Polyphenyl ether resin composition and use thereof in high-frequency circuit substrate

Abstract

The present invention relates to a polyphenyl ether resin composition and a use thereof in a high-frequency circuit substrate. The polyphenyl ether resin composition comprises a vinyl-modified polyphenyl ether resin and an organic silicon resin containing unsaturated double bonds and having a three-dimensional net structure. The high-frequency circuit substrate of the present invention has a high glass-transition temperature, a high thermal decomposition temperature, a high interlayer adhesive force, a low dielectric constant and a low dielectric loss tangent, and is very suitable as a circuit substrate of high-speed electronic equipment.

Claims

1. A polyphenylene ether resin composition, comprising a vinyl-modified polyphenylene ether resin and an organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure; the organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure comprises at least one member selected from the group consisting of TT organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional siloxane unit (T unit), and TQ organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional siloxane unit (T unit) and tetrafunctional siloxane unit (Q unit); wherein the TQ organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional siloxane unit (T unit) and tetrafunctional siloxane unit (Q unit) has the following structure:
(R.sub.25SiO.sub.3/2).sub.y(SiO.sub.4/2).sub.z1 wherein 4y1100, 1z1100, and 4y1/z110; R.sub.25 is selected from substituted or unsubstituted C2-C10 CC-containing groups.

2. The polyphenylene ether resin composition of claim 1, wherein the vinyl-modified polyphenylene ether resin has the following structure: ##STR00008## wherein 0x100, 0y100, 2x+y100; M is selected from: ##STR00009## N comprises at least one member selected from the group consisting of O, CO, SO, SC, SO.sub.2 and C(CH.sub.3).sub.2; R.sub.2, R.sub.4, R.sub.6, R.sub.8, R.sub.11, R.sub.13, R.sub.15 and R.sub.17 are each independently selected from the group consisting of substituted or unsubstituted C1-C8 linear alkyl, substituted or unsubstituted C1-C8 branched alkyl, and substituted or unsubstituted phenyl, or a combination of at least two of them; R.sub.1, R.sub.3, R.sub.5, R.sub.7, R.sub.10, R.sub.12, R.sub.14 and R.sub.16 are each independently selected from the group consisting of hydrogen atom, substituted or unsubstituted C1-C8 linear alkyl, substituted or unsubstituted C1-C8 branched alkyl, and substituted or unsubstituted phenyl, or a combination of at least two of them; R.sub.9 is selected from ##STR00010## wherein A is arylene, carbonyl, or alkylene having 1-10 carbon atoms; Z is an integer of 0-10; R.sub.21, R.sub.22 and R.sub.23 are each independently selected from hydrogen atom or alkyl having 1-10 carbon atoms.

3. The polyphenylene ether resin composition of claim 1, wherein the vinyl-modified polyphenylene ether resin has a number average molecular weight of 500-10,000 g/mol.

4. The polyphenylene ether resin composition of claim 1, wherein the TT organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional siloxane unit (T unit) has the following structure:
(R.sub.24SiO.sub.3/2).sub.x1 wherein 6x110; R.sub.24 is selected from substituted or unsubstituted C2-C10 CC-containing groups.

5. The polyphenylene ether resin composition of claim 1, wherein the weight of the organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure is 10-90 parts by weight, based on 100 parts by weight of the vinyl-modified polyphenylene ether resin.

6. The polyphenylene ether resin composition of claim 1, wherein the polyphenylene ether resin composition further comprises a free radical initiator.

7. The polyphenylene ether resin composition of claim 6, wherein the weight of the free radical initiator is 1-3 parts by weight, based on 100 parts by weight of the total weight of the vinyl-modified polyphenylene ether resin and the organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure.

8. The polyphenylene ether resin composition of claim 6, wherein the free radical initiator is selected from organic peroxide initiators.

9. The polyphenylene ether resin composition of claim 6, wherein the free radical initiator comprises at least one member selected from the group consisting of dicumyl peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate and butyl 4,4-di(tert-butylperoxy)valerate.

10. The polyphenylene ether resin composition of claim 1, wherein the polyphenylene ether resin composition further comprises a flame retardant.

11. The polyphenylene ether resin composition of claim 1, wherein based on 100 parts by weight of the total weight of the vinyl-modified polyphenylene ether resin and the organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure, the weight of the flame retardant is 0-40 parts by weight.

12. The polyphenylene ether resin composition of claim 1, wherein the flame retardant comprises at least one member selected from the group consisting of halogenated flame retardant, phosphorus flame retardant, and nitrogen flame retardant.

13. The polyphenylene ether resin composition of claim 1, wherein the flame retardant comprises at least one member selected from the group consisting of brominated flame retardant, phosphorus flame retardant and nitrogen flame retardant.

14. The polyphenylene ether resin composition of claim 13, wherein the brominated flame retardant comprises at least one member selected from the group consisting of decabromodiphenyl oxide, hexabromobenzene, decabromodiphenyl ethane, and ethylene bis(tetrabromophthalimide); the phosphorus flame retardant comprises at least one member selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene and 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; the nitrogen flame retardant comprises at least one member selected from the group consisting of melamine, melamine phosphate, guanidine phosphate, guanidine carbonate and guanidine sulfamate.

15. The polyphenylene ether resin composition of claim 1, wherein the polyphenylene ether resin composition further comprises a powder filler.

16. The polyphenylene ether resin composition of claim 15, wherein the powder filler comprises at least one member selected from the group consisting of crystalline silica, amorphous silica, spherical silica, fused silica, titania, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, barium titanate and strontium titanate.

17. The polyphenylene ether resin composition of claim 15, wherein the weight of the powder filler is 0-150 parts by weight, based on 100 parts by weight of the total weight of the vinyl-modified polyphenylene ether resin, the organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and the flame retardant.

18. A resin glue solution obtained by dissolving or dispersing the polyphenylene ether resin composition of claim 1 in a solvent.

19. A prepreg prepared by impregnating a reinforcing material with the resin glue solution of claim 18 and then drying it.

20. The prepreg of claim 19, wherein the weight of the reinforcing material is 50-230 parts by weight, based on 100 parts by weight of the total weight of the vinyl-modified polyphenylene ether resin, the organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure, the flame retardant and the powder filler.

21. A high-frequency circuit substrate prepared from at least one sheet of the prepreg of claim 19.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The technical solutions of the present invention are further explained below by specific embodiments in combination with the drawing.

(2) FIG. 1 shows a schematic diagram of the high-frequency circuit substrate according to the present invention.

(3) Reference numbers in the drawing of the present specification are as follows: 1prepreg; 2copper foil.

EMBODIMENTS

(4) To better illustrate the present invention and facilitate understanding of the technical solutions of the present invention, typical but non-limiting examples of the present invention are shown as follows.

(5) FIG. 1 is a schematic diagram of the high-frequency circuit substrate according to the present invention, wherein 2 represents a copper foil, and the copper foil is preferably high peeling inverted copper foil, low profile copper foil and ultra-low profile copper foil. In the FIGURE, the number of prepregs is nine. In the practice, the number of prepregs, the type of glass fiber cloth, and the weight fraction of the glass fiber cloth and the resin composition are decided by the requirements such as the thickness of the high-frequency circuit substrate for actual applications.

Preparation Example 1

(6) A mixture of concentrated hydrochloric acid, deionized water and ethanol was added into a three-necked flask, and a mechanical stirrer was started, and then triethyl vinylsilicate was added dropwise rapidly under rapid stirring and heating reflux for hydrolytic condensation. After hydrolysis for a certain period of time, toluene was added for extraction, and then the reaction solution was poured into a separatory funnel and allowed to stand for delamination. The water layer was removed, and the oil layer was washed with water until being neutral, and the solvent toluene was removed by distilling and drying, and then a vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) was obtained. The vinyl TT organosilicon resin V-1 has a molecular weight Mn of 2000.

Preparation Example 2

(7) A mixture of concentrated hydrochloric acid, deionized water and ethanol was added into a three-necked flask, and a mechanical stirrer was started, and then triethyl vinylsilicate and tetraethyl orthosilicate were added dropwise rapidly under rapid stirring and heating reflux for hydrolytic condensation. After hydrolysis for a certain period of time, toluene was added for extraction, and then the reaction solution was poured into a separatory funnel and allowed to stand for delamination. The water layer was removed, and the oil layer was washed with water until being neutral, and the solvent toluene was removed by distilling and drying, and then a vinyl TQ organosilicon resin V-2 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and tetrafunctional siloxane unit (Q unit) was obtained. The vinyl TQ organosilicon resin V-2 has a molecular weight Mn of 1900.

Preparation Example 3

(8) A mixture of concentrated hydrochloric acid, deionized water and ethanol was added into a three-necked flask, and a mechanical stirrer was started, and then triethyl phenylsilicate and dimethyldiethoxyl silane were added dropwise rapidly under rapid stirring and heating reflux for hydrolytic condensation. After hydrolysis for a certain period of time, toluene was added for extraction, and then the reaction solution was poured into a separatory funnel and allowed to stand for delamination. The water layer was removed, and the oil layer was washed with water until being neutral, and the solvent toluene was removed by distilling and drying, and then a methylvinyl DT organosilicon resin V-00 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of difunctional methyl-containing siloxane unit (D unit) and trifunctional phenyl-containing siloxane unit (T unit) was obtained. The methylvinyl DT organosilicon resin V-00 has a molecular weight Mn of 2000.

(9) To better illustrate the present invention and facilitate understanding of the technical solutions of the present invention, typical but non-limiting examples of the present invention are shown as follows.

(10) Raw materials used in Examples and Comparative Examples are shown in Table 1,

(11) TABLE-US-00001 TABLE 1 Raw materials used in Examples and Comparative Examples Product names Manufacturers or trademarks Descriptions for Materials Sabic SA9000 Methacrylate-modified polyphenylene ether resin Mitsubishi Chemical St-PPE-1 Vinylbenzylether-modified Corporation polyphenylene ether resin Runhe Chemical RH-Vi306 Linear organosilicon compound containing unsaturated double bonds WD Silicone WD-V4 Cyclic organosilicon compound containing unsaturated double bonds Self-made V-00 Methylphenyl DT organosilicon resin Self-made V-1 Vinyl TT organosilicon resin Self-made V-2 Vinyl TQ organosilicon resin Shanghai Gaoqiao DCP Dicumyl peroxide Dongguan Xinwei BPO Dibenzoyl peroxide Chemical Sibelco 525 Fused silica Albemarle, U.S. XP-7866 Phosphorus flame retardant Albemarle, U.S. XP-7866 Phosphorus flame retardant Shanghai Honghe 2116 Glass fiber cloth

Example 1

(12) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin powder SA9000, 10.0 parts by weight of vinylphenyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP) were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 2.

Example 2

(13) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin powder SA9000, 25.0 parts by weight of vinylphenyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP) were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 2.

Example 3

(14) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin powder SA9000, 30.0 parts by weight of vinylphenyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP) were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 2.

Example 4

(15) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin powder SA9000, 40.0 parts by weight of vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP) were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 2.

Example 5

(16) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin powder SA9000, 90.0 parts by weight of vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP) were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 2.

Example 6

(17) 100.0 parts by weight of styryl-modified polyphenylene ether resin powder St-PPE-1, 10.0 parts by weight of vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP) were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 2.

Example 7

(18) 100.0 parts by weight of styryl-modified polyphenylene ether resin powder St-PPE-1, 40.0 parts by weight of vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP) were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 2001 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 2.

Example 8

(19) 100.0 parts by weight of styryl-modified polyphenylene ether resin powder St-PPE-1, 90.0 parts by weight of vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP) were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 2.

Example 9

(20) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin powder SA9000, 40.0 parts by weight of vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit), 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP), 60.0 parts by weight of silica powder 525 and 30.0 parts by weight of a bromine-containing flame retardant BT-93W were dissolved and dispersed in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 3.

Example 10

(21) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin powder SA9000, 40.0 parts by weight of vinyl TQ organosilicon resin V-2 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and tetrafunctional siloxane unit (Q unit), 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP), 60.0 parts by weight of silica powder 525 and 30.0 parts by weight of a bromine-containing flame retardant BT-93W were dissolved and dispersed in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 3.

Example 11

(22) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin powder SA9000, 40.0 parts by weight of vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit), 3.0 parts by weight of a free radical initiator dibenzoyl peroxide (BPO), 60.0 parts by weight of silica powder 525 and 30.0 parts by weight of a bromine-containing flame retardant BT-93W were dissolved and dispersed in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 3.

Example 12

(23) 100.0 parts by weight of styryl-modified polyphenylene ether resin powder St-PPE-1, 40.0 parts by weight of vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit), 3.0 parts by weight of a free radical initiator dicumyl peroxide (DCP), 60.0 parts by weight of silica powder 525 and 30.0 parts by weight of a bromine-containing flame retardant BT-93W were dissolved and dispersed in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 glass fiber cloth was impregnated with the resulting resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove the toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate. Overall properties of the substrate are shown in Table 3.

Comparative Example 1

(24) This example is the same as Example 7, except that the vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) is replaced with linear organosilicon compound containing unsaturated double bonds RH-Vi306. Overall properties of the obtained substrate are shown in Table 3.

Comparative Example 2

(25) This example is the same as Example 7, except that the vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) is replaced with cyclic organosilicon compound containing unsaturated double bonds WD-V4. Overall properties of the obtained substrate are shown in Table 3.

Comparative Example 3

(26) This example is the same as Example 7, except that the vinyl TT organosilicon resin V-1 containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) is replaced with methylphenyl DT organosilicon resin V-00. Overall properties of the obtained substrate are shown in Table 3.

(27) TABLE-US-00002 TABLE 2 Materials and properties Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 SA9000 100 100 100 100 100 0 0 0 St-PPE-1 0 0 0 0 0 100 100 100 V-1 10 25 30 40 90 10 40 90 V-2 0 0 0 0 0 0 0 0 V-00 0 0 0 0 0 0 0 0 RH-Vi306 0 0 0 0 0 0 0 0 WD-V4 0 0 0 0 0 0 0 0 DCP 3 3 3 3 3 3 3 3 BPO 0 0 0 0 0 0 0 0 525 0 0 0 0 0 0 0 0 BT-93W 0 0 0 0 0 0 0 0 XP-7866 0 0 0 0 0 0 0 0 2116 80 80 80 80 155 155 155 80 Whether the No No No No No No No No organosilicon resin crosslinking agent is volatile Glass 180.0 190.0 210.0 210.0 210.0 200.0 210.0 210.0 transition temperature ( C.) Thermal 450.0 450.0 460.0 460.0 460.0 455.0 465.0 465.0 decomposition temperature ( C.) Solder >300 >300 >300 >300 >300 >300 >300 >300 dipping resistance 288 C. (s) Water 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.07 absorption (%) Interlayer 1.06-2.21 1.02-2.10 1.01-2.20 1.26-2.25 1.15-1.99 1.14-2.06 1.13-1.98 1.45-1.95 adhesive force (N/mm) Bending 456 456 460 460 460 450 465 465 strength (MPa) Dielectric 3.65 3.65 3.65 3.65 3.65 3.65 3.65 3.65 constant (10 GHz) Dielectric 0.0070 0.0065 0.006 0.0055 0.0045 0.0070 0.0055 0.0045 loss (10 GHz)

(28) TABLE-US-00003 TABLE 3 Materials and Example Example Example Comparative Comparative Comparative properties Example 9 10 11 12 Example 1 Example 2 Example 3 SA9000 100 100 100 0 100 100 100 St-PPE-1 0 0 0 100 0 0 0 V-1 40 0 40 40 0 0 0 V-2 0 40 0 0 0 0 0 V-00 0 0 0 0 0 0 40 RH-Vi306 0 0 0 0 40 0 0 WD-V4 0 0 0 0 0 40 0 DCP 3 3 0 3 3 3 3 BPO 0 0 3 0 0 0 0 525 60 60 60 60 60 60 60 BT-93W 30 30 0 0 30 30 30 XP-7866 0 0 30 30 0 0 0 2116 155 155 155 155 155 155 155 Whether the No No No No No Yes No organosilicon resin crosslinking agent is volatile Glass 210.0 210.0 210.0 210.0 210.0 210.0 160.0 transition temperature ( C.) Thermal 430.0 430.0 430.0 435.0 430.0 430.0 380.0 decomposition temperature ( C.) Solder >300 >300 >300 >300 >300 >300 1 dipping resistance 288 C. (s) Water 0.08 0.08 0.08 0.08 0.08 0.08 0.10 absorption (%) Interlayer 1.26-2.25 1.26-2.25 1.26-2.25 1.13-1.98 1.26-2.25 1.26-2.25 0.2-0.5 adhesive force (N/mm) Bending 460 460 460 465 340 460 100 strength (MPa) Dielectric 3.85 3.85 3.85 3.85 3.85 3.90 3.90 constant (10 GHz) Dielectric 0.0055 0.0055 0.0055 0.0055 0.0055 0.0065 0.0070 loss (10 GHz)

(29) As can be seen from comparisons of Comparative Example 1 with Example 9 and Example 10, the high-frequency circuit substrate prepared by using an organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure as a crosslinking agent has a higher blending strength compared to that prepared by using linear organosilicon compound RH-Vi306 containing unsaturated double bonds as a crosslinking agent. As can be seen from comparisons of Comparative Example 2 with Example 9 and Example 10, the organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure as a crosslinking agent does not have problem of volatilization during the sizing and baking process, compared to cyclic organosilicon compound WD-V4 containing unsaturated double bonds. The high-frequency circuit substrate prepared by using an organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure as a crosslinking agent has high glass transition temperature, high thermal decomposition temperature, low water absorption, high interlayer adhesion, high bending strength, low dielectric constant and low dielectric loss. Therefore, the organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure is a crosslinking agent with excellent overall properties, and thus can be used in the preparation of high-frequency circuit substrates.

(30) As can be seen from comparisons of Comparative Example 3 with Example 9 and Example 10, since methylphenyl DT organosilicon resin does not contain active vinyl groups, it cannot make a vinyl-modified thermosetting polyphenylene ether cured, and thus the prepared substrate has poor overall properties such as glass transition temperature, solder dipping resistance, interlayer adhesive force, bending strength, which cannot meet requirements on overall properties of high-frequency electronic circuit substrates by the terminals.

Example 13

(31) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin, 40.0 parts by weight of vinyl TT organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit), 3.0 parts by weight of a free radical initiator butyl 4,4-di(tert-butylperoxy)valerate, 50.0 parts by weight of silicon carbide and 40.0 parts by weight of a flame retardant tris(2,6-dimethylphenyl)phosphine were dissolved in a mixed solvent of toluene and butanone and the solution was adjusted to a suitable viscosity to obtain a resin glue solution. 120.0 parts by weight of 7628 glass fiber cloth was impregnated with the resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove solvent, and then a 7628 prepreg was obtained. Four sheets of 7628 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate.

(32) The methacrylate-modified polyphenylene ether has a structural formula of:

(33) ##STR00004##
wherein 15<x<50, 15<y<50, 15<x+y<100; and the molecular weight of the methacrylate-modified polyphenylene ether is 8000 g/mol.

(34) The organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure is a TT organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional siloxane unit (T unit) which has a structural formula of:
(R.sub.24SiO.sub.3/2).sub.x1
wherein x1=6; and R.sub.24 is selected from substituted or unsubstituted C2-C10 CC-containing groups.

Example 14

(35) 100.0 parts by weight of methacrylate-modified polyphenylene ether resin, 40.0 parts by weight of vinyl TT organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit), 1.5 parts by weight of a free radical initiator dibenzoyl peroxide (BPO), 125.0 parts by weight of aluminum nitride and 25.0 parts by weight of decabromodiphenyl ether were dissolved and dispersed in a toluene solvent and the solution was adjusted to a suitable viscosity. An emulsifier was used for emulsification, so that the powder filler and the flame retardant and others were uniformly dispersed in the mixed solution to obtain a resin glue solution. 500.0 parts by weight of 2116 glass fiber cloth was impregnated with the resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 10OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 90 min with a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 200 C. to obtain a high-frequency circuit substrate.

(36) The methacrylate-modified polyphenylene ether has a structural formula of:

(37) ##STR00005##
50<x<100, and the molecular weight of the methacrylate-modified polyphenylene ether resin is 8000 g/mol.

(38) The organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure is a TT organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional siloxane unit (T unit) which has a structural formula of:
(R.sub.24SiO.sub.3/2).sub.x1
wherein x1=8; and R.sub.24 is selected from substituted or unsubstituted C2-C10 CC-containing groups.

Example 15

(39) 100.0 parts by weight of styryl-modified polyphenylene ether resin, 50.0 parts by weight of vinyl TT organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation trifunctional vinyl-containing siloxane unit (T unit), 1.0 parts by weight of a free radical initiator dibenzoyl peroxide (BPO), 100.0 parts by weight of alumina and 30.0 parts by weight of decabromodiphenyl ether were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. An emulsifier was used for emulsification, so that the powder filler and the flame retardant were uniformly dispersed in the mixed solution to obtain a resin glue solution. 230.0 parts by weight of 2116 glass fiber cloth was impregnated with the resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 120 min with a curing pressure of 40 kg/cm.sup.2 and a curing temperature of 180 C. to obtain a high-frequency circuit substrate.

(40) The styryl-modified polyphenylene ether resin has a structural formula of:

(41) ##STR00006##
5<y<15, and the molecular weight of the styryl-modified polyphenylene ether resin is 1000 g/mol.

(42) The organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure is a TT organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional siloxane unit (T unit) which has a structural formula of:
(R.sub.24SiO.sub.3/2).sub.x1
wherein x1=10; and R.sub.24 is selected from substituted or unsubstituted C2-C10 CC-containing groups.

Example 16

(43) 100.0 parts by weight of styryl-modified polyphenylene ether resin, 50.0 parts by weight of vinyl TQ organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and tetrafunctional siloxane unit (Q unit), 1.5 parts by weight of a free radical initiator dibenzoyl peroxide (BPO), 125.0 parts by weight of boron nitride and 25.0 parts by weight of decabromodiphenyl ether were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. An emulsifier was used for emulsification, so that the powder filler and the flame retardant were uniformly dispersed in the mixed solution to obtain a resin glue solution. 450.0 parts by weight of 2116 glass fiber cloth was impregnated with the resin glue solution and was controlled to a suitable weight by a clamp shaft, and was dried in an oven to remove toluene solvent, and then a 2116 prepreg was obtained. Four sheets of 2116 prepregs were superimposed, with copper foils having a thickness of 1OZ overlaid at the upper and lower surfaces of the superimposed prepregs respectively, and then they were laminated and cured in a press machine in vacuum for 70 min with a curing pressure of 60 kg/cm.sup.2 and a curing temperature of 220 C. to obtain a high-frequency circuit substrate.

(44) The styryl-modified polyphenylene ether resin has a structural formula of:

(45) ##STR00007##
50<x<60, 25<y<45, 75<x+y<100, and the molecular weight of the styryl-modified polyphenylene ether resin is 9500 g/mol.

(46) The TQ organosilicon resin containing unsaturated double bonds and having a three-dimensional network structure and formed by hydrolytic condensation of trifunctional vinyl-containing siloxane unit (T unit) and tetrafunctional siloxane unit (Q unit) has a structural formula of:
(R.sub.25SiO.sub.3/2).sub.y1(SiO.sub.4/2).sub.z1
wherein y1=10, z1=2, and y1/z1=5; and R.sub.2 is selected from substituted or unsubstituted C2-C10 CC-containing groups.

(47) Table 4 shows test results of performances of high-frequency circuit substrates of Examples 13-16.

(48) TABLE-US-00004 TABLE 4 Exam- Exam- Exam- Exam- Performances ple 13 ple 14 ple 15 ple 16 Glass transition 205.0 210.0 215.0 225.0 temperature ( C.) Thermal decomposition 450.0 430. 435.0 435.0 temperature ( C.) Solder dipping resistance >300 >300 >300 >300 288 C.(s) Water absorption (%) 0.08 0.08 0.08 0.08 Interlayer adhesive 1.06- 1.11- 1.27- 0.09- force (N/mm) 1.98 1.90 2.12 1.61 Dielectric constant 3.85 3.90 4.10 3.95 (10 GHz) Dielectric loss tangent 0.0055 0.0056 0.0053 0.0055 (10 GHz)

(49) The applicant states that: the present invention illustrates detailed methods of the present invention by the above examples, but the present invention is not limited to the above detailed methods, that is to say, it does not mean that the present invention must be conducted relying on the above detailed methods. Those skilled in the art should understand that any modification to the present invention, any equivalent replacement of each raw material of the products of the present invention and the additions of auxiliary ingredients, the selections of specific embodiments and the like all fall into the protection scope and the disclosure scope of the present invention.