RESIN COMPOSITION AND PRE-PREG AND LAMINATE USING THE COMPOSITION

Abstract

Provided in the present invention are a resin composition and a pre-preg and a laminate using the composition. The resin composition comprises: (A) a prepolymer of a polyolefin resin and a bifunctional maleimide or a multifunctional maleimide; and, (B) vinyl thermosetting polyphenylene ether, where with the weight of the prepolymer of the polyolefin resin and the bifunctional maleimide or the multifunctional maleimide being 100 parts by weight, the weight of the vinyl thermosetting polyphenylene ether is 200 to 1000 parts by weight. The present invention, by employing the prepolymer of the polyolefin resin and the bifunctional maleimide or the multifunctional maleimide, solves the problem of incompatibility of the bifunctional maleimide or the multifunctional maleimide with the polyolefin resin and vinyl thermosetting polyphenylene ether. An aqueous glue solution so mixed is uniform and consistent, the pre-preg has a uniform expression, and a substrate resin area is free of a phase-separation problem.

Claims

1.-10. (canceled)

11. A resin composition, comprising: (A) a prepolymer of polyolefin resin and bifunctional maleimide or polyfunctional maleimide; and (B) a vinyl thermosetting polyphenylene ether; wherein, based on 100 parts by weight of the prepolymer of polyolefin resin and bifunctional maleimide or polyfunctional maleimide, the weight of the vinyl thermosetting polyphenylene ether is 200 to 1000 parts by weight.

12. The resin composition of claim 11, wherein the polyolefin resin comprises at least one member selected from the group consisting of a styrene-butadiene copolymer, a polybutadiene copolymer, and styrene-butadiene-divinylbenzene copolymer.

13. The resin composition of claim 11, wherein the polyolefin resin comprises at least one member selected from the group consisting of amino-modified, maleic anhydride-modified, epoxy-modified, acrylate-modified, hydroxy-modified or carboxy-modified styrene-butadiene copolymer, polybutadiene and styrene-butadiene-divinylbenzene copolymer.

14. The resin composition of claim 11, wherein the weight of bifunctional maleimide or polyfunctional maleimide is 10 to 100 parts by weight based on 100 parts by weight of polyolefin resin.

15. The resin composition of claim 11, wherein the bifunctional maleimide or polyfunctional maleimide has a structure: ##STR00009## wherein R.sub.16 is an aliphatic or aromatic organic group having a valence of z; R.sub.17 and R.sub.18 are independently anyone selected from the group consisting of hydrogen atom, halogen atom, substituted or unsubstituted C1-C8 linear alkyl group, and substituted or unsubstituted C1-C8 branched alkyl group; and z represents an integer greater than or equal to 2.

16. The resin composition of claim 11, wherein the bifunctional maleimide is ##STR00010##

17. The resin composition of claim 11, wherein the polyfunctional maleimide is ##STR00011##

18. The resin composition of claim 11, wherein the vinyl thermosetting polyphenylene ether has a structural formula represented by the following formula (1):
ZOY.sub.aOXOYO.sub.bZ(1) in formula (1), a and b are independently an integer of 1 to 30; Z has a structure of formula (2) or (3); (OY) has a structure of formula (4); and (OXO) has a structure of formula (5): ##STR00012## wherein in formula (3), A is arylene group, carbonyl group, or alkylene group having 1 to 10 carbon atoms; m is an integer of 0 to 10; R.sub.1, R.sub.2 and R.sub.3 are each independently hydrogen or alkyl group having 10 or less carbon atoms; ##STR00013## in formula (4), R.sub.4 and R.sub.6 are each independently hydrogen atom, halogen atom, alkyl group having 8 or less carbon atoms or phenyl group having 8 or less carbon atoms; R.sub.5 and R.sub.7 are each independently hydrogen atom, halogen atom, alkyl group having 8 or less carbon atoms or phenyl group having 8 or less carbon atoms; ##STR00014## in formula (5), R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14 and R.sub.15 are each independently hydrogen atom, halogen atom, alkyl group having 8 or less carbon atoms or phenyl group having 8 or less carbon atoms; B is hydrocarbylene group, O, CO, SO, SC, SO.sub.2 or C(CH.sub.3).sub.2; and n is 0 or 1.

19. The resin composition of claim 11, wherein the vinyl thermosetting polyphenylene ether has a number average molecular weight from 500 to 10,000 g/mol.

20. The resin composition of claim 11, further comprising an initiator.

21. The resin composition of claim 20, wherein the initiator is a radical initiator that is an organic peroxide initiator.

22. The resin composition of claim 21, wherein the radical initiator comprises at least one member selected from the group consisting of dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 2,2-di(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, cetyl peroxydicarbonate, tetradecyl peroxydicarbonate, di-tert amyl peroxide, dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, diisopropylbenzene hydroperoxide, isopropylbenzene hydroperoxide, tert-amyl hydroperoxide, tert-butyl hydroperoxide, tert-butyl cumyl peroxide, diisopropylbenzene hydroperoxide, peroxy carbonate-tert-butyl 2-ethylhexanoate, tert-butyl peroxy 2-ethylhexyl carbonate, n-butyl 4,4-di(tert-butylperoxy)valerate, methyl ethyl ketone peroxide and cyclohexane peroxide.

23. The resin composition of claim 20, wherein the weight of the initiator is 1-3 parts by weight, based on 100 parts by weight of the total weight of the prepolymer of polyolefin resin and bifunctional maleimide or polyfunctional maleimide, the vinyl thermosetting polyphenylene ether and the initiator.

24. The resin composition of claim 11, further comprising a flame retardant.

25. The resin composition of claim 24, wherein the flame retardant is at least one member selected from the group consisting of a bromine-containing flame retardant and a phosphorus-containing flame retardant.

26. The resin composition of claim 24, wherein the flame retardant is a phosphorus-containing flame retardant comprising a DOPO structure, and has a molecular formula of ##STR00015## wherein n is an integer of 0 to 10.

27. The resin composition of claim 24, wherein the weight of the flame retardant is 0-40 parts by weight, based on 100 parts by weight of the total weight of the prepolymer of polyolefin resin and bifunctional maleimide or polyfunctional maleimide, the vinyl thermosetting polyphenylene ether and the initiator.

28. The resin composition of claim 11, wherein the resin composition further comprises a filler; and wherein the filler is at least one member selected from the group consisting of crystalline silica, amorphous silica, spherical silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, barium titanate and strontium titanate.

29. The resin composition of claim 28, wherein the weight of the filler is 0-150 parts by weight, based on 100 parts by weight of the total weight of the prepolymer of polyolefin resin and bifunctional maleimide or polyfunctional maleimide, the vinyl thermosetting polyphenylene ether, the initiator and the flame retardant.

30. A prepreg comprising a substrate and the resin composition of claim 11 which is attached on the substrate after impregnation and drying.

31. A laminate comprising at least one superimposed prepreg of claim 30.

Description

EMBODIMENTS

[0051] Technical solutions of the present invention are further described by the following examples. Raw materials selected for preparing high-speed electronic circuit substrates in examples and comparative examples of the present invention are shown in Table 1 below.

TABLE-US-00001 TABLE 1 Name or trademark Manufacturer of materials Description for materials Sabic MX9000 Methyl methacrylate-modified polyphenylene ether Mitsubishi Chemical St-PPE-1 Styryl-modifiedd polyphenylene ether Asahi Kasei S202A Thermoplastic polyphenylene ether Wuhan ZHISHENG Maleimide Monofunctional maleimide Science &Technology K-I Chemical Maleimide Bifunctional maleimide Jinyi Chemical Maleimide Trifunctional maleimide Samtomer R100 Styrene-butadiene copolymer Nippon Soda B-1000 Polybutadiene Samtomer R250 Styrene-butadiene-divinylbenzene copolymer Shanghai Gaoqiao DCP Dicumyl peroxide Petrochemical Corp. Dongguan XINWEI BPO Dibenzoyl peroxide Chemical Industry Sibelco 525 Fused silica powder Albemarle, America BT-93W Bromine-containing flame retardant Albemarle, America XP-7866 Phosphorus-containing flame retardant Shanghai Honghe 2116 Glass fiber cloth

I. Prepolymerization of Polyolefin Resin and Bifunctional Maleimide or Polyfunctional Maleimide

1. Prepolymerization Example 1

[0052] 25 g of styrene-butadiene copolymer R100 was weighed and dissolved in 25 g of a toluene solvent. 5 g of bifunctional maleimide from K-I Chemical was weighed and dissolved in 20 g of a N,N-dimethylformamide solvent. The solution of styrene-butadiene copolymer R100 and the solution of bifunctional maleimide from K-I chemical were mixed and stirred uniformly. The mixed solution was heated to 120 C., and then 0.1 g of DCP dissolved in 10 g of toluene was added and the mixture was reacted for 1.5 hours. Then the heating was stopped and the mixture was cooled for use.

2. Prepolymerization Example 2

[0053] 25 g of polybutadiene B-1000 was weighed and dissolved in 25 g of a toluene solvent. 5 g of bifunctional maleimide from K-I Chemical was weighed and dissolved in 20 g of a N,N-dimethylformamide solvent. The solution of styrene-butadiene copolymer R100 and the solution of bifunctional maleimide from K-I Chemical were mixed and stirred uniformly. The mixed solution was heated to 120 C., and then 0.1 g of DCP dissolved in 10 g of toluene was added and the mixture was reacted for 1.5 hours. Then the heating was stopped and the mixture was cooled for use.

3. Prepolymerization Example 3

[0054] 25 g of styrene-butadiene-divinylbenzene copolymer R250 was weighed and dissolved in 25 g of a toluene solvent. 5 g of bifunctional maleimide from K-I Chemical was weighed and dissolved in 20 g of a N,N-dimethylformamide solvent. The solution of styrene-butadiene copolymer R100 and the solution of bifunctional maleimide from K-I Chemical were mixed and stirred uniformly. The mixed solution was heated to 120 C., and then 0.1 g of DCP dissolved in 10 g of toluene was added and the mixture was reacted for 1.5 hours. Then the heating was stopped and the mixture was cooled for use.

4. Prepolymerization Example 4

[0055] 25 g of styrene-butadiene copolymer R250 was weighed and dissolved in 25 g of a toluene solvent. 5 g of trifunctional maleimide from Jinyi Chemical was weighed and dissolved in 20 g of a N,N-dimethylformamide solvent. The solution of styrene-butadiene copolymer R100 and the solution of trifunctional maleimide from Jinyi Chemical were mixed and stirred uniformly. The mixed solution was heated to 120 C., and then 0.1 g of DCP dissolved in 10 g of toluene was added and the mixture was reacted for 1.5 hours. Then the heating was stopped and the mixture was cooled for use.

II. Preparation of High-Speed Electronic Circuit Substrates

1. Example 1

[0056] A prepolymer prepared by prepolymerization of 25 g parts by weight of styrene-butadiene copolymer R100 and 5 g parts by weight of bifunctional maleimide from KI Chemical, 70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of a curing initiator DCP and 30 g parts by weight of a bromine-containing flame retardant BT-93 W were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 2.

2. Example 2

[0057] A prepolymer prepared by prepolymerization of 25 g parts by weight of polybutadiene B-1000 and 5 g parts by weight of bifunctional maleimide from KI Chemical, 70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93 W and 50 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 2.

3. Example 3

[0058] A prepolymer prepared by prepolymerization of 25 g parts by weight of styrene-butadiene-divinylbenzene copolymer R250 and 5 g parts by weight of bifunctional maleimide from KI Chemical, 70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93 W and 50 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and a copper foil having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 2.

4. Example 4

[0059] A prepolymer prepared by prepolymerization of 25 g parts by weight of styrene-butadiene copolymer R100 and 5 g parts by weight of trifunctional maleimide from Jinyi Chemical, 70 g parts by weight of vinyl thermosetting polyphenylene ether St-PPE-1, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93 W and 50 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 2.

5. Example 5

[0060] A prepolymer prepared by prepolymerization of 25 g parts by weight of styrene-butadiene copolymer R100 and 5 g parts by weight of bifunctional maleimide from K-I Chemical, 70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of a curing initiator BPO, 30 g parts by weight of a phosphorus-containing flame retardant XP-7866 and 50 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 2.

6. Example 6

[0061] A prepolymer prepared by prepolymerization of 25 g parts by weight of styrene-butadiene copolymer R100 and 2.5 g parts by weight of bifunctional maleimide from K-I Chemical, 55 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93 W and 50 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 3.

7. Example 7

[0062] A prepolymer prepared by prepolymerization of 25 g parts by weight of styrene-butadiene copolymer R100 and 25 g parts by weight of bifunctional maleimide from K-I Chemical, 100 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93 W and 50 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 3.

8. Example 8

[0063] A prepolymer prepared by prepolymerization of 25 g parts by weight of styrene-butadiene copolymer R100 and 2.5 g parts by weight of bifunctional maleimide from K-I Chemical, 275 g parts by weight of vinyl thermosetting polyphenylene ether St-PPE-1, 3.0 parts by weight of a curing initiator DCP, 60 g parts by weight of a bromine-containing flame retardant BT-93 W and 100 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 3.

9. Example 9

[0064] A prepolymer prepared by prepolymerization of 25 g parts by weight of styrene-butadiene copolymer R100 and 25 g parts by weight of bifunctional maleimide from K-I Chemical, 500 g parts by weight of vinyl thermosetting polyphenylene ether St-PPE-1, 3.0 parts by weight of a curing initiator DCP, 90 g parts by weight of a bromine-containing flame retardant BT-93 W and 150 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 3.

10. Comparative Example 1

[0065] 70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000 dissolved in toluene, 5 g parts by weight of bifunctional maleimide from KI Chemical dissolved in N,N-dimethylformamide, 25 g parts by weight of butadiene-styrene copolymer R100, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93 W and 50 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 4.

11. Comparative Example 2

[0066] 70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000 dissolved in toluene, 5 g parts by weight of monofunctional maleimide from Wuhan ZHISHENG Science & Technology dissolved in N,N-dimethylformamide, 25 g parts by weight of butadiene-styrene copolymer R100, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93 W and 50 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 4.

12. Comparative Example 3

[0067] 70 g parts by weight of vinyl thermoplastic polyphenylene ether S202A dissolved in toluene, 25 g parts by weight of butadiene polymer B-1000 dissolved in toluene and 5 g parts by weight of bifunctional maleimide from K-I Chemical dissolved in N,N-dimethylformamide were mixed and stirred uniformly. The mixed solution was heated to 120 C., and then 0.1 g of DCP dissolved in toluene was added and the mixture was reacted for 1.5 hours. Then the heating was stopped and the mixture was cooled for use.

[0068] The above-mentioned semi-IPN type composite thermosetting resin composition, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93 W and 50 g of fused silica powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 4.

13. Comparative Example 4

[0069] A prepolymer prepared by prepolymerization of 70 g parts by weight of styrene-butadiene copolymer R100 and 5 g parts by weight of bifunctional maleimide from K-I Chemical, 25 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93 W and 50 g of fused silica powder 525 were dissolved in a toluene solvent and the solution was adjusted to a suitable viscosity. A 2116 fiberglass cloth was impregnated in the resulting glue 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 bonding sheet was obtained. Four 2116 bonding sheets were superimposed, and copper foils having a thickness of 1 OZ overlaid at the upper and lower surfaces of the superimposed bonding sheets, 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-speed electronic circuit substrate. Physical properties thereof are shown in Table 4.

TABLE-US-00002 TABLE 2 Raw materials and Properties Example 1 Example 2 Example 3 Example 4 Example 5 MX9000 70 70 70 0 70 St-PPE-1 0 0 0 70 0 S202A 0 0 0 0 0 R100 25 0 0 25 25 B-1000 0 25 0 0 0 R250 25 0 0 Monofunctional 0 0 0 0 0 maleimide Bifunctional 5 5 5 0 5 maleimide Trifunctional 0 0 0 5 0 maleimide DCP 3 3 3 3 0 BPO 0 0 0 0 3 BT-93W 30 30 30 0 0 XP-7866 0 0 0 30 30 525 50 50 50 50 50 Glass transition 210.0 210.0 210.0 220.0 210.0 temperature ( C.) Thermal 420.0 420.0 420.0 430.0 440.0 decomposition temperature ( C.) Thermal >60 min >60 min >60 min >120 min >60 min stratification time T288 Thermal 1.8% 1.8% 1.8% 1.8% 1.8% expansion coefficient 50-260 C. Flame Grade V-0 Grade V-0 Grade V-0 Grade V-0 Grade V-0 retardancy Dielectric 3.90 3.90 3.90 3.90 3.90 constant (10 GHz) Dielectric loss 0.0048 0.0048 0.0048 0.0048 0.0048 tangent (10 GHz) Appearance of Good Good Good Good Good prepreg appearance appearance appearance appearance appearance No crack No crack No crack No crack No crack Whether the No phase No phase No phase No phase No phase substrate resin separation separation separation separation separation area has a phase separation Whether No / / / / delamination occurs to a 28 layers of PCB after lead-free reflow soldering

TABLE-US-00003 TABLE 3 Raw materials and Properties Example 6 Example 7 Example 8 Example 9 MX9000 55 100 0 0 St-PPE-1 0 0 275 500 S202A 0 0 0 0 R100 25 25 25 25 B-1000 0 0 0 0 R250 0 0 0 0 Monofunctional 0 0 0 0 maleimide Bifunctional 2.5 25 2.5 25 maleimide Trifunctional 0 0 0 0 maleimide DCP 3 3 3 3 BPO 0 0 0 0 BT-93W 30 30 60 90 XP-7866 0 0 0 0 525 52 50 100 150 Glass transition 200.0 220.0 190.0 200.0 temperature ( C.) Thermal 400.0 410.0 400.0 420.0 decomposition temperature ( C.) Thermal >60 min >60 min >60 min >60 min stratification time T288 Thermal 2.0% 1.8% 2.3% 2.0% expansion coefficient 50-260 C. Flame Grade V-0 Grade V-0 Grade V-0 Grade V-0 retardancy Dielectric 3.70 4.00 4.10 4.20 constant (10 GHz) Dielectric loss 0.0045 0.0052 0.0060 0.0065 tangent (10 GHz) Appearance of Good Good Good Good prepreg appearance appearance appearance appearance No crack No crack No crack No crack Whether the No phase No phase No phase No phase substrate resin separation separation separation separation area has a phase separation Whether / / / / delamination occurs to a 28 layers of PCB after lead-free reflow soldering

TABLE-US-00004 TABLE 4 Raw materials and Comparative Comparative Comparative Comparative Properties Exampe 1 Exampe 2 Exampe 3 Exampe 4 MX9000 70 70 0 25 St-PPE-1 0 0 0 0 S202A 0 0 70 0 R100 25 25 0 70 B-1000 0 0 25 0 R250 0 0 0 0 Monofunctional 0 5 0 0 maleimide Bifunctional 5 0 5 5 maleimide Trifunctional 0 0 0 0 maleimide DCP 3 3 3 3 BPO 0 0 0 0 BT-93W 30 30 30 30 XP-7866 0 0 0 0 525 50 50 50 50 Glass transition 210.0 190.0 180.0 200.0 temperature ( C.) Thermal 420.0 390.0 400.0 390.0 decomposition temperature ( C.) Thermal >60 min <60 min <60 min <60 min stratification time T288 Thermal expansion 1.8% 2.7% 3.0% 3.0% coefficient 50-260 C. Flame retardancy Grade V-0 Grade V-0 Grade V-0 Grade V-0 Dielectric constant 3.90 3.90 3.90 3.70 (10 GHz) Dielectric loss 0.0048 0.0048 0.0048 0.0045 tangent (10 GHz) Appearance of Poor Poor Poor Good prepreg appearance appearance appearance appearance with with with stripes, No crack cracks cracks colloidal particles and dry flowers Whether the Phase Phase Microphase No phase substrate resin area separation separation phase separation has a phase occurs occurs separation separation Whether / / Yes Yes delamination occurs to a 28 layers of PCB after lead-free reflow soldering

Physical Properties Analysis:

[0070] As can be seen from Table 2 and Table 3, by prepolymerization of polyolefin resin and bifunctional maleimide or polyfunctional maleimide, the problem of incompatibility of vinyl thermosetting polyphenylene ether, polyolefin resin and maleimide is solved; the prepared prepreg has a good appearance and there is no phase separation in the substrate resin area. Cross-linking and curing can occur among polyolefin resin, vinyl thermosetting polyphenylene ether and maleimide, forming a three-dimensional network structure having a high cross-linking density. The use of vinyl thermosetting polyphenylene ether as the main resin ensures that the prepared electronic circuit substrate has excellent heat resistance. The prepared substrate has excellent comprehensive properties such as excellent dielectric properties and heat resistance, and is perfectly suitable for use as a substrate in high speed electronic circuit PCB.

[0071] As can be seen from Comparative Example 1, when styrene-butadiene copolymer and bifunctional maleimide are not subjected to prepolymerization, the prepreg has a poor appearance with defect of cracks, and there is a phase separation in the substrate resin area.

[0072] As can be seen from Comparative Example 2, when monofunctional maleimide is used and is not prepolymerized with styrene-butadiene copolymer, the prepreg has a poor appearance with defect of cracks, and there is a phase separation in the substrate resin area. In addition, heat resistance of the product is inferior (glass transition temperature is lower, thermal decomposition temperature is lower, thermal stratification time is shorter, and thermal expansion coefficient is larger) than that of a product prepared by using bifunctional maleimide.

[0073] As can be seen from Comparative Example 3, the electronic circuit substrate prepared using thermoplastic polyphenylene ether and polybutadiene by a compatibilization process has an insufficient heat resistance (lower glass transition temperature, lower heat decomposition temperature, shorter thermal stratification time, higher thermal expansion coefficient), and thus the prepared PCB used for high multi-layer high-speed electronic circuit has a significant heat resistance problem that delamination will occur after several harsh lead-free reflow solderings. Moreover, since the thermoplastic polyphenylene ether has a high molecular weight, the prepared prepreg has an appearance with defects of stripes, colloidal particles, dry flowers, and there is a phase separation in the substrate resin area.

[0074] As can be seen from Comparative Example 4, when polyolefin resin (styrene-butadiene copolymer in this example) rather than polyphenylene ether is used as the main resin, the prepared electronic circuit substrate has an insufficient heat resistance (lower glass transition temperature, lower heat decomposition temperature, shorter thermal stratification time, higher thermal expansion coefficient), and thus the prepared PCB used for high multi-layer high-speed electronic circuit has a significant heat resistance problem that delamination will occur after several harsh lead-free reflow solderings.

[0075] The examples of the present invention are described above and they are not intended to limit the present invention. Any changes and modifications made to the present invention according to the technical concept of the present invention fall within the protection scope of the present invention.

[0076] The applicant states that: the present application describes detailed means of the present invention by the aforesaid examples, but the present invention is not limited to the aforesaid detailed means. That is to say, it does not mean that the present invention cannot be fulfilled unless relying on the aforesaid detailed means. Those skilled in the art shall know that, any modification to the present invention, any equivalence replacement of each raw material of the product of the present invention and the addition of auxiliary ingredient, the selection of specific embodiment and the like all fall into the protection scope and the disclosure scope of the present invention.