TW201903024A - Polymer resin and use thereof in high-frequency circuit board - Google Patents

Abstract

The present invention relates to a vinyl benzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin composition, comprising: (1) a vinyl benzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin; and (2) a vinyl-modified polyphenyl ether resin. The present invention further relates to a prepreg comprising the resin composition and the use thereof in a high-frequency circuit board. A substrate prepared by using the resin composition not only has comprehensive properties such as a high glass transition temperature, a low dielectric constant, a low dielectric loss and a low thermal expansion coefficient, but also has a small "+"-shaped falling trace area produced under the action of a drop-hammer impact load, and good toughness, and can thus meet the toughness requirements for copper-clad plates.

Description

   A polymer resin and its application in high frequency circuit board   

The invention relates to the technical field of copper clad laminates, in particular to a resin composition and its application in a high-frequency circuit board, in particular to a vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin and Its application in high frequency circuit boards.

In recent years, with the rapid development of wireless communication technology and electronic products, electronic circuits have entered the stage of high-speed information processing and high-frequency signal transmission; however, when the frequency is greater than 300MHz and even reaches GHz or higher, the electrical performance of the substrate will be seriously affected The characteristics of electronic circuits place higher demands on the performance of substrates.

In terms of dielectric constant performance, in a high-frequency circuit, the relationship between the signal transmission rate and the dielectric constant D _k of the insulating material is: the lower the dielectric constant D _{k of} the insulating material, the faster the signal transmission rate. Therefore, in order to realize the high speed of the signal transmission rate, a substrate with a low dielectric constant must be developed. As the signal frequency becomes higher, the loss of the signal in the substrate can no longer be ignored. Relationship between frequency and signal loss, dielectric constant D _k, D _f is the dielectric loss: the smaller the dielectric constant of the substrate D _k, D _f smaller the dielectric loss, the less signal loss. Therefore, the development of a high-frequency circuit board with a low dielectric constant D _k and a low dielectric loss D _f has become a common development direction of CCL manufacturers.

In addition, with the increase of the transmission signal capacity and the density of the circuit design, the number of PCB layers prepared is getting higher and higher. The prepreg and its substrate can meet multiple lamination requirements, requiring multiple lead-free reflow soldering requirements. Etc., put forward higher requirements on the performance of the base resin composition with high heat resistance and low coefficient of thermal expansion.

Olefin resin such as polybutadiene or styrene butadiene polymer, which contains curable cross-linked vinyl double bonds, does not contain polar groups, the prepared substrate has low dielectric constant and dielectric loss, and can be widely used in high-frequency substrates Of preparation. However, it also has the shortcomings of olefin resin such as polybutadiene or styrene butadiene polymer under the conditions of polymerization and curing initiated by the initiator, low cross-linking density of the cured product, low glass transition temperature, and large thermal expansion coefficient of the prepared substrate. Peroxide free radical initiators initiate polymerization, which can lead to an increase in the dielectric constant and dielectric loss of the substrate.

Since poly-p-hydroxystyrene-based resin has a phenolic hydroxyl group as an active group, by modifying the group, an active group with a specific structure can be synthesized. Especially non-polar vinyl reactive groups. The prepared substrate has high glass transition temperature, low dielectric constant and dielectric loss, small thermal expansion coefficient, and good heat resistance, and can be used for the development of high-frequency circuit substrates.

CN87100741A discloses a thermosetting poly-p-hydroxystyrene-based derivative resin, and the vinyl active groups carried in the resin are allyl, isobutenyl, vinyl, propenyl acetyl, and methacryl acetyl. The resin composition is used for preparing prepregs and laminates with low dielectric constant, good heat resistance and good flame retardancy. However, the selected vinyl structure of the resin has the following problems: 1. For allyl, due to the conjugation of its free radical intermediate, it does not have the activity of free radical curing; 2. For acryloyl and methacryloyl, Since these two vinyl reactive groups contain a certain polarity of carbonyl chemical structure, it will cause the dielectric constant and dielectric loss of the prepared substrate to become larger; 3. For isobutenyl and vinyl, although they do not contain polar chemical structure, but isobutylene The base and vinyl need to be polymerized under the condition of initiator. The cured product has low cross-linking density, low glass transition temperature and high coefficient of thermal expansion. The use of peroxide radical initiator to initiate polymerization will cause the dielectric constant and medium of the substrate Increased loss.

Therefore, in response to the above problems, the inventors synthesized vinyl benzyl ether modified poly (p-hydroxystyrene-styrene) polymer resin, which contains reactive styrene groups, and can achieve self-curing under heating conditions without Initiation by peroxide radical initiator is required. The prepared substrate has high glass transition temperature, low dielectric constant and dielectric loss, and small thermal expansion coefficient, and can be applied to the preparation of high-frequency circuits. However, the base material prepared by vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin has high cross-linking density and high brittleness, which cannot meet the toughness requirements of copper clad laminates. The brittleness of the cured product of benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin is improved.

In view of the problems in the prior art, one of the objects of the present invention is to provide a composition containing vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin. In addition to the low dielectric constant, low dielectric loss, low thermal expansion coefficient and other comprehensive properties of the substrate prepared by using the resin composition, and the substrate under the impact load of the falling weight, the "ten" shape of the drop area is small , The toughness of the substrate is good, which can meet the toughness requirements of copper clad laminates.

The aforementioned composition containing a vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin, which comprises: (1) vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) ) Polymer resin; (2) vinyl modified polyphenylene ether resin.

The substrate prepared by using the resin composition not only has comprehensive properties such as low dielectric constant, low dielectric loss, and small coefficient of thermal expansion, but also has a small "ten" drop area under the impact load of the falling weight. The toughness of the substrate is good, which can meet the toughness requirements of copper clad laminates.

The vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin provided by the present invention has a chemical structure as shown in formula (I):

Among them, the chemical structure of R ₁ is shown in formula (II):

Among them, m and n are natural numbers, and m is not 0, for example, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 18 Or 20, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 18, 20, 25, 30, 35 or 40.

The aforementioned vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin, which has a reactive unsaturated styryl double bond, can be obtained lower than a resin containing a vinyl reactive group Substrate with dielectric constant and lower dielectric loss.

The aforementioned vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin, the relationship between m and n in its chemical structural formula (I) is: m / (m + n) = 15% ~ 100 %.

Specifically, m / (m + n) may be, for example, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%.

The vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin has a number average molecular weight of 1,000 to 20,000, for example, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000 , 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000 or 20000, ideally 2000 ~ 5000.

The aforementioned vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin is a poly (p-hydroxystyryl-styrene) polymer and vinyl benzyl chloride by the following reaction:

Among them, the chemical structure of R ₁ is: ; M and n are natural numbers, and m is not 0.

Although the substrate prepared by using the above-mentioned vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin has a high glass transition temperature, low dielectric constant and dielectric loss, and low coefficient of thermal expansion, there is crosslinking High density and brittleness can not meet the toughness requirements of copper clad laminates, so the brittleness of the cured product of poly (p-hydroxystyryl-styrene) polymer resin modified with vinyl benzyl ether needs to be improved.

In the present invention, by adding a vinyl-modified polyphenylene ether resin to a vinyl benzyl ether-modified poly (p-hydroxystyryl-styrene) polymer resin, it not only enables the substrate prepared by using the resin composition to have The comprehensive properties of high glass transition temperature, low dielectric constant, low dielectric loss, and low coefficient of thermal expansion also make the base material under the impact load of the drop weight produce a small "ten" -shaped drop area and good toughness of the base material. , To meet the toughness requirements of copper clad laminates.

The aforementioned vinyl modified polyphenylene ether resin has the following structure:

Among them, 1 e <100 (for example, it can be 1, 3, 5, 8, 10, 22, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc.), 1 f 100 (for example, 1, 3, 5, 8, 10, 22, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc.), 2 e + f 100 (for example can be 2 e + f 5, 10 e + f 20, 15 e + f 30, 25 e + f 40, 30 e + f 55, 35 e + f 45, 60 e + f 75, 65 e + f 85, 80 e + f 98 or 85 e + f 100 etc.); and M is selected from: Wherein, N is selected from any one of -O-, -CO-, -SO-, -SC-, -SO _2- , or -C (CH ₃ ) _2- , or a combination of at least two; R ₈ , R ₁₀ , R ₁₂ , R ₁₄ , R ₁₇ , R ₁₉ , R ₂₁ and R ₂₃ are independently selected from substituted or unsubstituted C1 ~ C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8, etc.) Linear alkyl, substituted or unsubstituted C1 ~ C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl, substituted or unsubstituted phenyl, any one or at least A combination of the two; R ₉ , R ₁₁ , R ₁₃ , R ₁₅ , R ₁₈ , R ₂₀ , R ₂₂ and R ₂₄ are independently selected from hydrogen atoms, substituted or unsubstituted C1 ~ C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8, etc.) linear alkyl, substituted or unsubstituted C1 ~ C8 (e.g. C1, C2, C3, C4, C5, C6, C7 or C8, etc.) Any one or a combination of at least two of substituted or unsubstituted phenyl; R _{16 is} selected from:

Ideally, the number-average molecular weight of the vinyl modified polyphenylene ether resin is 500 to 10000 g / mol, for example, 500 g / mol, 800 g / mol, 1000 g / mol, 1100 g / mol, 1500 g / mol, 4000 g / mol, 5600 g / mol, 8000g / mol or 10000g / mol, etc., preferably 800-8000g / mol, further preferably 1000-4000g / mol.

Ideally, based on the weight of the vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin being 100 parts by weight, the weight of the vinyl modified polyphenylene ether resin is 50 to 200 parts by weight, For example 50, 55, 60, 65, 70, 75, 80, 85, 90, 100, 115, 120, 125, 135, 140, 150, 160 Servings, 170 servings, 180 servings, 190 servings or 200 servings.

The aforementioned composition containing a vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin may further contain a flame retardant.

The aforementioned flame retardant is selected from any one or a mixture of at least two of bromine-based flame retardants, phosphorus-based flame retardants or nitrogen-based flame retardants, of which typical but non-limiting mixtures are: brominated flame retardants and A mixture of phosphorus flame retardants, a mixture of phosphorus flame retardants and nitrogen flame retardants, a mixture of bromine flame retardants and nitrogen flame retardants.

Ideally, the aforementioned bromine-based flame retardant is selected from any one or a mixture of at least two of decabromodiphenyl ether, decabromodiphenylethane, and ethylenebistetrabromophthalimide. Non-limiting mixtures are: a mixture of decabromodiphenyl ether and decabromodiphenylethane, a mixture of decabromodiphenylethane and ethylene bistetrabromophthalimide, decabromodiphenyl ether and A mixture of ethylene bistetrabromophthalimide.

Ideally, the aforementioned phosphorus-based flame retardant is selected from tris (2,6-dimethylphenyl) phosphine, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa- 10-phosphinophenanthrene-10-oxide, 2,6-bis (2,6-dimethylphenyl) phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa-10-phosphine Any one or a mixture of at least two of phenanthrene-10-oxide, of which a typical but non-limiting mixture is: tris (2,6-dimethylphenyl) phosphine and 10- (2,5-dihydroxy Phenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide mixture, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9- A mixture of oxa-10-phosphinophenanthrene-10-oxide and 2,6-bis (2,6-dimethylphenyl) phosphinobenzene, 2,6-bis (2,6-dimethylphenyl ) A mixture of phosphinobenzene and 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Ideally, the aforementioned nitrogen-based flame retardant is selected from any one or a mixture of at least two of melamine, melamine phosphate, guanidine phosphate, guanidine carbonate, or guanidine sulfamate, wherein a typical but non-limiting mixture is melamine Mixture with melamine phosphate, guanidine phosphate and guanidine carbonate, guanidine carbonate and guanidine sulfamate.

Ideally, the total weight of the vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin and the vinyl modified polyphenylene ether resin is 100 parts by weight, and the weight of the flame retardant is 0 ~ 40 parts by weight, for example, 1 part by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight Copies. The weight of the aforementioned flame retardant is 0 parts by weight, which means that the aforementioned resin composition does not contain a flame retardant.

The aforementioned composition containing a vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin may further contain a powder filler.

Ideally, the aforementioned powder filler is selected from crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, titanium Any one or a mixture of at least two of barium acid or strontium titanate, of which a typical but non-limiting mixture is: a mixture of crystalline silica and amorphous silica, spherical silica and fused silica Mixture of titanium dioxide and silicon carbide, aluminum oxide and barium titanate, glass fiber, aluminum nitride and strontium titanate.

In the resin composition described in the present invention, the powder filler plays a role of improving dimensional stability, lowering the coefficient of thermal expansion, and reducing the system cost. The shape and particle size of the foregoing powder filler are not limited by the present invention, and the particle size generally used is 0.2 to 10 μm, such as 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 8 μm, 9 μm, or 10 μm, for example, optional Spherical silica with a particle size of 0.2 ~ 10μm.

Based on the total weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin and flame retardant is 100 parts by weight, the weight of the powder filler is 0 ~ 150 parts by weight, for example, it can be 1 Parts by weight, 5 parts by weight, 15 parts by weight, 25 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 75 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight , 120 parts by weight, 130 parts by weight, 140 parts by weight, 145 parts by weight or 150 parts by weight. The weight of the powder filler is 0 parts by weight, which means that the powder filler is not contained in the resin composition.

As a method for preparing the resin composition of the present invention, it can be prepared by a conventional method by preparing, stirring, and mixing the aforementioned resin, flame retardant, powder filler, and various additives.

The second object of the present invention is to provide a resin glue obtained by dissolving or dispersing the composition as described above in a solvent.

The solvent in the present invention is not particularly limited, and specific examples include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, butyl Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, mesitylene, ethoxyethyl Esters such as ethyl acetate and ethyl acetate, nitrogen-containing solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone. The above solvents may be used alone or in combination of two or more. Ideally, aromatic hydrocarbon solvents such as toluene, xylene, mesitylene and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl iso Ketone fluxes such as butyl ketone and cyclohexanone are mixed and used. The use amount of the aforementioned solvent in this field can be selected according to one's own experience according to one's own experience, so that the obtained resin glue solution can reach a viscosity suitable for use.

In the process of dissolving or dispersing the resin composition as described above in the solvent, an emulsifier may be added. By dispersing with an emulsifier, powder fillers, etc. can be dispersed evenly in the glue.

The third object of the present invention is to provide a prepreg which is obtained by dipping a glass fiber cloth in the above-mentioned resin glue solution and then drying.

In the present invention, the glass fiber cloth is a reinforcing material, which plays a role in improving the strength, improving the dimensional stability, and reducing the shrinkage of thermosetting resin curing in the composite material. Different types of fiberglass cloth can be selected according to different requirements such as plate thickness. Exemplary glass fiber cloths are: 7628 glass fiber cloth, 2116 glass fiber cloth.

Based on the total weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin, vinyl modified polyphenylene ether resin, flame retardant and powder filler as 100 parts by weight, glass fiber cloth The weight is 50 ~ 230 parts by weight, for example, 50 parts by weight, 70 parts by weight, 90 parts by weight, 110 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 210 parts by weight, 220 parts by weight or 230 parts by weight Copies.

The aforementioned drying temperature is 80 to 220 ° C, for example, 80 ° C, 90 ° C, 110 ° C, 150 ° C, 170 ° C, 190 ° C, 200 ° C or 220 ° C; the aforementioned drying time is 1 to 30 minutes, for example 1 minute , 3 minutes, 5 minutes, 8 minutes, 13 minutes, 17 minutes, 21 minutes, 24 minutes, 28 minutes or 30 minutes.

The fourth object of the present invention is to provide a copper clad laminate containing at least one prepreg as described above.

The fifth object of the present invention is to provide an insulating board containing at least one prepreg as described above.

The sixth object of the present invention is to provide a high-frequency circuit board containing at least one prepreg as described above.

The substrate prepared by using the resin composition described in the present invention has low dielectric constant, low dielectric loss, low coefficient of thermal expansion and other comprehensive properties, and the substrate has good toughness. Under a small bending force, the surface and interior of the substrate No cracks are generated, which can meet the toughness requirements of copper clad laminates.

The preparation method of the high-frequency circuit substrate provided by the present invention may include the following steps:

At least one prepreg as described above is overlapped, and copper foil is placed on the upper and lower sides of the overlapped prepreg, which is prepared by lamination molding.

The aforementioned overlap ideally uses an automatic stacking operation to make the process operation easier.

The aforementioned lamination molding is ideally vacuum lamination molding, which can be realized by a vacuum laminator. The aforementioned lamination time is 70 to 120 minutes, for example, 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, 105 minutes, 110 minutes, 115 minutes or 120 minutes; The temperature is 180 ~ 220 ℃, for example, can be 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃ or 220 ℃; the pressure of the aforementioned lamination is 40 ~ 60kg / cm ² , for example, may be ^{40kg / cm 2, 45kg / cm} 2, 50kg / cm 2, 55kg / cm 2, 58kg / cm 2 or 60kg / cm ^2.

A typical but non-limiting method for preparing a high-frequency circuit substrate of the present invention is as follows: (1) Weigh each component according to the above-mentioned resin composition formula, specifically: poly (p-hydroxybenzene) modified with vinyl benzyl ether The weight of the vinyl-styrene) polymer resin is 100 parts by weight, and the weight of the vinyl-modified polyphenylene ether resin is 50 to 200 parts by weight; the poly (p-hydroxystyryl- Styrene) polymer resin and vinyl-modified polyphenylene ether resin, the total weight is calculated as 100 parts by weight, the weight of the flame retardant is 0 ~ 40 parts by weight; modified with vinyl benzyl ether poly (p-hydroxystyrene) -Styrene) polymer resin, vinyl modified polyphenylene ether resin and flame retardant, the total weight is 100 parts by weight, the weight of the powder filler is 0 ~ 150 parts by weight; (2) the vinyl benzyl ether Modified poly (p-hydroxystyrene-styrene) polymer resin, vinyl modified polyphenylene ether resin, flame retardant and powder filler are mixed, and an appropriate amount of solvent is added to stir and disperse evenly, so that the powder filler is evenly dispersed in the resin In the glue solution, infiltrate the glass fiber cloth with the prepared resin glue solution, dry, remove Remove the solvent to obtain a prepreg; (3) Overlap at least one prepreg, place copper foil on both sides of the prepreg, and laminate and cure in a vacuum laminator to obtain a high-frequency circuit substrate.

The "high frequency" described in the present invention means that the frequency is greater than 100MHz.

Compared with the prior art, the present invention has at least the following effects: (1) The present invention uses vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin and applies it to the field of copper clad laminates , Because its chemical structure does not contain polar groups, thus ensuring that the prepared substrate has excellent low dielectric constant and low dielectric loss performance; (2) the present invention by using vinyl benzyl ether modified poly (p-hydroxy Styrene-styrene) polymer resin, which is used in the field of copper clad laminates. Due to its high cross-linking density of cured products and a large amount of benzene ring rigid structure, relative to the substrate prepared by olefin resin, the prepared The substrate glass has a high glass transition temperature and a low coefficient of thermal expansion; (3) The present invention can improve vinyl benzyl ether modified poly (p-hydroxystyryl-benzene) by using vinyl modified polyphenyl ether resin as a toughening agent The brittleness of the cured product of ethylene) polymer resin, the base material under the impact of the falling weight impact load, the "ten" shape of the drop area is small, the base material has good toughness, which can meet the toughness requirements of copper clad laminates.

In short, using vinyl benzyl ether modified poly (p-hydroxystyrene-styrene) polymer resin composition, the prepared high frequency circuit substrate not only has high glass transition temperature, low dielectric constant, low dielectric loss, and small thermal expansion coefficient And the base material under the impact load of the falling weight produces a "ten" shaped drop mark area is small, the toughness of the base material is good, can meet the toughness requirements of copper clad laminates, very suitable for the preparation of circuit boards for high-frequency electronic equipment .

[Figure 1] is a schematic diagram of a test system for evaluating the toughness of a substrate using the drop hammer impact method; [Figure 2] is an appearance diagram of the drop weight, of which FIG. 2-1 is a visual diagram of the drop weight and FIG. 2-2 is the drop weight The bottom view of [Figure 3] is the appearance of a drop mark with a drop weight of 0.50kg and samples A, B, C, D, and E; [Figure 4] is a standard square frame with a side length of 50 ± 0.1mm. Schematic diagram of the center of the sample drop mark; [Figure 5] is a selection diagram of the effective area of the drop mark; [Figure 6] is a ratio diagram of the area of the drop mark and the standard frame.

The present invention will be described in further detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the patent application scope of the present invention. The protection scope of the present invention is subject to the patent application scope.

The technical means of the present invention will be further described below with reference to the drawings and through specific embodiments.

Under the effect of the drop weight impact load, the smaller the "ten" shape of the drop mark area, the better the toughness of the base material. The test principle for evaluating the toughness of the base material using the drop weight impact method is as follows: The figure is shown in Figure 1; the front end of the drop weight is a 10mm diameter ball head, and the drop weights are 0.50kg, 0.75kg, and 1.00kg, respectively. At the time of kg, the appearance of the "ten" shaped drop marks produced by the substrate is shown in Figure 3.

The analysis method for the area of the "ten" -shaped drop marks is shown in Figure 4, Figure 5 and Figure 6, in which the standard square frame with a side length of 50 ± 0.1mm is placed in the middle of the sample drop marks, as shown in Figure 4, the photo and Put the picture in the CAD software and enlarge the picture to observe the white spots on the edge of the falling mark. According to the function of the software, use the mouse to select the "10" marks and the surrounding white dot area of the mark to obtain Figure 5, and then select the standard square frame area in Figure 4 to obtain Figure 6. According to the function of the software, calculate the actual area of the selected area in Figure 5.

In order to better illustrate the present invention and facilitate understanding of the technical means of the present invention, typical but non-limiting embodiments of the present invention are as follows:

Table 1 shows the raw materials used in Examples and Comparative Examples.

Preparation Example 1

Synthesis of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-1:

Dissolve S-1 containing 1 mol of phenolic hydroxyl group in ethanol solvent, mechanically stir until completely dissolved, warm up to 50 ° C, and purge nitrogen for 30 minutes; add 1.2 mol of sodium methoxide and react for 1 hour; add 1.2 mol of vinyl benzyl Chlorine, reaction for 8 hours; after the reaction, the product is precipitated from ethanol, dissolved in toluene, washed with water once or twice; then dropped into ethanol to precipitate, and the precipitated product is dissolved in toluene to obtain vinyl benzyl ether modified poly ( P-hydroxystyryl-styrene) polymer SY-1, to be used.

Preparation Example 2

Synthesis of poly (p-hydroxystyryl-styrene) polymer SY-2 modified by vinyl benzyl ether:

Dissolve CST15 containing 1 mol of phenolic hydroxyl group in ethanol solvent, mechanically stir until completely dissolved, warm to 50 ° C, and introduce nitrogen for 30 minutes; add 1.2 mol of sodium methoxide and react for 1 hour; add 1.2 mol of vinyl benzyl chloride Reaction for 8 hours; after the reaction, the product is precipitated from ethanol, dissolved in toluene and washed once or twice with water; then dropped into ethanol to precipitate, and the precipitated product is dissolved in toluene to obtain vinyl benzyl ether modified poly (p-hydroxyl) Styrene-styrene) polymer SY-2, to be used.

Preparation Example 3

Synthesis of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-3:

Dissolve CST50 containing 1 mol of phenolic hydroxyl group in ethanol solvent, mechanically stir until completely dissolved, warm up to 50 ° C, and introduce nitrogen for 30 minutes; add 1.2 mol of sodium methoxide and react for 1 hour; add 1.2 mol of vinyl benzyl chloride, Reaction for 8 hours; after the reaction, the product is precipitated from ethanol, dissolved in toluene and washed once or twice with water; then dropped into ethanol to precipitate, and the precipitated product is dissolved in toluene to obtain vinyl benzyl ether modified poly (p-hydroxyl) Styrene-styrene) polymer SY-3, to be used.

Preparation Example 4

Synthesis of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-4:

Dissolve CST70 containing 1 mol of phenolic hydroxyl group in ethanol solvent, mechanically stir until completely dissolved, warm to 50 ° C, and introduce nitrogen for 30 minutes; add 1.2 mol of sodium methoxide and react for 1 hour; add 1.2 mol of vinyl benzyl chloride, Reaction for 8 hours; after the reaction, the product is precipitated from ethanol, dissolved in toluene and washed once or twice with water; then dropped into ethanol to precipitate, and the precipitated product is dissolved in toluene to obtain vinyl benzyl ether modified poly (p-hydroxyl) Styrene-styrene) polymer SY-4, to be used.

Preparation Example 5

Synthesis of vinyl modified poly (p-hydroxystyryl-styrene) polymer MT-2:

Dissolve S-1 containing 1 mol of phenolic hydroxyl group in ethanol solvent, mechanically stir until completely dissolved, warm up to 50 ° C, and introduce nitrogen for 30 minutes; add 1.2 mol of sodium methoxide and react for 1 hour; Reaction for 8 hours; after the reaction, the product is precipitated from ethanol, dissolved in toluene and washed once or twice with water; then dropped into ethanol to precipitate, and the precipitated product is dissolved in toluene to obtain vinyl benzyl ether modified poly (p-hydroxyl) Styrene-styrene) polymer MT-2, to be used.

Example 1

Dissolve 50 parts by weight of vinyl modified poly (p-hydroxystyryl-styrene) polymer SY-1 and 50 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST in toluene solvent and adjust To suit viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

Example 2

50 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-1, 50 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST and 30 parts by weight of BT -93w, dissolve in toluene solvent and adjust to suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

Example 3

50 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-1, 50 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 30 parts by weight of BT -93w and 130 parts by weight of silicon fine powder 525, dissolved in toluene solvent, and adjusted to a suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

Example 4

50 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-1, 50 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 30 parts by weight of XP -7866 and 130 parts by weight of silicon fine powder 525, dissolved in toluene solvent, and adjusted to a suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

Example 5

50 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-1, 50 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST and 130 parts by weight of silicon Fine powder 525, dissolved in toluene solvent, and adjusted to a suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

Comparative example 1

100 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-1 was dissolved in toluene solvent and adjusted to a suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

Comparative example 2

100 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-1 and 130 parts by weight of silicon fine powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

Comparative Example 3

Dissolve 50 parts by weight of vinyl modified poly (p-hydroxystyryl-styrene) polymer MT-2 and 50 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST in toluene solvent and adjust To suit viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

Comparative Example 4

50 parts by weight of vinyl modified poly (p-hydroxystyryl-styrene) polymer MT-2, 50 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST and 1.5 parts by weight of free radical initiator DCP, dissolved in toluene solvent, and adjusted to a suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

Comparative Example 5

Dissolve 50 parts by weight of styryl butadiene copolymer Ricon100, 50 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST and 1.5 parts by weight of free radical initiator DCP in toluene solvent and adjust to Suitable for viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 2.

It can be seen from Table 2: Compared with Example 1 and Comparative Example 1, the high-frequency circuit substrate prepared in Example 1 has a small "ten" -shaped drop area, while the high frequency produced in Comparative Example 1 The "ten" shape of the circuit board has a much larger drop area, which shows that Example 1 uses vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer and vinyl modified polybenzene The combination of ether resins, compared with vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer alone, the substrates obtained have good toughness. The "Ten" -shaped drop marks have a small area, which can meet the toughness requirements of copper clad laminates. Comparing Example 5 with Comparative Example 2, the same results can be obtained.

Based on this, it can be explained that the present invention uses vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer and vinyl modified polyphenylene ether resin to synthesize vinyl modified polyphenylene ether resin. As a toughening agent, it can improve the brittleness of the cured product of vinyl benzyl ether-modified poly (p-hydroxystyryl-styrene) polymer resin. The ten-shaped drop marks have a small area, and the substrate has good toughness, which can meet the toughness requirements of the substrate.

In addition, compared with Example 1 and Comparative Example 3, the high-frequency circuit substrate prepared in Example 1 has a high glass transition temperature, while the substrate prepared in Comparative Example 3 has a low glass transition temperature because MT-2 is not Caused by curing polymerization. SY-1 can be self-cured, but MT-2 cannot be self-cured, and it must be polymerized under the condition of peroxide radical initiator. However, if a peroxide radical initiator is used, as shown in Comparative Example 4, it will cause an increase in dielectric constant and dielectric loss.

Comparing Example 1 with Comparative Example 5, the high-frequency circuit substrate prepared in Example 1 has a high glass transition temperature, a low coefficient of thermal expansion, a low dielectric constant, and a dielectric loss, while those prepared in Comparative Example 5 The substrate has a high coefficient of thermal expansion, and the use of a peroxide radical initiator results in an increase in the substrate dielectric constant and dielectric loss.

Example 6

Dissolve 80 parts by weight of vinyl modified poly (p-hydroxystyryl-styrene) polymer SY-1, 20 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST in toluene solvent and adjust To suit viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 3.

Example 7

Dissolve 70 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-2, 30 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST in toluene solvent , And adjust to suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 3.

Example 8

60 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-3, 40 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST and 150 parts by weight of silicon Fine powder 525, dissolved in toluene solvent, and adjusted to a suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 3.

Example 9

75 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-4, 25 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST and 185 parts by weight of silicon Micro powder SC-2300SVJ, dissolved in toluene solvent, and adjusted to a suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 3.

Example 10

80 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-2, 20 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 30 parts by weight of XP -7866 and 130 parts by weight of silicon fine powder SC-2300SVJ are dissolved in toluene solvent and adjusted to a suitable viscosity. Infiltrate the resin glue with 2116 glass fiber cloth, control the suitable single weight through the pinch shaft, and dry in an oven to remove the toluene solvent to prepare 2116 prepreg. Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 3.

Example 11

80 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-2, 20 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST and 185 parts by weight of silicon Micro powder SC-2300SVJ, dissolved in toluene solvent, and adjusted to a suitable viscosity; 2116 glass fiber cloth is used to infiltrate the resin glue, controlled by the pinch shaft, suitable for single weight, and dried in an oven, the toluene solvent is removed, and 2116 prepreg is prepared 4 sheets of 2116 prepregs are overlapped, and the upper and lower sides are equipped with copper foil with a thickness of 1OZ, vacuum lamination and curing in a press for 90 minutes, curing pressure 50kg / cm ² , curing temperature 200 ℃, and a high frequency circuit board is prepared . The comprehensive performance of the substrate is shown in Table 3.

Example 12

75 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-3, 25 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 20 parts by weight of BT -93w and 150 parts by weight of silicon micropowder 525, dissolved in toluene solvent, and adjusted to a suitable viscosity; 2116 glass fiber cloth is used to infiltrate the resin glue, control the suitable single weight through the pinch shaft, and dried in an oven to remove the toluene solvent To produce 2116 prepregs; overlap 4 sheets of 2116 prepregs with copper foil of 1OZ thickness on the upper and lower sides, vacuum laminate and cure in the press for 90 minutes, curing pressure 50kg / cm ² , curing temperature 200 ℃, A high-frequency circuit board was produced. The comprehensive performance of the substrate is shown in Table 3.

Example 13

50 parts by weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer SY-1, 50 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST and 233 parts by weight of silicon Micropowder 525, dissolved in toluene solvent, and adjusted to a suitable viscosity; 2116 glass fiber cloth is used to infiltrate the resin glue, and the single weight is controlled through the clamping shaft, and dried in an oven, and the toluene solvent is removed to prepare 2116 prepreg; Four sheets of 2116 prepregs were overlapped with copper foil of 1 OZ thickness on the upper and lower sides, and vacuum-laminated and cured in a press for 90 minutes at a curing pressure of 50 kg / cm ² and a curing temperature of 200 ° C to produce a high-frequency circuit board. The comprehensive performance of the substrate is shown in Table 3.

As can be seen from Table 3, the present invention utilizes the combination of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer and vinyl modified polyphenylene ether resin to make the prepared substrate It has high glass transition temperature, low dielectric constant, low dielectric loss, low thermal expansion coefficient and other comprehensive properties, and the toughness of the substrate is good. Under the impact of the drop weight impact load, the resulting "ten" -shaped drop area is small, which can be Meet the toughness requirements of copper clad laminates.

The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented by relying on the above detailed structural features. Those skilled in the art should understand that any improvement to the present invention, equivalent replacement of selected components of the present invention, addition of auxiliary components, choice of specific modes, etc., fall within the scope of protection and disclosure of the present invention.

Claims (20)

    A composition containing vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin, characterized in that it contains: (1) vinyl benzyl ether modified poly (p-hydroxystyryl) -Styrene) polymer resin; (2) vinyl modified polyphenylene ether resin.     The composition as described in item 1 of the patent application scope, wherein the chemical structure of the aforementioned vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin is represented by formula (I): Moreover, the chemical structure of R ₁ is shown in formula (II): Both m and n are natural numbers, and m is not 0.     The composition as described in item 1 of the patent application scope, wherein the relationship between m and n in the aforementioned formula (I) is: m / (m + n) = 15% to 100%.         The composition as described in any one of claims 1 to 3, wherein the number average molecular weight of the vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin is 1000 to 20000.     The composition as described in any one of claims 1 to 3, wherein the vinyl modified polyphenylene ether resin has the following structure: And, 1 e 100, 1 f 100, 2 e + f 100; and M is selected from: N is selected from any one of -O-, -CO-, -SO-, -SC-, -SO _2- , or -C (CH ₃ ) ₂ -or a combination of at least two; R ₈ , R ₁₀ , R _{12, R 14, R 17,} R 19, R 21 and R ₂₃ are each independently selected from substituted or unsubstituted C1 ~ C8 straight chain alkyl group, a substituted or unsubstituted C1 ~ C8 branched alkyl, substituted or unsubstituted Any one or a combination of at least two of the substituted phenyl groups; R ₉ , R ₁₁ , R ₁₃ , R ₁₅ , R ₁₈ , R ₂₀ , R ₂₂ and R ₂₄ are all independently selected from hydrogen atoms, substituted or unsubstituted the C1 ~ C8 straight chain alkyl group, a substituted or unsubstituted C1 ~ C8 branched-chain alkyl group, a substituted or unsubstituted phenyl group, or any one of at least two thereof; R ₁₆ is selected from:     The composition as described in item 1 of the patent application range, wherein the number average molecular weight of the vinyl-modified polyphenylene ether resin is 500 to 10000 g / mol.         The composition as described in item 1 of the patent application scope, wherein the vinyl-modified polymer is calculated based on the weight of vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin as 100 parts by weight The weight of the phenyl ether resin is 50 to 200 parts by weight.         The composition as described in any one of claims 1 to 3, wherein the composition further includes a flame retardant.         The composition as described in item 8 of the patent application range, wherein the flame retardant is selected from any one or a mixture of at least two of bromine-based flame retardants, phosphorus-based flame retardants or nitrogen-based flame retardants.         The composition described in item 9 of the patent application scope, wherein the bromine-based flame retardant is selected from decabromodiphenyl ether, decabromodiphenylethane or ethylenebistetrabromophthalimide Any one of the group or a mixture of at least two.         The composition as described in item 9 of the patent application scope, wherein the phosphorus-based flame retardant is selected from tris (2,6-dimethylphenyl) phosphine and 10- (2,5-dihydroxyphenyl)- 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis (2,6-dimethylphenyl) phosphinobenzene or 10-phenyl-9,10 -Any one or a mixture of at least two of the group consisting of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.         The composition described in item 9 of the patent application scope, wherein the nitrogen-based flame retardant is selected from any one or at least two of the group consisting of melamine, melamine phosphate, guanidine phosphate, guanidine carbonate, or guanidine sulfamate. Species mixture.         The composition as described in item 8 of the patent application scope, wherein the total weight of the vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin and the vinyl modified polyphenylene ether resin is Based on 100 parts by weight, the weight of the flame retardant is 0-40 parts by weight.         The composition as described in any one of claims 1 to 3, wherein the composition further includes a powder filler.         The composition as described in item 14 of the patent application range, wherein the powder filler is selected from crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, Any one or a mixture of at least two of the group consisting of aluminum oxide, aluminum nitride, boron nitride, barium titanate, or strontium titanate.         The composition as described in item 14 of the patent application scope, in which vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin, vinyl modified polyphenyl ether resin and flame retardant The total weight is 100 parts by weight, and the weight of the powder filler is 0 to 150 parts by weight.         A resin glue, characterized in that it is obtained by dissolving or dispersing the composition as described in any one of claims 1 to 16 in a solvent.         A prepreg, characterized in that it is obtained by dipping a glass fiber cloth in the resin glue as described in item 17 of the patent application scope, and then drying it.         The prepreg described in item 18 of the patent application scope, in which vinyl benzyl ether modified poly (p-hydroxystyryl-styrene) polymer resin, vinyl modified polyphenylene ether resin, flame retardant The total weight of the agent and powder filler is 100 parts by weight, and the weight of the glass fiber cloth is 50 to 230 parts by weight.         A copper-clad board, an insulating board or a high-frequency circuit board, characterized by containing at least one prepreg as described in item 18 or 19 of the patent application range.