Polyphenyl ether resin composition and application thereof

Abstract

The invention discloses a polyphenyl ether resin composition and application thereof. The polyphenyl ether resin composition comprises the following components in parts by weight: 30-100 parts of polyphenyl ether resin; 5-70 parts by weight of nitrogen-containing polyether resin containing unsaturated double bonds; 10 to 60 parts by weight of a cross-linking agent; the structural units contained in the nitrogen-containing polyether resin containing the unsaturated double bonds are limited. Compared with the prior art, the polyphenyl ether resin composition provided by the invention adopts the polyphenyl ether resin and the nitrogen-containing polyether resin containing unsaturated double bonds, so that the polyphenyl ether resin composition not only has better compatibility, but also has excellent lamination process processability, and the resin composition with high heat resistance, low dielectric constant, low dielectric loss, high cohesiveness and low water absorption is obtained.

Description

Technical Field

[0001] This application belongs to the field of electronic materials technology and relates to a polyphenylene ether resin composition and its application in prepreg, laminate, insulating board, insulating film, circuit board and electronic device. Background Technology

[0002] With the advent of the 5G communication era, electronic components are rapidly developing towards higher speeds and higher integration. However, with the increasing wiring density of VLSI (Very Large Scale Integration), the resistance of metal interconnects and the capacitance of interlayer dielectrics within electronic components easily create RC (resistance capacitance delay) effects, leading to adverse effects such as signal transmission delay, noise interference, and power loss. In high-speed, high-frequency transmission technologies, dielectric materials are required to have high signal transmission speed (v) and low signal propagation loss rate (α), and both v and α values ​​are closely related to the dielectric properties of the dielectric material. Generally, the v value of a high-frequency circuit board is inversely proportional to the dielectric constant Dk of the dielectric material, while the α value is directly proportional to the dielectric constant Dk and the dielectric loss tangent Df. Therefore, developing insulating dielectric materials with low Dk and low Df is of great significance for reducing RC delay, minimizing energy consumption, and avoiding crosstalk.

[0003] Curable crosslinkable polyphenylene ether resin has a low dielectric constant and dielectric loss tangent, making it one of the most widely used low dielectric materials. However, due to its insufficient heat resistance and low adhesion, it cannot meet the process requirements for the fabrication of circuit boards for high-performance communication equipment. Summary of the Invention

[0004] This application provides a polyphenylene ether resin composition and prepreg, laminate, insulating board, insulating film, circuit board and electronic device made from the resin composition, to solve the problems of poor heat resistance and poor adhesion of polyphenylene ether resin.

[0005] To achieve the above-mentioned application objectives, one embodiment of this application provides a polyphenylene ether resin composition, comprising, by weight:

[0006] 30-100 parts by weight of polyphenylene ether resin;

[0007] 5-70 parts by weight of nitrogen-containing polyether resin containing unsaturated double bonds;

[0008] Crosslinking agent: 10-60 parts by weight;

[0009] The nitrogen-containing polyether resin containing unsaturated double bonds contains at least one of the following structural units:

[0010] Among them, R1, R2, R3, R4, R5, and R6 may be the same or different, and each is independently selected from hydrogen, C1-C5 alkyl or aromatic groups.

[0011] As a further improvement of one embodiment of this application, the polyphenylene ether resin contains unsaturated double bond groups.

[0012] As a further improvement of one embodiment of this application, the unsaturated double bond group is vinyl, allyl, or methacrylate.

[0013] As a further improvement to one embodiment of this application, the polyphenylene ether resin has the following structural formula:

[0014]

[0015] Among them, a, b, and c may be the same or different, and each is an independent integer from 0 to 50;

[0016] -OXO- is at least one of the following structures:

[0017] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 Whether the same or different, each is independently selected from hydrogen, C1-C5 alkyl, and phenyl;

[0018] The structural formula is R 21 R 22 R 23 and R 24 They may be the same or different, and are each independently selected from hydrogen, C1-C5 alkyl, and phenyl.

[0019] As a further improvement of one embodiment of this application, the nitrogen-containing polyether resin containing unsaturated double bonds is obtained by reacting polyphenolic compounds, nitrogen-containing aromatic halides and end-capping agents.

[0020] As a further improvement to one embodiment of this application, the polyphenol compound is selected from at least one of the following structures:

[0021] Structural formula (1);

[0022] Structural formula (2);

[0023] Structural formula (3);

[0024] Structural formula (4);

[0025] Where R is carbon-based;

[0026] R1, R2, R3, and R4 may be the same or different, and each is independently selected from hydrogen or C1-C8 alkyl groups;

[0027] Ar1 and Ar2 may be the same or different, and are each independently selected from hydrogen, C1-C8 alkyl groups,

[0028] R1 and R2 may be the same or different, and each is independently selected from hydrogen or C1-C5 alkyl groups;

[0029] Y represents a C1-C5 alkylene group without connecting bonds.

[0030] R1 and R2 may be the same or different, and each is independently selected from hydrogen or C1-C5 alkyl groups.

[0031] As a further improvement of one embodiment of this application, the polyphenol compound includes the polyphenol compound shown in structural formula (2).

[0032] As a further improvement of one embodiment of this application, the polyphenol compound is a mixture of a first component and a second component, wherein the first component is a bisphenol compound, the second component is at least one of a triphenol compound and a tetraphenol compound, and the molar percentage of the bisphenol compound in the polyphenol compound is 30-90%.

[0033] As a further improvement of one embodiment of this application, the nitrogen-containing aromatic halide is selected from at least one of pyrimidine halides and their derivatives, pyrazine halides and their derivatives, and pyridazine halides and their derivatives.

[0034] As a further improvement to one embodiment of this application, the structural formula of the nitrogen-containing aromatic halide is:

[0035] Where X is a chlorine atom, bromine atom, or fluorine atom, and Ar is selected from hydrogen, C1-C5 alkyl or aromatic groups.

[0036] As a further improvement of one embodiment of this application, the aromatic group is phenyl, biphenyl, naphthyl, phenyl with alkyl substituent, biphenyl with alkyl substituent, or naphthyl with alkyl substituent, wherein the alkyl substituent is C1-C5 alkyl.

[0037] As a further improvement of one embodiment of this application, the end-capping agent is at least one of chloromethylstyrene, bromomethylstyrene, methacrylic acid, methacryloyl chloride, and methacrylic anhydride.

[0038] As a further improvement of one embodiment of this application, the end-capping agent is chloromethylstyrene.

[0039] As a further improvement of one embodiment of this application, the preparation method of the nitrogen-containing polyether resin containing unsaturated double bonds includes: mixing polyphenolic compounds, nitrogen-containing aromatic halides, end-capping agents and organic solvents evenly, and then reacting them in the presence of alkali metal compounds to obtain the nitrogen-containing polyether resin containing unsaturated double bonds.

[0040] As a further improvement of one embodiment of this application, the method for preparing the nitrogen-containing polyether resin containing unsaturated double bonds includes: reacting a polyphenol compound, a nitrogen-containing aromatic halide and an organic solvent in the presence of an alkali metal compound to prepare a copolymer, and then adding a capping agent to react and obtain the nitrogen-containing polyether resin containing unsaturated double bonds.

[0041] As a further improvement of one embodiment of this application, when polyphenolic compounds, nitrogen-containing aromatic halides and organic solvents react in the presence of alkali metal compounds, the reaction temperature is 100-180°C and the reaction time is 3-8 hours.

[0042] As a further improvement of one embodiment of this application, the crosslinking agent is at least one of triallyl isocyanurate monomer, triallyl isocyanurate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, dicyclopentadiene dimethacrylate monomer, norbornene monomer, and cyclopentadiene monomer.

[0043] As a further improvement of one embodiment of this application, the crosslinking agent is triallyl isocyanurate monomer (TAIC), dicyclopentadiene dimethacrylate monomer (DCP), or a combination of the two.

[0044] As a further improvement to one embodiment of this application, the structural formula of the triallyl isocyanurate monomer (TAIC) is as follows:

[0045] The structural formula of the dicyclopentadiene dimethacrylate monomer (DCP) is as follows:

[0046] As a further improvement of one embodiment of this application, both the polyphenylene ether resin and the nitrogen-containing polyether resin containing unsaturated double bonds contain styrene ends.

[0047] As a further improvement of one embodiment of this application, in the polyphenylene ether resin composition, the content of the polyphenylene ether resin is greater than the content of the nitrogen-containing polyether resin containing unsaturated double bonds.

[0048] As a further improvement of one embodiment of this application, the polyphenylene ether resin composition further includes 5 to 60 parts by weight of an elastomer.

[0049] As a further improvement of one embodiment of this application, the elastomer is selected from at least one of hydrogenated styrene and butadiene diblock copolymer, hydrogenated styrene and butadiene triblock copolymer, hydrogenated styrene and pentadiene diblock copolymer, and hydrogenated styrene and pentadiene triblock copolymer.

[0050] As a further improvement of one embodiment of this application, the polyphenylene ether resin composition further includes 0.001 to 5 parts by weight of an initiator.

[0051] As a further improvement of one embodiment of this application, the initiator is selected from at least one of diacyl peroxide, peroxy ketal, peroxy carbonate, peroxy ester, ketone peroxide, dialkyl peroxide, and hydroperoxide.

[0052] As a further improvement of one embodiment of this application, the polyphenylene ether resin composition further includes 5 to 60 parts by weight of a flame retardant.

[0053] As a further improvement of one embodiment of this application, the flame retardant is selected from at least one of bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon flame retardants, and organometallic salt flame retardants.

[0054] As a further improvement of one embodiment of this application, the brominated flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, styrene bromide, or tetrabromophthalamide.

[0055] As a further improvement of one embodiment of this application, the phosphorus-based flame retardant is selected from inorganic phosphorus, 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-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, phosphazene, modified phosphazene.

[0056] As a further improvement of one embodiment of this application, the flame retardant is a condensed phosphate ester, hypophosphite, or a bisDOPO compound.

[0057] Furthermore, the aforementioned resin composition further comprises 10 to 250 parts by weight of filler, wherein the filler is selected from at least one of inorganic fillers, organic fillers, and composite fillers.

[0058] The inorganic filler is preferably selected from at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0059] The inorganic filler is more preferably made from spherical silica, alumina, or aluminum hydroxide.

[0060] The organic filler is selected from at least one of polytetrafluoroethylene powder, polyphenylene sulfide, and polyethersulfone powder.

[0061] This application also provides the application of the above-mentioned polyphenylene ether resin composition in prepregs, laminates, insulating boards, insulating films, circuit boards, and electronic devices, as detailed below:

[0062] This application also provides a semi-cured sheet comprising a reinforcing material and the aforementioned polyphenylene ether resin composition; the polyphenylene ether resin composition is coated on the reinforcing material.

[0063] This application also provides a laminate comprising a prepreg and a metal foil disposed on at least one surface of the prepreg; or comprising a composite sheet formed by stacking multiple prepregs and a metal foil disposed on at least one surface of the composite sheet.

[0064] The present invention also provides an insulating board comprising at least one of the aforementioned prepreg sheets.

[0065] The present invention also provides an insulating film comprising a carrier film and the aforementioned polyphenylene ether resin composition coated thereon.

[0066] This application also provides a circuit board, including at least one of the aforementioned prepreg and laminate.

[0067] This application also provides an electronic device, including the aforementioned circuit board.

[0068] Due to the application of the above technical solution, this application has the following beneficial effects compared with the prior art:

[0069] The polyphenylene ether resin composition of this application uses polyphenylene ether resin and nitrogen-containing polyether resin containing unsaturated double bonds, which not only has good compatibility, but also excellent lamination processability, resulting in a resin composition with high heat resistance, low dielectric constant and low dielectric loss, high adhesion and low water absorption. Detailed Implementation

[0070] The technical solution of this application will be further described below with reference to specific implementation methods. The following embodiments are only descriptive and not limiting, and cannot be used to limit the protection scope of this application.

[0071] One embodiment of this application provides a polyphenylene ether resin composition and its application in prepregs, laminates, insulating boards, insulating films, circuit boards, and electronic devices.

[0072] This application provides a polyphenylene ether resin composition, comprising, by weight:

[0073] 30-100 parts by weight of polyphenylene ether resin;

[0074] 5-70 parts by weight of nitrogen-containing polyether resin containing unsaturated double bonds;

[0075] Crosslinking agent: 10-60 parts by weight;

[0076] The nitrogen-containing polyether resin containing unsaturated double bonds contains at least one of the following structural units:

[0077] Among them, R1, R2, R3, R4, R5, and R6 may be the same or different, and each is independently selected from hydrogen, C1-C5 alkyl or aromatic groups.

[0078] The polyphenylene ether resin contains unsaturated double bond groups.

[0079] By using polyphenylene ether resin and nitrogen-containing polyether resin containing unsaturated double bonds, not only is there good compatibility, but there is also excellent lamination processability, resulting in a resin composition that combines high heat resistance, low dielectric constant and low dielectric loss, high adhesion and low water absorption.

[0080] Preferably, the unsaturated double bond group is vinyl, allyl, or methacrylate.

[0081] Preferably, the polyphenylene ether resin has the following structural formula:

[0082]

[0083] Among them, a, b, and c may be the same or different, and each is an independent integer from 0 to 50;

[0084] -OXO- is at least one of the following structures:

[0085] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R 11 R 12 R 13 R 14R 15 R 16 R 17 R 18 Whether the same or different, each is independently selected from hydrogen, C1-C5 alkyl, and phenyl;

[0086] The structural formula of -YO- is: R 21 R 22 R 23 and R 24 They may be the same or different, and are each independently selected from hydrogen, C1-C5 alkyl, and phenyl.

[0087] Specifically, the polyphenylene ether resin may be the OPE-2ST series manufactured by Mitsubishi Gas.

[0088] The nitrogen-containing polyether resin containing unsaturated double bonds is obtained by reacting polyphenolic compounds, nitrogen-containing aromatic halides, and end-capping agents.

[0089] The polyphenol compound is selected from at least one of the following structures:

[0090] , structural formula (1);

[0091] Structural formula (2);

[0092] Structural formula (3);

[0093] Structural formula (4);

[0094] Where R is carbon-based;

[0095] R1, R2, R3, and R4 may be the same or different, and each is independently selected from hydrogen or C1-C8 alkyl groups;

[0096] Ar1 and Ar2 may be the same or different, and are each independently selected from hydrogen, C1-C8 alkyl groups,

[0097] R1 and R2 may be the same or different, and each is independently selected from hydrogen or C1-C5 alkyl groups;

[0098] Y represents a C1-C5 alkylene group without connecting bonds.

[0099] R1 and R2 may be the same or different, and each is independently selected from hydrogen or C1-C5 alkyl groups.

[0100] Preferably, the polyphenol compound contains the polyphenol compound shown in structural formula (2). This allows for a further reduction in CTE while maintaining excellent heat resistance, and in particular, results in a smaller change in the Df value after moisture-absorbing treatment.

[0101] Preferably, the polyphenol compound is a mixture of a first component and a second component, wherein the first component is a bisphenol compound, the second component is at least one of a triphenol compound and a tetraphenol compound, and the molar percentage of the bisphenol compound in the polyphenol compound is 30-90%.

[0102] By using a mixture of the first and second components, the two-dimensional structure of the bisphenol compound is mixed with at least one of the three-dimensional structure of the triphenol compound and the four-dimensional structure of the tetraphenol compound, which can effectively increase the crosslinking density of the cured product, inhibit the decrease in heat resistance, and improve the resistance to damp heat.

[0103] The nitrogen-containing aromatic halides are selected from at least one of pyrimidine halides and their derivatives, pyrazine halides and their derivatives, and pyridazine halides and their derivatives.

[0104] Preferably, the structural formula of the nitrogen-containing aromatic halide is:

[0105] Where X is a chlorine atom, bromine atom, or fluorine atom, and Ar is selected from hydrogen, C1-C5 alkyl groups, or aromatic groups.

[0106] Preferably, the aromatic group is phenyl, biphenyl, naphthyl, phenyl with alkyl substituent, biphenyl with alkyl substituent, or naphthyl with alkyl substituent, wherein the alkyl substituent is C1-C5 alkyl.

[0107] The capping agent is at least one of chloromethylstyrene, bromomethylstyrene, methacrylic acid, methacryloxychloride, and methacrylic anhydride.

[0108] The end-capping agent is preferably chloromethylstyrene.

[0109] In one embodiment, the method for preparing the nitrogen-containing polyether resin containing unsaturated double bonds includes: mixing a polyphenol compound, a nitrogen-containing aromatic halide, a capping agent and an organic solvent evenly, and then reacting them in the presence of an alkali metal compound to obtain the nitrogen-containing polyether resin containing unsaturated double bonds.

[0110] In another embodiment, the method for preparing the nitrogen-containing polyether resin containing unsaturated double bonds includes: reacting a polyphenol compound, a nitrogen-containing aromatic halide, and an organic solvent in the presence of an alkali metal compound to prepare a copolymer, and then adding a capping agent to react and obtain the nitrogen-containing polyether resin containing unsaturated double bonds.

[0111] Preferably, when polyphenolic compounds, nitrogen-containing aromatic halides, and organic solvents react in the presence of alkali metal compounds, the reaction temperature is 100–180°C and the reaction time is 3–8 h.

[0112] The crosslinking agent is at least one of triallyl isocyanurate monomer, triallyl isocyanurate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, dicyclopentadiene dimethacrylate monomer, norbornene monomer, and cyclopentadiene monomer.

[0113] The crosslinking agent is preferably triallyl isocyanurate monomer (TAIC), dicyclopentadiene dimethacrylate monomer (DCP), or a combination of the two.

[0114] The structural formula of the triallyl isocyanurate monomer (TAIC) is as follows:

[0115] The structural formula of the dicyclopentadiene dimethacrylate monomer (DCP) is as follows:

[0116] Specifically, the triallyl isocyanurate monomer (TAIC) can be TAIC manufactured by Mitsubishi Chemical, TAIC manufactured by Evonik, or TAIC manufactured by Nippon Chemical; the dicyclopentadiene dimethacrylate monomer (DCP) can be A-DCP manufactured by Shin-Nakamura Chemical or DCP-A manufactured by Kyoeisha Chemical.

[0117] Preferably, both the polyphenylene ether resin and the nitrogen-containing polyether resin with unsaturated double bonds contain styrene terminals. When these two resins contain the same terminal groups and phenylene ether groups, the compatibility between the resins can be greatly improved, resulting in a very homogeneous resin solution. Furthermore, the reaction between the two resins can be made more complete, further increasing the curing crosslinking density, thereby obtaining a final cured product with high heat resistance, low dielectric constant, low water absorption, and high adhesion.

[0118] Preferably, in the polyphenylene ether resin composition, the content of the polyphenylene ether resin is greater than the content of the nitrogen-containing polyether resin containing unsaturated double bonds. This allows the polyphenylene ether resin composition to achieve high heat resistance and high adhesion while maintaining low dielectric properties.

[0119] Furthermore, the polyphenylene ether resin composition further comprises 5 to 60 parts by weight of an elastomer.

[0120] The elastomer is selected from at least one of hydrogenated styrene and butadiene diblock copolymer, hydrogenated styrene and butadiene triblock copolymer, hydrogenated styrene and pentadiene diblock copolymer, and hydrogenated styrene and pentadiene triblock copolymer.

[0121] Furthermore, the polyphenylene ether resin composition further includes 0.001 to 5 parts by weight of an initiator.

[0122] The initiator is selected from at least one of diacyl peroxide, peroxy ketal, peroxy carbonate, peroxy ester, ketone peroxide, dialkyl peroxide, and hydroperoxide.

[0123] Furthermore, the polyphenylene ether resin composition further includes 5 to 60 parts by weight of a flame retardant.

[0124] The flame retardant is selected from at least one of bromine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon flame retardants, and organometallic salt flame retardants.

[0125] The bromine-based flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, styrene bromide, or tetrabromophthalamide.

[0126] The phosphorus-based flame retardant is selected from inorganic phosphorus, condensed phosphate esters, phosphoric acid, hypophosphite, phosphorus oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. (m is an integer from 1 to 5)

[0127] 10-Phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphine, phosphazene, modified phosphazene.

[0128] Among them, the DOPO group is

[0129] The flame retardant is preferably a condensed phosphate ester, hypophosphite, or a bisDOPO compound.

[0130] This application also provides a semi-cured sheet comprising a reinforcing material and the aforementioned polyphenylene ether resin composition, wherein the polyphenylene ether resin composition is coated on the reinforcing material.

[0131] The method for preparing the prepreg is as follows: the aforementioned resin composition is dissolved in a solvent to form an adhesive solution, and then the adhesive solution is coated onto the reinforcing material by impregnation. The impregnated reinforcing material is then taken out and baked at a temperature of 100-180°C for 1-15 minutes. After drying, the prepreg is obtained.

[0132] The solvent may be selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0133] The reinforcing material can be selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics, preferably glass fiber cloth, and more preferably E glass fiber cloth, S glass fiber cloth, T glass fiber cloth, or Q glass fiber cloth. The glass fiber cloth is preferably an open-fiber cloth or a flat cloth.

[0134] Furthermore, when glass fiber cloth is used as the reinforcing material, it is pre-treated with a coupling agent to improve the interfacial bonding between the polyphenylene ether resin composition and the glass fiber cloth. The coupling agent is preferably an epoxy silane coupling agent or an amino silane coupling agent to give the reinforcing material good water resistance and heat resistance.

[0135] This application also provides a laminate, including a metal foil and the aforementioned prepreg; the metal foil is disposed on at least one side surface of the prepreg or a combination of multiple prepregs.

[0136] The laminate can be prepared by the following method: covering one or both surfaces of a prepreg sheet with metal foil, or stacking at least two prepreg sheets to form a composite sheet, covering one or both surfaces of the composite sheet with metal foil, and hot-pressing to obtain a metal foil laminate. The hot-pressing conditions are: pressure 0.2–2 MPa, temperature 150–250°C, and pressing time 2–4 h. The metal foil is selected from copper foil or aluminum foil, with a thickness of 5 μm, 8 μm, 12 μm, 18 μm, 35 μm, or 70 μm.

[0137] The present invention also provides an insulating board comprising at least one of the aforementioned prepreg sheets.

[0138] The present invention also provides an insulating film comprising a carrier film and the aforementioned polyphenylene ether resin composition coated thereon.

[0139] The insulating film is prepared by dissolving the aforementioned polyphenylene ether resin composition in a solvent to form an adhesive solution, coating the adhesive solution onto a carrier film, and then heating and drying the carrier film coated with the adhesive solution to obtain the insulating film.

[0140] 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.

[0141] The carrier film is selected from at least one of PET film, PP film, PE film, and PVC film.

[0142] This application also provides a circuit board, including at least one of the aforementioned prepreg and laminate.

[0143] This application also provides an electronic device, including the aforementioned circuit board.

[0144] The technical solutions of this application will be further described below with reference to some specific synthetic examples, embodiments, and comparative examples. Of course, these embodiments are only a part of the many variations contained in the implementation of this application, and not all of them.

[0145] Synthesis example 1

[0146] Take 2 mol of bisphenol compound, 0.8 mol of tetraphenol compound, 2 mol of 4,6-dichloro-2-phenylpyrimidine, and 60 g of calcium carbonate, and add 120 g of NMP solvent. React at 130 °C for 6 h under nitrogen protection. After the reaction is completed, cool to 10 °C and add 2 mol of chloromethylstyrene dropwise. Continue the reaction at 65 °C for another 6 h to obtain the reaction solution. After washing, filtering, and drying under reduced pressure, nitrogen-containing polyether resin A containing unsaturated double bonds is obtained.

[0147] The structural formula of the bisphenol compound is as follows:

[0148] The structural formula of the tetraphenol compound is as follows:

[0149] The structural formula of 4,6-dichloro-2-phenylpyrimidine is:

[0150] The structural formula of chloromethylstyrene is

[0151] Synthesis example 2

[0152] Take 2 mol of bisphenol compound, 1 mol of triphenol compound, 2.2 mol of 4,6-dichloro-2-phenylpyrimidine, and 60 g of calcium carbonate, and add 120 g of NMP solvent. React at 130 °C for 6 h under nitrogen protection. After the reaction is completed, cool to 10 °C and add 1.8 mol of chloromethylstyrene dropwise. Continue the reaction at 65 °C for another 6 h to obtain the reaction solution. After washing, filtering, and drying under reduced pressure, nitrogen-containing polyether resin B containing unsaturated double bonds is obtained.

[0153] The structural formula of the bisphenol compound is as follows:

[0154] The structural formula of the triphenol compound is as follows:

[0155] The structural formula of 4,6-dichloro-2-phenylpyrimidine is:

[0156] The structural formula of chloromethylstyrene is

[0157] Synthesis example 3

[0158] Take 3 mol of bisphenol compound, 2.2 mol of 4,6-dichloro-2-phenylpyrimidine, and 60 g of calcium carbonate, and add 120 g of NMP solvent. React at 130 °C for 6 h under nitrogen protection. After the reaction is completed, cool to 10 °C and add 2 mol of chloromethylstyrene dropwise. Continue the reaction at 65 °C for another 6 h to obtain the reaction solution. After washing, filtering, and drying under reduced pressure, nitrogen-containing polyether resin C containing unsaturated double bonds is obtained.

[0159] The structural formula of the bisphenol compound is as follows:

[0160] The structural formula of 4,6-dichloro-2-phenylpyrimidine is:

[0161] The structural formula of chloromethylstyrene is

[0162] Synthesis example 4

[0163] Take 2 mol of bisphenol compound, 1 mol of triphenol compound, 2.2 mol of 4,6-dichloro-2-phenylpyrimidine, and 60 g of calcium carbonate, and add 120 g of NMP solvent. React at 130 °C for 6 h under nitrogen protection. After the reaction is completed, cool to 10 °C and add 1.8 mol of methacryloyl chloride dropwise. Continue the reaction at 65 °C for another 6 h to obtain the reaction solution. After washing, filtering, and drying under reduced pressure, nitrogen-containing polyether resin D containing unsaturated double bonds is obtained.

[0164] The structural formula of the bisphenol compound is as follows:

[0165] The structural formula of the triphenol compound is as follows:

[0166] The structural formula of 4,6-dichloro-2-phenylpyrimidine is:

[0167] Examples and Comparative Examples

[0168] The chemical composition and content of the polyphenylene ether resin compositions of Examples 1-5 and Comparative Examples 1-3 are shown in Table 1.

[0169] Table 1

[0170]

[0171]

[0172] Among them, polyphenylene ether resin A is SA9000 manufactured by Sabiq, and polyphenylene ether resin B is OPE-2St-1200 manufactured by Mitsubishi Gas; the crosslinking agent is dicyclopentadiene dimethacrylate monomer, specifically A-DCP manufactured by Shin-Nakamura Chemicals; the initiator is Perbutyl-P manufactured by Nippon Oil; and the filler is silica manufactured by Lianrui, D... 50 =3μm.

[0173] The above embodiments and comparative examples also prepared semi-cured sheets, comprising E-glass fiber cloth as a reinforcing material and a resin composition coated on the glass fiber cloth by impregnation. The glass fiber cloth was a pre-treated open-fiber cloth using an epoxy silane coupling agent.

[0174] Specifically, the components of the polyphenylene ether resin compositions of Examples 1-5 and Comparative Examples 1-3 were dissolved in methyl ethyl ketone, stirred and mixed, and then diluted to a solid content of 65 wt%. The E-glass fiber cloth, which is used as a reinforcing material, was pretreated with an epoxy silane coupling agent, impregnated in the above adhesive solution, removed after wetting, and placed in a forced-air drying oven at 160°C for 3-6 minutes to obtain a semi-cured sheet.

[0175] The above embodiments and comparative examples also produced laminates, which were prepared by the following method:

[0176] Take two prepreg sheets and cut them to 300×300mm. Stack them into a composite sheet with a certain stacking structure. Then place a low profile electrolytic copper foil with a thickness of 12μm on each side of the composite sheet. Place it in a vacuum hot press and hot press it for 1.5h under a pressure of 1.5MPa and a temperature of 220℃ to obtain a copper-clad laminate.

[0177] The above embodiments and comparative examples also prepared an insulating board, including at least one of the aforementioned prepreg sheets.

[0178] The above embodiments and comparative examples also prepared insulating films, including a carrier film and the aforementioned polyphenylene ether resin composition coated thereon.

[0179] The above embodiments and comparative examples also prepared circuit boards, including one of the above-mentioned prepregs, which were prepared using conventional preparation methods of the prior art, and will not be described in detail here.

[0180] The copper-clad laminates obtained in Examples 1-5 and Comparative Examples 1-3 were subjected to performance testing, and the test results are shown in Table 2. The performance testing methods included:

[0181] (1) Glass transition temperature (Tg): The test was conducted using the DMA (thermomechanical analysis) method according to the method specified in IPC-TM-6502.4.25, with a heating rate of 10℃ / min and a frequency of 10Hz.

[0182] (2) Moisture and heat resistance: Take three 10cm×10cm samples with a thickness of 1mm and copper foil removed on both sides. Dry them at 100℃ for 2 hours, then treat them in a pressure cooker at 121℃ and 2 atmospheres for 1 hour. After that, immerse them in tin in a tin bath at 288℃ for 20 seconds and visually observe whether there is delamination. If delamination occurs in 0, 1, 2, or 3 of the three samples, record them as 0 / 3, 1 / 3, 2 / 3, and 3 / 3, respectively.

[0183] (3) Dk and Df under normal conditions: The dielectric constant Dk and dielectric loss Df at 10 GHz were determined using the plate method according to IPC-TM-650 2.5.5.9.

[0184] (4) Dk and Df after moisture absorption: After drying at 100℃ for 2 hours, the dielectric constant Dk and dielectric loss Df were tested at 10GHz using a pressure cooker tester at 121℃ and 2 atmospheres for 5 hours. The test was performed using the plate method according to IPC-TM-650 2.5.5.9.

[0185] (5) Water absorption rate (%): Tested according to IPC-TM-650 2.6.2.1 method;

[0186] (6) Peel strength (PS): The peel strength of the copper foil was tested according to the "post-thermal stress" test conditions in IPC-TM-650 2.4.8 method.

[0187] Table 2

[0188]

[0189] Referring to Table 2, compared with the comparative example, the copper-clad laminate prepared by the polyphenylene ether resin composition of the present application embodiment not only has excellent heat resistance, damp heat resistance, low dielectric constant and dielectric loss value, but also has high adhesion and low water absorption.

[0190] It should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This way of describing the specification is only for clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

[0191] The detailed descriptions listed above are merely specific descriptions of feasible implementation methods of this application, and are not intended to limit the scope of protection of this application. All equivalent implementation methods or modifications made without departing from the spirit of the art of this application should be included within the scope of protection of this application.

Claims

1. A polyphenylene ether resin composition, characterized in that, By weight, including: 30-100 parts by weight of polyphenylene ether resin; 5-70 parts by weight of nitrogen-containing polyether resin containing unsaturated double bonds; Crosslinking agent: 10-60 parts by weight; The nitrogen-containing polyether resin containing unsaturated double bonds contains at least one of the following structural units: Among them, R1, R2, R3, R4, R5, and R6 may be the same or different, and each is independently selected from hydrogen, C1-C5 alkyl or aromatic groups.

2. The polyphenylene ether resin composition according to claim 1, characterized in that, The polyphenylene ether resin contains unsaturated double bond groups.

3. The polyphenylene ether resin composition according to claim 2, characterized in that, The unsaturated double bond group is vinyl, allyl, or methacrylate.

4. The polyphenylene ether resin composition according to claim 1, characterized in that, The nitrogen-containing polyether resin containing unsaturated double bonds is obtained by reacting polyphenolic compounds, nitrogen-containing aromatic halides, and end-capping agents.

5. The polyphenylene ether resin composition according to claim 4, characterized in that, The polyphenol compound is selected from at least one of the following structures: Structural formula (1); Structural formula (2) ； Structural formula (3); Structural formula (4); Where R is carbon-based; R1, R2, R3, and R4 may be the same or different, and each is independently selected from hydrogen or C1-C8 alkyl groups; Ar1 and Ar2 may be the same or different, and are each independently selected from hydrogen, C1-C8 alkyl groups, R1 and R2 may be the same or different, and each is independently selected from hydrogen or C1-C5 alkyl groups; Y represents a C1-C5 alkylene group without connecting bonds. R1 and R2 may be the same or different, and each is independently selected from hydrogen or C1-C5 alkyl groups.

6. The polyphenylene ether resin composition according to claim 4, characterized in that, The polyphenol compound is a mixture of a first component and a second component, wherein the first component is a bisphenol compound and the second component is at least one of a triphenol compound and a tetraphenol compound, and the molar percentage of the bisphenol compound in the polyphenol compound is 30-90%.

7. The polyphenylene ether resin composition according to claim 4, characterized in that, The nitrogen-containing aromatic halides are selected from at least one of pyrimidine halides and their derivatives, pyrazine halides and their derivatives, and pyridazine halides and their derivatives.

8. The polyphenylene ether resin composition according to claim 1, characterized in that, The crosslinking agent is at least one of triallyl isocyanurate monomer, triallyl isocyanurate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, dicyclopentadiene dimethacrylate monomer, norbornene monomer, and cyclopentadiene monomer.

9. The polyphenylene ether resin composition according to claim 1, characterized in that, Both the polyphenylene ether resin and the nitrogen-containing polyether resin containing unsaturated double bonds contain styrene ends.

10. The use of a polyphenylene ether resin composition as described in any one of claims 1 to 9 in prepregs, laminates, insulating boards, insulating films, circuit boards, and electronic devices.

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