CN112703225B - 准不燃性酚醛树脂组合物及由其得到的准不燃材料 - Google Patents
准不燃性酚醛树脂组合物及由其得到的准不燃材料 Download PDFInfo
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- CN112703225B CN112703225B CN201980060939.8A CN201980060939A CN112703225B CN 112703225 B CN112703225 B CN 112703225B CN 201980060939 A CN201980060939 A CN 201980060939A CN 112703225 B CN112703225 B CN 112703225B
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- phenolic resin
- quasi
- resin composition
- incombustible
- foam
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 164
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 151
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 45
- 239000006260 foam Substances 0.000 claims abstract description 107
- 239000003063 flame retardant Substances 0.000 claims abstract description 87
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000011134 resol-type phenolic resin Substances 0.000 claims abstract description 29
- 239000004088 foaming agent Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 19
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 19
- 238000005187 foaming Methods 0.000 claims description 18
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 17
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 230000020169 heat generation Effects 0.000 claims description 15
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 7
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000010998 test method Methods 0.000 claims description 3
- 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 abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010439 graphite Substances 0.000 abstract description 11
- 229910002804 graphite Inorganic materials 0.000 abstract description 11
- 229910052736 halogen Inorganic materials 0.000 abstract description 11
- 150000002367 halogens Chemical class 0.000 abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 11
- 239000011574 phosphorus Substances 0.000 abstract description 11
- 239000012796 inorganic flame retardant Substances 0.000 abstract description 8
- 229920003987 resole Polymers 0.000 abstract description 7
- 238000010561 standard procedure Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- -1 phosphorus compound Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 8
- 239000002345 surface coating layer Substances 0.000 description 8
- 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 8
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 239000004604 Blowing Agent Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000006261 foam material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical compound FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 description 2
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000011094 fiberboard Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 210000000497 foam cell Anatomy 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- NUPBXTZOBYEVIR-UHFFFAOYSA-N 1,1,2,3,3,4,4-heptafluorobut-1-ene Chemical class FC(F)C(F)(F)C(F)=C(F)F NUPBXTZOBYEVIR-UHFFFAOYSA-N 0.000 description 1
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ISCYUDAHBJMFNT-UHFFFAOYSA-N 1,1-dichloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C(Cl)Cl ISCYUDAHBJMFNT-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BLEZTPDKUBSTII-UHFFFAOYSA-N 1-chloro-1-fluoroprop-1-ene Chemical compound CC=C(F)Cl BLEZTPDKUBSTII-UHFFFAOYSA-N 0.000 description 1
- CZHLPWNZCJEPJB-UHFFFAOYSA-N 1-chloro-3-methylbutane Chemical compound CC(C)CCCl CZHLPWNZCJEPJB-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 1
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical class FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- IZHPSCJEIFFRLN-UHFFFAOYSA-N 3,3,4,4,4-pentafluorobut-1-ene Chemical class FC(F)(F)C(F)(F)C=C IZHPSCJEIFFRLN-UHFFFAOYSA-N 0.000 description 1
- LQAPOTKKMIZDGP-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical class FC(F)(F)C(F)(F)C(F)(F)C=C LQAPOTKKMIZDGP-UHFFFAOYSA-N 0.000 description 1
- BNLLWAALHYCOQM-UHFFFAOYSA-N 3,3,4,4-tetrafluorobut-1-ene Chemical class FC(F)C(F)(F)C=C BNLLWAALHYCOQM-UHFFFAOYSA-N 0.000 description 1
- UAHVVXPNJLRMPX-UHFFFAOYSA-N 3-chloro-1,2,3-trifluoroprop-1-ene Chemical compound FC=C(F)C(F)Cl UAHVVXPNJLRMPX-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Chemical class 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供准不燃性酚醛树脂组合物,其能够确保由以Resol型酚醛树脂为必须成分的酚醛树脂组合物得到的发泡体的有用的特性,并且能够协同提高阻燃性能或防火性能而有利地形成建筑基准法中规定的准不燃材料。在酚醛树脂组合物中,含有Resol型酚醛树脂、发泡剂及酸固化剂并且组合并含有第一成分和第二成分作为阻燃剂,第一成分包含红磷粉末,第二成分包含选自由除红磷以外的其他磷系阻燃剂、无机系阻燃剂、卤素系阻燃剂及石墨系阻燃剂组成的组中的至少一种。
Description
技术领域
本发明涉及准不燃性酚醛树脂组合物及由其得到的准不燃材料,尤其涉及可有利地形成作为准不燃材料有用的酚醛树脂发泡体(酚醛泡沫)的准不燃性酚醛树脂组合物和由这样的酚醛树脂组合物得到的准不燃材料。
背景技术
一直以来,使包含规定发泡剂的酚醛树脂组合物发泡、固化而得到的酚醛树脂发泡体被认为是其本身阻燃性较高的发泡体,在该状态下,不会充分满足建筑、土木、电气制品、电气电子部件、汽车部件等领域中所要求的安全性基准,没有提供具有在日本的建筑基准法中规定的准不燃特性的材料,该准不燃特性通过利用锥形量热仪的发热性试验进行评价。
因此,为了实现这样的酚醛树脂发泡体的阻燃特性的提高,通过将规定的阻燃剂配合于酚醛树脂组合物而使其固化,从而能够实现目标酚醛树脂发泡体的阻燃性的提高。例如在日本特开平2-49037号公报中明确了下述内容:通过使用磷化合物、硫化合物或硼化合物作为阻燃剂,并且将它们配合于酚醛树脂发泡体制造用的树脂组合物中,从而可制造有用的阻燃性酚醛树脂发泡体。另外,在日本特开2007-161810号公报、日本特开2007-70511号公报等中也明确了下述内容:通过使用氢氧化铝、氢氧化镁等金属的氢氧化物;氧化钙、氧化铝等金属的氧化物;如锌末那样的金属粉末;碳酸钙、碳酸镁等金属的碳酸盐作为通常配合于酚醛树脂发泡体制造用的树脂组合物的无机填料,从而可提高进行发泡而得的酚醛树脂发泡体的阻燃性或耐火性。进而,在日本特开昭60-170636号公报、日本特开平8-176343号公报中明确了下述内容:配合红磷、聚磷酸铵作为可对树脂赋予高度阻燃性的非卤素系阻燃剂而制备酚醛树脂组合物,然后使其发泡、固化,由此能够得到阻燃性优异的酚醛树脂发泡体。
但是,在日本的建筑基准法中,关于材料的耐火·防火性能,分为阻燃材料、准不燃材料和不燃材料,从阻燃材料到准不燃材料、甚至不燃材料,要求更为严格的防火性能,为了赋予由酚醛树脂发泡体形成的酚醛树脂材料(该酚醛树脂是使用作为酚醛树脂之一的Resol型酚醛树脂,将其与酸固化剂、发泡剂等组合,使其发泡、固化而得到的)以高度的阻燃性,使用如上述公报中公开那样的阻燃剂,但是要满足所要求的防火性能仅次于不燃材料的准不燃材料的准不燃性能是极其困难的。特别是,为了得到该建筑基准法中所规定的对准不燃材料要求的特性、即在以辐射热强度:50kW/m2加热时从加热开始后起10分钟内的总发热量为8.0MJ/m2以下的准不燃特性,若对酚醛树脂组合物增加上述公知的阻燃剂的配合量,则会引起下述等问题:阻碍酚醛树脂组合物的固化反应而变得不能得到目标酚醛树脂发泡体,或者所得的酚醛树脂发泡体的导热率等物理或机械特性恶化。
需要说明的是,根据前述建筑基准法的规定(施行令第1条第五号),准不燃材料应满足上述的总发热量,并且最高发热速度不应大于10秒地连续超过200kW/m2,而且不应具有在防火上有害的、贯穿至背面的龟裂及孔,但是迄今为止的配合阻燃剂而成的酚醛树脂发泡体材料既不能确保作为酚醛树脂有用的物理或机械特性又不能充分应对这样的准不燃性能的要求。
尤其,在上述的日本特开昭60-170636号公报中指出通过制成含有红磷而成的酚醛树脂发泡体从而能够制成超过阻燃性的准不燃性等级的发泡体,根据本发明人仔细研究的结果可知,通过该红磷的配合,虽然能够有利地提高酚醛树脂发泡体的阻燃性能,但仍无法满足由日本的建筑基准法规定的对准不燃材料要求的防火性能,进而即使使红磷的配合量更进一步增大,也不能达成其目的。而且可知:若使这样的红磷的配合量增大,则红磷自身也会燃烧,因此还产生阻燃性能反而下降这样的问题。
现有技术文献
专利文献
专利文献1:日本特开平2-49037号公报
专利文献2:日本特开2007-161810号公报
专利文献3:日本特开2007-70511号公报
专利文献4:日本特开昭60-170636号公报
专利文献5:日本特开平8-176343号公报
发明内容
发明要解决的课题
为此,本申请的发明人为了进一步提高酚醛树脂发泡体(该酚醛树脂发泡体是使用作为酚醛树脂之一的Resol型酚醛树脂,并对其组合酸固化剂、发泡剂等而构成发泡性酚醛树脂组合物,再使发泡性酚醛树脂组合物发泡、固化而形成的)的阻燃性能或防火性能而进行了深入研究,结果发现通过以作为阻燃剂的红磷粉末作为第一成分,并对其组合包含规定的阻燃剂的第二成分而构成阻燃剂组合物,使该阻燃剂组合物存在于酚醛树脂组合物中,从而由该酚醛树脂组合物发泡、固化而形成的酚醛树脂发泡体既能有效确保作为发泡体的低导热率等特性,又能协同提高其阻燃性能或防火性能而有利地形成日本的建筑基准法中规定的准不燃材料,以至完成本发明。
因此,本发明要解决的课题在于提供准不燃性酚醛树脂组合物,其能够有效确保由含有Resol型酚醛树脂作为必须成分的发泡性酚醛树脂组合物得到的发泡体的低导热率特性,又能协同提高阻燃性能或防火性能而有利地形成日本的建筑基准法中规定的准不燃材料,另外,还在于使用这样的准不燃性酚醛树脂组合物而有利地得到具有该建筑基准法中所规定的准不燃特性的材料。
用于解决课题的手段
为了解决如上所述的课题,本发明的主旨在于准不燃性酚醛树脂组合物,其特征在于,含有Resol型酚醛树脂、发泡剂及酸固化剂并且组合并含有第一成分和第二成分作为阻燃剂,所述第一成分包含红磷粉末,所述第二成分包含选自由除红磷以外的其他磷系阻燃剂、无机系阻燃剂、卤素系阻燃剂及石墨系阻燃剂组成的组中的至少一种。
需要说明的是,根据该本发明的准不燃性酚醛树脂组合物的优选方式之一,相对于100质量份的前述Resol型酚醛树脂,以前述第一成分和前述第二成分的合计量成为2~35质量份的比例的方式含有前述阻燃剂,另外,相对于100质量份的前述Resol型酚醛树脂,分别以成为1~30质量份及1~10质量份的比例的方式含有构成这样的阻燃剂的第一成分及第二成分。
另外,根据本发明的准不燃性酚醛树脂组合物的另一优选方式,红磷粉末具有由金属的氧化物或氢氧化物和/或热固性树脂形成的表面涂层,由此可有利地形成具有本发明的优选特性的酚醛树脂发泡体。
进而,在本发明中,有利的是,优选使用形成有表面涂层的聚磷酸铵粉末作为前述除红磷以外的其他磷系阻燃剂,因此酚醛树脂组合物的固化反应可有效地进行,从而可更进一步有利地发挥本发明的阻燃性能或防火性能。
需要说明的是,根据该本发明的准不燃性酚醛树脂组合物的另一优选方式,前述聚磷酸铵粉末的表面涂层由难溶性热固性树脂形成。作为这样的难溶性热固性树脂,使用酚醛树脂、三聚氰胺树脂等,其中,优选使用三聚氰胺树脂。
另外,在本发明中,作为发泡剂,优选使用卤代烯烃、或者氯代脂肪族烃和/或脂肪族烃,其中,可有利地使用异戊烷与异丙基氯的混合物。
而且,本发明中所使用的Resol型酚醛树脂优选被调整成于25℃具有2000mPa·s以上的粘度。
而且,在本发明中,其主旨还在于包含使如上述那样的准不燃性酚醛树脂组合物发泡、固化而得的发泡体的准不燃材料。
另外,在这样的准不燃材料中,上述的发泡体通常具有下述特性:在按照ISO-5660中所规定的发热性试验方法而以放射热强度为50kW/m2进行加热时,从加热开始后起10分钟内的总发热量为8.0MJ/m2以下。
发明效果
像这样,在本发明的准不燃性酚醛树脂组合物中,通过并用并含有包含红磷粉末的第一成分和包含选自由除红磷以外的其他磷系阻燃剂、无机系阻燃剂、卤素系阻燃剂及石墨系阻燃剂组成的组中的至少一种的第二成分作为阻燃剂,从而能够利用这两个成分的协同作用来有效地提高使这样的准不燃性酚醛树脂组合物发泡、固化而得到的发泡体材料的阻燃性能或防火性,而且,还可有利地具备作为酚醛树脂发泡体有用的低导热率等特性。
而且,通过使用这样的本发明的准不燃性酚醛树脂组合物,从而可容易且有利地实现作为日本的建筑基准法中所规定的准不燃材料的酚醛树脂发泡体材料。
具体实施方式
如上所述,有利的是,本发明中所使用的Resol型酚醛树脂优选通过下述方式来制造:相对于酚类1摩尔,以1.0~3.0摩尔左右的比例、优选1.5~2.5摩尔左右的比例使用醛类,使它们在碱性反应催化剂的存在下且在例如50℃~回流温度的范围内的温度下反应后,实施中和处理,接着,在减压下进行脱水浓缩以达到规定的特性值、例如于25℃的粘度为2000mPa·s以上且水分含量为3~20质量%、优选为5~18质量%,然后,根据需要与以往同样地添加规定的添加物。
当然,除这样制造的Resol型酚醛树脂外,在本发明中也可采用通过酸固化剂固化而得到的、已知的各种Resol型酚醛树脂,进而,即使是通过适当的改性剂改性得到的Resol型酚醛树脂也同样可以使用。
而且,由此得到的Resol型酚醛树脂于25℃具有2000mPa·s以上、优选为2000~100000mPa·s、更优选为3000~80000mPa·s、进一步优选为4000~30000mPa·s的粘度,从而可更有效地实现目标树脂组合物的制备、尤其是可更有效地实现红磷粉末的分散、含有,而且可有利地提高其分散状态的稳定性,因此可实现阻燃性以及低导热率的更进一步的提高。需要说明的是,若该Resol型酚醛树脂的粘度小于2000mPa·s,则红磷粉末的沉降变得显著而引起其局部存在化,使所形成的酚醛树脂发泡体中产生不均而不能得到充分的阻燃性、低导热率,另外,相反地,若粘度变得过高、例如大于100000mPa·s,则引起难以得到目标酚醛树脂发泡体的问题。
但是,就作为上述本发明中所使用的Resol型酚醛树脂的原料之一的酚类而言,可列举苯酚、邻甲酚、间甲酚、对甲酚、对叔丁基苯酚、间二甲苯酚、双酚F、双酚A等,另外,就与上述酚类组合使用的、作为另一原料的醛类而言,可列举甲醛、多聚甲醛、三噁烷、聚甲醛、乙二醛等。进而,作为反应催化剂,可列举氢氧化钾、氢氧化钠、氢氧化钡、氢氧化钙、碳酸钾、氨等。当然,这些酚类、醛类及反应催化剂均决非限于上例,也可适当使用已知的各种的酚类、醛类及反应催化剂,另外,它们可以分别单独使用或者组和使用2种以上。
而且,在本发明中,如上述那样,通过与Resol型酚醛树脂一同使用规定的发泡剂(从一直以来已知的各种发泡剂中适当选择),由此构成酚醛树脂发泡体制造用的酚醛树脂组合物,但作为这样的发泡剂,有利的是使用全球变暖系数低的、氯代脂肪族烃和/或脂肪族烃、卤代烯烃。需要说明的是,尤其通过使用氯代脂肪族烃、卤代烯烃,从而发挥可更进一步提高由本发明的酚醛树脂组合物形成的发泡体的准不燃特性、低导热率的特征。
作为发泡剂的氯代脂肪族烃通常优选使用碳原子数为2~5个左右的直链状、支链状的脂肪族烃的氯化物,作为其氯原子的键合数,通常为1~4个左右。作为这样的氯代脂肪族烃的具体例,可列举二氯乙烷、丙基氯、异丙基氯、丁基氯、异丁基氯、戊基氯、异戊基氯等。它们可以单独使用1种,也可以组合2种以上,其中,优选丙基氯、异丙基氯等氯丙烷类,特别优选使用异丙基氯。
另外,在作为发泡剂的脂肪族烃中,可以适当选择使用一直以来已知的、碳原子数为3~7个左右的烃系发泡剂,具体而言,可列举丙烷、丁烷、戊烷、异戊烷、己烷、异己烷、新己烷、庚烷、异庚烷、环戊烷等,可以从它们当中使用1种或组合使用2种以上。
进而,在本发明中,还优选使用将上述的氯代脂肪族烃与脂肪族烃组合而成的混合发泡剂,作为其混合比率,可有利地采用按质量比计脂肪族烃:氯代脂肪族烃=25:75~5:95的范围内的混合比率。需要说明的是,作为这样的2种发泡剂的组合,推荐异戊烷与异丙基氯的组合,由此可更进一步有利地达成本发明的目的。
而且,在本发明中,还有利地使用卤代烯烃作为发泡剂,由此能够有助于更进一步提高所得酚醛树脂发泡体的特性、尤其是阻燃性或防火特性、低导热率。发挥这样特性的卤代烯烃(halogenated alkene)也包括被称为卤代链烯烃(halogenated olefin)、卤代氢烯烃(halogenated hydroolefin)的物质,通常为键合并含有作为卤素的氯、氟而成的碳原子数为2~6个左右的不饱和烃衍生物,例如在具有3~6个氟取代基的丙烯、丁烯、戊烯及己烯中取代并含有卤素、例如氟、氯而成的、四氟丙烯、氟氯丙烯、三氟单氯丙烯、五氟丙烯、氟氯丁烯、六氟丁烯、它们中的2种以上的混合物。
具体而言,就作为该卤代烯烃(卤代链烯烃)之一的氢氟烯烃(HFO)而言,可列举例如:1,2,3,3,3-五氟丙烯(HFO1225ye)等五氟丙烯;1,3,3,3-四氟丙烯(HFO1234ze)、2,3,3,3-四氟丙烯(HFO1234yf)、1,2,3,3-四氟丙烯(HFO1234ye)等四氟丙烯;3,3,3-三氟丙烯(HFO1243zf)等三氟丙烯;四氟丁烯异构体(HFO1354)类、五氟丁烯异构体(HFO1345)类、1,1,1,4,4,4-六氟-2-丁烯(HFO1336mzz)等六氟丁烯异构体(HFO1336)类、七氟丁烯异构体(HFO1327)类、七氟戊烯异构体(HFO1447)类、八氟戊烯异构体(HFO1438)类、九氟戊烯异构体(HFO1429)类等。另外,作为氢氯氟烯烃(HCFO),可列举1-氯-3,3,3-三氟丙烯(HCFO-1233zd)、2-氯-3,3,3-三氟丙烯(HCFO-1233xf)、二氯三氟丙烯(HCFO1223)、1-氯-2,3,3-三氟丙烯(HCFO-1233yd)、1-氯-1,3,3-三氟丙烯(HCFO-1233zb)、2-氯-1,3,3-三氟丙烯(HCFO-1233xe)、2-氯-2,2,3-三氟丙烯(HCFO-1233xc)、3-氯-1,2,3-三氟丙烯(HCFO-1233ye)、3-氯-1,1,2-三氟丙烯(HCFO-1233yc)等。
而且,本发明的酚醛树脂组合物中所含有的发泡剂、即如上所述的各发泡剂按其合计量计以相对于Resol型酚醛树脂100质量份而言通常为1~30质量份、优选为5~25质量份的比例来使用。
需要说明的是,在本发明中所使用的发泡剂中推荐如上述那样包含氯代脂肪族烃和/或脂肪族烃、或者卤代烯烃,但并不限定于此,只要不对本发明的目的带来不良影响,还能以适当的比例含有例如1,1,1,3,3-五氟丁烷等氟代烃(代替氟利昂)、三氯一氟甲烷、三氯三氟乙烷等氯氟代烃、水、异丙基醚等醚化合物、氮气、氩气、二氧化碳气体等气体以及空气等。
另外,如上所述,本发明中所使用的酸固化剂是用于促进Resol型酚醛树脂的固化反应的成分(固化催化剂),可适当选择并使用一直以来已知的酸固化剂。而且,作为这种酸固化剂,可列举例如:苯磺酸、苯酚磺酸、甲酚磺酸、甲苯磺酸、二甲苯磺酸、萘磺酸等芳香族磺酸;甲磺酸、三氟甲磺酸等脂肪族磺酸;硫酸、磷酸、聚磷酸、氢氟硼酸等无机酸等。它们可以单独使用,另外,也可以组合使用2种以上,均没有问题。需要说明的是,在这些例示的酸固化剂中,苯酚磺酸、甲苯磺酸、萘磺酸等芳香族磺酸在制造酚醛树脂发泡体时能够实现适度的固化速度,因此Resol型酚醛树脂的固化与基于发泡剂的发泡的均衡性变得更为良好,因此可实现期望的发泡结构,因而特别优选使用。其中,在本发明中推荐并用对甲苯磺酸和二甲苯磺酸,作为它们的使用比例,按质量基准计,优选对甲苯磺酸的使用量多于二甲苯磺酸的使用量。具体而言,可有利地采用按质量比计对甲苯磺酸:二甲苯磺酸为51:49~95:5的范围内的使用比例。
进而,作为上述酸固化剂的使用量,可根据其种类、与前述Resol型酚醛树脂混合时的温度条件等来适当设定,而在本发明中,优选的是:相对于Resol型酚醛树脂100质量份而言,通常为1~50质量份,优选为5~30质量份,特别优选为7~25质量份。其使用量小于1质量份时,固化的进行迟缓,相反,若大于50质量份,则固化速度变得过快,导致难以有利地得到目标酚醛树脂发泡体的问题。
而且,根据本发明,在添加并含有上述必须成分而成的酚醛树脂发泡体制造用的酚醛树脂组合物中,为了既能对由该酚醛树脂组合物形成的酚醛树脂发泡体有效地赋予准不燃性的阻燃特性,又能抑制或阻止导热率的上升、进而有利地确保由酚醛树脂形成的发泡体特性,而与包含红磷粉末的第一成分同时组合并配合包含选自由除红磷以外的其他磷系阻燃剂、无机系阻燃剂、卤素系阻燃剂及石墨系阻燃剂组成的组中的至少一种的第二成分作为阻燃剂,并使包含这两种成分的阻燃剂分散并含有在酚醛树脂组合物中。
需要说明的是,就此处所使用的作为阻燃剂的第一成分的红磷粉末而言,已知的红磷粉末均可作为其对象,通常从市售品中适当选择使用。可列举例如以磷化学工业株式会社制的“NOVARED”,“NOVAEXCEL”、日本化学工业株式会社制的“HISHIGUARD”、Clariant公司制的“EXOLIT”等名称所出售的产品。其中,就上述红磷粉末而言,在提高下述处理性或操作性、并且提高在树脂组合物中的分散性、有利地提高其添加效果方面,优选在其表面形成有涂层,具体而言,在粒子表面形成基于包含氢氧化铝、氢氧化镁、氢氧化锌、氢氧化钛等金属氢氧化物、氧化铝、氧化镁、氧化锌、氧化钛等金属氧化物的无机化合物、和/或酚醛树脂、呋喃树脂、二甲苯-甲醛树脂等热固性树脂的被覆层而成的红磷粉末可被有利地使用。需要说明的是,通常,相对于红磷100质量份,以1~30质量份左右的比例形成该被覆层。
另外,作为这样的红磷粉末的使用量,可在相对于Resol型酚醛树脂100质量份而言通常为1~30质量份、优选为1~25质量份、进一步优选为2~20质量份的范围内确定。这是由于,若该红磷粉末的使用量变得过少,则难以充分发挥对酚醛树脂发泡体的阻燃性能或防火性能的赋予效果,另外,若其使用量变得过多,则反而变得容易燃烧而阻燃性能或防火性能降低,并且使导热率恶化、或使添加有其的组合物的粘度上升、引起搅拌不良等问题,而且还会引起难以维持中长期内的低导热率等问题。
进而,该红磷粉末的平均粒径通常为1~100μm左右,优选为5~50μm左右。若该红磷粉末的粒径变得过小,则引起其处理性变得困难、难以在树脂组合物中均匀分散等问题,另外,即使其粒径变得过大,也难以得到在树脂组合物中的均匀分散效果,因此引起不能充分达成本发明目的的问题。
另一方面,在本发明中,作为阻燃剂的第二成分使用的、除红磷以外的其他磷系阻燃剂、无机系阻燃剂、卤素系阻燃剂及石墨系阻燃剂均可从已知的物质中适当选择,例如,作为除红磷以外的其他磷系阻燃剂,可使用各种磷酸及其盐、苯膦酸、苯次膦酸、磷酸胍衍生物、磷酸氨基甲酸酯衍生物、芳香族磷酸酯、芳香族缩合磷酸酯、卤代磷酸酯、磷酸铵、聚磷酸铵、具有表面涂层的聚磷酸铵等。其中,就聚磷酸铵的粉末而言,若其使用量相对于100质量份的Resol型酚醛树脂而言为数质量份以上,则阻碍酚醛树脂组合物的固化反应,因此通常需要控制在1~3质量份左右的比例,通过使用在聚磷酸铵粉末的表面形成规定的涂层而成的聚磷酸铵粉末,从而有利地消除这样的问题,由此既能有效地进行酚醛树脂组合物的固化反应,又能形成可有利地发挥优异的阻燃特性、压缩强度、隔热性能等特性的酚醛树脂发泡体。
需要说明的是,作为该有利地使用的具有表面涂层的聚磷酸铵粉末,可列举将聚磷酸铵的粒子用热固性树脂被覆或微囊化而成的聚磷酸铵粉末、用三聚氰胺单体、其他含氮有机化合物等被覆聚磷酸铵粒子的表面而成的聚磷酸铵粉末、进行了表面活性剂、硅处理的聚磷酸铵粉末等,通常可从市售品中适当选择使用。可列举例如;能够从ClariantChemicals株式会社获得的Exolit AP462;能够从CBC株式会社获得的FR CROS486、FRCROS487、TERRAJU C30、TERRAJU C60、TERRAJU C70、TERRAJU C80等。另外,这样的聚磷酸铵粉末中的表面涂层优选对呈液状的酚醛树脂组合物具有难溶性、尤其对水具有难溶性,其中,作为这样的难溶性热固性树脂,可使用酚醛树脂、三聚氰胺树脂等,尤其优选使用三聚氰胺树脂。另外,即使是易溶性的热固性树脂,通过使由其形成的表面涂层进行固化反应而制成难溶性的表面涂层,从而也可被有利地使用。而且,通过具有由这样的难溶性的热固性树脂形成的表面涂层,从而能够有利地得到具有压缩强度、隔热性能等优异的特性的酚醛树脂发泡体。
另外,作为无机系阻燃剂,可列举例如:氢氧化铝、氢氧化镁等金属氢氧化物;碳酸钙、碳酸镁、碳酸钡等金属碳酸盐;氧化钙、氧化镁、氧化铝、氧化锌等金属氧化物;硼酸锌、锡酸锌、碳酸锌等无机酸的锌盐;三氧化锑、五氧化锑等锑化合物;锌末等金属粉;硼砂、硼酸、硫酸铵等。尤其可利地使用硼酸锌、锡酸锌等锌盐。
进而,作为卤素系阻燃剂,可有利地使用氯乙烯树脂粉末、聚溴乙烯粉末、四氯双酚A、四溴化双酚A、十溴二苯基醚等的粉末,另外,作为石墨系阻燃剂,优选使用天然及人工的各种石墨类,尤其优选使用膨胀性石墨的粉末。
而且,在本发明中,如上述那样包含选自除红磷以外的其他磷系阻燃剂、无机系阻燃剂、卤素系阻燃剂及石墨系阻燃剂中的1种或多种构成阻燃剂的第二成分,相对于100质量份的Resol型酚醛树脂,以按合计量计为1~10质量份的比例、优选为8质量份以下的比例含有这样的第二成分。需要说明的是,若这样的第二成分的含量变得过少,则有可能难以充分发挥由与第一成分(红磷粉末)的并用带来的阻燃性能或防火性能的协同提高效果,另外,若其含量变得过多,则会引起使最终所得的酚醛树脂发泡体的特性降低、或阻碍酚醛树脂组合物的发泡固化反应等问题。
另外,构成本发明的酚醛树脂组合物中所含有的阻燃剂的、第一成分和第二成分的合计量根据对使这样的酚醛树脂组合物发泡、固化而得到的酚醛树脂发泡体所要求的阻燃特性或防火特性进行适当选定,通常,相对于100质量份的Resol型酚醛树脂,以2~35质量份左右、优选为3~30质量份左右、更优选为5~20质量份左右的范围内适当确定。需要说明的是,这是由于:若这些第一成分和第二成分的合计含量变得过少,则难以达成充分的阻燃特性或防火特性的提高效果,另外,若其含量变得过多,则引起阻碍酚醛树脂组合物的发泡固化反应或使所得的酚醛树脂发泡体的低导热率等特性降低等问题。
但是,在本发明的准不燃性酚醛树脂组合物中,可以如上所述与Resol型酚醛树脂同时添加并配合发泡剂及酸固化剂、以及作为阻燃剂的、特定的第一成分与第二成分的组合作为必须成分,此外,可以根据需要还含有一直以来已知的整泡剂、增塑剂、尿素以及本发明中所规定的除第一成分及第二成分以外的其他阻燃剂等。
此处,在根据需要添加并含有的上述添加剂中,整泡剂是为了实现酚醛树脂组合物中的混合成分的混合、乳化的辅助、产生气体的分散、泡沫孔膜(foam cell film)的稳定化等而配合的物质。而且,作为上述整泡剂,并无特别限定,一直以来在该技术领域中所使用的各种整泡剂均可被选择使用,其中,特别优选使用聚硅氧烷系化合物、聚氧乙烯山梨糖醇酐脂肪酸酯、烷基苯酚环氧乙烷加成物、蓖麻油的环氧乙烷加成物等非离子系表面活性剂。需要说明的是,这些整泡剂除可单独使用还可组合使用它们中的2种以上。另外,关于其使用量,也并无特别限制,通常在相对于Resol型酚醛树脂100质量份而言为0.5~10质量份的范围内使用。
另外,增塑剂是为了对酚醛树脂发泡体的气泡壁赋予柔软性、抑制隔热性能的经时性劣化而有利地添加的物质,与采用作为阻燃剂的第一成分及第二成分同样地,可以有利地有助于实现本发明的目的。作为该增塑剂,并无特别限制,可使用一直以来用于制造酚醛树脂发泡体的已知的增塑剂,例如磷酸三苯酯、对苯二甲酸二甲酯、间苯二甲酸二甲酯等,而且聚酯多元醇的使用也是有效的。特别是,聚酯多元醇具有包含亲水性且表面活性优异的酯键和羟基的结构,因此与亲水性的酚醛树脂液体的相容性良好,能够与酚醛树脂均匀地混合。另外,通过使用该聚酯多元醇,从而避免气泡的偏在,使气泡均匀地分布于发泡体整体,容易生成品质也均质的酚醛树脂发泡体(酚醛树脂发泡体),可以称得上优异的增塑剂。需要说明的是,这样的增塑剂相对于Resol型酚醛树脂100质量份而言通常以0.1~20质量份、优选0.5~15质量份、更优选1~12质量份的范围来使用,由此,能够在不损害所得酚醛树脂发泡体的其他性能的情况下良好地发挥对气泡壁赋予柔软性的效果,可更进一步良好地达成本发明的目的。
进而,在根据本发明而构成的准不燃性酚醛树脂组合物中优选添加并含有尿素。通过含有这样的尿素,从而能够有效地降低所得酚醛树脂发泡体的初始导热率,进而能够得到强度、尤其是低脆性的酚醛树脂发泡体,还有利地有助于将其中长期内的导热率维持得较低,因此容易得到长期稳定地具有优异隔热性能的酚醛树脂发泡体。
但是,含有如上所述的配合成分的、本发明的准不燃性酚醛树脂组合物例如可通过以下方式来制备:与前述的Resol型酚醛树脂组合前述的作为阻燃剂的特定的第一成分和第二成分并进行混合,再根据需要添加前述的整泡剂、以及增塑剂、尿素等并混合,然后向所得的混合物中添加例如前述的氯代脂肪族烃和/或脂肪族烃、或者卤代烯烃作为发泡剂,之后将其与酸固化剂一起供给至混合机中,进行搅拌。
另外,作为使用如此制备的酚醛树脂组合物而形成目标酚醛树脂发泡体的方法,可采用一直以来已知的各种方法,可列举例如:(1)使树脂组合物流出到环形传送带上而使其发泡、固化的成型方法;(2)定点填充并使其局部发泡、固化的方法;(3)填充到模具内并在加压状态下使其发泡、固化的方法;(4)填充到规定大的空间内而使其发泡、固化,从而形成发泡体块的方法;(5)一边压入到空洞中一边使其填充发泡的方法。
而且,在上述这些成型方法中,根据上述(1)的成型方法,可采用如下方法:将如前所述的酚醛树脂组合物排出到连续移动的载体上,该排出物经过加热区域而发泡并成型,从而制作所期望的酚醛树脂发泡体。具体而言,将前述酚醛树脂组合物排出到传送带上的面材上,然后将面材载置于该传送带上的树脂材料的上表面,移动至固化炉,然后,在固化炉中从上方用其他传送带按压,将该树脂材料调整为规定厚度,在60~100℃左右、2~15分钟左右的条件下使其发泡固化,然后,将从固化炉取出的发泡体切断成规定长度,由此制作目标形状的酚醛树脂发泡体。
需要说明的是,作为此处所使用的面材,并无特别限制,通常使用天然纤维、聚酯纤维、聚乙烯纤维等合成纤维、玻璃纤维等无机纤维等的无纺布、纸类、覆铝箔无纺布、金属板、金属箔等,通常优选使用玻璃纤维无纺布、纺粘无纺布、覆铝箔无纺布、金属板、金属箔、胶合板、结构用面板、刨花板、硬质纤维板、木质系水泥板、柔性板、珍珠岩板、硅酸钙板、碳酸镁板、纸浆水泥板、护套板、中密度纤维板、石膏板、板条板、火山玻璃质复合板、天然石、砖、瓦、玻璃成型体、轻量气泡混凝土成型体、水泥砂浆成型体、玻璃纤维增强水泥成型体等以水固化性水泥水合物作为粘合剂成分的成型体。而且,该面材可以设置于酚醛树脂发泡体的一面,也可以设置于两面,均没有问题。另外,在设置于两面的情况下,面材可以相同,也可以不同。进而,也可以是从后面使用粘接剂贴合面材而形成的面材,均没有问题。
这样,在由此得到的酚醛树脂发泡体中,同时分散并含有包含红磷粉末的第一成分和包含选自由除红磷以外的其他磷系阻燃剂、无机系阻燃剂、卤素系阻燃剂和石墨系阻燃剂中的至少一种的第二成分作为阻燃剂,因此可协同提高作为发泡体整体的阻燃特性或防火特性,在利用锥形量热仪的发热性试验中,可以有利地具备作为日本的建筑基准法中规定的准不燃材料的特性。具体而言,成为有利地具备在依据ISO-5660中所规定的发热性试验方法而以放射热强度:50kW/m2进行加热时从加热开始至经过10分钟为止的总发热量为8.0MJ/m2以下的特性的阻燃性材料,由此可作为准不燃材料而有利地用于各种用途中。
另外,有利的是,这样的酚醛树脂发泡体材料可被易于制造成具有通常为0.0230W/m·K(20℃)以下、优选为0.0200W/m·K(20℃)以下、进一步优选为0.0195W/m·K(20℃)以下的低导热率的发泡体,而且被构成为其独立气泡率通常为85%以上、优选为90%以上,由此被制造成在有利地发挥优异的准不燃特性同时还有利地发挥优异的低导热率特性等发泡体特性的发泡体。
进而,在根据本发明而得的酚醛树脂发泡体中,其密度为10~150kg/m3,优选为15~100kg/m3,更优选为15~70kg/m3,进一步优选为20~50kg/m3,最优选为20~40kg/m3。需要说明的是,密度低于10kg/m3的酚醛树脂发泡体的强度低,在搬运或施工时泡沫(发泡体)有可能破损。另外,若密度低,则具有使气泡膜变薄的倾向。而且,若气泡膜薄,则泡沫(发泡体)中的发泡剂容易与空气置换或在发泡时气泡膜容易破裂,因此具有难以得到高独立气泡结构、长期的隔热性能下降的倾向。另一方面,若密度大于150kg/m3,则来自以酚醛树脂为代表的固体成分的固体的热传导变大,因此具有酚醛树脂发泡体的隔热性能下降的倾向。
实施例
以下,示出若干本发明的实施例,通过与比较例进行对比,从而更具体明确本发明的特征,但本发明并不受这些实施例的记载的任何限制,这是不言而喻的。另外,本发明应理解为除了以下实施例以外,进而除了上述具体描述以外,还可以在不脱离本发明主旨的情况下,基于本领域技术人员的知识进行各种变更、修改、改良等。需要说明的是,只要没有特别说明,以下所示的百分率(%)及份均是按质量基准来表示。
-实施例1-
向具备回流器、温度计及搅拌机的三口反应烧瓶内,投入苯酚1600份、47%福尔马林2282份及50%氢氧化钠水溶液41.6份,使其在80℃的温度下反应70分钟。接着,冷却至40℃后,用50%对甲苯磺酸水溶液进行中和,然后在减压·加热条件下脱水浓缩直至水分率为10%为止,由此得到液状的Resol型酚醛树脂。该所得的酚醛树脂具有粘度为10000mPa·s/25℃、数均分子量为380、游离苯酚含量为4.0%的特性。
然后,向该所得的液状Resol型酚醛树脂100份中加入作为整泡剂的蓖麻油环氧乙烷加成物(加成摩尔数22)3份及作为添加剂的尿素5份,进行混合,得到均匀的酚醛树脂混合物。
接着,相对于该所得的酚醛树脂混合物108份,搅拌并混合作为阻燃剂的第一成分即表面涂布红磷粉末(磷化学工业株式会社制NOVAEXCEL140,平均粒径:25~35μm,表面涂布处理)5份及作为第二成分的聚磷酸铵粉末(CBC株式会社出售的FR CROS484,平均粒径:18μm)1份、作为发泡剂的以异丙基氯:异戊烷=85:15的质量比例形成的混合物9份、作为固化剂的对甲苯磺酸:二甲苯磺酸=2:1(质量比)的混合物16份,由此制备酚醛树脂发泡体制造用的酚醛树脂组合物。
然后,使用这样制备的发泡性酚醛树脂组合物,将其注入至预先加热至70~75℃的长度为300mm、宽度为300mm、厚度为50mm的模具框内后,将该模具框收纳于70~75℃的干燥机中,使其发泡固化10分钟,再以70℃的温度在加热炉内加热12小时,由此使其后固化,制作酚醛树脂发泡体(酚醛泡沫)。
-实施例2~4-
除了将实施例1中阻燃剂的第一成分即表面涂布红磷粉末和第二成分即表面涂布聚磷酸铵(CBC株式会社出售的TERRAJUC80,平均粒径:19μm)分别设为下述表1所示的添加量以外,与实施例1同样地分别制作各种酚醛树脂发泡体。
-实施例5~10-
除了将实施例1中阻燃剂的第一成分即表面涂布红磷粉末的添加量和第二成分即硼酸锌、锡酸锌、氢氧化铝、聚氯乙烯粉末、四溴化双酚A或膨胀性石墨的添加量分别设为下述表1所示的比例以外,与实施例1同样地分别制作各种酚醛树脂发泡体。
-实施例11-
将实施例2中的发泡剂变更为氢氟烯烃(1,1,1,4,4,4-六氟-2-丁烯:HFO-1336mzz,Chemours公司制品),并且将其添加量设为17.5份以外,与实施例2同样地制作酚醛树脂发泡体。
-比较例1-
除了完全不添加实施例1中作为阻燃剂的第一成分及第二成分以外,与实施例1同样地得到酚醛树脂发泡体。
-比较例2~5-
在实施例1中仅使用表面涂布红磷粉末作为阻燃剂,并且将其添加量设为下述表2所示的比例,除此以外,与实施例1同样地分别制作各种酚醛树脂发泡体。
-比较例6~20-
在实施例1中不添加第一成分即表面涂布红磷粉末而仅使用作为第二成分的FRCROS484、TERRAJUC80、硼酸锌、锡酸锌、氢氧化铝、聚氯乙烯粉末、四溴化双酚A或膨胀性石墨作为阻燃剂,并且将其添加量设为下述表2及表3所示的比例,除此以外,与实施例1同样地尝试制作各种酚醛树脂发泡体。然而,在比较例6、8、10及12中,酚醛树脂组合物未充分进行固化反应,无法得到能够进行物性测定的发泡体。
接着,使用这样得到的各种酚醛树脂发泡体(酚醛泡沫),针对其密度、吸水量、初始导热率、独立气泡率、压缩强度及用于评价准不燃性的燃烧试验(总发热量、最大发热速度、试验后的状况),分别按照以下的方法进行测定或评价,并将它们所得的结果示于下述表1~表3及表4~表6中。
(1)密度的测定
按照JIS-A-9511(2003)中的“5.6密度”的记载,测定各个发泡体的密度。
(2)吸水量的测定
按照JIS A9511:2006R中的“5.14(测定方法A)”进行了测定。
(3)初始导热率的测定
使用300mm见方的酚醛树脂发泡体样品,将其切割成200mm见方(厚度为50mm)后,设定于低温板温度为10℃、高温板温度为30℃,按照JIS-A-1412-2(1999)中规定的“热流计法”,使用导热率测定装置:HC-074 304(英弘精机株式会社制)进行测定。需要说明的是,此处的测定中,将酚醛树脂发泡体样品在70℃的气氛下放置4天后的导热率作为初始导热率。
(4)独立气泡率的测定
按照ASTM-D2856的规定,测定酚醛树脂发泡体样品的独立气泡率。
(5)压缩强度的测定
按照JIS-A-9511(2003)中的“5.9压缩强度”的记载,测定了酚醛树脂发泡体样品的压缩强度。
(6)燃烧试验(准不燃性评价)
从各酚醛树脂发泡体按照长×宽的尺寸分别成为99±1mm的方式切割试验体,准备各个试验体。需要说明的是,该试验体的厚度设为50mm。接着,针对这些试验体,使用锥形量热计(株式会社东洋精机制作所制CONE III),按照依据ISO-5660的规定的财团法人日本建筑综合试验所编“防耐火性能试验·评价业务方法书4.12.1发热性试验·评价方法”,分别测定加热时间为10分钟内的总发热量及最大发热速度。作为测定结果,对从各个发泡体切割出的3个试验体进行测定,采用该所得的测定值的平均值。另外,对评价试验后的试验体进行观察,调查有无贯穿至背面的裂纹、孔。
[表1]
[表2]
[表3]
[表4]
[表5]
[表6]
由上述表1及表4的结果可知:在实施例1~11中形成的酚醛树脂发泡体均是在燃烧试验(10分钟)中总发热量为8MJ/m2以下、且最大发热速度也为规定值以下,因此确认是作为日本的建筑基准法中所规定的准不燃材料有用的发泡体。而且,这些实施例中所得的酚醛树脂发泡体具有低初始导热率,并且压缩强度也充分,确认为隔热性优异并且物理物性或机械物性也优异的发泡体。
与此相对,比较例1为未添加阻燃剂的情况,另外,比较例2~20为使只有第一成分作为阻燃剂的使用量或仅有第二成分作为阻燃剂的使用量增大的情况,此处所得的酚醛树脂发泡体均是总发热量大于8MJ/m2的发泡体,被确认为不满足日本的建筑基准法中所规定的准不燃材料的标准。另外,在比较例6、8、10及12中,由于作为阻燃剂的第二成分的使用量变得过多,因此酚醛树脂组合物未顺利地进行固化反应,因而可知无法得到能够进行物性测定的发泡体。
-阻燃剂分散稳定性试验-
使用与实施例1同样得到的Resol型酚醛树脂,向其中适当添加水,制作具有下述表7所示粘度的各种Resol型酚醛树脂。此处,各Resol型酚醛树脂的粘度按照JIS-K-7117-1而使用Brookfield型旋转粘度计于试验温度为25℃进行测定。接着,将这些Resol型酚醛树脂各100份与实施例中使用的阻燃剂即红磷粉末5份及硼酸锌5份混合后,收纳于容量为110ml、主体直径为40mm的玻璃制螺纹管瓶中,在室温下静置1周,评价有无在该螺纹管瓶中产生沉淀物及沉淀层的高度。需要说明的是,在该评价时,将不能观察沉淀物的情况评价为○,将沉淀层的高度为5mm以下的情况评价为△,将沉淀层的高度大于5mm的情况评价为×,将其结果示于下述表7中。
[表7]
如上述表7所示,在Resol型酚醛树脂的粘度为1000mPa·s(25℃)的情况下,因与红磷粉末及硼酸锌混合而引起显著的沉淀,确认到产生高度高的沉淀层。与此相对,在具有3000mPa·s(25℃)以上的粘度的Resol型酚醛树脂中,即使将红磷粉末及硼酸锌混合,也未确认到该沉淀物的产生,因此也未确认到沉淀层的存在。另外,在Resol型酚醛树脂的粘度为2000mPa·s(25℃)的情况下,能够确认到因红磷粉末及硼酸锌的混合而存在某种程度的沉淀物,但判断其是在实用上没有问题的程度。
Claims (7)
1.准不燃性酚醛树脂组合物,其特征在于,含有Resol型酚醛树脂、发泡剂及酸固化剂并且组合并含有第一成分和第二成分作为阻燃剂,所述第一成分包含红磷粉末,所述第二成分为具有由难溶性热固性树脂形成的表面涂层的聚磷酸铵粉末,其中,相对于100质量份的所述Resol型酚醛树脂,以5~25质量份的比例含有所述红磷粉末,以1~5质量份的比例含有所述第二成分。
2.根据权利要求1所述的准不燃性酚醛树脂组合物,其特征在于,所述红磷粉末具有由金属的氧化物或氢氧化物和/或热固性树脂形成的表面涂层。
3.根据权利要求1或2所述的准不燃性酚醛树脂组合物,其含有卤代烯烃、或者氯代脂肪族烃和/或脂肪族烃作为所述发泡剂。
4.根据权利要求1或2所述的准不燃性酚醛树脂组合物,其中,所述发泡剂为异戊烷与异丙基氯的混合物。
5.根据权利要求1或2所述的准不燃性酚醛树脂组合物,其特征在于,所述Resol型酚醛树脂被调整成于25℃具有2000mPa·s以上的粘度。
6.准不燃材料,其包含使权利要求1~5中任一项所述的准不燃性酚醛树脂组合物发泡并固化而得的发泡体。
7.根据权利要求6所述的准不燃材料,其特征在于,在按照ISO-5660中规定的发热性试验方法并以放射热强度为50kW/m2进行加热时,所述发泡体从加热开始起10分钟内的总发热量为8.0MJ/m2以下。
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KR20210076898A (ko) | 2021-06-24 |
JPWO2020080148A1 (ja) | 2021-09-16 |
KR102469128B1 (ko) | 2022-11-21 |
EP3868826A4 (en) | 2022-06-22 |
WO2020080148A1 (ja) | 2020-04-23 |
EP3868826A1 (en) | 2021-08-25 |
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KR20220108829A (ko) | 2022-08-03 |
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