Modified bismaleimide prepolymer, resin composition and use of 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, in particular to modified bismaleimide prepolymers, resin compositions and uses of the resin compositions. [Background technology]

[0002] With the upgrade of technology, new requirements are being placed on PCBs in the automobile industry and the home electronics industry such as smartphones. Since commercial 5G was launched in the market in 2018, PCB substrates are increasingly required in terms of dielectric properties. Since high-frequency and high-speed copper-clad boards are one of the essential electronic substrates in the 5G era, PCB substrate materials must have low dielectric constants and dielectric dissipation factors to reduce signal delay, distortion and loss during high-speed transmission, as well as interference between signals. Therefore, there is a demand for a thermosetting resin composition that can produce printed circuit board materials that are capable of expressing sufficiently low dielectric constants and low dielectric dissipation factors in high-speed and high-frequency signal transmission (i.e., the lower the dielectric constant and dielectric dissipation factor, the better), as well as having high heat resistance, high elastic modulus, low CTE, etc.

[0003] Bismaleimide resin cured products 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 substrate-like PCBs. However, due to the problem of low dielectric properties, their use in the field of high-frequency, high-speed package substrates is limited.

[0004] In order to improve the problem of low dielectric properties of bismaleimide resin, polyphenylene ether resin was introduced into bismaleimide resin in the prior art, which reduced the dielectric properties of the cured bismaleimide resin to a certain extent, but polyphenylene ether resin has the properties of a thermoplastic resin and is poorly compatible with bismaleimide resin, making it difficult to obtain a very homogeneous adhesive liquid composite. In addition, there is a prior art in which reactive organic silicone resin is introduced into the bismaleimide resin system to improve heat resistance and reduce the CTE value, but there is still room for improvement in terms of dielectric properties. Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a modified bismaleimide prepolymer, a resin composition and use of the resin composition, in which a silicon-oxygen bond and a carbon-hydrogen bond are introduced into a bismaleimide compound and the weight ratio of the bismaleimide compound, the double bond-containing organic silicone resin and the hydrocarbon resin are controlled, thereby improving the processability of the prepolymerization and improving the toughness and dielectric properties of the bismaleimide cured system, thereby solving the problems of the prior art, that is, high brittleness and low dielectric properties of the bismaleimide cured system. [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 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).

[0007] As a further improvement of one embodiment of the present invention, the ratio of the sum of the double bond equivalents of the double bond-containing organosilicone resin and the hydrocarbon resin to the double bond equivalent 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 is reacted with the double bond-containing organic silicone resin at 50 to 90° C. for 30 to 120 minutes to obtain a preliminary reaction product; The hydrocarbon resin is added to the preliminary reaction product, and the mixture is 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, during the reaction of the bismaleimide compound with the double bond-containing organosilicon resin and the hydrocarbon resin, at least one of aminophenol, carboxylic acid, or 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] As a further refinement of one embodiment of the present invention, the composition 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 an 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, organometallic salt flame retardants, The brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, and tetrabromophthalamide; The phosphorus-based flame retardant is selected from inorganic phosphorus, phosphoric acid 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 oils, organic silicone rubbers, and organic silicone resins; The organometallic flame retardant is selected from ferrocene, acetylacetone metal complexes, and organometallic carbonyl compounds.

[0015] As a further improvement of one embodiment of the present invention, it 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] As 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-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. Effect of the Invention

[0018] One or more technical solutions provided in the present invention have at least the following technical effects or advantages: (1) In the present invention, a bismaleimide compound is reacted with a double bond-containing organic silicone resin and a hydrocarbon resin to introduce silicon-oxygen bonds and carbon-hydrogen bonds into the bismaleimide compound, thereby improving the processability of the prepolymerization and improving the toughness and dielectric properties of the bismaleimide compound cured system. (2) The present invention further controls the weight ratio of the bismaleimide compound, the double bond-containing organic silicone resin, and the hydrocarbon resin, thereby controlling the degree of modification in the bismaleimide compound, thereby improving the dielectric properties and brittleness while maintaining the inherent high heat resistance and low CTE, and effectively meeting the needs of use in the field of high frequency, high speed package substrates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0020] An embodiment of 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).

[0021] Furthermore, the ratio of the sum of the double bond equivalents of the double bond-containing organic silicone resin and the hydrocarbon resin to the double bond equivalent 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; A hydrocarbon resin is added to the preliminary reaction product, and the mixture is reacted at 90 to 130° C. for 30 to 150 minutes to obtain the modified bismaleimide prepolymer.

[0023] During the reaction of the bismaleimide compound with the double bond-containing organic silicone resin and the hydrocarbon 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 any of the phenolic hydroxyl group, carboxyl group, and acid anhydride group in the aminophenol, carboxylic acid, or carboxylic acid anhydride reacts 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] The double bond in the bismaleimide compound reacts with the double bond in the double-bond-containing organic silicone resin to introduce a silicon-oxygen bond into the bismaleimide compound, which improves the toughness of the bismaleimide compound. Furthermore, the hydrocarbon resin increases the crosslink density of the cured product, controls the overall reaction rate of radicals, and effectively retains unreacted carbon-carbon double bonds, improving the reactivity of the modified bismaleimide prepolymer.

[0026] Further, an appropriate amount of initiator may be added during the preparation of the modified bismaleimide prepolymer, and the initiator is 0.001 to 6 parts by weight based on 100 parts by weight of the resin composition. The initiator may be selected from azo-based initiators, peroxide-based initiators, and redox-based initiators, and is preferably one or more of the following initiators: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl benzoyl 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 group containing the carbon-carbon double bond 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 is one that enhances the reactivity during polymerization of the bismaleimide prepolymer.

[0031] Furthermore, the hydrocarbon resin contains 1,2-vinyl groups, and the content of the 1,2-vinyl groups is ≧70%, and preferably the content of the 1,2-vinyl groups in the hydrocarbon 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 the 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 a hydrogen atom, 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 from 1 to 10.

[0045] [ka]

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

[0047] [ka]

[0048] [ka]

[0049] Here, R is a hydrogen atom, 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 structures:

[0051] [ka]

[0052] In the formula, R3, R4, R5 and R6 are the same or different and are each a methyl group, an ethyl group or a tert-butyl group; B is 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 are the same or different and each is a methyl group, an ethyl group or a tert-butyl group; A is a methylene group, an ethylene group, a dimethylmethylene group, a sulfide group, a sulfonyl group or an aromatic hydrocarbon group; 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 from Arkema, LA-2330 from Kuraray, SG-P3 series or SG-80 series from 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 Co., Ltd.

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

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

[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, phosphoric acid 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 having product number SPB-100, modified phosphazenes having product numbers BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L manufactured by Nippon Otsuka Chemical Co., Ltd.

[0067] Furthermore, the resin composition further contains a filler, and the content is 20 to 80 parts by weight, assuming that the resin composition is 100 parts by weight. The filler includes an inorganic filler, an organic filler, and a composite filler. Among them, 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 further 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 plate, 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 reinforcing material from the immersion, and baking and drying the reinforcing material at 100 to 180°C for 1 to 15 minutes.

[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 at least one selected from 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, it is preferable to use open filament fiber cloth or plain weave fiber cloth. The glass fiber cloth is preferably E glass fiber cloth, S glass fiber cloth, or Q glass fiber cloth.

[0074] In addition, 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 to provide high water resistance and heat resistance.

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

[0076] The laminate is manufactured by the following method. Either one or both surfaces of one prepreg are covered with metal foil, or at least two prepregs are stacked to form a combined sheet, one or both surfaces of the combined sheet are covered with metal foil, and the combined sheet is subjected to hot-press molding to obtain a metal foil laminate. The hot-press pressure conditions are 0.2-2 MPa and 150-250°C for 2-4 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 prepregs described above.

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

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

[0081] The aforementioned 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, in which the heat resistance of the circuit board is greatly improved, so that the safety of the electronic device is significantly improved.

[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 Chemical Industry 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 raised to 110° C., 30 g of hydrocarbon resin (B3000 manufactured by Soda Co., Ltd.) is added, 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 raised to 120° C., 45 g of hydrocarbon resin (B2000 manufactured by Soda Co., Ltd.) is added, the reaction is continued at 120° C. for 30 minutes, and then 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 raised to 120° C., 25 g of hydrocarbon resin (B3000 manufactured by Soda Co., Ltd.) is added, the reaction is continued at 120° C. for 30 minutes, and then 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 Chemical Industry Co., Ltd., BMI-2300), 20 g of double bond-containing organic silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-164A), 30 g of hydrocarbon resin (manufactured by Soda Co., Ltd., B3000) and an appropriate amount of organic solvent are added, and the mixture is reacted at 100°C for 100 minutes to obtain a 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 (BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd.), 30 g of hydrocarbon resin (B3000, manufactured by Soda Co., Ltd.) 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 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 a preliminary reaction product Y4.

[0092] Comparative Synthesis Example 2 Modified bismaleimide prepolymer Y7 200 g of bismaleimide resin (manufactured by Daiwa Kasei, BMI-2300), 45 g of hydrocarbon resin (manufactured by Soda, B3000) and 0.1 g of initiator are added to a beaker and reacted at 110° C. for 120 minutes to obtain a preliminary reaction product Y5.

[0093] According to the data in Table 1, the corresponding solids are weighed out, and each weighed solid is adjusted with a solvent so that the solid content of the adhesive liquid is 60%. The adhesive liquid is applied to an E-glass fiber cloth, and after it is wetted, it is 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 to 300 x 300 mm, one electrolytic copper foil is placed on each side of the prepreg, stacked into a certain stacking structure, and fed into a vacuum press for pressure bonding to obtain a metal foil laminate (or copper clad laminate). The specific performance test is 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 the 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 2 hours, weighed and designated as W1, and then treated in a pressure cooker tester at 121°C and 2 atm for 2 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 by TMA (thermomechanical analysis), the heating rate is 10℃ / min, and the test temperature range is 30~100℃. 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 value. Among them, Example 2 has a higher Tg value, a lower dielectric constant and loss tangent than Comparative Example 1, and Example 1 has a higher Tg value, a lower dielectric constant and loss tangent, and a lower CTE and water absorption than Comparative Example 2.

[0100] It should be understood that although the present specification has been described in terms of embodiments, each embodiment does not include only one independent technical solution, and such description in the specification is merely for the purpose of clarification, and a person 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 can be understood by a person skilled in the art.

[0101] The above detailed description is merely a specific description of possible embodiments of the present invention, and does not limit the protection scope of the present invention. Any equivalent embodiments or modifications that do not depart 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): 【Chemical 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】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 (Wherein, n is 1.) 【Chemistry 7】 (Wherein, n is 1.) 【Chemistry 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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