Maleimide resin composition and use thereof

Abstract

A maleimide resin composition and the use thereof. The maleimide resin composition comprises 100 parts by weight of a maleimide resin or a modified prepolymer thereof, 5-60 parts by weight of a cyanate ester, and 10-60 parts by weight of a phosphorus-containing styrene copolymer. Also provided is the phosphorus-containing styrene copolymer as represented by structural formula (1). The resin composition not only has relatively good compatibility, but also has good flame retardance; in addition, the introduction of styryl can further reduce the dielectric constant and dielectric loss, and improve the heat resistance and the peel strength.

Description

Maleimide resin composition and application thereof

[0001] This application is based on the Chinese patent application with application number CN202311804603.2 and application date of December 26, 2023, and claims the priority of the Chinese patent application. The entire content of the above patent application is hereby introduced into this application as a reference. Technical Field

[0002] The present application belongs to the technical field of electronic materials and relates to a maleimide resin composition and the application of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates and electronic devices. Background Art

[0003] In recent years, with the development of computer technology and the development of information and communication equipment towards high performance, high functionality and networking, information and communication require high-speed transmission and processing of large amounts of information, and operating signals are also tending towards high frequencies. The realization of the above technological developments depends on the materials of circuit substrates.

[0004] Currently, epoxy resin and maleimide resin are the most widely used materials for printed circuit boards. Although epoxy resin has excellent bonding properties, circuit boards made from epoxy resin have high dielectric constants and dielectric loss tangents. The dielectric constant is greater than 4, and the dielectric loss tangent is approximately 0.02. The high-frequency characteristics are insufficient and cannot meet the requirements of high-frequency signals. Maleimide resin has excellent heat resistance, high modulus, and good machinability, making it suitable as a base resin for IC packaging substrates and similar substrates. However, maleimide resin has poor dielectric properties, which limits its application in the field of high-frequency and high-speed packaging substrates. Summary of the Invention

[0005] The present application provides a maleimide resin composition and the use of the resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates and electronic devices to solve the problem of poor dielectric properties of maleimide resins.

[0006] To achieve the above application objectives, one embodiment of the present application provides a maleimide resin composition, which comprises, by weight:

[0007] 100 parts by weight of maleimide resin or its modified prepolymer;

[0008] 5-60 parts by weight of cyanate;

[0009] 10-60 parts by weight of phosphorus-containing styrene copolymer;

[0010] The structure of the phosphorus-containing styrene copolymer is

[0011] In the structural formula (1), X is hydrogen or any C1-C5 alkyl group, and n is an integer of 1 to 20.

[0012] As a further improvement of one embodiment of the present application, in the structural formula (1), X is hydrogen or methyl.

[0013] As a further improvement of one embodiment of the present application, the cyanate ester is at least one of bisphenol A cyanate ester, bisphenol F cyanate ester, bisphenol E cyanate ester, bisphenol M cyanate ester, DCPD cyanate ester, naphthalene cyanate ester, phenolic cyanate ester, and biphenyl cyanate ester.

[0014] As a further improvement of one embodiment of the present application, the cyanate ester is selected from at least one of the following structures:

[0015] Structural formula (2), R is hydrogen or methyl, n is an integer from 1 to 10;

[0016] Structural formula (3), z is an integer from 1 to 10.

[0017] As a further improvement of one embodiment of the present application, the maleimide resin contains at least two maleimide groups in its molecular structure.

[0018] As a further improvement of one embodiment of the present application, the maleimide resin is preferably at least one of the following structures:

[0019] Structural formula (4);

[0020] Structural formula (5);

[0021] Structural formula (6);

[0022] Structural formula (7), R1 is methylene, ethylene or , R2 is hydrogen, methyl or ethyl, and n is an integer from 1 to 10;

[0023] Structural formula (8);

[0024] Structural formula (9), n is an integer from 1 to 10;

[0025] Structural formula (10), n is an integer from 1 to 10;

[0026] Structural formula (11), n ​​is an integer from 1 to 10;

[0027] Structural formula (12);

[0028] In the structural formula (13), R is hydrogen, methyl or ethyl, and n is an integer from 1 to 10.

[0029] As a further improvement of one embodiment of the present application, the modified prepolymer of maleimide resin is at least one of a prepolymer of a diallyl compound and a maleimide resin, a prepolymer of a diamine compound and a maleimide resin, and a prepolymer of an acidic phenol compound and a maleimide resin.

[0030] As a further improvement of one embodiment of the present application, the diallyl compound is a diallyl diphenol compound, and the diallyl diphenol compound is at least one of diallyl bisphenol A, diallyl bisphenol F, a diallyl biphenyl compound, and diallyl bisphenol S.

[0031] As a further improvement of one embodiment of the present application, the diamine compound is at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylenediamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenylfluorene, and diaminoanthraquinone.

[0032] As a further improvement of one embodiment of the present application, the acidic phenol compound is aminophenol.

[0033] As a further improvement of one embodiment of the present application, the maleimide resin composition further comprises 5 to 30 parts by weight of epoxy resin.

[0034] As a further improvement of one embodiment of the present application, the epoxy resin is preferably selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin.

[0035] As a further improvement of one embodiment of the present application, the epoxy resin is at least one of the following structures:

[0036] Structural formula (14), p is an integer from 1 to 10;

[0037] Structural formula (15), n is an integer from 1 to 10;

[0038] Structural formula (16), m is an integer from 1 to 10;

[0039] Structural formula (17), n is an integer from 1 to 10;

[0040] Structural formula (18), n is an integer from 1 to 10.

[0041] As a further improvement of one embodiment of the present application, the maleimide resin composition further includes 5 to 60 parts by weight of an elastomer; the elastomer is selected from at least one of a styrene elastomer, an acrylic elastomer, and a silicone elastomer.

[0042] As a further improvement of one embodiment of the present application, the styrene-based elastomer is at least one of a hydrogenated styrene and butadiene diblock copolymer, a hydrogenated styrene and butadiene triblock copolymer, a hydrogenated styrene and pentadiene diblock copolymer, and a hydrogenated styrene and pentadiene triblock copolymer.

[0043] As a further improvement of one embodiment of the present application, the structure of the acrylic elastomer is at least one of the following structures:

[0044] Structural formula (19), R1 is any one of C1-C5 alkyl groups, and x is an integer from 1 to 100;

[0045] In the structural formula (20), R2 is any one of C1-C5 alkyl groups, and y is an integer from 1 to 100.

[0046] As a further improvement of one embodiment of the present application, the silicone elastomer includes at least one of the following structures:

[0047] Structural formula (21), R is any one of C1-C12 hydrocarbon groups or any one of C1-C12 alkoxy groups;

[0048] Structural formula (22), R is any one of C1-C12 hydrocarbon groups or any one of C1-C12 alkoxy groups;

[0049] In the structural formula (23), X is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group.

[0050] As a further improvement of one embodiment of the present application, the maleimide resin composition further includes 30 to 250 parts by weight of an inorganic filler.

[0051] As a further improvement of one embodiment of the present application, the inorganic filler is selected from 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] As a further improvement of one embodiment of the present application, the inorganic filler is pre-surface-treated with a silane coupling agent, and the silane coupling agent is an aminosilane coupling agent.

[0053] As a further improvement of one embodiment of the present application, the maleimide resin composition further includes 0.01 to 5 parts by weight of a catalyst, and the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0054] As a further improvement of one embodiment of the present application, the catalyst is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole and zinc octoate.

[0055] The present application also provides applications of the maleimide resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates, and electronic devices.

[0056] Due to the application of the above-mentioned technical solution, the present application has the following beneficial effects compared with the prior art: by adding a phosphorus-containing styrene copolymer to the maleimide resin system, not only is the compatibility with the components in the resin composition better, but the larger DOPO group is also well introduced into the maleimide resin system, making it have excellent flame retardancy. In addition, the introduction of the styrene group can further reduce the dielectric constant and dielectric loss, improve heat resistance, and improve peel strength.

[0057] As used herein, the term "comprise" and variations of the term, such as "comprises," "comprised," "comprising," "including," and "containing" do not exclude other features, components, elements, or steps unless the context clearly requires otherwise. DETAILED DESCRIPTION

[0058] The technical solution of the present application will be further introduced below in conjunction with specific implementation methods. The following embodiments are merely descriptive and not restrictive, and should not be used to limit the scope of protection of the present application.

[0059] One embodiment of the present application provides a maleimide resin composition and a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate and an electronic device made using the maleimide resin composition, that is, the use of the maleimide resin composition in a prepreg, a laminate, an insulating board, an insulating film, a circuit substrate and an electronic device.

[0060] First, the present application provides a maleimide resin composition, comprising, by weight:

[0061] 100 parts by weight of maleimide resin or its modified prepolymer;

[0062] 5-60 parts by weight of cyanate;

[0063] 10-60 parts by weight of phosphorus-containing styrene copolymer;

[0064] The structure of the phosphorus-containing styrene copolymer is

[0065] In the structural formula (1), X is hydrogen or any C1-C5 alkyl group, and n is an integer of 1 to 20.

[0066] By adding a phosphorus-containing styrene copolymer to the maleimide resin system, not only is the compatibility with the various components in the resin composition improved, but the larger DOPO group is also well introduced into the maleimide resin system, giving it excellent flame retardancy. In addition, the introduction of the styrene group can further reduce the dielectric constant and dielectric loss, improve heat resistance, and increase peel strength.

[0067] Preferably, in the structural formula (1), X is hydrogen or methyl, which can further improve the compatibility of the components in the resin composition.

[0068] Preferably, the cyanate ester is at least one of bisphenol A cyanate ester, bisphenol F cyanate ester, bisphenol E cyanate ester, bisphenol M cyanate ester, DCPD cyanate ester, naphthalene cyanate ester, phenolic cyanate ester, and biphenyl cyanate ester.

[0069] Furthermore, the cyanate ester is selected from at least one of the following structures:

[0070] Structural formula (2), R is hydrogen or methyl, n is an integer from 1 to 10;

[0071] Structural formula (3), z is an integer from 1 to 10.

[0072] Preferably, the maleimide resin contains at least two maleimide groups in its molecular structure.

[0073] Furthermore, the maleimide resin is preferably at least one of the following structures:

[0074] Structural formula (4);

[0075] Structural formula (5);

[0076] Structural formula (6);

[0077] Structural formula (7), R1 is methylene, ethylene or , R2 is hydrogen, methyl or ethyl, and n is an integer from 1 to 10;

[0078] Structural formula (8);

[0079] Structural formula (9), n is an integer from 1 to 10;

[0080] Structural formula (10), n is an integer from 1 to 10;

[0081] Structural formula (11), n ​​is an integer from 1 to 10;

[0082] Structural formula (12);

[0083] In the structural formula (13), R is hydrogen, methyl or ethyl, and n is an integer from 1 to 10.

[0084] Preferably, the modified prepolymer of maleimide resin is at least one of a prepolymer of a diallyl compound and a maleimide resin, a prepolymer of a diamine compound and a maleimide resin, and a prepolymer of an acidic phenol compound and a maleimide resin.

[0085] The diallyl compound is preferably a diallyl diphenol compound, and the diallyl diphenol compound is at least one of diallyl bisphenol A, diallyl bisphenol F, a diallyl biphenyl compound, and diallyl bisphenol S.

[0086] The diamine compound is preferably at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylenediamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenylfluorene, and diaminoanthraquinone.

[0087] The acidic phenol compound is preferably an aminophenol.

[0088] Specifically, the maleimide resin can be selected from BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, BMI-7000H manufactured by Yamato Chemical Industry Co., Ltd.; BMI, BMI-70, BMI-80 manufactured by KI Chemical Industry Co., Ltd. of Japan; MIR-3000, MIR-5000 manufactured by Nippon Kayaku Co., Ltd.; X9-450, X9-470 manufactured by DIC Corporation of Japan; D936, D937, D939, D950 manufactured by Sichuan Dongcai Co., Ltd.

[0089] The maleimide resin is preferably BMI-2300 manufactured by Yamato Chemicals, BMI-70 and BMI-80 manufactured by KI Chemicals, or MIR-3000 manufactured by Nippon Kayaku Co., Ltd.

[0090] Furthermore, the maleimide resin composition further comprises 5 to 30 parts by weight of epoxy resin.

[0091] The epoxy resin is preferably selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl linear novolac epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ether epoxy resin, and glycidyl ester epoxy resin.

[0092] More preferably, the epoxy resin is at least one of the following structures:

[0093] Structural formula (14), p is an integer from 1 to 10;

[0094] Structural formula (15), n is an integer from 1 to 10;

[0095] Structural formula (16), m is an integer from 1 to 10;

[0096] Structural formula (17), n is an integer from 1 to 10;

[0097] Structural formula (18), n is an integer from 1 to 10.

[0098] Furthermore, the maleimide resin composition further comprises 5 to 50 parts by weight of a flame retardant, and the flame retardant is preferably at least one selected from the group consisting of a brominated flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, and an organometallic salt flame retardant.

[0099] Preferably, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide;

[0100] The phosphorus flame retardant is selected from inorganic phosphorus, phosphate ester, phosphoric acid, hypophosphorous acid, phosphorus oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (m is an integer from 1 to 5), , 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, phosphazene, modified phosphazene.

[0101] Among them, the DOPO group is .

[0102] Furthermore, the maleimide resin composition further comprises 5 to 60 parts by weight of an elastomer, preferably at least one selected from styrene elastomers, acrylic elastomers, and silicone elastomers.

[0103] Preferably, the styrene-based elastomer is at least one of a hydrogenated styrene and butadiene diblock copolymer, a hydrogenated styrene and butadiene triblock copolymer, a hydrogenated styrene and pentadiene diblock copolymer, and a hydrogenated styrene and pentadiene triblock copolymer.

[0104] Specifically, the styrene elastomer can be selected from H1041, H1043, H1051, H1052, H1053, H1221, P1500, P2000, M1911 or M1913 manufactured by Asahi Kasei Corporation; 8004, 8006, 8076, 8104, V9827, 2002, 2005, 2006, 2007, 2104, 7125, 4033, 4044, 4055, 4077 or 4099 manufactured by Kuraray.

[0105] The structure of the acrylic elastomer is at least one of the following structures:

[0106] Structural formula (19), R1 is any one of C1-C5 alkyl groups, and x is an integer from 1 to 100;

[0107] In the structural formula (20), R2 is any one of C1-C5 alkyl groups, and y is an integer from 1 to 100.

[0108] The acrylic elastomer may be selected from M51, M52, M22 or D51N manufactured by Arkema; ​​LA-2330 manufactured by Kuraray; SG-P3 series or SG-80 series manufactured by Nagase.

[0109] The silicone elastomer includes at least one of the following structures:

[0110] Structural formula (21), R is any one of C1-C12 hydrocarbon groups or any one of C1-C12 alkoxy groups;

[0111] Structural formula (22), R is any one of C1-C12 hydrocarbon groups or any one of C1-C12 alkoxy groups;

[0112] In the structural formula (23), X is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group.

[0113] Silicone elastomers can be selected from X-40-2670, R-170S, X-40-2705, X-40-2701, KMP-600, KMP-605, X-52-7030 manufactured by Shin-etsu Chemical Co., Ltd.; AY-42-119, EP-2600, EP-2601, EP-2720, TMS-2670, EXL-2315, EXL-2655 manufactured by DOW.

[0114] Furthermore, the maleimide resin composition further comprises 30 to 250 parts by weight of an inorganic filler.

[0115] The inorganic filler is preferably at least one selected from 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; more preferably selected from spherical silica.

[0116] More preferably, the inorganic filler is surface-treated with a silane coupling agent in advance, and the silane coupling agent is preferably an aminosilane coupling agent.

[0117] Specifically, the aminosilane coupling agent can be KBM-573, KBE-903, KBM-602, KBM-903, KBM-603, KBM-1403 manufactured by Shin-Etsu Chemical, or Z-6610 or Z-6883 manufactured by Dow Corning.

[0118] Preferably, the maleimide resin composition further comprises 0.01 to 5 parts by weight of a catalyst, wherein the catalyst is at least one of an imidazole catalyst, a pyridine catalyst, and an organic metal salt catalyst.

[0119] The catalyst is preferably at least one selected from 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole and zinc octoate.

[0120] The present application also provides applications of the maleimide resin composition in prepregs, laminates, insulating boards, insulating films, circuit substrates, and electronic devices, as specifically described below:

[0121] The present application also provides a prepreg, comprising a reinforcing material and the aforementioned maleimide resin composition, wherein the maleimide resin composition is wrapped on the reinforcing material.

[0122] The preparation method of the semi-cured sheet is as follows: the maleimide resin composition is dissolved in a solvent to prepare a glue solution, and then the reinforcing material is immersed in the glue solution. The immersed reinforcing material is taken out and baked at a temperature of 100-180°C for 1-15 minutes; after drying, the semi-cured sheet is obtained.

[0123] The solvent may be selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0124] The reinforcing material can be selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics, preferably glass fiber cloth, more preferably E glass fiber cloth, S glass fiber cloth, T glass fiber cloth, or Q glass fiber cloth. The glass fiber cloth is preferably open fiber cloth or flat cloth.

[0125] In addition, when glass fiber cloth is used as the reinforcing material, the glass fiber cloth is chemically treated with a coupling agent in advance to improve the interfacial bonding between the maleimide resin composition and the glass fiber cloth. The coupling agent is preferably an epoxy silane coupling agent or an amino silane coupling agent to impart good water resistance and heat resistance to the reinforcing material.

[0126] The present application also provides a laminate comprising a piece of the aforementioned prepreg and a metal foil disposed on at least one surface of the prepreg; or comprising a composite sheet formed by overlapping a plurality of the aforementioned prepregs and a metal foil disposed on at least one surface of the composite sheet.

[0127] The laminate is prepared by coating one or both sides of a prepreg with metal foil, or by stacking at least two prepregs to form a composite sheet, coating one or both sides of the composite sheet with metal foil, and then hot-pressing the sheet to produce a metal foil laminate. The hot-pressing conditions are: a pressure of 0.2-2 MPa, a temperature of 150-250°C, and a pressing time of 2-4 hours. The metal foil is selected from copper foil or aluminum foil and has a thickness of 5 μm, 8 μm, 12 μm, 18 μm, 35 μm, or 70 μm.

[0128] The present application also provides an insulating board comprising at least one of the aforementioned prepreg sheets.

[0129] The present application also provides an insulating film, comprising a carrier film and the aforementioned maleimide resin composition coated thereon, and the heat resistance of the insulating film is significantly improved.

[0130] The preparation method of the insulating film is as follows: dissolving the maleimide resin composition with a solvent to prepare a glue solution, then coating the glue solution on a carrier film, and heating and drying the carrier film coated with the glue solution to obtain the insulating film.

[0131] The solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0132] The carrier film is selected from at least one of PET film, PP film, PE film and PVC film.

[0133] The present application also provides a circuit substrate, comprising at least one of the aforementioned prepreg and laminate.

[0134] The present application also provides an electronic device comprising the aforementioned circuit substrate.

[0135] The technical solution of the present application is further described below with reference to some specific examples and comparative examples. Of course, these examples are only a part of the many variations of the embodiments of the present application, but not all of them.

[0136] The chemical components and contents of the maleimide resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1.

[0137] Table 1

[0138]

[0139] The maleimide resin is BMI-2300 manufactured by Yamato Chemicals Co., Ltd.; the modified prepolymer of the maleimide resin is a prepolymer of diallyl bisphenol A and a maleimide resin, which is obtained by reacting 100 g of maleimide resin (BMI-2300 manufactured by Yamato Chemicals Co., Ltd.) with 60 g of diallyl bisphenol A at 110° C. for 90 minutes.

[0140] The cyanate ester is bisphenol A produced by Tianqi; the epoxy resin is HP-6000 produced by DIC; the phosphorus-containing styrene copolymer is a product produced by Sankou; the flame retardant is DOPO produced by Sankou; the elastomer is SG-P3 produced by Nagase; the inorganic filler A is spherical silica surface-treated with an aminosilane coupling agent, and the aminosilane coupling agent is KBM-1403 produced by Shin-Etsu Chemical; the inorganic filler B is spherical silica without surface treatment; and the catalyst is 2-methylimidazole produced by Shikoku Chemical.

[0141] The above-mentioned embodiment and comparative example also disclose a prepreg, comprising glass fiber cloth as a reinforcing material and a maleimide resin composition coated on the glass fiber cloth by an impregnation method, wherein the glass fiber cloth is a fiber-spread cloth pretreated with an epoxy silane coupling agent.

[0142] Specifically, the components of the maleimide resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 in Table 1 were dissolved in butanone, stirred and mixed, and then diluted to form a glue solution with a solid content of 65 wt %. T-glass fiber cloth used as a reinforcing material was pretreated with an epoxy silane coupling agent and then immersed in the glue solution. After being soaked, the cloth was taken out and placed in a blast drying oven at 160° C. and baked for 3 to 6 minutes to obtain a prepreg.

[0143] The above embodiments and comparative examples also disclose a laminate, which is prepared by the following method:

[0144] The above-mentioned semi-cured sheet was cut into 300×300mm and stacked into a certain stacking structure. Then, a low-profile electrolytic copper foil with a thickness of 12μm was placed on both sides of the combined sheet. The sheet was placed in a vacuum hot press and hot pressed for 1.5h at a pressure of 1.5MPa and a temperature of 220℃ to obtain a copper-clad laminate.

[0145] The above embodiments and comparative examples further disclose an insulating board comprising at least one of the aforementioned prepregs.

[0146] The above embodiments and comparative examples further disclose an insulating film, comprising a carrier film and the aforementioned maleimide resin composition coated thereon.

[0147] The above embodiments and comparative examples also disclose a circuit substrate, comprising the above-mentioned prepreg, which is prepared by a conventional preparation method in the prior art, and will not be described in detail here.

[0148] The copper clad laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to performance testing, and the test results are shown in Table 2. The performance testing method includes:

[0149] (1) Glass transition temperature (Tg): The DMA (thermomechanical analysis) method was used in accordance with IPC-TM-650 2.4.25 using a dynamic mechanical properties tester (TA DMA Q800, USA) with a heating rate of 10°C / min and a nitrogen atmosphere.

[0150] (2) PCT water absorption rate: The test is carried out according to the method of IPC-TM-6502.6.2.1, specifically: take 3 samples with a length × width of 10 cm × 10 cm and a thickness of 0.8 mm, with the electrolytic copper foil removed from both sides, dry them at 120°C for 2 hours, weigh them, and record the weight as W1. Then, cook them in a pressure cooker at 121°C and 2 atmospheres for 7 hours. After absorbing the free water on the surface, put them in a desiccator and cool them down before weighing them. The weight is recorded as W2. The measured water absorption rate is (W2-W1) / W1×100%.

[0151] (3) Peel strength (PS): The peel strength of the copper foil layer of the laminate was tested according to the "after thermal stress" experimental conditions in IPC-TM-650 2.4.8 method.

[0152] (4) Dk and Df: The dielectric constant Dk and dielectric loss Df at 10 GHz were measured using the flat plate method in accordance with IPC-TM-650 2.5.5.9.

[0153] (5) Flame retardancy: measured according to UL 94 vertical burning method.

[0154] (6) X / Y axis thermal expansion coefficient (CTE): The TMA method was used to measure the CTE in accordance with IPC-TM-650, with a heating rate of 10°C / min and a test temperature range of 30~100°C.

[0155] Table 2

[0156]

[0157] Referring to Table 2, compared with the comparative example, the copper clad laminate further prepared from the maleimide resin composition of the embodiment of the present application not only has excellent heat resistance, excellent flame retardancy, and low CTE, but also has a lower dielectric constant and dielectric loss value.

[0158] It should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each implementation method can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

[0159] The detailed descriptions listed above are merely specific descriptions of feasible implementation methods of the present application. They are not intended to limit the scope of protection of the present application. Any equivalent implementation methods or changes that do not deviate from the technical spirit of the present application should be included in the scope of protection of the present application.

Claims

1. A maleimide resin composition, by weight, comprising: 100 parts by weight of maleimide resin or its modified prepolymer; 5 - 60 parts by weight of cyanate ester; 10 - 60 parts by weight of phosphorus-containing styrene copolymer; The structure of the phosphorus-containing styrene copolymer is Structural formula (1), X is hydrogen or any one of C1 - C5 alkyl groups, and n is an integer from 1 to 20.

2. The maleimide resin composition according to claim 1, wherein In the said structural formula (1), X is hydrogen or methyl.

3. The maleimide resin composition according to claim 1, wherein, The cyanate ester is at least one of bisphenol A type cyanate ester, bisphenol F type cyanate ester, bisphenol E type cyanate ester, bisphenol M type cyanate ester, DCPD type cyanate ester, naphthalene type cyanate ester, phenolic type cyanate ester, biphenyl cyanate ester.

4. The maleimide resin composition according to claim 3, characterized in that, The cyanate ester is selected from at least one of the following structures: Structural formula (2), R is hydrogen or methyl, and n is an integer from 1 to 10; Structural formula (3), z is an integer from 1 to 10.

5. The maleimide resin composition according to claim 1, wherein The molecular structure of the maleimide resin contains at least 2 maleimide groups.

6. The maleimide resin composition according to claim 1, wherein The maleimide resin is at least one of the following structures: Structural formula (4); Structural formula (5); Structural formula (6); Structural formula (7), R1 is methylene, ethylene or , R2 is hydrogen, methyl or ethyl, and n is an integer from 1 to 10; Structural formula (8); Structural formula (9), n is an integer from 1 to 10; Structural formula (10), n is an integer from 1 to 10; Structural formula (11), n is an integer from 1 to 10; Structural formula (12); Structural formula (13), R is hydrogen, methyl or ethyl, and n is an integer from 1 to 10.

7. The maleimide resin composition according to claim 1, wherein The modified prepolymer of the maleimide resin is at least one of the prepolymer of diallyl compound and maleimide resin, the prepolymer of diamine compound and maleimide resin, the prepolymer of acidic phenol compound and maleimide resin.

8. The maleimide resin composition according to claim 7, wherein The diallyl compound is diallyl diphenol compounds, and the diallyl diphenol compounds are at least one of diallyl bisphenol A, diallyl bisphenol F, diallyl biphenyl compound, diallyl bisphenol S.

9. The maleimide resin composition according to claim 7, characterized in that, The diamine compound is at least one of unsubstituted benzene diamine, methyl benzene diamine, dimethyl benzene diamine, trimethyl benzene diamine, tetramethyl benzene diamine, xylene diamine, diaminopyridine, diaminodiphenyl methane, substituted diamino diphenyl methane, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminonaphthalene, diaminodiphenyl fluorene, diaminoanthraquinone.

10. The maleimide resin composition according to claim 7, wherein The acidic phenol compound is aminophenol.

11. The maleimide resin composition according to claim 1, wherein, By weight, it further comprises 5 - 30 parts by weight of epoxy resin.

12. The maleimide resin composition according to claim 11, wherein The epoxy resin is selected from at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, phosphorus-containing epoxy resin, o-cresol novolac epoxy resin, bisphenol A phenolic epoxy resin, phenol phenolic epoxy resin, cresol phenolic epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate type epoxy resin, aralkyl linear phenolic epoxy resin, alicyclic epoxy resin, glycidylamine type epoxy resin, glycidyl ether type epoxy resin, and glycidyl ester type epoxy resin.

13. The maleimide resin composition according to claim 1, wherein By weight, it further includes 5 to 60 parts by weight of an elastomer; the elastomer is selected from at least one of styrene-based elastomers, acrylate-based elastomers, and silicone-based elastomers.

14. The maleimide resin composition according to claim 1, characterized in that, By weight, it further includes 30 to 250 parts by weight of an inorganic filler.

15. Use of a maleimide resin composition according to any one of claims 1 to 14 in a prepreg, a laminate, an insulating board, an insulating film, a circuit board, and an electronic device.

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