WO2023032827A1 - ポリウレタンを含む非発泡の成形体 - Google Patents
ポリウレタンを含む非発泡の成形体 Download PDFInfo
- Publication number
- WO2023032827A1 WO2023032827A1 PCT/JP2022/032142 JP2022032142W WO2023032827A1 WO 2023032827 A1 WO2023032827 A1 WO 2023032827A1 JP 2022032142 W JP2022032142 W JP 2022032142W WO 2023032827 A1 WO2023032827 A1 WO 2023032827A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- molded body
- line segment
- molded article
- polyurethane
- compact
- Prior art date
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 39
- 241000428199 Mustelinae Species 0.000 claims abstract description 22
- 230000003628 erosive effect Effects 0.000 claims abstract description 20
- 230000005484 gravity Effects 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001757 thermogravimetry curve Methods 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 29
- 229920005862 polyol Polymers 0.000 description 68
- 150000003077 polyols Chemical class 0.000 description 64
- 238000002425 crystallisation Methods 0.000 description 20
- 230000008025 crystallization Effects 0.000 description 20
- 229920005906 polyester polyol Polymers 0.000 description 20
- 239000013078 crystal Substances 0.000 description 15
- -1 isocyanate compound Chemical class 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 229920001228 polyisocyanate Polymers 0.000 description 12
- 239000005056 polyisocyanate Substances 0.000 description 12
- 239000000523 sample Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 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 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000013638 trimer Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000013500 performance material Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- OXWGYJSRWGUSAS-UHFFFAOYSA-N 2-[1-[bis[3-(dimethylamino)propyl]amino]propyl-(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)C(CC)N(CCCN(C)C)CCCN(C)C OXWGYJSRWGUSAS-UHFFFAOYSA-N 0.000 description 2
- WKFZFCHGVNDUGC-UHFFFAOYSA-N 2-[2-[bis[3-(dimethylamino)propyl]amino]ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound CN(C)CCCN(CCCN(C)C)CCN(CCO)CCO WKFZFCHGVNDUGC-UHFFFAOYSA-N 0.000 description 2
- QLEUIUXVMXQKAL-UHFFFAOYSA-N 2-[2-hydroxyethyl(2-piperidin-1-ylethyl)amino]ethanol Chemical compound OCCN(CCO)CCN1CCCCC1 QLEUIUXVMXQKAL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens 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
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000010068 moulding (rubber) Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 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 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-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
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- MPJZCYUPWINKPK-UHFFFAOYSA-N 1,4-diazabicyclo[2.2.2]octan-3-ylmethanol Chemical compound C1CN2C(CO)CN1CC2 MPJZCYUPWINKPK-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- BHKOCEZNSPECCQ-UHFFFAOYSA-N 1-[2-[2-(dimethylamino)ethyl-methylamino]ethyl-methylamino]propan-2-ol Chemical compound CC(O)CN(C)CCN(C)CCN(C)C BHKOCEZNSPECCQ-UHFFFAOYSA-N 0.000 description 1
- RASZDHABSJNFEW-UHFFFAOYSA-N 1-[bis[2-(dimethylamino)ethyl]amino]propan-2-ol Chemical compound CN(C)CCN(CC(O)C)CCN(C)C RASZDHABSJNFEW-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- CYYDNXCYDWWSPS-UHFFFAOYSA-N 2-(2,2,2-trichloroethyl)oxirane Chemical compound ClC(Cl)(Cl)CC1CO1 CYYDNXCYDWWSPS-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- YJLVHNUSDMJNLV-UHFFFAOYSA-N 2-[1-(dimethylamino)hexyl-(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCC(N(C)C)N(CCO)CCO YJLVHNUSDMJNLV-UHFFFAOYSA-N 0.000 description 1
- UUYDMQSUTMUOHL-UHFFFAOYSA-N 2-[1-(dimethylamino)propyl-(2-hydroxyethyl)amino]ethanol Chemical compound CCC(N(C)C)N(CCO)CCO UUYDMQSUTMUOHL-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- KOTHTSHIGYKYDO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-(2-hydroxyethyl)amino]ethanol Chemical compound CN(C)CCN(CCO)CCO KOTHTSHIGYKYDO-UHFFFAOYSA-N 0.000 description 1
- WVKTYUDLMQWYFG-UHFFFAOYSA-N 2-[2-[2-(dimethylamino)ethyl-methylamino]ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCN(C)CCO WVKTYUDLMQWYFG-UHFFFAOYSA-N 0.000 description 1
- IAXFZZHBFXRZMT-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(OCCO)=C1 IAXFZZHBFXRZMT-UHFFFAOYSA-N 0.000 description 1
- URMNSGRKNJZDMV-UHFFFAOYSA-N 2-[[1-(dimethylamino)-2,2-dimethylpropyl]-(2-hydroxyethyl)amino]ethanol Chemical compound CN(C)C(C(C)(C)C)N(CCO)CCO URMNSGRKNJZDMV-UHFFFAOYSA-N 0.000 description 1
- BNKMZHBUIBJDEY-UHFFFAOYSA-N 2-[bis[2-(dimethylamino)ethyl]amino]ethanol Chemical compound CN(C)CCN(CCO)CCN(C)C BNKMZHBUIBJDEY-UHFFFAOYSA-N 0.000 description 1
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- RHNUACKKOCDJJH-UHFFFAOYSA-N 3-[1-(dimethylamino)hexyl-(3-hydroxypropyl)amino]propan-1-ol Chemical compound CCCCCC(N(C)C)N(CCCO)CCCO RHNUACKKOCDJJH-UHFFFAOYSA-N 0.000 description 1
- HJAAUFMUUCJGDF-UHFFFAOYSA-N 3-[1-(dimethylamino)propyl-(3-hydroxypropyl)amino]propan-1-ol Chemical compound OCCCN(C(N(C)C)CC)CCCO HJAAUFMUUCJGDF-UHFFFAOYSA-N 0.000 description 1
- JXPOEOJVJFVVHS-UHFFFAOYSA-N 3-[2-(dimethylamino)ethyl-(3-hydroxypropyl)amino]propan-1-ol Chemical compound CN(C)CCN(CCCO)CCCO JXPOEOJVJFVVHS-UHFFFAOYSA-N 0.000 description 1
- DZFAPKNHRVWBDY-UHFFFAOYSA-N 3-[[1-(dimethylamino)-2,2-dimethylpropyl]-(3-hydroxypropyl)amino]propan-1-ol Chemical compound OCCCN(C(N(C)C)C(C)(C)C)CCCO DZFAPKNHRVWBDY-UHFFFAOYSA-N 0.000 description 1
- SPEHEHYVDRYEDX-UHFFFAOYSA-N 3-methyloxan-2-one Chemical compound CC1CCCOC1=O SPEHEHYVDRYEDX-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920004552 POLYLITE® Polymers 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000002950 deficient Effects 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
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000011187 glycerol Nutrition 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
- 238000001341 grazing-angle X-ray diffraction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WATYAKBWIQTPDE-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O WATYAKBWIQTPDE-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 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
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/794—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aromatic isocyanates or isothiocyanates
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N3/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N3/40—Investigating hardness or rebound hardness
- G01N3/42—Investigating hardness or rebound hardness by performing impressions under a steady load by indentors, e.g. sphere, pyramid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B1/00—Cleaning by methods involving the use of tools
- B08B1/10—Cleaning by methods involving the use of tools characterised by the type of cleaning tool
- B08B1/16—Rigid blades, e.g. scrapers; Flexible blades, e.g. wipers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/22—Component parts, details or accessories; Auxiliary operations
- B29C39/44—Measuring, controlling or regulating
-
- 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
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/201—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials by measuring small-angle scattering
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2203/00—Investigating strength properties of solid materials by application of mechanical stress
- G01N2203/0058—Kind of property studied
- G01N2203/0076—Hardness, compressibility or resistance to crushing
- G01N2203/0078—Hardness, compressibility or resistance to crushing using indentation
- G01N2203/0082—Indentation characteristics measured during load
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G21/00—Arrangements not provided for by groups G03G13/00 - G03G19/00, e.g. cleaning, elimination of residual charge
- G03G21/0005—Arrangements not provided for by groups G03G13/00 - G03G19/00, e.g. cleaning, elimination of residual charge for removing solid developer or debris from the electrographic recording medium
- G03G21/0011—Arrangements not provided for by groups G03G13/00 - G03G19/00, e.g. cleaning, elimination of residual charge for removing solid developer or debris from the electrographic recording medium using a blade; Details of cleaning blades, e.g. blade shape, layer forming
- G03G21/0017—Details relating to the internal structure or chemical composition of the blades
Definitions
- the present disclosure relates to a non-foamed molding containing polyurethane used for cleaning stains on window glass, floors, and the like.
- the present disclosure relates to non-foamed moldings containing polyurethane that can be used for cleaning and the like. Cleaning is carried out by bringing a rubber molded plate into contact with an object to be cleaned, such as a window glass of an automobile, a window glass of a building, a floor, an electrophotographic roller, or the like.
- wiper blades are made of various synthetic rubbers such as natural rubber, chloroprene rubber, and EPDM rubber (ethylene-propylene-diene rubber).
- polyurethane resin moldings are used as cleaning blades for the purpose of cleaning toner from rollers and the like.
- Japanese Patent Application Laid-Open No. 2004-200000 proposes a structure in which the inside of the cleaning blade has a lower hardness than the surface in order to achieve both a high surface hardness and followability to a roller, which is an object to be cleaned. More specifically, by impregnating a polyurethane molding with an isocyanate compound and allowing it to react, a hardened region is formed on the surface while keeping the inside of the cleaning blade flexible.
- Patent Document 1 a rubber molded body (cleaning blade) having a high-hardness contact surface with an object to be cleaned has been used for a long period of time.
- fine cracks may occur on the surface of the rubber molding due to insufficient toughness of the hardened surface.
- the effect of cleaning the object to be cleaned by the rubber molding may be lowered.
- One aspect of the present disclosure is directed to providing a molded article containing polyurethane that can stably exhibit superior cleaning performance over a long period of time while maintaining stable followability to an object to be cleaned. is.
- HM be the Martens hardness measured at the point SA on the surface of the compact where one end A of the line segment LM is located, Martens hardness measured at three points every 30 ⁇ m from the end A on the line segment LM to the other end of the line segment LM in the cross section of the molded body including the entire length of the line segment LM
- a molded article containing polyurethane that can stably exhibit superior cleaning performance over a long period of time while maintaining stable followability to an object to be cleaned. can.
- FIG. 1 is a schematic diagram of a compact according to one aspect of the present disclosure
- FIG. It is a figure which shows the measuring method of an erosion rate.
- FIG. 1 shows a schematic diagram of a non-foamed molding containing polyurethane according to one aspect of the present disclosure.
- a straight line L passing through the molded body 11 and passing through the center of gravity G of the molded body 11 and a point on the surface of the molded body 11 located closest to the center of gravity G is drawn.
- the length of the longest line segment LM among the portions overlapping the molded article 11 on the straight line L is at least 180 ⁇ m.
- a point SA is a point on the surface of the compact 11 where one end A of the line segment LM is located.
- the center of gravity is a point obtained by taking the arithmetic mean of all points belonging to the outline of the compact. Multiple integration may be used as a general technique for finding the center of gravity based on such a definition.
- a method using the outer product of vectors may be applied. Since these calculation methods are generally known mathematical concepts, detailed descriptions thereof are omitted here.
- a non-foamed that is, a solid molded article containing polyurethane satisfying the following conditions (1) to (4) has excellent chipping resistance and excellent cleaning performance. It has been found that a cleaning blade capable of exhibiting
- the HM 1 is 1.0 N/mm 2 or more.
- the erosion rate E measured using spherical alumina particles having an average particle diameter (D 50 ) of 3.0 ⁇ m in the surface region to be evaluated is 0.6 ⁇ m/g or less.
- the Martens hardness at point SA existing on the surface of the compact is defined as HM1 .
- three points (P 2 , P 3 and P 4 ) are taken as HM 2 , HM 3 and HM 4 respectively. Since HM 2 >HM 3 >HM 4 at that time, the molded body has a structure in which the hardness decreases from the surface toward the inside.
- the Martens hardness HM 1 of the outermost surface of the molded article according to the present disclosure is 1.0 N/mm 2 or more. If the Martens hardness of the outermost surface is 1.0 N/mm 2 or more, it is possible to contact the object to be cleaned with a high contact pressure. Also, the Martens hardness HM 1 of the outermost surface is preferably 5.0 N/mm 2 or less. If the Martens hardness HM 1 of the outermost surface is 5.0 N/mm 2 or less, when the molded body is used as a cleaning blade for a long period of time, it can flexibly contact the object to be cleaned even if it has streaky unevenness. It is possible to suppress the occurrence of poor cleaning.
- the index value K ⁇ is a value calculated by evaluating the surface area to be evaluated of the compact including the point SA by the oblique incidence X-ray method.
- the oblique incidence X-ray method can obtain information on locations with different depths from the surface by measuring while slightly changing the incident angle of X-rays, and by increasing the incident angle, it is possible to obtain information on deeper areas. can be obtained.
- Structural information at a depth of 10 ⁇ m to 65 ⁇ m can be obtained with characteristic X-rays from a Cu tube by changing the incident angle from 0.5 to 3°.
- the index value K ⁇ of the degree of crystallinity is calculated from the area ratio of the crystalline peak and the amorphous peak. A larger K ⁇ indicates a higher degree of crystallinity (more crystal components).
- the area of the surface region to be evaluated is equal to or larger than the X-ray irradiation area.
- the irradiation area is preferably 11.5 to 15.0 ⁇ m 2 .
- the erosion rate E is a value calculated by a micro slurry jet erosion (MSE) test.
- MSE micro slurry jet erosion
- the erosion rate E is a parameter that indicates the erosion depth per unit projection amount and indicates the brittleness of the object to be evaluated. That is, the larger the value of the erosion rate E, the more fragile the object to be evaluated. Therefore, a compact having a large erosion rate E is likely to have fine cracks due to long-term use.
- General polyurethane tends to become brittle as the hardness increases.
- the compact according to the present disclosure has a small parameter indicating brittleness (erosion rate E) calculated by the MSE test, although the surface thereof is hardened. That is, despite the high hardness of the surface, it is not brittle.
- the MSE test can also be considered a value that indicates the long-term durability of the molding. For example, a compact having a surface with an erosion rate E of 0.6 ⁇ m/g or less measured using spherical alumina particles having an average particle diameter (D 50 ) of 3.0 ⁇ m is sufficiently strength. Therefore, chipping is less likely to occur in the contact portion with the object to be cleaned even after cleaning over a long period of time, and the occurrence of defective cleaning due to chipping can be suppressed.
- the erosion rate E is particularly preferably 0.5 ⁇ m/g or less. It is more resistant to abrasion, and can more reliably suppress the occurrence of fine chipping of the contacted portion when used for cleaning purposes.
- the MSE test can be performed using, for example, an MSE-A type test apparatus (Palmeso Co., Ltd.).
- Molded bodies containing polyurethane according to the present disclosure are preferably non-foamed, that is, solid.
- the polyurethane is obtained mainly from raw materials such as polyol, polyisocyanate, chain extender, catalyst and other additives.
- the molded article according to the present disclosure is preferably non-foamed, that is, solid is that the molded article is less likely to break due to bubbles, and the mechanical properties of the molded article are less likely to be impaired.
- bubbles that are unavoidably mixed in during the manufacturing process are within the allowable range.
- the acceptable foam content is 10% by volume or less, preferably 1% by volume or less.
- Polyols that can be used in the production of molded articles according to the present disclosure include those having at least one hydroxyl group at a polymer terminal, branched chain terminal, or the like.
- Examples of the polyol include, but are not particularly limited to, commercially available polyols used for producing polyurethane.
- Polyester polyols obtained by polycondensation of polyhydric alcohols and polycarboxylic acids for example: Polyester polyols obtained by polycondensation of polyhydric alcohols and polycarboxylic acids, polyether polyols obtained by ring-opening polymerization of alkylene oxide, polymer polyols obtained by radical polymerization of vinyl monomers in polyether polyols polyesteramide polyols obtained by polycondensation of polyhydric alcohols, polycarboxylic acids and amino alcohols, polylactone polyols obtained by ring-opening polymerization of lactones, polyhydric alcohols and carbonates Polycondensation polycarbonate polyols, acrylic polyols, polybutadiene polyol and hydrogenated products thereof, polyisoprene polyol and hydrogenated products thereof, partially saponified ethylene-vinyl acetate copolymer, natural oils such as soybean oil and castor oil polyols, halogen- and/or phosphorus-based poly
- polyether polyols examples include the following. Polyether polyol compounds obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide to polymerization initiators such as ethylene diamine, tolylene diamine, sucrose, amino alcohols and diethylene glycol.
- alkylene oxides such as ethylene oxide and propylene oxide
- polymerization initiators such as ethylene diamine, tolylene diamine, sucrose, amino alcohols and diethylene glycol.
- halogen- and/or phosphorus-based polyols include the following. Halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, brominated pentaerythritol/sucrose-based polyols, halogen-based polyols such as tetrabromophthalic acid polyester, and alkylene oxides obtained by adding alkylene oxides to phosphoric acid compounds phosphorus-based polyol and the like;
- phenolic polyols examples include the following.
- Phenol or phenol derivatives such as nonylphenol and alkylphenol are Mannich-modified using formaldehyde and secondary amines such as diethanolamine, ammonia, primary amines, etc., and are obtained by ring-opening addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide. such as Mannich polyols.
- Polycarbonate polyols include, for example, reaction products of the above-described polyols and dialkyl carbonates such as dimethyl carbonate. Specific examples include polytetramethylene carbonate diol, poly3-methylpentamethylene carbonate diol, polyhexamethylene carbonate diol, and the like.
- polyether polyols include reaction products obtained by addition-polymerizing one or more of the following monomers using one or more of the following compounds having at least two active hydrogen atoms as an initiator. It may be block addition, random addition or a mixture of both.
- Monomers ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc.
- Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like.
- Polyolefin polyols include polyacrylate polyols, chlorinated polyolefin polyols, polybutadiene polyols, polychloroprene polyols, and polybutadiene styrene polyols.
- polyester polyols which are used for producing polyurethane, because they are readily available and have an excellent balance between the crystallization temperature and the melting point of crystallization.
- Polyester polyols can be obtained by known methods such as polycondensation of polyhydric alcohols and polycarboxylic acids.
- Polyester polyols include compounds derived from dibasic acids and polyhydric alcohols. Examples include, but are not limited to, the following. Polyester polyols derived from adipic acid, orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, succinic acid, azelaic acid, sebacic acid, linoselic acid, dimethyl terephthalate, polyethylene terephthalate, and the like. Also included are lactone-based polyester polyols obtained by ring-opening polymerization of cyclic esters such as ⁇ -caprolactone and methylvalerolactone.
- the crystallization temperature is 0 ° C. or higher and 150 ° C. or lower. It is preferable because it is suitable for Moreover, since it is required to be crystallized at room temperature, the melting point is preferably 30° C. or higher, more preferably 40° C. or higher.
- the melting point and crystallization temperature can be obtained by known methods such as differential scanning thermal analysis.
- R 1 and R 2 are linear divalent hydrocarbon groups having 4 to 10 carbon atoms, and R 1 and R 2 may be the same or different. n represents an integer of 1 or more.
- Polyester polyols in which R 1 and R 2 are different are preferred from the viewpoint of production and crystal structure characteristics. Further, it may contain a linear divalent hydrocarbon group having 2 to 3 carbon atoms.
- the number average molecular weight of the polyester polyol as a whole is preferably 400 to 10,000, particularly preferably 800 to 4,000. If it is 800 or more, the main chain of the polyol crystallizes, so that the obtained urethane has good hardness and chip resistance. excellent in hardness and good hardness.
- R 1 and R 2 in chemical formula (1) When the number of carbon atoms in R 1 and R 2 in chemical formula (1) is 3 or less, crystallization is difficult to progress and it is difficult to increase the hardness of the surface. In addition, when the number of carbon atoms in R 1 and R 2 is 11 or more, excessive crystallization occurs and embrittlement tends to occur.
- R 1 and R 2 are linear divalent hydrocarbon groups having 4 to 10 carbon atoms, the crystal structure formed by the orientation of the main chain portion of the polyol has a high hardness. disappears, the hardness becomes low. Therefore, when the crystal structure is attenuated from the surface to the inside, the hardness can be continuously lowered from the surface to the inside. Therefore, the molded body according to the present disclosure can increase the contact pressure against the object to be cleaned. In addition, it is possible to improve the followability to the shape of the object to be cleaned.
- the molded article according to the present disclosure has a high hardness region having a crystal structure in which main chains of polyols having linear alkyl chains having 4 to 10 carbon atoms are oriented by intermolecular forces. there is Therefore, the molded article according to the present disclosure is excellent in impact absorption. Therefore, when the molded article according to the present disclosure is applied as an elastic member of a cleaning blade, even when the cleaning blade is used for a long period of time, the lack of hard segments due to micro stress caused by unevenness in hardness does not occur. and excellent chipping resistance.
- polyester polyols having linear alkyl chains having 4 to 10 carbon atoms it is preferable to combine two or more polyester polyols having linear alkyl chains having 4 to 10 carbon atoms.
- the asymmetry of the crystal structure is increased, and a region with higher impact resistance can be formed.
- the first polyester polyol described below and the second polyester polyol described below are used in combination, the interaction between the crystal structures is promoted, and the impact resistance is further improved, which is preferable.
- Second polyester polyol having a linear alkyl chain having 7 to 10 carbon atoms and 4 to 6 carbon atoms Polyester polyols with both linear alkyl chains
- polyester polyols examples include the following. NIPPORUN (registered trademark) 164 (manufactured by Tosoh Corporation), NIPPOLAN (registered trademark) 4073 (manufactured by Tosoh Corporation), NIPPOLAN (registered trademark) 136 (manufactured by Tosoh Corporation), NIPPOLAN (registered trademark) 4009 (manufactured by Tosoh Corporation) Co., Ltd.), NIPPOLAN (registered trademark) 4010 (manufactured by Tosoh Corporation), NIPPOLAN (registered trademark) 3027 (manufactured by Tosoh Corporation), Polylight (registered trademark) OD-X-2555 (manufactured by DIC Corporation) ), Polylight (registered trademark) OD-X-2523 (manufactured by DIC Corporation), ETERNACOLL (registered trademark) 3000 series (manufactured by Ube Industries, Ltd.), and the like.
- the structure of chemical formula (1) can be determined using a direct sample introduction type mass spectrometer that ionizes sample molecules. Specifically, a sample sampled from the compact according to the present disclosure is heated and vaporized in an ionization chamber, and a direct sample introduction mass spectrometer that ionizes sample molecules is used at a temperature increase rate of 10 ° C./sec. , when the amount of all ions detected when heated to 1000° C. is M1, and the integrated intensity of the peak of the extracted ion thermogram corresponding to the m/z value derived from chemical formula (1) is M2, M2/M1 is It is preferably between 0.0001 and 0.10000. By including the structure of the chemical formula (1) in this range, the crystal structure of the surface can be formed more reliably.
- polyisocyanates examples include the following. 4,4'-diphenylmethane diisocyanate (MDI), 1,5-pentamethylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), xylene Diisocyanate (XDI), 1,5-naphthylene diisocyanate (1,5-NDI), P-phenylene diisocyanate (PPDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate ( Hydrogenated MDI), tetramethylxylene diisocyanate (TMXDI), carbodiimide-modified MDI, polymethylenephenyl polyisocyanate (PAPI), trimer compounds (isocyanurates) or polymer compounds of these diiso
- MDI 4,4'-
- a polyisocyanate react with various polyols.
- trimer nurate form
- monomer of xylylene diisocyanate because of its excellent mechanical properties.
- trimer isocyanate is particularly preferred because it has a branched structure and a strained structure in its skeleton, which can reduce the formation of hard segments.
- chain extender examples include the following. Ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol , tripropylene glycol and other aliphatic diols, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A and other alicyclic diols, bisphenol A, hydroquinone, bishydroxyethoxybenzene and other aromatic ring-containing polyhydric alcohols such as diols, trimethylolpropane, glycerin, pentaerythritol and sorbitol; These may be used alone or in combination of two or more.
- catalysts generally used for the curing reaction of polyurethane may be used in the present disclosure.
- examples of catalysts include the following. Tin compounds such as tin octoate and dibutyltin dilaurate, zinc compounds such as zinc octylate and zinc acetylacetone, organic carboxylates such as potassium acetate and potassium 2-ethylhexanoate, triethylenediamine, tetramethylbutanediamine, N, N -dimethyl-N',N'-bis(hydroxyethyl)ethylenediamine, N,N-dimethyl-N',N'-bis(hydroxyethyl)propanediamine, N,N-dimethyl-N',N'-bis( hydroxyethyl)neopentanediamine, N,N-dimethyl-N',N'-bis(hydroxyethyl)hex
- additives such as pigments, plasticizers, waterproofing agents, antioxidants, ultraviolet absorbers, light stabilizers, etc.
- additives such as pigments, plasticizers, waterproofing agents, antioxidants, ultraviolet absorbers, light stabilizers, etc.
- polyrotaxane can also be contained as a toughness improver, and in particular, polyrotaxane having a hydroxyl group can also be used as a polyol and can be preferably used.
- the reaction temperature and the reaction time of polyurethane are controlled so that the urethanization reaction proceeds reliably and the polyurethane is sufficiently cured.
- embrittlement associated with high hardness which has been a problem of conventional polyurethanes, can be prevented by setting the following curing conditions.
- the curing conditions are described in detail below.
- the polyurethane is cured by heating until the cross-linking is completed, and then aged under a predetermined atmosphere.
- curing is stopped before the polyurethane is completely crosslinked, and then secondary curing is performed by aging in an atmosphere below the crystallization temperature of the polyol.
- the unreacted polyol exists in a state of high molecular mobility. While maintaining this state, the semi-cured polyurethane is secondarily cured in an atmosphere below the crystallization temperature of the polyol. This creates a temperature gradient from the surface to the inside of the semi-cured polyurethane. Then, the surface of the semi-cured polyurethane is quickly cooled by being placed in the atmosphere, and crystallization of the remaining main chain portion of the polyol proceeds. On the other hand, the inside of the semi-cured polyurethane is cooled more slowly than the surface due to being placed in the atmosphere.
- the elastic member thus obtained has a high hardness in the vicinity of the surface due to crystallization of the main chain portion of the polyol.
- the crystallization of the polyol has not progressed relatively in the interior, and the hardness is low. Therefore, the Martens hardness is gradually attenuated from the surface toward the inside.
- the polyurethane When the polyurethane is cured until the cross-linking is completed as in the conventional method, the cross-linked structure of the polyurethane is sufficiently developed, so even if unreacted polyol remains, its molecular mobility is low. Therefore, even if aging is performed at a temperature below the crystallization temperature of the polyol after that, it is difficult to orient the main chain portion of the polyol, and crystallization of the surface hardly progresses.
- the urethane is chemically crosslinked even though the primary curing is incomplete, so the surface after the secondary curing has a structure in which the crystal structure of the main chain portion of the polyol and the chemical crosslinking of the urethane are mixed. It's becoming When only the crystal structure of the main chain of polyol exists on the surface, the Martens hardness of the surface becomes excessively high, and when used for a long time, the surface of the object to be cleaned becomes flexible with streak-like unevenness. It is not possible to make contact, resulting in poor cleaning.
- the crystallization of polyol can be adjusted by the progress of chemical cross-linking of urethane during primary curing and the difference between the ambient temperature during secondary curing and the crystallization temperature of polyol.
- the chemical cross-linking of urethane during primary curing is reduced, the molecular mobility of polyol after primary curing increases, the surface becomes more likely to crystallize, and the interior also becomes more likely to crystallize.
- the greater the difference between the ambient temperature during the secondary curing and the crystallization temperature of the polyol the easier the crystallization progresses, and the crystallization of the surface and the interior is accelerated.
- the above polyurethane raw material composition is injected into the mold, and the primary curing and secondary curing are performed as described above, whereby the molded body and the support member are integrally molded. you can get a body Alternatively, a polyurethane elastomer sheet cured under manufacturing conditions satisfying the above curing conditions may be molded, cut into strips, and adhered onto the support member.
- the bonding method can be selected from a method of coating or sticking an adhesive on the support member to adhere the molding, a method of superimposing the molding and the support member, heating and pressurizing them, and adhering them.
- cutting may be performed to adjust the shape of the edge of the molded article to be brought into contact with the object to be cleaned.
- cutting may be performed before or after adhesion.
- the polyol component was measured by a direct sample introduction method (DI method) in which the sample was not passed through a gas chromatograph (GC) but directly introduced into the ion source.
- DI method direct sample introduction method
- GC gas chromatograph
- DEP Direct Exposure Probe
- sample sampled in the SA was fixed to a filament located at the tip of the probe and inserted directly into the ionization chamber. After that, it was rapidly heated from room temperature to 1000° C. at a constant heating rate (10° C./s), and the vaporized gas was detected by a mass spectrometer.
- the detected amount M1 of all ions was the sum of integrated intensities of all peaks in the obtained total ion current thermogram.
- the detected amount M2 of the polyol component was the integrated intensity of the peak of the extracted ion thermogram corresponding to the m/z value calculated by the formula (2).
- R1 and R2 in formula (2) represent the number of carbon atoms of R1 and R2 in chemical formula (1), respectively.
- a numerical value obtained from a sample cut from point SA was taken as the M2/M1 value in the present disclosure.
- the area value obtained by I c1 and I a1 were substituted into the following formula (1) to obtain the crystallinity index K ⁇ 1 .
- I c2 and I a2 were substituted into the following formula (1) to obtain the index K ⁇ 2
- I c3 and I a3 were substituted into the following formula (1) to obtain the index K ⁇ 3 .
- K ⁇ [ Ic /( Ic + Ia )] ⁇ 100 (1) It was evaluated whether the obtained values of K ⁇ 1 , K ⁇ 2 , and K ⁇ 3 satisfy the following relationships. Then, it was described in the column of "Crystallinity analysis" in Tables 2 and 3 as “Y” when it was satisfied, and as "N” when it was not satisfied. Crystallinity: Y: When satisfying K ⁇ 1 >K ⁇ 2 >K ⁇ 3 N: When not satisfying K ⁇ 1 >K ⁇ 2 >K ⁇ 3
- Y The area of the surface region to be evaluated is equal to or larger than the X-ray irradiation area.
- N The area of the surface region to be evaluated is less than the X-ray irradiation area.
- erosion rate E The erosion rate was measured using a “MSE-A type testing device” manufactured by Palmeso Co., Ltd. Spherical alumina powder with an average particle diameter of 3.0 ⁇ m (product name “AX3-15” manufactured by Nippon Steel & Sumikin Materials Co., Ltd. Micro Company) is dispersed in water, and the spherical alumina is added at 3% by mass with respect to the total mass of the slurry. A slurry was prepared containing
- the compact 23 was fixed to a table (not shown) so that the slurry 22 projected from the nozzle 21 was perpendicular to the surface of the compact 23 .
- Slurry 22 in which spherical alumina 24 was dispersed in water 25 was sprayed with a distance of 4 mm between the surface of compact 23 and the lower end of nozzle 21 .
- the measurement environment is a temperature of 23° C. and a relative humidity of 55%
- the slurry projection speed is 100 m/sec
- the cutting depth is measured by a stylus-type surface profiler manufactured by Kosaka Laboratory Co., Ltd.
- a diamond needle with a tip radius R of 10 ⁇ m. was measured using a stylus.
- spherical silica powder with an average particle size of 3.0 ⁇ m (product name “AX3-15” manufactured by Nippon Steel & Sumikin Materials Co., Ltd. Micro Company) was dispersed in water, and the total mass of the slurry was A slurry containing 3% by mass of spherical alumina was prepared. The prepared slurry was applied to the surface of the glass substrate, and after drying, deionized water was again dropped onto the surface of the glass substrate. The glass substrate was fixed to the table of the surface property measuring instrument described below, and the surface of the molded body described below was coated with the slurry and dripped with 1 g of deionized water.
- a slide test was conducted by reciprocating the base on which the glass substrate was fixed, while contacting them at an angle of 24°.
- Surface property measuring machine TYPE38, manufactured by Shinto Kagaku Co., Ltd.
- Molded body Shape: Strip Size: Width 30mm, Length 20mm, Thickness 2mm Test condition: Sliding load: 100g Sliding speed: 100mm/sec Sliding time: 5 minutes Setting distance of reciprocating motion: 50mm
- the silica particles remaining in the cleaning range were visually checked to confirm the cleaning performance and evaluated using the following criteria. Then, in the column of "cleaning performance rank" in Tables 2 and 3, "A", "B” or "C” was written according to the evaluation results.
- Rank A All silica particles have been removed.
- Rank B Remaining silica particles were observed, but stains in which silica particles remained in streaks could not be confirmed.
- Rank C Contamination in which silica particles remain in streaks due to chipping of the molded body was confirmed.
- Polyester polyol trade name “Nippolan (registered trademark) 164” manufactured by Tosoh Corporation R 1 and R 2 in chemical formula (1) are a combination of 4 and 6 carbon atoms.
- Polyester polyol trade name “Nipporan (registered trademark) 4009” manufactured by Tosoh Corporation R 1 and R 2 in chemical formula (1) have 4 carbon atoms.
- Polyester polyol trade name “Polylite (registered trademark) OD-X-2555” manufactured by DIC Corporation A combination of R 1 and R 2 in chemical formula (1) having 6 and 10 carbon atoms.
- Example 1 A polyol component, a chain extender, and a urethanization catalyst were blended in the weights shown in Table 1. Each component was dehydrated by heating under reduced pressure, if necessary. The blended mixture was stirred under reduced pressure for 5 minutes to obtain a homogeneous polyol-based solution. A polyisocyanate component was blended in the solution containing the polyol as the main component in the mass shown in Table 1, stirred again under reduced pressure for 3 minutes, and then a mold (thickness 2 mm, height 40 mm, width 200 m) heated to 130 ° C. ). After primary curing for 3 minutes, the mold was rapidly cooled to 25° C. and held in the mold for 12 hours for secondary curing. After that, the mold was removed from the mold to obtain a compact 1.
- the mold used was coated with a release agent before injecting the polyurethane elastomer composition.
- a mixture of the following materials was used as the release agent.
- ELEMENT14 PDMS 1000-JC (trade name, manufactured by Momentive Performance Materials) 5.06 g ELEMENT14 PDMS 10K-JC (trade name, manufactured by Momentive Performance Materials) 6.19 g SR1000 (trade name, manufactured by Momentive Performance Materials) 3.75g EXXSOL (registered trademark) DSP145/160 (trade name, manufactured by Exxon Mobil) 85 g
- This molded body was appropriately cut to obtain a test piece used for the above evaluation. Table 2 shows the obtained evaluation results.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
ゴム成形体の板を、清掃対象物、例えば、自動車の窓ガラス、建物の窓ガラス、床、電子写真のローラなどに当接させ、清掃することが行われている。具体的には、例えば、ワイパーブレードには天然ゴムをはじめとしてクロロプレンゴム、EPDMゴム(エチレン・プロピレン・ジエンゴム)等の各種合成ゴムが使用されている。また、電子写真装置においては、ローラなどからトナーを清掃する目的で、ポリウレタン樹脂の成形体がクリーニングブレードとして使用されている。
しかし、本発明者らの検討によれば、特許文献1に記載されているように清掃対象物との当接面を高硬度化してなるゴム成形体(クリーニングブレード)を長期に亘って使用した場合、高硬度化した表面の靭性が不足することで、ゴム成形体の表面に微細な欠けが生じることがあった。その結果として、当該ゴム成形体による清掃対象物の清掃効果が低下することがあった。
該成形体の重心G、及び該重心Gに最も近い距離に位置する該成形体の表面上の点を通り、かつ、該成形体を貫く直線Lを引いたと仮定したとき、該直線Lにおいて該成形体と重なる部分のうちの最も長い線分LMの長さが少なくとも180μmであり、
該線分LMの一方の端部Aが位置する該成形体の表面上の点SAにおいて測定されるマルテンス硬度をHM1とし、
該線分LMの全長さを含む該成形体の断面において、該線分LM上の、該端部Aから該線分LMの他端に向かって30μm毎の3点で測定されるマルテンス硬度を各々HM2、HM3及びHM4としたとき、
HM1>HM2>HM3>HM4であり、
該HM1は、1.0N/mm2以上であり、
該点SAを含む該成形体の被評価表面領域に対して入射角θでCu管球からの特性X線を入射させて得られる散乱プロファイルから下記式(1)で求められる指標値Kωについて、θ=0.5°のときの該指標値をKω1、θ=1.0°のときの該指標値をKω2、θ=3.0°のときの該指標値をKω3としたとき、Kω1>Kω2>Kω3であり、
Kω=[Ic/(Ic+Ia)]×100 (1)
(Icは該散乱プロファイルの2θ=21.0°におけるピーク面積値、Iaは該散乱プロファイルの2θ=20.2°におけるピーク面積値である。)、かつ、
該被評価表面領域において平均粒子径(D50)が3.0μmの球形アルミナ粒子を用いて測定されるエロージョン率Eが0.6μm/g以下である成形体が提供される。
図1に、本開示の一態様に係るポリウレタンを含む非発泡の成形体の概略図を示す。
成形体11の重心G、及び該重心Gに最も近い距離に位置する成形体11の表面上の点を通り、かつ、成形体11を貫く直線Lを引いたと仮定する。成形体11においては、直線Lにおいて成形体11と重なる部分のうちの最も長い線分LMの長さが少なくとも180μmである。さらに、線分LMの一方の端部Aが位置する成形体11の表面上の点を点SAとする。
ここで、重心とは、成形体の輪郭線に属するすべての点に渡ってとった算術平均をとった点のことである。このような定義に基づいて重心を求める一般的な手法として、重積分を用いてもよい。また、本開示の成形体の密度は一様とみなせるので、ベクトルの外積を用いる方法を適用してもよい。これらの算出方法は、一般的に知られる数学的な概念であるため、ここでは詳細な説明を省略する。
該線分LM上の、該端部Aから該線分LMの他端(端部B)に向かって30μm毎の3点(P2、P3及びP4)で測定されるマルテンス硬度を各々HM2、HM3及びHM4としたとき、HM1>HM2>HM3>HM4である。
θ=0.5°のときの該指標値をKω1、θ=1.0°のときの該指標値をKω2、θ=3.0°のときの該指標値をKω3としたとき、Kω1>Kω2>Kω3である。
Kω=[Ic/(Ic+Ia)]×100 (1)
(Icは該散乱プロファイルの2θ=21.0°におけるピーク面積値、Iaは該散乱プロファイルの2θ=20.2°におけるピーク面積値である。)
内部に向かって結晶化度が徐々に低くなる状態を達成することで、本開示に好適な、成形体表面が適度に固く、かつ、内部が柔軟性を維持する構造が実現される。
一般的なポリウレタンは高硬度化するほど脆くなる傾向にある。しかしながら、本開示に係る成形体は、その表面が高硬度化されているにも関わらず、MSE試験によって算出される、脆性を示すパラメータ(エロージョン率E)が小さい。すなわち、当該表面は高硬度であるにも関わらず、脆くなっていない。
また、MSE試験は、該成形体の長期間にわたる耐久性を示す値と考えることもできる。例えば、平均粒子径(D50)3.0μmの球形アルミナ粒子を用いて測定されるエロージョン率Eが0.6μm/g以下の表面を有する成形体は、清掃用途に使用する場合においては、十分な強度を有する。そのため、長期に亘る清掃によっても清掃対象物との当接部に欠けが発生することが少なく、欠けに起因した清掃不良の発生を抑えることができる。本開示に係る成形体において、エロージョン率Eは、特には、0.5μm/g以下であることが好ましい。より摩耗に強く、また、清掃用途に用いた場合における被当接部の微細な欠けの発生をより確実に抑制し得る。
なお、MSE試験は、例えば、MSE―A型 試験装置((株)パルメソ)等を使用して行うことができる。
本開示に係る、ポリウレタンを含む成形体は、非発泡、すなわち、中実であることが好ましい。該ポリウレタンは、主にポリオール、ポリイソシアネート、鎖延長剤、触媒、その他添加剤等の原料から得られる。以下に、前述のような物性を実現するために好適な、これらの構成要素について詳細に説明する。
本開示に係る成形体は非発泡、すなわち、中実であることが好ましい理由としては、泡を起点とする破壊が生じ難く、成形体としての機械的性質が損なわれ難い。ただし、製造過程において不可避的に混入する泡は許容範囲内である。具体的には、例えば、許容できる泡の含有量は、10体積%以下であり、好ましくは1体積%以下である。
本開示に係る成形体の製造に用い得るポリオールとしては、ポリマー末端、分岐鎖末端等に少なくとも1個の水酸基を有しているものが挙げられる。
前記ポリオールとしては、特に限定されないが、ポリウレタンの製造に用いられる市販のポリオール等が挙げられる。例えば、以下のものが挙げられる。多価アルコールと多価カルボン酸類との重縮合で得られるポリエステルポリオール類、アルキレンオキシドの開環重合等により得られるポリエーテルポリオール類、ポリエーテルポリオール中でビニルモノマーをラジカル重合して得られるポリマーポリオール類、多価アルコール類と多価カルボン酸類とアミノアルコール類との重縮合により得られるポリエステルアミドポリオール類、ラクトン類の開環重合により得られるポリラクトンポリオール類、多価アルコール類とカーボネート類との重縮合により得られるポリカーボネートポリオール類、アクリルポリオール類、ポリブタジエンポリオール及びその水素添加物類、ポリイソプレンポリオール及びその水素添加物類、部分鹸化エチレン-酢酸ビニル共重合体、大豆油やひまし油等の天然油系ポリオール類、ハロゲン及び/又はリン系ポリオール、フェノール系ポリオール等。
・活性水素原子を少なくとも2個有する化合物:エチレングリコール、プロピレングリコール、1,3-ブチレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール、カテコール、ヒドロキノン、ビスフェノールA等
・モノマー:エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、スチレンオキサイド、エピクロルヒドリン、テトラヒドロフラン、シクロヘキシレン等
具体的には、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール等が挙げられる。
製造上および結晶構造の特性の観点から、R1、R2が異なるポリエステルポリオールであることが好ましい。また、炭素数2~3の直鎖状の2価の炭化水素基を含有していてもよい。
一方、R1、及びR2が炭素数4~10の直鎖状の2価の炭化水素基である場合、ポリオールの主鎖の部分の配向により形成される結晶構造は高硬度であり結晶構造が消失していくと低硬度化する。このため、表面から内部に向かって結晶構造が減衰したとき表面から内部に向かって連続的に低硬度化させることができる。そのため、本開示に係る成形体は、清掃対象物に対する当接圧を高くすることが可能となる。また、清掃対象物の形状への追従性をも高めることができる。
さらに、下記の第1のポリエステルポリオールと、下記の第2のポリエステルポリオールとを組み合わせて使用する場合、結晶構造間の相互作用が促進されることで、さらに耐衝撃性が向上するため好ましい。
・第1のポリエステルポリオール:炭素数4~6である直鎖状アルキル鎖を有するポリエステルポリオール
・第2のポリエステルポリオール:炭素数7~10である直鎖状アルキル鎖と炭素数4~6である直鎖状アルキル鎖の両方を有するポリエステルポリオール
具体的には、本開示に係る成形体からサンプリングされる試料を、イオン化室内で加熱気化させ、試料分子をイオン化する直接試料導入方式の質量分析計を用いて、昇温速度10℃/秒で、1000℃まで加熱したときの、全イオンの検出量をM1、化学式(1)に由来するm/z値に対応する抽出イオンサーモグラムのピークの積分強度をM2としたとき、M2/M1が0.0001~0.10000であることが好ましい。この範囲で化学式(1)の構造が含まれていることにより、表面の結晶構造をより確実に形成することができる。
ポリイソシアネートとしては、例えば、以下のものが挙げられる。
4,4′-ジフェニルメタンジイソシアネート(MDI)、1,5-ペンタメチレンジイソシアネート、2,4―トリレンジイソシアネート(2,4―TDI)、2,6-トリレンジイソシアネート(2,6-TDI)、キシレンジイソシアネート(XDI)、1,5-ナフチレンジイソシアネート(1,5-NDI)、P-フェニレンジイソシアネート(PPDI)、ヘキサメチレンジイソシアネート(HDI)、イソホロンジイソシアネート(IPDI)、4,4′-ジシクロヘキシルメタンジイソシアネート(水添MDI)、テトラメチルキシレンジイソシアネート(TMXDI)、カルボジイミド変性MDI、ポリメチレンフェニルポリイソシアネート(PAPI)、或いはこれらジイソシアネートの3量体化合物(イソシアヌレート)又は多量体化合物、アロファネート型ポリイソシアネート、ビュレット型ポリイソシアネート、水分散型ポリイソシアネート等。これらポリイソシアネートは単独でも、2種以上を組み合せて用いてもよい。また、ポリイソシアネートを各種ポリオールと反応させることで、プレポリマー化して用いてもよい。これらの中では、機械的特性が優れているので、キシリレンジイソシアネートの三量体(ヌレート体)とキシリレンジイソシアネート単量体の混合物を用いることが好ましい。これらは単独で用いても、2種以上を組み合わせて使用してもよい。
よって、ハードセグメントの形成を適切に保つため、適した化学結合量になるようにイソシアネートの種類と量を適宜調整する。中でも三量体のイソシアネートは分岐構造や骨格にひずみ構造を有することで、ハードセグメントの形成を低減できるため、特に好ましい。
鎖延長剤としては、例えば、以下のものが挙げられる。エチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコール、トリプロピレングリコール等の脂肪族ジオール、1,4-シクロヘキサンジオール、1,4-シクロヘキサンジメタノール、水素添加ビスフェノールA等の脂環族ジオール、ビスフェノールA、ハイドロキノン、ビスヒドロキシエトキシベンゼン等の芳香環含有ジオール、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ソルビトール等の多価アルコール類等。これらは単独で用いても、2種以上を組み合わせて使用してもよい。
ポリイソシアネートとポリオールのウレタン化反応を促進する目的で、本開示ではポリウレタンの硬化反応に一般的に用いられている触媒を用いてもよい。触媒としては、例えば、以下のものが挙げられる。オクチル酸錫、ジブチル錫ジラウレート等の錫化合物、オクチル酸亜鉛、アセチルアセトン亜鉛等の亜鉛化合物、酢酸カリウム、2-エチルヘキサン酸カリウム等の有機カルボン酸塩、トリエチレンジアミン、テトラメチルブタンジアミン、N,N-ジメチル-N’,N’-ビス(ヒドロキシエチル)エチレンジアミン、N,N-ジメチル-N’,N’-ビス(ヒドロキシエチル)プロパンジアミン、N,N-ジメチル-N’,N’-ビス(ヒドロキシエチル)ネオペンタンジアミン、N,N-ジメチル-N’,N’-ビス(ヒドロキシエチル)ヘキサンジアミン、N-(N,N-ビス(ヒドロキシエチル)アミノエチル)ピペリジン、N,N-ビス(ジメチルアミノプロピル)-N’,N’-ビス(ヒドロキシエチル)エチレンジアミン、N,N-ビス(ジメチルアミノプロピル)-N’,N’-ビス(ヒドロキシエチル)プロパンジアミン、N,N-ジメチル-N’,N’-ビス(ヒドロキシプロピル)エチレンジアミン、N,N-ジメチル-N’,N’-ビス(ヒドロキシプロピル)プロパンジアミン、N,N-ジメチル-N’,N’-ビス(ヒドロキシプロピル)ネオペンタンジアミン、N,N-ジメチル-N’,N’-ビス(ヒドロキシプロピル)ヘキサンジアミン、N-(N,N-ビス(ヒドロキシエチル)アミノエチル)ピペリジン、N,N-ビス(ジメチルアミノプロピル)-N’,N’-ビス(ヒドロキシエチル)エチレンジアミン、及びN,N-ビス(ジメチルアミノプロピル)-N’,N’-ビス(ヒドロキシエチル)プロパンジアミン、N-(2-ヒドロキシエチル)-N,N’,N”,N”-テトラメチルジエチレントリアミン、N’-(2-ヒドロキシエチル)-N,N,N”,N”-テトラメチルジエチレントリアミン、N-(2-ヒドロキシプロピル)-N,N’,N”,N”-テトラメチルジエチレントリアミン、N’-(2-ヒドロキシプロピル)-N,N,N”,N”-テトラメチルジエチレントリアミン、N’-(2-ヒドロキシプロピル)-N,N,N’-トリメチルービス(2-アミノエチル)エーテル、及びN’-(2-ヒドロキシエチル)-N,N,N’-トリメチルービス(2-アミノエチル)エーテル、1,5-ジアザビシクロ[4.3.0]ノナ-5-エン、1,8-ジアザビシクロ[5.4.0]ウンデカ-7-エン、2,3-ジメチル-3,4,5,6-テトラヒドロ-1,3-ジアジン、1,4-ジアザビシクロ[2.2.2]オクタン、1,4-ジアザビシクロ[2.2.2]オクタン-2-メタノール等のアミン化合物等。これらは単独で用いても、2種以上を組み合わせて使用してもよい。
必要に応じて、さらに、顔料、可塑剤、防水剤、酸化防止剤、紫外線吸収剤、光安定剤等の添加剤を配合することができる。また、靭性向上剤として、ポリロタキサンを含有することもでき、特に水酸基を有するポリロタキサンは、ポリオールとして用いることもでき、好適に用いることができる。
本開示に係る成形体の一態様について、その製造方法の一例を以下に説明する。
通常、ポリウレタンは、ウレタン化反応を確実に進行させて、十分に硬化するように反応温度と反応時間とが制御される。一方、本開示においては、下記の硬化条件とすることにより、従来のポリウレタンの課題であった高硬度に伴う脆化を防止し得る。以下詳細に硬化条件を説明する。
従来のポリウレタンの製造においては、ポリウレタンの架橋が完了するまで加熱して硬化させた後、所定の雰囲気下でエージングしている。それに対して、本開示に係る弾性部材の製造においては、ポリウレタンの架橋が完了する前に硬化を停止させ、引き続いて、ポリオールの結晶化温度以下の雰囲気下でエージングすることで二次硬化させる。
また、ポリウレタンの架橋が未完了の状態で硬化反応を停止させた後、ポリオールの結晶化温度を超える温度雰囲気下でエージングを行った場合、ポリオールの主鎖の部分の結晶化は進行せず、表面もポリウレタンの架橋が進行する。そのため、得られるポリウレタンの表面のマルテンス硬度を高めることは困難である。
また二次硬化後、成形体の清掃対象物へ当接させるエッジの形状を調整するための切断を行っても良い。なお、ポリウレタンエラストマーシートをあらかじめ作製し部材に接着する場合には、切断は接着前に行っても接着後に行っても良い。
以下、評価方法を示す。
ポリオール成分の測定は、サンプルをガスクロマトグラフ(GC)へ通さずにイオン源に直接導入する直接試料導入法(DI法)で行った。
装置はサーモフィッシャーサイエンティフィック(株)製のPOLARIS Qを使用し、Direct Exposure Probe(DEP)を用いた。
先端面に、先端側エッジに対して平行に、先端側エッジからの距離が10μmである第1の線分を引いたと仮定したときに、該第1の線分の長さをLとし、該第1の線分上の一端側から1/2Lの点SAからポリウレタンを、バイオカッターで削り取った。
該SAにおいてサンプリングされた試料約0.1μgをプローブの先端に位置するフィラメントに固定し、イオン化チャンバーの中に直接挿入した。その後、一定の昇温速度(10℃/s)で室温から1000℃まで急速に加熱し、気化したガスを質量分析計により検出した。
全てのイオンの検出量M1は得られたトータルイオンカレントサーモグラムにおいて全ピークの積分強度を合計したものとした。また、ポリオール成分の検出量M2は計算式(2)で算出されるm/z値に対応する抽出イオンサーモグラムのピークの積分強度とした。
m/z値:
M2=(200+{14×(R1-4)+14×(R2-4)}+1)±0.5 式(2)
式(2)中のR1、R2はそれぞれ化学式(1)中のR1、R2の炭素数を示す。
点SAから削り取った試料から得られた数値を、本開示における、M2/M1値とした。
マルテンス硬度は(株)島津製作所製「島津ダイナミック超微小硬度計「DUH―W211S」」を用いて測定した。測定環境は温度23℃、相対湿度55%下とした。圧子は稜間隔115°三角すいダイヤモンド圧子を用い、以下の計算式(3)よりマルテンス硬度を求めた。
マルテンス硬度:HM=α×P/D2 式(3)
式(3)中、αは圧子形状による定数を、Pは試験力(mN)を、また、Dは圧子のサンプルへの侵入量(押し込み深さ)(μm)を表す。なお測定条件は以下のとおりである。
α:3.8584
D:2.0μm
負荷速度:0.03mN/sec
保持時間:5秒
該直線Lにおいて該線分LMの一方の端部Aが位置する該成形体の表面上の点をSAとし、該SAの位置でマルテンス硬度HM1を測定した。
さらに、該線分LM上の点であって、測定点SAからの距離が30μm、60μm、90μmとなる各位置(P2、P3、P4)のマルテンス硬度(HM2、HM3、HM4)を測定した。
ポリウレタンの結晶化度は、X線回折装置(商品名:ATX-G;(株)リガク製)を用い、斜入射X線回折(XRD)により測定した。
X線入射角をω1=0.5°、ω2=1°、ω3=3°とし、各角度での測定時の結晶ピーク面積をそれぞれIc1、Ic2、Ic3とし、アモルファスピーク面積をIa1、Ia2、Ia3とした。X線入射角が小さいほど表面側の状態を表している。
・管球:Cu(40kV20mA)
・スリット条件:S2(縦1mm 横0.1mm)
・R.S.、G.S.:open
・Soller slit=0.41
結晶ピークの面積値Icは、ピークトップが2θ=21°のピークにおいて、ベースラインを2θ=3~40°で引いたときの、領域2θ=13~30°におけるベースラインから積分して得た面積値とした。
アモルファスピークの面積値Iaは、ピークトップが2θ=20.2°のピークにおいて、ベースラインを2θ=3~40°で引いたときの、領域2θ=13~30°におけるベースラインから積分して得た面積値とした。Ic1、Ia1を下記式(1)に代入して結晶化度の指標Kω1を得た。同様に、Ic2、Ia2を下記式(1)に代入して指標Kω2を、Ic3、Ia3を下記式(1)に代入して指標Kω3を得た。
Kω=[Ic/(Ic+Ia)]×100 (1)
得られたKω1、Kω2、Kω3の値が、下記の関係を満たすか否かを評価した。そして、満たす場合には「Y」、満たさない場合は「N」として、表2及び表3の「結晶化度解析」の欄に記載した。
結晶化度:
Y:Kω1>Kω2>Kω3を満たす場合
N:Kω1>Kω2>Kω3を満たさない場合
X線の照射面積は、スリット条件とX線入射角により決まる値である。本実施例に係るスリット条件においては、ω1=0.5°のときのX線照射面積は11.5mm2、ω2=1°のときのX線照射面積は5.8mm2、ω3=3°のときのX線照射面積は、1.9mm2となる。本実施例に係る成形体の被評価表面領域の面積について、上記X線照射面積に対してどのような関係にあるかを下記の基準で評価した。そして、表2及び表3における「被評価面積」の欄に、評価結果に応じて、「Y」または「N」と記載した。
Y:被評価表面領域の面積が、X線の照射面積以上である。
N:被評価表面領域の面積が、X線の照射面積未満である。
エロージョン率は、(株)パルメソ製「MSE―A型 試験装置」を用いて測定した。
平均粒子径3.0μmの球形アルミナ粉末(製品名「AX3―15」新日鉄住金マテリアルズ(株)マイクロカンパニー製)を水に分散させて、スラリーの総質量に対して球形アルミナを3質量%で含むスラリーを調製した。
測定環境は温度23℃、相対湿度55%下とし、スラリー投射速度を100m/secとし、切削深さは(株)小坂研究所製の触針式表面形状測定器で、先端半径R10μmのダイヤモンド針の触針を用いて測定した。このときの投射条件は以下の方法で調整した。
事前に先の測定環境にて既存の硬さ基準片(商品名「HRC―45」、(株)山本科学工具研究所製)を用いて、スラリー6.0gを投射した際に6.0μm切削されるようにスラリー投射条件を調整した。この際のエロージョン率Eは1.0μm/gとなる。
測定点SAにおいて測定を行い、切削深さ20μmになるまでスラリーを投射し、投射したスラリー量から下記式(3)を用いてエロージョン率Eを求めた。
エロージョン率E(μm/g)=切削深さ20μm/球形アルミナ粒子の投射量(g) (3)
清掃性能を評価するため、平均粒子径3.0μmの球形シリカ粉末(製品名「AX3―15」新日鉄住金マテリアルズ株式会社(株)マイクロカンパニー製)を水に分散させて、スラリーの総質量に対して球形アルミナを3質量%で含むスラリーを調製した。調製後のスラリーをガラス基板の表面に塗布し、乾燥後、再び、イオン交換水をガラス基板の表面に滴下した。
下記の表面性測定機の台に前記ガラス基板を固定し、下記の成形体を、ガラス基板の前記のスラリーを塗布しイオン交換水を1g滴下した面に、成形体とガラス基板がなす角が24°となるように当接させ、ガラス基板を固定した台を往復運動させて摺動試験を行った。
表面性測定機:TYPE38、新東科学(株)製
成形体:
形状:短冊状
サイズ:幅30mm、長さ、20mm、厚さ2mm
試験条件:
摺動時の荷重:100g
摺動速度:100mm/sec
摺動時間:5分間
往復運動の設定距離: 50mm
摺動試験後、清掃範囲に残っているシリカ粒子を目視で確認し、清掃性能を確認し、以下の基準を用いて評価した。そして、表2及び表3の「清掃性能ランク」の欄に、評価結果に応じて「A」、「B」または「C」と記載した。
ランクA:シリカ粒子が全て除去できた。
ランクB:シリカ粒子の残留が認められたが、シリカ粒子がスジ状に残留する汚れは確認できなかった。
ランクC:成形体の欠けに起因し、シリカ粒子がスジ状に残留する汚れが確認された。
以下、実施例において使用した材料を示す。
(1)キシリレンジイソシアネートの三量体(ヌレート体)とキシリレンジイソシアネート単量体との混合物(モル比-三量体:単量体=1:1.2):商品名「タケネート(登録商標)XD―131R」、三井化学(株)製
(2)主成分が4,4’―ジフェニルメタンジイソシアネート(MDI)の三量体:商品名「ミリオネート(登録商標) MR―200」東ソー(株)製
(3)1,5―ペンタメチレンジイソシアネートの三量体(イソシアヌレート体):商品名「スタビオ(登録商標) D―370N」三井化学(株)製
(4)キシリレンジイソシアネート:商品名「XDI」東京化成工業(株)製
(5)4,4’-ジフェニルメタンジイソシアネート:商品名「ミリオネート(登録商標)MT」(東ソー(株)製)
(1)ポリエステルポリオール:商品名「ニッポラン(登録商標)164」東ソー(株)製
化学式(1)におけるR1、R2の炭素数が4及び6の組み合わせである。
(2)ポリエステルポリオール:商品名「ニッポラン(登録商標)4009」東ソー(株)製
化学式(1)におけるR1、R2の炭素数が4である。
(3)ポリエステルポリオール:商品名「ポリライト(登録商標)OD―X-2555」DIC(株)製
化学式(1)におけるR1、R2の炭素数が6及び10の組み合わせである。
1,4-ブタンジオール(1,4-BD):東京化成工業(株)製
(1)ジラウリン酸ジブチル錫:東京化成工業(株)製
(2)三級アミン触媒:商品名「RZETA(登録商標)」東ソー(株)製
ポリオール成分、鎖延長剤、ウレタン化触媒を表1に記載の質量で配合した。各成分は必要に応じて、減圧下で加熱し、脱水処理を行った。配合した混合液を減圧下で5分間攪拌し、均一なポリオールを主成分とする溶液を得た。
前記ポリオールを主成分とする溶液に、ポリイソシアネート成分を表1の質量で配合し、再び減圧下で3分間攪拌した後、130℃に加熱した金型(厚さ2mm、高さ40mm、幅200m)に注型した。3分間一次硬化を行った後、金型を25℃まで急冷し、12時間金型内で保持して二次硬化した。その後、金型から脱型して、成形体1を得た。
ELEMENT14 PDMS 1000-JC(商品名、モメンティブ・パフォーマンス・マテリアルズ社製) 5.06g
ELEMENT14 PDMS 10K-JC(商品名、モメンティブ・パフォーマンス・マテリアルズ社製) 6.19g
SR1000(商品名、モメンティブ・パフォーマンス・マテリアルズ社製) 3.75g
EXXSOL(登録商標) DSP145/160(商品名、エクソンモービル社製) 85g
この成形体を、適宜切断して、前記の評価に使用する試験片を得た。得られた評価結果を表2に示す。
表1に示すとおり配合と硬化条件を変えた以外は実施例1と同様にして成形体2~10を得た。実施例1と同様の評価を行い、表2に示す。
表1に示すとおり配合と硬化条件を変えた以外は実施例1と同様にして成形体11~12を得た。得られた成形体11~12を実施例1と同様にして評価した。その結果を表3に示す。
下記の材料を混合して含浸剤を調製した。
ポリメリックMDI(MR―100、日本ポリウレタン製) 10g
シリコーン樹脂 (モディパーFS―700、日油(株)製) 2g
2―ブタノン(東京化成工業(株)製) 88g
比較例1と同様にして得た成形体11を、調製された含浸剤に180秒間浸漬した後、温度23℃/相対湿度55%の環境下で3時間エージングして成形体13を得た。得られた成形体13を実施例1と同様にして評価した。その結果を表3に示す。
21 ノズル
22 スラリー
23 成形体
24 球形アルミナ
25 水
Claims (6)
- ポリウレタンを含む非発泡の成形体であって、
該成形体の重心G、及び該重心Gに最も近い距離に位置する該成形体の表面上の点を通り、かつ、該成形体を貫く直線Lを引いたと仮定したとき、該直線Lにおいて該成形体と重なる部分のうちの最も長い線分LMの長さが少なくとも180μmであり、
該線分LMの一方の端部Aが位置する該成形体の表面上の点SAにおいて測定されるマルテンス硬度をHM1とし、
該線分LMの全長さを含む該成形体の断面において、該線分LM上の、該端部Aから該線分LMの他端に向かって30μm毎の3点で測定されるマルテンス硬度を各々HM2、HM3及びHM4としたとき、
HM2>HM3>HM4であり、
該HM1は、1.0N/mm2以上であり、
該点SAを含む該成形体の被評価表面領域に対して入射角θでCu管球からの特性X線を入射させて得られる散乱プロファイルから下記式(1)で求められる指標値Kωについて、θ=0.5°のときの該指標値をKω1、θ=1.0°のときの該指標値をKω2、θ=3.0°のときの該指標値をKω3としたとき、Kω1>Kω2>Kω3であり、
Kω=[Ic/(Ic+Ia)]×100 (1)
(Icは該散乱プロファイルの2θ=21.0°におけるピーク面積値、Iaは該散乱プロファイルの2θ=20.2°におけるピーク面積値である。)、かつ、
該被評価表面領域において平均粒子径(D50)が3.0μmの球形アルミナ粒子を用いて測定されるエロージョン率Eが0.6μm/g以下である、ことを特徴とする成形体。 - 前記被評価表面領域の面積が、前記X線の照射面積以上である請求項1に記載の成形体。
- 前記照射面積が1.5~11.5mm2である請求項2に記載の成形体。
- 前記成形体からサンプリングされる試料をイオン化室内で加熱気化させ、試料分子をイオン化する直接試料導入方式の質量分析計を用いて、昇温速度10℃/秒で1000℃まで加熱したときに得られる、全てのイオンの検出量をM1とし、前記化学式(1)に由来するm/z値の範囲に対応する抽出イオンサーモグラムのピークの積分強度をM2としたときに、M2/M1が、0.0001~0.10000である請求項4に記載の成形体。
- 前記HM1が5.0N/mm2以下である請求項1~5のいずれか一項に記載の成形体。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202280058730.XA CN117881516A (zh) | 2021-08-31 | 2022-08-26 | 含聚氨酯的非发泡成形体 |
EP22864411.8A EP4397466A1 (en) | 2021-08-31 | 2022-08-26 | Polyurethane-containing non-foamed molded body |
US18/587,732 US20240255403A1 (en) | 2021-08-31 | 2024-02-26 | Polyurethane-containing non-foamed molded body |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021141902 | 2021-08-31 | ||
JP2021-141902 | 2021-08-31 | ||
JP2022127858A JP7500668B2 (ja) | 2021-08-31 | 2022-08-10 | ポリウレタンを含む非発泡の成形体 |
JP2022-127858 | 2022-08-10 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/587,732 Continuation US20240255403A1 (en) | 2021-08-31 | 2024-02-26 | Polyurethane-containing non-foamed molded body |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023032827A1 true WO2023032827A1 (ja) | 2023-03-09 |
Family
ID=85412633
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/032142 WO2023032827A1 (ja) | 2021-08-31 | 2022-08-26 | ポリウレタンを含む非発泡の成形体 |
Country Status (3)
Country | Link |
---|---|
US (1) | US20240255403A1 (ja) |
EP (1) | EP4397466A1 (ja) |
WO (1) | WO2023032827A1 (ja) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5532376B2 (ja) | 2008-11-07 | 2014-06-25 | 株式会社リコー | クリーニングブレード、画像形成装置、プロセスカートリッジ、及び、画像形成方法 |
JP2018036363A (ja) * | 2016-08-30 | 2018-03-08 | 住友理工株式会社 | 電子写真機器用クリーニングブレード |
JP2018077466A (ja) * | 2016-10-31 | 2018-05-17 | キヤノン株式会社 | クリーニングブレード、プロセスカートリッジ及び電子写真画像形成装置 |
WO2021112123A1 (ja) * | 2019-12-04 | 2021-06-10 | キヤノン株式会社 | 電子写真用クリーニングブレード、プロセスカートリッジ、及び電子写真画像形成装置 |
JP2021141902A (ja) | 2012-10-31 | 2021-09-24 | バークレー ライツ,インコーポレイテッド | 生物学的微小物体用ペン |
JP2022127858A (ja) | 2021-02-22 | 2022-09-01 | 浜松ホトニクス株式会社 | 質量分析装置及び質量分析方法 |
-
2022
- 2022-08-26 WO PCT/JP2022/032142 patent/WO2023032827A1/ja active Application Filing
- 2022-08-26 EP EP22864411.8A patent/EP4397466A1/en active Pending
-
2024
- 2024-02-26 US US18/587,732 patent/US20240255403A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5532376B2 (ja) | 2008-11-07 | 2014-06-25 | 株式会社リコー | クリーニングブレード、画像形成装置、プロセスカートリッジ、及び、画像形成方法 |
JP2021141902A (ja) | 2012-10-31 | 2021-09-24 | バークレー ライツ,インコーポレイテッド | 生物学的微小物体用ペン |
JP2018036363A (ja) * | 2016-08-30 | 2018-03-08 | 住友理工株式会社 | 電子写真機器用クリーニングブレード |
JP2018077466A (ja) * | 2016-10-31 | 2018-05-17 | キヤノン株式会社 | クリーニングブレード、プロセスカートリッジ及び電子写真画像形成装置 |
WO2021112123A1 (ja) * | 2019-12-04 | 2021-06-10 | キヤノン株式会社 | 電子写真用クリーニングブレード、プロセスカートリッジ、及び電子写真画像形成装置 |
JP2022127858A (ja) | 2021-02-22 | 2022-09-01 | 浜松ホトニクス株式会社 | 質量分析装置及び質量分析方法 |
Also Published As
Publication number | Publication date |
---|---|
EP4397466A1 (en) | 2024-07-10 |
US20240255403A1 (en) | 2024-08-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5364251B2 (ja) | 電子写真装置用ブレード及びその製造方法 | |
EP4071555A1 (en) | Electrophotographic cleaning blade, process cartridge, and electrophotographic image forming device | |
BR112017026790B1 (pt) | Composição e método | |
CN108021008B (zh) | 清洁刮板、处理盒和电子照相图像形成设备 | |
JP2021515082A (ja) | 接着剤組成物 | |
EP3995553A1 (en) | Isocyanate-based adhesive | |
US4826914A (en) | Transparent cover for transparent substrates | |
WO2023032827A1 (ja) | ポリウレタンを含む非発泡の成形体 | |
JP7500668B2 (ja) | ポリウレタンを含む非発泡の成形体 | |
JP2021516278A (ja) | 接着剤組成物 | |
CN111095126B (zh) | 电子照相设备用刮板的制造方法以及电子照相设备用刮板 | |
EP2254959B1 (en) | A coating composition for strengthening glass | |
WO2022025262A1 (ja) | 清掃用ワイパーブレード | |
CN117881516A (zh) | 含聚氨酯的非发泡成形体 | |
KR100955032B1 (ko) | 연마용 폴리우레탄 흡착 패드 조성물, 연마용 폴리우레탄흡착 패드 및 그 제조방법 | |
JP3936813B2 (ja) | 摺動性ウレタンエラストマー成形体 | |
CN116457384A (zh) | 电子照相用清洁刮板、处理盒和电子照相图像形成设备 | |
US20200024448A1 (en) | One-Part Moisture-Curable Urethane Composition | |
JP2023035927A (ja) | 電子写真用クリーニングブレード、プロセスカートリッジ、及び電子写真画像形成装置 | |
WO2020107262A1 (zh) | 橡胶刮板及其制备方法 | |
WO2023120633A1 (ja) | ワイパー装置 | |
TW201726808A (zh) | 聚胺基甲酸酯組成物、及薄片 | |
WO2024135765A1 (ja) | ブレードラバーの再生方法及び再生ブレードラバーの製造方法 | |
JP3777930B2 (ja) | クリーニングブレード | |
JP2023095727A (ja) | ワイパー装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22864411 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 202280058730.X Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022864411 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2022864411 Country of ref document: EP Effective date: 20240402 |