Halogen-free low dielectric resin composition, and prepreg, metal-clad laminate, and printed circuit board prepared using the same

Patent metadata

Field	Value
Publication number	US-11015052-B2
Application number	US-201916277069-A
Country	US
Kind code	B2
Filing date	Feb 15, 2019
Priority date	Dec 6, 2018
Publication date	May 25, 2021
Grant date	May 25, 2021

Abstract

A halogen-free low dielectric resin composition is provided. The halogen-free low dielectric resin composition comprises:
(A) a resin system, which includes:
(a1) a polyphenylene ether resin with unsaturated functional groups, and (a2) a polyfunctional vinyl aromatic copolymer; and
(B) an allyl cyclophosphazene compound represented by the following formula (I):

in formula (I), t is an integer ranging from 2 to 6,

wherein, the polyfunctional vinyl aromatic copolymer (a2) is prepared by copolymerizing one or more divinyl aromatic compounds and one or more monovinyl aromatic compounds.

First claim

What is claimed is:

1. A halogen-free low dielectric resin composition, comprising:
(A) a resin system, which includes:
(a1) a polyphenylene ether resin with unsaturated functional groups; and
(a2) a polyfunctional vinyl aromatic copolymer; and

(B) an allyl cyclophosphazene compound represented by the following formula (I):

in formula (I), t is an integer ranging from 2 to 6,

wherein, the polyfunctional vinyl aromatic copolymer (a2) is prepared by copolymerizing one or more divinyl aromatic compounds and one or more monovinyl aromatic compounds,
wherein the polyfunctional vinyl aromatic copolymer (a2) comprises the following structural units:

wherein, R 1 and R 2 are independently a C6-C12 aromatic hydrocarbyl, R 3 is H or a C1-C12 hydrocarbyl, and
wherein the weight ratio of the polyphenylene ether resin (a1) with unsaturated functional groups to the polyfunctional vinyl aromatic copolymer (a2) is 9:1 to 3:7, and wherein the allyl cyclophosphazene compound (B) is in an amount ranging from 5 parts by weight to 60 parts by weight based on 100 parts by weight of the resin system (A).

2. The resin composition of claim 1 , wherein the polyphenylene ether resin (a1) with unsaturated functional groups comprises one or more polyphenylene ether resins represented by the following formula (II):

in formula (II),
R 31 , R 32 , R 33 and R 34 are independently H, or a substituted or unsubstituted C1-C5 alkyl; m and n are independently an integer from 0 to 100, with the proviso that m and n are not 0 at the same time;
X and Y are independently absent, or carbonyl or an alkenyl-containing group;

A 1 and A 2 are independently and

Z is absent, —O—, or aryl, wherein R 35 and R 36 are independently H or a C1-C12 alkyl.

3. The resin composition of claim 2 , wherein the polyphenylene ether resin (a1) with unsaturated functional groups comprises at least two polyphenylene ether resins represented by formula (II), wherein A 1 and A 2 are independently

Z is aryl or

X and Y are absent; R 31 , R 32 , R 33 and R 34 are methyl; and 20<(m+n)<25.

4. The resin composition of claim 1 , wherein the divinyl aromatic compound is slected from the group consisting of divinylbenzene, divinylnaphthalene, divinylbiphenyl and isomers thereof.

5. The resin composition of claim 1 , wherein the monovinyl aromatic compound is slected from the group consisting of a nuclear-alkyl-substituted vinyl aromatic compound, α-alkyl-substituted vinyl aromatic compound, (β-alkyl-substituted vinyl aromatic compound, and alkoxyl-substituted vinyl aromatic compound.

6. The resin composition of claim 1 , wherein the resin system (A) futher comprises:
(a3) an unsaturated functional group-containing crosslinking agent.

7. The resin composition of claim 6 , wherein the unsaturated functional group-containing crosslinking agent (a3) is selected from the group consisting of a polyfunctional allylic compound, a polyfunctional acrylate, a polyfunctional acrylamide, a polyfunctional styrenic compound, a bismaleimide compound, and combinations thereof.

8. The resin composition of claim 6 , wherein the unsaturated functional group-containing crosslinking agent (a3) is in an amount ranging from 1 part by weight to 20 parts by weight based on 100 parts by weight of the resin system (A).

9. The resin composition of claim 7 , wherein the unsaturated functional group-containing crosslinking agent (a3) is in an amount ranging from 1 part by weight to 20 parts by weight based on 100 parts by weight of the resin system (A).

10. The resin composition of claim 1 , wherein the allyl cyclophosphazene compound (B) is represented by the following formula (I-1):

11. The resin composition of claim 1 , further comprising a filler selected from the group consisting of silica, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, clay, aluminum nitride, boron nitride, silicon nitride, silicon aluminum carbide, silicon carbide, sodium carbonate, magnesium carbonate, titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond powder, diamond-like powder, graphite, graphene, potassium titanate, strontium titanate, barium titanate, ceramic fiber, zinc molybdate, ammonium molybdate, zinc borate, calcium phosphate, calcined kaolin, pryan, mica, boehmite, hydrotalcite, carbon nanotube, polytetrafluoroethylene (PTFE) powder, hollow glass bead, nanosized inorganic powder, and combinations thereof.

12. A prepreg, which is prepared by impregnating a substrate with the resin composition of claim 1 or by coating said resin composition onto a substrate and drying the impregnated or coated substrate.

13. A metal-clad laminate, which is prepared by laminating the prepreg of claim 12 and a metal foil.

14. A printed circuit board, which is prepared from the metal-clad laminate of claim 13 .

15. A metal-clad laminate, which is prepared by coating the resin composition of claim 1 onto a metal foil and drying the coated metal foil.

16. A printed circuit board, which is prepared from the metal-clad laminate of claim 15 .

Assignees

• Taiwan Union Technology Corp

Inventors

• Liu Shur-Fen
• Hung Chin-Hsien

Classifications

• C08J5/249

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

• C08J5/244

  using glass fibres · CPC title

• B32B2262/101

  Glass fibres · CPC title

• B32B2260/021

  Fibrous or filamentary layer · CPC title

• C08L47/00

  Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers (C08L45/00 takes precedence; of conjugated diene rubbers C08L9/00 - C08L21/00) · CPC title