A composite film and a preparation method and application thereof

Abstract

The application provides a composite film and a preparation method and application thereof. The composite film comprises a first resin layer and a second resin layer which are sequentially stacked; the first resin layer is a coating layer formed by a first resin composition; the second resin layer is a coating layer formed by a second resin composition; the first resin composition comprises a thermosetting resin and a modified mesoporous filler; and the modified mesoporous filler comprises a mesoporous filler and a first thermoplastic resin loaded on the mesoporous filler. Through the structural design of the composite film and the selection of the components of each layer, a layer of uniform and suitable roughness can be formed on the first resin layer of the composite film in the DESMEAR process in the SAP process, the bonding force between the copper layer and the resin layer of the film is strong, the tensile modulus is high, and the reliability problem of fine lines produced by the SAP process can be solved.

Description

Technical Field

[0001] This invention belongs to the field of laminated film technology, specifically relating to a composite film, its preparation method, and its application. Background Technology

[0002] In the future, electronic information products will mainly develop towards a design trend of being lightweight, thin, small, and multifunctional. As the main support for electronic components, printed circuit boards (PCBs) are also constantly improving in terms of technology to meet the requirements of high-density wiring, thinness, micro-aperture, and multi-dimensionality. In particular, when the dielectric layer thickness is 30 micrometers or even 20 micrometers or less, conventional glass cloth-reinforced prepregs cannot meet the requirements, and resin films are often used instead.

[0003] Unreinforced adhesive films are being developed and applied as a new generation of substrate materials due to their ability to achieve thinner profiles, high-density wiring, micro-pores, and multi-dimensional molding. Meanwhile, because traditional etching techniques struggle to create linewidths and spacings below 20 / 20 micrometers, a semi-additive process (SAP) is typically used to fabricate fine circuits and laser-drilled microvias. In the SAP process, after vacuum lamination, pre-curing, and laser drilling of the adhesive film, a DESMEAR process is usually performed on the surface of the resin layer to remove adhesive residue and roughen the surface. This requires a suitable surface roughness to ensure the adhesion between the copper layer and the resin during copper plating, and also to easily remove the underlying copper without affecting the fabrication of fine circuits. However, it is difficult to etch a uniform roughness onto the surface of typical multilayer adhesive films. Therefore, the adhesion of fine copper lines fabricated using the SAP process is often difficult to guarantee, frequently leading to reliability issues such as wire slippage, wire breakage, or short circuits during subsequent processing. Therefore, designing a composite film that can be pressed onto the core board to create a uniform roughness on its surface, and ensuring strong adhesion between the copper layer and the resin layer, is a key issue. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a composite film, its preparation method, and its application. Through the structural design of the composite film and the selection of each layer component, a uniform and suitable roughness can be formed on the resin layer of the composite film during the desmearing process in the semi-additive process (SAP). Furthermore, the bonding force between the copper layer and the resin layer is strong, and the tensile modulus is high, which can solve the reliability problem of fabricating fine lines using the SAP process.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a composite membrane comprising a first resin layer and a second resin layer sequentially stacked; the first resin layer is a coating formed of a first resin composition; the second resin layer is a coating formed of a second resin composition; the first resin composition comprises a thermosetting resin and a modified mesoporous filler; the modified mesoporous filler comprises a mesoporous filler and a first thermoplastic resin loaded on the mesoporous filler.

[0007] A schematic cross-sectional view of the composite membrane provided by this invention is shown below. Figure 1 As shown, it includes a first resin layer 3 and a second resin layer 2. The components of the first resin layer include modified mesoporous filler, which includes mesoporous filler and a first thermoplastic resin loaded on the mesoporous filler. Through the design of its structure and the selection of each layer component, when the second resin layer of the composite film is pressed onto the core board, the thermoplastic resin on the surface or inside of the mesoporous filler of the first resin layer is etched away by the DESMEAR process, so that the first resin layer can form a moderately rough surface. During copper plating, copper teeth can be implanted into the mesopores of the mesoporous filler, thereby forming a good bonding force.

[0008] 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.

[0009] As a preferred technical solution, the thickness of the first resin layer is 5-10 μm, for example, it can be 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm or 9.5 μm, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0010] In this invention, if the thickness of the first resin layer is too thin, there is a tendency for the resin layer to be difficult to prepare; if the thickness of the first resin layer is too thick, more mesoporous filler is required, increasing the production cost of the film.

[0011] Preferably, the mass percentage of modified mesoporous filler in the first resin composition is 1% to 18%, for example, it can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17% or 18%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0012] Preferably, the first thermoplastic resin includes any one or a combination of at least two of styrene-butadiene-styrene block copolymer, rubber, polyacrylate, phenolic resin, polycarbonate resin, polyvinyl acetal resin, polyamide-imide, or polyethersulfone.

[0013] Preferably, the rubber may include, for example, siloxane-based elastomers such as polydimethylsiloxane, olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butene terpolymer, etc., and acrylic-based thermoplastic elastomers such as poly(meth)acrylate, poly(meth)acrylate, poly(cyclohexyl methacrylate), poly(meth)acrylate, and poly(octyl methacrylate).

[0014] Preferably, the polyacrylate includes resins containing methacrylate or acrylate structures, such as acrylate copolymer resins containing carboxyl groups, acrylate copolymer resins containing epoxy groups, or acrylate copolymer resins containing hydroxyl groups.

[0015] Preferably, the mesoporous filler comprises any one or a combination of at least two of mesoporous silica, mesoporous alumina, or mesoporous magnesium oxide;

[0016] Preferably, the average particle size of the mesoporous filler is 0.01–5 μm, for example, it can be 0.01 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, or 5 μm. If the average particle size of the mesoporous filler is too small, it is not conducive to forming small pores on its surface for the implantation of copper-plated electrodes; if the average particle size of the mesoporous filler is too large, it is not conducive to the fabrication of fine circuits.

[0017] In this invention, the average particle size D50 is measured by laser diffraction, and the testing instrument is a Malvern laser particle size analyzer, model MS3000.

[0018] Preferably, the average pore size of the mesoporous filler is 3–50 nm, for example, it can be 3 nm, 5 nm, 6 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm. In this invention, the mesoporous filler refers to a porous filler with a porous structure and an average pore size of 3–50 nm. When the average pore size of the mesoporous filler is less than 3 nm, the amount of thermoplastic resin that can be loaded in the mesopores is small, making it difficult to anchor the copper teeth implanted in the mesopores during copper plating; when the average pore size of the mesoporous filler is greater than 50 nm, the mesoporous filler is easily broken, affecting the processability.

[0019] Preferably, the mesoporous packing material has a mesoporous volume greater than 0.7 mL / g, for example, it can be 0.8 mL / g, 0.85 mL / g, 0.9 mL / g, 1 mL / g, 1.25 mL / g, 1.5 mL / g, 2 mL / g, 2.5 mL / g or 3 mL / g, etc.

[0020] In this invention, whether the mesoporous filler is "porous" can be confirmed by observing its secondary electron image using an FE-SEM (JSM-6700F manufactured by Nippon Electron Ltd.) at an accelerating voltage of 5 kV. It can be observed that the mesopores have a depth of 0.001 μm or more. The first thermoplastic resin loaded on the modified mesoporous filler can be observed and measured using FE-SEM and infrared detection.

[0021] Preferably, the thermosetting resin includes any one or a combination of at least two of the following: a first epoxy resin, a phenolic resin, a cyanate ester resin, a maleimide resin, a benzoxazine resin, a styrene-butadiene resin, or a hydrocarbon resin.

[0022] Preferably, the first epoxy resin includes any one or a combination of at least two of the following: naphthalene-type epoxy resin, naphthalene-aralkyl-type epoxy resin, biphenyl-aralkyl-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, MDI-modified epoxy resin, phenolic epoxy resin, dicyclopentadiene-type epoxy resin, or alicyclic epoxy resin.

[0023] Preferably, the phenolic resin includes any one or a combination of at least two of the following: bisphenol A type phenolic resin, phenolic resin, biphenyl type phenolic resin, dicyclopentadiene type phenolic resin, allyl base linear phenolic resin, or naphthol-containing phenolic resin.

[0024] Preferably, the hydrocarbon resin includes any one or a combination of at least two of polybutadiene, polyisoprene, styrene-butadiene copolymer, alicyclic resin, styrene-butadiene-styrene block copolymer, or aromatic hydrocarbon resin.

[0025] Preferably, the first resin composition further includes a first curing agent and a first curing accelerator.

[0026] Preferably, the first curing agent comprises any one or a combination of at least two of the following: an active ester resin, an acid anhydride compound, or an amine compound.

[0027] Preferably, the first curing accelerator includes any one or a combination of at least two of imidazole, imidazole derivatives, or phosphine salts.

[0028] Preferably, the first resin composition further includes an initiator.

[0029] Preferably, the initiator comprises a peroxide and / or an azo compound.

[0030] Preferably, the mass ratio of the thermosetting resin to the first curing agent is 1:(0.1 to 2.5), for example, it can be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2 or 1:2.5, etc.

[0031] Preferably, the mass ratio of the thermosetting resin to the first curing accelerator is 1:(0.001 to 0.15), for example, it can be 1:0.001, 1:0.005, 1:0.01, 1:0.05, 1:0.1 or 1:0.15, etc.

[0032] Preferably, the mass ratio of the thermosetting resin to the initiator is 1:(0.001 to 0.15), for example, it can be 1:0.001, 1:0.005, 1:0.01, 1:0.05, 1:0.1 or 1:0.15, etc.

[0033] Preferably, the first resin composition further includes other fillers different from the mesoporous filler.

[0034] Preferably, the other fillers include any one or a combination of at least two of silica, alumina, or magnesium oxide.

[0035] Preferably, the particle size of the other fillers is ≤2μm, for example, it can be 0.1μm, 0.2μm, 0.4μm, 0.6μm, 0.8μm, 1μm, 1.2μm, 1.4μm, 1.6μm, 1.8μm or 2μm, etc.

[0036] Preferably, the mass percentage of other fillers in the first resin composition is ≤80%, for example, it can be 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70% or 80%, etc.

[0037] Preferably, the modified mesoporous filler is prepared by the following method, the method comprising: dissolving or melting the first thermoplastic resin and mixing it with the mesoporous filler to obtain the modified mesoporous filler.

[0038] Preferably, the mixing can be carried out by dry spraying, melt kneading, or solvent wet mixing.

[0039] Preferably, when the mixing is carried out by a solvent wet process, the modified mesoporous filler is prepared by: mixing the third solvent and the mesoporous filler in a first mixing, mixing and emulsifying the resulting mixture with the first thermoplastic resin in a second mixing to obtain a slurry containing the modified mesoporous filler.

[0040] Preferably, the third solvent includes any one or a combination of at least two of the following: butanone, acetone, cyclohexanone, ethyl acetate, butyl acetate, acetic acid cellosol, propylene glycol monomethyl ether acetate, cellosol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, or N-methylpyrrolidone.

[0041] Preferably, the mass ratio of the third solvent to the mesoporous filler is 1:(0.01-1), for example, it can be 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1, etc.

[0042] Preferably, the first mixing time is 60-120 min, for example, it can be 60 min, 70 min, 80 min, 90 min, 100 min, 110 min or 120 min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0043] Preferably, the first mixing is carried out under stirring, and the stirring speed is 4000-5000 rpm, for example, 4000 rpm, 4100 rpm, 4200 rpm, 4300 rpm, 4400 rpm, 4500 rpm, 4600 rpm, 4700 rpm, 4800 rpm, 4900 rpm or 5000 rpm, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0044] Preferably, the second mixing time is 60-120 min, for example, it can be 60 min, 70 min, 80 min, 90 min, 100 min, 110 min or 120 min, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0045] Preferably, the second mixing is carried out under stirring, and the stirring speed is 5000-6000 rpm, for example, it can be 5000 rpm, 5100 rpm, 5200 rpm, 5300 rpm, 5400 rpm, 5500 rpm, 5600 rpm, 5700 rpm, 5800 rpm, 5900 rpm or 6000 rpm, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0046] Preferably, when the mixing is carried out by the dry spray, the modified mesoporous filler is prepared by: putting the mesoporous filler into a mixer, mixing and atomizing the fourth solvent with the first thermoplastic resin and spraying it onto the mesoporous filler, stirring at 50-100°C for 5-30 minutes to obtain the modified mesoporous filler.

[0047] Preferably, the fourth solvent includes any one or a combination of at least two of the following: butanone, acetone, cyclohexanone, ethyl acetate, butyl acetate, acetic acid cellosolve, propylene glycol monomethyl ether acetate, cellosolve, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, or N-methylpyrrolidone.

[0048] Preferably, the mass ratio of the fourth solvent to the first thermoplastic resin is 1:(0.01-1), for example, it can be 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1, etc.

[0049] Preferably, the mass ratio of the first thermoplastic resin to the mesoporous filler is (0.8-4):1, for example, it can be 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 3:1, 3.2:1, 3.5:1, 3.8:1 or 4:1, etc.

[0050] Preferably, the process further includes a step of surface-treating the mesoporous filler with a surface treatment agent before the mixing is performed.

[0051] Preferably, the surface treatment agent includes any one or a combination of at least two of the following: silane coupling agents, alkoxysilanes, alkoxy oligomers, aluminum coupling agents, titanium coupling agents, or zirconium coupling agents.

[0052] Preferably, the surface treatment agent is 0.001% to 0.3% of the mass of the mesoporous filler, for example, 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, or 0.3%, etc.

[0053] Preferably, the surface treatment is performed by the following method, which includes: spraying the surface treatment agent onto the mesoporous filler under stirring to complete the surface treatment; the stirring time is 5 to 30 minutes, and the stirring temperature is 50 to 100°C.

[0054] Preferably, the thickness of the second resin layer is 5-90 μm, for example, it can be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm or 90 μm, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0055] Preferably, by weight, the second resin composition comprises 10-50 parts by weight of a second epoxy resin (e.g., 10, 15, 20, 25, 30, 35, 40, 45, or 50 parts by weight), 5-100 parts by weight of a second curing agent (e.g., 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 parts by weight), and 1-20 parts by weight of a second thermoplastic resin (e.g., 1, 5, 8, 10, 12, 15, 18, or 20 parts by weight). 0.001-3 parts by weight of a second curing accelerator (e.g., 0.002 parts by weight, 0.005 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1.0 parts by weight, 1.5 parts by weight, 2.0 parts by weight, 2.5 parts by weight, or 3 parts by weight) and 5-800 parts by weight of inorganic filler (e.g., 10 parts by weight, 50 parts by weight, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight, 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, or 800 parts by weight), wherein the inorganic filler does not include the mesoporous filler.

[0056] Preferably, the second epoxy resin includes any one or a combination of at least two of the following: naphthalene-type epoxy resin, naphthalene-aralkyl-type epoxy resin, biphenyl-aralkyl-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, MDI-modified epoxy resin, phenolic epoxy resin, dicyclopentadiene-type epoxy resin, or alicyclic epoxy resin.

[0057] Preferably, the second thermoplastic resin comprises any one or a combination of at least two of styrene-butadiene-styrene block copolymer, rubber, polyacrylate, phenolic resin, polycarbonate resin, polyvinyl acetal resin, polyamide-imide, or polyethersulfone.

[0058] Preferably, the second curing agent comprises any one or a combination of at least two of the following: an active ester resin, an acid anhydride compound, or an amine compound.

[0059] Preferably, the second curing accelerator comprises any one or a combination of at least two of imidazole, imidazole derivatives, or phosphine salts.

[0060] Preferably, the inorganic filler includes any one or a combination of at least two of silicon dioxide, aluminum oxide, or magnesium oxide.

[0061] Preferably, the composite membrane further includes a base membrane.

[0062] Preferably, the base film is bonded to the first resin layer.

[0063] Preferably, the thickness of the base film is 10-100 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, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0064] Preferably, the base film comprises any one of polyethylene terephthalate base film, polyethylene naphthalate base film, polyimide base film, polytetrafluoroethylene base film, polyethersulfone base film, polyphenylene sulfide base film, or polybenzimidazole base film.

[0065] Preferably, the composite film further includes a protective film.

[0066] Preferably, the protective film is bonded to the second resin layer.

[0067] Preferably, the thickness of the protective film is 10-50 μm, for example, it can be 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0068] Preferably, the protective film includes any one of polyethylene protective film, polypropylene protective film, or polyethylene terephthalate protective film.

[0069] In a second aspect, the present invention provides a method for preparing a composite membrane as described in the first aspect, the method comprising the following steps:

[0070] (S1) The first solvent and the first resin composition are mixed to obtain a first resin solution; the second solvent and the second resin composition are mixed to obtain a second resin solution;

[0071] (S2) The first resin solution is coated onto the base film and dried to form the first resin layer;

[0072] (S3) The second resin adhesive is coated onto the first resin layer and dried to form the second resin layer;

[0073] (S4) The protective film is laminated onto the surface of the second resin layer to obtain the composite film.

[0074] Preferably, the solid content of the first resin solution and the second resin solution is independently 40-70%, for example, it can be 40%, 45%, 50%, 55%, 58%, 60%, 62%, 65%, 68% or 70%.

[0075] Preferably, the first solvent and the second solvent each independently comprise any one or a combination of at least two of cyclohexanone, butanone, ethyl acetate, butyl acetate, acetic acid cellosolve, propylene glycol monomethyl ether acetate, toluene, xylene, or dimethylacetamide.

[0076] Preferably, the drying temperature in step (S2) is 80-150°C, for example, it can be 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0077] Preferably, the drying time in step (S2) is 3-5 min, for example, it can be 3 min, 3.2 min, 3.4 min, 3.6 min, 3.8 min, 4 min, 4.2 min, 4.4 min, 4.6 min, 4.8 min or 5 min, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0078] Preferably, the drying temperature in step (S3) is 80-150°C, for example, it can be 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0079] Preferably, the drying time in step (S3) is 3-5 min, for example, it can be 3 min, 3.2 min, 3.4 min, 3.6 min, 3.8 min, 4 min, 4.2 min, 4.4 min, 4.6 min, 4.8 min or 5 min, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0080] Preferably, the temperature of the composite is 60-120℃, for example, it can be 60℃, 70℃, 80℃, 90℃, 100℃, 110℃ or 120℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0081] Thirdly, the present invention provides an application of the composite film as described in the first aspect, wherein the composite film is used in a flip-chip ball grid array carrier.

[0082] Fourthly, the present invention provides a method for fabricating a flip-chip ball grid array carrier as described in the third aspect, the method comprising the following steps:

[0083] (1) Remove the protective film of the composite film as described in the first aspect, press the second resin layer of the composite film onto the core board with the inner layer circuit, and then perform pre-curing and drilling in sequence.

[0084] (2) Remove the base film of the composite film, perform desmearing and roughening treatment on the first resin layer, and then perform copper plating, pattern electroplating and flash etching in sequence to form fine lines.

[0085] (3) Repeat steps (1) and (2) to obtain the flip-chip ball grid array carrier.

[0086] The method for preparing a flip-chip ball grid array carrier provided by the present invention can produce 1 to 20 layers of fine lines. When only 1 layer of fine lines is produced, the flip-chip ball grid array (FCBGA) carrier can be obtained after step (2). When multiple layers of fine lines are produced, steps (1) and (2) are repeated to obtain the flip-chip ball grid array carrier.

[0087] In this invention, after the first resin layer is roughened, the surface Ra and Rz of the first resin layer after roughening can be tested using a laser confocal instrument (OLYMPUS).

[0088] Preferably, the pre-curing temperature is 170-190℃, for example, it can be 170℃, 172℃, 174℃, 176℃, 178℃, 180℃, 182℃, 184℃, 186℃, 188℃ or 190℃, and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0089] Preferably, the pre-curing time is 20-40 min, for example, it can be 20 min, 22 min, 24 min, 26 min, 28 min, 30 min, 32 min, 34 min, 36 min, 38 min or 40 min, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0090] Preferably, the line width and spacing of the fine lines are 8-20μm, for example, 8μm, 9μm, 10μm, 13μm, 15μm, 16μm, 18μm or 20μm, as well as specific point values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0091] Compared with the prior art, the present invention has the following beneficial effects:

[0092] The composite film provided by this invention can form a uniform and suitable roughness on the first resin layer in the DESMEAR process of SAP, with Ra being 114-126 nm and Rz being 1186-1230 nm; the adhesion between the copper layer of the copper plating and the first resin layer is above 4.7 N / cm, and after heat treatment, PS is above 4.4 N / cm, exhibiting good heat resistance of tin bleaching, without delamination or blistering, and a tensile modulus above 8.1 GPa. Attached Figure Description

[0093] Figure 1 This is a schematic cross-sectional view of the composite membrane provided in Example 1;

[0094] Wherein, 1-protective film, 2-second resin layer, 3-first resin layer, 4-base film. Detailed Implementation

[0095] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be considered as specific limitations thereof.

[0096] The sources of each component in the following examples and comparative examples are as follows:

[0097] (1) Thermosetting resin:

[0098] Naphthalene-type epoxy resin: HP-4032-SS from DIC Corporation;

[0099] Naphthalene alkyl group epoxy resin: Nippon Steel Chemical Materials Co., Ltd.'s ESN-475V;

[0100] Biphenyl aryl epoxy resin: NC-3000 from Nippon Kayaku Co., Ltd.;

[0101] (2) Reactive ester resin: HPC-8000-65T from DIC Corporation;

[0102] (3) Curing accelerator: 2-ethyl-4-methylimidazolium, 2E4MZ from Shikoku Chemical Industry Co., Ltd.

[0103] (4) Mesoporous silica: AGC Si-Tech's H31 has a D50 of 3μm, an average pore size of 5nm, and a mesoporous volume of 1mL / g.

[0104] (5) Mesoporous silica: H52 of AGC Si-Tech, with a D50 of 5μm, an average pore size of 10nm, and a mesoporous volume of 2mL / g;

[0105] (6) Mesoporous silica: Fuji Silicon Chemicals' Sylysia 430, with a D50 of 4.1 μm, an average pore size of 17 nm, and a mesoporous volume of 1.25 mL / g;

[0106] (7) Mesoporous silica: H121 from AGC Si-Tech, with a D50 of 12μm, an average pore size of 6nm, and a mesoporous volume of 1mL / g;

[0107] (8) Styrene-butadiene-styrene block copolymer: Kraton's 1118;

[0108] (9) Phenoxy resin: Nippon Steel Chemical's YP-50S;

[0109] (10) Allyl base linear phenolic resin: MEH-8000H from Meiwa Chemicals, Japan;

[0110] (11) Silica: SC-2050MB from Admatechs Corporation of Japan, with an average particle size D50 of 0.5 μm;

[0111] (12) Liquid styrene-butadiene resin: Ricon 100 from Sartomer;

[0112] (13) Dicumyl peroxide: DCP, Shanghai Fangruida Chemical.

[0113] The "parts by weight" mentioned in the thermosetting resin, epoxy resin, and curing agent of this invention are calculated based on solid content and do not include solvents, dispersants, etc.

[0114] Preparation Example 1

[0115] A modified mesoporous filler A comprises mesoporous silica H31 and styrene-butadiene-styrene block copolymer 1118 supported on the mesoporous silica H31. The preparation method of the modified mesoporous filler A includes: first, dispersing 5 parts by weight of mesoporous silica H31 with 50 parts by weight of methyl ethyl ketone (MEK solvent), stirring at high speed (4500 rpm) for 60 minutes; then adding 10 parts by weight of styrene-butadiene-styrene block copolymer 1118, and stirring and emulsifying at high speed (5500 rpm) for 60 minutes to obtain a slurry containing the modified mesoporous filler A. Infrared detection shows that the mass ratio of thermoplastic resin supported on the mesoporous filler to the mesoporous filler is 1.75:1.

[0116] Preparation Example 2

[0117] A modified mesoporous filler B comprises mesoporous silica H31 and styrene-butadiene-styrene block copolymer 1118 supported on the mesoporous silica H31. The preparation method of the modified mesoporous filler B includes: first, dispersing 13 parts by weight of mesoporous silica H31 with 50 parts by weight of methyl ethyl ketone (MEK solvent), stirring at high speed (4500 rpm) for 100 min, then adding 13 parts by weight of styrene-butadiene-styrene block copolymer 1118, and then stirring and emulsifying at high speed (5500 rpm) for 100 min to obtain a slurry containing the modified mesoporous filler B. Infrared spectroscopy shows that the mass ratio of thermoplastic resin supported on the mesoporous filler to the mesoporous filler is 0.83:1.

[0118] Preparation Example 3

[0119] A modified mesoporous filler C comprises mesoporous silica Sylysia 430 and phenolic resin YP-50S supported on the mesoporous silica Sylysia 430. The preparation method of the modified mesoporous filler C includes: first, dispersing 3 parts by weight of mesoporous silica Sylysia 430 with 50 parts by weight of methyl ethyl ketone (MEK solvent), stirring at 4500 rpm for 90 minutes; then adding 10 parts by weight of phenolic resin YP-50S, and stirring and emulsifying at 5500 rpm for 90 minutes to obtain a slurry containing the modified mesoporous filler C. Infrared spectroscopy shows that the mass ratio of thermoplastic resin supported on the mesoporous filler to the mesoporous filler is 2.93:1.

[0120] Preparation Example 4

[0121] A modified mesoporous filler D comprises mesoporous silica H52 and styrene-butadiene-styrene block copolymer 1118 supported on the mesoporous silica H52. The preparation method of the modified mesoporous filler D includes: firstly, dissolving 10 parts by weight of styrene-butadiene-styrene block copolymer 1118 in 50 parts by weight of methyl ethyl ketone (MEK solvent) to prepare a thermoplastic resin solution for later use. Then, adding 5 parts by weight of mesoporous silica H52 to a Henschel-type mixer, maintaining the temperature at 70°C, spraying 0.001 parts by weight of a silane coupling agent (Shin-Etsu Chemical's KBM-573), stirring the mesoporous silica H52 for 10 minutes, and then spraying the thermoplastic resin solution onto the aforementioned silane coupling agent-treated mesoporous silica H52, continuing to stir for 10 minutes to obtain the modified mesoporous filler D. Infrared detection shows that the mass ratio of thermoplastic resin supported on the mesoporous filler to the mesoporous filler is 1.94:1.

[0122] Preparation Example 5

[0123] A modified mesoporous filler E comprises mesoporous silica H121 and styrene-butadiene-styrene block copolymer 1118 supported on the mesoporous silica H121. The preparation method of the modified mesoporous filler E includes: first, dispersing 5 parts by weight of mesoporous silica H121 with 50 parts by weight of methyl ethyl ketone (MEK solvent), stirring at high speed (4500 rpm) for 60 min; then adding 10 parts by weight of styrene-butadiene-styrene block copolymer 1118, and stirring and emulsifying at high speed (5500 rpm) for 60 min to obtain a slurry containing the modified mesoporous filler E. Infrared detection shows that the mass ratio of thermoplastic resin supported on the mesoporous filler to the mesoporous filler is 1.78:1.

[0124] Comparative Preparation Example 1

[0125] A modified silica filler F comprises silica SC-2050MB and a styrene-butadiene-styrene block copolymer 1118 supported on the silica SC-2050MB. The preparation method of the modified silica filler F includes: first, dispersing 5 parts by weight of silica SC-2050MB with 50 parts by weight of methyl ethyl ketone (MEK solvent), stirring at high speed (4500 rpm) for 60 minutes; then adding 10 parts by weight of the styrene-butadiene-styrene block copolymer 1118, and stirring and emulsifying at high speed (5500 rpm) for 60 minutes to obtain a slurry containing the modified silica filler F. Infrared spectroscopy shows that the mass ratio of the thermoplastic resin supported on silica SC-2050MB to silica SC-2050MB is 0.0027:1.

[0126] Example 1

[0127] A composite membrane, the cross-sectional structure of which is as follows: Figure 1 As shown, the device comprises a polyethylene terephthalate (PET) base film 4, a first resin layer 3, a second resin layer 2, and a polypropylene (OPP) protective film 1, which are sequentially stacked. The PET base film has a thickness of 38 μm, the first resin layer has a thickness of 5 μm, the second resin layer has a thickness of 50 μm, and the polypropylene protective film has a thickness of 15 μm. The first resin layer is a coating formed from a first resin composition, and the second resin layer is a coating formed from a second resin composition.

[0128] The first resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 15 parts of modified mesoporous filler A, and 250 parts of silica SC-2050MB;

[0129] The second resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 10 parts of styrene-butadiene-styrene block copolymer 1118, and 255 parts of silica SC-2050MB;

[0130] The method for preparing the composite membrane includes the following steps:

[0131] (S1) 20 parts by weight of naphthalene-type epoxy resin HP-4032-SS, 10 parts by weight of naphthalene aralkyl-type epoxy resin ESN-475V, 10 parts by weight of biphenyl aralkyl-type epoxy resin NC-3000, 80 parts by weight of active ester resin HPC-8000-65T, 1 part by weight of curing accelerator 2E4MZ, 65 parts by weight of the slurry containing the modified mesoporous filler A prepared in Preparation Example 1, 250 parts by weight of silica SC-2050MB and cyclohexanone were mixed and the solid content was adjusted to 40%. The mixture was then uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the first resin solution.

[0132] The butanone and the second resin composition were mixed, the solid content was adjusted to 65%, and the mixture was uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the second resin solution.

[0133] (S2) The first resin solution is coated onto the PET base film and dried at 100°C for 4 minutes to form the first resin layer;

[0134] (S3) The second resin solution is coated onto the first resin layer and dried at 100°C for 4 minutes to form the second resin layer.

[0135] (S4) The polypropylene protective film is laminated onto the surface of the second resin layer at 80°C using a roller pressing device to obtain the composite film.

[0136] Example 2

[0137] A composite film includes a polyethylene terephthalate (PET) base film 4, a first resin layer 3, a second resin layer 2, and a polypropylene protective film 1, which are sequentially stacked. The PET base film has a thickness of 38 μm, the first resin layer has a thickness of 5 μm, the second resin layer has a thickness of 30 μm, and the polypropylene protective film has a thickness of 15 μm. The first resin layer is a coating formed from a first resin composition, and the second resin layer is a coating formed from a second resin composition.

[0138] The first resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 26 parts of modified mesoporous filler B, and 250 parts of silica SC-2050MB;

[0139] The second resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 13 parts of styrene-butadiene-styrene block copolymer 1118, and 263 parts of silica SC-2050MB;

[0140] The method for preparing the composite membrane includes the following steps:

[0141] (S1) 20 parts by weight of naphthalene-type epoxy resin HP-4032-SS, 10 parts by weight of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts by weight of biphenyl-arylene-type epoxy resin NC-3000, 80 parts by weight of active ester resin HPC-8000-65T, 1 part by weight of curing accelerator 2E4MZ, 76 parts by weight of slurry containing the modified mesoporous filler B prepared in Preparation Example 2, 250 parts by weight of silica SC-2050MB and cyclohexanone were mixed and the solid content was adjusted to 40%. The mixture was then uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the first resin solution.

[0142] The second resin composition is mixed with butanone to prepare a second resin solution with a solid content of 65%.

[0143] (S2) The first resin solution is coated onto the PET base film and dried at 100°C for 4 minutes to form the first resin layer;

[0144] (S3) The second resin solution is coated onto the first resin layer and dried at 100°C for 4 minutes to form the second resin layer.

[0145] (S4) The polypropylene protective film is laminated onto the surface of the second resin layer at 80°C using a roller pressing device to obtain the composite film.

[0146] Example 3

[0147] A composite film includes a polyethylene terephthalate (PET) base film 4, a first resin layer 3, a second resin layer 2, and a polypropylene protective film 1, which are sequentially stacked. The PET base film has a thickness of 38 μm, the first resin layer has a thickness of 10 μm, the second resin layer has a thickness of 30 μm, and the polypropylene protective film has a thickness of 15 μm. The first resin layer is a coating formed from a first resin composition, and the second resin layer is a coating formed from a second resin composition.

[0148] The first resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 13 parts of modified mesoporous filler C, and 250 parts of silica SC-2050MB;

[0149] The second resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 10 parts of phenolic resin YP-50S, and 253 parts of silica SC-2050MB;

[0150] The method for preparing the composite membrane includes the following steps:

[0151] (S1) 20 parts by weight of naphthalene-type epoxy resin HP-4032-SS, 10 parts by weight of naphthalene aralkyl-type epoxy resin ESN-475V, 10 parts by weight of biphenyl aralkyl-type epoxy resin NC-3000, 80 parts by weight of active ester resin HPC-8000-65T, 1 part by weight of curing accelerator 2E4MZ, 63 parts by weight of slurry containing the modified mesoporous filler C obtained in Preparation Example 3, 250 parts by weight of silica SC-2050MB and cyclohexanone were mixed and the solid content was adjusted to 40%. The mixture was then uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the first resin solution.

[0152] The second resin composition is mixed with butanone to prepare a second resin solution with a solid content of 65%.

[0153] (S2) The first resin solution is coated onto the PET base film and dried at 100°C for 4 minutes to form the first resin layer;

[0154] (S3) The second resin solution is coated onto the first resin layer and dried at 100°C for 4 minutes to form the second resin layer.

[0155] (S4) The polypropylene protective film is laminated onto the surface of the second resin layer at 80°C using a roller pressing device to obtain the composite film.

[0156] Example 4

[0157] A composite film includes a polyethylene terephthalate (PET) base film 4, a first resin layer 3, a second resin layer 2, and a polypropylene protective film 1, which are sequentially stacked. The PET base film has a thickness of 38 μm, the first resin layer has a thickness of 5 μm, the second resin layer has a thickness of 90 μm, and the polypropylene protective film has a thickness of 15 μm. The first resin layer is a coating formed from a first resin composition, and the second resin layer is a coating formed from a second resin composition.

[0158] The first resin composition comprises, by weight, 55 parts of liquid styrene-butadiene resin Ricon 100, 45 parts of allyl base linear phenolic resin MEH-8000H, 250 parts of silica SC-2050MB, 4 parts of dicumyl peroxide and 15 parts of modified mesoporous filler D.

[0159] The second resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 10 parts of styrene-butadiene-styrene block copolymer 1118, and 255 parts of silica SC-2050MB;

[0160] The method for preparing the composite membrane includes the following steps:

[0161] (S1) 55 parts by weight of liquid styrene-butadiene resin Ricon 100, 45 parts by weight of allyl base linear phenolic resin MEH-8000H, 250 parts by weight of silica SC-2050MB, 4 parts by weight of dicumyl peroxide, 15 parts by weight of modified mesoporous filler D prepared in Preparation Example 4 were mixed with xylene and the solid content was adjusted to 40% to obtain the first resin solution.

[0162] The second resin composition is mixed with butanone to prepare a second resin solution with a solid content of 65%.

[0163] (S2) The first resin solution is coated onto the PET base film and dried at 100°C for 4 minutes to form the first resin layer;

[0164] (S3) The second resin solution is coated onto the first resin layer and dried at 100°C for 4 minutes to form the second resin layer.

[0165] (S4) The polypropylene protective film is laminated onto the surface of the second resin layer at 80°C using a roller pressing device to obtain the composite film.

[0166] Example 5

[0167] A composite film includes a polyethylene terephthalate (PET) base film 4, a first resin layer 3, a second resin layer 2, and a polypropylene protective film 1, which are sequentially stacked. The PET base film has a thickness of 38 μm, the first resin layer has a thickness of 5 μm, the second resin layer has a thickness of 50 μm, and the polypropylene protective film has a thickness of 15 μm. The first resin layer is a coating formed from a first resin composition, and the second resin layer is a coating formed from a second resin composition.

[0168] The first resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 15 parts of modified mesoporous filler E, and 250 parts of silica SC-2050MB;

[0169] The second resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 10 parts of styrene-butadiene-styrene block copolymer 1118, and 255 parts of silica SC-2050MB;

[0170] The method for preparing the composite membrane includes the following steps:

[0171] (S1) 20 parts by weight of naphthalene-type epoxy resin HP-4032-SS, 10 parts by weight of naphthalene aralkyl-type epoxy resin ESN-475V, 10 parts by weight of biphenyl aralkyl-type epoxy resin NC-3000, 80 parts by weight of active ester resin HPC-8000-65T, 1 part by weight of curing accelerator 2E4MZ, 65 parts by weight of the slurry containing the modified mesoporous filler E prepared in Preparation Example 5, 250 parts by weight of silica SC-2050MB and cyclohexanone were mixed and the solid content was adjusted to 40%. The mixture was then uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the first resin solution.

[0172] The butanone and the second resin composition were mixed, the solid content was adjusted to 65%, and the mixture was uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the second resin solution.

[0173] (S2) The first resin solution is coated onto the PET base film and dried at 100°C for 4 minutes to form the first resin layer;

[0174] (S3) The second resin solution is coated onto the first resin layer and dried at 100°C for 4 minutes to form the second resin layer.

[0175] (S4) The polypropylene protective film is laminated onto the surface of the second resin layer at 80°C using a roller pressing device to obtain the composite film.

[0176] Comparative Example 1

[0177] A composite film includes a polyethylene terephthalate (PET) base film 4, a first resin layer 3, a second resin layer 2, and a polypropylene protective film 1, which are sequentially stacked. The PET base film has a thickness of 38 μm, the first resin layer has a thickness of 5 μm, the second resin layer has a thickness of 50 μm, and the polypropylene protective film has a thickness of 15 μm. The first resin layer is a coating formed from a first resin composition, and the second resin layer is a coating formed from a second resin composition.

[0178] The first resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 15 parts of modified silica filler F, and 250 parts of silica SC-2050MB;

[0179] The second resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 10 parts of styrene-butadiene-styrene block copolymer 1118, and 255 parts of silica SC-2050MB;

[0180] The method for preparing the composite membrane includes the following steps:

[0181] (S1) 20 parts by weight of naphthalene-type epoxy resin HP-4032-SS, 10 parts by weight of naphthalene aralkyl-type epoxy resin ESN-475V, 10 parts by weight of biphenyl aralkyl-type epoxy resin NC-3000, 80 parts by weight of active ester resin HPC-8000-65T, 1 part by weight of curing accelerator 2E4MZ, 65 parts by weight of slurry containing the modified silica filler F prepared in Comparative Preparation Example 1, 250 parts by weight of silica SC-2050MB and cyclohexanone were mixed and the solid content was adjusted to 40%. The mixture was then uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the first resin solution.

[0182] The butanone and the second resin composition were mixed, the solid content was adjusted to 65%, and the mixture was uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the second resin solution.

[0183] (S2) The first resin solution is coated onto the PET base film and dried at 100°C for 4 minutes to form the first resin layer;

[0184] (S3) The second resin solution is coated onto the first resin layer and dried at 100°C for 4 minutes to form the second resin layer.

[0185] (S4) The polypropylene protective film is laminated onto the surface of the second resin layer at 80°C using a roller pressing device to obtain the composite film.

[0186] Comparative Example 2

[0187] A composite film includes a polyethylene terephthalate (PET) base film 4, a first resin layer 3, a second resin layer 2, and a polypropylene protective film 1, which are sequentially stacked. The PET base film has a thickness of 38 μm, the first resin layer has a thickness of 5 μm, the second resin layer has a thickness of 50 μm, and the polypropylene protective film has a thickness of 15 μm. The first resin layer is a coating formed from a first resin composition, and the second resin layer is a coating formed from a second resin composition.

[0188] The first resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 10 parts of styrene-butadiene-styrene block copolymer 1118, 5 parts of mesoporous silica H31, and 250 parts of silica SC-2050MB;

[0189] The second resin composition comprises, by weight, 20 parts of naphthalene-type epoxy resin HP-4032-SS, 10 parts of naphthalene-arylene-type epoxy resin ESN-475V, 10 parts of biphenyl-arylene-type epoxy resin NC-3000, 80 parts of reactive ester resin HPC-8000-65T, 1 part of curing accelerator 2E4MZ, 10 parts of styrene-butadiene-styrene block copolymer 1118, and 255 parts of silica SC-2050MB;

[0190] The method for preparing the composite membrane includes the following steps:

[0191] (S1) 20 parts by weight of naphthalene-type epoxy resin HP-4032-SS, 10 parts by weight of naphthalene aralkyl-type epoxy resin ESN-475V, 10 parts by weight of biphenyl aralkyl-type epoxy resin NC-3000, 80 parts by weight of active ester resin HPC-8000-65T, 1 part by weight of curing accelerator 2E4MZ, 10 parts by weight of styrene-butadiene-styrene block copolymer 1118, 5 parts by weight of mesoporous silica H31, 250 parts by weight of silica SC-2050MB, 50 parts by weight of MEK solvent and cyclohexanone are mixed and the solid content is adjusted to 40%. The mixture is then uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the first resin solution.

[0192] The butanone and the second resin composition were mixed, the solid content was adjusted to 65%, and the mixture was uniformly dispersed using a high-speed rotary mixer (4500 rpm) to obtain the second resin solution.

[0193] (S2) The first resin solution is coated onto the PET base film and dried at 100°C for 4 minutes to form the first resin layer;

[0194] (S3) The second resin solution is coated onto the first resin layer and dried at 100°C for 4 minutes to form the second resin layer.

[0195] (S4) The polypropylene protective film is laminated onto the surface of the second resin layer at 80°C using a roller pressing device to obtain the composite film.

[0196] Application Example 1

[0197] A flip-chip ball grid array carrier and its fabrication method, the fabrication method comprising the following steps:

[0198] (1) Remove the polypropylene protective film of the composite film provided in Example 1, vacuum press the second resin layer of the composite film onto the BT core board with the inner layer circuit made, pre-cur at 180°C for 30 minutes, and then laser drill holes.

[0199] (2) Remove the PET base film of the composite film, use a 15% potassium permanganate solution to perform DESMEAR on the first resin layer to obtain a uniform surface roughness, and then perform copper plating, pattern electroplating and flash etching in sequence to obtain the flip chip ball grid array carrier.

[0200] Application Example 2

[0201] A flip-chip ball grid array carrier and its preparation method are disclosed. The only difference between this carrier and Application Example 1 is that the composite film in step (1) is the composite film provided in Example 2. The other raw materials, process parameters and steps are the same as in Application Example 1.

[0202] Application Example 3

[0203] A flip-chip ball grid array carrier and its preparation method are disclosed. The only difference between this carrier and Application Example 1 is that the composite film in step (1) is the composite film provided in Example 3. The other raw materials, process parameters and steps are the same as in Application Example 1.

[0204] Application Example 4

[0205] A flip-chip ball grid array carrier and its preparation method are disclosed. The only difference between this carrier and Application Example 1 is that the composite film in step (1) is the composite film provided in Example 4. The other raw materials, process parameters and steps are the same as in Application Example 1.

[0206] Application Example 5

[0207] A flip-chip ball grid array carrier and its preparation method are disclosed. The only difference between this carrier and Application Example 1 is that the composite film in step (1) is the composite film provided in Example 5. The other raw materials, process parameters and steps are the same as in Application Example 1.

[0208] Comparative Application Example 1

[0209] A flip-chip ball grid array carrier and its preparation method are disclosed. The only difference between this carrier and Application Example 1 is that the composite film in step (1) is the composite film provided in Comparative Example 1. The other raw materials, process parameters and steps are the same as in Application Example 1.

[0210] Comparative Application Example 2

[0211] A flip-chip ball grid array carrier and its preparation method are disclosed. The only difference between this carrier and Application Example 1 is that the composite film in step (1) is the composite film provided by Comparative Example 2. The other raw materials, process parameters and steps are the same as those in Application Example 1.

[0212] After curing the composite films in the examples and comparative examples, samples were prepared and the tensile modulus of their resin layers was tested. The curing conditions were 190℃ / 60 minutes. After preparing samples of the flip-chip ball grid array carriers in the application examples and comparative application examples, their copper plating adhesion and heat resistance were tested. The specific performance tests are as follows, and the test data are shown in Table 1.

[0213] (1) SAP copper peel strength (PS): Refer to IPC-TM-650 method;

[0214] (2) SAP copper layer PS after heat treatment: reflow soldering maximum temperature 260℃, after 3 treatments, peel strength PS is tested according to IPC-TM-650 method;

[0215] (3) Tin bleaching: 288℃ / 10 seconds, after 10 treatments, observe whether the sample has problems such as layering or bubbling;

[0216] (4) Tensile modulus: The tensile modulus was determined according to the DMA test method specified in IPC-TM-6502.4.24.4.

[0217] Table 1

[0218]

[0219]

[0220] As can be seen from the test data in Table 1, Application Examples 1-4 used the composite film provided in Examples 1-4. The peel strength (PS) of the SAP copper layer was higher than that of the comparative Application Examples 1-2. Moreover, after reflow soldering (maximum temperature 260℃) heat treatment, the PS retention rate of the SAP copper layer was better. At the same time, the heat resistance of the tin bleaching was good, with no delamination or blistering, and the tensile modulus was also superior. In Application Example 5, the average particle size of the mesoporous silica was too large, which was not conducive to the fabrication of fine circuits. It was difficult to etch a uniform roughness on the surface of the resin layer, and the peel strength (PS) of the SAP copper layer decreased sharply. After tin bleaching, local delamination and blistering occurred. Compared to Application Example 1, Application Example 1 used a composite film without mesoporous filler, resulting in a lower PS of the SAP copper layer and a reduced tensile modulus. In Application Example 2, the mesoporous filler was not modified with thermoplastic resin. In the first resin solution, the mesoporous filler was mostly loaded with thermosetting resin or curing agent in the mesopores. This made it difficult to remove the resin from the mesopores during the surface roughening process, affecting the effect of copper tooth implantation into the mesopores during copper plating. Therefore, its SAP copper layer PS was also relatively low, and the desired effect was not achieved.

[0221] 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 flip-chip ball grid array carrier board, characterized in that, The flip-chip ball grid array carrier includes a composite film; The composite membrane comprises a first resin layer and a second resin layer stacked sequentially. The first resin layer is a coating formed from a first resin composition; The second resin layer is a coating formed from a second resin composition; The first resin composition comprises a thermosetting resin and a modified mesoporous filler; The modified mesoporous filler includes a mesoporous filler and a first thermoplastic resin loaded on the mesoporous filler; The average particle size of the mesoporous filler is 0.01~5μm; The thermoplastic resin on the surface or inside of the first resin layer mesoporous filler is etched away by the DESMEAR process, followed by copper plating.

2. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The thickness of the first resin layer is 5-10 μm.

3. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The modified mesoporous filler in the first resin composition has a mass percentage content of 1-18%.

4. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The first thermoplastic resin includes any one or a combination of at least two of polyacrylate, phenolic resin, polycarbonate resin, polyvinyl acetal resin, polyamide imide, or polyethersulfone.

5. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The mesoporous filler includes any one or a combination of at least two of mesoporous silica, mesoporous alumina, or mesoporous magnesium oxide.

6. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The average pore size of the mesoporous filler is 3~50 nm.

7. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The mesoporous packing material has a mesoporous volume greater than 0.7 mL / g.

8. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The thermosetting resin includes any one or a combination of at least two of the following: a first epoxy resin, a phenolic resin, a cyanate ester resin, a maleimide resin, a benzoxazine resin, a styrene-butadiene resin, or a hydrocarbon resin.

9. The flip-chip ball grid array carrier board according to claim 8, characterized in that, The first epoxy resin includes any one or a combination of at least two of the following: naphthalene-type epoxy resin, naphthalene-arylene-type epoxy resin, biphenyl-arylene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, MDI-modified epoxy resin, phenolic epoxy resin, dicyclopentadiene-type epoxy resin, or alicyclic epoxy resin.

10. The flip-chip ball grid array carrier according to claim 8, characterized in that, The phenolic resin includes any one or a combination of at least two of the following: bisphenol A type phenolic resin, phenolic resin, biphenyl type phenolic resin, dicyclopentadiene type phenolic resin, allyl base linear phenolic resin, or naphthol-containing phenolic resin.

11. The flip-chip ball grid array carrier board according to claim 8, characterized in that, The hydrocarbon resin includes any one or a combination of at least two of polybutadiene, polyisoprene, styrene-butadiene copolymer, alicyclic resin or aromatic hydrocarbon resin.

12. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The first resin composition further includes a first curing agent and a first curing accelerator.

13. The flip-chip ball grid array carrier board according to claim 12, characterized in that, The first curing agent includes any one or a combination of at least two of the following: reactive ester resin, acid anhydride compound, or amine compound.

14. The flip-chip ball grid array carrier according to claim 12, characterized in that, The first curing accelerator includes any one or a combination of at least two of imidazole, imidazole derivatives, or phosphine salts.

15. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The first resin composition further includes an initiator.

16. The flip-chip ball grid array carrier according to claim 15, characterized in that, The initiator includes peroxides and / or azo compounds.

17. The flip-chip ball grid array carrier according to claim 12, characterized in that, The mass ratio of the thermosetting resin to the first curing agent is 1:(0.1~2.5).

18. The flip-chip ball grid array carrier according to claim 12, characterized in that, The mass ratio of the thermosetting resin to the first curing accelerator is 1:(0.001~0.15).

19. The flip-chip ball grid array carrier according to claim 15, characterized in that, The mass ratio of the thermosetting resin to the initiator is 1:(0.001~0.15).

20. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The first resin composition also includes other fillers different from the mesoporous filler.

21. The flip-chip ball grid array carrier according to claim 20, characterized in that, The other fillers include any one or a combination of at least two of silica, alumina, or magnesium oxide.

22. The flip-chip ball grid array carrier according to claim 20, characterized in that, The particle size of the other fillers is ≤2μm.

23. The flip-chip ball grid array carrier according to claim 20, characterized in that, The mass percentage of other fillers in the first resin composition is ≤80%.

24. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The modified mesoporous filler is prepared by the following method, which includes: dissolving or melting the first thermoplastic resin and mixing it with the mesoporous filler to obtain the modified mesoporous filler.

25. The flip-chip ball grid array carrier according to claim 24, characterized in that, The mass ratio of the first thermoplastic resin to the mesoporous filler is (0.8~4):

1.

26. The flip-chip ball grid array carrier according to claim 24, characterized in that, Prior to the mixing process, the process also includes a step of surface-treating the mesoporous filler with a surface-treatment agent.

27. The flip-chip ball grid array carrier according to claim 26, characterized in that, The surface treatment agent includes any one or a combination of at least two of the following: silane coupling agents, alkoxysilanes, alkoxy oligomers, aluminum coupling agents, titanium coupling agents, or zirconium coupling agents.

28. The flip-chip ball grid array carrier according to claim 26, characterized in that, Based on the mesoporous filler having a mass of 100%, the surface treatment agent has a mass of 0.001~0.3%.

29. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The thickness of the second resin layer is 5-90 μm.

30. The flip-chip ball grid array carrier according to claim 1, characterized in that, By weight, the second resin composition comprises 10-50 parts by weight of a second epoxy resin, 5-100 parts by weight of a second curing agent, 1-20 parts by weight of a second thermoplastic resin, 0.001-3 parts by weight of a second curing accelerator, and 5-800 parts by weight of an inorganic filler; the inorganic filler does not include the mesoporous filler.

31. The flip-chip ball grid array carrier according to claim 30, characterized in that, The second epoxy resin includes any one or a combination of at least two of the following: naphthalene-type epoxy resin, naphthalene-aralkyl-type epoxy resin, biphenyl-aralkyl-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, phosphorus-containing epoxy resin, MDI-modified epoxy resin, phenolic epoxy resin, dicyclopentadiene-type epoxy resin, or alicyclic epoxy resin.

32. The flip-chip ball grid array carrier board according to claim 30, characterized in that, The second thermoplastic resin includes any one or a combination of at least two of polyacrylate, phenolic resin, polycarbonate resin, polyvinyl acetal resin, polyamide imide, or polyethersulfone.

33. The flip-chip ball grid array carrier according to claim 30, characterized in that, The second curing agent includes any one or a combination of at least two of the following: reactive ester resin, acid anhydride compound, or amine compound.

34. The flip-chip ball grid array carrier according to claim 30, characterized in that, The second curing accelerator includes any one or a combination of at least two of imidazole, imidazole derivatives, or phosphine salts.

35. The flip-chip ball grid array carrier according to claim 30, characterized in that, The inorganic filler includes any one or a combination of at least two of silicon dioxide, aluminum oxide, or magnesium oxide.

36. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The composite membrane also includes a base membrane.

37. The flip-chip ball grid array carrier according to claim 36, characterized in that, The base film is bonded to the first resin layer.

38. The flip-chip ball grid array carrier according to claim 36, characterized in that, The thickness of the base film is 10-100 μm.

39. The flip-chip ball grid array carrier board according to claim 36, characterized in that, The base film includes any one of polyethylene terephthalate base film, polyethylene naphthalate base film, polyimide base film, polytetrafluoroethylene base film, polyethersulfone base film, polyphenylene sulfide base film, or polybenzimidazole base film.

40. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The composite membrane also includes a protective film.

41. The flip-chip ball grid array carrier according to claim 40, characterized in that, The protective film is bonded to the second resin layer.

42. The flip-chip ball grid array carrier board according to claim 40, characterized in that, The thickness of the protective film is 10-50 μm.

43. The flip-chip ball grid array carrier according to claim 40, characterized in that, The protective film includes any one of polyethylene protective film, polypropylene protective film, or polyethylene terephthalate protective film.

44. The flip-chip ball grid array carrier board according to claim 1, characterized in that, The composite membrane is prepared by the following method, which includes the following steps: (S1) The first solvent and the first resin composition are mixed to obtain a first resin solution; the second solvent and the second resin composition are mixed to obtain a second resin solution; (S2) The first resin solution is coated onto the base film and dried to form the first resin layer; (S3) The second resin solution is coated onto the first resin layer and dried to form the second resin layer; (S4) The protective film is laminated onto the surface of the second resin layer to obtain the composite film.

45. The flip-chip ball grid array carrier according to claim 44, characterized in that, The solid content of the first resin solution and the second resin solution is 40-70% each.

46. ​​The flip-chip ball grid array carrier according to claim 44, characterized in that, The first solvent and the second solvent each independently comprise any one or a combination of at least two of cyclohexanone, butanone, ethyl acetate, butyl acetate, acetic acid cellosol, propylene glycol monomethyl ether acetate, toluene, xylene, or dimethylacetamide.

47. The flip-chip ball grid array carrier according to claim 44, characterized in that, The drying temperature described in step (S2) is 80-150°C.

48. The flip-chip ball grid array carrier according to claim 44, characterized in that, The drying time in step (S2) is 3-5 minutes.

49. The flip-chip ball grid array carrier according to claim 44, characterized in that, The drying temperature described in step (S3) is 80-150°C.

50. The flip-chip ball grid array carrier according to claim 44, characterized in that, The drying time in step (S3) is 3-5 minutes.

51. The flip-chip ball grid array carrier board according to claim 44, characterized in that, The temperature for the composite process is 60-120℃.

52. A method for fabricating a flip-chip ball grid array carrier as described in any one of claims 1-51, characterized in that, The preparation method includes the following steps: (1) Remove the protective film of the composite film as described in claim 40, press the second resin layer of the composite film onto the core board with the inner layer circuit, and then perform pre-curing and drilling in sequence; (2) Remove the base film of the composite film, perform desmearing and roughening treatment on the first resin layer, and then perform copper plating, pattern electroplating and flash etching in sequence to form fine lines; (3) Repeat steps (1) and (2) to obtain the flip-chip ball grid array carrier.

53. The preparation method according to claim 52, characterized in that, The pre-curing temperature is 170-190℃.

54. The preparation method according to claim 52, characterized in that, The pre-curing time is 20-40 minutes.

55. The preparation method according to claim 52, characterized in that, The line width and spacing of the fine lines are 8-20 μm.

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