Halogen-free flame retardant resin composition and the use thereof

Patent metadata

Field	Value
Publication number	US-9745464-B2
Application number	US-201314652065-A
Country	US
Kind code	B2
Filing date	Feb 7, 2013
Priority date	Dec 13, 2012
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

The present invention relates to a halogen-free flame retardant resin composition, according to parts by weight, the resin composition comprises: (A) a mixture of phenoxyphosphazene compound (A1) and compound (A2) having a dihydrobenzoxazine ring, the mixture comprising 45-90 parts by weight, and the weight ratio of the phenoxyphosphazene compound (A1) and the compound (A2) having a dihydrobenzoxazine ring is between 1:25-1:2; (B) an epoxy resin with epoxy equivalent of 500-2000, the epoxy resin comprising 10-45 parts by weight; (C) a phenolic resin comprising 10-25 parts by weight; and (D) an amine curing agent comprising 0.5-10 parts by weight. The prepreg, laminate, and metal-clad laminate for the printed circuit prepared using the halogen-free flame retardant resin composition, have the advantages of high glass transition temperature (T g ), high thermal resistance, low dielectric dissipation factor, low water absorption as well as a low C.T.E.

First claim

What is claimed is:

1. A halogen-free flame retardant resin composition, according to parts by weight, the resin composition comprising:
(A) a mixture of phenoxyphosphazene compound (A1) and compound (A2) having dihydrobenzoxazine ring, the mixture comprising 45-90 parts by weight, and the weight ratio of the phenoxyphosphazene compound (A1) and the compound (A2) having dihydrobenzoxazine ring is 1:25-1:12;
(B) an epoxy resin with epoxy equivalent of 500-2000, the epoxy resin comprising 10-45 parts by weight;
(C) a phenolic resin, the phenolic resin comprising 10-25 parts by weight; and
(D) an amine curing agent, the curing agent comprising 0.5-10 parts by weight.

2. The halogen-free flame retardant resin composition of claim 1 , according to parts by weight, the resin composition comprising:
(A) a mixture of phenoxyphosphazene compound (A1) and compound (A2) having a dihydrobenzoxazine ring, the mixture comprising 50-90 parts by weight, and the weight ratio of the phenoxyphosphazene compound (A1) and the compound(A2) having a dihydrobenzoxazine ring is 1:20-1:12;
(B) an epoxy resin with epoxy equivalent of 500-2000, the epoxy resin comprising 10-40 parts by weight;
(C) a phenolic resin, the phenolic resin comprising 15-25 parts by weight; and
(D) an amine curing agent, the curing agent comprising 1-8 parts by weight.

3. The halogen-free flame retardant resin composition of claim 2 , according to parts by weight, the halogen-free resin composition comprising:
(A) a mixture of phenoxyphosphazene compound (A1) and compound (A2) having a dihydrobenzoxazine ring, the mixture comprising 60-90 parts by weight, and the weight ratio of the phenoxyphosphazene compound (A1) and the compound (A2) having a dihydrobenzoxazine ring is 1:15-1:12 1:15 1:5;
(B) an epoxy resin with epoxy equivalent of 500-2000, the epoxy resin comprising 10-35 parts by weight;
(C) a phenolic resin, the phenolic resin comprising 15-25 parts by weight, and
(D) an amine curing agent, the curing agent comprising 2-7 parts by weight.

4. The halogen-free flame retardant resin composition of claim 1 , wherein the softening point of the phenoxyphosphazene compound (A1) is 60-150° C., which is selected from a mixture of cyclic phenoxyphosphazene compound shown in structural formula (α) and chain-like phenoxyphosphazene compound shown in structural formula (β):

wherein m is an integer of 3-25; and

wherein X is —N═P(OC 6 H 5 ) 3 or —N—P(O)C 6 H 5 , Y is —P(OC 6 H 5 ) 4 or —P(O)(C 6 H 5 ) 2 ; and n is an integer of 3-100.

5. The halogen-free flame retardant resin composition of claim 4 , wherein the softening point of the phenoxyphosphazene compound (A1) is 60-150° C., which is selected from a mixture of cyclic phenoxyphosphazene compound shown in structural formula (α) and chain-like phenoxyphosphazene compound shown in structural formula (β), the specific composition is as follows:
{circle around (1)} the weight percentage of hexaphenoxycyclotriphosphazene compound is 70-90%;
{circle around (2)} the weight percentage of octaphenoxycyclotetraphosphazene compound is 3-20%;
{circle around (3)} the weight percentage of cyclic phenoxyphosphazene compound with m≧5 and chain-like phenoxyphosphazene compound is 1-10%; and
the weight percentages above take the sum of {circle around (1)}, {circle around (2)} and {circle around (3)} as a benchmark; and

wherein m is an integer of 3-25;

wherein X is —N—P(OC 6 H 5 ) 3 or —N═P(O)C 6 H 5 ; Y is —P(OC 6 H 5 ) 4 or —P(O)(C 6 H 5 ) 2 ; and n is an integer of 3-100.

6. The halogen-free flame retardant resin composition of claim 5 , wherein the compound (A2) having dihydrobenzoxazine ring is selected from a group consisting of bisphenol-A benzoxazine resin shown in structural formula (γ), bisphenol-F benzoxazine resin shown in structural formula (δ), phenolphthalein benzoxazine resin or 4,4′-diaminodiphenyl methane-type benzoxazine resin, or a combination of two or more thereof; and

wherein R is any one of —C(CH 3 ) 2 —, —CH 2 —, or

and
R 1 is

7. The halogen-free flame retardant resin composition of claim 1 wherein the epoxy resin is selected from a group consisting of bisphenol-A epoxy resin with epoxy equivalent of 500-1500, a carboxylated nitrile rubber-modified epoxy resin with epoxy equivalent of 700-2000, an oxazolidone ring containing halogen-free epoxy resin with epoxy equivalent of 600-1600, or a combination of two or more thereof.

8. The halogen-free flame retardant resin composition of claim 1 , wherein the phenolic resin is selected from a group consisting of a phenol novolac resin, a bisphenol-A novolac resin, a nitrogen-containing novolac resin, a phosphorus-containing novolac resin, or a combination of two or more thereof.

9. The halogen-free flame retardant resin composition of claim 1 , wherein the amine curing agent is an aromatic amine curing agent, selected from the group consisting of diaminodiphenyl ether, diaminodiphenyl sulfone, diaminodiphenyl methane, m-xylylenediamine and benzidine, or a combination of two or more thereof.

10. The halogen-free flame retardant resin composition of claim 1 , wherein the resin composition further comprises a curing accelerator.

11. The halogen-free flame retardant resin composition of claim 10 , wherein the curing accelerator is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, or a combination of two or more thereof.

12. The halogen-free flame retardant resin composition of claim 11 , wherein the amount of the curing accelerator is 0.01-1 parts by weight.

13. The halogen-free flame retardant resin composition of claim 11 , wherein the resin composition also comprises an inorganic filler, selected from a group consisting of aluminum hydroxide, Bohm stone, silica, talc, mica, barium sulfate, lithopone, calcium carbonate, wollastonite, kaolin, brucite, diatomite, bentonite or pumice, or a mixture of at least two thereof, preferred to be any one of aluminum hydroxide, Bohm stone, silica, talc or mica, or a combination of two or more thereof.

14. The halogen-free flame retardant resin composition of claim 13 , wherein the amount of the inorganic filler is 6-300 parts by weight.

15. The halogen-free flame retardant resin composition of claim 1 , wherein the phosphorus content of the halogen-free flame retardant resin composition is 0.5-3 wt %, the nitrogen content is 1-10 wt %, and the halogen content is less than 0.09 wt %.

16. A prepreg comprising a base material and the halogen-free flame retardant resin composition of claim 1 , wherein the halogen-free flame retardant resin composition is attached on the base material after impregnation and drying.

17. A laminate comprising at least one prepreg of claim 16 .

18. The halogen-free flame retardant resin compo

Assignees

• Shengyi Technology Co Ltd

Inventors

• He Yueshan
• Su Shiguo

Classifications

• C08L61/06

  of aldehydes with phenols · CPC title

• C08J2361/06

  of aldehydes with phenols · CPC title

• H05K2201/0209

  Inorganic, non-metallic particles · CPC title

• C08J2363/00

  Characterised by the use of epoxy resins; Derivatives of epoxy resins · CPC title

• B32B2260/025

  Particulate layer · CPC title