WO2024055238A1 - Method for producing phenylphosphonic acid zinc salt, powder of phenylphosphonic acid zinc salt, use of the same as crystal nucleating agent, and moisture-curable hotmelt urethane resin adhesive - Google Patents
Method for producing phenylphosphonic acid zinc salt, powder of phenylphosphonic acid zinc salt, use of the same as crystal nucleating agent, and moisture-curable hotmelt urethane resin adhesive Download PDFInfo
- Publication number
- WO2024055238A1 WO2024055238A1 PCT/CN2022/119019 CN2022119019W WO2024055238A1 WO 2024055238 A1 WO2024055238 A1 WO 2024055238A1 CN 2022119019 W CN2022119019 W CN 2022119019W WO 2024055238 A1 WO2024055238 A1 WO 2024055238A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phenylphosphonic acid
- zinc salt
- moisture
- acid zinc
- urethane resin
- Prior art date
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- WQJURGLUMGXTAR-UHFFFAOYSA-N phenylphosphonic acid;zinc Chemical compound [Zn].OP(O)(=O)C1=CC=CC=C1 WQJURGLUMGXTAR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims description 42
- 239000012943 hotmelt Substances 0.000 title claims description 36
- 239000000843 powder Substances 0.000 title claims description 33
- 239000000853 adhesive Substances 0.000 title claims description 31
- 230000001070 adhesive effect Effects 0.000 title claims description 31
- 239000003484 crystal nucleating agent Substances 0.000 title claims description 16
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical group 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 description 69
- 150000003077 polyols Chemical class 0.000 description 56
- -1 phenylphosphonic acid compound Chemical class 0.000 description 39
- 239000002253 acid Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 125000003118 aryl group Chemical group 0.000 description 23
- 229920003232 aliphatic polyester Polymers 0.000 description 19
- 125000001931 aliphatic group Chemical group 0.000 description 14
- 229920005906 polyester polyol Polymers 0.000 description 14
- 238000007711 solidification Methods 0.000 description 12
- 230000008023 solidification Effects 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 239000005056 polyisocyanate Substances 0.000 description 8
- 229920001228 polyisocyanate Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000011094 fiberboard Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical compound OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 description 1
- TZAYDOFUGNDAOB-UHFFFAOYSA-N decane-1,10-diol;dodecane-1,12-diol Chemical compound OCCCCCCCCCCO.OCCCCCCCCCCCCO TZAYDOFUGNDAOB-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3834—Aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
Abstract
A method for producing a phenylphosphonic acid zinc salt includes a step of reacting a phenylphosphonic acid represented by Formula (1) and a zinc compound with each other in the presence of polyethylene glycol in water:
Description
The present disclosure relates to a method for producing a phenylphosphonic acid zinc salt, powder of a phenylphosphonic acid zinc salt, the use of the same as a crystal nucleating agent, and a moisture-curable hotmelt urethane resin adhesive.
Background Art
Moisture-curable hotmelt urethane resins have excellent adhesiveness and can adjust an adhesion time relatively freely, are thus suitable for adhesives for use in adhesion processing requiring continuous production and forming processing such as sealing work, and are used in a wide variety of fields. However, in wood wrapping applications for decorative sheets, in which initial strength is required, and electric/electronic parts and automotive parts applications, in which continuous production on high-speed lines is required, the problem can arise that the parts are moved to the next process with urethane resin insufficiently cooled and solidified.
To solve the above problem, metal salts of phenylphosphonic acid compounds have been added to urethane resins as crystal nucleating agents to reduce a solidification time. WO 2011/030822, for example, discloses a method for producing a phenylphosphonic acid metal salt that reacts a phenylphosphonic acid compound and a metal salt, a metal oxide, or a metal hydroxide the amount of which exceeds the equivalent of the phenylphosphonic acid compound with each other as a method for producing a phenylphosphonic acid metal salt suitable as a crystal nucleating agent.
Summary of Invention
According to study by the inventors of the present invention, there is room to further reduce the solidification time of the moisture-curable hotmelt urethane resin when the phenylphosphonic acid metal salt is used as the crystal nucleating agent.
Given these circumstances, an object of an aspect of the present invention is to provide a method for producing a phenylphosphonic acid zinc salt that can be suitably used as a crystal nucleating agent that can further reduce the solidification time of a moisture-curable hotmelt urethane resin and powder of the phenylphosphonic acid zinc salt. An object of another aspect of the present invention is to provide a moisture-curable hotmelt urethane resin adhesive with a further reduced solidification time.
The inventors of the present invention have found out that by causing polyethylene glycol to coexist when phenylphosphonic acid and a zinc compound are reacted with each other in water, a phenylphosphonic acid zinc salt and its powder that can be suitably used as a crystal nucleating agent that can further reduce the solidification time of a moisture-curable hotmelt urethane resin can be obtained.
The present invention includes the following aspects.
[1] A method for producing a phenylphosphonic acid zinc salt, the method including a step of reacting a phenylphosphonic acid represented by Formula (1) and a zinc compound with each other in the presence of polyethylene glycol in water:
[2] The method for producing a phenylphosphonic acid zinc salt according to[1] , in which an amount of the zinc compound is 1 mole or less with respect to 1 mole of the phenylphosphonic acid represented by Formula (1) .
[3] Powder of a phenylphosphonic acid zinc salt represented by Formula (2) obtained by the method for producing a phenylphosphonic acid zinc salt according to [1] or [2] .
[4] Use of the powder according to [3] as a crystal nucleating agent.
[5] A moisture-curable hotmelt urethane resin adhesive containing an isocyanate group-terminated urethane prepolymer and the powder according to [3] .
[6] The moisture-curable hotmelt urethane resin adhesive according to [5] , in which a content of the powder is 0.1 to 10%by mass based on an entire amount of the moisture-curable hotmelt urethane resin adhesive.
An aspect of the present invention can provide a method for producing a phenylphosphonic acid zinc salt that can be suitably used as a crystal nucleating agent that can further reduce the solidification time of a moisture-curable hotmelt urethane resin and powder of the phenylphosphonic acid zinc salt. Another aspect of the invention can provide a moisture-curable hotmelt urethane resin adhesive with a further reduced solidification time.
Description of Embodiments
The following describes embodiments of the present invention in detail. An embodiment of the present invention is a method for producing a phenylphosphonic acid zinc salt, the method including a step of reacting a phenylphosphonic acid represented by Formula (1) and a zinc compound with each other in the presence of polyethylene glycol in water (a reaction step) :
In the reaction step, by adding an aqueous solution in which a zinc compound dissolved in water and a solution in which polyethylene glycol is dissolved in a solvent to an aqueous solution in which the phenylphosphonic acid represented by Formula (1) is dissolved in water, the phenylphosphonic acid represented by Formula (1) is reacted with the zinc compound, for example. In this process, the above reaction can be made to proceed by gradually adding an aqueous alkaline solution such as an aqueous sodium hydroxide solution, for example.
The amount of water in the aqueous solution of the phenylphosphonic acid represented by Formula (1) may be 1,000 parts by mass or more, 2,000 parts by mass or more, or 3,000 parts by mass or more and 10,000 parts by mass or less, 7,000 parts by mass or less, or 5,000 parts by mass or less with respect to 100 parts by mass of the phenylphosphonic acid represented by Formula (1) .
The zinc compound may be zinc halide, zinc oxide, or zinc acetate, for example. The zinc halide may be zinc fluoride, zinc chloride, zinc bromide, or zinc iodide.
The amount of water in the aqueous solution of the zinc compound may be 500 parts by mass or more, 1,000 parts by mass or more, or 2,000 parts by mass or more and 5,000 parts by mass or less, 4,000 parts by mass or less, or 3,000 parts by mass or less with respect to 100 parts by mass of the zinc compound.
The amount of the zinc compound may be 0.8 mole or more, 0.9 mole or more, or 0.95 mole or more and 1.1 mole or less, 1.05 mole or less, or 1 mole or less with respect to 1 mole of the phenylphosphonic acid represented by Formula (1) .
The number average molecular weight (Mn) of polyethylene glycol may be 200 or more, 500 or more, or 800 or more and 2,000 or less, 1,500 or less, or 1,200 or less.
The solvent dissolving polyethylene glycol may be an alcohol. The alcohol may be an aliphatic alcohol. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, and ethylene glycol.
The amount of the solvent in the polyethylene glycol solution may be 100 parts by mass or more, 150 parts by mass or more, or 200 parts by mass or more and 400 parts by mass or less, 350 parts by mass or less, or 300 parts by mass or less with respect to 100 parts by mass of polyethylene glycol.
A white precipitate precipitated by the reaction step is filtered out, is washed with water, and is then dried to obtain a phenylphosphonic acid zinc salt represented by Formula (2) as powder (white powder) . That is, another embodiment of the present invention is powder of the phenylphosphonic acid zinc salt represented by Formula (2) obtained by the method of production:
This powder of the phenylphosphonic acid zinc salt represented by Formula (2) is obtained by the method of production and can thereby further reduce the solidification time of a moisture-curable hotmelt urethane resin compared to commercially available powder of a phenylphosphonic acid zinc salt, for example. Although it is unclear what kinds of structure or characteristics of the powder of the phenylphosphonic acid zinc salt represented by Formula (2) contribute to such an effect, the inventors of the present invention assume the reason why the above effect is produced as follows.
Polyethylene glycol can function as a dispersion medium in the reaction step, whereby when crystals of the phenylphosphonic acid zinc salt represented by Formula (2) are formed, the dispersibility of the crystals in water becomes favorable, and crystals (powder) with less flocculation can be obtained. Thus, it is thought that when this powder as a crystal nucleating agent is mixed with the urethane resin, the contact area between the crystal nucleating agent and the urethane resin is larger, and thus crystallization of the urethane resin is promoted.
In an embodiment, the powder of the phenylphosphonic acid zinc salt represented by Formula (2) is obtained by the method of production and can thereby also achieve a reduction in the tack-free time of a moisture-curable hotmelt urethane resin adhesive, improvement in initial creep properties, and improvement in initial peeling strength compared to commercially available powder of a phenylphosphonic acid zinc salt, for example.
As described above, the powder of the phenylphosphonic acid zinc salt represented by Formula (2) can be suitably used as a crystal nucleating agent, and more specifically, as a crystal nucleating agent promoting crystallization of urethane resins. That is, another embodiment of the present invention is the use (application) of the powder of the phenylphosphonic acid zinc salt represented by Formula (2) .
Another embodiment of the present invention is a moisture-curable hotmelt urethane resin adhesive containing an isocyanate group-terminated urethane prepolymer and the powder of the phenylphosphonic acid zinc salt represented by Formula (2) above.
The isocyanate group-terminated urethane prepolymer can be obtained by reacting a polyol (A) and a polyisocyanate (B) with each other in the presence of the phenylphosphonic acid zinc salt represented by Formula (2) above and the zinc phosphate complex represented by Formula (4) above.
The polyol (A) may contain an aliphatic polyester polyol, contain two kinds of aliphatic polyester polyols (an aliphatic polyester polyol (a1) and an aromatic polyester polyol (a2) described below) , or contain the two kinds of aliphatic polyester polyols (the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) described below) and another polyol (a3) other than the aliphatic polyester polyols.
The aliphatic polyester polyol (a1) is a polyester polyol produced by a known and customary method with an aliphatic polycarboxylic acid and an aliphatic polyol as main components, and the method for producing the same is not limited to a particular method.
Preferred examples of the aliphatic polycarboxylic acid used in the synthesis of the aliphatic polyester polyol (a1) include C
4-12 aliphatic polycarboxylic acids such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, citraconic acid, itaconic acid, citraconic anhydride, and itaconic anhydride.
For the aliphatic polycarboxylic acid, lower alkyl ester derivatives such as methyl esters, acid anhydrides, and corresponding acid derivatives such as acid halides may be used, for example.
The aliphatic polyol used in the synthesis of the aliphatic polyester polyol (a1) is one having at least two hydroxy groups in the molecule and is preferably a C
2-12 aliphatic polyol. The (a1) may be linear, branched, or cyclic in structure.
Examples of the aliphatic polyol include linear aliphatic polyols such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol 1, 12-dodecanediol, diethylene glycol, triethylene glycol, triethylene glycol, and tetraethylene glycol; branched aliphatic polyols such as neopentyl glycol, 1, 3-butanediol, 2, 2-diethyl-1, 3-propanediol, 2, 2-diethylpropanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, 2-methyl-1, 8-octanediol, 2, 4-diethyl-1, 5-pentanediol, trimethylol ethane, trimethylol propane, and pentaerythritol; and alicyclic polyols such as cyclopentanediol, cyclohexanediol, and cyclohexanedimethanol. Among these, ethylene glycol, 1, 6-hexanediol, and neopentyl glycol are preferred.
Adducts with various alkylene oxides added to hydrogenated bisphenol A, hydrogenated bisphenol F, or the like can also be used. Polymerized products with γ-butyrolactone, ε-caprolactone, or the like subjected to ring-opening polymerization using a low molecular weight polyol as an initiator can also be used. They may be used alone or used in combination of two or more.
Among the combinations of the aliphatic polycarboxylic acid and the aliphatic polyol, the aliphatic polyester polyol (a1) produced by a combination of a C
4-12 aliphatic polycarboxylic acid and a C
2-12 aliphatic polyol is contained in the polyol (A) , whereby the viscosity stability of the hotmelt urethane resin adhesive during forming processing is further improved, and an excellent effect of preventing a reduction in melt viscosity can be produced, which is preferred.
The aromatic polyester polyol (a2) is a polyester polyol produced by a known and customary method with an aromatic polycarboxylic acid and an aliphatic polyol or an aliphatic polycarboxylic acid and an aromatic polyol as main components, and the method for producing the same is not limited to a particular method.
The aromatic polycarboxylic acid is a carboxylic acid in which at least two carboxy groups are bonded to an aromatic ring and is preferably a C8-24 aromatic polycarboxylic acid. Examples thereof include orthophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, biphenyldicarboxylic acid, and naphthalene dicarboxylic acid. They may be used alone or used in combination of two or more.
For the aromatic polycarboxylic acid, lower alkyl ester derivatives such as methyl esters, acid anhydrides, and corresponding acid derivatives such as acid halides may be used, for example.
Examples of the aliphatic polyol include the same as the aliphatic polyol that can be used in the synthesis of the aliphatic polyester polyol (a1) .
The aliphatic polyol that can be used in the synthesis of the aromatic polyester polyol (a2) and the aliphatic polyester polyol (a1) may be diethylene glycol, triethylene glycol, tetraethylene glycol, 1, 4-bis (β-hydroxyethoxy) benzene, or the like, in which part of its carbon atoms is replaced by oxygen atoms or aromatic rings. These aliphatic polyols may also be used alone or used in combination of two or more.
Furthermore, mixtures of polyester polyols obtained from the aromatic polycarboxylic acid and the aliphatic polyol may also be used.
Examples of the aliphatic polycarboxylic acid that can be used in the synthesis of the aromatic polyester polyol (a2) include C
4-12 aliphatic polycarboxylic acids, which are the same as those for the aliphatic polycarboxylic acid that can be used in the synthesis of the aliphatic polyester polyol (a1) .
The aromatic polyol is not limited to a particular aromatic polyol. Examples thereof include aromatic polyols obtained from aliphatic polyols such as ethylene glycol and neopentyl glycol and aromatic polycarboxylic acids such as orthophthalic acid and terephthalic acid.
As the aromatic polyol, adducts with alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide added to bisphenol A, bisphenol F, or the like can also be used, for example.
The equivalent ratio of hydroxy groups possessed by the aliphatic polyol and the aromatic polyol to carboxy groups of the aliphatic polycarboxylic acid and the aromatic polycarboxylic acid during the synthesis of the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) (that is, an [OH/COOH equivalent ratio] ) is preferably in a range of 1.03 to 1.50 and more preferably in a range of 1.05 to 1.30. When the [OH/COOH equivalent ratio] is in such a range, the hydroxy group-terminated polyols can be generated in a larger amount, and a urethanation reaction with the polyisocyanate (B) can be made to proceed more easily, which is preferred.
The polycondensation conditions during the synthesis of the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) are not limited to particular conditions so long as no abnormal reaction is caused and normal products can be obtained. Normally, certain amounts of the aliphatic polycarboxylic acid and the aliphatic polyol or the aromatic polycarboxylic acid and the aliphatic polyol may be subjected to an esterification reaction or an ester exchange reaction at an internal temperature of 150 to 250℃ for 5 to 50 hours in the presence or in the absence of a catalyst and then be subjected to a polycondensation reaction.
The polycondensation reaction is preferably performed in the presence of a catalyst because the reaction easily proceeds. The catalyst is not limited to a particular catalyst. Examples thereof include titanium-based catalysts such as titanium tetrabutoxide and tin-based catalysts such as dibutyltin oxide.
The catalyst may be charged together with the aliphatic polyol and the aliphatic polycarboxylic acid or the aliphatic polyol and the aromatic polycarboxylic acid or added after prepolymerization in the absence of a catalyst.
In the production of the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) , it is desirable to make almost all both ends hydroxy groups and to leave as few carboxy group ends as possible, and for this purpose it is effective and preferred to add the catalyst after performing the prepolymerization.
The number average molecular weight (hereinafter, referred to as "Mn" ) of the aliphatic polyester polyol (a1) and the aromatic polyester polyol (a2) is preferably in a range of 500 to 6,000, more preferably in a range of 1,000 to 5,000, and particularly preferably in a range of 2,000 to 4,000. When the Mn of (a1) and (a2) is in such a range, a balance of properties such as strength and elongation according to applications can be obtained, which is preferred.
Examples of the other polyol (a3) include polycarbonate polyols, polylactone polyols, and polyether polyols. Examples of the polycarbonate polyols include polycarbonate polyols obtained using the linear aliphatic polyols such as 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol. Examples of the polylactone polyols include polycaprolactone polyols obtained by ring-opening polymerization of caprolactone monomers. Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
The content ratio of the aliphatic polyester polyol (a1) /the aromatic polyester polyol (a2) /the other polyol (a3) may be 20 to 60 parts by mass/10 to 50 parts by mass/0 to 50 parts by mass and preferably 30 to 50 parts by mass/20 to 40 parts by mass/10 to 20 parts by mass in 100 parts by mass of the polyol (A) . When the content ratio is in such a range, the melt viscosity of the polyol (A) can be adjusted to an appropriate range, and a moisture-curable hotmelt urethane resin adhesive exhibiting excellent workability and miscibility and having further excellent solidification properties can be obtained.
Examples of the polyisocyanate (B) include known and customary aliphatic, aromatic, and alicyclic polyisocyanates. Examples thereof include aromatic diisocyanates such as diphenylmethane diisocyanate (MDI; a 4, 4′ form, a 2, 4′ form, a 2, 2′ form, mixtures thereof, and crude MDI) , carbodiimide-modified MDI (modified MDI) , polymethylene polyphenyl polyisocyanate, carbodiimidated diphenylmethane polyisocyanate, xylene diisocyanate, tolylene diisocyanate (TDI; a 2, 4 form, a 2, 6 form, and mixtures thereof) , xylylene diisocyanate (XDI) , 1, 5-naphthalene diisocyanate (NDI) , tetramethyl xylene diisocyanate, and phenylene diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate (HDI) , dimer acid diisocyanate, norbornene diisocyanate, lysine diisocyanate, and tetramethylxylylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate (IPDI) , hydrogenated diphenylmethane diisocyanate (hydrogenated MDI) , hydrogenated xylylene diisocyanate (hydrogenated XDI) , cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. Among these, MDI and XDI are preferred because of their fast reaction with the polyol (A) and moisture (water) to give excellent workability. They may be used alone or used in combination of two or more.
The ratio between the polyol (A) and the polyisocyanate (B) used when the isocyanate group-terminated urethane prepolymer (hereinafter, referred to as a "prepolymer" ) is synthesized may be in a range that does not adversely affect reaction behavior, product quality, and the like. Normally, the equivalent ratio of isocyanate groups possessed by the polyisocyanate (B) to hydroxy groups possessed by the polyol (A) (hereinafter, referred to as an [NCO/OH equivalent ratio] ) is preferably in a range of 1.2 to 4.0 and more preferably in a range of 1.5 to 3.0. When the [NCO/OH equivalent ratio] is in such a range, the melt viscosity of the objective moisture-curable hotmelt urethane resin composition is in an appropriate range and performance such as excellent workability, film properties, and further excellent solidification properties can be exhibited.
The reaction conditions may be set in a range that does not adversely affect reaction behavior, product quality, and the like and are not limited to particular conditions. Normally, the reaction is preferably conducted at a reaction temperature of 80 to 130℃ for 1 to 10 hours.
For the reaction method, a known reaction method such as batch reaction, semi-continuous reaction, or continuous reaction can be selected, for example.
The reaction can be performed in a solvent or solvent-free. However, when the reaction is performed in a solvent, it is preferable to remove the solvent during the reaction or after the end of the reaction to finally eliminate the solvent. The method of removing the solvent is not limited to a particular method.
The content of the phenylphosphonic acid zinc salt represented by Formula (2) may be 0.1%by mass or more, 10%by mass or less, or 0.1 to 10%by mass based on the entire amount of the moisture-curable hotmelt urethane resin adhesive. The lower limit of the total content may be 0.3%by mass, 0.5%by mass, or 1%by mass based on the entire amount of the moisture-curable hotmelt urethane resin adhesive. The upper limit of the total content may be 7%by mass, 5%by mass, or 3%by mass based on the entire amount of the moisture-curable hotmelt urethane resin adhesive.
The moisture-curable hotmelt urethane resin adhesive of the present embodiment may further contain other resins such as previously known thermoplastic resins and thermosetting resins and may further contain other additives. Examples of the other additives include foam stabilizers, antioxidants, antifoaming agents, UV absorbers, abrasive grains, fillers, pigments, dyes, colorants, thickeners, surfactants, fire retardants, plasticizers, lubricants, antistatic agents, heat-resistant stabilizers, adhesion imparting agents, curing catalysts, stabilizers, fluorescent whitening agents, silane coupling agents, and waxes.
The following describes the present invention further specifically based on examples. The present invention is not limited to the examples.
[Example 1]
(Production of phenylphosphonic acid zinc salt)
To a 1-liter four-neck flask, 10 parts by mass (63.3 mmol) of the phenylphosphonic acid represented by Formula (1) and 400 parts by mass of water were added to prepare an aqueous solution. To this flask, an aqueous solution that had been prepared from 8.6 parts by mass (63.1 mmol) of zinc chloride and 200 parts by mass of water and 6.9 parts by mass of polyethylene glycol (Mn = 1,000) dissolved in 19.7 parts by mass of ethanol were further added to be mixed together. To this solution, with stirring, 129 parts by mass of a 1.0 M aqueous sodium hydroxide solution was added over 3 hours to be reacted. The precipitated white precipitate was filtered out, was washed with water, and was then dried under reduced pressure at 80℃ for 2 hours or more to obtain the phenylphosphonic acid zinc salt represented by Formula (2) as white powder.
(Production of Moisture-Curable Hotmelt Urethane Resin Adhesive)
In a 1-liter four-neck flask, mixed together and melted were 30 parts by mass of polypropylene glycol (Mn = 1,000) , 40 parts by mass of an aliphatic polyester polyol (Mn = 4,500) obtained by reacting 1, 6-hexanediol (HD) and adipic acid (AA) with each other in a mass ratio of HD/AA = 46/54, and 30 parts by mass of an aromatic polyester polyol (Mn = 5,000) obtained by reacting 1, 6-hexanediol (HD) , neopentyl glycol (NPG) , ethylene glycol (EG) , isophthalic acid (iPA) , and terephthalic acid (tPA) with each other in a mass ratio of HD/NPG/EG/iPA/tPA = 7/14/18/40/21 to prepare a polyol (A) .
Next, 1.2 parts by mass (1.0%by mass based on the entire amount of the adhesive) of the powder of the phenylphosphonic acid zinc salt represented by Formula (2) obtained as described above as a crystal nucleating agent was added to the (A) , and the mixture was heated up to 110℃and was dehydrated until the moisture content reached 0.05%by mass under a reduced pressure condition.
Subsequently, it was cooled to 70℃, to which 19 parts by mass of 4, 4-diphenylmethane diisocyanate was added, and the mixture was then reacted at 90℃ for 3 hours until the NCO content (%) became constant to obtain a moisture-curable hotmelt urethane resin adhesive.
[Comparative Example 1]
The same operation as in Example 1 was performed except that the powder of the phenylphosphonic acid zinc salt represented by Formula (2) obtained as described above was not added to obtain a moisture-curable hotmelt urethane resin adhesive.
[Comparative Example 2]
The same operation as in Example 1 was performed except that Ecopromote (manufactured by Nissan Chemical Corporation) , which is commercially available powder of a phenylphosphonic acid zinc salt, was used in place of the powder of the phenylphosphonic acid zinc salt represented by Formula (2) obtained as described above to obtain a moisture-curable hotmelt urethane resin adhesive.
[Comparative Example 3]
The same operation as in Example 1 was performed except that Ecopromote NP (manufactured by Nissan Chemical Corporation) , which is commercially available powder of a phenylphosphonic acid zinc salt, was used in place of the powder of the phenylphosphonic acid zinc salt represented by Formula (2) obtained as described above to obtain a moisture-curable hotmelt urethane resin adhesive.
[Evaluation of Solidification Time (Open Time) ]
Each of the obtained moisture-curable hotmelt urethane resin adhesives of the examples and the comparative examples was made into a heated and melted state at 120℃ and was applied onto a polypropylene sheet as a base so as to have a thickness of 50 μm. Next, kraft paper as a surface member was placed on the adhesive layer applied as described above, which was immediately left in a thermostatic oven at 35℃. Based on the point in time when left in the thermostatic oven, a time (in seconds) until the kraft paper ceased to adhere to the adhesive layer was measured and was determined to be a solidification time at 35℃ (an open time at 35℃) . Furthermore, based on the point in time when left in the thermostat oven, a time (in seconds) until a feeling of adhesion by touching the adhesive layer with a finger was lost was measured to be a tack-free time at 35℃. The results are listed in Table 1.
[Evaluation of Initial Creep Properties]
Each of the obtained moisture-curable hotmelt urethane resin adhesives was made into a heated and melted state at 120℃, the melted moisture-curable hotmelt urethane resin adhesive was applied onto a polypropylene sheet with a width of 1 inch so as to have a thickness of 50 μm, and then a medium-density fiberboard (MDF) was placed on the applied adhesive layer and was bonded thereto. Three minutes after bonding, in a 35℃ atmosphere, a load of 150 g was applied to the MDF in a 90° direction, and a time (seconds) until a peeled length of 4 cm was reached was measured and was determined to be initial creep properties at 35℃. The results are listed in Table 1.
[Evaluation of Initial Peeling Strength]
Each of the obtained moisture-curable hotmelt urethane resin adhesives was made into a heated and melted state at 120℃, the melted moisture-curable hotmelt urethane resin adhesive was applied onto a polypropylene sheet with a width of 1 inch so as to have a thickness of 50 μm, and then a medium-density fiberboard (MDF) was placed on the applied adhesive layer and was bonded thereto. Three minutes after bonding, in a room temperature atmosphere, the MDF was peeled off in a 180° direction, and tensile strength (N) during the process was measured and was determined to be three-minutes-later initial peeling strength. The results are listed in Table 1.
[Table 1]
Claims (6)
- A method for producing a phenylphosphonic acid zinc salt, the method including a step of reacting a phenylphosphonic acid represented by Formula (1) and a zinc compound with each other in presence of polyethylene glycol in water:
- The method for producing a phenylphosphonic acid zinc salt according to claim 1, wherein an amount of the zinc compound is 1 mole or less with respect to 1 mole of the phenylphosphonic acid represented by Formula (1) .
- Powder of a phenylphosphonic acid zinc salt represented by Formula (2) obtained by the method for producing a phenylphosphonic acid zinc salt according to claim 1 or 2:
- Use of the powder according to claim 3 as a crystal nucleating agent.
- A moisture-curable hotmelt urethane resin adhesive comprising:an isocyanate group-terminated urethane prepolymer; andthe powder according to claim 3.
- The moisture-curable hotmelt urethane resin adhesive according to claim 5, wherein a content of the powder is 0.1 to 10%by mass based on an entire amount of the moisture-curable hotmelt urethane resin adhesive.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2022/119019 WO2024055238A1 (en) | 2022-09-15 | 2022-09-15 | Method for producing phenylphosphonic acid zinc salt, powder of phenylphosphonic acid zinc salt, use of the same as crystal nucleating agent, and moisture-curable hotmelt urethane resin adhesive |
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/CN2022/119019 WO2024055238A1 (en) | 2022-09-15 | 2022-09-15 | Method for producing phenylphosphonic acid zinc salt, powder of phenylphosphonic acid zinc salt, use of the same as crystal nucleating agent, and moisture-curable hotmelt urethane resin adhesive |
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| WO2024055238A1 true WO2024055238A1 (en) | 2024-03-21 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1938378A (en) * | 2004-03-30 | 2007-03-28 | 日产化学工业株式会社 | Polylactic acid resin composition |
| CN102482303A (en) * | 2009-09-09 | 2012-05-30 | 日产化学工业株式会社 | Method For Producing Metal Phosphonate And Thermoplastic Resin Composition Containing Metal Phosphonate |
| WO2015064566A1 (en) * | 2013-10-30 | 2015-05-07 | 日産化学工業株式会社 | Polylactic acid resin composition having excellent hydrolysis resistance |
| JP2018009115A (en) * | 2016-07-14 | 2018-01-18 | 日産化学工業株式会社 | Aromatic polyether ketone resin composition containing phosphonic acid metal salt |
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2022
- 2022-09-15 WO PCT/CN2022/119019 patent/WO2024055238A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1938378A (en) * | 2004-03-30 | 2007-03-28 | 日产化学工业株式会社 | Polylactic acid resin composition |
| CN102482303A (en) * | 2009-09-09 | 2012-05-30 | 日产化学工业株式会社 | Method For Producing Metal Phosphonate And Thermoplastic Resin Composition Containing Metal Phosphonate |
| WO2015064566A1 (en) * | 2013-10-30 | 2015-05-07 | 日産化学工業株式会社 | Polylactic acid resin composition having excellent hydrolysis resistance |
| JP2018009115A (en) * | 2016-07-14 | 2018-01-18 | 日産化学工業株式会社 | Aromatic polyether ketone resin composition containing phosphonic acid metal salt |
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| Title |
|---|
| MARTIN KEVIN J.ET AL.: "The crystal and molecular structure of zinc phenylphosphonate", INORGANICA CHIMICA ACTA, vol. 155, no. 1, 31 December 1989 (1989-12-31), pages 7 - 9, XP026607178, DOI: 10.1016/S0020-1693(00)89271-3 * |
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