Halogen-free resin composition and prepreg and laminate prepared therefrom

• US 10,336,875 B2
• Filed: 12/02/2014
• Issued: 07/02/2019
• Est. Priority Date: 11/11/2014
• Status: Active Grant

• Current Assignee: Shengyi Technology Co., Ltd.
• Original Assignee: Shengyi Technology Co., Ltd.
• Inventors: Li, Hui, Fang, Kehong
• Primary Examiner(s): Feely, Michael J
• Application Number:
  US15/525,884
• Publication Number:
  US 20180327558A1
• Time in Patent Office: 1,673 Days
• Field of Search: None
• CPC Class Codes: B32B 15/08 of synthetic resin
• CPC Class Codes: B32B 15/092 comprising epoxy resins
• 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 2255/02 on fibrous or filamentary layer
• CPC Class Codes: B32B 2255/26 Polymeric coating
• 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 2262/101 Glass fibres
• CPC Class Codes: B32B 2264/0214 Particles made of materials belonging to B32B27/00
• CPC Class Codes: B32B 2264/0257 Polyolefin particles, e.g. polyethylene or polypropylene homopolymers or ethylene-propylene copolymers
• CPC Class Codes: B32B 2264/10 Inorganic particles
• CPC Class Codes: B32B 2264/102 Oxide or hydroxide
• CPC Class Codes: B32B 2264/104 Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
• CPC Class Codes: B32B 2307/204 Di-electric
• 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 2307/7265 Non-permeable
• CPC Class Codes: B32B 2307/732 Dimensional properties
• CPC Class Codes: B32B 2457/08 PCBs, i.e. printed circuit boards
• CPC Class Codes: B32B 27/04 : as impregnant, bonding, or embedding substance not used
• CPC Class Codes: B32B 27/12 : next to a fibrous or filamentary layer
• CPC Class Codes: B32B 27/20 : using fillers, pigments, thixotroping agents
• CPC Class Codes: B32B 27/28 : comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
• CPC Class Codes: B32B 27/285 : comprising polyethers
• CPC Class Codes: B32B 27/302 : comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
• CPC Class Codes: B32B 27/38 : comprising epoxy resins
• CPC Class Codes: B32B 5/022 : Non-woven fabric
• CPC Class Codes: B32B 5/024 : Woven fabric
• CPC Class Codes: B32B 7/04 : Interconnection of layers
• CPC Class Codes: C08J 2363/00 : Characterised by the use of epoxy resins; Derivatives of epoxy resins
• CPC Class Codes: C08J 2435/06 : Copolymers with vinyl aromatic monomers
• CPC Class Codes: C08J 2471/12 : Polyphenylene oxides
• CPC Class Codes: C08J 2479/04 : Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: C08J 5/244 : using glass fibres
• CPC Class Codes: C08J 5/249 : characterised by the additives used in the prepolymer mixture
• CPC Class Codes: C08K 3/36 : Silica
• CPC Class Codes: C08L 2201/02 : Flame or fire retardant/resistant
• CPC Class Codes: C08L 35/06 : Copolymers with vinyl aromatic monomers
• CPC Class Codes: C08L 63/00 : Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 71/12 : Polyphenylene oxides
• CPC Class Codes: H05K 1/0373 : containing additives, e.g. fillers H05K1/036 takes precedence
• CPC Class Codes: H05K 1/038 : Textiles used as reinforcing materials for organic insulating substrates H05K1/0366
• CPC Class Codes: H05K 2201/012 : Flame-retardant; Preventing of inflammation
• CPC Class Codes: H05K 2201/0209 : Inorganic, non-metallic particles
• CPC Class Codes: H05K 2201/029 : Woven fibrous reinforcement or textile textile substrates H05K1/038

Abstract

A halogen-free resin composition and a prepreg and a laminate prepared therefrom. The halogen-free resin composition comprises the following ingredients in parts by weight: 50-100 parts of an epoxy resin, 20-70 parts of benzoxazine, 5-40 parts of polyphenyl ether, 5-30 parts of styrene-maleic anhydride, 5-40 parts of a halogen-free flame retardant, 0.2-5 parts of a curing accelerator, and 20-100 parts of a filler. The prepreg and the laminate, which are manufactured from the halogen-free resin composition, have the comprehensive properties of low dielectric constant, low dielectric loss, excellent heat resistance, adhesive property and wet resistance and the like, and are suitable for being applied to halogen-free high-frequency multilayer circuit boards.

Claims

1. A resin composition free of halogen-containing flame retardants, comprising the following components in parts by weight:

50-100 parts of an epoxy resin, at least comprising an epoxy resin having the dicyclopentadiene alkyl structure as shown in the following chemical formula;

2. The resin composition of claim 1, wherein the epoxy resin further comprises an epoxy resin selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl epoxy resin, alkyl novolac epoxy resin, dicyclopentadiene epoxy resin, bisphenol A type novolac epoxy resin, o-cresol type novolac epoxy resin, phenol type novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, isocyanate modified epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy resin, and a mixture of at least two of the foregoing.

3. The resin composition of claim 1, wherein the benzoxazine is selected from the group consisting of fluorinated benzoxazine resin, aliphatic benzoxazine resin, dicyclopentadiene benzoxazine resin, and a mixture of at least two of the foregoing.

4. The resin composition claimed in claim 3, wherein the fluorinated benzoxazine resin is selected from the group of the following chemical formulae, or a mixture of at least two selected therefrom:

5. The resin composition of claim 3, wherein the aliphatic benzoxazine resin has the chemical structural formula of:

6. The resin composition of claim 3, wherein the dicyclopentadiene benzoxazine resin has the chemical structural formula of:

7. The resin composition of claim 1, wherein the benzoxazine is selected from the group consisting of fluorinated benzoxazine resin, aliphatic benzoxazine resin, and a mixture of at least two of the foregoing.

8. The resin composition of claim 1, wherein the styrene-maleic anhydride has the chemical structural formula of:

9. The resin composition of claim 1, wherein the halogen-free flame retardant is selected from the group consisting of phosphazene, ammonium polyphosphate, tri-(2-carboxyethyl)-phosphine, tri-(isopropylchloro)phosphate, trimethyl phosphate, dimethyl-methyl phosphate, resorcinol bis-xylyl phosphate, phosphorus-nitrogen compounds, melamine polyphosphate, melamine cyanurate, tri-hydroxyethyl isocyanurate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO-containing novolac resin, and a mixture of at least two of the foregoing.

10. The resin composition of claim 1, wherein the curing accelerator is an imidazole accelerator.

11. The resin composition of claim 1, wherein the curing accelerator is selected from the group consisting of 2-methylimidazole, undecyl imidazole, 2-ethyl-4-methylimidazole, 2-phenyl-imidazole, 1 cyanoethyl substituted imidazole, and a mixture of at least two of the foregoing.

12. The resin composition of claim 1, wherein the filler is an inorganic or organic filler.

13. The resin composition of claim 1, wherein the filler is an inorganic filler selected from the group consisting of aluminum hydroxide, alumina, magnesium hydroxide, magnesium oxide, aluminum oxide, silicon dioxide, calcium carbonate, aluminum nitride, boron nitride, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, talc powder, silicon nitride, calcined kaolin, and a mixture of at least two of the foregoing.

14. The resin composition of claim 1, wherein the filler is an organic filler selected from the group consisting of polytetrafluoroethylene powder, polyphenylene sulfide, polyethersulfone powder, and a mixture of at least two of the foregoing.

15. The resin composition of claim 1, wherein the filler has a particle size of 0.01-50 μ

m.

16. A prepreg prepared from the resin composition of claim 1, wherein the prepreg comprises a matrix material and the resin composition attached thereon after impregnation and drying.

17. The prepreg of claim 16, wherein the matrix material is a non-woven or woven glass fiber cloth.

18. A laminate comprising the prepreg of claim 16.

19. A printed circuit board comprising the laminate of claim 18.