Resin composition and use thereof

Abstract

The present invention provides a resin composition and a use thereof. The resin composition comprises the following components: (A) high-dielectric-constant powder, (B) a maleimide compound, and (C) other thermosetting compounds. Based on the total volume of the component (A) being 100%, the proportion of particles having a particle size of 1.0-5.0 μm is not less than 50%. The component (A) has a specific surface area of 1-10 m2 / g. The component (A) is surface-modified with an anilino coupling agent. In the resin composition provided by the present invention, by adding the high-dielectric-constant powder that has the specific particle size and surface area and is surface-modified with the anilino coupling agent, it can be ensured that the bonding force between a C-staged cured resin composition and an ultra-roughened copper foil of greater than 0.4 N / mm, while the resin composition also has a high dielectric constant, a low dielectric loss tangent, a low thermal expansion coefficient, a high glass transition temperature, and the like.

Description

A resin composition and its application Technical Field

[0001] This invention belongs to the field of printed circuit board technology and relates to a resin composition and its application. Background Technology

[0002] Wireless communication has become an essential part of life, and antennas, as key devices for realizing wireless communication, are inevitably moving towards higher frequencies with the large-scale development of 5G (5th generation mobile communication system) and the development of 6G (6th generation mobile communication system). The higher the signal frequency, the greater the dielectric loss. To suppress this, the dielectric layer must be made of a material with a small dielectric loss tangent. On the other hand, with the trend towards lighter, thinner, shorter, and smaller electronic products, antenna miniaturization demands dielectric layers with high dielectric constants. To meet the miniaturization and integration requirements of 5G and 6G antennas, antenna packaging is also necessary, which also requires low warpage properties of the dielectric layer, necessitating a low coefficient of thermal expansion.

[0003] The relative permittivity (D) of the substrate material k The larger the relative permittivity (D) of the substrate material, the smaller the wavelength of signal propagation. k This technology enables the miniaturization of antennas or power amplifier devices. Existing technologies typically fill a resin matrix with high-dielectric-constant powder to obtain a high-dielectric-constant dielectric layer, such as CN116457417A. However, this does not solve the problem of a large dielectric loss tangent, failing to meet the requirements of low signal transmission loss in high-frequency electronic products. CN118234802A, by employing a resin composition with a specific structure, still cannot solve the problem of a large dielectric loss tangent. Furthermore, the glass transition temperature of the dielectric layer is low, failing to meet the high heat resistance requirements of packaging, and posing a risk of reliability failure during processing.

[0004] In the manufacturing process of multilayer printed circuit boards (PCBs), prepreg and core board are laminated together. During component mounting, the PCB or packaging substrate typically undergoes a high temperature of around 230–260°C. If the adhesion between the prepreg and the inner copper layer is insufficient, thermal reliability is poor, and the multilayer board is prone to delamination and blowout. However, the inner copper foil differs from ordinary copper foil; its surface roughness is extremely low. The industry often employs ultra-roughening surface treatment on the inner copper foil to enhance the adhesion between the copper foil and the prepreg, while simultaneously ensuring a low profile, which is beneficial for signal integrity. In practical applications, the adhesion between resin compositions filled with high dielectric constant powder and ultra-roughened copper foil after C-stage curing is often relatively low, presenting a challenge in balancing reliability and signal integrity.

[0005] Therefore, there is an urgent need in the field to develop a resin composition that combines high dielectric constant, low dielectric loss tangent, low coefficient of thermal expansion, high glass transition temperature, and high bonding strength with ultra-coarsened copper foil, making it suitable for use in the manufacture of insulating layers for printed circuit boards. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this invention is to provide a resin composition and its application.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a resin composition comprising the following components: (A) a high dielectric constant powder, (B) a maleimide compound, and (C) other thermosetting compounds;

[0009] Based on the total volume of component (A) as 100%, the proportion of particles with a particle size of 1.0 to 5.0 μm is not less than 50%, for example, it can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0010] The specific surface area (BET) of component (A) is 1–10 m². 2 / g, for example, can be 1m 2 / g, 1.5m 2 / g、2m 2 / g, 2.5m 2 / g、3m 2 / g, 3.5m 2 / g、4m 2 / g, 4.5m 2 / g、5m 2 / g, 5.5m 2 / g、6m 2 / g, 6.5m 2 / g、7m 2 / g, 7.5m 2 / g、8m 2 / g, 8.5m 2 / g、9m 2 / g, 9.5m 2 / g or 10m 2 / g, and the specific point values ​​between the above point values, due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range;

[0011] The (A) component is surface modified with a phenylamino coupling agent.

[0012] The resin composition provided by this invention, by incorporating high-dielectric-constant powder with a specific particle size and specific surface area and surface modified with a phenylamino coupling agent, ensures that the bonding force between the C-stage cured resin composition and the ultra-roughened copper foil is greater than 0.4 N / mm. Simultaneously, this resin composition also possesses high dielectric constant, low dielectric loss tangent, low coefficient of thermal expansion, and high glass transition temperature, making it suitable for high-frequency signal antenna module applications. The inventors hypothesize the following principle: the specific specific surface area and particle size distribution of the high-dielectric-constant powder prevent agglomeration due to excessively small particle size, resulting in good powder dispersibility in the resin system; simultaneously, the specific surface modification treatment with the coupling agent reduces the number of water-absorbing functional groups such as hydroxyl groups on the powder surface, making it less susceptible to moisture absorption in air and inhibiting the dissolution of A-site metals such as Ca and Sr from the powder. This solves the adverse effects of the high-dielectric-constant powder on the bonding force and dielectric loss tangent of the ultra-roughened copper foil.

[0013] Preferably, the phenylamino coupling agent comprises a coupling agent having the structure shown in formula (1): (R 1 O)3Si-C m H 2m -R 2 Equation (1);

[0014] Among them, R 1 Selected from methyl or ethyl, R 2 Selected from phenylamino, m is selected from an integer between 3 and 12 (e.g., 3, 4, 5, 6, 7, 8, 9, 10, 11, 12).

[0015] For example, the phenylamino coupling agent can be selected from Shin-Etsu Chemical's KBM-573 (N-phenyl-3-aminopropyltrimethoxysilane, structural formula: Shin-Etsu Chemical's KBM-6803 (N-phenyl-8-aminooctyltrimethoxysilane, structural formula: )wait.

[0016] Preferably, based on the total volume of component (A) as 100%, the proportion of particles with a particle size of 1.0 to 5.0 μm is not less than 80%, for example, it can be 80%, 82%, 84%, 85%, 86%, 88%, 90%, 92%, 94%, 95%, 96%, 98%, or 100%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0017] Preferably, the average particle size (D50) of component (A) is 1.0 to 3.0 μm, for example, it can be 1.0 μm, 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm, 2.0 μm, 2.2 μm, 2.4 μm, 2.6 μm, 2.8 μm, 3.0 μm, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0018] In this invention, by selecting different filters during the preparation of component (A), it is possible to obtain surface-modified components (A) with different particle sizes and distributions, as well as different specific surface areas.

[0019] In this invention, the particle size was obtained using an MS3000 Malvern laser particle size analyzer.

[0020] Preferably, component (A) comprises a titanium-based inorganic filler material that has undergone surface modification treatment with a phenylamino coupling agent.

[0021] Preferably, based on the total mass of component (A) as 100%, the content of the phenylamino coupling agent is 1‰ to 10‰, for example, it can be 1‰, 2‰, 3‰, 4‰, 5‰, 6‰, 7‰, 8‰, 9‰ or 10‰, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0022] Preferably, component (A) may also be surface modified with other amino coupling agents besides phenylamino coupling agents, such as commercially available ones, such as: KBM-602 (N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane), KBM-603 (N-2-(aminoethyl)-3-aminopropyltrimethoxysilane), KBM-903 (3-aminopropyltrimethoxysilane), KBE-903 (3-aminoethyltrimethoxysilane), KBE-9103P (partially hydrolyzed product of 3-triethoxymalkyl-N-(1,3-dimethyl-butylene)propylamine), etc.

[0023] Preferably, the titanium-based inorganic filler material includes titanium dioxide and / or a metal titanate salt, with a metal titanate salt being more preferred.

[0024] Preferably, the titanate metal salt includes any one or a combination of at least two of the following: alkali metal titanate, alkaline earth metal titanate, and lead titanate, with alkaline earth metal titanate being the most preferred.

[0025] Preferably, the alkaline earth metal titanate includes any one or a combination of at least two of barium titanate, calcium titanate, strontium titanate, magnesium titanate, zinc titanate, lanthanum titanate, neodymium titanate, and aluminum titanate, with calcium titanate and / or strontium titanate being more preferred.

[0026] Preferably, component (B) comprises an addition reaction product of a maleimide compound b1 containing at least two (e.g., two, three, four, etc.) N-substituted maleimide groups in one molecule and an amine compound b2 containing at least two (e.g., two, three, four, etc.) primary amino groups in one molecule.

[0027] Preferably, the raw materials for preparing the addition reactant, by weight, include: maleimide compound b1 containing at least two N-substituted maleimide groups in one molecule: 34 to 96 parts (e.g., 38 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 76 parts, 78 parts, 80 parts, 82 parts). 84, 86, 88, 90, 92, 94 or 96 parts); amine compounds containing at least two primary amino groups in one molecule: 2 to 40 parts (e.g., 4, 6, 8, 10, 12, 14, 15, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38 or 40 parts).

[0028] Preferably, the maleimide compound b1 is a maleimide compound containing two N-substituted maleimide groups in one molecule.

[0029] Preferably, the amine compound b2 is an amine compound containing two primary amino groups in one molecule.

[0030] Preferably, the amine compound b2 containing two primary amino groups in one molecule includes a siloxane compound containing two primary amino groups in one molecule.

[0031] The present invention does not limit the type of component (C), as long as it can react with the imide ring double bond on the maleimide compound (B). Preferably, (C) includes any one or a combination of at least two of the following: compounds having intramolecular carbon-carbon unsaturated double bonds, acid anhydride compounds, reactive ester compounds, cyanate ester resins, or epoxy resins. From the perspective of lower dielectric loss tangent, compounds having intramolecular carbon-carbon unsaturated double bonds are preferred.

[0032] Preferably, the compound having carbon-carbon unsaturated double bonds in the molecule includes any one or a combination of at least two of unsaturated polyphenylene ether compounds, polyfunctional vinyl compounds, allyl compounds, acrylate compounds, methacrylate compounds, acenaphthene compounds, or polybutadiene compounds, and more preferably any one or a combination of at least two of unsaturated polyphenylene ether compounds, polyfunctional vinyl compounds, allyl compounds, or acenaphthene compounds.

[0033] Preferably, the amount of component (A) is 20 to 350 parts, more preferably 50 to 250 parts, the amount of component (B) is 30 to 95 parts, and the amount of component (C) is 5 to 70 parts.

[0034] The "parts" and "parts by weight" used in this invention are calculated based on solid content and do not include solvents, dispersants, etc.

[0035] Preferably, the amount of component (A) can be, for example, 20 parts, 30 parts, 40 parts, 50 parts, 70 parts, 90 parts, 110 parts, 130 parts, 150 parts, 170 parts, 190 parts, 210 parts, 230 parts, 250 parts, 270 parts, 290 parts, 310 parts, 330 parts, or 350 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0036] Preferably, the amount of component (B) can be, for example, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts or 95 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0037] Preferably, the amount of component (C) can be, for example, 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts or 70 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0038] From the perspective of lower dielectric loss tangent, the resin composition also includes a styrene-based elastomer.

[0039] Preferably, the amount of the styrene-based elastomer is 5 to 40 parts, for example, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0040] Preferably, the resin composition further includes other fillers.

[0041] Preferably, the other fillers include any one or a combination of at least two of the following: silica, magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, boehmite, aluminum hydroxide, silicone rubber powder, and organosilicon composite powder, with silica being the most preferred.

[0042] Preferably, the other fillers are modified with coupling agents.

[0043] Preferably, the amount of the other filler is 5 to 100 parts, for example, 6 parts, 8 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts or 100 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0044] Preferably, the resin composition further includes a curing accelerator.

[0045] Preferably, the curing accelerator includes any one or a combination of at least two of the following: acidic curing accelerators, organophosphorus curing accelerators, imidazole curing accelerators, pyridine curing accelerators, amine curing accelerators, peroxides, or organometallic salts.

[0046] Preferably, the amount of the curing accelerator is 0.01 to 5 parts, for example, 0.01 parts, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts, 4 parts or 5 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0047] Preferably, the resin composition further includes a flame retardant.

[0048] Preferably, the amount of flame retardant is 2 to 30 parts, for example, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0049] Solvents may also be added to the above-mentioned resin composition. The amount of solvent added is selected by those skilled in the art based on experience and process requirements, so that the resin composition reaches a suitable viscosity for use, facilitating coating and other processes. During subsequent drying, semi-curing, or full curing stages, the solvent in the resin composition will partially or completely evaporate.

[0050] The solvent used in this invention is not particularly limited, and generally can be ketones such as acetone, butanone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, or butanol; alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, or butyl carbitol; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone. The solvent can be used alone or in mixtures of two or more. Preferably, ketones such as acetone, butanone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are used.

[0051] The resin composition provided by the present invention is prepared by the following method, the preparation method comprising: mixing and dispersing the components in the resin composition evenly to obtain the resin composition.

[0052] In a second aspect, the present invention provides a prepreg comprising a substrate and a resin composition as described in the first aspect attached to the substrate.

[0053] Preferably, the resin composition is adhered to the substrate after impregnation and drying.

[0054] Thirdly, the present invention provides a resin film comprising the resin composition as described in the first aspect.

[0055] Fourthly, the present invention provides a laminate comprising at least one prepreg as described in the second aspect.

[0056] Fifthly, the present invention provides a metal foil laminate comprising one or at least two laminated prepregs as described in the second aspect, and metal foils located on one or both sides of the laminated prepregs.

[0057] In a sixth aspect, the present invention provides a printed circuit board comprising at least one of the prepreg as described in the second aspect, a laminate as described in the fourth aspect, and a metal foil laminate as described in the fifth aspect.

[0058] In a seventh aspect, the present invention provides an antenna device comprising a metal foil laminate as described in the fifth aspect or a printed circuit board as described in the sixth aspect.

[0059] Eighthly, the present invention provides an antenna module, the antenna module comprising the antenna device as described in the seventh aspect.

[0060] In a ninth aspect, the present invention provides a communication device comprising a baseband signal processing circuit and an antenna module as described in the eighth aspect.

[0061] Compared with the prior art, the present invention has at least the following beneficial effects:

[0062] The resin composition provided by the present invention, by adding high dielectric constant powder with specific particle size and specific surface area and surface modified by phenylamino coupling agent, can ensure that the bonding force between the C-stage cured resin composition and the ultra-roughened copper foil is greater than 0.4 N / mm. At the same time, the resin composition also has high dielectric constant, low dielectric loss tangent, low coefficient of thermal expansion and high glass transition temperature. Detailed Implementation

[0063] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0064] The raw materials used in the following preparation examples are as follows:

[0065] ST-A, Strontium titanate, average particle size D 50 1.5μm, Fuji Titanium Industry Co., Ltd., Japan;

[0066] CT, calcium titanate, average particle size D 50 1.9μm, Fuji Titanium Industry Co., Ltd., Japan;

[0067] ST-03, Strontium titanate, average particle size D 50 0.9μm, Fuji Titanium Industry Co., Ltd., Japan;

[0068] KBM-573, N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Silicon Industries, Ltd., Japan;

[0069] KBM-6803, N-phenyl-8-aminooctyltrimethoxysilane, Shin-Etsu Silicon Industries, Ltd., Japan.

[0070] Preparation Example 1

[0071] This preparation example provides a modified strontium titanate, and the preparation method includes the following steps:

[0072] 100 parts by weight of strontium titanate ST-A were placed in a mixer. While spraying vaporized phenylamino coupling agent (0.250 parts by weight, N-phenyl-3-aminopropyltrimethoxysilane, KBM-573, Shin-Etsu Chemical) onto the strontium titanate, the mixture was stirred for 10 minutes. The modified filler was then sieved using a filter to obtain modified strontium titanate, designated as modified strontium titanate 1. The proportion of particles with a diameter of 1.0–5.0 μm was 75%, and the specific surface area was 4.8 m². 2 / g.

[0073] Preparation Example 2

[0074] This preparation example provides a modified strontium titanate, and the preparation method includes the following steps:

[0075] 100 parts by weight of strontium titanate ST-A were placed in a mixer. While spraying vaporized phenylamino coupling agent (0.375 parts by weight of N-phenyl-8-aminooctyltrimethoxysilane, KBM-6803, Shin-Etsu Chemical) onto the strontium titanate, the mixture was stirred for 10 minutes. The modified filler was then sieved using a filter to obtain modified strontium titanate, denoted as modified strontium titanate 2. The proportion of particles with a diameter of 1.0–5.0 μm was 80%, and the specific surface area was 5.3 m². 2 / g.

[0076] Preparation Example 3

[0077] This preparation example provides a modified calcium titanate, and the preparation method includes the following steps:

[0078] 100 parts by weight of calcium titanate CT were placed in a mixer. While spraying vaporized phenylamino coupling agent (0.375 parts by weight, N-phenyl-3-aminopropyltrimethoxysilane, KBM-573, Shin-Etsu Chemical) onto the calcium titanate, the mixture was stirred for 10 minutes. The modified filler was then sieved using a filter screen to obtain modified calcium titanate with 70% particles having a diameter of 1.0–5.0 μm and a specific surface area of ​​4.5 m². 2 / g.

[0079] Comparative Preparation Example 1

[0080] The only difference between this comparative preparation example and Preparation Example 1 is that the phenylamino coupling agent (KBM-573) was replaced with an equal amount of methacrylsilane coupling agent (3-methacryloyloxypropyltrimethoxysilane, KBM-503, Shin-Etsu Chemical). The resulting modified strontium titanate is designated as modified strontium titanate D1, with 73% of particles having a size of 1.0–5.0 μm and a specific surface area of ​​4.4 m². 2 / g.

[0081] Comparative Preparation Example 2

[0082] The only difference between this comparative preparation example and Preparation Example 1 is that Strontium titanate ST-A was replaced with an equal amount of Strontium titanate ST-03. The resulting modified Strontium titanate is designated as modified Strontium titanate D2, with 45% of the particles having a particle size of 1.0–5.0 μm and a specific surface area of ​​7.2 m². 2 / g.

[0083] Comparative preparation example 3

[0084] The only difference between this comparative preparation example and Preparation Example 1 is that the amount of phenylamino coupling agent (KBM-573) was reduced to 0.05 parts by weight. The resulting modified strontium titanate, designated as modified strontium titanate D3, had a particle size of 1.0–5.0 μm, a particle size ratio of 64%, and a specific surface area of ​​0.9 m². 2 / g.

[0085] Comparative preparation example 4

[0086] The only difference between this comparative preparation example and Preparation Example 1 is that the amount of phenylamino coupling agent (KBM-573) is increased to 1.20 parts by weight. The resulting modified strontium titanate is designated as modified strontium titanate D4, with 90% of the particles having a particle size of 1.0–5.0 μm and a specific surface area of ​​11 m². 2 / g.

[0087] The modified strontium titanate or modified calcium titanate obtained from the preparation examples and comparative preparation examples were tested using the following methods:

[0088] (1) Proportion of particles with a diameter of 1.0 to 5.0 μm: Particle size was measured by laser diffraction. The instrument used was a Malvern laser particle size analyzer, model MS3000, which can obtain statistical data on Malvern particle size distribution (calculated as volume percentage). The volume percentage of particles with a diameter of 1.0 to 5.0 μm can be directly obtained from the statistical data.

[0089] (2) Average particle size: The particle size at which the volume percentage of the Malvern particle size distribution (calculated as a volume percentage) is 50%, i.e., D 50 ;

[0090] (3) Specific surface area: The specific surface area was tested using a specific surface area analyzer, model GeminiⅦ2390; the sample was treated in a high temperature oven at 110℃ for 2 hours, and 0.1~0.5g of the sample was weighed for testing, and the test was carried out in accordance with the operating procedures.

[0091] The test results are shown in Table 1.

[0092] Table 1

[0093] The raw materials used in the following embodiments and comparative examples are as follows:

[0094] (A) High dielectric constant powder: Preparation examples and comparative preparation examples are provided.

[0095] (B) Maleimide compounds

[0096] Maleimide compound 1 is prepared by the following steps:

[0097] In a three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 2 parts by weight of the amine compound Kayahard AA (3,3'-diethyl-4,4'-diaminodiphenylmethane, Nippon Kayaku Co., Ltd.), 4 parts by weight of X-22-161A (a siloxane compound with two primary amino groups at the molecular end, Shin-Etsu Chemical Co., Ltd.), 34 parts by weight of BMI-4000 (bis(4-(4-maleimide-phenoxy)phenyl)methane, Yamato Chemical Co., Ltd.), and 40 parts by weight of the solvent propylene glycol monomethyl ether were added. The mixture was reacted at 110°C for 240 min to obtain maleimide compound 1, denoted as mBMI.

[0098] Maleimide compound 2:

[0099] Phenylaralkyl polymaleimide compound, MIR-5000-60T, Nippon Kayaku Kogyo Co., Ltd.

[0100] (C) Other thermosetting compounds, specifically compounds with intramolecular carbon-carbon unsaturated double bonds.

[0101] OPE-2st 1200, a polyphenylene ether compound containing vinyl benzyl groups at the end, Mitsubishi Chemical Corporation of Japan;

[0102] ODV-XET, an aromatic vinyl copolymer with a vinyl benzyl end, Nippon Steel Chemical Co., Ltd.

[0103] (D) Styrene-based elastomers

[0104] DYNARON 9901P, styrene content 53%, JSR Corporation of Japan.

[0105] (E) Other packings

[0106] SC2500-SXJ, spherical silica modified with phenylaminosiloxane, average particle size D 50 It is 0.5μm, from Admatechs Co., Ltd., Japan.

[0107] (F) Flame retardant

[0108] PX-200, 1,3-phenylenetetra(2,6-dimethylphenyl) ester, Daihachi Chemical Co., Ltd., Japan.

[0109] Example 1

[0110] This embodiment provides a resin composition, the specific components and amounts (parts by weight) of which are shown in Table 2.

[0111] This embodiment also provides a prepreg and a laminate, the specific preparation method of which is as follows:

[0112] (1) Mix and disperse each component of the resin composition with the solvent toluene according to the formula in Table 2 to prepare a resin solution with a solid content of 70%.

[0113] (2) Impregnate the glass fiber cloth (3313L glass fiber cloth manufactured by Hubel in Taiwan, China) with the resin solution, and then heat and dry it in a forced-air oven at 160°C for 5 minutes to transform the resin composition in the varnish state into a semi-cured resin composition with a thickness of 0.10 mm to obtain the prepreg.

[0114] (3) Stack two (or eight) sheets of prepreg obtained in step (2) together, and press an electrolytic copper foil with a thickness of 12 μm onto the top and bottom sides of the stack. Press the stack at 220°C and 45 kg / cm² in a press. 2 Under the conditions of hot pressing and curing for 1.5 hours, a metal foil laminate with a core board thickness of 0.20 mm (or 0.80 mm) is obtained. After etching the copper foil of the metal foil laminate, a laminate with a thickness of 0.20 mm (or 0.80 mm) is obtained.

[0115] The performance of the metal foil-coated laminate / laminate is tested using the following specific methods:

[0116] (1) Dielectric constant D k and dielectric loss tangent D f A laminate measuring 100 mm in length, 100 mm in width, and 0.20 mm in thickness was used as a sample. After ultrasonic cleaning to remove surface impurities in deionized water, the sample was dried in a 105°C oven for 1 hour and then cooled to room temperature in a desiccator. The dielectric constant D at a frequency of 10 GHz was measured using a cavity resonator. k and dielectric loss tangent D f ;

[0117] (2) Glass transition temperature Tg: A laminate with a length of 60 mm, a width of 10 mm, and a thickness of 0.80 mm was used as a sample and measured using a dynamic mechanical thermal analyzer (DMA) at a heating rate of 10 °C / min. The result was taken as the transition peak temperature of tanδ, in °C.

[0118] (3) Planar thermal expansion coefficient XY-CTE: A laminate with a length of 60 mm, a width of 4 mm, and a thickness of 0.20 mm was used as the sample. The glass fiber warp direction was Y and the glass fiber weft direction was X. The sample was dried in an oven at 105℃ for 1 h and then cooled to room temperature in a desiccator. The mechanical thermal analysis (TMA) method was used for measurement. The heating rate was 10℃ / min. The temperature was increased from room temperature to 200℃ twice. After the first heating was completed and the sample was cooled to room temperature, it was put back into place for the second heating. The result was the planar thermal expansion coefficient at the second heating from 60℃ to 120℃, and the unit was ppm / ℃.

[0119] (4) Adhesion test of ultra-roughened metal foil: The electrolytic copper foil GTS-MP-18μm (manufactured by Furukawa Electric Industries) was pretreated with MEC CZ-8401 for glossy surface spraying, and then roughened with AP-3002 to obtain a low profile copper foil with a surface roughness Ra of 0.04μm; after prepreg was laminated onto the surface of the low profile copper foil, it was pressed together, and after curing, the peel strength of the copper foil was tested. The higher the peel strength, the better.

[0120] The performance test results are shown in Table 2.

[0121] Examples 2-8, Comparative Examples 1-5

[0122] A resin composition and a prepreg and laminate containing the same are different from those in Example 1 in that the formulation of the resin composition is different, as shown in Tables 2 and 3; wherein the amount of each component is in "parts by weight"; the preparation method and performance testing method of the prepreg and laminate are the same as those in Example 1.

[0123] Table 2

[0124] Table 3

[0125] As can be seen from Table 2, the laminate prepared by the resin composition provided in the embodiments of the present invention has a high dielectric constant (4.0-14.7), a low dielectric loss tangent (0.0023-0.0038), a low coefficient of thermal expansion (9.8-11.4 ppm / ℃), a high glass transition temperature (244-274℃), and the resin composition has a high bonding force with the ultra-roughened copper foil (0.55-0.69 N / mm).

[0126] Compared to Example 1, Comparative Example 1 used strontium titanate without silane coupling agent, and Comparative Example 2 used strontium titanate modified with non-phenylaminosilane coupling agent. In addition to the decrease in adhesion to the ultra-roughened metal foil, it also caused a decrease in glass transition temperature. Comparative Example 3 used strontium titanate with a particle size of less than 1 μm and a particle size of 1.0 to 5.0 μm accounting for less than 50%. Due to the insufficient particle size of the filler, the riveting ability with the surface contour of the metal foil decreased, which ultimately led to a decrease in adhesion to the ultra-roughened metal foil. Comparative Examples 4 and 5 used strontium titanate treated with different amounts of phenylamino coupling agent. When the amount was too small, the affinity decreased. When the amount was too large, the resinification degree of the filler increased, and the riveting ability with the surface contour of the metal foil decreased. In both cases, it ultimately led to a decrease in adhesion to the ultra-roughened metal foil and a decrease in glass transition temperature.

[0127] The applicant declares that the above embodiments illustrate the resin composition and its application, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized by comprising: The resin composition comprises the following components: (A) high dielectric constant powder, (B) maleimide compound, and (C) other thermosetting compounds; Based on the total volume of component (A) as 100%, the proportion of particles with a particle size of 1.0 to 5.0 μm is not less than 50%; The specific surface area of the (A) component is 1 to 10 m 2 / g; The (A) component is surface modified with a phenylamino coupling agent.

2. The resin composition according to claim 1, characterized by The phenylamino coupling agent includes a coupling agent having a structure represented by the following formula (1): 1 O)3Si-C m H 2m -R 2 Formula (1); Among them, R 1 Selected from methyl or ethyl, R 2 Selected from phenylamino, m is selected from an integer between 3 and 12; Preferably, based on the total volume of component (A) as 100%, the proportion of particles with a particle size of 1.0 to 5.0 μm is not less than 80%; Preferably, the average particle size of component (A) is 1.0–3.0 μm; Preferably, component (A) comprises a titanium-based inorganic filler material that has undergone surface modification treatment with a phenylamino coupling agent; Preferably, the content of the phenylamino coupling agent is 1‰ to 10‰, based on the total mass of component (A) as 100%. Preferably, the titanium-based inorganic filler material includes titanium dioxide and / or a metal titanate salt, preferably a metal titanate salt; Preferably, the titanate metal salt includes any one or a combination of at least two of the following: alkali metal titanate, alkaline earth metal titanate, and lead titanate, with alkaline earth metal titanate being the most preferred. Preferably, the alkaline earth metal titanate includes any one or a combination of at least two of barium titanate, calcium titanate, strontium titanate, magnesium titanate, zinc titanate, lanthanum titanate, neodymium titanate, and aluminum titanate, with calcium titanate and / or strontium titanate being more preferred. Preferably, component (B) comprises an addition reaction product of maleimide compound b1 containing at least two N-substituted maleimide groups in one molecule and amine compound b2 containing at least two primary amino groups in one molecule; Preferably, the raw materials for preparing the addition reactant include, by weight parts: maleimide compound b1 containing at least two N-substituted maleimide groups in one molecule: 34 to 96 parts; amine compound b2 containing at least two primary amino groups in one molecule: 2 to 40 parts; Preferably, the maleimide compound b1 is a maleimide compound containing two N-substituted maleimide groups in one molecule; Preferably, the amine compound b2 is an amine compound containing two primary amino groups in one molecule; Preferably, the amine compound b2 containing two primary amino groups in one molecule includes a siloxane compound containing two primary amino groups in one molecule; Preferably, (C) includes any one or a combination of at least two of the following: compounds having carbon-carbon unsaturated double bonds in the molecule, acid anhydride compounds, active ester compounds, cyanate ester resins or epoxy resins, preferably compounds having carbon-carbon unsaturated double bonds in the molecule. Preferably, the compound having carbon-carbon unsaturated double bonds in the molecule includes any one or a combination of at least two of unsaturated polyphenylene ether compounds, polyfunctional vinyl compounds, allyl compounds, acrylate compounds, methacrylate compounds, acenaphthene compounds, or polybutadiene compounds, and more preferably any one or a combination of at least two of unsaturated polyphenylene ether compounds, polyfunctional vinyl compounds, allyl compounds, or acenaphthene compounds. Preferably, the amount of component (A) is 20 to 350 parts, more preferably 50 to 250 parts, the amount of component (B) is 30 to 95 parts, and the amount of component (C) is 5 to 70 parts; Preferably, the resin composition further includes a styrene-based elastomer; Preferably, the amount of the styrene-based elastomer is 5 to 40 parts; Preferably, the resin composition further includes other fillers; Preferably, the other fillers include any one or a combination of at least two of the following: silica, magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, boehmite, aluminum hydroxide, silicone rubber powder, and organosilicon composite powder, with silica being the most preferred. Preferably, the other fillers are modified with a coupling agent; Preferably, the amount of the other fillers used is 5 to 100 parts; Preferably, the resin composition further includes a flame retardant; Preferably, the amount of the flame retardant is 2 to 30 parts.

3. A prepreg, characterized by, The prepreg comprises a substrate and a resin composition as described in claim 1 or 2 attached to the substrate; Preferably, the resin composition is adhered to the substrate after impregnation and drying.

4. A resin film, characterized by, The resin film comprises the resin composition as described in claim 1 or 2.

5. A laminate characterized by The laminate comprises at least one sheet of prepreg as described in claim 3.

6. A metal-clad laminate characterized by comprising: The metal foil laminate includes one or at least two stacked prepregs as described in claim 3, and metal foils located on one or both sides of the stacked prepregs.

7. A printed circuit board, characterized in that, The printed circuit board includes at least one of the prepreg as described in claim 3, the laminate as described in claim 5, and the metal foil-coated laminate as described in claim 6.

8. An antenna device, characterized by The antenna device includes a metal foil laminate as described in claim 6 or a printed circuit board as described in claim 7.

9. An antenna module, characterized in that, The antenna module includes the antenna device as described in claim 8.

10. A communication device, characterized in that, The communication device includes a baseband signal processing circuit and an antenna module as described in claim 9.

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