JP2006117545A - Phosphazene compound - Google Patents
Phosphazene compound Download PDFInfo
- Publication number
- JP2006117545A JP2006117545A JP2004304332A JP2004304332A JP2006117545A JP 2006117545 A JP2006117545 A JP 2006117545A JP 2004304332 A JP2004304332 A JP 2004304332A JP 2004304332 A JP2004304332 A JP 2004304332A JP 2006117545 A JP2006117545 A JP 2006117545A
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- JP
- Japan
- Prior art keywords
- group
- phosphazene compound
- resin
- resin composition
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- -1 Phosphazene compound Chemical class 0.000 title claims abstract description 122
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 239000011342 resin composition Substances 0.000 claims abstract description 21
- 239000003063 flame retardant Substances 0.000 claims abstract description 13
- 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 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 7
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 125000003172 aldehyde group Chemical group 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 238000000465 moulding Methods 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000001723 curing Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 125000004104 aryloxy group Chemical group 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920001955 polyphenylene ether Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 0 COc1c(*)c(*)c(*)c(*)c1* Chemical compound COc1c(*)c(*)c(*)c(*)c1* 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 235000012211 aluminium silicate 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
- 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 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 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 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 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 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid 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
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- BIAWAXVRXKIUQB-UHFFFAOYSA-N 2-(2-phenylethenyl)pyridine Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=N1 BIAWAXVRXKIUQB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 1
- XHFOXACKHBOLCX-UHFFFAOYSA-N 2-n-[10-[(4,6-diamino-1,3,5-triazin-2-yl)amino]decyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCCCCCCCCCCNC=2N=C(N)N=C(N)N=2)=N1 XHFOXACKHBOLCX-UHFFFAOYSA-N 0.000 description 1
- KYCZUBOPFDXYAU-UHFFFAOYSA-N 2-n-[[(4,6-diamino-1,3,5-triazin-2-yl)amino]methyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCNC=2N=C(N)N=C(N)N=2)=N1 KYCZUBOPFDXYAU-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- IXDGHAZCSMVIFX-UHFFFAOYSA-N 6-(dibutylamino)-1h-1,3,5-triazine-2,4-dithione Chemical compound CCCCN(CCCC)C1=NC(=S)NC(=S)N1 IXDGHAZCSMVIFX-UHFFFAOYSA-N 0.000 description 1
- ZUHMEUFBTDOKPX-UHFFFAOYSA-N 6-[2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl]-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(CCC=2N=C(N)N=C(N)N=2)=N1 ZUHMEUFBTDOKPX-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 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
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 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
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 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
- 238000000071 blow moulding Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 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
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-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
- 239000000806 elastomer Substances 0.000 description 1
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Abstract
Description
本発明は樹脂に添加した場合に高度な難燃性を有し、且つ耐熱性、誘電特性に優れるホスファゼン化合物及び難燃性樹脂組成物に関する。 The present invention relates to a phosphazene compound and a flame retardant resin composition which have high flame retardancy when added to a resin, and which are excellent in heat resistance and dielectric properties.
近年、電気・電子機器分野において、使用される周波数帯が高周波数領域になるにつれて、樹脂組成物は高度な難燃性を有しながら、且つ、より優れた電気特性を有することが求められている。
樹脂の難燃剤として、分子内に反応性官能基を有するアリールオキシ基及びアリールオキシ基を有するホスファゼン化合物を用いる技術が報告されている（例えば、特許文献１参照。）。しかし、十分な難燃性を得る為には、多量のホスファゼン化合物を添加する必要がある上、耐熱性、誘電特性ともに十分ではなかった。また、ホスファゼン化合物の置換基に関しては未だ任意性が許されており、該特許文献からは、本願による特定の反応性官能基及び特定の置換基を有するアリールオキシ基を含有するホスファゼン化合物が、特に難燃性、耐熱性、勇断特性に優れることを見出すことが出来ず、本願により初めて成されたものである。
A technique using an aryloxy group having a reactive functional group in a molecule and a phosphazene compound having an aryloxy group as a flame retardant for a resin has been reported (for example, see Patent Document 1). However, in order to obtain sufficient flame retardancy, it is necessary to add a large amount of phosphazene compound, and neither heat resistance nor dielectric properties are sufficient. Further, the optionality of the substituent of the phosphazene compound is still allowed, and from this patent document, the phosphazene compound containing an aryloxy group having a specific reactive functional group and a specific substituent according to the present application is particularly This is the first time that the present application has made it impossible to find excellent flame retardancy, heat resistance, and brave characteristics.
本発明は、ハロゲン化合物を含まず、耐熱性、耐吸湿性に優れ、環境上好ましい、高度な難燃性、及び優れた電気特性を有するホスファゼン化合物及び樹脂組成物を提供するものである。 The present invention provides a phosphazene compound and a resin composition that do not contain a halogen compound, have excellent heat resistance and moisture absorption resistance, are environmentally preferable, have high flame retardancy, and excellent electrical properties.
本発明者らは上記課題を解決するために鋭意検討した結果、特定の反応性基及び、特定の置換基を有するアリールオキシ基を含有するホスファゼン化合物が、樹脂に添加した場合に優れた難燃性、耐熱性、及び誘電特性を有することを見出し、本発明に到達した。
すなわち、本発明は、
１．下記式（１）で示される環状ホスファゼン化合物、
ただし、式（１）中のｎは１〜８の整数であり、式（１）中のＸは少なくとも一つが下記式（２）で示される置換基を有するアリール基（式中のＲ１、Ｒ２、Ｒ３、Ｒ４及びＲ５は水素原子、炭素数が１〜５のアルキル基又はアルコキシ基、又はフェニル基を表し、Ｒ１〜Ｒ５の少なくとも二つ以上が水素原子以外の基であり、Ｒ１〜Ｒ５すべてが同時に水素原子であることはない）で、他の基が下記式（３）で示される反応性官能基を有するアリール基（式中のＲ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０のうち少なくとも一つが、ＯＨ基、ＳＨ基、アルデヒド基、グリシジル含有基、シアノ基の中から選ばれる少なくとも一種の基であり、それ以外が水素原子、炭素数が１〜５のアルキル基又はアルコキシ基、又はフェニル基である基）、
As a result of intensive studies to solve the above problems, the inventors of the present invention have excellent flame retardancy when a phosphazene compound containing a specific reactive group and an aryloxy group having a specific substituent is added to a resin. The present invention has been found.
That is, the present invention
1. A cyclic phosphazene compound represented by the following formula (1):
However, n in Formula (1) is an integer of 1-8, and X in Formula (1) is an aryl group having at least one substituent represented by the following Formula (2) (R1, R2 in the formula) , R3, R4 and R5 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, or a phenyl group, and at least two of R1 to R5 are groups other than a hydrogen atom, and all of R1 to R5 Are not simultaneously hydrogen atoms), and other groups having a reactive functional group represented by the following formula (3) (at least one of R6, R7, R8, R9, R10 in the formula: , An OH group, an SH group, an aldehyde group, a glycidyl-containing group, or a cyano group, the other being a hydrogen atom, an alkyl or alkoxy group having 1 to 5 carbon atoms, or a phenyl group Group),
２．反応性官能基が、ＯＨ基、アルデヒド基およびグリシジル含有基から選ばれる少なくとも一種であることを特徴とする上記１に記載のホスファゼン化合物、
３．置換基を有するアリール基において、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５のうち少なくとも二つがメチル基、エチル基およびターシャリーブチル基から選ばれる少なくとも一種の基であることを特徴とする上記１又は２いずれか一項に記載のホスファゼン化合物、
４．置換基を有するアリール基において、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５のうち少なくとも二つがメチル基であり、その他が水素原子であることを特徴とする上記１又は２いずれか一項に記載のホスファゼン化合物、
５．置換基を有するアリール基において、Ｒ１及びＲ５がメチル基であることを特徴とする上記１又は２いずれか一項に記載のホスファゼン化合物、
６．樹脂（Ａ）及び上記１〜５いずれか一項に記載のホスファゼン化合物（Ｂ）からなる樹脂組成物であって、（Ａ）成分１００重量部に対し、（Ｂ）成分を１〜７０重量部含有することを特徴とする難燃性樹脂組成物、
７．樹脂（Ａ）が、エポキシ樹脂であることを特徴とする上記６に記載の難燃性樹脂組成物、
である。
2. The phosphazene compound according to the above 1, wherein the reactive functional group is at least one selected from an OH group, an aldehyde group, and a glycidyl-containing group,
3. 1 or 2 above, wherein in the aryl group having a substituent, at least two of R1, R2, R3, R4 and R5 are at least one group selected from a methyl group, an ethyl group and a tertiary butyl group. The phosphazene compound according to any one of the above,
4). The phosphazene according to any one of 1 or 2 above, wherein in the aryl group having a substituent, at least two of R1, R2, R3, R4 and R5 are methyl groups, and the other is a hydrogen atom. Compound,
5. In the aryl group having a substituent, R1 and R5 are methyl groups, The phosphazene compound according to any one of the above 1 or 2,
6). It is a resin composition which consists of resin (A) and the phosphazene compound (B) as described in any one of said 1-5, Comprising: It is 1-70 weight part of (B) component with respect to 100 weight part of (A) component. Containing a flame retardant resin composition,
7). Resin (A) is an epoxy resin, The flame-retardant resin composition of said 6 characterized by the above-mentioned,
It is.
本発明は、ハロゲンを含まず、樹脂に添加した場合に耐熱性、誘電特性及び難燃性のバランスに優れた樹脂組成物を得ることができるホスファゼン化合物を提供する。 The present invention provides a phosphazene compound that does not contain a halogen and can provide a resin composition having an excellent balance of heat resistance, dielectric properties and flame retardancy when added to a resin.
以下、本発明を詳細に説明する。
本発明で好適に用いられるホスファゼン化合物は、
下記式（１）で示される環状ホスファゼン化合物、
ただし、式（１）中のｎは１〜８の整数であり、式（１）中のＸは少なくとも一つが下記式（２）で示される置換基を有するアリール基（式中のＲ１、Ｒ２、Ｒ３、Ｒ４及びＲ５は水素原子、炭素数が１〜５のアルキル基又はアルコキシ基、又はフェニル基を表し、Ｒ１〜Ｒ５の少なくとも二つ以上が水素原子以外の基であり、Ｒ１〜Ｒ５すべてが同時に水素原子であることはない）で、他の基が下記式（３）で示される反応性官能基を有するアリール基（式中のＲ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０のうち少なくとも一つが、ＯＨ基、ＳＨ基、アルデヒド基、グリシジル含有基、シアノ基の中から選ばれる少なくとも一種の基であり、それ以外が水素原子、炭素数が１〜５のアルキル基又はアルコキシ基、又はフェニル基である基）が必須である。
Hereinafter, the present invention will be described in detail.
The phosphazene compound suitably used in the present invention is
A cyclic phosphazene compound represented by the following formula (1):
However, n in Formula (1) is an integer of 1-8, and X in Formula (1) is an aryl group having at least one substituent represented by the following Formula (2) (R1, R2 in the formula) , R3, R4 and R5 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, or a phenyl group, and at least two of R1 to R5 are groups other than a hydrogen atom, and all of R1 to R5 Are not simultaneously hydrogen atoms), and other groups having a reactive functional group represented by the following formula (3) (at least one of R6, R7, R8, R9, R10 in the formula: , An OH group, an SH group, an aldehyde group, a glycidyl-containing group, or a cyano group, the other being a hydrogen atom, an alkyl or alkoxy group having 1 to 5 carbon atoms, or a phenyl group Group) is essential .
難燃性を決める因子の一つとして、分子中に含有するリン原子の濃度が挙げられる。ホスファゼン化合物において、鎖状構造を有する鎖状ホスファゼンは分子末端に置換基を有することから、環状ホスファゼン化合物よりもリン含有率が低くなり、同量を添加する場合、鎖状ホスファゼン化合物よりも環状ホスファゼン化合物の方がより難燃性付与効果が高いと考えられることから、本発明においては、環状ホスファゼン化合物を９５重量％以上含有するものが好ましい。
さらに、これらの化合物は国際公開番号ＷＯ００／０９５１８号に開示されている技術により、フェニレン基、ビフェニレン基および下記に示す基（４）からなる群より選ばれた架橋基によって架橋されていても良い。（式中Ｘは、−Ｃ（ＣＨ３）２−、−ＳＯ２−、−Ｓ−、または−Ｏ−を、ｙは０又は１を表す）
One factor that determines flame retardancy is the concentration of phosphorus atoms contained in the molecule. In a phosphazene compound, a chain phosphazene having a chain structure has a substituent at the molecular end, so that the phosphorus content is lower than that of a cyclic phosphazene compound. In the present invention, the compound containing 95% by weight or more of the cyclic phosphazene compound is preferable because the compound is considered to have a higher flame retardancy imparting effect.
Further, these compounds may be cross-linked by a cross-linking group selected from the group consisting of a phenylene group, a biphenylene group and a group (4) shown below by the technique disclosed in International Publication No. WO 00/09518. . (Wherein X represents —C (CH 3 ) 2 —, —SO 2 —, —S—, or —O—, and y represents 0 or 1).
これらの架橋構造を有するホスファゼン化合物は、具体的にはジクロルホスファゼンオリゴマーにフェノールのアルカリ金属塩および芳香族ジヒドロキシ化合物のアルカリ金属塩を反応させることにより製造される。これらのアルカリ金属塩は、ジクロルホスファゼンオリゴマーに対して理論量よりもやや過剰に添加される。これらのホスファゼン化合物は一種単独で用いても、二種以上の混合物として用いても良い。 The phosphazene compound having such a crosslinked structure is specifically produced by reacting a dichlorophosphazene oligomer with an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound. These alkali metal salts are added to the dichlorophosphazene oligomer slightly in excess of the theoretical amount. These phosphazene compounds may be used alone or as a mixture of two or more.
アリールオキシ基上の置換基Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５は特に制限はないが、一例としてメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−アミル基、イソアミル基等のアルキル基、フェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、２，６−ジメチルフェニル基、３，５−ジメチルフェニル基、２，５−ジメチルフェニル基、２，４−ジメチルフェニル基、３，４−ジメチルフェニル基、４−ターシャリーブチルフェニル基、２−メチル−４−ターシャリーブチルフェニル基等のアリール基、メトキシ基、エトキシ基、ｎ−プロピルオキシ基、イソプロピルオキシ基、ｎ−ブチルオキシ基、ｔｅｒｔ−ブチルオキシ基、ｓ−ブチルオキシ基が挙げられる。 Substituents R1, R2, R3, R4 and R5 on the aryloxy group are not particularly limited, but examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, tert. -Alkyl groups such as butyl group, n-amyl group, isoamyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethyl Aryl groups such as phenyl group, 2,5-dimethylphenyl group, 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 4-tertiarybutylphenyl group, 2-methyl-4-tertiarybutylphenyl group Methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, s-butyloxy group Shi group.
また、ｎ−アミルオキシ基、イソアミルオキシ基、ｔｅｒｔ−アミルオキシ基、ｎ−ヘキシルオキシ基等のアルコキシ基、メトキシメトキシ基、メトキシエトキシ基、メトキシエトキシメトキシ基、メトキシエトキシエトキシ基、メトキシプロピルオキシ基等のアルコキシ置換アルコキシ基、フェノキシ基、２−メチルフェノキシ基、３−メチルフェノキシ基、４−メチルフェノキシ基、２，６−ジメチルフェノキシ基、２，５−ジメチルフェノキシ基、２，４−ジメチルフェノキシ基、３，５−ジメチルフェノキシ基、３，４−ジメチルフェノキシ基、２，３，４−トリメチルフェノキシ基、２，３，５−トリメチルフェノキシ基、２，３，６−トリメチルフェノキシ基、２，４，６−トリメチルフェノキシ基、２，４，５−トリメチルフェノキシ基、３，４，５−トリメチルフェノキシ基が挙げられる。 Also, alkoxy groups such as n-amyloxy group, isoamyloxy group, tert-amyloxy group, n-hexyloxy group, methoxymethoxy group, methoxyethoxy group, methoxyethoxymethoxy group, methoxyethoxyethoxy group, methoxypropyloxy group, etc. Alkoxy-substituted alkoxy group, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 3,4-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,4 6-trimethylphenoxy group, 2,4,5-trimethyl Phenoxy group, and a 3,4,5-trimethyl phenoxy group.
２−エチルフェノキシ基、３−エチルフェノキシ基、４−エチルフェノキシ基、２，６−ジエチルフェノキシ基、２，５−ジエチルフェノキシ基、２，４−ジエチルフェノキシ基、３，５−ジエチルフェノキシ基、３，４−ジエチルフェノキシ基、４−ｎ−プロピルフェノキシ基、４−イソプロピルフェノキシ基、４−ターシャリーブチルフェノキシ基、２−メチル−４−ターシャリーブチルフェノキシ基、２−フェニルフェノキシ基、３−フェニルフェノキシ基、４−フェニルフェノキシ基等のアルキル置換フェノキシ基、アリール置換フェノキシ基ナフチル基、ナフチルオキシ基が好ましく、これらのホスファゼン化合物は一種単独で用いても、二種以上の混合物として用いても良い。 2-ethylphenoxy group, 3-ethylphenoxy group, 4-ethylphenoxy group, 2,6-diethylphenoxy group, 2,5-diethylphenoxy group, 2,4-diethylphenoxy group, 3,5-diethylphenoxy group, 3,4-diethylphenoxy group, 4-n-propylphenoxy group, 4-isopropylphenoxy group, 4-tertiarybutylphenoxy group, 2-methyl-4-tertiarybutylphenoxy group, 2-phenylphenoxy group, 3- Preferred are alkyl-substituted phenoxy groups such as phenylphenoxy group and 4-phenylphenoxy group, aryl-substituted phenoxy groups, naphthyl groups, and naphthyloxy groups. These phosphazene compounds may be used alone or as a mixture of two or more. good.
中でも、耐熱性、誘電特性を考慮すると、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５のうち少なくとも二つがメチル基、エチル基、ターシャリーブチル基から選ばれる少なくとも一種の基であることが好ましく、合成のし易さを考慮すると、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５のうち少なくとも二つがメチル基で、その他が水素原子であるキシレノキシ基がより好適に使用され、少なくともＲ１及びＲ５がメチル基である基が特に好適に使用される。
また、ホスファゼン化合物は環状三量体、環状四量体等の環状体や鎖状ホスファゼンといった構造の異なる混合物であるが、樹脂に添加した場合の加工性は環状三量体、四量体含有率が高いほど好ましい傾向にあり、具体的には環状三量体及び／又は四量体化合物を８０重量％以上含むホスファゼン化合物が好ましい。さらに好ましくは、三量体を７０重量％以上、より好ましくは三量体を８０重量％以上含有することが好ましい。
Among them, in consideration of heat resistance and dielectric properties, it is preferable that at least two of R1, R2, R3, R4 and R5 are at least one group selected from a methyl group, an ethyl group and a tertiary butyl group. In consideration of easiness, a xylenoxy group in which at least two of R1, R2, R3, R4 and R5 are methyl groups and the other is a hydrogen atom is more preferably used, and a group in which at least R1 and R5 are methyl groups. Is particularly preferably used.
The phosphazene compound is a mixture of different structures such as cyclic trimers and cyclic tetramers and chain phosphazenes, but the processability when added to the resin is cyclic trimer and tetramer content. Is higher, and a phosphazene compound containing 80% by weight or more of a cyclic trimer and / or tetramer compound is specifically preferable. More preferably, it is preferable to contain 70% by weight or more of trimer, more preferably 80% by weight or more of trimer.
また、ホスファゼン化合物は、置換基の種類や構造の違いによっても異なるが、液状、ワックス状、固体状等、さまざまな形態を取ることができ、本発明の効果を損なわないものであれば、どのような形状でも構わない。固体状態の場合、嵩密度が０．４５ｇ／ｃｍ３以上、好ましくは０．４５ｇ／ｃｍ３以上、０．７５ｇ／ｃｍ３以下であることが好ましい。
該ホスファゼン化合物中に含有するナトリウム、カリウム等のアルカリ金属成分はそれぞれ２００ｐｐｍ以下、さらに好ましくは５０ｐｐｍ以下であり、より好ましくは、全アルカリ金属成分が５０ｐｐｍ以下である。また、Ｐ−ＯＨ結合を含有するホスファゼン化合物の含有量が１重量％未満であることが望ましく、且つ、塩素含有量が１０００ｐｐｍ以下、好ましくは５００ｐｐｍ以下、さらに好ましくは３００ｐｐｍ以下であることが望ましい。
The phosphazene compound varies depending on the type and structure of the substituent, but can take various forms such as liquid, waxy, solid, etc., as long as it does not impair the effects of the present invention. Such a shape may be used. If the solid state, the bulk density is 0.45 g / cm 3 or higher, preferably 0.45 g / cm 3 or more and 0.75 g / cm 3 or less.
The alkali metal components such as sodium and potassium contained in the phosphazene compound are each 200 ppm or less, more preferably 50 ppm or less, and more preferably the total alkali metal components are 50 ppm or less. Further, the content of the phosphazene compound containing a P—OH bond is desirably less than 1% by weight, and the chlorine content is desirably 1000 ppm or less, preferably 500 ppm or less, and more preferably 300 ppm or less.
該ホスファゼン化合物においては、酸価が１．０以下、好ましくは０．７以下、より好ましくは０．５以下であるものを好適に使用できる。
置換基を有するアリールオキシ基と、反応性官能基を有するアリールオキシ基の比率は、本発明の効果が発揮できる比率であれば良く、特に規定はされない。反応性、耐吸湿性、半田耐熱性等のバランスを考慮すると、反応性官能基を有するアリールオキシ基は、全置換基中に２０〜８０ｍｏｌ％であることが好ましく、より好ましくは２５〜７５ｍｏｌ％、更に好ましくは３０〜７０ｍｏｌ％であることが好ましい。
In the phosphazene compound, those having an acid value of 1.0 or less, preferably 0.7 or less, more preferably 0.5 or less can be suitably used.
The ratio between the aryloxy group having a substituent and the aryloxy group having a reactive functional group is not particularly limited as long as it is a ratio capable of exhibiting the effects of the present invention. Considering the balance of reactivity, moisture absorption resistance, solder heat resistance, etc., the aryloxy group having a reactive functional group is preferably 20 to 80 mol%, more preferably 25 to 75 mol% in all substituents. Furthermore, it is more preferable that it is 30-70 mol%.
（使用用途）
本発明のホスファゼン化合物は、広範囲で好適に使用することができ、使用方法、使用分野は特に規定されない。好適な使用方法として、一例を挙げると、樹脂用難燃剤、塗料、コーティング剤、ゴム、潤滑剤、リチウムイオン電池、太陽電池、燃料電池、不燃性電解液、電池電装用、離形剤、離形膜、粗化面形成材、撥水剤等に好適に用いられる。
（ホスファゼン化合物の形状）
本発明におけるホスファゼン化合物の形状は、本発明の効果が達成できるものであれば特に規定するものではない。例えば、粉体、錠剤型、ペレット、塊状、ワックス、液体、オイル等の状態で供給される。また、必要であれば、ホスファゼン化合物の一部又は全部を気化させて用いることもできる。
(Use applications)
The phosphazene compound of the present invention can be suitably used in a wide range, and the usage method and field of use are not particularly defined. Examples of suitable usage methods include resin flame retardants, paints, coating agents, rubber, lubricants, lithium ion batteries, solar cells, fuel cells, non-flammable electrolytes, battery electrical equipment, release agents, release agents. It is suitably used for a shape film, a roughened surface forming material, a water repellent and the like.
(Shape of phosphazene compound)
The shape of the phosphazene compound in the present invention is not particularly defined as long as the effects of the present invention can be achieved. For example, it is supplied in the state of powder, tablet form, pellet, lump, wax, liquid, oil or the like. If necessary, part or all of the phosphazene compound can be vaporized and used.
（ホスファゼン化合物と樹脂との組合せ）
本発明のホスファゼン化合物は、従来公知の樹脂と組み合わせて使用することができる。使用に共される樹脂は何等規定されるものではなく、公知の硬化性樹脂、熱可塑性樹脂が好適に使用される。一例を挙げると、熱可塑性樹脂としては、ポリカーボネート系樹脂、ポリフェニレンエーテル系樹脂、ポリフェニレンサルファイド系樹脂、ポリプロピレン系樹脂、ポリエチレン系樹脂、ポリスチレン系樹脂、ハイインパクトポリスチレン、エラストマー含有ポリスチレン、シンジオタクテックポリスチレン系樹脂、ＡＢＳ系樹脂、ＡＳ系樹脂、生分解性樹脂、ポリカーボネート−ＡＢＳ樹脂のアロイ、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリトリメチレンテレフタレート等のポリアルキレンテレフタレート系樹脂、ポリアミド系樹脂、サーモトロピック液晶等が挙げられ、特にポリフェニレンエーテル系樹脂、ポリスチレン系樹脂、ＡＢＳ系樹脂、ポリケトン系樹脂、ポリフェニレンエーテルとポリスチレンのアロイ、ポリフェニレンエーテルとポリアミドのアロイ、ポリフェニレンエーテルとサーモトロピック液晶とのアロイ、ポリフェニレンエーテルとポリフェニレンサルファイドとのアロイが好適に使用される。
硬化性樹脂としては、不飽和ポリエステル樹脂、ビニルエステル樹脂、ジアリルフタレート樹脂、エポキシ樹脂、シアネート樹脂、キシレン樹脂、トリアジン樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、ベンゾグアナミン樹脂、ウレタン樹脂、オキセタン樹脂、ケトン樹脂、アルキド樹脂、フラン樹脂、スチリルピリジン樹脂、シリコン樹脂、合成ゴムがあり、特にエポキシ樹脂が好適に使用される。
本発明で使用される樹脂は、一種単独でも、二種以上の樹脂を組み合わせて用いても良い。
(Combination of phosphazene compound and resin)
The phosphazene compound of the present invention can be used in combination with a conventionally known resin. The resin used for use is not defined in any way, and known curable resins and thermoplastic resins are preferably used. For example, as a thermoplastic resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polypropylene resin, polyethylene resin, polystyrene resin, high impact polystyrene, elastomer-containing polystyrene, syndiotactic polystyrene Resin, ABS resin, AS resin, biodegradable resin, polycarbonate-ABS resin alloy, polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polytrimethylene terephthalate and other polyalkylene terephthalate resins, polyamide resins, thermotropic Liquid crystal and the like, and in particular, polyphenylene ether resin, polystyrene resin, ABS resin, polyketone resin, polyphenylene N'eteru polystyrene alloys, alloys of polyphenylene ether and polyamide, alloy of polyphenylene ether and thermotropic liquid crystal, alloy of polyphenylene ether and polyphenylene sulfide is preferably used.
As curable resins, unsaturated polyester resins, vinyl ester resins, diallyl phthalate resins, epoxy resins, cyanate resins, xylene resins, triazine resins, phenol resins, urea resins, melamine resins, benzoguanamine resins, urethane resins, oxetane resins, ketones There are resins, alkyd resins, furan resins, styrylpyridine resins, silicon resins, and synthetic rubbers. Epoxy resins are particularly preferably used.
The resins used in the present invention may be used singly or in combination of two or more resins.
（配合割合）
本発明によるホスファゼン化合物と樹脂との配合割合は、本発明の効果を得ることのできる割合であればよく特に規定はされないが、樹脂（Ａ）の１００重量部に対し、ホスファゼン化合物（Ｂ）を１〜７０重量部であることが好ましい。より好ましくは（Ａ）成分１００重量部に対し、（Ｂ）成分は２〜５０重量部であり、更に好ましくは、（Ａ）成分１００重量部に対し、（Ｂ）成分は３〜４０重量部であり、特に好ましくは（Ａ）成分１００重量部に対し、（Ｂ）成分は５〜３０重量部である。
(Mixing ratio)
The blending ratio of the phosphazene compound and the resin according to the present invention is not particularly limited as long as it is a ratio capable of obtaining the effects of the present invention, but the phosphazene compound (B) is added to 100 parts by weight of the resin (A). It is preferable that it is 1-70 weight part. More preferably, the component (B) is 2 to 50 parts by weight with respect to 100 parts by weight of the component (A), and more preferably 3 to 40 parts by weight of the component (B) with respect to 100 parts by weight of the component (A). Particularly preferably, the component (B) is 5 to 30 parts by weight per 100 parts by weight of the component (A).
（添加剤）
本発明によるホスファゼン化合物及び樹脂組成物においては、本発明の効果が達成できる範囲で、従来公知のノンハロゲン、ノンアンチモンの難燃剤を併用することができる。例示すると、トリアリールホスフィン、トリアルキルホスフィン、ビス（ジアリールホスフィノ）ベンゼン、トリス（ジアリールホスフィノ）ベンゼン等の三級ホスフィン類やその酸化物や硫化物、ホスフィン酸やホスホン酸等の金属塩、アミド、アンモニウム塩、メラミンとの誘導体、水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウム、アルミン酸カルシウム等の金属水酸化物、メラミン、メラム、メレム、メロン、メチレンジメラミン、エチレンジメラミン、デカメチレンジメラミン、１，３−シクロヘキシルジメラミン、４，４’−ジエチレンジメラミン、ジエチレントリメラミン、ベンゾグアナミン、ジベンゾグアナミン、サクシノグアナミン、メチルグアナミン、アセトグアナミン、メラミン樹脂等や、上記化合物のシアヌル酸塩、硫酸塩、リン酸塩、硼酸塩、２−ジブチルアミノ−４，６−ジメルカプト−Ｓ−トリアジン、２−Ｎ−フェニルアミノ−４，６−ジメルカプト−Ｓ−トリアジン、２，４，６−トリメルカプト−Ｓ−トリアジン、トリアリルシアヌレート、トリメタアリルイソシアヌレート等のトリアジン系化合物、バナジウム、二オブ、タンタル、鉄、ルテニウム、ニッケル、パラジウム、白金、銅、銀、金等の酸化物や硫化物、硼酸、硼酸亜鉛化合物等の硼素含有化合物、ポリオルガノシロキサン、シルセスキオキサン、シリコン樹脂等の珪素含有化合物、シリカ、カオリンクレー、タルク、ウォラストナイト等の無機珪素化合物を添加して更なる難燃性の向上も可能である。
(Additive)
In the phosphazene compound and the resin composition according to the present invention, conventionally known non-halogen and non-antimony flame retardants can be used in combination as long as the effects of the present invention can be achieved. Illustrative examples include tertiary phosphines such as triarylphosphine, trialkylphosphine, bis (diarylphosphino) benzene, tris (diarylphosphino) benzene, oxides and sulfides thereof, metal salts such as phosphinic acid and phosphonic acid, Amides, ammonium salts, derivatives with melamine, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide, calcium aluminate, melamine, melam, melem, melon, methylene dimelamine, ethylene dimelamine, decamethylene Dimelamine, 1,3-cyclohexyl dimelamine, 4,4′-diethylene dimelamine, diethylenetrimelamine, benzoguanamine, dibenzoguanamine, succinoguanamine, methylguanamine, acetoguanamine, melamine resin, etc. Anulate, sulfate, phosphate, borate, 2-dibutylamino-4,6-dimercapto-S-triazine, 2-N-phenylamino-4,6-dimercapto-S-triazine, 2,4, Oxidation of triazine compounds such as 6-trimercapto-S-triazine, triallyl cyanurate, trimethallyl isocyanurate, vanadium, niobium, tantalum, iron, ruthenium, nickel, palladium, platinum, copper, silver, gold, etc. Boron-containing compounds such as oxides, sulfides, boric acid, zinc borate compounds, polyorganosiloxanes, silsesquioxanes, silicon-containing compounds such as silicon resins, inorganic silicon compounds such as silica, kaolin clay, talc and wollastonite Thus, further improvement in flame retardancy is possible.
また、本発明のホスファゼン化合物及び樹脂組成物においては、機械物性を向上させる目的で、従来公知の充填材を配合することができる。例えば、シリカ、カオリンクレー、タルク、ウォラストナイト、酸化チタン、ガラスビーズ、ガラスフレーク、ガラス繊維、炭酸カルシウム、炭酸バリウム、硫酸カルシウム、硫酸バリウム、珪酸カルシウム、チタン酸カリウム、硼酸アルミニウム、硼酸マグネシウムや、ケナフ繊維、炭素繊維、シリカ繊維、アルミナ繊維、石英繊維等の繊維状補強剤や、非繊維状補強剤が挙げられる。これらは、有機物や無機物等で被覆されていたも良い。
本発明のホスファゼン化合物及び、ホスファゼン化合物を含有する難燃性樹脂組成物を使用する場合、剛性や寸法安定性等の他の特性を付与するため、本発明の効果を損なわない範囲で他の添加剤、例えば可塑剤、酸化防止剤、及び紫外線吸収剤、光安定剤などの安定剤、硬化剤、硬化促進剤、帯電防止剤、導電性付与剤、応力緩和剤、離型剤、結晶化促進剤、加水分解抑制剤、潤滑剤、衝撃付与剤、摺動性改良剤、相溶化剤、核剤、強化剤、補強剤、流動調整剤、染料、増感材、着色用顔料、ゴム質重合体、導電性高分子等を予め添加することができる。
In the phosphazene compound and the resin composition of the present invention, conventionally known fillers can be blended for the purpose of improving mechanical properties. For example, silica, kaolin clay, talc, wollastonite, titanium oxide, glass beads, glass flake, glass fiber, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, calcium silicate, potassium titanate, aluminum borate, magnesium borate and And fibrous reinforcing agents such as kenaf fiber, carbon fiber, silica fiber, alumina fiber, and quartz fiber, and non-fibrous reinforcing agent. These may be coated with an organic substance, an inorganic substance, or the like.
When using the phosphazene compound of the present invention and the flame retardant resin composition containing the phosphazene compound, other additions are made within the range not impairing the effects of the present invention in order to impart other characteristics such as rigidity and dimensional stability. Stabilizers such as plasticizers, antioxidants, UV absorbers, light stabilizers, curing agents, curing accelerators, antistatic agents, conductivity-imparting agents, stress relaxation agents, mold release agents, crystallization promotion agents Agent, hydrolysis inhibitor, lubricant, impact imparting agent, slidability improver, compatibilizer, nucleating agent, reinforcing agent, reinforcing agent, flow modifier, dye, sensitizer, coloring pigment, rubber weight A coalescence, a conductive polymer or the like can be added in advance.
（配合順序）
本発明における難燃性樹脂組成物において、各成分の配合方法は、本発明の効果が達成できる方法であれば特に規定するものでない。（Ａ）成分と（Ｂ）成分及び、他の成分を予め混合して用いても良いし、（Ａ）成分と（Ｂ）成分を混合した後、他の成分を配合しても良い。また、（Ａ）成分と他の成分を混合した後、（Ｂ）成分を配合しても良いし、（Ｂ）成分と他の成分を混合した後、（Ａ）成分を配合しても良い。
（配合方法）
本発明におけるホスファゼン化合物と樹脂との配合方法は、本発明の効果が達成できる方法であれば特に規定するものではない。例えば、押出機、加熱ロール、ニーダー、バンバリーミキサー等の混練機を用いて混練製造することができる。その中でも押出機による溶融混練が、生産性の面で好ましい。溶融混練温度は、ベース樹脂の好ましい加工温度に従えばよく、目安としては１４０〜３６０℃の範囲、好ましくは１８０〜３２０℃の範囲である。
(Mixing order)
In the flame retardant resin composition of the present invention, the blending method of each component is not particularly defined as long as the effect of the present invention can be achieved. The (A) component, the (B) component, and other components may be mixed and used in advance, or the other components may be blended after the (A) component and the (B) component are mixed. Moreover, (B) component may be mix | blended after mixing (A) component and another component, (A) component may be mix | blended after mixing (B) component and another component. .
(Mixing method)
The blending method of the phosphazene compound and the resin in the present invention is not particularly defined as long as the effect of the present invention can be achieved. For example, kneading can be performed using a kneader such as an extruder, a heating roll, a kneader, or a Banbury mixer. Among them, melt kneading with an extruder is preferable in terms of productivity. The melt-kneading temperature may be in accordance with the preferred processing temperature of the base resin, and as a guide, it is in the range of 140 to 360 ° C, preferably in the range of 180 to 320 ° C.
また本発明の該組成物の成形体は、射出成形、シート成形、ブロー成形、インジェクションブロー成形、インフレーション成形、押出成形、発泡成形、フィルム成形等、公知の方法で成形することが可能であり、圧空成形、真空成形等の二次加工成形法も用いることができる。
また、本発明によるホスファゼン化合物を硬化性樹脂に配合する場合には、樹脂組成物を製造するための成分を、無溶媒で、若しくは、必要に応じて均一に混合できる溶媒を用いて混合した後、溶媒を除去して樹脂混合物を得て、これを金型内へ注形し硬化させた後冷却し、型から取り出すことにより成型品を得る方法でも良い。また、型に注型し、熱プレスにより硬化させることもできる。各成分を溶解させる為の溶媒は各種材料を均一に混合することができ、且つ、使用することによって本発明の効果を損なわないものであれば特に限定されるものではない。一例としてはトルエン、キシレン、アセトン、メチルエチルケトン、ジエチルケトン、シクロペンタノン、シクロヘキサノン、ジメチルホルムアミド、メチルセルソルブ、メタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノール、ｎ−ブタノール、ｎ−ペンタノール、ｎ−ヘキサノール、シクロヘキサノール、ｎ−ヘキサン、ｎ−ペンタン等が挙げられる。
The molded product of the composition of the present invention can be molded by known methods such as injection molding, sheet molding, blow molding, injection blow molding, inflation molding, extrusion molding, foam molding, film molding, Secondary processing molding methods such as pressure forming and vacuum forming can also be used.
In addition, when the phosphazene compound according to the present invention is blended with a curable resin, the components for producing the resin composition are mixed without a solvent or with a solvent that can be uniformly mixed as necessary. Alternatively, a method may be used in which the solvent is removed to obtain a resin mixture, which is cast into a mold and cured, and then cooled and taken out from the mold. It can also be cast into a mold and cured by hot pressing. The solvent for dissolving each component is not particularly limited as long as various materials can be mixed uniformly and the effects of the present invention are not impaired by use. Examples include toluene, xylene, acetone, methyl ethyl ketone, diethyl ketone, cyclopentanone, cyclohexanone, dimethylformamide, methyl cellosolve, methanol, ethanol, n-propanol, iso-propanol, n-butanol, n-pentanol, n- Examples include hexanol, cyclohexanol, n-hexane, and n-pentane.
また、加熱ロール、ニーダー、バンバリーミキサー、押出機等の混練機を用いて混練製造した後、冷却、粉砕し、さらにトランスファー成形、射出成形、圧縮成形等により成形を行う方法も一例として挙げることができる。また、硬化方法は使用する硬化剤により異なるが、特に限定はされない。例としては、熱硬化、光硬化、ＵＶ硬化、圧力による硬化、湿気による硬化等が挙げられるが、本発明の効果が達成できる硬化方法であれば規定されるものではない。各成分を混合させる順序は、本発明の効果が達成できる方法であれば特に規定するものではない。樹脂組成物の製造方法は、それぞれの樹脂の適性に応じて、好ましい方法を用いることができる。 Another example is a method of kneading and manufacturing using a kneader such as a heating roll, kneader, Banbury mixer, or extruder, followed by cooling, pulverization, and molding by transfer molding, injection molding, compression molding, or the like. it can. The curing method varies depending on the curing agent used, but is not particularly limited. Examples include thermal curing, photocuring, UV curing, curing by pressure, curing by moisture, and the like, but are not defined as long as the curing method can achieve the effects of the present invention. The order of mixing the components is not particularly limited as long as the effect of the present invention can be achieved. As a method for producing the resin composition, a preferable method can be used according to the suitability of each resin.
（難燃性樹脂組成物の用途）
本発明のホスファゼン化合物を用いた難燃性樹脂組成物は、コイルボビン、フライバックトランス、コネクター、トレイ、偏光ヨーク等の電気・電子機器部品、プリント配線板、プリント基板、封止剤、電気絶縁材料、電気被覆剤、積層板、高速演算用ワニス、先端複合材料、電線、アンテナ剤、ケーブル、高性能成型材料等の電気・電子材料用途、塗料、接着剤、コーティング材、食器、ボタン、繊維・紙処理剤、化粧板、ＵＶ硬化型インキ、シーラント、合成皮革、断熱緩衝材料、塗膜防水材、防食ライニング、鋳型用バインダー、ラッカー、ペイント、インキの改質材、樹脂変性材、航空機内装剤、複合材料用マトリックス、家庭用品、ＯＡ機器、ＡＶ機器、電池電装用、照明機器、自動車部品用途、光学材料用途、ハウジング用途、ＥＴＣ、ＩＴＣ、携帯電話等に最適に使用される。
(Use of flame retardant resin composition)
The flame-retardant resin composition using the phosphazene compound of the present invention is a coil bobbin, a flyback transformer, a connector, a tray, a polarizing yoke, and other electrical / electronic equipment parts, a printed wiring board, a printed board, a sealant, and an electrical insulating material. , Electrical coatings, laminates, varnishes for high-speed computing, advanced composite materials, electric wires, antenna agents, cables, high-performance molding materials, etc., paints, adhesives, coating materials, tableware, buttons, textiles Paper treatment agent, decorative board, UV curable ink, sealant, synthetic leather, thermal insulation buffer material, waterproof coating material, anticorrosion lining, binder for mold, lacquer, paint, ink modifier, resin modifier, aircraft interior agent , Matrix for composite materials, household goods, OA equipment, AV equipment, battery electrical equipment, lighting equipment, automotive parts use, optical material use, housing use, TC, ITC, is optimally used in portable phones and the like.
以下、実施例によって本発明を具体的に説明するが、本発明は以下の例に限定されるものではない。また、本発明の組成物の調整方法は、各種材料を均一に混合することができる手法であれば特に限定されるものではない。
実施例および比較例で用いた各成分は以下のものである。
（Ａ）ビスフェノールＡ型エポキシ樹脂（Ｅｐｏｘｙ）
ＡＥＲ２５０（旭化成エポキシ（株）社製）；エポキシ当量１８４〜１８６
（Ｂ）ホスファゼン化合物
（Ｂ−１）水酸基含有ホスファゼン
上記化学式（１）において、ｎ＝３が９６ｗｔ％、ｎ＝４が３ｗｔ％、ｎ≧５が１ｗｔ％であり、１ＨＮＭＲ、３１ＰＮＭＲ、元素分析から求めた推定組成が［Ｎ＝Ｐ（ＯＸｙ−２，６）1.2（ＯＣ6Ｈ4ＯＨ）0.8］ｎであるホスファゼン化合物。
（Ｂ−２）グリジシル基含有ホスファゼン
（Ｂ−１）のホスファゼン化合物とエピクロルヒドリンから調製したグリシジル基含有ホスファゼン化合物。
（Ｂ−３）
上記化学式（１）においｔ、ｎ＝３が９２ｗｔ％、ｎ＝４が５ｗｔ％、ｎ≧５が３ｗｔ％であり、１ＨＮＭＲ、３１ＰＮＭＲ、元素分析から求めた推定組成が［Ｎ＝Ｐ（ＯＰｈ）1.0（ＯＣ6Ｈ4ＯＨ）1.0］ｎであるホスファゼン化合物。
（Ｂ−４）
上記化学式（１）においてｎ＝３が９３．６ｗｔ％、ｎ＝４が４．０ｗｔ％、ｎ≧５が２．４ｗｔ％であるフェノキシホスファゼン。
（Ｃ）硬化剤
ｍ−キシレン−α,α’−ジアミン（和光純薬工業（株）社製）。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following examples. Moreover, the adjustment method of the composition of this invention will not be specifically limited if it is a method which can mix various materials uniformly.
Each component used in the examples and comparative examples is as follows.
(A) Bisphenol A type epoxy resin (Epoxy)
AER250 (Asahi Kasei Epoxy Co., Ltd.); epoxy equivalents 184 to 186
(B) Phosphazene compound (B-1) Hydroxyl-containing phosphazene In the above chemical formula (1), n = 3 is 96 wt%, n = 4 is 3 wt%, n ≧ 5 is 1 wt%, 1 HNMR, 31 PNMR, element estimation composition determined from analysis [n = P (OXy-2,6 ) 1.2 (OC 6 H 4 OH) 0.8] phosphazene compound is n.
(B-2) Glycidyl group-containing phosphazene A glycidyl group-containing phosphazene compound prepared from the phosphazene compound (B-1) and epichlorohydrin.
(B-3)
In the chemical formula (1), t = n = 3 = 92 wt%, n = 4 = 5 wt%, n ≧ 5 = 3 wt%, and the estimated composition obtained from 1 HNMR, 31 PNMR, and elemental analysis is [N = P ( OPh) 1.0 (OC 6 H 4 OH) 1.0 ] A phosphazene compound which is n .
(B-4)
Phenoxyphosphazene in which n = 3 is 93.6 wt%, n = 4 is 4.0 wt%, and n ≧ 5 is 2.4 wt% in the chemical formula (1).
(C) Curing agent m-xylene-α, α′-diamine (manufactured by Wako Pure Chemical Industries, Ltd.).
（１） 難燃性
ＵＬ−９４垂直燃焼試験に基づき、長さ１２８ｍｍ×幅１２．８ｍｍ×厚さ２ｍｍの成形試験片を用いて評価を行った。
（２） 耐熱性（ＨＤＴ）
ＡＳＴＭ−Ｄ−６４８に基づき、表１〜３では厚さ２ｍｍの成形片で４．６ｋｇ荷重にて測定した。
（３） 誘電特性
厚さ約２ｍｍの成型片を用いて、比誘電正接を周波数１ＧＨｚにて測定した。
(1) Flame retardance Based on the UL-94 vertical combustion test, evaluation was performed using a molded specimen having a length of 128 mm, a width of 12.8 mm, and a thickness of 2 mm.
(2) Heat resistance (HDT)
Based on ASTM-D-648, in Tables 1 to 3, the measurement was performed at a load of 4.6 kg using a molded piece having a thickness of 2 mm.
(3) Dielectric properties Using a molded piece having a thickness of about 2 mm, the relative dielectric loss tangent was measured at a frequency of 1 GHz.
［実施例１〜２、比較例１〜２］
表１に示す量のエポキシ樹脂及びＰＰＥを、設定温度１４０℃のオイルバス中で溶解させて後、設定温度１３０℃のオイルバス中でホスファゼン化合物を混合し、温度を保ったまま、ｍＸＤＡを添加した後、型に流し込んだ。
次いで、１５０℃、０ｋｇｆ/ｃｍ２で１分間、１５０℃／１０ｋｇｆ/ｃｍ２で１分間、１５０℃／４０ｋｇｆ/ｃｍ２で１５分、熱プレス機で硬化させることにより試験片を成型して、物性評価を行い、表１の結果を得た。
[Examples 1-2, Comparative Examples 1-2]
After the amount of epoxy resin and PPE shown in Table 1 are dissolved in an oil bath at a set temperature of 140 ° C., the phosphazene compound is mixed in an oil bath at a set temperature of 130 ° C., and mXDA is added while maintaining the temperature. Then poured into the mold.
Then, a test piece was molded by curing with a hot press machine at 150 ° C., 0 kgf / cm 2 for 1 minute, 150 ° C./10 kgf / cm 2 for 1 minute, 150 ° C./40 kgf / cm 2 for 15 minutes, The physical properties were evaluated and the results shown in Table 1 were obtained.
Claims (8)
ただし、式（１）中のｎは１〜８の整数であり、式（１）中のＸは少なくとも一つが下記式（２）で示される置換基を有するアリール基（式中のＲ１、Ｒ２、Ｒ３、Ｒ４及びＲ５は水素原子、炭素数が１〜５のアルキル基又はアルコキシ基、又はフェニル基を表し、Ｒ１〜Ｒ５の少なくとも二つ以上が水素原子以外の基であり、Ｒ１〜Ｒ５すべてが同時に水素原子であることはない）で、他の基が下記式（３）で示される反応性官能基を有するアリール基（式中のＲ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０のうち少なくとも一つが、ＯＨ基、ＳＨ基、アルデヒド基、グリシジル含有基、シアノ基の中から選ばれる少なくとも一種の基であり、それ以外が水素原子、炭素数が１〜５のアルキル基又はアルコキシ基、又はフェニル基である基）。
However, n in Formula (1) is an integer of 1-8, and X in Formula (1) is an aryl group having at least one substituent represented by the following Formula (2) (R1, R2 in the formula) , R3, R4 and R5 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, or a phenyl group, and at least two of R1 to R5 are groups other than a hydrogen atom, and all of R1 to R5 Are not simultaneously hydrogen atoms), and other groups having a reactive functional group represented by the following formula (3) (at least one of R6, R7, R8, R9, R10 in the formula: , An OH group, an SH group, an aldehyde group, a glycidyl-containing group, or a cyano group, the other being a hydrogen atom, an alkyl or alkoxy group having 1 to 5 carbon atoms, or a phenyl group Group).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010037240A (en) * | 2008-08-02 | 2010-02-18 | Fushimi Pharm Co Ltd | Hydroxy group-containing cyclic phosphazene compound and its production method |
| JP2010037241A (en) * | 2008-08-02 | 2010-02-18 | Fushimi Pharm Co Ltd | Glycidyloxy group-containing cyclic phosphazene compound and its production method |
| JP2011088873A (en) * | 2009-10-26 | 2011-05-06 | Fushimi Pharm Co Ltd | Dihydrobenzoxazinoxy group-containing cyclic phosphazene compound and method for producing the same |
| JP2013103966A (en) * | 2011-11-11 | 2013-05-30 | Kyodo Yushi Co Ltd | Flame-retardant grease composition |
| JP2018172472A (en) * | 2017-03-31 | 2018-11-08 | 日本化薬株式会社 | Transparent flame-retardant sheet |
-
2004
- 2004-10-19 JP JP2004304332A patent/JP2006117545A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010037240A (en) * | 2008-08-02 | 2010-02-18 | Fushimi Pharm Co Ltd | Hydroxy group-containing cyclic phosphazene compound and its production method |
| JP2010037241A (en) * | 2008-08-02 | 2010-02-18 | Fushimi Pharm Co Ltd | Glycidyloxy group-containing cyclic phosphazene compound and its production method |
| JP2011088873A (en) * | 2009-10-26 | 2011-05-06 | Fushimi Pharm Co Ltd | Dihydrobenzoxazinoxy group-containing cyclic phosphazene compound and method for producing the same |
| JP2013103966A (en) * | 2011-11-11 | 2013-05-30 | Kyodo Yushi Co Ltd | Flame-retardant grease composition |
| JP2018172472A (en) * | 2017-03-31 | 2018-11-08 | 日本化薬株式会社 | Transparent flame-retardant sheet |
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