Copper-clad plate resin composition for ultralow-loss medium and preparation method of copper-clad plate resin composition

Abstract

The invention relates to the technical field of electronic materials, in particular to a copper-clad plate resin composition with an ultralow-loss medium and a preparation method of the copper-clad plate resin composition. The composition comprises the following components: modified polyphenyl ether, dicyclopentadiene epoxy resin, trifunctional epoxy resin, active ester, cyanate ester, DMAP, spherical silicon dioxide and a POSS-silicon dioxide compound, the preparation method comprises the following steps: carrying out surface norbornenylation modification on bimodal spherical silicon dioxide, and carrying out click reaction on the bimodal spherical silicon dioxide and octa-aminophenyl polysilsesquioxane with tetrazinyl at the tail end to prepare a POSS-silicon dioxide compound, so as to construct an interface transition layer with gradient modulus. According to the invention, collaborative optimization of dielectric loss, thermal mechanical properties and interface bonding strength is realized, and the material has excellent properties of low dielectric loss, high thermal stability, high peel strength and the like, and is suitable for the fields of 5G communication, high-frequency electronic equipment and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic materials, in particular to a copper-clad plate resin composition of ultra-low loss dielectric and a preparation method thereof. BACKGROUND

[0002] With the rapid development of 5G communication, millimeter wave radar and high-performance computing technologies, the demand for dielectric properties of high-frequency copper-clad plates is increasingly stringent. Traditional epoxy resin-based copper-clad plates have been difficult to meet the high-frequency application requirements in terms of dielectric properties, thermal stability and interfacial bonding strength, mainly in the following aspects: First, in terms of dielectric properties, traditional epoxy resin-based copper-clad plates have a high dielectric loss above 10 GHz. High-frequency signal transmission requires dielectric materials to have extremely low dielectric loss, but existing materials are difficult to meet this requirement. Second, in terms of thermal stability, high-density interconnection substrates require materials to have a thermal expansion coefficient in the z-axis direction of less than 50 ppm / °C (50-100°C) and 3.5% (50-260°C). However, existing materials have insufficient heat resistance and are prone to delamination in 288°C heat resistance tests. Third, in terms of interfacial properties, there has been a long-standing problem of interfacial compatibility between inorganic fillers and organic resins. This interfacial defect ultimately leads to problems such as high signal transmission loss and reduced reliability of devices.

[0003] Currently, the industry usually adopts three improvement schemes, but all have obvious limitations: the first scheme is to reduce the dielectric constant by adding fillers (such as spherical silica). Although simply increasing the content of inorganic fillers can reduce dielectric loss, the single particle size distribution of inorganic fillers can easily lead to insufficient packing density (porosity > 5%), which can cause problems such as deterioration of processing performance and reduction of mechanical strength (peeling strength reduction of 30%). In addition, there is a polarization loss problem at the interface between unfunctionalized fillers and resins. The second scheme is to use modified polyphenyl ether to reduce dielectric loss. However, modified polyphenyl ether has poor compatibility with the base epoxy resin, leading to phase separation after curing, which affects material performance. The third scheme is to improve thermal stability by increasing the crosslinking density of the base resin. This method can improve heat resistance, but it significantly increases the brittleness of the material, and delamination still occurs in 288°C heat resistance tests.

[0004] For high-frequency and high-speed application scenarios, existing solutions have obvious limitations in terms of dielectric properties, thermal stability and mechanical properties, and cannot achieve the synergistic optimization of high mechanical properties, high thermal stability and low dielectric loss. Therefore, it is urgent to develop a new type of copper-clad plate resin composition to solve the above technical problems. SUMMARY

[0005] Therefore, the present application aims to provide a copper-clad plate resin composition of ultra-low loss medium and a preparation method thereof to solve the problem that the conventional copper-clad plate resin composition cannot have low-loss medium, low thermal expansion coefficient and high peel strength.

[0006] Based on the above purpose, the present application provides a copper-clad plate resin composition of ultra-low loss medium, comprising the following raw materials by weight: 90-220 parts of xylene, 20-75 parts of modified polyphenyl ether, 100-330 parts of dicyclopentadiene epoxy resin, 15-50 parts of trifunctional epoxy resin, 120-450 parts of active ester, 9-27 parts of cyanate ester, 0.05-0.2 parts of DMAP, 117-378 parts of spherical silica, and 13-42 parts of POSS-silica composite.

[0007] Preferably, the modified polyphenyl ether is model SA90.

[0008] Preferably, the dicyclopentadiene epoxy resin is model SQDN-303, and the epoxy equivalent weight is 260-275.

[0009] Preferably, the trifunctional epoxy resin is model TT310, and the manufacturer is King Industries.

[0010] Preferably, the active ester is model HPC-8000-65T, and the manufacturer is Diayse.

[0011] Preferably, the cyanate ester is model kbd1303, and the manufacturer is Wuhan Cabot Chemical Co., Ltd.

[0012] Preferably, the particle size of the spherical silica is 2-3 μm.

[0013] Preferably, the preparation steps of the POSS-silica composite are as follows: S1: Small particle size silica and large particle size silica are added together into anhydrous toluene, uniformly dispersed, then vinyltrimethoxysilane, deionized water and glacial acetic acid are added, and stirred at 80℃ for 2-3h, after the reaction is completed, filtered and washed, and dried in a vacuum oven at 80℃ for 12h to obtain bimodal spherical silica with surface vinylization; S2: The bimodal spherical silica with surface vinylization is mixed with 5-norbornene-2-thiol and 2,2-dimethoxy-2-phenylphenylacetophenone, and then wetted with toluene, and then irradiated under 365nm ultraviolet light for 10-12min to obtain silica with surface borneol group; S3: Under the atmosphere of nitrogen, octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane, paraformaldehyde, 3, 6-dichloro-1, 2, 4, 5-tetrazine were dissolved in dichloromethane, triethylamine was added, and after stirring at room temperature for 12-14 h, it was washed with deionized water until neutral, and then dried with anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure to obtain octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane with tetrazine groups at the end, which was obtained by nucleophilic aromatic substitution of 3, 6-dichloro-1, 2, 4, 5-tetrazine (Cl-Tz-Cl), and the p-aminophenyl on the POSS was used as a nucleophile to replace the chlorine at the 3 / 6 position of the tetrazine ring in the presence of triethylamine, to obtain a POSS derivative with tetrazine groups at the end; paraformaldehyde acts as a water removal and hydrolysis inhibitor under the condition, reduces the hydrolysis of tetrazine and controls the generation of amine salt; S4: The octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane with tetrazine groups at the end was mixed with the silica with norbornene groups on the surface in toluene, and then heated to 150℃ for 15-30 min, and after the reaction was completed, the toluene was removed under reduced pressure to obtain a POSS-silica composite.

[0014] Preferably, the amount ratio of the small particle size silica, the large particle size silica, anhydrous toluene, vinyltrimethoxysilane, deionized water, glacial acetic acid in step S1 is 30-35g:70-75g:500-700mL:13-15g:10-20g:1-2g.

[0015] Preferably, the particle size of the small particle size silica in step S1 is 0.2μm.

[0016] Preferably, the particle size of the large particle size silica in step S1 is 2μm.

[0017] Preferably, the amount ratio of the surface vinylated bimodal spherical silica, 5-norbornene-2-thiol, 2, 2-dimethoxy-2-phenylphenylacetone, toluene in step S2 is 100-110g:2-4g:1-2g:100-150mL.

[0018] Preferably, the CAS number of 5-norbornene-2-thiol (Bicyclo[2.2.1]hept-5-ene-2-thiol) in step S2 is 4454-27-7, and the structural formula is as follows: .

[0019] Preferably, the amount ratio of the octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane, paraformaldehyde, 3, 6-dichloro-1, 2, 4, 5-tetrazine, dichloromethane, triethylamine in step S3 is 14-16g:1-3g:4-6g:150-300mL:6-10g.

[0020] Preferably, the amount ratio of the terminal tetrazine group-containing octaaminophenyl polysilsesquioxane, the surface norbornene group-containing silica and toluene in step S4 is 15-20 g: 100-105 g: 300-500 mL.

[0021] Further, the application also provides a preparation method of the copper-clad plate resin composition with ultra-low loss medium, comprising the following steps: At room temperature, the xylene, modified polyphenyl ether, dicyclopentadiene epoxy resin and trifunctional epoxy resin are mixed and stirred for 110-130 min, then the active ester and cyanate are continuously added and stirred for 110-130 min, then DMAP is added and stirred for 50-70 min, then the spherical silica and POSS-silica composite are added and stirred for 50-70 min, and the copper-clad plate resin composition with ultra-low loss medium is obtained.

[0022] The application has the following beneficial effects: The POSS-silica gradient interface structure constructed in the application effectively inhibits the dipole polarization and interface charge accumulation under high-frequency electric field through the unique cage-shaped molecular configuration, and maintains stable low-loss characteristics. This interface design retains the low dielectric properties of inorganic fillers and the processing performance advantages of organic matrix.

[0023] The self-adaptive interface layer formed by the tetrazine-norbornene click reaction can effectively constrain the polymer chain segment movement to improve the glass transition temperature, and can also buffer thermal stress through the energy rearrangement mechanism, realizing the unification of low thermal expansion coefficient and high toughness. The structure shows excellent size stability in long-term thermal aging test at 288 DEG C, overcoming the technical bottleneck of traditional material delamination at high temperature.

[0024] The application constructs a uniform stress transfer network at the nanoscale through the multi-point anchoring effect of the POSS molecule and the synergistic filling effect of the bimodal silica, so that the interface bonding strength is increased by more than 30%. This interface design realizes long-term stable interface bonding through the synergistic effect of chemical bonding and physical interlocking, and significantly improves the copper foil bonding strength.

[0025] The application adopts a bimodal particle size distribution silica system, and the bimodal particle size distribution silica forms a more compact filling structure by optimizing the packing density of the filler, effectively reducing the free volume of the resin matrix, thereby improving the size stability of the material; and significantly improving the mechanical properties and size stability of the material under high temperature conditions.

[0026] The application realizes the performance synergy of "low loss-high heat resistance-strong bonding" of the material through a molecular engineering strategy, provides key material support for the reliability and signal integrity of high-frequency high-speed electronic equipment, and has wide application prospects in the fields of 5G communication, artificial intelligence chip packaging, etc. Attached Figure Description

[0027] Figure 1 The Z-axis thermal expansion coefficient-temperature curves are shown for the copper-clad laminate resin compositions prepared in the embodiments and comparative examples of this invention.

[0028] Figure 2 The infrared spectrum of the silica with norbornene groups on the surface, the octaaminophenyl polysilsesquioxane with tetrazine groups at the end, and the POSS-silica complex in Example 2 of the present invention. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0030] The properties or sources of the raw materials used in the embodiments and comparative examples of this invention are as follows: Modified polyphenylene ether: Model SA90; Dicyclopentadiene epoxy resin: Model SQDN-303, epoxy equivalent 260-275; Trifunctional epoxy resin: Model TT310, Tiantai Chemical; Reactive ester: Model HPC-8000-65T, DISEN; Cyanate ester: Model kbd1303, Wuhan Kabuda Chemical Co., Ltd.; Spherical silica: 2-3μm; Small particle size silica: 0.2μm; Large particle size silica: 2μm.

[0031] Example 1: A copper-clad laminate resin composition for ultra-low loss dielectric, the specific preparation steps are as follows: (1) 30g of small-particle-size silica and 70g of large-particle-size silica were added to 500mL of anhydrous toluene and dispersed evenly. Then, 13g of vinyltrimethoxysilane, 10g of deionized water and 1g of glacial acetic acid were added. The mixture was refluxed and stirred at 80℃ for 2h. After the reaction was completed, the mixture was filtered and washed, and then dried in a vacuum oven at 80℃ for 12h to obtain surface-vinylated bimodal spherical silica. (2) 100g of surface-vinylened bimodal spherical silica was mixed with 2g of 5-norbornene-2-thiol and 1g of 2,2-dimethoxy-2-phenylacetophenone and moistened with 100mL of toluene. The mixture was then reacted under 365nm ultraviolet light for 10min to obtain silica with norbornene groups on the surface. (3) Under a nitrogen atmosphere, 14g of octaaminophenyl polysilsesquioxane, 1g of paraformaldehyde, and 4g of 3,6-dichloro-1,2,4,5-tetraazine were dissolved in 150mL of dichloromethane. 6g of triethylamine was added, and the mixture was stirred continuously at room temperature for 12h. The mixture was then washed with deionized water until neutral and dried with anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain octaaminophenyl polysilsesquioxane with tetraazine groups at the end. (4) 15 g of octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane with a tetrazine group at the end was mixed with 100 g of silica with a norbornene group on the surface in 300 mL of toluene, and then warmed to 150°C for 15 min. After the reaction was completed, the toluene was removed under reduced pressure to obtain a POSS-silica composite; (5) 220 g of xylene, 60 g of modified polyphenyl ether, 330 g of dicyclopentadiene epoxy resin, 50 g of trifunctional epoxy resin were mixed and stirred at room temperature for 110 min, then 450 g of active ester, 20 g of cyanate ester were added and stirred for 110 min, 0.1 g of DMAP was added and stirred for 50 min, then 334 g of spherical silica and 37 g of POSS-silica composite were added and stirred for 50 min to obtain a copper-clad plate resin composition of an ultra-low loss medium.

[0032] Example 2: A copper-clad plate resin composition of an ultra-low loss medium, the specific preparation steps are as follows: (1) 33 g of small particle size silica and 73 g of large particle size silica were added together into 600 mL of anhydrous toluene, and then 14 g of vinyltrimethoxysilane, 15 g of deionized water and 1.5 g of glacial acetic acid were added, and stirred at 80°C for 3 h. After the reaction was completed, it was filtered and washed, and dried in a vacuum oven at 80°C for 12 h to obtain bimodal spherical silica with a surface vinyl group; (2) 105 g of bimodal spherical silica with a surface vinyl group was mixed with 3 g of 5-norbornene-2-thiol and 1.5 g of 2,2-dimethoxy-2-phenylphenylacetophenone, and then wetted with 130 mL of toluene, and then irradiated with 365 nm ultraviolet light for 11 min to obtain silica with a norbornene group on the surface; (3) 15 g of octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane, 2 g of paraformaldehyde, 5 g of 3,6-dichloro-1,2,4,5-tetrazine were dissolved in 200 mL of dichloromethane under a nitrogen atmosphere, 8 g of triethylamine was added, and after stirring at room temperature for 13 h, it was washed with deionized water until neutral, and dried with anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure to obtain octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane having a tetrazine group at the end, and the nuclear magnetic peak position was as follows: 1H NMR (400 MHz, CDCl3, 298 K) δ 9.65 (br s, 8H, -NH-tetrazine), 7.35 (d, J = 8.6 Hz, 16H, Ar-H), 6.78 (d, J = 8.6 Hz, 16H, Ar-H), 3.80 (br s, 0.5H, -NH2, trace); impurity peaks: 7.26 (s, CHCl3), 5.32 (s, CH2Cl2), 7.18 (m, toluene ArH), 2.09 (s, toluene CH3), 2.60 (q, J = 7.2 Hz, Et3N-CH2), 1.56 (br, H2O / CDCl3), 1.26 (m, aliphatic), 1.15 (t, J = 7.2 Hz, Et3N-CH3), 0.88 (t, aliphatic); (4) 18 g of octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane having a tetrazine group at the end was mixed with 103 g of silica having a norbornene group on the surface in 400 mL of toluene, and then heated to 150°C for 20 min, and after the reaction was completed, the toluene was removed under reduced pressure to obtain a POSS-silica composite; (5) 165 g of xylene, 60 g of modified polyphenyl ether, 300 g of dicyclopentadiene epoxy resin, 50 g of trifunctional epoxy resin were mixed and stirred at room temperature for 120 min, and then 400 g of active ester, 25 g of cyanate ester were added and stirred for 120 min, 0.15 g of DMAP was added and stirred for 60 min, and then 360 g of spherical silica and 40 g of POSS-silica composite were added and stirred for 60 min to obtain a copper-clad plate resin composition of an ultra-low loss medium.

[0033] Example 3: A copper-clad plate resin composition of an ultra-low loss medium, the specific preparation steps are as follows: (1) 30 g of small particle size silica and 75 g of large particle size silica were added together in 700 mL of anhydrous toluene, and after being uniformly dispersed, 15 g of vinyltrimethoxysilane, 10 g of deionized water, and 2 g of glacial acetic acid were added, and stirred at 80°C under reflux for 3 h, and after the reaction was completed, it was filtered and washed, and dried in a 80°C vacuum oven for 12 h to obtain bimodal spherical silica with a surface vinyl group; (2) 110 g of the bimodal spherical silica surface-vinylated was mixed with 4 g of 5-norbornene-2-thiol and 2 g of 2,2-dimethoxy-2-phenylphenylacetone, and after being wetted with 100 mL of toluene, it was reacted under 365 nm ultraviolet light for 10 min to obtain the silica surface with norbornene groups; (3) 14 g of octakis(aminophenyl)polyhedral oligomeric silsesquioxane, 3 g of paraformaldehyde, and 6 g of 3,6-dichloro-1,2,4,5-tetrazine were dissolved in 300 mL of dichloromethane under a nitrogen atmosphere, 10 g of triethylamine was added, and after being stirred at room temperature for 12 h, it was washed with deionized water until neutral, and after being dried with anhydrous magnesium sulfate, the solvent was removed under reduced pressure to obtain octakis(aminophenyl)polyhedral oligomeric silsesquioxane with a tetrazine group at the end; (4) 20 g of octakis(aminophenyl)polyhedral oligomeric silsesquioxane with a tetrazine group at the end was mixed with 100 g of silica with a norbornene group on the surface in 500 mL of toluene, and then heated to 150°C for 30 min, and after the reaction was completed, the toluene was removed under reduced pressure to obtain a POSS-silica composite; (5) 180 g of xylene, 75 g of modified polyphenyl ether, 320 g of dicyclopentadiene epoxy resin, 45 g of trifunctional epoxy resin were mixed and stirred for 130 min, then 420 g of active ester, 27 g of cyanate ester were added and stirred for 110 min, then 0.2 g of DMAP was added and stirred for 70 min, then 378 g of spherical silica and 42 g of POSS-silica composite were added and stirred for 50 min to obtain a copper-clad plate resin composition of an ultra-low loss medium.

[0034] Example 4: A copper-clad plate resin composition of an ultra-low loss medium, the specific preparation steps are as follows: (1) 35 g of small particle size silica and 75 g of large particle size silica were added together in 700 mL of anhydrous toluene, and after being uniformly dispersed, 15 g of vinyltrimethoxysilane, 20 g of deionized water, and 2 g of glacial acetic acid were added, and after being stirred at 80°C for 3 h, the reaction was completed, and after being filtered and washed, it was dried in a vacuum oven at 80°C for 12 h to obtain bimodal spherical silica surface-vinylated; (2) 110 g of the bimodal spherical silica surface-vinylated was mixed with 4 g of 5-norbornene-2-thiol and 2 g of 2,2-dimethoxy-2-phenylphenylacetone, and after being wetted with 150 mL of toluene, it was reacted under 365 nm ultraviolet light for 12 min to obtain the silica surface with norbornene groups; (3) 16 g of octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane, 3 g of paraformaldehyde, and 6 g of 3,6-dichloro-1,2,4,5-tetrazine were dissolved in 300 mL of dichloromethane under a nitrogen atmosphere, 10 g of triethylamine was added, and the mixture was stirred at room temperature for 14 hours. After washing with deionized water until neutral and drying with anhydrous magnesium sulfate, the solvent was removed under reduced pressure to obtain octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane having a tetrazine group at the end; (4) 20 g of octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane having a tetrazine group at the end and 105 g of silica having a norbornene group on the surface were mixed in 500 mL of toluene, and then the temperature was increased to 150°C for 30 minutes. After the reaction was completed, the toluene was removed under reduced pressure to obtain a POSS-silica composite; (5) 90 g of xylene, 20 g of modified polyphenyl ether, 100 g of dicyclopentadiene epoxy resin, and 15 g of trifunctional epoxy resin were mixed and stirred at room temperature for 130 minutes. Then, 120 g of active ester, 9 g of cyanate ester, 0.08 g of DMAP, 117 g of spherical silica, and 13 g of the POSS-silica composite were added and stirred for 70 minutes to obtain a copper-clad plate resin composition for an ultra-low loss dielectric.

[0035] Comparative Example 1: The difference from Example 2 is that the POSS-silica composite is replaced with silica having a norbornene group on the surface in step (5).

[0036] Comparative Example 2: The difference from Example 2 is that the silica having a norbornene group on the surface is replaced with bimodal spherical silica having a vinyl group on the surface in step (4).

[0037] Comparative Example 3: The difference from Example 2 is that the octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane having a tetrazine group at the end is replaced with octakis (p-aminophenyl) polyhedral oligomeric silsesquioxane in step (4).

[0038] Comparative Example 4: The difference from Example 2 is that the small-particle-size silica is replaced with an equal amount of large-particle-size silica in step (1).

[0039] Performance Test The curing time was measured using a hot plate at 180°C (Varnish-GT); A 2116 glass fabric having a size of 31 cm*35 cm was immersed in a high-speed copper-clad plate resin mixture, and after being completely immersed in the glue solution, it was baked at 185°C for 2 minutes in a dipping machine to produce a PP. The PP was cut to a size of 28.5 cm*28.5 cm to obtain a prepreg. Six prepregs were stacked in a cross shape, and a copper foil was placed on top and bottom. The copper-clad plate was obtained by pressing using a press machine at a curing temperature of 250°C for 150 minutes. After the press machine was cooled to 70°C, the copper-clad plate was removed and cooled to room temperature. The physical properties of the copper-clad plate were measured. The glass transition temperature was tested using a differential thermal analyzer, Tg180 program (50-250℃) was selected, and the temperature raising rate was 10℃ / min; A mechanical thermal analyzer was used, TMA program was selected, the temperature raising rate was 10℃ / min, the temperature was raised to 288℃, and the temperature was kept constant for 60min, 60-100℃ was selected, z-CTE1 was analyzed, 200-250℃ was selected, z-CTE2 was analyzed, 50-260℃ was selected, z-CTE3 was analyzed, the data of the test time period of 25-75min was analyzed, whether the sample was delaminated under the condition of 288℃ for 60min was analyzed, and the z-axis thermal expansion coefficient-temperature curve is shown in Figure 1 A universal tensile testing machine was used, a 2.5cm*12.5cm copper-containing sample was prepared, two 3.5-4.0mm wide copper strips were drawn on the copper-containing surface using a knife to test the copper foil peeling strength; A network analyzer was used and equipped with a 10GHZ SPDR to test Df (dielectric loss factor).

[0040] An infrared analyzer was used to test the infrared spectrum, and the results are shown in Figure 2

[0041] Data analysis: As can be seen from Table 1, the ultra-low loss medium copper-clad plate resin composition prepared by the present application exhibits excellent comprehensive performance, and the technical advantages mainly come from the surface norbornene group of the bimodal spherical silica and the precise coupling of the terminal tetrazine group POSS, which constructs a cross-scale interface anchoring network; this structure realizes the interface optimization of inorganic fillers and organic resin at the molecular level, in which the POSS cage structure as a "molecular bridge" effectively reduces the interfacial polarization loss between silica and resin matrix, thereby significantly improving the dielectric properties; at the same time, the bimodal particle size distribution of silica optimizes the packing density, while maintaining a low coefficient of thermal expansion, and the dynamic covalent bond (tetrazine-norbornene click reaction product) in the system endows the material with self-adapting stress buffering capacity, so that it can still maintain excellent dimensional stability under high temperature conditions.

[0042] As can be seen from the data difference between Example 2 and Comparative Example 1 in Table 1, the introduction of POSS-silica composite significantly improves the material performance: On the one hand, the low polarization cage structure of POSS reduces the dielectric loss, the synergistic filling effect of bimodal silica effectively inhibits the Z-direction thermal expansion, and the multiple reaction sites provided by the eight amino phenyl POSS significantly enhance the interface bonding strength and simplify the complexity of the POSS component; ​​On the other hand, the crosslinked network formed by the tetrazine-norbornene click reaction between the POSS cage structure and the norbornene groups on the silica surface constructs the interfacial transition layer with gradient modulus, which not only maintains the rigid characteristics of the inorganic filler but also realizes stress buffering through the molecular-level dispersion of POSS, thereby improving the dimensional stability of the material, and the organic-inorganic hybrid characteristics effectively reduce the thermal mismatch between the resin and the filler.

[0043] As can be seen from the data difference between Example 2 and Comparative Example 2 in Table 1, the combination of the silica modified by surface norbornene group and the POSS material according to the present application significantly improves the comprehensive performance of the resin composition: On the one hand, the specific click chemistry reaction between the norbornene group and the tetrazine group constructs the organic-inorganic interfacial layer with precise molecular structure on the surface of the silica, which pre-constructs the covalent bridge between the POSS and the silica and then is introduced into the main system. The fast ring-opening reaction without metal catalysis avoids the adverse effects of metal ions on the dielectric properties, and the pre-formed POSS-silica covalent bridge composite avoids the process problems that may be caused by the reaction in the main glue solution system, while ensuring the interfacial stability and moisture resistance, which has a positive effect on maintaining the copper foil peel strength at high temperature.

[0044] As can be seen from the data comparison between Example 2 and Comparative Example 3 in Table 1, the combination of the POSS material modified by the terminal tetrazine group and the norbornene group silica according to the present application significantly improves the comprehensive performance of the resin composition: the high reactivity of the tetrazine group may promote the efficient coupling with the norbornene group to form a stable covalent bond connection, which significantly enhances the interfacial bonding strength compared with physical adsorption, and the rigid cage structure of the POSS molecule may improve the dimensional stability of the material by limiting the movement of the polymer chain segment; in addition, the multi-point bonding of the POSS molecule and the surface of the silica may form a more uniform stress distribution network, which helps to improve the mechanical strength and interfacial adhesion performance of the material.

[0045] As can be seen from the data comparison between Example 2 and Comparative Example 4 in Table 1, the use of the bimodal particle size distribution silica system according to the present application significantly improves the comprehensive performance of the resin composition of the copper-clad plate. The bimodal particle size distribution silica forms a more compact filling structure by optimizing the packing density of the filler, effectively reducing the free volume of the resin matrix, thereby improving the dimensional stability of the material; at the same time, the small particle size silica fills the gap between the large particle size silica, reducing the interfacial defects and improving the stress transfer efficiency, which helps to maintain the mechanical properties and dimensional stability of the material under high temperature conditions.

[0046] As can be seen from the data comparison between Example 2 and Comparative Example 4 in Table 1, the use of the bimodal particle size distribution silica system according to the present application significantly improves the comprehensive performance of the resin composition of the copper-clad plate. The bimodal particle size distribution silica forms a more compact filling structure by optimizing the packing density of the filler, effectively reducing the free volume of the resin matrix, thereby improving the dimensional stability of the material; at the same time, the small particle size silica fills the gap between the large particle size silica, reducing the interfacial defects and improving the stress transfer efficiency, which helps to maintain the mechanical properties and dimensional stability of the material under high temperature conditions. Figure 2It can be seen that the sample of silica with norbornene group shows a norbornene C=C absorption at 1640-1650 cm -1 , accompanied by =C-H at 3005-3020 cm -1 and C-S (sulfur-ene grafting) at 710 cm -1 ; the sample of octakis(aminophenyl) polyhedral oligomeric silsesquioxane with terminal tetrazine group shows a strong tetrazine ring C=N / N=N absorption at 1580 cm -1 , N-N / ring vibration at 1360 cm -1 , and a clear POSS cage-like Si-O-Si strong band at 1110 cm -1 . After the click reaction, the tetrazine at 1580 cm -1 and the norbornene C=C at 1645 cm -1 in the complex are significantly weakened / disappeared, and a new C=N band at 1610-1620 cm -1 appears, indicating the successful complexation; all of them show Si-O-Si characteristics at 1090-1120 cm -1 and 800 cm -1 , and the bands of the complex in this region are wider and stronger, reflecting the inorganic phase superposition and interface construction effect.

[0047] It should be understood by those of ordinary skill in the art that the above discussion of any of the embodiments is merely exemplary and is not intended to suggest that the scope of the present application is limited to these examples; under the idea of the present application, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other changes of different aspects of the present application as described above. In order to be brief, they are not provided in details.

Claims

1. An ultra-low loss dielectric copper clad laminate resin composition, characterized by, Comprising the following weight parts of raw materials: 90-220 parts of xylene, 20-75 parts of modified polyphenyl ether, 100-330 parts of dicyclopentadiene epoxy resin, 15-50 parts of trifunctional epoxy resin, 120-450 parts of active ester, 9-27 parts of cyanate, 0.05-0.2 parts of DMAP, 117-378 parts of spherical silica, 13-42 parts of POSS-silica composite; The preparation steps of the POSS-silica composite are as follows: S1: uniformly mix small particle size silica, large particle size silica, anhydrous toluene, vinyltrimethoxysilane, deionized water, glacial acetic acid, reflux and stir, purify to obtain bimodal spherical silica with surface vinyl group; S2: uniformly mix bimodal spherical silica with surface vinyl group, 5-norbornene-2-thiol, 2,2-dimethoxy-2-phenylacetophenone, toluene, and then obtain silica with surface norbornene group under ultraviolet light irradiation; S3: uniformly mix octakis(aminophenyl)polyhedral oligomeric silsesquioxane, paraformaldehyde, 3,6-dichloro-1,2,4,5-tetrazine, dichloromethane, triethylamine under nitrogen atmosphere, stir and purify to obtain octakis(aminophenyl)polyhedral oligomeric silsesquioxane with tetrazine group at the end; S4: uniformly mix octakis(aminophenyl)polyhedral oligomeric silsesquioxane with tetrazine group at the end, silica with surface norbornene group, toluene, incubate at 150℃ for 15-30 min, purify to obtain POSS-silica composite; The particle size of the small particle size silica in step S1 is 0.2 μm; the particle size of the large particle size silica is 2 μm.

2. The ultra-low loss dielectric copper-clad board resin composition according to claim 1, characterized by, The modified polyphenyl ether is SA90; the dicyclopentadiene epoxy resin is SQDN-303 with an epoxy equivalent of 260-275; the trifunctional epoxy resin is TT310 from Tiancai Chemical.

3. The ultra-low loss dielectric copper-clad board resin composition according to claim 1, characterized by, The active ester is HPC-8000-65T from Diayes.

4. The ultra-low loss dielectric copper-clad board resin composition of claim 1, wherein, The cyanate is kbd1303 from Wuhan Cabot Chemical Co., Ltd.; the particle size of the spherical silica is 2-3 μm.

5. The ultra-low loss dielectric copper-clad board resin composition of claim 1, wherein, The amount ratio of the small particle size silica, large particle size silica, anhydrous toluene, vinyltrimethoxysilane, deionized water, glacial acetic acid in step S1 is 30-35 g:70-75 g:500-700 mL:13-15 g:10-20 g:1-2 g.

6. The ultra-low loss dielectric copper-clad board resin composition of claim 1, wherein, The amount ratio of the bimodal spherical silica with surface vinyl group, 5-norbornene-2-thiol, 2,2-dimethoxy-2-phenylacetophenone, toluene in step S2 is 100-110 g:2-4 g:1-2 g:100-150 mL.

7. The ultra-low loss dielectric copper-clad board resin composition of claim 1, wherein, The amount ratio of the octakis(aminophenyl)polyhedral oligomeric silsesquioxane, paraformaldehyde, 3,6-dichloro-1,2,4,5-tetrazine, dichloromethane, triethylamine in step S3 is 14-16 g:1-3 g:4-6 g:150-300 mL:6-10 g.

8. The ultra-low loss dielectric copper-clad board resin composition of claim 1, wherein, The amount ratio of the octakis(aminophenyl)polyhedral oligomeric silsesquioxane with tetrazine group at the end, silica with surface norbornene group, toluene in step S4 is 15-20 g:100-105 g:300-500 mL.

9. A method for producing the resin composition for a copper-clad plate of an ultra-low loss dielectric according to any one of claims 1 to 8, characterized by, The method comprises the following steps: mixing and stirring xylene, modified polyphenyl ether, dicyclopentadiene epoxy resin and trifunctional epoxy resin, and then continuously adding active ester, cyanate, DMAP, spherical silicon dioxide and POSS-silica composite, and obtaining a copper-clad plate resin composition of ultra-low loss medium after stirring.

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