A resin composition, a prepreg prepared by using the same, and a copper clad laminate

Abstract

The present invention provides a resin composition, a prepreg, and a copper clad laminate prepared by using the same. The resin composition comprises the following components by weight percentage: 20-60% of an aqueous polymer resin; 1-10% of a curing agent; 10-60% of magnetic boron nitride fibers; 5-25% of spherical boron nitride powder; and 1-10% of a flame retardant. The resin composition provided by the present invention does not need to add a solvent, and an environment-friendly aqueous polymer resin is selected to replace an oil-based epoxy resin as a matrix, reducing the contact of production personnel with toxic solvents during the production process and the environmental pollution. By using the aqueous polymer resin, the present invention can increase the dosage of high thermal conductivity and low dielectric powder or fiber. When used for a prepreg, the thermal conductivity of the prepreg can be improved, solving the problems of poor heat dissipation effect and communication signal loss during the use of a metal-based copper clad laminate.

Description

Technical Field

[0001] The present invention belongs to the technical field of heat dissipation of electronic components, and relates to a resin composition, a prepreg prepared by using the same, and a copper clad laminate, and particularly relates to a high thermal conductivity and low dielectric resin composition, a prepreg prepared by using the same, and a copper clad laminate. Background Art

[0002] In existing copper clad laminates, all currently used are oily compounds, such as epoxy compounds, polyphenylene ether compounds, allylphenol compounds, bismaleimide polymers, cyanate ester compounds, etc. These polymers are difficult to process, transport, and clean due to their high viscosity. At the same time, they are hardly soluble in water and are only soluble in organic solvents such as aromatic hydrocarbons, alcohol ethers, and alcohols. These solvents are not only expensive but also volatile, easily endangering human health and polluting the environment. Moreover, with the increasing emphasis on environmental protection and safety at home and abroad, relevant laws and regulations have become increasingly strict. Preparing materials that contain no or less organic compounds and developing green and environmentally friendly materials have become an inevitable requirement of today's society. Water-based compounds have the advantages of being non-toxic, odorless, having low volatile organic compounds, and being convenient for construction operations, and can replace oily compounds to prepare prepregs and copper clad laminates to achieve the same functions.

[0003] With the popularization of 5G, electronic components are becoming increasingly miniaturized and high-powered, and operate in the millimeter wave band. The biggest advantage of 5G is its fast propagation speed, but the accompanying disadvantages are poor penetration, large attenuation, and high heat generation. Therefore, the dielectric constant and dielectric loss of the propagation medium material in the copper clad laminate PCB need to be low, and higher heat dissipation performance is required to ensure the high-temperature reliability of electronic devices. Currently, a copper clad laminate is a plate-like material made by impregnating an electronic glass fiber cloth or other reinforcing materials with a resin and covering one or both sides with a copper foil and then thermocompressing. The thermal conductivity of the glass fiber cloth or resin therein is very poor, not exceeding 0.3 w / m·K. The conventional method to improve the thermal conductivity of the copper clad laminate is to fill the resin with powders such as silicon carbide (SiC), aluminum oxide (AL 2 O 3 )), zinc oxide (ZnO), aluminum nitride (AlN), boron nitride (BN), etc. to establish a heat conduction channel to achieve rapid heat transfer. However, due to the high viscosity of the resin, the filling amount is not high, and the improvement of thermal conductivity is limited. Moreover, with the addition of powders, the electrical properties such as breakdown voltage will deteriorate, and the addition of high-dielectric powders also increases the dielectric constant.

[0004] CN109776864A discloses a modified hexagonal boron nitride for preparing a thermally conductive semi-cured sheet. Although it completely uses low-dielectric powder boron nitride BN, its highest thermal conductivity does not exceed 1 W / m·K. CN113930026A discloses a method for preparing a high-thermal-conductivity and low-dielectric semi-cured sheet and copper clad laminate based on spherical boron nitride. This method uses an oily resin, and the filling amount of boron nitride is too small, and its highest thermal conductivity can only reach 3 W / m·K, which still has certain limitations for the application of current high-power devices.

[0005] In order to solve the environmental problems caused by the use of oily resins in current semi-cured sheets, the problems of low thermal conductivity and high dielectric constant, in this field, it is desired to develop a resin composition for semi-cured sheets, which is not only environmentally friendly but also has high thermal conductivity and low dielectric properties at the same time. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a resin composition and a semi-cured sheet and copper clad laminate prepared by using the same, and in particular to provide a high-thermal-conductivity and low-dielectric resin composition and a semi-cured sheet and copper clad laminate prepared by using the same.

[0007] To achieve the purpose of this invention, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a resin composition, which, calculated by weight percentage, comprises the following components:

[0009]

[0010]

[0011] The resin composition provided by the present invention does not need to add a solvent. An environmentally friendly water-based polymer resin is selected to replace the oily epoxy resin as the matrix, reducing the contact of production personnel with toxic solvents during the production process and environmental pollution; by using the water-based polymer resin, the present invention can increase the amount of high-thermal-conductivity and low-dielectric powder or fiber (i.e., magnetic boron nitride fiber and spherical boron nitride powder). When used for semi-cured sheets, the thermal conductivity of the semi-cured sheet can be improved, solving the problem of poor heat dissipation effect during the use of metal-based copper clad laminates. In addition, the resin composition provided by the present invention includes magnetic boron nitride fibers. In subsequent processes, the magnetic boron nitride fibers can be oriented and arranged in the matrix through an orientation process, so that even with a small addition amount of spherical boron nitride powder, the semi-cured sheet prepared from the resin composition of the present invention can obtain a very high thermal conductivity.

[0012] In the present invention, in terms of weight percentage, the amount of the aqueous polymer resin in the resin composition can be 20%, 23%, 25%, 28%, 30%, 33%, 35%, 38%, 40%, 43%, 45%, 48%, 50%, 53%, 55%, 58% or 60%, etc.

[0013] In the present invention, in terms of weight percentage, the amount of the curing agent in the resin composition can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc.

[0014] In the present invention, in terms of weight percentage, the amount of the magnetic boron nitride fiber in the resin composition can be 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33%, 35%, 38%, 40%, 43%, 45%, 48%, 50%, 53%, 55%, 58% or 60%, etc.

[0015] In the present invention, in terms of weight percentage, the amount of the spherical boron nitride powder in the resin composition can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%, etc.

[0016] In the present invention, in terms of weight percentage, the amount of the flame retardant in the resin composition can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc.

[0017] Preferably, the raw materials for preparing the magnetic boron nitride fiber include the following components in terms of weight parts:

[0018] 100 parts of boron nitride fiber;

[0019] 0.1 - 3 parts of emulsifier;

[0020] 2 - 10 parts of magnetic powder.

[0021] Preferably, in terms of weight parts, the amount of the emulsifier in the raw materials for preparing the magnetic boron nitride fiber can be 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts, etc.

[0022] Preferably, in terms of weight parts, the amount of the magnetic powder in the raw materials for preparing the magnetic boron nitride fiber can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, etc.

[0023] Preferably, the diameter of the boron nitride fiber is 1-10 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, etc., and the aspect ratio is (5-10):1, such as 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc.

[0024] Preferably, the emulsifier includes any one or a combination of at least two of fatty alcohol polyoxyethylene ether, polyol fatty acid ester, dopamine, bis(3-trimethoxysilylpropyl)amine or phosphate.

[0025] Preferably, the magnetic powder includes nano-ferroferric oxide.

[0026] Preferably, the particle size of the magnetic powder is 10-100 nm, such as 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm, etc.

[0027] Preferably, the magnetic boron nitride fiber is prepared by the following method:

[0028] (1) Mix the emulsifier, ethanol and deionized water to obtain an emulsifier solution;

[0029] (2) Bake the boron nitride fiber and the magnetic powder separately, then mix and disperse them to obtain a mixture, then spray the emulsifier solution obtained in step (1) onto the mixture, continue to disperse, then place it at room temperature, and then bake it to remove the residual ethanol and water to obtain the magnetic boron nitride fiber.

[0030] As a preferred technical solution of the present invention, the magnetic boron nitride fiber is prepared by the following method:

[0031] (1) Mix the emulsifier, ethanol and deionized water with a mass ratio of 1:4:0.5 to obtain an emulsifier solution;

[0032] (2) Bake the boron nitride fiber and the magnetic powder separately in a vacuum oven at 100 °C for 1 h, then stir and disperse them evenly in a disperser to obtain a mixture, then spray the emulsifier solution obtained in step (1) onto the mixture, continue to stir and disperse in the disperser for 30 min, then place it at room temperature for 30 min, and then bake it in a constant temperature oven at 125 °C for 1 h to remove the residual ethanol and water to obtain the magnetic boron nitride fiber.

[0033] In the present invention, using magnetic powder to modify boron nitride fiber can make the magnetic powder adsorbed on the boron nitride fiber. On the one hand, it can make the magnetic boron nitride fiber disperse better in water, and at the same time endow it with magnetism, which is convenient for the subsequent process to carry out orientation.

[0034] Preferably, the aqueous polymer resin includes any one or a combination of at least two of aqueous epoxy resin, aqueous phenolic epoxy resin, aqueous special epoxy resin, aqueous brominated epoxy resin or phenoxy resin.

[0035] Preferably, the curing agent includes any one or a combination of at least two of dicyandiamide, diaminodiphenyl sulfone, m-xylenediamine, linear phenolic resin, amino resin, benzoxazine resin or active ester.

[0036] Preferably, the particle size of the spherical boron nitride powder is 1-30 μm, such as 1 μm, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm or 30 μm, etc.

[0037] Preferably, the spherical boron nitride powder includes a combination of spherical boron nitride powders with particle sizes of 5 μm, 10 μm and 30 μm respectively.

[0038] As a preferred technical solution of the present invention, when the spherical boron nitride powder includes a combination of spherical boron nitride powders with particle sizes of 5 μm, 10 μm and 30 μm respectively, the thermal conductivity of the resin composition can be improved, thereby improving the heat dissipation effect of the copper clad laminate prepared from the resin composition and extending the service life of the copper clad laminate.

[0039] Preferably, the flame retardant includes any one or a combination of at least two of phosphorus-containing flame retardants, nitrogen-containing flame retardants, magnesium hydroxide, aluminum hydroxide, calcium hydroxide or antimony trioxide.

[0040] In a second aspect, the present invention provides a prepreg, which is prepared from the resin composition described in the first aspect.

[0041] Preferably, the prepreg is prepared by the following method:

[0042] (1) Add the formulated amounts of the aqueous polymer resin, curing agent and flame retardant to water, stir, and then add magnetic boron nitride fibers and spherical boron nitride powder, and continue to stir to obtain a resin composition slurry;

[0043] (2) Coat the resin composition slurry obtained in step (1) on a release film, and then pass the release film through a vertical magnetic field for orientation by a conveyor belt and dry it to obtain the prepreg.

[0044] It should be noted that in step (1) of the present invention, the amount of water added is not specifically limited because the water will be removed in the subsequent drying step (2).

[0045] In the present invention, by adopting the orientation technology, the thermal conductivity of the prepreg in the vertical direction can be increased to 6 W / m·k, and since the amount of powder used is small, it has little impact on the electrical properties of the prepreg such as breakdown voltage and insulation strength.

[0046] Preferably, the stirring and continuous stirring in step (1) are each independently carried out in a sand mill, a high-speed mixer or a high-speed emulsifier.

[0047] Preferably, the thickness of the coating in step (2) is 0.05 - 0.5 mm, such as 0.05 mm, 0.08 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm or 0.5 mm, etc.

[0048] Preferably, the speed of the conveyor belt passing through the vertical magnetic field in step (2) is 5 - 15 r / min, such as 5 r / min, 8 r / min, 10 r / min or 15 r / min, etc.

[0049] Preferably, the drying in step (2) is carried out in a drying tunnel at 60 - 150 °C (such as 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C or 150 °C, etc.).

[0050] In a third aspect, the present invention provides a copper clad laminate, which includes at least 1 sheet of prepreg as described in the second aspect, and copper foils disposed on one or both sides of the prepreg;

[0051] Preferably, the copper clad laminate includes an aluminum plate, a prepreg and a copper foil stacked in sequence.

[0052] Preferably, the copper clad laminate is prepared by the following method: placing the prepreg on the aluminum plate, then covering a layer of copper foil on the surface of the prepreg, stacking them neatly, and then hot pressing in a vacuum press. The hot pressing parameters are set as follows: hot pressing temperature 150 - 200 °C (such as 150 °C, 160 °C, 170 °C, 180 °C, 190 °C or 200 °C, etc.), pressure 10 - 50 kgf (such as 10 kgf, 20 kgf, 30 kgf, 40 kgf or 50 kgf, etc.), and hot pressing time 30 - 240 min (such as 30 min, 60 min, 90 min, 120 min, 150 min, 180 min, 210 min or 240 min, etc.), and thus the copper clad laminate is obtained.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] The resin composition provided by the present invention does not require the addition of a solvent. An environmentally friendly water-based polymer resin is selected to replace the oil-based epoxy resin as the matrix, which is equivalent to using water as the solvent, reducing the exposure of production personnel to toxic solvents during the production process and environmental pollution. By using the water-based polymer resin, the present invention can increase the dosage of high thermal conductivity and low dielectric powder or fiber (i.e., magnetic boron nitride fiber and spherical boron nitride powder). When used in prepregs, the thermal conductivity of the prepregs can be improved, solving the problems of poor heat dissipation effect and communication signal loss during the use of metal-based copper clad laminates. In addition, the resin composition provided by the present invention includes magnetic boron nitride fibers. In subsequent processes, the magnetic boron nitride fibers can be oriented and arranged in the matrix through an orientation process. Even with a small addition amount of spherical boron nitride powder, the prepregs prepared from the resin composition of the present invention can obtain a very high thermal conductivity (2.98 - 6.12 W / m·k). BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 Scanning electron microscope image of the prepreg provided in Example 1 DETAILED DESCRIPTION OF THE EMBODIMENTS

[0056] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0057] Some information about the raw materials used in the preparation examples and embodiments of the present invention is as follows:

[0058] Fatty alcohol polyoxyethylene ether: AEO-5, Guangzhou HeCheng Environmental Protection Technology Co., Ltd.;

[0059] Dopamine: D806618, 98%, Shanghai Macklin;

[0060] Bis(3-trimethoxysilylpropyl)amine: A1170 Nanjing Pining coupling agent;

[0061] Spherical boron nitride powder: Suzhou Jinyi;

[0062] Water-based epoxy resin: BH-685, Dongguan Guangtong Chemical Products Co., Ltd.;

[0063] Water-based phenolic epoxy resin: BH-652, Dongguan Guangtong Chemical Products Co., Ltd.;

[0064] Ammonium polyphosphate: HY85858, Shandong Guangshen Electronic Technology Co., Ltd.

[0065] Preparation Example 1

[0066] In this preparation example, a magnetic boron nitride fiber is provided. The raw materials for preparing the magnetic boron nitride fiber include the following components in parts by weight:

[0067] Boron nitride fiber 100 parts;

[0068] 2 parts of emulsifier;

[0069] 6 parts of magnetic powder.

[0070] The diameter of the boron nitride fiber is 5 μm and the length is 40 μm, the emulsifier is fatty alcohol polyoxyethylene ether, and the magnetic powder is nano-ferroferric oxide (particle size is 50 nm).

[0071] Magnetic boron nitride fiber is prepared by the following method:

[0072] (1) mixing an emulsifier, ethanol and deionized water in a mass ratio of 1:4:0.5 to obtain an emulsifier solution;

[0073] (2) The boron nitride fiber and the magnetic powder are baked in a vacuum oven at 100°C for 1 hour, respectively, and then stirred and dispersed evenly in a disperser to obtain a mixture, and then the emulsifier solution obtained in step (1) is sprayed into the mixture, and the mixture is stirred and dispersed in the disperser for 30 minutes, and then placed at room temperature for 30 minutes, and then baked in a constant temperature oven at 125°C for 1 hour to remove residual ethanol and water to obtain the magnetic boron nitride fiber.

[0074] Preparation Example 2

[0075] In this preparation example, a magnetic boron nitride fiber is provided. The raw materials for preparing the magnetic boron nitride fiber include the following components in parts by weight:

[0076] Boron nitride fiber 100 parts;

[0077] Emulsifier 0.1 part;

[0078] 2 parts of magnetic powder.

[0079] The diameter of the boron nitride fiber is 5 μm, the length is 40 μm, the emulsifier is dopamine, and the magnetic powder is nano-ferroferric oxide (the particle size is 10 nm).

[0080] The preparation method of magnetic boron nitride fiber is the same as that in Preparation Example 1.

[0081] Preparation Example 3

[0082] In this preparation example, a magnetic boron nitride fiber is provided. The raw materials for preparing the magnetic boron nitride fiber include the following components in parts by weight:

[0083] Boron nitride fiber 100 parts;

[0084] 3 parts of emulsifier;

[0085] 10 parts of magnetic powder.

[0086] Among them, the diameter of the boron nitride fiber is 5 μm, the length is 40 μm, the emulsifier is bis(3-trimethoxysilylpropyl)amine, and the magnetic powder is nano-sized magnetite (particle size is 100 nm).

[0087] The preparation method of the magnetic boron nitride fiber is the same as that of Preparation Example 1.

[0088] Example 1

[0089] In this example, a resin composition is provided. The resin composition, by weight percentage, comprises the following components:

[0090]

[0091] Among them, the water-based polymer resin is water-based epoxy resin, the curing agent is dicyandiamide, the magnetic boron nitride fiber is prepared from Preparation Example 1, the spherical boron nitride powder comprises a combination of spherical boron nitride powders with particle sizes of 5 μm, 10 μm and 30 μm respectively (the mass ratio of the three is 1:3:6), and the flame retardant is a combination of ammonium polyphosphate and calcium hydroxide (the mass ratio of the two is 1:1).

[0092] In this example, a prepreg is also provided. The prepreg is prepared from the above resin composition, and the preparation method comprises the following steps:

[0093] (1) Add the formulated amounts of the water-based polymer resin, curing agent, and flame retardant to water (the addition amount of water is 20% based on the total weight of the resin composition), stir with a stirrer at 500 r / min for 30 min. After stirring evenly, add the magnetic boron nitride fiber and the spherical boron nitride powder, and continue to stir at 500 r / min for 1 h. After stirring evenly, a resin composition slurry is obtained;

[0094] (2) Coat the resin composition slurry of step (1) on a release film with a coating thickness of 0.3 mm, and then pass the release film through a vertical magnetic field at a speed of 10 r / min by a conveyor belt, and dry it through 9 drying channels (60 °C for the 1st - 2nd segments, 80 °C for the 3rd - 4th segments, 100 °C for the 5th - 6th segments, 120 °C for the 7th segment, 150 °C for the 8th segment, 80 °C for the 9th segment) to obtain the prepreg.

[0095] Test the prepreg provided in this example by a scanning electron microscope, and the results are as Figure 1 shown. It can be seen that the magnetic boron nitride fibers in the prepreg are significantly oriented.

[0096] Example 2

[0097] In this embodiment, a resin composition is provided. By weight percentage, the resin composition comprises the following components:

[0098]

[0099]

[0100] Among them, the aqueous polymer resin is an aqueous epoxy resin, the curing agent is dicyandiamide, the magnetic boron nitride fiber is prepared from Preparation Example 1, the spherical boron nitride powder comprises a combination of spherical boron nitride powders with particle sizes of 5 μm, 10 μm, and 30 μm respectively (the mass ratio of the three is 1:3:6), and the flame retardant is a combination of ammonium polyphosphate and calcium hydroxide (the mass ratio of the two is 1:1).

[0101] In this embodiment, a prepreg is further provided. The prepreg is prepared from the above resin composition, and the preparation method comprises the following steps:

[0102] (1) Add the formulated amounts of the aqueous polymer resin, curing agent, and flame retardant to water (calculated based on the total weight of the resin composition being 100%, the addition amount of water is 11%), stir with a stirrer at 500 r / min for 30 min. After stirring evenly, add the magnetic boron nitride fiber and spherical boron nitride powder, and continue to stir at 500 r / min for 1 h. After stirring evenly, a resin composition slurry is obtained;

[0103] (2) Coat the resin composition slurry obtained in step (1) on a release film with a coating thickness of 0.05 mm, and then pass the release film through a vertical magnetic field for orientation at a speed of 15 r / min by a conveyor belt, and dry it through 9 drying channels (60 °C for sections 1-2, 80 °C for sections 3-4, 100 °C for sections 5-6, 120 °C for section 7, 150 °C for section 8, 80 °C for section 9) to obtain the prepreg.

[0104] Example 3

[0105] In this embodiment, a resin composition is provided. By weight percentage, the resin composition comprises the following components:

[0106]

[0107]

[0108] Among them, the aqueous polymer resin is an aqueous phenolic epoxy resin, the curing agent is dicyandiamide, the magnetic boron nitride fiber is prepared from Preparation Example 1, the spherical boron nitride powder comprises a combination of spherical boron nitride powders with particle sizes of 5 μm, 10 μm, and 30 μm respectively (the mass ratio of the three is 1:3:6), and the flame retardant is aluminum hydroxide.

[0109] In this embodiment, a prepreg is further provided. The prepreg is prepared from the above resin composition, and the preparation method includes the following steps:

[0110] (1) Add the formulated amounts of the aqueous polymer resin, curing agent, and flame retardant into water (with the addition amount of water being 40% based on the total weight of the resin composition being 100%). Stir with a stirrer at 500 r / min for 30 min. After stirring evenly, add the magnetic boron nitride fibers and spherical boron nitride powder, and continue to stir at 500 r / min for 1 h. After stirring evenly, a resin composition slurry is obtained;

[0111] (2) Coat the resin composition slurry of step (1) on a release film with a coating thickness of 0.5 mm using a knife coater. Then, pass the release film through a vertical magnetic field at a speed of 5 r / min using a conveyor belt, and dry it through 9 drying channels (60 °C for sections 1 - 2, 60 °C for sections 3 - 4, 80 °C for sections 5 - 6, 100 °C for section 7, 120 °C for section 8, 80 °C for section 9) to obtain the prepreg.

[0112] Example 4

[0113] In this embodiment, a resin composition is provided. The resin composition includes the following components by weight percentage:

[0114]

[0115] Among them, the aqueous polymer resin is aqueous phenolic epoxy resin, the curing agent is m - xylylenediamine, the magnetic boron nitride fibers are prepared from Preparation Example 1, the spherical boron nitride powder includes a combination of spherical boron nitride powders with particle sizes of 5 μm, 10 μm, and 30 μm respectively (the mass ratio of the three is 1:3:6), and the flame retardant is aluminum hydroxide.

[0116] In this embodiment, a prepreg is further provided. The prepreg is prepared from the above resin composition, and the preparation method includes the following steps:

[0117] (1) Add the formulated amounts of the aqueous polymer resin, curing agent, and flame retardant into water (with the addition amount of water being 1% based on the total weight of the resin composition being 100%). Stir with a stirrer at 500 r / min for 30 min. After stirring evenly, add the magnetic boron nitride fibers and spherical boron nitride powder, and continue to stir at 500 r / min for 1 h. After stirring evenly, a resin composition slurry is obtained;

[0118] (2) The resin composition slurry in step (1) is coated on a release film with a doctor blade coater, and the coating thickness is 0.3 mm. Then, the release film is passed through a vertical magnetic field at a speed of 10 r / min by a conveyor belt for orientation, and dried in a 9-stage drying oven (60 °C for stages 1-2, 80 °C for stages 3-4, 100 °C for stages 5-6, 120 °C for stage 7, 150 °C for stage 8, and 80 °C for stage 9) to obtain the prepreg.

[0119] Example 5

[0120] The difference between this example and Example 1 is only that the magnetic boron nitride fiber is the magnetic boron nitride fiber prepared in Preparation Example 2.

[0121] Example 6

[0122] The difference between this example and Example 1 is only that the magnetic boron nitride fiber is the magnetic boron nitride fiber prepared in Preparation Example 3.

[0123] Example 7

[0124] The difference between this example and Example 1 is only that the spherical boron nitride powder only includes one kind of powder with a particle size of 5 μm.

[0125] Example 8

[0126] The difference between this example and Example 1 is only that the spherical boron nitride powder only includes one kind of powder with a particle size of 10 μm.

[0127] Example 9

[0128] The difference between this example and Example 1 is only that the spherical boron nitride powder only includes one kind of powder with a particle size of 30 μm.

[0129] Comparative Example 1

[0130] The difference between this comparative example and Example 1 is only that the magnetic boron nitride fiber is replaced with an equal amount of boron nitride fiber (i.e., boron nitride fiber without magnetic modification).

[0131] Comparative Example 2

[0132] The difference between this comparative example and Example 2 is only that the spherical boron nitride powder is replaced with an equal amount of boron nitride fiber (with a diameter of 5 μm and a length of 40 μm).

[0133] Comparative Example 3

[0134] The difference between this comparative example and Example 3 is only that the weight percentage of the magnetic boron nitride fiber is 63%, and correspondingly, the weight percentage of the spherical boron nitride powder is 4.5%.

[0135] Comparative Example 4

[0136] The only difference between this comparative example and Example 2 is that the weight percentage of the spherical boron nitride powder is 30%, and correspondingly, the weight percentage of the magnetic boron nitride fiber is 10%.

[0137] Comparative Example 5

[0138] The only difference between this comparative example and Example 1 is that both the magnetic boron nitride fiber and the spherical boron nitride powder are replaced with an equal amount of Al 2 O 3 powder (with particle sizes of 5 μm and 10 μm respectively, and the mass ratio of the two is 1:1).

[0139] Comparative Example 6

[0140] The only difference between this comparative example and Example 1 is that in the preparation of the prepreg, step (2) does not include the orientation step.

[0141] Perform performance tests on the prepregs provided in the examples and comparative examples. The test methods are as follows:

[0142] (1) Thermal conductivity: Test according to the method of ASTM D5470;

[0143] (2) Peel strength: Test according to the method of IPC TM-650 2.4.8;

[0144] (3) Thermal stress: Test according to the method of IPC TM-650 2.4.41.1;

[0145] (4) Breakdown voltage: Test according to the method of IPC TM-650 2.5.6;

[0146] (5) Dielectric constant and dielectric loss: Test according to the method of IPC TM-650 2.5.5;

[0147] (6) Tg: Test using a DSC tester with a heating rate of 20 °C / min;

[0148] (7) Td: Test using a TGA tester in a nitrogen atmosphere with a heating rate of 10 °C / min, and record the temperature at 5% loss.

[0149] The performance test results are shown in Table 1.

[0150] Table 1

[0151]

[0152]

[0153] As can be seen from Table 1, the prepregs provided in Examples 1-9 of the present invention all have good thermal conductivity (thermal conductivity: 2.98-6.12 W / m·k). From Examples 1, 5, and 6, it can be seen that compared with fatty alcohol polyoxyethylene ether and bis(3-trimethoxysilylpropyl)amine, using dopamine to modify boron nitride fibers results in prepregs with more excellent thermal conductivity, and its thermal conductivity can reach 6.11 W / m·k (Example 5).

[0154] From the comparison between Comparative Example 1, Comparative Example 6 and Example 1, it can be seen that the present invention enables the magnetic boron nitride fibers to be oriented and arranged in the matrix, which can improve the thermal conductivity of the prepreg.

[0155] Compared with Example 2, the thermal conductivity of the prepregs provided in Comparative Example 2 and Comparative Example 4 decreased. Compared with Example 3, the prepreg product provided in Comparative Example 3 had powder falling off and could not be tested. This shows that only when magnetic boron nitride fibers and spherical boron nitride powder are used in combination, and the contents of both are within the limited range, can the prepreg have a high thermal conductivity.

[0156] Compared with Example 1, all the thermal conductive fillers in Comparative Example 5 are Al 2 O 3 powders. Under the same filling amount, the thermal conductivity of the prepreg provided in Comparative Example 5 is relatively low, and its dielectric constant is nearly twice as high. It is not suitable for application on copper clad laminates.

[0157] The applicant declares that the present invention uses the above examples to illustrate the resin composition of the present invention and the prepreg prepared therefrom, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of the raw materials selected by the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. An environmentally friendly resin composition for prepreg, characterized in that, the resin composition comprises the following components by weight percentage: The raw materials for preparing the magnetic boron nitride fiber comprise the following components by weight parts: boron nitride fiber 100 parts; emulsifier 0.1 - 3 parts; magnetic powder 2 - 10 parts.

2. The resin composition according to claim 1, characterized in that, the diameter of the boron nitride fiber is 1 - 10 μm, and the aspect ratio is (5 - 10):

1.

3. The resin composition according to claim 1, characterized in that, the emulsifier comprises any one or a combination of at least two of fatty alcohol polyoxyethylene ether, polyol fatty acid ester, dopamine, bis(3-trimethoxysilylpropyl)amine or phosphate.

4. The resin composition according to claim 1, characterized in that, the magnetic powder comprises nano-sized magnetite.

5. The resin composition according to claim 1, characterized in that, the particle size of the magnetic powder is 10 - 100 nm.

6. The resin composition according to claim 1, characterized in that, the magnetic boron nitride fiber is prepared by the following method: (1) Mix the emulsifier, ethanol and deionized water to obtain an emulsifier solution; (2) Bake the boron nitride fiber and the magnetic powder respectively, then mix and disperse to obtain a mixture, then spray the emulsifier solution obtained in step (1) onto the mixture, continue to disperse, then place at room temperature, and then bake to remove the residual ethanol and water to obtain the magnetic boron nitride fiber.

7. The resin composition according to claim 1, characterized in that, the aqueous polymer resin comprises any one or a combination of at least two of aqueous epoxy resin, aqueous phenolic epoxy resin, aqueous special epoxy resin, aqueous brominated epoxy resin or phenoxy resin.

8. The resin composition according to claim 1, characterized in that, the curing agent comprises any one or a combination of at least two of dicyandiamide, diaminodiphenyl sulfone, m-xylenediamine, linear phenolic resin, amino resin, benzoxazine resin or reactive ester.

9. The resin composition according to claim 1, characterized in that, the particle size of the spherical boron nitride powder is 1 - 30 μm.

10. The resin composition according to claim 1, characterized in that, the spherical boron nitride powder comprises a combination of spherical boron nitride powders with particle sizes of 5 μm, 10 μm and 30 μm respectively.

11. The resin composition according to claim 1, characterized in that, the flame retardant comprises any one or a combination of at least two of phosphorus-containing flame retardants, nitrogen-containing flame retardants, magnesium hydroxide, aluminum hydroxide, calcium hydroxide or antimony trioxide.

12. A prepreg, characterized in that, the prepreg is prepared from the resin composition according to any one of claims 1 - 11.

13. The prepreg according to claim 12, characterized in that, the prepreg is prepared by the following method: (1) Add the formulated amount of aqueous polymer resin, curing agent, and flame retardant into water, stir, and then add magnetic boron nitride fibers and spherical boron nitride powder, and continue stirring to obtain a resin composition slurry; (2) Coat the resin composition slurry of step (1) on a release film, and then pass the release film through a vertical magnetic field by a conveyor belt for orientation, and dry it to obtain the prepreg.

14. The prepreg according to claim 13, characterized in that, the coating thickness in step (2) is 0.05 - 0.5 mm.

15. The prepreg according to claim 13, characterized in that, the speed of the conveyor belt passing through the vertical magnetic field in step (2) is 5 - 15 r / min.

16. A copper clad laminate, characterized in that, the copper clad laminate comprises at least 1 sheet of the prepreg according to any one of claims 12 - 15, and copper foils provided on one or both sides of the prepreg.

17. The copper clad laminate according to claim 16, characterized in that, the copper clad laminate comprises an aluminum plate, a prepreg, and a copper foil stacked in sequence.

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