Photo-thermal dual-curing packaging adhesive as well as preparation method and application thereof

Abstract

The invention provides a photo-thermal dual-curing packaging adhesive as well as a preparation method and application thereof, and belongs to the technical field of packaging adhesives. The epoxy resin modified alicyclic polyamine is used as a curing agent of the thermocuring mixed sizing material, and the equivalent weight of reactive hydrogen is controlled, so that the thermocuring mixed sizing material can be stored for a long time at room temperature without crosslinking; after the thermocuring mixed glue material and the photocuring mixed glue material are mixed, the thermocuring mixed glue material is excited by heat generated by photocuring reaction of the photocuring mixed glue material to perform deep curing, so that a packaging layer formed after the photothermal dual-curing packaging glue is cured has excellent mechanical property and stability. According to the invention, the silane coupling agent is utilized to improve the adhesion of the photo-thermal dual-curing packaging adhesive. The main antioxidant and the auxiliary antioxidant are utilized to improve the weather resistance of a packaging layer formed after the photo-thermal dual-curing packaging adhesive is cured, so that the packaging layer has good stability.

Description

Technical Field

[0001] The present invention relates to the technical field of encapsulation adhesives, and particularly to a photo-thermal dual-curing encapsulation adhesive, a preparation method thereof, and an application thereof. Background Art

[0002] The encapsulation adhesive for traditional electronic components is epoxy resin. This is because epoxy resin encapsulation adhesive performs excellently in improving the optical transparency of electronic components, and at the same time, with the high-strength characteristic of epoxy resin, it provides more solid physical protection for electronic components. However, the curing period of epoxy resin is long, resulting in low production efficiency; moreover, with the extension of the use time, epoxy resin turns yellow, affecting the visual effect of electronic components. The optical performance of acrylic adhesive is good, and it can be quickly encapsulated through photocuring technology. However, the performance of pure acrylic colloid is brittle after curing. Under the condition of large-area potting, heat accumulation is likely to occur, resulting in volume shrinkage, material deformation, and the bottom and shadow areas cannot achieve deep curing.

[0003] Currently, there are related prior arts that use acrylic monomers, catalysts, inhibitors, and epoxy resin as raw materials to prepare epoxy-modified acrylic resin, which can quickly surface-dry in 4 - 8 s under the light intensity of 250 - 400 mJ / cm 2 and can form a film and cure in 1 - 5 h at 50 - 70 °C, realizing photo-thermal dual curing. However, this method still requires heating the epoxy-modified acrylic resin after ultraviolet light irradiation, and there are still problems of long curing period and reduced production efficiency; moreover, the epoxy-modified acrylic resin also has the problem of short storage period, resulting in inability to store for a long time before use.

[0004] Therefore, there is an urgent need to provide a photo-thermal dual-curing encapsulation adhesive with a long storage period, fast curing, good mechanical properties, and good stability. Summary of the Invention

[0005] The purpose of the present invention is to provide a photo-thermal dual-curing encapsulation adhesive with a long storage period, fast curing, good mechanical properties, and good stability, a preparation method thereof, and an application thereof.

[0006] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions: The present invention provides a photo-thermal dual-curing encapsulation adhesive, which includes a photocuring mixed rubber material, a thermal curing mixed rubber material, a silane coupling agent, a main antioxidant, a secondary antioxidant, and an auxiliary agent; the mass ratio of the photocuring mixed rubber material to the thermal curing mixed rubber material is 10:1 - 4; the ratio of the total mass of the photocuring mixed rubber material and the thermal curing mixed rubber material to the mass of the silane coupling agent, the mass of the main antioxidant, the mass of the secondary antioxidant, and the mass of the auxiliary agent is 100:(1 - 5):(0.3 - 0.5):(0.3 - 0.5):(0.001 - 0.2); The photocuring hybrid sizing material comprises the following components in parts by weight: 100 parts of modified acrylate, 20-40 parts of acrylate active diluent, 1-3 parts of photoinitiator and 1-3 parts of co-initiator; The thermocuring hybrid sizing material comprises the following components in parts by weight: 100 parts of epoxy resin and 20-40 parts of epoxy resin modified alicyclic polyamine; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 42-79 g / mol.

[0007] Preferably, the modified acrylate is one or two of epoxy-modified acrylate, polyurethane-modified acrylate and silicone-modified acrylate.

[0008] Preferably, the acrylate active diluent comprises one or more of monofunctional active diluent, difunctional active diluent and polyfunctional active diluent.

[0009] Preferably, the photoinitiator comprises one or more of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxy-cyclohexyl-phenylmethanone.

[0010] Preferably, the co-initiator is triethanolamine.

[0011] Preferably, the epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin.

[0012] Preferably, the alicyclic polyamine in the epoxy resin modified alicyclic polyamine is one of MDA, IPDA and N -AEP; the epoxy resin in the epoxy resin modified alicyclic polyamine is bisphenol A epoxy resin or bisphenol F epoxy resin.

[0013] Preferably, the additives include one or more of light diffusing agent, titanium dioxide, defoaming agent and dispersant.

[0014] The present invention also provides a preparation method for the photothermal dual-curing encapsulation sizing material described in the above technical solution, comprising: Mixing the modified acrylate, acrylate active diluent, photoinitiator and co-initiator in the dark to obtain a photocuring hybrid sizing material; Mixing the epoxy resin and epoxy resin modified alicyclic polyamine to obtain a thermocuring hybrid sizing material; Mixing the photocuring hybrid sizing material, the thermocuring hybrid sizing material, silane coupling agent, main antioxidant, auxiliary antioxidant and additives in the dark to obtain a photothermal dual-curing encapsulation sizing material.

[0015] The present invention also provides an application of the photo-thermal dual-curing encapsulation adhesive described in the above technical solution in encapsulating electronic components, including: coating the photo-thermal dual-curing encapsulation adhesive on the surface of the electronic components, and performing photo-thermal dual-curing reaction under ultraviolet light to obtain encapsulated electronic components; the time of the photo-thermal dual-curing reaction is 30 to 70 s.

[0016] The present invention provides a photo-thermal dual-curing encapsulation adhesive, which includes a photo-curing mixed compound, a thermal-curing mixed compound, a silane coupling agent, a main antioxidant, a secondary antioxidant and an auxiliary agent; the mass ratio of the photo-curing mixed compound to the thermal-curing mixed compound is 10:1 to 4; the ratio of the total mass of the photo-curing mixed compound and the thermal-curing mixed compound to the mass of the silane coupling agent, the mass of the main antioxidant, the mass of the secondary antioxidant and the mass of the auxiliary agent is 100:(1 to 5):(0.3 to 0.5):(0.3 to 0.5):(0.05 to 0.5); the photo-curing mixed compound includes the following components in parts by weight: 100 parts of modified acrylate, 20 to 40 parts of acrylate active diluent, 1 to 3 parts of photoinitiator and 1 to 3 parts of co-initiator; the thermal-curing mixed compound includes the following components in parts by weight: 100 parts of epoxy resin and 20 to 40 parts of epoxy resin-modified alicyclic polyamine; the active hydrogen equivalent of the epoxy resin-modified alicyclic polyamine is 42 to 79 g / mol. In the present invention, the epoxy resin-modified alicyclic polyamine is used as the curing agent of the thermal-curing mixed compound. When the active hydrogen equivalent of the epoxy resin-modified alicyclic polyamine is 42 to 79 g / mol, its reaction activity can be reduced, so that the thermal-curing mixed compound can be stored at room temperature for a long time without cross-linking; after the thermal-curing mixed compound and the photo-curing mixed compound are mixed, the heat generated by the photo-curing reaction of the photo-curing mixed compound is used to stimulate the deep curing of the thermal-curing mixed compound, so that the photo-thermal dual-curing encapsulation adhesive has excellent mechanical properties and stability after curing. The present invention uses a silane coupling agent to improve the adhesion of the photo-thermal dual-curing encapsulation adhesive and improve the stability of the encapsulation layer formed after the photo-thermal dual-curing encapsulation adhesive is cured. The present invention uses a main antioxidant and a secondary antioxidant to improve the weather resistance of the encapsulation layer formed after the photo-thermal dual-curing encapsulation adhesive is cured, so that the encapsulation layer has good stability. The results of the examples show that the photo-thermal dual-curing encapsulation adhesive provided by the present invention can be rapidly cured only under ultraviolet light irradiation for 30 to 70 s without further heat treatment; the tensile strength of the encapsulation layer formed after curing is ≥32 MPa, and the impact strength is ≥30 KJ / m 2 and has excellent mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is a schematic diagram of the synthesis mechanism of the epoxy resin-modified alicyclic polyamine used in the examples of the present invention; Figure 2The infrared spectrogram of R1-I-E51-P prepared from E51 and IPDA used in the embodiments of the present invention. Detailed implementation manners

[0018] The present invention provides a photo-thermal dual-curing encapsulation adhesive, which includes a photo-curing mixed rubber compound, a thermal-curing mixed rubber compound, a silane coupling agent, a main antioxidant, an auxiliary antioxidant, and an auxiliary agent; the mass ratio of the photo-curing mixed rubber compound to the thermal-curing mixed rubber compound is 10:1 to 4; the ratio of the total mass of the photo-curing mixed rubber compound and the thermal-curing mixed rubber compound to the mass of the silane coupling agent, the mass of the main antioxidant, the mass of the auxiliary antioxidant, and the mass of the auxiliary agent is 100:(1 to 5):(0.3 to 0.5):(0.3 to 0.5):(0.001 to 0.2); The photo-curing mixed rubber compound includes the following components in parts by weight: 100 parts of a modified acrylate, 20 to 40 parts of an acrylate active diluent, 1 to 3 parts of a photoinitiator, and 1 to 3 parts of a co-initiator; The thermal-curing mixed rubber compound includes the following components in parts by weight: 100 parts of an epoxy resin and 20 to 40 parts of an epoxy resin-modified alicyclic polyamine; the active hydrogen equivalent of the epoxy resin-modified alicyclic polyamine is 42 to 79 g / mol.

[0019] The photo-thermal dual-curing encapsulation adhesive provided by the present invention includes a photo-curing mixed rubber compound.

[0020] In the present invention, the photo-curing mixed rubber compound includes 100 parts by weight of a modified acrylate. In the present invention, the modified acrylate is preferably one or two of an epoxy-modified acrylate, a polyurethane-modified acrylate, and a silicone-modified acrylate, and more preferably an epoxy acrylate and a polyurethane acrylate. In the present invention, the mass ratio of the epoxy acrylate (EA) to the polyurethane acrylate (PUA) is preferably 1 to 9:9 to 1, and more preferably 1:1. In the present invention, the epoxy-modified acrylate, the polyurethane-modified acrylate, and the silicone-modified acrylate all come from Changxing Materials Industry Co., Ltd. Among the above-mentioned modified acrylates provided by the present invention, the epoxy-modified acrylate has a low cost, good solvent resistance and chemical corrosion resistance, shows excellent adhesion to a variety of substrates (such as metals, glasses, etc.), and the cured coating has a high hardness and good wear resistance; the polyurethane-modified acrylate has good flexibility and adhesion, and can firmly adhere to the substrate material; the Si-O-Si bond energy in the structure of the silicone-modified acrylate is high, and the anti-ultraviolet and oxidation abilities are strong, so that the resin has a long service life in the outdoor environment.

[0021] Based on 100 parts by weight of the modified acrylate, the photocurable adhesive composition comprises 20 to 40 parts by weight of an acrylate reactive diluent. As an embodiment of the present invention, the weight parts of the acrylate reactive diluent can be 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts or 40 parts.

[0022] In the present invention, the acrylate reactive diluent preferably comprises one or more of a monofunctional reactive diluent, a difunctional reactive diluent and a polyfunctional reactive diluent, more preferably a compound of a monofunctional reactive diluent, a difunctional reactive diluent and a polyfunctional reactive diluent. In the present invention, the monofunctional reactive diluent is preferably 2-hydroxyethyl methacrylate (HEMA) and / or 2-hydroxyethyl acrylate (HEA); the difunctional reactive diluent is preferably one or more of hydrolyzed polymaleic anhydride (HPMA), tri(propylene glycol) diacrylate (TPGDA), polyethylene glycol diacrylate (PEGDA) and 1,6-hexanediol diacrylate (HDDA); the polyfunctional reactive diluent is preferably trimethylolpropane triglycidyl ether (TMPTA).

[0023] In the present invention, the mass ratio of the monofunctional reactive diluent, the difunctional reactive diluent and the polyfunctional reactive diluent in the compound of the monofunctional reactive diluent, the difunctional reactive diluent and the polyfunctional reactive diluent is preferably (1 to 10):(1 to 10):(20 to 30), more preferably (2 to 8):(2 to 8):(22 to 28). By adding the acrylate reactive diluent, the present invention enables the photo-thermal dual-curing encapsulation adhesive to have excellent fluidity, controllable regulation of the amount of remaining glue and the thickness of the encapsulation adhesive, ensures that the light can effectively penetrate and diverge, and at the same time, the monofunctional and difunctional reactive diluents can provide good toughness in the system; the polyfunctional reactive diluent has multiple reaction sites, which can increase the reaction rate and the crosslinking density of the system, and increase the strength of the encapsulation layer formed after the photo-thermal dual-curing encapsulation adhesive is cured.

[0024] In the present invention, the compound of the monofunctional reactive diluent, the difunctional reactive diluent and the multifunctional reactive diluent is further preferably a compound of HEA, HDDA and TPMTA, and the mass ratio of HEA, HDDA and TPMTA in the compound of HEA, HDDA and TPMTA is preferably (1-10): (1-10): (20-30), and more preferably (2-8): (2-8): (22-28). When the present invention uses the compound of HEA, HDDA and TPMTA as the acrylate reactive diluent, hydroxyethyl acrylate can form strong hydrogen bonds on the surface of the substrate material due to the presence of hydroxyl groups, thereby improving the adhesion of the encapsulation glue on the surface of the substrate material, and the hydroxyl groups are hydrophilic, so that the adhesion can remain stable even in a humid environment. In the present invention, the acrylate reactive diluents are all derived from Changxing Materials Industry Co., Ltd.

[0025] Based on 100 parts by weight of the modified acrylate, the photocurable mixed adhesive includes 1 to 3 parts of a photoinitiator. As an embodiment of the present invention, the weight of the photoinitiator may be 1 part, 2 parts or 3 parts. In the present invention, the photoinitiator preferably includes one or more of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxy-cyclohexyl-phenyl ketone. In the present invention, by adding a photoinitiator, the photothermal dual-curing encapsulation adhesive generates free radicals after being irradiated with ultraviolet rays (UV) of an appropriate wavelength, and quickly reacts with the double bonds (usually C=C double bonds) in the modified acrylate or acrylate reactive diluent to carry out a chain growth reaction to achieve photocuring. In the present invention, the photoinitiators are all derived from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0026] Based on 100 parts by weight of the modified acrylate, the photocurable mixed adhesive includes 1 to 3 parts of a co-initiator. As an embodiment of the present invention, the weight of the co-initiator can be 1 part, 2 parts or 3 parts. In the present invention, the co-initiator is preferably triethanolamine. The present invention can improve the efficiency of photocuring by using a co-initiator. In the present invention, the co-initiator is derived from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0027] In the present invention, the mass ratio of the photoinitiator to the co-initiator is preferably 1:1 to 2, and more preferably 1:1.5 to 2. The present invention controls the mass ratio of the photoinitiator to the co-initiator to be within the above range, which is more conducive to exerting the synergistic effect of the photoinitiator and the co-initiator and improving the efficiency of photocuring.

[0028] The photocuring and thermocuring encapsulating adhesive provided by the present invention comprises a thermocuring mixed stock.

[0029] The thermocuring mixed stock provided by the present invention comprises 100 parts by weight of an epoxy resin. In the present invention, the epoxy resin is preferably a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, more preferably a bisphenol A type epoxy resin. In the present invention, the bisphenol A type epoxy resin is preferably E-51 or E-44, and the epoxy value of the bisphenol A type epoxy resin is preferably 0.45-0.54. The above epoxy resin is used in the present invention for the curing reaction and can also be used to modify an alicyclic polyamine to obtain an epoxy resin-modified alicyclic polyamine. In the present invention, the epoxy resin is sourced from Changxing Materials Industry Co., Ltd.

[0030] Based on 100 parts by weight of the epoxy resin, the thermocuring mixed stock comprises 20-40 parts by weight of an epoxy resin-modified alicyclic polyamine. As an embodiment of the present invention, the parts by weight of the epoxy resin-modified alicyclic polyamine can be 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts or 40 parts. In the present invention, the active hydrogen equivalent of the epoxy resin-modified alicyclic polyamine is 42-79 g / mol. As an embodiment of the present invention, the active hydrogen equivalent of the epoxy resin-modified alicyclic polyamine can be 42-43 g / mol, 43-54 g / mol, 54-60 / mol, 60-67 g / mol, 67-74 g / mol or 74-79 g / mol. By using the above epoxy resin-modified alicyclic polyamine as a thermocuring agent in the present invention, the epoxy resin can exhibit high tensile strength, flexural strength and impact toughness after curing, and after curing, the epoxy resin exhibits high light transmittance and low yellowing rate. When its active hydrogen equivalent is within the above range, its reaction activity can be reduced, so that the photocuring and thermocuring encapsulating adhesive still has good activity while the storage period is extended.

[0031] In the present invention, the alicyclic polyamine in the epoxy resin-modified alicyclic polyamine is preferably one of 4,4'-diaminodimethane (MDA), isophorone diamine (IPDA) and N-(2-aminoethyl)piperazine ( N -AEP). The above alicyclic polyamine is selected in the present invention, and each molecule contains 3-4 active hydrogens. It can be modified by an epoxy resin, and a part of the active hydrogens need to be consumed during the modification process. The active hydrogen equivalent of the obtained epoxy resin-modified alicyclic polyamine is 42-79 g / mol. Since the active hydrogen equivalent of the epoxy resin-modified alicyclic polyamine in the present invention affects the curing effect of the epoxy resin, so with MDA, IPDA or N-As an alicyclic polyamine, when the epoxy resin-modified alicyclic polyamine obtained has the same active hydrogen equivalent, it has quite good technical effects. In the present invention, the alicyclic amine is sourced from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0032] In the present invention, the epoxy resin in the epoxy resin-modified alicyclic polyamine is preferably bisphenol A epoxy resin or bisphenol F epoxy resin, more preferably bisphenol A epoxy resin. In the present invention, the bisphenol A epoxy resin is preferably E-51 or E-44, and its epoxy value is preferably 0.45 - 0.54. The present invention uses the above-mentioned epoxy resin to modify the alicyclic polyamine to obtain the epoxy resin-modified alicyclic polyamine. In the present invention, the epoxy resin is sourced from Changxing Materials Industry Co., Ltd.

[0033] In the present invention, the mass ratio of the photocurable mixed adhesive to the thermosetting mixed adhesive is 10:1 - 4. As an embodiment of the present invention, the mass ratio of the photocurable mixed adhesive to the thermosetting mixed adhesive can be 10:1, 10:2, 10:3 or 10:4. The present invention controls the mass ratio of the photocurable mixed adhesive to the thermosetting mixed adhesive within the above range, so that the heat generated during the photocuring of the photocurable mixed adhesive can completely cure the thermosetting mixed adhesive.

[0034] The photo-thermally dual-curable encapsulating adhesive provided by the present invention includes a silane coupling agent. In the present invention, the silane coupling agent preferably includes one of KH550, KH560 and KH570, more preferably KH570. In the present invention, one end of KH570 is methacryloyloxy (-OCO-CH=CH2), which can undergo a free radical reaction with acrylate and better blend in the system; the other end is three methoxy groups (-OCH3) connected to the silicon atom, and these methoxy groups can be converted into silanol groups (-OH) under hydrolysis conditions, and then form hydrogen bonds with the hydroxyl groups on the surface of the substrate material or form stable siloxane bonds through a condensation reaction, improving the adhesion between the resin adhesive and the substrate material. In the present invention, the silane coupling agent is sourced from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0035] The photo-thermally dual-curable encapsulating adhesive provided by the present invention includes a primary antioxidant. In the present invention, the primary antioxidant is preferably a hindered phenol antioxidant, and the hindered phenol antioxidant is preferably one or more of BHT (2,6-di-tert-butyl-p-cresol), HQ (p-methoxyphenol) and 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), more preferably BHT. In the present invention, the primary antioxidant is sourced from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0036] The photo-thermal dual-curing encapsulation adhesive provided by the present invention includes a secondary antioxidant. In the present invention, the secondary antioxidant is preferably a phosphite, and the phosphite is preferably one or more of tris(2,4-di-tert-butylphenyl) phosphite, dilauryl thiodipropionate, and didodecyl thiodipropionate, more preferably tris(2,4-di-tert-butylphenyl) phosphite. In the present invention, the secondary antioxidant is sourced from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0037] The photo-thermal dual-curing encapsulation adhesive provided by the present invention includes additives. In the present invention, the additives preferably include one or more of a light diffusing agent, titanium dioxide, an antifoaming agent, and a dispersant. In the examples of the present invention, when the additives are a light diffusing agent, titanium dioxide, an antifoaming agent, and a dispersant, the mass ratio of the light diffusing agent, titanium dioxide, antifoaming agent, and dispersant can be 1:1:1:1. The present invention emits light by adding a light diffusing agent, making the light softer. While protecting the human eye, it has a high light transmittance, enabling the light to propagate well. By adding titanium dioxide as a pigment, the present invention can prepare the encapsulation adhesive into colors that meet different scenarios and requirements, increasing the aesthetic appearance of electronic components. By adding an antifoaming agent and a dispersant, the present invention can defoam and promote more uniform dispersion of each component.

[0038] In the present invention, the light diffusing agent is preferably an organosilicon-based light diffusing agent or an acrylic-based light diffusing agent, more preferably an acrylic-based light diffusing agent. The particle size of the light diffusing agent is preferably 200 - 500 nm, more preferably 300 - 400 nm. In the present invention, the light diffusing agent is sourced from Shenzhen Haiyang Powder Technology Co., Ltd.

[0039] In the present invention, the particle size of the titanium dioxide is preferably 100 - 500 nm, more preferably 200 - 400 nm. In the present invention, the titanium dioxide is sourced from Shenzhen Haiyang Powder Technology Co., Ltd.

[0040] In the present invention, the antifoaming agent is preferably DU-1052; the dispersant is preferably BYK-180.

[0041] In the present invention, the ratio of the total mass of the photocurable mixed sizing material and the thermosetting mixed sizing material to the mass of the silane coupling agent, the main antioxidant, the auxiliary antioxidant, and the additive is 100:(1 - 5):(0.3 - 0.5):(0.3 - 0.5):(0.001 - 0.2), preferably 100:(2 - 4):(0.4 - 0.5):(0.4 - 0.5):(0.01 - 0.2). By controlling the ratio of the total mass of the photocurable mixed sizing material and the thermosetting mixed sizing material to the mass of the silane coupling agent, the main antioxidant, the auxiliary antioxidant, and the additive within the above range, the photo-thermally dual-curable encapsulating adhesive of the present invention can have the advantages of rapid curing, good mechanical properties, and good stability.

[0042] The present invention also provides a preparation method for the photo-thermally dual-curable encapsulating adhesive described in the above technical solution, including: Mixing a modified acrylate, an acrylate active diluent, a photoinitiator, and a co-initiator in the dark to obtain a photocurable mixed sizing material; Mixing an epoxy resin and an epoxy resin-modified alicyclic polyamine to obtain a thermosetting mixed sizing material; Mixing the photocurable mixed sizing material, the thermosetting mixed sizing material, the silane coupling agent, the main antioxidant, the auxiliary antioxidant, and the additive in the dark to obtain a photo-thermally dual-curable encapsulating adhesive.

[0043] In the present invention, a modified acrylate, an acrylate active diluent, a photoinitiator, and a co-initiator are mixed in the dark to obtain a photocurable mixed sizing material.

[0044] In the present invention, the method for mixing the modified acrylate, the acrylate active diluent, the photoinitiator, and the co-initiator is preferably stirring in the dark. In the present invention, the rotation speed of the stirring in the dark is preferably 300 - 500 rpm, more preferably 340 - 450 rpm; the time of the stirring in the dark is preferably 20 - 30 min, more preferably 25 - 30 min. In the present invention, the stirring in the dark is preferably carried out under heating, and the heating temperature is preferably 80 - 100 °C, more preferably 85 - 95 °C. By adopting the above mixing method, the present invention can fully dissolve each component to form a photocurable mixed sizing material, and the darkness can prevent the photocurable mixed sizing material from curing in advance.

[0045] In the present invention, an epoxy resin and an epoxy resin-modified alicyclic polyamine are mixed to obtain a thermosetting mixed sizing material.

[0046] In the present invention, the preparation method of the epoxy resin-modified alicyclic polyamine preferably includes the following steps: (1) Dissolving an alicyclic polyamine in a solvent to obtain an alicyclic polyamine solution; (2) Dissolving a part of the epoxy resin in a solvent to obtain an epoxy resin solution; (3) Dissolve the remaining epoxy resin and epoxy active diluent in a solvent to obtain a diluted epoxy resin solution; (4) Under condensation reflux, dropwise add the epoxy resin solution obtained in step (2) to the alicyclic polyamine solution obtained in step (1), and perform a first ring-opening reaction during the dropping process to obtain a first intermediate solution; (5) Under condensation reflux, dropwise add the diluted epoxy resin solution obtained in step (3) to the first intermediate solution obtained in step (4), and perform a second ring-opening reaction during the dropping process to obtain a second intermediate solution; (6) Perform a third ring-opening reaction on the second intermediate solution obtained in step (5) to obtain an epoxy resin-modified alicyclic polyamine.

[0047] In the present invention, preferably, the alicyclic polyamine is dissolved in a solvent to obtain an alicyclic polyamine solution.

[0048] In the present invention, the alicyclic polyamine is preferably one of MDA, IPDA and N -AEP.

[0049] In the present invention, the solvent is preferably acetone. There is no special limitation on the amount of the solvent used in the present invention, and it can be adjusted to completely dissolve the alicyclic polyamine. In the examples of the present invention, when the mass of the alicyclic polyamine is 42 - 46 g, the volume of the acetone can be 20 mL.

[0050] After obtaining the alicyclic polyamine solution, preferably, part of the epoxy resin is dissolved in a solvent to obtain an epoxy resin solution.

[0051] In the present invention, the epoxy resin is preferably bisphenol A epoxy resin or bisphenol F epoxy resin, more preferably bisphenol A epoxy resin, and the bisphenol A epoxy resin is preferably E-51 or E-44.

[0052] In the present invention, the solvent is preferably acetone. There is no special limitation on the amount of the solvent used in the present invention, and it can be adjusted to completely dissolve the epoxy resin. In the examples of the present invention, when the mass of the epoxy resin is 3 - 20 g, the volume of the acetone can be 10 - 20 mL.

[0053] In the present invention, the mass ratio of the epoxy resin to the alicyclic polyamine is preferably (3 - 20):(42 - 46), more preferably (3 - 4):(42 - 46), (4 - 10):(42 - 46), (10 - 14):(42 - 46), (14 - 17):(42 - 46) or (17 - 20):(42 - 46).

[0054] In an embodiment of the present invention, the mass of the partial epoxy resin is preferably half of the total mass of the epoxy resin for modification.

[0055] After obtaining the epoxy resin solution, the present invention preferably dissolves the remaining partial epoxy resin and the epoxy active diluent in a solvent to obtain a diluted epoxy resin solution.

[0056] In the present invention, the epoxy active diluent preferably includes one of BGE, PGE, and BPGE, more preferably PGE, and the epoxy equivalent of the PGE is preferably 151-163 g / mol. The above epoxy active diluent can not only dilute the epoxy resin but also promote and participate in the reaction in the present invention. In the present invention, the epoxy active diluent is sourced from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0057] In the present invention, the mass ratio of the alicyclic polyamine to the epoxy active diluent is preferably (42-46):(1-9), more preferably (42-46):(1-2), (42-46):(2-4), (42-46):(4-5), (42-46):(5-7), or (42-46):(7-9).

[0058] In the present invention, the solvent is preferably acetone. The present invention has no special limitation on the dosage of the solvent, and it can be adjusted as long as the epoxy resin and the epoxy active diluent can be completely dissolved. In an embodiment of the present invention, when the mass of the epoxy resin is 3-20 g, the volume of the acetone can be 10-20 mL.

[0059] After obtaining the diluted epoxy resin solution, the present invention preferably drops the epoxy resin solution into the alicyclic polyamine solution under reflux condensation, and a first ring-opening reaction occurs during the dropping process to obtain a first intermediate solution.

[0060] In the present invention, the temperature of the first ring-opening reaction is preferably 60-80 °C, and the time of the first ring-opening reaction is preferably 1-3 h, more preferably 2 h. In the present invention, the epoxy resin and the alicyclic polyamine undergo a ring-opening reaction during the dropping process.

[0061] After obtaining the first intermediate solution, the present invention preferably drops the diluted epoxy resin solution into the first intermediate solution under reflux condensation, and a second ring-opening reaction occurs during the dropping process to obtain a second intermediate solution.

[0062] In the present invention, the temperature of the second ring-opening reaction is preferably 60-80 °C, and the time of the second ring-opening reaction is preferably 1-3 h, more preferably 2 h. In the present invention, the epoxy resin and the first intermediate undergo a ring-opening reaction during the dropping process.

[0063] After obtaining the second intermediate solution, the present invention preferably subjects the second intermediate solution to a third ring-opening reaction to obtain an epoxy resin-modified alicyclic polyamine.

[0064] In the present invention, the temperature of the third ring-opening reaction is preferably 80-90°C, more preferably 90°C; the time of the third ring-opening reaction is preferably 1-4 h, more preferably 2 h. The present invention carries out the third ring-opening reaction by ring-opening the epoxy group under condensation reflux.

[0065] The present invention preferably samples for infrared testing during the third ring-opening reaction. When the epoxy characteristic peak at the 915 cm -1 position disappears in the spectrum, it indicates that the reaction is complete, and heating can be stopped.

[0066] The present invention preferably uses a rotary evaporator to spin-dry the obtained transparent liquid after stopping heating to obtain an epoxy resin-modified alicyclic polyamine.

[0067] In the present invention, the synthesis mechanism diagram of the epoxy resin-modified alicyclic polyamine is preferably as Figure 1 shown. In Figure 1 , AP is an alicyclic polyamine, EP is an epoxy resin, and M is an epoxy active diluent.

[0068] In the present invention, the method of mixing the epoxy resin and the epoxy resin-modified alicyclic polyamine is preferably stirring. The rotation speed of the stirring is preferably 100-400 rpm, more preferably 200-300 rpm; the stirring time is preferably 3-10 h, more preferably 6-8 h, and the stirring temperature is preferably 60-90°C. Through the above mixing method, the present invention can fully dissolve each component to obtain a thermosetting mixed adhesive.

[0069] After obtaining the photocurable mixed adhesive and the thermosetting mixed adhesive, the present invention mixes the photocurable mixed adhesive, the thermosetting mixed adhesive, a silane coupling agent, a primary antioxidant, a secondary antioxidant, and an additive to obtain a photo-thermally dual-curable encapsulating adhesive.

[0070] In the present invention, the method of mixing the photocurable mixed adhesive, the thermosetting mixed adhesive, a silane coupling agent, a primary antioxidant, a secondary antioxidant, and an additive is preferably grinding. The present invention has no special limitation on the specific method of the grinding, and it is only necessary to mix each component evenly.

[0071] The method provided by the present invention is simple to operate and easy to control, and can obtain a photo-thermally dual-curable encapsulating adhesive with stable dispersion.

[0072] The present invention also provides an application of the photothermal dual-curing encapsulation adhesive described in the above technical solution in encapsulating electronic components, including: coating the photothermal dual-curing encapsulation adhesive on the surface of an electronic component lamp, and performing a photothermal dual-curing reaction under ultraviolet light to obtain an encapsulated electronic component; the time of the photothermal dual-curing reaction is 30 to 70 s.

[0073] In the present invention, the electronic component preferably includes an LED light strip, a chip or an integrated circuit.

[0074] The present invention has no special limitation on the coating method, and any conventional coating method can be used. In the embodiments of the present invention, the coating method is preferably dot coating with a dispensing machine.

[0075] In the present invention, the thickness of the photothermal dual-curing encapsulation adhesive coating is preferably 2 to 5 mm, more preferably 3 to 4 mm.

[0076] In the present invention, the ultraviolet light is preferably provided by an LED ultraviolet curing lamp, and the wavelength of the ultraviolet light is preferably 365 to 395 nm. The present invention can promote the photothermal dual-curing reaction of the photothermal dual-curing encapsulation adhesive at the above wavelength.

[0077] In the present invention, the time of the photothermal dual-curing reaction is 30 to 70 s, preferably 40 to 60 s. Since the prepared photothermal dual-curing encapsulation adhesive has excellent activity in the present invention, it can rapidly and fully undergo a photothermal dual-curing reaction under ultraviolet light irradiation.

[0078] The photothermal dual-curing encapsulation adhesive provided by the present invention has excellent activity. After being used for encapsulating electronic components, the obtained encapsulation layer has excellent mechanical properties and stability.

[0079] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the embodiments in the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0080] The preparation method of the modified amine curing agent used in the embodiments of the present invention, taking R1-I-E51-P as an example: (1) Dissolve 46 g of IPDA in 20 mL of acetone to obtain an alicyclic polyamine solution; (2) Dissolve 1.79 g of epoxy resin E51 in 10 mL of acetone to obtain an epoxy resin solution; (3) Dissolve 1.79 g of E51 and 1.43 g of PGE in 10 mL of acetone to obtain a diluted epoxy resin solution; (4) Under reflux condensation, the epoxy resin solution obtained in step (2) is added dropwise to the alicyclic polyamine solution obtained in step (1). A first ring-opening reaction occurs during the addition process. The addition time is 2 h to obtain a first intermediate solution. (5) Under reflux condensation, the diluted epoxy resin solution obtained in step (3) is added dropwise to the first intermediate solution obtained in step (4). A second ring-opening reaction occurs during the addition process. The addition time is 2 h to obtain a second intermediate solution. (6) The second intermediate solution obtained in step (5) is subjected to a third ring-opening reaction at 90 °C. Samples are taken at the same interval for infrared testing. When the epoxy characteristic peak at the 915 position disappears in the spectrum, it indicates that the reaction is complete, and heating can be stopped. The obtained transparent liquid is dried by rotary evaporation at 70 °C to obtain a transparent viscous epoxy resin-modified alicyclic polyamine with an active hydrogen equivalent of 48 g / mol.

[0081] In the present invention, the infrared spectrum of R1-I-E51-P prepared using E51 and IPDA is as Figure 2 shown. From Figure 2 it can be seen that the stretching vibration of -NH2 is at the 3310 cm -1 position. The absorption peak decreases significantly before and after modification, but there is still a broad and strong peak, which is due to the reaction of part of the epoxy group with it. The stretching vibration of C-N is at the 1298 cm -1 position. The absorption peak at this position decreases significantly after modification, which is because primary amine generates secondary amine after the reaction, and the intensity of the secondary amine peak is significantly lower than that of the primary amine, which can prove the occurrence of the reaction. The stretching vibration of C-O is at the 1248 cm -1 position. The absorption peak at this position increases significantly after modification, but decreases relative to E51, which indicates that after the reaction of -NH2 with the epoxy group, the C-O-C bond is transformed into secondary alcohol. The bending vibration of secondary alcohol is at the 1396 cm -1 position, and there is a significant increase after modification, which also indicates that IPDA reacts with E51 and PGE. In the infrared spectrum after modification, there is no obvious epoxy characteristic peak at the 910 cm -1 position, which indicates that the epoxy group has been consumed completely during the reaction. Therefore, it is proved that the modified amine R1-I-E51-P with certain activity and storage period is successfully prepared.

[0082] Using the above experimental method and the formulation in Table 1, modified amine curing agents with different active hydrogen equivalents are prepared.

[0083] Table 1 Formulation and active hydrogen equivalent of modified amine curing agents

[0084] The numbering rule of the modified amine shown in Table 1 is RX-Y-Z-K, where RX represents the degree of modification, and X is represented by a number from 0 to 5; the letter Y is one of I, M, and N, where I represents IPDA, M represents MDA, and N represents N -AEP; Z represents the type of EP, which is E51 or E44; the last letter K is one of P, B, and E, where P represents PGE, B represents BGE, and E represents BPGE.

[0085] Example 1 A photo-thermal dual-curing encapsulation adhesive is composed of a photo-curing mixed rubber, a thermal-curing mixed rubber, a silane coupling agent, a main antioxidant, a co-antioxidant, and additives (defoamer and dispersant); the mass ratio of the photo-curing mixed rubber to the thermal-curing mixed rubber is 10:1; the ratio of the total mass of the photo-curing mixed rubber and the thermal-curing mixed rubber to the mass of the silane coupling agent, the mass of the main antioxidant, the mass of the co-antioxidant, and the mass of the additives is 100:1:0.3:0.3:0.2; The photo-curing mixed rubber is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 35 parts of acrylate active diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator 2,4,6-trimethylbenzoyl diphenylphosphine oxide (TPO), and 1.5 parts of co-initiator triethanolamine; The thermal-curing mixed rubber is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 25 parts of epoxy resin modified alicyclic polyamine R1-I-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 48 g / mol; The preparation method for the photo-thermal dual-curing encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 35 g of acrylate active diluent, and 100 g of modified acrylate are mechanically stirred at 80 °C and 300 rpm in the dark for 30 min to be fully dissolved and mixed evenly to obtain the photo-curing mixed rubber; 25 g of R1-I-E51-P is stirred with 100 g of E-51 at 60 °C to obtain the thermal-curing mixed rubber; 100 g of the photo-curing mixed rubber and the thermal-curing mixed rubber, 1 g of silane coupling agent, 0.3 g of main antioxidant, 0.3 g of co-antioxidant, 0.1 g of defoamer (DU-1052), and 0.1 g of dispersant (BYK-180) are mechanically stirred at 40 °C and 500 rpm in the dark for 60 min, and then the resin material is added to a three-roll mill for grinding to obtain the photo-thermal dual-curing encapsulation adhesive.

[0086] Example 2 A photo-thermal dual-curing encapsulation adhesive is composed of a photo-curing mixed rubber material, a thermal-curing mixed rubber material, a silane coupling agent, a main antioxidant, a secondary antioxidant, and additives (a defoaming agent and a dispersant); the mass ratio of the photo-curing mixed rubber material to the thermal-curing mixed rubber material is 10:1; the ratio of the total mass of the photo-curing mixed rubber material and the thermal-curing mixed rubber material to the mass of the silane coupling agent, the mass of the main antioxidant, the mass of the secondary antioxidant, and the mass of the additives is 100:1:0.3:0.3:0.2; The photo-curing mixed rubber material is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 35 parts of acrylate active diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO, and 1.5 parts of co-initiator triethanolamine; The thermal-curing mixed rubber material is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 40 parts of epoxy resin modified alicyclic polyamine R5-I-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 74.66 g / mol; The preparation method for the photo-thermal dual-curing encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 35 g of acrylate active diluent, and 100 g of modified acrylate are mechanically stirred at 80 °C and 300 rpm in the dark for 30 min to be fully dissolved and mixed evenly, obtaining the photo-curing mixed rubber material; 40 g of R5-I-E51-P is stirred with 100 g of E-51 at 60 °C to obtain the thermal-curing mixed rubber material; 100 g of the photo-curing mixed rubber material and the thermal-curing mixed rubber material in total, 1 g of silane coupling agent, 0.3 g of main antioxidant, 0.3 g of secondary antioxidant, 0.1 g of defoaming agent, and 0.1 g of dispersant are mechanically stirred at 40 °C and 500 rp in the dark for 60 min, and then the resin material is added to a three-roll mill for grinding to obtain the photo-thermal dual-curing encapsulation adhesive.

[0087] Example 3 A photo-thermal dual-curing encapsulation adhesive is composed of a photo-curing mixed rubber material, a thermal-curing mixed rubber material, a silane coupling agent, a main antioxidant, a secondary antioxidant, and additives (a defoaming agent and a dispersant); the mass ratio of the photo-curing mixed rubber material to the thermal-curing mixed rubber material is 10:1; the ratio of the total mass of the photo-curing mixed rubber material and the thermal-curing mixed rubber material to the mass of the silane coupling agent, the mass of the main antioxidant, the mass of the secondary antioxidant, and the mass of the additives is 100:1:0.3:0.3:0.02; The photocurable hybrid adhesive is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 35 parts of acrylate reactive diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO, and 1.5 parts of co-initiator triethanolamine; The thermocurable hybrid adhesive is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 32 parts of epoxy resin modified alicyclic polyamine R3-I-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 60.58 g / mol; The preparation method for the photo-thermo dual-curing encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 35 g of acrylate reactive diluent and 100 g of modified acrylate are mechanically stirred at 80 °C and 300 rpm in the dark for 30 min to be fully dissolved and mixed evenly, obtaining the photocurable hybrid adhesive; 32 g of R3-I-E51-P is stirred with 100 g of E-51 at 60 °C to obtain the thermocurable hybrid adhesive; 100 g in total of the photocurable hybrid adhesive and the thermocurable hybrid adhesive, 1 g of silane coupling agent, 0.3 g of main antioxidant, 0.3 g of auxiliary antioxidant, 0.01 g of defoaming agent and 0.01 g of dispersant are mechanically stirred at 40 °C and 500 rpm in the dark for 60 min, and then the resin material is added to a three-roll mill for grinding to obtain the photo-thermo dual-curing encapsulation adhesive.

[0088] Example 4 A photo-thermo dual-curing encapsulation adhesive is composed of a photocurable hybrid adhesive, a thermocurable hybrid adhesive, a silane coupling agent, a main antioxidant, an auxiliary antioxidant and additives (defoaming agent and dispersant); the mass ratio of the photocurable hybrid adhesive to the thermocurable hybrid adhesive is 10:4; the ratio of the total mass of the photocurable hybrid adhesive and the thermocurable hybrid adhesive to the mass of the silane coupling agent, the mass of the main antioxidant, the mass of the auxiliary antioxidant and the mass of the additives is 100:1:0.3:0.3:0.02; The photocurable hybrid adhesive is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 35 parts of acrylate reactive diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO, and 1.5 parts of co-initiator triethanolamine; The thermocurable hybrid adhesive is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 32 parts of epoxy resin modified alicyclic polyamine R3-M-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 60.58 g / mol; The preparation method for the photo-thermo dual-curing encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 35 g of acrylate active diluent and 100 g of modified acrylate were mechanically stirred at 80 °C and 300 rpm for 30 min in the dark to fully dissolve and mix them evenly, obtaining a photocurable mixed adhesive; 32 g of R3-M-E51-P and 100 g of E-51 were stirred at 60 °C to obtain a thermosetting mixed adhesive; 100 g in total of the photocurable mixed adhesive and the thermosetting mixed adhesive, 1 g of silane coupling agent, 0.3 g of primary antioxidant, 0.3 g of secondary antioxidant, 0.01 g of defoamer and 0.01 g of dispersant were mechanically stirred at 40 °C and 500 rpm in the dark for 60 min, and then the resin material was added to a three-roll mill for grinding to obtain a photo-thermosetting encapsulating adhesive.

[0089] Example 5 A photo-thermosetting encapsulating adhesive is composed of a photocurable mixed adhesive, a thermosetting mixed adhesive, a silane coupling agent, a primary antioxidant, a secondary antioxidant and additives (defoamer and dispersant); the mass ratio of the photocurable mixed adhesive to the thermosetting mixed adhesive is 10:4; the ratio of the total mass of the photocurable mixed adhesive and the thermosetting mixed adhesive to the mass of the silane coupling agent, the mass of the primary antioxidant, the mass of the secondary antioxidant and the mass of the additives is 100:1:0.3:0.3:0.02; The photocurable mixed adhesive is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 20 parts of acrylate active diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO and 1.5 parts of co-initiator triethanolamine; The thermosetting mixed adhesive is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 33 parts of epoxy resin modified alicyclic polyamine R3-N-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 63.25 g / mol; The preparation method for the photo-thermosetting encapsulating adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 20 g of acrylate active diluent and 100 g of modified acrylate were mechanically stirred at 80 °C and 300 rpm for 30 min in the dark to fully dissolve and mix them evenly, obtaining a photocurable mixed adhesive; 33 g of R3-N-E51-P and 100 g of E-51 were stirred at 60 °C to obtain a thermosetting mixed adhesive; Mix 100 g of the photocuring mixed adhesive and the thermocuring mixed adhesive, 1 g of silane coupling agent, 0.3 g of primary antioxidant, 0.3 g of secondary antioxidant, 0.01 g of defoamer and 0.01 g of dispersant, and stir mechanically in the dark at 40 °C and 500 rpm for 60 min. Then add the resin material to a three-roll mill for grinding to obtain the photo-thermo dual-curing encapsulation adhesive.

[0090] Example 6 A photo-thermo dual-curing encapsulation adhesive is composed of a photocuring mixed adhesive, a thermocuring mixed adhesive, a silane coupling agent, a primary antioxidant, a secondary antioxidant and additives (defoamer and dispersant); the mass ratio of the photocuring mixed adhesive to the thermocuring mixed adhesive is 10:4; the mass ratio of the total mass of the photocuring mixed adhesive and the thermocuring mixed adhesive to the mass of the silane coupling agent, the mass of the primary antioxidant, the mass of the secondary antioxidant and the mass of the additives is 100:1:0.3:0.3:0.02; The photocuring mixed adhesive is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 40 parts of acrylate active diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO and 1.5 parts of co-initiator triethanolamine; The thermocuring mixed adhesive is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 32 parts of epoxy resin modified alicyclic polyamine R3-I-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 60.58 g / mol; The preparation method for the photo-thermo dual-curing encapsulation adhesive is as follows: Mix 2 g of TPO, 1.5 g of triethanolamine, 40 g of acrylate active diluent and 100 g of modified acrylate, and stir mechanically in the dark at 80 °C and 300 rpm for 30 min to fully dissolve and mix evenly to obtain the photocuring mixed adhesive; Stir 32 g of R3-I-E51-P with 100 g of E-51 at 60 °C to obtain the thermocuring mixed adhesive; Mix 100 g of the photocuring mixed adhesive and the thermocuring mixed adhesive, 1 g of silane coupling agent, 0.3 g of primary antioxidant, 0.3 g of secondary antioxidant, 0.01 g of defoamer and 0.01 g of dispersant, and stir mechanically in the dark at 40 °C and 500 rpm for 60 min. Then add the resin material to a three-roll mill for grinding to obtain the photo-thermo dual-curing encapsulation adhesive.

[0091] Example 7 A photothermal dual-curing encapsulation adhesive is composed of a photocuring mixed rubber compound, a thermal curing mixed rubber compound, a silane coupling agent, a main antioxidant, a secondary antioxidant, and additives (a defoaming agent and a dispersant); the mass ratio of the photocuring mixed rubber compound to the thermal curing mixed rubber compound is 10:4; the ratio of the total mass of the photocuring mixed rubber compound and the thermal curing mixed rubber compound to the mass of the silane coupling agent KH550, the mass of the main antioxidant, the mass of the secondary antioxidant, and the mass of the additives is 100:2:0.3:0.3:0.02; The photocuring mixed rubber compound is composed of the following components in parts by weight: 100 parts of a modified acrylate (EA:PUA = 1:1), 35 parts of an acrylate active diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of a photoinitiator TPO, and 1.5 parts of a co-initiator triethanolamine; The thermal curing mixed rubber compound is composed of the following components in parts by weight: 100 parts of an epoxy resin E51 and 32 parts of an epoxy resin modified alicyclic polyamine R3-I-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 60.58 g / mol; The preparation method for the photothermal dual-curing encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 35 g of an acrylate active diluent, and 100 g of a modified acrylate are mechanically stirred at 80 °C and 300 rpm in the dark for 30 min to be fully dissolved and mixed uniformly to obtain a photocuring mixed rubber compound; 32 g of R3-I-E51-P is stirred with 100 g of E-51 at 60 °C to obtain a thermal curing mixed rubber compound; 100 g of the photocuring mixed rubber compound and the thermal curing mixed rubber compound, 2 g of a silane coupling agent, 0.3 g of a main antioxidant, 0.3 g of a secondary antioxidant, 0.01 g of a defoaming agent, and 0.01 g of a dispersant are mechanically stirred at 40 °C and 500 rpm in the dark for 60 min, and then the resin material is added to a three-roll mill for grinding to obtain the photothermal dual-curing encapsulation adhesive.

[0092] Example 8 A photothermal dual-curing encapsulation adhesive is composed of a photocuring mixed rubber compound, a thermal curing mixed rubber compound, a silane coupling agent, a main antioxidant, a secondary antioxidant, and additives (a defoaming agent, a dispersant, and titanium dioxide); the mass ratio of the photocuring mixed rubber compound to the thermal curing mixed rubber compound is 10:4; the ratio of the total mass of the photocuring mixed rubber compound and the thermal curing mixed rubber compound to the mass of the silane coupling agent KH570, the mass of the main antioxidant, the mass of the secondary antioxidant, and the mass of the additives is 100:2:0.3:0.3:0.12; The photocurable hybrid adhesive is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 35 parts of acrylate reactive diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO, and 1.5 parts of co-initiator triethanolamine; The thermocurable hybrid adhesive is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 32 parts of epoxy resin modified alicyclic polyamine R3-I-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 60.58 g / mol; The preparation method for the photo-thermo dual-curing encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 35 g of acrylate reactive diluent and 100 g of modified acrylate are mechanically stirred at 80 °C and 300 rpm for 30 min in the dark to fully dissolve and mix evenly, obtaining the photocurable hybrid adhesive; 32 g of R3-I-E51-P is stirred with 100 g of E-51 at 60 °C to obtain the thermocurable hybrid adhesive; 100 g of the photocurable hybrid adhesive and the thermocurable hybrid adhesive, 2 g of silane coupling agent, 0.3 g of primary antioxidant, 0.3 g of secondary antioxidant, 0.01 g of defoamer, 0.01 g of dispersant and 0.1 g of titanium dioxide are mechanically stirred at 40 °C and 500 rpm in the dark for 60 min, and then the resin material is added to a three-roll mill for grinding to obtain the photo-thermo dual-curing encapsulation adhesive.

[0093] Example 9 A photo-thermo dual-curing encapsulation adhesive is composed of a photocurable hybrid adhesive, a thermocurable hybrid adhesive, a silane coupling agent, a primary antioxidant, a secondary antioxidant and additives (defoamer, dispersant and titanium dioxide); the mass ratio of the photocurable hybrid adhesive to the thermocurable hybrid adhesive is 10:4; the mass ratio of the total mass of the photocurable hybrid adhesive and the thermocurable hybrid adhesive to the mass of the silane coupling agent KH570, the mass of the primary antioxidant, the mass of the secondary antioxidant and the mass of the additives is 100:2:0.3:0.3:0.12; The photocurable hybrid adhesive is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 35 parts of acrylate reactive diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO, and 1.5 parts of co-initiator triethanolamine; The thermocurable hybrid adhesive is composed of the following components in parts by weight: 100 parts of epoxy resin E44 and 32 parts of epoxy resin modified alicyclic polyamine R3-I-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 60.58 g / mol; The preparation method for the photothermal dual-curing encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 35 g of acrylate active diluent and 100 g of modified acrylate are mechanically stirred at 80 °C and 300 rpm in the dark for 30 min to fully dissolve and mix evenly, obtaining a photocuring mixed stock; 32 g of R3-I-E51-P is stirred with 100 g of E-44 at 60 °C to obtain a thermocuring mixed stock; 100 g in total of the photocuring mixed stock and the thermocuring mixed stock, 2 g of silane coupling agent, 0.3 g of primary antioxidant, 0.3 g of secondary antioxidant, 0.01 g of defoamer, 0.01 g of dispersant and 0.1 g of titanium dioxide are mechanically stirred at 40 °C and 500 rpm in the dark for 60 min, and then the resin stock is added to a three-roll mill for grinding to obtain the photothermal dual-curing encapsulation adhesive.

[0094] Comparative Example 1 A photothermal dual-curing encapsulation adhesive is composed of a photocuring mixed stock, a thermocuring mixed stock, a silane coupling agent, a primary antioxidant, a secondary antioxidant and additives (defoamer and dispersant); the mass ratio of the photocuring mixed stock to the thermocuring mixed stock is 10:1; the mass ratio of the total mass of the photocuring mixed stock and the thermocuring mixed stock to the mass of the silane coupling agent KH570, the mass of the primary antioxidant, the mass of the secondary antioxidant and the mass of the additives is 100:2:0.3:0.3:0.02; The photocuring mixed stock is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 35 parts of acrylate active diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO and 1.5 parts of co-initiator triethanolamine; The thermocuring mixed stock is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 24 parts of cycloaliphatic polyamine MDA; The preparation method for the photothermal dual-curing encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 35 g of acrylate active diluent and 100 g of modified acrylate are mechanically stirred at 80 °C and 300 rpm in the dark for 30 min to fully dissolve and mix evenly, obtaining a photocuring mixed stock; 24 g of MDA is stirred with 100 g of E-51 at room temperature to obtain a thermocuring mixed stock; A total of 100 g of photocurable mixed adhesive and thermosetting mixed adhesive, 2 g of silane coupling agent, 0.3 g of primary antioxidant, 0.3 g of secondary antioxidant, 0.01 g of defoaming agent and 0.01 g of dispersant are mechanically stirred in the dark at 40 °C and 500 rpm for 60 min, and then the resin material is added to a three-roll mill for grinding to obtain a photo-thermosetting encapsulation adhesive.

[0095] Comparative Example 2 A photo-thermosetting encapsulation adhesive is composed of photocurable mixed adhesive, thermosetting mixed adhesive, silane coupling agent, primary antioxidant, secondary antioxidant and additives (defoaming agent and dispersant); the mass ratio of the photocurable mixed adhesive to the thermosetting mixed adhesive is 10:1; the mass ratio of the total mass of the photocurable mixed adhesive and the thermosetting mixed adhesive to the mass of silane coupling agent KH570, the mass of primary antioxidant, the mass of secondary antioxidant and the mass of additives is 100:2:0.3:0.3:0.02; The photocurable mixed adhesive is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 35 parts of acrylate active diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO and 1.5 parts of co-initiator triethanolamine; The thermosetting mixed adhesive is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 21 parts of dicyandiamide; The preparation method for the photo-thermosetting encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine and 35 g of acrylate active diluent are mechanically stirred with 100 g of modified acrylate (EA:PUA = 1:1) in the dark at 80 °C and 300 rpm for 30 min to fully dissolve and mix evenly to obtain a photocurable mixed adhesive; 21 g of dicyandiamide is stirred with 100 g of E-51 at room temperature to obtain a thermosetting mixed adhesive; A total of 100 g of photocurable mixed adhesive and the thermosetting mixed adhesive, 2 g of silane coupling agent, 0.3 g of primary antioxidant, 0.3 g of secondary antioxidant, 0.01 g of defoaming agent and 0.01 g of dispersant are mechanically stirred in the dark at 40 °C and 500 rpm for 60 min, and then the resin material is added to a three-roll mill for grinding to obtain a photo-thermosetting encapsulation adhesive.

[0096] Comparative Example 3 A photo-thermal dual-curing encapsulation adhesive is composed of a photo-curing mixed compound, a thermal-curing mixed compound, a silane coupling agent, a primary antioxidant, a secondary antioxidant, and additives (a defoaming agent and a dispersant); the mass ratio of the photo-curing mixed compound to the thermal-curing mixed compound is 10:5; the ratio of the total mass of the photo-curing mixed compound and the thermal-curing mixed compound to the mass of the silane coupling agent, the mass of the primary antioxidant, the mass of the secondary antioxidant, and the mass of the additives is 100:1:0.3:0.3:0.02; The photo-curing mixed compound is composed of the following components in parts by weight: 100 parts of modified acrylate (EA:PUA = 1:1), 35 parts of acrylate active diluent (HEA:HDDA:TMPTA = 5:5:25), 2 parts of photoinitiator TPO, and 1.5 parts of co-initiator triethanolamine; The thermal-curing mixed compound is composed of the following components in parts by weight: 100 parts of epoxy resin E51 and 32 parts of epoxy resin modified alicyclic polyamine R3-I-E51-P; the active hydrogen equivalent of the epoxy resin modified alicyclic polyamine is 60.58 g / mol; The preparation method for the photo-thermal dual-curing encapsulation adhesive is as follows: 2 g of TPO, 1.5 g of triethanolamine, 35 g of acrylate active diluent, and 100 g of modified acrylate are mechanically stirred at 80 °C and 300 rpm for 30 min in the dark to be fully dissolved and mixed evenly, obtaining the photo-curing mixed compound; 32 g of R3-I-E51-P is stirred with 100 g of E-51 at 60 °C to obtain the thermal-curing mixed compound; 100 g of the photo-curing mixed compound and the thermal-curing mixed compound, 2 g of silane coupling agent, 0.3 g of primary antioxidant, 0.3 g of secondary antioxidant, 0.01 g of defoaming agent, and 0.01 g of dispersant are mechanically stirred at 40 °C and 500 rpm in the dark for 60 min, and then the resin material is added to a three-roll mill for grinding to obtain the photo-thermal dual-curing encapsulation adhesive.

[0097] Test Example The encapsulation performance of the photo-thermal dual-curing encapsulation adhesives prepared in Examples 1 to 9 and Comparative Examples 1 to 3 is tested. The adhesion is evaluated according to the standard of GB / T9286-2021 and obtained by the cross-cut method; the tensile strength is evaluated according to the standard of GB / T 7124-2008 and obtained by testing with a tensile testing machine; the impact strength is evaluated according to the standard of GB / T 1843-2008 and obtained by testing with an impact testing machine; the storage period is evaluated according to the exothermic situation and obtained by a differential scanning calorimeter. The results are shown in Table 2.

[0098] Table 2 Performance test results of the photo-thermal dual-curing encapsulation adhesives prepared in Examples 1 to 9 and Comparative Examples 1 to 3

[0099] As can be seen from Table 2, the photo-thermal dual-curing encapsulation adhesive prepared by the present invention can be stored for a long time without curing. Under ultraviolet light irradiation, the curing reaction can occur within 30 to 70 s. This is because the present invention modifies the alicyclic polyamine, and the obtained epoxy resin-modified alicyclic polyamine as a curing agent enables the epoxy resin not to cure at room temperature, thereby extending the storage time. However, under ultraviolet light irradiation, while photo-curing occurs, the released heat excites the thermo-curing mixed adhesive to perform deep curing, and no further heat treatment is required, which can significantly improve the encapsulation efficiency. In addition, the encapsulation layer obtained after curing the photo-thermal dual-curing encapsulation adhesive prepared by the present invention has excellent tensile strength and impact strength. When using the conventional curing agent MDA, curing occurs at room temperature, shortening the storage period of the photo-thermal dual-curing encapsulation adhesive. When using the conventional curing agent dicyandiamide, the photo-thermal dual-curing encapsulation adhesive cannot be completely cured.

[0100] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A photo-thermal dual-curing encapsulation adhesive, characterized in that, It includes a photocuring mixed adhesive, a thermocuring mixed adhesive, a silane coupling agent, a main antioxidant, a secondary antioxidant and an auxiliary agent; the mass ratio of the photocuring mixed adhesive to the thermocuring mixed adhesive is 10:1 to 4; the ratio of the total mass of the photocuring mixed adhesive and the thermocuring mixed adhesive to the mass of the silane coupling agent, the mass of the main antioxidant, the mass of the secondary antioxidant and the mass of the auxiliary agent is 100:(1 to 5):(0.3 to 0.5):(0.3 to 0.5):(0.001 to 0.2); The photocuring mixed adhesive includes the following components in parts by weight: 100 parts of a modified acrylate, 20 to 40 parts of an acrylate active diluent, 1 to 3 parts of a photoinitiator and 1 to 3 parts of a co-initiator; The thermocuring mixed adhesive includes the following components in parts by weight: 100 parts of an epoxy resin and 20 to 40 parts of an epoxy resin-modified alicyclic polyamine; the active hydrogen equivalent of the epoxy resin-modified alicyclic polyamine is 42 to 79 g / mol.

2. The photo-thermal dual-curing encapsulation adhesive according to claim 1, characterized in that, The modified acrylate is one or two of an epoxy-modified acrylate, a polyurethane-modified acrylate and a silicone-modified acrylate.

3. The photo-thermal dual-curing encapsulation adhesive according to claim 1, characterized in that, The acrylate active diluent includes one or more of a monofunctional active diluent, a difunctional active diluent and a polyfunctional active diluent.

4. The photo-thermal dual-curing encapsulation adhesive according to claim 1, characterized in that, The photoinitiator includes one or more of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and 1-hydroxy-cyclohexyl-phenylmethanone.

5. The photo-thermal dual-curing encapsulation adhesive according to claim 1, characterized in that, The co-initiator is triethanolamine.

6. The photo-thermal dual-curing encapsulation adhesive according to claim 1, characterized in that, The epoxy resin is a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.

7. The photo-thermal dual-curing encapsulation adhesive according to claim 1, characterized in that, The alicyclic polyamine in the epoxy resin-modified alicyclic polyamine is one of MDA, IPDA, and N -AEP; the epoxy resin in the epoxy resin-modified alicyclic polyamine is bisphenol A epoxy resin or bisphenol F epoxy resin.

8. The photo-thermal dual-curing encapsulation adhesive according to claim 1, characterized in that, The auxiliary agent includes one or more of a light diffusing agent, titanium dioxide, an antifoaming agent and a dispersing agent.

9. A preparation method for the photo-thermal dual-curing encapsulation adhesive according to any one of claims 1 to 8, comprising: Mix the modified acrylate, the acrylate active diluent, the photoinitiator and the co-initiator in the dark to obtain a photocuring mixed adhesive; Mix the epoxy resin and the epoxy resin-modified alicyclic polyamine to obtain a thermocuring mixed adhesive; Mix the photocuring mixed adhesive, the thermocuring mixed adhesive, the silane coupling agent, the main antioxidant, the secondary antioxidant and the auxiliary agent in the dark to obtain a photo-thermal dual-curing encapsulation adhesive.

10. An application of the photo-thermal dual-curing encapsulation adhesive according to any one of claims 1 to 8 in encapsulating electronic components, comprising: Coat the photo-thermal dual-curing encapsulation adhesive on the surface of an electronic component and carry out a photo-thermal dual-curing reaction under ultraviolet light to obtain an encapsulated electronic component; The time of the photo-thermal dual-curing reaction is 30 to 70 s.

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