Resin composition and application thereof

Abstract

The invention provides a resin composition and application thereof. The resin composition comprises the following components in parts by weight: 100 parts of epoxy resin, 20-50 parts of semi-hollow filler and 30-100 parts of a curing agent, the semi-hollow filler comprises an inner core and an inorganic shell coating the inner core; the inner core has a net-shaped structure or a filiform structure; an internal cavity is formed between the core and the shell of the semi-hollow filler; the density of the semi-hollow filler is 0.6-1.1 g / cm < 3 >; the D100 particle size of the semi-hollow filler is 5-20 [mu] m. According to the resin composition provided by the invention, the density of the metal foil-coated laminated board can be reduced, hole wall roughness and abnormal copper plating caused by filler crushing and drilling are avoided, so that the metal foil-coated laminated board has a low thermal expansion coefficient, a low dielectric constant and low dielectric loss, and meanwhile, excellent heat resistance and CAF resistance are kept.

Description

Technical Field

[0001] This invention belongs to the field of laminate technology, specifically relating to a resin composition and its application. Background Technology

[0002] With the rapid development of high-end fields such as 5G communication, intelligent vehicles, and aerospace electronics, electronic devices are rapidly iterating towards higher frequencies, smaller sizes, and lighter weights, placing stringent demands on the performance of core materials. Copper-clad laminates, as the basic material for printed circuit boards (PCBs), not only need to possess low dielectric constants (D... k ) and low dielectric loss (D f To ensure high-frequency signal transmission efficiency, lightweight design is also required to meet the integration and weight reduction needs of equipment such as 5G base stations, millimeter-wave radar, and low-orbit satellites.

[0003] Hollow fillers (including hollow glass microspheres, hollow ceramic microspheres, etc.) have a density of 0.15-1.6 g / cm³. 3 With its ultra-low density, intrinsic low dielectric properties of 3.0-4.0 (10GHz), and excellent mechanical and thermal stability, hollow filler has become the core filler for achieving synergistic optimization of lightweight copper clad laminate (CCL) and low dielectric performance. However, the current application of hollow filler in CCL still faces key technical bottlenecks: First, the surface energy mismatch between low dielectric hollow filler and copper foil leads to insufficient interfacial adhesion and peel strength that is difficult to meet the requirements; second, the mismatch between the thermal expansion coefficient (CTE) of hollow filler and the substrate easily causes delamination, warping, and other phenomena during thermal cycling; third, the compressive strength of hollow filler is insufficient to meet the requirements of CCL processing, and breakage leads to delamination, board bursting, and abnormal copper plating.

[0004] CN117103825A discloses a method for preparing a low-dielectric-strength, low-expansion polytetrafluoroethylene (PTFE) high-frequency copper-clad laminate. It uses hollow, closed-cell spherical fillers—hollow glass microspheres and hollow spherical silicon—to replace conventional fillers such as silica, titanium dioxide, and alumina, significantly reducing the density and thermal expansion coefficient of the laminate. The production process is similar to conventional procedures, demonstrating good production feasibility. CN113980370A discloses a high-hardness, high-peel-strength, and yellowing-resistant hydrocarbon resin composition. This is achieved by modifying hydrocarbon resin with phenol containing rigid structural units to synthesize a modified hydrocarbon resin with high strength and high peel strength. An antioxidant is then added and mixed uniformly to prepare a hydrocarbon resin composition with high hardness, high peel strength, yellowing resistance, low dielectric constant, and low dielectric loss. This effectively solves the problem of insufficient bonding strength, increasing the peel strength from 0.4 N / m to 1.3 N / m. However, existing resin compositions cannot enable metal-clad laminates to simultaneously possess low density, low coefficient of thermal expansion, good dielectric properties, good heat resistance, and good CAF resistance. Therefore, it is urgent to develop a resin composition to improve the overall performance of metal-clad laminates. This is of great significance for promoting the localization of high-end electronic materials and meeting the strategic needs of 5G / 6G and aerospace fields. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a resin composition and its application. Through the design of the components, the resin composition has good flowability and enables the metal foil laminate to have low density, low coefficient of thermal expansion, good dielectric properties, good heat resistance, good CAF resistance and high mechanical strength.

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

[0007] In a first aspect, the present invention provides a resin composition comprising, by weight, the following components:

[0008] 100 parts by weight of epoxy resin

[0009] 20-50 parts by weight of semi-hollow packing

[0010] 30-100 parts by weight of curing agent;

[0011] The semi-hollow filler comprises a core and an inorganic shell covering the core; the core has a mesh structure or a filamentous structure; the core and shell of the semi-hollow filler have an internal cavity; the density of the semi-hollow filler is 0.6-1.1 g / cm³. 3 The D of the semi-hollow packing 100 The particle size is 5-20μm.

[0012] This invention controls the density and D of the semi-hollow packing.100 Particle size can control the wall thickness of the inorganic shell, reducing the density of the metal-clad foil laminate while maintaining the internal semi-hollow structure, thereby reducing the dielectric constant and dielectric loss of the metal-clad foil laminate. The network or filament structure of the semi-hollow filler core can improve the compressive strength of the semi-hollow filler on the one hand, and on the other hand, the network or filament structure can effectively reduce the migration of copper ions and copper growth after the semi-hollow filler is broken, as well as the rough hole wall and abnormal copper plating caused by drilling, thus improving the resistance of the metal-clad foil laminate to CAF.

[0013] The semi-hollow filler in the resin composition is 20-50 parts by weight, for example, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, or 50 parts by weight.

[0014] The curing agent in the resin composition is 30-100 parts by weight, for example, it can be 30 parts by weight, 32 parts by weight, 33 parts by weight, 36 parts by weight, 40 parts by weight, 43 parts by weight, 49 parts by weight, 51 parts by weight, 55 parts by weight, 58 parts by weight, 60 parts by weight, 62 parts by weight, 66 parts by weight, 68 parts by weight, 71 parts by weight, 73 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 83 parts by weight, 86 parts by weight, 88 parts by weight, 90 parts by weight, 92 parts by weight, 94 parts by weight, or 100 parts by weight.

[0015] The density of the semi-hollow filler is 0.6-1.1 g / cm³. 3 For example, it can be 0.6 g / cm³ 3 0.63g / cm 3 0.65g / cm 3 0.68g / cm 3 0.7g / cm 3 0.73g / cm 3 0.75g / cm 3 0.78g / cm 3 0.8g / cm 3 0.83g / cm 3 0.85g / cm 3 0.88g / cm 3 0.9g / cm 3 0.93g / cm 3 0.95g / cm 3 0.98g / cm 3 1g / cm 3 1.03 g / cm 31.05g / cm 3 1.08g / cm 3 1.1g / cm 3 wait.

[0016] In this invention, the density of the semi-hollow packing is obtained by gas specific gravity testing using a true density meter (AccuPyc III). First, the semi-hollow packing is dried, calibrated using a standard ball, the sample is weighed, and then placed in a measuring chamber where inert gas is introduced to count the volume of the discharged gas. The density of the semi-hollow packing is calculated by density = weight / volume.

[0017] The D of the semi-hollow packing 100 The particle size is 5-20μm, for example, it can be 5μm, 5.5μm, 6μm, 6.5μm, 7μm, 7.5μm, 8μm, 8.5μm, 9μm, 9.5μm, 10μm, 10.5μm, 11μm, 11.5μm, 12μm, 12.5μm, 13μm, 13.5μm, 14μm, 14.5μm, 15μm, 15.5μm, 16μm, 16.5μm, 17μm, 17.5μm, 18μm, 18.5μm, 19μm, 19.5μm or 20μm, etc.

[0018] In this invention, the D of the semi-hollow packing 100 The particle size was tested using the Malvern method (ISO 13320:2009) and the testing equipment was a Malvern 3000. The semi-hollow filler was sonicated in methyl ethyl ketone (MEK) for 30 minutes, the pipeline was cleaned with MEK, and then the light was calibrated. The sample and ethanol solvent parameters were set, and the particle size distribution was tested.

[0019] In this invention, the term "semi-hollow" in the context of the semi-hollow filler does not refer to the internal cavity occupying half of the total volume of the inorganic shell. Rather, it is used to illustrate that the inorganic shell is not completely hollow. In other words, any filler in an inorganic shell that is not completely hollow is within the scope of this invention.

[0020] This invention does not limit the shape of the semi-hollow filler core; any shape is acceptable as long as it meets the requirements of D. 100 Only the particle size and density requirements need to be specified; for example, the kernel can be ellipsoidal or spherical.

[0021] 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.

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

[0023] Preferably, the epoxy equivalent of the epoxy resin is 100-600 g / eq, for example, it can be 100 g / eq, 120 g / eq, 140 g / eq, 160 g / eq, 189 g / eq, 200 g / eq, 226 g / eq, 240 g / eq, 260 g / eq, 289 g / eq, 300 g / eq, 320 g / eq, 340 g / eq, 365 g / eq, 380 g / eq, 400 g / eq, 420 g / eq, 440 g / eq, 460 g / eq, 480 g / eq, 500 g / eq, 512 g / eq, 520 g / eq, 540 g / eq, 560 g / eq, 580 g / eq, 600 g / eq, etc.

[0024] Preferably, the curing agent comprises any one or a combination of at least two of the following: phenolic resin, cyanate ester resin, reactive ester, polyphenylene ether resin, maleimide resin, acid anhydride curing agent, styrene-maleic anhydride copolymer, amine curing agent, or benzoxazine resin.

[0025] Preferably, the phenolic resin includes any one or a combination of at least two of bisphenol A type phenolic resin, phosphorus-containing phenolic resin, phenolic resin, biphenyl type phenolic resin, dicyclopentadiene type phenolic resin, or naphthol-containing phenolic resin.

[0026] Preferably, the core is formed from any one of nano-three-dimensional network fiber felt, fumed silica, or polyacrylonitrile fiber.

[0027] When the core is formed from fumed silica, the fumed silica will agglomerate and form a network structure, thus still meeting the requirement that the core has a network structure.

[0028] When the core is formed from polyacrylonitrile fibers, the core has a filamentous structure.

[0029] Preferably, the nano-three-dimensional network fiber felt includes either titanium dioxide fiber felt or ceramic nanofiber felt.

[0030] Preferably, the nano-three-dimensional network fiber felt is ellipsoidal with a major axis length of 0.2-18 μm, for example, it can be 0.2 μm, 0.6 μm, 0.9 μm, 1.6 μm, 2.0 μm, 2.6 μm, 3.6 μm, 4.8 μm, 5.1 μm, 5.8 μm, 6.3 μm, 6.9 μm, 7.6 μm, 8.8 μm, 9.6 μm, 10.3 μm, 11 μm, 12.8 μm, 13.6 μm, 1 The micrometers are 4.2μm, 15μm, 16.9μm, 17.3μm, or 18μm, etc., with a minor axis length of 0.2-12μm, such as 0.2μm, 0.6μm, 0.9μm, 1.6μm, 2.0μm, 2.6μm, 3.6μm, 4.8μm, 5.1μm, 5.8μm, 6.3μm, 6.9μm, 7.6μm, 8.8μm, 9.6μm, 10.3μm, 11μm, or 12μm, etc.

[0031] In this invention, the major axis length and minor axis length of the nano-three-dimensional network fiber felt are obtained by electron microscopy (SEM) (Hitachi SU3800).

[0032] Preferably, the average particle size of the fumed silica is 0.05-0.80 μm, for example, it can be 0.05 μm, 0.09 μm, 0.12 μm, 0.19 μm, 0.23 μm, 0.29 μm, 0.33 μm, 0.35 μm, 0.38 μm, 0.45 μm, 0.58 μm, 0.66 μm, 0.71 μm or 0.80 μm, etc.

[0033] The particle size of the fumed silica was obtained by scanning electron microscopy (SEM).

[0034] Preferably, the length of the polyacrylonitrile fiber is 0.2-8 μm, for example, it can be 0.2 μm, 0.6 μm, 0.9 μm, 1.6 μm, 2.0 μm, 2.6 μm, 3.6 μm, 4.8 μm, 5.1 μm, 5.8 μm, 6.3 μm, 6.9 μm, 7.6 μm or 8 μm; and the diameter is 0.1-2 μm, for example, it can be 0.2 μm, 0.4 μm, 0.6 μm, 0.8 μm, 1 μm, 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm, etc.

[0035] Preferably, the material of the inorganic shell includes silicon dioxide and / or aluminum oxide.

[0036] Preferably, with the mass of the semi-hollow filler being 100%, the mass of the core is 10-30%, for example, it can be 10%, 12%, 13.8%, 14.5%, 15.8%, 17%, 18.9%, 20.1%, 22%, 26%, 27.8%, or 30%, etc.

[0037] Preferably, the semi-hollow packing is prepared by the following method, the method comprising:

[0038] After surface treatment of the core-forming material with a silane coupling agent, an inorganic shell precursor is added to react and the semi-hollow filler is obtained.

[0039] Preferably, the silane coupling agent comprises any one or a combination of at least two of aminosilane, epoxysilane, vinylsilane, or phenylaminosilane.

[0040] Preferably, the mass ratio of the silane coupling agent to the core formation is (1-5):100, for example, it can be 1:100, 1.5:100, 2.1:100, 3:100, 3.3:100, 3.5:100, 4.3:100, 4.6:100 or 5:100, etc.

[0041] Preferably, the precursor of the inorganic shell comprises tetraethyl silicate or alumina nanospheres.

[0042] Preferably, the surface treatment temperature is 50-100℃, for example, it can be 50℃, 56℃, 59℃, 61℃, 67℃, 72℃, 78℃, 85℃, 91℃, 96℃ or 100℃, etc.

[0043] Preferably, the surface treatment time is 1-4 hours, for example, it can be 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.3 hours, 2.5 hours, 2.9 hours, 3.2 hours, 3.8 hours or 4 hours.

[0044] Preferably, the reaction temperature is 18-35℃, for example, it can be 20℃, 22℃, 24℃, 26℃, 28℃, 30℃, 32℃, 34℃, etc.

[0045] Preferably, the reaction time is 8-24 hours, for example, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, etc.

[0046] Preferably, the reaction is carried out at a pH of 8-10 (e.g., 8.2, 8.4, 8.6, 8.8, 9, 9.2, 9.4, 9.6, 9.8, etc.).

[0047] Preferably, the reaction further includes airflow staged treatment after completion.

[0048] Preferably, the resin composition further includes a flame retardant.

[0049] Preferably, the flame retardant includes any one or a combination of at least two of the following: brominated flame retardants, phosphorus-containing flame retardants, or nitrogen-containing flame retardants.

[0050] Preferably, the brominated flame retardant includes any one or a combination of at least two of tetrabromobisphenol A, decabromodiphenyl ether, or tetrabromoethane.

[0051] Preferably, the phosphorus-containing flame retardant includes any one or a combination of at least two of organophosphates, phosphazene compounds, or DOPO derivatives.

[0052] Preferably, the nitrogen-containing flame retardant comprises any one or a combination of at least two of melamine, melamine phosphate, dicyandiamide flame retardants, or guanidine salt flame retardants.

[0053] Preferably, the flame retardant in the resin composition is 10-20 parts by weight, for example, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, etc.

[0054] Preferably, the resin composition further includes a curing accelerator.

[0055] Preferably, the curing accelerator includes any one or a combination of at least two of imidazole accelerators, pyridine accelerators, Lewis acid accelerators, amine accelerators, phenolic accelerators, cyanate ester accelerators, or active ester accelerators.

[0056] Preferably, the curing accelerator includes any one or a combination of at least two of 2-ethyl-4-methylimidazolium, 4-dimethylaminopyridine, boron trifluoride, or triphenylphosphine.

[0057] Preferably, the curing accelerator in the resin composition is 0.1-1 parts by weight, for example, it can be 0.1 parts by weight, 0.12 parts by weight, 0.15 parts by weight, 0.23 parts by weight, 0.29 parts by weight, 0.36 parts by weight, 0.41 parts by weight, 0.56 parts by weight, 0.60 parts by weight, 0.68 parts by weight, 0.73 parts by weight, 0.86 parts by weight, 0.91 parts by weight, or 1 part by weight.

[0058] In a second aspect, the present invention provides a resin adhesive solution obtained by dissolving or dispersing the resin composition as described in the first aspect in a solvent.

[0059] Preferably, the solvent includes any one or a combination of at least two of acetone, butanone, cyclohexanone, toluene, or xylene.

[0060] Preferably, the solid content of the resin solution is 50-75%, for example, it can be 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, etc.

[0061] Thirdly, the present invention provides a prepreg comprising a substrate and a resin composition as described in the first aspect attached to the substrate.

[0062] Preferably, the resin composition is adhered to the substrate after impregnation and drying.

[0063] Preferably, the substrate comprises any one of glass fiber cloth, organic fiber cloth, or glass fiber paper.

[0064] Preferably, the fiberglass cloth includes any one of Q-fiberglass cloth, E-fiberglass cloth, D-fiberglass cloth, L-fiberglass cloth, M-fiberglass cloth, S-fiberglass cloth, T-fiberglass cloth or NE-fiberglass cloth.

[0065] Preferably, the organic fiber cloth includes any one of polyimide fiber cloth, polyamide fiber cloth, polyester fiber cloth, polyphenylene ether fiber cloth, or liquid crystal polymer fiber cloth.

[0066] For example, the prepreg is prepared by impregnating a substrate with a resin solution containing the resin composition and then drying it to obtain the prepreg.

[0067] Preferably, the drying temperature is 100-180℃, such as 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃ or 175℃.

[0068] Preferably, the drying time is 1-10 min, such as 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min or 9 min.

[0069] Fourthly, the present invention provides a metal foil laminate comprising one or at least two laminated prepregs as described in the third aspect, and metal foils located on one or both sides of the laminated prepregs.

[0070] Preferably, the metal foil is a copper foil.

[0071] Preferably, the prepreg in the metal foil laminate is 1-20 sheets, for example, 1 sheet, 3 sheets, 5 sheets, 7 sheets, 9 sheets, 10 sheets, 11 sheets, 13 sheets, 15 sheets, 17 sheets or 19 sheets, etc.

[0072] For example, the method for preparing the metal-clad laminate is as follows: pressing metal foils onto both sides of a prepreg and curing to obtain the metal-clad laminate; or, stacking at least two prepregs, then pressing metal foils onto both sides of the stacked prepregs and curing to obtain the metal-clad laminate.

[0073] Preferably, the curing is carried out in a laminator.

[0074] Preferably, the curing temperature is 180-250℃, such as 180℃, 186℃, 192℃, 198℃, 206℃, 212℃, 218℃, 225℃, 228℃, 230℃, 235℃, 240℃ or 245℃, etc.

[0075] Preferably, the curing pressure is 180-500 Psi, for example, it can be 180 Psi, 189 Psi, 206 Psi, 239 Psi, 278 Psi, 300 Psi, 366 Psi, 398 Psi, 426 Psi, 456 Psi, 468 Psi, 488 Psi or 500 Psi.

[0076] Preferably, the curing time is 30-180 min, such as 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min or 175 min.

[0077] Fifthly, the present invention provides a printed circuit board comprising a prepreg as described in the third aspect or a metal foil laminate as described in the fourth aspect.

[0078] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range.

[0079] Compared with the prior art, the present invention has the following beneficial effects:

[0080] The resin composition provided by this invention has good flowability and enables metal foil-coated laminates to possess low density, low coefficient of thermal expansion, good dielectric properties, good heat resistance, good CAF resistance, and high mechanical strength; wherein the resin density is 0.92-1.18 g / cm³. 3 The coefficient of thermal expansion is 1.68-2.9%, the dielectric constant is 3.62-3.95, the dielectric loss is 0.0065-0.0098, the CAF resistance is 1254-2065h, T288>60min, and there are no grooves on the edge of the metal foil laminate. Attached Figure Description

[0081] Figure 1 This is a SEM image of the semi-hollow packing material B1 provided in Example 1;

[0082] Figure 2 This is a SEM image of the polyacrylonitrile fiber core of the semi-hollow filler in Example 4 after stirring and dispersion treatment.

[0083] Figure 3 This is a SEM image of the network structure formed by the fumed silica core of the semi-hollow filler in Preparation Example 5 after stirring and dispersing. Detailed Implementation

[0084] 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.

[0085] The sources of some components in the following examples and comparative examples are as follows:

[0086] (1) Epoxy resin:

[0087] A1: CNE type epoxy resin (o-cresol epoxy resin), NPCN-704, epoxy equivalent is 200-220g / eq, Nan Ya Resin;

[0088] A2: NC-3000H, biphenyl type epoxy resin, epoxy equivalent is 290-300g / eq, Nippon Kayaku;

[0089] A3: Bisphenol A type epoxy resin, KE-8128, epoxy equivalent is 185-190g / eq, KOLON Korea;

[0090] (2) Hollow packing: im16k, D 100 The particle size is 20 μm and the density is 0.86 g / cm³. 3 3M;

[0091] (3) Curing agent:

[0092] C1: Styrene-maleic anhydride copolymer, SMA-EF30, CrayValley, USA;

[0093] C2: Active ester, DFE-617L, Sichuan Dongcai;

[0094] (4) Phosphate ester flame retardant: PX200, Daihachi, Japan;

[0095] (5) Curing accelerator: 2-ethyl-4-methylimidazole, Shikoku Kasei.

[0096] Preparation Example 1: Preparation of Semi-hollow Packing Material B1

[0097] 100g of ellipsoidal ceramic nanofiber felt (Shusaimei New Materials, grade SSM-T105, major axis length 0.2-6μm, minor axis length 0.2-2μm) was treated with 2g of aminosilane KH-550 at 80℃ for 4h, then immersed in 500mL of a mixed solvent of ethanol and water in a volume ratio of 1:4, ultrasonically dispersed for 30min, and the pH was adjusted to 8 by slowly adding ammonia water. Under continuous stirring, 160kg of 1%wt TEOS ethanol solution was added dropwise, and the reaction was carried out at room temperature for 16h. After centrifugation and washing to remove water and ethanol, and magnetic separation to remove magnetic impurities, the material was graded by high-speed airflow, with 30% of particles having a diameter of 5μm. After washing and drying, the semi-hollow filler B1 was obtained. 100 The particle size is 8 μm and the density is 0.98 g / cm³. 3 ;

[0098] The semi-hollow filler B1 was scanned and tested using a scanning electron microscope (SEM). The test results are as follows: Figure 1 As shown, by Figure 1 It can be seen that the semi-hollow filler is nearly ellipsoidal, with a particle size of 0.5-8μm, and its surface is covered with a dense silica shell.

[0099] Preparation Example 2: Preparation of Semi-hollow Packing Material B2

[0100] 100g of ellipsoidal ceramic nanofiber felt (Shusaimei New Materials, grade SSM-T105, major axis length 0.2-3μm, minor axis length 0.2-1μm) was treated with 2g of aminosilane KH-550 at 80℃ for 4h, then immersed in 500mL of a mixed solvent of ethanol and water at a volume ratio of 1:4, ultrasonically dispersed for 30min, and the pH was adjusted to 8 by slowly adding ammonia water. Under continuous stirring, 160kg of 1%wt TEOS ethanol solution was added dropwise, and the reaction was carried out at room temperature for 16h. After centrifugation and washing to remove water and ethanol, and magnetic separation to remove magnetic impurities, the material was classified by high-speed airflow, with 30% of the particles having a diameter greater than 3μm. After washing and drying, the semi-hollow filler B2 was obtained. 100 The particle size is 5 μm and the density is 1.1 g / cm³. 3 .

[0101] Preparation Example 3: Preparation of Semi-hollow Packing Material B3

[0102] 100g of ellipsoidal ceramic nanofiber felt (Shusaimei New Materials, grade SSM-T105, major axis length 0.2-18μm, minor axis length 0.2-10μm) was treated with 2g of aminosilane KH-550 at 80℃ for 4h, then immersed in 500mL of a mixed solvent of ethanol and water at a volume ratio of 1:4, ultrasonically dispersed for 30min, and the pH was adjusted to 8 by slowly adding ammonia water. Under continuous stirring, 160kg of 1%wt TEOS ethanol solution was added dropwise, and the reaction was carried out at room temperature for 16h. After centrifugation and washing to remove water and ethanol, and magnetic separation to remove magnetic impurities, the material was classified by high-speed airflow, with 50% of the particles having a diameter greater than 10μm. After washing and drying, the semi-hollow filler B3 was obtained. 100 The particle size is 20 μm and the density is 0.78 g / cm³. 3 .

[0103] Preparation Example 4: Preparation of Semi-hollow Packing Material B4

[0104] 100g of polyacrylonitrile fiber (Surface Energy Technology Group Co., Ltd., brand: Surforce, diameter 0.3μm, length 0.2-3μm) was stirred evenly in an ethanol solution (its SEM image is shown below). Figure 2 (Exhibiting a filamentous structure), after being treated with 2g of aminosilane KH-550 at 80℃ for 4h, it was immersed in 500mL of a mixed solvent of ethanol and water in a volume ratio of 1:4, ultrasonically dispersed for 30min, and ammonia was slowly added dropwise to adjust the pH to 8. Under continuous stirring, 160kg of 1%wt TEOS ethanol solution was added dropwise, and the reaction was carried out at room temperature for 16h. After centrifugation and washing to remove water and ethanol, magnetic separation was used to remove magnetic impurities, and then the mixture was classified by high-speed airflow. The particle size of particles larger than 3μm accounted for 40%, and after washing and drying, the semi-hollow filler B4 was obtained. 100 The particle size is 5 μm and the density is 1.06 g / cm³. 3 .

[0105] Preparation Example 5: Preparation of Semi-hollow Packing Material B5

[0106] 100g of fumed silica (Evonik, average particle size 200-300nm) was stirred in ethanol solvent (SEM image shown). Figure 3As shown, it exhibits a network structure. After being treated with 2g of aminosilane KH-550 at 80℃ for 4h, it was immersed in 500mL of a mixed solvent of ethanol and water with a volume ratio of 1:4, ultrasonically dispersed for 30min, and ammonia was slowly added dropwise to adjust the pH to 8. Under continuous stirring, 160kg of an ethanol solution of 1%wt alumina nanospheres (Ruibaide New Materials Co., Ltd., brand DC3) was added dropwise. The reaction was carried out at room temperature for 16h. After centrifugation and washing to remove water and ethanol, magnetic separation was used to remove magnetic impurities. After classification by high-speed airflow, 40% of the particles had a particle size of 5μm. After washing and drying, the semi-hollow filler B5 was obtained. 100 The particle size is 7 μm and the density is 0.6 g / cm³. 3 .

[0107] Preparation of Comparative Example 1: Synthesis of Semi-hollow Packing Material B1-1

[0108] 100g of ellipsoidal ceramic nanofiber felt (Shusaimei New Materials, grade SSM-T105, major axis length 0.2-3μm, minor axis length 0.2-1μm) was treated with 2g of aminosilane KH-550 at 80℃ for 4h, then immersed in 500mL of a mixed solvent of ethanol and water at a volume ratio of 1:4, ultrasonically dispersed for 30min, and the pH was adjusted to 8 by slowly adding ammonia water. Under continuous stirring, 160kg of 1%wt TEOS ethanol solution was added dropwise, and the reaction was carried out at room temperature for 16h. After centrifugation and washing to remove water and ethanol, and magnetic separation to remove magnetic impurities, the material was graded by high-speed airflow, with 10% of particles having a diameter of 3μm. After washing and drying, the semi-hollow filler B1-1 was obtained. 100 The particle size is 5 μm and the density is 1.3 g / cm³. 3 .

[0109] Preparation of Comparative Example 2: Synthesis of Semi-hollow Packing Material B1-2

[0110] 100g of ellipsoidal ceramic nanofiber felt (manufacturer: Shusaimei New Materials, SSM-T105, major axis length 0.2-23μm, minor axis length 0.2-12μm) was treated with 2g of aminosilane KH-550 at 80℃ for 4h, then immersed in 500mL of a mixed solvent of ethanol and water at a volume ratio of 1:4, ultrasonically dispersed for 30min, and the pH was adjusted to 8 by slowly adding ammonia water. Under continuous stirring, 160kg of 1%wt TEOS ethanol solution was added dropwise, and the reaction was carried out at room temperature for 16h. After centrifugation and washing to remove water and ethanol, and magnetic separation to remove magnetic impurities, the material was graded by high-speed airflow, with 30% of particles having a diameter greater than 20μm. After washing and drying, the semi-hollow filler B1-2 was obtained. 100 The particle size is 25 μm and the density is 0.63 g / cm³. 3 .

[0111] Preparation of Comparative Example 3: Synthesis of Semi-hollow Packing Material B1-3

[0112] 100g of ellipsoidal ceramic nanofiber felt (manufacturer: Shusaimei New Materials, SSM-T105, major axis length 0.2-2μm, minor axis length 0.2-1μm) was treated with 2g of aminosilane KH-550 at 80℃ for 4h, then immersed in 500mL of a mixed solvent of ethanol and water at a volume ratio of 1:4, ultrasonically dispersed for 30min, and the pH was adjusted to 8 by slowly adding ammonia water. Under continuous stirring, 160kg of 1%wt TEOS ethanol solution was added dropwise, and the reaction was carried out at room temperature for 16h. After centrifugation and washing to remove water and ethanol, and magnetic separation to remove magnetic impurities, the material was graded by high-speed airflow, with 70% of the particles having a diameter greater than 3μm. After washing and drying, the semi-hollow filler B1-3 was obtained. 100 The particle size is 4 μm and the density is 1.02 g / cm³. 3 .

[0113] Preparation of Comparative Example 4: Synthesis of Semi-hollow Packing Material B1-4

[0114] 100g of ellipsoidal ceramic nanofiber felt (Shusaimei New Materials, grade SSM-T105, major axis length 0.2-6μm, minor axis length 0.2-2μm) was treated with 2g of aminosilane KH-550 at 80℃ for 4h, then immersed in 500mL of a mixed solvent of ethanol and water in a volume ratio of 1:4, ultrasonically dispersed for 30min, and the pH was adjusted to 8 by slowly adding ammonia water. Under continuous stirring, 160kg of 1%wt TEOS ethanol solution was added dropwise, and the reaction was carried out at room temperature for 16h. After centrifugation and washing to remove water and ethanol, and magnetic separation to remove magnetic impurities, the material was classified by high-speed airflow, with 80% of the particles having a diameter greater than 5μm. After washing and drying, the semi-hollow filler B1-4 was obtained. 100 The particle size is 8 μm and the density is 0.56 g / cm³. 3 .

[0115] Example 1

[0116] A resin composition comprising, by weight, the following components:

[0117] Epoxy resin A1100 parts by weight

[0118] Semi-hollow packing material B135 parts by weight

[0119] Curing agent C120 parts by weight

[0120] Curing agent C220 parts by weight

[0121] 20 parts by weight of phosphate flame retardant

[0122] 0.15 parts by weight of 2-ethyl-4-methylimidazole;

[0123] A prepreg comprising the resin composition and a metal foil-coated laminate are prepared by the following method:

[0124] (1) The components of the resin composition and butanone are placed in a container according to the formula amount, and stirred evenly to prepare a resin solution with a solid content of 60%.

[0125] (2) Impregnate 2116 electronic grade fiberglass cloth (purchased from Honghe) with the resin solution, and bake it in an oven at 170°C for 5 minutes to obtain a prepreg with a thickness of 0.13 mm;

[0126] (3) Stack the 6 prepregs obtained in step (2) and press copper foil with a thickness of 18μm on the top and bottom sides. After pressing and curing in a laminator, the metal foil laminate is obtained. The lamination operation conditions are 80℃, heating rate is 1.8℃ / min, full pressure is applied when the outer layer material temperature is 120℃, the full pressure is about 350Psi, the curing temperature is above 200℃, and the curing time is above 100min.

[0127] Examples 2-5, Comparative Examples 1-7

[0128] A resin composition, prepreg, and metal foil laminate differ from Example 1 in that the formulation of the resin composition is different, as shown in Tables 1 and 2; wherein the amount of each component is in "parts by weight"; and the preparation methods of the prepreg and metal foil laminate are the same as in Example 1.

[0129] Table 1

[0130]

[0131]

[0132] Table 2

[0133]

[0134] Performance testing

[0135] (1) Resin density: After removing the copper foil from the metal foil laminate, the core board is obtained. The core board is composed of fiberglass cloth and resin composition, and the density of the resin composition is the resin density. The weight m1 of the core board is weighed using a balance, the length a and width b of the core board are measured with a ruler, and the thickness c of the core board is measured with a thickness gauge. The volume of the core board is V1 = a × b × c; the single weight of 2116 electronic grade fiberglass cloth is 104 g / m. 2 The density of glass fiber is 2.56 g / cm³. 3The weight of the fiberglass cloth on the core board can be calculated as m2 = 104 × a × b × 6, and the volume of the fiberglass cloth is V2 = m2 / 2.56. The density can be calculated using the following formula: resin density = (m1 - m2) / (V1 - V2).

[0136] (2) Z-axis coefficient of thermal expansion (Z-CTE): Measured using a thermomechanical analyzer (Mettler, Switzerland, model TMA / SDTA 2+) according to IPC-TM-650 2.4.24;

[0137] (3) Dielectric constant and dielectric loss (10GHz): measured according to SPDR method, in accordance with section 2.5.5.9 of IPC-TM-650;

[0138] (4) CAF resistance: According to IPC-TM650 2.6.25 test, the failure is judged by a resistance value <2E+07Ω;

[0139] (5) Heat resistance (T288): The test was performed using a thermomechanical analyzer (Mettler, Switzerland, model TMA / SDTA 2+) according to IPC-TM-650 2.4.24.1;

[0140] (6) Board grooves: Visually inspect the surface of the metal foil-coated laminate edges. This indicates the presence of severe grooves (groove length / board length ≥ 0.02). × indicates the presence of slight grooves (0 < groove length / board length < 0.02); × indicates no grooves.

[0141] The metal foil laminates provided in the examples and comparative examples were tested according to the above method, and the test results are shown in Table 3 below:

[0142] Table 3

[0143]

[0144] As can be seen from the test data in Table 3, the resin composition provided by the present invention has excellent flowability and can make the metal foil laminate have low density, low coefficient of thermal expansion, good dielectric properties, good heat resistance and good CAF resistance, resulting in excellent comprehensive performance of the metal foil laminate.

[0145] As can be seen from the comparison between Example 2 and Comparative Example 1, the density of the semi-hollow filler is too high, the internal cavity volume is small, and the air content is low, resulting in a higher resin density of the board and a higher dielectric constant and dielectric loss of the metal foil laminate.

[0146] A comparison of Example 3 and Comparative Example 2 shows that the D of the semi-hollow packing... 100If the particle size is too large, the flowability of the resin composition deteriorates, grooves appear on the edges of the metal foil laminate, and the D-size of the semi-hollow filler also increases. 100 If the particle size is too large, copper ion channels are easily formed after drilling, which reduces the CAF resistance of the metal foil laminate.

[0147] A comparison of Example 2 and Comparative Example 3 shows that the D of the semi-hollow packing... 100 When the particle size is too small, the wall thickness of the semi-hollow filler is reduced and the strength is decreased, making it prone to breakage. The resin density and thermal expansion coefficient of the board are too large, and the dielectric constant and dielectric loss are also high.

[0148] As can be seen from the comparison between Example 1 and Comparative Example 4, if the density of the semi-hollow filler is too small, the porosity is large when the particle size is similar, and the internal structure is difficult to support the pressure during pressing, resulting in breakage. Therefore, the actual resin density and thermal expansion coefficient of the board are too large, and the dielectric constant and dielectric loss are relatively high.

[0149] As can be seen from the comparison between Example 3 and Comparative Example 5, when hollow filler is used to replace semi-hollow filler, the filler breaks during the pressing process, resulting in increased resin density, dielectric constant, and dielectric loss. Furthermore, since hollow filler does not have a mesh or filament structure inside, the cavity of hollow filler is filled with copper after copper plating, and the CAF resistance of the metal foil laminate is significantly reduced.

[0150] A comparison of Example 1 and Comparative Examples 6-7 shows that insufficient semi-hollow filler (Comparative Example 6) resulted in a higher coefficient of thermal expansion, poorer dielectric properties, and a resin density >1.2 g / cm³ for the metal foil-coated laminate. 3 Excessive content (Comparative Example 7) reduced the CAF resistance of the metal foil laminate, and slight grooves appeared on the board due to the mismatch in flowability between epoxy resin and semi-hollow filler.

[0151] The applicant declares that the above embodiments illustrate the resin composition and its application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition comprises the following components in parts by weight: 100 parts by weight of epoxy resin 20-50 parts by weight of semi-hollow packing 30-100 parts by weight of curing agent; The semi-hollow filler includes a core and an inorganic shell covering the core; the core has a mesh structure or a filament structure; and there is an internal cavity between the core and shell of the semi-hollow filler. The density of the semi-hollow filler is 0.6-1.1 g / cm³. 3 The D of the semi-hollow packing 100 The particle size is 5-20μm.

2. The resin composition according to claim 1, characterized in that, The epoxy resin includes any one or a combination of at least two of the following: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenolic resin, phosphorus-containing epoxy resin, MDI-modified epoxy resin, phenolic epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene-containing epoxy resin, or alicyclic epoxy resin. Preferably, the epoxy equivalent of the epoxy resin is 100-600 g / eq; Preferably, the curing agent comprises any one or a combination of at least two of the following: phenolic resin, cyanate ester resin, reactive ester, polyphenylene ether resin, maleimide resin, acid anhydride curing agent, styrene-maleic anhydride copolymer, amine curing agent, or benzoxazine resin. Preferably, the phenolic resin includes any one or a combination of at least two of bisphenol A type phenolic resin, phosphorus-containing phenolic resin, phenolic resin, biphenyl type phenolic resin, dicyclopentadiene type phenolic resin, or naphthol-containing phenolic resin.

3. The resin composition according to claim 1 or 2, characterized in that, The core is formed from any one of nano-three-dimensional network fiber felt, fumed silica or polyacrylonitrile fiber; Preferably, the nano-three-dimensional network fiber felt includes either titanium dioxide fiber felt or ceramic nanofiber felt; Preferably, the material of the inorganic shell includes silicon dioxide and / or aluminum oxide; Preferably, the mass of the core is 10-30% of the mass of the semi-hollow filler, which is 100% of the mass of the core.

4. The resin composition according to any one of claims 1-3, characterized in that, The semi-hollow packing is prepared by the following method: After surface treatment of the core-forming material with a silane coupling agent, an inorganic shell precursor is added to react and the semi-hollow filler is obtained. Preferably, the silane coupling agent comprises any one or a combination of at least two of aminosilane, epoxysilane, vinylsilane or phenylaminosilane; Preferably, the mass ratio of the silane coupling agent to the core formation is (1-5):100; Preferably, the precursor of the inorganic shell comprises tetraethyl silicate or alumina nanospheres; Preferably, the surface treatment temperature is 50-100℃; Preferably, the surface treatment time is 1-4 hours; Preferably, the reaction temperature is 18-35°C; Preferably, the reaction time is 8-24 hours; Preferably, the reaction is carried out under conditions of pH 8-10; Preferably, the reaction further includes airflow staged treatment after completion.

5. The resin composition according to any one of claims 1-4, characterized in that, The resin composition also includes a flame retardant; Preferably, the flame retardant includes any one or a combination of at least two of the following: brominated flame retardants, phosphorus-containing flame retardants, or nitrogen-containing flame retardants; Preferably, the brominated flame retardant includes any one or a combination of at least two of tetrabromobisphenol A, decabromodiphenyl ether, or tetrabromoethane; Preferably, the phosphorus-containing flame retardant comprises any one or a combination of at least two of organophosphates, phosphazene compounds, or DOPO derivatives; Preferably, the nitrogen-containing flame retardant comprises any one or a combination of at least two of melamine, melamine phosphate, dicyandiamide flame retardants, or guanidine salt flame retardants; Preferably, the flame retardant in the resin composition is 10-20 parts by weight.

6. The resin composition according to any one of claims 1-5, characterized in that, The resin composition further includes a curing accelerator; Preferably, the curing accelerator includes any one or a combination of at least two of imidazole accelerators, pyridine accelerators, Lewis acid accelerators, amine accelerators, phenolic accelerators, cyanate ester accelerators, or active ester accelerators; Preferably, the curing accelerator in the resin composition is 0.1-1 parts by weight.

7. A resin adhesive, characterized in that, The resin solution is obtained by dissolving or dispersing the resin composition as described in any one of claims 1-6 in a solvent; Preferably, the solid content of the resin solution is 50-75%.

8. A prepreg, characterized in that, The prepreg comprises a substrate and a resin composition as described in any one of claims 1-6 attached to the substrate; Preferably, the resin composition is adhered to the substrate after impregnation and drying.

9. A metal foil-coated laminate, characterized in that, The metal foil laminate comprises one or at least two stacked prepregs as described in claim 8, and metal foils located on one or both sides of the stacked prepregs.

10. A printed circuit board, characterized in that, The printed circuit board includes the prepreg as described in claim 8 or the metal foil laminate as described in claim 9.

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