WO2017067140A1 - Polyphenyl ether resin composition and prepreg, laminated board and printed circuit board containing same - Google Patents

Abstract

Provided are a thermosetting polyphenyl ether resin composition and a prepreg and a laminated board containing same. The polyphenyl ether resin composition comprises: (1) a pentafunctional or higher multifunctional vinylbenzyl ether-modified thermosetting polyphenyl ether resin; and (2) a vinyl resin cross-linking agent, the weight of the vinyl resin cross-linking agent being 40-100 parts by weight based on 100 parts by weight of the pentafunctional or higher multifunctional vinylbenzyl ether-modified thermosetting polyphenyl ether resin. The vinylbenzyl ether-modified thermosetting polyphenyl ether resin, due to containing a pentafunctional or higher multifunctional styrene active group, can cross-link more vinyl resin cross-linking agents. The prepared high-speed electronic circuit substrate has low dielectric constant and dielectric loss, so that the high-speed electronic circuit substrate has a better thermo-oxidative ageing resistance; furthermore, the stability of the dielectric constant and dielectric loss of the substrate is good during long-term use.

Description

Polyphenylene ether resin composition and prepreg, laminate and printed circuit board containing same Technical field

The invention belongs to the technical field of copper clad laminates, and particularly relates to a polyphenylene ether resin composition and a prepreg, a laminate and a printed circuit board containing the same.

Background technique

In recent years, with the development of electronic information technology, the miniaturization and high density of electronic equipment installation, the increase in the capacity of information, and the high-speed and high-speed transmission of signals have been applied to high-end communication network hardware devices such as routers, switches, and servers. The use of electronic circuit board transmission lines is becoming longer and longer, requiring electronic circuit substrates with lower dielectric constants and lower dielectric losses.

For high-speed electronic circuit substrates, maintaining the dielectric constant and dielectric loss stability of the substrate during long-term use has a major impact on the characteristic impedance of the substrate and signal integrity. The stability of dielectric constant and dielectric loss consists of three aspects: dielectric constant and dielectric loss of temperature drift, wet drift and resistance to thermal aging.

For the thermal aging properties, in the curing process of the substrate resin, the resin will undergo thermal oxygen aging during long-term use, and the dielectric constant and dielectric loss of the substrate will increase, thereby affecting the stability and ultimately the substrate. The complete performance of the signal deteriorates. Therefore, the good resistance to thermal oxygen aging of the substrate resin curing system is an important performance requirement of high speed electronic circuit substrates.

The vinyl benzyl ether modified thermosetting polyphenylene ether resin has a large number of benzene ring structures and no strong polar groups, which gives the polyphenylene ether resin excellent properties such as high glass transition temperature and dimensional stability. Good, low thermal expansion coefficient, low water absorption, especially excellent low dielectric constant and low dielectric loss, making it an ideal resin material for high-speed circuit substrates.

A vinyl resin cross-linking agent such as a polybutadiene has no polar groups in its molecular chain structure and has an excellent low The dielectric constant and low dielectric loss are generally used as a crosslinking agent for preparing a high-speed circuit substrate.

CN102807658A discloses a set of polyphenylene ether resin compositions comprising: a functionalized polyphenylene ether; a cross-linking curing agent; an initiator. The polyphenylene ether used in the invention is a difunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin, and the crosslinking curing agent comprises a hydrocarbon resin such as polybutadiene or styrene-butadiene copolymer, which can be used for preparing high-speed electronic circuits. Substrate.

CN101624467A discloses a group of resin compositions comprising: polyphenylene ether; a crosslinking curing agent. The polyphenylene ether used in the invention is a 1-4 functional vinyl vinyl ether modified thermosetting polyphenylene ether resin, and the crosslinking curing agent comprises a hydrocarbon resin such as polybutadiene and styrene-butadiene copolymer, which can be used for preparation. High speed electronic circuit substrate.

The above prior art has the following problems: in order to obtain a lower dielectric constant and a lower dielectric loss, it is necessary to increase the use ratio of a vinyl resin crosslinking agent such as polybutadiene. Although the prepared substrate has a lower low dielectric constant and lower dielectric loss, the difunctional or tetrafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin has a limited styrene reactive group. Excess vinyl resin crosslinkers such as polybutadiene side chain double bonds cannot be completely reacted. Non-reactive vinyl crosslinkers such as polybutadiene side chain double bonds have poor resistance to thermal oxidative aging, which seriously affects the dielectric constant of the substrate and the stability of the dielectric loss during long-term use, thereby enabling the substrate to The complete performance of the signal deteriorates and cannot meet the needs of customers.

Summary of the invention

According to the problems in the prior art, one of the objects of the present invention is to provide a polyphenylene ether resin composition, a high-speed electronic circuit substrate (copper-clad laminate) obtained by using the polyphenylene ether resin composition, It has low dielectric constant and dielectric loss, and has good resistance to thermal aging. The dielectric constant and dielectric loss of the substrate remain stable during long-term use.

In order to achieve the above object, the present invention adopts the following technical solutions:

A thermosetting polyphenylene ether resin composition comprising:

(1) a pentafunctional or pentafunctional vinyl vinyl ether modified thermosetting polyphenylene ether resin;

(2) a vinyl resin cross-linking agent having a weight of 100 to 100 parts by weight of the penta-functional or penta-functional vinyl benzyl ether-modified thermosetting polyphenylene ether resin, and the weight of the vinyl resin crosslinking agent is 40 to 100 Parts by weight;

Wherein, the structure of the pentafunctional or penta-functional vinylbenzyl ether-modified thermosetting polyphenylene ether resin is as shown in the formula (1):

In the formula (1), R ₁ , R ₂ , R ₃ and R _{4 are the} same or different and are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C8 (for example, C2, C3, C4, C5, C6, An alkyl group of C7 and C8) or a substituted or unsubstituted aryl group.

a and c are independently an integer of 1 to 15, and b is an integer of 3 to 10, preferably an integer of 4-6.

The a is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14, and the c is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, said b being for example 3, 4, 5, 6, 7, 8, or 9.

Z has the structure shown in formula (2):

X has a structure represented by formula (3), formula (4), formula (5) or formula (6):

R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ The same or different, each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 (for example, C2, C3, C4, C5, C6, C7 and C8) alkyl group or a substituted or unsubstituted aryl group; n is an integer from 1 to 10, such as 2, 3, 4, 5, 6, 7, 8, or 9;

B is an alkylene group, -O-, -CO-, -SO-, -SC-, -SO ₂ - or -C(CH ₃ ) ₂ -.

Y has the structure shown by formula (7) or formula (8):

R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ and R _{31 are the} same or different and are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C8 (for example, C2, C3, C4, C5). , C6, C7 and C8) alkyl or substituted or unsubstituted aryl.

In the present invention, when b is from 3 to 10, when Y is a structure represented by the formula (7), the functionality of the polyphenylene ether resin is b + 2, that is, 5 to 12, and when Y is a formula (8) In the structure shown, the polyphenylene ether resin has a functionality of 2+2b, i.e., 8-22.

In the present invention, since the vinyl benzyl ether modified thermosetting polyphenylene ether resin contains a pentafunctional or pentafunctional or higher amount of a styrene reactive group, thereby being capable of crosslinking more vinyl resin crosslinking agent, it is prepared. The high-speed electronic circuit substrate not only has low dielectric constant and dielectric loss, but also the vinyl resin cross-linking side chain double bond reacts completely in the resin curing system, so that the high-speed electronic circuit substrate has better resistance to thermal aging. The substrate dielectric constant and dielectric loss are good during long-term use. The invention achieves a low dielectric constant and dielectric loss and excellent performance by the cooperation relationship between the addition amount of the vinyl benzyl ether modified thermosetting polyphenylene ether resin and the specific vinyl resin crosslinking agent with specific functionality. Resistance to thermal aging. In the present invention, the thermal aging performance is manifested in that the absolute value of the change in the dielectric constant and the dielectric loss is smaller after the substrate is subjected to thermal oxygen aging for a certain period of time at a certain temperature.

In the present invention, by selecting an n value of 3 to 10, it is overcome that the polyfunctionality of the polyphenylene ether is too large, so that it is difficult to dissolve, even if the viscosity of the dissolved glue is large.

The weight of the vinyl resin crosslinking agent is, for example, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight or 95 parts by weight, preferably modified with a penta-functional or penta-functional vinyl benzyl ether The weight of the thermosetting polyphenylene ether resin is 100 parts by weight, and the weight of the vinyl resin crosslinking agent is 50 to 80 parts by weight.

Preferably, the pentafunctional or pentafunctional or higher vinylbenzyl ether-modified thermosetting polyphenylene ether resin has a number average molecular weight of from 500 to 10,000 g/mol, preferably from 800 to 8,000 g/mol, further preferably from 1,000 to 4,000 g/mol.

Preferably, the vinyl resin crosslinking agent is selected from any one or at least two of a styrene-butadiene copolymer, a polybutadiene or a styrene-butadiene-divinylbenzene copolymer. mixture.

Preferably, the styrene-butadiene copolymer, polybutadiene or styrene-butadiene-divinylbenzene copolymer is independently modified by amino group, maleic anhydride, and epoxy group. Properties, acrylate modification, hydroxyl modification or carboxyl modification. That is, the vinyl resin crosslinking agent is selected from the group consisting of amino-modified, maleic anhydride-modified, epoxy-modified, acrylate-modified, hydroxyl-modified, carboxyl-modified styrene-butyl Any one or a mixture of at least two of a diene copolymer, a polybutadiene or a styrene-butadiene-divinylbenzene copolymer.

Exemplary vinyl resin crosslinking agents such as styrene-butadiene copolymer Ricon 100 from Sammeter, polybutadiene B-1000 from Soda, Japan.

Preferably, the polyphenylene ether resin composition further includes an initiator which is a radical initiator for initiating cross-linking curing of the polymer.

Preferably, the radical initiator is selected from the group consisting of organic peroxide initiators, and further preferably from dilauroyl peroxide, dibenzoyl peroxide, cumene peroxy neodecanoate, and tertiary oxidized neodecanoate. Butyl ester, pivalyl peroxypivalate, tert-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy-3,5,5-trimethylhexanoate, Tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,2-di(tert-butylperoxide) Butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydiester, di-t-amyl peroxide, diisopropylbenzene peroxide , bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butyl Peroxy hexyne, dicumyl hydroperoxide, cumene hydroperoxide, tetraamyl hydroperoxide, t-butyl hydroperoxide, t-butyl peroxybenzene, dicumyl peroxide Hydrogen, tert-butyl peroxycarbonate-2-ethylhexanoate, 2-ethylhexyl t-butyl peroxycarbonate, n-butyl 4,4-di(tert-butylperoxy)pentanoate, Any one or a mixture of at least two of methyl ethyl ketone or cyclohexane peroxide.

Preferably, the sum of the weight of the penta-functional or penta-functional vinyl vinyl ether-modified thermosetting polyphenylene ether resin and the vinyl resin crosslinking agent is 100 parts by weight, and the weight of the initiator is 1 to 3 parts by weight. For example, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2.0 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight or 2.8 parts by weight.

Preferably, the polyphenylene ether resin composition further includes a flame retardant.

Preferably, the flame retardant is a bromine-containing flame retardant or/and a phosphorus-containing flame retardant.

Preferably, the weight of the flame retardant is 0 by weight of the sum of the weight of the pentafunctional or pentafunctional or higher vinyl vinyl ether-modified thermosetting polyphenylene ether resin, the vinyl resin crosslinking agent, and the initiator. 40 parts by weight, for example, 0.5 parts by weight, 4 parts by weight, 8 parts by weight, 12 parts by weight, 16 parts by weight, 20 parts by weight, 24 parts by weight, 28 parts by weight, 32 parts by weight or 36 parts by weight.

Preferably, the polyphenylene ether resin composition further comprises a powder filler.

Preferably, the powder filler is an organic filler and/or an inorganic filler.

Preferably, the inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass frit, aluminum nitride, boron nitride, silicon carbide, silicon aluminum silicate, and hydroxide. Any of aluminum, magnesium hydroxide, titanium dioxide, barium titanate, barium titanate, zinc oxide, zirconium oxide, aluminum oxide, cerium oxide, magnesium oxide, barium sulfate, talc, clay, calcium silicate, calcium carbonate or mica One or a mixture of at least two.

Preferably, the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, polyetherimide, polyphenylene ether or polyethersulfone powder.

Preferably, the sum of the weight of the pentafunctional or penta-functional vinyl benzyl ether-modified thermosetting polyphenylene ether resin, the vinyl resin crosslinking agent, the initiator, and the flame retardant is 100 parts by weight, and the powder filler The weight is 0 to 150 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 Parts by weight, 120 parts by weight, 130 parts by weight or 140 parts by weight.

The term "comprising" as used in the present invention means that it may include other components in addition to the components, and these other components impart different characteristics to the polyphenylene ether resin composition. In addition, the "include" of the present invention may also be replaced by a closed "for" or "consisting of".

For example, the polyphenylene ether resin composition may further contain various additives, and specific examples thereof include a coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or a lubricant. Agents, etc. These various additives may be used singly or in combination of two or more kinds.

Another object of the present invention is to provide a prepreg made of a polyphenylene ether resin composition comprising a reinforcing material and a polyphenylene ether resin composition as described above adhered thereto by impregnation and drying.

Another object of the present invention is to provide a laminate comprising at least one prepreg as described above.

It is still another object of the present invention to provide a metal foil-clad laminate made of a polyphenylene ether resin composition containing at least one prepreg as described above and covering the side of the prepreg after lamination Or on both sides Metal foil.

It is still another object of the present invention to provide a printed circuit board comprising at least one prepreg as described above.

An exemplary high speed electronic circuit substrate, ie, a method of making a copper clad laminate, comprising the steps of:

(1) Weighing the resin composition raw material: the weight of the vinyl cross-linking resin is 40 to 100 by weight based on 100 parts by weight of the penta-functional or penta-functional vinyl vinyl ether-modified thermosetting polyphenylene ether resin. The weight by weight of the penta- or penta-functional vinyl vinyl ether-modified thermosetting polyphenylene ether resin and the vinyl resin crosslinking agent is 100 parts by weight, and the weight of the initiator is 1 to 3 parts by weight. The weight of the flame retardant is from 0 to 40, based on 100 parts by weight of the weight of the penta- or penta-functional vinyl vinyl ether-modified thermosetting polyphenylene ether resin, the vinyl resin crosslinking agent, and the initiator. Parts by weight; the sum of the weight of the penta- or penta-functional vinyl benzyl ether-modified thermosetting polyphenylene ether resin, the vinyl resin crosslinking agent, the initiator, and the flame retardant is 100 parts by weight, based on the powder filler The weight is 0 to 150 parts by weight;

(2) mixing a pentafunctional or penta-functional vinyl benzyl ether modified thermosetting polyphenylene ether resin, a vinyl resin crosslinking agent, an initiator, a powder filler, and a flame retardant, and adding an appropriate amount of solvent, stirring and dispersing uniformly The powder filler and the flame retardant are uniformly dispersed in the glue. Using a prepared glue to infiltrate a reinforcing material such as a fiberglass cloth, and baking it in an oven at a suitable temperature for a certain period of time to remove the solvent to form a prepreg;

(3) At least one prepreg is neatly overlapped, and copper foil is placed on top and bottom, and laminated and solidified in a press to obtain a high-speed electronic circuit substrate, that is, a copper-clad laminate.

Compared with the prior art, the present invention has the following beneficial effects:

In the present invention, since the vinyl benzyl ether-modified thermosetting polyphenylene ether resin contains a pentafunctional or pentafunctional or higher styrene reactive group, it is possible to crosslink more vinyl resin crosslinking agent, and the prepared high speed Electronic circuit substrate not only has low dielectric constant and dielectric loss, but also vinyl resin crosslinker The side chain double bond reacts completely in the resin curing system, so that the high-speed electronic circuit substrate has better resistance to thermal aging, and the substrate dielectric constant and dielectric loss are good in long-term use. The invention achieves a low dielectric constant and dielectric loss and excellent performance by the cooperation relationship between the addition amount of the vinyl benzyl ether modified thermosetting polyphenylene ether resin and the specific vinyl resin crosslinking agent with specific functionality. Resistance to thermal aging.

detailed description

The technical solution of the present invention will be further described below by way of specific embodiments.

Preparation Example 1

Synthesis of VBMP-1 with a Pentafunctional Vinylbenzyl Ether Modified Thermosetting Polyphenylene Ether Resin:

Methylphenol 32.4g, 2,6-dimethylphenol 24.4g, formaldehyde aqueous solution (formaldehyde content (24wt%) 50.0g, hydrochloric acid aqueous solution (HCL content 32wt%) 1.0g added to the machine with mechanical stirring, condensing tube The four-neck reaction flask was heated to 80-90 ° C, and after 6 hours of reaction, it was washed three times with water, and the water was distilled off under reduced pressure. After cooling to 50 ° C, 125 g of polyphenylene ether (number average molecular weight = 2500), 300 g of toluene, and heating to 80 ° were added. At 90 ° C, 2 g of benzoyl peroxide was added in portions, and after 8 hours of reaction, the mixture was washed three times with water, and toluene and water were removed by distillation under reduced pressure. The number average molecular weight of the polyphenylene ether was determined by GPC to be 1340. The obtained polyphenylene ether was dissolved in a toluene solution. Medium (polyphenylene ether content 40wt%), adding sodium methoxide 30g (0.55mol) in batches, adding vinyl benzyl chloride 76g (0.5mol), the temperature is controlled at 50-55 ° C, the solution will be obtained after 5h reaction The mixture was dropped into water to obtain a solid, and distilled water was washed three times with water, and then washed once with methanol, followed by drying. The pentafunctional vinyl benzyl ether-modified thermosetting polyphenylene ether resin VBPM-1 obtained by GPC test had a number average molecular weight of 1,800.

Preparation Example 2

Synthesis of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-2:

32.4g of methylphenol, 24.4g of 2,6-dimethylphenol, formaldehyde solution (formaldehyde content (24wt%) 50.0g, hydrochloric acid aqueous solution (HCL content 32wt%) 1.0g added to the machine with mechanical stirring, condensation The four-neck reaction flask of the tube was heated to 80-90 ° C, and after 6 hours of reaction, it was washed three times with water, and the water was distilled off under reduced pressure. After cooling to 50 ° C, 125 g of polyphenylene ether (number average molecular weight = 10000), 300 g of toluene, and heating to 80-90 ° C, 2 g of benzoyl peroxide were added in portions, and after 8 hours of reaction, the mixture was washed three times with water, and toluene was removed by distillation under reduced pressure. The number average molecular weight of the polyphenylene ether detected by GPC was 1,340. The obtained polyphenylene ether was dissolved in a toluene solution (polyphenylene ether content was 40% by weight), 30 g of sodium methoxide (0.55 mol) was added in portions, and 76 g (0.5 mol) of vinylbenzyl chloride was added thereto, and the temperature was controlled at 50 °. After 55 h of reaction at 55 ° C, the obtained solution was dropped into water to obtain a solid, which was washed three times with distilled water, washed once with methanol, and then dried. The pentafunctional vinyl benzyl ether-modified thermosetting polyphenylene ether resin VBPM-2 obtained by the GPC test had a number average molecular weight of 6,000.

Preparation Example 3

Synthesis of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-3:

Methylphenol 32.4g, 2,6-dimethylphenol 24.4g, formaldehyde aqueous solution (formaldehyde content (24wt%) 50.0g, hydrochloric acid aqueous solution (HCL content 32wt%) 1.0g added to the machine with mechanical stirring, condensing tube In a four-neck reaction flask, the mixture was heated to 80-90 ° C, and after 6 hours of reaction, it was washed three times with water, and the water was distilled off under reduced pressure. After cooling to 50 ° C, 125 g of polyphenylene ether (number average molecular weight = 15000), 300 g of toluene, and heating to 80 ° were added. At 90 ° C, 2 g of benzoyl peroxide was added in portions, and after 8 hours of reaction, the mixture was washed three times with water, and toluene and water were removed by distillation under reduced pressure. The number average molecular weight of the polyphenylene ether was determined by GPC to be 1340. The obtained polyphenylene ether was dissolved in a toluene solution. Medium (polyphenylene ether content 40wt%), adding sodium methoxide 30g (0.55mol) in batches, adding vinyl benzyl chloride 76g (0.5mol), the temperature is controlled at 50-55 ° C, the solution will be obtained after 5h reaction The mixture was dropped into water to obtain a solid, and distilled water was washed three times with water, and then washed once with methanol, followed by drying. The pentafunctional vinyl benzyl ether-modified thermosetting polyphenylene ether resin VBPM-3 obtained by GPC test had a number average molecular weight of 9000.

Preparation Example 4

Synthesis of a Heptafunctional Vinylbenzyl Ether Modified Thermosetting Polyphenylene Ether Resin VBMP-4:

54.0 g of methylphenol, 24.4 g of 2,6-dimethylphenol, aqueous formaldehyde solution (formaldehyde content is (24wt%) 83.4g, hydrochloric acid aqueous solution (HCL content of 32wt%) 1.0g was added to a four-neck reaction flask equipped with mechanical stirring and condensation tube, heated to 80-90 ° C, reacted for 6 hours, washed three times with water, distilled under reduced pressure Moisture, cooled to 50 ° C, add 125g of polyphenylene ether (number average molecular weight = 2500), 300g of toluene, heated to 80 ~ 90 ° C, 2g of benzoyl peroxide was added in batches, after 8h of reaction, washed three times, distilled off under reduced pressure Toluene and water, the number average molecular weight of the polyphenylene ether detected by GPC was 1,340. The obtained polyphenylene ether was dissolved in a toluene solution (polyphenylene ether content was 40% by weight), 50 g (0.92 mol) of sodium methoxide was added in portions, 126.7 g (0.84 mol) of vinylbenzyl chloride was added, and the temperature was controlled at 50. After the reaction was carried out for 5 hours at ～55 ° C, the obtained solution was dropped into water to obtain a solid, which was washed three times with distilled water, washed once with methanol, and then dried. The pentafunctional vinyl benzyl ether-modified thermosetting polyphenylene ether resin VBPM-4 obtained by the GPC test had a number average molecular weight of 2,000.

Preparation Example 5

Synthesis of 12-functional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-5:

108 g of methylphenol, 24.4 g of 2,6-dimethylphenol, an aqueous solution of formaldehyde (formaldehyde content (24 wt%) 166.7 g, 1.0 g of aqueous hydrochloric acid (HCL content: 32 wt%)) was added to a mechanically stirred, condensed tube. In a four-neck reaction flask, the mixture was heated to 80-90 ° C, and after 6 hours of reaction, it was washed three times with water, and the water was distilled off under reduced pressure. After cooling to 50 ° C, 125 g of polyphenylene ether (number average molecular weight = 2500), 300 g of toluene, and heating to 80-90 were added. °C, 2g of benzoyl peroxide was added in batches, after 8 hours of reaction, it was washed three times with water, distilled to remove toluene and water under reduced pressure, and the number average molecular weight of polyphenylene ether was determined by GPC to be 1340. The obtained polyphenylene ether was dissolved in toluene solution. (Polyphenyl ether content is 40wt%), 100g (1.84mol) of sodium methoxide is added in batches, 253.3g (1.67mol) of vinylbenzyl chloride is added, the temperature is controlled at 50-55 ° C, and the solution obtained after 5 hours of reaction The mixture was dropped into water to obtain a solid, and distilled water was washed three times with water, and then washed once with methanol, followed by drying. The DPC-functional vinyl benzyl ether-modified thermosetting polyphenylene ether resin VBPM-5 obtained by GPC test had a number average molecular weight of 2,500.

Preparation Example 6

Synthesis of tetrafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-6:

Methylphenol 129.6g, 2,6-dimethylphenol 24.4g, formaldehyde aqueous solution (formaldehyde content (24wt%) 200.0g, hydrochloric acid aqueous solution (HCL content 32wt%) 1.0g added to the machine with mechanical stirring, condensing tube In a four-neck reaction flask, the mixture was heated to 80-90 ° C, and after 6 hours of reaction, it was washed three times with water, and the water was distilled off under reduced pressure. After cooling to 50 ° C, 125 g of polyphenylene ether (number average molecular weight = 2500), 300 g of toluene, and heating to 80 ° were added. At 90 ° C, 2 g of benzoyl peroxide was added in portions, and after 8 hours of reaction, the mixture was washed three times with water, and toluene and water were removed by distillation under reduced pressure. The number average molecular weight of the polyphenylene ether was determined by GPC to be 1340. The obtained polyphenylene ether was dissolved in a toluene solution. Medium (polyphenylene ether content 40wt%), adding 120g (2.2mol) of sodium methoxide in batches, adding 304.0g (2.0mol) of vinylbenzyl chloride, the temperature is controlled at 50-55 ° C, and the reaction will be obtained after 5h reaction. The solution was dropped into water to obtain a solid, and the distilled water was washed three times with water, and then washed once with methanol, followed by drying. The four-functional vinyl benzyl ether-modified thermosetting polyphenylene ether resin VBPM-6 obtained by GPC test had a number average molecular weight of 3,000. .

Preparation Example 7

Synthesis of tetrafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-7:

40.0 g of tetraphenol ethane, 125 g of polyphenylene ether (number average molecular weight = 2500), 300 g of toluene, heated to 80-90 ° C, 2 g of benzoyl peroxide were added in portions, and after 8 hours of reaction, it was washed three times with water, and distilled under reduced pressure. The toluene and water were removed, and the number average molecular weight of the polyphenylene ether detected by GPC was 1,340. The obtained polyphenylene ether was dissolved in a toluene solution (polyphenylene ether content was 40 wt%), sodium methoxide 30 g (0.55 mol) was added in portions, and vinyl benzyl chloride 60.8 g (0.4 mol) was added, and the temperature was controlled at 50. After the reaction was carried out for 5 hours at ～55 ° C, the obtained solution was dropped into water to obtain a solid, which was washed three times with distilled water, washed once with methanol, and then dried. The tetrafunctional vinyl benzyl ether-modified thermosetting polyphenylene ether resin VBPM-7 obtained by the GPC test had a number average molecular weight of 1,750.

Example

The raw materials selected for preparing the high-speed electronic circuit substrate according to the embodiment of the present invention are as follows:

Table 1

Example 1

50.0 g parts by weight of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-1, 20.0 g parts by weight of styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of curing initiator DCP, dissolved In a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

Example 2

50.0 g parts by weight of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-1, 30.0 g parts by weight of styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of curing initiator DCP, dissolved In a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

Example 3

50.0 g parts by weight of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-1, 50.0 g parts by weight of styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of curing initiator DCP, dissolved In a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

Example 4

50.0 g parts by weight of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-1, 30.0 g parts by weight of styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of curing initiator DCP, 15.0 g parts by weight of the bromine-containing flame retardant BT-93W, 25.0 g of the molten silicon fine powder 525, dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

Example 5

50.0 g parts by weight of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-2, 30.0 g parts by weight of styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of curing initiator DCP, 15.0 g parts by weight of the bromine-containing flame retardant BT-93W, 25.0 g of the molten silicon fine powder 525, dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Due to the large number average molecular weight of VBMP-2, the viscosity of the glue is large, which affects the wettability of the bonded sheet to some extent. Physical properties are shown in Table 2.

Example 6

50.0 g parts by weight of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-3, 30.0 g parts by weight of styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of curing initiator DCP, 15.0 g parts by weight of the bromine-containing flame retardant BT-93W, 25.0 g of the molten silicon fine powder 525, dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Due to the large number average molecular weight of VBMP-3, the viscosity of the glue is large, which affects the wettability of the bonding sheet to some extent. Physical properties are shown in Table 2.

Example 7

50.0 g parts by weight of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-1, 30.0 g parts by weight of styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of curing initiator DCP, 15.0 g parts by weight of the phosphorus-containing flame retardant XP-7866, 25.0 g of molten silica fine powder 525, dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

Example 8

50.0 g parts by weight of a hexafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-4, 30.0 g parts by weight of a styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of a curing initiator DCP, 15.0 g parts by weight of the phosphorus-containing flame retardant XP-7866, 25.0 g of molten silica fine powder 525, dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

Example 9

50.0 g parts by weight of a dodecyl vinylbenzyl ether modified thermosetting polyphenylene ether resin VBMP-5, 30.0 g parts by weight of a styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of a curing initiator DCP, 15.0 g parts by weight of a phosphorus-containing flame retardant XP-7866, 25.0 g of molten silicon fine powder 525, dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

Example 10

50.0 g parts by weight of a tetrafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-5, 30.0 g parts by weight of a styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of a curing initiator DCP, 15.0 g parts by weight of a phosphorus-containing flame retardant XP-7866, 25.0 g of molten silicon fine powder 525, dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

Example 11

50.0 g parts by weight of pentafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-1, 30.0 g parts by weight of benzene polybutadiene B-1000, 1.5 g parts by weight of curing initiator BPO, 15.0 g The parts by weight of the phosphorus-containing flame retardant XP-7866 and 25.0 g of the molten silicon fine powder 525 were dissolved and dispersed in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

Comparative example 1

50.0 g parts by weight of a tetrafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-7, 30 g parts by weight of a styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of a curing initiator DCP, 15.0 g The bromine-containing flame retardant BT-93W and 25.0 g of the molten silica fine powder 525 were dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, a curing pressure of 50 Kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

Comparative example 2

50.0 g parts by weight of a difunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin OPE-2st, 30.0 g parts by weight of a styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of a curing initiator DCP, 15.0 g parts by weight of the bromine-containing flame retardant BT-93W, 25.0 g of the molten silicon fine powder 525, dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

Comparative example 3

50.0 g parts by weight of a difunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin OPE-2st, 10.0 g parts by weight of a styrene-butadiene copolymer Ricon 100, 1.5 g parts by weight of a curing initiator DCP, 15.0 g parts by weight of the bromine-containing flame retardant BT-93W, 25.0 g of the molten silicon fine powder 525, dissolved and dispersed in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet. Four sheets of 2116 bonding sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

Table 2

table 3

Comparative Example 1 compared with Example 4, which uses a tetrafunctional vinyl benzyl ether modified thermosetting polyphenylene ether resin VBMP-7, which cannot be used to make an excessive amount of a vinyl resin crosslinking agent such as poly because of its limited reactive groups. The butadiene side chain double bond reaction is complete. The unreacted vinyl resin cross-linking polybutadiene side chain double bond has poor resistance to thermal oxidative aging, resulting in poor resistance to thermal aging of the substrate obtained in Comparative Example 1, medium constant and dielectric loss during long-term use. Poor stability. Comparative Example 2 compared with Example 4, which uses a low-functionality vinyl vinyl benzyl ether modified thermosetting polyphenylene ether resin OPE-2st. Due to its limited reactive groups, it is not possible to make an excessive amount of vinyl resin crosslinking agent. For example, the polybutadiene side chain double bond reaction is complete. The unreacted vinyl resin cross-linking polybutadiene side chain double bond has poor resistance to thermal aging, which seriously affects the dielectric constant of the substrate and the stability of the dielectric loss during long-term use, thereby enabling the substrate to Signal integrity performance deteriorates. Therefore, the electronic circuit substrate prepared by using the pentafunctional or higher vinyl benzyl ether modified thermosetting polyphenylene ether resin of the present invention has not only the bifunctional or tetrafunctional vinyl benzyl ether modified polyphenylene ether resin Low dielectric constant and dielectric loss, and better resistance to thermal aging, ensuring that the dielectric constant and dielectric loss of the substrate are more stable during long-term use.

Further, by comparison of Comparative Example 1, Comparative Example 3 and Example 4, it was found that the tetrafunctional vinyl benzyl ether-modified thermosetting polyphenylene ether resin PPO-7 was cross-linked with an appropriate amount of a vinyl resin, or less The amount of vinyl resin cross-linked and cured low-functionality vinyl benzyl ether modified thermosetting polyphenylene ether resin OPE-2st can not achieve low dielectric constant, dielectric loss and excellent resistance to thermal aging. The combination of a specific structure of a thermosetting polyphenylene ether resin and a specific content of a vinyl resin crosslinking agent is a necessary condition for simultaneously achieving low dielectric constant, dielectric loss, and excellent resistance to thermal aging.

The Applicant declares that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims (10)

1. A thermosetting polyphenylene ether resin composition comprising:

   (1) a pentafunctional or pentafunctional vinyl vinyl ether modified thermosetting polyphenylene ether resin;

   (2) a vinyl resin cross-linking agent having a weight of 100 to 100 parts by weight of the penta-functional or penta-functional vinyl benzyl ether-modified thermosetting polyphenylene ether resin, and the weight of the vinyl resin crosslinking agent is 40 to 100 Parts by weight;

   Wherein, the structure of the pentafunctional or penta-functional vinylbenzyl ether-modified thermosetting polyphenylene ether resin is as shown in the formula (1):

   

   In the formula (1), R ₁ , R ₂ , R ₃ and R _{4 are the} same or different and are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 alkyl group or a substituted or unsubstituted aryl group;

   a and c are independently an integer of 1 to 15, and b is an integer of 3 to 10;

   Z has the structure shown in formula (2):

   

   X has a structure represented by formula (3), formula (4), formula (5) or formula (6):

   

   

   R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ The same or different, each independently being a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 alkyl group or a substituted or unsubstituted aryl group; n is an integer of from 1 to 10;

   B is an alkylene group, -O-, -CO-, -SO-, -SC-, -SO ₂ - or -C(CH ₃ ) ₂ -;

   Y has the structure shown by formula (7) or formula (8):

   

   R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ and R _{31 are the} same or different and are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 alkyl group or a substituted or unsubstituted group. Aryl.
2. The polyphenylene ether resin composition according to claim 1, wherein n is an integer of 4 to 6.
3. The polyphenylene ether resin composition according to claim 1 or 2, wherein the weight of the penta-functional or penta-functional vinylbenzyl ether-modified thermosetting polyphenylene ether resin is 100 parts by weight, vinyl The weight of the resin crosslinking agent is 50 to 80 parts by weight.
4. The polyphenylene ether resin composition according to any one of claims 1 to 3, wherein the penta-functional or penta-functional vinylbenzyl ether-modified thermosetting polyphenylene ether resin has a number average molecular weight of 500 - 10000g / mol, preferably 800 ~ 8000g / mol, further preferably 1000 ~ 4000g / mol;

   Preferably, the vinyl resin crosslinking agent is selected from any one or at least two of a styrene-butadiene copolymer, a polybutadiene or a styrene-butadiene-divinylbenzene copolymer. mixture;

   Preferably, the styrene-butadiene copolymer, polybutadiene or styrene-butadiene-divinylbenzene copolymer is independently modified by amino group, maleic anhydride, and epoxy group. Properties, acrylate modification, hydroxyl modification or carboxyl modification.
5. The polyphenylene ether resin composition according to any one of claims 1 to 4, wherein the polyphenylene ether resin composition further comprises an initiator, the initiator being a radical initiator;

   Preferably, the radical initiator is selected from the group consisting of organic peroxide initiators, and further preferably from dilauroyl peroxide, dibenzoyl peroxide, cumene peroxy neodecanoate, and tertiary oxidized neodecanoate. Butyl ester, pivalyl peroxypivalate, tert-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy-3,5,5-trimethylhexanoate, Tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butyl peroxide ring Hexane, 2,2-di(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, Di-t-amyl peroxide, diisopropylbenzene peroxide, double (tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butyl Oxidized hexyne, dicumyl hydroperoxide, cumene hydroperoxide, tetraamyl hydroperoxide, t-butyl hydroperoxide, t-butyl peroxybenzene, dicumyl hydroperoxide, Tert-butyl peroxycarbonate-2-ethylhexanoate, 2-ethylhexyl t-butyl peroxycarbonate, n-butyl 4,4-di(tert-butylperoxy)pentanoate, methyl ethyl ketone peroxide Or any one or a mixture of at least two of cyclohexane;

   Preferably, the sum of the weight of the penta-functional or penta-functional vinyl vinyl ether-modified thermosetting polyphenylene ether resin and the vinyl resin crosslinking agent is 100 parts by weight, and the weight of the initiator is 1 to 3 parts by weight. .
6. The polyphenylene ether resin composition according to any one of claims 1 to 5, wherein the polyphenylene ether resin composition further comprises a flame retardant;

   Preferably, the flame retardant is a bromine-containing flame retardant or/and a phosphorus-containing flame retardant;

   Preferably, the weight of the flame retardant is 0 by weight of the sum of the weight of the pentafunctional or pentafunctional or higher vinyl vinyl ether-modified thermosetting polyphenylene ether resin, the vinyl resin crosslinking agent, and the initiator. ～40 parts by weight;

   Preferably, the polyphenylene ether resin composition further comprises a powder filler;

   Preferably, the powder filler is an organic filler and/or an inorganic filler.
7. The polyphenylene ether resin composition according to claim 6, wherein the inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass frit, and nitriding. Aluminum, boron nitride, silicon carbide, silicon aluminum silicate, aluminum hydroxide, magnesium hydroxide, titanium dioxide, barium titanate, barium titanate, zinc oxide, zirconium oxide, aluminum oxide, barium oxide, magnesium oxide, barium sulfate, talc Any one or a mixture of at least two of powder, clay, calcium silicate, calcium carbonate or mica;

   Preferably, the organic filler is selected from any one of a polytetrafluoroethylene powder, a polyphenylene sulfide, a polyetherimide, a polyphenylene ether or a polyethersulfone powder or a mixture of at least two;

   Preferably, the sum of the weight of the pentafunctional or penta-functional vinyl benzyl ether-modified thermosetting polyphenylene ether resin, the vinyl resin crosslinking agent, the initiator, and the flame retardant is 100 parts by weight, and the powder filler The weight is 0 to 150 parts by weight.
8. A prepreg comprising a reinforcing material and a polyphenylene ether resin composition according to any one of claims 1 to 7 adhered thereto by impregnation and drying.
9. A laminate comprising at least one prepreg according to claim 8.
10. A printed circuit board comprising at least one prepreg according to claim 8. .