Resin composition and use thereof

Abstract

The application provides a resin composition and application thereof, which comprises the following components in weight: 1-80 parts of a benzoxazine resin; 20-100 parts of an epoxy resin; and 5-50 parts of a curing agent; the benzoxazine resin contains the following structural formula (1a) or structural formula (1b): wherein Ar is methylene or ethylene; the resin composition provided by the application contains the benzoxazine resin with allyl and benzocyclobutene groups, which can reduce the dielectric constant and dielectric loss of the resin composition, and make the resin composition be able to be applied to high-performance electronic substrates.

Description

TECHNICAL FIELD

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

[0002] With the rapid development of high-frequency communication technology, especially in the fifth generation communication system "5G" which is now accelerating the development, in order to promote large capacity and high speed communication, the demand for low dielectric constant and low dielectric loss tangent materials is increasing. As an important component in electronic devices, the performance of copper-clad plate is directly related to the performance of the whole device. In the process of high-frequency and high-speed signal transmission, the traditional copper-clad plate often has problems such as high dielectric constant and large thermal expansion coefficient, which can cause integrated circuit leakage current to increase, heat seriously, and further affect the stability and life of the device. Under this background, it is particularly important to study the use of benzoxazine resin as a material with excellent heat resistance and electrical properties to develop a resin composition with low dielectric and high heat resistance.

[0003] Benzoxazine resin has small curing shrinkage in the process of polymerization 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 plate, but 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, 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 larger due to the long-chain structure of carbon hydrogen.

[0004] Epoxy resin has excellent mechanical properties, electrical properties, chemical properties, adhesive properties, easy molding processing, low cost and other advantages. In recent years, its application has been expanded to structural adhesive materials, semiconductor packaging materials, fiber reinforced materials, laminated boards, copper foils, integrated circuits and other electronic and electrical packaging materials. However, epoxy resin has a three-dimensional network structure, and there is a lack of sliding between molecular chains, resulting in high internal stress and easy cracking, deformation and other problems. SUMMARY

[0005] The present application aims to provide a resin composition and application thereof. The resin composition includes benzoxazine resin and epoxy resin, wherein the benzoxazine resin includes benzoxazine compounds with allyl and benzocyclobutene structures, which can reduce the dielectric constant and dielectric loss of the resin composition, and solve the problem of poor dielectric performance of the resin composition in the copper-clad laminated plate in the prior art.

[0006] To achieve one of the above-mentioned purposes, one embodiment of the present application provides a resin composition, which includes the following components by weight:

[0007] Benzoxazine resin: 1-80 parts by weight;

[0008] Epoxy resin: 20 to 100 parts by weight;

[0009] Curing agent: 5 to 50 parts by weight;

[0010] The benzoxazine resin contains the following structural formula (1a) or structural formula (1b):

[0011]

[0012] wherein Ar is methylene, ethylene, -O-, -S-, or

[0013] As a further improvement of an embodiment of the present application, the benzoxazine resin further comprises a non-benzocyclobutene-based benzoxazine resin, wherein the non-benzocyclobutene-based benzoxazine resin comprises 10 to 80 parts by weight based on 100 parts by weight of the benzoxazine resin.

[0014] As a further improvement of an embodiment of the present application, the non-benzocyclobutene-based benzoxazine resin is selected from one or a combination of at least two of a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin, a phenolphthalein type benzoxazine resin, a dicyclopentadiene type benzoxazine resin, a phosphorus-containing benzoxazine resin, a diamine type benzoxazine resin, or an allyl benzoxazine resin.

[0015] As a further improvement of an embodiment of the present application, the non-benzocyclobutene-based benzoxazine resin is at least one of the following structural formulae:

[0016] wherein R is a vinyl group, an allyl group, a propenyl group, or a methacrylate group; Ar is methylene, ethylene, -O-, -S-,

[0017] or no connecting group;

[0018] wherein Ar is methylene, ethylene, -O-, -S-, or no connecting group;

[0019] wherein R is a vinyl group, an allyl group, a propenyl group, or a methacrylate group; Ar is methylene, ethylene, -O-, -S-, or no connecting group.

[0020] As a further improvement of an embodiment of the present application, the epoxy resin is selected from any one or a combination of at least two of a dicyclopentadiene epoxy resin, a carbon-carbon double bond containing epoxy resin, a phosphorus containing epoxy resin, an isocyanate modified epoxy resin, a biphenyl epoxy resin, a bisphenol A epoxy resin, a phenol novolac epoxy resin, an o-cresol novolac epoxy resin, an epoxidized polybutadiene resin, a naphthalene ring containing epoxy resin, a bisphenol F epoxy resin.

[0021] As a further improvement of an embodiment of the present application, the epoxy resin is selected from at least one of the following structures:

[0022] wherein m is an integer from 0 to 10;

[0023] wherein n is an integer from 1 to 20;

[0024] wherein p is an integer from 1 to 20;

[0025] wherein n is an integer from 0 to 7 and R is H or -CH3;

[0026] wherein X1is H or an alkyl group of C1-C5; and X2is H or an alkyl group of C1-C5;

[0027] wherein X1is H or an alkyl group of C1-C5;

[0028] wherein n is an integer from 0 to 7 and R is -O- or -Co-.

[0029] As a further improvement of an embodiment of the present application, the curing agent is selected from at least one of an amine curing agent, an active ester curing agent, a phenolic curing agent, an acid anhydride curing agent, a maleimide curing agent, a cyanate ester curing agent.

[0030] As a further improvement of an embodiment of the present application, the amine curing agent is selected from at least one of diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, bis-carboxyphthalimide, dicyandiamide, or imidazole;

[0031] The phenolic curing agent is selected from at least one of a bisphenol A novolac resin, a phenol novolac resin, a naphthalene type novolac resin, a biphenyl phenol type novolac resin, a biphenyl phenol type naphthol resin, a dicyclopentadiene phenol addition type resin;

[0032] The acid anhydride curing agent is selected from at least one of phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, or styrene-maleic anhydride;

[0033] The cyanate ester curing agent is selected from 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, phenol-formaldehyde cyanate ester, or diphenyl cyanate ester;

[0034] The active ester curing agent is a compound containing the following structural formula:

[0035] wherein X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents the repeating unit, and is 0.25-1.25.

[0036] As a further improvement of the embodiment of the present application, 5-30 parts by weight of a flame retardant is further included, and the flame retardant is selected from at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organic silicon flame retardant, and an organic metal salt flame retardant.

[0037] As a further improvement of the embodiment of the present application, the bromine-based flame retardant is selected from at least one of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalic acid amide;

[0038] The phosphorus-based flame retardant is selected from condensed phosphoric acid ester, 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 of 1-5), 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl) phosphorus, phosphazene, modified phosphazene, wherein the structure of the DOPO group is

[0039] The embodiment of the present application also provides an application of the resin composition as described above in a prepreg, a laminated board, an insulating film, an insulating board, a circuit substrate, and an electronic device.

[0040] The one or more technical solutions provided by the present application have at least the following technical effects or advantages:

[0041] The resin composition provided by the present application includes a benzoxazine resin and an epoxy resin, wherein the benzoxazine resin contains a benzoxazine compound having an allyl group and a benzocyclobutene group, the dielectric constant and dielectric loss of the resin composition are reduced, and the benzoxazine ring-opening reaction and the epoxy group maintain appropriate reaction during curing, so that the crosslinking density is increased and the heat resistance is improved. DETAILED DESCRIPTION

[0042] The present application will be described in detail below with reference to the specific embodiments, but these embodiments do not limit the present application, and the conversion of the reaction conditions, reactants or raw material amounts made by those skilled in the art according to these embodiments are included in the protection scope of the present application.

[0043] The resin composition provided by the present application includes the following components by weight:

[0044] The benzoxazine resin: 1-80 parts by weight;

[0045] The epoxy resin: 20-100 parts by weight;

[0046] The curing agent: 5-50 parts by weight;

[0047] The benzoxazine resin contains the following structural formula (1a) or structural formula (1b):

[0048]

[0049] Among them, Ar is methylene, ethylene, -O-, -S- or

[0050] The resin composition provided by the present application includes a benzoxazine resin and an epoxy resin, and the benzoxazine resin contains a benzoxazine compound shown in the above structural formula (1a) or structural formula (1b), which has an allyl group and a benzocyclobutene group. Both structures can improve the dielectric properties of the resin composition. The benzoxazine ring-opening reaction and the epoxy group maintain appropriate reaction during curing of the resin composition, so that the crosslinking density is increased and the heat resistance is further improved.

[0051] 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.

[0052] In some embodiments, the allyl bisphenol compound is shown in the structural formula (1c) or structural formula (1d):

[0053] wherein Ar is methylene, ethylene, -O-, -S-, or

[0054]

[0055] When the allyl bisphenol compound is selected as bisphenol A, Ar in structural formula (1a) and structural formula (1c) is When the allyl bisphenol compound is selected as bisphenol A, Ar in structural formula (1a) and structural formula (1c) is When the allyl bisphenol compound is selected as bisphenol A, Ar in structural formula (1a) and structural formula (1c) is

[0056] In some embodiments, when the allyl bisphenol compound, the aminobenzocyclobutene and the formaldehyde are reacted, a catalyst is added, 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.

[0057] In some embodiments, the catalyst is one or a mixture of two or more of zinc chloride, indium trihalide, ferric trichloride, antimony pentachloride, triflate, morpholine trifluoroacetate, aluminum trichloride-nitroalkyl complex, wherein the halogen in the indium trihalide includes F, Cl, Br, I.

[0058] In some embodiments, the benzoxazine resin further comprises a non-benzocyclobutene-based benzoxazine resin, and the non-benzocyclobutene-based benzoxazine resin comprises 10-80 parts by weight based on 100 parts by weight of the benzoxazine resin.

[0059] Preferably, the non-benzocyclobutene-based benzoxazine resin is selected from 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 allyl benzoxazine resin.

[0060] In some embodiments, the non-benzocyclobutene-based benzoxazine resin is at least one of the following structural formulae:

[0061] wherein R is a vinyl group, an allyl group, a propenyl group or a methacrylate group; Ar is methylene, ethylene, -O-, -S-, or Or without linking groups;

[0062] Where Ar represents methylene, ethylene, ... -O-、-S-、 Or without linking groups;

[0063] Wherein, R is vinyl, allyl, propenyl, or methacrylate; Ar is methylene, ethylene, or... -O-、-S-、 Or without a linking group.

[0064] The aforementioned "no connecting group" specifically refers to the benzene rings on both sides of Ar being directly connected without being connected by other groups.

[0065] In some embodiments, the epoxy resin is selected from any one or a combination of at least two of the following: dicyclopentadiene epoxy resin, carbon-carbon double bond epoxy resin, phosphorus-containing epoxy resin, isocyanate-modified epoxy resin, biphenyl epoxy resin, bisphenol A type epoxy resin, phenolic epoxy resin, o-cresolic epoxy resin, epoxidized polybutadiene resin, naphthalene ring-containing epoxy resin, and bisphenol F type epoxy resin.

[0066] Preferably, the epoxy resin is selected from at least one of the following structures:

[0067] Where m is an integer from 0 to 10;

[0068] Where, n is an integer from 1 to 20;

[0069] Where p is an integer from 1 to 20;

[0070] Where n is an integer from 0 to 7, and R is H or -CH3;

[0071] Wherein, X1 is H or a C1-C5 alkyl group; X2 is H or a C1-C5 alkyl group;

[0072] Wherein, X1 is H or a C1-C5 alkyl group;

[0073] Where n is an integer from 0 to 7, and R is... -O- or -Co-.

[0074] Preferably, the epoxy resin contains allyl group. The allyl group is contained in the aforementioned structural formula (1a) and structural formula (1b), and when the allyl group-containing epoxy resin is used in combination with the allyl group-containing benzoxazine, the compatibility between the two is very excellent, the benzocyclobutene with large volume is better introduced into the crosslinking network system during the curing reaction process, and the dielectric properties of the resin composition can be well improved, the water absorption is reduced, and the heat resistance is improved.

[0075] The epoxy resin is selected from any one or more of the following brands of materials:

[0076] HP4032, HP4032D, HP4032SS, HP4700, HP4710, N-690, N-695, HP7200, HP7200H, HP7200HH, EXA7311, HP6000 produced by DIC Corporation of Japan, NC3000, NC7000, NC3100 produced by Nippon Kayaku, ESN475V, ESN485 produced by JFE Chemicals, and MADGIC produced by Shikoku Chemicals Corporation.

[0077] In some embodiments, the curing agent is selected from at least one of an amine curing agent, an active ester curing agent, a phenolic curing agent, an acid anhydride curing agent, a maleimide curing agent, and a cyanate ester curing agent.

[0078] Preferably, the amine curing agent is selected from at least one of diaminodiphenyl methane, diaminodiphenyl sulfone, diethylene triamine, bis-carboxy phthalimide, bis-cyanamide, or imidazole;

[0079] The phenolic curing agent is selected from at least one of bisphenol A novolac resin, phenol novolac resin, naphthalene type phenolic resin, biphenyl phenol type phenolic resin, biphenyl phenol type naphthol resin, and dicyclopentadiene phenol addition type resin;

[0080] The acid anhydride curing agent is selected from at least one of phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, or styrene-maleic anhydride;

[0081] The cyanate ester curing agent is selected from 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;

[0082] The active ester compound is a compound containing the following structural formula:

[0083] wherein X is phenyl or naphthyl; j is 0 or 1; k is 0 or 1; n represents the repeating unit, and is 0.25-1.25.

[0084] Further preferably, the curing agent is selected from active ester compounds, and the reaction between the active ester group and the epoxy group does not generate a hydroxyl group having strong polarity, which is advantageous for improving dielectric properties.

[0085] In some embodiments, the resin composition 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.

[0086] 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, or a hydrogenated styrene and pentadiene triblock copolymer.

[0087] The silicone-based elastomer contains at least one of structural formula (13), structural formula (14), and structural formula (15):

[0088] In structural formula (13), R is a C1-C6 hydrocarbon group or -O-R1, and R1 is a C1-C6 hydrocarbon group. 12 12

[0089] In structural formula (14), R is a C1-C6 hydrocarbon group or -O-R1, and R1 is a C1-C6 hydrocarbon group. 12 12

[0090] In structural formula (15), X is a mercapto group, an epoxy group, a hydroxyl group, or a methoxy group.

[0091] The methacrylate-based elastomer contains structural formula (16) and / or structural formula (17):

[0092] In structural formula (16), R1 is a C1-C5 alkyl group, and x is an integer of 1 to 100.

[0093] In structural formula (17), R2 is a C1-C5 alkyl group, and y is an integer of 1 to 100.

[0094] In some embodiments, the resin composition further comprises 0.01 to 8 parts by weight of a catalyst selected from at least one of an imidazole, a pyridine, an organophosphorus, or a metal salt. 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.

[0095] ​​​​In some embodiments, the resin composition further comprises 5-30 parts by weight of a flame retardant selected from at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organic silicon flame retardant, and an organic metal salt flame retardant.

[0096] Preferably, the bromine-based flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalic amide.

[0097] The phosphorus-based flame retardant is selected from condensed phosphoric acid ester, 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) phosphorus, phosphazene, modified phosphazene. Among them, the DOPO group is

[0098] Further preferably, the flame retardant is condensed phosphoric acid ester, hypophosphite, or a double DOPO compound (i.e., the aforementioned compound containing two DOPO groups).

[0099] In some embodiments, the resin composition further comprises 30-200 parts by weight of a filler selected from at least one of inorganic fillers, organic fillers, or composite fillers. The inorganic fillers are selected from at least one of silicon dioxide, aluminum hydroxide, aluminum oxide, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder. The organic fillers are selected from at least one of polytetrafluoroethylene powder, polyphenylene sulfide powder, and polyether sulfone powder.

[0100] Preferably, the filler is spherical silicon dioxide, aluminum oxide, or aluminum hydroxide, and more preferably, the filler is spherical silicon dioxide.

[0101] Further, the filler is surface treated with a silane coupling agent, which is at least one of an amino silane coupling agent, a carbon-carbon double bond-containing silane coupling agent, or an epoxy silane coupling agent.

[0102] Preferably, the silane coupling agent is selected from 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.

[0103] The present application also provides the use of the above-mentioned resin composition in semi-cured sheets, laminated boards, insulating films, insulating boards, copper-clad boards, circuit substrates, and electronic devices, which are specifically described as follows:

[0104] The present application provides a prepreg comprising the reinforcing material and the aforementioned resin composition, and a method for preparing the prepreg by dissolving the resin composition in a solvent to form a glue solution, then impregnating the reinforcing material in the glue solution, and baking the impregnated reinforcing material at 100-180°C for 1-15 minutes.

[0105] The solvent is at least one selected from the group consisting 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.

[0106] The reinforcing material is at least one selected from the group consisting of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics. Preferably, the reinforcing material is a glass fiber cloth, and more preferably, the glass fiber cloth is an open fiber cloth or a flat cloth, and even more preferably, the glass fiber cloth is an E-glass fiber cloth, an S-glass fiber cloth, a T-glass fiber cloth, or a Q-glass fiber cloth.

[0107] 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.

[0108] The present application also provides a laminate comprising one piece of the aforementioned prepreg and a metal foil arranged on at least one side surface of the prepreg, or comprising a composite piece formed by stacking a plurality of the aforementioned prepregs, and a metal foil arranged on at least one side surface of the composite piece.

[0109] The laminate is prepared by arranging a metal foil on one side or both sides of a piece of the prepreg, or stacking at least two pieces of the prepreg to form a composite piece, and arranging a metal foil on one side or both sides of the composite piece, and then hot-pressing to form the metal foil laminate. The hot-pressing is performed at a pressure of 0.2-2 MPa and a temperature of 150-250°C for 2-4 hours.

[0110] Preferably, the metal foil is 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.

[0111] The present application also provides an insulating board comprising at least one piece of the aforementioned prepreg.

[0112] The present application also provides an insulating film comprising a carrier film and the aforementioned resin composition coated thereon, and the heat resistance of the insulating film is significantly improved.

[0113] The insulating film is prepared by the following method: dissolving the aforementioned resin composition with a solvent to form a glue solution, then coating the glue solution on a carrier film, and drying the carrier film coated with the glue solution to obtain the insulating film.

[0114] 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.

[0115] The carrier film is selected from at least one of PET film, PP film, PE film, and PVC film.

[0116] The present application also provides a circuit substrate comprising one or more of the aforementioned prepreg, laminated board, insulating board, and insulating film.

[0117] The present application also 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.

[0118] The technical solutions of the present application are further described below in combination with some specific synthesis examples and comparative examples.

[0119] Synthesis Example 1

[0120] 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 bottle to obtain a mixed solution, the solution was heated to about 50°C and stirred uniformly. 2 mol of formaldehyde solution was added dropwise into the solution within 30 min while stirring, 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 the solution was left to stand for 20 min, after the solution was layered, the upper aqueous phase and a small amount of emulsions were removed. The solvent was recovered by heating and reducing pressure (heating to 90°C and reducing pressure to 90 mmHg) to obtain a diallyl bisphenol A type benzoxazine compound.

[0121] Synthesis Example 2

[0122] 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 bottle to obtain a mixed solution, the solution was heated to about 50°C and stirred uniformly. 2 mol of formaldehyde solution was added dropwise into the solution within 30 min while stirring, 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 the solution was left to stand for 20 min, after the solution was layered, the upper aqueous phase and a small amount of emulsions were removed. The solvent was recovered by heating and reducing pressure (heating to 90°C and reducing pressure to 90 mmHg) to obtain a diallyl bisphenol A type benzoxazine compound.

[0123] The chemical components and contents of the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 2 are shown in Table 1.

[0124] Table 1 Resin composition ingredient table

[0125]

[0126]

[0127] Table 2 Material table

[0128]

[0129] The components of the resin compositions of Examples 1 to 6 and Comparative Examples 1 to 2 in Table 1 above were respectively dissolved in butanone, stirred and mixed uniformly, and then diluted to a glue solution with a solid content of 65 wt%; the E-glass fiber cloth 2116 as the reinforcing material was pretreated with an epoxy silane coupling agent, then immersed in the glue solution, taken out after soaking, and placed in a blast drying oven at 160°C, and baked for 3 to 6 min to obtain a prepreg.

[0130] Two of the above prepregs were cut to 300 x 300 mm and stacked into a combined sheet, then a low-profile electrolytic copper foil with a thickness of 12 μm was placed on both sides of the combined sheet, and placed in a vacuum hot press, and hot-pressed at a pressure of 1.5 MPa and a temperature of 220°C for 1.5 h to obtain a copper-clad laminate, and the specific performance was detected as shown in Table 3.

[0131] The performance of the copper-clad laminates prepared in the above examples and comparative examples was tested by the following method:

[0132] (1) Tg: DMA was used, the temperature rise rate was 10°C / min, and the frequency was 10 Hz;

[0133] (2) Water absorption (%): tested according to IPC-TM-650 2.6.2.1 method;

[0134] (3) Dk and Df: the dielectric properties at 10 GHz were tested according to IPC-TM-650 2.5.5.9 using the flat plate method.

[0135] Table 3

[0136]

[0137] It should be understood that although the present specification describes only a single embodiment, the disclosure of this specification includes any and all embodiments having any one of the features set forth in the specification and / or attached claims. Moreover, although individual embodiments of this specification can only disclose one independent technical solution, the 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.

[0138] The above detailed description of a series of specific embodiments is merely for the feasibility of the present application, and is not intended to limit the protection scope of the present application. Any equivalent embodiments or changes made without departing from the spirit of the present application shall be included in the protection scope of the present application.

Claims

1. A resin composition, characterized by comprising: By weight, the composition comprises: a benzoxazine resin: 1 to 80 parts by weight; an epoxy resin: 20 to 100 parts by weight; a curing agent: 5 to 50 parts by weight; the benzoxazine resin contains the following structural formula (1a) or structural formula (1b): wherein Ar is methylene, ethylene, -O-, -S- or 2. The resin composition according to claim 1, characterized by the benzoxazine resin further comprises a non-benzocyclobutene-based benzoxazine resin, wherein the non-benzocyclobutene-based benzoxazine resin comprises 10 to 80 parts by weight based on 100 parts by weight of the benzoxazine resin.

3. The resin composition according to claim 2, characterized by the non-benzocyclobutene-based benzoxazine resin is selected from one or a combination of at least two of a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin, a phenolphthalein type benzoxazine resin, a dicyclopentadiene type benzoxazine resin, a phosphorus-containing benzoxazine resin, a diamine type benzoxazine resin, or an allyl benzoxazine resin.

4. The resin composition according to claim 2, characterized by the non-benzocyclobutene-based benzoxazine resin is at least one of the following structural formulae: wherein R group is a vinyl, allyl, propenyl, or methacrylate group; Ar is a methylene, ethylene, -O-, -S-, or no linker; wherein Ar is methylene, ethylene, -O-, -S-, or no linker; wherein R group is a vinyl, allyl, propenyl, or methacrylate group; Ar is methylene, ethylene, -O—, -S-, or no linker.

5. The resin composition according to claim 1, characterized by the epoxy resin is selected from any one or a combination of at least two of a dicyclopentadiene epoxy resin, a carbon-carbon double bond-containing epoxy resin, a phosphorus-containing epoxy resin, an isocyanate-modified epoxy resin, a biphenyl epoxy resin, a bisphenol A type epoxy resin, a phenol type novolac epoxy resin, an o-cresol novolac type epoxy resin, an epoxidized polybutadiene resin, a naphthalene ring-containing epoxy resin, a bisphenol F type epoxy resin.

6. The resin composition according to claim 1, characterized by the epoxy resin is at least one of the following structures: wherein m is an integer from 0 to 10; wherein, n is an integer from 1 to 20; wherein p is an integer from 1 to 20; wherein n is an integer from 0 to 7, and R is H or -CH3; wherein X1is H or C1-C5 alkyl; X2is H or C1-C5 alkyl; wherein X1is H or C1-C5 alkyl; wherein n is an integer from 0 to 7, R is -O- or -CO-.

7. The resin composition according to claim 1, characterized by the curing agent is selected from at least one of an amine type curing agent, an active ester curing agent, a phenolic type curing agent, an acid anhydride type curing agent, a maleimide type curing agent, a cyanate ester type curing agent.

8. The resin composition according to claim 7, characterized by the amine type curing agent is selected from at least one of diaminodiphenylmethane, diaminodiphenyl sulfone, diethylenetriamine, bis-carboxyphthalimide, dicyandiamide, or imidazole; the phenolic type curing agent is selected from at least one of a bisphenol A novolac resin, a phenol novolac resin, a naphthalene type novolac resin, a biphenyl phenol type novolac resin; the acid anhydride type curing agent is selected from at least one of phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, hydrogenated phthalic anhydride, nadic anhydride, or styrene-maleic anhydride; the cyanate ester type curing agent is selected from at least one of a bisphenol A type cyanate ester, a bisphenol F type cyanate ester, a bisphenol E type cyanate ester, a bisphenol M type cyanate ester, a DCPD type cyanate ester, a naphthalene type cyanate ester, a phenolic type cyanate ester, a biphenyl cyanate ester; the active ester type curing agent is a compound containing the following structural formula: wherein X is phenyl or naphthyl; j is 0 or 1 ; k is 0 or 1 ; n represents the number of repeating units and is from 0.25 to 1.

25.

9. The resin composition according to claim 1, characterized by further comprising 5 to 30 parts by weight of a flame retardant selected from at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, a silicone-based flame retardant, an organic metal salt-based flame retardant.

10. The resin composition according to claim 9, characterized by the bromine-based flame retardant is selected from at least one of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalic diamide; The phosphorus-based flame retardant is selected from the group consisting of 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, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, phosphazene, modified phosphazene, wherein m is an integer from 1 to 5, and the structure of the above DOPO group is 11. Use of the resin composition according to any one of claims 1 to 10 in a prepreg, a laminate, an insulating film, an insulating board, a circuit substrate, and an electronic device.

Images