Additional adhesive film for multi-component filler FC-BGA packaging carrier plate, and preparation method therefor and use thereof

Abstract

Provided in the present application are an additional adhesive film for a multi-component filler FC-BGA packaging carrier plate, and a preparation method therefor and the use thereof. The additional 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 additional adhesive film, coating a substrate with the mixture, and drying the mixture to obtain an additional adhesive film. By using the specific filler in the present application, the thermal expansion coefficient of the layer-adding adhesive film can be effectively reduced, the product yield is ensured, meanwhile, the dielectric loss of the layer-adding adhesive film is reduced, and the problem that the signal transmission loss is too large in the using process is solved.

Description

Multi-component filler build-up adhesive film for FC-BGA package carrier board and preparation method and application thereof Technical Field

[0001] The present application relates to the technical field of resin composite materials, for example, to a build-up adhesive film for a multi-component filler FC-BGA package carrier board, and a preparation method and application thereof. Background Art

[0002] Flip-chip ball grid array (FC-BGA) packaging substrates are the future development direction of semiconductor packaging substrates, with wide applications and broad market prospects. FC-BGA substrates are high-density packaging substrates that enable high-speed and multifunctional chips, and build-up adhesive films are one of the key core materials in the semi-additive manufacturing process (SAP) for FC-BGA substrates. However, the thermal expansion of the resin system in existing build-up adhesive films will generate thermal stress. If the thermal stress is too large, it will damage the reliability of the FC-BGA packaging substrate and its packaging system. At the same time, thermal expansion coefficient mismatch can easily cause through-hole cracks and delamination failures. At the same time, the high dielectric loss of traditional build-up adhesive films can easily lead to slow signal transmission rates and high losses. The higher the frequency, the more obvious the impact of dielectric properties on transmission loss.

[0003] CN114058278A discloses a high-temperature-resistant insulating adhesive film, its preparation method, and its application. The film comprises a substrate layer and an adhesive layer. The adhesive layer contains the following components, by weight: 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 adhesive film provided by this technical solution has poor dielectric properties.

[0004] Therefore, how to reduce the thermal expansion coefficient of the build-up film to ensure product yield, while reducing the dielectric loss of the build-up film and avoiding excessive signal transmission loss during use has become a technical problem that needs to be solved urgently.

[0005] Summary of the Invention

[0006] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0007] This application provides a multi-component filler build-up film for FC-BGA package carriers, as well as its preparation method and application. By designing the components of the build-up film and further using specific fillers, this application effectively reduces the thermal expansion coefficient of the build-up film, ensuring product yield, while also reducing dielectric loss in the build-up film and addressing the issue of excessive signal transmission loss during use.

[0008] In a first aspect, the present application provides a build-up adhesive film, comprising the following components in parts by weight:

[0009] 130-175 parts of filler, 60-120 parts of polyphenylene ether resin, 15-30 parts of epoxy resin, 10-20 parts of curing agent, 15-20 parts of phosphate compound, 2-5 parts of curing accelerator;

[0010] The filler includes filler A and filler B;

[0011] The filler A is silicon dioxide;

[0012] The filler B is boron nitride and / or carbon nanotubes.

[0013] In this application, by designing the components of the build-up film and further using specific fillers, the thermal expansion coefficient of the build-up film can be effectively reduced, the product yield can be ensured, and the dielectric loss of the build-up film can be reduced, thereby solving the problem of excessive signal transmission loss during use.

[0014] In the present application, based on components such as polyphenylene ether resin, epoxy resin, curing agent, phosphonate compound, and curing accelerator, multi-component fillers such as boron nitride, carbon nanotubes, and silica are introduced for modification. The boron nitride filler has excellent thermal stability and an extremely low thermal expansion coefficient, forming a good resin / boron nitride microscopic contact interface in the composite material system. The boron nitride in the interface part has a strong mechanical restraint effect, thereby limiting the deformation and displacement of the polymer chain segments. In addition, the carbon nanotubes are small in size and can be filled in the gaps between other fillers or the main resin polymer segments, thereby reducing the free activity space of the polymer segments and limiting the movement of the polymer segments, thereby reducing thermal expansion, meeting the application of the build-up film in the FC-BGA package carrier.

[0015] In the present application, the weight proportion of the filler in the build-up film may be 130 parts, 135 parts, 140 parts, 145 parts, 150 parts, 155 parts, 160 parts, 165 parts, 170 parts or 175 parts, etc.

[0016] The weight proportions of the polyphenylene ether resin may be 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.

[0017] The weight proportions of the epoxy resin may be 15 parts, 18 parts, 20 parts, 21 parts, 24 parts, 25 parts, 27 parts or 30 parts, etc.

[0018] The weight proportions of the curing agent may be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, etc.

[0019] The weight proportion of the phosphate compound may be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts.

[0020] The weight proportion of the curing accelerator can be 2 parts, 3 parts, 4 parts or 5 parts.

[0021] The following are optional technical solutions for this application, but are not intended to limit the technical solutions provided in this application. Through the following optional technical solutions, the objectives and beneficial effects of this application can be better achieved and realized.

[0022] As an optional technical solution of the present application, the boron nitride is amino boron nitride.

[0023] In the present application, the boron nitride filler particles are subjected to an amino surface modification treatment to obtain amino-treated boron nitride. The amino groups on the amino-treated boron nitride can react with epoxy groups, thereby improving the compatibility between the boron nitride and the resin matrix, improving the dispersibility of the boron nitride particles in the resin matrix, and constructing an interconnected network structure, thereby restricting the movement of the epoxy resin molecular segments and reducing the thermal expansion coefficient of the system.

[0024] In one embodiment, the raw materials for preparing the amino-boron nitride include urea and boron nitride.

[0025] In one embodiment, the mass ratio of the urea to the boron nitride is (2-5):1, for example, 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.

[0026] In one embodiment, the amino boron nitride is prepared by the following method, which comprises the following steps:

[0027] Urea, boron nitride and organic solvent A are ground in a ball mill and allowed to stand. The upper suspension is filtered, and the filtered solid is dried and ground to obtain the amino boron nitride.

[0028] In one embodiment, the organic solvent A is selected from any one of isopropyl alcohol, ethylene glycol, propylene glycol, or glycerol, or a combination of at least two thereof.

[0029] In one embodiment, the mass ratio of boron nitride to organic solvent A is 1:(15-25), for example, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24 or 1:25.

[0030] In one embodiment, when the ball mill is used 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.

[0031] In one embodiment, when the ball mill is used 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.

[0032] In one embodiment, the filtering method comprises suction filtration.

[0033] In one embodiment, the pore size of the filter membrane in the filtration is 0.1-0.5 μm, for example, it can be 0.1 μm, 0.15 μm, 0.2 μm, 0.22 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm or 0.5 μm, etc.

[0034] In one embodiment, the drying method comprises vacuum drying.

[0035] In one embodiment, the drying temperature is 75-85°C, for example, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C or 85°C.

[0036] In one embodiment, the drying time is 10-15 hours, for example, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours.

[0037] In one embodiment, the amino boron nitride is prepared by the following method, which comprises the following steps:

[0038] Urea, boron nitride and organic solvent A are placed in a ball mill and ground at 250-350 rpm for 40-50 hours. The mixture is then allowed to stand and 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 vacuum dried at 75-85° C. for 10-15 hours, cooled to room temperature, and ground to obtain the amino boron nitride.

[0039] In one embodiment, the carbon nanotubes have a diameter of 10-100 nm (for example, 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 (for example, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm or 500 nm, etc.).

[0040] In one embodiment, the carbon nanotubes are amino-treated carbon nanotubes.

[0041] In the present application, 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 ability of this interface region on dipole polarization, the less loss caused by dipole polarization can be reduced, thereby reducing the dielectric loss of the system. After the aminated carbon nanotubes react with the epoxy resin, the packing density of the molecular chains can be increased. The denser the stacking, the smaller the free volume. The space for movement of the epoxy resin molecular chain segments is restricted, thereby obtaining a lower thermal expansion coefficient.

[0042] In one embodiment, the amino-modified carbon nanotubes are prepared by the following method, which comprises the following steps:

[0043] (1) dispersing carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid, reacting to obtain acidified carbon nanotubes;

[0044] (2) mixing the acidified carbon nanotubes, the organic solvent B, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and acrylic acid, and reacting them to obtain carboxylated carbon nanotubes;

[0045] (3) Mixing the carboxylated carbon nanotubes, the organic solvent C, and polyethylene polyamine, and reacting them to obtain amino-treated carbon nanotubes.

[0046] In one embodiment, 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.

[0047] In one embodiment, the mass ratio of carbon nanotubes to concentrated sulfuric acid in step (1) is 1:(25-35), for example, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30, 1:31, 1:32, 1:33, 1:34 or 1:35.

[0048] In one embodiment, the dispersion method in step (1) comprises ultrasonic dispersion, and the power of the ultrasound is 500-800W, for example, 500W, 550W, 600W, 650W, 700W, 750W or 800W.

[0049] In one embodiment, the dispersion time in step (1) is 30-60 min, for example, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min or 60 min.

[0050] In one embodiment, the reaction temperature of step (1) is 140-160°C (for example, 140°C, 144°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C or 160°C, etc.), and the reaction time is 60-80 min (for example, 60 min, 63 min, 66 min, 70 min, 72 min, 75 min or 80 min, etc.).

[0051] In one embodiment, the mass ratio of the 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.

[0052] In one embodiment, the dispersion method in step (2) includes ultrasonic dispersion, and the power of the ultrasound is 500-800W, for example, 500W, 550W, 600W, 650W, 700W, 750W or 800W.

[0053] In one embodiment, the dispersion time in step (2) is 30-50 min, for example, 30 min, 33 min, 36 min, 40 min, 42 min, 46 min or 50 min.

[0054] In one embodiment, the reaction in step (2) is carried out under an inert atmosphere.

[0055] In one embodiment, the reaction temperature of step (2) is 80-90°C (for example, 80°C, 82°C, 84°C, 86°C, 88°C or 90°C), and the reaction time is 20-30h (for example, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h or 30h, etc.).

[0056] In one embodiment, the reaction in step (2) further includes a post-treatment step, and the post-treatment method includes washing, filtering, and drying.

[0057] In one embodiment, the mass ratio of the carboxylated carbon nanotubes to polyethylene polyamine in step (3) is 1:(2-3), for example, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8 or 1:3.

[0058] In one embodiment, the dispersion method in step (3) includes ultrasonic dispersion, and the power of the ultrasound is 500-800W, for example, 500W, 550W, 600W, 650W, 700W, 750W or 800W.

[0059] In one embodiment, the dispersion time in step (3) is 30-50 min, for example, 30 min, 33 min, 36 min, 40 min, 42 min, 46 min or 50 min.

[0060] In one embodiment, the reaction in step (3) is carried out under the protection of an inert atmosphere.

[0061] It should be noted that, in the present application, the inert atmosphere includes nitrogen atmosphere, argon atmosphere, etc.

[0062] In one embodiment, the reaction time of step (3) is 20-30 h, for example, it can be 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h, 29 h or 30 h.

[0063] In one embodiment, the reaction in step (3) further includes a post-treatment step, and the post-treatment method includes washing, filtering, and drying.

[0064] In one embodiment, the amino-modified carbon nanotubes are prepared by the following method, which comprises the following steps:

[0065] (1) Weighing carbon nanotubes (1 g) and dispersing them in a mixture of concentrated sulfuric acid (20-25 mL) and concentrated nitric acid (16-30 mL), ultrasonically dispersing them at a power of 500-800 W for 30-60 min, then refluxing them at 140-160° C. for 60-80 min. The product was washed with distilled water several times until neutral, filtered, and dried to obtain acidified carbon nanotubes.

[0066] (2) Weighing acidified carbon nanotubes (50 mg) and dispersing them in N, N-dimethylformamide (40-50 mL), ultrasonically dispersing them at a power of 500-800 W for 30-50 min to obtain a suspension, then weighing dicyclohexylcarbodiimide (0.2-0.3 g), 4-dimethylaminopyridine (0.015-0.02 g) and acrylic acid (0.5-0.7 g), dissolving them in N, N-dimethylformamide (40-50 mL), and adding them to the suspension, protecting them with an inert atmosphere, and reacting them at 80-90° C. for 20-30 h; washing, filtering, and drying to obtain carboxylated carbon nanotubes;

[0067] (3) Weigh carboxylated carbon nanotubes (0.2 g) and disperse them in N,N-dimethylformamide (50-60 mL). Ultrasonic dispersion is performed at a power of 500-800 W for 30-50 min. Then, polyethylene polyamine (0.4-0.6 g) is added and reacted at room temperature in an inert atmosphere for 20-30 h. The mixture is washed, filtered, and dried to obtain amino-containing carbon nanotubes.

[0068] As an optional technical solution of the present application, the particle size of the silicon dioxide is 600-800 nm, for example, it can be 600 nm, 620 nm, 640 nm, 660 nm, 680 nm, 700 nm, 720 nm, 740 nm, 760 nm, 780 nm or 800 nm.

[0069] In one embodiment, the mass ratio of filler A to 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.

[0070] In the present application, by controlling the mass ratio of filler A to filler B within a specific range, the resulting build-up film exhibits a low thermal expansion coefficient and low dielectric loss. If the mass ratio of filler A to filler B is too large, that is, if the amount of boron nitride and / or carbon nanotubes used is too small, the thermal expansion coefficient of the build-up film is relatively large. If the mass ratio of filler A to filler B is too small, that is, if the amount of boron nitride and / or carbon nanotubes used is too large, the boron nitride and carbon nanotubes in the build-up film tend to agglomerate, resulting in poor dispersion within the film system and poor film-forming properties.

[0071] In one embodiment, the filler is a combination of silica, amino-bonded boron nitride, and amino-bonded carbon nanotubes.

[0072] In the present application, a combination of silicon dioxide, amino-bonded boron nitride and amino-bonded carbon nanotubes can be optionally included as fillers to further reduce the thermal expansion coefficient and dielectric loss of the build-up film.

[0073] As an optional technical solution of the present application, the polyphenylene ether is selected from any one of "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, "OPE-2St2200" manufactured by Mitsubishi Gas Chemical Company, and "OPE-2St" manufactured by Mitsubishi Gas Chemical Company, or a combination of at least two thereof.

[0074] In one embodiment, the epoxy resin is selected from any one of bisphenol epoxy resin, biphenyl epoxy resin, phenol epoxy resin, naphthol epoxy resin, linear phenolic epoxy resin, dicyclopentadiene epoxy resin, aralkyl phenolic epoxy resin, aralkyl biphenyl phenolic epoxy resin or naphthol phenolic epoxy resin, or a combination of at least two thereof.

[0075] In one embodiment, the curing agent is selected from any one of active ester curing agents, cyanate curing agents, phenol curing agents, and benzoxazine curing agents, or a combination of at least two thereof.

[0076] As an optional technical solution of the present application, the phosphonate compound is selected from any one of dimethyl vinyl phosphonate, diethyl vinyl phosphonate, and diphenyl vinyl phosphonate, or a combination of at least two thereof.

[0077] In one embodiment, 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;

[0078] As an optional technical solution of the present application, the build-up film also includes 1-2 parts of an initiator, for example, it can be 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.

[0079] It should be noted that there is no particular limitation on the specific selection of initiators in the present application, and any initiators commonly used in the art are applicable, including but not limited to: "Pahekishin 25B" manufactured by NOF Corporation and "Trigonox 311" manufactured by Kayaku Akzo Corporation.

[0080] In one embodiment, the raw materials for preparing the build-up adhesive film further include 3-9 parts of an auxiliary agent, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts.

[0081] In one embodiment, the auxiliary agent is selected from any one or a combination of at least two of a thickener, a defoaming agent, a leveling agent, a leveling agent, an adhesion-imparting agent, and a colorant.

[0082] It should be noted that there is no particular restriction on the specific selection of thickeners, defoamers, leveling agents, leveling agents, adhesion-imparting agents and colorants in this application, and all the above-mentioned additives commonly used in the art are applicable.

[0083] In one embodiment, the build-up adhesive film further includes 200-300 parts of an organic solvent, for example, 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts or 300 parts.

[0084] In one embodiment, 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.

[0085] As an optional technical solution of the present application, the thickness of the build-up 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.

[0086] In a second aspect, the present application provides a method for preparing the build-up adhesive film according to the first aspect, the preparation method comprising the following steps:

[0087] The components of the build-up adhesive film are mixed uniformly, coated on a substrate, and dried to obtain the build-up adhesive film.

[0088] As an optional technical solution of the present application, the thickness of the substrate is 10 to 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 can further be 25 to 50 μm.

[0089] It should be noted that the present application does not specifically limit the choice of substrate; any commonly used substrate in the art can be used, including, but not limited to, PET release film, polyethylene film, polypropylene film, or polyvinyl chloride film. To facilitate subsequent removal of the substrate, the polyethylene film, polypropylene film, or polyvinyl chloride film can be corona treated before use.

[0090] In one embodiment, the drying temperature is 80-130°C, for example, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C or 130°C.

[0091] In one embodiment, the drying time is 3-10 min, for example, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min.

[0092] In one embodiment, the drying step further includes a post-processing step.

[0093] In one embodiment, the post-treatment method is to remove the substrate.

[0094] In one embodiment, the preparation method specifically comprises the following steps:

[0095] After uniformly mixing the components of the build-up adhesive film, the film is coated on a substrate, dried at 80-130° C. for 3-10 minutes, and the substrate is removed to obtain the build-up adhesive film.

[0096] In a third aspect, the present application provides an application of the build-up film as described in the first aspect in an FC-BGA package carrier.

[0097] Compared with the related art, this application has the following beneficial effects:

[0098] In this application, by designing the components of the build-up film, further by using specific fillers, by combining silicon dioxide with amino-bonded boron nitride and / or amino-bonded carbon nanotubes, and controlling their mass ratio within a specific range, the thermal expansion coefficient of the build-up film can be effectively reduced, the product yield can be ensured, and the dielectric loss of the build-up film can be reduced, thereby solving the problem of excessive signal transmission loss during use. The build-up film prepared in this way has a thermal expansion coefficient of 20-27 and a dielectric loss of 0.0045-0.0061.

[0099] Still other aspects will become apparent upon reading and understanding the detailed description. DETAILED DESCRIPTION

[0100] To facilitate understanding of the present application, the present application lists the following examples. Those skilled in the art should understand that the examples are only provided to help understand the present application and should not be considered as specific limitations of the present application.

[0101] The sources of some components in the following preparation examples, embodiments and comparative examples are as follows:

[0102] Silicon dioxide: "SOC2" manufactured by Yaduma Co., Ltd. of Japan;

[0103] Boron nitride: CAS No. 10043-11-5;

[0104] Carbon nanotubes: CAS No. 516291-96-6;

[0105] Polyphenylene ether resin: "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0106] Biphenyl type epoxy resin: "NC3000L" manufactured by Nippon Kayaku Co., Ltd.

[0107] Cyanate ester curing agent: "PT30" manufactured by Lonza;

[0108] Initiator: PAHEXIN 25B manufactured by NOF Corporation;

[0109] Leveling agent: "KP341" manufactured by Shin-Etsu Chemical Co., Ltd. of Japan;

[0110] PET release film: “SP4020” manufactured by Toyobo Co., Ltd., Japan.

[0111] Preparation Example 1

[0112] This preparation example provides an amination boron nitride and a preparation method thereof, and the preparation method is as follows:

[0113] (1) First, weigh 1g of boron nitride powder and 4g of urea, measure 25mL of isopropanol solution, add them to a 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 place it in a beaker and let it stand.

[0114] (2) The upper suspension of the mixture was taken with a syringe and injected into a filtration flask, and filtered through a filter membrane with a pore size of 0.22 μm. The sample on the filter membrane was placed in a vacuum drying oven at 80°C for 12 hours. After cooling to room temperature, it was placed in a mortar and ground to obtain amino boron nitride.

[0115] Preparation Example 2

[0116] This preparation example provides an amino-modified carbon nanotube and a preparation method thereof, and the preparation method is as follows:

[0117] (1) Weigh 1 g of carbon nanotubes and disperse them in a mixture of 20 mL of concentrated sulfuric acid and 20 mL of concentrated nitric acid. Ultrasonic dispersion is performed for 30 min, followed by reflux at 140° C. for 60 min. The product is washed with distilled water several times until neutral, filtered, and dried to obtain acidified carbon nanotubes.

[0118] (2) Weigh 50 mg of acidified carbon nanotubes and disperse them in 40 mL of N, N-dimethylformamide. Ultrasonic dispersion is performed for 30 min to obtain a suspension. Then, 0.2 g of dicyclohexylcarbodiimide, 0.015 g of 4-dimethylaminopyridine and 0.5 g of acrylic acid are weighed and dissolved in 40 mL of N, N-dimethylformamide. The mixture is added to the suspension and reacted at 85°C for 24 h under nitrogen atmosphere. The mixture is washed, filtered and dried to obtain carboxylated carbon nanotubes.

[0119] (3) Weigh 0.2 g of carboxylated carbon nanotubes and disperse them in 50 mL of N,N-dimethylformamide. Ultrasonic dispersion is performed for 30 min. Then, 0.4 g of polyethylene polyamine is added. The mixture is reacted at room temperature for 24 h in a nitrogen atmosphere. The mixture is washed, filtered, and dried to obtain amino-containing carbon nanotubes.

[0120] The amination-treated boron nitride mentioned in the following examples and comparative examples is the amination-treated boron nitride provided in Preparation Example 1, and the amination-treated carbon nanotubes mentioned are the amination-treated carbon nanotubes provided in Preparation Example 2.

[0121] Example 1

[0122] This embodiment provides a build-up adhesive film and a preparation method thereof. The build-up adhesive film includes the following components in parts by weight:

[0123] 175 parts of filler, 100 parts of polyphenylene ether resin, 15 parts of biphenyl epoxy resin, 15 parts of cyanate ester curing agent, 20 parts of dimethyl vinyl phosphonate, 4 parts of 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 part of initiator, 5 parts of leveling agent, 300 parts of cyclohexanone;

[0124] The filler is composed of silicon dioxide and amino boron nitride in a mass ratio of 27:8.

[0125] The preparation method of the above-mentioned build-up film is as follows:

[0126] The components of the build-up adhesive film were mixed uniformly, coated on a PET release film, dried at 100° C. for 5 minutes, and the PET release film was removed to obtain the build-up adhesive film.

[0127] Example 2

[0128] This embodiment provides a build-up adhesive film and a preparation method thereof. The build-up adhesive film includes the following components in parts by weight:

[0129] 130 parts of filler, 60 parts of polyphenylene ether resin, 30 parts of biphenyl epoxy resin, 20 parts of cyanate ester curing agent, 15 parts of diethyl vinyl phosphonate, 2 parts of 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2 parts of initiator, 3 parts of leveling agent, 200 parts of butanone;

[0130] The filler is composed of silicon dioxide and amino carbon nanotubes in a mass ratio of 10:3.

[0131] The preparation method of the above-mentioned build-up film is as follows:

[0132] The components of the build-up adhesive film were mixed uniformly, coated on a PET release film, dried at 130° C. for 3 minutes, and the PET release film was removed to obtain the build-up adhesive film.

[0133] Example 3

[0134] This embodiment provides a build-up adhesive film and a preparation method thereof. The build-up adhesive film includes the following components in parts by weight:

[0135] 175 parts of filler, 100 parts of polyphenylene ether resin, 15 parts of biphenyl epoxy resin, 15 parts of cyanate ester curing agent, 20 parts of diphenyl vinyl phosphonate, 5 parts of 2-ethyl-4-methylimidazole, 2 parts of initiator, 9 parts of leveling agent, 300 parts of cyclohexanone;

[0136] The filler is composed of silicon dioxide, amino boron nitride and amino carbon nanotubes in a mass ratio of 28:4:3.

[0137] The preparation method of the above-mentioned build-up film is as follows:

[0138] The components of the build-up adhesive film were mixed uniformly, coated on a PET release film, dried at 80° C. for 10 min, and the PET release film was removed to obtain the build-up adhesive film.

[0139] Example 4

[0140] This embodiment provides a build-up adhesive film and a preparation method thereof. The build-up adhesive film includes the following components in parts by weight:

[0141] 160 parts of filler, 120 parts of polyphenylene ether resin, 25 parts of biphenyl epoxy resin, 10 parts of cyanate ester curing agent, 18 parts of dimethyl vinyl phosphonate, 3 parts of 1-cyanoethyl-2-ethyl-4-methylimidazole, 2 parts of initiator, 240 parts of N,N-dimethylformamide;

[0142] The filler is composed of silicon dioxide, amino boron nitride and amino carbon nanotubes in a mass ratio of 6:1:1.

[0143] The preparation method of the above-mentioned build-up film is as follows:

[0144] The components of the build-up adhesive film were mixed uniformly, coated on a PET release film, dried at 90° C. for 7 minutes, and the PET release film was removed to obtain the build-up adhesive film.

[0145] Example 5

[0146] This embodiment provides a build-up adhesive film and a preparation method thereof. The difference from Example 1 is that the filler is composed of silicon dioxide and amino boron nitride in a mass ratio of 4:1. Other conditions are the same as those in Example 1.

[0147] Example 6

[0148] This embodiment provides a build-up adhesive film and a preparation method thereof. The difference from Example 1 is that the filler is composed of silicon dioxide and amino boron nitride in a mass ratio of 3:1, and other conditions are the same as Example 1.

[0149] Example 7

[0150] This embodiment provides a build-up adhesive film and a preparation method thereof. The difference from Example 1 is that the filler is composed of silicon dioxide and amino boron nitride in a mass ratio of 4:3. Other conditions are the same as those in Example 1.

[0151] Example 8

[0152] This embodiment provides a build-up adhesive film and a preparation method thereof. The difference from Example 1 is that the filler is composed of silicon dioxide and amino boron nitride in a mass ratio of 6:1. Other conditions are the same as those in Example 1.

[0153] Example 9

[0154] This embodiment provides a build-up adhesive film and a preparation method thereof. The difference from Example 1 is that the amination-treated boron nitride in the filler is replaced with boron nitride, and other conditions are the same as those in Example 1.

[0155] Example 10

[0156] This embodiment provides a build-up adhesive film and a preparation method thereof. The difference from Example 2 is that the amination-treated carbon nanotubes as filler are replaced with carbon nanotubes, and other conditions are the same as those in Example 2.

[0157] Comparative Example 1

[0158] This comparative example provides a build-up adhesive film and a preparation method thereof, which differs from Example 1 only in that, under the premise that the total amount of filler remains unchanged, the filler is only silicon dioxide, and other conditions are the same as Example 1.

[0159] Comparative Example 2

[0160] This comparative example provides a build-up adhesive film and a preparation method thereof, which differs from Example 1 only in that, under the premise that the total amount of filler remains unchanged, the filler is only amino-bonded boron nitride, and other conditions are the same as Example 1.

[0161] Comparative Example 3

[0162] This comparative example provides a build-up adhesive film and a preparation method thereof, which differs from Example 1 only in that, under the premise that the total amount of filler remains unchanged, the filler is only amino-treated carbon nanotubes, and other conditions are the same as Example 1.

[0163] The performance of the build-up films provided in the above examples and comparative examples was tested, and the specific testing methods are as follows:

[0164] Thermal expansion coefficient: The layered adhesive film with PET release film provided in the above-mentioned embodiments and comparative examples was cured at 100°C for 30 min and at 190°C for 90 min, and then the release film was peeled off to obtain a test sample; the test sample was cut into test pieces with a width of about 3 mm and a length of about 120 mm, and a thermal mechanical analysis was performed using a thermomechanical analysis device ("TMA450" of TA Company, USA) 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 thermal expansion coefficient in the range of 25°C to 150°C.

[0165] Dielectric loss: The build-up adhesive with PET release film provided in the above-mentioned embodiments and comparative examples was cured at 180°C for 30 minutes, and then the release film was peeled off to obtain a pre-cured build-up adhesive film; the pre-cured build-up adhesive film was cut into 2 mm × 80 mm test pieces (3 pieces), and then the dielectric loss of each test piece was measured using the "HP8362B" of Agilent Technologies Inc. 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 three test pieces was calculated as the dielectric loss.

[0166] Film-forming property: Mix all components of the build-up film evenly and use a coating machine to quickly and evenly coat it on a substrate such as a PET release film in the longitudinal and transverse directions to form a uniform film without any gaps or overflow. If the film is considered to be film-forming, it is considered to be unfilm-forming.

[0167] The performance test results of the build-up films provided in the above examples and comparative examples are shown in Table 1 below:

[0168] Table 1

[0169] From the above content, it can be seen that in this application, by designing the components of the build-up film, further by using specific fillers, by combining silica with amino-bonded boron nitride and / or amino-bonded carbon nanotubes, and controlling their mass ratio within a specific range, the thermal expansion coefficient of the build-up film can be effectively reduced, the product yield can be ensured, and at the same time, the dielectric loss of the build-up film can be reduced, thereby solving the problem of excessive signal transmission loss during use. The thermal expansion coefficient of the build-up film prepared in this way is 20-27, and the dielectric loss is 0.0045-0.0061.

[0170] Compared with Example 1, if the mass ratio of filler A to filler B is too small (Example 7), film formation is impossible; if the mass ratio of filler A to filler B is too large (Example 8), the thermal expansion coefficient of the prepared build-up film is too large.

[0171] Compared with Examples 1-2, if boron nitride / carbon nanotubes and silicon dioxide are used together as fillers (Examples 9-10), the thermal expansion coefficient of the prepared build-up adhesive film is higher.

[0172] Compared with Example 1, if any one of silicon dioxide, amino boron nitride or amino carbon nanotubes is selected as the filler (Comparative Examples 1-3), the prepared build-up adhesive film has poor film-forming properties, a high thermal expansion coefficient and a large dielectric loss.

[0173] In summary, in this application, by designing the components of the build-up film, further by using specific fillers, by combining silica with amino-bonded boron nitride and / or amino-bonded carbon nanotubes, and controlling their mass ratio within a specific range, the thermal expansion coefficient of the build-up film can be effectively reduced, the product yield can be ensured, and at the same time, the dielectric loss of the build-up film can be reduced, thereby solving the problem of excessive signal transmission loss during use.

[0174] The applicant declares that while the above-mentioned embodiments are used to illustrate the detailed process flow of the present application, the present application is not limited to the above-mentioned detailed process flow, which does not mean that the present application must rely on the above-mentioned detailed process flow in order to be implemented. Those skilled in the art should understand that any improvements to the present application, equivalent replacements for the raw materials of the present application's products, addition of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present application.

Claims

1. A multi-component filler FC-BGA package carrier board build-up film, wherein: The build-up adhesive film comprises the following components in parts by weight: 130-175 parts of filler, 60-120 parts of polyphenylene ether resin, 15-30 parts of epoxy resin, 10-20 parts of curing agent, 15-20 parts of phosphate compound, 2-5 parts of curing accelerator; The filler includes filler A and filler B; The filler A is silicon dioxide; The filler B is boron nitride and / or carbon nanotubes.

2. The build-up adhesive film according to claim 1, wherein: The boron nitride is amidated boron nitride.

3. The build-up adhesive film according to claim 2, wherein: The raw materials for preparing the amination boron nitride include urea and boron nitride.

4. The build-up adhesive film according to claim 3, wherein: The mass ratio of the urea to the boron nitride is (2-5):

1.

5. The build-up adhesive film according to claim 2, wherein: The amination boron nitride is prepared by the following method, which comprises the following steps: Grinding urea, boron nitride and organic solvent A in a ball mill and letting it stand, filtering the upper suspension, drying the filtered solid and grinding it to obtain the amino boron nitride; Optionally, the organic solvent A is selected from any one or a combination of at least two of isopropanol, ethylene glycol, propylene glycol or glycerol; Optionally, the mass ratio of the boron nitride to the organic solvent is 1:(15-25); Optionally, when the ball mill is used for grinding, the rotation speed of the ball mill is 250-350 rpm, and the grinding time is 40-50 h; Optionally, the filtering method includes suction filtration; Optionally, the pore size of the filter membrane in the filtration is 0.1-0.5 μm; Optionally, the drying method includes vacuum drying; Optionally, the drying temperature is 75-85° C., and the drying time is 10-15 h.

6. The build-up adhesive film according to any one of claims 1 to 5, wherein: The carbon nanotubes have a diameter of 10-100 nm and a length of 50-500 nm; Optionally, the carbon nanotubes are amino-treated carbon nanotubes; Optionally, the amino-modified carbon nanotubes are prepared by the following method, which comprises the following steps: (1) dispersing carbon nanotubes in a mixture of concentrated sulfuric acid and concentrated nitric acid to react and obtain acidified carbon nanotubes; (2) mixing the acidified carbon nanotubes, the organic solvent B, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and acrylic acid, and reacting them to obtain carboxylated carbon nanotubes; (3) mixing the carboxylated carbon nanotubes, the organic solvent C, and polyethylene polyamine, and reacting them to obtain the amino carbon nanotubes; Optionally, in step (1), the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 1:(0.8-1.2); Optionally, in step (1), the mass ratio of carbon nanotubes to concentrated sulfuric acid is 1:(25-35); Optionally, the dispersion method in step (1) includes ultrasonic dispersion, and the power of the ultrasound is 500-800W; Optionally, the dispersion time in step (1) is 30-60 min; Optionally, the reaction temperature in step (1) is 140-160° C., and the reaction time is 60-80 min; Optionally, in step (2), the mass ratio of the acidified carbon nanotubes, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and acrylic acid is 0.05:(0.2-0.3):(0.015-0.02):(0.5-0.7); Optionally, the dispersion method in step (2) includes ultrasonic dispersion, and the power of the ultrasound is 500-800W; Optionally, the dispersion time in step (2) is 30-50 min; Optionally, the reaction in step (2) is carried out under the protection of an inert atmosphere; Optionally, the reaction temperature in step (2) is 80-90° C., and the reaction time is 20-30 h; Optionally, the step (2) further comprises a post-treatment step after the reaction, and the post-treatment method comprises washing, filtering, and drying; Optionally, the mass ratio of the carboxylated carbon nanotubes to polyethylene polyamine in step (3) is 1:(2-3); Optionally, the dispersion method in step (3) includes ultrasonic dispersion, and the power of the ultrasound is 500-800W; Optionally, the dispersion time in step (3) is 30-50 min; Optionally, the reaction in step (3) is carried out under the protection of an inert atmosphere; Optionally, the reaction time in step (3) is 20-30h; Optionally, the reaction in step (3) further includes a post-treatment step, and the post-treatment method includes washing, filtering and drying.

7. The build-up adhesive film according to any one of claims 1 to 6, wherein: The particle size of the silicon dioxide is 600-800nm; Optionally, the mass ratio of filler A to filler B is (3-4):1; Optionally, the filler is a combination of silicon dioxide, amino-bonded boron nitride and amino-bonded carbon nanotubes.

8. The build-up adhesive film according to any one of claims 1 to 7, wherein: The epoxy resin is selected from any one or a combination of at least two of bisphenol epoxy resin, biphenyl epoxy resin, phenol epoxy resin, naphthol epoxy resin, linear phenolic epoxy resin, dicyclopentadiene epoxy resin, aralkyl phenolic epoxy resin, aralkyl biphenyl phenolic epoxy resin or naphthol phenolic epoxy resin; Optionally, the curing agent is selected from active ester curing agents, cyanate curing agents, phenol curing agents, Any one or a combination of at least two of benzoxazine type curing agents; Optionally, 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; Optionally, the curing accelerator is selected from any one 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, or a combination of at least two thereof.

9. The build-up adhesive film according to any one of claims 1 to 8, wherein: The build-up adhesive film also includes 1-2 parts of an initiator; Optionally, the raw materials for preparing the build-up adhesive film further include 3-9 parts of an auxiliary agent; Optionally, the auxiliary agent is selected from any one or a combination of at least two of a thickener, a defoamer, a leveling agent, a leveling agent, an adhesion-imparting agent and a colorant; Optionally, the build-up adhesive film further comprises 200-300 parts of an organic solvent; Optionally, 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.

10. The build-up adhesive film according to any one of claims 1 to 9, wherein: The thickness of the build-up adhesive film is 10-100 μm.

11. A method for preparing a build-up adhesive film according to any one of claims 1 to 10, comprising the following steps: The components of the build-up adhesive film are mixed uniformly, coated on a substrate, and dried to obtain the build-up adhesive film.

12. The preparation method according to claim 11, wherein The thickness of the substrate is 10 to 150 μm, and can be further 25 to 50 μm.

13. The preparation method according to claim 11 or 12, wherein: The drying temperature is 80-130°C; Optionally, the drying time is 3-10 minutes.

14. The preparation method according to any one of claims 11 to 13, wherein: The drying step also includes a post-processing step; Optionally, the post-treatment method is to remove the substrate; Optionally, the preparation method specifically comprises the following steps: After the components of the build-up adhesive film are uniformly mixed, the film is coated on a substrate, dried at 80-130° C. for 3-10 minutes, and the substrate is removed to obtain the build-up adhesive film.

15. Use of the build-up adhesive film according to any one of claims 1 to 10 in a FC-BGA package carrier.

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