Thermosetting resin composition, prepreg made therefrom, laminate clad with metal foil, and high-frequency circuit board

Abstract

Disclosed are a thermosetting resin composition, a prepreg made therefrom, a laminate clad with a metal foil, and a high-frequency circuit board, wherein the thermosetting resin composition contains thermosetting ingredients. The thermosetting ingredients include a phosphorus-containing monomer or a phosphorus-containing resin and a polyphenylene ether resin containing an unsaturated group, and the phosphorus-containing monomer or the phosphorus-containing resin has a structure as shown in formula I. By using the phosphorus-containing monomer or the phosphorus-containing resin as a cross-linking agent of the polyphenylene ether resin containing an unsaturated group and by means of a cross-linking reaction of a large number of unsaturated double bonds in the resin, the high-frequency dielectric properties and high-temperature-resistance required by a circuit substrate are provided.

Claims

1. A thermosetting resin composition, wherein the thermosetting resin composition comprises thermosetting ingredients which comprise a phosphorus-containing monomer or a phosphorus-containing resin and a polyphenylene ether resin containing unsaturated groups, wherein the phosphorus-containing monomer or the phosphorus-containing resin has a structure as shown in Formula I: ##STR00024## wherein R represents a linear or branched alkyl, ##STR00025## each X and Y are independently selected from the group consisting of hydrogen, allyl, linear alkyl, branched alkyl, and a combination of at least two selected therefrom; each A is a phosphorus-containing capping group; and n is an integer of 1-20.

2. The thermosetting resin composition of claim 1, wherein R represents —CH.sub.2—, ##STR00026## n is an integer of 1-20; each X and Y are independently selected from the group consisting of hydrogen, allyl, linear alkyl, branched alkyl, and a combination of at least two selected therefrom; and each A is a phosphorus-containing capping group.

3. The thermosetting resin composition of claim 1, wherein the phosphorus-containing monomer or the phosphorus-containing resin is prepared by the following method comprising the steps of: (1) a phenolic compound or a phenolic resin of Formula II is reacted with an allylation reagent to obtain an allyl etherified resin of Formula III, wherein the exemplary reaction formula is as follows: ##STR00027## (2) the allyl etherified resin of Formula III is heated under the protection of protective gas, and an intramolecular rearrangement reaction occurs to obtain an allylated phenolic resin of Formula IV: ##STR00028## (3) the allylated phenolic resin of formula III is reacted with a phosphorus-containing capping reagent to obtain the phosphorus-containing monomer or the phosphorus-containing resin of Formula I: ##STR00029## wherein R.sub.1 is selected from the group consisting of linear or branched alkyl, ##STR00030## R.sub.2 is selected from the group consisting of linear or branched alkyl, ##STR00031## R.sub.3 is selected from the group consisting of linear or branched alkyl, ##STR00032## R is selected from the group consisting of linear or branched alkyl, ##STR00033## each X and Y are independently selected from the group consisting of hydrogen, allyl, linear alkyl, branched alkyl, and a combination of at least two selected therefrom; each A is a phosphorus-containing capping group; and n is an integer of 1-20.

4. The thermosetting resin composition of claim 1, wherein the polyphenylene ether resin containing unsaturated groups is a polyphenylene ether resin containing double bonds or triple bonds.

5. The thermosetting resin composition claimed in claim 4, wherein the polyphenylene ether resin containing unsaturated groups is anyone selected from the group consisting of allyl-terminated polyphenylene ether resin, acrylate-terminated polyphenylene ether resin, vinyl-terminated polyphenylene ether resin, and a combination of at least two selected therefrom.

6. The thermosetting resin composition of claim 1, wherein the thermosetting resin composition further comprises a powder filler.

7. A prepreg, wherein the prepreg comprises a reinforcing material and the thermosetting resin composition of claim 1 which is adhered thereto after impregnation and drying.

8. A laminate, wherein the laminate comprises at least one prepreg of claim 7.

9. A metal foil-clad laminate, wherein the metal foil-clad laminate comprises one or at least two laminated prepregs of claim 7, and metal foil on one side or both sides of the laminated prepreg.

10. A high-frequency circuit board, wherein the high-frequency circuit board comprises one or at least two laminated prepregs of claim 7.

11. The thermosetting resin composition claimed in claim 1, wherein A is a DOPO-containing group.

12. The thermosetting resin composition claimed in claim 11, wherein A is anyone selected from the group consisting of ##STR00034##

13. The thermosetting resin composition claimed in claim 1, wherein the phosphorus-containing monomer or the phosphorus-containing resin is a phosphorus-containing monomer or a phosphorus-containing resin having a phosphorus content greater than 3%.

14. The thermosetting resin composition claimed in claim 1, wherein the phosphorus-containing monomer or the phosphorus-containing resin is anyone selected from the group consisting of the compounds having the following structures of Formulae A-D, and a combination of at least two selected therefrom: ##STR00035## wherein n is an integer of 1-20.

15. The thermosetting resin composition claimed in claim 1, wherein the polyphenylene ether resin containing unsaturated groups has a number average molecular weight of 700-8,000.

16. The thermosetting resin composition claimed in claim 1, wherein the thermosetting ingredients account for 5 to 90% by weight of the thermosetting resin composition; the phosphorus-containing monomer or the phosphorus-containing resin accounts for 20 to 75% of the total weight of the polyphenylene ether resin containing unsaturated groups and the phosphorus-containing monomer or the phosphorus-containing resin.

17. The thermosetting resin composition claimed in claim 1, wherein the thermosetting resin composition further comprises a curing initiator.

18. The thermosetting resin composition claimed in claim 1, wherein the thermosetting resin composition further comprises a co-crosslinking agent comprising a monomer or a low-molecular copolymer having unsaturated double bonds or unsaturated triple bonds in the molecular structure.

19. The thermosetting resin composition claimed in claim 1, wherein the co-crosslinking agent is anyone selected from the group consisting of triallyl tripolyisocyanurate, triallyl tripolycyanurate, divinylbenzene, polyfunctional acrylate, bismaleimide, and a combination of at least two selected therefrom.

20. The thermosetting resin composition claimed in claim 1, wherein the thermosetting resin composition further comprises other thermosetting resins.

21. The thermosetting resin composition claimed in claim 20, wherein the other thermosetting resins selected from the group consisting of cyanate resin, polybutadiene resin, bismaleimide resin, vinyl-terminated silicone resin, and a combination of at least two selected therefrom.

Description

PREPARATION EXAMPLE 1

(1) 188 g of acetone was added to a three-necked reaction flask. 228 g of bisphenol A was then added to the reaction flask, stirred and dissolved, and 106 g of sodium carbonate was added. 153 g of a chloropropene solution was slowly added dropwise, and then the reaction was stopped after raising the temperature for 4 hours. Filtration, removal of most of the solvent and washing were carried out, and then removal of residual solvent and water gave bisphenol A diallyl ether.

(2) 134 g of the prepared bisphenol A diallyl ether was placed in the reaction flask, and subjected to a rearrangement reaction by heating for 6 hours. The mixture was cooled to obtain a brown viscous liquid, i.e. diallyl bisphenol A.

(3) An inert gas was introduced into the three-necked reaction flask for protection. 300 g of dichloromethane was added. 134 g of the prepared diallyl bisphenol A was placed in the reaction flask, stirred and dissolved. 40 g of sodium hydroxide was added, and 152 g of carbon tetrachloride was added. 230 g of 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-4-phenol was slowly added dropwise, and the reaction was stopped after reacting for 4 hours. An aqueous solution of sodium hydroxide was added to wash to neutrality, then washing was conducted several times to remove residual solvent and water, thereby obtaining phosphorus-containing esterified diallyl bisphenol A, i.e. the low-polarity intrinsic flame-retardant resin having the structure thereof as follows:

(4) ##STR00021##

PREPARATION EXAMPLE 2

(5) 300 g of n-butanol was added to a three-necked reaction flask. 114 g of linear phenolic resin was then added to the reaction flask, stirred and dissolved, and 56 g of potassium hydroxide was added. 153 g of a bromopropane solution was slowly added dropwise, and then the reaction was stopped after raising the temperature for 4 hours. Filtration, removal of most of the solvent and washing were carried out, and then removal of residual solvent and water gave an allyl etherified phenolic resin.

(6) 141 g of the prepared allyl etherified phenolic resin was placed in the reaction flask, and subjected to a rearrangement reaction by heating for 4 hours. The mixture was cooled to obtain a brown viscous liquid, i.e. allyl phenolic resin.

(7) An inert gas was introduced into the three-necked reaction flask for protection. 350 g of dichloromethane was added. 141 g of the prepared allyl phenolic resin was placed in the reaction flask, stirred and dissolved. 72 g of triethylamine was added, and 152 g of carbon tetrachloride was added. 230 g of 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-4-phenol was slowly added dropwise, and the reaction was stopped after reacting for 4 hours. An aqueous solution of sodium hydroxide was added to wash to neutrality, then washing was conducted several times to remove residual solvent and water, thereby obtaining phosphorus-containing esterified allyl phenolic resin, i.e. the low-polarity intrinsic flame-retardant resin having Mn of 1,300 and the structure thereof is as follows:

(8) ##STR00022##

PREPARATION EXAMPLE 3

(9) 250 g of toluene was added to a three-necked reaction flask. 118 g of o-cresol novolac resin was then added to the reaction flask, stirred and dissolved, and 100 g of an aqueous solution of sodium hydroxide (having a concentration of 40%) was added, and then lg of tetrabutylammonium bromide was further added. After the temperature became constant, 153g of a chloropropene solution was slowly added dropwise. The reaction was stopped after raising the temperature for 4 hours. Washing and removal of the solvent were carried out to obtain allyl etherified o-cresol novolac resin.

(10) 159g of the prepared allyl etherified o-cresol novolac resin was placed in the reaction flask, and subjected to a rearrangement reaction by heating for 4 hours. The mixture was cooled to obtain a dark brown semisolid, i.e. allyl o-cresol novolac resin.

(11) An inert gas was introduced into the three-necked reaction flask for protection. 350 g of dichloromethane was added. 159 g of the prepared allyl o-cresol novolac resin was placed in the reaction flask, stirred and dissolved. 103 g of pyridine was added, and 152 g of carbon tetrachloride was added. 230 g of 2-(6H-dibenzo(c,e)(1,2)-5-oxa-6-phosphono-6-phenyl-3-phenol was slowly added dropwise, and the reaction was stopped after reacting for 4 hours. An aqueous solution of sodium hydroxide was added to wash to neutrality, then washing was conducted several times to remove residual solvent and water, thereby obtaining phosphorus-containing esterified allyl o-cresol novolac resin, i.e. the low-polarity intrinsic flame-retardant resin having Mn of 1,200 and the structure thereof is as follows:

(12) ##STR00023##

EXAMPLE 1

(13) 80 parts by weight of SA9000, 20 parts by weight of phosphorus-containing esterified diallyl bisphenol A prepared in Preparation Example 1, 85 parts by weight of silica (525), and 6.5 parts by weight of an initiator DCP were mixed, adjusted to a suitable viscosity with a solvent of toluene, stirred and uniformly mixed to uniformly disperse the filler in the resin, so as to obtain a varnish. 1080 glass fiber cloth was impregnated with the varnish above, and then dried to remove the solvent to obtain a prepreg. Eight sheets of prepared prepregs were laminated, and pressed on both sides thereof with copper foils having a thickness of 1 oz (ounce), and cured in a press for 2 hours at a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 190° C. The physical property data are shown in Table 2 below.

EXAMPLE 2

(14) The production process was the same as that in Example 1, except for that the compounding ratio of the thermosetting resin composition was changed as shown in Table 2, so as to prepare a copper clad laminate. The performance data thereof are shown in Table 2 below.

EXAMPLES 3-4

(15) The production processes were the same as that in Example 1, except for that the co-crosslinking agent bismaleimide was added. The compounding ratio of the resin composition and the performance data of the prepared copper clad laminates are shown in Table 2 below.

EXAMPLE 5

(16) 80 parts by weight of OPE-ST-1200, 20 parts by weight of the phosphorus-containing esterified allyl phenolic resin prepared in Preparation Example 2, 85 parts by weight of silica (525), and 6.5 parts by weight of an initiator DCP were mixed, adjusted to a suitable viscosity with a solvent of toluene, stirred and uniformly mixed to uniformly disperse the filler in the resin, so as to obtain a varnish. 1080 glass fiber cloth was impregnated with the varnish above, and then dried to remove the solvent to obtain a prepreg. Eight sheets of prepared prepregs were laminated, and pressed on both sides thereof with copper foils having a thickness of 1 oz (ounce), and cured in a press for 2 hours at a curing pressure of 50 kg/cm.sup.2 and a curing temperature of 190° C. The physical property data are shown in Table 2 below.

EXAMPLE 6

(17) The production process was the same as that in Example 1, except that a small amount of phosphorus-containing esterified diallyl bisphenol A was added. The material ratio and the performance data of the prepared copper clad laminate are shown in Table 2 below.

COMPARISON EXAMPLES 1-2

(18) The production processes were the same as that in Example 1, except for that the phosphorus-containing esterified diallyl bisphenol A was removed, or the phosphorus-containing esterified allyl phenolic resin was replaced by an allyl phenolic resin and a DOPO flame retardant. The material ratio and the performance data of the copper clad laminates prepared are shown in Table 2 below.

(19) TABLE-US-00002 TABLE 2 Materials and Example Example Example Example Example Example Com. Com. properties 1 2 3 4 5 6 Example 1 Example 2 SA9000 80 60 80 35 90 80 OPE-ST-1200 80 80 Phosphorus-containing 20 40 65 10 0 esterified diallyl bisphenol A Phosphorus-containing 20 esterified allyl phenolic resin Phosphorus-containing 20 esterified allyl o-cresol novolac resin Allyl phenolic 20 resin 9,10-dihydro- 20 9-oxa-10- phosphaphenanthrene- 10-oxide 525 85 240 85 85 85 85 85 85 Bismaleimide 0 0 10 15 0 BM-3000 DCP 6.5 7.5 5.6 5.3 6.5 6 5.8 6 1080 glass fiber 80.7 125 78 85 80.7 86 92 85 cloth Dielectric constant 3.78 3.86 3.83 3.96 3.80 3.53 3.5 4.08 (10 GHZ) Dielectric loss 0.0053 0.0056 0.0056 0.0057 0.0053 0.0048 0.004 0.023 tangent (10 GHZ) Dip soldering >120 >120 >120 >120 >120 20 15 10 resistance 288° C., (s) Glass transition 160 173 210 225 165 100 80 135 temperature (° C.) (DSC) Flame retardancy V-1 V-0 V-1 V-0 V-1 combustion Combustion V-1 Glass impregnation Good Good Good Good Good Worse Worse worse operation

Physical Analysis

(20) As can be seen from the results of the physical property data in Table 2, the copper clad laminates prepared in Examples 1-6 have better heat resistance, dip soldering resistance and flame retardancy than those prepared in Comparison Examples 1 and 2.

(21) As can be seen from the results of the physical property data in Table 2, the addition of bismaleimide within the compounding ratio range of the present invention can achieve better heat resistance.

(22) The thermosetting resin composition of the present invention, the prepreg, the metal foil-clad laminate, and the high-frequency circuit board prepared therefrom are described in the above examples. However, the present invention is not limited to the above examples, i.e. it does not mean that the present invention must rely upon the above examples. Those skilled in the art shall know that any modifications of the present invention, equivalent substitutions of the materials selected for use in the present invention, and addition of auxiliary ingredients, and specific manner in which they are selected, all are within the protection scope and disclosure scope of the present invention.