TWI816882B - Composition for polyurethane integral surface layer foaming, polyurethane integral surface layer foaming and manufacturing method thereof - Google Patents
Composition for polyurethane integral surface layer foaming, polyurethane integral surface layer foaming and manufacturing method thereof Download PDFInfo
- Publication number
- TWI816882B TWI816882B TW108133359A TW108133359A TWI816882B TW I816882 B TWI816882 B TW I816882B TW 108133359 A TW108133359 A TW 108133359A TW 108133359 A TW108133359 A TW 108133359A TW I816882 B TWI816882 B TW I816882B
- Authority
- TW
- Taiwan
- Prior art keywords
- mdi
- diphenylmethane diisocyanate
- mass
- organic polyisocyanate
- foaming
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 238000005187 foaming Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000004814 polyurethane Substances 0.000 title claims abstract description 9
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 9
- 239000002344 surface layer Substances 0.000 title claims description 12
- 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 claims abstract description 96
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 49
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 49
- 239000012948 isocyanate Substances 0.000 claims abstract description 37
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 37
- 229920005862 polyol Polymers 0.000 claims abstract description 37
- 150000003077 polyols Chemical class 0.000 claims abstract description 36
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- -1 polytetramethylene diethylene glycol Polymers 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 7
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 125000005442 diisocyanate group Chemical group 0.000 claims 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 description 23
- 229920000909 polytetrahydrofuran Polymers 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000004925 denaturation Methods 0.000 description 6
- 230000036425 denaturation Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 150000001718 carbodiimides Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920005830 Polyurethane Foam Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000011496 polyurethane foam Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 239000003398 denaturant Substances 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- WHLZPGRDRYCVRQ-UHFFFAOYSA-N 1-butyl-2-methylimidazole Chemical compound CCCCN1C=CN=C1C WHLZPGRDRYCVRQ-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- APWRLAZEMYLHKZ-UHFFFAOYSA-N 2-amino-5,6-dimethyl-1h-pyrimidin-4-one Chemical compound CC=1NC(N)=NC(=O)C=1C APWRLAZEMYLHKZ-UHFFFAOYSA-N 0.000 description 1
- SVNWKKJQEFIURY-UHFFFAOYSA-N 2-methyl-1-(2-methylpropyl)imidazole Chemical compound CC(C)CN1C=CN=C1C SVNWKKJQEFIURY-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- LAWHHRXCBUNWFI-UHFFFAOYSA-N 2-pentylpropanedioic acid Chemical compound CCCCCC(C(O)=O)C(O)=O LAWHHRXCBUNWFI-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
- GPZYYYGYCRFPBU-UHFFFAOYSA-N 6-Hydroxyflavone Chemical compound C=1C(=O)C2=CC(O)=CC=C2OC=1C1=CC=CC=C1 GPZYYYGYCRFPBU-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 229920006309 Invista Polymers 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002323 Silicone foam Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- ROPXFXOUUANXRR-YPKPFQOOSA-N bis(2-ethylhexyl) (z)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)\C=C/C(=O)OCC(CC)CCCC ROPXFXOUUANXRR-YPKPFQOOSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- OROGSEYTTFOCAN-DNJOTXNNSA-N codeine Chemical compound C([C@H]1[C@H](N(CC[C@@]112)C)C3)=C[C@H](O)[C@@H]1OC1=C2C3=CC=C1OC OROGSEYTTFOCAN-DNJOTXNNSA-N 0.000 description 1
- 229960004126 codeine Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MBZFMVVPAZRBEN-UHFFFAOYSA-N cyclohexane ethanol Chemical compound CCO.CCO.C1CCCCC1 MBZFMVVPAZRBEN-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 229940043276 diisopropanolamine Drugs 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229960004578 ethylmorphine Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 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 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000013514 silicone foam Substances 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
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Abstract
[課題] 本發明的目的是提供具有高反彈彈性係數，優異的機械強度、生產性的ISF，及該ISF的製造方法。 [解決手段] 藉由聚氨酯整體表層發泡用組合物來解決，其為由有機聚異氰酸酯組合物、多元醇成分、觸媒及發泡劑所得到的聚氨酯整體表層發泡組合物，其特徵在於，其中有機聚異氰酸酯組合物為包含異氰酸酯基末端預聚物者，該包含異氰酸酯基末端預聚物者由包含MDI的異氰酸酯成分與DPG所得，其中包含該MDI的異氰酸酯成分中的MDI的含有率為97質量%以上，且包含該MDI的異氰酸酯成分中的MDI中MDI異構物佔有的合計含有量未滿3質量%，以及有機聚異氰酸酯組合物的異氰酸酯基含有率為15~25質量%。[Problem] The object of the present invention is to provide an ISF having a high rebound elastic coefficient, excellent mechanical strength, and productivity, and a method for manufacturing the ISF. [Solution] The problem is solved by a polyurethane integral surface foaming composition, which is a polyurethane integral surface foaming composition obtained from an organic polyisocyanate composition, a polyol component, a catalyst and a foaming agent, and is characterized by: , wherein the organic polyisocyanate composition contains an isocyanate group terminal prepolymer, and the isocyanate group terminal prepolymer is obtained from an isocyanate component containing MDI and DPG, wherein the content rate of MDI in the isocyanate component containing the MDI is 97% by mass or more, and the total content of MDI isomers in MDI in the isocyanate component containing the MDI is less than 3% by mass, and the isocyanate group content of the organic polyisocyanate composition is 15 to 25% by mass.
Description
本發明係有關於聚氨酯整體表層發泡（以下，亦可稱為「ISF」）用組合物、ISF以及該ISF的製造方法。The present invention relates to a composition for polyurethane integral surface foaming (hereinafter, may also be referred to as "ISF"), ISF, and a method for manufacturing the ISF.
ISF，由於其良好的生產性，機械強度、良好的觸感等，因此以鞋底用素材、方向盤等等為首、已廣泛使用在汽車車內裝潢零件，但目前尚未知具有適合於高性能鞋底等的高反彈彈性係數、同時具有優異的機械強度的ISF的技術。ISF, due to its good productivity, mechanical strength, good touch, etc., has been widely used in automobile interior decoration parts, including shoe sole materials, steering wheels, etc., but it is not known that it is suitable for high-performance shoe soles, etc. ISF technology with high rebound elastic coefficient and excellent mechanical strength.
在專利文獻1中，曾揭示使用二苯甲烷二異氰酸酯(以下，亦可稱為「MDI」)而具有較高密度之高彈性軟質聚氨酯發泡。Patent Document 1 discloses a highly elastic soft polyurethane foam having a relatively high density using diphenylmethane diisocyanate (hereinafter, may also be referred to as "MDI").
但是，該聚氨酯發泡使用交聯劑，並藉由增加化學交聯量而實現高彈性係數，在作為鞋底用樹脂等恐怕有無法得到充分的伸長率、撕裂強度等的機械強度之虞。However, this polyurethane foam uses a cross-linking agent and increases the amount of chemical cross-linking to achieve a high elastic modulus. Therefore, there is a risk that it may not be able to obtain sufficient mechanical strength such as elongation and tear strength when used as a resin for shoe soles.
又，在專利文獻2中，記載提供做為鞋底構件之低密度聚氨酯成形物的方法，但步驟複雜，而且所揭示的彈性係數亦不充分。Furthermore, Patent Document 2 describes a method of providing a low-density polyurethane molded article used as a shoe sole member, but the steps are complicated and the disclosed elastic coefficient is insufficient.
進而，在專利文獻3中，記載提供具有高彈性係數的聚氨酯發泡的方法。Furthermore, Patent Document 3 describes a method of providing polyurethane foam having a high elastic modulus.
但是，由於該聚氨酯發泡使用MDI的聚合物(polymeric)、碳二亞胺(carbodiimide)變性體等，因此恐怕無法得到高機械強度。進而，所使用的異氰酸酯為使用高結晶度的聚四亞甲基醚二醇，由於異氰酸酯基的含有率低，因此黏度高並且預期難以在室溫下保持液狀，必須小心操作。 [現有技術文件] [專利文獻]However, since this polyurethane foam uses MDI polymers, carbodiimide modifications, etc., high mechanical strength may not be obtained. Furthermore, the isocyanate used is polytetramethylene ether glycol with high crystallinity. Since the isocyanate group content is low, the viscosity is high and it is expected to be difficult to maintain a liquid state at room temperature, so careful handling is required. [Prior Art Document] [Patent Document]
[專利文獻1] 特開第2003-342343號 [專利文獻2] 特表第2015-507513號 [專利文獻3] 特開第2017-105913號[Patent Document 1] Japanese Patent Application Publication No. 2003-342343 [Patent Document 2] Special List No. 2015-507513 [Patent Document 3] Japanese Patent Application Publication No. 2017-105913
[本發明要解決的問題][Problems to be solved by this invention]
鑑於上述先前技術，本發明的目的是提供具有高反彈彈性係數，優異的機械強度、生產性等的ISF及該ISF的製造方法。 [解決問題的手段]In view of the above-described prior art, an object of the present invention is to provide an ISF having a high rebound elastic coefficient, excellent mechanical strength, productivity, etc., and a method for manufacturing the ISF. [Methods to solve problems]
本發明人累積深入研究的結果，藉由使用由特定的MDI成分與二丙二醇（以下，亦有稱為「DPG」的情形）所得的具有特定的異氰酸酯基含有率的有機聚異氰酸酯組合物，發現可以解決這些的課題並完成本發明。As a result of accumulated intensive research, the inventors of the present invention discovered that by using an organic polyisocyanate composition having a specific isocyanate group content obtained from a specific MDI component and dipropylene glycol (hereinafter also referred to as "DPG"), The present invention can be accomplished by solving these problems.
即，本發明包含以下（1）至（6）的實施方式。That is, the present invention includes the following embodiments (1) to (6).
（1）一種ISF用組合物，其包含有機聚異氰酸酯組合物（A）、多元醇成分（B）、觸媒（C）及發泡劑（D）的ISF用組合物，其中有機聚異氰酸酯組合物（A）為由包含MDI的異氰酸酯成分與DPG所得之包含異氰酸酯基末端預聚物者，其中包含該MDI的異氰酸酯成分中的4,4’-MDI與2,2’-MDI與2,4’-MDI的合計含有率為97質量%以上，且包含該MDI的異氰酸酯成分中的MDI中2,2’-MDI與2,4’-MDI佔有的合計含有率未滿3質量%，以及有機聚異氰酸酯組合物（A）的異氰酸酯基含有率為15~25質量%。(1) A composition for ISF, which contains an organic polyisocyanate composition (A), a polyol component (B), a catalyst (C) and a foaming agent (D), wherein the organic polyisocyanate composition Material (A) is an isocyanate group-terminated prepolymer obtained from an isocyanate component containing MDI and DPG, which contains 4,4'-MDI, 2,2'-MDI and 2,4 in the isocyanate component of MDI. The total content of '-MDI is 97% by mass or more, and the total content of 2,2'-MDI and 2,4'-MDI in the MDI in the isocyanate component containing the MDI is less than 3% by mass, and organic The polyisocyanate composition (A) has an isocyanate group content of 15 to 25% by mass.
（2）如上述（1）中所述之ISF用組合物，其中多元醇成分（B）包含數量平均分子量為600~3,500的聚四亞甲基二醇(Polytetramethylene glycol)（b1）（以下，亦有稱為「PTMEG」之情形）。(2) The composition for ISF as described in the above (1), wherein the polyol component (B) contains polytetramethylene glycol (b1) with a number average molecular weight of 600 to 3,500 (hereinafter, Also known as "PTMEG").
（3）一種ISF，由如上述（1）或（2）所述之ISF用組合物所得。(3) ISF obtained from the composition for ISF as described in (1) or (2) above.
（4）如上述（3）中所述之ISF，其中發泡密度為200~400kg/m3 。(4) ISF as described in (3) above, wherein the foaming density is 200~400kg/m 3 .
（5）如上述（3）或（4）中所述之ISF，其中反彈彈性係數為50%以上，撕裂強度為100N/cm以上，且分層撕裂強度(split tear strength)為2.50kg/cm以上。(5) ISF as described in (3) or (4) above, in which the rebound elastic coefficient is more than 50%, the tear strength is more than 100N/cm, and the split tear strength is 2.50kg /cm or above.
（6）一種ISF的製造方法，其為在觸媒（C）及發泡劑（D）的存在下使有機聚異氰酸酯組合物（A）與多元醇成分（B）反應、發泡而得的ISF的製造方法，其中有機聚異氰酸酯組合物（A）為由包含MDI的異氰酸酯成分與DPG所得之包含異氰酸酯基末端預聚物者，其中包含該MDI的異氰酸酯成分中的4,4’-MDI與2,2’-MDI與2,4’-MDI的合計含有率為97質量%以上，且包含該MDI的異氰酸酯成分中的MDI中2,2’-MDI與2,4’-MDI佔有的合計含有率未滿3質量%，以及有機聚異氰酸酯組合物（A）的異氰酸酯基含有率為15~25質量%。 [本發明的效果](6) A method for producing ISF, which is obtained by reacting and foaming an organic polyisocyanate composition (A) and a polyol component (B) in the presence of a catalyst (C) and a foaming agent (D). A manufacturing method for ISF, wherein the organic polyisocyanate composition (A) is an isocyanate group-terminated prepolymer obtained from an isocyanate component containing MDI and DPG, wherein 4,4'-MDI and 4,4'-MDI in the isocyanate component of the MDI are obtained. The total content of 2,2'-MDI and 2,4'-MDI is 97% by mass or more, and the total proportion of 2,2'-MDI and 2,4'-MDI in the MDI including the isocyanate component of the MDI The content rate is less than 3% by mass, and the isocyanate group content rate of the organic polyisocyanate composition (A) is 15 to 25% by mass. [Effects of the present invention]
根據本發明，能夠在ISF中具有高反彈彈性係數，同時顯著地提高機械強度。再者，由本發明所得的ISF非常適合用於可廣泛用於鞋底用樹脂等需要高彈性性能的材料。此外，在製造ISF時，能夠以一般的發泡裝置實現高生產穩定性。According to the present invention, it is possible to have a high rebound elastic coefficient in the ISF while significantly improving the mechanical strength. Furthermore, the ISF obtained by the present invention is very suitable for use in materials requiring high elastic properties such as resins for shoe soles. In addition, when manufacturing ISF, high production stability can be achieved using a general foaming device.
[用以實施本發明的形態][Mode for carrying out the present invention]
進而詳細地說明本發明。Next, the present invention will be described in detail.
本發明的ISF用組合物為包含有機聚異氰酸酯組合物（A）、多元醇成分（B）、觸媒（C）及發泡劑（D）之物，其中有機聚異氰酸酯組合物（A）包含MDI與DPG的異氰酸酯基末端預聚物者。The composition for ISF of the present invention is a thing containing an organic polyisocyanate composition (A), a polyol component (B), a catalyst (C) and a foaming agent (D), wherein the organic polyisocyanate composition (A) contains Isocyanate group-terminated prepolymer of MDI and DPG.
用於得到此異氰酸酯基末端預聚物時、包含MDI的異氰酸酯成分是該異氰酸酯成分中包含MDI（包含4,4’-MDI、2,2’-MDI、2,4’-MDI）的合計為97質量%以上，且該MDI中的2,2’-MDI與2,4’-MDI的合計含有量（以下，也稱為MDI異構體含有量）未滿3質量%。When used to obtain this isocyanate group-terminated prepolymer, the isocyanate component containing MDI is such that the total of the isocyanate components containing MDI (including 4,4'-MDI, 2,2'-MDI, and 2,4'-MDI) is 97% by mass or more, and the total content of 2,2'-MDI and 2,4'-MDI in the MDI (hereinafter also referred to as the MDI isomer content) is less than 3% by mass.
在本發明中，含有MDI的異氰酸酯成分中的MDI含有率為97質量%以上，較佳為98質量%以上。當MDI含有率未滿97質量%時，由於異氰酸酯官能基數量增加，導致ISF的機械強度降低。In the present invention, the MDI content rate in the isocyanate component containing MDI is 97 mass% or more, preferably 98 mass% or more. When the MDI content is less than 97% by mass, the mechanical strength of ISF decreases due to the increase in the number of isocyanate functional groups.
又，MDI中的MDI異構體的含有比率為未滿3質量%，較佳為未滿2質量%。當MDI異構體的含有比率為3質量%以上時，由於MDI部分的結晶度降低，導致ISF的機械強度降低。Furthermore, the content ratio of MDI isomers in MDI is less than 3% by mass, and preferably less than 2% by mass. When the content ratio of MDI isomers is 3% by mass or more, the mechanical strength of ISF decreases due to the decrease in crystallinity of the MDI part.
本發明中所使用的有機聚異氰酸酯組合物（A）的異氰酸酯基含有率為15~25質量%，較佳為16~24質量%。當異氰酸酯基的含有率低於15質量%時，有機聚異氰酸酯的黏度變得非常高，使得難以將其導入至發泡裝置中，同時在一般的發泡裝置的異氰酸酯、多元醇類等等的混合能力的方面來說，無法充分均勻的混合。另一方面，25質量%以上的異氰酸酯基含有率，異氰酸酯與多元醇與作為發泡劑的水之間的反應變得隨機，推測特別是由異氰酸酯與水的反應所產生的尿素鍵結(urea bond)重複單位的巨大化作為原因，而顯著降低機械強度。The isocyanate group content of the organic polyisocyanate composition (A) used in the present invention is 15 to 25 mass%, preferably 16 to 24 mass%. When the isocyanate group content is less than 15% by mass, the viscosity of the organic polyisocyanate becomes very high, making it difficult to introduce it into a foaming device. At the same time, in general foaming devices, isocyanates, polyols, etc. In terms of mixing ability, it cannot be fully and evenly mixed. On the other hand, when the isocyanate group content is 25% by mass or more, the reaction between isocyanate, polyol, and water as a foaming agent becomes random, and it is speculated that urea bonding (urea bond) is especially generated by the reaction between isocyanate and water. The mechanical strength is significantly reduced due to the enlargement of the repeating units of bond).
本發明中使用的有機聚異氰酸酯組合物（A）除了由含MDI的異氰酸酯成分與DPG所得到的異氰酸酯基末端預聚物以外，還可以併用由PTMEG所得到的異氰酸酯基末端預聚物。得到有機聚異氰酸酯組合物（A）時所用的PTMEG的數量平均分子量為1,250~3,500，較佳的數量平均分子量為1,500~3,500。如果數量平均分子量低於下限，則PTMEG鏈將無法充分發揮作為軟段(soft segment)的作用，因此難以達成反彈彈性係數的目標值。另一方面，當分子量超過上限值時，存在無法獲得作為適用於鞋底等用途的ISF的硬度，同時PTMEG鏈的結晶性增加而有機聚異氰酸酯的黏度變得過高的問題。The organic polyisocyanate composition (A) used in the present invention may use an isocyanate group-terminated prepolymer obtained from PTMEG in addition to an isocyanate group-terminated prepolymer obtained from an isocyanate component containing MDI and DPG. The number average molecular weight of PTMEG used to obtain the organic polyisocyanate composition (A) is 1,250 to 3,500, and the preferred number average molecular weight is 1,500 to 3,500. If the number average molecular weight is lower than the lower limit, the PTMEG chain will not fully function as a soft segment, making it difficult to achieve the target value of the rebound elastic coefficient. On the other hand, when the molecular weight exceeds the upper limit, there is a problem that hardness as an ISF suitable for applications such as shoe soles cannot be obtained, and the crystallinity of the PTMEG chain increases, causing the viscosity of the organic polyisocyanate to become too high.
用於得到有機聚異氰酸酯組合物（A）的PTMEG，較佳為僅藉由四氫呋喃開環聚合，又，較佳為雙官能。使用這樣的PTMEG，因為能夠得到以反彈彈性係數、伸長率、撕裂強度為中心的良好的機械物性，因此較佳。The PTMEG used to obtain the organic polyisocyanate composition (A) is preferably one that undergoes only ring-opening polymerization of tetrahydrofuran, and is preferably bifunctional. It is preferable to use such PTMEG because it can obtain good mechanical properties including rebound elastic coefficient, elongation, and tear strength.
另外，如果PTMEG在聚合前的原料單體成分為10莫耳%為止的話，則即使將四氫呋喃以外的醚單元導入分子內，也不會大幅損害本發明的效果。通常，以PTMEG在室溫下液化為目的能夠導入1,3-丙二醇、3-甲基-1,5-戊二醇、新戊二醇等。In addition, if the raw material monomer component of PTMEG before polymerization is 10 mol%, even if ether units other than tetrahydrofuran are introduced into the molecule, the effect of the present invention will not be significantly impaired. Generally, 1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, etc. can be introduced for the purpose of liquefying PTMEG at room temperature.
另外，在有機聚異氰酸酯組合物（A）中使用的MDI還可以包含具有類似結構的聚伸苯基聚甲基聚異氰酸酯（聚合MDI，之後也稱為p-MDI），但是由於異氰酸酯官能基數量的增加，恐怕產生ISF的伸長率降低，源自p-MDI的ISF著色等，因此，相對於有機聚異氰酸酯組合物（A）中使用的MDI，p-MDI的含有率較佳為3質量%以下，更佳為2質量%以下，最佳為不使用p-MDI。In addition, the MDI used in the organic polyisocyanate composition (A) may also contain polyphenylenepolymethylpolyisocyanate (polymeric MDI, hereafter also referred to as p-MDI) having a similar structure, but due to the number of isocyanate functional groups An increase may cause a decrease in the elongation of ISF and coloration of ISF due to p-MDI. Therefore, the content of p-MDI is preferably 3% by mass relative to the MDI used in the organic polyisocyanate composition (A). or less, more preferably 2 mass % or less, and most preferably no p-MDI is used.
有機聚異氰酸酯組合物（A）包含上述胺甲酸乙酯變性體，但也可以併用MDI與在常溫下為液狀的MDI（以下稱為「液狀MDI」），適當地使用於含有用DPG、PTMEG等進行胺甲酸乙酯變性的異氰酸酯基末端預聚物的有機聚異氰酸酯組合物。The organic polyisocyanate composition (A) contains the above-mentioned urethane denatured form. However, MDI and MDI that is liquid at normal temperature (hereinafter referred to as "liquid MDI") may be used together, and may be suitably used in DPG for containing, An organic polyisocyanate composition of an isocyanate group-terminated prepolymer modified with urethane such as PTMEG.
可用於有機聚異氰酸酯組合物（A）中的液狀MDI，可舉例由已知的方法得到者，例如： （1）使MDI在200℃以上反應， （2）在MDI中添加磷酸三甲酯、磷酸三乙酯等作為觸媒後，在170℃以上使之反應，或者 （3）在MDI中添加3-甲基-1-苯基-2-磷烯-1-氧化物等的磷烯(phospholene)化合物作為觸媒後，在70℃以上使之反應，並以預定的反應速率添加反應停止劑， 等的方法所得的MDI的部分碳二亞胺變性物及部分脲酮亞胺(uretonimine)變性物所組的群組中的至少一種。Liquid MDI that can be used in the organic polyisocyanate composition (A) can be obtained by known methods, for example: (1) Make MDI react above 200℃, (2) After adding trimethyl phosphate, triethyl phosphate, etc. as a catalyst to MDI, react it at a temperature above 170°C, or (3) After adding a phospholene compound such as 3-methyl-1-phenyl-2-phosphorene-1-oxide as a catalyst to MDI, react it at a temperature above 70°C and set it to a predetermined temperature. Add reaction stopper to the reaction rate, At least one of the group consisting of a partially carbodiimide denatured product and a partially uretonimine denatured product of MDI obtained by a method.
另外，在完成上述反應並添加反應終止劑後，將得到的液狀MDI在50℃以下的溫度下保存24小時以上，並且將大部分碳二亞胺鍵轉變為脲酮亞胺鍵的狀態，藉由不分解脲酮亞胺鍵的方法如凝膠滲透層析法(gel permeation chromatography)測定液狀MDI中的碳二亞胺變性MDI及脲酮亞胺變性MDI的合計含有率較佳為5~40質量%，更佳為10~35質量%。當碳二亞胺變性MDI及脲酮亞胺變性MDI的合計含有率在上述範圍內時，可以獲得適合的異氰酸酯官能基數目，並且可以在使用時設定為合適的黏度。此外，將其設為ISF時，可以滿足強度、反彈彈性係數等。In addition, after completing the above reaction and adding the reaction terminator, the obtained liquid MDI is stored at a temperature below 50°C for more than 24 hours, and most of the carbodiimide bonds are converted into the state of uretonimine bonds, The total content of carbodiimide-denatured MDI and uretonimine-denatured MDI in liquid MDI is preferably measured by a method that does not decompose the uretonimine bond, such as gel permeation chromatography. ~40% by mass, more preferably 10~35% by mass. When the total content of carbodiimide-denatured MDI and uretonimine-denatured MDI is within the above range, a suitable number of isocyanate functional groups can be obtained, and a suitable viscosity can be set during use. In addition, when it is set to ISF, strength, rebound elastic coefficient, etc. can be satisfied.
此液狀MDI，作為碳二亞胺變性前或脲酮亞胺變性前的MDI，2,2’-MDI、2,4’-MDI的合計含有率較佳為60質量%以下。異構體含有率超過60質量%時，由於反應性降低，因此有可能使生產性惡化。In this liquid MDI, as MDI before carbodiimide denaturation or uretonimine denaturation, the total content of 2,2'-MDI and 2,4'-MDI is preferably 60 mass% or less. When the isomer content exceeds 60% by mass, the reactivity is reduced, thereby possibly worsening the productivity.
此外，可以用於有機聚異氰酸酯（A）的液狀MDI在碳二亞胺變性前或脲酮亞胺變性前的MDI中可以含有少量的p-MDI。In addition, the liquid MDI that can be used for the organic polyisocyanate (A) may contain a small amount of p-MDI in the MDI before carbodiimide denaturation or before uretonimine denaturation.
但是，與液狀MDI相比，p-MDI具有更高的異氰酸酯平均官能基數目，作為碳二亞胺變性前或脲酮亞胺變性前的MDI，並且必須保持最大為3質量%，更佳為2質量%以下，進一步更佳為不包含。However, p-MDI has a higher average number of isocyanate functional groups than liquid MDI, as MDI before carbodiimide denaturation or uretonimine denaturation, and must be maintained at a maximum of 3 mass %, which is better It is 2 mass % or less, and it is more preferable that it does not contain it.
作為本發明中的PTMEG（b1），數量平均分子量較佳為600~3,500，更佳為1,000~3,500。另外，多元醇成分（B）中的（b1）的含有量較佳為80質量%以上，更佳為90質量%以上。在下限以下的話，所得的ISF的反彈彈性係數不足夠高，因此可能降低如撕裂強度等的機械物性。As PTMEG (b1) in the present invention, the number average molecular weight is preferably 600 to 3,500, more preferably 1,000 to 3,500. In addition, the content of (b1) in the polyol component (B) is preferably 80 mass% or more, more preferably 90 mass% or more. If it is below the lower limit, the rebound elastic coefficient of the resulting ISF is not high enough, so mechanical properties such as tear strength may be reduced.
作為用於本發明的多元醇成分（B），可以使用具有2~4個官能基數目的交聯劑（b2）。具體地，例如，可以使用乙二醇、二乙二醇、丙二醇、二丙二醇、丁二醇、新戊二醇，四亞甲基醚二醇、環己烷二乙醇、甘油、新戊四醇、三羥甲基丙烷、單乙醇胺、二乙醇胺、三乙醇胺、二異丙醇胺、三異丙醇胺等。其中，較佳具有反應性特別高的胺系醇。As the polyol component (B) used in the present invention, a cross-linking agent (b2) having a functional group number of 2 to 4 can be used. Specifically, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, tetramethylene ether glycol, cyclohexane diethanol, glycerol, neopentyl erythritol can be used , trimethylolpropane, monoethanolamine, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, etc. Among them, amine-based alcohols having particularly high reactivity are preferred.
另外，作為多元醇成分（B），可以在不降低上述反彈彈性係數的範圍內添加其他多元醇（b3）。作為其他多元醇，可列舉一般用於胺甲酸乙酯樹脂的聚丙烯醚多元醇（簡稱為PPG）、聚酯多元醇、蓖麻油等天然衍生的多元醇、聚丁二烯多元醇、二聚酸酯多元醇等。In addition, as the polyol component (B), other polyol (b3) may be added within a range that does not reduce the above-mentioned rebound elastic coefficient. Examples of other polyols include polypropylene ether polyol (PPG) generally used in urethane resins, polyester polyols, naturally derived polyols such as castor oil, polybutadiene polyols, and dimer polyols. Acid ester polyols, etc.
作為觸媒（C），可以使用本領域已知的各種胺甲酸乙酯化觸媒。可列舉，例如，三乙胺、三丙胺、三丁胺、N-甲基嗎福林、N-乙基嗎福林、二甲基芐胺、N,N,N’,N’-四甲基六亞甲基二胺，N,N,N’,N” N”-五甲基二伸乙基三胺，雙（2-二甲基胺基乙基）醚、三伸乙基二胺、1,8-二氮雜雙環[5.4.0]十一烯-7、1,2-二甲基咪唑，1-丁基-2-甲基咪唑等的3級胺及其有機酸鹽；二甲基乙醇胺，N-三氧乙烯-N,N-二甲基胺、N,N-二甲基-N-己醇胺等胺基醇類及其有機酸鹽；辛酸亞錫(stannous octoate)、二丁基錫二月桂酸酯、二辛基錫二月桂酸酯、環烷酸鋅等的有機金屬化合物等。這些觸媒可以視需要混合使用兩種以上。此外，這些觸媒亦可基於低黏度化、液狀化、提高成形機械之計量精密度而增加體積等之理由而使用各種溶劑、多元醇、塑形劑等加以溶解後使用。As the catalyst (C), various urethanation catalysts known in the art can be used. Examples include triethylamine, tripropylamine, tributylamine, N-methylmorphine, N-ethylmorphine, dimethylbenzylamine, N,N,N',N'-tetramethyl Hexamethylenediamine, N,N,N',N” N”-pentamethyldiethylenediamine, bis(2-dimethylaminoethyl)ether, triethylenediamine , 1,8-diazabicyclo[5.4.0]undecene-7, 1,2-dimethylimidazole, 1-butyl-2-methylimidazole and other tertiary amines and their organic acid salts; Dimethylethanolamine, N-trioxyethylene-N,N-dimethylamine, N,N-dimethyl-N-hexanolamine and other amino alcohols and their organic acid salts; stannous octoate ), organometallic compounds such as dibutyltin dilaurate, dioctyltin dilaurate, zinc naphthenate, etc. Two or more types of these catalysts may be mixed and used as necessary. In addition, these catalysts can also be dissolved and used using various solvents, polyols, plasticizers, etc. for reasons such as lowering the viscosity, liquefaction, improving the metering precision of the molding machine and increasing the volume.
作為本發明中使用的發泡劑（D），雖然期望為水，但是可以視需要使用對地球環境具有較少顯著影響的公知者。此種已知的發泡劑有兩種：非活性低沸點溶劑與反應性發泡劑，前者之例可列舉：二氯甲烷、氫氟碳化物、氫氟烯烴、丙酮、甲酸甲酯、己烷、戊烷、異戊烷、環戊烷等，進一步為氮氣氣體、二氧化碳氣體、空氣等。後者之例，可列舉以較室溫高之溫度等分解所產生的氣體，例如偶氮(azo)化合物、碳酸氫鈉等。As the foaming agent (D) used in the present invention, water is desirably used, but a known one having less significant impact on the global environment may be used if necessary. There are two types of known blowing agents: inactive low-boiling point solvents and reactive blowing agents. Examples of the former include: methylene chloride, hydrofluorocarbons, hydrofluoroolefins, acetone, methyl formate, hexane alkane, pentane, isopentane, cyclopentane, etc., and further nitrogen gas, carbon dioxide gas, air, etc. Examples of the latter include gases generated by decomposition at temperatures higher than room temperature, such as azo compounds, sodium bicarbonate, and the like.
在本發明中，可以使用黏度低減劑來降低ISF用組合物的黏度。作為黏度低減劑，可列舉在一般用於降低高黏度液體的黏度的液狀物質中不包含與異氰酸酯基反應的活性氫基、碳化二醯亞胺基、甲醯基等。作為此種，從降低黏度效果的方面出發，在25℃時的黏度為100mPa‧s以下，從操作方面來說，熔點為0℃以下，從安全方面來說，以JIS K2265的方法計測的閃點為70℃以上，且毒性、環境污染性等低者較佳。具體地，可列舉：鄰苯二甲酸二乙酯、鄰苯二甲酸二丙酯、鄰苯二甲酸二丁酯、鄰苯二甲酸系二辛酯、鄰苯二甲酸二異壬酯、己二酸二乙酯、己二酸二丙酯、己二酸二丁酯、己二酸二辛酯、己二酸二異壬酯、順丁烯二酸二乙酯、順丁烯二酸二丙酯、順丁烯二酸二丁酯、順丁烯二酸二辛酯、磷酸三甲苯酯、磷酸參-β-氯化丙酯、乙醯基檸檬酸三丁酯、二苄醚等。In the present invention, a viscosity reducing agent can be used to reduce the viscosity of the composition for ISF. Examples of the viscosity reducing agent include liquid substances generally used to reduce the viscosity of high-viscosity liquids, such as active hydrogen groups, carbodiimide groups, and formyl groups that do not react with isocyanate groups. For this purpose, the viscosity at 25°C is 100 mPa‧s or less from the viewpoint of the viscosity-reducing effect, the melting point is 0°C or less from the operational standpoint, and the flashover measured according to the JIS K2265 method from the safety standpoint Those with a temperature above 70°C and low toxicity and environmental pollution are preferred. Specific examples include: diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, diisononyl phthalate, and hexane dicarboxylate. Diethyl adipate, dipropyl adipate, dibutyl adipate, dioctyl adipate, diisononyl adipate, diethyl maleate, dipropylene adipate Ester, dibutyl maleate, dioctyl maleate, tricresyl phosphate, ginseng-β-propyl chloride, acetyl tributyl citrate, dibenzyl ether, etc.
相對於有機聚異氰酸酯組合物（A）、多元醇成分（B）、觸媒（C）和發泡劑（D）的合計量，黏度低減劑的添加量較佳為15質量%以下。如果超過15質量%，則存在ISF成型物的成型性惡化、反彈彈性係數及撕裂強度等的機械物性下降的風險。又，黏度低減劑可以預先添加到有機聚異氰酸酯組合物（A）或多元醇成分（B）中，或者可以在發泡製造期間單獨添加。The added amount of the viscosity reducing agent is preferably 15% by mass or less based on the total amount of the organic polyisocyanate composition (A), polyol component (B), catalyst (C), and foaming agent (D). If it exceeds 15% by mass, there is a risk that the formability of the ISF molded article will deteriorate and mechanical properties such as rebound elasticity and tear strength will decrease. In addition, the viscosity reducing agent may be added to the organic polyisocyanate composition (A) or the polyol component (B) in advance, or may be added separately during foam production.
在本發明中，可以視需要使用輔助劑。作為此種輔助劑，例如，可列舉泡沫穩定劑、顏料或染料、雲母，玻璃纖維等的強化材或填充劑、抗燃劑、抗氧化劑、紫外線吸收劑、光安定化劑、防黴劑、抗菌劑、VOC吸收劑等，可以視需要而使用。In the present invention, auxiliary agents may be used as necessary. Examples of such auxiliaries include foam stabilizers, pigments or dyes, mica, reinforcements or fillers such as glass fiber, flame retardants, antioxidants, ultraviolet absorbers, light stabilizers, and antifungal agents. Antibacterial agents, VOC absorbers, etc. can be used as needed.
作為泡沫穩定劑，可列舉一般聚氨酯整體表層發泡製造所使用的公知者。例如：聚二甲基矽氧烷-聚環氧烷嵌段聚合物、乙烯基矽烷-聚烯多元醇聚合物等。Examples of the foam stabilizer include known ones generally used in the production of polyurethane integral surface layer foam. For example: polydimethylsiloxane-polyalkylene oxide block polymer, vinylsilane-polyolefin polyol polymer, etc.
本發明的ISF可以從上述ISF用組合物獲得。該ISF，例如，在觸媒（C）、發泡劑（D）及視需要的輔助劑等的存在下將有機聚異氰酸酯組合物（A）與多元醇成分（B）攪拌混合後，注入模具中獲得模具發泡，或者以注入具含上下左右壁面的輸送機中獲得連續片狀發泡等進行製造。兩種製造方法，均能夠以預先準備將有機聚異氰酸酯組合物（A）以外的成分混合之多元醇預混物，再將其與有機聚異氰酸酯組合物（A）之2種成分混合發泡的方法；以部分或全部成分各別導入攪拌混合機之混合供料口，加以發泡的方法操作。The ISF of the present invention can be obtained from the above-mentioned composition for ISF. This ISF is prepared by, for example, stirring and mixing the organic polyisocyanate composition (A) and the polyol component (B) in the presence of a catalyst (C), a foaming agent (D), and optional auxiliary agents, and then injecting it into a mold. It can be manufactured by foaming in a mold, or by injecting it into a conveyor with upper, lower, left and right walls to obtain continuous sheet foam. Both manufacturing methods can be achieved by preparing a polyol premix mixed with components other than the organic polyisocyanate composition (A) in advance, and then mixing it with the two components of the organic polyisocyanate composition (A) for foaming. Method: Introduce some or all of the ingredients into the mixing feed port of the mixer and perform foaming operations.
本發明的有機聚異氰酸酯組合物中的全異氰酸酯基與含水的異氰酸酯反應性化合物中的全異氰酸酯反應性基的莫耳比（異氰酸酯基/NCO反應性基）較佳為0.4~1.2（異氰酸酯指數（NCO INDEX）＝40~120），更佳為0.5~1.1（NCO INDEX＝50~110）。The molar ratio (isocyanate group/NCO reactive group) of the perisocyanate group in the organic polyisocyanate composition of the present invention and the perisocyanate reactive group in the water-containing isocyanate reactive compound is preferably 0.4 to 1.2 (isocyanate index ( NCO INDEX)=40~120), preferably 0.5~1.1 (NCO INDEX=50~110).
另外，根據本發明ISF的密度較佳為200~400kg/m3 。特別地，考慮到經濟效率、生產率等，較佳為調整至350kg/m3 以下。In addition, according to the present invention, the density of ISF is preferably 200~400kg/m 3 . In particular, considering economic efficiency, productivity, etc., it is preferable to adjust it to 350 kg/ m3 or less.
儘管取決於觸媒（C）的種類、混合量等，但是當僅使用水作為發泡劑時，用於達成此密度範圍所須的水的添加份數，相對於多元醇成分（B）100質量份，較佳為0.3~3.0質量份。Although it depends on the type, mixing amount, etc. of the catalyst (C), when only water is used as the foaming agent, the amount of water required to achieve this density range is 100% of the polyol component (B) Parts by mass, preferably 0.3~3.0 parts by mass.
如上所述，對本發明的ISF的用途沒有特別限制，但是如反彈彈性係數為50%以上，撕裂強度為100N/cm以上，並且分層撕裂強度(split tear strength)為2.50kg/cm以上，由於其具有高反彈彈性係數、高機械強度，因此藉由由本發明的ISF代替用於以往的鞋底、部分的鞋底、鞋墊等的發泡樹脂、ISF等，可以獲得非常優異的使用感、強度、耐久性。 [實施例]As mentioned above, the use of the ISF of the present invention is not particularly limited, but if the rebound elastic coefficient is 50% or more, the tear strength is 100 N/cm or more, and the split tear strength (split tear strength) is 2.50 kg/cm or more , due to its high rebound elasticity coefficient and high mechanical strength, by replacing the foamed resin, ISF, etc. used in conventional soles, partial soles, insoles, etc., with the ISF of the present invention, very excellent usability and strength can be obtained , durability. [Example]
在下文中，進一步說明本發明的具體實例，但是，本發明不限於這些實例。在實施例中，除非另有說明，所有的份和%均為質量基準。Hereinafter, specific examples of the present invention are further explained, but the present invention is not limited to these examples. In the examples, unless otherwise stated, all parts and % are based on mass.
[有機聚異氰酸酯組合物 合成例I-1] 在附有攪拌器、溫度計、冷卻器及氮氣導入管的容量1L反應器中，加入859g低異構體比率MDI，升溫到75℃後，加入141g DPG，保持溫度的同時以攪拌葉均勻混合，邊進行胺甲酸乙酯化反應3小時。冷卻至40℃以獲得有機聚異氰酸酯組合物「I-1」（MDI含有比率為100%，MDI異構體比率為1%，NCO基含有率為20.0%，在40℃時的黏度為2330mPa‧s）。[Organic polyisocyanate composition synthesis example I-1] In a 1L reactor equipped with a stirrer, thermometer, cooler and nitrogen inlet pipe, add 859g of low isomer ratio MDI. After raising the temperature to 75°C, add 141g of DPG and mix evenly with a stirring blade while maintaining the temperature. The urethanization reaction was carried out for 3 hours. Cool to 40°C to obtain organic polyisocyanate composition "I-1" (MDI content ratio is 100%, MDI isomer ratio is 1%, NCO group content ratio is 20.0%, viscosity at 40°C is 2330mPa‧ s).
[有機聚異氰酸酯組合物 合成例I-2] 在附有攪拌器、溫度計、冷卻器和氮氣導入管的容量1L反應器中，加入773g低異構體比率MDI，升溫至75℃後，加入127g DPG，保持溫度的同時以攪拌葉均勻混合，邊進行胺甲酸乙酯化反應3小時。之後，加入100g DOM，在50℃下以攪拌葉均勻混合1小時後，冷卻至40℃以獲得有機聚異氰酸酯組合物「I-2」（MDI含有比率為100%，MDI異構體比率為1%，NCO基含有率為18.0%，在40℃下的黏度為860mPa‧s）。[Organic polyisocyanate composition synthesis example I-2] In a 1L reactor equipped with a stirrer, thermometer, cooler and nitrogen inlet pipe, add 773g low isomer ratio MDI. After raising the temperature to 75°C, add 127g DPG and mix evenly with a stirring blade while maintaining the temperature. The urethanization reaction was carried out for 3 hours. After that, 100 g of DOM was added, and the mixture was uniformly mixed with a stirring blade at 50°C for 1 hour, and then cooled to 40°C to obtain the organic polyisocyanate composition "I-2" (MDI content ratio: 100%, MDI isomer ratio: 1 %, the NCO group content is 18.0%, and the viscosity at 40°C is 860mPa‧s).
[有機聚異氰酸酯組合物 合成例I-5] 在附有攪拌器、溫度計、冷卻器和氮氣導入管的容量1L反應器中，加入577g低異構體比率MDI、115g液狀MDI，升溫至75℃後，加入107g DPG，保持溫度的同時以攪拌葉均勻混合，邊進行胺甲酸乙酯化反應3小時。之後，加入200g DOM，在50℃下以攪拌葉均勻混合1小時後，冷卻至40℃以獲得有機聚異氰酸酯組合物「I-5」（MDI含有比率為95%，MDI異構體比率為1%，NCO基含有率為18.0%，在40℃下的黏度為450mPa‧s）。[Organic polyisocyanate composition synthesis example I-5] In a 1L reactor equipped with a stirrer, thermometer, cooler and nitrogen inlet pipe, add 577g of low isomer ratio MDI and 115g of liquid MDI. After raising the temperature to 75°C, add 107g of DPG. While maintaining the temperature, Stir the leaves to mix evenly while performing the urethane esterification reaction for 3 hours. After that, 200 g of DOM was added, and the mixture was uniformly mixed with a stirring blade at 50°C for 1 hour, and then cooled to 40°C to obtain an organic polyisocyanate composition "I-5" (MDI content ratio: 95%, MDI isomer ratio: 1 %, the NCO group content rate is 18.0%, and the viscosity at 40°C is 450mPa‧s).
[異氰酸酯合成例I-3~4，I-6~11] 使用如表1~2中所示的原料，藉由進行與I-1、I-2、I-5相同的操作獲得有機聚異氰酸酯組合物I-3~4、I-6~11。表中的原料成分以質量份表示。[Isocyanate synthesis examples I-3~4, I-6~11] Using the raw materials shown in Tables 1 to 2, organic polyisocyanate compositions I-3 to 4 and I-6 to 11 were obtained by performing the same operations as I-1, I-2 and I-5. The raw material ingredients in the table are expressed in parts by mass.
[表1]
[表2]
[多元醇成分的製備] 以表3中所示的比例均勻混合原料，以製備作為多元醇預混物的多元醇成分P-1和P-2。另外，原料成分以質量份表示。[Preparation of polyol ingredients] The raw materials were uniformly mixed in the ratio shown in Table 3 to prepare polyol components P-1 and P-2 as a polyol premix. In addition, raw material components are expressed in parts by mass.
[表3]
表1至表3中使用的原料如下。 ‧低異構體比率MDI：MDI含有比率為100%，MDI異構體比率為1%，NCO基含有率為33.5%。 ‧高異構體比率MDI：MDI含有比率為100%，MDI異構體比率為55%，NCO基含有率為33.5%。 ‧液狀MDI：MDI含有比率為70%，MDI異構體比率為1%，NCO基含有率為29.0%的碳二亞胺變性及脲酮亞胺變性MDI ‧DPG：二丙二醇（ADEKA公司製） ‧DOM：雙（2-乙基己基）馬來酸酯（大八化學工業公司製） ‧PG：丙二醇（東京化學工業公司製） ‧DEG：二乙二醇（三菱化學公司製） ‧MPO：2-甲基-1,3-丙二醇（東京化成工業公司製） ‧PTG-3000SN：PTMEG，數量平均分子量＝3000（商品名，保土谷化學公司製） ‧PTMEG2000：PTMEG，數量平均分子量＝2000（商品名，由INVISTA公司製） ‧DABCO NCIM：1-異丁基-2-甲基咪唑（商品名，Evonik公司製） ‧SRX-280A：矽酮泡沫穩定劑（商品名，Toray Dow Corning公司製）。The raw materials used in Tables 1 to 3 are as follows. ‧Low isomer ratio MDI: MDI content ratio is 100%, MDI isomer ratio is 1%, NCO group content ratio is 33.5%. ‧High isomer ratio MDI: MDI content ratio is 100%, MDI isomer ratio is 55%, and NCO group content ratio is 33.5%. ‧Liquid MDI: carbodiimide-denatured and uretonimine-denatured MDI with an MDI content ratio of 70%, an MDI isomer ratio of 1%, and an NCO group content of 29.0% ‧DPG: Dipropylene glycol (manufactured by ADEKA) ‧DOM: Bis(2-ethylhexyl)maleate (manufactured by Daihachi Chemical Industry Co., Ltd.) ‧PG: Propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) ‧DEG: Diethylene glycol (manufactured by Mitsubishi Chemical Corporation) ‧MPO: 2-methyl-1,3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) ‧PTG-3000SN: PTMEG, number average molecular weight = 3000 (trade name, manufactured by Hodogaya Chemical Co., Ltd.) ‧PTMEG2000: PTMEG, number average molecular weight = 2000 (trade name, manufactured by INVISTA) ‧DABCO NCIM: 1-isobutyl-2-methylimidazole (trade name, manufactured by Evonik Corporation) ‧SRX-280A: Silicone foam stabilizer (trade name, manufactured by Toray Dow Corning Co., Ltd.).
[ISF的製作] 使用異氰酸酯基末端的預聚物I-1~I-11，多元醇預混料P-1~P-2作為有機聚異氰酸酯組合物製作ISF。[Production of ISF] Use isocyanate group-terminated prepolymers I-1 to I-11 and polyol premixes P-1 to P-2 as organic polyisocyanate compositions to prepare ISF.
即，以表4~表5中所示的比例調整至40℃的溫度的各種有機聚異氰酸酯組合物與多元醇預混合物以7000r.p.m的回轉數、藉由桌上攪拌機混合攪拌。加熱至60℃並塗佈離型劑後，將此混合物倒入尺寸為200mm×200mm×10mm的乾燥金屬模中，蓋起並使之硬化7分鐘。硬化後，從模中取出以獲得ISF測試片（以下簡稱TP）。對於得到的TP，在70℃下加熱固化24小時後，實施密度、硬度、機械物性等評價。That is, various organic polyisocyanate compositions and polyol premixes adjusted to a temperature of 40° C. in the proportions shown in Tables 4 and 5 were mixed and stirred with a table mixer at a rotation speed of 7000 r.p.m. After heating to 60°C and applying a release agent, pour the mixture into a dry metal mold with dimensions of 200mm × 200mm × 10mm, cover it and allow it to harden for 7 minutes. After hardening, take it out from the mold to obtain the ISF test piece (hereinafter referred to as TP). The obtained TP was heat-cured at 70° C. for 24 hours, and then evaluated for density, hardness, mechanical properties, and the like.
>物性測定> ‧密度：根據JIS K7222測定。 ‧硬度（ASKER-C，附表層的表面硬度）：根據JIS K7312測定。 ‧反彈彈性係數：根據JIS K6400-3測定。 ‧TR（撕裂強度，使用B型啞鈴）：根據JIS K6400-5測定。 ‧分層撕裂強度根據ISO20875測定。>Physical property measurement> ‧Density: measured according to JIS K7222. ‧Hardness (ASKER-C, surface hardness of attached surface layer): Measured according to JIS K7312. ‧Rebound elastic coefficient: measured according to JIS K6400-3. ‧TR (tear strength, using B-type dumbbells): measured according to JIS K6400-5. ‧Lamination tear strength is measured according to ISO20875.
>綜合評價> 在以下三個項目的物性項目中，超過標準值的項目被判定為良好。 ‧反彈彈性係數：50%以上 ‧TR：100N/cm以上 ‧撕裂強度：2.50kg/cm以上。>Comprehensive evaluation> Among the physical properties of the following three items, items exceeding the standard value are judged to be good. ‧Rebound elasticity coefficient: more than 50% ‧TR: 100N/cm or more ‧Tear strength: above 2.50kg/cm.
製作的ISF的評價結果示於表4~表5。The evaluation results of the prepared ISF are shown in Tables 4 and 5.
[表4]
[表5]
從表4~表5顯而易見，根據本發明，從在室溫下為液狀的異氰酸酯得到的ISF具有高反彈彈性係數和優異的機械強度。It is apparent from Tables 4 to 5 that according to the present invention, ISF obtained from isocyanate that is liquid at room temperature has a high rebound elastic coefficient and excellent mechanical strength.
根據本發明，在以往市場中沒有的高反彈彈性係數與優異的機械物性的聚氨酯整體表層發泡，在鞋底、鞋墊、產業用機械的零件、玩具、樂器等中產生提升使用感、輕量化等的優異的效果。According to the present invention, the polyurethane integral surface layer foaming with high elasticity coefficient and excellent mechanical properties not previously available in the market can be used in shoe soles, insoles, parts of industrial machinery, toys, musical instruments, etc. to improve the use feeling and reduce weight. of excellent results.
無。without.
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