A light-curing adhesive for glass substrate packaging and its preparation method and application

Abstract

This invention belongs to the technical field of photocurable materials, specifically relating to a photocurable adhesive for glass substrate encapsulation, its preparation method, and its application. The photocurable adhesive comprises the following components, measured by weight: 20% to 40% organosilicon-modified alicyclic epoxy resin; 5% to 20% fluorine-modified epoxy resin; 25% to 45% flexible acrylate monomer; 20% to 40% organosilicon-modified acrylate; 5% to 10% adhesion promoter; 0.3% to 3% free radical photoinitiator; and 0.1% to 2% cationic photoinitiator. By adding the organosilicon-modified alicyclic epoxy resin and coordinating the components with each other, and adjusting the weight ratio of each component, the photocurable adhesive for glass substrate encapsulation exhibits excellent toughness and elongation, improves adhesion, and is applicable to a wide range of light source wavelengths, thereby enhancing the processing efficiency of the encapsulation adhesive.

Description

Technical Field

[0001] The invention relates to a light-curing adhesive for glass substrate packaging and a preparation method and application thereof, belonging to the technical field of light-curing materials. Background Art

[0002] Glass substrates currently play an important role in the fields of packaging and lithography. One of their most attractive properties is their low dielectric constant, which can minimize signal propagation delays and crosstalk between adjacent interconnects, which is critical for high-speed electronic devices. It also reduces the capacitance between interconnects, thereby enabling faster signal transmission and improving overall performance. In speed-critical applications such as data centers, telecommunications, and high-performance computing, the use of glass substrates can significantly improve system efficiency and data throughput. The low dielectric constant also enables better impedance control, ensuring signal integrity throughout the circuit, which is particularly attractive in RF applications because impedance matching is critical to maximizing power transfer and minimizing signal loss. By providing consistent electrical properties across the entire substrate surface, glass substrates facilitate the design and manufacture of high-frequency circuits with higher reliability.

[0003] Another key advantage of glass substrates is their exceptional thermal stability, which is crucial for maintaining device performance under fluctuating thermal conditions. Unlike copper-clad laminates, which can deform or delaminate under thermal stress, glass substrates exhibit minimal dimensional change over a wide temperature range. In applications where thermal management is critical, such as automotive electronics, aerospace systems, and industrial controls, glass's ability to withstand thermal cycling and maintain dimensional integrity under stress helps prevent electrical shorts, open circuits, or other reliability issues often associated with temperature-induced mechanical strain.

[0004] However, glass substrates also have their limitations. A major challenge facing glass substrate lithography technology is their inherent fragility, a problem that has become particularly prominent as the industry shifts to thinner substrates to meet higher device integration and performance requirements. Addressing the fragility of glass requires the use of substrate edge encapsulant to mitigate the risk of handling glass substrates. Conventional encapsulation technology generally uses thermal curing solutions, but this is inefficient, and the encapsulant's acid, alkali, and high temperature resistance requirements are insufficient. It also has low adhesion to the film material attached to the glass substrate, reducing the reliability of the glass substrate. Summary of the Invention

[0005] The present invention aims to solve the technical problems that the existing glass substrate edge encapsulation glue adopts a heat curing process, has low processing efficiency and the performance of the encapsulation glue cannot meet the requirements, and provides a light-curing glue for glass substrate encapsulation and its preparation method and application.

[0006] The technical solution of the present invention to solve the above technical problems is as follows:

[0007] One of the purposes of the present invention is to provide a light-curing adhesive for glass substrate encapsulation, which comprises the following components by weight percentage:

[0008] Silicone-modified alicyclic epoxy resin 20% to 40%;

[0009] Fluorine-modified epoxy resin 5% to 20%;

[0010] Flexible acrylate monomer 25% to 45%;

[0011] Silicone modified acrylate 20% to 40%;

[0012] Adhesion promoter 5% to 10%;

[0013] Free radical photoinitiator 0.3% to 3%;

[0014] Cationic photoinitiator 0.1%~2%.

[0015] The beneficial effects of the present invention are as follows: the present invention provides a cationic light-curing adhesive for glass substrate encapsulation, which, by adding an organosilicon-modified alicyclic epoxy resin and coordinating with other components and regulating the weight ratio of each component, makes the light-curing adhesive for glass substrate encapsulation have excellent toughness and elongation, improves adhesion, and is applicable to a wide range of light source wavelengths, thereby improving the processing efficiency of the encapsulation adhesive.

[0016] On the basis of the above technical solution, the present invention can also make the following improvements:

[0017] Furthermore, the organosilicon-modified alicyclic epoxy resin has a structure shown in formula (I):

[0018]

[0019] (I),

[0020] Wherein, a≥10, b≥3, and both a and b are integers.

[0021] The beneficial effect of adopting the above-mentioned further technical solution is that the silicone-modified alicyclic epoxy resin used in the present invention is a silicone oligomer containing 3 or more alicyclic epoxy groups, and the alicyclic epoxy groups are on the side chain. By rationally designing the chain segment structure of the silicone and the position and number of the epoxy functional groups, the silicone-modified alicyclic epoxy resin has excellent toughness and elongation, which greatly improves the toughness and elongation of the photocurable adhesive.

[0022] Furthermore, the preparation method of the organosilicon-modified alicyclic epoxy resin is as follows:

[0023] 1,2-epoxy-4-vinylcyclohexane and a platinum catalyst are mixed evenly and heated, and hydrogenated silicone oil is added dropwise, the temperature is controlled below 60° C. during the addition process, and the addition speed is controlled so that the addition is completed within 60 minutes. After the addition is completed, the temperature is raised to 60° C. to 90° C. and reacted to obtain the organosilicon-modified alicyclic epoxy resin;

[0024] The reaction formula involved in the above reaction is as follows:

[0025] .

[0026] Furthermore, the fluorine-modified epoxy resin refers to a polymer of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and (chloromethyl)ethylene oxide.

[0027] Furthermore, the fluorine-modified epoxy resin has a structure shown in formula (II):

[0028]

[0029] (II).

[0030] The beneficial effect of adopting the above-mentioned further technical solution is that: fluorine-modified epoxy resin is an epoxy resin containing fluorine elements in the molecular chain. It has a high CF bond energy (about 485 kJ / mol) and is extremely resistant to strong acids (such as concentrated sulfuric acid, aqua regia), strong bases, oxidants and organic solvents, which can further improve the acid and alkali resistance of the cured adhesive.

[0031] Furthermore, the organosilicon-modified acrylate is a product of polymerization of a double-terminated monoalkylhydroxy organosilicon and isocyanate ethyl acrylate, and has a structure shown in formula (III):

[0032]

[0033] (III),

[0034] Here, n is an integer ≥10.

[0035] The beneficial effect of adopting the above further technical solution is that the silicone-modified acrylate synthesized by double-terminal monoalkylhydroxy silicone and isocyanate ethyl acrylate has a lower viscosity, and the silicone segment on the molecular chain can greatly improve the toughness and elongation of the photocurable adhesive.

[0036] Furthermore, the preparation method of the organosilicon-modified acrylate is as follows:

[0037] Mixing double-terminated monoalkylhydroxyl organosilicon and isocyanate ethyl acrylate and heating them at a reaction temperature of 70° C. to 85° C. for 2 h to 4 h, testing NCO, and terminating the reaction after NCO completely disappears to obtain the organosilicon-modified acrylate;

[0038] The reaction formula involved in the above reaction is as follows:

[0039] .

[0040] Furthermore, the flexible acrylate monomer refers to a polyalkyl acrylate having a flexible segment. Preferably, the flexible acrylate monomer is selected from any one or two or more of dodecyl acrylate, tridecyl acrylate, octadecyl acrylate, dodecyl methacrylate, tridecyl methacrylate or octadecyl methacrylate.

[0041] Furthermore, the adhesion promoter is rosin phenol, which has a structure shown in formula (IV):

[0042]

[0043] (IV);

[0044] The free radical photoinitiator is selected from any one or two or more of anthracene derivatives, benzoin derivatives, benzophenone and its derivatives, acetophenone and its derivatives, and methyl o-benzoylbenzoate;

[0045] The cationic photoinitiator is selected from any one or two or more of aromatic diazonium salts, triarylsulfonium salts, diaryliodonium salts, and aromatic ferrocenium salts. Preferably, the triarylsulfonium salt is a mixed triarylsulfonium hexafluoroantimonate salt, and the aromatic ferrocenium salt is selected from IRGACURE 250, IRGACURE 261, IRGACURE 262, etc.

[0046] The beneficial effect of adopting the above-mentioned further technical solution is that: rosin phenol is the reactant of rosin and phenol, and the molecular structure of rosin phenol contains both carboxyl and hydroxyl structures. Among them, the hydroxyl structure reacts with the alicyclic epoxy to connect the rosin phenol to the polymer macromolecule, and the carboxyl structure has good adhesion to glass and membrane materials such as ABF (Ajinomoto stacking film).

[0047] A second object of the present invention is to provide a method for preparing the above-mentioned light-curing adhesive for glass substrate packaging, comprising the following steps:

[0048] Weigh silicone-modified alicyclic epoxy resin, fluorine-modified epoxy resin, flexible acrylate monomer, silicone-modified acrylate, adhesion promoter, free radical photoinitiator and cationic photoinitiator, add them into the blender in sequence, evacuate to a vacuum degree of -0.08 MPa to -0.05 MPa, control the speed to 500 r / min ~ 1000 r / min, stir for 0.5 h ~ 2 h, let it dry naturally to room temperature, and seal it for packaging.

[0049] A third object of the present invention is to provide an application of the above-mentioned light-curing adhesive for glass substrate packaging in chip glass substrate packaging.

[0050] Furthermore, the application uses a UV-LIPO (Low-Injection Pressure Overmolding) process to encapsulate the light-curing adhesive for glass substrate encapsulation at the edge of the electronic material, thereby effectively protecting the electronic material.

[0051] Furthermore, the electronic material is a glass substrate and an ABF substrate, and the wavelength of the light source of the UV-LIPO process is 365nm to 470nm.

[0052] Compared with the prior art, the present invention has the following technical effects:

[0053] The light-curing adhesive for glass substrate encapsulation of the present invention has the advantages of high adhesion, especially higher adhesion to ABF materials than conventional thermosetting materials; has higher temperature resistance, better impact resistance and more excellent acid and alkali resistance, and higher aging reliability than conventional materials; and has higher production efficiency. DETAILED DESCRIPTION

[0054] The principles and features of the present invention are described below. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0055] Synthesis example 1

[0056] Preparation of silicone modified alicyclic epoxy resin:

[0057] 12.4 g of 1,2-epoxy-4-vinylcyclohexane and a platinum catalyst were weighed and mixed evenly, then heated to 40° C., and 200 g of side hydrogenated silicone oil was added dropwise. The dropping rate was controlled and the addition was completed within 60 min. The temperature was controlled not to exceed 60° C. during the addition. After the addition was completed, the temperature was raised to 80° C. and the reaction was carried out for 2 hours to obtain a silicone-modified alicyclic epoxy resin, wherein the mass content of the platinum catalyst in the reaction system (the total amount of 1,2-epoxy-4-vinylcyclohexane and side hydrogenated silicone oil) was 10 ppm.

[0058] Synthesis example 2

[0059] Preparation of silicone modified acrylate:

[0060] Weigh 150g of double-terminal monoalkylhydroxy silicone (Silok Polymer Company, brand 8802F2) and 21g of isocyanate ethyl acrylate into a three-necked flask, mix well, heat to 70℃-85℃, react for 3 hours, and terminate the reaction after NCO completely disappears to obtain silicone-modified acrylate.

[0061] Example 1

[0062] Accurately weigh the following raw materials:

[0063] 30g of silicone-modified alicyclic epoxy resin, 10g of fluorine-modified epoxy resin, 35g of dodecyl acrylate monomer, 30g of silicone-modified acrylate, 8g of rosin phenol, 1.6g of 9,10-dibutoxyanthracene, 0.8g of IRGACURE 261;

[0064] Add the above components into a dual planetary power mixing mixer in sequence, evacuate to a vacuum degree of -0.08MPa, stir at 500r / min for 2 hours, stir evenly, let it dry naturally to room temperature, and seal it for packaging.

[0065] Example 2

[0066] Accurately weigh the following raw materials:

[0067] 25g of silicone-modified alicyclic epoxy resin, 10g of fluorine-modified epoxy resin, 35g of tridecyl acrylate monomer, 40g of silicone-modified acrylate, 8g of rosin phenol, 3g of benzoin methyl ether, and 0.9g of IRGACURE 250; add the above components in sequence into a dual planetary power mixing mixer, evacuate to a vacuum degree of -0.05MPa, stir at 750r / min for 1 hour, stir until uniform, let it air-dry to room temperature, and seal and package.

[0068] Example 3

[0069] Accurately weigh the following raw materials:

[0070] 30g of silicone-modified alicyclic epoxy resin, 6.4g of fluorine-modified epoxy resin, 50g of octadecyl acrylate monomer, 23g of silicone-modified acrylate, 10g of rosin phenol, 1g of photoinitiator TPO, 1g of IRGACURE 262;

[0071] Add the above components into a dual planetary power mixing mixer in sequence, evacuate to a vacuum degree of -0.06MPa, stir at 700r / min for 1.5 hours, stir evenly, let it dry naturally to room temperature, and seal it for packaging.

[0072] Example 4

[0073] Accurately weigh the following raw materials:

[0074] Silicone-modified alicyclic epoxy resin 40g, fluorine-modified epoxy resin 10g, dodecyl methacrylate monomer 29g, silicone-modified acrylate 24g, rosin phenol 10g, 4,4'-bis(diethylamino)benzophenone 1.5g, IRGACURE 262 0.8g, IRGACURE 250 0.4g;

[0075] Add the above components into a dual planetary power mixing mixer in sequence, evacuate to a vacuum degree of -0.07 MPa, stir at 800 r / min for 1 hour, stir evenly, let it dry naturally to room temperature, and seal it for packaging.

[0076] Example 5

[0077] Accurately weigh the following raw materials:

[0078] 30g of silicone-modified alicyclic epoxy resin, 20g of fluorine-modified epoxy resin, 45g of octadecyl methacrylate monomer, 30g of silicone-modified acrylate, 8g of rosin phenol, 1.9g of methyl o-benzoylbenzoate, 10.7g of IRGACURE 26;

[0079] Add the above components into a dual planetary power mixing mixer in sequence, evacuate to a vacuum degree of -0.08 MPa, stir at 1000 r / min for 0.5 hour, stir evenly, let it dry naturally to room temperature, and seal it for packaging.

[0080] Comparative Example 1

[0081] Accurately weigh the following raw materials:

[0082] CELLOXIDE 2021P 45g, MBS 15g, OXT-221 19g, polycaprolactone diol 12g, 9,10-dibutoxyanthracene 1.5g, IRGACURE 261 1.5g;

[0083] Add the above components into a dual planetary power mixing mixer in sequence, evacuate to a vacuum degree of -0.08MPa, stir at 500r / min for 2 hours, stir evenly, let it dry naturally to room temperature, and seal it for packaging.

[0084] MBS resin is a terpolymer of methyl methacrylate (M), butadiene (B) and styrene (S) (Arkema, XT100).

[0085] Comparative Example 2

[0086] Accurately weigh the following raw materials:

[0087] Bisphenol A epoxy resin 45g, mercaptan curing agent 23g, latent curing agent 21g, toughening agent 25g, stabilizer 0.2g;

[0088] Add the above components into a dual planetary power mixing mixer in sequence, evacuate to a vacuum degree of -0.08MPa, stir at 500r / min for 2 hours, stir evenly, let it dry naturally to room temperature, and seal it for packaging.

[0089] Comparative Example 3

[0090] Accurately weigh the following raw materials:

[0091] Modified silane 75g, plasticizer 12g, crosslinker 1g, moisture catalyst 0.5g, filler 19g;

[0092] Add the above components into a dual planetary power mixing mixer in sequence, evacuate to a vacuum degree of -0.08MPa, stir at 500r / min for 2 hours, stir evenly, let it dry naturally to room temperature, and seal it for packaging.

[0093] Comparative Example 4

[0094] Accurately weigh the following raw materials:

[0095] Silicone-modified alicyclic epoxy resin 30g, fluorine-modified epoxy resin 20g, octadecyl methacrylate monomer 45g, polyurethane-modified acrylate 30g, rosin phenol 5g, methyl o-benzoylbenzoate 1.9g, IRGACURE 2610.7g;

[0096] Add the above components into a dual planetary power mixing mixer in sequence, evacuate to a vacuum degree of -0.08 MPa, stir at 1000 r / min for 0.5 hour, stir evenly, let it dry naturally to room temperature, and seal it for packaging.

[0097] The performance of each embodiment and comparative example was tested by the following performance tests.

[0098] Curing light source (UV curing): 365nm LED lamp, light intensity 500mW / cm 2 .

[0099] Modulus: DMA test.

[0100] Peel strength: tested by universal testing machine, substrate: glass and ABF material.

[0101] Impact resistance test: drop from a height of 1.8m 200 times to determine whether the glass substrate is cracked.

[0102] Acid and alkali resistance test: Soak the encapsulated glass substrate in 5% hydrochloric acid solution and 5% NaOH solution respectively. After soaking for 78 hours, check whether the film falls off.

[0103] Heat aging test: Place the encapsulated glass substrate in a 150°C oven and take it out after 168 hours to observe whether it turns yellow.

[0104] The test results are shown in Table 1.

[0105] Table 1 Performance comparison test results

[0106]

[0107] As can be seen from the results in Table 1 above, compared with conventional packaging adhesives, the light-curing adhesive of the present invention has higher peel strength, which makes the light-curing adhesive of the present invention have the advantage of high adhesion, especially higher adhesion to ABF materials than conventional materials; it has higher temperature resistance, better impact resistance and more excellent acid and alkali resistance, and higher aging reliability than conventional materials; it has higher production efficiency, and the light-curing packaging process of the present invention cures faster than conventional heat-curing and moisture-curing packaging processes.

[0108] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A light-curing adhesive for glass substrate packaging, characterized in that: Calculated by weight percentage, it includes the following components: Silicone-modified alicyclic epoxy resin 20% to 40%; Fluorine-modified epoxy resin 5% to 20%; Flexible acrylate monomer 25% to 45%; Silicone modified acrylate 20% to 40%; Adhesion promoter 5% to 10%; Free radical photoinitiator 0.3% to 3%; Cationic photoinitiator 0.1% to 2%; The organosilicon-modified alicyclic epoxy resin has a structure shown in formula (I): (I), Wherein, a≥10, b≥3, and both a and b are integers; The fluorine-modified epoxy resin has a structure shown in formula (II): (Ⅱ); The organosilicon-modified acrylate has a structure shown in formula (III): (Ⅲ), Here, n is an integer ≥10.

2. The light-curing adhesive for glass substrate encapsulation according to claim 1, characterized in that: The preparation method of the organosilicon-modified alicyclic epoxy resin is as follows: 1,2-epoxy-4-vinylcyclohexane and a platinum catalyst are mixed evenly and heated, and hydrogenated silicone oil is added dropwise. During the addition process, the temperature is controlled below 60° C., and the dropwise addition speed is controlled so that the addition is completed within 60 minutes. After the addition is completed, the temperature is raised to 60° C.-90° C. and reacted to obtain the silicone-modified alicyclic epoxy resin.

3. The light-curing adhesive for glass substrate encapsulation according to claim 1, wherein: The preparation method of the organosilicon-modified acrylate is as follows: The double-terminated monoalkylhydroxy organosilicon and isocyanate ethyl acrylate are mixed and heated at a reaction temperature of 70° C. to 85° C. for 2 h to 4 h. The reaction is terminated after the NCO group completely disappears to obtain the organosilicon-modified acrylate.

4. The light-curing adhesive for glass substrate encapsulation according to claim 1, wherein: The flexible acrylate monomer is selected from any one or two or more of dodecyl acrylate, tridecyl acrylate, octadecyl acrylate, dodecyl methacrylate, tridecyl methacrylate or octadecyl methacrylate.

5. The light-curing adhesive for glass substrate encapsulation according to claim 1, wherein: The adhesion promoter is rosin phenol; The free radical photoinitiator is selected from any one or two or more of anthracene derivatives, benzoin derivatives, benzophenone and its derivatives, acetophenone and its derivatives, and methyl o-benzoylbenzoate; The cationic photoinitiator is selected from any one or two or more of aromatic diazonium salts, triarylsulfonium salts, diaryliodonium salts, and aromatic ferrocenium salts.

6. A method for preparing a light-curing adhesive for glass substrate packaging according to any one of claims 1 to 5, characterized in that: The following steps are involved: Weigh silicone-modified alicyclic epoxy resin, fluorine-modified epoxy resin, flexible acrylate monomer, silicone-modified acrylate, adhesion promoter, free radical photoinitiator and cationic photoinitiator, add them into the blender in sequence, evacuate to a vacuum degree of -0.08 MPa to -0.05 MPa, control the speed to 500 r / min ~ 1000 r / min, stir for 0.5 h ~ 2 h, let it dry naturally to room temperature, and seal and package.

7. Use of the light-curing adhesive for glass substrate packaging according to any one of claims 1 to 5 in chip glass substrate packaging.

Images