Bismaleimide resin composition and application thereof
By combining the modified bismaleimide prepolymer with an epoxy resin and grafting the benzo�cinazine group and nitrile group on the molecular chain of the bismaleimide resin, the problem of insufficient comprehensive performance when used alone is solved, and a high-performance thermosetting resin composition is achieved, which is suitable for high-performance electronic components.
Patent Information
- Application Number
- CN202411902454.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-23
- Publication Date
- 2025-04-08
AI Technical Summary
When bismaleimide resin is used in electronic components, the individual comprehensive properties (including heat resistance, flame retardant, water absorption, mechanical properties, and dielectric properties) cannot meet the market's demand for high-performance products.
By combining the modified bismaleimide prepolymer with an epoxy resin, the polymeric monomer of the modified bismaleimide prepolymer includes a bismaleimide resin and an allylated benzopusazine nitrile compound, and the benzopusazine and nitrile groups are grafted on the molecular chain of the bismaleimide by reacting the bismaleimide resin with an allyl group.
Thermoset resin composition with excellent heat resistance, low water absorption, high modulus, good flame retardancy and excellent dielectric properties is obtained, and is suitable for high-performance printed circuit board fields such as integrated circuit packaging and high frequency and high speed.
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Figure CN119775702A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to the field of semiconductor technology, and in particular to a bismaleimide resin composition and application thereof. Background Art
[0002] With the rapid development of science and technology, the requirements for materials used in industries such as microelectronics, aerospace, and communications are getting higher and higher. Especially in the field of electronics industry, as the parts of electronic products continue to develop in the direction of light, thin, short, and small, electronic components require higher signal propagation speed and transmission efficiency, thus putting forward higher requirements on the performance of various aspects of the materials used.
[0003] Bismaleimide resin is a thermosetting resin that can be used to make PCB boards in electronic components. However, when bismaleimide resin is used alone, its comprehensive properties (including heat resistance, flame retardancy, water absorption, mechanical properties, and dielectric properties) cannot meet the market's performance requirements for products. How to modify it to improve its comprehensive performance is an important research direction. Summary of the invention
[0004] Based on this, the first aspect of the present application provides a bismaleimide resin composition, and its technical solution is as follows:
[0005] A bismaleimide resin composition comprises a modified bismaleimide prepolymer and an epoxy resin, wherein the mass proportion of the modified bismaleimide prepolymer in the bismaleimide resin composition is 40% to 50%, and the polymerization monomer of the modified bismaleimide prepolymer comprises a bismaleimide resin and an allylated benzoxazine nitrile compound, wherein the allylated benzoxazine nitrile compound has a structure shown in Formula I:
[0006]
[0007] Formula I;
[0008] Wherein, R is selected from -CR1R2-, -SO2-, -O- or ; R1 and R2 are independently selected from -H or -CH3; n1 and n2 are independently selected from 1 or 2.
[0009] A second aspect of the present application provides a prepreg, the raw materials of which include a reinforcing material and the bismaleimide resin composition as described above.
[0010] The third aspect of the present application provides a laminate, the raw materials of which include metal foil and the prepreg as described above, or include metal foil and the bismaleimide resin composition as described above.
[0011] Compared with the traditional solution, this application has the following beneficial effects:
[0012] The bismaleimide resin composition of the present application includes a modified bismaleimide prepolymer and an epoxy resin, wherein the polymerized monomer of the modified bismaleimide prepolymer includes a bismaleimide resin and an allylated benzoxazine nitrile compound, and the bismaleimide resin reacts with the allyl group to graft benzoxazine groups and nitrile groups on the molecular chain of the bismaleimide. The modified bismaleimide prepolymer having the above structure can combine the advantages of bismaleimide, benzoxazine and benzonitrile, and has excellent heat resistance, low water absorption, high modulus, good flame retardancy and excellent dielectric properties, and obtains a thermosetting resin composition with excellent performance in all aspects, which can be applied to the fields of high-performance printed circuit boards such as integrated circuit packaging, high frequency and high speed. DETAILED DESCRIPTION
[0013] The present application will be further described in detail below in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thoroughly understood.
[0014] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.
[0015] the term
[0016] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:
[0017] In this application, "optionally", "optional" and "optional" refer to optional, that is, to any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.
[0018] In this application, in the "first aspect", "second aspect", "third aspect", "fourth aspect", etc., the terms "first", "second", "third", "fourth", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.
[0019] In the present application, when referring to a numerical interval (i.e., a numerical range), unless otherwise specified, the optional numerical distribution within the above numerical interval is deemed to be continuous and includes the two numerical endpoints of the numerical range (i.e., the minimum value and the maximum value), and every numerical value between the two numerical endpoints.
[0020] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.
[0021] The first aspect of the present application provides a bismaleimide resin composition, which includes a modified bismaleimide prepolymer and an epoxy resin, wherein the mass proportion of the modified bismaleimide prepolymer in the bismaleimide resin composition is 40% to 50%, and the polymerization monomer of the modified bismaleimide prepolymer includes a bismaleimide resin and an allylated benzoxazine nitrile compound, and the allylated benzoxazine nitrile compound has a structure shown in Formula I:
[0022]
[0023] Formula I;
[0024] Wherein, R is selected from -CR1R2-, -SO2-, -O- or ; R1 and R2 are independently selected from -H or -CH3; n1 and n2 are independently selected from 1 or 2.
[0025] The bismaleimide resin composition of the present application includes a modified bismaleimide prepolymer and an epoxy resin, wherein the polymerized monomer of the modified bismaleimide prepolymer includes a bismaleimide resin and an allylated benzoxazine nitrile compound, and the bismaleimide resin reacts with the allyl group to graft benzoxazine groups and nitrile groups on the molecular chain of the bismaleimide. The modified bismaleimide prepolymer having the above structure can combine the advantages of bismaleimide, benzoxazine and benzonitrile, and has excellent heat resistance, low water absorption, high modulus, good flame retardancy and excellent dielectric properties, and obtains a thermosetting resin composition with excellent performance in all aspects, which can be applied to the fields of high-performance printed circuit boards such as integrated circuit packaging, high frequency and high speed.
[0026] Among them, the bismaleimide structure has good heat resistance and thermal stability after curing, low curing shrinkage, good thermal expansion performance, but high cross-linking density and brittle material after curing. The benzonitrile structure has good high temperature resistance, mechanical properties, flame retardant properties, chemical resistance, low water absorption and photoelectric properties after curing, but it is difficult to cure. Usually, a curing agent needs to be introduced to reduce the difficulty of its curing reaction to improve its curing activity and final performance. Common curing agents include aromatic diamines, Lewis acid metal salts, organic protonic acids, etc., but there are also some problems with the use of the above curing agents, such as causing gaps and pores in the resin cured product, poor compatibility with the resin, or difficulty in meeting the curing conditions of the high temperature resistant resin. Benzoxazine contains N, O hexacyclic rings, and after curing, it forms a cross-linked network structure similar to phenolic resin. There is no small molecule release and zero volume shrinkage during the curing process. At the same time, it has a high glass transition temperature, low water absorption, good flame retardancy, etc., but its high temperature resistance is poor. The modified bismaleimide prepolymer includes the above structure at the same time, making full use of the advantages of each of the above structures, and complementing their disadvantages, thereby obtaining a thermosetting resin composition having excellent heat resistance, low water absorption, good flame retardancy, low dielectric properties and better mechanical properties. For example, when the above prepolymer is cured, the oxadiazine ring opens and the nitrile group self-polymerizes. At this time, the oxadiazine ring opening and the nitrile group self-polymerization reaction promote each other, which can reduce the temperature of the nitrile group curing to form a triazine ring, shorten the time for the nitrile group to cure to form a triazine ring, and reduce the difficulty of the curing reaction of the nitrile group without adding a curing agent.
[0027] Wherein, the mass proportion of the modified bismaleimide prepolymer in the bismaleimide resin composition is 40% to 50%. For example, the mass proportion is 40%, 42%, 44%, 46%, 48%, and 50%. After experimental verification, the mass proportion of the modified bismaleimide prepolymer in the bismaleimide resin composition exceeds 50%, which will affect the various properties of the composition.
[0028] Optionally, the mass ratio of the bismaleimide resin to the allylated benzoxazine nitrile compound is 1:(1.1-2). For example, the mass ratio of the bismaleimide resin to the allylated benzoxazine nitrile compound is 1:1.1, 1:1.25, 1:1.4, 1:1.5, 1:2.
[0029] Optionally, the weight average molecular weight of the modified bismaleimide prepolymer is 1500 to 4500. For example, the weight average molecular weight is 1500, 3000, or 4500.
[0030] Optionally, the method for preparing the modified bismaleimide prepolymer comprises the following steps:
[0031] The allylated benzoxazine nitrile compound and the bismaleimide resin are mixed, first prepolymerized at 100°C to 150°C for 60min to 120min, then heated to 160°C to 180°C and reacted for 60min to 120min to obtain the modified bismaleimide prepolymer.
[0032] Optionally, the polymerized monomer of the modified bismaleimide prepolymer further comprises a bismaleimide resin modifier. Optionally, the bismaleimide resin modifier comprises one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F and bisphenol A bisallyl ether. Optionally, the mass ratio of the bismaleimide resin to the bismaleimide resin modifier is 1:(0.55~1). For example, 1:0.55, 1:0.8, 1:1. Optionally, the preparation method of the modified bismaleimide prepolymer comprises the following steps:
[0033] The allylated benzoxazine nitrile compound, the bismaleimide modifier and the bismaleimide resin are mixed, first prepolymerized at 100°C to 150°C for 60min to 120min, then heated to 160°C to 180°C and reacted for 60min to 120min to obtain a modified bismaleimide prepolymer.
[0034] Optionally, the bismaleimide resin includes an organic compound containing two or more maleimide groups in the structure. Optionally, the bismaleimide resin includes one or more of N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, two (4-maleimidophenyl)methane, 2,2-bis (4-(4-maleimidophenoxy)-phenyl)propane, two (3,5-dimethyl-4-maleimidophenyl)methane, two (3-ethyl-5-methyl-4-maleimidophenyl)methane, two (3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide, bismaleimide containing biphenyl structure and multimaleimide.
[0035] Optionally, the mass proportion of the epoxy resin in the bismaleimide resin composition is 20% to 35%. For example, the mass proportion is 20%, 23%, 26%, 29%, 32%, or 35%.
[0036] Optionally, one or more of other functional resins, fillers and additives are also included.
[0037] Optionally, the other functional resins include one or more of styrene-butadiene-styrene block copolymer (SBS), modified epoxy resin, polyimide resin, polyphenylene ether and hydrocarbon resin.
[0038] Optionally, the mass proportion of the other functional resin in the bismaleimide resin composition is 5% to 10%. For example, the mass proportion is 5%, 8%, 10%,
[0039] Optionally, the filler is selected from inorganic fillers. Optionally, the filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silicon dioxide (spherical, composite and molten), quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin.
[0040] Optionally, the filler accounts for 10% to 20% by mass in the bismaleimide resin composition. For example, the filler accounts for 10%, 15%, or 20% by mass.
[0041] Optionally, the auxiliary agent includes one or more of a curing accelerator, a coupling agent and a toughening agent. Optionally, the curing accelerator includes 2-methylimidazole.
[0042] Optionally, the mass proportion of the auxiliary agent in the bismaleimide resin composition is 1% to 5%, for example, 1%, 3%, or 5%.
[0043] A second aspect of the present application provides a prepreg, the raw materials of which include a reinforcing material and the bismaleimide resin composition as described above.
[0044] It can be understood that the method for preparing the prepreg comprises the following steps:
[0045] The bismaleimide resin composition is mixed with a solvent to prepare a bismaleimide resin composition glue solution, and then the bismaleimide resin composition is covered on the surface of the reinforcing material by an impregnation method, and heated to semi-solidification to obtain a semi-cured sheet.
[0046] Optionally, the reinforcing material is a well-known inorganic or organic fiber material, and the inorganic fiber-reinforced substrate includes but is not limited to glass fiber (including different types such as E, NE, D, S, T, etc.), carbon fiber, silicon carbide fiber, asbestos fiber, etc. The organic fiber-reinforced substrate includes but is not limited to nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, cotton fiber, etc.
[0047] Optionally, the process parameters for heating to semi-solidification include: heating to 150° C. to 250° C. and maintaining the temperature for 2 min to 10 min.
[0048] The method for preparing the bismaleimide resin composition glue solution comprises the following steps:
[0049] The modified bismaleimide prepolymer, epoxy resin and other functional resins are dissolved in a solvent, and then fillers and auxiliary agents are added and stirred.
[0050] Optionally, stirring can be performed in a stirring instrument, the stirring speed is 1000 rpm / min~2000 rpm / min, and the stirring time is 1.5h~3h. Optionally, the solvent includes butanone, xylene and cyclohexanone. Further optionally, the mass ratio of butanone, xylene and cyclohexanone is 1:(0.5~1.5):(0.5~1.5).
[0051] The third aspect of the present application provides a laminate, the raw materials of which include metal foil and the prepreg as described above, or include metal foil and the bismaleimide resin composition as described above.
[0052] Optionally, the method for preparing the laminate comprises the following steps:
[0053] A plurality of prepregs are laminated, and before lamination, a metal foil, such as a metal copper foil, is coated on one side or both sides of a laminate composed of the plurality of prepregs.
[0054] The lamination process parameters include: temperature of 150°C to 300°C, pressure of 10kgf / cm 2 ~30kgf / cm 2 , vacuum degree <2kPa, hot pressing time is 200min~400min.
[0055] The “several prepregs” refers to at least one prepreg.
[0056] Optionally, the metal copper foil has a thickness of 3 μm to 70 μm.
[0057] The following is further described in conjunction with specific embodiments and comparative examples. The raw materials involved in the following specific embodiments and comparative examples, unless otherwise specified, can all be commercially available, the instruments used, unless otherwise specified, can all be commercially available, and the processes involved, unless otherwise specified, are all routinely selected by those skilled in the art.
[0058] Among them, bismaleimide resin was purchased from KI Chemical, model BMI-80. Bisphenol A epoxy resin was purchased from Nan Ya, model NPSN 901X75. 2,2'-Diallyl bisphenol A was purchased from Honghu Shuangma Resin Factory. Polyformaldehyde was purchased from Nanjing Senbega Biotechnology Co., Ltd., model SBJ-0384. SBS resin was purchased from Kraton, USA, model D1116K. Spherical silica was purchased from Yaduma, model SC6500-SXD. 2-Methylimidazole was purchased from Shikoku Chemical.
[0059] Example 1
[0060] This embodiment provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0061] Step 1, Preparation of Allylated Benzo[pi]oxazine Nitrile Compounds
[0062] Weigh 2,2'-diallyl bisphenol A (30.8 g, 0.1 mol), paraformaldehyde (13.2 g, 0.44 mol), and 4-(4-aminophenoxy)phthalonitrile (47.0 g, 0.2 mol), add them to a 500 mL single-necked flask, add 300 mL of toluene, and stir to completely dissolve them. Continue to stir and reflux the dissolved reaction mixture for 5 hours, and finally detect the reaction status by spot plate. After the reaction is completed, the reaction mixture is first treated with 3N NaOH aqueous solution, and then washed three times with distilled water. The solvent in the washed mixture is removed by reduced pressure distillation on a rotary evaporator, and the resulting liquid is purified by column chromatography (eluent: pure petroleum ether), and the petroleum ether is removed by rotary evaporation to obtain a liquid. The liquid product is vacuum dried at 60°C for 48 hours to obtain an allylated benzoxazine nitrile compound with a yield of about 83%. The structural formula is .
[0063] Step 2: Preparation of modified bismaleimide prepolymer
[0064] 120 g of allylated benzoxazine nitrile compound and 80 g of bismaleimide resin were mixed evenly, reacted at 130°C for 120 min, then heated to 160°C and continued to react for 120 min, and then cooled to room temperature to obtain modified bismaleimide prepolymer A, and its weight average molecular weight was tested to be 2500.
[0065] Step 3: Preparation of bismaleimide resin composition glue
[0066] 40 grams of the modified bismaleimide prepolymer A, 25 grams of bisphenol A epoxy resin and 5 grams of SBS resin were dissolved in a mixed solvent of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone were mixed in a mass ratio of 1:1:1. Under stirring conditions, 10 grams of spherical silica and 1 gram of 2-methylimidazole were added, and stirring was continued to obtain a uniform bismaleimide resin composition glue.
[0067] Step 4: Preparation of prepreg and laminate
[0068] 2116 glass fiber cloth (basic weight 105g / m 2 ) was immersed in the above-mentioned bismaleimide resin composition glue solution, taken out and placed in a hot air circulation oven for baking at 200°C for 3 minutes to obtain a semi-cured sheet with a glue content of 50wt%.
[0069] Take 8 prepregs and stack them. Cover the upper and lower sides of the stack with an electrolytic copper foil of 18 μm in thickness. Place them in a vacuum press with programmable temperature and pressure control. 2 Under the pressure of , after hot pressing and curing according to the procedure of pressing at 160°C for 1h, pressing at 180°C for 1h, pressing at 200°C for 2h, and pressing at 220°C for 2h, a copper clad laminate with a thickness of 0.8mm was made.
[0070] Example 2
[0071] This embodiment provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0072] Step 1 is the same as in Example 1.
[0073] Step 2 is the same as in Example 1.
[0074] Step 3: Preparation of bismaleimide resin composition glue
[0075] 65 grams of the modified bismaleimide prepolymer A, 40 grams of bisphenol A epoxy resin and 7.5 grams of SBS resin were dissolved in a mixed solvent of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone were mixed in a mass ratio of 1:1:1. Under stirring conditions, 20 grams of spherical silica and 3 grams of 2-methylimidazole were added, and stirring was continued to obtain a uniform bismaleimide resin composition glue.
[0076] Step 4 is the same as in Example 1.
[0077] Example 3
[0078] This embodiment provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0079] Step 1 is the same as in Example 1.
[0080] Step 2 is the same as in Example 1.
[0081] Step 3: Preparation of bismaleimide resin composition glue
[0082] 80 grams of the modified bismaleimide prepolymer A, 50 grams of bisphenol A epoxy resin and 15 grams of SBS resin were dissolved in a mixed solvent of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone were mixed in a mass ratio of 1:1:1. Under stirring conditions, 30 grams of spherical silica and 5 grams of 2-methylimidazole were added, and stirring was continued to obtain a uniform bismaleimide resin composition glue.
[0083] Step 4 is the same as in Example 1.
[0084] Example 4
[0085] This embodiment provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0086] Step 1 is the same as in Example 1.
[0087] Step 2 is the same as in Example 1.
[0088] Step 3: Preparation of bismaleimide resin composition glue
[0089] 100 grams of the modified bismaleimide prepolymer A, 75 grams of bisphenol A epoxy resin and 20 grams of SBS resin are dissolved in a mixed solvent consisting of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone are mixed in a mass ratio of 1:1:1. Under stirring conditions, 30 grams of spherical silica and 7 grams of 2-methylimidazole are added, and stirring is continued to obtain a uniform bismaleimide resin composition glue.
[0090] Step 4 is the same as in Example 1.
[0091] Example 5
[0092] This embodiment provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0093] Step 1 is the same as in Example 1.
[0094] Step 2: Preparation of modified bismaleimide prepolymer
[0095] 100 g of allylated benzoxazine nitrile compound and 80 g of bismaleimide resin were mixed evenly, reacted at 130°C for 120 min, then heated to 160°C and continued to react for 120 min before cooling to room temperature to obtain modified bismaleimide prepolymer B, and its weight average molecular weight was tested to be 1800.
[0096] Step 3: Preparation of bismaleimide resin composition glue
[0097] 80 grams of the modified bismaleimide prepolymer B, 50 grams of bisphenol A epoxy resin and 15 grams of SBS resin were dissolved in a mixed solvent of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone were mixed in a mass ratio of 1:1:1. Under stirring conditions, 30 grams of spherical silica and 5 grams of 2-methylimidazole were added, and stirring was continued to obtain a uniform bismaleimide resin composition glue.
[0098] Step 4 is the same as in Example 1.
[0099] Example 6
[0100] This embodiment provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0101] Step 1, Preparation of Allylated Benzo[pi]oxazine Nitrile Compounds
[0102] Weigh 2,2'-diallylbisphenol A (30.8 g, 0.1 mol), paraformaldehyde (13.2 g, 0.44 mol), and 4-(4-aminophenoxy)benzonitrile (42.0 g, 0.2 mol), add them to a 500 mL single-necked flask, add 300 mL of toluene, and stir to completely dissolve them. Continue to stir and reflux the dissolved reaction mixture for 5 hours, and finally detect the reaction condition by spot plate. After the reaction is completed, the reaction mixture is first treated with 3N NaOH aqueous solution, and then washed three times with distilled water. The solvent in the washed mixture is removed by reduced pressure distillation on a rotary evaporator, and the resulting liquid is purified by column chromatography (eluent: pure petroleum ether), and the petroleum ether is removed by rotary evaporation to obtain a liquid. The liquid product is vacuum dried at 60°C for 48 hours to obtain an allylated benzoxazine nitrile compound with a yield of about 86%, and the structural formula is .
[0103] Step 2: Preparation of modified bismaleimide prepolymer
[0104] 120 g of allylated benzoxazine nitrile compound and 80 g of bismaleimide resin were mixed evenly, reacted at 130°C for 120 min, then heated to 160°C and continued to react for 120 min before cooling to room temperature to obtain modified bismaleimide prepolymer C, and its weight average molecular weight was tested to be 3000.
[0105] Step 3: Preparation of bismaleimide resin composition glue
[0106] 80 grams of the modified bismaleimide prepolymer C, 50 grams of bisphenol A epoxy resin and 15 grams of SBS resin were dissolved in a mixed solvent of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone were mixed in a mass ratio of 1:1:1. Under stirring conditions, 30 grams of spherical silica and 5 grams of 2-methylimidazole were added, and stirring was continued to obtain a uniform bismaleimide resin composition glue.
[0107] Step 4 is the same as in Example 1.
[0108] Example 7
[0109] This embodiment provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0110] Step 1 is the same as in Example 1.
[0111] Step 2: Preparation of modified bismaleimide prepolymer
[0112] 60 g of allylated benzoxazine nitrile compound, 60 g of 2,2'-diallyl bisphenol A and 80 g of bismaleimide resin were mixed evenly, reacted at 130°C for 120 min, then heated to 160°C and continued to react for 120 min, and then cooled to room temperature to obtain modified bismaleimide prepolymer E, and its weight average molecular weight was tested to be 2600.
[0113] Step 3: Preparation of bismaleimide resin composition glue
[0114] 80 grams of the modified bismaleimide prepolymer E, 50 grams of bisphenol A epoxy resin and 15 grams of SBS resin were dissolved in a mixed solvent of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone were mixed in a mass ratio of 1:1:1. Under stirring conditions, 30 grams of spherical silica and 5 grams of 2-methylimidazole were added, and stirring was continued to obtain a uniform bismaleimide resin composition glue.
[0115] Step 4 is the same as in Example 1.
[0116] Comparative Example 1
[0117] This comparative example provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0118] Step 1, preparation of allylated benzoxazine compounds
[0119] Weigh 2,2'-diallyl bisphenol A (30.8 g, 0.1 mol), paraformaldehyde (13.2 g, 0.44 mol), and 4-phenoxyaniline (37.0 g, 0.2 mol), add them to a 500 mL single-necked flask, add 300 mL of toluene, and stir to completely dissolve them. Continue to stir and reflux the dissolved reaction mixture for 5 hours. After the reaction is completed, detect the reaction status by spot plate. Use a rotary evaporator to remove the solvent in the washed mixture by reduced pressure distillation, and purify the resulting liquid by column chromatography (eluent: pure petroleum ether). Rotary evaporation removes petroleum ether to obtain a liquid. The liquid product is vacuum dried at 60 ° C for 48 hours to obtain an allylated benzoxazine compound with a yield of about 89%. The structural formula is .
[0120] Step 2: Preparation of modified bismaleimide prepolymer
[0121] 120 g of allylated benzoxazine compound and 80 g of bismaleimide resin were mixed evenly, reacted at 130°C for 120 min, then heated to 160°C and continued to react for 120 min before cooling to room temperature to obtain modified bismaleimide prepolymer D, and its weight average molecular weight was tested to be 2100.
[0122] Step 3: Preparation of bismaleimide resin composition glue
[0123] 80 grams of the modified bismaleimide prepolymer D, 50 grams of bisphenol A epoxy resin and 15 grams of SBS resin were dissolved in a mixed solvent of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone were mixed in a mass ratio of 1:1:1. Under stirring conditions, 30 grams of spherical silica and 5 grams of 2-methylimidazole were added, and stirring was continued to obtain a uniform bismaleimide resin composition glue.
[0124] Step 4 is the same as in Example 1.
[0125] Comparative Example 2
[0126] This comparative example provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0127] Step 1: Preparation of bismaleimide resin composition glue
[0128] 80 grams of bismaleimide resin, 50 grams of bisphenol A epoxy resin and 15 grams of SBS resin were dissolved in a mixed solvent of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone were mixed in a mass ratio of 1:1:1. Under stirring conditions, 30 grams of spherical silica and 5 grams of 2-methylimidazole were added, and stirring was continued to obtain a uniform bismaleimide resin composition glue.
[0129] Step 2 is the same as in Example 1.
[0130] Comparative Example 3
[0131] This comparative example provides a method for preparing a bismaleimide resin composition, a composition adhesive, a prepreg, and a laminate, and the steps are as follows:
[0132] Step 1 is the same as in Example 1.
[0133] Step 2 is the same as in Example 1.
[0134] Step 3: Preparation of bismaleimide resin composition glue
[0135] 120 grams of the modified bismaleimide prepolymer A, 40 grams of bisphenol A epoxy resin and 7.5 grams of SBS resin were dissolved in a mixed solvent of butanone, xylene and cyclohexanone, wherein butanone, xylene and cyclohexanone were mixed in a mass ratio of 1:1:1. Under stirring conditions, 20 grams of spherical silica and 3 grams of 2-methylimidazole were added, and stirring was continued to obtain a uniform bismaleimide resin composition glue.
[0136] Step 4 is the same as in Example 1.
[0137] The copper clad laminates prepared in the above embodiments and comparative examples were subjected to performance tests. The test items are as follows and the test results are shown in Table 1.
[0138] Peel strength: The test method is carried out in accordance with IPC-TM650 2.4.8.
[0139] Glass transition temperature (Tg): Tested according to IPC-TM650 2.4.25D.
[0140] Thermal decomposition temperature (Td): Tested according to IPC-TM650 2.4.24.6.
[0141] Elastic modulus: tested according to GB / T 22315-2008.
[0142] Flame retardant: tested according to IPC-TM650 2.3.10.
[0143] Water absorption: Tested according to IPC-TM650 2.6.2.1.
[0144] Dk / Df: Tested according to IPC-TM650 2.5.5.2.
[0145] Table 1
[0146]
[0147] It can be seen that after combining the structures of bismaleimide, benzoxazine and benzonitrile, the obtained bismaleimide resin composition has excellent heat resistance, low water absorption, high modulus, good flame retardancy and excellent dielectric properties after curing.
[0148] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0149] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.
Claims
1. A bismaleimide resin composition, characterized in that The invention comprises a modified bismaleimide prepolymer and an epoxy resin, wherein the mass proportion of the modified bismaleimide prepolymer in the bismaleimide resin composition is 40% to 50%, and the polymerization monomer of the modified bismaleimide prepolymer comprises a bismaleimide resin and an allylated benzo[pi]oxazine nitrile compound, and the allylated benzo[pi]oxazine nitrile compound has a structure shown in Formula I: Formula I; Wherein, R is selected from -CR1R2-, -SO2-, -O- or ; R1 and R2 are independently selected from -H or -CH3; n1 and n2 are independently selected from 1 or 2.
2. The bismaleimide resin composition according to claim 1, characterized in that The mass ratio of the bismaleimide resin to the allylated benzoxazine nitrile compound is 1:(1.1-2).
3. The bismaleimide resin composition according to claim 1, characterized in that The weight average molecular weight of the modified bismaleimide prepolymer is 1500-4500.
4. The bismaleimide resin composition according to claim 1, characterized in that The preparation method of the modified bismaleimide prepolymer comprises the following steps: The allylated benzoxazine nitrile compound and the bismaleimide resin are mixed, first prepolymerized at 100°C to 150°C for 60min to 120min, then heated to 160°C to 180°C and reacted for 60min to 120min to obtain the modified bismaleimide prepolymer.
5. The bismaleimide resin composition according to claim 1, characterized in that: The polymerized monomers of the modified bismaleimide prepolymer further include a bismaleimide resin modifier, and the bismaleimide resin modifier includes one or more of diallyl bisphenol A, diallyl bisphenol S, diallyl bisphenol F and bisphenol A bisallyl ether.
6. The bismaleimide resin composition according to any one of claims 1 to 5, characterized in that The bismaleimide resin includes one or more of N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, polyphenylmethane bismaleimide, bismaleimide containing biphenyl structure and polymaleimide.
7. The bismaleimide resin composition according to any one of claims 1 to 5, characterized in that Includes at least one of the following features: (1) The epoxy resin includes one or more of bisphenol A epoxy resin, novolac epoxy resin, bisphenol F epoxy resin, multifunctional epoxy resin, alicyclic epoxy resin, bisphenol S epoxy resin and dicyclopentadiene phenol epoxy resin; (2) The epoxy resin accounts for 20% to 35% by weight of the bismaleimide resin composition.
8. The bismaleimide resin composition according to any one of claims 1 to 5, characterized in that It also includes one or more of other functional resins, fillers and additives.
9. The bismaleimide resin composition according to claim 8, characterized in that: Includes at least one of the following features: (1) The other functional resins include one or more of styrene-butadiene-styrene block copolymers, modified epoxy resins, polyimide resins, polyphenylene ethers and hydrocarbon resins; (2) The mass proportion of the other functional resin in the bismaleimide resin composition is 5% to 10%; (3) The filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin; (4) The mass proportion of the filler in the bismaleimide resin composition is 10% to 20%; (5) The auxiliary agent includes one or more of a curing accelerator, a coupling agent and a toughening agent; (6) The mass proportion of the auxiliary agent in the bismaleimide resin composition is 1% to 5%.
10. A prepreg, characterized in that: The raw materials include a reinforcing material and the bismaleimide resin composition according to any one of claims 1 to 9.
11. A laminated board, characterized in that: The raw materials include metal foil and the prepreg according to claim 10, or include metal foil and the bismaleimide resin composition according to any one of claims 1 to 9.