Method for improving flame retardant efficiency of phenoxyphosphazene compound, and prepreg. laminate for printed circuit made by the method

• US 8,518,527 B2
• Filed: 08/29/2010
• Issued: 08/27/2013
• Est. Priority Date: 09/04/2009
• Status: Active Grant

• Current Assignee: Guangdong Shengyi SCI Tech Company Limited
• Original Assignee: Guangdong Shengyi SCI Tech Company Limited
• Inventors: He, Yueshan, Cheng, Tao, Su, Shiguo, Wang, Biwu, Li, Jie
• Primary Examiner(s): ZACHARIA, RAMSEY E
• Application Number:
  US12/870,830
• Publication Number:
  US 20110059324A1
• Time in Patent Office: 1,094 Days
• Field of Search: None
• US Class Current: 428/301.4
• CPC Class Codes: B32B 15/14 next to a fibrous or filamentary layer
• CPC Class Codes: B32B 15/20 comprising aluminium or copper B32B15/016 and B32B15/017 take precedence
• CPC Class Codes: B32B 2260/021 Fibrous or filamentary layer layers of natural mineral fibres or particles being impregnated in a plastic substance B32B19/02
• CPC Class Codes: B32B 2260/046 Synthetic resin
• CPC Class Codes: B32B 2262/02 Synthetic macromolecular fibres
• CPC Class Codes: B32B 2262/06 Vegetal fibres
• CPC Class Codes: B32B 2262/08 Animal fibres, e.g. hair, wool, silk
• CPC Class Codes: B32B 2262/10 Inorganic fibres layered products comprising a layer of natural mineral fibres B32B19/00
• CPC Class Codes: B32B 2307/20 having particular electrical or magnetic properties, e.g. piezoelectric
• CPC Class Codes: B32B 2307/306 Resistant to heat
• CPC Class Codes: B32B 2307/3065 Flame resistant or retardant, fire resistant or retardant
• CPC Class Codes: B32B 2307/50 having particular mechanical properties
• CPC Class Codes: B32B 2307/546 Flexural strength; Flexion stiffness
• CPC Class Codes: B32B 2307/714 Inert, i.e. inert to chemical degradation, corrosion
• CPC Class Codes: B32B 2307/7246 Water vapor barrier
• CPC Class Codes: B32B 2307/7265 Non-permeable
• CPC Class Codes: B32B 2457/08 PCBs, i.e. printed circuit boards
• CPC Class Codes: B32B 5/022 Non-woven fabric
• CPC Class Codes: B32B 5/22 characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed layer formed of natural mineral fibres or particles next to a foam layer B32B19/047, next to a layer made of particles B32B19/048, or next to a fibrous or filamentary layer B32B19/06; paper layer or cardboard layer next to a paper layer or cardboard layer B32B29/005, next to a foam layer B32B29/007, next to a fibrous or filamentary layer B32B29/02, or next to a particulate layer B32B29/04
• CPC Class Codes: B32B 5/26 another layer next to it also being fibrous or filamentary relative arrangement of fibres or filaments of different layers B32B5/12
• CPC Class Codes: C08K 5/357 : Six-membered rings
• CPC Class Codes: C08K 5/5399 : Phosphorus bound to nitrogen
• CPC Class Codes: C08L 2203/20 : use in electrical or conductive gadgets
• CPC Class Codes: C08L 2666/14 : Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 63/00 : Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 85/02 : containing phosphorus
• CPC Class Codes: Y10T 428/249952 : At least one thermosetting synthetic polymeric material layer
• CPC Class Codes: Y10T 428/31511 : Of epoxy ether
• CPC Class Codes: Y10T 428/31529 : Next to metal
• CPC Class Codes: Y10T 428/31678 : Of metal

Abstract

The present invention provides a method for improving the flame retardant efficiency of a phenoxyphosphazene compound, and provides a prepreg, a laminate, and a laminate for printed circuit that are made by the method. The present invention compounds a phenoxyphosphazene compound and a dihydrobenzoxazine ring-containing compound in a halogen-free flame retardant resin composition, so as to effectively improve the flame-retardant efficiency of the phenoxyphosphazene compound. Besides, the prepreg, the laminate and the laminate for printed circuit that are made by the method for improving the flame retardant efficiency of a phenoxyphosphazene compound have excellent flame retardancy, chemical resistance, anti-CAF property, high glass transition temperature (Tg), high thermal resistance, low dielectric dissipation factor, low moisture, and low C.T.E, etc. Furthermore, epoxy resins are interfused to greatly overcome the brittleness of the benzoxazine resin, so, the cured resin has comparatively high flexural strength and good processability.

Claims

1. A method for improving the flame retardant efficiency of a phenoxyphosphazene compound, comprising the following steps:

compounding a dihydrobenzoxazine ring-containing compound and the phenoxyphosphazene compound in a halogen-free flame retardant resin composition, wherein, the weight ratio between the phenoxyphosphazene compound and the dihydrobenzoxazine ring-containing compound is between 1;

10 and 1;

2, wherein the softening point of the phenoxyphosphazene compound is between 60°

C. and 150°

C.;

the phenoxyphosphazene compound is a mixture of the cyclophenoxyphosphazene compounds shown with the structural formula (α

) and the linear phenoxyphosphazene compounds shown with the structural formula (β

), and the components comprise the following;

hexaphenoxycyclotriphosphazene compound, wherein m=3, of which the weight ratio is between 70% and 90%;

octaphenoxycyclotetraphosphazene compound, wherein m=4, of which the weight ratio is between 3% and 20%; and

other cyclophenoxyphosphazene compounds, wherein m≧

5, and the linear phenoxyphosphazene compounds, of which the weight ratio are between 1% and 10%;

2. The method for improving the flame retardant efficiency of a phenoxyphosphazene compound of claim 1, wherein the dihydrobenzoxazine ring-containing compound comprises at least one of the bisphenol-A benzoxazine resin, bisphenol-F benzoxazine resin, phenolphthalein benzoxazine resin, and MDA (4,4′

-Methylenedianiline) benzoxazine resin shown with the structural formula (γ

) or (δ

) relatively;

3. The method for improving the flame retardant efficiency of a phenoxyphosphazene compound of claim 1, wherein the halogen-free flame retardant resin composition further comprises a polyepoxy compound, a phenolic resin type hardener, and an imidazole type curing accelerator.

4. The method for improving the flame retardant efficiency of a phenoxyphosphazene compound of claim 3, wherein, calculating according to the parts by weight of organic solids, the halogen-free flame retardant resin composition comprises the following components:

40-80 parts by weight of the mixture of the phenoxyphosphazene compound and the dihydrobenzoxazine ring-containing compound, and, the weight ratio between the phenoxyphosphazene compound and the dihydrobenzoxazine ring-containing compound being between 1;

10 and 1;

2;

15-45 parts by weight of a polyepoxy compound;

5-25 parts by weight of a phenolic resin type hardener;

0.1-1 parts by weight of an imidazole type curing accelerator.

5. The method for improving the flame retardant efficiency of a phenoxyphosphazene compound of claim 4, wherein the polyepoxy compound is at least one selected from bisphenol-A epoxy resin, bisphenol-F epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol-A novolac epoxy resin, oxazolidone ring-containing halogen-free epoxy resin, and epoxide polybutadiene;

the phenolic resin type hardener is at least one selected from phenol novolac resin, bisphenol-A novolac resin, nitrogen-containing novolac resin, and phosphorus-containing novolac resin;

the imidazole type compound is at least one selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-undecylimidazole.

6. The method for improving the flame retardant efficiency of a phenoxyphosphazene compound of claim 4, wherein the halogen-free flame retardant resin composition further comprises 6-300 parts by weight of an inorganic filler;

the inorganic filler is one of (a) a mixture of aluminium hydroxide with other inorganic fillers, (b) a mixture of silica with other inorganic fillers and (c) a mixture of both aluminium hydroxide and silica with other inorganic fillers.

7. A prepreg made by the method for improving the flame-retardant efficiency of a phenoxyphosphazene compound of claim 1, comprising a base material and a halogen-free flame retardant resin composition, the halogen-free flame retardant resin composition adhering to the base material after the base material being impregnated in the resin composition and then being dried.

8. A laminate made by the method for improving the flame-retardant efficiency of a phenoxyphosphazene compound of claim 1, comprising a plurality of prepregs mutually overlapped;

each prepreg including a base material and a halogen-free flame retardant resin composition, the halogen-free flame retardant resin composition adhering to the base material after the base material being impregnated in the resin composition and then being dried.

9. A laminate for printed circuit made by the method for improving the flame-retardant efficiency of a phenoxyphosphazene compound of claim 1, comprising a plurality of prepregs mutually overlapped and a metal foil arranged to one or two surfaces of the overlapped prepregs;

each prepreg including a base material and a halogen-free flame retardant resin composition, the halogen-free flame retardant resin composition adhering to the base material after the base material being impregnated in the resin composition and then being dried.