Benzoxazine compound, benzoxazine mixture, resin composition and application of resin composition

Abstract

The invention provides a benzoxazine compound, a benzoxazine mixture, a resin composition and application of the resin composition, the structural formula of the benzoxazine compound is a structural formula (1a) or a structural formula (1b), # imgabs 0 #, Ar is methylene, ethylidene and # imgabs 1 #, the benzoxazine compound provided by the invention has allyl and benzocyclobutene groups, and the benzoxazine compound has a structure shown in the description. Dielectric properties of the benzoxazine compound can be improved, and heat resistance and dimensional stability of the benzoxazine compound can be maintained.

Description

Technical Field

[0001] The present application relates to the technical field of electronic materials, and in particular to a benzoxazine compound, a benzoxazine mixture, a resin composition, and an application of the resin composition. Background Art

[0002] With the development of communication technology, printed circuit boards (PCBs) need to carry more chips and modules, requiring copper clad laminates to have higher modulus, higher heat resistance and lower thermal expansion coefficient. As electronic products become smaller and smaller, and circuit designs become more and more dense, more and more design manufacturers are using HDI processes, requiring substrate materials to have improved performance in terms of dimensional stability, multiple hot and cold shocks, and long-term thermal oxidation aging. The various properties of traditional resin formulation systems can no longer meet existing requirements. On the other hand, in recent years, with the development of high performance, high functionality and networking of computers and information and communication equipment, in order to transmit and process large-capacity information at high speed, operating signals tend to be high-frequency, which puts forward lower dielectric constant and dielectric loss requirements for circuit substrate materials.

[0003] Benzoxazine resin has a small curing shrinkage rate during the polymerization reaction at high temperature, and the cured product has high heat resistance, high carbon residue rate and excellent thermal stability, so it is widely used in the field of copper clad laminates, but there is a disadvantage of poor dielectric properties. In the prior art, it is relatively difficult to achieve low dielectric constant (Dk), low dielectric loss factor (Df) and high heat resistance and low dimensional stability at the same time. For example, the combination of hydrocarbon and hollow filler, although low Dk and low Df are achieved, the heat resistance and dimensional stability are significantly larger due to the long chain structure of hydrocarbon, so it is difficult for benzoxazine to reduce the dielectric constant and dielectric loss and maintain its heat resistance and dimensional stability. Summary of the invention

[0004] The purpose of the present application is to provide a benzoxazine compound, a benzoxazine mixture, a resin composition and an application of the resin composition, to introduce allyl and benzocyclobutene structures into the benzoxazine resin, to reduce the dielectric constant and dielectric loss of the benzoxazine, to maintain the excellent heat resistance of the benzoxazine, and to solve the problem of poor dielectric properties of the benzoxazine compounds in the prior art.

[0005] In order to achieve one of the above-mentioned purposes of the invention, an embodiment of the present application provides a benzoxazine compound having a structural formula of structural formula (1a) or structural formula (1b),

[0006]

[0007] Wherein, Ar is methylene, ethylene, -O-, -S- or

[0008] As a further improvement of one embodiment of the present application, the benzoxazine compound is obtained by reacting an allyl bisphenol compound, aminobenzocyclobutene and formaldehyde, and the molar ratio of the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde is 1:(2-6):(1-3).

[0009] As a further improvement of one embodiment of the present application, the allyl bisphenol compound is represented by structural formula (1c) or structural formula (1d):

[0010]

[0011] Wherein, Ar is methylene, ethylene, -O-, -S- or

[0012]

[0013] As a further improvement of one embodiment of the present application, a catalyst is added during the reaction of the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde, and the amount of the catalyst added is 0.01 to 2% of the total weight of the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde.

[0014] As a further improvement of one embodiment of the present application, the catalyst is one or a mixture of two or more of zinc chloride, indium trihalide, ferric chloride, antimony pentachloride, trifluoromethanesulfonate, morpholine trifluoroacetate, and aluminum trichloride-nitroalkyl complex, wherein the halogen in the indium trihalide includes F, Cl, Br, and I.

[0015] One embodiment of the present application further provides a benzoxazine mixture, comprising the aforementioned benzoxazine compound.

[0016] As a further improvement of one embodiment of the present application, it also includes one or a combination of at least two of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin or other allyl benzoxazine resins other than structural formula (1a) and structural formula (1b).

[0017] As a further improvement of one embodiment of the present application, the benzoxazine mixture is a mixture of a benzoxazine compound represented by structural formula (1a) and / or structural formula (1b) and an allylbenzoxazine compound other than structural formula (1a) and structural formula (1b), and based on 100 parts by weight of the benzoxazine mixture, the allylbenzoxazine compound other than structural formula (1a) and structural formula (1b) accounts for 5 to 60 parts by weight.

[0018] One embodiment of the present application further provides a resin composition, which comprises the following components by weight:

[0019] (a) benzoxazine resin: 5 to 70 parts by weight;

[0020] (b) maleimide resin: 20 to 100 parts by weight;

[0021] The benzoxazine resin includes the aforementioned benzoxazine compound and / or the aforementioned benzoxazine mixture.

[0022] As a further improvement of one embodiment of the present application, the maleimide resin is a modified prepolymer selected from allyl-modified maleimide prepolymer, amino-modified maleimide prepolymer or cyanate-modified maleimide prepolymer.

[0023] As a further improvement of one embodiment of the present application, it further includes 5 to 60 parts by weight of an elastomer, wherein the elastomer is selected from at least one of a styrene elastomer, a silicone elastomer or a methacrylate elastomer.

[0024] 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;

[0025] The silicone elastomer contains at least one of the structural formula (2), structural formula (3) and structural formula (4):

[0026] In the structural formula (2), R is C1-C 12 A hydrocarbon group or -OR', R' is C1-C 12 The hydrocarbon group;

[0027] In the structural formula (3), R is C1-C 12 A hydrocarbon group or -OR', R' is C1-C 12 The hydrocarbon group;

[0028] In the structural formula (4), X is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group;

[0029] The methacrylate elastomer is a compound having structural formula (5) and / or structural formula (6):

[0030] In the structural formula (5), R1 is a C1-C5 alkyl group, and x is an integer of 1-100;

[0031] In the structural formula (6), R2 is a C1-C5 alkyl group, and y is an integer of 1-100.

[0032] One embodiment of the present application also provides a use of the resin composition as described above in a prepreg, a laminate, an insulating film, an insulating board, a circuit substrate and an electronic device.

[0033] One or more technical solutions provided by this application have at least the following technical effects or advantages:

[0034] The benzoxazine compound provided in the present application introduces allyl and benzocyclobutene structures into the benzoxazine resin, thereby reducing the dielectric constant and dielectric loss of the benzoxazine while maintaining excellent heat resistance. When combined with an allyl-modified maleimide resin, the two can be mixed to obtain a very homogeneous mixture with good compatibility. The allyl and maleimide groups in the benzoxazine maintain appropriate reactions without affecting the self-curing cross-linking reaction of the maleimide resin, thereby obtaining excellent low dielectric properties while achieving high heat resistance, low water absorption, and further improving toughness and dimensional stability. DETAILED DESCRIPTION

[0035] The present invention will be described in detail below in conjunction with specific embodiments, but these embodiments do not limit the present invention, and changes in reaction conditions, reactants or raw material amounts made by ordinary technicians in the field according to these embodiments are all included in the protection scope of the present invention.

[0036] The present application provides a benzoxazine compound having a structural formula of structural formula (1a) or structural formula (1b).

[0037]

[0038] Wherein, Ar is methylene, ethylene, -O-, -S- or

[0039] The benzoxazine compound provided in the present application introduces allyl and benzocyclobutene structures, which can reduce the dielectric constant and dielectric loss of the benzoxazine compound, while maintaining the heat resistance, dimensional stability and thermal stability of the benzoxazine itself, and can be applied to high-performance circuit substrates.

[0040] In some embodiments, the benzoxazine compound is obtained by reacting an allyl bisphenol compound, aminobenzocyclobutene and formaldehyde, wherein the molar ratio of the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde is 1:(2-6):(1-3). The reaction temperature of the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde is 50-100° C., and the reaction time is 1-15 hours.

[0041] In some embodiments, the allyl bisphenol compound is represented by structural formula (1c) or structural formula (1d):

[0042] Wherein, Ar is methylene, ethylene, -O-, -S- or

[0043]

[0044] When diallyl bisphenol A is selected as the allyl bisphenol compound, Ar in the structural formula (1a) or the structural formula (1c) is When the allyl bisphenol compound is diallyl bisphenol methane, Ar in the structural formula (1a) and the structural formula (1c) is a methylene group; when the allyl bisphenol compound is diallyl bisphenol ethane, Ar in the structural formula (1a) and the structural formula (1c) is an ethylene group; when the allyl bisphenol compound is diallyl bisphenol S, Ar in the structural formula (1a) and the structural formula (1c) is When the allyl bisphenol compound is diallyl phenyl ether, Ar in the structural formula (1a) and the structural formula (1c) is -O-. Preferably, the allyl bisphenol compound is diallyl bisphenol A.

[0045] In some embodiments, a catalyst is added during the reaction of the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde, and the amount of the catalyst added is 0.01-2% of the total weight of the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde.

[0046] In some embodiments, the catalyst is one or a mixture of two or more of zinc chloride, indium trihalide, ferric chloride, antimony pentachloride, trifluoromethanesulfonate, morpholine trifluoroacetate, aluminum trichloride-nitroalkyl complex, wherein the halogen in the indium trihalide includes F, Cl, Br, and I.

[0047] The present application also provides a benzoxazine mixture, comprising the aforementioned benzoxazine compound.

[0048] Furthermore, the benzoxazine mixture also includes one or a combination of at least two of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin or other allyl benzoxazine resins other than structural formula (1a) and structural formula (1b).

[0049] Preferably, the benzoxazine mixture is a mixture of a benzoxazine compound represented by structural formula (1a) and / or structural formula (1b) and an allylbenzoxazine compound other than structural formula (1a) and structural formula (1b), and based on 100 parts by weight of the benzoxazine mixture, the allylbenzoxazine compound other than structural formula (1a) and structural formula (1b) accounts for 5 to 60 parts by weight.

[0050] Any benzoxazine compound in the benzoxazine mixture contains an allyl group, which can make the benzoxazine mixture have a lower dielectric constant and contact loss. When it is mixed with other resins, a cured product with a low dielectric constant, low dielectric loss, high heat resistance and high dimensional stability can be obtained after curing.

[0051] The present application also provides a resin composition, which comprises the following components by weight:

[0052] (a) benzoxazine resin: 5 to 70 parts by weight;

[0053] (b) maleimide resin: 20 to 100 parts by weight;

[0054] The benzoxazine resin includes the aforementioned benzoxazine compound and / or the aforementioned benzoxazine mixture.

[0055] The maleimide resin is selected from at least one of the following structures:

[0056]

[0057]

[0058] R2 is hydrogen, methyl or ethyl, R1 is methylene, ethylene or n is an integer from 1 to 10;

[0059]

[0060] n is an integer from 1 to 10;

[0061] n is an integer from 1 to 10;

[0062] R is hydrogen, methyl or ethyl, and n is an integer of 1-10.

[0063] Preferably, the maleimide resin is selected from any one or more of the following grades of materials:

[0064] 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 produced by Yamato Chemical Co., Ltd.; BMI, BMI-70, BMI-80 produced by KI Chemical Co., Ltd. of Japan; MIR-3000, MIR-5000 produced by Nippon Kayaku Co., Ltd.; X9-450, X9-470 or X9500 produced by DIC Corporation of Japan; D936, D937, D939, D950 produced by Sichuan Dongcai Co., Ltd.

[0065] In some embodiments, the maleimide resin is a modified prepolymer selected from an allyl-modified maleimide prepolymer, an amino-modified maleimide prepolymer, or a cyanate-modified maleimide prepolymer.

[0066] Preferably, the maleimide resin is an allyl-modified maleimide prepolymer. The allyl-modified maleimide prepolymer has the same allyl group as the benzoxazine compound provided in the present application, so that the allyl-modified maleimide prepolymer and the benzoxazine compound provided in the present application have good compatibility, and a very homogeneous glue mixture can be obtained after the two are mixed, wherein the allyl group and the maleimide group maintain a proper reaction, but do not affect the curing and cross-linking reaction of the maleimide resin, and excellent low dielectric properties can be obtained while maintaining high heat resistance, low water absorption and high dimensional stability.

[0067] More preferably, the maleimide resin is modified by at least one of diallyl bisphenol A, diallyl bisphenol methane, diallyl bisphenol ethane, diallyl bisphenol S and diallyl phenyl ether.

[0068] In some embodiments, the resin composition further comprises 5 to 60 parts by weight of an elastomer, wherein the elastomer is selected from at least one of a styrene elastomer, a silicone elastomer, or a methacrylate elastomer.

[0069] In some embodiments, the styrenic 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;

[0070] The silicone elastomer contains at least one of the structural formula (2), structural formula (3) and structural formula (4):

[0071] In the structural formula (2), R is C1-C 12 A hydrocarbon group or -OR', R' is C1-C12 The hydrocarbon group;

[0072] In the structural formula (3), R is C1-C 12 A hydrocarbon group or -OR', R' is C1-C 12 The hydrocarbon group;

[0073] In the structural formula (4), X is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group;

[0074] The methacrylate elastomer is a compound having the structural formula (5) and / or the structural formula (6):

[0075] In the structural formula (5), R1 is a C1-C5 alkyl group, and x is an integer of 1-100;

[0076] In the structural formula (6), R2 is a C1-C5 alkyl group, and y is an integer of 1-100.

[0077] In some embodiments, the resin composition further comprises 30 to 200 parts by weight of a filler, wherein the filler is selected from an inorganic filler, an organic filler or a composite filler. The inorganic filler is selected from at least one of silicon dioxide, 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; the organic filler is selected from at least one of polytetrafluoroethylene powder, polyphenylene sulfide powder, and polyether sulfone powder.

[0078] Preferably, the filler is spherical silica, alumina or aluminum hydroxide, more preferably spherical silica.

[0079] Furthermore, the filler is surface treated with a silane coupling agent, and the silane coupling agent is at least one of an aminosilane coupling agent, a carbon-carbon double bond-containing silane coupling agent, or an epoxy silane coupling agent.

[0080] Preferably, the silane coupling agent is selected from the group consisting of KBM-573 produced by Shin-Etsu Chemical Co., Ltd., Z-6883 produced by Dow Corning Corporation, KBM-1003 produced by Shin-Etsu Chemical Co., Ltd., and KBM-1403 produced by Shin-Etsu Chemical Co., Ltd.

[0081] In some embodiments, the resin composition further comprises 0.01 to 8 parts by weight of a catalyst, wherein the catalyst is selected from at least one of an imidazole catalyst, a pyridine catalyst, an organic phosphorus catalyst, or a metal salt catalyst. Preferably, the catalyst is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, modified imidazole, zinc octanoate, and triphenylphosphine.

[0082] In some embodiments, the resin composition further comprises 5-30 parts by weight of a flame retardant, wherein the flame retardant is selected from at least one of a bromine flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, an organosilicon flame retardant, and an organometallic salt flame retardant.

[0083] Preferably, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalamide;

[0084] The phosphorus flame retardant is selected from condensed phosphate esters, phosphoric acid, hypophosphite, 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-phosphophanate-10-oxide, tris(2,6-dimethylphenyl)phosphine, phosphazene, modified phosphazene. Among them, the DOPO group is

[0085] More preferably, the flame retardant is a condensed phosphate ester, a hypophosphite or a bis-DOPO compound (ie, the aforementioned compound containing two DOPO groups).

[0086] The present invention also provides the use of the resin composition in prepregs, laminates, insulating films, insulating boards, copper-clad boards, circuit substrates and electronic devices, which are specifically described as follows:

[0087] The present invention also provides a prepreg, comprising a reinforcing material and the above-mentioned resin composition. The preparation method of the prepreg is: dissolving the resin composition with a solvent to prepare a glue solution, then immersing the reinforcing material in the above-mentioned glue solution, taking out the immersed reinforcing material and baking it at 100-180°C for 1-15 minutes; after drying, the prepreg is obtained.

[0088] 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.

[0089] The reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. Preferably, the reinforcing material is glass fiber cloth; among the glass fiber cloth, open fiber cloth or flat cloth is preferably used; and the glass fiber cloth is preferably E glass fiber cloth, S glass fiber cloth, T glass fiber cloth, or Q glass fiber cloth.

[0090] In addition, when the reinforcing material is 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 is preferably an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0091] An embodiment of the present invention also provides a laminate, comprising a piece of the aforementioned prepreg and a metal foil disposed on at least one side 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 side of the composite sheet.

[0092] The laminate is prepared by the following method: a metal foil is coated on one or both sides of a prepreg, or at least two prepregs are stacked to form a composite sheet, a metal foil is coated on one or both sides of the composite sheet, and the metal foil laminate is obtained by hot pressing. The pressing conditions of hot pressing are: pressing at 0.2-2MPa and 150-250°C for 2-4 hours.

[0093] Preferably, the metal foil is selected from copper foil or aluminum foil. The thickness of the metal foil is 5 micrometers, 8 micrometers, 12 micrometers, 18 micrometers, 35 micrometers or 70 micrometers.

[0094] An embodiment of the present invention further provides an insulating board, comprising at least one of the aforementioned prepreg sheets.

[0095] The embodiment of the present invention further provides an insulating film, comprising a carrier film and the above-mentioned resin composition coated thereon, and the heat resistance of the insulating film is significantly improved.

[0096] The insulating film is prepared by the following method: the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is then coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.

[0097] The aforementioned 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.

[0098] The carrier film is selected from at least one of PET film, PP film, PE film and PVC film.

[0099] An embodiment of the present invention further provides a circuit substrate, comprising one or more of the aforementioned prepreg, laminate, insulating plate, and insulating film.

[0100] An embodiment of the present invention further provides an electronic device, comprising the aforementioned circuit substrate; since the heat resistance of the circuit substrate is greatly improved, the safety of the electronic device is significantly improved.

[0101] The technical solution of the present application is further described below in conjunction with some specific synthesis examples and comparative examples.

[0102] Synthesis example 1

[0103] 1 mol of diallyl bisphenol A, 3 mol of 4-aminobenzocyclobutene, 0.5 g of zinc chloride and 400 g of toluene are added to a reaction bottle and stirred to obtain a mixed solution. The solution is heated to about 50°C and stirred evenly. During stirring, 2 mol of formaldehyde solution is added dropwise to the solution within 30 minutes, and the solution is heated and maintained at a temperature between 85°C and 90°C and reacted for 3 hours. After the reaction, the heating is stopped and the solution is allowed to stand for 20 minutes. After the solution is separated, the upper aqueous phase and a trace amount of emulsified product are removed. The solvent is recovered by heating and decompression (heating to 90°C and decompression to 90 mmHg) to obtain a diallyl bisphenol A type benzoxazine compound.

[0104] Synthesis example 2

[0105] 1 mol of diallylbisphenol methane, 3 mol of 4-aminobenzocyclobutene, 0.5 g of zinc chloride and 400 g of toluene are added to a reaction flask and stirred to obtain a mixed solution. The solution is heated to about 50°C and stirred evenly. During stirring, 2 mol of formaldehyde solution is added dropwise to the solution within 30 minutes, and the solution is heated and maintained at a temperature between 85°C and 90°C and reacted for 3 hours. After the reaction, the heating is stopped and the solution is allowed to stand for 20 minutes. After the solution is separated, the upper aqueous phase and a trace amount of emulsified product are removed. The solvent is recovered by heating and decompression (heating to 90°C and decompression to 90 mmHg) to obtain a diallylbisphenol methane type benzoxazine compound.

[0106] Synthesis example 3:

[0107] 100 g of 4,4'-diphenyl ether bismaleimide and 70 g of allyl bisphenol A were put into a 500 ml beaker and reacted at 130-150° C. for 65 min to obtain allyl-modified maleimide resin.

[0108] The chemical components and contents of the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2 are shown in Table 1.

[0109] Table 1 Resin composition composition

[0110]

[0111] Table 2 Materials

[0112]

[0113] The components of the resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2 in Table 1 were dissolved in butanone, stirred and mixed, and then diluted to a glue solution with a solid content of 65 wt %; the E glass fiber cloth 2116 used as a reinforcing material was pretreated with an epoxy silane coupling agent, immersed in the above glue solution, taken out after infiltration, placed in a 160° C. blast drying oven, and baked for 3 to 6 minutes to obtain a semi-cured sheet.

[0114] Take two of the above-mentioned semi-cured sheets, cut them into 300×300 mm, and stack them into a composite sheet. Then, a low-profile electrolytic copper foil with a thickness of 12 μm is placed on both sides of the composite sheet, respectively. The composite sheet is placed in a vacuum hot press and hot-pressed for 1.5 h at a pressure of 1.5 MPa and a temperature of 220°C to obtain a copper-clad laminate. The specific performance tests are shown in Table 3.

[0115] The properties of the copper-clad laminates prepared in the above examples and comparative examples were tested as follows:

[0116] (1) Tg: DMA, heating rate 10°C / min, frequency 10 Hz;

[0117] (2) Water absorption (%): Tested according to IPC-TM-650 2.6.2.1 method;

[0118] (3) Dk and Df: Dielectric properties at 10 GHz using the flat plate method in accordance with IPC-TM-650 2.5.5.9;

[0119] (4) X / Y thermal expansion coefficient (CTE): TMA (thermomechanical analysis) was used with a heating rate of 10°C / min and a test temperature range of 30 to 100°C.

[0120] Table 3

[0121] performance Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Tg(DMA) 331 335 327 329 315 307 Dk(10GHz) 3.15 3.08 3.20 3.14 3.68 3.88 Df(10GHz) 0.0052 0.0053 0.0055 0.0058 0.0092 0.0098 Water absorption (%) 0.41 0.42 0.43 0.45 0.46 0.49 CTE (XY axis) 9.1 8.7 9.4 8.9 10.6 11.6

[0122] It should be understood that although this specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description 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 mode may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

[0123] The series of detailed descriptions listed above are only 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 benzoxazine compound, characterized in that: The structural formula is structural formula (1a) or structural formula (1b), Wherein, Ar is methylene, ethylene, -O-, -S- or 2. The benzoxazine compound according to claim 1, characterized in that The benzoxazine compound is obtained by reacting an allyl bisphenol compound, aminobenzocyclobutene and formaldehyde, and the molar ratio of the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde is 1:(2-6):(1-3).

3. The benzoxazine compound according to claim 2, characterized in that The allyl bisphenol compound is represented by structural formula (1c) or structural formula (1d): Wherein, Ar is methylene, ethylene, -O-, -S- or 4. The benzoxazine compound according to claim 2, characterized in that When the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde react, a catalyst is added, and the amount of the catalyst added is 0.01-2% of the total weight of the allyl bisphenol compound, aminobenzocyclobutene and formaldehyde.

5. The benzoxazine compound according to claim 4, characterized in that The catalyst is one or a mixture of two or more of zinc chloride, indium trihalide, ferric chloride, antimony pentachloride, trifluoromethanesulfonate, morpholine trifluoroacetate, and aluminum trichloride-nitroalkyl complex, wherein the halogen in the indium trihalide includes F, Cl, Br, and I.

6. A benzoxazine mixture, characterized in that: The benzoxazine compound according to any one of claims 1 to 5 is included.

7. The benzoxazine mixture according to claim 6, characterized in that: It also includes one or a combination of at least two of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin or other allyl benzoxazine resins other than structural formula (1a) and structural formula (1b).

8. The benzoxazine mixture according to claim 7, characterized in that: The benzoxazine mixture is a mixture of a benzoxazine compound represented by structural formula (1a) and / or structural formula (1b) and an allylbenzoxazine compound other than structural formula (1a) and structural formula (1b), and based on 100 parts by weight of the benzoxazine mixture, the allylbenzoxazine compound other than structural formula (1a) and structural formula (1b) accounts for 5 to 60 parts by weight.

9. A resin composition, characterized in that By weight, it includes the following components: (a) benzoxazine resin: 5 to 70 parts by weight; (b) maleimide resin: 20 to 100 parts by weight; Wherein, the benzoxazine resin comprises the benzoxazine compound according to any one of claims 1 to 5 and / or the benzoxazine mixture according to any one of claims 6 to 8.

10. The resin composition according to claim 9, characterized in that The maleimide resin is a modified prepolymer selected from allyl-modified maleimide prepolymer, amino-modified maleimide prepolymer or cyanate-modified maleimide prepolymer.

11. The resin composition according to claim 9, characterized in that The invention also comprises 5 to 60 parts by weight of an elastomer, wherein the elastomer is selected from at least one of styrene elastomers, silicone elastomers and methacrylate elastomers.

12. The resin composition according to claim 10, characterized in that The styrene 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; The silicone elastomer contains at least one of the structural formula (2), structural formula (3) and structural formula (4): In the structural formula (2), R is C1-C 12 A hydrocarbon group or -OR', R' is C1-C 12 The hydrocarbon group; In the structural formula (3), R is C1-C 12 A hydrocarbon group or -OR', R' is C1-C 12 The hydrocarbon group; In the structural formula (4), X is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group; The acrylic elastomer is a compound having structural formula (5) and / or structural formula (6): In the structural formula (5), R1 is a C1-C5 alkyl group, and x is an integer of 1-100; In the structural formula (6), R2 is a C1-C5 alkyl group, and y is an integer of 1-100.

13. Use of the resin composition according to any one of claims 9 to 12 in prepregs, laminates, insulating films, insulating boards, circuit substrates and electronic devices.

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