WO2019198766A1 - Epoxy resin composition and molded body thereof - Google Patents
Epoxy resin composition and molded body thereof Download PDFInfo
- Publication number
- WO2019198766A1 WO2019198766A1 PCT/JP2019/015668 JP2019015668W WO2019198766A1 WO 2019198766 A1 WO2019198766 A1 WO 2019198766A1 JP 2019015668 W JP2019015668 W JP 2019015668W WO 2019198766 A1 WO2019198766 A1 WO 2019198766A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- resin composition
- mass
- epoxy
- compound
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 96
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 96
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 97
- 239000000463 material Substances 0.000 claims description 35
- 239000004065 semiconductor Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 239000003566 sealing material Substances 0.000 claims description 5
- 230000009970 fire resistant effect Effects 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 65
- 239000003795 chemical substances by application Substances 0.000 description 34
- 229920005989 resin Polymers 0.000 description 32
- 239000011347 resin Substances 0.000 description 32
- 239000011342 resin composition Substances 0.000 description 32
- -1 silver halide Chemical class 0.000 description 32
- 239000003063 flame retardant Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- 239000000835 fiber Substances 0.000 description 21
- 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 20
- 229920003986 novolac Polymers 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 15
- 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 14
- 239000010410 layer Substances 0.000 description 13
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 239000002184 metal Chemical class 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- 239000011256 inorganic filler Substances 0.000 description 10
- 229910003475 inorganic filler Inorganic materials 0.000 description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 9
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000004891 communication Methods 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229940106691 bisphenol a Drugs 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 2
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000007922 dissolution test Methods 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920012128 methyl methacrylate acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical class N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QKUSYGZVIAWWPY-UHFFFAOYSA-N 1,3-dioxane;7-oxabicyclo[4.1.0]heptane Chemical compound C1COCOC1.C1CCCC2OC21 QKUSYGZVIAWWPY-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- BPHYZRNTQNPLFI-UHFFFAOYSA-N 2,4,6-trihydroxytoluene Chemical compound CC1=C(O)C=C(O)C=C1O BPHYZRNTQNPLFI-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- FVCHRIQAIOHAIC-UHFFFAOYSA-N 2-[1-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COC(C)COCC1CO1 FVCHRIQAIOHAIC-UHFFFAOYSA-N 0.000 description 1
- NZHNJOJQMPJLFA-UHFFFAOYSA-N 2-[3,5-bis(oxiran-2-yl)phenyl]oxirane Chemical compound C1OC1C1=CC(C2OC2)=CC(C2OC2)=C1 NZHNJOJQMPJLFA-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 description 1
- HVMHLMJYHBAOPL-UHFFFAOYSA-N 4-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)propan-2-yl]-7-oxabicyclo[4.1.0]heptane Chemical compound C1CC2OC2CC1C(C)(C)C1CC2OC2CC1 HVMHLMJYHBAOPL-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000288673 Chiroptera Species 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- WLLGXSLBOPFWQV-UHFFFAOYSA-N MGK 264 Chemical compound C1=CC2CC1C1C2C(=O)N(CC(CC)CCCC)C1=O WLLGXSLBOPFWQV-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GLROGUSVUGSGPO-UHFFFAOYSA-N bis(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1C2OC2CC(C)C1OC(=O)CCCCC(=O)OC1CC2OC2CC1C GLROGUSVUGSGPO-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- KVRAGBDTQYNMNO-UHFFFAOYSA-N bis[2,4-bis(oxiran-2-ylmethoxy)phenyl]methanone Chemical compound C=1C=C(OCC2OC2)C=C(OCC2OC2)C=1C(=O)C(C(=C1)OCC2OC2)=CC=C1OCC1CO1 KVRAGBDTQYNMNO-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- BZDKYAZTCWRUDZ-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC=C.C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 BZDKYAZTCWRUDZ-UHFFFAOYSA-N 0.000 description 1
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- POZYRLCPPLVJLY-UHFFFAOYSA-N diphenylmethanediamine;oxiran-2-ylmethanamine Chemical compound NCC1CO1.C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 POZYRLCPPLVJLY-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002365 multiple layer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003012 phosphoric acid amides Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000004980 phosphorus peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002490 poly(thioether-sulfone) polymer Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- 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
Definitions
- Epoxy resins are excellent in heat resistance and moldability, and are used in many applications such as electrical, electronic and communication equipment, automobile parts, and fiber reinforced plastics. In particular, in electrical, electronic and communication equipment, there is a high demand for epoxy resin products having excellent flame retardancy.
- the compound represented by the formula (1) can be obtained, for example, by reacting hexachlorocyclotriphosphazene (2) and 2,2'-biphenol (3) in a solvent such as monochlorobenzene.
- 2,2'-biphenol (3) is preferably used in an amount of about 3 mol per 1 mol of hexachlorocyclotriphosphazene (2).
- the reaction temperature is preferably about 20 to 140 ° C., and the reaction time is preferably about 0.5 to 20 hours.
- the mixture represented by the formula (4) is mixed with the mixture represented by the formula (5) and 2,2′- It can be produced by reacting biphenol with a base.
- the mixture represented by the formula (5) can be produced by a known method. For example, JP-A 57-87427, JP-B 58-19604, JP-B 61- It can be produced according to the method described in Japanese Patent No. 1363 or Japanese Patent Publication No. Sho 62-20124.
- a general resin additive can be blended with the flame retardant resin composition of the present invention as long as the preferable characteristics are not impaired.
- the resin additive is not particularly limited, and examples thereof include ultraviolet absorbers (benzophenone, benzotriazole, cyanoacrylate, triazine, etc.), light stabilizers (hindered amine, etc.), antioxidants (hindered phenols).
- the mounting method is not particularly limited.
- a lead frame package a surface mounting package [SOP (small outline package), SOJ (small outline j-leaded package), QFP (quad flat package), BGA (ball grid array), etc. ],
- SOP small outline package
- SOJ small outline j-leaded package
- QFP quad flat package
- BGA ball grid array
- CSP chip size / scale package
Landscapes
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Provided are: a fire-resistant epoxy resin for which bleed out does not tend to occur; and a molded body thereof. The epoxy resin composition and the molded body thereof according to the present invention comprise a compound represented by formula (1).
Description
本発明は、エポキシ樹脂組成物及びその成型体に関する。
The present invention relates to an epoxy resin composition and a molded body thereof.
エポキシ樹脂は耐熱性及び成型性等に優れることから、電気、電子及び通信機器、自動車部品、並びに繊維強化プラスチック等の多くの用途で使用されている。特に電気、電子及び通信機器においては、難燃性能に優れたエポキシ樹脂製品の需要が高い。
Epoxy resins are excellent in heat resistance and moldability, and are used in many applications such as electrical, electronic and communication equipment, automobile parts, and fiber reinforced plastics. In particular, in electrical, electronic and communication equipment, there is a high demand for epoxy resin products having excellent flame retardancy.
代表的な難燃化方法として、難燃剤を樹脂に添加することが行われている。難燃剤としては、ハロゲン系難燃剤、リン系難燃剤、金属水酸化物系難燃剤等があり、これらの中では、安全性の配慮から、リン系難燃剤が多用されている。
As a typical flame retardant method, a flame retardant is added to a resin. Examples of flame retardants include halogen flame retardants, phosphorus flame retardants, metal hydroxide flame retardants, etc. Among these flame retardants, phosphorus flame retardants are frequently used from the viewpoint of safety.
リン系難燃剤としては、リン酸エステル、リン酸アミド、ポリリン酸アンモニウム、ホスファゼン等があり、その中でもホスファゼンは加水分解性が小さい等の理由から、特に環境安定性に優れている。しかし、エポキシ樹脂にホスファゼンを多量に添加した場合、得られた成型体は、高温状態にさらされることにより、該成型体表面にホスファゼンが溶出する現象（ブリードアウト）が生じ、難燃性能の低下、及び別の成型体又は材料との接着性の低下が起こるおそれがある。
Phosphorus flame retardants include phosphoric acid esters, phosphoric acid amides, ammonium polyphosphates, phosphazenes, etc. Among them, phosphazenes are particularly excellent in environmental stability because of their low hydrolyzability. However, when a large amount of phosphazene is added to the epoxy resin, the resulting molded body is exposed to a high temperature condition, causing a phenomenon (bleed out) that phosphazene elutes on the surface of the molded body, resulting in a decrease in flame retardancy. , And there is a possibility that the adhesiveness with another molded body or material may be lowered.
上記ブリードアウトの問題を解決するために、様々な方法が提案されている（例えば、特許文献１及び２）。特許文献１には、ホスファゼンをポリマー基材でマイクロカプセル化する方法が記載されており、特許文献２には、樹脂反応性の置換基を有するホスファゼンを用いて樹脂と反応させる方法が記載されている。しかしながら、特許文献１の方法においては、マイクロカプセルを構成する成分を添加物として樹脂に混合した際、樹脂の性能が大きく変化するおそれがあり、また、特許文献２の方法においては、ホスファゼンの置換基とエポキシ樹脂の反応部位との反応制御が難しいという欠点がある。
Various methods have been proposed to solve the above bleed-out problem (for example, Patent Documents 1 and 2). Patent Document 1 describes a method of microencapsulating phosphazene with a polymer substrate, and Patent Document 2 describes a method of reacting with a resin using phosphazene having a resin-reactive substituent. Yes. However, in the method of Patent Document 1, there is a possibility that the performance of the resin may change greatly when the components constituting the microcapsules are mixed as an additive with the resin. In the method of Patent Document 2, the substitution of phosphazene There is a drawback that it is difficult to control the reaction between the group and the reaction site of the epoxy resin.
また、電気・電子機器に使用されるプリント配線板は、機器の小型化及び高機能化が進んでおり、信頼性の向上等が要求されている。基板材料である樹脂への要求は、より一層の熱安定性又は耐熱性である。しかしながら、難燃性を付与するために添加もしくは配合する難燃剤は、エポキシ樹脂の成型体が本来有している熱安定性を低下する問題が生じる。
Also, printed wiring boards used for electrical and electronic equipment are becoming smaller and more functional, and there is a demand for improved reliability. The requirement for the resin that is the substrate material is more thermal stability or heat resistance. However, the flame retardant added or blended in order to impart flame retardancy has a problem of lowering the thermal stability inherent to the epoxy resin molding.
よって、ブリードアウトが生じず、しかも上記のような欠点を有さない、熱安定性に優れた難燃性エポキシ樹脂成型体の開発が求められている。
Therefore, there is a demand for the development of a flame-retardant epoxy resin molded article that does not cause bleed-out and does not have the above-described drawbacks and has excellent thermal stability.
本発明は、ブリードアウトが生じにくい難燃性エポキシ樹脂組成物及びその成型体を提供することを課題とする。
An object of the present invention is to provide a flame-retardant epoxy resin composition that hardly causes bleed-out and a molded body thereof.
本発明者らは、種々検討した結果、エポキシ樹脂と式（１）の化合物とを含む樹脂組成物から作製した成型体は、ブリードアウトが生じにくく、本発明の課題を解決できることを見出し、本発明を完成させるに至った。
As a result of various studies, the present inventors have found that a molded body produced from a resin composition containing an epoxy resin and a compound of formula (1) is less likely to bleed out and can solve the problems of the present invention. The invention has been completed.
すなわち、本発明は、下記項１～６に示すエポキシ樹脂組成物及び成型体等を提供する。
項１ 式（１）で表される化合物及びエポキシ樹脂を含むエポキシ樹脂組成物。 That is, the present invention provides an epoxy resin composition, a molded article and the like shown in the following items 1 to 6.
Item 1 An epoxy resin composition comprising a compound represented by formula (1) and an epoxy resin.
項１ 式（１）で表される化合物及びエポキシ樹脂を含むエポキシ樹脂組成物。 That is, the present invention provides an epoxy resin composition, a molded article and the like shown in the following items 1 to 6.
Item 1 An epoxy resin composition comprising a compound represented by formula (1) and an epoxy resin.
項２ エポキシ樹脂１００質量部に対して、式（１）で表される化合物が１～５０質量部含まれる項１に記載のエポキシ樹脂組成物。
項３ 項１又は２に記載のエポキシ樹脂組成物を用いて作製された成型体。
項４ 項１又は２に記載のエポキシ樹脂組成物を用いて作製された電気又は電子部品。
項５ 項１又は２に記載のエポキシ樹脂組成物を含む半導体素子用封止材。
項６ 項１又は２に記載のエポキシ樹脂組成物を用いて作製された基板材料。 Item 2 The epoxy resin composition according to Item 1, wherein 1 to 50 parts by mass of the compound represented by the formula (1) is contained with respect to 100 parts by mass of the epoxy resin.
Item 3 A molded article produced using the epoxy resin composition according to Item 1 or 2.
Item 4 An electrical or electronic component produced using the epoxy resin composition according to Item 1 or 2.
Item 5 A sealing material for a semiconductor element comprising the epoxy resin composition according to Item 1 or 2.
Item 6 A substrate material produced using the epoxy resin composition according to Item 1 or 2.
項３ 項１又は２に記載のエポキシ樹脂組成物を用いて作製された成型体。
項４ 項１又は２に記載のエポキシ樹脂組成物を用いて作製された電気又は電子部品。
項５ 項１又は２に記載のエポキシ樹脂組成物を含む半導体素子用封止材。
項６ 項１又は２に記載のエポキシ樹脂組成物を用いて作製された基板材料。 Item 2 The epoxy resin composition according to Item 1, wherein 1 to 50 parts by mass of the compound represented by the formula (1) is contained with respect to 100 parts by mass of the epoxy resin.
Item 3 A molded article produced using the epoxy resin composition according to Item 1 or 2.
Item 4 An electrical or electronic component produced using the epoxy resin composition according to Item 1 or 2.
Item 5 A sealing material for a semiconductor element comprising the epoxy resin composition according to Item 1 or 2.
Item 6 A substrate material produced using the epoxy resin composition according to Item 1 or 2.
本発明のエポキシ樹脂組成物は、難燃剤として式（１）で表される化合物を有しており、該樹脂組成物で成型体を作製した場合に、表面への該化合物の溶出を抑制することができる。その結果、前記成型体は、該化合物本来の難燃性能を発揮することができるとともに、別の材料との接着性に悪影響を与えることもない。さらに、本発明の成型体は、上記特許文献１及び２に記載されている欠点を有さない。よって、本発明の成型体は、電気、電子又は通信機器に好適に使用することができる。
The epoxy resin composition of the present invention has a compound represented by the formula (1) as a flame retardant, and suppresses elution of the compound to the surface when a molded body is produced from the resin composition. be able to. As a result, the molded body can exhibit the inherent flame retardancy of the compound and does not adversely affect the adhesion to other materials. Furthermore, the molded article of the present invention does not have the drawbacks described in Patent Documents 1 and 2 above. Therefore, the molded object of this invention can be used conveniently for an electric, electronic, or communication apparatus.
以下、本発明について詳細に説明する。
Hereinafter, the present invention will be described in detail.
式（１）で表される化合物
本発明のエポキシ樹脂組成物は、組成物内に式（１）で表される化合物を含有することを特徴としており、当該樹脂組成物を用いて製造される成型体は、ブリードアウトの発生が抑制されるだけでなく、熱安定性にも優れる。上記化合物は、エポキシ樹脂組成物内に添加しても溶出しないため、難燃効果を維持することができる。よって、式（１）で表される化合物は、エポキシ樹脂用の難燃剤として好適に使用することができる。 Compound represented by formula (1) The epoxy resin composition of the present invention contains a compound represented by formula (1) in the composition, and is produced using the resin composition. The molded body not only suppresses the occurrence of bleed-out, but also has excellent thermal stability. Since the above compound does not elute even when added to the epoxy resin composition, the flame retardant effect can be maintained. Therefore, the compound represented by Formula (1) can be suitably used as a flame retardant for epoxy resins.
本発明のエポキシ樹脂組成物は、組成物内に式（１）で表される化合物を含有することを特徴としており、当該樹脂組成物を用いて製造される成型体は、ブリードアウトの発生が抑制されるだけでなく、熱安定性にも優れる。上記化合物は、エポキシ樹脂組成物内に添加しても溶出しないため、難燃効果を維持することができる。よって、式（１）で表される化合物は、エポキシ樹脂用の難燃剤として好適に使用することができる。 Compound represented by formula (1) The epoxy resin composition of the present invention contains a compound represented by formula (1) in the composition, and is produced using the resin composition. The molded body not only suppresses the occurrence of bleed-out, but also has excellent thermal stability. Since the above compound does not elute even when added to the epoxy resin composition, the flame retardant effect can be maintained. Therefore, the compound represented by Formula (1) can be suitably used as a flame retardant for epoxy resins.
式（１）で表される化合物は、ハロゲン化銀写真感光材料（日本国特開２００２－１６９２４３号公報）、ポリエステル用の難燃剤（米国特許３８６５７８３号公報）等としての使用が報告されている公知の物質である。
The compound represented by the formula (1) has been reported to be used as a silver halide photographic light-sensitive material (Japanese Patent Laid-Open No. 2002-169243), a flame retardant for polyester (US Pat. No. 3,865,783), and the like. It is a known substance.
式（１）で表される化合物は、公知の製造方法を用いて製造することができる。例えば、次の反応式－１に示されるように、米国特許３３５６７６９号公報に記載の方法等により、式（１）で表される化合物を製造することができる。
The compound represented by Formula (1) can be manufactured using a well-known manufacturing method. For example, as shown in the following reaction formula-1, the compound represented by the formula (1) can be produced by the method described in US Pat. No. 3,356,769.
式（２）で表されるヘキサクロロシクロトリホスファゼンは、公知の方法、すなわち五塩化リンと塩化アンモニウムとの反応に基づく製造方法により製造することができる。また、市販のものを用いることもできる。
The hexachlorocyclotriphosphazene represented by the formula (2) can be produced by a known method, that is, a production method based on a reaction between phosphorus pentachloride and ammonium chloride. Commercially available products can also be used.
反応式－１中の塩基として、アルカリ金属塩、アミン化合物等が挙げられ、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム等のアルカリ金属塩が好ましい。
Examples of the base in Reaction Formula-1 include alkali metal salts and amine compounds, and alkali metal salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate are preferable.
式（１）で表される化合物は、例えば、ヘキサクロロシクロトリホスファゼン（２）と２，２’－ビフェノール（３）とを、モノクロロベンゼン等の溶媒中において反応させることにより得ることができる。２，２’－ビフェノール（３）は、ヘキサクロロシクロトリホスファゼン（２）１ｍｏｌに対して３ｍｏｌ程度使用することが好ましい。反応温度は、２０～１４０℃程度が好ましく、反応時間は０．５～２０時間程度が好ましい。
The compound represented by the formula (1) can be obtained, for example, by reacting hexachlorocyclotriphosphazene (2) and 2,2'-biphenol (3) in a solvent such as monochlorobenzene. 2,2'-biphenol (3) is preferably used in an amount of about 3 mol per 1 mol of hexachlorocyclotriphosphazene (2). The reaction temperature is preferably about 20 to 140 ° C., and the reaction time is preferably about 0.5 to 20 hours.
本発明のエポキシ樹脂組成物には、式（１）で表される化合物が含まれていればよい。
The epoxy resin composition of the present invention only needs to contain a compound represented by the formula (1).
本発明のエポキシ樹脂組成物における、式（１）で表される化合物の配合量は、エポキシ樹脂１００質量部に対して、好ましくは１～５０質量部程度であり、より好ましくは３～４０質量部程度であり、更に好ましくは５～３０質量部程度である。
The compounding amount of the compound represented by the formula (1) in the epoxy resin composition of the present invention is preferably about 1 to 50 parts by mass, more preferably 3 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin. Part, more preferably about 5 to 30 parts by weight.
本発明のエポキシ樹脂組成物は、式（１）で表される化合物を含む、下記式（４）で表される混合物が配合される態様を包含する。
The epoxy resin composition of the present invention includes an embodiment in which a mixture represented by the following formula (4) including a compound represented by the formula (1) is blended.
式（４）で表される混合物は当該混合物１００質量％中に、例えば、式（４）においてｎが３である化合物（式（１）で表される化合物）を５０～９０質量％、式（４）においてｎが４である化合物を５～４０質量％、式（４）においてｎが５である化合物を０～３０質量％、及び式（４）においてｎが６～１５である化合物を０～２０質量％含んでいることが好ましい。
The mixture represented by the formula (4) contains, for example, 50 to 90% by mass of a compound in which n is 3 in the formula (4) (a compound represented by the formula (1)) in 100% by mass of the mixture. A compound in which n is 4 in (4) is 5 to 40% by mass, a compound in which n is 5 in formula (4) is 0 to 30% by mass, and a compound in which n is 6 to 15 in formula (4) The content is preferably 0 to 20% by mass.
本発明のエポキシ樹脂組成物に、式（１）で表される化合物を式（４）で表される混合物の形態で配合する場合は、式（４）で表される混合物を、式（４）で表される混合物中のｎが３である化合物（式（１）で表される化合物）が、エポキシ樹脂１００質量部に対して、好ましくは１～５０質量部程度であり、より好ましくは３～４０質量部程度であり、更に好ましくは５～３０質量部程度となるように配合すればよい。
When blending the compound represented by the formula (1) in the form of the mixture represented by the formula (4) with the epoxy resin composition of the present invention, the mixture represented by the formula (4) is represented by the formula (4). ) In the mixture represented by formula (1) is preferably about 1 to 50 parts by mass, more preferably about 100 parts by mass of the epoxy resin. The amount is about 3 to 40 parts by mass, and more preferably about 5 to 30 parts by mass.
式（４）で表される混合物は、上記式（１）で表される化合物の製造方法においてヘキサクロロシクロトリホスファゼンを使用する替わりに、式（５）で表される混合物と２，２’－ビフェノールとを塩基存在下で反応させることで製造することができる。なお、式（５）で表される混合物は、式（５）においてｍが３である化合物（式（２）で表される化合物）を５０～９０質量％、式（５）においてｍが４である化合物を５～４０質量％、式（５）においてｍ＝５である化合物を０～３０質量％、及び式（５）においてｍが６～１５である化合物を０～２０質量％含むことが好ましい。式（５）で表される混合物は、公知の方法により製造することができ、例えば、日本国特開昭５７－８７４２７号公報、日本国特公昭５８－１９６０４号公報、日本国特公昭６１－１３６３号公報、又は日本国特公昭６２－２０１２４号公報等に記載の方法に従って製造することができる。
Instead of using hexachlorocyclotriphosphazene in the method for producing the compound represented by the above formula (1), the mixture represented by the formula (4) is mixed with the mixture represented by the formula (5) and 2,2′- It can be produced by reacting biphenol with a base. The mixture represented by formula (5) is 50 to 90% by mass of the compound (compound represented by formula (2)) in which m is 3 in formula (5), and m is 4 in formula (5). 5 to 40% by mass of the compound of formula (5), 0 to 30% by mass of the compound of m = 5 in the formula (5), and 0 to 20% by mass of the compound of m (6 to 15 in the formula (5)). Is preferred. The mixture represented by the formula (5) can be produced by a known method. For example, JP-A 57-87427, JP-B 58-19604, JP-B 61- It can be produced according to the method described in Japanese Patent No. 1363 or Japanese Patent Publication No. Sho 62-20124.
エポキシ樹脂
本発明のエポキシ樹脂組成物で使用されるエポキシ樹脂は、この分野で公知のものを広く使用することができる。 Epoxy Resin As the epoxy resin used in the epoxy resin composition of the present invention, those known in this field can be widely used.
本発明のエポキシ樹脂組成物で使用されるエポキシ樹脂は、この分野で公知のものを広く使用することができる。 Epoxy Resin As the epoxy resin used in the epoxy resin composition of the present invention, those known in this field can be widely used.
エポキシ樹脂としては、例えば、フェノール類とアルデヒド類との反応により得られるノボラック型エポキシ樹脂；フェノール類とエピクロルヒドリンとの反応により得られるフェノール型エポキシ樹脂；トリメチロールプロパン、オリゴプロピレングリコール、水添ビスフェノール－Ａ等のアルコールとエピクロルヒドリンとの反応により得られる脂肪族エポキシ樹脂；ヘキサヒドロフタル酸、テトラヒドロフタル酸又はフタル酸と、エピクロルヒドリン又は２－メチルエピクロルヒドリンとの反応により得られるグリシジルエステル系エポキシ樹脂；ジアミノジフェニルメタン、アミノフェノール等のアミンとエピクロルヒドリンとの反応により得られるグリシジルアミン系エポキシ樹脂；イソシアヌル酸等のポリアミンとエピクロルヒドリンとの反応により得られる複素環式エポキシ樹脂；及びこれらの変性エポキシ樹脂等を挙げることができる。
Examples of epoxy resins include novolak type epoxy resins obtained by reaction of phenols with aldehydes; phenol type epoxy resins obtained by reaction of phenols with epichlorohydrin; trimethylolpropane, oligopropylene glycol, hydrogenated bisphenol- Aliphatic epoxy resins obtained by reaction of alcohols such as A with epichlorohydrin; glycidyl ester epoxy resins obtained by reaction of hexahydrophthalic acid, tetrahydrophthalic acid or phthalic acid with epichlorohydrin or 2-methylepichlorohydrin; diaminodiphenylmethane Glycidylamine epoxy resin obtained by reaction of amine such as aminophenol and epichlorohydrin; polyamine such as isocyanuric acid and epichloro Heterocyclic epoxy resins obtained by reaction of drinks; and can be exemplified those modified epoxy resin.
前記ノボラック型エポキシ樹脂として、フェノールノボラック型エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂及びナフトールノボラック型エポキシ樹脂等が挙げられる。
Examples of the novolak type epoxy resin include phenol novolak type epoxy resin, brominated phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, and naphthol novolak type epoxy resin.
前記フェノール型エポキシ樹脂として、ビスフェノール－Ａ型エポキシ樹脂、臭素化ビスフェノール－Ａ型エポキシ樹脂、ビスフェノール－Ｆ型エポキシ樹脂、ビスフェノール－ＡＤ型エポキシ樹脂、ビスフェノール－Ｓ型エポキシ樹脂、アルキル置換ビフェノール型エポキシ樹脂、トリス（ヒドロキシフェニル）メタン型エポキシ樹脂等が挙げられる。
As the phenol type epoxy resin, bisphenol-A type epoxy resin, brominated bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-AD type epoxy resin, bisphenol-S type epoxy resin, alkyl-substituted biphenol type epoxy resin And tris (hydroxyphenyl) methane type epoxy resin.
これらの中でも、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ビスフェノール－Ａ型エポキシ樹脂、ビスフェノール－Ｆ型エポキシ樹脂、及びフェノール型エポキシ樹脂が好ましい。これらの樹脂は、１種単独で又は２種以上を混合して使用することができる。
Among these, phenol novolac type epoxy resins, orthocresol novolak type epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, and phenol type epoxy resins are preferable. These resins can be used singly or in combination of two or more.
あるいは、エポキシ樹脂を使用せずに、組成物中においてエポキシ樹脂を製造することも可能である。例えば、組成物にエポキシ化合物と硬化剤とを添加し、加熱することで樹脂化させることにより、エポキシ樹脂を得ることができる。
Alternatively, it is possible to produce an epoxy resin in the composition without using an epoxy resin. For example, an epoxy resin can be obtained by adding an epoxy compound and a curing agent to the composition, and making it resin by heating.
後述する全ての実施例にも示されるとおり、エポキシ樹脂は、エポキシ化合物と硬化剤との反応物である。
As shown in all examples described later, the epoxy resin is a reaction product of an epoxy compound and a curing agent.
エポキシ化合物としては、エポキシ基を有する化合物を制限なく使用することができる。
As the epoxy compound, a compound having an epoxy group can be used without limitation.
エポキシ化合物としては、例えば、フェノール類とアルデヒド類との反応物とエピクロルヒドリン又は２－メチルエピクロルヒドリン等のエピクロルヒドリン類との反応により得られるノボラック型エポキシ化合物；フェノール類とエピクロルヒドリン類との反応により得られるフェノール型エポキシ化合物；トリメチロールプロパン、オリゴプロピレングリコール、水添ビスフェノール－Ａ等のアルコールとエピクロルヒドリン類との反応により得られる脂肪族エポキシ化合物；ヘキサヒドロフタル酸、テトラヒドロフタル酸又はフタル酸と、エピクロルヒドリン類との反応により得られるグリシジルエステル系エポキシ化合物；ジアミノジフェニルメタン、アミノフェノール等のアミンとエピクロルヒドリン類との反応により得られるグリシジルアミン系エポキシ化合物；イソシアヌル酸等のポリアミンとエピクロルヒドリン類との反応により得られる複素環式エポキシ化合物；及びこれらの変性エポキシ化合物等を挙げることができる。
Examples of the epoxy compound include a novolak-type epoxy compound obtained by reacting a reaction product of a phenol and an aldehyde with an epichlorohydrin such as epichlorohydrin or 2-methylepichlorohydrin; a phenol obtained by a reaction of a phenol with epichlorohydrin Type epoxy compounds; aliphatic epoxy compounds obtained by reaction of alcohols such as trimethylolpropane, oligopropylene glycol, hydrogenated bisphenol-A and epichlorohydrins; hexahydrophthalic acid, tetrahydrophthalic acid or phthalic acid, and epichlorohydrins Glycidyl ester epoxy compound obtained by the reaction of: obtained by reaction of amine such as diaminodiphenylmethane and aminophenol with epichlorohydrin Rishijiruamin based epoxy compounds; heterocyclic epoxy compound obtained by reaction of a polyamine with epichlorohydrin such as isocyanuric acid; and can be exemplified those modified epoxy compound or the like.
前記ノボラック型エポキシ化合物として、フェノールノボラック型エポキシ化合物、臭素化フェノールノボラック型エポキシ化合物、オルトクレゾールノボラック型エポキシ化合物及びナフトールノボラック型エポキシ化合物等が挙げられる。
Examples of the novolak type epoxy compound include a phenol novolak type epoxy compound, a brominated phenol novolak type epoxy compound, an orthocresol novolak type epoxy compound, and a naphthol novolak type epoxy compound.
前記フェノール型エポキシ化合物として、ビスフェノール－Ａ型エポキシ化合物、臭素化ビスフェノール－Ａ型エポキシ化合物、ビスフェノール－Ｆ型エポキシ化合物、ビスフェノール－ＡＤ型エポキシ化合物、ビスフェノール－Ｓ型エポキシ化合物、アルキル置換ビフェノール型エポキシ化合物、トリス（ヒドロキシフェニル）メタン型エポキシ化合物等が挙げられる。
As the phenol type epoxy compound, bisphenol-A type epoxy compound, brominated bisphenol-A type epoxy compound, bisphenol-F type epoxy compound, bisphenol-AD type epoxy compound, bisphenol-S type epoxy compound, alkyl-substituted biphenol type epoxy compound And tris (hydroxyphenyl) methane type epoxy compound.
これらの中でも、フェノールノボラック型エポキシ化合物、オルトクレゾールノボラック型エポキシ化合物、ビスフェノール－Ａ型エポキシ化合物、ビスフェノール－Ｆ型エポキシ化合物、及びフェノール型エポキシ化合物が好ましい。これらの化合物は、１種単独で又は２種以上を混合して使用することができる。
Among these, phenol novolac type epoxy compounds, orthocresol novolac type epoxy compounds, bisphenol-A type epoxy compounds, bisphenol-F type epoxy compounds, and phenol type epoxy compounds are preferable. These compounds can be used individually by 1 type or in mixture of 2 or more types.
また、上記エポキシ化合物に単官能性のエポキシ化合物、２官能性のエポキシ化合物又は３官能性以上の多官能性のエポキシ化合物を加えることで、エポキシ樹脂を変性することができる。
Moreover, the epoxy resin can be modified by adding a monofunctional epoxy compound, a bifunctional epoxy compound, or a trifunctional or higher polyfunctional epoxy compound to the epoxy compound.
単官能性のエポキシ化合物の具体例として、例えば、ブチルグリシジルエーテル、フェニルグリシジルエーテル、クレジルグリシジルエーテル、アリルグリシジルエーテル、アルコールのグリシジルエーテル等を挙げることができる。
Specific examples of the monofunctional epoxy compound include butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, glycidyl ether of alcohol, and the like.
２官能性のエポキシ化合物の具体例として、例えば、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ビスフェノールＡのジグリシジルエーテル、ブタジエンジエポキシド、３，４－エポキシシクロヘキシルメチル－（３，４－エポキシ）シクロヘキサンカルボキシレート、ビニルシクロヘキサンジオキシド、４，４’－ジ（１，２－エポキシエチル）ジフェニルエーテル、４，４’－（１，２－エポキシエチル）ビフェニル、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、レゾルシンのグリシジルエーテル、フロログルシンのジグリシジルエーテル、メチルフロログルシンのジグリシジルエーテル、ビス（２，３’－エポキシシクロペンチル）エーテル、２－（３，４－エポキシ）シクロヘキサン－５，５－スピロ（３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン、ビス（３，４－エポキシ－６－メチルシクロヘキシル）アジペート、Ｎ，Ｎ’－ｍ－フェニレンビス（４，５－エポキシ－１，２－シクロヘキサン）ジカルボキシイミド等を挙げることができる。
Specific examples of the bifunctional epoxy compound include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, butadiene Diepoxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, vinylcyclohexane dioxide, 4,4′-di (1,2-epoxyethyl) diphenyl ether, 4,4 ′-(1 , 2-epoxyethyl) biphenyl, 2,2-bis (3,4-epoxycyclohexyl) propane, resorcin glycidyl ether, phloroglucin diglycidyl ether, methylphloroglucin di Lysidyl ether, bis (2,3′-epoxycyclopentyl) ether, 2- (3,4-epoxy) cyclohexane-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, bis (3,4 -Epoxy-6-methylcyclohexyl) adipate, N, N'-m-phenylenebis (4,5-epoxy-1,2-cyclohexane) dicarboximide and the like.
３官能性以上の多官能性のエポキシ化合物の具体例として、例えば、ｐ－アミノフェノールのトリグリシジルエーテル、ポリアリルグリシジルエーテル、１，３，５－トリ（１，２－エポキシエチル）ベンゼン、２，２’，４，４’－テトラグリシドキシベンゾフェノン、フェノールホルムアルデヒドノボラックのポリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル等を挙げることができる。
Specific examples of the trifunctional or higher polyfunctional epoxy compound include, for example, p-aminophenol triglycidyl ether, polyallyl glycidyl ether, 1,3,5-tri (1,2-epoxyethyl) benzene, 2 2,2 ', 4,4'-tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolak, triglycidyl ether of trimethylolpropane, triglycidyl ether of trimethylolpropane, and the like.
これらの単官能性のエポキシ化合物、２官能性のエポキシ化合物又は３官能性以上の多官能性のエポキシ化合物は、それぞれ１種を単独で、又は２種以上を併用することができる。
These monofunctional epoxy compounds, bifunctional epoxy compounds, or trifunctional or higher polyfunctional epoxy compounds can be used alone or in combination of two or more.
硬化剤としては、この分野で公知のものを広く使用することができる。硬化剤として、例えば、ジシアンジアミド（ＤＩＣＹ）化合物、ノボラック型フェノール樹脂、アミノ変性ノボラック型フェノール樹脂、ポリビニルフェノール樹脂、有機酸ヒドラジド、ジアミノマレオニトリル化合物、メラミン化合物、アミンイミド、ポリアミン塩、モレキュラーシーブ、アミン化合物、酸無水物、ポリアミド、イミダゾール、光又は紫外線硬化剤等を挙げることができる。
As the curing agent, those known in this field can be widely used. Examples of curing agents include dicyandiamide (DICY) compounds, novolac-type phenol resins, amino-modified novolac-type phenol resins, polyvinylphenol resins, organic acid hydrazides, diaminomaleonitrile compounds, melamine compounds, amine imides, polyamine salts, molecular sieves, amine compounds. , Acid anhydrides, polyamides, imidazoles, light or ultraviolet curing agents, and the like.
これらの中でも、アミン化合物で硬化させたエポキシ樹脂と上記式（１）で表される化合物とを含む組成物を用いて作製された成型体は、ホスファゼン（式（１）で表される化合物）の溶出抑制効果が特に高いことから、アミン化合物が好ましい。アミン化合物の具体例として、例えば、ジアミノジフェニルスルフォン、ｍ－キシリレンジアミン、Ｎ－アミノエチルピペラジン、ジエチレントリアミン、ジアミノジフェニルメタン等が挙げられる。
Among these, the molded object produced using the composition containing the epoxy resin hardened with the amine compound and the compound represented by the above formula (1) is phosphazene (compound represented by the formula (1)). An amine compound is preferred because of its particularly high elution suppression effect. Specific examples of the amine compound include diaminodiphenyl sulfone, m-xylylenediamine, N-aminoethylpiperazine, diethylenetriamine, and diaminodiphenylmethane.
これらの硬化剤は、１種単独で又は２種以上を混合して使用することができる。
These curing agents can be used singly or in combination of two or more.
硬化剤の配合量は、エポキシ化合物のエポキシ当量、硬化剤の活性水素当量又はアミン当量（アミン系硬化剤の活性水素の当量）等より、エポキシ化合物及び硬化剤の官能基数に基づいて適宜調整すればよい。
The compounding amount of the curing agent is appropriately adjusted based on the number of functional groups of the epoxy compound and the curing agent from the epoxy equivalent of the epoxy compound, the active hydrogen equivalent of the curing agent, or the amine equivalent (equivalent of active hydrogen of the amine curing agent). That's fine.
例えば、エポキシ当量が１６０～１７０のビスフェノールＦ型（三菱ケミカル株式会社製、エピコート８０６）のエポキシ化合物をアミン当量が６２の硬化剤であるジアミノジフェニルスルフォンで硬化させる場合、エポキシ化合物１質量部に対して、最適な硬化剤の配合量は、０．３６～０．３９質量部である。
For example, when an epoxy compound of bisphenol F type (Epicoat 806, manufactured by Mitsubishi Chemical Corporation) having an epoxy equivalent of 160 to 170 is cured with diaminodiphenyl sulfone, which is a curing agent having an amine equivalent of 62, with respect to 1 part by mass of the epoxy compound The optimum amount of the curing agent is 0.36 to 0.39 parts by mass.
エポキシ当量が１８４～１９４のビスフェノールＡ型（三菱ケミカル株式会社製、エピコート８２８）のエポキシ化合物をアミン当量が６２の硬化剤であるジアミノジフェニルスルフォンで硬化させる場合、エポキシ化合物１質量部に対して、最適な硬化剤の配合量は、０．３２～０．３４質量部である。
When the epoxy compound of bisphenol A type having an epoxy equivalent of 184 to 194 (Epicoat 828, manufactured by Mitsubishi Chemical Corporation) is cured with diaminodiphenyl sulfone, which is a curing agent having an amine equivalent of 62, with respect to 1 part by mass of the epoxy compound, The optimum amount of the curing agent is 0.32 to 0.34 parts by mass.
エポキシ当量が１７６～１８０のフェノールノボラック型（三菱ケミカル株式会社製、エピコート１５４）のエポキシ化合物をアミン当量が６２の硬化剤であるジアミノジフェニルスルフォンで硬化させる場合、エポキシ化合物１質量部に対して、最適な硬化剤の配合量は、０．３４～０．３５質量部である。
When a phenol novolac type epoxy compound having an epoxy equivalent of 176 to 180 (Epicoat 154, manufactured by Mitsubishi Chemical Corporation) is cured with diaminodiphenyl sulfone, which is a curing agent having an amine equivalent of 62, with respect to 1 part by mass of the epoxy compound, The optimum amount of the curing agent is 0.34 to 0.35 parts by mass.
エポキシ当量が１９１～２０７のクレゾールノボラック型（日本化薬株式会社製、ＥＯＣＮ－１０２０）のエポキシ化合物をアミン当量が６２の硬化剤であるジアミノジフェニルスルフォンで硬化させる場合、エポキシ化合物１質量部に対して、最適な硬化剤の配合量は、０．３０～０．３２質量部である。
When an epoxy compound of cresol novolac type (EOCN-1020, manufactured by Nippon Kayaku Co., Ltd.) having an epoxy equivalent of 191 to 207 is cured with diaminodiphenyl sulfone, which is a curing agent having an amine equivalent of 62, to 1 part by mass of the epoxy compound The optimum amount of the curing agent is 0.30 to 0.32 parts by mass.
エポキシ当量が１５８～１７８のフェノール型（日本化薬株式会社製、ＥＰＰＮ－５０２Ｈ）のエポキシ化合物をアミン当量が６２の硬化剤であるジアミノジフェニルスルフォンで硬化させる場合、エポキシ化合物１質量部に対して、最適な硬化剤の配合量は、０．３５～０．３９質量部である。
When a phenol type epoxy compound having an epoxy equivalent of 158 to 178 (EPPN-502H, manufactured by Nippon Kayaku Co., Ltd.) is cured with diaminodiphenyl sulfone, which is a curing agent having an amine equivalent of 62, to 1 part by mass of the epoxy compound The optimum amount of the curing agent is 0.35 to 0.39 parts by mass.
また、硬化を促進するために、硬化助剤を添加してもよい。硬化助剤としては、この分野で公知のものを広く使用することができる。硬化助剤として、例えば、第三級アミン、イミダゾール、芳香族アミン及びトリフェニルホスフィン等を挙げることができる。これらの硬化助剤は、１種単独で又は２種以上混合して使用することができる。硬化助剤の配合量は特に制限されず、通常、エポキシ樹脂１００質量部に対して、１０質量部以下、好ましくは５質量部以下、より好ましくは１質量部以下である。硬化助剤の配合量の下限値は特に限定されず、例えばエポキシ樹脂１００質量部に対して０．０１質量部とすることが好ましく、０．１質量部とすることがより好ましい。
Also, a curing aid may be added to accelerate curing. As the curing aid, those known in this field can be widely used. Examples of the curing aid include tertiary amine, imidazole, aromatic amine and triphenylphosphine. These curing aids can be used singly or in combination of two or more. The compounding quantity of a hardening adjuvant is not restrict | limited in particular, Usually, it is 10 mass parts or less with respect to 100 mass parts of epoxy resins, Preferably it is 5 mass parts or less, More preferably, it is 1 mass part or less. The lower limit of the compounding amount of the curing aid is not particularly limited. For example, it is preferably 0.01 parts by mass, more preferably 0.1 parts by mass with respect to 100 parts by mass of the epoxy resin.
本発明の樹脂組成物は、樹脂として少なくともエポキシ樹脂を含むが、エポキシ樹脂以外にその他の樹脂を含んでもよい。その他の樹脂として、例えば、ポリエチレン、ポリプロピレン、ポリイソプレン、塩素化ポリエチレン、ポリ塩化ビニル、ポリブタジエン、ポリスチレン、耐衝撃性ポリスチレン、アクリロニトリル－スチレン樹脂（ＡＳ樹脂）、アクリロニトリル－ブタジエン－スチレン樹脂（ＡＢＳ樹脂）、メチルメタクリレート－ブタジエン－スチレン樹脂（ＭＢＳ樹脂）、メチルメタクリレート－アクリロニトリル－ブタジエン－スチレン樹脂（ＭＡＢＳ樹脂）、アクリロニトリル－アクリルゴム－スチレン樹脂（ＡＡＳ樹脂）、ポリメチル（メタ）アクリレート、ポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等）、ポリカーボネート、ポリフェニレンエーテル、変性ポリフェニレンエーテル、ポリアミド（脂肪族系及び／又は芳香族系）、ポリフェニレンスルフィド、ポリイミド、ポリエーテルエーテルケトン、ポリスルホン、ポリアリレート、ポリエーテルケトン、ポリエーテルニトリル、ポリチオエーテルスルホン、ポリエーテルスルホン、ポリベンズイミダゾール、ポリカルボジイミド、ポリアミドイミド、ポリエーテルイミド、液晶ポリマー、ポリウレタン、フェノール樹脂、メラミン樹脂、尿素樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、シリコン樹脂、ポリ乳酸等が挙げられる。これらは、１種を単独で使用することができ、又は２種以上を併用することできる。
The resin composition of the present invention contains at least an epoxy resin as a resin, but may contain other resins in addition to the epoxy resin. Other resins include, for example, polyethylene, polypropylene, polyisoprene, chlorinated polyethylene, polyvinyl chloride, polybutadiene, polystyrene, high impact polystyrene, acrylonitrile-styrene resin (AS resin), and acrylonitrile-butadiene-styrene resin (ABS resin). , Methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acrylic rubber-styrene resin (AAS resin), polymethyl (meth) acrylate, polyester (polyethylene terephthalate, Polybutylene terephthalate, polyethylene naphthalate, etc.), polycarbonate, polyphenylene ether, modified polyphenylene ether , Polyamide (aliphatic and / or aromatic), polyphenylene sulfide, polyimide, polyetheretherketone, polysulfone, polyarylate, polyetherketone, polyethernitrile, polythioethersulfone, polyethersulfone, polybenzimidazole, poly Examples thereof include carbodiimide, polyamideimide, polyetherimide, liquid crystal polymer, polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicon resin, and polylactic acid. These can be used individually by 1 type or can use 2 or more types together.
樹脂としてエポキシ樹脂以外の樹脂を含む場合、その配合量は、エポキシ樹脂１００質量部に対して、通常０．０１～１００質量部程度、好ましくは０．１～５０質量部である。
When a resin other than an epoxy resin is included as the resin, the blending amount is usually about 0.01 to 100 parts by mass, preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin.
その他の添加剤
本発明の難燃性樹脂組成物には、必要に応じて、その難燃性能、特にドリッピング（燃焼時の滴下による延焼）防止性能をより一層向上させる目的で、フッ素樹脂、無機充填材等を配合することができる。これらは、いずれかを単独で配合することができ、又は両方を同時に配合することができる。 Other additives For the flame retardant resin composition of the present invention, if necessary, in order to further improve the flame retardant performance, in particular, the dripping (spreading by dripping during combustion) prevention performance, An inorganic filler or the like can be blended. Any of these can be blended alone, or both can be blended simultaneously.
本発明の難燃性樹脂組成物には、必要に応じて、その難燃性能、特にドリッピング（燃焼時の滴下による延焼）防止性能をより一層向上させる目的で、フッ素樹脂、無機充填材等を配合することができる。これらは、いずれかを単独で配合することができ、又は両方を同時に配合することができる。 Other additives For the flame retardant resin composition of the present invention, if necessary, in order to further improve the flame retardant performance, in particular, the dripping (spreading by dripping during combustion) prevention performance, An inorganic filler or the like can be blended. Any of these can be blended alone, or both can be blended simultaneously.
フッ素樹脂としては公知のものを使用することができる。フッ素樹脂として、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン－エチレン共重合体（ＥＴＦＥ）、ポリ（トリフルオロクロロエチレン）（ＣＴＦＥ）、ポリフルオロビニリデン（ＰＶｄＦ）等が挙げられる。これらの中でも、ＰＴＦＥが好ましい。フッ素樹脂は１種を単独で使用することができ、又は２種以上を併用することができる。
A well-known thing can be used as a fluororesin. Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-ethylene copolymer. Examples include coalescence (ETFE), poly (trifluorochloroethylene) (CTFE), and polyfluorovinylidene (PVdF). Among these, PTFE is preferable. A fluororesin can be used individually by 1 type, or can use 2 or more types together.
フッ素樹脂の配合量は特に制限されず、エポキシ樹脂１００質量部に対し、通常、０．０１～２．５質量部程度であり、好ましくは、０．１～１．２質量部程度である。
The blending amount of the fluororesin is not particularly limited, and is usually about 0.01 to 2.5 parts by mass, preferably about 0.1 to 1.2 parts by mass with respect to 100 parts by mass of the epoxy resin.
無機充填材は、ドリッピング防止効果を増強させるとともに、樹脂組成物の機械的強度、電気的性能（例えば、絶縁性、導電性、異方導電性、誘電性、耐湿性等）、熱的性能（例えば、耐熱性、ハンダ耐熱性、熱伝導性、低熱収縮性、低熱膨張性、低応力性、耐熱衝撃性、耐ヒートサイクル性、耐リフロークラック性、保存安定性、温度サイクル性等）、作業性又は成形性（流動性、硬化性、接着性、粘着性、圧着性、密着性、アンダーフィル性、ボイドフリー性、耐摩耗性、潤滑性、離型性、高弾性、低弾性、可とう性、屈曲性等）も向上させることができる。
Inorganic fillers enhance the anti-dripping effect, as well as the mechanical strength, electrical performance (eg, insulation, conductivity, anisotropic conductivity, dielectric, moisture resistance, etc.) and thermal performance of the resin composition. (For example, heat resistance, solder heat resistance, thermal conductivity, low thermal shrinkage, low thermal expansion, low stress, thermal shock resistance, heat cycle resistance, reflow crack resistance, storage stability, temperature cycle characteristics, etc.), Workability or moldability (fluidity, curability, adhesiveness, adhesiveness, pressure-bonding, adhesion, underfill, void-free, wear resistance, lubricity, releasability, high elasticity, low elasticity, good Flexibility, flexibility, etc.) can also be improved.
無機充填材としては、特に制限はなく、公知の無機充填材を使用することができる。無機充填材として、例えば、マイカ、カオリン、タルク、溶融シリカ、結晶シリカ、アルミナ、クレー、硫酸バリウム、炭酸バリウム、炭酸カルシウム、硫酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、珪酸カルシウム、酸化チタン、酸化亜鉛、ホウ酸亜鉛、窒化アルミニウム、窒化ホウ素、窒化珪素、ガラスビーズ、ガラスバルーン、ガラスフレーク、ガラスファイバー、繊維状チタン酸アルカリ金属塩（チタン酸カリウム繊維、チタン酸ナトリウム繊維等）、繊維状ホウ酸塩（ホウ酸アルミニウム繊維、ホウ酸マグネシウム繊維、ホウ酸亜鉛繊維等）、酸化亜鉛繊維、酸化チタン繊維、酸化マグネシウム繊維、石膏繊維、珪酸アルミニウム繊維、珪酸カルシウム繊維、炭化珪素繊維、炭化チタン繊維、窒化珪素繊維、窒化チタン繊維、炭素繊維、アルミナ繊維、アルミナ－シリカ繊維、ジルコニア繊維、石英繊維、薄片状チタン酸塩、薄片状酸化チタン等が挙げられる。
There is no restriction | limiting in particular as an inorganic filler, A well-known inorganic filler can be used. Examples of inorganic fillers include mica, kaolin, talc, fused silica, crystalline silica, alumina, clay, barium sulfate, barium carbonate, calcium carbonate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, calcium silicate, titanium oxide, and oxidation. Zinc, zinc borate, aluminum nitride, boron nitride, silicon nitride, glass beads, glass balloon, glass flake, glass fiber, fibrous alkali metal titanate (potassium titanate fiber, sodium titanate fiber, etc.), fibrous boron Acid salts (aluminum borate fiber, magnesium borate fiber, zinc borate fiber, etc.), zinc oxide fiber, titanium oxide fiber, magnesium oxide fiber, gypsum fiber, aluminum silicate fiber, calcium silicate fiber, silicon carbide fiber, titanium carbide fiber , Silicon nitride fiber, titanium nitride Down fibers, carbon fibers, alumina fibers, alumina - silica fibers, zirconia fibers, quartz fibers, flaky titanate include flaky titanium oxide or the like.
これらの中でも、機械的強度を向上させるための無機充填材としては、繊維状物、マイカ、薄片状（又は板状）チタン酸塩、薄片状酸化チタン等の形状異方性を有するものが好ましく、繊維状チタン酸アルカリ金属塩、繊維状ホウ酸塩、酸化亜鉛繊維、珪酸カルシウム繊維、薄片状チタン酸塩、薄片状酸化チタン等が特に好ましい。また、電気的性能、熱的性能、作業性又は成形性等を向上させるための無機充填材としては、溶融シリカ、結晶シリカ、アルミナ、タルク、窒化アルミニウム、窒化ホウ素、窒化珪素、酸化チタン、硫酸バリウム等の球状物又は粉末状物が好ましく、溶融シリカ、結晶シリカ、アルミナ、窒化アルミニウム等の球状物又は粉末状物が特に好ましい。
Among these, as the inorganic filler for improving the mechanical strength, those having shape anisotropy such as fibrous material, mica, flaky (or plate-like) titanate, flaky titanium oxide are preferable. Particularly preferred are fibrous alkali metal titanates, fibrous borates, zinc oxide fibers, calcium silicate fibers, flaky titanates, flaky titanium oxides, and the like. Examples of inorganic fillers for improving electrical performance, thermal performance, workability or moldability include fused silica, crystalline silica, alumina, talc, aluminum nitride, boron nitride, silicon nitride, titanium oxide, sulfuric acid Spherical or powdery materials such as barium are preferred, and spherical or powdery materials such as fused silica, crystalline silica, alumina and aluminum nitride are particularly preferred.
これらの無機充填材は、１種を単独で使用することができ、又は２種以上を併用することができる。
These inorganic fillers can be used alone or in combination of two or more.
また、エポキシ樹脂の劣化を抑える目的で、無機充填材の表面を表面処理用のシランカップリング剤、チタンカップリング剤等を用いて被覆したものを用いてもよい。
In addition, for the purpose of suppressing deterioration of the epoxy resin, a surface of the inorganic filler coated with a silane coupling agent or a titanium coupling agent for surface treatment may be used.
無機充填材の配合量は、エポキシ樹脂１００質量部に対し、通常０．０１～９０質量部程度、好ましくは１～８０質量部程度である。
The compounding amount of the inorganic filler is usually about 0.01 to 90 parts by mass, preferably about 1 to 80 parts by mass with respect to 100 parts by mass of the epoxy resin.
本発明の難燃性樹脂組成物には、その好ましい特性を損なわない範囲で、その他の添加剤を配合することができる。その他の添加剤として、各種難燃剤等を挙げることができる。難燃剤としては特に制限されず、公知のものを使用することができる。例えば、上記式（１）の化合物以外のホスファゼン化合物、ハロゲンを含まない有機リン化合物、無機系難燃剤等が挙げられる。これらは、１種を単独で使用でき、又は２種以上を併用できる。
The flame retardant resin composition of the present invention can be blended with other additives as long as the preferable characteristics are not impaired. Examples of other additives include various flame retardants. It does not restrict | limit especially as a flame retardant, A well-known thing can be used. For example, a phosphazene compound other than the compound of the above formula (1), an organic phosphorus compound containing no halogen, an inorganic flame retardant and the like can be mentioned. These can be used individually by 1 type or can use 2 or more types together.
更に本発明の難燃性樹脂組成物には、その好ましい特性を損なわない範囲で、一般的な樹脂添加剤を配合することができる。該樹脂添加剤としては、特に制限はなく、例えば、紫外線吸収剤（ベンゾフェノン系、ベンゾトリアゾール系、シアノアクリレート系、トリアジン系等）、光安定剤（ヒンダードアミン系等）、酸化防止剤（ヒンダードフェノール系、有機リン系過酸化物分解剤、有機硫黄系過酸化物分解剤等）、遮光剤（ルチル型酸化チタン、酸化クロム、酸化セリウム等）、金属不活性剤（ベンゾトリアゾール系等）、消光剤（有機ニッケル等）、天然ワックス類、合成ワックス類、高級脂肪酸、高級脂肪酸の金属塩、防曇剤、防黴剤、抗菌剤、防臭剤、可塑剤、帯電防止剤、界面活性剤、重合禁止剤、架橋剤、顔料（べんがら等）、染料、着色剤（カーボンブラック等）、増感剤、硬化促進剤、希釈剤、流動性調整剤、消泡剤、発泡剤、レベリング剤、接着剤、粘着剤、粘着性付与剤、滑剤、離型剤、潤滑剤、核剤、強化剤、相溶化剤、導電材、アンチブロッキング剤、アンチトラッキング剤、畜光剤、各種安定剤等が挙げられる。
Furthermore, a general resin additive can be blended with the flame retardant resin composition of the present invention as long as the preferable characteristics are not impaired. The resin additive is not particularly limited, and examples thereof include ultraviolet absorbers (benzophenone, benzotriazole, cyanoacrylate, triazine, etc.), light stabilizers (hindered amine, etc.), antioxidants (hindered phenols). , Organic phosphorus peroxide decomposer, organic sulfur peroxide decomposer, etc.), light-shielding agent (rutile titanium oxide, chromium oxide, cerium oxide, etc.), metal deactivator (benzotriazole, etc.), quenching Agents (organic nickel, etc.), natural waxes, synthetic waxes, higher fatty acids, metal salts of higher fatty acids, antifogging agents, antifungal agents, antibacterial agents, deodorants, plasticizers, antistatic agents, surfactants, polymerization Inhibitors, crosslinking agents, pigments (bengal etc.), dyes, colorants (carbon black etc.), sensitizers, curing accelerators, diluents, fluidity modifiers, antifoaming agents, foaming agents, leveling agents, Adhesives, adhesives, tackifiers, lubricants, mold release agents, lubricants, nucleating agents, reinforcing agents, compatibilizers, conductive materials, antiblocking agents, antitracking agents, daylighting agents, various stabilizers, etc. It is done.
（本発明の樹脂組成物の製造）
本発明の樹脂組成物は、各種原材料を均一に分散混合できるのであれば、どのような方法を用いて製造してもよい。例えば、ペイントシェイカー、ビーズミル、プラネタリミキサ、撹拌型分散機、自公転撹拌混合機、三本ロール等を用いて混合すればよい。また、混合順序は、特に制限はなく、一部の成分を混合してから残りの成分を混合してもよく、又は全ての成分を一括して混合してもよい。 (Production of resin composition of the present invention)
The resin composition of the present invention may be produced by any method as long as various raw materials can be uniformly dispersed and mixed. For example, mixing may be performed using a paint shaker, a bead mill, a planetary mixer, a stirring type disperser, a self-revolving stirring mixer, a triple roll, or the like. Further, the mixing order is not particularly limited, and after mixing some components, the remaining components may be mixed, or all components may be mixed together.
本発明の樹脂組成物は、各種原材料を均一に分散混合できるのであれば、どのような方法を用いて製造してもよい。例えば、ペイントシェイカー、ビーズミル、プラネタリミキサ、撹拌型分散機、自公転撹拌混合機、三本ロール等を用いて混合すればよい。また、混合順序は、特に制限はなく、一部の成分を混合してから残りの成分を混合してもよく、又は全ての成分を一括して混合してもよい。 (Production of resin composition of the present invention)
The resin composition of the present invention may be produced by any method as long as various raw materials can be uniformly dispersed and mixed. For example, mixing may be performed using a paint shaker, a bead mill, a planetary mixer, a stirring type disperser, a self-revolving stirring mixer, a triple roll, or the like. Further, the mixing order is not particularly limited, and after mixing some components, the remaining components may be mixed, or all components may be mixed together.
（本発明の成型体）
本発明の難燃性エポキシ樹脂組成物は、例えば、注型、射出成形、圧縮成形およびトランスファー成形等の公知の成型方法により、単一層又は複数層の樹脂板、シート、フィルム、球状、方状、異形品等の任意の形状の成型体とすることができる。 (Molded product of the present invention)
The flame-retardant epoxy resin composition of the present invention is a single-layer or multiple-layer resin plate, sheet, film, sphere, square, and the like by known molding methods such as casting, injection molding, compression molding and transfer molding. A molded body having an arbitrary shape such as a deformed product can be obtained.
本発明の難燃性エポキシ樹脂組成物は、例えば、注型、射出成形、圧縮成形およびトランスファー成形等の公知の成型方法により、単一層又は複数層の樹脂板、シート、フィルム、球状、方状、異形品等の任意の形状の成型体とすることができる。 (Molded product of the present invention)
The flame-retardant epoxy resin composition of the present invention is a single-layer or multiple-layer resin plate, sheet, film, sphere, square, and the like by known molding methods such as casting, injection molding, compression molding and transfer molding. A molded body having an arbitrary shape such as a deformed product can be obtained.
本発明の難燃性エポキシ樹脂組成物は、エポキシ樹脂が使用可能なあらゆる分野で適用することができる。使用可能な分野として、例えば、電気、電子又は通信機器、精密機器、自動車等の輸送機器、繊維製品、各種製造機械類、食品包装フィルム、容器、農林水産分野、建設用資材、医療用品、家具類の構成部品等が挙げられる。
The flame-retardant epoxy resin composition of the present invention can be applied in all fields where epoxy resins can be used. Usable fields include, for example, electrical, electronic or communication equipment, precision equipment, transportation equipment such as automobiles, textile products, various manufacturing machinery, food packaging films, containers, agriculture, forestry and fisheries, construction materials, medical supplies, furniture And the like.
特に、本発明の樹脂組成物から作製される成型体は、電気、電子又は通信機器での使用が好ましい。電気、電子又は通信機器としては、例えば、プリンタ、コンピュータ、ワードプロセッサー、キーボード、小型情報端末機（ＰＤＡ）、電話機、携帯端末（携帯電話、スマートフォン、タブレット型端末等）、ファクシミリ、複写機、電子式金銭登録機（ＥＣＲ）、電卓、電子手帳、電子辞書等のＯＡ機器、洗濯機、冷蔵庫、炊飯器、掃除機、電子レンジ、照明器具、エアコン、アイロン、こたつ等の家電製品、テレビ、チューナー、ＶＴＲ、ビデオカメラ、カムコーダー、デジタルスチルカメラ、ラジカセ、テープレコーダー、ＭＤプレーヤー、ＣＤプレーヤー、ＤＶＤプレーヤー、ＬＤプレーヤー、ＨＤＤ（ハードディスクドライブ）、スピーカー、カーナビゲーション、液晶ディスプレイ、ＥＬディスプレイ、プラズマディスプレイ等のＡＶ製品等のハウジング、機構部品又は構造部品の一部又は全部を構成する材料、電線、ケーブル等の被覆抵抗、サーモスタット、温度ヒューズ等の電気素子を収納するためのケース、モーター用ベアリング、スペーサー、ドットプリンター用ワイヤーガイド等の摺動部品の一部又は全部を構成する材料等が挙げられる。
In particular, the molded body produced from the resin composition of the present invention is preferably used in electrical, electronic or communication equipment. Examples of electrical, electronic, or communication devices include printers, computers, word processors, keyboards, small information terminals (PDAs), telephones, mobile terminals (cell phones, smartphones, tablet terminals, etc.), facsimiles, copiers, and electronic devices. Cash register machines (ECR), calculators, electronic notebooks, electronic dictionaries and other office equipment, washing machines, refrigerators, rice cookers, vacuum cleaners, microwave ovens, lighting equipment, air conditioners, irons, kotatsu and other household appliances, televisions, tuners, VTR, video camera, camcorder, digital still camera, radio cassette recorder, tape recorder, MD player, CD player, DVD player, LD player, HDD (hard disk drive), speaker, car navigation, liquid crystal display, EL display, plasma display, etc. Housing for AV products etc., materials for constituting part or all of mechanical parts or structural parts, covering resistance for electric wires, cables, etc., cases for housing electrical elements such as thermostats, thermal fuses, motor bearings, spacers, Examples thereof include materials constituting part or all of sliding parts such as wire guides for dot printers.
電気、電子又は通信機器の中でも、本発明の成型体は、これらに使用される電気又は電子部品、例えば、各種半導体素子の封止材、配線板の基板材料等への使用が特に好ましい。半導体素子等を封止するに当たっては、従来公知の方法を広く採用することができる。例えば、リードフレーム、配線済みのテープキャリア、配線板、ガラス、シリコンウエハ等の支持部材に、半導体チップ、トランジスタ、ダイオード、発光ダイオード（ＬＥＤ）、サイリスタ等の能動素子、コンデンサ、抵抗体、コイル等の受動素子等の半導体素子を実装し、予め形成されている回路パターンに接続し、必要な部分を本発明の樹脂組成物の溶液又はペーストで封止することにより、電子部品を製造することができる。
Among electrical, electronic or communication devices, the molded body of the present invention is particularly preferably used for electrical or electronic parts used in these, for example, sealing materials for various semiconductor elements, substrate materials for wiring boards, and the like. In sealing semiconductor elements and the like, a conventionally known method can be widely adopted. For example, lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers and other supporting members, semiconductor chips, transistors, diodes, light emitting diodes (LEDs), active elements such as thyristors, capacitors, resistors, coils, etc. It is possible to manufacture an electronic component by mounting a semiconductor element such as a passive element, connecting to a pre-formed circuit pattern, and sealing a necessary part with the solution or paste of the resin composition of the present invention. it can.
実装方法としては特に制限はなく、例えば、リードフレームパッケージ、面実装パッケージ〔ＳＯＰ（small outline package）、ＳＯＪ（small outline j-leaded package）、ＱＦＰ（quad flat package）、ＢＧＡ（ball grid array）等〕、ＣＳＰ（chip size/scale package）等の方法を採用することができる。
The mounting method is not particularly limited. For example, a lead frame package, a surface mounting package [SOP (small outline package), SOJ (small outline j-leaded package), QFP (quad flat package), BGA (ball grid array), etc. ], A method such as CSP (chip size / scale package) can be employed.
回路パターンとの接続方法も特に制限されず、例えば、ワイヤボンディング、ＴＡＢ（tape automated bonding）接続、フリップチップ接続等の公知の方法を採用することができる。
The connection method with the circuit pattern is not particularly limited, and for example, a known method such as wire bonding, TAB (tape-automated bonding) connection, flip-chip connection, or the like can be adopted.
封止方法としては低圧トランスファー成形法が最も一般的であるが、インジェクション成形法、圧縮成形法、注型法等を用いてもよい。この際、素子を実装する支持部材の種類、実装する素子の種類、実装方法、接続方法、封止方法等の各種の条件に応じて、本発明の樹脂組成物の組成を適宜変更することができる。また、支持部材に半導体素子、ハンダボール、リードフレーム、ヒートスプレッダー、スティフナ等の部品を実装するために、本発明の樹脂組成物を接着剤として用いてもよい。
As the sealing method, the low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, a casting method, or the like may be used. At this time, the composition of the resin composition of the present invention can be changed as appropriate according to various conditions such as the type of support member for mounting the element, the type of element to be mounted, the mounting method, the connection method, and the sealing method. it can. The resin composition of the present invention may be used as an adhesive in order to mount components such as semiconductor elements, solder balls, lead frames, heat spreaders, and stiffeners on the support member.
更に本発明の樹脂組成物を予めフィルム状に成形し、このフィルムを、例えば二次実装用封止材として用いることもできる。このような方法で製造される電子部品としては、例えば、テープキャリアにバンプで接続した半導体チップを、本発明の樹脂組成物で封止したＴＣＰ（tape carrier package）を挙げることができる。また、配線板又はガラス上に形成した配線に、ワイヤボンディング、フリップチップボンディング、はんだ等で接続した半導体チップ、集積回路、大規模集積回路、トランジスタ、ダイオード、サイリスタ等の能動素子及び／又はコンデンサ、抵抗体、コイル等の受動素子を、本発明の樹脂組成物で封止したＣＯＢモジュール、ハイブリッド集積回路、マルチチップモジュール等を挙げることができる。
Furthermore, the resin composition of the present invention can be formed into a film in advance, and this film can be used, for example, as a sealing material for secondary mounting. As an electronic component manufactured by such a method, for example, a TCP (tape carrier carrier package) in which a semiconductor chip connected to a tape carrier by a bump is sealed with the resin composition of the present invention can be cited. In addition, a semiconductor chip, an integrated circuit, a large-scale integrated circuit, a transistor, a diode, a thyristor or other active element and / or a capacitor connected to a wiring formed on a wiring board or glass by wire bonding, flip chip bonding, solder, etc. Examples thereof include a COB module, a hybrid integrated circuit, and a multichip module in which passive elements such as resistors and coils are sealed with the resin composition of the present invention.
本発明の樹脂組成物を配線板用の基板材料として用いる場合も、従来の方法と同様に実施すればよい。例えば、本発明の樹脂組成物を、紙、ガラス繊維布、アラミド繊維布等の基材に含浸させて、９０～２２０℃程度の温度で１～５分間程度乾燥させる方法等で半硬化させることによりプリプレグを製造し、このプリプレグを配線板用の基板材料とすればよい。また、本発明の樹脂組成物をフィルム状に成形し、このフィルムを配線板用の基板材料として用いることもできる。この時、導電性物質又は誘電性物質を配合すれば、導電性層、異方導電性層、導電率制御層、誘電性層、異方誘電性層、誘電率制御層等の機能性膜とすることもできる。
When the resin composition of the present invention is used as a substrate material for a wiring board, it may be carried out in the same manner as in the conventional method. For example, the resin composition of the present invention is semi-cured by a method of impregnating a base material such as paper, glass fiber cloth, aramid fiber cloth, etc., and drying at a temperature of about 90 to 220 ° C. for about 1 to 5 minutes. A prepreg may be manufactured by using the prepreg as a substrate material for a wiring board. Moreover, the resin composition of this invention can be shape | molded in a film form, and this film can also be used as a board | substrate material for wiring boards. At this time, if a conductive substance or a dielectric substance is blended, functional films such as a conductive layer, an anisotropic conductive layer, a conductivity control layer, a dielectric layer, an anisotropic dielectric layer, a dielectric constant control layer, etc. You can also
更に、樹脂製バンプ又はスルーホール内側に形成する導電性層として用いることもできる。プリプレグ又はフィルムを積層して配線板を製造する際に、本発明の樹脂組成物を接着剤として用いることもできる。この時にも、フィルム化する場合と同様に、導電性無機物質、誘電性無機物質等が含まれていてもよい。
Furthermore, it can also be used as a conductive layer formed inside a resin bump or through hole. When the prepreg or film is laminated to produce a wiring board, the resin composition of the present invention can be used as an adhesive. At this time, as in the case of forming a film, a conductive inorganic substance, a dielectric inorganic substance, or the like may be included.
本発明では、本発明の樹脂組成物を基材に含浸させてなるプリプレグ及び／又は本発明の樹脂組成物を成形してなるフィルムのみで配線板を製造してもよいし、これらと共に従来の配線板用プリプレグ及び／又はフィルムを併用してもよい。配線板としては特に制限されず、例えば、リジットタイプ又はフレキシブルタイプのものであってもよいし、形状もシート状又はフィルム状から板状のものまで適宜選択することができる。例えば、金属箔張積層板、プリント配線板、ボンディングシート、キャリア付き樹脂フィルム等を挙げることができる。
In the present invention, a wiring board may be produced only with a prepreg obtained by impregnating a base material with the resin composition of the present invention and / or a film formed by molding the resin composition of the present invention. A prepreg for a wiring board and / or a film may be used in combination. The wiring board is not particularly limited, and may be, for example, a rigid type or a flexible type, and the shape can be appropriately selected from a sheet shape or a film shape to a plate shape. For example, a metal foil-clad laminate, a printed wiring board, a bonding sheet, a resin film with a carrier, and the like can be given.
金属箔張積層板として、より具体的には、銅張積層板、コンポジット銅張積層板、フレキシブル銅張積層板等が挙げられる。これらの金属箔張積層板は、従来の方法と同様に作製することができる。例えば、上述したプリプレグを１枚で又は複数枚重ね、その片面又は両面に厚み２～７０μｍ程度の金属（銅、アルミニウム等）箔を配置し、多段プレス機、連続成形機等を用いて、温度１８０～３５０℃程度、加熱時間１００～３００分間程度、及び面圧２０～１００ｋｇ／ｃｍ２程度で積層成形することにより、金属箔張積層板を作製することができる。
More specifically, examples of the metal foil-clad laminate include a copper-clad laminate, a composite copper-clad laminate, and a flexible copper-clad laminate. These metal foil-clad laminates can be produced in the same manner as conventional methods. For example, one or a plurality of the above-mentioned prepregs are stacked, and a metal (copper, aluminum, etc.) foil having a thickness of about 2 to 70 μm is disposed on one or both sides thereof, and the temperature is measured using a multistage press, a continuous molding machine, etc. A metal foil-clad laminate can be produced by laminate molding at about 180 to 350 ° C., a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg / cm 2 .
プリント配線板として、より具体的には、ビルドアップ型多層プリント配線板、フレキシブルプリント配線板等が挙げられる。これらのプリント配線板は、従来の方法と同様に作製することができる。例えば、金属箔張積層板の表面にエッチング処理を施し、内層回路を形成することにより内装基板を作製し、内層回路の表面にプリプレグを数枚重ね、その外側に外装回路用の金属箔を積層し、加熱及び加圧することで一体成型して多層の積層体を得る。得られた多層の積層体に穴をあけ、この穴の壁面に内層回路と外層回路用の金属箔とを導通させるめっき金属皮膜を形成する。さらに、外層回路用の金属箔にエッチング処理を施し、外層回路を形成することにより、プリント配線板を作製することができる。
More specifically, examples of the printed wiring board include a build-up type multilayer printed wiring board and a flexible printed wiring board. These printed wiring boards can be produced in the same manner as conventional methods. For example, the surface of a metal foil-clad laminate is etched to form an inner layer circuit to produce an interior substrate, several prepregs are stacked on the surface of the inner layer circuit, and a metal foil for an exterior circuit is stacked on the outside Then, it is integrally molded by heating and pressing to obtain a multilayer laminate. A hole is made in the obtained multilayer laminate, and a plated metal film is formed on the wall surface of the hole to conduct the inner layer circuit and the metal foil for the outer layer circuit. Furthermore, a printed wiring board can be produced by etching the metal foil for the outer layer circuit to form the outer layer circuit.
ボンディングシートは、従来の方法と同様に作製することができる。例えば、本発明の樹脂組成物を溶剤に溶解させた溶液を、ロールコーター、コンマコーター等を用いて、ポリエチレンフィルム、ポリプロピレンフィルム等の剥離可能なプラスチックフィルムの支持材に塗布し、これを４０～１６０℃程度で１～２０分間程度加熱処理し、ロール等で圧着することによりボンディングシートを作製することができる。
The bonding sheet can be produced in the same manner as the conventional method. For example, a solution obtained by dissolving the resin composition of the present invention in a solvent is applied to a support material for a peelable plastic film such as a polyethylene film or a polypropylene film using a roll coater, a comma coater, or the like. A bonding sheet can be produced by heat treatment at about 160 ° C. for about 1 to 20 minutes and pressure bonding with a roll or the like.
キャリア付き樹脂フィルムは、従来の方法と同様に作製することができる。例えば、本発明の樹脂組成物を溶剤に溶解させた溶液を、ポリエチレンフィルム、ポリプロピレンフィルム等の剥離可能なプラスチックフィルムの支持材に、バーコーダー、ドクターブレード等で塗布し、８０～２００℃程度の温度で１～１８０分間程度乾燥することによりキャリア付き樹脂フィルムを作製することができる。
The resin film with a carrier can be produced in the same manner as a conventional method. For example, a solution obtained by dissolving the resin composition of the present invention in a solvent is applied to a support material for a peelable plastic film such as a polyethylene film or a polypropylene film with a bar coder, a doctor blade or the like, and the temperature is about 80 to 200 ° C. A resin film with a carrier can be produced by drying at a temperature for about 1 to 180 minutes.
その他の用途としては、精密機器、輸送機器、製造機器、家庭用品、土木建設資材等が挙げられる。精密機器の具体例としては、時計、顕微鏡、カメラ等のハウジング、機構部品又は構造部品の一部又は全部を構成する材料が挙げられる。輸送機器の具体例としては、ヨット、ボート等の船舶、電車、自動車、自転車、オートバイ、航空機等の車体、機構部品又は構造部品（フレーム、パイプ、シャフト、コンバーチブルトップ、ドアトリム、サンバイザー、ホイールカバー、吊り手、吊り手帯等）の一部又は全部を構成する材料、各種輸送機器の内装部品（アームレスト、パッケージトレイ、サンバイザー、マットレスカバー等）の一部又は全部を構成する材料が挙げられる。製造機器の具体例としては、ロボットアーム、ロール、ロール軸、スペーサー、インシュレータ、ガスケット、スラストワッシャー、ギヤ、ボビン、ピストン部材、シリンダ部材、プーリー、ポンプ部材、軸受け、軸部材、板バネ、ハニカム構造材、マスキング治具、分電盤、防水パン等の機構部品又は構造部品の一部又は全部を構成する材料、水槽、浄化槽、ロータンク等の工業用タンク類又はパイプ類、樹脂型、ヘルメット等の一部又は全部を構成する材料が挙げられる。家庭用品の具体例としては、バトミントン又はテニスのラケットフレーム、ゴルフクラブのシャフト又はヘッド、ホッケーのスティック、スキーのポール又は板、スノーボード板、スケートボード板、釣竿ロッド、バット、テントの支柱等のスポーツ又はレジャー用品、浴槽、洗面器、便器、これらの付属品等の衛生機器、シート、バケツ、ホース等の一部又は全部を構成する材料、家具の天板又はテーブル等の表面に設けられる耐熱積層体材料、家具、キャビネット等の化粧材等が挙げられる。土木建築資材の具体例としては、各種建造物の内外装材、屋根材、床材、壁紙、窓ガラス、窓ガラスのシーリング材、コンクリート構造建築物（コンクリート製橋脚、コンクリート製支柱等）又はコンクリート構造物（コンクリート製柱、壁面、道路等）の補強材、下水管等の管路補修材等が挙げられる。
Other applications include precision equipment, transportation equipment, manufacturing equipment, household goods, and civil engineering construction materials. Specific examples of precision instruments include materials that constitute part or all of housings, mechanical parts, or structural parts such as watches, microscopes, cameras, and the like. Specific examples of transportation equipment include yachts, boats and other ships, trains, automobiles, bicycles, motorcycles, aircraft bodies, etc., mechanical parts or structural parts (frames, pipes, shafts, convertible tops, door trims, sun visors, wheel covers , Materials constituting part or all of suspension hands, suspension belts, etc., and materials constituting part or all of interior parts (armrest, package tray, sun visor, mattress cover, etc.) of various transportation equipment. . Specific examples of manufacturing equipment include robot arms, rolls, roll shafts, spacers, insulators, gaskets, thrust washers, gears, bobbins, piston members, cylinder members, pulleys, pump members, bearings, shaft members, leaf springs, honeycomb structures Materials such as materials, masking jigs, distribution boards, waterproof pans, materials constituting part or all of structural parts, industrial tanks such as water tanks, septic tanks, low tanks, pipes, resin molds, helmets, etc. The material which comprises a part or all is mentioned. Specific examples of household goods include badminton or tennis racket frames, golf club shafts or heads, hockey sticks, ski poles or boards, snowboard boards, skateboard boards, fishing rods, bats, tent posts, and other sports. Or heat-resistant laminate provided on the surface of materials such as sanitary equipment such as leisure goods, bathtubs, washbasins, toilets, accessories, sheets, buckets, hoses, etc., furniture top plates, tables, etc. Examples include body materials, furniture, and decorative materials such as cabinets. Specific examples of civil engineering and building materials include interior and exterior materials for various buildings, roofing materials, flooring materials, wallpaper, window glass, window glass sealing materials, concrete structures (concrete piers, concrete supports, etc.) or concrete. Examples include reinforcing materials for structures (concrete columns, wall surfaces, roads, etc.), pipe repair materials such as sewage pipes, and the like.
以下に、実施例及び比較例によって本発明を具体的に説明するが、本発明はこれらによって何ら限定されるものではない。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
ヘキサクロロシクロトリホスファゼンの製造
還流冷却装置を取り付けた１Ｌフラスコに、モノクロロベンゼン５００ｍｌ、五塩化リン８７３．６ｇ及び塩化アンモニウム２２４．３ｇを入れ、５時間還流させた。還流終了後、加熱を止め、濾過し、蒸留することで、ヘキサクロロシクロトリホスファゼン４８３ｇを得て、以下の製造例で用いた。 Production of hexachlorocyclotriphosphazene 500 ml of monochlorobenzene, 873.6 g of phosphorus pentachloride and 224.3 g of ammonium chloride were placed in a 1 L flask equipped with a reflux cooling apparatus and refluxed for 5 hours. After completion of the reflux, heating was stopped, filtered and distilled to obtain 483 g of hexachlorocyclotriphosphazene, which was used in the following production examples.
還流冷却装置を取り付けた１Ｌフラスコに、モノクロロベンゼン５００ｍｌ、五塩化リン８７３．６ｇ及び塩化アンモニウム２２４．３ｇを入れ、５時間還流させた。還流終了後、加熱を止め、濾過し、蒸留することで、ヘキサクロロシクロトリホスファゼン４８３ｇを得て、以下の製造例で用いた。 Production of hexachlorocyclotriphosphazene 500 ml of monochlorobenzene, 873.6 g of phosphorus pentachloride and 224.3 g of ammonium chloride were placed in a 1 L flask equipped with a reflux cooling apparatus and refluxed for 5 hours. After completion of the reflux, heating was stopped, filtered and distilled to obtain 483 g of hexachlorocyclotriphosphazene, which was used in the following production examples.
製造例１：式（１）で表される化合物の製造
ディーンスターク装置を取り付けた５Ｌフラスコに、２，２’－ビフェノール（４９１．１ｇ，２．６ｍｏｌ）とシクロヘキサクロロトリホスファゼンを２６．８質量％含むモノクロロベンゼン溶液（１０６４．７ｇ，２．５ｍｏｌ）と４８％水酸化ナトリウム水溶液（４４１．６ｇ，５．３ｍｏｌ）とモノクロロベンゼン（２．３Ｌ）とを入れ、窒素ガスを流し、１２時間加熱還流させた。還流終了後、加熱を止め、残った反応混合物に脱イオン水（１．２Ｌ）を加え、２時間撹拌した。反応器内に析出している結晶を分取し、脱イオン水及びメタノールで洗浄し、乾燥させることで、白色固体を得た（４１３．８８ｇ）。 Production Example 1 Production of Compound Represented by Formula (1) 26.8 mass of 2,2′-biphenol (491.1 g, 2.6 mol) and cyclohexachlorotriphosphazene was added to a 5 L flask equipped with a Dean-Stark apparatus. % Monochlorobenzene solution (1064.7 g, 2.5 mol), 48% aqueous sodium hydroxide solution (441.6 g, 5.3 mol) and monochlorobenzene (2.3 L) were added, and nitrogen gas was passed through and heated for 12 hours. Refluxed. After completion of the reflux, heating was stopped, deionized water (1.2 L) was added to the remaining reaction mixture, and the mixture was stirred for 2 hours. Crystals precipitated in the reactor were collected, washed with deionized water and methanol, and dried to obtain a white solid (413.88 g).
ディーンスターク装置を取り付けた５Ｌフラスコに、２，２’－ビフェノール（４９１．１ｇ，２．６ｍｏｌ）とシクロヘキサクロロトリホスファゼンを２６．８質量％含むモノクロロベンゼン溶液（１０６４．７ｇ，２．５ｍｏｌ）と４８％水酸化ナトリウム水溶液（４４１．６ｇ，５．３ｍｏｌ）とモノクロロベンゼン（２．３Ｌ）とを入れ、窒素ガスを流し、１２時間加熱還流させた。還流終了後、加熱を止め、残った反応混合物に脱イオン水（１．２Ｌ）を加え、２時間撹拌した。反応器内に析出している結晶を分取し、脱イオン水及びメタノールで洗浄し、乾燥させることで、白色固体を得た（４１３．８８ｇ）。 Production Example 1 Production of Compound Represented by Formula (1) 26.8 mass of 2,2′-biphenol (491.1 g, 2.6 mol) and cyclohexachlorotriphosphazene was added to a 5 L flask equipped with a Dean-Stark apparatus. % Monochlorobenzene solution (1064.7 g, 2.5 mol), 48% aqueous sodium hydroxide solution (441.6 g, 5.3 mol) and monochlorobenzene (2.3 L) were added, and nitrogen gas was passed through and heated for 12 hours. Refluxed. After completion of the reflux, heating was stopped, deionized water (1.2 L) was added to the remaining reaction mixture, and the mixture was stirred for 2 hours. Crystals precipitated in the reactor were collected, washed with deionized water and methanol, and dried to obtain a white solid (413.88 g).
実施例１～５及び比較例１～１０：エポキシ樹脂成型体の作製
表１及び２に記載の各成分の量を測りとり、１００℃で温めながら均一になるように混合した。その後、１２０℃で１時間、１５０℃で１時間、更に２００℃で２時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を作製した。 Examples 1 to 5 and Comparative Examples 1 to 10: Preparation of epoxy resin moldings The amounts of each component described in Tables 1 and 2 were measured and mixed uniformly while warming at 100 ° C. Then, it heated at 120 degreeC for 1 hour, 150 degreeC for 1 hour, and also 200 degreeC for 2 hours, it was made to harden, and the obtained hardened | cured material was cooled to room temperature, and the epoxy resin molding was produced.
表１及び２に記載の各成分の量を測りとり、１００℃で温めながら均一になるように混合した。その後、１２０℃で１時間、１５０℃で１時間、更に２００℃で２時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を作製した。 Examples 1 to 5 and Comparative Examples 1 to 10: Preparation of epoxy resin moldings The amounts of each component described in Tables 1 and 2 were measured and mixed uniformly while warming at 100 ° C. Then, it heated at 120 degreeC for 1 hour, 150 degreeC for 1 hour, and also 200 degreeC for 2 hours, it was made to harden, and the obtained hardened | cured material was cooled to room temperature, and the epoxy resin molding was produced.
（溶出試験）
実施例１～５及び比較例１～１０で作製したエポキシ樹脂成型体の質量を測り、アセトンのついたキムワイプ（登録商標）で成型体表面に付着した難燃剤の溶出分をふき取り、成型体表面を十分乾燥させた後、再度、成型体の質量を測定し、以下の式から溶出度を算出した。その結果を表１及び２に示す。 (Dissolution test)
Measure the mass of the epoxy resin moldings produced in Examples 1 to 5 and Comparative Examples 1 to 10, wipe off the eluate of the flame retardant adhering to the molding body surface with Kimwipe (registered trademark) with acetone. After sufficiently drying, the mass of the molded body was measured again, and the elution degree was calculated from the following equation. The results are shown in Tables 1 and 2.
実施例１～５及び比較例１～１０で作製したエポキシ樹脂成型体の質量を測り、アセトンのついたキムワイプ（登録商標）で成型体表面に付着した難燃剤の溶出分をふき取り、成型体表面を十分乾燥させた後、再度、成型体の質量を測定し、以下の式から溶出度を算出した。その結果を表１及び２に示す。 (Dissolution test)
Measure the mass of the epoxy resin moldings produced in Examples 1 to 5 and Comparative Examples 1 to 10, wipe off the eluate of the flame retardant adhering to the molding body surface with Kimwipe (registered trademark) with acetone. After sufficiently drying, the mass of the molded body was measured again, and the elution degree was calculated from the following equation. The results are shown in Tables 1 and 2.
溶出度[％] ＝ Ａ/Ｂ × １００
Ａ＝（アセトンでふき取る前の成型体質量）－（アセトンでふき取った後の成型体質量）
Ｂ＝（アセトンでふき取る前の成型体質量） Dissolution rate [%] = A / B x 100
A = (Molded mass before wiping with acetone) − (Molded mass after wiping with acetone)
B = (Molded mass before wiping with acetone)
Ａ＝（アセトンでふき取る前の成型体質量）－（アセトンでふき取った後の成型体質量）
Ｂ＝（アセトンでふき取る前の成型体質量） Dissolution rate [%] = A / B x 100
A = (Molded mass before wiping with acetone) − (Molded mass after wiping with acetone)
B = (Molded mass before wiping with acetone)
実施例６～８及び比較例１１：エポキシ樹脂成型体の作製、並びに硬化時の溶出試験
表３に記載の実施例６、７、及び比較例１１の各成分の量を測りとり、１００℃で温めながら均一になるように混合し、樹脂組成物の重量（重量Ａ）を測定した。その後樹脂組成物を１５０℃で１時間、更に２００℃で２時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を作製した。また、表３に記載の実施例８の各成分の量を測りとり、１００℃で温めながら均一になるように混合し、樹脂組成物の重量（重量Ａ）を測定した。その後樹脂組成物を１００℃で１時間、更に１５０℃で３時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を作製した。得られたエポキシ樹脂成型体の重量（重量Ｂ）を測定し、以下の式から硬化時の溶出度を算出した。結果を表３に示す。 Examples 6 to 8 and Comparative Example 11: Preparation of epoxy resin molded body and dissolution test during curing Measure the amount of each component of Examples 6 and 7 and Comparative Example 11 listed in Table 3 at 100 ° C. The mixture was mixed uniformly while warming, and the weight (weight A) of the resin composition was measured. Thereafter, the resin composition was heated at 150 ° C. for 1 hour and further at 200 ° C. for 2 hours to be cured, and the obtained cured product was cooled to room temperature to produce an epoxy resin molded body. Moreover, the amount of each component of Example 8 described in Table 3 was measured, mixed while being uniformly heated at 100 ° C., and the weight (weight A) of the resin composition was measured. Thereafter, the resin composition was heated at 100 ° C. for 1 hour and further at 150 ° C. for 3 hours to be cured, and the obtained cured product was cooled to room temperature to produce an epoxy resin molded body. The weight (weight B) of the obtained epoxy resin molding was measured, and the elution degree at the time of curing was calculated from the following formula. The results are shown in Table 3.
表３に記載の実施例６、７、及び比較例１１の各成分の量を測りとり、１００℃で温めながら均一になるように混合し、樹脂組成物の重量（重量Ａ）を測定した。その後樹脂組成物を１５０℃で１時間、更に２００℃で２時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を作製した。また、表３に記載の実施例８の各成分の量を測りとり、１００℃で温めながら均一になるように混合し、樹脂組成物の重量（重量Ａ）を測定した。その後樹脂組成物を１００℃で１時間、更に１５０℃で３時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を作製した。得られたエポキシ樹脂成型体の重量（重量Ｂ）を測定し、以下の式から硬化時の溶出度を算出した。結果を表３に示す。 Examples 6 to 8 and Comparative Example 11: Preparation of epoxy resin molded body and dissolution test during curing Measure the amount of each component of Examples 6 and 7 and Comparative Example 11 listed in Table 3 at 100 ° C. The mixture was mixed uniformly while warming, and the weight (weight A) of the resin composition was measured. Thereafter, the resin composition was heated at 150 ° C. for 1 hour and further at 200 ° C. for 2 hours to be cured, and the obtained cured product was cooled to room temperature to produce an epoxy resin molded body. Moreover, the amount of each component of Example 8 described in Table 3 was measured, mixed while being uniformly heated at 100 ° C., and the weight (weight A) of the resin composition was measured. Thereafter, the resin composition was heated at 100 ° C. for 1 hour and further at 150 ° C. for 3 hours to be cured, and the obtained cured product was cooled to room temperature to produce an epoxy resin molded body. The weight (weight B) of the obtained epoxy resin molding was measured, and the elution degree at the time of curing was calculated from the following formula. The results are shown in Table 3.
硬化時の溶出度[％] ＝ Ａ/Ｂ × １００
Ａ＝（重量Ａ）－（重量Ｂ）
Ｂ＝（重量Ａ） Elution degree [%] at curing = A / B × 100
A = (weight A) − (weight B)
B = (weight A)
Ａ＝（重量Ａ）－（重量Ｂ）
Ｂ＝（重量Ａ） Elution degree [%] at curing = A / B × 100
A = (weight A) − (weight B)
B = (weight A)
（熱安定性試験：荷重たわみ温度（ＨＤＴ）測定）
表４に記載の参考例１（ブランク）、実施例９、及び比較例１２～１３の各成分の量を測りとり、１００℃で温めながら均一になるように混合した。その後、１２０℃で１時間、１５０℃で１時間、更に２００℃で２時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を板状に作製した。また、表４に記載の参考例２（ブランク）、実施例１０、及び比較例１４～１６の各成分の量を測りとり、１００℃で温めながら均一になるように混合した。その後、１００℃で１時間、更に１５０℃で３時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を板状に作製した。得られた板状成型体を、長さ１２０ｍｍＸ横１０ｍｍＸ厚さ４ｍｍに切断して試験片とし、支点間距離１００ｍｍで１．８ＭＰａの荷重をかけ、ＪＩＳ Ｋ７１９１に準じて荷重たわみ温度試験を測定した。なお、測定にはＨＤＴ．ＶＳＰＴ．ＴＥＳＴＥＲ（型番Ｓ－３Ｍ）株式会社東洋精機製作所製を用いた。 (Thermal stability test: deflection temperature under load (HDT) measurement)
The amount of each component of Reference Example 1 (blank), Example 9 and Comparative Examples 12 to 13 shown in Table 4 was measured and mixed uniformly while warming at 100 ° C. Then, it heated at 120 degreeC for 1 hour, 150 degreeC for 1 hour, and also 200 degreeC for 2 hours, it was made to harden | cure, the obtained hardened | cured material was cooled to room temperature, and the epoxy resin molding was produced in plate shape. Further, the amount of each component of Reference Example 2 (blank), Example 10 and Comparative Examples 14 to 16 shown in Table 4 was measured and mixed uniformly while warming at 100 ° C. Then, it heated at 100 degreeC for 1 hour, and also at 150 degreeC for 3 hours, it was made to harden, the obtained hardened | cured material was cooled to room temperature, and the epoxy resin molding was produced in plate shape. The obtained plate-shaped molded body was cut into a length of 120 mm × width 10 mm × thickness 4 mm to obtain a test piece. . Note that HDT. VSPT. TESTER (model number S-3M) manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
表４に記載の参考例１（ブランク）、実施例９、及び比較例１２～１３の各成分の量を測りとり、１００℃で温めながら均一になるように混合した。その後、１２０℃で１時間、１５０℃で１時間、更に２００℃で２時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を板状に作製した。また、表４に記載の参考例２（ブランク）、実施例１０、及び比較例１４～１６の各成分の量を測りとり、１００℃で温めながら均一になるように混合した。その後、１００℃で１時間、更に１５０℃で３時間加熱し、硬化させ、得られた硬化物を室温まで冷却させてエポキシ樹脂成型体を板状に作製した。得られた板状成型体を、長さ１２０ｍｍＸ横１０ｍｍＸ厚さ４ｍｍに切断して試験片とし、支点間距離１００ｍｍで１．８ＭＰａの荷重をかけ、ＪＩＳ Ｋ７１９１に準じて荷重たわみ温度試験を測定した。なお、測定にはＨＤＴ．ＶＳＰＴ．ＴＥＳＴＥＲ（型番Ｓ－３Ｍ）株式会社東洋精機製作所製を用いた。 (Thermal stability test: deflection temperature under load (HDT) measurement)
The amount of each component of Reference Example 1 (blank), Example 9 and Comparative Examples 12 to 13 shown in Table 4 was measured and mixed uniformly while warming at 100 ° C. Then, it heated at 120 degreeC for 1 hour, 150 degreeC for 1 hour, and also 200 degreeC for 2 hours, it was made to harden | cure, the obtained hardened | cured material was cooled to room temperature, and the epoxy resin molding was produced in plate shape. Further, the amount of each component of Reference Example 2 (blank), Example 10 and Comparative Examples 14 to 16 shown in Table 4 was measured and mixed uniformly while warming at 100 ° C. Then, it heated at 100 degreeC for 1 hour, and also at 150 degreeC for 3 hours, it was made to harden, the obtained hardened | cured material was cooled to room temperature, and the epoxy resin molding was produced in plate shape. The obtained plate-shaped molded body was cut into a length of 120 mm × width 10 mm × thickness 4 mm to obtain a test piece. . Note that HDT. VSPT. TESTER (model number S-3M) manufactured by Toyo Seiki Seisakusho Co., Ltd. was used.
試験結果が示すように、エポキシ樹脂に難燃剤を配合すると、配合しないもの（参考例）に比較して荷重たわみ温度が極端に低下することがわかる（比較例１２～１６）。それに対して、式（１）で表される化合物を配合した樹脂組成物の成型体では、荷重たわみ温度が低下することなく、むしろ上昇するものが認められ（実施例９～１０）、本発明の樹脂組成物及びその成型体は熱安定性に優れることがわかる。この効果は、エポキシ樹脂に止まらず、その他熱硬化型樹脂組成物においても同様に認められるものである。
As shown in the test results, it can be seen that when a flame retardant is blended with an epoxy resin, the deflection temperature under load is extremely reduced as compared with those not blended (reference examples) (Comparative Examples 12 to 16). On the other hand, in the molded body of the resin composition containing the compound represented by the formula (1), it is recognized that the deflection temperature under load does not decrease but rather increases (Examples 9 to 10). It can be seen that the resin composition and its molded product are excellent in thermal stability. This effect is not limited to the epoxy resin, and is similarly recognized in other thermosetting resin compositions.
※１：ビスフェノールＦ型エポキシ化合物（三菱ケミカル株式会社製、エピコート８０６）７２質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２８質量部
※２：ビスフェノールＡ型エポキシ化合物（三菱ケミカル株式会社製、エピコート８２８）７５質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２５質量部
※３：フェノールノボラック型エポキシ化合物（三菱ケミカル株式会社製、エピコート１５４）７４質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２６質量部
※４：クレゾールノボラック型エポキシ化合物（日本化薬株式会社製、ＥＯＣＮ－１０２０）７６質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２４質量部
※５：フェノール型エポキシ化合物（日本化薬株式会社製、ＥＰＰＮ－５０２Ｈ）７３質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２７質量部
※６：トリフェニルホスフィン（和光純薬工業株式会社製）
※７：ヘキサフェノキシシクロトリホスファゼン（和光純薬工業株式会社製）
※８：ＰＸ－２００（大八化学工業株式会社製）
※９：ビスフェノールＦ型エポキシ化合物（三菱ケミカル株式会社製、エピコート８０６）７３質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２７質量部
※１０：ビスフェノールＦ型エポキシ化合物（三菱ケミカル株式会社製、エピコート８０６）７７質量部＋硬化剤（東京化成工業株式会社製、ジアミノジフェニルメタン）２３質量部
※１１：ＦＰ－７００（株式会社ＡＤＥＫＡ製） * 1: Bisphenol F type epoxy compound (Mitsubishi Chemical Corporation, Epicoat 806) 72 parts by mass + curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) * 2: Bisphenol A type epoxy compound (Mitsubishi) Chemical Co., Ltd., Epicoat 828) 75 parts by mass + curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) 25 parts by mass * 3: Phenol novolac type epoxy compound (Mitsubishi Chemical Corporation, Epicoat 154) 74 parts by mass Part + curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) 26 parts by mass * 4: 76 parts by mass of cresol novolac epoxy compound (Nippon Kayaku Co., Ltd., EOCN-1020) + curing agent (Wako Pure Chemicals) Kogyo Co., Ltd., diaminodiphenylsulfone) 24 quality * 5: Phenol type epoxy compound (Nippon Kayaku Co., Ltd., EPPN-502H) 73 parts by mass + Curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) 27 parts by mass * 6: Triphenylphosphine (Japanese Manufactured by Kojun Pharmaceutical Co., Ltd.)
* 7: Hexaphenoxycyclotriphosphazene (Wako Pure Chemical Industries, Ltd.)
* 8: PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.)
* 9: 73 parts by mass of bisphenol F type epoxy compound (Mitsubishi Chemical Corporation, Epicoat 806) + 27 parts by mass of curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) * 10: Bisphenol F type epoxy compound (Mitsubishi) Chemical Co., Ltd., Epicoat 806) 77 parts by mass + curing agent (Tokyo Chemical Industry Co., Ltd., diaminodiphenylmethane) 23 parts by mass * 11: FP-700 (manufactured by ADEKA Corporation)
※２：ビスフェノールＡ型エポキシ化合物（三菱ケミカル株式会社製、エピコート８２８）７５質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２５質量部
※３：フェノールノボラック型エポキシ化合物（三菱ケミカル株式会社製、エピコート１５４）７４質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２６質量部
※４：クレゾールノボラック型エポキシ化合物（日本化薬株式会社製、ＥＯＣＮ－１０２０）７６質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２４質量部
※５：フェノール型エポキシ化合物（日本化薬株式会社製、ＥＰＰＮ－５０２Ｈ）７３質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２７質量部
※６：トリフェニルホスフィン（和光純薬工業株式会社製）
※７：ヘキサフェノキシシクロトリホスファゼン（和光純薬工業株式会社製）
※８：ＰＸ－２００（大八化学工業株式会社製）
※９：ビスフェノールＦ型エポキシ化合物（三菱ケミカル株式会社製、エピコート８０６）７３質量部＋硬化剤（和光純薬工業株式会社製、ジアミノジフェニルスルフォン）２７質量部
※１０：ビスフェノールＦ型エポキシ化合物（三菱ケミカル株式会社製、エピコート８０６）７７質量部＋硬化剤（東京化成工業株式会社製、ジアミノジフェニルメタン）２３質量部
※１１：ＦＰ－７００（株式会社ＡＤＥＫＡ製） * 1: Bisphenol F type epoxy compound (Mitsubishi Chemical Corporation, Epicoat 806) 72 parts by mass + curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) * 2: Bisphenol A type epoxy compound (Mitsubishi) Chemical Co., Ltd., Epicoat 828) 75 parts by mass + curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) 25 parts by mass * 3: Phenol novolac type epoxy compound (Mitsubishi Chemical Corporation, Epicoat 154) 74 parts by mass Part + curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) 26 parts by mass * 4: 76 parts by mass of cresol novolac epoxy compound (Nippon Kayaku Co., Ltd., EOCN-1020) + curing agent (Wako Pure Chemicals) Kogyo Co., Ltd., diaminodiphenylsulfone) 24 quality * 5: Phenol type epoxy compound (Nippon Kayaku Co., Ltd., EPPN-502H) 73 parts by mass + Curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) 27 parts by mass * 6: Triphenylphosphine (Japanese Manufactured by Kojun Pharmaceutical Co., Ltd.)
* 7: Hexaphenoxycyclotriphosphazene (Wako Pure Chemical Industries, Ltd.)
* 8: PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.)
* 9: 73 parts by mass of bisphenol F type epoxy compound (Mitsubishi Chemical Corporation, Epicoat 806) + 27 parts by mass of curing agent (Wako Pure Chemical Industries, Ltd., diaminodiphenyl sulfone) * 10: Bisphenol F type epoxy compound (Mitsubishi) Chemical Co., Ltd., Epicoat 806) 77 parts by mass + curing agent (Tokyo Chemical Industry Co., Ltd., diaminodiphenylmethane) 23 parts by mass * 11: FP-700 (manufactured by ADEKA Corporation)
本発明は、ブリードアウトが生じにくい難燃性エポキシ樹脂組成物及びその成型体を提供することができる。
The present invention can provide a flame-retardant epoxy resin composition that hardly causes bleed-out and a molded body thereof.
Claims (6)
- 式（１）で表される化合物及びエポキシ樹脂を含むエポキシ樹脂組成物。
- エポキシ樹脂１００質量部に対して、式（１）で表される化合物が１～５０質量部含まれる請求項１に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, wherein 1 to 50 parts by mass of the compound represented by the formula (1) is contained with respect to 100 parts by mass of the epoxy resin.
- 請求項１又は２に記載のエポキシ樹脂組成物を用いて作製された成型体。 The molded object produced using the epoxy resin composition of Claim 1 or 2.
- 請求項１又は２に記載のエポキシ樹脂組成物を用いて作製された電気又は電子部品。 An electrical or electronic component produced using the epoxy resin composition according to claim 1.
- 請求項１又は２に記載のエポキシ樹脂組成物を含む半導体素子用封止材。 The sealing material for semiconductor elements containing the epoxy resin composition of Claim 1 or 2.
- 請求項１又は２に記載のエポキシ樹脂組成物を用いて作製された基板材料。 The board | substrate material produced using the epoxy resin composition of Claim 1 or 2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021113249A (en) * | 2020-01-16 | 2021-08-05 | 株式会社伏見製薬所 | Flame-retardant resin composition |
| WO2022019021A1 (en) | 2020-07-22 | 2022-01-27 | 株式会社伏見製薬所 | Cyclic phosphazene compound having oxaphosphorin ring-containing structure |
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| JP2007153747A (en) * | 2005-11-30 | 2007-06-21 | Fushimi Pharm Co Ltd | Hydroxy group-containing cyclic phosphazene compound and method for producing the same |
| JP2008247800A (en) * | 2007-03-30 | 2008-10-16 | Fushimi Pharm Co Ltd | Cyclic phosphazene compound containing reactive group and method for producing the same |
| CN103896985A (en) * | 2013-05-06 | 2014-07-02 | 深圳市华力兴工程塑料有限公司 | Synthesizing method and device of phosphonitrilic chloride trimer as well as preparation method of terphenyl cycloposphazene |
-
2019
- 2019-04-10 WO PCT/JP2019/015668 patent/WO2019198766A1/en active Application Filing
- 2019-04-10 JP JP2020513435A patent/JPWO2019198766A1/en active Pending
- 2019-04-12 TW TW108112889A patent/TW201943792A/en unknown
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| US3356769A (en) * | 1964-07-13 | 1967-12-05 | American Cyanamid Co | Phosphonitrilic halide derivatives and adducts thereof |
| US3865783A (en) * | 1972-05-18 | 1975-02-11 | Akzona Inc | Flame-retardant polyester |
| JP2004115815A (en) * | 1997-02-14 | 2004-04-15 | Otsuka Chemical Holdings Co Ltd | Flame-retardant, flame-retardant resin composition, and flame-retardant resin molding |
| JP2007153747A (en) * | 2005-11-30 | 2007-06-21 | Fushimi Pharm Co Ltd | Hydroxy group-containing cyclic phosphazene compound and method for producing the same |
| JP2008247800A (en) * | 2007-03-30 | 2008-10-16 | Fushimi Pharm Co Ltd | Cyclic phosphazene compound containing reactive group and method for producing the same |
| CN103896985A (en) * | 2013-05-06 | 2014-07-02 | 深圳市华力兴工程塑料有限公司 | Synthesizing method and device of phosphonitrilic chloride trimer as well as preparation method of terphenyl cycloposphazene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021113249A (en) * | 2020-01-16 | 2021-08-05 | 株式会社伏見製薬所 | Flame-retardant resin composition |
| JP7557119B2 (en) | 2020-01-16 | 2024-09-27 | 株式会社伏見製薬所 | Flame-retardant resin composition |
| WO2022019021A1 (en) | 2020-07-22 | 2022-01-27 | 株式会社伏見製薬所 | Cyclic phosphazene compound having oxaphosphorin ring-containing structure |
| JP2022021767A (en) * | 2020-07-22 | 2022-02-03 | 株式会社伏見製薬所 | Cyclic phosphazene compound having an oxaphosphorin ring-containing structure |
| CN116194552A (en) * | 2020-07-22 | 2023-05-30 | 株式会社伏见制药所 | Cyclic phosphazene compound with oxaphosphaphenanthrene ring structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2019198766A1 (en) | 2021-05-20 |
| TW201943792A (en) | 2019-11-16 |
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