Halogen-free resin composition, and prepreg and laminate for printed circuits using the same

Patent metadata

Field	Value
Publication number	US-9493651-B2
Application number	US-201414563398-A
Country	US
Kind code	B2
Filing date	Dec 8, 2014
Priority date	Jul 22, 2014
Publication date	Nov 15, 2016
Grant date	Nov 15, 2016

Abstract

Halogen-free resin composition, prepreg, and laminate for printed circuits using same. Based on 100 parts by weight of organic solid matter, the resin composition comprises: (A) bisphenol-type epoxy resin: 30˜60 parts by weight; (B) benzoxazine resin: 5˜45 parts by weight; (C) alkyl phenol novolac hardener: 10˜30 parts by weight; (D) phosphorus-containing flame retardant. The bisphenol-type epoxy resin, with numerous alkyl branched chains and benzene rings in its structure, makes the composition possess high glass transition temperature, low water absorption, good thermal resistance, and excellent dielectric properties. Taking the alkyl phenol novolac as the hardener can sufficiently exert the advantages of excellent dielectric properties and low water absorption resulted from containing numerous alkyls. The prepreg and laminate for printed circuits made from halogen-free resin composition have high glass transition temperature, low dielectric constant, low dielectric dissipation factor, low water absorption, high thermal resistance, and good flame retardancy, processability and chemical resistance.

First claim

The invention claimed is:

1. A halogen-free resin composition, based on 100 parts by weight of the organic solid matter, comprising:
(A) bisphenol-type epoxy resin: 30˜60 parts by weight, wherein the bisphenol-type epoxy resin comprises at least two epoxy resins of formula (a), formula (b) or formula (c):

wherein, n 1 , n 2 and n 3 are any independent integer between 2-20;
(B) benzoxazine resin: 5˜45 parts by weight;
(C) alkyl phenol novolac hardener: 10˜30 parts by weight;
(D) phosphorus-containing flame retardant,
wherein the benzoxazine resin (B) is any one selected from bisphenol-A benzoxazine of formula (I), bisphenol-A benzoxazine of formula (II), bisphenol-F benzoxazine, 4,4′-methylenedianiline benzoxazine, phenolphthalein-type benzoxazine or dicyclopentadiene-benzoxazine, or a mixture of at least two;

wherein R 1 of formula (I) is any one selected from

 and R 2 is independently

wherein the alkyl phenol novolac hardener (C) has the following structure:

wherein R 3 , R 4 and R 5 are substituted or unsubstituted straight chain alkyl or branched alkyl with 4˜8 carbon atoms independently and n 4 is an integer between 2˜20.

2. The halogen-free resin composition according to claim 1 , wherein, based on 100 parts by weight of the total additive amounts of component (A), component (B), and component (C), the additive amount of the phosphorus-containing flame retardant (D) is 5-50 parts by weight.

3. The halogen-free resin composition according to claim 1 , wherein the phosphorus-containing flame retardant is any one of tri(2,6-dimethylphenyl)phosphine, 10-(2,5dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphino benzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate, polyphosphate, polyphosphonate or phosphonate-carbonate copolymer, or a mixture of at least two of the foregoing.

4. The halogen-free resin composition according to claim 1 , wherein the halogen-free resin composition further comprises a curing accelerator (E).

5. The halogen-free resin composition according to claim 4 , wherein the curing accelerator (E) comprises any one of imidazole compounds, imidazole compounds derivatives, piperidine compounds, Lewis acids and triphenylphosphine, or a mixture of at least two of the foregoing.

6. The halogen-free resin composition according to claim 5 , wherein the curing accelerator comprises any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, triphenylphosphine, 2-undecylimidazole, 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methyl-piperidine, 2-amino-4-methyl piperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine and 2-amino-4,4-dimethyl piperidine, or a mixture of at least two of the foregoing.

7. The halogen-free resin composition according to claim 4 , wherein, based on 100 parts by weight of the total additive amounts of component (A), component (B), component (C), and component (D), the additive amount of the curing accelerator (E) is 0.01˜1 parts by weight.

8. The halogen-free resin composition according to claim 1 , wherein the halogen-free resin composition further comprises a filler (F).

9. The halogen-free resin composition according to claim 8 , wherein the filler (F) is surface-treated inorganic filler.

10. The halogen-free resin composition according to claim 9 , wherein the surface-treated inorganic filler comprises surface-treated silica, and the surface treating agent for surface treatment is any one selected from silane coupling agent, silicone oligomer or titanate coupling agent, or a mixture of at least two of the foregoing.

11. The halogen-free resin composition according to claim 9 , wherein, based on 100 parts by weight of the surface-treated inorganic filler, the additive amount of the surface treating agent is 0.1˜5.0 parts by weight.

12. The halogen-free resin composition according to claim 8 , wherein the median particle size of the filler is 0.01˜50 μm.

13. The halogen-free resin composition according to claim 8 , wherein, based on 100 parts by weight of the total additive amounts of component (A), component (B), component (C), and component (D), the additive amount of the filler (F) is 5˜200 parts by weight.

14. A prepreg, comprising a reinforcing material and the halogen-free resin composition according to claim 1 attached thereon after impregnation and drying.

15. A laminate, comprising at least one prepreg according to claim 14 .

Assignees

• Shengyi Technology Co Ltd

Inventors

• You Jiang

Classifications

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08K5/0066

  Flame-proofing or flame-retarding additives · CPC title

• C08L63/04

  Epoxynovolacs · CPC title

• C08L2203/20

  use in electrical or conductive gadgets · CPC title

• C08L61/04

  Condensation polymers of aldehydes or ketones with phenols only · CPC title