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

• US 10,400,099 B2
• Filed: 09/08/2016
• Issued: 09/03/2019
• 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:
  US15/318,787
• Publication Number:
  US 20170298218A1
• Time in Patent Office: 1,090 Days
• CPC Class Codes: B32B 15/06 of natural rubber or synthetic rubber
• 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 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 2307/204 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 2307/4026 : within the layer by addition of a colorant, e.g. pigments, dyes
• CPC Class Codes: B32B 2307/724 : Permeability to gases, adsorption
• CPC Class Codes: B32B 2307/748 : Releasability
• CPC Class Codes: B32B 2457/08 : PCBs, i.e. printed circuit boards
• CPC Class Codes: B32B 25/02 : with fibres or particles being present as additives in the layer
• CPC Class Codes: B32B 25/042 : of natural rubber or synthetic rubber
• CPC Class Codes: B32B 27/08 : of synthetic resin
• 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 27/281 : comprising polyimides
• 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 27/32 : comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/325 : comprising polycycloolefins
• CPC Class Codes: B32B 27/34 : comprising polyamides
• CPC Class Codes: B32B 27/36 : comprising polyesters
• 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: 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 59/42 : Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
• CPC Class Codes: C08G 59/4238 : heterocyclic
• CPC Class Codes: C08G 59/4284 : together with other curing agents
• CPC Class Codes: C08G 59/5046 : heterocyclic
• CPC Class Codes: C08G 59/621 : Phenols
• CPC Class Codes: C08G 73/0233 : Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
• CPC Class Codes: C08G 73/06 : Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
• CPC Class Codes: C08J 2363/00 : Characterised by the use of epoxy resins; Derivatives of epoxy resins
• CPC Class Codes: C08J 2363/02 : Polyglycidyl ethers of bis-phenols
• CPC Class Codes: C08J 2363/08 : Epoxidised polymerised polyenes
• CPC Class Codes: C08J 5/043 : with glass fibres
• 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 13/02 : Organic and inorganic ingredients
• CPC Class Codes: C08K 3/01 : characterized by their specific function
• CPC Class Codes: C08K 5/0025 : Crosslinking or vulcanising agents; including accelerators
• CPC Class Codes: C08L 2201/02 : Flame or fire retardant/resistant
• CPC Class Codes: C08L 2201/22 : Halogen free composition
• CPC Class Codes: C08L 2203/20 : use in electrical or conductive gadgets
• CPC Class Codes: C08L 2205/02 : containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2205/05 : containing polymer components which can react with one another
• 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 63/08 : Epoxidised polymerised polyenes
• 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: H01B 3/40 : epoxy resins
• CPC Class Codes: H05K 1/0326 : containing O
• CPC Class Codes: H05K 1/0346 : containing N
• CPC Class Codes: H05K 1/0366 : reinforced, e.g. by fibres, fabrics H05K1/036 takes precedence
• CPC Class Codes: H05K 1/0373 : containing additives, e.g. fillers H05K1/036 takes precedence
• 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 2201/0212 : Resin particles
• CPC Class Codes: H05K 2201/0242 : Shape of an individual particle

Abstract

The present invention relates to a halogen-free epoxy resin composition, a prepreg, a laminate and a printed circuit board containing the same. The halogen-free epoxy resin composition comprises an epoxy resin and a curing agent. Taking the total equivalent amount of the epoxy groups in the epoxy resin as 1, the active groups in the curing agent which react with the epoxy groups have an equivalent amount of 0.5-0.95. By controlling the equivalent ratio of the epoxy groups in the epoxy resin to the active groups in the curing agent to be 0.5-0.95, the present invention ensures the Df value stability of prepregs under different curing temperature conditions while maintaining a low dielectric constant and a 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 consisting of an epoxy resin, a curing agent, a halogen-free flame retardant, a filler, a curing accelerator which is selected from imidazole accelerators and a solvent,

wherein taking the total equivalent amount of the epoxy groups in the epoxy resin as 1, the active groups in the curing agent which react with the epoxy groups have an equivalent amount of 0.7-0.85, the curing agent is styrene-maleic anhydride and benzoxazine resin, where taking the total equivalent amount of the epoxy groups in the epoxy resin as 1, the benzoxazine resin has an equivalent amount of 0.4-0.5, and the styrene-maleic anhydride has an equivalent amount of 0.3-0.35,

wherein the epoxy resin is biphenyl epoxy resin or dicyclopentadiene epoxy resin.

3. The halogen-free epoxy resin composition claimed in claim 1, wherein the halogen-free epoxy resin composition comprises one or more selected from the group consisting of polyphenyl ether resin, cyanate ester resin, bismaleimide, active ester, styrene resin, butadiene resin, phenoxy resin, rubber resin, nuclear shell resin, polyamide and polyimide.

4. The halogen-free epoxy resin composition claimed in claim 1, wherein the halogen-free flame retardant is anyone selected from the group consisting of phosphorus-containing novolac, phosphorus-nitrogen based compound, 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.

5. The halogen-free epoxy resin composition claimed in claim 4, wherein the phosphorus-containing novolac is anyone selected from the group consisting of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-modified novolac resin, 10-(2,5-dihydroxylphenyl)9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-modified novolac resin, 10-(2,9-dihydroxylnaphthyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-modified novolac resin, or a mixture of at least two selected therefrom.

6. The halogen-free epoxy resin composition claimed in claim 1, wherein the halogen-free flame retardant comprises a phosphorus-containing novolac and a phosphorus-nitrogen based compound, wherein the phosphorus-containing novolac is in a weight of ⅙

-⅔

of the weight of the epoxy resin, and the phosphorus-nitrogen based compound is in a weight of ⅙

-⅚

of the weight of the epoxy resin.

7. The halogen-free epoxy resin composition claimed in claim 1, wherein the filler is an organic or/and inorganic filler.

8. The halogen-free epoxy resin composition claimed in claim 7, wherein the inorganic filler is anyone selected from the group consisting of aluminum hydroxide, alumina, magnesium hydroxide, magnesium oxide, aluminum 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 wherein the organic filler is anyone selected from the group consisting of polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder, or a mixture of at least two selected therefrom.

9. The halogen-free epoxy resin composition claimed in claim 1, wherein the filler has a particle size of from 0.01 to 50 μ

m.

10. The halogen-free epoxy resin composition claimed in claim 1, wherein the curing accelerator is anyone 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.

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

12. A laminate, comprising at least one prepreg claimed in claim 11.

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

14. The halogen-free epoxy resin composition claimed in claim 1, wherein the benzoxazine resin is anyone selected from the benzoxazine resins having the following structures, or a combination of at least two selected therefrom

2. The halogen-free epoxy resin composition claimed in 1, wherein the styrene-maleic anhydride has a number average molecular weight of 1000-50000.

15. The halogen-free epoxy resin composition claimed in 1, wherein the styrene-maleic anhydride has a structural formula of