Multicomponent filling FC-BGA package carrier board build-up adhesive film, preparation method and application thereof

Abstract

The application provides a multicomponent filler FC-BGA packaging carrier laminating adhesive film and a preparation method and application thereof. The laminating adhesive film comprises the following components in parts by weight: 130-175 parts of a filler, 60-120 parts of a polyphenyl ether resin, 15-30 parts of an epoxy resin, 10-20 parts of a curing agent, 15-20 parts of a phosphate compound and 2-5 parts of a curing accelerator. The preparation method comprises the following steps: uniformly mixing the components of the laminating adhesive film, coating the mixture on a substrate, and drying to obtain the laminating adhesive film. By using the specific filler, the thermal expansion coefficient of the laminating adhesive film can be effectively reduced, the product yield is ensured, the dielectric loss of the laminating adhesive film is reduced, and the problem of excessive signal transmission loss in use is solved.

Description

Technical Field

[0001] This invention belongs to the field of resin composite material technology, specifically relating to a multi-component filler FC-BGA encapsulation carrier layer laminate, its preparation method, and its application. Background Technology

[0002] Flip-chip ball grid array (FC-BGA) packaging substrates represent the future direction of semiconductor packaging substrates, with wide applications and broad market prospects. FC-BGA substrates are high-density packaging substrates capable of enabling high-speed and multifunctional chips. Additive coatings are one of the key materials in the SAP (Semi-Additive Processing) manufacturing process of FC-BGA substrates. However, the thermal expansion of the resin system in existing additive coatings generates thermal stress. Excessive thermal stress can damage the reliability of the FC-BGA packaging substrate and its packaging system. Furthermore, mismatch in the coefficient of thermal expansion can easily cause via cracks and delamination failures. Additionally, the high dielectric loss of traditional additive coatings can lead to slow signal transmission rates and high losses, with the impact of dielectric properties on transmission loss becoming more pronounced at higher frequencies.

[0003] CN114058278A discloses a high-temperature resistant insulating film, its preparation method, and its application. The high-temperature resistant insulating film includes a substrate layer and an adhesive layer. By weight, the adhesive layer comprises the following components: 100 parts epoxy resin, 20-100 parts toughening agent, 50-150 parts flame retardant, 5-30 parts curing agent, and 0.1-5 parts curing accelerator. The insulating film provided by this technical solution has poor dielectric properties.

[0004] Therefore, how to reduce the coefficient of thermal expansion of the laminate film, ensure product yield, reduce dielectric loss of the laminate film, and avoid excessive signal transmission loss during use has become an urgent technical problem to be solved. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a multi-component filler-based adhesive film for FC-BGA packaging substrates, its preparation method, and its applications. By designing the composition of the adhesive film and using specific fillers, the present invention effectively reduces the coefficient of thermal expansion of the adhesive film, ensuring product yield, while simultaneously reducing dielectric loss and solving the problem of excessive signal transmission loss during use.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a laminated adhesive film, the laminated adhesive film comprising the following components in parts by weight:

[0008] 130-175 parts filler, 60-120 parts polyphenylene ether resin, 15-30 parts epoxy resin, 10-20 parts curing agent, 15-20 parts phosphate ester compound, and 2-5 parts curing accelerator;

[0009] The packing includes packing A and packing B;

[0010] The filler A is silicon dioxide;

[0011] The filler B is boron nitride and / or carbon nanotubes.

[0012] In this invention, by designing the composition of the laminated film and further using specific fillers, the thermal expansion coefficient of the laminated film can be effectively reduced, ensuring product yield. At the same time, the dielectric loss of the laminated film is reduced, solving the problem of excessive signal transmission loss during use.

[0013] In this invention, based on components such as polyphenylene ether resin, epoxy resin, curing agent, phosphonate compound, and curing accelerator, modification is achieved by introducing multi-component fillers such as boron nitride, carbon nanotubes, and silica. Among these, boron nitride filler exhibits excellent thermal stability and has an extremely low coefficient of thermal expansion, forming a good resin / boron nitride micro-interface within the composite material system. The boron nitride at the interface provides a strong mechanical binding effect, thereby restricting the deformation and displacement of polymer chain segments. In addition, the small size of carbon nanotubes allows them to fill the gaps between other fillers or the polymer chain segments of the main resin, thereby reducing the free space for polymer chain segment movement and limiting the movement of polymer chain segments, thus reducing thermal expansion and meeting the application requirements of the laminated film in FC-BGA encapsulation substrates.

[0014] In this invention, the weight percentage of filler in the laminated film can be 130 parts, 135 parts, 140 parts, 145 parts, 150 parts, 155 parts, 160 parts, 165 parts, 170 parts, or 175 parts, etc.

[0015] The polyphenylene ether resin can be in the following weight proportions: 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, or 120 parts, etc.

[0016] The epoxy resin can be in parts by weight of 15, 18, 20, 21, 24, 25, 27, or 30 parts, etc.

[0017] The curing agent can be present in parts by weight of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 parts, etc.

[0018] The weight parts of the phosphate ester compound can be 15, 16, 17, 18, 19, or 20 parts, etc.

[0019] The curing accelerator can be present in 2, 3, 4, or 5 parts by weight, etc.

[0020] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0021] As a preferred embodiment of the present invention, the boron nitride is aminated boron nitride.

[0022] In this invention, boron nitride filler particles are subjected to aminated surface modification treatment to obtain aminated boron nitride. The amino groups on the aminated boron nitride can react with epoxy groups, thereby improving the compatibility between boron nitride and the resin matrix, enhancing the dispersibility of boron nitride particles in the resin matrix, and constructing an interconnected network structure. This restricts the movement of epoxy resin molecular chain segments and reduces the coefficient of thermal expansion of the system.

[0023] Preferably, the raw materials for preparing the aminated boron nitride include urea and boron nitride.

[0024] Preferably, the mass ratio of urea to boron nitride is (2-5):1, for example, it can be 2:1, 2.2:1, 2.5:1, 2.7:1, 3:1, 3.3:1, 3.6:1, 4:1, 4.2:1, 4.6:1, 4.8:1 or 5:1, etc.

[0025] Preferably, the aminated boron nitride is prepared by the following method, which includes the following steps:

[0026] Urea, boron nitride, and organic solvent A are placed in a ball mill for grinding and then allowed to stand. The upper suspension is then filtered, and the filtered solid is dried and ground to obtain the amino boron nitride.

[0027] Preferably, the organic solvent A is selected from any one or a combination of at least two of isopropanol, ethylene glycol, propylene glycol, or glycerol.

[0028] Preferably, the mass ratio of boron nitride to organic solvent A is 1:(15-25), for example, it can be 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24 or 1:25, etc.

[0029] Preferably, when using the ball mill for grinding, the rotation speed of the ball mill is 250-350 rpm, for example, it can be 250 rpm, 260 rpm, 270 rpm, 280 rpm, 290 rpm, 300 rpm, 310 rpm, 320 rpm, 330 rpm, 340 rpm or 350 rpm, etc.

[0030] Preferably, when using the ball mill for grinding, the grinding time is 40-50 hours, for example, 40 hours, 41 hours, 42 hours, 43 hours, 44 hours, 45 hours, 46 hours, 47 hours, 48 ​​hours, 49 hours, or 50 hours.

[0031] Preferably, the filtration method includes vacuum filtration.

[0032] Preferably, the pore size of the filter membrane in the filtration process is 0.1-0.5μm, for example, it can be 0.1μm, 0.15μm, 0.2μm, 0.22μm, 0.3μm, 0.35μm, 0.4μm, 0.45μm or 0.5μm, etc.

[0033] Preferably, the drying method includes vacuum drying.

[0034] Preferably, the drying temperature is 75-85℃, for example, it can be 75℃, 76℃, 77℃, 78℃, 79℃, 80℃, 81℃, 82℃, 83℃, 84℃ or 85℃, etc.

[0035] Preferably, the drying time is 10-15 hours, for example, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours.

[0036] Preferably, the aminated boron nitride is prepared by the following method, which includes the following steps:

[0037] Urea, boron nitride, and organic solvent A are placed in a ball mill and ground at 250-350 rpm for 40-50 hours. After standing, the upper suspension is filtered using a filter membrane with a pore size of 0.1-0.5 μm. The solid on the filter membrane is then vacuum dried at 75-85℃ for 10-15 hours, cooled to room temperature, and ground to obtain the amino-modified boron nitride.

[0038] Preferably, the carbon nanotubes have a diameter of 10-100 nm (e.g., 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 100 nm, etc.) and a length of 50-500 nm (e.g., 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, or 500 nm, etc.).

[0039] Preferably, the carbon nanotubes are aminated carbon nanotubes.

[0040] In this invention, the amino groups of the aminated carbon nanotubes can react with the epoxy groups in the epoxy resin to form a carbon nanotube / epoxy resin interface region. The stronger the constraint of this interface region on dipole polarization, the more it can reduce the loss caused by dipole polarization, thereby reducing the dielectric loss of the system. After the aminated carbon nanotubes react with the epoxy resin, the molecular chain packing density can be increased. The denser the packing, the smaller the free volume, and the space for movement of epoxy resin molecular chain segments is restricted, thereby obtaining a reduced coefficient of thermal expansion.

[0041] Preferably, the aminated carbon nanotubes are prepared by the following method, which includes the following steps:

[0042] (1) Disperse carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid, and react to obtain acidified carbon nanotubes;

[0043] (2) Acidified carbon nanotubes, organic solvent B, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and acrylic acid are mixed and reacted to obtain carboxylated carbon nanotubes.

[0044] (3) Mix carboxylated carbon nanotubes, organic solvent C, and polyethylene polyamine, and react to obtain aminolated carbon nanotubes.

[0045] Preferably, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in step (1) is 1:(0.8-1.2), for example, it can be 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1, 1:1.15 or 1:1.2, etc.

[0046] Preferably, the mass ratio of carbon nanotubes to concentrated sulfuric acid in step (1) is 1:(25-35), for example, it can be 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34 or 1:35, etc.

[0047] Preferably, the dispersion method in step (1) includes ultrasonic dispersion, wherein the power of the ultrasonic wave is 500-800W, for example, it can be 500W, 550W, 600W, 650W, 700W, 750W or 800W, etc.

[0048] Preferably, the dispersion time in step (1) is 30-60 minutes, for example, it can be 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes or 60 minutes.

[0049] Preferably, the reaction temperature in step (1) is 140-160℃ (e.g., 140℃, 144℃, 146℃, 148℃, 150℃, 152℃, 154℃, 156℃, 158℃ or 160℃, etc.), and the reaction time is 60-80min (e.g., 60min, 63min, 66min, 70min, 72min, 75min or 80min, etc.).

[0050] Preferably, the mass ratio of acidified carbon nanotubes, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and acrylic acid in step (2) is 0.05:(0.2-0.3):(0.015-0.02):(0.5-0.7), for example, it can be 0.05:0.2:0.015:0.5, 0.05:0.25:0.015:0.5, 0.05:0.3:0.015:0.5, 0.05:0.2:0.02:0.5, 0.05:0.2:0.015:0.6, 0.05:0.2:0.015:0.7, 0.05:0.2:0.02:0.5, etc.

[0051] Preferably, the dispersion method in step (2) includes ultrasonic dispersion, wherein the power of the ultrasonic wave is 500-800W, for example, it can be 500W, 550W, 600W, 650W, 700W, 750W or 800W, etc.

[0052] Preferably, the dispersion time in step (2) is 30-50 min, for example, it can be 30 min, 33 min, 36 min, 40 min, 42 min, 46 min or 50 min.

[0053] Preferably, the reaction in step (2) is carried out under an inert atmosphere.

[0054] Preferably, the reaction temperature in step (2) is 80-90℃ (e.g., 80℃, 82℃, 84℃, 86℃, 88℃ or 90℃, etc.), and the reaction time is 20-30h (e.g., 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h or 30h, etc.).

[0055] Preferably, the reaction in step (2) further includes a post-processing step, wherein the post-processing method includes washing, filtering, and drying.

[0056] Preferably, the mass ratio of carboxylated carbon nanotubes to polyethylene polyamine in step (3) is 1:(2-3), for example, it can be 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8 or 1:3, etc.

[0057] Preferably, the dispersion method in step (3) includes ultrasonic dispersion, wherein the power of the ultrasonic wave is 500-800W, for example, it can be 500W, 550W, 600W, 650W, 700W, 750W or 800W, etc.

[0058] Preferably, the dispersion time in step (3) is 30-50 min, for example, it can be 30 min, 33 min, 36 min, 40 min, 42 min, 46 min or 50 min.

[0059] Preferably, the reaction in step (3) is carried out under an inert atmosphere.

[0060] It should be noted that in this invention, the inert atmosphere includes nitrogen atmosphere, argon atmosphere, etc.

[0061] Preferably, the reaction time in step (3) is 20-30 hours, for example, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours or 30 hours.

[0062] Preferably, the reaction in step (3) further includes a post-processing step, wherein the post-processing method includes washing, filtering, and drying.

[0063] Preferably, the aminated carbon nanotubes are prepared by the following method, which includes the following steps:

[0064] (1) Weigh 1g of carbon nanotubes and disperse them in a mixture of concentrated sulfuric acid (20-25mL) and concentrated nitric acid (16-30mL). Under the condition of 500-800W, ultrasonically disperse for 30-60min, and then reflux at 140-160℃ for 60-80min. Wash the product with distilled water several times until neutral, filter, and dry to obtain acidified carbon nanotubes.

[0065] (2) Weigh 50 mg of acidified carbon nanotubes and disperse them in 40-50 mL of N,N-dimethylformamide. Under the condition of 500-800 W power, ultrasonically disperse for 30-50 min to obtain a suspension. Then weigh 0.2-0.3 g of dicyclohexylcarbodiimide, 0.015-0.02 g of 4-dimethylaminopyridine and 0.5-0.7 g of acrylic acid and dissolve them in 40-50 mL of N,N-dimethylformamide. Add them to the suspension and react under an inert atmosphere at 80-90 °C for 20-30 h. Wash, filter and dry to obtain carboxylated carbon nanotubes.

[0066] (3) Weigh 0.2g of carboxylated carbon nanotubes and disperse them in 50-60mL of N,N-dimethylformamide. Under the condition of 500-800W, ultrasonically disperse for 30-50min. Then add polyethylene polyamine (0.4-0.6g) and react at room temperature in an inert atmosphere for 20-30h. Wash, filter and dry to obtain aminated carbon nanotubes.

[0067] As a preferred embodiment of the present invention, the particle size of the silicon dioxide is 600-800nm, for example, it can be 600nm, 620nm, 640nm, 660nm, 680nm, 700nm, 720nm, 740nm, 760nm, 780nm or 800nm, etc.

[0068] Preferably, the mass ratio of the filler A to the filler B is (3-4):1, for example, it can be 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1 or 4:1, etc.

[0069] In this invention, by controlling the mass ratio of filler A to filler B within a specific range, the prepared laminated film exhibits a low coefficient of thermal expansion and a low dielectric loss. If the mass ratio of filler A to filler B is too large, i.e., the amount of boron nitride and / or carbon nanotubes is too small, the coefficient of thermal expansion of the laminated film is relatively large; if the mass ratio of filler A to filler B is too small, i.e., the amount of boron nitride and / or carbon nanotubes is too large, the boron nitride and carbon nanotubes in the laminated film are prone to agglomeration, resulting in poor dispersion in the film system and poor film formation.

[0070] Preferably, the filler is a combination of silicon dioxide, aminated boron nitride, and aminated carbon nanotubes.

[0071] In this invention, a combination of silicon dioxide, aminated boron nitride, and aminated carbon nanotubes is preferred as a filler, which can further reduce the coefficient of thermal expansion and dielectric loss of the laminated film.

[0072] As a preferred embodiment of the present invention, the polyphenylene ether is selected from any one or a combination of at least two of the following: "OPE-2St1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd., "OPE-2St2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., and "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0073] Preferably, the epoxy resin is selected from any one or a combination of at least two of the following: bisphenol type epoxy resin, biphenyl type epoxy resin, phenol type epoxy resin, naphthol type epoxy resin, linear phenolic epoxy resin, dicyclopentadiene type epoxy resin, aralkyl type phenolic epoxy resin, aralkyl biphenyl type phenolic epoxy resin, or naphthol type phenolic epoxy resin.

[0074] Preferably, the curing agent is selected from any one or a combination of at least two of the following: active ester type curing agent, cyanate ester type curing agent, phenol type curing agent, and benzoxazine type curing agent.

[0075] As a preferred embodiment of the present invention, the phosphonate compound is selected from any one or a combination of at least two of dimethyl vinylphosphonate, diethyl vinylphosphonate, and diphenyl vinylphosphonate.

[0076] Preferably, the curing accelerator is selected from any one or a combination of at least two of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-ethyl-4-methylimidazole, 4-dimethylaminopyridine, and 2-phenylimidazole.

[0077] As a preferred embodiment of the present invention, the extended film further includes 1-2 parts of an initiator, for example, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, or 2 parts, etc.

[0078] It should be noted that there are no special restrictions on the specific selection of the initiator in this invention. Commonly used initiators in the art are applicable, including but not limited to: "Perhekishin 25B" manufactured by Nippon Oil Company and "Trigonox 311" manufactured by Kayaku Akzo Company.

[0079] Preferably, the raw materials for preparing the laminated film also include 3-9 parts of additives, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts, etc.

[0080] Preferably, the additive is selected from any one or a combination of at least two of the following: thickener, defoamer, homogenizer, leveling agent, adhesion promoter, and colorant.

[0081] It should be noted that there are no special restrictions on the specific selection of thickeners, defoamers, homogenizers, leveling agents, adhesion promoters and colorants in this invention, and the above-mentioned additives commonly used in the art are all applicable.

[0082] Preferably, the thickening film further includes 200-300 parts of organic solvent, such as 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts, or 300 parts.

[0083] Preferably, the organic solvent is selected from any one or a combination of at least two of toluene, xylene, butanone, methyl ethyl ketone, cyclohexanone, ethyl acetate, or N,N-dimethylformamide.

[0084] As a preferred embodiment of the present invention, the thickness of the laminated film is 10 to 100 μm, for example, it can be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm.

[0085] In a second aspect, the present invention provides a method for preparing the laminated film as described in the first aspect, the method comprising the following steps:

[0086] After the components of the laminate film are mixed evenly, they are coated onto the substrate and dried to obtain the laminate film.

[0087] As a preferred embodiment of the present invention, the thickness of the substrate is 10-150 μm (for example, it can be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm, etc.), and more preferably 25-50 μm.

[0088] It should be noted that the present invention does not have any special limitations on the choice of substrate; commonly used substrates in the art can be used, including but not limited to: PET release film, polyethylene film, polypropylene film, or polyvinyl chloride film. Furthermore, to facilitate subsequent removal of the substrate, the polyethylene film, polypropylene film, or polyvinyl chloride film can be pre-treated with corona discharge before use.

[0089] Preferably, the drying temperature is 80-130℃, for example, it can be 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃ or 130℃, etc.

[0090] Preferably, the drying time is 3-10 minutes, for example, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes or 10 minutes.

[0091] Preferably, the drying process further includes a post-processing step.

[0092] Preferably, the post-processing method is to remove the substrate.

[0093] Preferably, the preparation method specifically includes the following steps:

[0094] After the components of the laminated adhesive film are mixed evenly, the mixture is coated onto a substrate and dried at 80-130℃ for 3-10 minutes. The substrate is then removed to obtain the laminated adhesive film.

[0095] Thirdly, the present invention provides an application of the laminated adhesive film as described in the first aspect in an FC-BGA packaging substrate.

[0096] Compared with the prior art, the present invention has the following beneficial effects:

[0097] In this invention, by designing the composition of the laminated film and further using specific fillers, the combination of silica with aminated boron nitride and / or aminated carbon nanotubes, and controlling their mass ratio within a specific range, the coefficient of thermal expansion of the laminated film can be effectively reduced, ensuring product yield. At the same time, the dielectric loss of the laminated film is reduced, solving the problem of excessive signal transmission loss during use. The laminated film prepared in this way has a coefficient of thermal expansion of 20-27 and a dielectric loss of 0.0045-0.0061. Detailed Implementation

[0098] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0099] The sources of some components in the following preparation examples, embodiments, and comparative examples are as follows:

[0100] Silicon dioxide: "SOC2" manufactured by Yatuma Corporation of Japan;

[0101] Boron nitride: CAS No. 10043-11-5;

[0102] Carbon nanotubes: CAS No. 516291-96-6;

[0103] Polyphenylene oxide resin: "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0104] Biphenyl-type epoxy resin: "NC3000L" manufactured by Nippon Kayaku Co., Ltd.

[0105] Cyanate ester type curing agent: Lonza "PT30";

[0106] Initiator: Nippon Oil Company's "Perhekishin 25B";

[0107] Leveling agent: KP341 manufactured by Shin-Etsu Chemical Co., Ltd., Japan;

[0108] PET release film: SP4020 manufactured by Toyobo Co., Ltd., Japan.

[0109] Preparation Example 1

[0110] This preparation example provides an amino boron nitride and its preparation method, which is as follows:

[0111] (1) First, weigh 1g of boron nitride powder and 4g of urea, measure 25mL of isopropanol solution, add it to the ball mill and stir evenly. Set the ball mill speed to 300r / min and run it continuously for 48h. Then, take out the mixture and put it into a beaker to stand.

[0112] (2) Use a syringe to inject the upper suspension of the mixture into a vacuum filtration flask, filter it through a filter membrane with a pore size of 0.22 μm, put the sample on the filter membrane into a vacuum drying oven and dry it at 80°C for 12 h. After cooling to room temperature, grind it in a mortar to obtain aminated boron nitride.

[0113] Preparation Example 2

[0114] This preparation example provides an aminated carbon nanotube and its preparation method, which is as follows:

[0115] (1) Weigh 1g of carbon nanotubes and disperse them in a mixture of 20mL concentrated sulfuric acid and 20mL concentrated nitric acid. Disperse them by ultrasonication for 30min, and then reflux them at 140℃ for 60min. Wash the product with distilled water several times until neutral, filter, and dry to obtain acidified carbon nanotubes.

[0116] (2) Weigh 50 mg of acidified carbon nanotubes and disperse them in 40 mL of N,N-dimethylformamide. Sonicate the dispersion for 30 min to obtain a suspension. Then weigh 0.2 g of dicyclohexylcarbodiimide, 0.015 g of 4-dimethylaminopyridine and 0.5 g of acrylic acid, dissolve them in 40 mL of N,N-dimethylformamide and add them to the suspension. Under nitrogen atmosphere protection, react at 85 °C for 24 h. Wash, filter and dry to obtain carboxylated carbon nanotubes.

[0117] (3) Weigh 0.2g of carboxylated carbon nanotubes and disperse them in 50mL of N,N-dimethylformamide. Disperse them by sonication for 30min. Then add 0.4g of polyethylene polyamine and react at room temperature in a nitrogen atmosphere for 24h. Wash, filter and dry to obtain aminated carbon nanotubes.

[0118] The aminated boron nitride mentioned in the following examples and comparative examples are all aminated boron nitride provided in Preparation Example 1 above, and the aminated carbon nanotubes mentioned are all aminated carbon nanotubes provided in Preparation Example 2 above.

[0119] Example 1

[0120] This embodiment provides an additive film and its preparation method, wherein the additive film comprises the following components in parts by weight:

[0121] 175 parts filler, 100 parts polyphenylene ether resin, 15 parts biphenyl epoxy resin, 15 parts cyanate ester curing agent, 20 parts dimethyl vinyl phosphonate, 4 parts 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1 part initiator, 5 parts leveling agent, and 300 parts cyclohexanone.

[0122] The filler is composed of silicon dioxide and amino boron nitride in a mass ratio of 27:8.

[0123] The preparation method of the above-mentioned thickened adhesive film is as follows:

[0124] After the components of the extended adhesive film are mixed evenly, they are coated onto a PET release film and dried at 100°C for 5 minutes. The PET release film is then removed to obtain the extended adhesive film.

[0125] Example 2

[0126] This embodiment provides an additive film and its preparation method, wherein the additive film comprises the following components in parts by weight:

[0127] 130 parts filler, 60 parts polyphenylene ether resin, 30 parts biphenyl epoxy resin, 20 parts cyanate ester curing agent, 15 parts diethylvinylphosphonate, 2 parts 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2 parts initiator, 3 parts leveling agent, and 200 parts methyl ethyl ketone.

[0128] The filler is composed of silica and aminated carbon nanotubes in a mass ratio of 10:3.

[0129] The preparation method of the above-mentioned thickened adhesive film is as follows:

[0130] After the components of the extended adhesive film are mixed evenly, they are coated onto a PET release film and dried at 130°C for 3 minutes. The PET release film is then removed to obtain the extended adhesive film.

[0131] Example 3

[0132] This embodiment provides an additive film and its preparation method, wherein the additive film comprises the following components in parts by weight:

[0133] 175 parts filler, 100 parts polyphenylene ether resin, 15 parts biphenyl epoxy resin, 15 parts cyanate ester curing agent, 20 parts diphenylvinylphosphonate, 5 parts 2-ethyl-4-methylimidazolium, 2 parts initiator, 9 parts leveling agent, and 300 parts cyclohexanone.

[0134] The filler is composed of silicon dioxide, aminated boron nitride, and aminated carbon nanotubes in a mass ratio of 28:4:3.

[0135] The preparation method of the above-mentioned thickened adhesive film is as follows:

[0136] After the components of the extended adhesive film are mixed evenly, they are coated onto a PET release film, dried at 80°C for 10 minutes, and the PET release film is removed to obtain the extended adhesive film.

[0137] Example 4

[0138] This embodiment provides an additive film and its preparation method, wherein the additive film comprises the following components in parts by weight:

[0139] 160 parts filler, 120 parts polyphenylene ether resin, 25 parts biphenyl epoxy resin, 10 parts cyanate ester curing agent, 18 parts dimethyl vinyl phosphonate, 3 parts 1-cyanoethyl-2-ethyl-4-methylimidazolium, 2 parts initiator, and 240 parts N,N-dimethylformamide.

[0140] The filler is composed of silicon dioxide, aminated boron nitride, and aminated carbon nanotubes in a mass ratio of 6:1:1.

[0141] The preparation method of the above-mentioned thickened adhesive film is as follows:

[0142] After the components of the laminated adhesive film are mixed evenly, they are coated onto a PET release film and dried at 90°C for 7 minutes. The PET release film is then removed to obtain the laminated adhesive film.

[0143] Example 5

[0144] This embodiment provides a layered adhesive film and its preparation method. The difference from Embodiment 1 is that the filler is composed of silicon dioxide and aminated boron nitride in a mass ratio of 4:1, while other conditions are the same as in Embodiment 1.

[0145] Example 6

[0146] This embodiment provides a layered adhesive film and its preparation method. The difference from Embodiment 1 is that the filler is composed of silicon dioxide and aminated boron nitride in a mass ratio of 3:1, while other conditions are the same as in Embodiment 1.

[0147] Example 7

[0148] This embodiment provides a layered adhesive film and its preparation method. The difference from Embodiment 1 is that the filler is composed of silicon dioxide and aminated boron nitride in a mass ratio of 4:3, while other conditions are the same as in Embodiment 1.

[0149] Example 8

[0150] This embodiment provides a layered adhesive film and its preparation method. The difference from Embodiment 1 is that the filler is composed of silicon dioxide and aminated boron nitride in a mass ratio of 6:1, while other conditions are the same as in Embodiment 1.

[0151] Example 9

[0152] This embodiment provides a layered adhesive film and its preparation method. The difference from Embodiment 1 is that the aminated boron nitride in the filler is replaced with boron nitride, while other conditions are the same as in Embodiment 1.

[0153] Example 10

[0154] This embodiment provides a layered adhesive film and its preparation method. The difference from Embodiment 2 is that the filler aminated carbon nanotubes are replaced with carbon nanotubes, while other conditions are the same as in Embodiment 2.

[0155] Comparative Example 1

[0156] This comparative example provides a layered adhesive film and its preparation method. The only difference from Example 1 is that, under the premise that the total amount of filler remains unchanged, only silicon dioxide is used as the filler, and other conditions are the same as in Example 1.

[0157] Comparative Example 2

[0158] This comparative example provides a layered adhesive film and its preparation method. The only difference from Example 1 is that, under the premise that the total amount of filler remains unchanged, only aminated boron nitride is used as the filler, and other conditions are the same as in Example 1.

[0159] Comparative Example 3

[0160] This comparative example provides a layered adhesive film and its preparation method. The only difference from Example 1 is that, under the premise that the total amount of filler remains unchanged, only aminated carbon nanotubes are used as filler. Other conditions are the same as in Example 1.

[0161] The performance of the laminated films provided in the above embodiments and comparative examples was tested, and the specific test methods are as follows:

[0162] Coefficient of thermal expansion: The PET release film-coated adhesive film provided in the above examples and comparative examples was cured at 100°C for 30 min and at 190°C for 90 min. Then the release film was peeled off to obtain the test sample. The test sample was cut into test pieces with a width of about 3 mm and a length of about 120 mm. Thermomechanical analysis was performed using a thermomechanical analysis device (TA Instruments' "TMA450") under the conditions of a preload force of 0.02 N, a heating range of 25°C to 260°C, and a heating rate of 10°C / min to obtain the coefficient of thermal expansion in the range of 25°C to 150°C.

[0163] Dielectric loss: The PET release film-coated adhesive provided in the above examples and comparative examples was cured at 180°C for 30 min, and then the release film was peeled off to obtain a pre-cured adhesive film. The pre-cured adhesive film was cut into 2 mm × 80 mm test pieces (3 pieces). Then, using Agilent Technologies' "HP8362B", the dielectric loss of each test piece was measured using the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. The average value of the 3 test pieces was then calculated as the dielectric loss.

[0164] Film-forming properties: Mix all components of the laminated adhesive film evenly, and use a coating machine to quickly and evenly coat it onto a substrate such as PET release film in both longitudinal and transverse directions to form a uniform adhesive film without any gaps or overflows. If the film is uniform, it is considered to be able to form a film; otherwise, it is considered to be unable to form a film.

[0165] The performance test results of the laminated films provided in the above embodiments and comparative examples are shown in Table 1 below:

[0166] Table 1

[0167] coefficient of thermal expansion Dielectric loss Film-forming properties Example 1 26 0.0060 Film-forming Example 2 25 0.0045 Film-forming Example 3 20 0.0052 Film-forming Example 4 22 0.0050 Film-forming Example 5 27 0.0061 Film-forming Example 6 25 0.0061 Film-forming Example 7 - - Non-film-forming Example 8 33 0.0060 Film-forming Example 9 39 0.0063 Film-forming Example 10 38 0.0061 Film-forming Comparative Example 1 44 0.0065 Film-forming Comparative Example 2 - - Non-film-forming Comparative Example 3 - - Non-film-forming

[0168] As can be seen from the above, by designing the composition of the laminated film in this invention, and further by using specific fillers, and by using silicon dioxide in combination with aminated boron nitride and / or aminated carbon nanotubes, and controlling their mass ratio within a specific range, the coefficient of thermal expansion of the laminated film can be effectively reduced, ensuring product yield. At the same time, the dielectric loss of the laminated film is reduced, solving the problem of excessive signal transmission loss during use. The laminated film prepared in this way has a coefficient of thermal expansion of 20-27 and a dielectric loss of 0.0045-0.0061.

[0169] Compared with Example 1, if the mass ratio of filler A to filler B is too small (Example 7), a film cannot be formed; if the mass ratio of filler A to filler B is too large (Example 8), the coefficient of thermal expansion of the prepared laminated film is too large.

[0170] Compared with Examples 1-2, if boron nitride / carbon nanotubes are used in combination with silicon dioxide as fillers (Examples 9-10), the resulting laminated film has a higher coefficient of thermal expansion.

[0171] Compared with Example 1, if any one of silica, aminated boron nitride, or aminated carbon nanotubes is selected as the filler (Comparative Examples 1-3), the prepared laminated films have poor film-forming properties, high coefficient of thermal expansion, and large dielectric loss.

[0172] In summary, by designing the composition of the laminated film and further using specific fillers, the present invention utilizes silica in combination with aminated boron nitride and / or aminated carbon nanotubes, and controls their mass ratio within a specific range. This effectively reduces the coefficient of thermal expansion of the laminated film, ensures product yield, and reduces dielectric loss of the laminated film, thus solving the problem of excessive signal transmission loss during use.

[0173] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A multi-component filler FC-BGA encapsulation substrate extension film, characterized in that, The laminated film comprises the following components in parts by weight: 130-175 parts filler, 60-120 parts polyphenylene ether resin, 15-30 parts epoxy resin, 10-20 parts curing agent, 15-20 parts phosphate ester compound, and 2-5 parts curing accelerator; The packing includes packing A and packing B; The filler A is silicon dioxide; The filler B is boron nitride and / or carbon nanotubes; The boron nitride is an amino boron nitride; The carbon nanotubes are aminated carbon nanotubes; The mass ratio of packing A to packing B is (3-4):

1.

2. The laminated adhesive film according to claim 1, characterized in that, The raw materials for preparing the aminated boron nitride include urea and boron nitride.

3. The laminated adhesive film according to claim 2, characterized in that, The mass ratio of urea to boron nitride is (2-5):

1.

4. The laminated adhesive film according to claim 1, characterized in that, The aminated boron nitride is prepared by the following method, which includes the following steps: Urea, boron nitride, and organic solvent A are placed in a ball mill for grinding and then allowed to stand. The upper suspension is then filtered, and the filtered solid is dried and ground to obtain the amino boron nitride.

5. The laminated adhesive film according to claim 4, characterized in that, The organic solvent A is selected from any one or a combination of at least two of isopropanol, ethylene glycol, propylene glycol, or glycerol.

6. The laminated adhesive film according to claim 4, characterized in that, The mass ratio of boron nitride to organic solvent is 1:(15-25).

7. The laminated adhesive film according to claim 4, characterized in that, When using the ball mill for grinding, the rotation speed of the ball mill is 250-350 rpm, and the grinding time is 40-50 hours.

8. The laminated adhesive film according to claim 4, characterized in that, The filtration method includes vacuum filtration.

9. The laminated film according to claim 8, characterized in that, The pore size of the filter membrane in the filtration process is 0.1-0.5 μm.

10. The laminated film according to claim 4, characterized in that, The drying method includes vacuum drying.

11. The laminated film according to claim 4, characterized in that, The drying temperature is 75-85℃, and the drying time is 10-15 hours.

12. The laminated film according to claim 1, characterized in that, The carbon nanotubes have a diameter of 10-100 nm and a length of 50-500 nm.

13. The laminated film according to claim 1, characterized in that, The aminated carbon nanotubes were prepared by the following method, which includes the following steps: (1) Disperse carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid, and react to obtain acidified carbon nanotubes; (2) Acidified carbon nanotubes, organic solvent B, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and acrylic acid are mixed and reacted to obtain carboxylated carbon nanotubes. (3) Mix carboxylated carbon nanotubes, organic solvent C, and polyethylene polyamine, and react to obtain aminolated carbon nanotubes.

14. The laminated film according to claim 13, characterized in that, In step (1), the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 1:(0.8-1.2).

15. The laminated film according to claim 13, characterized in that, In step (1), the mass ratio of carbon nanotubes to concentrated sulfuric acid is 1:(25-35).

16. The laminated film according to claim 13, characterized in that, The dispersion method in step (1) includes ultrasonic dispersion, wherein the power of the ultrasonic wave is 500-800W.

17. The laminated film according to claim 13, characterized in that, The dispersion time in step (1) is 30-60 minutes.

18. The laminated film according to claim 13, characterized in that, The reaction temperature in step (1) is 140-160℃, and the reaction time is 60-80 min.

19. The laminated film according to claim 13, characterized in that, The mass ratio of acidified carbon nanotubes, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and acrylic acid in step (2) is 0.05:(0.2-0.3):(0.015-0.02):(0.5-0.7).

20. The laminated film according to claim 13, characterized in that, The dispersion method in step (2) includes ultrasonic dispersion, wherein the power of the ultrasonic wave is 500-800W.

21. The laminated film according to claim 13, characterized in that, The dispersion time in step (2) is 30-50 minutes.

22. The laminated film according to claim 13, characterized in that, The reaction described in step (2) is carried out under an inert atmosphere.

23. The laminated film according to claim 13, characterized in that, The reaction temperature in step (2) is 80-90℃, and the reaction time is 20-30h.

24. The laminated film according to claim 13, characterized in that, Step (2) includes a post-processing step after the reaction, and the post-processing method includes washing, filtering and drying.

25. The laminated film according to claim 13, characterized in that, The mass ratio of carboxylated carbon nanotubes to polyethylene polyamine in step (3) is 1:(2-3).

26. The laminated film according to claim 13, characterized in that, The dispersion method in step (3) includes ultrasonic dispersion, wherein the power of the ultrasonic wave is 500-800W.

27. The laminated film according to claim 13, characterized in that, The dispersion time in step (3) is 30-50 minutes.

28. The laminated film according to claim 13, characterized in that, The reaction described in step (3) is carried out under an inert atmosphere.

29. The laminated film according to claim 13, characterized in that, The reaction time in step (3) is 20-30 hours.

30. The laminated film according to claim 13, characterized in that, Step (3) includes a post-processing step after the reaction, and the post-processing method includes washing, filtering and drying.

31. The laminated film according to claim 1, characterized in that, The silica has a particle size of 600-800 nm.

32. The laminated film according to claim 1, characterized in that, The filler is a combination of silicon dioxide, aminated boron nitride, and aminated carbon nanotubes.

33. The laminated film according to claim 1, characterized in that, The epoxy resin is selected from any one or a combination of at least two of the following: bisphenol type epoxy resin, biphenyl type epoxy resin, phenol type epoxy resin, naphthol type epoxy resin, linear phenolic epoxy resin, dicyclopentadiene type epoxy resin, aralkyl type phenolic epoxy resin, aralkyl biphenyl type phenolic epoxy resin, or naphthol type phenolic epoxy resin.

34. The laminated film according to claim 1, characterized in that, The curing agent is selected from any one or a combination of at least two of the following: active ester type curing agent, cyanate ester type curing agent, phenol type curing agent, and benzoxazine type curing agent.

35. The laminated film according to claim 1, characterized in that, The phosphate compound is selected from any one or a combination of at least two of dimethyl vinyl phosphonate, diethyl vinyl phosphonate, and diphenyl vinyl phosphonate.

36. The laminated film according to claim 1, characterized in that, The curing accelerator is selected from any one or a combination of at least two of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-ethyl-4-methylimidazole, 4-dimethylaminopyridine, and 2-phenylimidazole.

37. The laminated film according to claim 1, characterized in that, The thickened film also includes 1-2 parts of initiator.

38. The laminated film according to claim 1, characterized in that, The raw materials for preparing the laminated film also include 3-9 parts of additives.

39. The laminated film according to claim 38, characterized in that, The additives are selected from any one or a combination of at least two of the following: thickeners, defoamers, homogenizers, leveling agents, adhesion promoters, and colorants.

40. The laminated film according to claim 1, characterized in that, The laminated film also includes 200-300 parts of organic solvent.

41. The laminated film according to claim 40, characterized in that, The organic solvent is selected from any one or a combination of at least two of toluene, xylene, butanone, methyl ethyl ketone, cyclohexanone, ethyl acetate, or N,N-dimethylformamide.

42. The laminated film according to claim 1, characterized in that, The thickness of the laminated film is 10–100 μm.

43. A method for preparing a laminated film as described in any one of claims 1-42, characterized in that, The preparation method includes the following steps: After the components of the laminate film are mixed evenly, they are coated onto the substrate and dried to obtain the laminate film.

44. The preparation method according to claim 43, characterized in that, The thickness of the substrate is 10–150 μm.

45. The preparation method according to claim 44, characterized in that, The thickness of the substrate is 25–50 μm.

46. ​​The preparation method according to claim 43, characterized in that, The drying temperature is 80-130℃.

47. The preparation method according to claim 43, characterized in that, The drying time is 3-10 minutes.

48. The preparation method according to claim 43, characterized in that, The drying process also includes a post-processing step.

49. The preparation method according to claim 48, characterized in that, The post-processing method involves removing the substrate.

50. The preparation method according to claim 43, characterized in that, The preparation method specifically includes the following steps: After the components of the laminated adhesive film are mixed evenly, the mixture is coated onto a substrate and dried at 80-130℃ for 3-10 minutes. The substrate is then removed to obtain the laminated adhesive film.

51. The application of the laminated adhesive film as described in any one of claims 1-42 in an FC-BGA packaging substrate.