Modified maleimide prepolymer, resin composition and application thereof

Abstract

The invention provides a modified maleimide prepolymer, a resin composition and application thereof, the modified maleimide prepolymer comprises 5-70 parts by weight of a first maleimide compound as shown in a structural formula (1), 10-80 parts by weight of a second maleimide compound as shown in a structural formula (2), and 5-70 parts by weight of a third maleimide compound as shown in a structural formula (3), 5-70 parts by weight of a diamino compound, 0.1-10 parts by weight of a reaction aid and a structural formula (1), n is an integer of 1-20, R1 is hydrogen or C1-C5 alkyl, and a is an integer of 0-4; in the structural formula (2), R is hydrogen, C1-C5 alkyl, phenyl or n is an integer of 1-20; in the structural formula (3), R1 and R2 are hydrogen or C1-C5 alkyl, X is hydrogen or, and a is an integer of 0-4. When the modified maleimide prepolymer is applied to the laminated board, the modified maleimide prepolymer has relatively good reactivity, solubility and dielectricity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic materials, in particular to a modified maleimide prepolymer, a resin composition containing the modified maleimide prepolymer and application of the resin composition. BACKGROUND

[0002] In recent years, information technology has entered a stage of signal high-speed and transmission high-frequency. In order to match the increasing data processing amount, the frequency of electronic devices is getting higher and higher, which puts forward higher requirements on the electrical properties of substrates to reduce the loss and delay of high-frequency signals as much as possible. With the advent of the 5G era, represented by applications such as high-frequency RF (such as PA, WiGig, WiHD / 60GHz, etc.), large-size chips, DDR5 (3.2-6.4Gbps), higher requirements are put forward for the performance of packaging substrate materials, and substrate materials with low planar thermal expansion coefficient, lower dielectric constant and dielectric loss, higher heat resistance and more stable comprehensive performance are needed.

[0003] Bismaleimide resin (BMI) is a kind of high-temperature resistant and high-modulus resin, and is one of the indispensable main resin materials in the field of packaging substrates. However, bismaleimide resin is difficult to dissolve in low-boiling-point solvents such as acetone and ethanol, and can only be dissolved in high-boiling-point strong polar solvents (high toxicity and high price), such as N-dimethylformamide (DMF). When preparing prepreg, if a large amount of these solvents is used, not only serious environmental pollution will be caused, but also great difficulty will be brought to the processing technology, and even the quality of the copper-clad substrate will be affected. Therefore, improving the solubility of bismaleimide resin has been an important research topic at home and abroad. In the prior art, the method of modifying prepolymers is often used to improve the solubility of maleimide resin, and allyl compounds, aromatic diamine compounds or cyanate ester compounds are generally used for prepolymers modification. This method improves the processability of maleimide resin to some extent, but there are limitations in the structure of maleimide resin. When there are unreacted maleimide groups in the cured product, the water absorption of the prepreg or the electrical copper-clad substrate increases during use, the dielectric properties decrease, and the reliability of the substrate is affected. SUMMARY

[0004] The purpose of the present application is to provide a modified maleimide prepolymer, which is modified by maleimide compounds and diamino compounds with different structures, not only optimizes the reactivity and solubility of the maleimide prepolymer, but also improves the dielectric properties, solving the problem of poor solubility and reactivity of maleimide resin in the prior art, which leads to the decrease of dielectric properties when applied to prepreg.

[0005] In order to achieve one of the above-mentioned purposes, one embodiment of the present application provides a modified maleimide prepolymer, comprising: a first maleimide compound represented by structural formula (1): 5-70 parts by weight, a second maleimide compound represented by structural formula (2): 10-80 parts by weight, a third maleimide compound represented by structural formula (3): 5-70 parts by weight, a diamino compound: 5-70 parts by weight, a reaction aid: 0.1-10 parts by weight, structural formula (1), n is an integer of 1-20, R1 is hydrogen or C1-C5 alkyl, and a is an integer of 0-4; structural formula (2), R is hydrogen, C1-C5 alkyl, phenyl or n is an integer of 1-20; structural formula (3), R1 and R2 are the same or different, and are hydrogen or C1-C5 alkyl, X is hydrogen or a is an integer of 0-4.

[0006] In one embodiment of the present application, the third maleimide compound represented by structural formula (3) is at least one of the following structures: structural formula (3-1), m is an integer of 1-10; structural formula (3-2), m is an integer of 1-10; structural formula (3-3), m is an integer of 1-10.

[0007] In one embodiment of the present application, the content of the first maleimide compound is 10-50 parts by weight, the content of the second maleimide compound is 20-50 parts by weight, the content of the third maleimide compound is 10-50 parts by weight, the content of the diamino compound is 10-40 parts by weight, and the content of the reaction aid is 0.5-3 parts by weight.

[0008] In one embodiment of the present application, the diamino compound is selected from at least one of an aromatic diamino compound, an aliphatic diamino compound, and a silicone diamino compound.

[0009] In one embodiment of the present application, the aromatic diamino compound is selected from at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodi phenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenyl fluorene, diaminanthraquinone; The aliphatic diamino compound is selected from at least one of dimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, diaminocyclohexane, tetramethyldisiloxane diamine, polydiamine, or bisaminocyclohexyl methane; The organosilicon diamino compound is shown in the following structural formula (4): In the structural formula (4), n is an integer from 1 to 20, and m is an integer from 1 to 5.

[0010] In one embodiment of the present application, the amino equivalent weight of the diamino compound is from 400 to 1600 g / mol.

[0011] In one embodiment of the present application, the reaction aid is an amino phenol, a carboxylic acid, or a carboxylic anhydride.

[0012] In one embodiment of the present application, the amino phenol is 4-aminophenol, the carboxylic acid is at least one of maleic acid, phthalic acid, succinic acid, and acetic acid, and the carboxylic anhydride is at least one of citric anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride.

[0013] One embodiment of the present application further provides a resin composition, comprising: the aforementioned modified maleimide prepolymer: 50 to 100 parts by weight; polyphenylene ether resin: 20 to 80 parts by weight; In the polyphenylene ether resin, a carbon-carbon double bond is contained.

[0014] In one embodiment of the present application, the polyphenylene ether resin contains the following structural formula (5) or structural formula (6): In the structural formula (5), R1, R2, and R3 are the same or different, and are hydrogen or C1-C5 alkyl, and Ar is phenylene, substituted phenylene, naphthylene, or substituted naphthylene. In the structural formula (6), R is hydrogen or C1-C5 alkyl.

[0015] In one embodiment of the present application, the polyphenylene ether resin is represented by structural formula (7) or / and structural formula (8): structural formula (7), structural formula (8); wherein R1, R2, R3, R4, R5, R6, R7, R8 are the same or different, selected from hydrogen or any one of C1-C5 alkyl, Y is no bond, -O-, methylene, ethylene, , or , n is an integer of 1-20, and m is an integer of 1-20.

[0016] In one embodiment of the present application, the resin composition further comprises 5-60 parts by weight of a hydrocarbon.

[0017] In one embodiment of the present application, the hydrocarbon is at least one of polybutadiene, di-functional styrene compound, tri-functional or multi-functional styrene compound, polyisoprene, epoxy-modified polyisoprene, hydroxyl-modified polyisoprene, styrene-butadiene copolymer, styrene-divinylbenzene-butadiene copolymer, styrene-divinylbenzene copolymer, styrene-isoprene copolymer, maleic anhydride-modified styrene-butadiene copolymer, and maleic anhydride-modified styrene-isoprene copolymer.

[0018] In one embodiment of the present application, the hydrocarbon is at least one of the following structures: wherein R is methylene, ethylene or hexylene, , .

[0019] One embodiment of the present application further provides an application of the aforementioned resin composition in a prepreg, a laminated board, and a circuit substrate.

[0020] The one or more technical solutions provided by the present application have at least the following technical effects or advantages: The modified maleimide prepolymer provided by the application is modified by reacting three low-dielectric maleimide compounds with different structures and different reactivities with a diamino compound, which not only maintains the high heat resistance of the maleimide resin itself, but also well adjusts the solvent solubility and reactivity of the maleimide compound. Excellent compatibility is maintained between different maleimide compounds, the reaction with the diamino compound is fully carried out, and suitable fluidity is maintained. When the modified maleimide prepolymer provided by the application is combined with other resins to form a composition and applied to a circuit substrate, the thickness uniformity of the substrate material and the substrate quality can be well improved, and finally a copper-clad plate material with low dielectric, high heat resistance, low CTE, high modulus and high processability is obtained. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0022] The embodiment of the application provides a modified maleimide prepolymer, which comprises: a first maleimide compound shown in structural formula (1): 5-70 parts by weight, a second maleimide compound shown in structural formula (2): 10-80 parts by weight, a third maleimide compound shown in structural formula (3): 5-70 parts by weight, a diamino compound: 5-70 parts by weight, a reaction aid: 0.1-10 parts by weight, Structural formula (1), n is an integer of 1-20, R1 is hydrogen or C1-C5 alkyl, and a is an integer of 0-4; Structural formula (2), R is hydrogen, C1-C5 alkyl, phenyl or n is an integer of 1-20; Structural formula (3), R1 and R2 are the same or different, and are hydrogen or C1-C5 alkyl, X is hydrogen or a is an integer of 0-4.

[0023] It should be noted that a in structural formula (1) and structural formula (3) is the number of connections of the corresponding groups R1 and X on the benzene ring connected thereto, which can be referred to as structural formula (3-2) below.

[0024] The application uses three low dielectric maleimide compounds with different structures and different reactivity to react with diamino compounds for modification, which not only maintains the high heat resistance of maleimide resin itself, but also well adjusts the solvent solubility and reactivity of maleimide compounds. The different maleimide compounds maintain excellent compatibility, the reaction with diamino compounds is fully carried out, and the appropriate flowability is maintained. When the modified maleimide prepolymer provided by the application is combined with other resins to form a composition and applied to a circuit substrate, the thickness uniformity of the substrate material and the substrate quality can be well improved, and finally a copper-clad plate material with low dielectric, high heat resistance, low CTE, high modulus and high processability is obtained.

[0025] Preferably, the third maleimide compound represented by the structural formula (3) is at least one of the following structures: The structural formula (3-1), m is an integer of 1-10; The structural formula (3-2), m is an integer of 1-10; The structural formula (3-3), m is an integer of 1-10.

[0026] The first maleimide compound represented by the structural formula (1) is selected from X-9470 or X-9480 or X-9450 prepared by DIC Company of Japan; the second maleimide compound represented by the structural formula (2) is selected from MIR3000 prepared by Japan Chemical Company; and the third maleimide compound represented by the structural formula (3) is selected from MIR5000 prepared by Japan Chemical Company or X-9500 prepared by DIC Company of Japan.

[0027] In some embodiments of the application, the content of the first maleimide compound is 10-50 parts by weight, the content of the second maleimide compound is 20-50 parts by weight, the content of the third maleimide compound is 10-50 parts by weight, the content of the diamino compound is 10-40 parts by weight, and the content of the reaction aid is 0.5-3 parts by weight.

[0028] In some embodiments of the application, the diamino compound is selected from at least one of aromatic diamino compounds, aliphatic diamino compounds and organosilicon diamino compounds.

[0029] Preferably, the aromatic diamino compound is at least one selected from the group consisting of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodi phenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenyl fluorene, and diaminanthraquinone.

[0030] The aliphatic diamino compound is selected from the group consisting of dimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, diaminocyclohexane, tetramethyldisiloxane diamine, polydiamine, and bisaminocyclohexyl methane.

[0031] The organosilicon diamino compound is shown in the following structural formula (4): In the structural formula (4), n is an integer from 1 to 20, and m is an integer from 1 to 5.

[0032] Among the various substances listed above, all isomers of the listed substances are included.

[0033] Preferably, the amino equivalent weight of the diamino compound is 400-1600 g / mol.

[0034] The diamino compound is preferably an organosilicon diamino compound shown in the structural formula (4), which is distributed in a long chain in a high-rigidity maleimide crosslinking network system, effectively improving the toughness of the substrate material, thereby reducing the thermal expansion coefficient while maintaining high heat resistance.

[0035] The organosilicon diamino compound shown in the above structural formula (4) is selected from the group consisting of diamino compounds with trade names KF8010, X-22-161A or X-22-161B, and DOWSIL™ BY 16-853, which are prepared by Shin-Etsu Chemical Co., Ltd.

[0036] In some embodiments of the present application, the reaction aid is an amino phenol, a carboxylic acid, or a carboxylic anhydride.

[0037] Preferably, the amino phenol is 4-aminophenol, the carboxylic acid is at least one selected from the group consisting of maleic acid, phthalic acid, succinic acid, and acetic acid, and the carboxylic anhydride is at least one selected from the group consisting of citric anhydride, phthalic anhydride, succinic anhydride, and acetic anhydride.

[0038] The method for preparing the modified maleimide prepolymer is not particularly limited and can be obtained by the following method.

[0039] The first maleimide compound shown in structural formula (1), the second maleimide compound shown in structural formula (2), the third maleimide compound shown in structural formula (3), the diamino compound and the reaction aid are mixed and stirred uniformly, or are added to a reaction container in different sequences, and are reacted at a temperature of 90-160°C for 0.5-6 hours.

[0040] The application further provides a resin composition comprising: The modified maleimide prepolymer described above: 50-100 parts by weight; The polyphenyl ether resin: 20-80 parts by weight; The polyphenyl ether resin contains carbon-carbon double bonds.

[0041] The modified maleimide prepolymer is mixed with the polyphenyl ether resin containing carbon-carbon double bonds, which can improve the dielectric properties of the resin composition and enhance the reactivity of the resin composition.

[0042] Further, the polyphenyl ether resin contains the following structural formula (5) or structural formula (6) to provide carbon-carbon unsaturated double bonds: Structural formula (5), R1, R2 and R3 are the same or different, hydrogen or C1-C5 alkyl, and Ar is phenylene, substituted phenylene, naphthylene or substituted naphthylene; Structural formula (6), R is hydrogen or C1-C5 alkyl.

[0043] Preferably, the polyphenyl ether resin is shown in structural formula (7) or / and structural formula (8): Structural formula (7), Structural formula (8); wherein R1, R2, R3, R4, R5, R6, R7 and R8 are the same or different, selected from hydrogen or any one of C1-C5 alkyl, Y is no connection, -O-, methylene, ethylene, , or n is an integer of 1-20, and m is an integer of 1-20. Y is no connection, specifically, the benzene rings on the left and right sides of Y in structural formula (7) and structural formula (8) are directly connected.

[0044] The polyphenyl ether resin can be prepared by Mitsubishi Gas, with a brand of OPE-2St, or prepared by Shabik, with a brand of SA9000.

[0045] In some embodiments of the application, the resin composition further comprises 5-60 parts by weight of hydrocarbons.

[0046] Preferably, the hydrocarbon compound is at least one of polybutadiene, di-functional styrene compound, tri-functional or multi-functional styrene compound, polyisoprene, epoxy-modified polyisoprene, hydroxyl-modified polyisoprene, styrene-butadiene copolymer, styrene-divinylbenzene-butadiene copolymer, styrene-divinylbenzene copolymer, styrene-isoprene copolymer, maleic anhydride-modified styrene-butadiene copolymer, and maleic anhydride-modified styrene-isoprene copolymer.

[0047] In some embodiments of the present application, the hydrocarbon compound contains at least one of the following structures (9) and / or (10): Structure (9), R is hydrogen, C1-C5 alkyl or aryl, and n is an integer from 1 to 50. Structure (10), * is a connection point.

[0048] In some embodiments of the present application, the hydrocarbon compound further contains at least one of butadiene unit, isoprene unit, norbornene unit, acenylene unit, or fluorene unit.

[0049] In some embodiments of the present application, the hydrocarbon compound is at least one of the following structures: R is methylene, ethylene or hexylene, , ,

[0050] The hydrocarbon resin can be ODV resin prepared by Nippon Shokubai, styrene-butadiene resin prepared by Nippon Zeon, divinylbenzene fluorene compound or multi-functional styrene compound prepared by Nippon Kayaku, etc.

[0051] In some embodiments of the present application, the resin composition further contains 30-200 parts by weight of inorganic filler, which is at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0052] In some embodiments of the present application, the resin composition further contains 0.001-5 parts by weight of catalyst, which is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole, and 1-cyanoethyl-2-methylimidazole.

[0053] The application further provides application of the resin composition in a prepreg, a laminated board and a circuit substrate.

[0054] Specifically, the application further provides a prepreg comprising the reinforcing material and the resin composition. The prepreg is prepared by dissolving the resin composition in a solvent to form a glue solution, then immersing the reinforcing material in the glue solution, and taking out the immersed reinforcing material and baking it at 100-180°C for 1-15 min. The prepreg is obtained after drying.

[0055] The solvent is at least one selected from acetone, butanone, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene and cyclohexane.

[0056] The reinforcing material is at least one selected from natural fibers, organic synthetic fibers, organic fabrics and inorganic fabrics. Preferably, the reinforcing material is a glass fiber cloth. The glass fiber cloth preferably uses an open fiber cloth or a flat cloth. The glass fiber cloth is preferably an E glass fiber cloth, a T glass fiber cloth, an S glass fiber cloth or a Q glass fiber cloth.

[0057] In addition, when the reinforcing material is a glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent to improve the interface bonding between the resin composition and the glass fiber cloth. The coupling agent preferably uses an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0058] The application further provides a laminated board comprising a piece of the prepreg and a metal foil arranged on at least one side surface of the prepreg, or comprising a combined piece formed by stacking a plurality of the prepregs on each other and a metal foil arranged on at least one side surface of the combined piece.

[0059] The laminated board is prepared by covering a metal foil on one side or both sides of a piece of the prepreg, or stacking at least two pieces of the prepreg to form a combined piece, covering a metal foil on one side or both sides of the combined piece, and hot-pressing to form the metal foil laminated board. The pressing condition of the hot-pressing is 0.2-2 MPa and 150-250°C for 2-5 hours.

[0060] Preferably, the metal foil is selected from a copper foil or an aluminum foil. The thickness of the metal foil is 5 microns, 8 microns, 12 microns, 18 microns, 35 microns or 70 microns.

[0061] The application further provides a circuit substrate comprising at least one of the prepreg and the laminated board.

[0062] The technical solutions of the application are further described below in combination with some specific embodiments.

[0063] Synthesis Example 1: Modified maleimide prepolymer A In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser tube, and a volume of 1 L, 15.0 g of a diamino silicone resin (Shin-Etsu Chemical, X-22-161A), 40 g of a maleimide compound (Structural Formula (2), X-9470 manufactured by DIC, Japan), 1.5 g of 4-aminophenol, 200 g of propylene glycol monomethyl ether were added, and after reacting at 120°C for 2 h, the prepolymer number average molecular weight was 980 as measured by gel permeation chromatography (GPC), and then 30 g of a maleimide compound (Structural Formula (1), MIR3000 manufactured by DIC, Japan) and 30 g of a maleimide compound (Structural Formula (3), MIR5000 manufactured by DIC, Japan) were sequentially added, and the reaction was continued at 120°C for 2 h to obtain the final modified maleimide prepolymer A.

[0064] Synthesis Example 2: Modified maleimide prepolymer B In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser tube, and a volume of 1 L, 12.0 g of a diamino silicone resin (Shin-Etsu Chemical, X-22-161B), 20 g of a maleimide compound (Structural Formula (2), X-9470 manufactured by DIC, Japan), 0.5 g of 4-aminophenol, 200 g of propylene glycol monomethyl ether were added, and after reacting at 120°C for 2 h, the prepolymer number average molecular weight was 920 as measured by gel permeation chromatography (GPC), and then 40 g of a maleimide compound (Structural Formula (1), MIR3000 manufactured by DIC, Japan) and 40 g of a maleimide compound (Structural Formula (3), MIR5000 manufactured by DIC, Japan) were sequentially added, and the reaction was continued at 120°C for 2 h to obtain the final modified maleimide prepolymer B.

[0065] Synthesis Example 3: Modified maleimide prepolymer C In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser tube, and a volume of 1 L, 10.0 g of a diamino silicone resin (Shin-Etsu Chemical, X-22-161B), 10 g of a diamino diphenyl methane, 40 g of a maleimide compound (Structural Formula (2), X-9470 manufactured by DIC, Japan), 1.5 g of 4-aminophenol, 200 g of propylene glycol monomethyl ether were added, and after reacting at 125°C for 2 h, the prepolymer number average molecular weight was 1050 as measured by gel permeation chromatography (GPC), and then 30 g of a maleimide compound (Structural Formula (1), MIR3000 manufactured by DIC, Japan) and 30 g of a maleimide compound (Structural Formula (3), MIR5000 manufactured by DIC, Japan) were sequentially added, and the reaction was continued at 120°C for 2 h to obtain the final modified maleimide prepolymer C.

[0066] Synthesis Example 4: Modified maleimide prepolymer D In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1 L, 20 g of diaminodiphenylmethane, 40 g of a maleimide compound (Structural Formula (2), X-9470 manufactured by DIC, Japan), 1.5 g of 4-aminophenol, and 200 g of propylene glycol monomethyl ether were added, and after reaction at 125°C for 2 h, the number average molecular weight of the prepolymer was 870 as measured by gel permeation chromatography (GPC), and then 30 g of a maleimide compound (Structural Formula (1), MIR3000 manufactured by Japan Fine Chemical) and 30 g of a maleimide compound (Structural Formula (3), MIR5000 manufactured by Japan Fine Chemical) were sequentially added, and the reaction was continued at 120°C for 2 h to obtain a final modified maleimide prepolymer D.

[0067] Synthesis Example 5: Modified Maleimide Prepolymer G In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1 L, 20 g of diaminodiphenylmethane, 40 g of a maleimide compound (Structural Formula (2), X-9470 manufactured by DIC, Japan), 1.5 g of 4-aminophenol, and 200 g of propylene glycol monomethyl ether were added, and after reaction at 125°C for 2 h, the number average molecular weight of the prepolymer was 870 as measured by gel permeation chromatography (GPC), and then 30 g of a maleimide compound (Structural Formula (1), MIR3000 manufactured by Japan Fine Chemical) and 30 g of a maleimide compound (Structural Formula (3), MIR5000 manufactured by Japan Fine Chemical) were sequentially added, and the reaction was continued at 120°C for 2 h to obtain a final modified maleimide prepolymer D.

[0068] Comparative Synthesis Example 1: Modified Maleimide Prepolymer E In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1 L, 20 g of diaminodiphenylmethane, 40 g of a maleimide compound (Structural Formula (2), X-9470 manufactured by DIC, Japan), 1.5 g of 4-aminophenol, and 200 g of propylene glycol monomethyl ether were added, and after reaction at 125°C for 2 h, the number average molecular weight of the prepolymer was 870 as measured by gel permeation chromatography (GPC), and then 30 g of a maleimide compound (Structural Formula (1), MIR3000 manufactured by Japan Fine Chemical) and 30 g of a maleimide compound (Structural Formula (3), MIR5000 manufactured by Japan Fine Chemical) were sequentially added, and the reaction was continued at 120°C for 2 h to obtain a final modified maleimide prepolymer D.

[0069] Comparative Synthesis Example 2: Modified Maleimide Prepolymer F In a reaction vessel equipped with a thermometer, a stirring device, a reflux condenser, and a volume of 1 L, 20 g of diaminodiphenylmethane, 40 g of a maleimide compound (Structural Formula (2), X-9470 manufactured by DIC, Japan), 1.5 g of 4-aminophenol, and 200 g of propylene glycol monomethyl ether were added, and after reaction at 125°C for 2 h, the number average molecular weight of the prepolymer was 870 as measured by gel permeation chromatography (GPC), and then 30 g of a maleimide compound (Structural Formula (1), MIR3000 manufactured by Japan Fine Chemical) and 30 g of a maleimide compound (Structural Formula (3), MIR5000 manufactured by Japan Fine Chemical) were sequentially added, and the reaction was continued at 120°C for 2 h to obtain a final modified maleimide prepolymer D.

[0070] Table 1

[0071] Note: Polyphenylene ether resin is selected from OPE-2St-1200 made by Mitsubishi Gas, ODV resin is selected from made by JFE Chemical, and spherical silica is selected from D50 of 3.0 μm made by Lianrui.

[0072] According to the data in Table 1, the corresponding solid substances were weighed, the glue solution of each solid substance was adjusted to a solid content of 65% by butanone, the glue solution was coated on 2116E glass fiber cloth, and after soaking, it was taken out and placed in a 160℃ air drying oven for 5min to prepare a prepreg.

[0073] Two pieces of the above obtained prepreg were neatly stacked into a laminate, and one piece of 12μm low profile electrolytic copper foil was stacked on the upper and lower sides of the laminate, respectively, and then placed in a vacuum hot press to press at a pressure of 2Mpa and a temperature of 220℃ for 3 hours to obtain a laminate, and the specific performance detection is shown in Table 2.

[0074] Table 2

[0075] The above performance test methods are as follows: (1) Tg (DMA): measured by dynamic mechanical analysis (DMA) according to the DMA method specified in IPC-TM-650 2.4.24.4, unit: ℃; (2) Peel strength (PS): according to the experimental conditions of "after thermal stress" in IPC-TM-650 2.4.8 method, the peel strength of the plate is tested, and the unit of peel strength is N / mm; (3) Thickness uniformity: five samples are taken at the four corners and the middle position of the plate to test the thickness of the plate, if the thickness of the plate meets the third level tolerance of the copper-clad plate, the thickness uniformity is good, if the thickness of the plate cannot meet the third level tolerance of the copper-clad plate, the thickness uniformity is poor; (4) CTE: the laminate with a length of 60mm, a width of 4mm and a thickness of 0.20mm is taken as a sample, the glass fiber warp direction is Y direction, and the glass fiber weft direction is X direction, the sample is baked in a 105℃ oven for 1h and then cooled to room temperature in a dryer. The thermal analysis mechanical method (TMA) is used for measurement, the temperature rising rate is 10℃ / min, the temperature is raised from room temperature to 300℃, and the second temperature rising is carried out after the first temperature rising is cooled to room temperature and the sample is placed again, the result is the planar direction thermal expansion coefficient at 50℃ to 130℃ of the second temperature rising, unit: ppm / ℃; (5) Dk and Df: measured at 10GHz according to the method specified in IPC-TM-650 2.5.5.13 using the separated medium column resonant cavity method (SPDR); (6) Subsurface quality: after the copper foil is etched and removed, the internal quality of the substrate is observed under a microscope. When there are no defects such as resin defects, white lines, cavities, and dry flowers, the subsurface quality is good. When there are defects such as resin defects, white lines, cavities, and dry flowers, the subsurface quality is poor.

[0076] It should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the present specification is described in this way only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

[0077] The series of detailed descriptions listed above are only specific descriptions of the feasible embodiments of the present application, and are not intended to limit the protection scope of the present application. Any equivalent embodiments or changes made without departing from the spirit of the present application should be included in the protection scope of the present application.

Claims

1. A modified maleimide prepolymer, characterized in that, include: The first maleimide compound shown in structural formula (1): 5-70 parts by weight, The second maleimide compound shown in structural formula (2): 10-80 parts by weight, The third maleimide compound shown in structural formula (3): 5-70 parts by weight, Diamino compound: 5-70 parts by weight, Reaction aid: 0.1-10 parts by weight Structural formula (1), n ​​is an integer from 1 to 20, R1 is hydrogen or C1-C5 alkyl, a is an integer from 0 to 4; Structural formula (2), where R is hydrogen, C1-C5 alkyl, phenyl, or n is an integer from 1 to 20; In structural formula (3), R1 and R2 may be the same or different, and are hydrogen or C1-C5 alkyl groups, and X is hydrogen or , where a is an integer between 0 and 4.

2. The modified maleimide prepolymer according to claim 1, characterized in that, The third maleimide compound represented by structural formula (3) is at least one of the following structures: The structural formula is (3-1), where m is an integer from 1 to 10; The structure is (3-2), where m is an integer from 1 to 10; The structure is (3-3), where m is an integer from 1 to 10.

3. The modified maleimide prepolymer according to claim 1, characterized in that, The first maleimide compound is present in a content of 10-50 parts by weight, the second maleimide compound is present in a content of 20-50 parts by weight, the third maleimide compound is present in a content of 10-50 parts by weight, the diamino compound is present in a content of 10-40 parts by weight, and the reaction auxiliary is present in a content of 0.5-3 parts by weight.

4. The modified maleimide prepolymer according to claim 1, characterized in that, The diamino compound is selected from at least one of aromatic diamino compounds, aliphatic diamino compounds, and organosilicon diamino compounds.

5. The modified maleimide prepolymer according to claim 4, characterized in that, The aromatic diamino compound is selected from at least one of the following: unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl sulfone, diaminodiphenyl fluorene, and diaminoanthraquinone. The aliphatic diamino compound is selected from dimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminocyclohexane, tetramethyldisiloxanediamine, polydiamine, or diaminocyclohexylmethane. Organosilicon diamino compounds are shown in structural formula (4): The structure is (4), where n is an integer from 1 to 20 and m is an integer from 1 to 5.

6. The modified maleimide prepolymer according to claim 5, characterized in that, The amino equivalent of the diamino compound is 400-1600 g / mol.

7. The modified maleimide prepolymer according to claim 1, characterized in that, The reaction aid is aminophenol, carboxylic acid, or carboxylic anhydride.

8. The modified maleimide prepolymer according to claim 7, characterized in that, The aminophenol is 4-aminophenol, the carboxylic acid is at least one of maleic acid, phthalic acid, succinic acid and acetic acid, and the carboxylic anhydride is at least one of citric anhydride, phthalic anhydride, succinic anhydride and acetic anhydride.

9. A resin composition, characterized in that, include: The modified maleimide prepolymer according to any one of claims 1 to 8: 50-100 parts by weight; Polyphenylene ether resin: 20-80 parts by weight; The polyphenylene ether resin contains carbon-carbon double bonds.

10. The resin composition according to claim 9, characterized in that, The polyphenylene ether resin contains the following structural formula (5) or structural formula (6): Structural formula (5), R1, R2 and R3 are the same or different, are hydrogen or C1-C5 alkyl, and Ar is phenylene, substituted phenylene, naphthylene or substituted naphthylene; The structural formula is (6), where R is hydrogen or a C1-C5 alkyl group.

11. The resin composition according to claim 10, characterized in that, The polyphenylene ether resin is as shown in structural formula (7) or / and structural formula (8): Structural formula (7). Structure (8); Wherein, R1, R2, R3, R4, R5, R6, R7, and R8 may be the same or different, and are selected from hydrogen or any alkyl group of C1-C5; Y is a no-linking bond, -O-, methylene, ethylene, etc. , or n is an integer from 1 to 20, and m is an integer from 1 to 20.

12. The resin composition according to claim 9, characterized in that, It also includes 5-60 parts by weight of hydrocarbons.

13. The resin composition according to claim 12, characterized in that, The hydrocarbon is selected from at least one of the following: polybutadiene, difunctional vinylbenzene compound, trifunctional or polyfunctional vinylbenzene compound, polypentadiene, epoxy-modified polypentadiene, hydroxyl-modified polypentadiene, styrene-butadiene copolymer, styrene-divinylbenzene-butadiene copolymer, styrene-divinylbenzene copolymer, styrene-pentadiene copolymer, maleic anhydride-modified styrene-butadiene copolymer, and maleic anhydride-modified styrene-pentadiene copolymer.

14. The resin composition according to claim 12, characterized in that, The hydrocarbon is at least one of the following structures: R is methylene, ethylene, or hexylene. ， 。 15. The use of a resin composition as described in any one of claims 9 to 14 in prepreg, laminate, or circuit board.

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