POLYPHENYL ETHER RESIN COMPOSITION AND PREPREG, LAMINATED BOARD AND PRINTED CIRCUIT BOARD CONTAINING SAME

Abstract

Provided are a polyphenyl ether resin composition and a prepreg and a laminated board containing same. The polyphenyl ether resin composition comprises the following components: (1) a tetrafunctional or higher multifunctional acrylate-modified thermosetting polyphenyl ether resin; and (2) a vinyl eresin cross-linking agent, the weight of the vinyl resin cross-linking agent being 40-100 parts by weight based on 100 parts by weight of the tetrafunctional or higher multifunctional acrylate-modified thermosetting polyphenyl ether resin. The modified thermosetting polyphenyl ether resin, due to containing a tetrafunctional or higher multifunctional acrylate active group, can cross-link more vinyl resin cross-linking agents. Not only the prepared high-speed electronic circuit substrate has low dielectric constant and dielectric loss, but also double bonds in side chains of the vinyl resin cross-linking agent are reacted completely in a resin curing system, so that the high-speed electronic circuit substrate has a better thermo-oxidative aging resistance.

Claims

11. A polyphenyl ether resin composition, it comprises the following components: (1) a tetrafunctional or higher multifunctional acrylate group-modified thermosetting polyphenyl ether resin; and (2) a vinyl resin crosslinking agent, the weight of which is 40 to 100 parts by weight, based on 100 parts by weight of the tetrafunctional or higher multifunctional acrylate group-modified thermosetting polyphenyl ether resin; wherein the tetrafunctional or higher multifunctional acrylate group-modified thermosetting polyphenyl ether resin has a structure shown by formula (1): ##STR00008## in formula (1), R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are the same or different and are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 alkyl group or a substituted or unsubstituted aryl group; a and c are each independently an integer from 1 to 15 and b is an integer from 2 to 10; Z has a structure shown by formula (2): ##STR00009## in formula (2), R.sub.5, R.sub.6, and R.sub.7 are the same or different and are each independently a hydrogen atom or a substituted or unsubstituted C1-C10 alkyl group; X has a structure shown by formula (3), formula (4), formula (5), or formula (6): ##STR00010## R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18, R.sub.19, R.sub.20, R.sub.21, R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26 and R.sub.27 are the same or different and are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 alkyl group or a substituted or unsubstituted aryl group; and n is an integer from 1 to 10; B is an alkylene group, O, CO, SO, SC, SO.sub.2 or C(CH.sub.3).sub.2; Y has a structure shown by formula (7) or formula (8): ##STR00011## R.sub.28, R.sub.29, R.sub.30, R.sub.31, R.sub.32, R.sub.33 and R.sub.34 are the same or different and are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 alkyl group or a substituted or unsubstituted aryl group.

12. The polyphenyl ether resin composition according to claim 11, wherein b is an integer from 4 to 6.

13. The polyphenyl ether resin composition according to claim 11, wherein the weight of the vinyl resin crosslinking agent is 50 to 80 parts by weight, based on 100 parts by weight of the tetrafunctional or higher multifunctional acrylate group-modified thermosetting polyphenyl ether resin.

14. The polyphenyl ether resin composition according to claim 11, wherein the number average molecular weight of the tetrafunctional or higher multifunctional acrylate group-modified thermosetting polyphenyl ether resin is 500 to 10000 g/mol.

15. The polyphenyl ether resin composition according to claim 14, the vinyl resin crosslinking agent is at least one member selected from a group consisting of a styrene-butadiene copolymer, a polybutadiene and a styrene-butadiene-divinylbenzene copolymer.

16. The polyphenyl ether resin composition according to claim 15, the styrene-butadiene copolymer, the polybutadiene or the styrene-butadiene-divinylbenzene copolymer are independently amino-modified, maleic anhydride-modified, epoxy-modified, acrylate-modified, hydroxyl-modified or carboxyl-modified.

17. The polyphenyl ether resin composition according to claim 11, wherein the polyphenyl ether resin composition further comprises an initiator, and the initiator is a radical initiator.

18. The polyphenyl ether resin composition according to claim 17, the radical initiator is an organic peroxide initiator.

19. The polyphenyl ether resin composition according to claim 18, the radical initiator is at least one member selected from a group consisting of dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-amyl peroxypivalate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, 1,1-di-t-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-bis (t-butylperoxy)butane, bis(4-tert-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxodicarbonate, tetradecyl peroxydicarbonate, di-t-amyl peroxide, dicumyl peroxide, bis(t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne, dicumyl hydroperoxide, cumyl hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide, t-butyl cumyl peroxide, dicumyl hydroperoxide, t-butyl peroxycarbonate 2-ethylhexanoate, 2-ethylhexyl-t-butylperoxycarbonate, n-butyl 4,4-di(t-butylperoxy)pentanoate, methyl ethyl ketone peroxide and cyclohexane peroxide.

20. The polyphenyl ether resin composition according to claim 17, the weight of the initiator is 1 to 3 parts by weight, based on 100 parts by weight of a sum of the weight of the tetrafunctional or higher multifunctional acrylate group-modified thermosetting polyphenyl ether resin and the vinyl resin crosslinking agent.

21. The polyphenyl ether resin composition according to claim 11, wherein the polyphenyl ether resin composition further comprises a flame retardant.

22. The polyphenyl ether resin composition according to claim 21, the flame retardant comprises at least one member selected from the group consisting of a bromine-containing flame retardant and a phosphorus-containing flame retardant.

23. The polyphenyl ether resin composition according to claim 21, the weight of the flame retardant is 0 to 40 parts by weight, based on 100 parts by weight of a sum of the weight of the tetrafunctional or higher multifunctional acrylate group-modified thermosetting polyphenyl ether resin, the vinyl resin crosslinking agent and the initiator.

24. The polyphenyl ether resin composition according to claim 21, the polyphenyl ether resin composition further comprises a powder filler.

25. The polyphenyl ether resin composition according to claim 24, the powder filler comprises at least one member selected from the group consisting of an organic filler and an inorganic filler.

26. The polyphenyl ether resin composition according to claim 25, wherein the inorganic filler is at least one member selected from a group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass frit, aluminum nitride, boron nitride, silicon carbide, aluminum silicon carbide, aluminum hydroxide, magnesium hydroxide, titanium dioxide, strontium titanate, barium titanate, zinc oxide, zirconium oxide, aluminum oxide, beryllium oxide, magnesium oxide, barium sulfate, talcum powder, clay, calcium silicate, calcium carbonate and mica.

27. The polyphenyl ether resin composition according to claim 25, the organic filler is at least one member selected from a group consisting of polytetrafluoroethylene powder, polyphenylene sulfide, polyetherimide, polyphenyl ether and polyether sulfone powder.

28. The polyphenyl ether resin composition according to claim 24, the weight of the powder filler is 0 to 150 parts by weight, based on 100 parts by weight of a sum of the weight of the tetrafunctional or higher multifunctional acrylate group-modified thermosetting polyphenyl ether resin, the vinyl resin crosslinking agent, the initiator and the flame retardant.

29. A prepreg comprising a reinforcing material and the polyphenyl ether resin composition according to claim 11 adhered thereon after being impregnated and dried.

30. A laminate comprising at least one prepreg according to claim 29.

Description

DETAILED DESCRIPTION

[0058] The technical solutions of the present disclosure will be further described below by way of specific embodiments.

Synthesis Of Tetrafunctional Methyl Methacrylate Group-Modified Thermosetting Polyphenyl Ether PPO-1

[0059] 32.4 g of methylphenol, 24.4 g of 2,6-dimethylphenol, 50.0 g of aqueous formaldehyde solution (formaldehyde content of 24 wt %) and 1.0 g of aqueous hydrochloric acid solution (HCl content of 32 wt %) were charged into a four-necked reaction flask equipped with a mechanical stirrer and a condenser, then heated to 80 to 90 C. The reaction mixture was washed with water for three times after reacted for 6 hours, then distilled under reduced pressure to remove water. The reaction mixture was cooled to 50 C., 125 g of polyphenyl ether (number average molecular weight=2500) and 300 g of toluene were added, the mixture was heated to 80 to 90 C., to which 2 g of benzoyl peroxide was added in portions, the reaction mixture was washed with water for three times after reacted for 8 hours, then distilled under reduced pressure to remove toluene and water, the number average molecular weight of polyphenyl ether was 1540 as measured by GPC. The resulting polyphenyl ether was dissolved in toluene solution (polyphenyl ether content of 40 wt %), then 5.0 g of 4-dimethylaminopyridine as a catalyst was added. After the catalyst was dissolved, 77 g (0.5 mol) of methacrylic anhydride was added, the temperature was controlled at 80 to 85 C., and toluene was distilled off under reduced pressure after the reaction was conducted for 2 hours. The number average molecular weight of the obtained multifunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-1 was 1900 as measured by GPC.

Synthesis Of Tetrafunctional Methyl Methacrylate Group-Modified Thermosetting Polyphenyl Ether PPO-2

[0060] 32.4 g of methylphenol, 24.4 g of 2,6-dimethylphenol, 50.0 g of aqueous formaldehyde solution (formaldehyde content of 24 wt %) and 1.0 g of aqueous hydrochloric acid solution (HCl content of 32 wt %) were charged into a four-necked reaction flask equipped with a mechanical stirrer and a condenser, then heated to 80 to 90 C. The reaction mixture was washed with water for three times after reacted for 6 hours, then distilled under reduced pressure to remove water. The reaction mixture was cooled to 50 C., 125 g of polyphenyl ether (number average molecular weight=10000) and 300 g of toluene were added, the mixture was heated to 80 to 90 C., to which 2 g of benzoyl peroxide was added in portions, the reaction mixture was washed with water for three times after reacted for 8 hours, then distilled under reduced pressure to remove toluene and water, the number average molecular weight of polyphenyl ether was 7000 as measured by GPC. The resulting polyphenyl ether was dissolved in toluene solution (polyphenyl ether content of 40 wt %), then 5.0 g of 4-dimethylaminopyridine as a catalyst was added. After the catalyst was dissolved, 77 g (0.5 mol) of methacrylic anhydride was added, the temperature was controlled at 80 to 85 C., and toluene was distilled off under reduced pressure after the reaction was conducted for 2 hours. The number average molecular weight of the obtained multifunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-2 was 7500 as measured by GPC.

Synthesis Of Tetrafunctional Methyl Methacrylate Group-Modified Thermosetting Polyphenyl Ether PPO-3

[0061] 32.4 g of methylphenol, 24.4 g of 2,6-dimethylphenol, 50.0 g of aqueous formaldehyde solution (formaldehyde content of 24 wt %) and 1.0 g of aqueous hydrochloric acid solution (HCl content of 32 wt %) were charged into a four-necked reaction flask equipped with a mechanical stirrer and a condenser, then heated to 80 to 90 C. The reaction mixture was washed with water for three times after reacted for 6 hours, then distilled under reduced pressure to remove water. The reaction mixture was cooled to 50 C., 125 g of polyphenyl ether (number average molecular weight=15000) and 300 g of toluene were added, the mixture was heated to 80 to 90 C., to which 2 g of benzoyl peroxide was added in portions, the reaction mixture was washed with water for three times after reacted for 8 hours, then distilled under reduced pressure to remove toluene and water, the number average molecular weight of polyphenyl ether was 10000 as measured by GPC. The resulting polyphenyl ether was dissolved in toluene solution (polyphenyl ether content of 40 wt %), then 5.0 g of 4-dimethylaminopyridine as a catalyst was added. After the catalyst was dissolved, 77 g (0.5 mol) of methacrylic anhydride was added, the temperature was controlled at 80 to 85 C., and toluene was distilled off under reduced pressure after the reaction was conducted for 2 hours. The number average molecular weight of the obtained multifunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-3 was 10600 as measured by GPC.

Synthesis Of Hexafunctional Methyl Methacrylate Group-Modified Thermosetting Polyphenyl Ether PPO-4

[0062] 64.8 g of methylphenol, 24.4 g of 2,6-dimethylphenol, 100.0g of aqueous formaldehyde solution (formaldehyde content of 24 wt %) and 1.0 g of aqueous hydrochloric acid solution (HCl content of 32 wt %) were charged into a four-necked reaction flask equipped with a mechanical stirrer and a condenser, then heated to 80 to 90 C. The reaction mixture was washed with water for three times after reacted for 6 hours, then distilled under reduced pressure to remove water. The reaction mixture was cooled to 50 C., 125 g of polyphenyl ether (number average molecular weight=2500) and 300 g of toluene were added, the mixture was heated to 80 to 90 C., to which 2 g of benzoyl peroxide was added in portions, the reaction mixture was washed with water for three times after reacted for 8 hours, then distilled under reduced pressure to remove toluene and water, the number average molecular weight of polyphenyl ether was 1700 as measured by GPC. The resulting polyphenyl ether was dissolved in toluene solution (polyphenyl ether content of 40 wt %), then 5.0 g of 4-dimethylaminopyridine as a catalyst was added. After the catalyst was dissolved, 154 g (1.0 mol) of methacrylic anhydride was added, the temperature was controlled at 80 to 85 C., and toluene was distilled off under reduced pressure after the reaction was conducted for 2 hours. The number average molecular weight of the obtained multifunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-4 was 2100 as measured by GPC.

Synthesis Of Decafunctional Methyl Methacrylate Group-Modified Thermosetting Polyphenyl Ether PPO-5

[0063] 129.6 g of methylphenol, 24.4 g of 2,6-dimethylphenol, 200.0 g of aqueous formaldehyde solution (formaldehyde content of 24 wt %) and 1.0 g of aqueous hydrochloric acid solution (HCl content of 32 wt %) were charged into a four-necked reaction flask equipped with a mechanical stirrer and a condenser, then heated to 80 to 90 C. The reaction mixture was washed with water for three times after reacted for 6 hours, then distilled under reduced pressure to remove water. The reaction mixture was cooled to 50 C., 125 g of polyphenyl ether (number average molecular weight=2500) and 300 g of toluene were added, the mixture was heated to 80 to 90 C., to which 2 g of benzoyl peroxide was added in portions, the reaction mixture was washed with water for three times after reacted for 8 hours, then distilled under reduced pressure to remove toluene and water, the number average molecular weight of polyphenyl ether was 2200 as measured by GPC. The resulting polyphenyl ether was dissolved in toluene solution (polyphenyl ether content of 40 wt %), then 5.0 g of 4-dimethylaminopyridine as a catalyst was added. After the catalyst was dissolved, 308 g (2.0 mol) of methacrylic anhydride was added, the temperature was controlled at 80 to 85 C., and toluene was distilled off under reduced pressure after the reaction was conducted for 2 hours. The number average molecular weight of the obtained multifunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-5 was 2700 as measured by GPC.

Synthesis Of Tetradecafunctional Methyl Methacrylate Group-Modified Thermosetting Polyphenyl Ether PPO-6

[0064] 194.4 g of methylphenol, 24.4 g of 2,6-dimethylphenol, 300.0 g of aqueous formaldehyde solution (formaldehyde content of 24 wt %) and 1.0 g of aqueous hydrochloric acid solution (HCl content of 32 wt %) were charged into a four-necked reaction flask equipped with a mechanical stirrer and a condenser, then heated to 80 to 90 C. The reaction mixture was washed with water for three times after reacted for 6 hours, then distilled under reduced pressure to remove water. The reaction mixture was cooled to 50 C., 125 g of polyphenyl ether (number average molecular weight=2500) and 300 g of toluene were added, the mixture was heated to 80 to 90 C., to which 2 g of benzoyl peroxide was added in portions, the reaction mixture was washed with water for three times after reacted for 8 hours, then distilled under reduced pressure to remove toluene and water, the number average molecular weight of polyphenyl ether was 2800 as measured by GPC. The resulting polyphenyl ether was dissolved in toluene solution (polyphenyl ether content of 40 wt %), then 5.0 g of 4-dimethylaminopyridine as a catalyst was added. After the catalyst was dissolved, 462 g (3.0 mol) of methacrylic anhydride was added, the temperature was controlled at 80 to 85 C., and toluene was distilled off under reduced pressure after the reaction was conducted for 2 hours. The number average molecular weight of the obtained multifunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-6 was 3200 as measured by GPC.

Synthesis Of Hexafunctional Methyl Methacrylate Group-Modified Thermosetting Polyphenyl Ether PPO-7

[0065] A four-necked reaction flask equipped with a mechanical stirrer and a condenser was heated to 100 C. 300 g of polyphenyl ether (number average molecular weight of 1100) and 1168 g of epichlorohydrin were added thereto. 34.4 g of sodium ethoxide was dissolved in 120 g of ethanol and then added dropwise to the reaction flask over 60 minutes. After reacting for 5 hours with stirring, the product was washed with pure water to remove impurities such as salts. The excess epichlorohydrin was then removed by distillation under reduced pressure. After drying, 330 g of epoxidation-modified polyphenyl ether having a number average molecular weight of 1210 was obtained.

[0066] To a four-necked reaction flask equipped with a mechanical stirrer and a condenser, 330 g of epoxidation-modified polyphenyl ether, 32 g of methacrylic acid, 160 g of toluene, 1.0 g of triethylamine and 1 mg of hydroquinone methyl ether were added. The mixture was heated to 120 C., the acid value was tested while stirring to react until the acid value of the solution reached 2 mg KOH/g. The solution obtained from the reaction was added dropwise to a methanol solution to precipitate, and filtered to obtain a solid product, which was dried under reduced pressure to obtain 250 g of an epoxymethacrylate modified polyphenyl ether having a number average molecular weight of 1700.

[0067] To a four-necked reaction flask equipped with a mechanical stirrer and a condenser, 250 g of epoxymethylate modified polyphenyl ether, 54 g of triethylamine and 4000 g of dichloromethane were added. The reaction flask was cooled to 0 C., 49 g of methacryloyl chloride was dissolved in 1000 g of dichloromethane, the resulting solution was added dropwise to the reaction flask over 60 minutes, and then the reaction temperature was raised to room temperature, and the reaction was stirred for 2 hours. The mixture was washed with pure water, and the organic layer was added dropwise to a methanol solution to precipitate. The precipitate was dried under reduced pressure to obtain 200 g of a hexafunctional methacrylate group-modified thermosetting polyphenyl ether PPO-7 having a number average molecular weight of 2000.

[0068] The molecular structure of PPO-7 was shown in the following formula (8):

##STR00005##

[0069] X has a structure shown by formula (9):

##STR00006##

[0070] Y has a structure shown by formula (10):

##STR00007##

[0071] The raw materials selected for preparing the high-speed electronic circuit substrate in the examples of the present disclosure are shown in the following table:

TABLE-US-00001 TABLE 1 Manufacturer Product name or Brand name Description of the materials Self-prepared PPO-1 (number average molecular Tetrafunctional methyl methacrylate weight of 1900) group-modified thermosetting polyphenyl ether resin Self-prepared PPO-2 (number average molecular Tetrafunctional methyl methacrylate weight of 7500) group-modified thermosetting polyphenyl ether resin Self-prepared PPO-3 (number average molecular Tetrafunctional methyl methacrylate weight of 10600) group-modified thermosetting polyphenyl ether resin Self-prepared PPO-4 (number average molecular Hexafunctional methyl methacrylate weight of 2100) group-modified thermosetting polyphenyl ether resin Self-prepared PPO-5 (number average molecular Decafunctional methyl methacrylate weight of 2700) group-modified thermosetting polyphenyl ether resin Self-prepared PPO-6 (number average molecular Tetradecafunctional methyl weight of 3200) methacrylate group-modified thermosetting polyphenyl ether resin Self-prepared PPO-7 (number average molecular Hexafunctional methyl methacrylate weight of 2000) group-modified thermosetting polyphenyl ether resin Sabic SA9000 (number average molecular Bifunctional methyl methacrylate weight of 1900) group-modified thermosetting polyphenyl ether resin Samtomer Ricon100 Styrene-butadiene copolymer Nippon Soda B-1000 Polybutadiene Shanghai DCP Dicumyl peroxide Gaoqiao Dongguan BPO Dibenzoyl peroxide Sonic Chemical Sibelco 525 Fused silica powder Albemarle BT-93W Bromine-containing flame retardant Corporation Albemarle XP-7866 Phosphorous-containing flame Corporation retardant Shanhai 2116 Glass fiber cloth Honghe

EXAMPLE 1

[0072] 50 g parts by weight of tetrafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-1, 20 g parts by weight of styrene-butadiene copolymer Ricon100, and 1.5 parts by weight of a curing initiator DCP were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum. laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 2.

EXAMPLE 2

[0073] 50 g parts by weight of tetrafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-1, 30 g parts by weight of styrene-butadiene copolymer Ricon100, and 1.5 parts by weight of a curing initiator DCP were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 2.

EXAMPLE 3

[0074] 50 g parts by weight of tetrafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-1, 50 g parts by weight of styrene-butadiene copolymer Ricon100, and 1.5 parts by weight of a curing initiator DCP were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 2.

EXAMPLE 4

[0075] 50 g parts by weight of tetrafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-1, 30 g parts by weight of styrene-butadiene copolymer Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of bromine-containing flame retardant BT-93W, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 2.

EXAMPLE 5

[0076] 50 g parts by weight of tetrafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-2, 30 g parts by weight of styrene-butadiene copolymer Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of bromine-containing flame retardant BT-93W, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Due to the large molecular weight of PPO-2, the viscosity of the glue was larger, so that the wettability of the adhesive sheet was affected to a certain extent, Physical properties were as shown in Table 2.

EXAMPLE 6

[0077] 50 g parts by weight of tetrafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-3, 30 g parts by weight of styrene-butadiene copolymer Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of bromine-containing flame retardant BT-93W, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Due to the large molecular weight of PPO-3, the viscosity of the glue was large, so that the wettability of the adhesive sheet was affected to a certain extent. Physical properties were as shown in Table 2.

EXAMPLE 7

[0078] 50 g parts by weight of tetrafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-1, 30 g parts by weight of styrene-butadiene copolymer Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of phosphorous-containing flame retardant XP-7866, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 3.

EXAMPLE 8

[0079] 50 g parts by weight of hexafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-4, 30 g parts by weight of styrene-butadiene copolymer Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of phosphorous-containing flame retardant XP-7866, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 3.

EXAMPLE 9

[0080] 50 g parts by weight of decafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-5, 30 g parts by weight of styrene-butadiene copolymer Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of phosphorous-containing flame retardant XP-7866, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 3.

EXAMPLE 10

[0081] 50 g parts by weight of tetradecafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-6, 30 g parts by weight of styrene-butadiene copolymer Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of bromine-containing flame retardant BT-93W, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained, Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 3.

EXAMPLE 11

[0082] 50 g parts by weight of tetrafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-1, 30 g parts by weight of polybutadiene B-1000, 1.5 parts by weight of a curing initiator BPO, 15.0 g parts by weight of phosphorous-containing flame retardant XP-7866, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained, Physical properties were as shown in Table 3.

COMPARATIVE EXAMPLE 1

[0083] 50 g parts by weight of hexafunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin PPO-7, 30 g parts by weight of styrene-butadiene Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of phosphorous-containing flame retardant XP-7866, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 4.

COMPARATIVE EXAMPLE 2

[0084] 50 g parts by weight of bifunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin SA9000, 30 g parts by weight of styrene-butadiene copolymer Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of bromine-containing flame retardant BT-93W, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 4.

COMPARATIVE EXAMPLE 3

[0085] 50 g parts by weight of bifunctional methyl methacrylate group-modified thermosetting polyphenyl ether resin SA9000, 10 g parts by weight of styrene-butadiene copolymer Ricon100, 1.5 parts by weight of a curing initiator DCP, 15.0 g parts by weight of bromine-containing flame retardant BT-93W, and 25.0 g of fused silica powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. A 2116 glass fiber cloth was soaked with the glue, a suitable piece weight was controlled through a clamp shaft, and the cloth was baked in an oven to remove the toluene solvent, so that a 2116 adhesive sheet was obtained. Four 2116 adhesive sheets were overlapped with copper foils having a thickness of 10Z disposed on both top and bottom sides, vacuum laminated and cured in a press for 90 minutes, the curing pressure was 50 Kg/cm.sup.2 and the curing temperature was 200 C., so that a high-speed electronic circuit substrate was obtained. Physical properties were as shown in Table 4.

TABLE-US-00002 TABLE 2 The raw materials and properties Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PPO-1 50 50 50 50 0 0 PPO-2 0 0 0 0 50 0 PPO-3 0 0 0 0 0 50 PPO-4 0 0 0 0 0 0 PPO-5 0 0 0 0 0 0 PPO-6 0 0 0 0 0 0 PPO-7 0 0 0 0 0 0 SA9000 0 0 0 0 0 0 Ricon100 20 30 50 30 30 30 B-1000 0 0 0 0 0 0 DCP 1.5 1.5 1.5 1.5 1.5 1.5 BPO 0 0 0 0 0 0 BT-93W 0 0 0 15 15 15 XP-7866 0 0 0 0 0 0 525 0 0 0 25 25 25 Dielectric constant 3.7 3.6 3.5 3.8 3.8 3.8 (10 GHz) Dielectric loss (10 GHz) 0.0052 0.0048 0.0042 0.0048 0.0048 0.0048 Thermal-oxidative 0.3 0.2 0.3 0.2 0.3 0.3 aging resistance 150 C./56 day Absolute value of change in Dk Thermal-oxidative 0.004 0.003 0.004 0.003 0.004 0.004 aging resistance 150 C./56 day Absolute value of change in Df

TABLE-US-00003 TABLE 3 The raw materials Example Example and properties Example 7 Example 8 Example 9 10 11 PPO-1 50 0 0 0 50 PPO-2 0 0 0 0 0 PPO-3 0 0 0 0 0 PPO-4 0 50 0 0 0 PPO-5 0 0 50 0 0 PPO-6 0 0 0 50 0 PPO-7 0 0 0 0 0 SA9000 0 0 0 0 0 Ricon100 30 30 30 30 0 B-1000 0 0 0 0 30 DCP 1.5 1.5 1.5 1.5 0 BPO 0 0 0 0 1.5 BT-93W 0 0 0 15 0 XP-7866 15 15 15 0 15 525 25 25 25 25 25 Dielectric constant 3.8 3.8 3.8 3.8 3.8 (10 GHz) Dielectric loss (10 GHz) 0.0048 0.0048 0.0048 0.0048 0.0048 Thermal-oxidative 0.2 0.1 0.2 0.4 0.2 aging resistance 150 C./56 day Absolute value of change in Dk Thermal-oxidative 0.003 0.002 0.003 0.004 0.003 aging resistance 150 C./56 day Absolute value of change in Df

TABLE-US-00004 TABLE 4 The raw materials and Comparative Comparative Comparative properties Example 1 Example 2 Example 3 PPO-1 0 0 0 PPO-2 0 0 0 PPO-3 0 0 0 PPO-4 0 0 0 PPO-5 0 0 0 PPO-6 0 0 0 PPO-7 50 0 0 SA9000 0 50 50 Ricon100 30 30 10 B-1000 0 0 0 DCP 1.5 1.5 1.5 BPO 0 0 0 BT-93W 0 15 15 XP-7866 15 0 0 525 25 25 25 Dielectric constant (10 GHz) 3.8 3.8 4.1 Dielectric loss (10 GHz) 0.0048 0.0048 0.009 Thermal-oxidative aging 0.4 0.4 0.1 resistance 150 C./56 day Absolute value of change in Dk Thermal-oxidative aging 0.006 0.009 0.002 resistance 150 C./56 day Absolute value of change in Df

[0086] When compared with Example 8, Comparative Example 1 employs the multifunctional acrylate group-modified thermosetting polyphenyl ether resin PPO-7 of which the active groups, i.e., the methacrylate groups are all grafted onto the aliphatic chains such as the secondary or tertiary carbon atoms, resulting in the poor thermal-oxidative aging resistance of the substrate obtained in Comparative Example 1, and the poor stability of the dielectric constant and the dielectric loss during a long-term use. When compared with Example 4, Comparative Example 2 employs a methyl methacrylate group-modified thermosetting polyphenyl ether resin SA9000 with low functionality, due to its limited active groups, the excess double bonds on the side chains of the vinyl resin crosslinking agent such as polybutadiene cannot completely react. The incompletely reacted double bonds on the side chains of the vinyl resin crosslinking agent such as polybutadiene have poor thermal-oxidative aging resistance, which can seriously affect the stability of the dielectric constant and the dielectric loss of the substrate during a long-term use, thereby deteriorating the signal integrity of the substrate. Therefore, with respect to the multifunctional acrylate group-modified polyphenyl ether resin of which the bifunctional group or the active group acrylate group are all grafted onto the aliphatic chains such as the secondary or tertiary carbon atoms, the electronic circuit substrate prepared by use of the multifunctional acrylate group-modified thermosetting polyphenyl ether resin of the present disclosure not only has a low dielectric constant and dielectric loss, but also has a better thermal-oxidative aging resistance, ensuring that the dielectric constant and the dielectric loss of the substrate can maintain better stability during a long-term use.

[0087] In addition, it can be found by the comparison between Comparative Example 1 and Example 8, and the comparison between Comparative Example 3 and Example 4 that use of an appropriate amount of the vinyl resin to crosslink and cure the multifunctional acrylate group-modified thermosetting polyphenyl ether resin PPO-7 of which the active group, i.e., the acrylate groups are all grafted onto the aliphatic chains such as the secondary or tertiary carbon atoms, or use of a smaller amount of a vinyl resin to crosslink and cure methyl acrylate group-modified thermosetting polyphenyl ether resin SA9000 with low functionality cannot achieve the low dielectric constant and dielectric loss, as well as the excellent thermal-oxidative aging resistance simultaneously. A cooperation between the thermosetting polyphenyl ether resin in a specific structure and the vinyl resin crosslinking agent in a specified content is a necessary condition to achieve the low dielectric constant and dielectric loss, as well as the excellent thermal-oxidative aging resistance simultaneously.

[0088] Applicant has stated that although the detailed methods of the present disclosure have been described by the above examples in the present disclosure, the present disclosure is not limited thereto, that is to say, it is not meant that the present disclosure has to be implemented depending on the above detailed methods. It will be apparent to those skilled in the art that any improvements made to the present disclosure, equivalent replacements and addition of adjuvant ingredients to the raw materials of the products of the present disclosure, and selections of the specific implementations, etc., all fall within the protection scope and the disclosure scope of the present disclosure. cm 1.-10. (canceled)