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0077] Dual-curing terminal olefin resin B74 parts, polymethyl hydrogen siloxane 4.6 parts, other steps remain unchanged.

[0078] Example 13

[0079] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0080] 92 parts of dual-curing terminal olefin resin B and 6 parts of polymethyl hydrogen siloxane, and the other steps remain unchanged.

[0081] Embodiment 14

[0082] The difference between this embodiment and embodiment 1 is that the contents of the following components are different:

[0083] 101 parts of dual-cured terminal olefin resin B and 6.6 parts of polymethyl hydrogen siloxane, and the other steps remain unchanged.

[0084] Comparative Example 1

[0085] 82 parts of vinyl-terminated polydimethylsiloxane, 6.8 parts of polymethylhydrogensiloxane, and 6×10 -6 60 x 10 ethynyl cyclohexanol -6 0.2 parts of silane coupling agent, and auxiliary agents (0.2 parts of antioxidant and 3 parts of fumed silica) were added into a reaction kettle, and stirred for 5 hours under the conditions of vacuum degree -0.2MPa and temperature 40°C to obtain an organic silicone adhesive.

[0086] Test Case

[0087] The products prepared in the examples and comparative examples were subjected to the following performance tests.

[0088] (1) Gel time

[0089] Use a dispensing machine to apply about 0.5g of the adhesive to be tested to the surface of the aluminum substrate, and use a UV light source (800mJ / cm 2 ) After radiation curing, the adhesive was placed on a heating table at 80°C to test the gel time, which is the turning point when the adhesive composition changes from liquid to solid.

[0090] (2) Tensile strength

[0091] The tensile strength test was carried out according to GB / T 528 / 92 standard. The adhesives obtained in the above examples and comparative examples were placed in a dumbbell-shaped polytetrafluoroethylene mold and exposed to ultraviolet light (1500 mJ / cm 2 ) radiation curing, then put it into a 130℃ oven for curing for 30 minutes, take it out, and test it at room temperature for 24 hours. Measure the width and thickness of the narrow parallel part of the dumbbell-shaped specimen, evenly place the dumbbell-shaped specimen on the upper and lower clamps, stretch it at a test speed of 500mm / min, and measure the tensile strength of the specimen.

[0092] (3) Tensile shear strength

[0093] Wipe the surface of the aluminum substrate with ethanol, wait for the ethanol to evaporate completely, stick a 0.2 mm aluminum foil tape on one end of the substrate, and apply the adhesive obtained in the above examples and comparative examples on one end of the aluminum substrate to ensure that the adhesive is evenly applied on the bonding part and then overlapped with the polycarbonate substrate, and clamped with a clamp. The sample in the example is exposed to ultraviolet light (1500 mJ / cm 2 ) After sufficient radiation curing, the samples were taken out and then put into a 130°C oven for curing for 30 minutes before testing; the comparative samples were overlapped in the same way, but only put into a 130°C oven for curing for 30 minutes before testing; the tensile shear strength test was carried out according to GB / T 7124-2008 standard, and the tensile shear strength test was carried out on an electronic tensile testing machine, the test temperature was 25°C, and the overlap area was 312.5mm 2 , the test rate is 5mm / min.

[0094] (4) Tensile shear strength retention rate after double 85

[0095] After the samples are prepared according to the tensile shear strength sample preparation method, they are placed in a constant temperature and humidity chamber with a set condition of 85℃ / 85%RH for 300h of double 85 aging test. After the test is completed, the tensile shear strength test after double 85 is carried out. The ratio of the measured result to the percentage of the initial tensile shear strength is the tensile shear strength retention rate after double 85.

[0096] (5) Tensile shear strength retention after thermal shock

[0097] After the sample is prepared according to the tensile shear strength sample preparation method, it is placed in a hot and cold shock box with a set condition of -40 ~ 85 ℃ for aging test. The -40 ℃ and 85 ℃ are kept warm for 30 minutes each, and the temperature zone conversion time is 10 ~ 20s for one cycle. A total of 500 cycles are tested. After the test is completed, the tensile shear strength test after hot and cold shock is carried out. The ratio of the measured result to the initial tensile shear strength is the tensile shear strength retention rate after hot and cold shock.

[0098] The performance test results of the products obtained in the embodiments and comparative examples are shown in Table 1:

[0099] Table 1

[0100]

[0101]

[0102] Combined with the data in Table 1, Comparative Example 1 uses the traditional vinyl siloxane adhesive obtained by heat curing only. It is obvious that it requires a long gel time of more than 200s, which is difficult to adapt to the application requirements of electronic devices that need to be quickly positioned and installed; in addition, its tensile strength and tensile shear strength are only 3.2MPa and 2.3MPa, and the mechanical properties of the adhesive are poor, and the bonding strength to the substrate is insufficient; the tensile shear strength retention rate after the double 85 and hot and cold shock tests is seriously reduced, indicating that the adhesive has poor moisture and heat resistance and insufficient flexibility, and cannot meet the protection requirements of electronic products in harsh environments of high temperature, high humidity, and alternating hot and cold.

[0103] By comparing Comparative Example 1 and Examples 1-14, it can be seen that the high-toughness, moisture-heat-resistant, UV-light and heat-resistant dual-curing silicone adhesive prepared in the present application can achieve a faster gel time, and at the same time, its mechanical properties and bonding properties are excellent, and can achieve a tensile strength greater than 6MPa and a tensile shear strength of not less than 5MPa; the tensile shear strength retention rates after double 85% and hot and cold shocks are effectively improved, and the retention rates are all greater than 85%.

[0104] From Examples 1-5 and 10-14, it can be seen that the dual-cure terminal olefin resin prepared by using different types or different molecular weights of terminal hydroxyl polyisobutylene, alicyclic diisocyanate, and terminal olefin alcohol reasonably matched, the dual-cure terminal olefin resin A and the dual-cure terminal olefin resin B prepared have excellent properties.

[0105] From the comparison between Example 1 and Examples 6-9, it can be seen that when the ratio of Si-H to Si-Vi is changed, the performance will be affected; in Example 1, when the ratio of Si-H to Si-Vi is 1.4, the performance of the cured adhesive is optimal, and it can be seen that the cross-linking effect is optimal at this ratio, and the performance indicators are all optimal; in Example 6, when the ratio of Si-H to Si-Vi is 1.5, due to the addition of excessive hydrogen-containing silicone oil, the toughness and bonding properties are reduced, which may be due to the self-polymerization of excessive Si-H bonds under platinum catalysis to generate hydrogen, making the adhesive layer brittle; in Example 8, when the ratio of Si-H to Si-Vi is greater than 1.5, it has little effect on the gel time, but the mechanical strength of the adhesive layer is significantly reduced, which reduces the moisture and heat resistance of the adhesive layer and is not suitable for use in specific environments. In Example 6, when the ratio of Si-H to Si-Vi is 1.2, the mechanical properties and moisture and heat resistance are slightly reduced, and the thermal shock resistance is slightly reduced due to insufficient crosslinking density; in Example 9, when the ratio of Si-H to Si-Vi is lower than 1, due to severe lack of active groups and low crosslinking density, the mechanical properties, moisture and heat resistance, and thermal shock resistance all drop sharply, and it is also not suitable for use in specific environments.

[0106] In summary, the prepared dual-cured terminal olefin resin as the main resin of UV and heat dual-cured silicone adhesive, in combination with hydrogen-containing silicone oil, and matched with suitable catalysts, stabilizers, silane coupling agents, and additives, can meet the requirements of rapid positioning, moisture and heat resistance, and cold and hot shock resistance in the field of electronic adhesives, and has high practical application value.

[0107] The above-described embodiments are only preferred embodiments for fully illustrating the present invention, and the protection scope of the present invention is not limited thereto. Equivalent substitutions or changes made by those skilled in the art based on the present invention are within the protection scope of the present invention. The protection scope of the present invention shall be subject to the claims.

Claims

1. A high-toughness, moisture-resistant, ultraviolet and heat-resistant dual-curing organic silicone adhesive, characterized in that: It includes dual-curing olefin-terminated resin, hydrogen-containing silicone oil, dual-curing catalyst, stabilizer and auxiliary agent; The dual-cured terminal olefin resin is prepared from alicyclic diisocyanate monomers, terminal olefin alcohols and dual-terminal hydroxyl hydrogenated polybutadiene, and has a structure as shown in formula (I): Among them, R 1 is an alicyclic group, R 2 is a C3-C5 alkyl group, and n is a positive integer of 20-60; The hydrogen content of the hydrogen-containing silicone oil is 0.1 to 2.5 wt %; The dual-cure catalyst is a metal platinum catalyst; The stabilizer is an acetylenic alcohol compound or a maleate compound; The molar ratio of hydrogen in the hydrogen-containing silicone oil to vinyl in the dual-cured terminal olefin resin is between 1 and 1.

5.

2. The method for preparing a high-toughness, moisture-heat-resistant, ultraviolet and heat-resistant dual-curing organic silicone adhesive as claimed in claim 1, characterized in that: The number average molecular weight of the dual-cured olefin-terminated resin is 2000 to 4000, preferably 2000 to 3000; The hydrogen content of the hydrogen-containing silicone oil is 1 to 2 wt%; The molar ratio of hydrogen in the hydrogen-containing silicone oil to vinyl in the dual-cured olefin-terminated resin is between 1.3 and 1.5, preferably 1.

4.

3. The high-toughness, moisture-heat-resistant, ultraviolet and heat-resistant dual-curing organic silicone adhesive according to claim 1, characterized in that: The UV and heat dual-curing organic silicone adhesive comprises the following components in parts by weight:

4. The high-toughness, moisture-heat-resistant, UV- and heat-resistant dual-curing organic silicone adhesive according to claim 1, characterized in that: The preparation method of the dual-cured terminal olefin resin is as follows: S1. Mix the diisocyanate monomer, the first catalyst, the antioxidant and the polymerization inhibitor under light-proof conditions, and add terminal olefin alcohol dropwise at 40-50° C. When the NCO content in the reaction reaches 50% of the initial theoretical value, an intermediate product 1 is obtained; S2. In a light-proof condition, the double-terminal hydroxyl hydrogenated polybutadiene and the second catalyst are mixed, the temperature is raised to 60-80° C., the intermediate product 1 is added dropwise, and the reaction is carried out until the NCO mass content reaches 0.1%, thereby obtaining the dual-cured terminal olefin resin.

5. The method for preparing a high-toughness, moisture-heat-resistant, ultraviolet and heat-resistant dual-curing organic silicone adhesive as claimed in claim 4, characterized in that: In step S1, the molar ratio of the diisocyanate monomer to the terminal alkenyl alcohol is 0.9 to 1.1; In step S2, the molar ratio of the intermediate product 1 to the dihydroxy-terminated hydrogenated polybutadiene is 1.8 to 2.

2.

6. The high-toughness, moisture-heat-resistant, UV- and heat-resistant dual-curing organic silicone adhesive as claimed in claim 4, characterized in that: The alicyclic diisocyanate monomer is selected from one or more of cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1-isocyanato-2-diisocyanatomethylcyclopentane, isophorone diisocyanate, bis-(4-isocyanatocyclohexyl)-methane, 2,4-dicyclohexylmethane diisocyanate, 1,3- or 1,4-bis-(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methylcyclohexyl)-methane, 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane, and 2,4- or 2,6-hexahydrotoluene diisocyanate. The number average molecular weight of the double-terminal hydroxyl hydrogenated polybutadiene is between 1000 and 3500.

7. The high-toughness, moisture-heat-resistant, ultraviolet and heat-resistant dual-curing organic silicone adhesive as claimed in claim 4, characterized in that: The terminal alkenyl alcohol is a C3-C5 alkyl group having an olefinic bond at one end and a hydroxyl group at the other end, preferably 3-butene-1-ol and 4-pentene-1-ol.

8. The high-toughness, moisture-heat-resistant, ultraviolet and heat-resistant dual-curing organic silicone adhesive according to claim 1, characterized in that: The metal platinum catalyst is selected from any one or more of acetylacetonate platinum, trimethylmethylcyclopentadiene platinum, cis-dichlorotri(butylphosphine)platinum, cis-dichlorobis(dimethylphenylphosphine)platinum, tetrakis(1-phenyl-3-hexyltriazene)platinum, platinum / oxalate complex and β-dicarbonylplatinum. In the present invention, acetylacetonate platinum or trimethylmethylcyclopentadiene platinum is preferred.

9. The high-toughness, moisture-heat-resistant, UV- and heat-resistant dual-curing organic silicone adhesive as claimed in claim 1, characterized in that: The auxiliary agent is selected from one or more of a diluent, an antioxidant, an adhesion promoter, a coupling agent, a defoamer, a leveling agent, a wetting agent, a leveling agent, a toughening agent, a flame retardant, a pigment and a filler.

10. A method for preparing a high-toughness, moisture-heat-resistant, ultraviolet and heat-resistant dual-curing organic silicone adhesive according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: mixing the dual-curing terminal olefin resin, hydrogen-containing silicone oil, dual-curing catalyst, stabilizer and auxiliary agent, stirring for 1 to 5 hours under the conditions of vacuum degree -0.005MPa to -0.2MPa and temperature 20 to 40°C to obtain ultraviolet light and heat dual-curing organic silicone adhesive.

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