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

Patent metadata

Field	Value
Publication number	US-11319397-B2
Application number	US-201716633012-A
Country	US
Kind code	B2
Filing date	Nov 2, 2017
Priority date	Jul 26, 2017
Publication date	May 3, 2022
Grant date	May 3, 2022

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 another thermosetting 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 other thermosetting 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.

First claim

The invention claimed is:

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 other thermosetting resins containing unsaturated groups, wherein the phosphorus-containing monomer or the phosphorus-containing resin has a structure as shown in Formula I:

wherein R represents a linear or branched alkyl,

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; 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 2 —,

n is an integer of 1-20;
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
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:

(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:

(3) the allylated phenolic resin of formula IV is reacted with a phosphorus-containing capping reagent to obtain the phosphorus-containing monomer or the phosphorus-containing resin of Formula I:

wherein R 1 is selected from the group consisting of linear or branched alkyl,

R 2 is selected from the group consisting of linear or branched alkyl,

R 3 is selected from the group consisting of linear or branched alkyl,

R is selected from the group consisting of linear or branched alkyl,

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;
A is a phosphorus-containing capping group; and
n is an integer of 1-20.

4. The thermosetting resin composition of claim 1 , wherein said other thermosetting resins containing unsaturated groups are thermosetting resins containing double bonds or triple bonds.

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

6. 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.

7. A laminate, wherein the laminate comprises at least one prepreg of claim 6 .

8. A metal foil-clad laminate, wherein the metal foil-clad laminate comprises one or at least two laminated prepregs of claim 6 , and metal foil on one side or both sides of the laminated prepreg.

9. A high-frequency circuit board, wherein the high-frequency circuit board comprises one or at least two laminated prepregs of claim 6 .

10. The thermosetting resin composition of claim 1 , wherein A is a 9,10-dihydro-9-oxy-10-phosphaphenanthrene-10-oxide (DOPO)-containing group.

11. The thermosetting resin composition of claim 10 , wherein A is selected from the group consisting of

12. The thermosetting resin composition of claim 1 , wherein the phosphorus-containing monomer or the phosphorus-containing resin is 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:

wherein n is an integer of 1-20.

13. The thermosetting resin composition claimed in claim 4 , wherein said other thermosetting resins containing unsaturated groups are selected from the group consisting of allyl-terminated polyphenylene ether resin, acrylate-terminated polyphenylene ether resin, vinyl-terminated polyphenylene ether resin, thermosetting polybutadiene resin, a copolymer resin of thermosetting polybutadiene and styrene (styrene-butadiene resin), bismaleimide resin, cyanate resin, allylated phenolic resin, vinyl-terminated siloxane resin, and a combination of at least two selected therefrom.

14. The thermosetting resin composition claimed in claim 1 , wherein said other thermosetting resins containing unsaturated groups are thermosetting resins based on polybutadiene or a copolymer resin of polybutadiene and styrene containing 60% or more of vinyl groups, having a molecular weight of 11,000 or less and consisting of carbon and hydrogen.

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

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

17. 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.

18. The thermosetting resin composition claimed in claim 17 , wherein the co-crosslinking agent is selected from the group consisting of triallyl tripolyisocyanurate, triallyl tripolycyanurate, divinylbenzene, polyfunctional acrylate, bismaleimide, and a combination of at least two selected therefrom.

Assignees

• Shengyi Technology Co Ltd

Inventors

• Su Minshe
• Yang Zhongqiang

Classifications

• C08J5/249

  characterised by the additives used in the prepolymer mixture · CPC title

• C08J5/244

  using glass fibres · CPC title

• C08G8/36

  by etherifying · CPC title

• C08F8/40

  Introducing phosphorus atoms or phosphorus-containing groups · CPC title

• C08F287/00 Primary

  Macromolecular compounds obtained by polymerising monomers on to block polymers · CPC title