JPH0488054A - Curable polyphenylene ether-based resin composition - Google Patents
Curable polyphenylene ether-based resin compositionInfo
- Publication number
- JPH0488054A JPH0488054A JP20248990A JP20248990A JPH0488054A JP H0488054 A JPH0488054 A JP H0488054A JP 20248990 A JP20248990 A JP 20248990A JP 20248990 A JP20248990 A JP 20248990A JP H0488054 A JPH0488054 A JP H0488054A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- composite material
- ether resin
- resin composition
- curable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 69
- 239000011342 resin composition Substances 0.000 title claims description 36
- 229920005989 resin Polymers 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000011888 foil Substances 0.000 claims abstract description 17
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 15
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 13
- 239000005062 Polybutadiene Substances 0.000 claims description 13
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 7
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000003989 dielectric material Substances 0.000 abstract description 3
- 239000011810 insulating material Substances 0.000 abstract description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 abstract 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 abstract 1
- 239000002648 laminated material Substances 0.000 abstract 1
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- -1 alkenyl halide Chemical class 0.000 description 21
- 238000001723 curing Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 14
- 239000004744 fabric Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002431 hydrogen Chemical group 0.000 description 5
- 125000003107 substituted aryl group Chemical group 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- WWUYJANHYBSHDZ-UHFFFAOYSA-N 2-methyl-6-(3-methylbut-2-enyl)phenol Chemical compound CC(C)=CCC1=CC=CC(C)=C1O WWUYJANHYBSHDZ-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005422 blasting Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 2
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- AVMHMVJVHYGDOO-NSCUHMNNSA-N (e)-1-bromobut-2-ene Chemical compound C\C=C\CBr AVMHMVJVHYGDOO-NSCUHMNNSA-N 0.000 description 1
- AVMHMVJVHYGDOO-IHWYPQMZSA-N (z)-1-bromobut-2-ene Chemical compound C\C=C/CBr AVMHMVJVHYGDOO-IHWYPQMZSA-N 0.000 description 1
- YTKRILODNOEEPX-IHWYPQMZSA-N (z)-1-chlorobut-2-ene Chemical compound C\C=C/CCl YTKRILODNOEEPX-IHWYPQMZSA-N 0.000 description 1
- LOYZVRIHVZEDMW-UHFFFAOYSA-N 1-bromo-3-methylbut-2-ene Chemical compound CC(C)=CCBr LOYZVRIHVZEDMW-UHFFFAOYSA-N 0.000 description 1
- LNNXOEHOXSYWLD-UHFFFAOYSA-N 1-bromobut-2-yne Chemical compound CC#CCBr LNNXOEHOXSYWLD-UHFFFAOYSA-N 0.000 description 1
- BKZDYWLQNSCDLY-UHFFFAOYSA-N 1-iodohex-3-yne Chemical compound CCC#CCCI BKZDYWLQNSCDLY-UHFFFAOYSA-N 0.000 description 1
- BIXFMRXHWVNDBA-UHFFFAOYSA-N 1-iodopent-2-yne Chemical compound CCC#CCI BIXFMRXHWVNDBA-UHFFFAOYSA-N 0.000 description 1
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- PTLAGVNFTMIZDI-UHFFFAOYSA-N 2,6-bis(3-phenylprop-2-enyl)phenol Chemical compound C(C=CC1=CC=CC=C1)C1=C(C(=CC=C1)CC=CC1=CC=CC=C1)O PTLAGVNFTMIZDI-UHFFFAOYSA-N 0.000 description 1
- BILVIMICBJCGQC-UHFFFAOYSA-N 2,6-dimethyl-3-phenylphenol Chemical compound CC1=C(O)C(C)=CC=C1C1=CC=CC=C1 BILVIMICBJCGQC-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WREVCRYZAWNLRZ-UHFFFAOYSA-N 2-allyl-6-methyl-phenol Chemical compound CC1=CC=CC(CC=C)=C1O WREVCRYZAWNLRZ-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- WWGJQIIRJXBTEQ-UHFFFAOYSA-N 2-but-2-enyl-6-methylphenol Chemical compound CC=CCc1cccc(C)c1O WWGJQIIRJXBTEQ-UHFFFAOYSA-N 0.000 description 1
- DIOCMSHPASIORH-UHFFFAOYSA-N 2-methyl-6-(3-phenylprop-2-enyl)phenol Chemical compound C(C=CC1=CC=CC=C1)C1=C(C(=CC=C1)C)O DIOCMSHPASIORH-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- WGCICQJXVYFFCA-UHFFFAOYSA-N 3-iodoprop-1-yne Chemical compound ICC#C WGCICQJXVYFFCA-UHFFFAOYSA-N 0.000 description 1
- DMAYBPBPEUFIHJ-UHFFFAOYSA-N 4-bromobut-1-ene Chemical compound BrCCC=C DMAYBPBPEUFIHJ-UHFFFAOYSA-N 0.000 description 1
- XLYOGWXIKVUXCL-UHFFFAOYSA-N 4-bromobut-1-yne Chemical compound BrCCC#C XLYOGWXIKVUXCL-UHFFFAOYSA-N 0.000 description 1
- UNXURIHDFUQNOC-UHFFFAOYSA-N 5-bromo-2-methylpent-2-ene Chemical compound CC(C)=CCCBr UNXURIHDFUQNOC-UHFFFAOYSA-N 0.000 description 1
- LPNANKDXVBMDKE-UHFFFAOYSA-N 5-bromopent-1-ene Chemical compound BrCCCC=C LPNANKDXVBMDKE-UHFFFAOYSA-N 0.000 description 1
- KEKBNXAJNJSILY-UHFFFAOYSA-N 5-bromopent-1-yne Chemical compound BrCCCC#C KEKBNXAJNJSILY-UHFFFAOYSA-N 0.000 description 1
- XXTLMXOGRBXMQF-UHFFFAOYSA-N 5-bromopent-2-yne Chemical compound CC#CCCBr XXTLMXOGRBXMQF-UHFFFAOYSA-N 0.000 description 1
- RIMXEJYJXDBLIE-UHFFFAOYSA-N 6-bromohex-1-ene Chemical compound BrCCCCC=C RIMXEJYJXDBLIE-UHFFFAOYSA-N 0.000 description 1
- WDNFOERVYIUQPG-UHFFFAOYSA-N 6-bromohex-1-yne Chemical compound BrCCCCC#C WDNFOERVYIUQPG-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000004830 Super Glue Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 108010021119 Trichosanthin Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- YTKRILODNOEEPX-NSCUHMNNSA-N crotyl chloride Chemical compound C\C=C\CCl YTKRILODNOEEPX-NSCUHMNNSA-N 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
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- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、硬化性ポリフェニレンエーテル系樹脂組成物
およびこれを硬化して得られる硬化体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a curable polyphenylene ether resin composition and a cured product obtained by curing the same.
さらに本発明は、該樹脂組成物と基材からなる複合材料
、その硬化体、硬化体と金属箔からなる積層体、および
硬化体と金属板からなる積層板に関する。Furthermore, the present invention relates to a composite material made of the resin composition and a base material, a cured product thereof, a laminate made of the cured product and metal foil, and a laminate made of the cured product and a metal plate.
本発明の樹脂組成物は、硬化後において優れた耐薬品性
、誘電特性、耐熱性を示し、電気産業、電子産業、宇宙
・航空機産業等の分野において誘電材料、絶縁材料、耐
熱材料等に用いることができる。特に片面、両面、多層
プリント基板、フレキシブルプリント基板、セミリジッ
ト基板、放熱特性に優れた基板等として用いることがで
きる。The resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, and heat resistance after curing, and is used for dielectric materials, insulating materials, heat-resistant materials, etc. in fields such as the electrical industry, electronic industry, space and aircraft industry, etc. be able to. In particular, it can be used as single-sided, double-sided, multilayer printed circuit boards, flexible printed circuit boards, semi-rigid circuit boards, and boards with excellent heat dissipation properties.
近年、通信用、民生用、産業用等の電子機器の分野にお
ける実装方法の小型化、高密度化への指向は著しいもの
があり、それに伴って材料の面でもより優れた耐熱性、
寸法安定性、電気特性が要求されつつある。例えばプリ
ント配線基板としては、従来からフェノール樹脂やエポ
キシ樹脂などの熱硬化性樹脂を材料とする銅張り積層板
が用いられてきた。これらは各種の性能をバランスよく
有するものの、電気特性、特に高周波領域での誘電特性
が悪いという欠点を持っている。この問題を解決する新
しい材料としてポリフェニレンエテルが近年注目をあび
銅張り積層板への応用が試みられている。In recent years, there has been a remarkable trend towards miniaturization and higher density packaging methods in the field of electronic equipment for communications, consumer use, industrial use, etc., and along with this, materials with better heat resistance,
Dimensional stability and electrical properties are increasingly required. For example, as printed wiring boards, copper-clad laminates made of thermosetting resins such as phenol resins and epoxy resins have traditionally been used. Although these have a good balance of various performances, they have the disadvantage of poor electrical properties, particularly poor dielectric properties in the high frequency range. Polyphenylene ether has recently attracted attention as a new material to solve this problem, and attempts have been made to apply it to copper-clad laminates.
ところが、ポリフェニレンエーテルは、芳香族系、ある
いはハロゲン系溶媒に対する耐薬品性が劣っている。However, polyphenylene ether has poor chemical resistance to aromatic or halogen solvents.
特公昭５９−１９３９２９号公報には、ポリフェニレン
エーテルと、ポリブタジェン樹脂との組み合わせが開示
されている。このポリブタジェン樹脂としては、１，２
−ポリブタジェン樹脂が使用され、ジクミルパーオキサ
イド等公知の開始剤を用いることによって硬化が行われ
ている。しかしながらこの硬化物の耐薬品性については
、同明細書中に何ら説明がなされていない。Japanese Patent Publication No. 59-193929 discloses a combination of polyphenylene ether and polybutadiene resin. As this polybutadiene resin, 1,2
- Polybutadiene resins are used and curing is carried out using known initiators such as dicumyl peroxide. However, the same specification does not provide any explanation regarding the chemical resistance of this cured product.
耐薬品性を改善した材料として、特開昭６２１４８５１
２号には、ポリフェニレンエーテル、架橋性ポリマおよ
び架橋性モノマ、ならびに、ラジカル発生剤を配合した
ものをラジカル架橋させるポリフェニレンエーテル固化
物の改質法が開示されている。しかしながら、この硬化
体においても耐トリクロロエチレン性の改善はなお不十
分であり、最近盤々要求特性が厳しくなっている。As a material with improved chemical resistance, JP-A-6214851
No. 2 discloses a method for modifying a solidified polyphenylene ether by radically crosslinking a mixture of polyphenylene ether, a crosslinkable polymer, a crosslinkable monomer, and a radical generator. However, even in this cured product, the improvement in trichlorethylene resistance is still insufficient, and the required properties have recently become increasingly strict.
本発明は以−１〕のような事情に鑑みてなされたもので
あり、ポリフェニレンエーテルの優れた誘電特性を損う
ことなく、かつ硬化後において優れた耐薬品性と耐熱性
を示す硬化性ポリフェニレンエーテル系樹脂組成物を提
供しようとするものである。The present invention was made in view of the following circumstances, and it provides a curable polyphenylene ether that exhibits excellent chemical resistance and heat resistance after curing without impairing the excellent dielectric properties of polyphenylene ether. The present invention aims to provide an ether-based resin composition.
本発明者らは上述のような課題を解決するため鋭意検討
を重ねた結果、本発明の目的に沿った樹脂組成物を見い
出し本発明を完成するに到った。As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a resin composition that meets the purpose of the present invention and have completed the present invention.
本発明は次に述べる７つの発明より構成される。The present invention is comprised of the following seven inventions.
すなわち本発明の第１は、 （ａ）不飽和基を含むポリ
フェニレンエーテル樹脂と くｂ）トリアリルイソシア
ヌレ−１・および／またはトリアリルシアヌレートと
（ｃ）スチレン系熱可塑性樹脂および／またはポリブタ
ジェン樹脂からなることを特徴とする硬化性ポリフェニ
レンエーテル系樹脂組成物を提供する。That is, the first aspect of the present invention is (a) a polyphenylene ether resin containing an unsaturated group, and b) triallylisocyanurate-1 and/or triallyl cyanurate.
(c) A curable polyphenylene ether resin composition is provided, which is characterized by comprising a styrene thermoplastic resin and/or a polybutadiene resin.
本発明の第２は、上記第１発明の硬化性ポリフェニレン
エーテル系樹脂組成物を硬化して得られた硬化ポリフェ
ニレンエーテル系樹脂組成物を提供する。A second aspect of the present invention provides a cured polyphenylene ether resin composition obtained by curing the curable polyphenylene ether resin composition of the first aspect.
本発明の第３は、上記第１発明の硬化性ポリフェニレン
エーテル系樹脂組成物と基材からなる硬化性複合材料を
提供する。A third aspect of the present invention provides a curable composite material comprising the curable polyphenylene ether resin composition of the first aspect and a base material.
本発明の第４は、上記第３発明の硬化性複合材料を硬化
して得られた硬化複合材料を提供する。A fourth aspect of the present invention provides a cured composite material obtained by curing the curable composite material of the third aspect.
本発明の第５は、上記第４発明の硬化複合材料と金属箔
からなる積層体を提供する。A fifth aspect of the present invention provides a laminate comprising the cured composite material of the fourth aspect and metal foil.
本発明の第６は、金属ベース上に上記第４発明の硬化複
合材料からなる絶縁層を積層した積層板を提供する。A sixth aspect of the present invention provides a laminate in which an insulating layer made of the cured composite material of the fourth aspect is laminated on a metal base.
最後に本発明の第７は、金属ベース１−の少なくとも片
面に］−記第４発明の硬化複合材料からなる絶縁層が積
層されており、かつ該絶縁層の少なくとも最表層に金属
箔が積層された金属張り積層板を提供する。Finally, in a seventh aspect of the present invention, an insulating layer made of the cured composite material according to the fourth aspect of the present invention is laminated on at least one side of the metal base 1-, and a metal foil is laminated on at least the outermost layer of the insulating layer. To provide metal-clad laminates made of
以上の７つの発明について以下に詳しく説明する。The above seven inventions will be explained in detail below.
まず本発明の第１および第２である硬化性ポリフェニレ
ンエーテル系樹脂組成物とその硬化体について説明する
。First, the first and second curable polyphenylene ether resin compositions of the present invention and their cured products will be explained.
硬化性ポリフェニレンエーテル系樹脂組成物の（ａ）成
分として用いられる不飽和基を含むポリフェニレンエー
テル樹脂とは、ポリフェニレンエーテル類に対して側鎖
として炭素−炭素二重結合および／または炭素−炭素三
重結合を含む官能基を導入したものを指す。その好適な
例としては、例えば次の一般式（Ｉ）で表わされるポリ
フェニレンエーテル樹脂と一般式（Ｉ［［）のアルケニ
ルハライドおよび／または一般式（ＩＶ）のアルキニル
ハライドの反応生成物からなる樹脂であって、Ｑ＋Ｊ−
Ｈ）［Ｉｌ （■）ｃ式中、ｍは１〜６の整
数であり、Ｊは次式（ＩＩ）で表わされる単位から実質
的に構成されるポリフェニレンエーテル鎖であり、
Ｑはｍが１のとき水素原子を表わし、ｍが２以上のとき
は一分子中に２〜６個のフェノール性水酸基を持ち、フ
ェノール性水酸基のオルト位およびパラ位に重合不活性
な置換基を有する多官能性フェノール化合物の残基を表
わす。〕
／
Ｒ
Ｙ−（−ＣＨ２−升、Ｃ三重−Ｒ４（ＩＶ）（式中、Ω
、には各々独立に１〜４の整数であり、Ｘ、Ｙは各々独
立に塩素、臭素またはヨウ素であり、Ｒ１−Ｒ４は各々
独立に水素、メチル基またはエチル基である。〕
Ｘおよび／またはＹ１下記アルケニル基および／または
アルキニル基がそれぞれ共有的にポリフェニレンエーテ
ル樹脂に結合している樹脂を挙げることができる。The polyphenylene ether resin containing an unsaturated group used as component (a) of the curable polyphenylene ether resin composition refers to a polyphenylene ether resin containing a carbon-carbon double bond and/or a carbon-carbon triple bond as a side chain to the polyphenylene ether. Refers to products that have introduced functional groups including. Suitable examples thereof include, for example, a resin made of a reaction product of a polyphenylene ether resin represented by the following general formula (I) and an alkenyl halide of the general formula (I[[) and/or an alkynyl halide of the general formula (IV)]. And Q+J-
H) [Il (■)c In the formula, m is an integer of 1 to 6, J is a polyphenylene ether chain substantially composed of units represented by the following formula (II), and Q is a polyphenylene ether chain in which m is 1 When m is 2 or more, it represents a hydrogen atom, and when m is 2 or more, it has 2 to 6 phenolic hydroxyl groups in one molecule, and has a polymerizable inert substituent at the ortho and para positions of the phenolic hydroxyl group. Represents the residue of a phenolic compound. ] / RY-(-CH2-masu, C Mie-R4(IV) (in the formula, Ω
, are each independently an integer of 1 to 4, X and Y are each independently chlorine, bromine or iodine, and R1 to R4 are each independently hydrogen, a methyl group or an ethyl group. ] X and/or Y1 The following alkenyl groups and/or alkynyl groups are each covalently bonded to a polyphenylene ether resin.
／
Ｒ
−（−ＣＲ２−）−、、Ｃ＝ Ｃ−Ｒ４（■′ ）
一般式（１）のポリフェニレンエーテル樹脂について説
明すると、Ｑの代表的な例としては、次の４種の一般式
で表わされる化合物群が挙げられる。/ R -(-CR2-)-,,C=C-R4(■') To explain the polyphenylene ether resin of general formula (1), typical examples of Q include the following four general formulas. The represented compound groups are mentioned.
（以下余白）
〔式中、Ａ 、Ａ２は同一または異なる炭素数１〜４
の直鎖状アルキル基を表わし、Ｘは脂肪族炭化水素残基
およびそれらの置換誘導体、アラルキル基およびそれら
の置換誘導体、酸素、硫黄、スルホニル基、カルボニル
基を表わし、Ｙは脂肪族炭化水素残基およびそれらの置
換誘導体、芳香族炭化水素残基およびそれらの置換誘導
体、アラルキル基およびそれらの置換誘導体を表わし、
Ｚは酸素、硫黄、スルホニル基、カルボニル基を表わし
Ａ２と直接結合した２つのフェニル基、Ａ２とＸ、 Ａ
とＹ、Ａ２とＺの結合位置はすべてフェノール性水
酸基のオルト位およびパラ位を示し、ｒは０〜４、Ｓは
２〜６の整数を表わす。〕具体例として、
（以下余白）
ＣＨ３ＣＨ３ＣＨ３
一般式（Ｉ）中のＪで表わされるポリフェニレンエーテ
ル鎖中には、該ポリフェニレンエーテル樹脂の耐熱性、
熱安定性を低下させない限りにおいて以下に述べる単位
または末端基のうち一種または二種具」二が含まれてい
てもよい。(The following is a blank space) [In the formula, A and A2 are the same or different carbon numbers 1 to 4
represents a linear alkyl group, X represents an aliphatic hydrocarbon residue and substituted derivatives thereof, an aralkyl group and substituted derivatives thereof, oxygen, sulfur, a sulfonyl group, a carbonyl group, and Y represents an aliphatic hydrocarbon residue. represents groups and substituted derivatives thereof, aromatic hydrocarbon residues and substituted derivatives thereof, aralkyl groups and substituted derivatives thereof,
Z represents oxygen, sulfur, a sulfonyl group, a carbonyl group, and two phenyl groups directly bonded to A2, A2 and X, A
The bonding positions of and Y, A2 and Z all represent the ortho and para positions of the phenolic hydroxyl group, r represents an integer of 0 to 4, and S represents an integer of 2 to 6. ] As a specific example, (blank below) CH3CH3CH3 In the polyphenylene ether chain represented by J in the general formula (I), the heat resistance of the polyphenylene ether resin,
One or more of the units or terminal groups described below may be included as long as thermal stability is not reduced.
ｉ）次の一般式で表わされる単位であって（ＩＩ）以外
のもの、
〔式中、Ｒ５−Ｒ８は各々独立に水素、アルキル基、置
換アルキル基、アリール基、置換アリール基を表わす。i) Units other than (II) represented by the following general formula, [wherein R5 to R8 each independently represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.
〕
１１） 次の一般式で表わされる単位、Ｒ
〔式中、Ｒ９−Ｒ１５は各々独立に水素、アルキル基、
置換アルキル基、アリール基、置換アリール基を表わし
、Ｒ１４，Ｒ１，が同時に水素であることはない。〕
１ｆｉ） 次の一般式で表わされる末端基、酸メチル
などの不飽和結合を持つ重合性モノマをグラフト重合さ
せて得られる単位または末端基。] 11) A unit represented by the following general formula, R [wherein R9 to R15 are each independently hydrogen, an alkyl group,
It represents a substituted alkyl group, aryl group, or substituted aryl group, and R14 and R1 are never hydrogen at the same time. ] 1fi) A terminal group represented by the following general formula, a unit or terminal group obtained by graft polymerization of a polymerizable monomer having an unsaturated bond such as acid methyl.
一般式（Ｖ）の単位の例としては、 等が挙げられる。Examples of units in general formula (V) are: etc.
一般式（Ｖｌ）の単位の例としては、
〔式中、Ｒ１６〜Ｒ２ｏは各々独立に水素、アルキル基
、置換アルキル基、アリール基、置換アリール基を表わ
し、Ｒ２、〜Ｒ２３は各々独立に水素、アルキル基、置
換アルキル基、アルケニル基、置換アルケニル基、アリ
ール基、置換アリール基を表わし、Ａｒはアリール基、
置換アリール基を表わす。〕
ｉｖ）上記式（ｎ）および一般式（Ｖ）〜（■）の単位
または末端基に対し、スチレン、メタクリル等が挙げら
れる。Examples of units of general formula (Vl) include: [wherein R16 to R2o each independently represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and R2 and to R23 each independently represent hydrogen; , represents an alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, substituted aryl group, Ar is an aryl group,
Represents a substituted aryl group. ] iv) For the units or terminal groups of the above formula (n) and general formulas (V) to (■), examples include styrene and methacryl.
一般式（■）の末端基の例としては、 等が挙げられる。As an example of the terminal group of general formula (■), etc.
次に一般式（ｍ）のアルケニルハライドの具体的な例を
挙げると、アリルクロライド、アリルブロマイド、アリ
ルアイオダイド、４−ブロモ−１−ブテン、トランス−
および／またはシス１−ブロモ−２−ブテン、トランス
−および／またはシス−１−クロロ−２−ブテン、１−
クロロ−２−メチル−２−プロペン、５−ブロモ１−ペ
ンテン、４−ブロモ−２−メチル−２−ブテン、６−ブ
ロモ−１−ヘキセン、５−ブロモ−２−メチル−２−ペ
ンテン等がある。Next, specific examples of the alkenyl halide of general formula (m) include allyl chloride, allyl bromide, allyl iodide, 4-bromo-1-butene, trans-
and/or cis-1-bromo-2-butene, trans- and/or cis-1-chloro-2-butene, 1-
Chloro-2-methyl-2-propene, 5-bromo-1-pentene, 4-bromo-2-methyl-2-butene, 6-bromo-1-hexene, 5-bromo-2-methyl-2-pentene, etc. be.
一般式（ＩＶ）のアルキニルハライドの具体的な例を挙
げるとプロパルギルクロライド、プロパルギルブロマイ
ド、プロパルギルアイオダイド、４−ブロモ−１−ブチ
ン、４−ブロモ−２−ブチン、５−ブロモ−１−ペンチ
ン、５−ブロモ−２−ペンチン、１−ヨード−２−ペン
チン、１ヨード−３−ヘキシン、６−ブロモ−１−ヘキ
シン等がある。Specific examples of the alkynyl halide of general formula (IV) include propargyl chloride, propargyl bromide, propargyl iodide, 4-bromo-1-butyne, 4-bromo-2-butyne, 5-bromo-1-pentyne, Examples include 5-bromo-2-pentyne, 1-iodo-2-pentyne, 1-iodo-3-hexyne, 6-bromo-1-hexyne, and the like.
これらのアルケニルハライドおよびアルキニルハライド
は、一種のみあるいは二種以上をあわせて用いることが
できる。These alkenyl halides and alkynyl halides can be used alone or in combination of two or more.
本発明の（ａ）成分に用いられる不飽和基が導入された
ポリフェニレンエーテル樹脂は、例えば特開昭６４−６
９６２８号、同６４−６９６２９号、特開平１−１１３
４２５号、同１−１１３４２６号、特願平１−５２０４
１号、同１−５３７０３号に開示された方法に従い、一
般式（Ｉ）のポリフェニレンエーテル樹脂を有機金属で
メタル化し、続いてアルケニルハライド（ｍ）および／
またはアルキニルハライド（ＩＶ）で置換反応すること
により製造することができる。The polyphenylene ether resin into which an unsaturated group is introduced, which is used as the component (a) of the present invention, is disclosed in Japanese Patent Application Laid-Open No. 64-64, for example.
No. 9628, No. 64-69629, JP-A-1-113
No. 425, No. 1-113426, Patent Application No. 1-5204
According to the method disclosed in No. 1, No. 1-53703, the polyphenylene ether resin of general formula (I) is metalized with an organometallic compound, and then alkenyl halide (m) and/or
Alternatively, it can be produced by substitution reaction with alkynyl halide (IV).
本方法に従って製造されるポリフェニレンエテル樹脂は
、少なくとも次の２種ないし３種の構造式で表わされる
単位より構成される。The polyphenylene ether resin produced according to this method is composed of units represented by at least two or three of the following structural formulas.
（以下余白）
〔式中、Ｒは前記アルケニル基（■′）および／または
アルキニル基（■′）を表わす。〕さらには−１−記の
他、次の単位を含むこともある。(Left below) [In the formula, R represents the alkenyl group (■') and/or the alkynyl group (■'). ] Furthermore, in addition to -1-, the following units may be included.
上記一般式（■）に由来するハロゲンの含量は、該ポリ
フェニレンエーテル樹脂を基準として０以上３０重量％
以下の範囲であり、より好ましくは〇以上２０重量％以
下の範囲である。本発明に用いられる不飽和基が導入さ
れたポリフェニレンエーテル樹脂中には、必ずしもハロ
ゲンが含まれる必要はない。しかしながらハロゲンが特
に塩素、臭素である場合には、本発明の硬化性ポリフェ
ニレンエーテル系樹脂組成物に難燃性を付与できるとい
う効果がある。難燃性を付与する場合好ましいハロゲン
の含量は１重量％以」二である。しかし３０重量％を越
えるとポリフェニレンエーテル樹脂自体の熱安定性が低
下するので好ましくない。The content of halogen derived from the above general formula (■) is 0 or more and 30% by weight based on the polyphenylene ether resin.
The content is in the following range, and more preferably in the range of 0 to 20% by weight. The polyphenylene ether resin into which unsaturated groups are introduced for use in the present invention does not necessarily need to contain halogen. However, when the halogen is particularly chlorine or bromine, there is an effect that flame retardancy can be imparted to the curable polyphenylene ether resin composition of the present invention. When imparting flame retardancy, the preferred halogen content is 1% by weight or more. However, if it exceeds 30% by weight, the thermal stability of the polyphenylene ether resin itself decreases, which is not preferable.
上記の方法で得られる不飽和基が導入されたポリフェニ
レンエーテル樹脂の好ましい例としては、以下に述べる
樹脂とアリルブロマイド、アリルクロライド、プロパル
ギルブロマイド、プロパルギルクロライドの反応生成物
からなる樹脂を挙げることができる。Preferred examples of polyphenylene ether resins with unsaturated groups introduced by the above method include resins made from reaction products of the following resins and allyl bromide, allyl chloride, propargyl bromide, and propargyl chloride. .
２．６−ジメチルフェノールの単独重合で得られるポリ
（２，６−シメチルー１，４−フェニレンエテル）、ポ
リ（２，６−シメチルー１，４−フェニレンエーテル）
のポリスチレングラフト共重合体、２．６−ジメチルフ
ェノールと２．３．６− ）ジメチルフェノールの共重
合体、２，６−シメチルフエノルと２．６−シメチルー
３−フェニルフェノールの共重合体、２，６−ジメチル
フェノールを多官能性フェノール化合物Ｑ＋Ｈ）
（ｍは１〜６の整数）の存在下で重合して得られた多官
能性ポリフェニレンエーテル樹脂、例えば特開昭６３３
０１２２２号、特開平１−２９７４８号に開示されてい
るような一般式（Ｖ）および（Ｖｌ）の単位を含む共重
合体、例えば特願平１−１３５７６３号に開示されてい
るような一般式（Ｖ）の単位および一般式（■）の末端
基を含む樹脂等。Poly(2,6-dimethyl-1,4-phenylene ether) and poly(2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2.6-dimethylphenol
polystyrene graft copolymer of 2,6-dimethylphenol and 2.3.6-) dimethylphenol, copolymer of 2,6-dimethylphenol and 2,6-dimethyl-3-phenylphenol, 2, 6-dimethylphenol as a polyfunctional phenol compound Q+H)
(m is an integer of 1 to 6) Polyfunctional polyphenylene ether resin obtained by polymerization in the presence of, for example, JP-A-633
Copolymers containing units of general formulas (V) and (Vl) as disclosed in Japanese Patent Application No. 1-135763, such as those disclosed in Japanese Patent Application No. 1-135763; Resins etc. containing units of (V) and terminal groups of general formula (■).
本発明の硬化性ポリフェニレンエーテル系樹脂組成物に
用いられる不飽和基を含むポリフェニレンエーテル樹脂
の他の例としては、次のような繰り返し単位を含む樹脂
を挙げることができる。Other examples of the polyphenylene ether resin containing an unsaturated group used in the curable polyphenylene ether resin composition of the present invention include resins containing the following repeating units.
（以下余白）
〔式中、Ｒ２４，Ｒ２，は各々独立に水素、アルキル基
、フェニル基を表わす。〕
具体的な例としては、米国特許第３４２２０６２号に開
示されているような２−アリル−６〜メチルフエノール
と、２，６−ジメチルフェノールの共重合体、米国特許
第３２８１３９３号に開示されているような２．６−ジ
アリル−４−ブロモフェノールと２．６−ジメチル−４
−ブロモフェノールの共重合体、特公昭６３−４７７３
３’ｔ−に開示されているような２．６ −ジブレニル
フェノールと２．６−ジメチルフェノールの共重合体、
同じ＜２，６−ビス（２ブテニル）フェノールと２，６
−シメチルフエノルの共重合体、同じ＜２，６−ジシン
ナミルフエノールと２，６−シメチルフエノールの共重
合体、特開昭５８−２７７１９号に開示されているよう
な２プレニル−６−メチルフェノールの単独重合体、同
じく２−プレニル−６−メチルフェノールと２，６−シ
メチルフエノールの共重合体、同じく２− （２−ブテ
ニル）−６−メチルフェノールの単独重合体、同じ＜２
−（２−ブテニル）−６メチルフエノールと２，６−シ
メチルフエノールの共重合体、同じく２〜シンナミル−
６−メチルフェノールの単独重合体、同じく２−シンナ
ミル−６−メチルフェノールと２，６−シメチルフエノ
ールの共重合体等が挙げられる。(Left below) [In the formula, R24 and R2 each independently represent hydrogen, an alkyl group, or a phenyl group. ] Specific examples include a copolymer of 2-allyl-6-methylphenol and 2,6-dimethylphenol as disclosed in U.S. Pat. No. 3,422,062, and a copolymer of 2,6-dimethylphenol as disclosed in U.S. Pat. No. 3,281,393. 2,6-diallyl-4-bromophenol and 2,6-dimethyl-4
-Copolymer of bromophenol, Japanese Patent Publication No. 63-4773
A copolymer of 2,6-dibrenylphenol and 2,6-dimethylphenol as disclosed in 3't-,
Same <2,6-bis(2-butenyl)phenol and 2,6
- copolymers of 2,6-dicinnamylphenol and 2,6-dimethylphenol, 2-prenyl-6-methylphenol as disclosed in JP-A-58-27719; A homopolymer of 2-prenyl-6-methylphenol and 2,6-dimethylphenol, a homopolymer of 2-(2-butenyl)-6-methylphenol, the same <2
Copolymer of -(2-butenyl)-6methylphenol and 2,6-dimethylphenol, also 2-cinnamyl-
Examples include a homopolymer of 6-methylphenol and a copolymer of 2-cinnamyl-6-methylphenol and 2,6-dimethylphenol.
また米国特許第４８３４７４２号に開示されたポリ（２
，６−シメチルー１，４−フェニレンエーテル）の２．
６位のメチル基をビニル基に変換して得られる樹脂、同
じくポリ（２，６−シメチルー１，４−フェニレンエー
テル）のフェニル基の３，５位にビニル基を導入して得
られる樹脂も本発明に用いられる不飽和基を含むポリフ
ェニレンエーテル樹脂の好ましい例の一つである。Also, poly(2) disclosed in U.S. Pat.
, 6-dimethyl-1,4-phenylene ether).
A resin obtained by converting the methyl group at the 6-position to a vinyl group, and a resin obtained by introducing a vinyl group into the 3- and 5-positions of the phenyl group of poly(2,6-dimethyl-1,4-phenylene ether) are also available. This is one of the preferred examples of the polyphenylene ether resin containing an unsaturated group used in the present invention.
本発明において用いられる不飽和基を含むポリフェニレ
ンエーテル樹脂の不飽和基の含量の範囲は、次式の定義
に従った場合０．１モル％以上１００モル％以下、より
好ましくは０．５モル％以上５０モル％以下が好適であ
る。The range of the content of unsaturated groups in the polyphenylene ether resin containing unsaturated groups used in the present invention is 0.1 mol% or more and 100 mol% or less, more preferably 0.5 mol%, according to the definition of the following formula. The content is preferably 50 mol% or more.
不飽和基の含量が０．１モル％を下まわると硬化後の耐
薬品性の改善が不十分となるので好ましくない。逆に１
００モル％を越えると硬化後において非常に脆くなるの
で好ましくない。If the content of unsaturated groups is less than 0.1 mol %, the chemical resistance after curing will be insufficiently improved, which is not preferable. On the contrary, 1
If it exceeds 00 mol%, it becomes extremely brittle after curing, which is not preferable.
また本発明において用いられる不飽和基が導入されたポ
リフェニレンエーテル樹脂の分子量については、３０６
Ｃ，０，５ｇ／ｄ！のクロロホルム溶液で測定した粘度
数η３ｐ／Ｃが０．１〜１．０の範囲にあるものが良好
に使用できる。Furthermore, the molecular weight of the polyphenylene ether resin into which unsaturated groups are introduced used in the present invention is 306
C, 0.5g/d! Those having a viscosity number η3p/C in the range of 0.1 to 1.0 as measured with a chloroform solution of can be used satisfactorily.
本発明の硬化性ポリフェニレンエーテル樹脂組成物の（
ｂ）成分として用いられるトリアリルイソシアヌレート
および／またはトリアリルシアヌレートとは、それぞれ
次の構造式で表される３官能性モノマーである。The curable polyphenylene ether resin composition of the present invention (
Triallyl isocyanurate and/or triallyl cyanurate used as component b) are trifunctional monomers each represented by the following structural formula.
０ＣＨ２ＣＨ＝ＣＨ２
本発明を実施する上においては、トリアリルイソシアヌ
レートおよびトリアリルシアヌレ−ｊ・はそれぞれ単独
で用いられるだけでなく、両者を任意の割合で混合して
使用することが可能である。0CH2CH=CH2 In carrying out the present invention, triallyl isocyanurate and triallyl cyanurate-j. can be used not only alone, but also by mixing them in any ratio. .
本発明において、トリアリルイソシアヌレートおよびト
リアリルシアヌレートは、可塑剤ならびに架橋剤として
その効果を発揮する。すなわち、プレス時の樹脂流れの
向Ｉ−と架橋密度の向１−をもたらす。In the present invention, triallyl isocyanurate and triallyl cyanurate exhibit their effects as a plasticizer and a crosslinking agent. That is, the resin flow direction I- and the crosslinking density direction 1- during pressing are brought about.
本発明の硬化性ポリフェニレンエーテル系樹脂組成物の
（ｃ）成分として用いられるスチレン系熱可塑性樹脂と
は、特に限定されるわけではないが公知のものが一種の
みもしくは二種以上組み合わせて用いられる。代表的な
例としてはスチレン・ブタジェンブロックコポリマー、
スチレン、イソプレンブロックポリマー等が挙げられる
。The styrenic thermoplastic resin used as component (c) of the curable polyphenylene ether resin composition of the present invention is not particularly limited, but known ones may be used alone or in combination of two or more. Typical examples are styrene-butadiene block copolymers,
Examples include styrene and isoprene block polymers.
ブロック状態としては、例えば、ＡＢ、ＡＢＡ。For example, the block status is AB or ABA.
ＡＢＡＢ （例えば、Ａはポリスチレン、Ｂはポリブタ
ジェンまたはポリイソプレン）等が挙げられる。ABAB (for example, A is polystyrene, B is polybutadiene or polyisoprene), and the like.
また本発明の硬化性ポリフェニレンエーテル系樹脂組成
物の（ｃ）成分として用いられるポリブタジェン樹脂と
は、特に限定されるわけではないが公知のものが一種の
みもしくは二種以上組み合わせて用いられる。代表的な
例としては、■、２−ポリブタジェン、 １，４−ポリ
ブタジェン等が挙げられる。またポリブタジェンの分子
鎖末端もしくは側鎖に官能基をｈ゛するものを用いるこ
とも可能である。官能基の代表的な例としては、水酸基
、カルボキシル基、エポキシ基、ウレタン基、アクリル
基、メタクリル基、不飽和酸無水物基等が挙げられる。Further, the polybutadiene resin used as the component (c) of the curable polyphenylene ether resin composition of the present invention is not particularly limited, but known resins may be used alone or in combination of two or more. Typical examples include 1, 2-polybutadiene, 1,4-polybutadiene, and the like. It is also possible to use a polybutadiene having a functional group at the end or side chain of the molecular chain. Typical examples of the functional group include a hydroxyl group, a carboxyl group, an epoxy group, a urethane group, an acrylic group, a methacryl group, an unsaturated acid anhydride group, and the like.
以」二の原料を配合する割合は、特に限定されないが、
（ａ）不飽和基を含むポリフェニレンエーテル樹脂、
（ｂ）トリアリルイソシアヌレートおよび／またはト
リアリルシアヌレート、 （ｃ）スチレン系熱可塑性樹
脂および／またはポリブタジェン樹脂からなる硬化性ポ
リフェニレンエーテル系樹脂組成物であって、（ａ）成
分と（ｂ）成分の和１００重量部を基準として（ａ）成
分が９８〜４０重量部、（ｂ）成分が２〜６０重量部で
ある。The ratio of blending the following two raw materials is not particularly limited, but
(a) polyphenylene ether resin containing an unsaturated group,
(b) triallyl isocyanurate and/or triallyl cyanurate; (c) a curable polyphenylene ether resin composition comprising a styrene thermoplastic resin and/or a polybutadiene resin; The component (a) is 98 to 40 parts by weight, and the component (b) is 2 to 60 parts by weight, based on a total of 100 parts by weight of the components.
（ｂ）成分が２重量部未満では耐薬品性の改善が不十分
であり好ましくない。逆に６０重量部を超えると誘電特
性、難燃性、吸湿特性が低下し、また硬化後において非
常に脆い材料となるので好ましくない。If the amount of component (b) is less than 2 parts by weight, the improvement in chemical resistance will be insufficient, which is not preferable. On the other hand, if it exceeds 60 parts by weight, the dielectric properties, flame retardance, and moisture absorption properties will deteriorate, and the material will become extremely brittle after curing, which is not preferable.
また（ｃ）成分の配合割合は、 （ａ）〜（ｃ）成分の
和１００重量部を基準として、スチレン系熱可塑性樹脂
が１０〜９０重量部であることが好ましい。スチレン系
熱可塑性樹脂が、１０重量部未満であると、耐衝撃性等
の物性が悪くなり、９０重量部を超えると耐熱性、耐薬
品性が悪くなる。またポリブタジェン樹脂が２０重量部
を超えると表面のべたつきを生じたりする。The blending ratio of component (c) is preferably 10 to 90 parts by weight of the styrenic thermoplastic resin based on the total of 100 parts by weight of components (a) to (c). If the styrenic thermoplastic resin is less than 10 parts by weight, physical properties such as impact resistance will deteriorate, and if it exceeds 90 parts by weight, heat resistance and chemical resistance will deteriorate. Moreover, if the polybutadiene resin exceeds 20 parts by weight, the surface may become sticky.
上記の（ａ）〜（ｃ）の３つの成分を混合する方法とし
ては、王者を溶媒中に均一に溶解または分散させる溶液
混合法、あるいは押し出し機等により加熱して行う溶融
ブレンド法等が利用できる。The above three components (a) to (c) can be mixed by a solution mixing method, in which the king is uniformly dissolved or dispersed in a solvent, or a melt blending method, which is performed by heating with an extruder, etc. can.
溶液混合に用いられる溶媒としては、ジクロロメタン、
クロロホルム、トリクロロエチレンなどのハロゲン系溶
媒；ベンゼン、トルエン、キシレンなどの芳香族系溶媒
が単独で、あるいは二種以上を組み合わせて用いられる
。Solvents used for solution mixing include dichloromethane,
Halogen solvents such as chloroform and trichloroethylene; aromatic solvents such as benzene, toluene and xylene may be used alone or in combination of two or more.
本発明の樹脂組成物は、特に限定するものではないが、
フィルム状として良好に使用することができる。その製
造方法としては、例えば通常の溶媒成膜法（キャスティ
ング法）等が利用でき、任意の厚みのものが製造できる
。フィルムの製造に適した組成は、特に限定するもので
はないが、（ａ）成分と（ｂ）成分の和１００重量部を
基準として（ａ）成分が９８〜５０重量部、（ｂ）成分
が２〜５０重量部の範囲であり、かつ（ａ）〜（ｃ）成
分の和１００重量部を基準として、スチレン系熱可塑性
樹脂は、１０〜９０重曾部であり、ポリブタジェン樹脂
は、２０重量部以下である。（ｂ）成分が上記の範囲未
満では、耐薬品性が不七分であり好ましくない。逆に上
記の範囲を超えるとフィルムが脆くなったり、べたつき
が生じて取り扱い性に劣るため好ましくない。Although the resin composition of the present invention is not particularly limited,
It can be used satisfactorily in the form of a film. As a manufacturing method, for example, a normal solvent film forming method (casting method) can be used, and a material having an arbitrary thickness can be manufactured. The composition suitable for producing the film is not particularly limited, but the component (a) is 98 to 50 parts by weight, and the component (b) is 98 to 50 parts by weight, based on the sum of 100 parts by weight of components (a) and (b). The amount of the styrene thermoplastic resin is 10 to 90 parts by weight, and the amount of the polybutadiene resin is 20 parts by weight, based on the sum of 100 parts by weight of components (a) to (c). below. If component (b) is less than the above range, the chemical resistance will be unfavorable. On the other hand, if it exceeds the above range, the film becomes brittle or sticky, resulting in poor handling properties, which is not preferable.
本発明の樹脂組成物は、後述するように加熱等の手段に
より架橋反応を起こして硬化するが、その際の温度を低
くしたり架橋反応を促進する目的でラジカル開始剤を含
有させて使用することができる。The resin composition of the present invention is cured by causing a crosslinking reaction by heating or other means as described below, and it is used by containing a radical initiator for the purpose of lowering the temperature at that time or promoting the crosslinking reaction. be able to.
ラジカル開始剤としては、通常の過酸化物が使用できる
。As the radical initiator, common peroxides can be used.
本発明の樹脂組成物は、ｌ−記のラジカル開始剤の他に
その用途に応じて所望の性能を（−Ｊ与する目的で本来
の性質を損わない範囲の量の充填材や添加剤を配合して
用いることができる。充填材は繊維状であっても粉末状
であってもよく、ガラス繊維、アラミド繊維、カーボン
繊維、ボロン繊維、セラミック繊維、アスベスト繊維、
カーボンブラック、シリカ、アルミナ、タルク、雲母、
ガラスピーズ、ガラス中空球などを挙げることができる
。添加剤としては、酸化防止剤、熱安定剤、帯電防止剤
、可塑剤、顔料、染料、着色剤などが挙げられる。また
難燃性の一層の向」−を図る目的で、塩素系、臭素系、
リン系の難燃材や、Ｓ ｂ ２０ｓ 。In addition to the radical initiator described in I-, the resin composition of the present invention may contain fillers and additives in an amount within a range that does not impair the original properties for the purpose of imparting desired performance (-J) depending on its use. The filler may be in the form of fibers or powder, and may include glass fibers, aramid fibers, carbon fibers, boron fibers, ceramic fibers, asbestos fibers,
carbon black, silica, alumina, talc, mica,
Examples include glass beads and glass hollow spheres. Examples of additives include antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes, and colorants. In addition, in order to further improve flame retardancy, chlorine-based, bromine-based,
Phosphorus-based flame retardant materials and S b 20s.
Ｓｂ Ｏ、Ｎａ５ｂＯ・ｌ／４ Ｈ２０等の難燃助剤
を併用することもできる。さらには、ポリフェニレンエ
ーテルをはじめとする熱可塑性樹脂、あるいは他の熱硬
化性樹脂を一種または二種以上配合することも可能であ
る。Flame retardant aids such as SbO, Na5bO.l/4H20, etc. can also be used in combination. Furthermore, it is also possible to blend one or more thermoplastic resins such as polyphenylene ether or other thermosetting resins.
本発明の第２の硬化ポリフェニレンエーテル系樹脂組成
物は、以上に述べた硬化性ポリフェニレンエーテル系樹
脂組成物を硬化することにより得られるものである。硬
化の方法は任意であり、熱、光、電子線等による方法を
採用することができる。 加熱により硬化を行う場合そ
の温度は、ラジカル開始剤の有無やその種類によっても
異なるが、１００〜３５０℃、より好ましくは１５０〜
３ｏ。The second cured polyphenylene ether resin composition of the present invention is obtained by curing the curable polyphenylene ether resin composition described above. The curing method is arbitrary, and methods using heat, light, electron beams, etc. can be employed. When curing is performed by heating, the temperature varies depending on the presence or absence of a radical initiator and its type, but is preferably 100 to 350°C, more preferably 150 to 350°C.
3o.
℃の範囲で選ばれる。また時間は１分〜５時間程度、よ
り好ましくは１分〜３時間である。Selected in the range of °C. Moreover, the time is about 1 minute to 5 hours, more preferably 1 minute to 3 hours.
得られた硬化ポリフェニレンエーテル系樹脂組成物は、
赤外吸収スペクトル法、高分解能固体核磁気共鳴スペク
トル法、熱分解ガスクロマトグラフィー等の方法を用い
て樹脂組成を解析することができる。The obtained cured polyphenylene ether resin composition is
The resin composition can be analyzed using methods such as infrared absorption spectroscopy, high-resolution solid-state nuclear magnetic resonance spectroscopy, and pyrolysis gas chromatography.
本発明の硬化ポリフェニレンエーテル系樹脂組成物は、
特に限定するものではないが、フィルム状として良好に
使用することができる。The cured polyphenylene ether resin composition of the present invention is
Although not particularly limited, it can be favorably used in the form of a film.
またこの硬化ポリフェニレンエーテル系樹脂組成物は、
第４発明として後述する硬化複合材料と同様、金属箔お
よび／または金属板と張り合せて用いることができる。In addition, this cured polyphenylene ether resin composition is
Similar to the cured composite material described below as the fourth invention, it can be used by laminating it with a metal foil and/or a metal plate.
次に本発明の第３および第４である硬化性複合材料とそ
の硬化体について説明する。Next, the third and fourth curable composite materials of the present invention and their cured products will be explained.
本発明の硬化性複合材料は、本発明の第１として上で説
明した硬化性ポリフェニレンエーテル系樹脂組成物と基
材より構成される。本発明に用いられる基材としては、
ロービングクロス、クロス、チョツプドマット、サーフ
ェシングマットなどの各種ガラス布またはガラス不織布
；セラミック繊維布、アスベスト布、金属繊維布および
その他合成もしくは天然の無機繊維布；ポリビニルアル
コール繊維、ポリエステル繊維、アクリル繊維、全芳香
族ポリアミド繊維などの合成繊維から得られる織布また
は不織布；綿布、麻布、フェルトなどの天然繊維布；カ
ーボン繊維布；クラフト紙、コツトン紙、紙−ガラス混
繊紙などの天然セルロース系布などが、それぞれ単独で
、あるいは２種以上併せて用いられる。The curable composite material of the present invention is composed of the curable polyphenylene ether resin composition described above as the first aspect of the present invention and a base material. The base material used in the present invention is
Various glass cloths or non-woven glass cloths such as roving cloths, cloths, chopped mats, surfacing mats; Ceramic fiber cloths, asbestos cloths, metal fiber cloths and other synthetic or natural inorganic fiber cloths; Polyvinyl alcohol fibers, polyester fibers, acrylic fibers, Woven or non-woven fabrics obtained from synthetic fibers such as aromatic polyamide fibers; Natural fiber fabrics such as cotton fabrics, linen fabrics, and felt; Carbon fiber fabrics; Natural cellulose fabrics such as kraft paper, cotton paper, paper-glass mixed paper, etc. These may be used alone or in combination of two or more.
本発明の硬化性複合材料における基祠の占める割合は、
硬化性複合材料１００重量部を基準として５〜９０重量
部、より好ましくは１０〜８０重量部、さらに好ましく
は２０〜７０市量部の範囲である。基祠が５小量部より
少なくなると複合材料の硬化後の寸法安定性や強度が不
十分であり、また基材が９０重量％より多くなると複合
材料の誘電特性や難燃性が劣り好ましくない。The proportion of the base in the curable composite material of the present invention is
Based on 100 parts by weight of the curable composite material, the amount ranges from 5 to 90 parts by weight, more preferably from 10 to 80 parts by weight, and still more preferably from 20 to 70 parts by weight. If the amount of the base material is less than 5 parts by weight, the dimensional stability and strength of the composite material after curing will be insufficient, and if the amount of the base material is more than 90% by weight, the dielectric properties and flame retardance of the composite material will be poor, which is undesirable. .
本発明の複合材料には、必要に応じて樹脂と基材の界面
における接着性を改善する目的でカップリング剤を用い
ることができる。カップリング剤としては、シランカッ
プリング剤、チタネート系カップリング剤、アルミニウ
ム系カップリング剤、ジルコアルミネートカップリング
剤等一般のものが使用できる。A coupling agent can be used in the composite material of the present invention, if necessary, for the purpose of improving adhesiveness at the interface between the resin and the base material. As the coupling agent, common ones such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, etc. can be used.
本発明の複合材料を製造する方法としては、例えば本発
明第１の項で説明した（ａ）〜（ｃ）成分と、必要に応
じて他の成分を前述のハロゲン系、芳香族系等の溶媒も
しくはその混合溶媒中に均一に溶解または分散させ、基
材に含浸させた後乾燥する方法が挙げられる。As a method for producing the composite material of the present invention, for example, components (a) to (c) explained in the first section of the present invention and other components as necessary may be added to the above-mentioned halogen-based, aromatic, etc. Examples include a method in which the material is uniformly dissolved or dispersed in a solvent or a mixed solvent thereof, impregnated into a base material, and then dried.
含浸は浸漬（ディッピング）、塗布等によって行われる
。含浸は必要に応じて複数回繰り返すことも可能であり
、またこの際組成や濃度の異なる複数の溶液を用いて含
浸を繰り返し、最終的に希望とする樹脂組成および樹脂
量に調整することも可能である。Impregnation is performed by dipping, coating, etc. Impregnation can be repeated multiple times if necessary, and it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and resin amount. It is.
本発明第４の硬化複合材料は、このようにして得た硬化
性複合材料を加熱等の方法により硬化することによって
得られるものである。その製造方法は特に限定されるも
のではなく、例えば該硬化性複合材料を複数枚重ね合わ
せ、加熱加圧下に各層間を接着せしめると同時に熱硬化
を行い、所望の厚みの硬化複合材料を得ることができる
。また−度接着硬化させた硬化複合材料と硬化性複合材
料を組み合わせて新たな層構成の硬化複合材料を得るこ
とも可能である。The fourth cured composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The manufacturing method thereof is not particularly limited, and for example, a plurality of sheets of the curable composite material may be stacked, each layer may be bonded under heat and pressure, and at the same time, heat curing may be performed to obtain a cured composite material with a desired thickness. I can do it. It is also possible to obtain a cured composite material with a new layer structure by combining a cured composite material that has been adhesively cured with a curable composite material.
積層成形と硬化は、通常熱プレス等を用い同時に行われ
るが、両者をそれぞれ単独で行ってもよい。すなわち、
あらかじめ積層成形して得た未硬化あるいは半硬化の複
合材料を、熱処理または別の方法で処理することによっ
て硬化させることができる。Laminate molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is,
An uncured or semi-cured composite material obtained by prior lamination molding can be cured by heat treatment or other treatment.
成形および硬化は、温度１００〜３５０℃、圧力０．１
〜１０００ｋｇ／ｃ＃、時間１分〜５時間の範囲、より
好ましくは、温度１５０〜３００℃、圧力１〜５００ｋ
ｇ／ｃＪ、時間１分〜３時間の範囲で行うことができる
。Molding and curing are performed at a temperature of 100 to 350°C and a pressure of 0.1
~1000kg/c#, time range from 1 minute to 5 hours, more preferably temperature 150~300℃, pressure 1~500k
g/cJ and for a time ranging from 1 minute to 3 hours.
最後に本発明の第５．第６．および第７である積層体、
積層板、金属張り積層板について説明する。Finally, the fifth aspect of the present invention. 6th. and a seventh laminate,
Laminated plates and metal-clad laminates will be explained.
本発明の積層体とは、本発明の第４として一層で説明し
た硬化複合材料と金属箔より構成されるものである。ま
た積層板とは、同じく硬化複合材料と金属板より構成さ
れるものであり、金属張り積層板とは、硬化複合材料、
金属箔、および金属板より構成されるものである。The laminate of the present invention is composed of the cured composite material described as a single layer as the fourth aspect of the present invention and metal foil. A laminate is also composed of a hardened composite material and a metal plate, and a metal-clad laminate is a hardened composite material and a metal plate.
It is composed of metal foil and metal plate.
ここで用いられる金属箔としては、例えば銅箔、アルミ
ニウム箔等が挙げられる。その厚みは特に限定されない
が、５〜２００μｍ、より好ましくは５〜１００μｍの
範囲である。Examples of the metal foil used here include copper foil, aluminum foil, and the like. The thickness is not particularly limited, but is in the range of 5 to 200 μm, more preferably 5 to 100 μm.
また金属板としては、例えば鉄板、アルミニウム板、ケ
イ素鋼板、ステンレス板等が挙げられる。Further, examples of the metal plate include an iron plate, an aluminum plate, a silicon steel plate, and a stainless steel plate.
その厚みは特に限定されないが、０．２ｍｍ〜１０闘、
より好ましくは０．２ｍｍ〜５ｍｍの範囲である。金属
板は使用に先立ち、その接着性を改善するため研磨紙や
研磨布によるサンディング、湿式ブラスト、乾式ブラス
ト等の機械的研磨を行い、さらに脱脂、エツチング、ア
ルマイト処理、化成皮膜処理等を施して用いることがで
きる。アルミニウム板では、研磨後戻酸ナトリウムで脱
脂し、水酸化ナトリウムでエツチングするのが好ましい
が、特にこの方法に限定されない。The thickness is not particularly limited, but is 0.2 mm to 10 mm,
More preferably, it is in the range of 0.2 mm to 5 mm. Before use, metal plates are mechanically polished by sanding with abrasive paper or abrasive cloth, wet blasting, dry blasting, etc. to improve their adhesion, and are also subjected to degreasing, etching, alumite treatment, chemical conversion coating treatment, etc. Can be used. For aluminum plates, it is preferable to degrease with recycled sodium chloride after polishing and then etch with sodium hydroxide, but the method is not particularly limited.
本発明の積層体、積層板、および金属張り積層板を製造
する方法としては、例えば本発明第３として上で説明し
た硬化性複合材料と、金属箔および／または金属板を目
的に応じた層構成で積層し、加熱加圧下に各層間を接着
せしめると同時に熱硬化させる方法を挙げることができ
る。As a method for manufacturing the laminate, laminate, and metal-clad laminate of the present invention, for example, the curable composite material described above as the third aspect of the present invention and a metal foil and/or metal plate may be layered in accordance with the purpose. One example is a method in which the layers are laminated, the layers are bonded together under heat and pressure, and at the same time the layers are thermally cured.
例えば積層体においては、硬化性複合材料と金属箔が任
意の層構成で積層される。金属箔は表層としても中間層
としても用いることができる。For example, in a laminate, a curable composite material and metal foil are laminated in an arbitrary layer configuration. Metal foil can be used both as a surface layer and as an intermediate layer.
積層板においては、金属板をベースとしその片面または
両面に硬化性複合材料が積層される。In a laminate, a curable composite material is laminated on one or both sides of a metal plate as a base.
金属張り積層板においては、金属板をベースとしその片
面または両面に硬化性複合材料を介して金属箔が積層さ
れる。この際金属箔は最表層として用いられるが、最表
層以外に中間層として用いてもよい。In a metal-clad laminate, a metal plate is used as a base, and metal foil is laminated on one or both sides of the base with a curable composite material interposed therebetween. In this case, the metal foil is used as the outermost layer, but it may be used as an intermediate layer in addition to the outermost layer.
−１−記の他、積層と硬化を複数回繰り返して多層化す
ることも可能である。In addition to the method described in -1-, it is also possible to repeat lamination and curing multiple times to form a multilayer structure.
金属箔および金属板の接着には接着剤を用いることもで
きる。接着剤としては、エポキシ系、アクリル系、フェ
ノール系、シアノアクリレート系等が挙げられるが、特
にこれらに限定されない。An adhesive can also be used to bond the metal foil and metal plate. Examples of adhesives include epoxy, acrylic, phenol, and cyanoacrylate adhesives, but are not particularly limited thereto.
上記の積層成形と硬化は、本発明第４と同様の条件で行
うことができる。The above lamination molding and curing can be performed under the same conditions as in the fourth aspect of the present invention.
以下、本発明を一層明確にするために実施例を挙げて説
明するが、本発明の範囲をこれらの実施例に限定するも
のではない。EXAMPLES Hereinafter, in order to further clarify the present invention, the present invention will be explained using Examples, but the scope of the present invention is not limited to these Examples.
以下の実施例には各成分として次のようなものを用いた
。The following components were used in the following examples.
スチレン系熱可塑性樹脂：
・スチレンブタジェンコポリマ
旭化成 ツルプレンＴ４０６
ブタジエン樹脂：
日本ゼオン Ｎ１ｐｏｌ ＢＲ１２２０口本曹達Ｎｌ５
ＳＯＢ−１，０００
・開始剤：
２．５−ジメチル−２，５−ジ（ｔ−ブチルパオキシ）
ヘキシン−３（日本油脂 パーヘキシン２５Ｂ）
難燃剤：
・デカブロモジフェニルオキサイド
旭硝子 Ａ Ｐ Ｒ−１０２１
難燃助剤：
５ｂＯ（日本精鉱 ＰＡ ＴＯＸ−Ｍ）ガラスクロス：
Ｅガラス製、目付４８ｇ／ゴまたは１０５ｇ／イＤガラ
ス製、目付８７ｇ／ｒｒｒ
実施例 １〜３
平均置換率１４％、η ／ Ｃ＝ ０．６２ （３０°
Ｃ，０，５Ｓｐ
ｇ／ｄｉ、クロロホルム溶液）のアリル基置換ポリフェ
ニレンエーテルを特開昭６４−６９６２９号に開示され
た公知の方法に従ってη３．／ Ｃ＝ ０．５６のポリ
（２，６−シメチルー１，４−フェニレンエーテル）よ
り合成した。Styrene-based thermoplastic resin: - Styrene-butadiene copolymer Asahi Kasei Tulprene T406 Butadiene resin: Nippon Zeon N1pol BR1220 Kuchimoto Soda Nl5
SOB-1,000 ・Initiator: 2,5-dimethyl-2,5-di(t-butylpaoxy)
Hexine-3 (NOF Perhexine 25B) Flame retardant: Decabromodiphenyl oxide Asahi Glass APR-1021 Flame retardant aid: 5bO (Nippon Seiko PA TOX-M) Glass cloth: E glass, fabric weight 48 g/g or 105g/I D glass, basis weight 87g/rrr Examples 1 to 3 Average substitution rate 14%, η/C=0.62 (30°
C,0,5Sp g/di, chloroform solution), the allyl group-substituted polyphenylene ether of η3. /C=0.56 poly(2,6-dimethyl-1,4-phenylene ether).
上記アリル基置換ポリフェニレンエーテルと、トリアリ
ルイソシアヌレート、スチレン系熱可塑性樹脂、ポリブ
タジェン樹脂を表１に示した組成でクロロホルムに溶解
させ、テフロン板上に流して成膜した。得られたフィル
ムは厚さが約１００μｍであった。成膜性はいずれも良
好であった。The allyl group-substituted polyphenylene ether, triallylisocyanurate, styrene thermoplastic resin, and polybutadiene resin were dissolved in chloroform with the composition shown in Table 1, and poured onto a Teflon plate to form a film. The resulting film had a thickness of about 100 μm. Film formability was good in all cases.
このフィルムをエアーオーブン中で乾燥させた後、真空
プレス中で２００℃×２時間の条件で成形、硬化させ、
厚さ約１ｍｍの硬化物を得た。After drying this film in an air oven, it was molded and cured in a vacuum press at 200°C for 2 hours.
A cured product with a thickness of about 1 mm was obtained.
この硬化物は、トリクロロエチレン中で５分間煮沸して
も外観に変化は認められなかった。No change in the appearance of this cured product was observed even when it was boiled in trichlorethylene for 5 minutes.
比較例 １，２
アリル基置換ポリフェニレンエーテルの代りにポリ（２
，６−シメチルー１，４−フェニレンエーテル）（ηＳ
ｐ／ Ｃ＝ ０．５８）を用いて、表１の組成で実施例
１〜４と同じ操作を繰り返した。得られた硬化物をトリ
クロロエチレン中で５分間煮沸したところ著しい膨潤と
反りが認められた。Comparative Examples 1, 2 Poly(2
,6-dimethyl-1,4-phenylene ether) (ηS
p/C=0.58), and the same operations as in Examples 1 to 4 were repeated with the composition in Table 1. When the obtained cured product was boiled in trichlorethylene for 5 minutes, significant swelling and warping were observed.
（以下余白）
３つ
実施例 ４〜１１
不飽和基を含むポリフェニレンエーテル樹脂の合成
実施例４〜７および９では、実施例１〜３で用いたもの
と同じポリマーを用いた。(Left below) Three Examples 4-11 Synthesis of polyphenylene ether resin containing unsaturated groups In Examples 4-7 and 9, the same polymers as used in Examples 1-3 were used.
実施例８では、同様の方法で平均置換率２８％。In Example 8, the average substitution rate was 28% using the same method.
ηＳｐ／ Ｃ＝ ０．５０のアリル基置換ポリフェニレ
ンエーテルを合成した。An allyl group-substituted polyphenylene ether with ηSp/C=0.50 was synthesized.
実施例１０では、実施例１〜Ｂで合成したアリル基置換
ポリフェニレンエーテルを、特開昭６４６９６２８号に
開示された公知の方法に従って平均置換率１４％、ηＳ
ｐ／Ｃ＝０．５８のプロパルギル基置換ポリフェニレン
エーテルに変換して用いた。In Example 10, the allyl group-substituted polyphenylene ethers synthesized in Examples 1 to B were prepared according to the known method disclosed in JP-A-6469628 with an average substitution rate of 14% and ηS.
It was converted into propargyl group-substituted polyphenylene ether with p/C=0.58 and used.
実施例４１では、２，２−ビス（３，５−ジメチル４−
ヒドロキシフェニル）プロパンの共存下に２．６−ジメ
チルフェノールを酸化重合して得た２官能性ポ１叡エニ
レンエーテル（ηＳｐ／ Ｃ＝ ｆ）、４０）を用い、
特開平１−１１３４２６号に開示された公知の方法に従
って３−ブテニル基を導入して用いた。平均置換率は１
８％、ηＳｐ／Ｃは０．３８であった。In Example 41, 2,2-bis(3,5-dimethyl 4-
Using bifunctional polyenylene ether (ηSp/C=f), 40) obtained by oxidative polymerization of 2,6-dimethylphenol in the coexistence of hydroxyphenyl)propane,
A 3-butenyl group was introduced and used according to the known method disclosed in JP-A-1-113426. The average replacement rate is 1
8%, and ηSp/C was 0.38.
硬化性複合材料
表２に示した組成で各成分をトリクロロエチレン中に溶
解または分散させた。この溶液にガラスクロスを浸漬し
て含浸を行い、エアーオーブン中で乾燥させた。実施例
４，６では目付４１３ｇ／ｒｒ？のＥガラスクロスを、
実施例７では目付８’１ｇ／ｒｄのＤガラスクロスを、
実施例５および８〜１１では目付１０５ｇ／ｒＴＩ’の
Ｅガラスクロスをそれぞれ用いた。Curable Composite Material Each component was dissolved or dispersed in trichlorethylene according to the composition shown in Table 2. A glass cloth was dipped in this solution for impregnation and dried in an air oven. In Examples 4 and 6, the basis weight was 413 g/rr? E glass cloth,
In Example 7, D glass cloth with a basis weight of 8'1 g/rd was used.
In Examples 5 and 8 to 11, E glass cloth with a basis weight of 105 g/rTI' was used, respectively.
得られた硬化性複合材料はいずれも表面のべたつきが無
く、取り扱い性に優れたものであった。All of the obtained curable composite materials had no stickiness on the surface and were excellent in handleability.
積層体
成形後の厚みが約０．８ｍｍとなるように−１−記の硬
化性複合材料を複数枚重ね合わせ、その両面に厚さ３５
μｍの銅箔を置いて、プレス成形機により成形硬化させ
て積層体を得た。各実施例の硬化条件を表３に示した。A plurality of sheets of the curable composite material described in -1- are stacked so that the thickness after forming the laminate is approximately 0.8 mm, and a thickness of 35 mm is applied to both sides of the curable composite material.
A laminate was obtained by placing a μm thick copper foil and molding and hardening it using a press molding machine. Table 3 shows the curing conditions for each example.
圧力はずべて４０ｋｇ／ｒｒｌ’とした。The pressure was 40 kg/rrl' in all cases.
いずれの実施例もプレス時の樹脂流れは良好であった。In all Examples, the resin flowed well during pressing.
このようにして得られた積層体の諸物性を以下の方法で
測定し、表３に示した通りの良好な結果を得た。Various physical properties of the thus obtained laminate were measured by the following methods, and good results as shown in Table 3 were obtained.
■、耐トリクロロエチレン性
銅箔を除去した積層体を２５ｍｍ角に切り出し、トリク
ロロエチレン中で５分間煮沸し、外観の変化を目視によ
り観察した。(2) The laminate from which the trichlorethylene-resistant copper foil had been removed was cut into 25 mm squares, boiled in trichlorethylene for 5 minutes, and changes in appearance were visually observed.
２、誘電率、誘電正接 １Ｍ！−１ｚで測定を行った。2. Dielectric constant, dielectric loss tangent 1M! Measurements were made at −1z.
３、ハンダ耐熱性
銅箔を除去した積層体を２５ｍｍ角に切り出し、２６０
℃のハンダ浴中に１２０秒間浮かべ、外観の変化を目視
により観察した。3. Cut the laminate from which the solder heat-resistant copper foil has been removed into 25 mm square pieces,
It was floated for 120 seconds in a solder bath at 0.degree. C., and changes in appearance were visually observed.
４、銅箔引き剥し強さ
積層体から幅２０ｍｍ、長さ１００ｍｍの試験片を切り
出し、銅箔面に幅１．０ｍｍの平行な切り込みを入れた
後、面に対して垂直なる方向に５０ｍｍ／分の速さで連
続的に銅箔を引き剥し、その時の応力を引張り試験機に
て測定し、その応力の最低値を示した。4. Copper foil peel strength A test piece with a width of 20 mm and a length of 100 mm was cut out from the laminate, and a parallel cut of 1.0 mm in width was made on the surface of the copper foil. The copper foil was continuously peeled off at a speed of 1 minute, and the stress at that time was measured using a tensile tester, and the lowest stress value was shown.
５、難燃性
銅箔を除去した積層体から長さ１２７ｍｍ、幅１２．７
ｍの試験片を切り出し、ＬＪ１９４の試験法に準じて行
った。5. Length 127 mm, width 12.7 mm from the laminate with flame-retardant copper foil removed
A test piece of m was cut out and tested according to the test method of LJ194.
比較例 ３，４
実施例７および８において、アリル基置換ボリフＪ−ニ
レンエーデルの代りに、η８．／ Ｃ＝ ０．５６のポ
リ（２，６−ジメチル−１，４−フエニレンエーテル）
を用い、同様の操作を行い、積層板を作製した。Comparative Examples 3 and 4 In Examples 7 and 8, η8. / C=0.56 poly(2,6-dimethyl-1,4-phenylene ether)
A laminate was produced using the same procedure as above.
この積層板の耐トリクロロエチレン性を測定したところ
、表面の著しい白化とガラスクロスの露出が認められた
。When the trichlorethylene resistance of this laminate was measured, significant whitening of the surface and exposure of the glass cloth were observed.
（以下余白）
実施例 １２
研磨、脱脂、エツチング処理を施した厚さ１．０ｍｍの
アルミニウム板」−に実施例って得られた硬化性複合材
料３枚を積層し、２２０℃、３０分、 ４０ｋｇ／ｃｔ
の条件でプレス成形して積層板を作製した。(Leaving space below) Example 12 Three sheets of the curable composite material obtained in the example were laminated on a 1.0 mm thick aluminum plate that had been subjected to polishing, degreasing, and etching treatment, and then heated at 220°C for 30 minutes. 40kg/ct
A laminate was produced by press forming under the following conditions.
この積層板の熱抵抗は２５°Ｃ／Ｗであり、アルミニウ
ム板を使用しない場合（６１℃／Ｗ）に比べて熱放散性
に優れたものであった。The thermal resistance of this laminate was 25°C/W, which was superior in heat dissipation compared to the case where no aluminum plate was used (61°C/W).
熱抵抗は、３５ｍｍ Ｘ ５０ｍｍのサンプル上に回路
を形成し、１００Ωのチップ抵抗をハンダ付けし、電圧
印加後の温度上昇を測定することにより行った。Thermal resistance was determined by forming a circuit on a 35 mm x 50 mm sample, soldering a 100 Ω chip resistor, and measuring the temperature rise after voltage application.
実施例 １３
研磨、脱脂、エツチング処理を施した厚さ１．０ｍｍの
アルミニウム板上に実施例５で得られた硬化性複合材料
３枚と厚さ３５μｍの銅箔を積層し、２２０°Ｃ１３０
分、 ４０ｋｇ／ｃ＋ｆＴの条件でプレス成形して金属
張り積層板を作製した。Example 13 Three sheets of the curable composite material obtained in Example 5 and a 35 μm thick copper foil were laminated on a 1.0 mm thick aluminum plate that had been polished, degreased, and etched, and heated at 220°C at 130°C.
A metal-clad laminate was produced by press forming under the conditions of 40 kg/c+fT.
この金属張り積層板の熱抵抗を実施例１１と同様の方法
で測定したところ２４°Ｃ／Ｗであり、熱放散性に優れ
たものであった。The thermal resistance of this metal-clad laminate was measured in the same manner as in Example 11 and was found to be 24°C/W, indicating excellent heat dissipation.
本発明の硬化性ポリフェニレンエーテル系樹脂組成物は
、溶媒成膜性が良好であり、取り扱い性に優れたフィル
ムや硬化性複合材料が得られる。The curable polyphenylene ether resin composition of the present invention has good solvent film-forming properties, and provides films and curable composite materials with excellent handling properties.
本発明の硬化性ポリフェニレンエーテル系樹脂組成物を
用いて得られる積層体、積層板、金属張り積層板は、良
好な耐薬品性と優れた誘電特性を兼ね備えた材料である
。The laminates, laminates, and metal-clad laminates obtained using the curable polyphenylene ether resin composition of the present invention are materials that have both good chemical resistance and excellent dielectric properties.
すなわち、煮沸トリクロロエチレンに対する十分な耐性
を持ち、３．０以下の誘電率を示す。That is, it has sufficient resistance to boiling trichlorethylene and exhibits a dielectric constant of 3.0 or less.
本発明の積層体、積層板、金属張り積層板は、この他耐
熱性、金属との接着性、寸法安定性、あるいは熱放散性
等の諸物性においてバランスのとれた特性を示す。The laminates, laminates, and metal-clad laminates of the present invention exhibit well-balanced physical properties such as heat resistance, adhesion to metals, dimensional stability, and heat dissipation properties.
従って本発明の材料は、電気産業、電子産業、宇宙・航
空機産業等の分野において誘電材料、絶縁材料、耐熱材
料等として用いることができる。Therefore, the material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, etc. in fields such as the electrical industry, the electronic industry, and the space/aircraft industry.
特に片面、両面、多層プリント基板、フレキシブルプリ
ント基板、セミリジット基板、金属ベース基板、多層プ
リント基板用プリプレグとして好適４つ
に用いられる。In particular, it is suitably used as prepreg for single-sided, double-sided, multilayer printed circuit boards, flexible printed circuit boards, semi-rigid circuit boards, metal base boards, and multilayer printed circuit boards.
Claims (1)
と（ｂ）トリアリルイソシアヌレートおよび／またはト
リアリルシアヌレートと（ｃ）スチレン系熱可塑性樹脂
および／またはポリブタジエン樹脂からなることを特徴
とする硬化性ポリフェニレンエーテル系樹脂組成物。 ２）形状がフィルムである請求項１記載の硬化性ポリフ
ェニレンエーテル系樹脂組成物。 ３）請求項１記載の硬化性ポリフェニレンエーテル系樹
脂組成物を硬化して得られた硬化ポリフェニレンエーテ
ル系樹脂組成物。 ４）形状がフィルムである請求項３記載の硬化ポリフェ
ニレンエーテル系樹脂組成物。 ５）（ａ）不飽和基を含むポリフェニレンエーテル樹脂
と（ｂ）トリアリルイソシアヌレートおよび／またはト
リアリルシアヌレートと（ｃ）スチレン系熱可塑性樹脂
および／またはポリブタジエン樹脂と（ｄ）基材からな
ることを特徴とする硬化性複合材料。 ６）請求項５記載の硬化性複合材料を硬化して得られた
硬化複合材料。 ７）請求項６記載の硬化複合材料と金属箔からなる積層
体。 ８）金属ベース上に請求項６記載の硬化複合材料からな
る絶縁層を積層した積層板。 ９）金属ベース上の少なくとも片面に請求項６記載の硬
化複合材料からなる絶縁層が積層されており、かつ該絶
縁層の少なくとも最表層に金属箔が積層されていること
を特徴とする金属張り積層板。[Claims] 1) Consisting of (a) a polyphenylene ether resin containing an unsaturated group, (b) triallyl isocyanurate and/or triallyl cyanurate, and (c) a styrenic thermoplastic resin and/or a polybutadiene resin A curable polyphenylene ether resin composition. 2) The curable polyphenylene ether resin composition according to claim 1, which has a film shape. 3) A cured polyphenylene ether resin composition obtained by curing the curable polyphenylene ether resin composition according to claim 1. 4) The cured polyphenylene ether resin composition according to claim 3, which has a film shape. 5) Consisting of (a) polyphenylene ether resin containing an unsaturated group, (b) triallyl isocyanurate and/or triallyl cyanurate, (c) styrenic thermoplastic resin and/or polybutadiene resin, and (d) base material A curable composite material characterized by: 6) A cured composite material obtained by curing the curable composite material according to claim 5. 7) A laminate comprising the cured composite material according to claim 6 and metal foil. 8) A laminate in which an insulating layer made of the cured composite material according to claim 6 is laminated on a metal base. 9) A metal cladding characterized in that an insulating layer made of the cured composite material according to claim 6 is laminated on at least one side of a metal base, and a metal foil is laminated on at least the outermost layer of the insulating layer. Laminated board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20248990A JPH0488054A (en) | 1990-08-01 | 1990-08-01 | Curable polyphenylene ether-based resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20248990A JPH0488054A (en) | 1990-08-01 | 1990-08-01 | Curable polyphenylene ether-based resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0488054A true JPH0488054A (en) | 1992-03-19 |
Family
ID=16458350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20248990A Pending JPH0488054A (en) | 1990-08-01 | 1990-08-01 | Curable polyphenylene ether-based resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0488054A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004007617A1 (en) * | 2002-07-12 | 2004-01-22 | Daicel-Degussa Ltd. | Composite dispersion and process for producing the same |
| JP2005522553A (en) * | 2002-04-09 | 2005-07-28 | ゼネラル・エレクトリック・カンパニイ | Thermosetting composition, method and article |
| JP2005522552A (en) * | 2002-04-09 | 2005-07-28 | ゼネラル・エレクトリック・カンパニイ | Thermosetting composition, method and article |
| JP2006083364A (en) * | 2004-08-19 | 2006-03-30 | Mitsubishi Gas Chem Co Inc | Curable resin composition, curable film and film |
| JP2006516297A (en) * | 2003-01-28 | 2006-06-29 | 松下電工株式会社 | Polyphenylene ether resin composition, prepreg, laminate |
| JP2007507591A (en) * | 2003-10-03 | 2007-03-29 | ゼネラル・エレクトリック・カンパニイ | Flame retardant thermosetting composition, method and product |
| US7208539B2 (en) | 2002-04-16 | 2007-04-24 | Hitachi Chemical Co., Ltd. | Thermosetting resin composition, and prepreg and laminated board using the same |
| JP2007191681A (en) * | 2005-12-22 | 2007-08-02 | Mitsubishi Gas Chem Co Inc | Curable resin composition excellent in storage stability, curable film and film |
| JP2009249552A (en) * | 2008-04-09 | 2009-10-29 | Sumitomo Electric Ind Ltd | Flame-retardant resin composition, and insulated electric wire and flat cable using the same |
| JP2011519983A (en) * | 2008-04-23 | 2011-07-14 | サビック・イノベーティブ・プラスチックス・アイピー・ベスローテン・フェンノートシャップ | Electrical insulating varnish composition and use thereof |
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-
1990
- 1990-08-01 JP JP20248990A patent/JPH0488054A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005522553A (en) * | 2002-04-09 | 2005-07-28 | ゼネラル・エレクトリック・カンパニイ | Thermosetting composition, method and article |
| JP2005522552A (en) * | 2002-04-09 | 2005-07-28 | ゼネラル・エレクトリック・カンパニイ | Thermosetting composition, method and article |
| US7208539B2 (en) | 2002-04-16 | 2007-04-24 | Hitachi Chemical Co., Ltd. | Thermosetting resin composition, and prepreg and laminated board using the same |
| US7553912B2 (en) | 2002-07-12 | 2009-06-30 | Daicel-Evonik Ltd. | Composite dispersion and process for producing the same |
| WO2004007617A1 (en) * | 2002-07-12 | 2004-01-22 | Daicel-Degussa Ltd. | Composite dispersion and process for producing the same |
| CN100345909C (en) * | 2002-07-12 | 2007-10-31 | 大赛璐－德固萨株式会社 | Composite dispersion and process for producing the same |
| JP2006516297A (en) * | 2003-01-28 | 2006-06-29 | 松下電工株式会社 | Polyphenylene ether resin composition, prepreg, laminate |
| US7413791B2 (en) | 2003-01-28 | 2008-08-19 | Matsushita Electric Works, Ltd. | Poly (phenylene ether) resin composition, prepreg, and laminated sheet |
| US7838576B2 (en) | 2003-01-28 | 2010-11-23 | Panasonic Electric Works Co., Ltd | Poly (phenylene ether) resin composition, prepreg, and laminated sheet |
| JP2007507591A (en) * | 2003-10-03 | 2007-03-29 | ゼネラル・エレクトリック・カンパニイ | Flame retardant thermosetting composition, method and product |
| JP2006083364A (en) * | 2004-08-19 | 2006-03-30 | Mitsubishi Gas Chem Co Inc | Curable resin composition, curable film and film |
| JP2007191681A (en) * | 2005-12-22 | 2007-08-02 | Mitsubishi Gas Chem Co Inc | Curable resin composition excellent in storage stability, curable film and film |
| JP2009249552A (en) * | 2008-04-09 | 2009-10-29 | Sumitomo Electric Ind Ltd | Flame-retardant resin composition, and insulated electric wire and flat cable using the same |
| JP2011519983A (en) * | 2008-04-23 | 2011-07-14 | サビック・イノベーティブ・プラスチックス・アイピー・ベスローテン・フェンノートシャップ | Electrical insulating varnish composition and use thereof |
| JP2018504511A (en) * | 2014-12-22 | 2018-02-15 | ドゥーサン コーポレイション | High-frequency thermosetting resin composition, prepreg, laminate sheet and printed circuit board using the same |
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| US10590272B2 (en) | 2014-12-22 | 2020-03-17 | Doosan Corporation | Thermosetting resin composition for frequency, and prepreg, laminated sheet and printed circuit board using same |
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