Modified bismaleimide prepolymer, resin composition, and use of the resin composition

Abstract

The present invention provides a modified bismaleimide prepolymer obtained by reacting a bismaleimide compound, a double-bond-containing organosilicon resin, and a hydrocarbon resin, in which the ratio of the mass of the bismaleimide compound: the mass of the double-bond-containing organosilicon resin: the mass of the hydrocarbon resin is 100:(3-40):(5-50). The present invention introduces a silicon-oxygen bond and a carbon-hydrogen bond into the bismaleimide compound and controls the mass ratio of the bismaleimide compound, the double-bond-containing organosilicon resin, and the hydrocarbon resin, thereby improving the processability of the prepolymerization and improving the toughness and dielectric properties of the bismaleimide compound cured system.

Description

[Technical Field]

[0001] The present invention relates to the technical field of electronic materials, and in particular to modified bismaleimide prepolymers, resin compositions and uses of the resin compositions. [Background technology]

[0002] With technological upgrades, new requirements are being placed on PCBs in the automotive and smartphone and other consumer electronics industries. Since the commercial launch of 5G in 2018, PCB substrates have increasingly higher dielectric properties. High-frequency, high-speed copper-clad boards are essential electronic substrates in the 5G era, and PCB substrate materials must have low dielectric constants and dielectric dissipation factors to reduce signal delay, distortion, and loss, as well as signal interference during high-speed transmission. Therefore, there is a need for thermosetting resin compositions capable of producing printed circuit board materials that are sufficiently low in dielectric constant and dielectric dissipation factor for high-speed, high-frequency signal transmission (i.e., the lower the dielectric constant and dielectric dissipation factor, the better), while also exhibiting high heat resistance, a high modulus of elasticity, a low CTE, and other properties.

[0003] Cured bismaleimide resins have excellent properties such as high temperature resistance, humidity and heat resistance, high elastic modulus, low CTE, and high strength, making them suitable for use as matrix resins for IC package substrates and PCB-like substrates. However, their poor dielectric properties limit their use in the field of high-frequency, high-speed package substrates.

[0004] To address the issue of poor dielectric properties of bismaleimide resins, prior art has incorporated polyphenylene ether resins into bismaleimide resins, reducing the dielectric properties of the cured bismaleimide resins to a certain extent. However, polyphenylene ether resins have thermoplastic properties and are poorly compatible with bismaleimide resins, making it difficult to obtain highly homogeneous adhesive liquid composites. Additionally, prior art has incorporated reactive organic silicone resins into bismaleimide resin systems to improve heat resistance and reduce CTE values, but there is still room for improvement in terms of dielectric properties. Summary of the Invention [Problem to be solved by the invention]

[0005] The object of the present invention is to provide a modified bismaleimide prepolymer, a resin composition, and use of the resin composition, which is obtained by introducing a silicon-oxygen bond and a carbon-hydrogen bond into a bismaleimide compound, and mixing the bismaleimide compound, a double bond-containing organic silicone resin, and a carbon-containing organic silicone resin. change Controlling the weight ratio of the hydrogen resin improves the processability of the prepolymerization and also improves the toughness and dielectric properties of the bismaleimide cured system, thereby resolving the problems of the prior art, such as high brittleness and low dielectric properties of bismaleimide cured systems. [Means for solving the problem]

[0006] In order to achieve one of the above objects of the invention, one embodiment of the present invention provides a polymerizable composition comprising a bismaleimide compound, a double bond-containing organic silicone resin, and a carbon black. change The bismaleimide compound is obtained by reacting the bismaleimide compound with a hydrogenated resin, and the ratio of the mass of the bismaleimide compound to the mass of the double bond-containing organosilicon resin is 1:1. change A modified bismaleimide prepolymer is provided, in which the mass ratio of hydrogen resin is 100:(3-40):(5-50).

[0007] As a further improvement of one embodiment of the present invention, the double bond-containing organosilicone resin and the carbon change The ratio of the sum of the double bond equivalents of the hydrogen resin to the double bond equivalents of the bismaleimide compound is 1:(5 to 0.8).

[0008] As a further improvement of one embodiment of the present invention, The bismaleimide compound and the double bond-containing organic silicone resin are reacted at 50 to 90°C for 30 to 120 minutes to obtain a preliminary reaction product; The preliminary reaction product is then mixed with the carbon dioxide. change The hydrogen resin is added and reacted at 90 to 130° C. for 30 to 150 minutes to obtain the modified bismaleimide prepolymer.

[0009] As a further improvement of one embodiment of the present invention, the bismaleimide compound is mixed with a double bond-containing organosilicone resin and a carbon black. change During the reaction of the hydrogen resin, at least one of aminophenol, carboxylic acid, and carboxylic acid anhydride is added in an amount of 0.1 to 10 parts by weight.

[0010] As a further improvement of one embodiment of the present invention, the resulting modified bismaleimide prepolymer contains reactive double bonds.

[0011] One embodiment of the present invention comprises, by weight: (a) 10 to 80 parts of a modified bismaleimide prepolymer; (b) 10 to 80 parts of a maleimide compound or a derivative thereof; wherein the modified bismaleimide prepolymer is the modified bismaleimide prepolymer described above.

[0012] A further refinement of one embodiment of the present invention further comprises 3 to 50 parts of an elastomer, said elastomer being at least one of a styrene-based elastomer, a methacrylate-based elastomer, and an organosilicone-based elastomer.

[0013] As a further improvement of one embodiment of the present invention, the resin composition further comprises 5 to 50 parts by weight of a flame retardant.

[0014] As a further improvement of one embodiment of the present invention, the flame retardant is selected from bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicone flame retardants, and organometallic salt flame retardants; the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalamide; The phosphorus-based flame retardant is selected from inorganic phosphorus, phosphate ester, phosphoric acid, hypophosphoric acid, phosphorus oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), a compound (1) represented by the following structural formula (1), a compound (2) represented by the following structural formula (2), 10-phenyl-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphorus, phosphazene, and modified phosphazene, [ka] [ka] the nitrogen-based flame retardant is selected from a triazine compound, a cyanuric acid compound, an isocyanic acid compound, and a phenothiazine; the organic silicone flame retardant is selected from organic silicone oil, organic silicone rubber, and organic silicone resin; The organometallic flame retardant is selected from ferrocene, acetylacetone metal complexes, and organometallic carbonyl compounds.

[0015] A further improvement of one embodiment of the present invention further comprises a silane coupling agent and a dispersant, wherein the weight ratio of the silane coupling agent to the dispersant is (2-10):1.

[0016] In a further improvement of an embodiment of the present invention, the silane coupling agent is an epoxy silane coupling agent, and the dispersant is a phosphate ester-based dispersant and / or a modified polyurethane-based dispersant.

[0017] One embodiment of the present invention further provides the use of the aforementioned resin composition for prepregs, laminates, insulating thin films, insulating boards, copper-clad boards, circuit boards and electronic devices. [Effects of the Invention]

[0018] One or more technical solutions provided in the present invention have at least the following technical effects or advantages: (1) The present invention relates to a method for producing a bismaleimide compound by using a double bond-containing organic silicone resin and a carbon black. change By reacting with hydrogen resin and introducing silicon-oxygen bonds and carbon-hydrogen bonds into the bismaleimide compound, the processability of the prepolymerization is improved, and the toughness and dielectric properties of the bismaleimide compound cured system are improved. (2) The present invention further provides a polymerizable composition comprising a bismaleimide compound, a double bond-containing organic silicone resin, and a carbon black. change By controlling the weight ratio with hydrogen resin and the degree of modification in the bismaleimide compound, the dielectric properties and brittleness are improved while maintaining the original high heat resistance and low CTE, effectively meeting the needs of use in the field of high-frequency, high-speed package substrates. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in detail below in connection with specific embodiments, but these embodiments do not limit the present invention, and any changes to reaction conditions, reactants or amounts of raw materials made by those skilled in the art based on these embodiments are included within the protection scope of the present invention.

[0020] The present invention is directed to a method for producing a bismaleimide compound, a double bond-containing organic silicone resin, and a carbon black. change The mass of the bismaleimide compound is obtained by reacting the bismaleimide compound with the hydrogenated resin, and the mass of the double bond-containing organic silicone resin is the same as that of the carbon-containing organic silicone resin. change A modified bismaleimide prepolymer is provided, in which the mass ratio of hydrogen resin is 100:(3-40):(5-50).

[0021] Furthermore, double bond-containing organic silicone resins and carbon change The ratio of the sum of the double bond equivalents of the hydrogen resin to the double bond equivalents of the bismaleimide compound is 1:(5 to 0.8).

[0022] The modified bismaleimide prepolymer is A bismaleimide compound is reacted with a double bond-containing organic silicone resin at 50 to 90°C for 30 to 120 minutes to obtain a preliminary reaction product; The preliminary reaction mixture was then mixed with charcoal. change The hydrogen resin is added and reacted at 90 to 130° C. for 30 to 150 minutes to obtain the modified bismaleimide prepolymer.

[0023] Bismaleimide compounds, double bond-containing organic silicone resins, and carbon change During the reaction with the hydrogen resin, at least one of aminophenol, carboxylic acid, and carboxylic acid anhydride is added in an amount of 0.1 to 10 parts by weight, and all of the phenolic hydroxyl group, carboxyl group, and acid anhydride group in the aminophenol, carboxylic acid, or carboxylic acid anhydride react with the bismaleimide compound, thereby improving the reactivity.

[0024] Furthermore, the modified bismaleimide prepolymer produced by the above reaction contains reactive double bonds that can improve the reactivity of the modified bismaleimide prepolymer during curing.

[0025] When the double bond in the bismaleimide compound reacts with the double bond in the double bond-containing organosilicon resin, a silicon-oxygen bond is introduced into the bismaleimide compound, and the silicon-oxygen bond can improve the toughness of the bismaleimide compound, and further, carbon change The hydrogen resin increases the crosslink density of the cured product, controls the reaction rate of the entire radical, effectively preserves unreacted carbon-carbon double bonds, and improves the reactivity of the modified bismaleimide prepolymer.

[0026] Furthermore, an appropriate amount of initiator may be added during the preparation of the modified bismaleimide prepolymer, and the initiator may be added in an amount of 0.001 to 6 parts by weight per 100 parts by weight of the resin composition. The initiator may be selected from azo initiators, peroxide initiators, and redox initiators, and is preferably one or more of the following initiators: dicumyl peroxide, di-tert-butyl peroxide, tert-butylbenzoyl peroxide, dicyclohexyl peroxydicarbonate, cumene hydroperoxide, and azobisisobutyronitrile.

[0027] Furthermore, the double bond-containing organic silicone resin is as shown in the following structural formula (3).

[0028] [ka]

[0029] In the formula, R and R' are C1 to C5 alkyl groups or at least one is a reactive group, R'' is a C1 to C5 alkylene group, and n is an integer of 1 to 30.

[0030] Preferably, the side chains R and R' of the double bond-containing organosilicone resin contain at least one carbon-carbon double bond, and the carbon-carbon double bond-containing group is a vinyl group, an allyl group, a propenyl group, a styryl group, or a methacrylate group. The reactive group in the side chain of the double bond-containing organosilicone resin improves reactivity during polymerization of the bismaleimide prepolymer.

[0031] Furthermore, charcoal change The hydrogenated resin contains 1,2-vinyl groups, and the content of 1,2-vinyl groups is ≧70%, and preferably carbon change The content of 1,2-vinyl groups in the hydrogen resin is 80 to 98%.

[0032] An embodiment of the present invention comprises, by weight: (a) 10 to 80 parts of a modified bismaleimide prepolymer; (b) 10 to 80 parts of a maleimide resin or a derivative thereof.

[0033] Here, the modified bismaleimide prepolymer is the above-mentioned modified bismaleimide prepolymer.

[0034] Furthermore, the bismaleimide compound in the maleimide resin or modified bismaleimide prepolymer is selected from at least one of the following structures:

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] Here, R2 is hydrogen, a methyl group, or an ethyl group, R1 is a methylene group, an ethylene group, or a dimethylmethylene group, and n is an integer of 1 to 10.

[0040] [ka]

[0041] [ka]

[0042] In the formula, n is an integer of 1 to 10.

[0043] [ka]

[0044] Here, n is an integer of 1 to 10.

[0045] [ka]

[0046] Here, n is an integer of 1 to 10.

[0047] [ka]

[0048] [ka]

[0049] Here, R is hydrogen, a methyl group, or an ethyl group, and n is an integer of 1 to 10.

[0050] Furthermore, the resin composition further contains 0.001 to 5 parts by weight of a catalyst, and the catalyst is selected from at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, 1-cyanoethyl-2-methylimidazole, and modified imidazoles represented by the following structure:

[0051] [ka]

[0052] In the formula, R3, R4, R5, and R6 are the same or different and each represents a methyl group, an ethyl group, or a tert-butyl group; B represents a methylene group, an ethylene group, a dimethylmethylene group, a sulfide group, or a sulfonyl group; and P200F50 manufactured by JER can be used.

[0053] [ka]

[0054] In the formula, R3, R4, R5 and R6 may be the same or different and each represents a methyl group, an ethyl group or a tert-butyl group; A represents a methylene group, an ethylene group, a dimethylmethylene group, a sulfide group, a sulfonyl group or an aromatic carbon atom; change It is a hydrogen group, and G8009L manufactured by Daiichi Kogyo can be used.

[0055] Furthermore, the resin composition further contains 3 to 50 parts by weight of an elastomer, and the elastomer is at least one of a styrene-based elastomer, a methacrylate-based elastomer, and an organic silicone-based elastomer.

[0056] The styrene-based elastomer is selected from H1041, H1043, H1051, H1052, H1053, H1221, P1500, P2000, M1911 or M1913 manufactured by Asahi Kasei Corporation of Japan, and 8004, 8006, 8076, 8104, V9827, 2002, 2005, 2006, 2007, 2104, 7125, 4033, 4044, 4055, 4077 or 4099 manufactured by Kuraray Co., Ltd.

[0057] The methacrylates are selected from M51, M52, M22 or D51N of Arkema, LA-2330 of Kuraray, and SG-P3 series or SG-80 series of Nagase.

[0058] The organic silicone elastomer may be selected from X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, and X-52-7030 manufactured by Shin-Etsu Chemical Co., Ltd., and AY-42-119, EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, and EXL-2655 manufactured by Dow Corporation.

[0059] Furthermore, the resin composition further contains a silane coupling agent and a dispersant, the silane coupling agent being an epoxy silane coupling agent, and the weight ratio of the silane coupling agent to the dispersant is (2 to 10): 1. Here, the dispersant is a phosphate ester-based dispersant and / or a modified polyurethane-based dispersant.

[0060] Furthermore, the resin composition further contains 5 to 50 parts by weight of a flame retardant, which is selected from bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organic silicone flame retardants, organic metal salt flame retardants, etc.

[0061] Specifically, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalamide.

[0062] The phosphorus-based flame retardant is selected from inorganic phosphorus, phosphate ester, phosphoric acid, hypophosphoric acid, phosphorus oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), compound (1) represented by the following structural formula (1), compound (2) represented by the following structural formula (2), 10-phenyl-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphorus, phosphazene, modified phosphazene, and other phosphorus-containing organic compounds. [ka] [ka]

[0063] The nitrogen-based flame retardant is selected from triazine compounds, cyanuric acid compounds, isocyanic acid compounds, phenothiazines, and the like.

[0064] The organic silicone flame retardant is selected from organic silicone oil, organic silicone rubber, organic silicone resin, and the like.

[0065] The organometallic flame retardant is selected from ferrocene, acetylacetone metal complexes, organometallic carbonyl compounds, and the like.

[0066] The flame retardant is selected from phosphazene SPB-100, modified phosphazene BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L manufactured by Otsuka Chemical Co., Ltd. of Japan.

[0067] The resin composition further contains a filler, the content of which is 20 to 80 parts by weight per 100 parts by weight of the resin composition. The filler includes inorganic fillers, organic fillers, and composite fillers. The inorganic filler is selected from at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder. The organic filler is selected from at least one of polytetrafluoroethylene powder, polyphenylene sulfide powder, and polyethersulfone powder.

[0068] The filler is surface-treated with a silane coupling agent, and the silane coupling agent is selected from one or more of Shin-Etsu Chemical Co., Ltd. product number KBM-573, Dow Corning Corporation product number Z-6883, Shin-Etsu Chemical Co., Ltd. product number KBM-1003, and Shin-Etsu Chemical Co., Ltd. product number KBM-1403.

[0069] Furthermore, a dye, such as a fluorescent dye or a black dye, may be added to the resin composition.

[0070] The present invention further provides the use of the above resin composition for prepreg, laminate, insulating thin film, insulating board, circuit board and electronic device, the specific description is as follows:

[0071] The present invention further provides a prepreg comprising a reinforcing material and the aforementioned resin composition. The prepreg can be produced by dissolving the resin composition in a solvent to form an adhesive liquid, immersing the reinforcing material in the adhesive liquid, removing the immersed reinforcing material, baking it in an environment of 100 to 180°C for 1 to 15 minutes, and drying it to obtain the prepreg.

[0072] Here, the solvent is selected from at least one of acetone, butanone, toluene, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzene, toluene, xylene, and cyclohexane.

[0073] The reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. Preferably, glass fiber cloth is used as the reinforcing material. Of the glass fiber cloths, open filament fiber cloth or plain weave fiber cloth is preferably used. The glass fiber cloth is preferably E-glass fiber cloth, S-glass fiber cloth, or Q-glass fiber cloth.

[0074] When glass fiber cloth is used as the reinforcing material, the glass fiber cloth is chemically treated with a coupling agent to improve the interfacial bond between the resin composition and the glass fiber cloth. The coupling agent is preferably an epoxy silane coupling agent or an amino silane coupling agent, which provides high water resistance and heat resistance.

[0075] An embodiment of the present invention further provides a laminate including one prepreg and metal foil provided on at least one surface of the prepreg, or including a combination sheet formed by stacking a plurality of the prepregs and metal foil provided on at least one surface of the combination sheet.

[0076] Laminates are manufactured by the following method: Either one or both surfaces of a single prepreg are coated with metal foil, or at least two prepregs are stacked together to form a combined sheet, one or both surfaces of the combined sheet are coated with metal foil, and the resulting sheet is then thermo-compressed to obtain a metal foil laminate. The thermo-compression conditions are 0.2 to 2 MPa and 150 to 250°C for 2 to 4 hours.

[0077] Preferably, the metal foil is selected from copper foil or aluminum foil, and the thickness of the metal foil is 5 microns, 8 microns, 12 microns, 18 microns, 35 microns, or 70 microns.

[0078] An embodiment of the present invention further provides an insulating board comprising at least one of the above-described prepregs.

[0079] An embodiment of the present invention further provides a thin insulating film comprising a carrier film and the aforementioned resin composition applied thereon, with a significantly improved thermal index.

[0080] The insulating thin film is produced by the following method: the resin composition is dissolved in a solvent to form an adhesive liquid, the adhesive liquid is then applied to a carrier film, and the carrier film coated with the adhesive liquid is heated and dried to obtain the insulating thin film.

[0081] The solvent is selected from at least one of acetone, butanone, toluene, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzene, toluene, xylene, and cyclohexane.

[0082] The carrier film is selected from at least one of a PET film, a PP film, a PE film, and a PVC film.

[0083] An embodiment of the present invention further provides a circuit board including one or more of the prepreg, laminate, insulating plate, and insulating thin film described above.

[0084] An embodiment of the present invention further provides an electronic device including the aforementioned circuit board, and the heat resistance of the circuit board is greatly improved, thereby significantly improving the safety of the electronic device.

[0085] The technical solutions of the present application are further illustrated below in conjunction with some specific synthesis examples and comparative examples.

[0086] Synthesis Example 1 Modified bismaleimide prepolymer Y1 In step 1, 200 g of bismaleimide resin (manufactured by Daiwa Kasei Co., Ltd., BMI-2300), 20 g of double bond-containing organic silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-164A), and an appropriate amount of organic solvent are added to a beaker and reacted at 80°C for 70 minutes to obtain a preliminary reaction product. In step 2, the temperature is increased to 110°C and 30g of charcoal is added. change Hydrogen resin (B3000 manufactured by Soda Co., Ltd.) is added, and the reaction is continued at 110°C for 30 minutes, and then discharged to obtain modified bismaleimide prepolymer Y1.

[0087] Synthesis Example 2 Modified bismaleimide prepolymer Y2 In step 1, 200 g of bismaleimide resin (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.), 30 g of double bond-containing organic silicone resin (X-22-164A, manufactured by Shin-Etsu Chemical Co., Ltd.), and an appropriate amount of organic solvent are added to a beaker and reacted at 90°C for 60 minutes to obtain a preliminary reaction product. In step 2, the temperature is increased to 120°C and 45g of charcoal is added. change Hydrogen resin (B2000 manufactured by Soda Co., Ltd.) was added, and the reaction was continued at 120°C for 30 minutes, and then the mixture was discharged to obtain modified bismaleimide prepolymer Y2.

[0088] Synthesis Example 3 Modified bismaleimide prepolymer Y3 In step 1, 200 g of bismaleimide resin (MIR-3000, manufactured by Nippon Kayaku Co., Ltd.) and 40 g of double bond-containing organic silicone resin (X-22-164A) are added to a beaker and reacted at 90°C for 60 minutes to obtain a preliminary reaction product. In step 2, the temperature is increased to 120°C and 25g of charcoal is added. change Hydrogen resin (B3000 manufactured by Soda Co., Ltd.) was added, and the reaction was continued at 120°C for 30 minutes, and then the mixture was discharged to obtain modified bismaleimide prepolymer Y3.

[0089] Synthesis Example 4 Modified bismaleimide prepolymer Y4 In a beaker, 200 g of bismaleimide resin (manufactured by Daiwa Kasei Co., Ltd., BMI-2300), 20 g of double bond-containing organic silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-164A), and 30 g of charcoal were added. change Hydrogen resin (B3000 manufactured by Soda Co., Ltd.) and an appropriate amount of organic solvent are added, and the mixture is reacted at 100°C for 100 minutes to obtain modified bismaleimide prepolymer Y4.

[0090] Synthesis Example 5 Modified bismaleimide prepolymer Y5 (Compare with Synthesis Example 1) In step 1, 200 g of bismaleimide resin (manufactured by Daiwa Kasei Co., Ltd., BMI-2300) and 30 g of charcoal were placed in a beaker. change Hydrogen resin (B3000 manufactured by Soda Co., Ltd.) and an appropriate amount of organic solvent are added, and the mixture is reacted at 80°C for 70 minutes to obtain a preliminary reaction product. In step 2, the temperature is raised to 110°C, 20 g of a double bond-containing organic silicone resin (X-22-164A, manufactured by Shin-Etsu Chemical Co., Ltd.) is added, the reaction is continued at 110°C for 30 minutes, and the mixture is discharged to obtain a modified bismaleimide prepolymer Y5.

[0091] Comparative Synthesis Example 1 Modified Bismaleimide Prepolymer Y6 200 g of bismaleimide resin (manufactured by Daiwa Kasei Co., Ltd., BMI-2300), 20 g of double bond-containing organic silicone resin (X-22-164A), and an appropriate amount of organic solvent are added to a beaker, and the mixture is reacted at 110°C for 120 minutes to obtain preliminary reaction product Y4.

[0092] Comparative Synthesis Example 2: Modified bismaleimide prepolymer Y7 Put 200g of bismaleimide resin (manufactured by Daiwa Kasei Co., Ltd., BMI-2300) and 45g of charcoal into a beaker. change Hydrogen resin (B3000 manufactured by Soda Co., Ltd.) and 0.1 g of initiator were added, and the mixture was reacted at 110° C. for 120 minutes to obtain a preliminary reaction product Y5.

[0093] The corresponding solids were weighed according to the data in Table 1, and each weighed solid was adjusted with a solvent so that the solid content of the adhesive liquid was 60%. The adhesive liquid was applied to an E-glass fiber cloth, and after it had soaked, it was removed and placed in a 160°C air drying oven and baked for 3 to 6 minutes to produce a prepreg.

[0094] The prepreg is cut into 300 x 300 mm pieces, and one electrolytic copper foil is placed on each side of the prepreg. The stacked layers are then placed in a vacuum press and pressed together to produce a metal foil laminate (or copper clad laminate). The specific performance characteristics are shown in Table 2.

[0095] [Table 1]

[0096] [Table 2]

[0097] The prepregs and copper-clad laminates produced in all of the above Examples 1 to 5 and Comparative Examples 1 to 3 are subjected to performance tests.

[0098] 1) The glass transition temperature is measured by DMA (thermomechanical analysis) at a heating rate of 10°C / min. 2) For PCT 2HR water absorption measurement, three samples of 10 cm x 10 cm and 0.40 mm thickness were taken from which the metal foil on both sides had been removed, dried at 100°C for two hours, weighed and designated as W1, and then treated in a pressure cooker tester at 121°C and 2 atmospheres for two hours, weighed and designated as W2, and the water absorption was calculated as (W2-W1) / W1 x 100%. 3) X / Y coefficient of thermal expansion (CTE) is measured using TMA (thermomechanical analysis), with a heating rate of 10°C / min and a test temperature range of 30 to 100°C. 4) Dk and Df are measured at 10 GHz using the parallel plate method in accordance with IPC-TM-650 2.5.5.9.

[0099] As can be seen from the above experimental data, Examples 1 to 5 have excellent performance, such as high Tg, low dielectric constant and loss tangent, low water absorption, and low CTE. Among them, Example 2 has a higher Tg value, low dielectric constant and loss tangent compared to Comparative Example 1, and Example 1 has a higher Tg value, low dielectric constant and loss tangent, and lower CTE and water absorption compared to Comparative Example 2.

[0100] It should be understood that although this specification has been described in terms of embodiments, each embodiment does not include only one independent technical solution, and the description style of the specification is merely for the purpose of clarification. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that are understandable to those skilled in the art.

[0101] The above series of detailed descriptions are merely specific descriptions of possible embodiments of the present invention, and do not limit the protection scope of the present invention; any equivalent embodiments or modifications that do not deviate from the technical spirit of the present invention shall be included in the protection scope of the present invention.

Claims

1. the composition is obtained by reacting a bismaleimide compound, a double bond-containing organic silicone resin, and a hydrocarbon resin, wherein the ratio of the mass of the bismaleimide compound to the mass of the double bond-containing organic silicone resin to the mass of the hydrocarbon resin is 100:(3 to 40):(5 to 50), and the hydrocarbon resin contains a 1,2-vinyl group; The double bond-containing organic silicone resin is represented by the following structural formula (3): 【Chemistry 1】 In the formula, R and R' are C1 to C5 alkyl groups or at least one is a reactive group, R'' is a C1 to C5 alkylene group, and n is an integer from 1 to 30; A modified bismaleimide prepolymer, characterized in that the bismaleimide compound is selected from at least one of the following structures: 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】 (Wherein, n is 1.) 【Transformation 7】 (Wherein, n is 1.) 【Transformation 8】 (Wherein, n is 1.) 【Chemistry 9】 【Chemistry 10】 (wherein R is hydrogen, a methyl group, or an ethyl group, and n is 1.)

2. By weight, (a) 10 to 80 parts of a modified bismaleimide prepolymer; (b) 10 to 80 parts of a maleimide compound or a derivative thereof; 2. A resin composition comprising the following components: wherein the modified bismaleimide prepolymer is the modified bismaleimide prepolymer according to claim 1.

3. The resin composition according to claim 2, further comprising 3 to 50 parts of an elastomer, the elastomer being at least one of a styrene-based elastomer, a methacrylate-based elastomer, and an organic silicone-based elastomer.

4. The resin composition according to claim 2, further comprising 5 to 50 parts by weight of a flame retardant.

5. the flame retardant is selected from a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organic silicone flame retardant, and an organic metal salt flame retardant; the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalamide; The phosphorus-based flame retardant is selected from inorganic phosphorus, phosphate ester, phosphoric acid, hypophosphoric acid, phosphorus oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), a compound (1) represented by the following structural formula (1), a compound (2) represented by the following structural formula (2), 10-phenyl-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphorus, phosphazene, and modified phosphazene, 【Chemistry 11】 【Chemistry 12】 the nitrogen-based flame retardant is selected from a triazine compound, a cyanuric acid compound, an isocyanic acid compound, and a phenothiazine; the organic silicone flame retardant is selected from organic silicone oil, organic silicone rubber, and organic silicone resin; 5. The resin composition according to claim 4, wherein the organometallic salt flame retardant is selected from the group consisting of ferrocene, acetylacetone metal complexes, and organometallic carbonyl compounds.

6. The resin composition according to claim 2, further comprising a silane coupling agent and a dispersant, wherein the weight ratio of the silane coupling agent to the dispersant is (2 to 10):

1.

7. 7. The resin composition according to claim 6, wherein the silane coupling agent is an epoxy silane coupling agent, and the dispersant is a phosphate ester dispersant and / or a modified polyurethane dispersant.

8. Use of the resin composition according to claim 2 for prepregs, laminates, insulating thin films, insulating boards, copper-clad boards, circuit boards and electronic devices.

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