JP2003138264A - Granular flame retardant having low concentration of fine particle - Google Patents
Granular flame retardant having low concentration of fine particleInfo
- Publication number
- JP2003138264A JP2003138264A JP2001332327A JP2001332327A JP2003138264A JP 2003138264 A JP2003138264 A JP 2003138264A JP 2001332327 A JP2001332327 A JP 2001332327A JP 2001332327 A JP2001332327 A JP 2001332327A JP 2003138264 A JP2003138264 A JP 2003138264A
- Authority
- JP
- Japan
- Prior art keywords
- flame retardant
- tba
- granular
- weight
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 138
- 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 title claims abstract description 110
- 239000010419 fine particle Substances 0.000 title description 5
- 239000000843 powder Substances 0.000 claims abstract description 96
- 239000002245 particle Substances 0.000 claims abstract description 85
- -1 2,2-bis[3,3-dibromo-4-(2,3-dibromopropyloxy)phenyl]propane Chemical compound 0.000 claims abstract description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000001294 propane Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000002904 solvent Substances 0.000 description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- 238000000034 method Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 239000008187 granular material Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 15
- 229910052794 bromium Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 238000009826 distribution Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000007873 sieving Methods 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000003014 phosphoric acid esters Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 239000005662 Paraffin oil Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 3
- 238000010332 dry classification Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 238000010333 wet classification Methods 0.000 description 3
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 description 2
- FJNNYLPBIOZVIQ-UHFFFAOYSA-N 1,2,3-tribromo-4-prop-2-enoxybenzene Chemical compound BrC1=CC=C(OCC=C)C(Br)=C1Br FJNNYLPBIOZVIQ-UHFFFAOYSA-N 0.000 description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 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
- 150000008282 halocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005550 wet granulation Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- OZHJEQVYCBTHJT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-methylbenzene Chemical compound CC1=C(Br)C(Br)=C(Br)C(Br)=C1Br OZHJEQVYCBTHJT-UHFFFAOYSA-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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadis***e 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- KUJHYJBRSXWIFB-UHFFFAOYSA-N 1,3,5-tribromo-2-[1-(2,4,6-tribromophenoxy)ethoxy]benzene Chemical compound BrC=1C=C(Br)C=C(Br)C=1OC(C)OC1=C(Br)C=C(Br)C=C1Br KUJHYJBRSXWIFB-UHFFFAOYSA-N 0.000 description 1
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 description 1
- PWXTUWQHMIFLKL-UHFFFAOYSA-N 1,3-dibromo-5-[2-(3,5-dibromo-4-prop-2-enoxyphenyl)propan-2-yl]-2-prop-2-enoxybenzene Chemical compound C=1C(Br)=C(OCC=C)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC=C)C(Br)=C1 PWXTUWQHMIFLKL-UHFFFAOYSA-N 0.000 description 1
- GZLWISGTCCQWNC-UHFFFAOYSA-N 1-bromo-1-phenoxyethanol Chemical compound BrC(C)(O)OC1=CC=CC=C1 GZLWISGTCCQWNC-UHFFFAOYSA-N 0.000 description 1
- LGLDFUCDJASSJQ-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,15-octacosachlorocyclopentadecan-1-one Chemical compound ClC1(Cl)C(=O)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C1(Cl)Cl LGLDFUCDJASSJQ-UHFFFAOYSA-N 0.000 description 1
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- HREXIBFZDJHFCF-UHFFFAOYSA-N 2,6-dibromo-4-propylphenol Chemical compound CCCC1=CC(Br)=C(O)C(Br)=C1 HREXIBFZDJHFCF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YGVXCFJYHCMCLO-UHFFFAOYSA-N 3,12-dihydroxy-2,4,11,13-tetraoxa-3lambda5,12lambda5-diphosphatricyclo[12.4.0.05,10]octadeca-1(18),5,7,9,14,16-hexaene 3,12-dioxide Chemical compound C1=CC=C2C(=C1)OP(=O)(OC3=CC=CC=C3OP(=O)(O2)O)O YGVXCFJYHCMCLO-UHFFFAOYSA-N 0.000 description 1
- QEJPOEGPNIVDMK-UHFFFAOYSA-N 3-bromo-2,2-bis(bromomethyl)propan-1-ol Chemical compound OCC(CBr)(CBr)CBr QEJPOEGPNIVDMK-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LWFBRHSTNWMMGN-UHFFFAOYSA-N 4-phenylpyrrolidin-1-ium-2-carboxylic acid;chloride Chemical compound Cl.C1NC(C(=O)O)CC1C1=CC=CC=C1 LWFBRHSTNWMMGN-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KMFCCQHPXGFOOL-UHFFFAOYSA-N C(Cl)C1CO1.CCC Chemical compound C(Cl)C1CO1.CCC KMFCCQHPXGFOOL-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 description 1
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 239000012535 impurity Substances 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
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- SVHOVVJFOWGYJO-UHFFFAOYSA-N pentabromophenol Chemical compound OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br SVHOVVJFOWGYJO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- QLORRTLBSJTMSN-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C QLORRTLBSJTMSN-UHFFFAOYSA-N 0.000 description 1
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、粒径が制御されて
おり、且つ粒状難燃剤中に含まれる微粉濃度が低いこと
により、流動性が良好であり、付着性及び固着性が改善
された低微粉濃度の粒状難燃剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a controlled particle size and a low concentration of fine powder contained in a granular flame retardant, so that the fluidity is good, and the adhesion and stickiness are improved. It relates to a granular flame retardant having a low fine powder concentration.
【０００２】[0002]
【従来の技術】難燃剤は、火災を防止すること、及び火
災の進行を遅らせることを目的に、易燃性である樹脂に
溶融混練混合された後に成形されるという工程の流れを
経て、家電分野、ＯＡ機器分野、電気・電子分野等の各
種分野で使用されている、産業上有用な化合物である。2. Description of the Related Art A flame retardant is melted, kneaded and mixed with an easily flammable resin for the purpose of preventing a fire and delaying the progress of a fire, and then molded into a home appliance. Industrially useful compounds that are used in various fields such as fields, OA equipment fields, and electric / electronic fields.
【０００３】しかしながら、難燃剤の取り扱い性につい
ては、市販の難燃剤に含まれる微粉の濃度が高く、易燃
性である樹脂と混合する為に、供給機を使用して溶融混
練押出機へ難燃剤を供給する際、混合容器及び供給機へ
難燃剤を補充する際、或いは難燃剤を製造する段階にお
ける梱包作業の際に、難燃剤の流動性が悪く、難燃剤が
凝集し易いためにホッパ内でブリッジを起こしたり、溶
融混練押出機へ難燃剤を供給するための供給機に付着
し、さらには固着することによって工程の流れに支障を
きたしたり、さらには易燃性樹脂への分散が不均一にな
るために目標の品質に到達しなかったり、粉末が飛散す
る等の取り扱い性に問題があった。これらの問題を解決
するべく、粉体の性質を改良するための種々の製造手段
が提案されている。However, regarding the handling property of the flame retardant, since it is mixed with a resin which has a high concentration of fine powder contained in a commercially available flame retardant and is easily flammable, it is difficult to form a melt kneading extruder using a feeder. When supplying the flame retardant, when replenishing the flame retardant to the mixing container and the feeder, or during the packaging work in the stage of manufacturing the flame retardant, the flowability of the flame retardant is poor and the flame retardant easily aggregates. May cause a bridge in the interior, adhere to a feeder for supplying the flame retardant to the melt-kneading extruder, and further adhere to the flow of the process to hinder the dispersion of the flame-retardant resin. There was a problem in handling such that the target quality was not reached due to non-uniformity, and the powder was scattered. In order to solve these problems, various manufacturing means for improving the properties of powder have been proposed.
【０００４】例えば、難燃剤の微粉が提起する、易燃性
熱可塑性樹脂内への分散の不均一性については、ハロゲ
ン化炭化水素難燃剤、或いは該難燃剤と無機質難燃剤化
合物との混合物をロール圧縮機で圧粉体化し、次いで篩
造粒機で造粒された約２ｍｍと約４ｍｍの間の粒の大き
さの分布をもつ粒状難燃剤が提案されている（特開昭６
２−１４９７３８号公報）。しかしながら、この造粒物
は比較的に大きな粒であることから、流動性という点で
ある程度の改善効果を期待できるものの、易燃性樹脂と
混合した際に分級を起こしたり、また、易燃性樹脂との
溶融混合の際、一粒の大きさが大きいことによって、一
粒が溶融する迄に時間を要し、易燃性熱可塑性樹脂内へ
の分散が不均一になる等の不利な点がある。また、具体
例では、造粒した段階で所望の大きさの分布である２〜
４ｍｍの粒が２５％〜５７％であり、所望の大きさの分
布の粒と、より小さい大きさの分布を持つ粒とを分離し
ているものの、歩留まりという点で不利である。For example, regarding the nonuniformity of the dispersion in the flammable thermoplastic resin caused by the fine powder of the flame retardant, a halogenated hydrocarbon flame retardant or a mixture of the flame retardant and an inorganic flame retardant compound is used. A granular flame retardant having a particle size distribution of between about 2 mm and about 4 mm, which has been compacted by a roll compactor and then granulated by a sieve granulator, has been proposed (Japanese Patent Laid-Open No. Sho 6-62).
No. 2-149738). However, since this granulated product is a relatively large particle, it can be expected to have some improvement effect in terms of fluidity, but it may cause classification when mixed with a flammable resin, and may be easily flammable. Disadvantages such as the large size of one particle during melting and mixing with the resin, which takes time until one particle melts and the dispersion in the flammable thermoplastic resin becomes uneven. There is. In addition, in a specific example, a desired size distribution at the stage of granulation is 2 to
Grains of 4 mm are 25% to 57%, and although grains having a desired size distribution and grains having a smaller size distribution are separated, they are disadvantageous in terms of yield.
【０００５】さらに、特開平８−９２５６２号公報に
は、形状安定性、ポリマーへの分散性の改善を目的とし
て、難燃剤の粉体を造粒して粒状難燃剤を得ることが示
されており、具体的には可塑剤としてパラフィンオイル
を用いて粉状難燃剤を乾式造粒して粒状難燃剤を得てい
る。しかしながら、かかる粒状化方法では、別に粉状難
燃剤とパラフィンオイルを混合する操作が必要となり、
また得られた粒状難燃剤は、難燃剤として使用する際に
パラフィンオイルが樹脂の難燃性の低下、成形時のヤ
ケ、物性の低下等を引き起こすことがある等の不利な点
がある。Further, Japanese Patent Application Laid-Open No. 8-92562 discloses that a flame retardant powder is granulated to obtain a granular flame retardant for the purpose of improving shape stability and dispersibility in a polymer. Specifically, a granular flame retardant is obtained by dry granulating a powdery flame retardant using paraffin oil as a plasticizer. However, such a granulation method requires an operation of separately mixing the powdery flame retardant and paraffin oil,
Further, the obtained granular flame retardant has the disadvantages that when used as a flame retardant, the paraffin oil may cause a decrease in the flame retardancy of the resin, burns during molding, deterioration of the physical properties, and the like.
【０００６】また、特開平８−１１３５４７号公報に
は、平均粒子径が１ｍｍよりも大きい耐熱着色性および
粉体物性の良好な２，２−ビス［３，５−ジブロモ−４
−（２，３−ジブロモプロピルオキシ）フェニル］プロ
パン（以下、ＴＢＡ−ＢＥと略称することがある）の不
定形顆粒状物が開示されている。しかしながら、粒子径
は顕微鏡で観察されたものであり、粒度分布を制御する
ことについては触れられておらず、また、該公報に示さ
れているＴＢＡ−ＢＥの良溶媒溶液を、種結晶存在下、
加熱したメタノール中に添加すると同時に良溶媒を留去
し、晶析させる製法では、スケールアップなどによる装
置特性の変化、或いは撹拌状態、良溶媒と貧溶媒の混合
割合、原料の組成、混合時の温度などの、添加中に起る
微妙な変化により、目的の粒径或いは粒度分布に制御し
難く、微粉濃度を制御する方法について課題を残してい
た。Further, in JP-A-8-113547, 2,2-bis [3,5-dibromo-4, which has an average particle diameter of more than 1 mm and is excellent in heat resistance coloring property and powder physical properties, is disclosed.
An amorphous granular substance of-(2,3-dibromopropyloxy) phenyl] propane (hereinafter sometimes abbreviated as TBA-BE) is disclosed. However, the particle size was observed under a microscope, and there was no mention of controlling the particle size distribution. Further, a good solvent solution of TBA-BE shown in the publication was used in the presence of seed crystals. ,
In the manufacturing method in which the good solvent is distilled off at the same time as it is added to the heated methanol, and crystallization is performed, changes in the device characteristics due to scale-up, or the stirring state, the mixing ratio of the good solvent and the poor solvent, the composition of the raw materials, and the time of mixing Due to subtle changes that occur during the addition such as temperature, it is difficult to control the target particle size or particle size distribution, and there remains a problem with the method for controlling the fine powder concentration.
【０００７】また、特開昭５５−１１１４２９号公報に
は、５００〜１０００μｍの平均粒子直径を有する顆粒
の状態であるＴＢＡ−ＢＥ、及び０．７〜１．０ｇ／ｃ
ｍ3の平均嵩密度を有するＴＢＡ−ＢＥを製造する方法
が開示されている。しかしながら、粒度分布を制御する
ことについては触れられておらず、また、該公報に示さ
れているＴＢＡ−ＢＥの良溶媒溶液を、種結晶存在下、
メタノール中に添加し、晶析させる製法では、目的の粒
径或いは粒度分布に制御し難く、微粉濃度を制御する方
法について課題を残していた。Further, in JP-A-55-111429, TBA-BE in the form of granules having an average particle diameter of 500 to 1000 μm, and 0.7 to 1.0 g / c.
process for producing TBA-BE having an average bulk density of m 3 are disclosed. However, there is no mention of controlling the particle size distribution, and a solution of TBA-BE in a good solvent described in the publication is added in the presence of seed crystals.
In the production method in which crystallization is carried out by adding to methanol, it is difficult to control the target particle size or particle size distribution, and there remains a problem with the method for controlling the fine powder concentration.
【０００８】さらに、特開２０００−１６７６号公報に
は、難燃剤粉体を静置した状態で該粉体の自重により、
または積み重ね等による荷重が加わった場合、および環
境温度の上昇により生じ易い固結の改善を目的として、
かさ比重０．８以上を有するＴＢＡ−ＢＥと高級脂肪酸
金属塩とを均一にブレンドしてなる粉末状難燃剤組成物
を提示している。しかしながら、かさ比重が０．８未満
のＴＢＡ−ＢＥ粉末に対する静置状態での固結改善効果
に課題を残していること、高級脂肪酸金属塩が樹脂の難
燃性の低下、表面外観の悪化、物性の低下等を引き起こ
すことがある等の不利な点がある。Further, in Japanese Patent Laid-Open No. 2000-1676, the flame retardant powder is allowed to stand still by the weight of the powder.
Or when a load is applied due to stacking, etc., and for the purpose of improving the consolidation that tends to occur due to the rise in environmental temperature,
Disclosed is a powdery flame retardant composition obtained by uniformly blending TBA-BE having a bulk specific gravity of 0.8 or more and a higher fatty acid metal salt. However, there is still a problem in the effect of improving the solidification of TBA-BE powder having a bulk specific gravity of less than 0.8 in a stationary state, the higher fatty acid metal salt lowers the flame retardancy of the resin, and deteriorates the surface appearance. There are disadvantages such as deterioration of physical properties.
【０００９】また、特開２００１−３９９１５号公報に
は、平均粒径０．２〜６ｍｍの円柱状のＴＢＡ−ＢＥ粒
体が開示されている。この公報では、ＴＢＡ−ＢＥの湿
潤微粒子を造粒することにより、上記円柱状のＴＢＡ−
ＢＥ粒体を得ている。このＴＢＡ−ＢＥ粒体は、耐熱
性、流動性及び保存安定性（ブロッキング性）がある程
度良好であるけれども、樹脂と溶融混練するとき、ＴＢ
Ａ−ＢＥ粒体をスクリューフィーダーで供給する際にシ
リンダー内で付着及び固着が起こる場合があり、その改
善が求められており、また、ブロッキング性も不十分で
ありより優れたものが求められている。Further, Japanese Patent Laid-Open No. 2001-39915 discloses a cylindrical TBA-BE granule having an average particle diameter of 0.2 to 6 mm. In this publication, the cylindrical fine particles of TBA-BE are formed by granulating wet fine particles of TBA-BE.
BE particles are obtained. Although the TBA-BE granules have good heat resistance, fluidity and storage stability (blocking property) to some extent, when they are melt-kneaded with a resin, they are
Adhesion and sticking may occur in the cylinder when the A-BE granules are fed by the screw feeder, and improvement thereof is demanded. Further, the blocking property is insufficient and a superior one is demanded. There is.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、流動性が良
好であり、特にスクリューフィーダーによる供給時の付
着性及び固着性が改善された低微粉濃度の粒状難燃剤を
提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a granular flame retardant having a low fine powder concentration, which has good fluidity, and in particular, has improved adhesiveness and stickiness when fed by a screw feeder. To do.
【００１１】本発明者は、かかる目的を達成すべく鋭意
検討した結果、粒状難燃剤中に含まれる微粉濃度を制御
した粒状難燃剤は、その流動性、またスクリューフィー
ダーによる供給時の付着性及び固着性が良好であること
を見出し、本発明に到達した。The inventors of the present invention have made extensive studies to achieve such an object, and as a result, the granular flame retardant in which the concentration of fine powder contained in the granular flame retardant is controlled has its fluidity and the adhesiveness at the time of feeding by a screw feeder and The inventors have found that the adhesiveness is good and have reached the present invention.
【００１２】[0012]
【課題を解決するための手段】すなわち、本発明によれ
ば、粒状難燃剤であって、該粒状難燃剤は、（ａ）平均
粒径が０．８〜２ｍｍであり、（ｂ）該粒状難燃剤の全
体量を１００重量％としたとき、目開き０．７２ｍｍの
篩を通過する微粉粒子の量が１２重量％以下であり、
（ｃ）該粒状難燃剤の全体量を１００重量％としたと
き、目開き０．２５ｍｍの篩を通過する微粉粒子の量が
９重量％以下である、ことを特徴とする低微粉濃度の粒
状難燃剤が提供される。That is, according to the present invention, a granular flame retardant, wherein the granular flame retardant has (a) an average particle size of 0.8 to 2 mm, and (b) the granular particle. When the total amount of the flame retardant is 100% by weight, the amount of fine powder particles passing through a sieve having an opening of 0.72 mm is 12% by weight or less,
(C) When the total amount of the granular flame retardant is 100% by weight, the amount of fine powder particles passing through a sieve having an opening of 0.25 mm is 9% by weight or less, and the granular material has a low fine powder concentration. A flame retardant is provided.
【００１３】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【００１４】本発明で使用される難燃剤は、火災を防止
すること、及び火災の進行を遅らせることを目的に、易
燃性である熱可塑性樹脂に混合される化合物である。The flame retardant used in the present invention is a compound mixed with a flammable thermoplastic resin for the purpose of preventing a fire and delaying the progress of the fire.
【００１５】本発明の粒状難燃剤は、常温で固体であ
り、また、有機系難燃剤、無機系難燃剤、或いは有機系
難燃剤と無機系難燃剤との組合せの中から選ばれるもの
が挙げられる。The granular flame retardant of the present invention is solid at room temperature, and may be selected from organic flame retardants, inorganic flame retardants, or combinations of organic flame retardants and inorganic flame retardants. To be
【００１６】前記有機系難燃剤としては、ハロゲン系難
燃剤、リン系難燃剤、或いはグアニジン系難燃剤が挙げ
られる。これらの有機系難燃剤は単独若しくは二種以上
混合して使用される。Examples of the organic flame retardants include halogen flame retardants, phosphorus flame retardants, and guanidine flame retardants. These organic flame retardants may be used alone or in admixture of two or more.
【００１７】前記ハロゲン系難燃剤としては、臭素系難
燃剤或いは塩素系難燃剤、好ましくは臭素系難燃剤が挙
げられる。これらのハロゲン系難燃剤は単独若しくは二
種以上混合して使用される。Examples of the halogen-based flame retardant include bromine-based flame retardants or chlorine-based flame retardants, preferably bromine-based flame retardants. These halogen-based flame retardants may be used alone or in admixture of two or more.
【００１８】前記臭素系難燃剤としては、デカブロモジ
フェニルオキサイド、２，２−ビス［３，５−ジブロモ
−４−（２−ヒドロキシエチルエーテル）フェニル］プ
ロパン、２，２−ビス［３，５−ジブロモ−４−（２，
３−ジブロモプロピルオキシ）フェニル］プロパン（Ｔ
ＢＡ−ＢＥ）、２，２−ビス（４−アリルオキシ−３，
５−ジブロモフェニル）プロパン、ポリ［オキシカルボ
ニルオキシ（２，６−ジブロモ−１，４−フェニレン）
（１−メチルエチリデン）（３，５−ジブロモ−１，４
−フェニレン）］、２，２−ビス（３，５−ジブロモ−
４−ヒドロキシフェニル）プロパン−エピクロルヒドリ
ンポリマー、トリブロモフェニルアリルエーテル、トリ
ブロモネオペンチルアルコール、ビス（２，４，６−ト
リブロモフェノキシ）エタン、ポリジブロモフェニレン
エーテル、テトラブロモシクロオクタン、ブロモ化ポリ
スチレン、エチレンビステトラブロモフタルイミド、エ
チレンビスペンタブロモジフェニル、ヘキサブロモシク
ロドデカン、ヘキサブロモベンゼン、オクタブロモジフ
ェニルエーテル、ジブロモスチレン、トリス（２，３−
ジブロモプロピル）イソシアヌレート、ビス（３，５−
ジブロモ−４−ヒドロキシフェニル）プロパン、ビス
（３，５−ジブロモ−４−ヒドロキシフェニル）スルホ
ン、ペンタブロモトルエン等の添加型の臭素系難燃剤、
或いは、テトラブロモフタレート、テトラブロモフタレ
ートジソジウム、テトラクロロ無水フタル酸、トリブロ
モフェノール、ジブロモネオペンチルグリコール、ポリ
（ペンタブロモベンジルポリアクリレート）、ペンタブ
ロモフェノール、ブロモフェノキシエタノール、ブロモ
化フェノール、ブロモ化芳香族トリアジン等の反応型の
臭素系難燃剤が挙げられ、中でも、デカブロモジフェニ
ルオキサイド、ＴＢＡ−ＢＥ、ＴＢＡエポキシオリゴマ
ー、トリブロモフェニルアリルエーテル、エチレンビス
テトラブロモフタルイミド、ヘキサブロモシクロドデカ
ン、オクタブロモジフェニルエーテル、ビス（３，５−
ジブロモ−４−ヒドロキシフェニル）プロパン、ポリ
（ペンタブロモベンジルポリアクリレート）が、取り扱
い性についての改善効果をさらに期待できるという点で
好ましく、さらには、本発明の効果が十分に発揮される
ＴＢＡ−ＢＥが好ましい。これらの臭素系難燃剤は、一
種の化合物を単独で使用しても良いし、二種以上を混合
して使用しても良い。As the brominated flame retardant, decabromodiphenyl oxide, 2,2-bis [3,5-dibromo-4- (2-hydroxyethyl ether) phenyl] propane, 2,2-bis [3,5] -Dibromo-4- (2,
3-dibromopropyloxy) phenyl] propane (T
BA-BE), 2,2-bis (4-allyloxy-3,
5-dibromophenyl) propane, poly [oxycarbonyloxy (2,6-dibromo-1,4-phenylene)
(1-Methylethylidene) (3,5-dibromo-1,4
-Phenylene)], 2,2-bis (3,5-dibromo-)
4-hydroxyphenyl) propane-epichlorohydrin polymer, tribromophenylallyl ether, tribromoneopentyl alcohol, bis (2,4,6-tribromophenoxy) ethane, polydibromophenylene ether, tetrabromocyclooctane, brominated polystyrene, Ethylenebistetrabromophthalimide, ethylenebispentabromodiphenyl, hexabromocyclododecane, hexabromobenzene, octabromodiphenyl ether, dibromostyrene, tris (2,3-
Dibromopropyl) isocyanurate, bis (3,5-
Addition-type brominated flame retardants such as dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, and pentabromotoluene,
Alternatively, tetrabromophthalate, tetrabromophthalate disodium, tetrachlorophthalic anhydride, tribromophenol, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate), pentabromophenol, bromophenoxyethanol, brominated phenol, brominated aroma Examples thereof include reactive brominated flame retardants such as group triazine, and among them, decabromodiphenyl oxide, TBA-BE, TBA epoxy oligomer, tribromophenyl allyl ether, ethylenebistetrabromophthalimide, hexabromocyclododecane, octabromodiphenyl ether. , Screw (3,5-
Dibromo-4-hydroxyphenyl) propane and poly (pentabromobenzyl polyacrylate) are preferable in that the effect of improving the handling property can be further expected, and furthermore, TBA-BE in which the effect of the present invention is sufficiently exhibited. Is preferred. These bromine-based flame retardants may be used alone or as a mixture of two or more kinds.
【００１９】前記塩素系難燃剤としては、塩素化パラフ
ィン、塩素化ポリエチレン、パークロロシクロペンタデ
カノン等の添加型の塩素系難燃剤、或いは、テトラクロ
ロ無水フタル酸、クロレント酸、無水クロレント酸等の
反応型の塩素系難燃剤が挙げられる。これらの塩素系難
燃剤は、一種の化合物を単独で使用しても良いし、二種
以上を混合して使用しても良い。As the chlorine-based flame retardant, an addition-type chlorine-based flame retardant such as chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecanone, or tetrachlorophthalic anhydride, chlorentic acid, chlorentic anhydride, etc. Reactive chlorine-based flame retardants of One of these chlorine-based flame retardants may be used alone, or two or more thereof may be mixed and used.
【００２０】前記リン系難燃剤としては、リン酸エステ
ル系難燃剤、含ハロゲンリン酸エステル系難燃剤、縮合
リン酸エステル系難燃剤、含ハロゲン縮合リン酸エステ
ル系難燃剤、ポリリン酸塩系難燃剤、赤リン等が挙げら
れる。これらのリン系難燃剤は単独若しくは二種以上混
合して使用される。Examples of the phosphorus-based flame retardants include phosphoric acid ester-based flame retardants, halogen-containing phosphoric acid ester-based flame retardants, condensed phosphoric acid ester-based flame retardants, halogen-containing condensed phosphoric acid ester-based flame retardants, and polyphosphate-based flame retardants. Examples include flammable agents and red phosphorus. These phosphorus-based flame retardants are used alone or in combination of two or more.
【００２１】前記リン酸エステル系難燃剤としては、ト
リフェニルホスフェート、トリス（２，６−ジメチルフ
ェニル）ホスフェート等が挙げられ、一種の化合物を単
独で使用しても良いし、二種以上を混合して使用しても
良い。Examples of the phosphoric acid ester flame retardant include triphenyl phosphate and tris (2,6-dimethylphenyl) phosphate. One compound may be used alone, or two or more compounds may be mixed. You may use it.
【００２２】前記含ハロゲンリン酸エステル系難燃剤と
しては、トリス（トリブロモネオペンチル）ホスフェー
ト、或いはトリス（２，４，６−トリブロモフェニル）
ホスフェート等が挙げられ、一種の化合物を単独で使用
しても良いし、二種以上を混合して使用しても良い。As the halogen-containing phosphate ester flame retardant, tris (tribromoneopentyl) phosphate or tris (2,4,6-tribromophenyl) is used.
Phosphate and the like can be mentioned, and one kind of compound may be used alone, or two or more kinds thereof may be mixed and used.
【００２３】前記縮合リン酸エステル系難燃としては、
固体状の１，３−フェニレンビス（ジ−２，６−ジメチ
ルフェニルホスフェート）、ハイドロキノン ビス（ジ
−２，６−キシリル）ホスフェート、或いはテトラキス
（２，６−ジメチルフェニル）−４，４′−ジフェニレ
ンビスホスフェート等が挙げられ、一種の化合物を単独
で使用しても良いし、二種以上を混合して使用しても良
い。As the condensed phosphoric acid ester flame retardant,
Solid 1,3-phenylene bis (di-2,6-dimethylphenyl phosphate), hydroquinone bis (di-2,6-xylyl) phosphate, or tetrakis (2,6-dimethylphenyl) -4,4'- Examples thereof include diphenylene bisphosphate and the like, and one type of compound may be used alone, or two or more types may be mixed and used.
【００２４】前記含ハロゲン縮合リン酸エステル系難燃
剤としては、１，３−フェニレンビス（ジ−２，６−ジ
ブロモジフェニルホスフェート）等が挙げられ、一種の
化合物を単独で使用しても良いし、二種以上を混合して
使用しても良い。Examples of the halogen-containing condensed phosphoric acid ester flame retardant include 1,3-phenylene bis (di-2,6-dibromodiphenyl phosphate) and the like, and one compound may be used alone. Alternatively, two or more kinds may be mixed and used.
【００２５】前記ポリリン酸塩系難燃剤としては、ポリ
リン酸アンモニウム、或いはポリ燐酸メラミン等が挙げ
られ、一種の化合物を単独で使用しても良いし、二種以
上を混合して使用しても良い。Examples of the polyphosphate-based flame retardant include ammonium polyphosphate, melamine polyphosphate and the like. One kind of compound may be used alone, or two or more kinds thereof may be mixed and used. good.
【００２６】前記グアニジン系難燃剤としては、スルフ
ァミン酸グアニジン、リン酸グアニジン、リン酸グアニ
ル尿素、或いは硫酸メラミン等が挙げられ、一種の化合
物を単独で使用しても良いし、二種以上を混合して使用
しても良い。Examples of the guanidine flame retardant include guanidine sulfamate, guanidine phosphate, guanylurea phosphate, and melamine sulfate. One compound may be used alone, or two or more compounds may be mixed. You may use it.
【００２７】前記無機系難燃剤としては、水酸化アルミ
ニウム、三酸化アンチモン、五酸化アンチモン、アンチ
モン酸ソーダ、四酸化アンチモン、水酸化マグネシウ
ム、ホウ酸亜鉛等が挙げられ、一種の化合物を単独で使
用しても良いし、二種以上を混合して使用しても良い。Examples of the inorganic flame retardant include aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate, antimony tetroxide, magnesium hydroxide, zinc borate, etc., and one compound is used alone. Alternatively, two or more kinds may be mixed and used.
【００２８】本発明の粒状難燃剤の平均粒径は０．８〜
２ｍｍであり、好ましくは０．８〜１．８ｍｍ、より好
ましくは０．８〜１．５ｍｍ、さらに好ましくは０．８
〜１．３ｍｍである。平均粒径が０．８ｍｍより小さく
なると、該難燃剤の流動性が低下し、付着性及び固着性
が増し、また、粉末が飛散しやすくなることから好まし
くなく、２ｍｍを越えると、易燃性樹脂と混合した際に
分級を起こしたり、また、易燃性樹脂との溶融混合の
際、一粒の大きさが大きいことによって、一粒が溶融す
る迄に時間を要し、易燃性樹脂内への分散が不均一にな
る等の不利な点がある。The average particle size of the granular flame retardant of the present invention is 0.8 to
2 mm, preferably 0.8 to 1.8 mm, more preferably 0.8 to 1.5 mm, still more preferably 0.8.
~ 1.3 mm. If the average particle size is smaller than 0.8 mm, the fluidity of the flame retardant is lowered, the adhesiveness and the sticking property are increased, and the powder tends to scatter, which is not preferable. Classification occurs when mixed with resin, and when melt-mixed with flammable resin, it takes time for one grain to melt due to the large size of one grain. There are disadvantages such as uneven distribution inside.
【００２９】本発明で言う平均粒径とは、粒状難燃剤
を、篩分けした後、重量を基準として得られた粒度分布
データから求めた重量平均粒径である。篩の種類につい
ては、一般的に使用される標準篩を使用し、目開きとし
ては、７．０ｍｍ、６．０ｍｍ、５．６ｍｍ、４．０ｍ
ｍ、２．８ｍｍ、１．７ｍｍ、１．０ｍｍ、０．７５ｍ
ｍ、０．７２ｍｍ、０．６ｍｍ、０．３５ｍｍ、０．２
５ｍｍ、０．１５ｍｍ、０．０７５ｍｍの群から、約８
種類を粒径に併せて選択し、使用することが採用され
る。また、篩分け中の振動条件については、振動回数が
３６００回／分、振幅が２ｍｍ、振動時間が２分間で、
該振動時間の内訳が１０秒間振動運転し、２秒間停止す
るパターンの繰り返しである方法が採用される。The average particle size referred to in the present invention is the weight average particle size obtained from the particle size distribution data obtained on the basis of weight after sieving the granular flame retardant. Regarding the type of sieve, a commonly used standard sieve is used, and the openings are 7.0 mm, 6.0 mm, 5.6 mm, 4.0 m.
m, 2.8 mm, 1.7 mm, 1.0 mm, 0.75 m
m, 0.72 mm, 0.6 mm, 0.35 mm, 0.2
From the group of 5mm, 0.15mm, 0.075mm, about 8
It is adopted that the type is selected and used according to the particle size. Regarding the vibration conditions during sieving, the number of vibrations was 3600 times / minute, the amplitude was 2 mm, and the vibration time was 2 minutes.
A method in which the breakdown of the vibration time is a pattern of repeating vibration operation for 10 seconds and stopping for 2 seconds is adopted.
【００３０】前記粒度分布データは、篩分け作業後に各
種篩上の粒体重量を量り、篩分けに使用した全粒体重量
に対する各篩上の各粒体重量の割合に換算し、ある篩の
目開きをＤｍｍ、篩分けに使用した粒体全量に対する該
篩を通過した粒体重量の割合をＷ％として扱った頻度分
布データである。平均粒径は、この粒度分布データにつ
いて、ｘ軸に粒径の代替値であるＤｍｍを採り、且つ該
ｘ軸を対数目盛りとし、また、ｙ軸に累計通過率とも呼
ばれる、Ｄの中で最も小さな値であるＤ１ｍｍに対応し
たＷ１％から、使用した篩の目開きであるＤｎｍｍに対
応したＷｎ％迄のＷ％の和を求めた値（累計通過率）を
採ることによって作成した片対数グラフにおいてＷが５
０％である時のＤの値である。The above-mentioned particle size distribution data is obtained by measuring the weight of granules on various sieves after sieving and converting it into the ratio of the weight of each granule on each sieve to the total weight of granules used for sieving. It is frequency distribution data in which the mesh size was treated as Dmm and the ratio of the weight of the granules that passed through the sieve to the total amount of the granules used for sieving was treated as W%. For the average particle size, the D-axis, which is an alternative value of the particle size, is taken on the x-axis, the x-axis is set to a logarithmic scale, and the y-axis is also called the cumulative passage rate, and the average particle size is the most significant in D. A semi-logarithmic graph created by taking the value (cumulative passage rate) of the sum of W1% from W1% corresponding to a small value D1mm to Wn% corresponding to the opening Dnmm of the used sieve. W is 5
It is the value of D when it is 0%.
【００３１】本発明で規定する目開き０．７２ｍｍの篩
を通過する微粉粒子は、振動回数が３６００回／分、振
幅が２ｍｍ、振動時間が２分間で、該振動時間の内訳が
１０秒間振動運転し、２秒間停止するパターンの繰り返
しである方法により、目開き０．７２ｍｍである金網を
通過する粒子である。The fine powder particles passing through the sieve having an opening of 0.72 mm defined in the present invention have a vibration frequency of 3600 times / min, an amplitude of 2 mm, a vibration time of 2 minutes, and a vibration time of 10 seconds. The particles are particles that pass through a wire net having an opening of 0.72 mm by a method of repeating a pattern of running and stopping for 2 seconds.
【００３２】本発明の粒状難燃剤に含まれる目開き０．
７２ｍｍの篩を通過する微粉粒子の量は、粒状難燃剤全
体量を１００重量％としたときに１２重量％以下であ
り、好ましくは１１重量％以下であり、より好ましくは
１０重量％以下であり、さらに好ましくは９重量％以下
である。１２重量％を超えると、粒状難燃剤の流動性が
低下し、特にスクリューフィーダーによる供給時の付着
性及び固着性が増し、また、粉末が飛散しやすくなるこ
とから好ましくない。Apertures included in the granular flame retardant of the present invention.
The amount of fine powder particles passing through a 72 mm sieve is 12% by weight or less, preferably 11% by weight or less, and more preferably 10% by weight or less, when the total amount of the granular flame retardant is 100% by weight. , And more preferably 9% by weight or less. If it exceeds 12% by weight, the fluidity of the granular flame retardant is lowered, the adhesiveness and the stickiness are particularly increased during the feeding by the screw feeder, and the powder tends to be scattered, which is not preferable.
【００３３】本発明で規定する目開き０．２５ｍｍの篩
を通過する微粉粒子は、振動回数が３６００回／分、振
幅が２ｍｍ、振動時間が２分間で、該振動時間の内訳が
１０秒間振動運転し、２秒間停止するパターンの繰り返
しである方法により、目開き０．２５ｍｍである金網を
通過する粒子である。Fine powder particles passing through a sieve having an opening of 0.25 mm defined in the present invention have a vibration frequency of 3600 times / minute, an amplitude of 2 mm, a vibration time of 2 minutes, and a vibration time of 10 seconds. The particles are particles that pass through a wire mesh having an opening of 0.25 mm by a method in which the pattern is repeated by operating and stopping for 2 seconds.
【００３４】本発明の粒状難燃剤に含まれる目開き０．
２５ｍｍの篩を通過する微粉粒子の量は、粒状難燃剤全
体量を１００重量％としたときに９重量％以下であり、
好ましくは８重量％以下であり、より好ましくは７重量
％以下であり、特に好ましくは６重量％以下である。か
かる目開き０．２５ｍｍの篩を通過する微粉粒子の量が
９重量％を越えると、粒状難燃剤の流動性が低下し、特
にスクリューフィーダーによる供給時の付着性及び固着
性が増し、また、粉末が飛散しやすくなることから好ま
しくない。The openings included in the granular flame retardant of the present invention are 0.
The amount of fine powder particles passing through a 25 mm sieve is 9% by weight or less when the total amount of the granular flame retardant is 100% by weight,
It is preferably 8% by weight or less, more preferably 7% by weight or less, and particularly preferably 6% by weight or less. When the amount of the fine powder particles passing through the sieve having the opening of 0.25 mm exceeds 9% by weight, the fluidity of the granular flame retardant is lowered, and particularly the adhesiveness and the sticking property at the time of feeding by the screw feeder are increased, and It is not preferable because the powder easily scatters.
【００３５】本発明の粒状難燃剤の製造方法は、目的の
難燃剤粉末を湿潤粉体として、この湿潤粉体を造粒機を
用いて造粒し、乾燥して、さらに分級する方法が好適に
採用される。The method for producing the granular flame retardant of the present invention is preferably a method in which the target flame retardant powder is used as a wet powder, the wet powder is granulated using a granulator, dried and further classified. Adopted by.
【００３６】前記造粒は、１次粒子間を結合させるた
め、或いは乾燥粉体の可塑性を向上させる為の、貧溶
媒、或いは良溶媒のいずれかからなる単独成分、或いは
二種以上を混合した成分を含む湿潤粉体を原料とする湿
式造粒が採用される。前記１次粒子は、造粒物を構成す
る最小単位の粒子である。In the above granulation, a single component composed of either a poor solvent or a good solvent for the purpose of binding primary particles to each other or for improving the plasticity of the dry powder, or a mixture of two or more thereof. Wet granulation using a wet powder containing the components as a raw material is adopted. The primary particles are particles of the smallest unit that constitutes a granulated product.
【００３７】本発明で用いられる造粒機としては、転動
造粒機、流動層造粒機、噴流層造粒機、撹拌造粒機、解
砕造粒機、圧縮造粒機および押出造粒機等が挙げられ、
一種の造粒機を用いても良いし、二種以上を組み合わせ
て用いても良いし、或いは機能を複合化させた造粒機を
用いても良い。さらに、湿式造粒において、造粒機内で
の付着、或いは固着によるトラブルが少なく、貧溶媒或
いは良溶媒のいずれかからなる単独成分、或いは二種以
上を混合した成分が滲み出すことによるトラブルが少な
く、或いは、造粒物にバリができることによって発生す
る微粉が少ないということから、押出造粒機が好ましく
採用される。The granulator used in the present invention includes a rolling granulator, a fluidized bed granulator, a spouted bed granulator, a stirring granulator, a crushing granulator, a compression granulator and an extrusion granulator. Granulator etc. are mentioned,
One type of granulator may be used, two or more types may be used in combination, or a granulator having a composite function may be used. Further, in wet granulation, there are few troubles due to adhesion or sticking in the granulator, and there are few troubles due to exudation of a single component consisting of a poor solvent or a good solvent, or a component obtained by mixing two or more kinds. Alternatively, an extrusion granulator is preferably used because the amount of fine powder generated due to burrs on the granulated product is small.
【００３８】前記押出造粒機の機構は、湿潤粉体をスク
リーンに押し込んで造粒する機構であれば良く、例え
ば、スクリューにて押し込むタイプ（スクリュー型）、
ロールにて押し込むタイプ（ロール型）、へら状の回転
体で押し込むタイプ（ブレード型）、また二つのギヤタ
イプのロール間で難燃剤の湿潤粉体に圧力をかける際に
一方ないしは両方のギヤの凹部へ穴を設けてあり、該ロ
ールがスクリーンの役割をも果たすもの（自己成形型）
等が挙げられる。中でも、造粒機内での固着によるトラ
ブルが少ないということから、ロール型が好ましい。The mechanism of the extrusion granulator may be any mechanism that pushes wet powder into the screen for granulation. For example, a type of pushing with a screw (screw type),
Roll type (roll type), spatula-shaped rotating body type (blade type), and recesses in one or both gears when pressing wet powder of flame retardant between two gear type rolls. Holes are provided so that the roll also functions as a screen (self-molding type)
Etc. Among them, the roll type is preferable because there are few troubles due to sticking in the granulator.
【００３９】前記押出造粒機で用いるスクリーンの目開
きは、０．５〜２．０ｍｍが好ましく、０．６〜１．５
ｍｍがより好ましく、０．７〜１．０ｍｍがさらに好ま
しい。スクリーンの目開きが０．５ｍｍ以上であると、
得られる粒状難燃剤は微粉量がある程度少なくなり、ス
クリーンの目開きが２．０ｍｍ以下であると、得られる
粒状難燃剤を易燃性樹脂と混合した際に分級を起こし難
く、また、易燃性樹脂との溶融混合の際、一粒の大きさ
が適度であり、易燃性樹脂内への分散が均一となり易く
好ましい。The opening of the screen used in the extrusion granulator is preferably 0.5 to 2.0 mm, and 0.6 to 1.5.
mm is more preferable, and 0.7 to 1.0 mm is further preferable. If the opening of the screen is 0.5 mm or more,
The amount of fine powder in the obtained granular flame retardant is reduced to some extent, and when the opening of the screen is 2.0 mm or less, classification is difficult to occur when the obtained granular flame retardant is mixed with the flame-retardant resin, and the flame-retardant property is increased. When melt-mixing with the resin, the size of one particle is appropriate, and the dispersion in the flammable resin becomes uniform, which is preferable.
【００４０】前記造粒された粒状難燃剤は、次いで乾燥
される。かかる乾燥方法は、特に限定されるものではな
く、静置乾燥、流動乾燥、振動流動乾燥、真空乾燥等の
公知の方法で乾燥される。乾燥後の粒状難燃剤に含まれ
る残留溶媒の割合は０．０１〜１重量％が好ましく、
０．０１〜０．８重量％がより好ましい。The granulated granular flame retardant is then dried. The drying method is not particularly limited, and may be a known method such as static drying, fluidized drying, vibration fluidized drying, or vacuum drying. The proportion of the residual solvent contained in the dried flame retardant is preferably 0.01 to 1% by weight,
It is more preferably 0.01 to 0.8% by weight.
【００４１】前記乾燥後の粒状難燃剤は、さらに分級を
行うことにより、本発明の微粉量が極めて低減された粒
状難燃剤を得ることができる。分級とは、粒径の違いに
よって粉体を分ける操作を指し、本発明においては、目
開き０．７２ｍｍの篩を通過する微粉粒子の量および目
開き０．２５ｍｍの篩いを通過する微粉粒子の量を低下
させ、平均粒径が０．８〜２ｍｍである粒状難燃剤を分
離して回収することを目的とする。By further classifying the dried granular flame retardant, the granular flame retardant of the present invention in which the amount of fine powder is extremely reduced can be obtained. The classification refers to an operation of separating powders according to a difference in particle size, and in the present invention, the amount of fine powder particles passing through a sieve having an opening of 0.72 mm and the amount of fine powder particles passing through a sieve having an opening of 0.25 mm. The purpose is to reduce the amount and separate and collect the granular flame retardant having an average particle diameter of 0.8 to 2 mm.
【００４２】分級の方法としては、粒子を分散浮遊させ
る媒体が液体であれば湿式分級が採用され、或いは粒子
を分散浮遊させる媒体が気体であれば乾式分級が採用さ
れる。湿式分級は、湿式分級後に固液分離、さらには乾
燥を行なわければならず、固液分離或いは乾燥段階で微
粉が発生し易いという点で不利であり、乾式分級は、乾
式分級後の粒状物をそのまま製品として扱えるという点
で好ましい。As the classification method, wet classification is adopted when the medium in which the particles are dispersed and suspended is a liquid, or dry classification is adopted when the medium in which the particles are dispersed and suspended is a gas. Wet classification is disadvantageous in that solid-liquid separation and further drying must be performed after wet classification, and fine powder is likely to be generated in the solid-liquid separation or drying stage, and dry classification is a granular material after dry classification. Is preferable because it can be used as a product as it is.
【００４３】分級機としては、湿式分級機或いは乾式分
級機等が挙げられ、一種の分級機を用いても良いし、或
いは二種以上を組み合わせて用いても良い。Examples of the classifier include a wet classifier and a dry classifier. One kind of classifier may be used, or two or more kinds may be used in combination.
【００４４】前記湿式分級機としては、液中での粒子の
沈降を利用する沈降分離機、貧溶媒を添加することによ
る液流と粒子の沈降速度との差を利用する水力分級機、
或いは遠心力場における粒子の沈降速度を利用する遠心
分級機等が挙げられ、一種の分級機を用いても良いし、
二種以上を組み合わせて用いても良いし、或いは機能を
複合させた分級機を用いても良い。As the wet classifier, a settling separator utilizing the settling of particles in a liquid, a hydraulic classifier utilizing the difference between the liquid flow by adding a poor solvent and the settling rate of the particles,
Alternatively, a centrifugal classifier that utilizes the sedimentation velocity of particles in a centrifugal force field may be used, and a classifier may be used,
Two or more kinds may be used in combination, or a classifier having combined functions may be used.
【００４５】前記乾式分級機としては、篩を用いる篩分
け機、気流と粒子の沈降速度との差を利用する重力分級
機、遠心力場における粒子の沈降速度を利用する遠心分
級機、或いは気流と共に浮遊する粒子の慣性を利用する
慣性分級機等が挙げられ、一種の分級機を用いても良い
し、二種以上を組み合わせて用いても良いし、或いは機
能を複合させた分級機を用いても良い。なかでも、篩分
け機は、分級中に変動する制御因子が殆ど無いという点
で運転が容易であることから好ましく用いられる。As the dry classifier, a sieve classifier using a sieve, a gravity classifier utilizing the difference between the air flow and the sedimentation velocity of particles, a centrifugal classifier utilizing the sedimentation velocity of particles in a centrifugal force field, or an air stream Inertia classifiers that utilize the inertia of particles that float together are included, and one type of classifier may be used, two or more types may be used in combination, or a classifier that combines functions may be used. May be. Among them, the sieving machine is preferably used because it is easy to operate in that there are few control factors that fluctuate during classification.
【００４６】前述した造粒に供される湿潤粉体は、湿潤
粉体全重量を１００重量％としたときに、貧溶媒または
良溶媒のいずれかからなる単独成分、或いは二種以上を
混合した成分を１〜４０重量％、好ましくは５〜３７重
量％、より好ましくは１０〜３５重量％、さらに好まし
くは２０〜３３重量％、最も好ましくは２２〜３２重量
％含む粉体である。但し、本発明においては、難燃剤
に、該難燃剤の粉体の可塑性を向上させるために用いら
れるデンプンやパラフィンオイル等のバインダーを添加
する必要はない。該バインダーを含んだ粒状難燃剤は、
該粒状難燃剤と易燃性樹脂との相溶性が悪くなったり、
該粒状難燃剤を添加した樹脂製品の難燃性が低下した
り、該樹脂製品が着色したり、或いは該樹脂製品の機械
物性、耐光性等の各種の物性が低下する等の不利な点が
ある。The wet powder used for the above-mentioned granulation is a single component consisting of either a poor solvent or a good solvent, or a mixture of two or more thereof, when the total weight of the wet powder is 100% by weight. It is a powder containing 1 to 40% by weight, preferably 5 to 37% by weight, more preferably 10 to 35% by weight, further preferably 20 to 33% by weight, and most preferably 22 to 32% by weight. However, in the present invention, it is not necessary to add a binder such as starch or paraffin oil, which is used for improving the plasticity of the powder of the flame retardant, to the flame retardant. Granular flame retardant containing the binder,
The compatibility between the granular flame retardant and the flammable resin becomes poor,
There are disadvantages such that the flame retardancy of the resin product to which the granular flame retardant is added is lowered, the resin product is colored, or various physical properties such as mechanical properties and light resistance of the resin product are lowered. is there.
【００４７】本発明において好適に使用されるＴＢＡ−
ＢＥを例として、前記湿潤粉体およびその貧溶媒または
良溶媒について以下説明する。TBA-which is preferably used in the present invention
The above wet powder and its poor solvent or good solvent will be described below by taking BE as an example.
【００４８】ＴＢＡ−ＢＥに対する貧溶媒としては、Ｔ
ＢＡ−ＢＥの溶解度が０．０８ｇ／溶媒１００ｇ以下、
好ましくは０．０５ｇ／溶媒１００ｇ以下、特に好まし
くは０．０１ｇ／溶媒１００ｇ以下のものが有利であ
る。ここで溶解度とは２５℃の温度で測定された値であ
る。良溶媒および混合溶媒の溶解度も２５℃で測定され
た値を意味するものとする。また、１３０℃で揮発する
貧溶媒が好ましく、乾燥の容易性から８０℃で揮発する
貧溶媒がより好ましい。ＴＢＡ−ＢＥに対する貧溶媒の
具体例としては、例えば、水、メタノール、エタノー
ル、ｉ−プロパノール等の炭素数１〜５の飽和１価アル
コール、ジエチルエーテル、ジプロピルエーテル、ジイ
ソプロピルエーテルおよびｎ−ペンタン、ｎ−ヘキサ
ン、ｎ−オクタン等の炭素数５〜１０の飽和炭化水素等
が挙げられ、水、メタノール、エタノール、ｉ−プロパ
ノールおよびジイソプロピルエーテルが好ましく、水、
メタノール、エタノール、ｉ−プロパノールがより好ま
しく、メタノールが特に好ましく用いられる。これらの
貧溶媒は単独若しくは二種以上混合して使用される。As a poor solvent for TBA-BE, T
The solubility of BA-BE is 0.08 g / solvent 100 g or less,
Advantageously, 0.05 g / solvent 100 g or less, particularly preferably 0.01 g / solvent 100 g or less are advantageous. Here, the solubility is a value measured at a temperature of 25 ° C. The solubilities of the good solvent and the mixed solvent also mean the values measured at 25 ° C. Further, a poor solvent that volatilizes at 130 ° C. is preferable, and a poor solvent that volatilizes at 80 ° C. is more preferable because of easy drying. Specific examples of the poor solvent for TBA-BE include water, methanol, ethanol, saturated monohydric alcohol having 1 to 5 carbon atoms such as i-propanol, diethyl ether, dipropyl ether, diisopropyl ether and n-pentane, Examples thereof include saturated hydrocarbons having 5 to 10 carbon atoms such as n-hexane and n-octane, and water, methanol, ethanol, i-propanol and diisopropyl ether are preferable, and water,
Methanol, ethanol and i-propanol are more preferable, and methanol is particularly preferable. These poor solvents may be used alone or in admixture of two or more.
【００４９】ＴＢＡ−ＢＥに対する良溶媒としては、Ｔ
ＢＡ−ＢＥの溶解度が１ｇ／溶媒１００ｇ以上、好まし
くは２ｇ／溶媒１００ｇ以上であるものが好ましい。ま
た、１３０℃で揮発する良溶媒が好ましく、乾燥の容易
性から８０℃で揮発する良溶媒がより好ましい。ＴＢＡ
−ＢＥに対する良溶媒の具体例としては、塩化メチレ
ン、クロロホルム、１，２−ジクロロエタン、１，１−
ジクロロエタン、シクロヘキサノン、酢酸エチルおよび
トルエンから選択されるものが好ましく、これらは一種
でも二種以上の混合物であっても良い。これらのなか
で、より好ましいのは塩化メチレン、クロロホルムの如
きハロゲン化炭化水素であり、中でも塩化メチレンが最
も好ましい。A good solvent for TBA-BE is T
It is preferred that the solubility of BA-BE is 1 g / solvent 100 g or more, preferably 2 g / solvent 100 g or more. A good solvent that volatilizes at 130 ° C is preferable, and a good solvent that volatilizes at 80 ° C is more preferable because of easy drying. TBA
Specific examples of the good solvent for -BE include methylene chloride, chloroform, 1,2-dichloroethane, 1,1-
Those selected from dichloroethane, cyclohexanone, ethyl acetate and toluene are preferable, and these may be one kind or a mixture of two or more kinds. Of these, halogenated hydrocarbons such as methylene chloride and chloroform are more preferable, and methylene chloride is most preferable.
【００５０】前記貧溶媒と良溶媒を混合した成分は均一
溶液であり、かかる混合成分に対するＴＢＡ−ＢＥの溶
解度が０．０２〜１０ｇ／溶媒１００ｇ、好ましくは
０．０２〜５ｇ／溶媒１００ｇ、より好ましくは０．０
２〜４ｇ／溶媒１００ｇである成分である。かかる範囲
であればＴＢＡ−ＢＥ湿潤粉体の造粒がスムーズに進行
し好ましい。例えば、ＴＢＡ−ＢＥに対する、前記良溶
媒と貧溶媒との重量比が９０：１０〜１０：９０、好ま
しくは８０：２０〜１０：９０、より好ましくは７０：
３０〜１０：９０、さらに好ましくは６０：４０〜１
０：９０になるように調節すれば良い。The component obtained by mixing the poor solvent and the good solvent is a homogeneous solution, and the solubility of TBA-BE in the mixed component is 0.02 to 10 g / solvent 100 g, preferably 0.02 to 5 g / solvent 100 g. Preferably 0.0
It is a component that is 2 to 4 g / 100 g of solvent. Within such a range, granulation of the TBA-BE wet powder proceeds smoothly, which is preferable. For example, the weight ratio of the good solvent and the poor solvent to TBA-BE is 90:10 to 10:90, preferably 80:20 to 10:90, more preferably 70 :.
30 to 10:90, more preferably 60:40 to 1
It may be adjusted to be 0:90.
【００５１】前記ＴＢＡ−ＢＥの湿潤粉体を得る方法と
しては例えば以下の方法が採用される。As a method for obtaining the wet powder of TBA-BE, for example, the following method is adopted.
【００５２】ＴＢＡ−ＢＥを製造する方法として、２，
２−ビス（４−アリルオキシ−３，５−ジブロモフェニ
ル）プロパン（以下、ＴＢＡ−ＡＥと略称することがあ
る）の溶液に、ＴＢＡ−ＡＥ １モルに対して２〜６モ
ルの臭素を０〜６０℃で滴下し、ＴＢＡ−ＡＥのアリル
基の二重結合に対する臭素の付加反応を完全に終了させ
た後、反応溶液中に残った未反応臭素を亜硫酸水素水溶
液で還元し、さらに該還元によって生成した臭化水素を
中和し、反応液を水洗することにより、ＴＢＡ−ＢＥ溶
液を得る方法が通常採用される。As a method for producing TBA-BE, 2,
To a solution of 2-bis (4-allyloxy-3,5-dibromophenyl) propane (hereinafter sometimes abbreviated as TBA-AE), 2 to 6 mol of bromine is added to 1 mol of TBA-AE. After dropwise addition at 60 ° C. to completely complete the addition reaction of bromine to the double bond of the allyl group of TBA-AE, unreacted bromine remaining in the reaction solution was reduced with an aqueous hydrogen sulfite solution, and further reduced by the reduction. A method of obtaining a TBA-BE solution by neutralizing the produced hydrogen bromide and washing the reaction solution with water is usually adopted.
【００５３】かかるＴＢＡ−ＢＥ溶液を濃縮することに
より溶媒を除去した後に得られる塊状のＴＢＡ−ＢＥを
粉砕したり、貧溶媒中に添加することによりＴＢＡ−Ｂ
Ｅを沈殿させる等の処理を経て、ＴＢＡ−ＢＥ微粒子を
得て、これに溶媒の割合が上記範囲となるように良溶媒
および貧溶媒を加えて造粒に供するＴＢＡ−ＢＥの湿潤
粉体を得ることができる。TBA-BE obtained by removing the solvent by concentrating the TBA-BE solution is crushed or added to a poor solvent to obtain TBA-B.
TBA-BE fine particles are obtained through a treatment such as precipitation of E, and a good solvent and a poor solvent are added to the TBA-BE fine particles so that the ratio of the solvent is in the above range, and a wet powder of TBA-BE to be granulated is obtained. Obtainable.
【００５４】また、上記ＴＢＡ−ＢＥの製造方法により
得られたＴＢＡ−ＢＥ溶液は、下記の精製方法を適用す
ることが好ましい。The TBA-BE solution obtained by the above TBA-BE production method is preferably subjected to the following purification method.
【００５５】かかる精製方法は、上記ＴＢＡ−ＢＥ溶液
を下記（ｉ）〜（ｉｉ）の条件を満足するスラリー中に
供給して、種結晶の存在下、溶液中のＴＢＡ−ＢＥを析
出させることが肝要である。そしてその際スラリー中の
溶媒は、下記（ｉｉ）のようにＴＢＡ−ＢＥの良溶媒と
貧溶媒との混合溶媒である。
（ａ）良溶媒、貧溶媒及びＴＢＡ−ＢＥの結晶からなる
スラリー中の該ＴＢＡ−ＢＥの結晶の割合が５〜５０重
量％、好ましくは５〜４５重量％、より好ましくは５〜
４３重量％、さらに好ましくは５〜４０重量％のスラリ
ー濃度であること、（ｂ）スラリー中の良溶媒および貧
溶媒の混合溶媒に対する該ＴＢＡ−ＢＥの溶解度が０．
０２〜１０ｇ／溶媒１００ｇ、好ましくは０．０２〜５
ｇ／溶媒１００ｇ、より好ましくは０．０２〜４ｇ／溶
媒１００ｇである成分であること。In this purification method, the above TBA-BE solution is fed into a slurry satisfying the following conditions (i) to (ii) to precipitate TBA-BE in the solution in the presence of seed crystals. Is essential. And the solvent in the slurry at that time is a mixed solvent of a good solvent and a poor solvent of TBA-BE as shown in (ii) below. (A) The proportion of the TBA-BE crystals in the slurry composed of the good solvent, the poor solvent and the TBA-BE crystals is 5 to 50% by weight, preferably 5 to 45% by weight, more preferably 5 to 5% by weight.
The slurry concentration is 43% by weight, more preferably 5 to 40% by weight, and (b) the solubility of the TBA-BE in a mixed solvent of a good solvent and a poor solvent in the slurry is 0.
02-10 g / solvent 100 g, preferably 0.02-5
g / solvent 100 g, more preferably 0.02 to 4 g / solvent 100 g.
【００５６】かかる精製方法は、析出容器中において、
前記（ｉ）および（ｉｉ）の条件を維持しつつ、ＴＢＡ
−ＢＥ溶液をその容器中に供給することにより実施され
る。スラリーを形成しているＴＢＡ−ＢＥの結晶の一部
は、溶液から析出するＴＢＡ−ＢＥの種結晶として作用
し、一方、混合溶媒の組成は、ＴＢＡ−ＢＥの析出を促
進し、不純物の析出を抑制し、且つその溶存を保持する
作用を果たしているものと考えられる。The purification method is as follows:
While maintaining the above conditions (i) and (ii), TBA
Performed by feeding the BE solution into the container. Some of the TBA-BE crystals forming the slurry act as seed crystals of TBA-BE precipitated from the solution, while the composition of the mixed solvent promotes the precipitation of TBA-BE and precipitates impurities. It is considered that it has the function of suppressing the above and maintaining its dissolution.
【００５７】この精製方法によって得られたＴＢＡ−Ｂ
Ｅ結晶を含むスラリーは、遠心沈降、遠心濾過、重力濾
過、或いは真空濾過等の方法によって、湿潤粉体と母液
とに分離し、湿潤粉体はそのまま、又は乾燥して若しく
は良溶媒或いは貧溶媒を添加して、前記溶媒の割合を満
足させＴＢＡ−ＢＥ湿潤粉体として造粒工程に供するこ
とができる。TBA-B obtained by this purification method
The slurry containing the E crystals is separated into a wet powder and a mother liquor by a method such as centrifugal sedimentation, centrifugal filtration, gravity filtration, or vacuum filtration, and the wet powder is as it is or after it is dried or in a good solvent or a poor solvent. Can be added to satisfy the ratio of the solvent, and can be subjected to the granulation step as TBA-BE wet powder.
【００５８】本発明で好適に使用されるＴＢＡ−ＢＥ
は、その純度が９０％以上が好ましく、９１％以上がよ
り好ましく、９２％以上がさらに好ましい。また、ＤＳ
Ｃピーク温度が９０℃以上が好ましく、１００℃以上が
より好ましい。これらを満足するＴＢＡ−ＢＥ湿潤粉体
を造粒して得られるＴＢＡ−ＢＥ粉体は、耐熱性および
ブロッキング性により優れることとなると共に、任意の
割合で他の難燃剤、或いは易燃性樹脂と混合することが
でき、任意の組成の、品質の安定した本発明の粒状難燃
剤、或いは樹脂製品を製造することができるようにな
る。TBA-BE preferably used in the present invention
Is preferably 90% or higher in purity, more preferably 91% or higher, still more preferably 92% or higher. Also, DS
The C peak temperature is preferably 90 ° C or higher, more preferably 100 ° C or higher. The TBA-BE powder obtained by granulating the TBA-BE wet powder satisfying these is superior in heat resistance and blocking property, and at the same time, other flame retardant or flame-retardant resin. It becomes possible to produce the granular flame retardant or resin product of the present invention having any composition and stable quality.
【００５９】以上の方法により得られた本発明の粒状難
燃剤は、粒径が制御されており、且つ粒状難燃剤中に含
まれる微粉濃度が極めて低減されていることにより、流
動性が良好であり、付着性及び固着性が改善された粒状
難燃剤であり、易燃性樹脂用の難燃剤として優れた性能
を発揮する。また、上記流動性の指標となる差角は５度
以上が好ましく、５〜３０度の範囲が好ましい。The particle size of the granular flame retardant of the present invention obtained by the above method is controlled, and the concentration of fine powder contained in the granular flame retardant is extremely reduced, so that the fluidity is good. It is a granular flame retardant with improved adhesiveness and stickiness, and exhibits excellent performance as a flame retardant for flammable resins. The difference angle serving as an index of fluidity is preferably 5 degrees or more, and more preferably 5 to 30 degrees.
【００６０】[0060]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれら実施例のみに限定されるものでは
ない。なお、平均粒径、粒状難燃剤中に含まれる微粉濃
度、かさ密度、安息角、崩壊角、差角、付着性、固着
性、ブロッキング性及び飛散度についての測定及び評価
は次の方法に従った。
（１）平均粒径と微粉濃度
目開きが５．６ｍｍ、４．０ｍｍ、１．７ｍｍ、１．０
ｍｍ、０．７２ｍｍ、０．２５ｍｍ、０．１５ｍｍ、
０．０７５ｍｍである篩及び電磁しんとう機を使用し、
振動回数が３６００回／分、振幅が２ｍｍ、振動時間が
２分間で、該振動時間の内訳が１０秒間振動運転し、２
秒間停止するパターンの繰り返しである条件下で篩分け
た。該篩分け作業後に各種篩上の粒子重量を量り、篩分
けに使用した全粒子重量に対する各篩上の各粒子重量の
割合に換算した。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The average particle diameter, the concentration of fine powder contained in the granular flame retardant, the bulk density, the angle of repose, the collapse angle, the difference angle, the adhesiveness, the stickiness, the blocking property and the scattering degree are measured and evaluated according to the following methods. It was (1) Average particle size and fine powder density opening are 5.6 mm, 4.0 mm, 1.7 mm, 1.0
mm, 0.72 mm, 0.25 mm, 0.15 mm,
Using a 0.075 mm sieve and electromagnetic agitator,
The vibration frequency is 3600 times / min, the amplitude is 2 mm, the vibration time is 2 minutes, and the breakdown of the vibration time is 10 seconds.
Sieving was carried out under conditions that were a repeating pattern of pauses for seconds. After the sieving operation, the weight of particles on various sieves was measured and converted into the ratio of the weight of each particle on each sieve to the weight of all particles used for sieving.
【００６１】この粒度分布データについて、ｘ軸に篩の
目開きであって粒径の代替値であるＤｍｍを採り、且つ
該ｘ軸を対数目盛りとし、また、ｙ軸に累計通過率とも
呼ばれる、目開きが０．０７５ｍｍである篩を通過した
粒子重量の割合Ｗ１％から、使用した篩の目開きである
Ｄｎｍｍに対応したＷｎ％迄のＷ％の和を求めた値（累
計通過率）を採ることによって作成した片対数グラフに
おいてＷが５０％である時のＤの値を求めた。このＤの
値を平均粒径とした。With respect to this particle size distribution data, the x-axis is the mesh opening of the sieve and the alternative value of the particle size is Dmm, the x-axis is the logarithmic scale, and the y-axis is also called the cumulative passage rate. A value (cumulative passage rate) obtained by calculating the sum of W% from the proportion W1% of the weight of the particles having passed through the sieve having an opening of 0.075 mm to Wn% corresponding to the opening Dnmm of the sieve used. The value of D when W was 50% was obtained in the semi-logarithmic graph created by taking. The value of D was used as the average particle size.
【００６２】また、目開きが０．０７５ｍｍである篩を
通過した粒子重量の割合Ｗ１％から、目開きが０．７２
ｍｍである金網を通過した粒子重量の割合Ｗ２％迄の和
Ｗ３％を求めた。このＷ３％を目開き０．７２ｍｍの篩
を通過する微粉粒子の濃度とした。Further, from the proportion W1% of the weight of the particles which passed through the sieve having an opening of 0.075 mm, the opening was 0.72.
The sum W3% up to the percentage W2% of the weight of the particles that passed through the wire mesh of mm was determined. This W3% was defined as the concentration of fine powder particles passing through a sieve having an opening of 0.72 mm.
【００６３】一方、目開きが０．０７５ｍｍである篩を
通過した粒子重量の割合Ｗ１％から、目開きが０．２５
ｍｍである金網を通過した粒子重量の割合Ｗ４％迄の和
Ｗ５％を求めた。このＷ５％を目開き０．２５ｍｍの篩
を通過する微粉粒子の濃度とした。On the other hand, from the proportion W1% of the weight of the particles having passed through the sieve having an opening of 0.075 mm, the opening is 0.25.
The sum W5% up to the percentage W4% of the weight of the particles that passed through the wire mesh of mm was determined. This W5% was defined as the concentration of fine powder particles that passed through a sieve with an opening of 0.25 mm.
【００６４】（２）かさ密度、安息角、崩壊角、及び差
角
ホソカワミクロン製パウダテスタＰＴ−Ｎ型、表１およ
び表２記載の目開きである篩、及び表１および表２記載
の足の内径である漏斗を使用することによって、かさ密
度、安息角、及び崩壊角を測定し、さらに安息角の値と
崩壊角の値との差を取ることによって差角を求めた。(2) Bulk Density, Angle of Repose, Collapse Angle, and Difference Angle Powder Tester PT-N Model made by Hosokawa Micron, sieve having openings shown in Table 1 and Table 2, and inner diameter of foot shown in Table 1 and Table 2. The bulk density, the angle of repose, and the collapse angle were measured by using a funnel, and the difference angle was determined by taking the difference between the value of the angle of repose and the value of the collapse angle.
【００６５】該差角は、該粒状難燃剤の流動性、或いは
凝集性の指標とし、差角が小さい値になるほど流動性が
悪いこと、或いは凝集性が高くてブリッジを起こし易い
ことを示すものである。The difference angle is used as an index of the fluidity or cohesiveness of the granular flame retardant, and indicates that the smaller the difference angle is, the poorer the fluidity is, or the higher the cohesiveness is and the more easily the bridge is caused. Is.
【００６６】（３）付着性及び固着性
池貝工業製 ＰＣＭ−３０ 押出機の原料供給装置である
単軸スクリューフィーダに粒状難燃剤を供給し、スクリ
ューとシリンダー内壁とのクリアランスが０．５ｍｍで
あり、スクリュー回転数が３０ｒｐｍであり、且つ該ス
クリューを回転させる為のモーターを保護するための安
全装置の電流設定値が０．９Ａである運転条件下、スク
リュー周りのシリンダー内壁における付着及び固着によ
って該モーターが過負荷となって、安全装置が作動する
ことで該モーターが停止するまでの時間を測定するとい
う加促試験により評価した。(3) Adhesiveness and stickiness The granular flame retardant was supplied to the single screw feeder which is the raw material supply device of the PCM-30 extruder manufactured by Ikegai Kogyo Co., Ltd., and the clearance between the screw and the inner wall of the cylinder was 0.5 mm. The screw rotation speed is 30 rpm, and the current setting value of the safety device for protecting the motor for rotating the screw is 0.9 A, the adhesion and sticking on the inner wall of the cylinder around the screw The motor was overloaded and the safety device was activated to measure the time until the motor stopped, which was evaluated by a forced test.
【００６７】（４）ブロッキング性
底板の上に内径５１ｍｍ、高さ９０ｍｍの円筒を立て、
この中に試料１２０ｇを入れた後、試料上に１０ｋｇの
錘を乗せ、さらに４５℃に保たれた乾燥機内で１６時間
静置した。その後、乾燥機から取り出し、放冷し、次い
で７℃に保たれた冷蔵庫内で１６時間静置した。その
後、冷蔵庫から取り出して直ぐに円筒内の粉体をステン
レス製バット上に静かに押し出し、その際の試料のブロ
ッキング状態を以下の基準により評価した。(4) Blocking property A cylinder having an inner diameter of 51 mm and a height of 90 mm is erected on the bottom plate,
After putting 120 g of the sample therein, a 10 kg weight was placed on the sample, and the sample was allowed to stand for 16 hours in a dryer kept at 45 ° C. Then, it was taken out from the dryer, allowed to cool, and then left standing for 16 hours in a refrigerator kept at 7 ° C. Then, immediately after taking out from the refrigerator, the powder in the cylinder was gently extruded onto a stainless steel vat, and the blocking state of the sample at that time was evaluated according to the following criteria.
【００６８】○：部分部分が欠けた不完全な円柱状の成
形体ができ、該成形体を指で力をかけずに容易にほぐす
ことができる。
△：一部分が欠けてはいるものの、ほぼ円柱状の成形体
ができ、該成形体の大部分を指で力をかけずに容易にほ
ぐすことができるものの、一部に指で圧縮する程度の力
を入れないとほぐれない状態の部分がある。
×：円柱状の成形体ができ、該成形体の一部分を指で力
をかけずに容易にほぐすことができるものの、殆どの部
分が指で圧縮する程度の力を入れないとほぐれない状態
である。◯: An incomplete columnar molded body with a partial cutout is formed, and the molded body can be easily loosened without applying force with fingers. Δ: Although a part is lacking, a substantially columnar molded body is formed, and most of the molded body can be easily disentangled without applying force with fingers, but it is only partially compressed with fingers. There are some parts that cannot be unraveled if you do not put effort. ×: A columnar molded body is formed, and a part of the molded body can be easily loosened without applying force with fingers, but most of the portion cannot be loosened unless the force is compressed with fingers. is there.
【００６９】（５）飛散度
ホソカワミクロン製パウダテスタＰＴ−Ｎ型の分散度測
定ユニットを使うことによって、１０．０ｇの粉体を６
２５ｍｍ下にあるウオッチグラスに向けて落下させた後
に、ウオッチグラスに乗った粉体重量を測り、ウオッチ
グラス外に飛散した粉体重量を算出し、さらに、１０．
０ｇの粉体に対するウオッチグラス外に飛散した粉体の
割合を求めた。飛散度の値が大きいほど、飛散しやすい
ことを示す。(5) Scattering rate By using a powder tester PT-N type dispersion measuring unit made by Hosokawa Micron, 10.0 g of powder is
After dropping it toward the watch glass under 25 mm, the weight of the powder on the watch glass was measured, and the weight of the powder scattered outside the watch glass was calculated.
The ratio of the powder scattered outside the watch glass to 0 g of the powder was determined. The larger the value of the scattering degree, the easier the scattering.
【００７０】［参照例１］（ＴＢＡ−ＢＥの合成）
温度計、攪拌機、還流冷却管を取り付けた３００ｍＬの
フラスコにＴＢＡ−ＡＥ（帝人化成（株）製 ＦＧ−３
２００）１００ｇ塩化メチレン１５０ｇを入れ、２０℃
で溶解させた。この溶液を０℃まで冷却した後、反応溶
液の温度を０〜１０℃の範囲に保持しながら、臭素５４
ｇを１時間かけて滴下し、さらに０〜１０℃の範囲で攪
拌を１時間続け、臭素の付加反応を終了した。Reference Example 1 (Synthesis of TBA-BE) A TBA-AE (FG-3 manufactured by Teijin Chemicals Ltd.) was placed in a 300 mL flask equipped with a thermometer, a stirrer and a reflux condenser.
200) Add 100g methylene chloride 150g, 20 ℃
Dissolved in. After cooling this solution to 0 ° C., while maintaining the temperature of the reaction solution in the range of 0 to 10 ° C., bromine 54
g was added dropwise over 1 hour and stirring was continued for 1 hour in the range of 0 to 10 ° C. to complete the addition reaction of bromine.
【００７１】次いで、この溶液中の過剰の臭素を２５重
量％亜硫酸水素ナトリウム水溶液３０ｍＬで中和し、そ
の後、１５０ｍＬの純水で洗浄してＴＢＡ−ＢＥの５０
重量％塩化メチレン溶液を得た。この溶液の一部を取り
出し濃縮後、メタノールを加えて固化させ、次いで溶媒
留去、乾燥作業を経て固体を回収し、分析したところ、
ＴＢＡ−ＢＥの純度は９０％であった。Then, excess bromine in this solution was neutralized with 30 mL of a 25 wt% sodium hydrogen sulfite aqueous solution, and then washed with 150 mL of pure water to obtain 50 parts of TBA-BE.
A wt% methylene chloride solution was obtained. After taking out a part of this solution and concentrating it, methanol was added to solidify it, then the solvent was distilled off, and the solid was recovered through a drying operation and analyzed.
The purity of TBA-BE was 90%.
【００７２】［参照例２］（ＴＢＡ−ＢＥ溶液の精製お
よびＴＢＡ−ＢＥ湿潤粉体の調整１）
図１に記載の１０Ｌのフラスコに、塩化メチレン２．４
ｋｇ、メタノール３．６ｋｇ及び純度９０％のＴＢＡ−
ＢＥ結晶２．４ｋｇを入れ、混合した（容量は７Ｌとな
る）。フラスコ内を攪拌しながら、４０℃の温度で、参
照例１で得られたＴＢＡ−ＢＥの塩化メチレン溶液３７
ｋｇ及びメタノール２８ｋｇを、定量ポンプによってそ
れぞれ０．０８ｋｇ／分、０．０６ｋｇ／分の速度で８
時間連続的に添加した。添加を開始してから１０分後よ
り、ポンプ５によってフラスコ中のスラリーを３．５Ｌ
／分の速度で循環させつつ、スラリーを０．１Ｌ／分の
速度で抜き取り口７より抜き取ることによりフラスコ内
のスラリーの容量を７Ｌに維持した。添加開始から８時
間が経過するまでに抜き取ったスラリーを遠心濾過し、
ＴＢＡ−ＢＥ湿潤粉体を得た。このＴＢＡ−ＢＥ湿潤粉
体は、溶媒の割合が２９重量％（塩化メチレンとメタノ
ールとの重量比は４０：６０、２５℃におけるＴＢＡ−
ＢＥの溶解度は０．２ｇ／溶媒１００ｇ）であった。Reference Example 2 (Purification of TBA-BE Solution and Preparation of TBA-BE Wet Powder 1) In a 10 L flask shown in FIG. 1, methylene chloride 2.4 was added.
kg, methanol 3.6 kg and 90% pure TBA-
2.4 kg of BE crystals were added and mixed (volume becomes 7 L). While stirring the inside of the flask, at a temperature of 40 ° C., a methylene chloride solution of TBA-BE obtained in Reference Example 1 37
8 kg and 28 kg of methanol at a rate of 0.08 kg / min and 0.06 kg / min respectively by a metering pump.
Added continuously over time. After 10 minutes from the start of addition, 3.5 L of the slurry in the flask was pumped.
The volume of the slurry in the flask was maintained at 7 L by withdrawing the slurry from the extraction port 7 at a rate of 0.1 L / min while circulating at a rate of / min. Centrifugal filtration of the extracted slurry within 8 hours from the start of addition,
A TBA-BE wet powder was obtained. This TBA-BE wet powder had a solvent ratio of 29% by weight (the weight ratio of methylene chloride and methanol was 40:60, TBA-at 25 ° C).
The solubility of BE was 0.2 g / 100 g of solvent).
【００７３】［参照例３］（ＴＢＡ−ＢＥ溶液の精製お
よびＴＢＡ−ＢＥ湿潤粉体の調整２）
図１に記載の１０Ｌのフラスコに、塩化メチレン１．３
ｋｇ、メタノール５．２ｋｇ及び純度９０％のＴＢＡ−
ＢＥ結晶１．０ｋｇを入れ、混合した（容量は７Ｌとな
る）。フラスコ内を攪拌しながら、４０℃の温度で、参
照例１で得られたＴＢＡ−ＢＥの塩化メチレン溶液３７
ｋｇ及びメタノール５４ｋｇを、定量ポンプによってそ
れぞれ０．０３ｋｇ／分、０．０６ｋｇ／分の速度で１
５時間連続的に添加した。添加を開始してから１０分
後、ポンプ５によってフラスコ中のスラリーを３．５Ｌ
／分の速度で循環させつつ、スラリーを０．１Ｌ／分の
速度で抜き取り口７より抜き取った。添加開始から８時
間が経過するまでに抜き取ったスラリーを遠心濾過し、
ＴＢＡ−ＢＥ湿潤粉体を得た。このＴＢＡ−ＢＥ湿潤粉
体は、溶媒の割合が２９重量％（塩化メチレンとメタノ
ールとの重量比は２０：８０、２５℃におけるＴＢＡ−
ＢＥの溶解度は０．１ｇ／溶媒１００ｇ）であった。Reference Example 3 (TBA-BE Solution Purification and TBA-BE Wet Powder Preparation 2) In a 10 L flask shown in FIG.
kg, 5.2 kg of methanol and 90% pure TBA-
1.0 kg of BE crystal was added and mixed (volume becomes 7 L). While stirring the inside of the flask, at a temperature of 40 ° C., a methylene chloride solution of TBA-BE obtained in Reference Example 1 37
1 kg of methanol and 54 kg of methanol at a rate of 0.03 kg / min and 0.06 kg / min respectively by a metering pump.
It was added continuously for 5 hours. Ten minutes after the addition was started, 3.5 L of the slurry in the flask was pumped.
The slurry was extracted from the extraction port 7 at a rate of 0.1 L / min while circulating at a rate of / min. Centrifugal filtration of the extracted slurry within 8 hours from the start of addition,
A TBA-BE wet powder was obtained. This TBA-BE wet powder has a solvent ratio of 29% by weight (the weight ratio of methylene chloride and methanol is 20:80, TBA-at 25 ° C.).
The solubility of BE was 0.1 g / solvent 100 g).
【００７４】［参照例４］（ＴＢＡ−ＢＥの造粒および
微粉量の調整）
参照例２或いは参照例３で得られた湿潤粉体１０ｋｇ
を、目開きが０．９ｍｍであるスクリーンを取り付けた
不二パウダル製 ファインディスクペレッタ（ロール型
押出造粒機）に、２５℃で手投入し、造粒物を得た。こ
の得られたＴＢＡ−ＢＥ造粒物について、熱風乾燥機を
用いて８０℃で静置乾燥を行った。次いで、このＴＢＡ
−ＢＥ造粒物を、目開きが０．６０ｍｍである金網を取
り付けた振動式篩分け機で分級して、微粉量を低下させ
たＴＢＡ−ＢＥ粒体を得た。[Reference Example 4] (TBA-BE granulation and adjustment of fine powder amount) 10 kg of the wet powder obtained in Reference Example 2 or Reference Example 3
Was manually put at 25 ° C. into a fine disk pelleter made by Fuji Paudal (roll type extrusion granulator) equipped with a screen having an opening of 0.9 mm to obtain a granulated product. The TBA-BE granules thus obtained were dried by standing using a hot air dryer at 80 ° C. Then this TBA
The -BE granulated product was classified by a vibrating type sieving machine equipped with a wire mesh having an opening of 0.60 mm to obtain a TBA-BE granule having a reduced amount of fine powder.
【００７５】以下に、実施例１〜５及び比較例１〜２で
使用したＴＢＡ−ＢＥ粉粒体を示す。The TBA-BE powders used in Examples 1-5 and Comparative Examples 1-2 are shown below.
【００７６】ＦＲ−１：参照例２で得られた湿潤粉体を
乾燥した粉体（比較例１）。
ＦＲ−２：参照例２で得られた湿潤粉体を造粒機で造粒
し、造粒物を乾燥した粒体（比較例２）。
ＦＲ−３：参照例２で得られた湿潤粉体を、参照例４の
方法で造粒、乾燥し、分級した粒体（実施例１）。
ＦＲ−４：ＦＲ−３の粒体を、さらに目開きが０．７２
ｍｍである金網で分級した粒体（実施例２）。
ＦＲ−５：ＦＲ−３の粒体を、さらに目開きが０．２５
ｍｍである金網で分級した粒体（実施例３）。
ＦＲ−６：ＦＲ−４の粒体に、目開きが０．２５ｍｍで
ある金網を通過した微粉を添加したもの（実施例４）。
ＦＲ−７：参照例３で得られた湿潤粉体を、参照例４の
方法で造粒、乾燥し、分級した粒体を、さらに目開きが
０．７２ｍｍである金網で分級した粒体（実施例５）。FR-1: Powder obtained by drying the wet powder obtained in Reference Example 2 (Comparative Example 1). FR-2: Granules obtained by granulating the wet powder obtained in Reference Example 2 with a granulator and drying the granulated product (Comparative Example 2). FR-3: Granules obtained by granulating, drying and classifying the wet powder obtained in Reference Example 2 by the method of Reference Example 4 (Example 1). FR-4: The grain size of FR-3 is 0.72.
Granules classified with a wire mesh having a size of mm (Example 2). FR-5: FR-3 granules with an opening of 0.25
Granules classified with a wire mesh having a size of mm (Example 3). FR-6: A granule of FR-4 to which fine powder having passed through a wire net having an opening of 0.25 mm was added (Example 4). FR-7: The wet powder obtained in Reference Example 3 was granulated and dried by the method of Reference Example 4, and the classified particles were further classified with a wire mesh having an opening of 0.72 mm ( Example 5).
【００７７】［実施例１］ＦＲ−３について、平均粒
径、粒状難燃剤中に含まれる微粉濃度、かさ密度、安息
角、崩壊角、差角、付着性並びに固着性、ブロッキング
性及び飛散度についての測定及び評価を行った。難燃剤
の種類、測定結果及び評価結果を表１に示した。また、
ＦＲ−３の平均粒径を求める過程で作成した片対数グラ
フを図２に示した。[Example 1] With respect to FR-3, the average particle diameter, the fine powder concentration contained in the granular flame retardant, the bulk density, the angle of repose, the collapse angle, the difference angle, the adhesiveness and the sticking property, the blocking property and the scattering degree. Was measured and evaluated. Table 1 shows the types of flame retardants, the measurement results, and the evaluation results. Also,
A semi-logarithmic graph prepared in the process of obtaining the average particle size of FR-3 is shown in FIG.
【００７８】［実施例２〜５］表１に示す難燃剤につい
て、実施例１と同様に測定及び評価を行った。難燃剤の
種類、測定結果及び評価結果を表１に示した。[Examples 2 to 5] The flame retardants shown in Table 1 were measured and evaluated in the same manner as in Example 1. Table 1 shows the types of flame retardants, the measurement results, and the evaluation results.
【００７９】［比較例１及び２］ＦＲ−１及びＦＲ−２
について、実施例１と同様に測定及び評価を行った。難
燃剤の種類、測定結果及び評価結果を表１に示した。ま
た、ＦＲ−１の平均粒径を求める過程で作成した片対数
グラフを図２に示した。[Comparative Examples 1 and 2] FR-1 and FR-2
Was measured and evaluated in the same manner as in Example 1. Table 1 shows the types of flame retardants, the measurement results, and the evaluation results. A semilogarithmic graph prepared in the process of obtaining the average particle size of FR-1 is shown in FIG.
【００８０】[0080]
【表１】 [Table 1]
【００８１】造粒、乾燥後に分級を行って得られた実施
例１〜実施例５に示される臭素系の円柱形粒状難燃剤
は、造粒及び分級を行っていない比較例１に示される臭
素系の不定形粒状難燃剤に比べて、付着性並びに固着
性、ブロッキング性及び飛散性が改善されており、特に
付着性並びに固着性においてモーターが停止する迄の時
間が４倍以上に飛躍した。また、分級を行っていない比
較例２に示される臭素系の円柱形粒状難燃剤に比べて、
付着性並びに固着性、ブロッキング性が改善されてい
る。The bromine-based cylindrical granular flame retardants shown in Examples 1 to 5 obtained by granulating and drying and then classifying were bromine as shown in Comparative Example 1 which was not granulated and classified. Adhesiveness and sticking property, blocking property and scattering property are improved as compared with the amorphous granular flame retardant of the system, and in particular, in the adhesiveness and sticking property, the time until the motor is stopped jumped four times or more. Further, as compared with the brominated cylindrical granular flame retardant shown in Comparative Example 2 in which classification is not performed,
Adhesion, stickiness and blocking property are improved.
【００８２】［参照例５］（ＴＢＡ−ＢＥ溶液の調整）
参照例１で得られたＴＢＡ−ＢＥの塩化メチレン溶液
１．５ｋｇに塩化メチレン０．７５ｋｇを添加してＴＢ
Ａ−ＢＥの３３重量％塩化メチレン溶液を得た。Reference Example 5 (Preparation of TBA-BE Solution) To 1.5 kg of the methylene chloride solution of TBA-BE obtained in Reference Example 1, 0.75 kg of methylene chloride was added to TB.
A 33 wt% methylene chloride solution of A-BE was obtained.
【００８３】［参照例６］（ＴＢＡ−ＢＥ粉体の調整）
１０Ｌのフラスコに、メタノール４ｋｇ及び純度９０％
のＴＢＡ−ＢＥ結晶０．６ｋｇを入れ、撹拌を行いなが
ら、温度を５０℃に調節した。次いで、温度を４３℃以
上に維持し、溶媒を留去しながら、参照例５で得られた
ＴＢＡ−ＢＥの塩化メチレン溶液６ｋｇを、定量ポンプ
によってそれぞれ０．０３ｋｇ／分の速度で２０時間連
続的に添加した。添加終了後、生成したスラリーを吸引
濾過し、ＴＢＡ−ＢＥ湿潤粉体を得た。該湿潤粉体につ
いて、熱風乾燥機を用いて８０℃で静置乾燥を行った。[Reference Example 6] (Preparation of TBA-BE powder) In a 10 L flask, 4 kg of methanol and 90% of purity were obtained.
0.6 kg of TBA-BE crystal of was added and the temperature was adjusted to 50 ° C. while stirring. Next, while maintaining the temperature at 43 ° C. or higher and distilling off the solvent, 6 kg of the methylene chloride solution of TBA-BE obtained in Reference Example 5 was continuously fed for 20 hours at a rate of 0.03 kg / min by a metering pump. Was added. After the addition was completed, the resulting slurry was suction filtered to obtain a TBA-BE wet powder. The wet powder was statically dried at 80 ° C. using a hot air dryer.
【００８４】以下に、実施例６及び比較例３〜４で使用
したＴＢＡ−ＢＥ粉体を示す。The TBA-BE powders used in Example 6 and Comparative Examples 3 to 4 are shown below.
【００８５】ＦＲ−８：参照例６で得られた粉体（比較
例３）。
ＦＲ−９：参照例６で得られた粉体を、目開きが０．７
２ｍｍである金網で分級したもの（実施例６）。
ＦＲ−１０：参照例６で得られた粉体を、目開きが０．
２５ｍｍである金網で分級したもの（比較例４）。FR-8: Powder obtained in Reference Example 6 (Comparative Example 3). FR-9: The powder obtained in Reference Example 6 had an opening of 0.7.
Classified with a wire net of 2 mm (Example 6). FR-10: The powder obtained in Reference Example 6 had an opening of 0.
What was classified with a wire net of 25 mm (Comparative Example 4).
【００８６】［実施例６］ＦＲ−９について、平均粒
径、粒状難燃剤中に含まれる微粉濃度、かさ密度、安息
角、崩壊角、差角、付着性並びに固着性、及び飛散度に
ついての測定及び評価を行った。難燃剤の種類、測定結
果及び評価結果を表２に示した。[Example 6] With respect to FR-9, the average particle size, the fine powder concentration contained in the granular flame retardant, the bulk density, the angle of repose, the collapse angle, the difference angle, the adhesiveness and the sticking property, and the scattering degree were measured. Measurement and evaluation were performed. Table 2 shows the types of flame retardants, the measurement results, and the evaluation results.
【００８７】［比較例３及び比較例４］ＦＲ−８及びＦ
Ｒ−１０について、実施例６と同様に測定及び評価を行
った。難燃剤の種類、測定結果及び評価結果を表２に示
した。また、ＦＲ−８について、平均粒径を求める過程
で作成した片対数グラフを図２に示した。[Comparative Example 3 and Comparative Example 4] FR-8 and F
R-10 was measured and evaluated in the same manner as in Example 6. Table 2 shows the types of flame retardants, the measurement results, and the evaluation results. A semi-logarithmic graph of FR-8 prepared in the process of obtaining the average particle size is shown in FIG.
【００８８】[0088]
【表２】 [Table 2]
【００８９】目開きが０．７２ｍｍである金網で分級を
行った、実施例６に示される臭素系の不定形粒状難燃剤
は、分級を行っていない比較例３に示される臭素系の不
定形粒状難燃剤に比べて、流動性、及び付着性並びに固
着性が改善されており、特にモーターが停止する迄の時
間が２倍以上に飛躍した。また、目開きが０．２５ｍｍ
である金網で分級を行った比較例４に示される臭素系の
不定形粒状難燃剤は、比較例３に示される臭素系の不定
形粒状難燃剤に比べて、付着性並びに固着性、及び飛散
性が改善されておらず、粒径が０．２５ｍｍ未満の微粉
粒子を取り除くだけでは不十分であることが理解され
る。The bromine-based amorphous flame retardant shown in Example 6, which was classified by a wire mesh having an opening of 0.72 mm, was the bromine-based amorphous form shown in Comparative Example 3 in which no classification was carried out. Compared to the granular flame retardant, the fluidity, the adhesion and the stickiness were improved, and in particular, the time until the motor stopped stopped was more than doubled. Also, the opening is 0.25 mm
The bromine-based amorphous granular flame retardant shown in Comparative Example 4 which was classified by a wire mesh is compared to the bromine-based amorphous granular flame retardant shown in Comparative Example 3 in adhesiveness, stickiness, and scattering. It is understood that the property is not improved, and it is not enough to remove fine powder particles having a particle size of less than 0.25 mm.
【００９０】[0090]
【発明の効果】本発明により得られる粒状難燃剤は、粒
径が制御されており、且つ粒状難燃剤中に含まれる微粉
濃度が低いことにより、流動性が良好であり、付着性及
び固着性が改善された粒状難燃剤であり、易燃性樹脂用
の難燃剤として好適に使用され、その工業的効果は格別
なものである。INDUSTRIAL APPLICABILITY The granular flame retardant obtained according to the present invention has a controlled particle size and has a low concentration of fine powder contained in the granular flame retardant, so that it has good fluidity, adhesiveness and stickiness. Is an improved granular flame retardant, which is preferably used as a flame retardant for a flammable resin, and its industrial effect is exceptional.
【図１】参照例３におけるＴＢＡ−ＢＥ晶析精製を行う
装置の一例である。FIG. 1 is an example of an apparatus for refining TBA-BE crystallization in Reference Example 3.
【図２】実施例及び比較例における、難燃剤ＦＲ−１、
ＦＲ−３及びＦＲ−８について、平均粒径を求める過程
で作成した片対数グラフである。FIG. 2 shows a flame retardant FR-1, in Examples and Comparative Examples.
It is a semilogarithmic graph created in the process of calculating | requiring an average particle diameter about FR-3 and FR-8.
１．ＴＢＡ−ＢＥの塩化メチレン溶液供給口 ２．メタノール供給口 ３．還流冷却器 ４．温度計 ５．スラリー循環用ポンプ ６．循環したスラリーの添加口 ７．スラリー抜き取り口 ８．攪拌翼 1. TBA-BE methylene chloride solution supply port 2. Methanol supply port 3. Reflux condenser 4. thermometer 5. Slurry circulation pump 6. Circulation slurry addition port 7. Slurry outlet 8. Stirring blade
フロントページの続き (72)発明者 冨田 博史 東京都千代田区内幸町１丁目２番２号 帝 人化成株式会社内 Ｆターム(参考） 4H028 AA28 BA06 4J002 AA001 AE052 BC112 DA056 DE076 DE126 DE146 DE186 DH056 DK006 EB096 EB136 EC036 ED076 EH146 EJ016 EJ056 EL136 EP016 ER006 ER026 EU186 EV216 EW046 EW056 FD132 FD136 GQ00Continued front page (72) Inventor Hiroshi Tomita 1-2-2 Uchisaiwaicho, Chiyoda-ku, Tokyo Human Kasei Co., Ltd. F-term (reference) 4H028 AA28 BA06 4J002 AA001 AE052 BC112 DA056 DE076 DE126 DE146 DE186 DH056 DK006 EB096 EB136 EC036 ED076 EH146 EJ016 EJ056 EL136 EP016 ER006 ER026 EU186 EV216 EW046 EW056 FD132 FD136 GQ00
Claims (3)
（ａ）平均粒径が０．８〜２ｍｍであり、（ｂ）該粒状
難燃剤の全体量を１００重量％としたとき、目開き０．
７２ｍｍの篩を通過する微粉粒子の量が１２重量％以下
であり、（ｃ）該粒状難燃剤の全体量を１００重量％と
したとき、目開き０．２５ｍｍの篩を通過する微粉粒子
の量が９重量％以下である、ことを特徴とする低微粉濃
度の粒状難燃剤。1. A granular flame retardant, which comprises:
(A) The average particle size is 0.8 to 2 mm, and (b) when the total amount of the granular flame retardant is 100% by weight, the mesh size is 0.
The amount of fine powder particles passing through a 72 mm sieve is 12% by weight or less, and (c) when the total amount of the granular flame retardant is 100% by weight, the amount of fine powder particles passing through a sieve having an opening of 0.25 mm. Is 9% by weight or less, and a granular flame retardant having a low fine powder concentration.
項１記載の粒状難燃剤。2. The granular flame retardant according to claim 1, wherein the flame retardant is a brominated flame retardant.
ジブロモ−４−（２，３−ジブロモプロピルオキシ）フ
ェニル］プロパンである請求項１記載の粒状難燃剤。3. The flame retardant is 2,2-bis [3,5-
The granular flame retardant according to claim 1, which is dibromo-4- (2,3-dibromopropyloxy) phenyl] propane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001332327A JP2003138264A (en) | 2001-10-30 | 2001-10-30 | Granular flame retardant having low concentration of fine particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001332327A JP2003138264A (en) | 2001-10-30 | 2001-10-30 | Granular flame retardant having low concentration of fine particle |
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| Publication Number | Publication Date |
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| JP2003138264A true JP2003138264A (en) | 2003-05-14 |
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ID=19147758
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014001222A1 (en) | 2014-01-29 | 2015-07-30 | Clariant lnternational Ltd | Halogen-free solid flame retardant mixture and its use |
| CN110918989A (en) * | 2019-11-30 | 2020-03-27 | 湖南云箭集团有限公司 | Simple automatic powder screening device for laser selective melting technology |
| WO2022131284A1 (en) * | 2020-12-16 | 2022-06-23 | 株式会社Adeka | Flame retardant agent composition, flame-retardant resin composition, and molded body |
-
2001
- 2001-10-30 JP JP2001332327A patent/JP2003138264A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014001222A1 (en) | 2014-01-29 | 2015-07-30 | Clariant lnternational Ltd | Halogen-free solid flame retardant mixture and its use |
| EP3505596A1 (en) | 2014-01-29 | 2019-07-03 | Clariant International Ltd | Halogen-free fixed flame retardant mixture and its use |
| EP3505597A1 (en) | 2014-01-29 | 2019-07-03 | Clariant International Ltd | Halogen-free fixed flame retardant mixture and its use |
| EP3505599A1 (en) | 2014-01-29 | 2019-07-03 | Clariant International Ltd | Halogen-free fixed flame retardant mixture and its use |
| EP3505598A1 (en) | 2014-01-29 | 2019-07-03 | Clariant International Ltd | Halogen-free fixed flame retardant mixture and its use |
| EP3521402A1 (en) | 2014-01-29 | 2019-08-07 | Clariant International Ltd | Halogen-free fixed flame retardant mixture and its use |
| CN110918989A (en) * | 2019-11-30 | 2020-03-27 | 湖南云箭集团有限公司 | Simple automatic powder screening device for laser selective melting technology |
| WO2022131284A1 (en) * | 2020-12-16 | 2022-06-23 | 株式会社Adeka | Flame retardant agent composition, flame-retardant resin composition, and molded body |
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