WO2018227746A1 - 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 "十"-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

Polymer resin and its application in high frequency circuit board Technical field

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

Background technique

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 or even above GHz, the electrical performance of the substrate will be seriously affected. The characteristics of electronic circuits place higher demands on substrate performance.

For dielectric constant on performance, high-frequency circuits, signal transmission rate and the relationship between the insulating material is a dielectric constant D _k: the lower the dielectric constant D _k dielectric material, the faster the transmission rate of the signal. Therefore, in order to increase the speed of the signal transmission rate, it is necessary to develop a substrate having a low dielectric constant. As the frequency of the signal increases, the loss of the signal in the substrate can no longer be ignored. The relationship between the signal loss and the frequency, the dielectric constant D _k , and the dielectric loss D _{f is} such that the smaller the substrate dielectric constant D _{k is, the} smaller the dielectric loss D _{f is, and the} smaller the signal loss is. Therefore, the development of a high-frequency circuit substrate having a low dielectric constant D _k and a low dielectric loss D _f has become a research and development direction common to CCL manufacturers.

In addition, with the high capacity of the transmission signal, the high density of the circuit design, the number of PCB layers prepared is getting higher and higher, the prepreg and its substrate can meet the multiple lamination requirements, and it is required to pass multiple lead-free reflow soldering. Requirements such as high heat resistance and low thermal expansion coefficient of the base resin composition are required.

An olefin resin such as polybutadiene or styrene-butadiene polymer, which contains a curable cross-linked vinyl double bond, does not contain a polar group, and has a low dielectric constant and dielectric loss, and can be used in a large amount in a high frequency group. Preparation of materials. However, it also exists in the presence of an olefin resin such as polybutadiene or styrene-butadiene polymer in the initiator-initiated polymerization curing strip. Under the condition, the crosslink density of the cured product is low, the glass transition temperature is low, the prepared substrate has a large thermal expansion coefficient, and the polymerization is initiated by using a peroxide radical initiator, which causes the dielectric constant and dielectric loss of the substrate. Raise.

The polypara-hydroxystyrene-based resin can synthesize an active group having a specific structure by modifying the group by modifying it with a reactive group phenolic hydroxyl group. In particular, 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-hydroxystyryl) derivative resin having a vinyl reactive group which is an allyl group, an isobutenyl group, a vinyl group, an acryloyl group or a methacryloyl group. The resin composition is used for preparing prepregs and laminates having a low dielectric constant, good heat resistance, and good flame retardancy. However, the vinyl structure selected for the resin has the following problems: 1. For the allyl group, since the radical intermediate is conjugated, it does not have the activity of radical curing; 2. For the acryloyl group, the methacryloyl group, The two vinyl reactive groups contain a certain polar carbonyl chemical structure, which leads to a large dielectric constant and dielectric loss of the prepared substrate. 3. For isobutenyl and vinyl groups, although it does not contain a polar chemical structure, isobutylene The base and the vinyl need to initiate polymerization under the conditions of the initiator, the crosslink density of the cured product is low, the glass transition temperature is low, the coefficient of thermal expansion is high, and the polymerization is initiated by using a peroxide radical initiator, which causes the dielectric constant of the substrate and An increase in dielectric loss.

Therefore, in response to the above problems, the inventors synthesized a vinyl benzyl ether modified poly(p-hydroxystyrene-styrene) polymer resin which contains an active styrene group and can be self-cured under heating without The initiation of a peroxide free 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 preparation of high frequency circuits. However, the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin has a high crosslink density and high brittleness, which cannot meet the toughness requirements of the copper clad laminate. Benzyl ether modified poly(p-hydroxybenzene) The brittleness of the vinyl-styrene polymer resin cured product is improved.

Summary of the invention

In view of the problems of the prior art, it is an object of the present invention to provide a composition comprising a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin. The substrate prepared by using the resin composition has a low dielectric constant, low dielectric loss, low thermal expansion coefficient and the like, and the substrate has a small area of "ten" shaped drop under the action of falling weight impact load. The toughness of the substrate is good, which can meet the requirements of the toughness of the copper clad laminate.

The composition comprising a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin, comprising:

(1) a 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 low dielectric constant, low dielectric loss, small thermal expansion coefficient and the like, and the substrate has a small area of "ten"-shaped falling marks under the action of falling weight impact load. The toughness of the substrate is good, which can meet the requirements of the toughness of the copper clad laminate.

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

Wherein, the chemical structure of R ₁ is as shown in formula (II):

Where m and n are both natural numbers and m is not 0, and 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 vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin having an active unsaturated styrene-based double bond, which is more effective than a vinyl-containing reactive group resin A substrate with low dielectric constant and lower dielectric loss.

The vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin, wherein the relationship between m and n in the chemical structural formula (I) is:

m/(m+n) = 15% to 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, and may be, for example, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000 or 20000, preferably 2000-5000.

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

Wherein, the chemical structure of R ₁ is:

Both m and n are natural numbers, and m is not zero.

Although the substrate prepared by modifying the poly(p-hydroxystyryl-styrene) polymer resin with the above vinyl benzyl ether has high glass transition temperature, low dielectric constant and dielectric loss, and small thermal expansion coefficient, it exists in the presence of The joint density is high and the brittleness is large, which cannot meet the requirements of the toughness of the copper clad laminate. Therefore, the brittleness of the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin cured product needs to be improved.

The present invention adds a vinyl-modified polyphenylene ether resin to a vinyl benzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin, which not only has a substrate prepared using the resin composition The comprehensive properties of high transformation temperature, low dielectric constant, low dielectric loss, low thermal expansion coefficient, etc., also make the substrate have a small area of "ten"-shaped falling marks under the impact load of falling weight, and the toughness of the substrate is good. It can meet the requirements of toughness of CCL.

The vinyl modified polyphenylene ether resin has the following structure:

Wherein, 1≤e≤100 (for example, may be 1, 3, 5, 8, 10, 22, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc.), 1≤f≤100 (for example) It can be 1, 3, 5, 8, 10, 22, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc., 2 ≤ e + f ≤ 100 (for example, it 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 each independently selected from substituted or unsubstituted C1 to C8 (eg, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) a linear alkyl group, a substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl group, substituted or unsubstituted phenyl group Any one or a combination of at least two;

R ₉ , R ₁₁ , R ₁₃ , R ₁₅ , R ₁₈ , R ₂₀ , R ₂₂ and R ₂₄ are each independently selected from a hydrogen atom, a substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5). , C6, C7 or C8, etc.) linear alkyl, substituted or unsubstituted C1-C8 (eg C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl, substituted or unsubstituted Any one of phenyl groups or a combination of at least two;

R _{16 is} selected from:

Preferably, the vinyl modified polyphenylene ether resin has a number average molecular weight of 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, 8000 g/mol or 10000 g/mol, etc., preferably 800 to 8000 g/mol, further preferably 1000 to 4000 g/mol.

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

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

The flame retardant is selected from any one or a mixture of at least two of a bromine-based flame retardant, a phosphorus-based flame retardant or a nitrogen-based flame retardant, wherein a typical but non-limiting mixture is: bromine-based flame retardant a mixture of a phosphorus-based flame retardant, a mixture of a phosphorus-based flame retardant and a nitrogen-based flame retardant, and a mixture of a bromine-based flame retardant and a nitrogen-based flame retardant.

Preferably, the bromine-based flame retardant is selected from any one or a mixture of at least two of decabromodiphenyl ether, decabromodiphenylethane, ethylene bistetrabromophthalimide, wherein A typical but non-limiting mixture is a mixture of decabromodiphenyl ether and decabromodiphenylethane, a mixture of decabromodiphenylethane and ethylene bistetrabromophthalimide, decabromodiphenyl. A mixture of ether and ethylene bis-tetrabromophthalimide.

Preferably, the phosphorus-based flame retardant is selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa -10-phosphinophen-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa-10- Any one or a mixture of at least two of phosphaphenanthrene-10-oxides, wherein a typical but non-limiting mixture is: tris(2,6-dimethylphenyl)phosphine and 10-(2,5- a mixture of dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro- a mixture of 9-oxa-10-phosphaphenanthrene-10-oxide and 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 2,6-di(2,6-dimethyl A mixture of phenyl)phosphinobenzene and 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

Preferably, the nitrogen-based flame retardant is selected from any one or a mixture of at least two of melamine, melamine phosphate, strontium phosphate, cesium carbonate or bismuth sulfamate, wherein a typical but non-limiting mixture is: a mixture of melamine and melamine phosphate, a mixture of strontium phosphate and cesium carbonate, a mixture of cesium carbonate and bismuth sulfamate.

Preferably, the weight of the flame retardant is 0, based on 100 parts by weight of the total weight of the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin and the vinyl modified polyphenylene ether resin. ～40 parts by weight, for example, may be 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. Share. The weight of the flame retardant is 0 parts by weight, meaning that the resin composition does not contain a flame retardant.

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

Preferably, the powder filler is selected from the group consisting of crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, Any one or a mixture of at least two of barium titanate or barium titanate, wherein a typical but non-limiting mixture is: a mixture of crystalline silica and amorphous silica, spherical silica and molten A mixture of fused silica, a mixture of titanium dioxide and silicon carbide, a mixture of alumina and barium titanate, a mixture of glass fibers, aluminum nitride and barium titanate.

In the resin composition of the present invention, the powder filler functions to improve dimensional stability, lower thermal expansion coefficient, lower system cost, and the like. The shape and particle diameter of the powder filler are not limited in the present invention, and the particle diameter generally used is 0.2 to 10 μm, for example, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 8 μm, 9 μm or 10 μm, for example, Spherical silica having a particle diameter of 0.2 to 10 μm is selected.

The weight of the powder filler is 0 to 150 parts by weight, based on 100 parts by weight of the total weight of the polyvinyl benzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin and the flame retardant, and may be, for example, 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, meaning that the resin composition does not contain a powder filler.

The preparation method of the resin composition of the present invention can be prepared by a known method of formulating, stirring, and mixing the above-mentioned resin, flame retardant, powder filler, and various additives.

Another 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 thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl. Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more. Preferred are aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl group. Butyl ketone, A ketone flux such as cyclohexanone is used in combination. The amount of the solvent to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable for use.

An emulsifier may be added during the process of dissolving or dispersing the resin composition as described above in a solvent. By dispersing by an emulsifier, the powder filler or the like can be uniformly dispersed in the glue.

A third object of the present invention is to provide a prepreg obtained by dipping a glass fiber cloth in a resin glue as described above and drying it.

In the present invention, the glass fiber cloth is a reinforcing material, and functions to increase strength, improve dimensional stability, and reduce shrinkage of curing of the thermosetting resin in the composite material. Different types of fiberglass cloth can be used depending on the thickness of the sheet and the like. Exemplary glass fiber cloths are: 7628 fiberglass cloth, 2116 fiberglass cloth.

The total weight of the poly(p-hydroxystyryl-styrene) polymer resin, the vinyl modified polyphenylene ether resin, the flame retardant and the powder filler modified with vinyl benzyl ether is 100 parts by weight, and the glass fiber cloth is used. The weight is 50 to 230 parts by weight, and may be, 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. Share.

The drying temperature is 80-220 ° C, for example, 80 ° C, 90 ° C, 110 ° C, 150 ° C, 170 ° C, 190 ° C, 200 ° C or 220 ° C; the drying time is 1 ~ 30 min, for example, may be 1 min , 3 min, 5 min, 8 min, 13 min, 17 min, 21 min, 24 min, 28 min or 30 min.

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

A fifth object of the present invention is to provide an insulating sheet comprising at least one prepreg as described above.

A sixth object of the present invention is to provide a high frequency circuit substrate comprising at least one prepreg as described above.

The substrate prepared by using the resin composition of the invention has the advantages of low dielectric constant, low dielectric loss, low thermal expansion coefficient, etc., and the toughness of the substrate is good, and the surface and interior of the substrate are under a small bending force. No cracks are formed, which can meet the requirements of toughness of copper clad laminates.

The high frequency circuit substrate provided by the present invention may be prepared by the following steps:

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

The overlap preferably employs an automated stacking operation to make the process operation easier.

The laminate molding is preferably vacuum lamination molding, and the vacuum lamination molding can be carried out by a vacuum laminator. The lamination time is 70-120 min, for example, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min or 120 min; the lamination temperature is 180-220 ° C, for example Is 180 ° C, 185 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C, 215 ° C or 220 ° C; the pressure of the lamination is 40 ~ 60 kg / cm ² , for example, may be 40 kg / 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) According to the resin composition formulation as described above, each component is weighed, specifically: the weight of the poly(p-hydroxystyryl-styrene) polymer resin modified with vinyl benzyl ether is 100 parts by weight. The weight of the vinyl modified polyphenylene ether resin is 50 to 200 parts by weight; the poly(p-hydroxystyryl-styrene) polymer resin modified with vinyl benzyl ether and the vinyl modified polyphenylene ether resin The total weight is 100 parts by weight, the weight of the flame retardant is 0-40 parts by weight; the poly(p-hydroxystyryl-styrene) polymer resin modified with vinyl benzyl ether, vinyl modified polyphenylene ether The total weight of the resin and the flame retardant is 100 parts by weight, and the weight of the powder filler is 0 to 150 parts by weight;

(2) mixing vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin, vinyl modified polyphenylene ether resin, flame retardant and powder filler, adding appropriate amount of solvent, stirring and dispersing Evenly, Dispersing the powder filler uniformly in the resin glue, infiltrating the glass fiber cloth with the prepared resin glue, drying, and removing the solvent to obtain a prepreg;

(3) Overlaying at least one prepreg, placing copper foil on both sides of the prepreg, and laminating and solidifying in a vacuum laminator to obtain a high-frequency circuit substrate.

"High frequency" as used herein means that the frequency is greater than 100 MHz.

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

(1) The present invention is applied to a copper clad laminate by modifying a poly(p-hydroxystyryl-styrene) polymer resin with a vinyl benzyl ether, since the chemical structure does not contain a polar group, thereby Ensure that the prepared substrate has excellent low dielectric constant and low dielectric loss performance;

(2) The present invention is applied to a copper clad laminate by modifying a poly(p-hydroxystyryl-styrene) polymer resin with a vinyl benzyl ether, which has a high crosslink density and a large amount of benzene. The ring-rigid structure has a high glass transition temperature and a low coefficient of thermal expansion relative to the substrate prepared by the olefin resin;

(3) The present invention can improve the brittleness of a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin cured product by using a vinyl modified polyphenylene ether resin as a toughening agent. Under the impact load of the falling weight, the material has a small area of "ten"-shaped falling marks and good toughness of the substrate, which can meet the requirements of the toughness of the copper-clad board.

In summary, the poly(p-hydroxystyrene-styrene) polymer resin composition modified with vinyl benzyl ether has a high-frequency circuit substrate having high glass transition temperature, low dielectric constant, low dielectric loss, and thermal expansion coefficient. Small, and the substrate has a small area of "ten"-shaped falling marks under the impact load of the falling weight, and the toughness of the substrate is good, which can meet the requirements of the toughness of the copper-clad board, and is very suitable for the circuit for preparing high-frequency electronic equipment. Substrate.

DRAWINGS

Figure 1 is a schematic diagram of a test system for evaluating the toughness of a substrate using a drop hammer impact method;

Figure 2 is an external view of the drop hammer, wherein Figure 2-1 is a visual view of the drop hammer, and Figure 2-2 is a bottom view of the drop hammer;

Figure 3 is the appearance of the drop of 0.50 kg of falling weight and the effect of samples A, B, C, D, E;

Figure 4 is a schematic view showing a standard square frame having a side length of 50 ± 0.1 mm placed in the middle of a sample drop;

Figure 5 is a selection diagram of the effective area of the drop;

Figure 6 is a scale view of the area of the drop and the standard frame.

The invention is further described in detail below. However, the following examples are merely illustrative of the invention and are not intended to limit the scope of the invention, and the scope of the invention is defined by the appended claims.

detailed description

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

Under the action of falling weight impact load, the smaller the area of the "ten" shape of the falling mark, the better the toughness of the substrate. The test principle of evaluating the toughness of the substrate by the drop hammer impact method is as follows:

Among them, the test system diagram is shown in Figure 1; the front end of the drop hammer is a 10mm diameter ball head with a drop weight of 0.50kg, 0.75kg and 1.00kg respectively, the appearance of which is shown in Figure 2; under the action of the drop hammer impact load When the weight is 0.50 kg, the appearance of the "ten"-shaped falling marks produced by the substrate is as shown in FIG.

The "ten" shape of the falling area analysis method is shown in Fig. 4, Fig. 5 and Fig. 6, in which a standard square frame with a side length of 50 ± 0.1 mm is placed in the middle of the sample drop, see Fig. 4, and photographed. Place the image in the CAD software and zoom in to the white spot that can be finely observed at the edge of the drop. According to the function of the software, use the mouse to select the "ten" pattern of the falling mark and the white point area around it, and obtain the Figure 5, and then select the standard square box area in Figure 4 to obtain Figure 6. Calculate the actual area of the selected area according to the function of the software.

In order to better explain the present invention, it is convenient to understand the technical solution of the present invention, and a typical but non-limiting embodiment of the present invention is as follows:

Table 1 shows the materials used in the examples and comparative examples.

Table 1

Preparation Example 1

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

S-1 containing 1 mol of phenolic hydroxyl group was dissolved in ethanol solvent, mechanically stirred until completely dissolved, heated to 50 ° C, nitrogen gas was introduced for 30 min; 1.2 mol of sodium methoxide was added for 1 hour; 1.2 mol of ethylene was added. The benzyl chloride is reacted for 8 hours; after the reaction, the product is precipitated from ethanol, dissolved in toluene, washed once or twice with water; precipitated in ethanol, and the precipitated product is dissolved in toluene to obtain vinyl benzyl ether. Poly(p-hydroxystyryl-styrene) polymer SY-1, to be used.

Preparation Example 2

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

The CST15 containing 1 mol of phenolic hydroxyl group was dissolved in an ethanol solvent, mechanically stirred until completely dissolved, and the temperature was raised to 50 ° C, and nitrogen gas was introduced for 30 min; 1.2 mol of sodium methoxide was added for 1 hour; and 1.2 mol of vinylbenzyl chloride was added thereto. 8 hours; after the end of the reaction, the product is precipitated from ethanol, dissolved in toluene, washed once or twice with water; precipitated in ethanol, and the precipitated product is dissolved in toluene to obtain a vinyl benzyl ether modified poly(p-hydroxybenzene). Vinyl-styrene) polymer SY-2, ready for use.

Preparation Example 3

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

The CST50 containing 1 mol of phenolic hydroxyl group was dissolved in an ethanol solvent, mechanically stirred until completely dissolved, and the temperature was raised to 50 ° C, and nitrogen gas was introduced for 30 min; 1.2 mol of sodium methoxide was added for 1 hour; and 1.2 mol of vinylbenzyl chloride was added thereto. 8 hours; after the end of the reaction, the product is precipitated from ethanol, dissolved in toluene, washed once or twice with water; precipitated in ethanol, and the precipitated product is dissolved in toluene to obtain a vinyl benzyl ether modified poly(p-hydroxybenzene). Vinyl-styrene) polymer SY-3, ready for use.

Preparation Example 4

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

The CST70 containing 1 mol of phenolic hydroxyl group is dissolved in an ethanol solvent, mechanically stirred until completely dissolved, and the temperature is raised to 50 ° C, nitrogen gas was introduced for 30 min; 1.2 mol of sodium methoxide was added for 1 hour; 1.2 mol of vinylbenzyl chloride was added for 8 hours; after the reaction, the product was precipitated from ethanol, dissolved in toluene, washed once or 2 times. Then, it was precipitated by dropping into ethanol, and the precipitated product was dissolved in toluene to obtain a vinylbenzyl ether-modified poly(p-hydroxystyryl-styrene) polymer SY-4, which was used.

Preparation Example 5

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

S-1 containing 1 mol of phenolic hydroxyl group was dissolved in ethanol solvent, mechanically stirred until completely dissolved, heated to 50 ° C, nitrogen gas was introduced for 30 min; 1.2 mol of sodium methoxide was added for 1 hour; 1.2 mol of vinyl chloride was added, and the reaction was carried out. 8 hours; after the end of the reaction, the product is precipitated from ethanol, dissolved in toluene, washed once or twice with water; precipitated in ethanol, and the precipitated product is dissolved in toluene to obtain a vinyl benzyl ether modified poly(p-hydroxybenzene). Vinyl-styrene) polymer MT-2, ready for use.

Example 1

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, dissolved in toluene solvent, and adjusted To the viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall 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, dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall 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 the silica fine powder 525, dissolved in a toluene solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall 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 the silica fine powder 525, dissolved in a toluene solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall 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 The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative example 1

100 parts by weight of a vinylbenzyl ether-modified poly(p-hydroxystyryl-styrene) polymer SY-1 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative example 2

100 parts by weight of the vinylbenzyl ether-modified poly(p-hydroxystyryl-styrene) polymer SY-1 and 130 parts by weight of the silica fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and solidified in a press for 90 min, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative example 3

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, dissolved in toluene solvent, and adjusted To the viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative example 4

50 parts by weight of a vinyl-modified poly(p-hydroxystyryl-styrene) polymer MT-2, 50 parts by weight of a vinyl-modified polyphenylene ether resin OPE-2ST, and 1.5 parts by weight of a radical initiator DCP, dissolved in toluene solvent, and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative Example 5

50 parts by weight of styrene-butadiene copolymer Ricon 100, 50 parts by weight of vinyl-modified polyphenylene ether resin OPE-2ST, and 1.5 parts by weight of a radical initiator DCP, dissolved in a toluene solvent, and adjusted to Suitable for viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Table 2

It can be seen from Table 2 that the high-frequency circuit substrate prepared in Example 1 has a small area of "ten"-shaped falling marks, and the high-frequency circuit prepared in Comparative Example 1 is compared with that of Comparative Example 1. The area of the "ten"-shaped drop of the substrate is much larger, which indicates that Example 1 modified the poly(p-hydroxystyryl-styrene) polymer and vinyl-modified polyphenylene ether resin by using vinyl benzyl ether. Combination of vinyl benzyl alone The ether-modified poly(p-hydroxystyryl-styrene) polymer has good toughness of the prepared substrate, and the substrate has a small area of "ten"-shaped falling marks under the action of falling weight impact load. Can meet the toughness requirements of copper clad laminates. Comparing Example 5 with Comparative Example 2, the same results were obtained.

It can be explained that the present invention is prepared by blending a poly(p-hydroxystyryl-styrene) polymer modified with a vinyl benzyl ether with a vinyl modified polyphenylene ether resin, and a vinyl modified polyphenylene ether resin as The toughening agent can improve the brittleness of the cured product of the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin, and the prepared substrate is produced under the action of falling weight impact load The shape of the drop is small and the toughness of the substrate is good, which can meet the requirements of the substrate for toughness.

Further, in comparison with Example 1 and Comparative Example 3, the high-frequency circuit substrate prepared in Example 1 had a high glass transition temperature, and the substrate prepared in Comparative Example 3 had a low glass transition temperature due to MT- 2 uncured polymerization results. SY-1 is self-curing, while MT-2 is not self-curing and must be polymerized under peroxide free radical initiator conditions. However, if a peroxide radical initiator is used, as shown in Comparative Example 4, an increase in dielectric constant and dielectric loss is caused.

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

Example 6

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, dissolved in toluene solvent, and adjusted To the viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.

Example 7

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, dissolved in toluene solvent And adjusted to suit the viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall 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 The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall 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 The micropowder SC-2300SVJ is dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall 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 the silica micropowder SC-2300SVJ were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall 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 Micropowder SC-2300SVJ, dissolved in toluene solvent, and adjusted to the appropriate viscosity; infiltrated the resin glue with 2116 glass fiber cloth, controlled by single axis, and dried in an oven to remove toluene solvent to obtain 2116 prepreg Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to prepare a high-frequency circuit substrate. The overall 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 silica micropowder 525, dissolved in toluene solvent, and adjusted to a suitable viscosity; impregnated with a 2116 glass fiber cloth, controlled by a pinch shaft suitable for single weight, and dried in an oven to remove toluene solvent 2116 prepreg is prepared; 4 sheets of 2116 prepreg are overlapped, and the upper and lower sides are provided with copper foil of 1OZ thickness, vacuum laminated and cured for 90 min in a press, curing pressure 50 kg/cm ² , curing temperature 200 ° C, system A high frequency circuit substrate is obtained. The overall 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 The fine powder 525 is dissolved in a toluene solvent and adjusted to a suitable viscosity; the resin glue is impregnated with a 2116 glass fiber cloth, controlled by a pinch shaft, and dried in an oven to remove the toluene solvent to obtain a 2116 prepreg; Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated 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-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.

table 3

As can be seen from Table 3, the present invention utilizes a combination of a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer and a vinyl modified polyphenylene ether resin to provide a prepared substrate having High glass flower 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 action of the falling weight impact load, the "ten"-shaped falling mark area is small. Meet the requirements of toughness of CCL.

The Applicant claims that the detailed structural features of the present invention are described by the above-described embodiments, but the present invention is not limited to the above detailed structural features, that is, the present invention is not necessarily limited to the above detailed structural features. It is to be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the components selected for the present invention, and the addition of the components, the selection of the specific means, and the like, are all within the scope of the present invention.

Claims (10)

1. A composition comprising a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin, comprising:

   (1) a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin;

   (2) Vinyl modified polyphenylene ether resin.
2. The composition according to claim 1, wherein said vinylbenzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin has a chemical structure as shown in formula (I):

   

   Wherein, the chemical structure of R ₁ is as shown in formula (II):

   

   Where m and n are both natural numbers and m is not zero.
3. The composition according to claim 1, wherein the relationship between m and n in the formula (I) is: m/(m+n) = 15% to 100%.
4. The composition according to any one of claims 1 to 3, wherein the vinyl benzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin has a number average molecular weight of 1,000 to 20,000. Preferably it is from 2,000 to 5,000.
5. The composition according to any one of claims 1 to 4, wherein the vinyl-modified polyphenylene ether resin has the following structure:

   

   Wherein, 1≤e≤100, 1≤f≤100, 2≤e+f≤100; 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 each independently selected from a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1-C8 branch. Any one or a combination of at least two of an alkyl group, a substituted or unsubstituted phenyl group;

   R ₉ , R ₁₁ , R ₁₃ , R ₁₅ , R ₁₈ , R ₂₀ , R ₂₂ and R ₂₄ are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1. Any one or a combination of at least two of a C8 branched alkyl group, a substituted or unsubstituted phenyl group;

   R _{16 is} selected from:

   

   Preferably, the vinyl modified polyphenylene ether resin has a number average molecular weight of 500 to 10000 g/mol, preferably Selected from 800 to 8000 g / mol, further preferably from 1000 to 4000 g / mol;

   Preferably, the weight of the vinyl-modified polyphenylene ether resin is 50 to 200 parts by weight based on 100 parts by weight of the weight of the vinyl benzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin.
6. The composition according to any one of claims 1 to 5, wherein the composition further comprises a flame retardant;

   Preferably, the flame retardant is selected from any one or a mixture of at least two of a bromine-based flame retardant, a phosphorus-based flame retardant or a nitrogen-based flame retardant;

   Preferably, the bromine-based flame retardant is selected from any one or a mixture of at least two of decabromodiphenyl ether, decabromodiphenylethane or ethylene bis-tetrabromophthalimide;

   Preferably, the phosphorus-based flame retardant is selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa -10-phosphinophen-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa-10- Any one or a mixture of at least two of phosphaphenanthrene-10-oxide;

   Preferably, the nitrogen-based flame retardant is selected from the group consisting of melamine, melamine phosphate, strontium phosphate, strontium carbonate or bismuth sulfamate, or a mixture of at least two;

   Preferably, the weight of the flame retardant is 0, based on 100 parts by weight of the total weight of the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin and the vinyl modified polyphenylene ether resin. ～40 parts by weight.
7. The composition according to any one of claims 1 to 6, wherein the composition further comprises a powder filler;

   Preferably, the powder filler is selected from the group consisting of crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, Any one or a mixture of at least two of barium titanate or barium titanate;

   Preferably, the total weight of the polyvinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin, the vinyl modified polyphenylene ether resin, and the flame retardant is 100 parts by weight, and the powder filler Weight is 0 to 150 parts by weight.
8. A resin glue obtained by dissolving or dispersing a composition according to any one of claims 1 to 7 in a solvent.
9. a prepreg characterized in that the glass fiber cloth is wetted in the resin glue according to claim 8 and dried;

   Preferably, the total weight of the polyvinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin, the vinyl modified polyphenylene ether resin, the flame retardant, and the powder filler is 100 parts by weight. The glass fiber cloth has a weight of 50 to 230 parts by weight.
10. A copper clad laminate, an insulating board or a high frequency circuit substrate, characterized in that it contains at least one prepreg according to claim 9.

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