Halogen-free resin composition and use thereof

Abstract

This invention provides a halogen-free resin composition and its applications. The halogen-free resin composition comprises the following components in parts by weight: 100 parts by weight of epoxy resin, including at least epoxidized polybutadiene resin; 50-100 parts by weight of p-aminophenol-modified maleimide resin, wherein the weight-average molecular weight of the p-aminophenol-modified maleimide resin is 500-800; and 70-90 parts by weight of benzoxazine resin. The halogen-free resin composition of this invention has a high heat resistance (Tg), excellent heat resistance, effectively reduces the warpage height of resin composition products, has a low coefficient of thermal expansion, and improves the reliability of laminated sheets with polyphenylene ether resin systems or hydrocarbon resin systems. It also provides excellent processability for prepregs and printed circuit board laminates.

Description

Technical Field

[0001] This invention belongs to the field of laminate technology and relates to a halogen-free resin composition and its application. Background Technology

[0002] With the completion of 5G backbone network construction in some parts of China, the supporting 5G application equipment is being rapidly deployed. This equipment requires good electrical performance and has high cost requirements. While using low-dielectric materials for all PCB layers can meet electrical performance needs, the cost is high. As a typical balanced design, some design layers in the PCB design are replaced with the relatively inexpensive FR-4 material, while critical signal layers still use the more expensive low-dielectric material. This structure requires the FR-4 material and the low-dielectric material to use the same thermosetting conditions.

[0003] Low dielectric materials mostly use polyphenylene ether resin, hydrocarbon resin and other materials as the main materials. They are free radical reaction materials. When common FR-4 materials are mixed with such materials, the mixed-pressed boards are very prone to a sharp decrease in reliability, which poses a great challenge to the reliability of the products.

[0004] Therefore, in this field, there is a desire to develop a resin composition that has good heat resistance, good processability, and can solve the problem of reliability in mixed pressing. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a halogen-free resin composition and its application.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] On one hand, the present invention provides a halogen-free resin composition comprising the following components in parts by weight:

[0008] (A) 100 parts by weight of epoxy resin, wherein at least epoxy polybutadiene resin is included;

[0009] (B) 50-100 parts by weight of p-aminophenol modified maleimide resin, wherein the weight-average molecular weight of the p-aminophenol modified maleimide resin is 500-800.

[0010] (C) 70-90 parts by weight of benzoxazine resin.

[0011] In this invention, the combination of epoxy resin, p-aminophenol-modified maleimide resin, and benzoxazine resin results in a halogen-free resin composition with a high Tg, excellent heat resistance, effectively reduced warpage height of the resin composition product, low coefficient of thermal expansion, improved reliability of mixed-pressed boards with polyphenylene ether resin system or hydrocarbon resin system, and excellent processability of prepreg and printed circuit board laminates.

[0012] In this invention, the epoxy polybutadiene resin contained in the epoxy resin can significantly increase the glass transition temperature of the resin composition, improve the processability of the laminate, and enhance the reliability of the mixed-pressed sheets with polyphenylene ether resin systems or hydrocarbon resin systems. The combination of aminophenol-modified maleimide resin and benzoxazine resin results in a resin composition with lower viscosity and better heat resistance. The introduction of epoxy polybutadiene resin into the epoxy resin increases the crosslinking density with the maleimide resin, reducing the dielectric constant and dielectric loss.

[0013] In this invention, the amount of the p-aminophenol-modified maleimide resin can be 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, or 100 parts by weight. In this invention, if the amount of the p-aminophenol-modified maleimide resin is less than 50 parts by weight, the heat resistance, Tg, and peel strength of the resin composition will decrease; if the amount of the p-aminophenol-modified maleimide resin is greater than 100 parts by weight, the water absorption rate of the resin composition will increase, and the processability will deteriorate.

[0014] In this invention, the amount of benzoxazine resin can be 70 parts by weight, 73 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 83 parts by weight, 85 parts by weight, 88 parts by weight, or 90 parts by weight. In this invention, if the amount of benzoxazine resin is less than 70 parts by weight, the water absorption rate of the resin composition increases, and the processability deteriorates; if the amount of benzoxazine resin is greater than 90 parts by weight, the heat resistance reliability decreases when the resin composition is mixed with polyphenylene ether resin, hydrocarbon resin, or other systems.

[0015] Preferably, the epoxy resin comprises 5-20 parts by weight of epoxidized polybutadiene resin, for example, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, or 20 parts by weight. In this invention, if the amount of epoxidized polybutadiene resin is less than 5 parts by weight, the heat resistance reliability decreases when the resin composition is mixed with polyphenylene ether resin, hydrocarbon resin, or other systems; if the amount of epoxidized polybutadiene resin is greater than 20 parts by weight, the manufacturing processability of the metal foil laminate deteriorates, and a good process yield cannot be obtained.

[0016] The "parts" and "parts by weight" used in this invention are calculated based on solid content and do not include solvents, dispersants, etc.

[0017] Preferably, the epoxy resin also includes other epoxy resins.

[0018] Preferably, the other epoxy resins include trifunctional epoxy resins and / or tetrafunctional epoxy resins.

[0019] Preferably, the other epoxy resins include any one or a combination of at least two of the following: dicyclopentadiene epoxy resin, dimethylphenol-type phenolic epoxy resin, tetramethylbiphenyl epoxy resin, biphenyl epoxy resin, phenol-type phenolic epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, C1-C6 alkyl epoxy resin, MDI-modified epoxy resin, o-cresol-type phenolic epoxy resin, or naphthalene-containing epoxy resin.

[0020] In this invention, the weight-average molecular weight of the p-aminophenol-modified maleimide resin is controlled between 500 and 800, for example, 500, 550, 600, 650, 700, 750, or 800. If the weight-average molecular weight of the p-aminophenol-modified maleimide resin is too low, the resin composition is difficult to cure completely; if the weight-average molecular weight of the p-aminophenol-modified maleimide resin is too high, the coefficient of thermal expansion will increase.

[0021] In this invention, the weight-average molecular weight of the p-aminophenol-modified maleimide resin is obtained by GPC (gel permeation chromatography) during the synthesis process. Specifically, during the synthesis of the p-aminophenol-modified maleimide resin, samples are taken at regular intervals. These samples are dissolved in tetrahydrofuran (THF), shaken well, and then placed in a GPC apparatus to test their weight-average molecular weight. If the weight-average molecular weight reaches the range specified in this invention, the synthesis reaction is terminated. In this invention, the weight-average molecular weight test method is GB / T21863-2008, and is determined by gel permeation chromatography (GPC) based on polystyrene calibration.

[0022] In this invention, the maleimide resin modified with p-aminophenol is selected from any one or a combination of at least two of the following: 4,4'-bismaleimide diphenylmethane, benzene maleimide oligomer, m-extrinyl bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-extrinyl bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzenemaleimide, 2,2-bis(4-(4-maleimide-phenoxy)-phenyl)propane, 2,6-dimethylbenzenemaleimide, or N-phenylmaleimide.

[0023] Preferably, the maleimide in the p-aminophenol modified maleimide resin is selected from well-known commercial brands, such as BMI, BMI-70, BMI-80, BMI-50P from KI Chemical, BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2300, BMI-3000, BMI-3000H, BMI-4000, BMI-5100, BMI-7000, BMI-7000H, BMI-TMH from Daiwakasei Industry, and DFE930, DFE936, DFE950 from Sichuan Dongcai Technology.

[0024] Preferably, the ratio m1 / m2 of the molar number of maleimide groups m1 in the p-aminophenol-modified maleimide resin to the molar number of primary amine groups m2 in p-aminophenol can preferably be 7.0 to 4.1, for example 7.0, 6.9, 6.5, 6.0, 5.5, 5.0, 4.5, 4.2 or 4.1.

[0025] Preferably, the benzoxazine resin is selected from any one or a combination of at least two of the following: bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, DDM type benzoxazine resin, ODA type benzoxazine resin, phenolphthalein type benzoxazine resin, DCPD type benzoxazine resin, allyl-containing benzoxazine resin, or vinyl-containing benzoxazine resin.

[0026] Preferably, the halogen-free resin composition further includes (D) filler.

[0027] Preferably, the filler is selected from any one or a combination of at least two of the following: aluminum hydroxide, silicon dioxide, talc, boehmite, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, clay, or mica.

[0028] Preferably, the median particle size D50 of the filler is 0.5-1.5 μm (e.g., 0.5 μm, 0.8 μm, 1.0 μm, 1.2 μm, 1.4 μm or 1.5 μm), and the maximum particle size D100 is 2.0-5.0 μm (e.g., 2.0 μm, 2.5 μm, 3.0 μm, 3.5 μm, 4.0 μm, 4.5 μm or 5.0 μm).

[0029] The particle size involved in this invention is measured using laser diffraction, and the testing instrument is a Malvern laser particle size analyzer, model MS3000.

[0030] In this invention, the physical form of the filler can be sheet-like, rod-like, spherical, hollow spherical, granular, fibrous, or plate-like, etc.

[0031] Preferably, the filler is a filler treated with a coupling agent, and the coupling agent is preferably a silane coupling agent.

[0032] Preferably, the filler content in the halogen-free resin composition is 40-600 parts by weight, for example 40 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 400 parts by weight, 450 parts by weight, 500 parts by weight, 550 parts by weight, or 600 parts by weight.

[0033] Preferably, the halogen-free resin composition further includes any one or a combination of at least two of the following: a curing accelerator, an antioxidant, an ion scavenger, a phosphorus-based flame retardant, a molybdenum-containing smoke retardant, or a core-shell rubber with a particle size of less than 5 micrometers.

[0034] On the other hand, the present invention provides a resin adhesive containing the halogen-free resin composition and solvent as described above.

[0035] Preferably, the solvent includes any one or a combination of at least two of butanone, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate, or N-methylpyrrolidone.

[0036] On the other hand, the present invention provides a prepreg comprising a reinforcing material and a halogen-free resin composition as described above, which is attached thereto after impregnation and drying.

[0037] On the other hand, the present invention provides a laminate comprising at least one prepreg as described above.

[0038] On the other hand, the present invention provides a metal foil laminate, the metal foil laminate comprising at least one prepreg as described above and a metal foil covering one or both sides of the laminated prepreg.

[0039] On the other hand, the present invention provides a printed circuit board comprising at least one prepreg as described above.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] This invention combines epoxy resin containing epoxidized polybutadiene resin with p-aminophenol-modified maleimide resin and benzoxazine resin, resulting in a halogen-free resin composition with a high Tg and excellent heat resistance. Simultaneously, it effectively reduces the warpage height of the resin composition product, has a low coefficient of thermal expansion, and improves the reliability of mixed-pressed boards with polyphenylene ether resin systems or hydrocarbon resin systems. Furthermore, it enables prepregs and printed circuit board laminates to possess excellent processability and good dielectric properties. Detailed Implementation

[0042] 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.

[0043] Synthesis example 1

[0044] 262 g of 4,4'-bismaleimide diphenylmethane (KI Company BMI), 31.8 g of p-aminophenol, and 292 g of N,N-dimethylacetamide were added to a 1 L reaction vessel equipped with a thermometer, stirrer, and reflux condenser. The mixture was reacted at 100 °C for 5 hours to obtain a solution of modified maleimide resin (B1). Using gel permeation chromatography (GPC), and converted from a calibration curve using standard polystyrene, its weight-average molecular weight was determined to be 518.

[0045] Synthesis example 2

[0046] 262.0 g of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (Yamato Kasei Corporation BMI-5100), 21.2 g of p-aminophenol, 200 g of N,N-dimethylacetamide, and 92 g of propylene glycol methyl ether acetate were added to a 1 L reaction vessel equipped with a thermometer, stirrer, and reflux condenser. The mixture was reacted at 110 °C for 5 hours to obtain a solution of modified maleimide resin (B2). Using gel permeation chromatography (GPC), the weight-average molecular weight was determined to be 567, calculated from a calibration curve using standard polystyrene.

[0047] Synthesis example 3

[0048] 262 g of 2,2-bis(4-(4-maleiminophenoxy)-phenyl)propane (Yamato Chemical Co., Ltd. BMI-4000), 24 g of p-aminophenol, 200 g of propylene glycol methyl ether, and 92 g of cyclohexanone were added to a 1 L reaction vessel equipped with a thermometer, stirrer, and reflux condenser. The mixture was reacted at 120 °C for 5 hours to obtain a solution of modified maleimide resin (B3). Using gel permeation chromatography (GPC), and converted from a calibration curve using standard polystyrene, its weight-average molecular weight was determined to be 680.

[0049] Synthesis example 4

[0050] 262.0 g of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (Yamato Kasei Corporation BMI-5100), 19.3 g of p-aminophenol, 200 g of N,N-dimethylacetamide, and 92 g of propylene glycol methyl ether acetate were added to a 1 L reaction vessel equipped with a thermometer, stirrer, and reflux condenser. The mixture was reacted at 110 °C for 5 hours to obtain a solution of modified maleimide resin (B4). The weight-average molecular weight was determined to be 551 using gel permeation chromatography (GPC) and converted from a calibration curve using standard polystyrene.

[0051] Comparative Synthesis Example 1

[0052] 260 g of 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (Yamato Kasei Corporation BMI-5100), 14 g of p-aminophenol, 200 g of N,N-dimethylacetamide, and 92 g of propylene glycol methyl ether acetate were added to a 1 L reaction vessel equipped with a thermometer, stirrer, and reflux condenser. The mixture was reacted at 110 °C for 5 hours to obtain a solution of modified maleimide resin (B5). Using gel permeation chromatography (GPC), and converted from a calibration curve using standard polystyrene, its weight-average molecular weight was determined to be 482.

[0053] Comparative Synthesis Example 2

[0054] 262 g of benzyl maleimide oligomer (Sichuan Dongcai Technology DFE950, with a measured weight-average molecular weight of 413), 20 g of p-aminophenol, 200 g of N,N-dimethylacetamide, and 92 g of propylene glycol methyl ether acetate were added to a 1 L reaction vessel equipped with a thermometer, stirrer, and reflux condenser. The mixture was reacted at 110 °C for 5 hours to obtain a solution of modified maleimide resin (B6). Using gel permeation chromatography (GPC), and converted from a calibration curve using standard polystyrene, its weight-average molecular weight was determined to be 841.

[0055] The sources of the raw materials used in the following examples and comparative examples are as follows:

[0056] A1: NC-3000H, biphenyl epoxy resin, purchased from Nippon Kayaku, epoxy equivalent 290g / eq;

[0057] A2: CN202, o-cresol type phenolic epoxy resin, purchased from Chang Chun, Taiwan, China, epoxy equivalent 200g / eq;

[0058] A3: PB-3600, epoxy polybutadiene resin, purchased from Daicel, epoxy equivalent 193g / eq;

[0059] A4: JP100, epoxy polybutadiene resin, purchased from Japan Soda, epoxy equivalent 200g / eq;

[0060] A5: Ricon 130MA8, maleic anhydride modified polybutadiene, purchased from Cray Valley, USA;

[0061] A6: B1000, polybutadiene, purchased from Japan Soda;

[0062] B1: p-Aminophenol-modified maleimide resin, a self-made synthetic product;

[0063] B2: p-Aminophenol-modified maleimide resin, a self-made synthetic product;

[0064] B3: p-Aminophenol-modified maleimide resin, a self-made synthetic product;

[0065] B4: p-Aminophenol-modified maleimide resin, a self-made synthetic product;

[0066] B5: p-Aminophenol-modified maleimide resin, a self-made synthetic product;

[0067] B6: p-Aminophenol-modified maleimide resin, a self-made synthetic product;

[0068] C1: DDM type benzoxazine resin, D125, purchased from Sichuan Dongcai Technology;

[0069] C2: ODA type benzoxazine resin, D129, purchased from Sichuan Dongcai Technology;

[0070] C3: Bisphenol A type benzoxazine resin, CB3170, purchased from Chengdu Keyi;

[0071] C4: Allyl-containing benzoxazine resin, KZH5031M70, purchased from KOLON;

[0072] C5: Acid anhydride, B4500, purchased from Dai Nippon Ink;

[0073] D1: Phosphate ester, PX200, purchased from Daihachi Chemicals, Japan;

[0074] D2: Phosphazene compound, SPB-100, purchased from Otsuka, Japan;

[0075] D3: Spherical silica, NQ2025W, purchased from Jiangsu Lianrui New Materials Co., Ltd.;

[0076] D4: Spherical silica, BQS30E, purchased from Jiangsu Lianrui New Materials Co., Ltd.

[0077] D5: Boehmite, BG403, purchased from Anhui Yishitong;

[0078] D6: Talc powder, AG609, purchased from US specialty ore;

[0079] 2E4Mz: Diethyltetramethylimidazole, a curing accelerator, purchased from Shikoku Chemical.

[0080] C11z: 2-Undecylimidazole, curing accelerator, purchased from Shikoku Chemical.

[0081] Examples 1-4, Comparative Examples 1-8

[0082] Examples 1-4 and Comparative Examples 1-8 provide a halogen-free resin composition, the composition of which is shown in Tables 1-3, wherein the amount of each component is based on solid weight parts. Resin liquid, prepreg using the same, metal foil-coated laminate, and composite laminate are also provided. The preparation method is as follows:

[0083] (1) Mix each component in the formula of the halogen-free resin composition evenly in a mixed solvent of butanone and N,N-dimethylacetamide, and disperse evenly at room temperature to obtain a resin solution with a solid content of 70%.

[0084] (2) The resin solution obtained in step (1) was impregnated with reinforcing material (glass fiber cloth, 2116, Hubel Corporation, Taiwan, China), and then baked in an oven at 165°C for 5 minutes to achieve semi-curing, so as to prepare prepregs with thicknesses of 133μm and 100μm respectively.

[0085] (3) Place the 6 sheets of 133μm thick prepreg or 1 sheet of 100μm thick prepreg between two 35μm copper foils (manufacturer: Suzhou Futian), laminate them in a hot press at 210℃ and 2.1MPa pressure for 2h, and cure them to prepare metal foil laminates with thicknesses of 0.80mm and 0.10mm respectively.

[0086] (4) The prepreg is pressed together with Synamic 6B bonding sheets commercially available from Guangdong Shengyi Technology Co., Ltd. to obtain a mixed-pressed board. Specifically, three sheets of Synamic 6B 2116 (RC = 57%) are sequentially stacked and pressed together with three sheets of 2116 prepreg (thickness of 133 μm) of the present invention, wherein the Synamic 6B is in direct contact with the prepreg of the present invention, the heating rate is controlled at 1.5-3.5℃ / min, and the curing conditions are set at 210℃ / 120 minutes to obtain the mixed-pressed board.

[0087] The performance of the metal foil-coated laminates and hybrid laminates provided in the above embodiments and comparative examples were tested respectively, and the test standards / methods are as follows:

[0088] (1) Glass transition temperature (Tg): The glass transition temperature was determined by using a 0.80 mm thick metal foil laminate and the aforementioned mixed-pressed material, according to the TMA method specified in IPC-TM-650.

[0089] (2) Dielectric constant D k and dielectric loss factor D f A 0.80mm thick metal foil laminate was selected and tested according to the Split Post Dielectric Resonator (SPDR) method at a frequency of 10GHz.

[0090] (3) T288 (with copper) thermal delamination time: Select a 0.80mm thick metal foil laminate and the aforementioned mixed-pressed material, refer to IPC-TM-650 2.4.24, and test at 288℃ when using copper foil.

[0091] (4) Coefficient of thermal expansion (CTE) test: 0.80 mm thick metal foil laminate was selected and thermomechanical analyzer (TMA) was used, and the standard method of IPC-TM-650 2.4.24 was adopted.

[0092] (5) Peel strength (PS): The peel strength of the copper foil was tested under the “receiving state” test conditions specified in standard IPC-TM-6502.4.8 using a 0.80 mm thick metal-coated laminate.

[0093] (6) Warpage height: Select a 0.10mm thick metal foil laminate, etch away the copper foil, take a 300×300mm sample and place it horizontally on a flat marble tabletop, observe the maximum warpage value, in mm.

[0094] (7) Water absorption rate: Take a metal foil laminate with a length of 50 mm, a width of 50 mm, and a thickness of 0.80 mm, and etch away the copper foil as a sample. After the sample is ultrasonically cleaned in deionized water to remove surface impurities, it is dried in an oven at 105℃ for 1 hour and weighed as W0. It is then soaked in water at 30℃ for 24 hours, removed and air-dried naturally, and weighed as W1. Water absorption rate = 100% × (W1 - W0) / W0.

[0095] Table 1

[0096]

[0097]

[0098] Table 2

[0099]

[0100]

[0101] Table 3

[0102]

[0103]

[0104] The performance data in Tables 1-3 show that the glass transition temperature (Tg) of the metal foil laminates prepared in Examples 1-4 is 205-224℃, the dielectric constant is 4.30-4.45, the dielectric loss is 0.008-0.010, the thermal delamination time T288 is greater than 60 min, the CTE is 1.37%-1.65%, the peel strength is 1.20-1.38 N / cm, the warpage height is 1.0-1.2 cm, and the water absorption rate is 0.09%-0.12%. The glass transition temperature (Tg) of the mixed-pressed board is 195-207℃, and the thermal delamination time T288 is greater than 60 min.

[0105] Compared with Example 1, Comparative Example 1 does not include epoxidized polybutadiene resin in the epoxy resin, but only other epoxy resins, and the thermal delamination time T288 of the mixed-pressed sheet is only 21 min.

[0106] Compared with Example 1, Comparative Example 2 replaced the epoxidized polybutadiene resin with an equal weight of polybutadiene, and the thermal delamination time T288 of the mixed-pressed sheet was only 8 minutes.

[0107] Compared with Example 1, Comparative Example 3 replaced the epoxidized polybutadiene resin with an equal amount of maleic anhydride-modified polybutadiene, and the thermal delamination time T288 of the mixed-pressed sheet was only 15 min.

[0108] Compared with Example 1, Comparative Example 4 does not contain maleimide resin modified with p-aminophenol, and the thermal delamination time T288 of the metal foil laminate is only 13 min, and the glass transition temperature (Tg) is 178°C.

[0109] Compared with Example 1, the weight-average molecular weight of the maleimide resin modified with aminophenol in Comparative Examples 5 and 6 is not in the range of 500-800. The resin composition of Comparative Example 5 is difficult to cure completely, resulting in poor heat resistance and reduced reliability of the mixed-pressed board. The coefficient of thermal expansion of Comparative Example 6 increases, resulting in reduced reliability of the mixed-pressed board.

[0110] Compared with Example 1, Comparative Examples 7 and 8 are different. Comparative Example 7 does not contain benzoxazine resin, while Comparative Example 8 replaces benzoxazine resin with an acid anhydride compound, resulting in increased water absorption, significantly increased warpage height of the metal foil laminate, and greatly reduced thermal delamination time of the metal foil laminate and the mixed-pressed board.

[0111] The applicant declares that the present invention is illustrated by the above embodiments to demonstrate the halogen-free 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, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A halogen-free resin composition, characterized in that, The halogen-free resin composition comprises the following components in parts by weight: (A) 100 parts by weight of epoxy resin, wherein at least epoxy polybutadiene resin is included; (B) 50-100 parts by weight of p-aminophenol modified maleimide resin, wherein the weight-average molecular weight of the p-aminophenol modified maleimide resin is 518-800. (C) 70-90 parts by weight of benzoxazine resin; The ratio of the molar number of maleimide groups m1 in the p-aminophenol-modified maleimide resin to the molar number of primary amine groups m2 in p-aminophenol, m1 / m2, is 7.0~4.

1.

2. The halogen-free resin composition according to claim 1, characterized in that, The epoxy resin includes 5-20 parts by weight of epoxidized polybutadiene resin.

3. The halogen-free resin composition according to claim 1, characterized in that, The epoxy resin also includes other epoxy resins.

4. The halogen-free resin composition according to claim 3, characterized in that, The other epoxy resins include trifunctional epoxy resins and / or tetrafunctional epoxy resins.

5. The halogen-free resin composition according to claim 4, characterized in that, The other epoxy resins include any one or a combination of at least two of the following: dicyclopentadiene epoxy resin, dimethylphenol-type phenolic epoxy resin, tetramethylbiphenyl epoxy resin, biphenyl epoxy resin, phenol-type phenolic epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, C1-C6 alkyl epoxy resin, MDI-modified epoxy resin, o-cresol-type phenolic epoxy resin, or naphthalene-containing epoxy resin.

6. The halogen-free resin composition according to claim 1, characterized in that, The p-aminophenol-modified maleimide resin is selected from any one or a combination of at least two of the following: 4,4'-bismaleimide diphenylmethane, benzene maleimide oligomer, m-extrin phenyl bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-extrin phenyl bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzenemaleimide, 2,2-bis(4-(4-maleimide-phenoxy)-phenyl)propane, 2,6-dimethylbenzenemaleimide, or N-phenylmaleimide.

7. The halogen-free resin composition according to claim 1, characterized in that, The benzoxazine resin is selected from any one or a combination of at least two of the following: bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, DDM type benzoxazine resin, ODA type benzoxazine resin, phenolphthalein type benzoxazine resin, DCPD type benzoxazine resin, allyl-containing benzoxazine resin, or vinyl-containing benzoxazine resin.

8. The halogen-free resin composition according to claim 1, characterized in that, The halogen-free resin composition further includes (D) filler.

9. The halogen-free resin composition according to claim 8, characterized in that, The filler is selected from any one or a combination of at least two of the following: aluminum hydroxide, silicon dioxide, talc, boehmite, zeolite, wollastonite, magnesium oxide, calcium silicate, calcium carbonate, clay, or mica.

10. The halogen-free resin composition according to claim 9, characterized in that, The packing material is a packing material treated with a coupling agent, preferably a silane coupling agent.

11. The halogen-free resin composition according to claim 8, characterized in that, The filler content in the halogen-free resin composition is 40-600 parts by weight.

12. The halogen-free resin composition according to claim 1, characterized in that, The halogen-free resin composition further includes any one or a combination of at least two of the following: a curing accelerator, an antioxidant, an ion scavenger, a phosphorus-based flame retardant, a molybdenum-containing smoke retardant, or a core-shell rubber with a particle size of less than 5 micrometers.

13. A resin adhesive, characterized in that, The resin solution contains the halogen-free resin composition and solvent as described in any one of claims 1-12.

14. A prepreg, characterized in that, The prepreg includes a reinforcing material and a halogen-free resin composition as described in any one of claims 1-12, which is attached thereto after impregnation and drying.

15. A laminate, characterized in that, The laminate comprises at least one sheet of prepreg as described in claim 14.

16. A metal foil-coated laminate, characterized in that, The metal foil laminate includes at least one prepreg as described in claim 14 and a metal foil covering one or both sides of the laminated prepreg.

17. A printed circuit board, characterized in that, The printed circuit board includes at least one sheet of prepreg as described in claim 14.

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