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

Abstract

The application provides a benzoxazine compound, a benzoxazine mixture, a resin composition and application of the resin composition. The structural formula of the benzoxazine compound is structural formula (1a) or structural formula (1b), wherein Ar is methylene or ethylene. The benzoxazine compound provided by the application is provided with an allyl group and a benzocyclobutene group, which can improve the dielectric property of the benzoxazine compound, and meanwhile, the heat resistance and the dimensional stability of the benzoxazine compound can be maintained.

Description

TECHNICAL FIELD

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

[0002] With the development of communication technology, more chips and modules need to be carried on the printed circuit board (PCB), and the copper-clad plate is required to have high modulus, high heat resistance and low thermal expansion coefficient. As electronic products become smaller and smaller, circuit design becomes more and more dense, and more and more design manufacturers use HDI technology, which requires the performance of the substrate material to be improved in terms of dimensional stability, multiple cold and hot impact, long-term thermal aging and the like. The performance of the traditional resin formulation system cannot meet the current requirements. On the other hand, in recent years, with the development of high performance and high functionality of computer and information communication equipment and networking, in order to transmit and process large capacity information at high speed, the operating signal tends to be high frequency, and therefore a material for a circuit substrate is required to have lower dielectric constant and dielectric loss.

[0003] Benzoxazine resin has small curing shrinkage in the polymerization reaction process at high temperature, and the cured product has high heat resistance, high carbon residue rate and excellent thermal stability, and therefore is widely used in the field of copper-clad plate. However, it has the disadvantage of poor dielectric performance. It is relatively difficult to simultaneously achieve low dielectric constant (Dk), low dielectric loss factor (Df) and high heat resistance and low dimensional stability in the prior art, such as combination of carbon hydrogen and hollow filler. Although low Dk and low Df are achieved, the heat resistance and dimensional stability are significantly greater due to the long-chain structure of carbon hydrogen, and therefore it is difficult for benzoxazine to reduce the dielectric constant and dielectric loss while maintaining its heat resistance and dimensional stability. SUMMARY

[0004] The purpose of the present application is to provide a benzoxazine compound, a benzoxazine mixture, a resin composition and application of the resin composition, which introduces allyl and benzocyclobutene structures on the benzoxazine resin, reduces the dielectric constant and dielectric loss of benzoxazine, maintains the excellent heat resistance of benzoxazine, and solves the problem of poor dielectric performance of benzoxazine compounds in the prior art.

[0005] To achieve one of the above-mentioned purposes, an embodiment of the present application provides a benzoxazine compound, the structural formula of which is structural formula (1a) or structural formula (1b),

[0006]

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

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

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

[0010]

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

[0012]

[0013] As a further improvement of the embodiment of the present application, a catalyst is added when the allyl bisphenol compound, the aminobenzocyclobutene and the formaldehyde are reacted, and the amount of the catalyst added is 0.01-2% of the total weight of the allyl bisphenol compound, the aminobenzocyclobutene and the formaldehyde.

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

[0015] The embodiment of the present application also provides a benzoxazine mixture comprising the aforementioned benzoxazine compound.

[0016] As a further improvement of the embodiment of the present application, it further comprises a combination of one or 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 resin except structural formula (1a) and structural formula (1b).

[0017] As a further improvement of the embodiment of the present application, the benzoxazine mixture is a mixture of the benzoxazine compound shown in structural formula (1a) and / or structural formula (1b) and the allyl benzoxazine compound except structural formula (1a) and structural formula (1b), and the allyl benzoxazine compound except structural formula (1a) and structural formula (1b) accounts for 5-60 parts by weight based on 100 parts by weight of the benzoxazine mixture.

[0018] The embodiment of the present application also provides a resin composition comprising 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] wherein the benzoxazine resin comprises 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 an allyl-modified maleimide prepolymer, an amino-modified maleimide prepolymer, or a cyanate-modified maleimide prepolymer.

[0023] As a further improvement of one embodiment of the present application, it further comprises 5 to 60 parts by weight of an elastomer selected from at least one of a styrene-based elastomer, a silicone-based elastomer, or a methacrylate-based 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, or a hydrogenated styrene and pentadiene triblock copolymer.

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

[0026] In structural formula (2), R is a C1-C4 hydrocarbon group or -O-R', and R' is a C1-C4 hydrocarbon group. 12 12

[0027] In structural formula (3), R is a C1-C4 hydrocarbon group or -O-R', and R' is a C1-C4 hydrocarbon group. 12 12

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

[0029] The methacrylate-based elastomer comprises structural formula (5) and / or structural formula (6):

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

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

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

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

[0034] The benzoxazine compound provided by the application introduces an allyl group and a benzocyclobutene structure on the benzoxazine resin, reduces the dielectric constant and dielectric loss of the benzoxazine, and can maintain excellent heat resistance. When the allyl-modified maleimide resin is combined, a very homogeneous mixture can be obtained, and the benzoxazine has good compatibility. The allyl group and the maleimide group in the benzoxazine maintain appropriate reaction, do not affect the self-curing crosslinking reaction of the maleimide resin, and obtain excellent low dielectric properties, high heat resistance, low water absorption, and further improved toughness and dimensional stability. DETAILED DESCRIPTION

[0035] The application will be described in detail below with reference to the specific embodiments, but these embodiments do not limit the application, and the conversion of the reaction conditions, reactants or raw material amounts made by those skilled in the art based on these embodiments is included in the protection scope of the application.

[0036] The application provides a benzoxazine compound, which has a structural formula (1a) or a structural formula (1b),

[0037]

[0038] wherein Ar is a methylene group, an ethylene group, an -O- group, an -S- group or

[0039] The benzoxazine compound provided by the application introduces an allyl group and a benzocyclobutene structure, can reduce the dielectric constant and dielectric loss of the benzoxazine compound, and can maintain 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, an aminobenzocyclobutene and formaldehyde, and the molar ratio of the allyl bisphenol compound, the aminobenzocyclobutene and the formaldehyde is 1:(2-6):(1-3). The reaction temperature of the allyl bisphenol compound, the aminobenzocyclobutene and the formaldehyde is 50-100°C, and the reaction time is 1-15 hours.

[0041] In some embodiments, the allyl bisphenol compound is shown in a structural formula (1c) or a 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 diallylbisphenol methane is selected as the allylbisphenol compound, Ar in the structural formula (1a) and the structural formula (1c) is a methylene group; when diallylbisphenol ethane is selected as the allylbisphenol compound, Ar in the structural formula (1a) and the structural formula (1c) is an ethylene group; when diallylbisphenol S is selected as the allylbisphenol compound, Ar in the structural formula (1a) and the structural formula (1c) is When diallylphenyl ether is selected as the allyl bisphenol compound, 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. 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 invention also provides a benzoxazine mixture comprising the aforementioned benzoxazine compound.

[0048] Furthermore, the benzoxazine mixture further comprises one or a combination of at least two of bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, phenolphthalein benzoxazine resin, dicyclopentadiene benzoxazine resin, phosphorus-containing benzoxazine resin, diamine 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 of the benzoxazine compounds in the benzoxazine mixture contains an allyl group, which enables the benzoxazine mixture to have a low dielectric constant and dielectric loss, and when mixed with other resins, a cured product with 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 comprising the following components by weight:

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

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

[0054] The benzoxazine resin comprises 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 from 1 to 10.

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

[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 prepared by Daicel Chemical Industries, Ltd.; BMI, BMI-70, BMI-80 prepared by KI Chemical Industry Co., Ltd.; MIR-3000, MIR-5000 prepared by Japan Synthetic Rubber Co., Ltd.; X9-450, X9-470 or X9500 prepared by DIC Corporation; D936, D937, D939, D950 prepared 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 ester-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 herein, so that the allyl-modified maleimide prepolymer and the benzoxazine compound provided herein have good compatibility, and a very homogeneous sizing mixture can be obtained after mixing the two, in which the allyl group and the maleimide group maintain appropriate reaction, but do not affect the curing crosslinking reaction of the maleimide resin, so that excellent low dielectric properties can be obtained while maintaining high heat resistance, low water absorption, and high dimensional stability.

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

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

[0069] In some embodiments, 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, a hydrogenated styrene and pentadiene triblock copolymer.

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

[0071] In structural formula (2), R is a C1-C 12 hydrocarbon group or -O-R', R' is a 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 structural formula (5) and / or structural formula (6):

[0075] In the structural formula (5), R1 is a C1-C5 alkyl group, and x is an integer from 1 to 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 selected from an inorganic filler, an organic filler, or a composite filler. The inorganic filler is selected from at least one of 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; and the organic filler is selected from at least one of polytetrafluoroethylene powder, polyphenylene sulfide powder, and polyethersulfone 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 manufactured by Shin-Etsu Chemical Co., Ltd., Z-6883 manufactured by Dow Corning Corporation, KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd., and KBM-1403 manufactured 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 organophosphorus 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, a modified imidazole, zinc octoate, 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 brominated 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] Phosphorus flame retardants are selected from condensed phosphates, 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-phosphaphenanthrene-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, a hypophosphite or a bis-DOPO compound (ie, the aforementioned compound containing two DOPO groups).

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

[0087] The present invention also provides a prepreg, comprising a reinforcing material and the aforementioned resin composition. The prepreg is prepared by dissolving the resin composition in a solvent to prepare a glue solution, then immersing the reinforcing material in the glue solution, taking out the immersed reinforcing material and baking it at 100 to 180° C. for 1 to 15 minutes; and 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; preferably, open fiber cloth or flat cloth is used as the reinforcing material; and preferably, the glass fiber cloth is 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 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 is preferably an epoxy silane coupling agent or an amino silane coupling agent to provide good water resistance and heat resistance.

[0091] The present application also provides a laminate, which comprises one of the aforementioned prepregs and a metal foil arranged on at least one side surface of the prepreg; or comprises a combined sheet formed by stacking a plurality of the aforementioned prepregs on each other and a metal foil arranged on at least one side surface of the combined sheet.

[0092] The laminate is prepared by coating a metal foil on one side or both sides of a prepreg, or stacking at least two prepregs to form a combined sheet, coating a metal foil on one side or both sides of the combined sheet, and hot-pressing to form the metal foil laminate. The hot-pressing is performed under a pressure of 0.2-2 MPa and a temperature of 150-250°C for 2-4 hours.

[0093] 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.

[0094] The present application also provides an insulating board, which comprises at least one of the aforementioned prepregs.

[0095] The present application also provides an insulating film, which comprises a carrier film and the aforementioned resin composition coated thereon. The heat resistance of the insulating film is significantly improved.

[0096] The insulating film is prepared by dissolving the aforementioned resin composition with a solvent to form a glue solution, coating the glue solution on a carrier film, and drying the carrier film coated with the glue solution 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] The present application also provides a circuit substrate, which comprises one or more of the aforementioned prepregs, laminates, insulating boards, and insulating films.

[0100] The present application also provides an electronic device, which comprises the aforementioned circuit substrate. The safety of the electronic device is significantly improved due to the greatly improved heat resistance of the circuit substrate.

[0101] The technical solutions of the present application will be further described below in combination 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 were added to a reaction flask and stirred to obtain a mixed solution. The solution was warmed to about 50°C and stirred uniformly. 2 mol of formaldehyde solution was dropped into the solution within 30 min while stirring, and the solution was heated and maintained at a temperature between 85°C and 90°C and reacted for 3 hours. After the reaction, heating was stopped and left for 20 min. After the solution was layered, the upper aqueous phase and a small amount of emulsion were removed. The solvent was recovered by heating and reducing pressure (warming to 90°C and reducing pressure to 90 mmHg) to obtain a diallyl bisphenol A type benzoxazine compound.

[0104] Synthesis Example 2

[0105] 1 mol of diallyl bisphenol A, 3 mol of 4-aminobenzocyclobutene, 0.5 g of zinc chloride and 400 g of toluene were added to a reaction flask and stirred to obtain a mixed solution. The solution was warmed to about 50°C and stirred uniformly. 2 mol of formaldehyde solution was dropped into the solution within 30 min while stirring, and the solution was heated and maintained at a temperature between 85°C and 90°C and reacted for 3 hours. After the reaction, heating was stopped and left for 20 min. After the solution was layered, the upper aqueous phase and a small amount of emulsion were removed. The solvent was recovered by heating and reducing pressure (warming to 90°C and reducing pressure to 90 mmHg) to obtain a diallyl bisphenol A type benzoxazine compound.

[0106] Synthesis Example 3:

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

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

[0109] Table 1 Resin composition ingredient table

[0110]

[0111] Table 2 Material table

[0112]

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

[0114] Two pieces of the prepreg above were cut to 300x300 mm, stacked to form a combined sheet, and then one piece of low-profile electrolytic copper foil with a thickness of 12 μm was placed on each side of the combined sheet, and placed in a vacuum hot press to hot-press at a pressure of 1.5 MPa and a temperature of 220°C for 1.5 h 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 by the following methods:

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

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

[0118] (3) Dk and Df: flat plate method according to IPC-TM-650 2.5.5.9, dielectric properties at 10 GHz were tested;

[0119] (4) X / Y thermal expansion coefficient (CTE): TMA (thermal mechanical analysis), heating rate of 10°C / min, test temperature range of 30-100°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 (10 GHz) 3.15 3.08 3.20 3.14 3.68 3.88 Df (10 GHz) 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 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.

[0123] The above series of detailed descriptions 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, and 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 benzoxazine compound, characterized in that The structural formula is structural formula (1a), Structural formula (1a), Wherein, Ar is methylene, ethylene, .

2. The benzoxazine compound according to claim 1, wherein The benzoxazine compound is obtained by reacting an allyl bisphenol compound, 4-aminobenzocyclobutene and formaldehyde under the catalysis of a catalyst, wherein the molar ratio of the allyl bisphenol compound, 4-aminobenzocyclobutene and formaldehyde is 1:(2-6):(1-3); The amount of catalyst added is 0.01-2% of the total weight of the allyl bisphenol compound, 4-aminobenzocyclobutene and formaldehyde; 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; Among them, the allyl bisphenol compound is shown in structural formula (1c): Structural formula (1c), wherein Ar is methylene, ethylene, .

3. A benzoxazine mixture, characterized in that: Comprising the benzoxazine compound according to any one of claims 1 to 2.

4. The benzoxazine mixture according to claim 3, characterized in that The present invention also includes one or a combination of at least two of bisphenol A benzoxazine resins, bisphenol F benzoxazine resins, phenolphthalein benzoxazine resins, dicyclopentadiene benzoxazine resins, phosphorus-containing benzoxazine resins, diamine benzoxazine resins, or other allyl benzoxazine resins other than structural formula (1a).

5. The benzoxazine mixture according to claim 4, characterized in that The benzoxazine mixture is a mixture of a benzoxazine compound represented by structural formula (1a) and an allylbenzoxazine compound other than structural formula (1a), and based on 100 parts by weight of the benzoxazine mixture, the allylbenzoxazine compound other than structural formula (1a) accounts for 5 to 60 parts by weight.

6. 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; The benzoxazine resin comprises the benzoxazine compound according to any one of claims 1 to 2 and / or the benzoxazine mixture according to any one of claims 3 to 5.

7. The resin composition according to claim 6, 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.

8. The resin composition according to claim 6, characterized in that The invention also includes 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.

9. The resin composition according to claim 7, 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 structural formula (2), structural formula (3) and structural formula (4): Structural formula (2), where R is C1-C 12 hydrocarbon or , R' is C1-C 12 The hydrocarbon group; Structural formula (3), where R is C1-C 12 hydrocarbon or , R' is C1-C 12 The hydrocarbon group; Structural formula (4), wherein X is a mercapto group, an epoxy group, a hydroxyl group or a methoxy group; The acrylic elastomer comprises structural formula (5) and / or structural formula (6): Structural formula (5), wherein R1 is a C1-C5 alkyl group, and x is an integer from 1 to 100; Structural formula (6), wherein R2 is a C1-C5 alkyl group, and y is an integer of 1-100.

10. Use of the resin composition according to any one of claims 6 to 9 in prepregs, laminates, insulating films, insulating boards, circuit substrates and electronic devices.

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