Resin composition containing modified hollow microspheres, prepreg sheet and printed circuit board
Through the preparation method of modified hollow microspheres, the problem of poor compatibility between hollow silica fillers and dielectric substrates is solved, and the low dielectric characteristics and excellent mechanical properties of dielectric substrates are achieved, and it is suitable for electronic components with high frequency transmission.
Patent Information
- Application Number
- CN202311604694.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-27
- Publication Date
- 2025-05-27
AI Technical Summary
In the prior art, the compatibility of the hollow silica filler with the dielectric substrate is poor, resulting in increased dielectric loss, reduced thermal stability and fragile mechanical properties of the dielectric substrate.
By the preparation method of modified hollow microspheres, hollow spherical silica is uniformly mixed with silicone coupling agent, and stirred and dried under an alkaline environment to obtain modified hollow microspheres. The modified hollow microspheres are combined with the resin composition to form a dielectric substrate with excellent compatibility and electrical characteristics.
The electrical characteristics of the dielectric substrate are improved, the dielectric constant and dielectric loss are reduced, the thermal stability and mechanical properties are improved, and the problem of poor compatibility between the hollow microspheres and the dielectric substrate is solved.
Smart Images
Figure CN120040943A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a resin composition prepreg and a printed circuit board, in particular to a resin composition prepreg containing modified hollow microspheres and a printed circuit board. Background Art
[0002] In order to meet the needs of high-frequency transmission, the dielectric substrate used in electronic components must have characteristics such as low dielectric constant and low dielectric loss. The existing technology adds hollow fillers to the dielectric substrate and uses the characteristics of air with low dielectric constant in the fillers to reduce the dielectric constant and dielectric loss of the dielectric substrate.
[0003] Furthermore, borosilicate glass hollow microspheres are widely used in dielectric substrate materials. However, borosilicate glass hollow microspheres contain sodium oxide (Na 2 O), boron oxide (B 2 O 3 ) and iron oxide (Fe 2 O 3 ) and other metal oxides, which will lead to increased dielectric loss and reduced thermal stability. In addition, the addition of insulating glass can easily cause the dielectric substrate to have brittle mechanical properties.
[0004] Therefore, hollow silica fillers with preferred heat resistance, mechanical properties, and electrical properties are also used in the prior art. However, the compatibility of the hollow silica fillers with the organic phase molecules in the dielectric matrix is poor.
[0005] Therefore, how to improve the compatibility of hollow silica fillers through molecular design improvements to overcome the above-mentioned defects has become one of the important issues that this business wants to solve. Summary of the invention
[0006] The technical problem to be solved by the present invention is to provide a resin composition, a prepreg and a printed circuit board containing modified hollow microspheres in view of the shortcomings of the prior art, so as to improve the problems of incompatibility and processability after adding the existing hollow microsphere silica directly into the resin composition, and at the same time improve the electrical properties of the dielectric substrate.
[0007] In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide a resin composition containing modified hollow microspheres, which includes: 10 to 80 parts by weight of modified hollow microspheres; 5 to 60 parts by weight of polyphenylene ether resin; and 5 to 30 parts by weight of hardener, based on the total weight of the resin composition being 100 parts by weight. The modified hollow microspheres are prepared by the following steps: (a) uniformly mixing hollow spherical silica, siloxane coupling agent and ethanol solution and stirring for a first predetermined time; (b) adding alkaline solution and continuously stirring for a second predetermined time; (c) centrifuging and pouring out the ethanol clarified liquid to take out the powder; and (d) drying the powder under a vacuum environment to obtain the modified hollow microspheres.
[0008] Furthermore, the resin composition further includes 0.1 to 5 parts by weight of a catalyst.
[0009] Furthermore, the catalyst is a peroxide, an azo compound, a redox initiator or an azide.
[0010] Furthermore, the hardener is trimethylallyl isocyanate (TMAIC), triallyl isocyanurate (TAIC), 1,3-isopropenyl-α-methylstyrene / 1,4-isopropenyl-α-methylstyrene (1,3-Isopropenyl-alpha-Methylstyrene / 1,4-Isopropenyl-alpha-Methylstyrene, IP-AMS), 2,2'-diallyl bisphenol A (Di-ally BPA), divinylbenzene (DVB), and 1,2-bis(p-vinylphenyl)ethane (BVPE).
[0011] Furthermore, the weight ratio of the hollow silica to the siloxane coupling agent is 1:10 to 1:25.
[0012] Furthermore, the alkaline solution is a 25% ammonium chloride solution.
[0013] Furthermore, the siloxane coupling agent is vinyltrimethoxysilane, vinyltriethoxysilane, p-phenylenetrimethoxysilane, 3-methacrylatepropylmethyldimethoxysilane, 3-methacrylatepropyltrimethoxysilane, 3-methacrylatepropylmethyldiethoxysilane, 3-methacrylatepropyltriethoxysilane or 3-acrylatepropyltrimethoxysilane.
[0014] In order to solve the above technical problems, another technical solution adopted by the present invention is to provide a prepreg sheet, which is formed by impregnating a reinforcing substrate into the aforementioned resin composition containing modified hollow microspheres.
[0015] In order to solve the above technical problems, another technical solution adopted by the present invention is to provide a printed circuit board, which includes a dielectric substrate layer and a conductive metal layer formed on the dielectric substrate layer, and the dielectric substrate layer is formed by the above-mentioned prepreg sheet.
[0016] Furthermore, the dielectric constant of the dielectric substrate layer at 10 GHz is less than 2.9, and the dielectric loss of the dielectric substrate layer at 10 GHz is less than 0.003.
[0017] One of the beneficial effects of the present invention is that the resin composition, prepreg and printed circuit board containing modified hollow microspheres provided by the present invention can improve the problems of incompatibility and processability after direct addition of hollow spherical silica in the existing resin composition, and improve the electrical properties of the dielectric layer by the technical scheme of "the total weight of the resin composition is 100 parts by weight, including 10 to 80 parts by weight of modified hollow microspheres" and "the modified hollow microspheres are prepared by the following steps: (a) uniformly mixing hollow spherical silica, siloxane coupling agent and ethanol solution and stirring for a first predetermined time; (b) adding alkaline solution and continuously stirring for a second predetermined time; (c) centrifuging and pouring out the ethanol clarified liquid to take out the powder; and (d) drying the powder under a vacuum environment to obtain the modified hollow microspheres".
[0018] To further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are only for reference and description and are not intended to limit the present invention. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 The flowchart of the method for manufacturing modified hollow microspheres of the present invention is shown in FIG.
[0020] Figure 2 Schematic diagram of the method for manufacturing modified hollow microspheres of the present invention.
[0021] Figure 3 To compare the Fourier transform infrared spectra of hollow microspheres before and after modification.
[0022] Figure numerals: S1~S4: steps. DETAILED DESCRIPTION
[0023] The following is an explanation of the implementation methods of the "resin composition containing modified hollow microspheres, prepreg and printed circuit board" disclosed in the present invention through specific embodiments. Those skilled in the art can understand the advantages and effects of the present invention from the contents disclosed in this specification. The present invention can be implemented or applied through other different specific embodiments, and the details in this specification can also be modified and changed in various ways based on different viewpoints and applications without departing from the concept of the present invention. In addition, the drawings of the present invention are only simple schematic illustrations and are not depicted according to actual dimensions. It is stated in advance. The following embodiments will further explain the relevant technical contents of the present invention in detail, but the disclosed contents are not intended to limit the scope of protection of the present invention.
[0024] It should be understood that, although the terms "first", "second", "third" and the like may be used herein to describe various elements or features, these elements or features should not be limited by these terms. These terms are mainly used to distinguish one element from another element, or one feature from another feature. In addition, the term "or" used herein may include any one or more combinations of the associated listed items depending on the actual situation.
[0025] The method for manufacturing the modified hollow microspheres of the present invention is to first modify the surface of the hollow spherical silica with a silane coupling agent. Compared with the prior art of adding a silane coupling agent to bridge the hollow spherical silica with organic phase molecules, the modified hollow microspheres of the present invention have better compatibility and processability.
[0026] See also Figures 1 to 3 As shown, the present invention provides a method for manufacturing modified hollow microspheres, which comprises at least the following steps: step S1: uniformly mixing hollow spherical silica, siloxane coupling agent and ethanol solution and stirring for a first predetermined time; step S2: adding alkaline solution and continuously stirring for a second predetermined time; step S3: centrifuging and pouring out the ethanol clarified liquid to take out the powder; and step S4: drying the powder under a vacuum environment to obtain the modified hollow microspheres.
[0027] Specifically, steps S1 to S3 are performed at room temperature, and room temperature refers to 20 to 30° C. The alkaline solution of step S2 is an ammonium chloride solution, a sodium bicarbonate solution or a sodium hydroxide solution and an alkali metal group (IA) alkaline solution, and its pH value is 10 to 12 (for example, any positive integer between 10 and 12). In one embodiment of the present invention, the first predetermined time is 30 to 60 minutes, preferably 30 to 40 minutes (for example, any positive integer between 30 and 40). The second predetermined time is 24 to 36 hours, preferably 24 to 30 hours (for example, any positive integer between 24 and 30).
[0028] like Figure 2As shown, the present invention uses a siloxane coupling agent to modify hollow spherical silica. Figure 2 R1, R2 and R3 in the above-mentioned may be C1-C12 alkyl or C1-C12 isomers thereof. In one embodiment of the present invention, the siloxane coupling agent may be vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl triethoxysilane or 3-acryloxypropyl trimethoxysilane. However, the above example is only one feasible embodiment and is not intended to limit the present invention.
[0029] Furthermore, the weight ratio of hollow silica to siloxane coupling agent is 1:10 to 1:25 to obtain a hollow silica having CH 3 -CH 2 、C-CH 3 , C=C and -OH functional groups. In a preferred embodiment of the present invention, the weight ratio of hollow silica to siloxane coupling agent is 1:10 to 1:20. For example, the weight ratio of hollow silica to siloxane coupling agent can be 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20. In a more preferred embodiment of the present invention, the weight ratio of hollow silica to siloxane coupling agent is 1:15.
[0030] See also Figure 3 As shown in the figure, the hollow silica has 825 and 1110 cm -1 The characteristic peaks of hollow microspheres are 1420 and 2972 cm -1 There is a characteristic peak at 3 -CH 2 、C-CH3 Functional group. The modified hollow silica is at 1620cm -1 There is a characteristic peak at 3503cm -1 There is a characteristic peak at , which represents the hydroxyl functional group (-OH) of the hollow silica after modification. 3 -CH 2 、C-CH 3 , C=C and -OH functional groups.
[0031] The method for preparing the modified hollow microspheres of the present invention is detailed in the following Synthesis Examples 1 to 10.
[0032] Synthesis example 1
[0033] 1 g of hollow spherical silica, 15 ml of vinyl trimethoxysilane and 100 ml of ethanol were placed in a 250 ml reaction bottle equipped with a thermometer and a stirrer and stirred at room temperature for 30 minutes. Subsequently, 10 ml of 25% NH 4 OH alkaline solution, stirred at room temperature for 24 hours. Then, centrifuged at 2000 rpm for 3 times, the ethanol clarified liquid was removed and the powder was taken out. The powder was placed in a vacuum environment for 12 hours, and then dried at 100°C for 2 hours to obtain the modified hollow microsphere powder (MS1-HS-SiO 2 ).
[0034] Synthesis example 2
[0035] The same process conditions as in Synthesis Example 1 were used, except that the siloxane coupling agent was changed to vinyl triethoxysilane to obtain a modified hollow microsphere powder (MS2-HS-SiO 2 ).
[0036] Synthesis example 3
[0037] The same process conditions as in Synthesis Example 1 were used, except that the siloxane coupling agent was changed to p-phenylethylenetrimethoxysilane to obtain a modified hollow microsphere powder (MS3-HS-SiO 2 ).
[0038] Synthesis example 4
[0039] The same process conditions as in Synthesis Example 1 were used, except that the siloxane coupling agent was changed to 3-methacrylate propylmethyldimethoxysilane to obtain a modified hollow microsphere powder (MS4-HS-SiO 2 ).
[0040] Synthesis example 5
[0041] The same process conditions as in Synthesis Example 1 were used, except that the siloxane coupling agent was changed to 3-methacrylate propyltrimethoxysilane to obtain a modified hollow microsphere powder (MS5-HS-SiO 2 ).
[0042] Synthesis example 6
[0043] The same process conditions as in Synthesis Example 1 were used, except that the siloxane coupling agent was changed to 3-methacrylate propylmethyldiethoxysilane to obtain a modified hollow microsphere powder (MS6-HS-SiO 2 ).
[0044] Synthesis Example 7
[0045] The same process conditions as in Synthesis Example 1 were used, except that the siloxane coupling agent was changed to 3-methacrylate propyltriethoxysilane to obtain a modified hollow microsphere powder (MS7-HS-SiO 2 ).
[0046] Synthesis example 8
[0047] The same process conditions as in Synthesis Example 1 were used, except that the siloxane coupling agent was changed to 3-propyltrimethoxysilane to obtain a modified hollow microsphere powder (MS8-HS-SiO 2 ).
[0048] Synthesis example 9
[0049] 1g of hollow spherical silica, 15ml of vinyl trimethoxysilane and 100ml of ethanol were placed in a 250ml reaction bottle equipped with a thermometer and a stirrer, and stirred at room temperature for 30 minutes. Subsequently, 10ml of 1% HCL acidic solution was added under continuous stirring, and stirred at room temperature for 24 hours. Next, centrifuge was used to centrifuge 3 times at 2000rpm, the ethanol clarified liquid was poured out and the powder was taken out. The powder was placed in a vacuum environment for 12 hours, and then a drying step was performed at 100C for 2 hours to obtain a modified hollow microsphere powder (MS9-HS-SiO 2 ).
[0050] Synthesis example 10
[0051] The same process conditions as in Synthesis Example 9 were used, except that the siloxane coupling agent was changed to 3-propyltrimethoxysilane to obtain a modified hollow microsphere powder (MS10-HS-SiO 2 ).
[0052] Furthermore, the present invention also provides a resin composition containing modified hollow microspheres, which comprises 100 parts by weight of the total weight of the resin composition: 10 to 80 parts by weight of modified hollow microspheres, 5 to 60 parts by weight of polyphenylene ether resin, and 5 to 30 parts by weight of a hardener. If the content of the modified hollow microspheres is less than 10 parts by weight, the dielectric constant and dielectric loss cannot be effectively reduced. If the content of the modified hollow microspheres is higher than 80 parts by weight, the coating characteristics of the resin composition will be affected. If the content of the polyphenylene ether resin is less than 5 parts by weight, the physical and mechanical properties, heat resistance and electrical insulation of the resin composition will be poor. If the content of the polyphenylene ether resin is higher than 60 parts by weight, the melt viscosity of the resin composition will be large and difficult to process. If the content of the hardener is less than 5 parts by weight, the resin will not be able to harden smoothly after coating. If the content of the hardener is higher than 30 parts by weight, the texture of the resin composition after curing will be too hard and brittle.
[0053] In a preferred embodiment of the present invention, the resin composition of the modified hollow microspheres includes 30 to 70 parts by weight of the modified hollow microspheres, 10 to 50 parts by weight of the polyphenylene ether resin, and 5 to 20 parts by weight of the hardener. In a more preferred embodiment of the present invention, the resin composition of the modified hollow microspheres includes 50 to 70 parts by weight of the modified hollow microspheres, 20 to 30 parts by weight of the polyphenylene ether resin, and 10 to 20 parts by weight of the hardener. In a more preferred embodiment of the present invention, the weight ratio of the modified hollow microspheres, the polyphenylene ether resin, and the hardener is 65:24:11.
[0054] Specifically, the hardener may be trimethylallyl isocyanate (TMAIC), triallyl isocyanurate (TAIC), 1,3-isopropenyl-alpha-methylstyrene / 1,4-isopropenyl-alpha-methylstyrene (1,3-Isopropenyl-alpha-Methylstyrene / 1,4-Isopropenyl-alpha-Methylstyrene, IP-AMS), 2,2'-diallyl bisphenol A (Di-ally BPA), divinylbenzene (DVB), 1,2-bis(p-vinylphenyl)ethane (BVPE). However, the above examples are only feasible embodiments and are not intended to limit the present invention.
[0055] The modified hollow microsphere powder obtained by the method of the present invention is mixed with a resin, a hardener, a catalyst, a reinforcing material, etc. to form a resin composition, that is, mixed with a homogenizer and dissolved or dispersed in a solvent to form a varnish for subsequent processing. For example, the catalyst can be a peroxide, an azo compound (such as α, α′-azobis(isobutyronitrile)), a redox initiator (such as a combination of peroxides, for example, a combination of hydrogen peroxide and a ferrous salt) or an azide (such as ethylene azide). In one embodiment of the present invention, the catalyst can be a peroxide-based hardening accelerator, such as cyclohexanone peroxide, tert-butyl perbenzoate, methyl ethyl ketone peroxide, diisopropylbenzene peroxide, tert-butyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide. Preferably, the peroxide-based hardening accelerator is diisopropylbenzene peroxide (DCP) commercially available from Arkema.
[0056] The solvent may be any inert solvent that can dissolve or disperse the components of the resin composition but does not react with the components. The aforementioned solvents include but are not limited to: toluene, γ-butyrolactone, methyl ethyl ketone, cyclohexanone, butanone, acetone, xylene, methyl isobutyl ketone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-pyrrolidone (NMP). Each solvent may be used alone or in combination. There is no particular restriction on the amount of solvent used, as long as the components of the resin composition can be uniformly dissolved or dispersed therein. In the following examples, a mixture of toluene, methyl ethyl ketone, and γ-butyrolactone is used as the solvent.
[0057] The present invention also provides a prepreg, which is obtained by impregnating or coating a substrate with a resin composition of modified hollow microspheres, and drying the impregnated or coated substrate. The impregnated or coated substrate can be dried at a temperature of 80°C to 180°C for 1 to 10 minutes (e.g., any positive integer between 1 and 10) to obtain a semi-cured prepreg. In one embodiment of the present invention, 2116 reinforced glass fiber cloth is used as a substrate (reinforcement material), and is heated and dried at 175°C for 2 to 15 minutes (e.g., any positive integer between 2 and 15) to obtain a semi-cured prepreg.
[0058] Furthermore, the metal foil laminate and printed circuit board can be prepared by laminating the above-mentioned prepreg and metal foil. In one embodiment of the present invention, four prepregs impregnated or coated with the above-mentioned resin composition can be laminated, and a 0.5 ounce copper foil is laminated on the outermost layer of each side, and then placed in a hot press for high-temperature hot pressing and curing to obtain a printed circuit board. Specifically, the hot pressing conditions are: heating at a heating rate of 3.0°C / min to 200°C to 220°C (for example, any positive integer between 200 and 220), and at this temperature, hot pressing at a full pressure of 15 kg / cm2 (initial pressure of 8 kg / cm2) for 180 minutes.
[0059] Next, the dielectric substrate layer was subjected to glass transition temperature (glass transition temperature, Tg), coefficient of thermal expansion (coefficient of thermal expansion, CTE), dielectric constant (Dk), dielectric loss (Df) and compatibility characteristics tests, and the components of the resin composition and the test results are listed in Table 1. In Table 1, EX1-EX8 represent Examples 1 to 8, and C1-C12 represent Comparative Examples 1 to 12.
[0060] CTE Test
[0061] According to IPC-TM-650 2.4.24.5, a thermal mechanical analyzer (TMA) is used to measure the coefficient of thermal expansion (CTE) change rate in the Z-axis direction (total z-CTE) of the sample at a temperature below Tg.
[0062] Compatibility test
[0063] Powder filler is added to varnish solution and left to stand at room temperature for 2 hours before being observed to see if the powder is suspended. If it is suspended on the surface, mark it with (X); otherwise, it is evenly mixed with (O).
[0064] Dielectric constant and dielectric loss test
[0065] The laminated substrate was removed from the hot press and the copper foil was removed by etching to form a test coupon; the dielectric constant and dissipation factor were tested at 10 GHz using the clamped stripline test method described in IPC-TM-6502.5.5.5.1.
[0066] The composition and physical property measurement results of the embodiment of the present case are shown in Table 1, and the composition and physical property measurement results of the comparative example are shown in Table 2. The contents in Table 1 and Table 2 are expressed in parts by weight. The composition of the embodiment of the present case is based on the total volume of all components as 100%, of which 50% by volume is hollow microspheres, 25% by volume is reinforcing material, and 25% by volume is resin, catalyst and flame retardant.
[0067] Table 1
[0068]
[0069]
[0070] Table 2
[0071]
[0072]
[0073] Table 2 (continued)
[0074]
[0075]
[0076] In Table 1 and Table 2, silane 1 is vinyltrimethoxysilane; silane 4 is 3-methacryloxypropyl methyldimethoxysilane; and peroxide is diisopropyl peroxide (DCP) commercially available from Arkema.
[0077] As shown in Table 1, the modified hollow microspheres of the present invention have excellent compatibility with other materials of the dielectric substrate, and the use of the modified hollow microspheres of the present invention can make the dielectric constant of the dielectric substrate at 10 GHz less than 2.9, and the dielectric loss of the dielectric substrate layer at 10 GHz less than 0.003.
[0078] The modified hollow microspheres of the present invention are manufactured in an alkaline environment to obtain a lower dielectric constant and dielectric loss. For example, in Comparative Examples C1 and C2, although the siloxane coupling agent used is the same as that of the embodiment of the present case, the modified hollow microspheres of Comparative Examples C1 and C2 are modified in an acidic environment (pH 3 to 5.5), resulting in poor electrical properties of the modified hollow microspheres.
[0079] In addition, although the unmodified hollow microspheres used in Comparative Examples C3 to C5 also have lower dielectric constants and dielectric losses, their compatibility is poor. Comparative Examples C6 and C7 use glass hollow microspheres and spherical silica, which have poor compatibility and poor electrical properties, respectively.
[0080] In addition, Comparative Examples C8 to C12 show that even if glass hollow microspheres or spherical silica are mixed with the modified hollow microspheres of the present invention, there are still disadvantages such as poor compatibility and poor electrical properties. Therefore, the modified hollow microspheres of the present invention need to be used in a specific amount to achieve the effect of taking into account both compatibility and electrical properties.
[0081] Advantageous Effects of Embodiments
[0082] One of the beneficial effects of the present invention is that the resin composition, prepreg and printed circuit board containing modified hollow microspheres provided by the present invention can improve the problems of incompatibility and processability after direct addition of hollow spherical silica in the existing resin composition, and improve the electrical properties of the dielectric layer by the technical scheme of "the total weight of the resin composition is 100 parts by weight, including 10 to 80 parts by weight of modified hollow microspheres" and "the modified hollow microspheres are prepared by the following steps: (a) uniformly mixing hollow spherical silica, siloxane coupling agent and ethanol solution and stirring for a first predetermined time; (b) adding alkaline solution and continuously stirring for a second predetermined time; (c) centrifuging and pouring out the ethanol clarified liquid to take out the powder; and (d) drying the powder under a vacuum environment to obtain the modified hollow microspheres".
[0083] Furthermore, the resin composition containing modified hollow microspheres provided by the method of the present invention has low dielectric properties and excellent mechanical properties, and thus has a wide range of applications in the fields of electronics, aerospace, etc., and is particularly suitable for manufacturing prepregs and printed circuit boards.
[0084] The contents disclosed above are only preferred feasible embodiments of the present invention, and are not intended to limit the protection scope of the claims of the present invention. Therefore, all equivalent technical changes made using the contents of the present invention description and drawings are included in the protection scope of the claims of the present invention.
Claims
1. A resin composition containing modified hollow microspheres, characterized in that, based on 100 parts by weight of the total weight of the resin composition, the resin composition containing modified hollow microspheres includes: 10 to 80 parts by weight of modified hollow microspheres; 5 to 60 parts by weight of polyphenylene ether resin; and 5 to 30 parts by weight of a hardener; wherein, the modified hollow microspheres are prepared by the following steps: (a) Uniformly mixing hollow spherical silica, a siloxane coupling agent and an ethanol solution and stirring for a first predetermined time; (b) Adding an alkaline solution and continuously stirring for a second predetermined time; (c) Centrifuging and pouring out the ethanol clear liquid, and taking out the powder; and (d) Drying the powder in a vacuum environment to obtain the modified hollow microspheres; wherein, the weight ratio of the hollow silica to the siloxane coupling agent is 1:10 to 1:
25.
2. The resin composition containing modified hollow microspheres according to claim 1, characterized in that, the resin composition further includes 0.1 to 5 parts by weight of a catalyst.
3. The resin composition containing modified hollow microspheres according to claim 2, characterized in that, the catalyst is a peroxide, an azo compound, a redox initiator or an azide.
4. The resin composition containing modified hollow microspheres according to claim 1, characterized in that, the hardener is trimethallyl isocyanate, triallyl isocyanurate, 1,3 - isopropenyl - α - methylstyrene / 1,4 - isopropenyl - α - methylstyrene, 2,2'-diallyl bisphenol A, divinylbenzene, 1,2 - bis(p - vinylphenyl)ethane.
5. The resin composition containing modified hollow microspheres according to claim 1, characterized in that, the weight ratio of the hollow silica to the siloxane coupling agent is 1:10 to 1:
25.
6. The resin composition containing modified hollow microspheres according to claim 1, characterized in that, the alkaline solution is a 25% ammonium chloride solution.
7. The resin composition containing modified hollow microspheres according to claim 1, characterized in that, the siloxane coupling agent is vinyltrimethoxysilane, vinyltriethoxysilane, p - styryltrimethoxysilane, 3 - methacryloxypropylmethyldimethoxysilane, 3 - methacryloxypropyltrimethoxysilane, 3 - methacryloxypropylmethyldiethoxysilane, 3 - methacryloxypropyltriethoxysilane or 3 - acryloxypropyltrimethoxysilane.
8. A prepreg, characterized in that, the prepreg is formed by impregnating a reinforcing substrate in the resin composition containing modified hollow microspheres according to any one of claims 1 to 7.
9. A printed circuit board, characterized in that, the printed circuit board includes a dielectric substrate layer and a conductive metal layer formed on the dielectric substrate layer, and the dielectric substrate layer is formed by the prepreg according to claim 8.
10. The printed circuit board according to claim 9, characterized in that, The dielectric substrate layer has a dielectric constant less than 2.9 at 10 GHz, and the dielectric substrate layer has a dielectric loss less than 0.003 at 10 GHz.