Halogen-free epoxy resin composition, prepreg, laminate and printed circuit board containing the same

• US 10,513,605 B2
• Filed: 09/14/2016
• Issued: 12/24/2019
• Est. Priority Date: 12/04/2015
• Status: Active Grant

• Current Assignee: Shengyi Technology Co., Ltd.
• Original Assignee: Shengyi Technology Co., Ltd.
• Inventors: Li, Hui, Fang, Kehong, Xu, Yongjing
• Primary Examiner(s): Brooks, Kregg T
• Application Number:
  US15/316,880
• Publication Number:
  US 20170283610A1
• Time in Patent Office: 1,196 Days
• 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 17/04 bonded with or embedded in a plastic substance
• CPC Class Codes: B32B 2250/05 5 or more layers
• CPC Class Codes: B32B 2255/02 on fibrous or filamentary layer
• CPC Class Codes: B32B 2255/10 on synthetic resin layer or on natural or synthetic rubber layer
• CPC Class Codes: B32B 2255/205 Metallic coating
• CPC Class Codes: B32B 2260/023 Two or more layers
• 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 2264/107 Ceramic
• CPC Class Codes: B32B 2264/12 Mixture of at least two particles made of different materials
• CPC Class Codes: B32B 2270/00 Resin or rubber layer containing a blend of at least two different polymers
• CPC Class Codes: B32B 2307/20 having particular electrical or magnetic properties, e.g. piezoelectric
• CPC Class Codes: B32B 2307/204 : Di-electric
• CPC Class Codes: B32B 2307/21 : Anti-static
• CPC Class Codes: B32B 2307/302 : Conductive
• 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 2307/308 : Heat stability dimensional stability B32B2307/734
• CPC Class Codes: B32B 2307/402 : Coloured
• CPC Class Codes: B32B 2307/724 : Permeability to gases, adsorption
• CPC Class Codes: B32B 2307/732 : Dimensional properties
• CPC Class Codes: B32B 2307/748 : Releasability
• CPC Class Codes: B32B 2457/08 : PCBs, i.e. printed circuit boards
• CPC Class Codes: B32B 27/18 : characterised by the use of special additives
• CPC Class Codes: B32B 27/20 : using fillers, pigments, thixotroping agents
• CPC Class Codes: B32B 27/26 : using curing 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 27/302 : comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
• CPC Class Codes: B32B 27/325 : comprising polycycloolefins
• CPC Class Codes: B32B 27/38 : comprising epoxy resins
• CPC Class Codes: B32B 27/42 : comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
• CPC Class Codes: B32B 5/022 : Non-woven fabric
• CPC Class Codes: B32B 5/024 : Woven fabric
• 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: B32B 7/04 : Interconnection of layers
• CPC Class Codes: C07D 233/00 : Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
• CPC Class Codes: C07D 265/36 : condensed with one six-membered ring
• CPC Class Codes: C08F 214/28 : Hexyfluoropropene
• CPC Class Codes: C08G 14/06 : and monomers containing hydrogen attached to nitrogen
• CPC Class Codes: C08G 59/40 : characterised by the curing agents used
• CPC Class Codes: C08G 59/4014 : Nitrogen containing compounds
• CPC Class Codes: C08G 59/42 : Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• CPC Class Codes: C08G 59/4223 : aromatic
• 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 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: C08K 5/0066 : Flame-proofing or flame-retarding additives
• CPC Class Codes: C08K 5/49 : Phosphorus-containing compounds C08K5/0091 takes precedence
• CPC Class Codes: C08K 5/51 : Phosphorus bound to oxygen
• CPC Class Codes: C08K 5/5399 : Phosphorus bound to nitrogen
• CPC Class Codes: C08L 35/06 : Copolymers with vinyl aromatic monomers
• CPC Class Codes: C08L 61/34 : Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
• CPC Class Codes: C08L 63/00 : Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 63/10 : Epoxy resins modified by unsaturated compounds
• CPC Class Codes: C08L 79/04 : Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: H05K 1/03 : Use of materials for the substrate
• CPC Class Codes: H05K 1/0313 : Organic insulating material
• CPC Class Codes: H05K 1/0353 : consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
• CPC Class Codes: H05K 1/05 : Insulated conductive substrates, e.g. insulated metal substrate

Abstract

The present invention relates to a halogen-free epoxy resin composition, a prepreg and a laminate containing the same. The halogen-free epoxy resin composition comprises 60 parts by weight of epoxy resin, from 15 to 28 parts by weight of benzoxazine resin, and from 10 to 20 parts by weight of styrene-maleic anhydride. The present invention discloses using from 15 to 28 parts by weight of benzoxazine resin and from 10 to 20 parts by weight of styrene-maleic anhydride to cure 60 parts by weight of epoxy resin, to ensure the Df stability of prepregs at different curing temperature conditions while maintaining low dielectric constant and low dielectric loss. The prepregs and laminates prepared from the resin composition have comprehensive performances, such as low dielectric constant, low dielectric loss, excellent flame retardancy, heat resistance, cohesiveness, low water absorption and moisture resistance, and are suitable for use in halogen-free multilayer circuit boards.

Claims

1. A halogen-free epoxy resin composition, comprising 60 parts by weight of epoxy resin, from 20 to 25 parts by weight of benzoxazine resin, and from 15 to 18 parts by weight of styrene-maleic anhydride,

wherein the epoxy resin is any one selected from the group consisting of biphenyl epoxy resin, and dicyclopentadiene epoxy resin,

wherein the benzoxazine resin is any one selected from the benzoxazine resins having the following structures:

2. The halogen-free epoxy resin composition claimed in claim 1, wherein the halogen-free epoxy resin composition further comprises a halogen-free flame retardant selected from the group consisting of ammonium polyphosphate, tri(2-carboxyethyl)phosphine, tri(isopropylchloro)phosphate, trimethyl phosphate, dimethyl-methyl phosphate, resorcinol bis-xylyl phosphate, melamine polyphosphate, melamine cyanurate and tri-hydroxyethyl isocyanurate, or a combination of at least two selected therefrom.

3. The halogen-free epoxy resin composition claimed in claim 1, wherein the halogen-free epoxy resin composition further comprises from 20 to 100 parts by weight of a filler.

4. The halogen-free epoxy resin composition claimed in claim 3, wherein the filler is an organic or/and inorganic filler.

5. The halogen-free epoxy resin composition claimed in claim 4, wherein the inorganic filler is any one selected from the group consisting of aluminum hydroxide, alumina, magnesium hydroxide, magnesium oxide, silica calcium carbonate, aluminum nitride, boron nitride, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, talcum powder, silicon nitride and calcined kaolin, or a mixture of at least two selected therefrom, and the organic filler is any one selected from the group consisting of polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder, or a mixture of at least two selected therefrom.

6. The halogen-free epoxy resin composition claimed in claim 3, wherein the filler has a particle size of from 0.01 to 50 μ

m.

7. The halogen-free epoxy resin composition claimed in claim 1, wherein the halogen-free epoxy resin composition comprises a curing accelerator which is any one selected from imidazole accelerators.

8. The halogen-free epoxy resin composition claimed in claim 7, wherein the curing accelerator is any one selected from the group consisting of 2-methyl imidazole, undecyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole and 1-cyanoethyl-substituted imidazole, or a combination of at least two selected therefrom.

9. A prepreg comprising a reinforcing material and the halogen-free epoxy resin composition in claim 1 attached thereon after impregnation and drying.

10. A laminate, comprising at least one overlapped prepreg claimed in claim 9.

11. A printed circuit board, comprising at least one overlapped prepreg claimed in claim 9.