Magnetic dielectric resin composition and application thereof

Abstract

The invention provides a magnetic dielectric resin composition and application thereof. The magnetic dielectric resin composition comprises a combination of resin and a composite hexagonal magnetic filler, wherein molecules of the composite hexagonal magnetic filler comprise a combination of M-type magnetic molecules and Y-type magnetic molecules; the chemical formula of the M type magnetic molecule is BaFe12O19; the chemical formula of the Y-type magnetic molecule is BaMeFe6O11, and Me comprises any one or a combination of at least two of Co, Ca or Sr; the total mass of the magnetic dielectric resin composition is 100%, and the mass fraction of the composite hexagonal magnetic filler is 20-90%. The magnetic dielectric resin composition has high magnetic conductivity and low magnetic loss angle tangent and is relatively low in cost through synergistic cooperation of the Y-type hexagonal magnetic molecules and the M-type hexagonal magnetic molecules and adoption of the specific content of the composite hexagonal magnetic filler.

Description

Technical Field

[0001] The present invention belongs to the technical field of laminates, and relates to a magnetodielectric resin composition and its application. Background Art

[0002] With the development of emerging microfabrication technologies such as microelectronics and micromechanics, in the trend of high-density mounting technology, drive capacitors, integrated circuits, circuit modules, and antenna radio frequency modules are continuously developing towards miniaturization. As a key component in radar and modern wireless communication systems, and the bottleneck of miniaturization, the reduction of antenna size has attracted great attention.

[0003] One way to reduce the antenna size is to use high-dielectric materials. High-dielectric constant plates are disclosed in CN103101252A and CN103351578A. Such plates can reduce the antenna size, but this method will reduce the antenna gain and degrade the overall antenna performance.

[0004] Another way to reduce the antenna size is to use magnetodielectric materials as substrates. Magnetodielectric plates can be used as embedded inductors, which can reduce the antenna size, thereby reducing the size of electronic products and optimizing the performance of electronic products. The characteristic parameters of the antenna are shown in Equation 1 below, where (ε r μ r ) 1 / 2 is the miniaturization factor. The higher the dielectric constant ε r and the higher the magnetic permeability μ r , the higher the miniaturization factor, and the more beneficial it is for miniaturization. In the case where the dielectric constant cannot be changed, increasing the magnetic permeability can effectively reduce the antenna size while maintaining or increasing the antenna gain and bandwidth.

[0005] λ = c / f(ε r μ r ) 1 / 2 (1)

[0006] Spinel ferrites have high magnetic permeability values, such as NiZn ferrites and MnZn ferrites. However, these spinel ferrites have a low cut-off frequency and are difficult to use above 1 GHz. Planar hexagonal ferrites have a high cut-off frequency, such as Co2Z hexagonal ferrites, but have a low magnetic permeability and are difficult to significantly reduce the antenna size. US20190264005A discloses a technical solution of polytetrafluoroethylene + Co2Z, but the magnetic permeability of the material is low and the cost is high. CN1099444C discloses a polymer / magnetic nanocomposite microwave dielectric material, but the prepared plates have a high magnetic loss at 1 GHz.

[0007] Therefore, it is desirable to develop a magnetodielectric material with low cost, high magnetic permeability, and low magnetic loss. Summary of the Invention

[0008] In view of the deficiencies of the prior art, the object of the present invention is to provide a magnetodielectric resin composition and its applications. In the molecule of the composite hexagonal magnetic filler of the magnetodielectric resin composition of the present invention, the M-type magnetic molecule has the advantages of high frequency and low magnetic loss, and the Y-type magnetic molecule has the advantage of high magnetic permeability. The Y-type and M-type magnetic molecules can cooperate synergistically to obtain excellent composite properties of high magnetic permeability, high frequency and low magnetic loss. Therefore, through the synergistic cooperation of the Y-type hexagonal magnetic molecule and the M-type hexagonal magnetic molecule, and by using a specific content of the composite hexagonal magnetic filler, the magnetodielectric resin composition can have high magnetic permeability and low magnetic loss tangent, and the cost is relatively low.

[0009] To achieve this purpose, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a magnetodielectric resin composition, which comprises a combination of a resin and a composite hexagonal magnetic filler, and the molecule of the composite hexagonal magnetic filler comprises a combination of an M-type magnetic molecule and a Y-type magnetic molecule;

[0011] The chemical formula of the M-type magnetic molecule is BaFe 12 O 19 ; the chemical formula of the Y-type magnetic molecule is BaMeFe6O 11 , wherein Me includes any one or a combination of at least two of Co, Ca or Sr;

[0012] Based on the total mass of the magnetodielectric resin composition being 100%, the mass fraction of the composite hexagonal magnetic filler is 20-90%, for example, it can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, etc.

[0013] It should be noted that the composite hexagonal magnetic filler of the present invention has a new crystal form different from the M-type magnetic crystal form and the Y-type magnetic crystal form, and simultaneously includes an M-type magnetic structure and a Y-type magnetic structure at the microscale, rather than a simple physical mixture of the M-type magnetic and Y-type magnetic structures.

[0014] The present invention provides a magnetodielectric resin composition. In the molecule of the composite hexagonal magnetic filler therein, the M-type magnetic molecule has the advantages of high frequency and low magnetic loss, and the Y-type magnetic molecule has the advantage of high magnetic permeability. The Y-type and M-type magnetic molecules can cooperate synergistically to obtain excellent composite properties of high magnetic permeability, high frequency and low magnetic loss. Therefore, through the synergistic cooperation of the Y-type hexagonal magnetic molecule and the M-type hexagonal magnetic molecule, and by using a specific content of the composite hexagonal magnetic filler, the magnetodielectric resin composition can have high magnetic permeability and low magnetic loss tangent, and the cost is relatively low.

[0015] In the present invention, when the mass fraction of the composite hexagonal magnetic filler is too small, the magnetic permeability will be too small; when the mass fraction of the composite hexagonal magnetic filler is too large, the processability will be poor.

[0016] Preferably, the average particle size of the composite hexagonal magnetic filler is 0.1 - 30 μm, for example, it can be 0.1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 13 μm, 16 μm, 19 μm, 22 μm, 25 μm, 28 μm or 30 μm, etc. The particle size of the filler is measured by the laser diffraction method, and the measuring instrument is the Malvern laser particle size analyzer, model MS3000.

[0017] Preferably, based on the total mass of the composite hexagonal magnetic filler being 100%, the mass fraction of the M-type magnetic molecules is 5 - 20%, for example, it can be 5%, 7%, 10%, 12%, 15% or 20%, etc. If the content of the M-type magnetic molecules is too small, the high-frequency magnetic loss is high; if it is too much, the magnetic permeability is small.

[0018] Preferably, the molecules of the composite hexagonal magnetic filler further include BaFe 15 O 23 .

[0019] In the present invention, the substance with the chemical formula BaFe 15 O 23 existing in the composite hexagonal magnetic filler can effectively improve the high-frequency magnetic loss of the material.

[0020] Preferably, based on the total mass of the composite hexagonal magnetic filler being 100%, the mass fraction of BaFe 15 O 23 is 15 - 30%, for example, it can be 15%, 17%, 18%, 20%, 22%, 25%, 28% or 30%, etc.

[0021] Preferably, the molecules of the composite hexagonal magnetic filler further include single metal oxide molecules.

[0022] Preferably, the single metal oxide molecules include any one or a combination of at least two of manganese oxide molecules, zinc oxide molecules, nickel oxide molecules or copper oxide molecules.

[0023] Preferably, based on the total mass of the composite hexagonal magnetic filler being 100%, the mass fraction of the single metal oxide molecules is 5 - 10%, for example, it can be 5%, 6%, 7%, 8%, 9% or 10%, etc.

[0024] Preferably, the composite hexagonal magnetic filler is prepared by the following method, and the method includes:

[0025] Co-fire the M-type magnetic material and the Y-type magnetic material, or co-fire the raw materials of the M-type magnetic material and the raw materials of the Y-type magnetic material to obtain the composite hexagonal magnetic filler;

[0026] The chemical formula of the M-type magnetic material is BaFe 12 O 19 ; The chemical formula of the Y-type magnetic material is BaMeFe6O 11 , where Me includes any one or a combination of at least two of Co, Ca, or Sr.

[0027] In the present invention, compared with the blending method, the co-firing or co-burning method is used to prepare the composite hexagonal magnetic filler, which can improve the magnetic permeability of the material and reduce the high-frequency magnetic loss.

[0028] In the present invention, after co-firing the M-type magnetic material and the Y-type magnetic material, or after co-burning the raw materials of the M-type magnetic material and the raw materials of the Y-type magnetic material, in the molecule of the obtained composite hexagonal magnetic filler, in addition to the M-type magnetic molecules and the Y-type magnetic molecules, it also contains BaFe 15 O 23 .

[0029] Preferably, the co-firing and co-burning temperatures are each independently 700 - 1300 °C, for example, it can be 700 °C, 800 °C, 900 °C, 910 °C, 920 °C, 930 °C, 940 °C, 950 °C, 960 °C, 970 °C, 980 °C, 990 °C, 1000 °C, 1100 °C, 1200 °C or 1300 °C, etc., preferably 900 - 1000 °C.

[0030] In the present invention, when preparing the composite hexagonal magnetic filler, if the co-firing temperature is too high or too low, the crystal forms cannot be effectively fused, and the effect of high magnetic permeability and low high-frequency magnetic loss cannot be obtained. The same is true for co-burning.

[0031] Preferably, the co-firing and co-burning times are each independently 2 - 8 h, for example, it can be 2 h, 3 h, 4 h, 5 h, 6 h, 7 h or 8 h, etc., preferably 3 - 4 h.

[0032] Preferably, after the co-firing, the co-fired product is wet ball-milled and dried to obtain the composite hexagonal magnetic filler. The same is true for co-burning.

[0033] Preferably, the time of the wet ball-milling is 1 - 5 h, for example, it can be 1 h, 2 h, 3 h or 4 h, etc. By controlling the ball-milling time, the particle size of the composite hexagonal magnetic filler is adjusted.

[0034] Preferably, the resin includes any one or a combination of at least two of epoxy resin, cyanate resin, polyphenylene ether resin, polybutadiene resin, styrene-butadiene resin, bismaleimide-triazine resin, bismaleimide resin, polytetrafluoroethylene resin, polyimide resin, phenolic resin, acrylic resin, liquid crystal resin, benzoxazine resin, nitrile rubber, carboxyl-terminated nitrile rubber or hydroxyl-terminated nitrile rubber.

[0035] Preferably, based on the total mass of the magnetodielectric resin composition being 100%, the mass fraction of the resin is 10-80%, for example, it can be 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70% or 80%, etc.

[0036] Preferably, the magnetodielectric resin composition further includes non-magnetic fillers and a promoter.

[0037] Preferably, based on the total mass of the magnetodielectric resin composition being 100%, the mass fraction of the non-magnetic filler is 5-20%, for example, it can be 5%, 7%, 10%, 12%, 15% or 20%, etc.

[0038] Preferably, based on the total mass of the magnetodielectric resin composition being 100%, the mass fraction of the promoter is 0.1-8%, for example, it can be 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 5% or 8%, etc.

[0039] Preferably, the non-magnetic filler includes any one or a combination of at least two of silica, titanium dioxide, barium titanate, strontium titanate, magnesium titanate, calcium titanate, strontium barium titanate, barium calcium titanate, lead titanate, lead zirconate titanate, lead lanthanum zirconate titanate, barium lanthanum titanate, barium zirconate titanate, hafnium dioxide, lead magnesium niobate, barium magnesium niobate, lithium niobate, potassium niobate, strontium aluminum tantalate, potassium tantalum niobate, strontium barium niobate, barium lead niobate, barium titanium niobate, bismuth strontium tantalate, bismuth titanate, rubidium barium titanate, copper titanate or lead titanate-lead magnesium niobate.

[0040] Preferably, the promoter includes any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole or 1-cyanoethyl-2-methylimidazole.

[0041] Preferably, the magnetodielectric resin composition further includes an initiator.

[0042] Preferably, based on the total mass of the magnetodielectric resin composition being 100%, the mass fraction of the initiator is 0.1-8%, for example, it can be 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 5% or 8%, etc.

[0043] Preferably, the initiator includes any one or a combination of at least two of a,a'-bis(tert-butylperoxy-m-isopropylbenzene)benzene, dicumyl peroxide, tert-butylcumyl peroxide, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, tert-butyl octanoate, tert-butyl peroxybenzoate, triethylamine, triethylamine salt compound, quaternary ammonium salt compound, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, imidazoles, tripentylphenol amide, monophenol compound, polyphenol compound, boron trifluoride, complex of boron trifluoride and organic compound, phosphoric acid or triphenyl phosphite.

[0044] Preferably, the magnetodielectric resin composition further includes a crosslinking agent.

[0045] Preferably, based on the total mass of the magnetodielectric resin composition being 100%, the mass fraction of the crosslinking agent is 5-20%, such as 5%, 7%, 10%, 12%, 15% or 20%, etc.

[0046] Preferably, the crosslinking agent includes any one or a combination of at least two of triallyl isocyanurate, poly(triallyl isocyanurate), triallyl cyanurate, trimethacrylic acid, diallyl phthalate, divinylbenzene or acrylate.

[0047] Preferably, the present invention provides a resin solution, and the resin solution contains the magnetodielectric resin composition described in the first aspect and a solvent.

[0048] Preferably, the solvent includes any one or a combination of at least two of ethers, ketones, aromatic hydrocarbons, esters or nitrogen-containing solvents.

[0049] Preferably, the solvent includes ethers such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, or any one or a combination of at least two of acetone, butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, mesitylene, ethoxyethyl acetate, ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone.

[0050] In the second aspect, the present invention provides a prepreg, and the prepreg includes a reinforcing material and the magnetodielectric resin composition described in the first aspect attached to the reinforcing material.

[0051] Preferably, the reinforcing material includes a glass fiber cloth.

[0052] In a third aspect, the present invention provides a magnetic film, which comprises the magnetodielectric resin composition described in the first aspect. The magnetic film is obtained by coating the magnetodielectric resin composition on a release material and then drying and / or baking it.

[0053] In a fourth aspect, the present invention provides a magnetic paste, which comprises the magnetodielectric resin composition described in the first aspect.

[0054] In a fifth aspect, the present invention provides a metal-clad laminate, which comprises at least one prepreg described in the second aspect, and metal foil is covered on at least one side surface (such as one side surface or both side surfaces) after the prepregs are laminated. The at least one prepreg can be, for example, 1, 2, 3, 4, 5, 7, or 10 sheets, etc.

[0055] In a sixth aspect, the present invention provides a printed circuit board, which comprises at least one of the prepreg described in the second aspect and the metal-clad laminate described in the fifth aspect.

[0056] The numerical ranges described in the present invention not only include the above-listed point values, but also include any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the ranges.

[0057] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0058] The present invention provides a magnetodielectric resin composition. In the molecule of the composite hexagonal magnetic filler therein, the M-type magnetic molecule has the advantage of low magnetic loss at high frequencies, and the Y-type magnetic molecule has the advantage of high magnetic permeability. The Y-type and M-type magnetic molecules can cooperate synergistically, and excellent composite properties of high magnetic permeability and low magnetic loss at high frequencies can be obtained. Therefore, through the synergistic cooperation of the Y-type hexagonal magnetic molecule and the M-type hexagonal magnetic molecule, and by using a specific content of the composite hexagonal magnetic filler, the magnetodielectric resin composition can have high magnetic permeability and low magnetic loss tangent, and the cost is relatively low. Specific Embodiments

[0059] The technical solutions of the present invention will be further described below through specific embodiments.

[0060] Preparation Examples

[0061] The molecular composition and properties of the composite hexagonal magnetic filler used in the following examples and comparative examples of the present invention are shown in Table 1. In Table 1, the content of each molecule in the composite hexagonal magnetic filler is the mass percentage content.

[0062] Table 1

[0063]

[0064] The preparation method of the composite hexagonal magnetic filler is as follows:

[0065] Take the M-type magnetic material BaFe 12 O 19 、the Y-type magnetic material BaMeFe6O 11 、BaFe 15 O 23 and the single metal oxide MnO, and carry out physical dry mixing for 1 h to prepare a ring-shaped green body, and then sinter at 1000 °C for 4 h; the obtained sintered product is a ring-shaped sample (inner diameter 3.04 mm, outer diameter 6.96 mm and thickness 3 mm); wet ball mill and crush the sintered product in a ball mill at a rotation speed of 3000 r / min for 2 h, and the particle size of the zirconium beads is compounded at 1-10 mm; dry after ball milling to obtain a composite hexagonal magnetic filler with the molecular composition shown in Table 1.

[0066] In Table 1, the average particle size of the composite hexagonal magnetic filler is measured by the laser diffraction method, and the measuring instrument is a Malvern laser particle size analyzer, model MS3000.

[0067] In Table 1, the test methods for the magnetic permeability and the magnetic loss tangent at 2 GHz are as follows:

[0068] For the above-mentioned sintered ring-shaped sample, use the Keysight E5071C network analyzer + N1500 test system as the test instrument to test the relative magnetic permeability and magnetic loss tangent of the material at 2 GHz.

[0069] The materials used in the following examples and comparative examples are specifically as follows:

[0070] Hydrocarbon resin: Nippon Soda B3000

[0071] Polyphenylene ether resin: Sabic SA9000;

[0072] Brominated epoxy resin B: Changchun Plastics (Taiwan, China) BEB531A80P;

[0073] Phenoxy resin C: Nippon Steel YP-50EK35;

[0074] Epoxy resin A: Nippon Steel ZX1059;

[0075] 1,4-bis(tert-butylperoxy)cumene (BIPB) initiator: Hunan Fangruida Chemical Co., Ltd.;

[0076] 2-methylimidazole (2-MI): BASF (Germany).

[0077] Example 1

[0078] This embodiment provides a magnetodielectric resin composition, comprising 74 g of polyphenylene ether resin SA9000, 6 g of BIPB initiator, and 20 g of composite hexagonal magnetic filler A.

[0079] The magnetodielectric resin composition is used for the preparation of a copper clad laminate, and the specific method is as follows:

[0080] (1) Mix the magnetodielectric resin composition with ethylene glycol monomethyl ether and disperse evenly at room temperature to obtain a resin glue solution;

[0081] (2) Impregnate the resin glue solution obtained in step (1) with a reinforcing material (glass fiber cloth), place it in an oven at 155 °C and bake for 5 min to achieve curing to obtain a prepreg; Place 6 sheets of prepreg with a thickness of 5 mil between two copper foils, laminate and cure at 210 °C and 5 MPa pressure in a hot press for 2 h to obtain the copper clad laminate.

[0082] Example 2

[0083] This embodiment provides a magnetodielectric resin composition, comprising 4 g of epoxy resin A, 5 g of brominated epoxy resin B, 0.9 g of phenoxy resin C, 0.1 g of 2-MI, and 90 g of composite hexagonal magnetic filler B.

[0084] The magnetodielectric resin composition is used for the preparation of a copper clad laminate, and the specific method is the same as that in Example 1 to obtain the copper clad laminate.

[0085] Example 3

[0086] This embodiment provides a magnetodielectric resin composition, comprising 45 g of hydrocarbon resin, 5 g of BIPB initiator, and 50 g of composite hexagonal magnetic filler C.

[0087] The magnetodielectric resin composition is used for the preparation of a copper clad laminate, and the specific method is the same as that in Example 1 to obtain the copper clad laminate.

[0088] Example 4

[0089] This embodiment provides a magnetodielectric resin composition, which is only different from that in Example 2 in that the composite hexagonal magnetic filler B is replaced with the composite hexagonal magnetic filler D in equal mass.

[0090] The magnetodielectric resin composition is used for the preparation of a copper clad laminate, and the specific method is the same as that in Example 1 to obtain the copper clad laminate.

[0091] Example 5

[0092] This embodiment provides a magnetodielectric resin composition, which is only different from that in Example 2 in that the composite hexagonal magnetic filler B is replaced with the composite hexagonal magnetic filler F in equal mass.

[0093] The magnetic dielectric resin composition is used for the preparation of a copper clad laminate. The specific method is the same as that in Example 1, and the copper clad laminate is obtained.

[0094] Comparative Example 1

[0095] This comparative example provides a magnetic dielectric resin composition, which is only different from that in Example 1 in that the mass of the composite hexagonal magnetic filler A is adjusted to 8 g.

[0096] The magnetic dielectric resin composition is used for the preparation of a copper clad laminate. The specific method is the same as that in Example 1, and the copper clad laminate is obtained.

[0097] Comparative Example 2

[0098] This comparative example provides a magnetic dielectric resin composition, which is only different from that in Example 2 in that the mass of the composite hexagonal magnetic filler B is adjusted to 95 g.

[0099] The magnetic dielectric resin composition is used for the preparation of a copper clad laminate. The specific method is the same as that in Example 1, and the copper clad laminate is obtained.

[0100] Comparative Example 3

[0101] This comparative example provides a magnetic dielectric resin composition, which is only different from that in Example 2 in that the composite hexagonal magnetic filler B is replaced with the composite hexagonal magnetic filler E.

[0102] The magnetic dielectric resin composition is used for the preparation of a copper clad laminate. The specific method is the same as that in Example 1, and the copper clad laminate is obtained.

[0103] Comparative Example 4

[0104] This comparative example provides a magnetic dielectric resin composition, which is only different from that in Example 2 in that the composite hexagonal magnetic filler B is replaced with a simple mixture of 20 wt% M-type magnetic filler (BaFe 12 O 19 ), 40 wt% Y-type magnetic filler (BaCoFe6O 11 ), 30 wt% BaFe 15 O 23 and 10 wt% MnO, denoted as the hexagonal magnetic filler mixture.

[0105] The magnetic dielectric resin composition is used for the preparation of a copper clad laminate. The specific method is the same as that in Example 1, and the copper clad laminate is obtained.

[0106] Comparative Example 5

[0107] This comparative example provides a magnetodielectric resin composition, which is only different from that of Example 2 in that the composite hexagonal magnetic filler B is replaced with a Co2Z-type hexagonal magnetic filler. The Co2Z-type hexagonal magnetic filler is composed of Co2Z and MnO, and its preparation method includes:

[0108] Take Co2Z and MnO, perform physical dry mixing for 1 h to prepare a ring-shaped green body, and then sinter at 1100 °C for 4 h to obtain a sintered product; wet ball-mill and crush the sintered product in a ball mill at a rotation speed of 3000 r / min for 2 h, and the particle size of the zirconium beads is compounded at 1-10 mm; dry after ball milling to obtain the Co2Z-type hexagonal magnetic filler.

[0109] The magnetodielectric resin composition is used for the preparation of a copper clad laminate, and the specific method is the same as that of Example 1 to obtain the copper clad laminate.

[0110] Performance Test

[0111] (1) Sample preparation: Use a CNC milling machine to process the copper clad laminate into a ring-shaped sample (inner diameter 3.04 mm, outer diameter 6.96 mm, thickness 3 mm);

[0112] (2) Use an Agilent E5071C network analyzer + N1500 test system as the test instrument to test the relative magnetic permeability and magnetic loss tangent of the material at 2 GHz.

[0113] Test the performance of the copper clad laminates obtained in Examples 1-4 and Comparative Examples 1-5 according to the above performance test method, and summarize the components of the magnetodielectric resin composition and the performance test results of the copper clad laminates containing it, as shown in Table 2.

[0114] Table 2

[0115]

[0116]

[0117] Analysis:

[0118] As can be seen from Table 2, the copper clad laminates prepared in Examples 1 to 4 have high magnetic permeability, low high-frequency magnetic loss, and excellent comprehensive performance.

[0119] From the data results of Example 5 and Example 2, it can be seen that if the mass fraction of M-type magnetic molecules in the composite hexagonal magnetic filler is too large, the magnetic permeability of the material is low.

[0120] From the data results of Comparative Example 1 and Example 1, it can be seen that too low a filler addition ratio will result in a small magnetic permeability.

[0121] From the data results of Comparative Example 2 and Example 2, it can be seen that if the filler addition ratio is too high, the processability is poor and qualified products cannot be prepared.

[0122] From the data results of Comparative Example 3 and Example 2, it can be seen that if there are no M-type magnetic molecules in the composite hexagonal magnetic filler, the magnetic loss tangent of the material at 2 GHz is high.

[0123] From the data results of Comparative Example 4 and Example 2, it can be seen that if the M-type magnetic filler (BaFe 12 O 19 ), Y-type magnetic filler (BaCoFe6O 11 ), BaFe 15 O 23 and MnO are mixed in a physical mixing manner, the relative magnetic permeability of the material is low, and the magnetic loss tangent of the material at 2 GHz is high.

[0124] From the data results of Comparative Example 5 and Example 2, it can be seen that when the hexagonal magnetic filler is Co2Z-type hexagonal magnetic filler, the magnetic permeability of the copper clad laminate is low.

[0125] In summary, the copper clad laminate prepared from the composition provided by the present invention has excellent comprehensive properties such as high magnetic permeability and small magnetic loss, and can meet the performance requirements of the magnetodielectric substrate.

[0126] The above is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A magnetodielectric resin composition, characterized in that, The magnetic dielectric resin composition includes a combination of a resin and composite hexagonal magnetic fillers, and the molecules of the composite hexagonal magnetic fillers include a combination of M-type magnetic molecules and Y-type magnetic molecules; The chemical formula of the M-type magnetic molecule is BaFe 12 O 19 ; the chemical formula of the Y-type magnetic molecule is BaMeFe6O 11 , where Me includes any one or a combination of at least two of Co, Ca or Sr; Based on the total mass of the magnetic dielectric resin composition being 100%, the mass fraction of the composite hexagonal magnetic fillers is 20 - 90%.

2. The magnetodielectric resin composition according to claim 1, wherein The average particle size of the composite hexagonal magnetic fillers is 0.1 - 30 μm; Preferably, based on the total mass of the composite hexagonal magnetic fillers being 100%, the mass fraction of the M-type magnetic molecules is 5 - 20%; Preferably, the molecule of the composite hexagonal magnetic filler further includes BaFe 15 O 23 ; Preferably, based on the total mass of the composite hexagonal magnetic filler being 100%, the mass fraction of BaFe 15 O 23 is 15 to 30%; Preferably, the molecules of the composite hexagonal magnetic fillers further include single metal oxide molecules; Preferably, the single metal oxide molecules include any one or a combination of at least two of manganese oxide molecules, zinc oxide molecules, nickel oxide molecules, or copper oxide molecules; Preferably, based on the total mass of the composite hexagonal magnetic fillers being 100%, the mass fraction of the single metal oxide molecules is 5 - 10%.

3. The magnetodielectric resin composition according to claim 1 or 2, wherein The composite hexagonal magnetic fillers are prepared by the following method, and the method includes: Co-firing the M-type magnetic material and the Y-type magnetic material, or co-firing the raw materials of the M-type magnetic material and the raw materials of the Y-type magnetic material to obtain the composite hexagonal magnetic fillers; The chemical formula of the M-type magnetic material is BaFe 12 O 19 ; the chemical formula of the Y-type magnetic material is BaMeFe6O 11 , where Me includes any one or a combination of at least two of Co, Ca or Sr; Preferably, the temperatures of the co-firing and the co-mixing are each independently 700 - 1300 °C; Preferably, the times of the co-firing and the co-mixing are each independently 2 - 8 h.

4. The magnetodielectric resin composition according to any one of claims 1 to 3, characterized in that The resin includes any one or a combination of at least two of epoxy resin, cyanate resin, polyphenylene ether resin, polybutadiene resin, styrene-butadiene resin, bismaleimide-triazine resin, bismaleimide resin, polytetrafluoroethylene resin, polyimide resin, phenolic resin, acrylic resin, liquid crystal resin, benzoxazine resin, nitrile rubber, carboxyl-terminated nitrile rubber, or hydroxyl-terminated nitrile rubber; Preferably, based on the total mass of the magnetic dielectric resin composition being 100%, the mass fraction of the resin is 10 - 80%.

5. The magnetodielectric resin composition according to any one of claims 1-4, characterized in that The magnetic dielectric resin composition further includes non-magnetic fillers and a promoter; Preferably, the non-magnetic fillers include any one or a combination of at least two of silica, titanium dioxide, barium titanate, strontium titanate, magnesium titanate, calcium titanate, strontium barium titanate, barium calcium titanate, lead titanate, lead zirconate titanate, lead lanthanum zirconate titanate, barium lanthanum titanate, barium zirconate titanate, hafnium dioxide, lead magnesium niobate, barium magnesium niobate, lithium niobate, potassium niobate, strontium aluminum tantalate, potassium tantalum niobate, strontium barium niobate, barium lead niobate, barium titanium niobate, bismuth strontium tantalate, bismuth titanate, rubidium barium titanate, copper titanate, or lead titanate-lead magnesium niobate; Preferably, the promoter includes any one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, or 1-cyanoethyl-2-methylimidazole; Preferably, the magnetic dielectric resin composition further includes an initiator; Preferably, the initiator includes any one or a combination of at least two of a,a'-bis(tert-butylperoxy-m-isopropylbenzene)benzene, dicumyl peroxide, tert-butylcumyl peroxide, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, tert-butyl octoate, tert-butyl perbenzoate, triethylamine, triethylamine salt compound, quaternary ammonium salt compound, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, imidazoles, tripentylphenol amide, monophenol compound, polyphenol compound, boron trifluoride, complex of boron trifluoride and organic compound, phosphoric acid or triphenyl phosphite; Preferably, the magnetodielectric resin composition further includes a crosslinking agent; Preferably, the crosslinking agent includes any one or a combination of at least two of triallyl isocyanurate, poly(triallyl isocyanurate), triallyl cyanurate, trimethacrylic acid, diallyl phthalate, divinylbenzene or acrylate; 6. A prepreg, characterized in that, The prepreg includes a reinforcing material and the magnetodielectric resin composition according to any one of claims 1-5 adhered to the reinforcing material; Preferably, the reinforcing material includes a glass fiber cloth.

7. A magnetic film, characterized in that, The magnetic film includes the magnetodielectric resin composition according to any one of claims 1-5.

8. A magnetic paste, characterized in that, The magnetic paste includes the magnetodielectric resin composition according to any one of claims 1-5.

9. A metal-clad laminate, characterized in that, The metal-clad laminate includes at least one prepreg according to claim 6, and metal foil is covered on at least one surface after the prepregs are laminated.

10. A printed circuit board, characterized in that, The printed circuit board includes at least one of the prepreg according to claim 6 and the metal-clad laminate according to claim 9.

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