JP4114012B2 - Multi-branched polyether polyol - Google Patents
Multi-branched polyether polyol Download PDFInfo
- Publication number
- JP4114012B2 JP4114012B2 JP2005100813A JP2005100813A JP4114012B2 JP 4114012 B2 JP4114012 B2 JP 4114012B2 JP 2005100813 A JP2005100813 A JP 2005100813A JP 2005100813 A JP2005100813 A JP 2005100813A JP 4114012 B2 JP4114012 B2 JP 4114012B2
- Authority
- JP
- Japan
- Prior art keywords
- polyether polyol
- polyol
- branched polyether
- component
- hydroxyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005862 polyol Polymers 0.000 title claims description 130
- 150000003077 polyols Chemical class 0.000 title claims description 127
- 239000004721 Polyphenylene oxide Substances 0.000 title claims description 70
- 229920000570 polyether Polymers 0.000 title claims description 70
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 71
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 54
- -1 hydroxyalkyl oxetane Chemical compound 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000004593 Epoxy Substances 0.000 claims description 20
- 238000007142 ring opening reaction Methods 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 31
- 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 27
- 239000005056 polyisocyanate Substances 0.000 description 22
- 229920001228 polyisocyanate Polymers 0.000 description 22
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 19
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- 238000012360 testing method Methods 0.000 description 15
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 14
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- 239000003505 polymerization initiator Substances 0.000 description 11
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- 230000015572 biosynthetic process Effects 0.000 description 6
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
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- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 2
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 2
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- JZXXNKPEWUSLLN-UHFFFAOYSA-N N=C=O.N=C=O.C1C2=C1C(C1)=C1C1=CC=CC=C21 Chemical compound N=C=O.N=C=O.C1C2=C1C(C1)=C1C1=CC=CC=C21 JZXXNKPEWUSLLN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
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- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 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 2
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- OEEXXZYUVANONO-UHFFFAOYSA-N [O-][Sb]([O-])([O-])=O.C(c1ccccc1)[n+]1ccccc1.C(c1ccccc1)[n+]1ccccc1.C(c1ccccc1)[n+]1ccccc1 Chemical compound [O-][Sb]([O-])([O-])=O.C(c1ccccc1)[n+]1ccccc1.C(c1ccccc1)[n+]1ccccc1.C(c1ccccc1)[n+]1ccccc1 OEEXXZYUVANONO-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 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
- 230000005587 bubbling Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- VRZVPALEJCLXPR-UHFFFAOYSA-N ethyl 4-methylbenzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=C(C)C=C1 VRZVPALEJCLXPR-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 238000004898 kneading Methods 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- IZDROVVXIHRYMH-UHFFFAOYSA-N methanesulfonic anhydride Chemical compound CS(=O)(=O)OS(C)(=O)=O IZDROVVXIHRYMH-UHFFFAOYSA-N 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 1
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- JKXONPYJVWEAEL-UHFFFAOYSA-N oxiran-2-ylmethyl acetate Chemical compound CC(=O)OCC1CO1 JKXONPYJVWEAEL-UHFFFAOYSA-N 0.000 description 1
- XRQKARZTFMEBBY-UHFFFAOYSA-N oxiran-2-ylmethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1CO1 XRQKARZTFMEBBY-UHFFFAOYSA-N 0.000 description 1
- YLNSNVGRSIOCEU-UHFFFAOYSA-N oxiran-2-ylmethyl butanoate Chemical compound CCCC(=O)OCC1CO1 YLNSNVGRSIOCEU-UHFFFAOYSA-N 0.000 description 1
- QNAJAJLBHMMOJB-UHFFFAOYSA-N oxiran-2-ylmethyl propanoate Chemical compound CCC(=O)OCC1CO1 QNAJAJLBHMMOJB-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 1
- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- 238000004394 yellowing prevention Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Images
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- Polyethers (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
本発明は、ウレタン系樹脂組成物のポリオール成分として有用な新規な多分岐ポリエーテルポリオール、及び、作業性に優れると共に、硬質な硬化物を与えるウレタン系樹脂組成物に関する。 The present invention relates to a novel multi-branched polyether polyol useful as a polyol component of a urethane-based resin composition, and a urethane-based resin composition that is excellent in workability and gives a hard cured product.
ポリオール成分とポリイソシアネート成分とからなるウレタン系樹脂組成物は、硬化性や硬化塗膜の伸びが良好であるという特長から建設材料用床材などの被覆材に広く用いられている。しかし乍ら、かかるウレタン系樹脂組成物は、一般に軟質である他、塗膜が吸湿して発泡し易く、被膜外観に劣るという問題を有しており、近年、硬質タイプのウレタン系樹脂組成物が種々検討されてきた（例えば、特許文献１参照）。一方、被覆材の硬質化を図るには、一般にポリオール成分とポリイソシアネート成分との反応性を高めればよいが、この場合、両者混合時に速やかにこれらが反応してしまう為、十分な可使時間を確保できないものであった。そこで、従来より、ビスフェノール型エポキシ樹脂に高級脂肪酸を反応させた構造のポリオールと、ひまし油脂肪酸との混合物をポリオール成分として用い、かつ、ピュアＭＤＩとポリメリックＭＤＩとを所定割合で配合したものをポリイソシアネート成分として用いることによって、可使時間を十分に確保し乍らも硬質で、かつ、高温多湿下であっても発泡し難い硬質タイプのウレタン系被服用樹脂組成物が知られている（下記、特許文献２参照）。 A urethane-based resin composition comprising a polyol component and a polyisocyanate component is widely used for coating materials such as flooring materials for construction materials because of its good curability and elongation of a cured coating film. However, such a urethane resin composition is generally soft, and has a problem that the coating film absorbs moisture and easily foams, resulting in a poor appearance of the coating film. Recently, a hard type urethane resin composition is used. Have been studied in various ways (see, for example, Patent Document 1). On the other hand, in order to increase the hardness of the coating material, it is generally sufficient to increase the reactivity between the polyol component and the polyisocyanate component, but in this case, since these react quickly when mixed, sufficient pot life Could not be secured. Therefore, conventionally, a polyisocyanate is obtained by using a mixture of a polyol having a structure in which a higher fatty acid is reacted with a bisphenol-type epoxy resin and castor oil fatty acid as a polyol component and blending pure MDI and polymeric MDI in a predetermined ratio. By using it as a component, a hard type urethane-based resin composition for clothing that is sufficiently hard to secure a pot life and hard to foam even under high temperature and high humidity is known (the following, Patent Document 2).
しかし、このビスフェノール型エポキシ樹脂に高級脂肪酸を反応させた構造のポリオールと、ひまし油との混合物をポリオール成分として用い、かつ、ポリイソシアネート成分としてピュアＭＤＩとポリメリックＭＤＩとを所定割合で配合したものを用いる技術は、確かに可使時間が長く、かつ、硬質な塗膜が形成されるものの、とりわけポリオール成分の粘度が著しく高いため、刷毛塗りやローラー塗り、スプレー塗布といった、熟練を要することなく、かつ、表面仕上がりに斑の生じない塗工方法への適用が困難なものであった。
本発明が解決しようとする課題は、ウレタン系樹脂組成物におけるポリオール成分として、十分な可使時間を確保でき、また、高い硬度を硬化塗膜に付与できると共に、更に、粘度が従来になく低い新規な多分岐ポリエーテルポリオール、及び、これを含有する作業性と塗膜硬度に優れるウレタン系樹脂組成物を提供することにある。 The problem to be solved by the present invention is that a sufficient pot life can be secured as a polyol component in a urethane-based resin composition, a high hardness can be imparted to a cured coating film, and the viscosity is lower than ever before. It is an object of the present invention to provide a novel multi-branched polyether polyol and a urethane resin composition excellent in workability and coating film hardness containing the same.
本発明者等は、前記課題を解決すべく鋭意検討した結果、ヒドロキシアルキルオキセタンと１官能性エポキシ化合物とを開環反応によって共重合させて得られる多分岐構造を有し、かつ、１級水酸基と２級水酸基とを有し、更に、所定の全水酸基量及び分子量を有する化合物をウレタン系樹脂組成物におけるポリオール成分として用いることにより、可使時間も長く且つ硬化時の架橋密度も高くなると同時に、当該化合物の慣性半径が小さくなり、低粘度化を図ることができることを見いだし、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have a multibranched structure obtained by copolymerizing a hydroxyalkyl oxetane and a monofunctional epoxy compound by a ring-opening reaction, and have a primary hydroxyl group. And a secondary hydroxyl group, and furthermore, by using a compound having a predetermined total hydroxyl group amount and molecular weight as a polyol component in the urethane-based resin composition, the pot life is long and the crosslinking density at the time of curing is also increased. The inventors have found that the radius of inertia of the compound is reduced and the viscosity can be reduced, and the present invention has been completed.
すなわち本発明は、ヒドロキシアルキルオキセタン（ａ１）と、１官能性エポキシ化合物（ａ２）とを（ａ１）／（ａ２）＝１／１〜１／３（モル比）で開環反応させて得られる多分岐ポリエーテルポリオールであって、その分子構造中に１級水酸基（Ｈ１）と２級水酸基（Ｈ２）とを有しており、かつ、その分子構造中に２級水酸基（Ｈ２）を、全水酸基数に対して２０〜７０％の割合で有しており、前記多分岐ポリエーテルポリオールの数平均分子量（Ｍｎ）が１０００〜３５００、水酸基価が１５０〜３５０ｍｇ・ＫＯＨ／ｇであることを特徴とする多分岐ポリエーテルポリオールに関する。 That is, the present invention is obtained by ring-opening reaction of hydroxyalkyl oxetane (a1) and monofunctional epoxy compound (a2) at (a1) / (a2) = 1/1 to 1/3 (molar ratio). It is a multi-branched polyether polyol having a primary hydroxyl group (H1) and a secondary hydroxyl group (H2) in its molecular structure , and all of the secondary hydroxyl groups (H2) in its molecular structure. The polybranched polyether polyol has a number average molecular weight (Mn) of 1000 to 3500 and a hydroxyl value of 150 to 350 mg · KOH / g. To a multi-branched polyether polyol.
本発明によれば、ウレタン系樹脂組成物におけるポリオール成分として、十分な可使時間を確保でき、また、高い硬度を硬化塗膜に付与できると共に、更に、粘度を従来になく低くいポリエーテルポリオールを提供できる。よって、これを含有するウレタン系樹脂組成物は、優れた作業性と塗膜硬度とを兼備させることができる。 According to the present invention, as a polyol component in the urethane-based resin composition, a sufficient pot life can be secured, a high hardness can be imparted to the cured coating film, and a polyether polyol having a viscosity which is not low as in the prior art. Can provide. Therefore, the urethane type resin composition containing this can combine the outstanding workability | operativity and coating-film hardness.
以下本発明をさらに詳細に説明する。
本発明の多分岐ポリエーテルポリオールは、ヒドロキシアルキルオキセタン（ａ１）と、１官能性エポキシ化合物（ａ２）とを開環反応させて得られる多分岐ポリエーテルポリオールである。本発明では、このような構造を有することから、当該多分岐ポリエーテルポリオールの慣性半径が小さくなって、分子同士の絡みが少なくなる結果、粘度が低くなる。
The present invention is described in further detail below.
The multi-branched polyether polyol of the present invention is a multi-branched polyether polyol obtained by ring-opening reaction of a hydroxyalkyl oxetane (a1) and a monofunctional epoxy compound (a2). In this invention, since it has such a structure, the inertial radius of the said multibranched polyether polyol becomes small, resulting in less entanglement between molecules, resulting in a lower viscosity.
ここで、ヒドロキシアルキルオキセタン（ａ１）は、下記一般式（１）で表される構造を有するものが挙げられる。 Here, examples of the hydroxyalkyl oxetane (a1) include those having a structure represented by the following general formula (1).
ここで、一般式（１）中、Ｒ１は、メチレン基、エチレン基、若しくはプロピレン基であり、一方、Ｒ２は、水素原子、炭素原子数１〜８のアルキル基、炭素原子数１〜５のアルコキシアルキル基、又は炭素原子数１〜６のヒドロキシアルキル基を表す。また、炭素原子数１〜８のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、及び２−エチルヘキシル基が挙げられ、炭素原子数１〜５のアルコキシアルキル基としては、メトキシメチル基、エトキシメチル基、プロポキシメチル基、メトキシエチル基、エトキシエチル基、プロポキシエチル基が挙げられる。また、炭素原子数１〜３のヒドロキシアルキル基としては、ヒドロキシメチル基、ヒドロキシエチル基、及びヒドロキシプロピル基が挙げられる。
Here, in the general formula (1), R 1 is a methylene group, ethylene group, or propylene group, while R 2 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or 1 to 1 carbon atoms. 5 represents an alkoxyalkyl group or a hydroxyalkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a 2-ethylhexyl group. As the alkoxyalkyl group having 1 to 5 carbon atoms, Includes a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, and a propoxyethyl group. Moreover, as a C1-C3 hydroxyalkyl group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group are mentioned.
かかる一般式（１）で表されるヒドロキシアルキルオキセタンの中でも、慣性半径がより小さくなって粘度低減に効果的であり、また、硬化物の硬度も良好となる点から、Ｒ１がメチレン基であり、かつ、Ｒ２が炭素原子数１〜７のアルキル基である化合物、とりわけ３−ヒドロキシメチル−３−エチルオキセタン、及び３−ヒドロキシメチル−３−メチルオキセタンが好ましい。 Among the hydroxyalkyl oxetanes represented by the general formula (1), R 1 is a methylene group because the radius of inertia is smaller and effective in reducing the viscosity, and the hardness of the cured product is improved. And R 2 is an alkyl group having 1 to 7 carbon atoms, particularly 3-hydroxymethyl-3-ethyloxetane and 3-hydroxymethyl-3-methyloxetane.
次に、上記ヒドロキシアルキルオキセタン（ａ１）と開環反応させる１官能性エポキシ化合物（ａ２）は、オレフィンエポキサイド、アルキルグリシジルエーテル、アルキルグリシジルエステル等が挙げられる。 Next, examples of the monofunctional epoxy compound (a2) that undergoes a ring-opening reaction with the hydroxyalkyl oxetane (a1) include olefin epoxides, alkyl glycidyl ethers, and alkyl glycidyl esters.
ここで、オレフィンエポキサイドは、具体的には、プロピレンオキサイド、１−ブテンオキサイド、１−ペンテンオキサイド、１−ヘキセンオキサイド、１，２−エポキシオクタン、１，２−エポキシドデカン、シクロヘキセンオキシド、シクロオクテンオキシド、シクロドデセンオキシド、スチレンオキシド、及び、フッ素原子数１〜１８のフロロアルキルエポキシドが挙げられる。 Here, the olefin epoxide specifically includes propylene oxide, 1-butene oxide, 1-pentene oxide, 1-hexene oxide, 1,2-epoxyoctane, 1,2-epoxydodecane, cyclohexene oxide, cyclooctene oxide. , Cyclododecene oxide, styrene oxide, and fluoroalkyl epoxide having 1 to 18 fluorine atoms.
アルキルグリシジルエーテルは、メチルグリシジルエーテル、エチルグリシジルエーテル、ｎ−プロピルグリシジルエーテル、ｉ−プロピルグリシジルエーテル、ｎ−ブチルグリシジルエーテル、ｉ−ブチルグリシジルエーテル、ｎ−ペンチルグリシジルエーテル、２−エチルヘキシル−グリシジルエーテル、ウンデシルグリシジルエーテル、ヘキサデシルグリシジルエーテル、アリールグリシジルエーテル、フェニルグリシジルエーテル、２−メチルフェニルグリシジルエーテル、４−ｔ−ブチルフェニルグリシジルエーテル、４−ノニルフェニルグリシジルエーテル、４−メトキシフェニルグリシジルエーテル、及び、１〜１８のフッ素原子数を有するフロロアルキルグリシジルエーテルが挙げられる。 Alkyl glycidyl ether is methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, i-propyl glycidyl ether, n-butyl glycidyl ether, i-butyl glycidyl ether, n-pentyl glycidyl ether, 2-ethylhexyl-glycidyl ether, Undecyl glycidyl ether, hexadecyl glycidyl ether, aryl glycidyl ether, phenyl glycidyl ether, 2-methylphenyl glycidyl ether, 4-t-butylphenyl glycidyl ether, 4-nonylphenyl glycidyl ether, 4-methoxyphenyl glycidyl ether, and Examples thereof include fluoroalkyl glycidyl ether having 1 to 18 fluorine atoms.
アルキルグリシジルエステルは、グリシジルアセテート、グリシジルプロピオネート、グリシジルブチレート、グリシジルメタクリレート、及びグリシジルベンゾエートが挙げられる。 Alkyl glycidyl esters include glycidyl acetate, glycidyl propionate, glycidyl butyrate, glycidyl methacrylate, and glycidyl benzoate.
これらの中でも特に、塗膜硬度が良好であり、また、分子量が小さくなる点からオレフィンエポキサイドが好ましく、とりわけプロピレンオキサイド、１−ブテンオキサイド、１−ペンテンオキサイド、又は１−ヘキセンオキサイドが好ましい。 Among these, olefin epoxide is preferable from the viewpoint of good coating film hardness and low molecular weight, and propylene oxide, 1-butene oxide, 1-pentene oxide, or 1-hexene oxide is particularly preferable.
ここで、ヒドロキシアルキルオキセタン（ａ１）と、１官能性エポキシ化合物（ａ２）とを開環反応させる方法は、具体的には、以下の（方法１）〜（方法３）が挙げられる。 Here, specific examples of the method of ring-opening reaction of the hydroxyalkyl oxetane (a1) and the monofunctional epoxy compound (a2) include the following (Method 1) to (Method 3).
（方法１）
方法１は、ヒドロキシアルキルオキセタン（ａ１）と、１官能性エポキシ化合物（ａ２）とを、モル基準で、（ヒドロキシアルキルオキセタン（ａ１）／１官能性エポキシ化合物（ａ２））＝１／１〜１／３となる割合で混合し、これらをパーオキサイドフリーの有機溶媒、例えば、ジエチルエーテル、ジ−ｉ−プロピルエーテル、ジ−ｎ−ブチルエーテル、ジ−ｉ−ブチルエーテル、ジ−ｔ−ブチルエーテル、ｔ−アミルメチルエーテル、又はジオキソランで、原料成分／有機溶剤の質量比が１／１〜１／５、好ましくは１／１．５〜１／２．５となる割合で溶解する。
(Method 1)
得られた溶液を−１０℃〜−１５℃まで攪拌しながら冷却、次いで、重合開始剤を単独で、或いは溶液状態で、０．１〜１時間、好ましくは０．３〜０．５時間かけて滴下する。ここで、重合開始剤は、原料モノマーの全質量に対して０．０１〜１質量％、好ましくは０．７５〜０．３質量％なる割合で使用できる。また、重合開始剤を溶液状態で使用する場合、当該溶液中の重合開始剤の濃度は、１〜９０質量％、特に２５〜５０質量％であることが好ましい。ついで、この重合溶液を２５℃になる迄攪拌し、次いで、リフラックスする温度まで加熱し、０．５〜３時間かけて原料成分を全て反応するまで反応を行う。原料モノマーの転化率は、ＧＣ、ＮＭＲ、又はＩＲスペクトルによって確認することによって制御できる。 The resulting solution is cooled while stirring to -10 ° C to -15 ° C, and then the polymerization initiator alone or in the solution state is 0.1 to 1 hour, preferably 0.3 to 0.5 hour. And dripping. Here, the polymerization initiator can be used at a ratio of 0.01 to 1% by mass, preferably 0.75 to 0.3% by mass, based on the total mass of the raw material monomers. Moreover, when using a polymerization initiator in a solution state, it is preferable that the density | concentration of the polymerization initiator in the said solution is 1-90 mass%, especially 25-50 mass%. Next, the polymerization solution is stirred until it reaches 25 ° C., then heated to a refluxing temperature, and the reaction is carried out until all the raw material components are reacted over 0.5 to 3 hours. The conversion rate of the raw material monomer can be controlled by confirming with GC, NMR, or IR spectrum.
重合後、得られた前記多分岐ポリエーテルポリオールは、前記重合開始剤と当量の水酸化アルカリ水溶液による攪拌、又は、前記重合開始剤と当量のナトリウムアルコキシドやカリウムアルコキシドの添加によって中和する。中和後、濾過し、溶媒で目的物を抽出後、減圧下に溶媒を留去し、目的とする多分岐ポリエーテルポリオールを得ることができる。 After the polymerization, the obtained multi-branched polyether polyol is neutralized by stirring with an alkali hydroxide aqueous solution equivalent to the polymerization initiator or by adding sodium alkoxide or potassium alkoxide equivalent to the polymerization initiator. After neutralization, the mixture is filtered and the desired product is extracted with a solvent, and then the solvent is distilled off under reduced pressure to obtain the desired multi-branched polyether polyol.
（方法２）
方法２は、ヒドロキシアルキルオキセタン（ａ１）と、１官能性エポキシ化合物（ａ２）とを、モル基準で、（ヒドロキシアルキルオキセタン（ａ１）／１官能性エポキシ化合物（ａ２））＝１／１〜１／３となる割合で、７０℃以上の沸点を有する炭化水素系溶媒中に溶解する。ここで、炭化水素系溶媒は、例えば、ｎ−ヘプタン、ｉ−オクタン、シクロヘキサンが挙げられ、とりわけ溶解性の点からシクロヘキサンが好ましい。また、原料モノマーと炭化水素系溶媒との比率は、前者：後者が１：１〜１：１０、特に１：２．５〜１：３．５であることが好ましい。
(Method 2)
この混合物の温度は、０〜２５℃、好ましくは５〜１５℃、特に好ましくは１０〜１５℃に保持され、次いで、攪拌下に原料モノマーの全量に対して０．０１〜１モル％、特に０．０５〜０．１５モル％の重合開始剤を一度に加える。
重合開始剤の添加直後、系内は不均一系になって２５〜４０℃まで系内温度が上昇する。一旦、１５〜２５℃まで冷却した後、反応混合物を４０〜７０℃、好ましくは５０〜６０℃まで加熱して、１〜５時間、好ましくは２〜３時間の間、原料モノマーが全て転化するまで反応を行う。反応終了後は、方法１と同様にして中和、濾過し、次いで、溶媒を留去する。
The temperature of the mixture is maintained at 0 to 25 ° C., preferably 5 to 15 ° C., particularly preferably 10 to 15 ° C., and then 0.01 to 1 mol% with respect to the total amount of raw material monomers with stirring, in particular 0.05 to 0.15 mol% of polymerization initiator is added at once.
Immediately after the addition of the polymerization initiator, the system becomes heterogeneous and the system temperature rises to 25-40 ° C. Once cooled to 15-25 ° C., the reaction mixture is heated to 40-70 ° C., preferably 50-60 ° C., and all the raw material monomers are converted for 1-5 hours, preferably 2-3 hours. Perform the reaction until After completion of the reaction, the solution is neutralized and filtered in the same manner as in
（方法３）
方法３は、原料モノマーの全量に対して０．０１〜１モル％、特に０．０５〜０．１５モル％となる量の重合開始剤を、７０℃以上の沸点を有する炭化水素系有機溶媒に溶解し、これを０〜２５℃、好ましくは５〜１５℃、特に好ましくは１０〜１５℃に保持する。ここで、炭化水素系溶媒は、例えば、ｎ−ヘプタン、ｉ−オクタン、シクロヘキサンが挙げられ、とりわけ溶解性の点からシクロヘキサンが好ましい。また、該炭化水素系溶媒中の重合開始剤濃度は、０．０１〜１質量％、特に０．０２５〜０．２５質量％であることが好ましい。
(Method 3)
この溶液に対して、ヒドロキシアルキルオキセタン（ａ１）と、１官能性エポキシ化合物（ａ２）とを、モル基準で、（ヒドロキシアルキルオキセタン（ａ１）／１官能性エポキシ化合物（ａ２））＝１／１〜１／３となる割合で、混合した混合物を、系内の温度が２０〜３５℃になるように連続的に滴下する。滴下終了後も系内の温度が２０〜２５℃になるまで攪拌を行う。次いで、反応混合物を４０〜７０℃、好ましくは５０〜６０℃まで加熱して、１〜５時間、好ましくは２〜３時間の間、原料モノマーが全て転化するまで反応を行う。原料モノマーの転化率は、ＧＣ、ＮＭＲ、又はＩＲスペクトルによって確認することによって制御できる。反応終了後は、方法１と同様にして中和、濾過し、次いで、溶媒を留去する。
To this solution, hydroxyalkyloxetane (a1) and monofunctional epoxy compound (a2) on a molar basis, (hydroxyalkyloxetane (a1) / 1 functional epoxy compound (a2)) = 1/1 The mixed mixture is continuously added dropwise at a ratio of ˜1 / 3 so that the temperature in the system is 20 to 35 ° C. Stirring is continued until the temperature in the system reaches 20 to 25 ° C. even after completion of the dropping. Next, the reaction mixture is heated to 40 to 70 ° C., preferably 50 to 60 ° C., and the reaction is performed for 1 to 5 hours, preferably 2 to 3 hours until all the raw material monomers are converted. The conversion rate of the raw material monomer can be controlled by confirming with GC, NMR, or IR spectrum. After completion of the reaction, the solution is neutralized and filtered in the same manner as in
ここで用いる重合開始剤は、Ｈ２ＳＯ４、ＨＣｌ、ＨＢＦ４、ＨＰＦ６、ＨＳｂＦ６、ＨＡｓＦ６、ｐ−トルエンスルホン酸、トリフロロメタンスルホン酸などのブロンステッド酸、ＢＦ３、ＡｌＣｌ３、ＴｉＣｌ４、ＳｎＣｌ４などのルイス酸、トリアリールスルフォニウム−ヘキサフルオロホスフェート、トリアリールスルフォニウム−アンチモネート、ジアリールイオドニウム−ヘキサフルオロホスフェート、ジアリールイオドニウム−アンチモネート、Ｎ−ベンジルピリジニウム−ヘキサフルオロホスフェート、Ｎ−ベンジルピリジニウム−アンチモネートなどのオニウム塩化合物、トリフェニルカルボニウム−テトラフルオロボレート、トリフェニルカルボニウム−ヘキサフルオロホスフェート、トリフェニルカルボニウム−ヘキサフルオロアンチモネートなどのトリフェニルカルボニウム塩、ｐ−トルエンスルホニルクロライド、メタンスルホニルクロライド、トリフルオロメタンスルホニルクロライド、ｐ−トルエンスルホン酸無水物、メタンスルホン酸無水物、トリフルオロメタンスルホン酸無水物、ｐ−トルエンスルホン酸メチルエステル、ｐ−トルエンスルホン酸エチルエステル、メタンスルホン酸メチルエステル、トリフルオロメタンスルホン酸メチルエステル、トリフルオロメタンスルホン酸トリメチルシリルエステルなどのアルキル化剤が挙げられる。
The polymerization initiator used here, H 2 SO 4, HCl,
これらのなかでも特に、ＨＰＦ６、ＨＳｂＦ６、ＨＡｓＦ６、トリフェニルカルボニウム−ヘキサフルオロホスフェートが活性に優れる点から好ましく、特にＨＰＦ６及びトリフェニルカルボニウム−ヘキサフルオロホスフェートが好ましい。 Among these, HPF 6 , HSbF 6 , HAsF 6 , and triphenylcarbonium-hexafluorophosphate are particularly preferable from the viewpoint of excellent activity, and HPF 6 and triphenylcarbonium-hexafluorophosphate are particularly preferable.
このようにして得られる多分岐ポリエーテルポリオールは、その分子構造中に１級水酸基（Ｈ１）と２級水酸基（Ｈ２）とを有しており、かつ、前記多分岐ポリエーテルポリオールの数平均分子量（Ｍｎ）が１，０００〜３，５００、水酸基価が１５０〜３５０ｍｇ・ＫＯＨ／ｇであることを特徴としている。 The multibranched polyether polyol thus obtained has a primary hydroxyl group (H1) and a secondary hydroxyl group (H2) in its molecular structure, and the number average molecular weight of the multibranched polyether polyol. (Mn) is 1,000 to 3,500, and a hydroxyl value is 150 to 350 mg · KOH / g.
即ち、本発明の多分岐ポリエーテルポリオールは、ヒドロキシアルキルオキセタン（ａ１）と、１官能性エポキシ化合物（ａ２）とを開環反応させて得られる多分岐構造を有することから該多分岐ポリエーテルポリオールの慣性半径が小さくなり、更に、数平均分子量（Ｍｎ）が１，０００〜３，５００という低い値を有することから、従来になく流動性が極めて良好となり、ウレタン系樹脂組成物として作業性が飛躍的に改善される。また、水酸基価が１５０〜３５０ｍｇ・ＫＯＨ／ｇであり、分子量が小さい割に多くの水酸基を有することから硬化時の架橋密度が高くなって、硬質の塗膜を形成できる。 That is, the multi-branched polyether polyol of the present invention has a multi-branched structure obtained by ring-opening reaction of hydroxyalkyl oxetane (a1) and monofunctional epoxy compound (a2). And the number average molecular weight (Mn) has a low value of 1,000 to 3,500, so that the fluidity is extremely good compared to the prior art, and workability as a urethane resin composition is improved. Dramatically improved. Moreover, since it has a hydroxyl value of 150 to 350 mg · KOH / g and a large number of hydroxyl groups for a small molecular weight, the crosslinking density at the time of curing is increased, and a hard coating film can be formed.
更に、分子構造中に１級水酸基（Ｈ１）のみならず、２級水酸基（Ｈ２）を有することから、該２級水酸基（Ｈ１）の反応遅延性に起因して可使時間を長時間確保することができる。本発明においてこのような反応性の低い２級水酸基（Ｈ２）を有しながらも、最終的な硬化物の硬度が良好となるのは、当該多分岐ポリエーテルポリオールの分子構造が球状形状をとり、該球状体の外側に向けて水酸基が存在するため、反応速度が低下しても、最終的には殆どの水酸基が十分に反応に寄与し、硬化物の架橋密度が極めて高くなるためである。このような可使時間と硬化物硬度とのバランスの点から特に前記２級水酸基（Ｈ２）の存在割合が全水酸基数に対して２０〜７０％となる割合である。
Further, since the molecular structure has not only the primary hydroxyl group (H1) but also the secondary hydroxyl group (H2), the pot life is secured for a long time due to the reaction delay of the secondary hydroxyl group (H1). be able to. In the present invention, the hardness of the final cured product is good although it has such a low reactive secondary hydroxyl group (H2). The molecular structure of the multi-branched polyether polyol has a spherical shape. This is because, since the hydroxyl group exists toward the outside of the spherical body, even if the reaction rate decreases, finally, most of the hydroxyl group contributes sufficiently to the reaction, and the crosslink density of the cured product becomes extremely high. . Such existing ratio of especially the secondary hydroxyl group from the viewpoint (H2) of the balance of pot life and the cured hardness of Ru ratio der to be 20% to 70% relative to the total number of hydroxyl groups.
なお、多分岐ポリエーテルポリオール中の全水酸基数に対する２級水酸基（Ｈ２）の割合は、多分岐ポリエーテルポリオールをトリフロロ酢酸エステルとを反応させた後、１９Ｆ−ＮＭＲで測定することによって特定することができる。 The ratio of secondary hydroxyl groups (H2) to the total number of hydroxyl groups in the multi-branched polyether polyol is specified by measuring 19 F-NMR after reacting the multi-branched polyether polyol with trifluoroacetic acid ester. be able to.
このような多分岐ポリエーテルポリオールの具体的構造は、ヒドロキシアルキルオキセタン（ａ１）と、１官能性エポキシ化合物（ａ２）とを開環反応させて得られる種々の構造が含まれる。具体的には、下記一般式（１） Specific structures of such a multi-branched polyether polyol include various structures obtained by ring-opening reaction of hydroxyalkyl oxetane (a1) and monofunctional epoxy compound (a2). Specifically, the following general formula (1)
で表されるヒドロキシアルキルオキセタン（ａ１）と、下記一般式（２）
And a hydroxyalkyl oxetane (a1) represented by the following general formula (2)
ここで、前記各構造単位において実線部分は当該構造単位内の単結合を示し、破線部分は、他の構造単位とエーテル結合を形成する単結合を示す。また、前記ＯＲ１〜ＯＲ３、ＯＥ１、及びＯＥ２は、ヒドロキシアルキルオキセタン（ａ１）に起因する構造単位であって、ＯＲ１〜ＯＲ３は繰り返し単位を表し、ＯＥ１及びＯＥ２は末端構造単位を表す。
また、ＥＲ１、ＥＥ１、及びＥＥ２は、前記１官能性エポキシ化合物（ａ２）に起因する構造単位であって、ＥＲ１は繰り返し単位を表し、ＥＥ１及びＥＥ２は末端構造単位を表す。
Here, in each of the structural units, a solid line portion indicates a single bond in the structural unit, and a broken line portion indicates a single bond that forms an ether bond with another structural unit. Moreover, said OR1-OR3, OE1, and OE2 are structural units resulting from a hydroxyalkyl oxetane (a1), OR1-OR3 represents a repeating unit, and OE1 and OE2 represent a terminal structural unit.
Further, ER1, EE1, and EE2 are structural units derived from the monofunctional epoxy compound (a2), ER1 represents a repeating unit, and EE1 and EE2 represent terminal structural units.
本発明の多分岐ポリエーテルポリオールは、前記ＯＲ１〜ＯＲ３及びＥＲ１から選択される繰り返し単位によって多分岐構造が形成され、末端に前記ＯＥ１、ＯＥ２、ＥＥ１、及びＥＥ２から選択される末端構造単位を有するものである。なお、これらの繰り返し単位及び末端構造単位はランダムに存在していてもよいし、ＯＲ１〜ＯＲ３が分子構造の中心部分を構成し、末端に前記末端構造単位を有するものであってもよい。なお、本発明では２級水酸基（Ｈ２）が必須であることから、前記ＥＥ１は必須の構造単位として多分岐ポリエーテルポリオール中に存在する。 The multi-branched polyether polyol of the present invention has a multi-branched structure formed by repeating units selected from the OR1 to OR3 and ER1, and has a terminal structural unit selected from the OE1, OE2, EE1, and EE2 at the terminal. Is. In addition, these repeating units and terminal structural units may exist at random, OR1-OR3 may comprise the center part of molecular structure, and may have the said terminal structural unit at the terminal. In the present invention, since the secondary hydroxyl group (H2) is essential, the EE1 is present in the multi-branched polyether polyol as an essential structural unit.
本発明のウレタン系樹脂組成物は、ポリオール成分（Ａ）及びポリイソシアネート成分（Ｂ）との二成分系硬化性組成物であって、当該ポリオール成分（Ａ）として、前記多分岐ポリエーテルポリオールを用いることを特徴としている。
本発明では、ポリオール成分（Ａ）として、前記多分岐ポリエーテルポリオールに加え、水酸基含有高級脂肪酸アルキルエステルを併用することが、２液混合状態での混合物の疎水性が高まり硬化時の発泡を抑制できる点から好ましい。
The urethane-based resin composition of the present invention is a two-component curable composition with a polyol component (A) and a polyisocyanate component (B), and the multi-branched polyether polyol is used as the polyol component (A). It is characterized by use.
In the present invention, as the polyol component (A), in addition to the multi-branched polyether polyol, the use of a hydroxyl group-containing higher fatty acid alkyl ester increases the hydrophobicity of the mixture in a two-component mixed state and suppresses foaming during curing. It is preferable because it can be performed.
かかる水酸基含有脂肪酸アルキルエステルとは、ステアリン酸、リノール酸等の高級脂肪酸を、グリコール及びグリセリンなどの多価アルコールと水酸基が残存するように反応させた水酸基含有のエステル化合物、リシノール酸などの水酸基含有高級脂肪酸をモノアルコール、グリコール、グリセリン、トリメチロールプロパンなどと反応させたエステル化合物などの他、ひまし油等の水酸基含有天然油脂が挙げられる。
また、椰子油、大豆油などの水酸基を実効量含有しない天然油脂であっても、これらを多価アルコールとエステル交換反応させて水酸基を導入したものであってもよい。
The hydroxyl group-containing fatty acid alkyl ester is a hydroxyl group-containing ester compound obtained by reacting a higher fatty acid such as stearic acid or linoleic acid with a polyhydric alcohol such as glycol or glycerine so that the hydroxyl group remains, and a hydroxyl group containing ricinoleic acid or the like. In addition to ester compounds obtained by reacting higher fatty acids with monoalcohol, glycol, glycerin, trimethylolpropane, and the like, hydroxyl group-containing natural fats and oils such as castor oil are exemplified.
Further, even natural oils and fats such as coconut oil and soybean oil that do not contain an effective amount of hydroxyl groups may be those obtained by transesterifying these with polyhydric alcohol to introduce hydroxyl groups.
更に、上記した水酸基含有脂肪酸アルキルエステルのうち、アルキル鎖に二重結合を含むものは、更に疎水性を高めるべく、ジシクロペンタジエンで変性したものも好ましく用いることができる。これらのなかでも特に、塗膜の疎水性向上の効果が顕著である点から、水酸基価１００〜３００ｍｇ・ＫＯＨ／ｇ、かつ、アルキル鎖部分の炭素原子数１０〜２５のものがとりわけ好ましい。 Further, among the hydroxyl group-containing fatty acid alkyl esters described above, those having a double bond in the alkyl chain can be preferably used those modified with dicyclopentadiene to further increase the hydrophobicity. Among these, particularly those having a hydroxyl value of 100 to 300 mg · KOH / g and an alkyl chain portion of 10 to 25 carbon atoms are particularly preferred since the effect of improving the hydrophobicity of the coating film is remarkable.
なお、ポリオール成分（Ａ）中において、多分岐ポリマーポリオールと水酸基含有高級脂肪酸アルキルエステルとの使用割合は、前者／後者の質量比で、３／７〜９／１であることが発泡抑制の効果の点から好ましい。 In the polyol component (A), the ratio of the use of the hyperbranched polymer polyol and the hydroxyl group-containing higher fatty acid alkyl ester is 3/7 to 9/1 in terms of the former / latter mass ratio. From the point of view, it is preferable.
前記ポリオール成分（Ａ）としては、更に本発明の効果を損なわない範囲で、公知慣用のエチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，４ブタンジオール、１，３ブタンジオール、３−メチルペンタンジオール、３，３−ジメチロールヘプタン、トリメチロールプロパン等の単鎖ポリオール類、これら単鎖ポリオール類とアルキレンオキサイド類（例えば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等）を重合させたポリアルキレンエーテルポリオール類あるいはフタル酸、マレイン酸、アジピン酸、ヘット酸、コハク酸、水添ダイマー酸等の二塩基酸と前述の単鎖グリコール類とのエステル化反応によって得られるポリエステルポリオール類、ポリオール類に付加重合させたイプシロンカプロラクトンのポリオールやポリテトラメチレンエーテルグリコール、ポリブタジエンポリオール、ポリオール型キシレンホルムアルデヒド樹脂等を用いることができる。 As the polyol component (A), a publicly known and commonly used ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4 butanediol, 1,3 butanediol, 3-methyl may be used as long as the effects of the present invention are not impaired. Polyesters obtained by polymerizing single-chain polyols such as pentanediol, 3,3-dimethylolheptane and trimethylolpropane, and these single-chain polyols and alkylene oxides (for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc.) Polyester polyols obtained by esterification reaction of alkylene ether polyols or dibasic acids such as phthalic acid, maleic acid, adipic acid, het acid, succinic acid, and hydrogenated dimer acid with the aforementioned single-chain glycols Can be used polyols and polytetramethylene ether glycol epsilon caprolactone obtained by addition polymerization in polyols, polybutadiene polyols, the polyol type xylene formaldehyde resin and the like.
次に、本発明のウレタン系樹脂組成物において前記ポリオール成分（Ａ）と組み合わされる、ポリイソシアネート成分（Ｂ）は、例えば、公知の脂肪族系ポリイソシアネート及び芳香族系ポリイソシアネートを用いることができる。 Next, for the polyisocyanate component (B) combined with the polyol component (A) in the urethane resin composition of the present invention, for example, known aliphatic polyisocyanates and aromatic polyisocyanates can be used. .
ここで、脂肪族系ポリイソシアネートとしては、ヘキサメチレンジイソシアネート（以下、「ＨＤＩ」と略記する。）などのアルキレンジイソシアネート、脂環式炭化水素構造含有ジイソシアネート、ビューレット変性ＨＤＩ及びイソシアヌレート変性ＨＤＩなどのジイソシアネート化合物の３量体、並びにＨＤＩとトリメチロールプロパンとの付加反応化合物などが挙げられる。 Here, examples of the aliphatic polyisocyanate include alkylene diisocyanates such as hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), alicyclic hydrocarbon structure-containing diisocyanates, burette-modified HDI, and isocyanurate-modified HDI. Examples include trimers of diisocyanate compounds, addition reaction compounds of HDI and trimethylolpropane, and the like.
次に、芳香族系ポリイソシアネートとしては、ジフェニルメタンジイソシアネート（以下、「ＭＤＩ」と略称する。）、ポリメチレンポリフェニルポリイソシアネート（以下、「ポリメリックＭＤＩ」と略記する。）、トリレンジイソシアネート（以下、「ＴＤＩ」と略記する。）、キシリレンジイソシアネート（以下、「ＸＤＩ」と略記する。）、あるいは、ウレチジオン変性ＴＤＩなどのジイソシアネート化合物の２量体などが挙げられる。 Next, as the aromatic polyisocyanate, diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”), polymethylene polyphenyl polyisocyanate (hereinafter abbreviated as “polymeric MDI”), tolylene diisocyanate (hereinafter referred to as “MDI”). Abbreviated as "TDI"), xylylene diisocyanate (hereinafter abbreviated as "XDI"), or dimers of diisocyanate compounds such as uretidione-modified TDI.
これらの中でも特に硬化物の硬度に優れる点から、芳香族系ポリイソシアネートが好ましく、とりわけポリメリックＭＤＩが硬度の改善効果が顕著である点から好ましい。ここで、ポリメリックＭＤＩは、アニリンとホルマリンとの重縮合によって得られる高分子量体をイソシアネート化したものであり、ＭＤＩ、及びそれ以上の核体数を有するものの混合物として用いられる。通常、核体数が増加するに従い、硬化物の硬度は高まるものの増粘しやすくなり、その一方で、核体数が低下するに従い、ポリオール成分（Ａ）との相溶性が良好で、粘度は低くなるものの、結晶化しやすくなって低温での安定性に劣る。そこで、本発明ではポリメリックＭＤＩに占める前記ＭＤＩの割合、即ち、２官能性成分の割合を５０〜８０質量％となる割合に調節することがこれらの性能バランスの点から好ましい。とりわけこの物性バランスに優れ、かつ、被膜面の色斑防止といった、所謂、仕上がり性が良好となる点から６０〜７０質量％であることが好ましい。 Among these, aromatic polyisocyanate is preferable from the viewpoint of excellent hardness of the cured product, and polymeric MDI is particularly preferable from the viewpoint of remarkable hardness improvement effect. Here, polymeric MDI is obtained by isocyanate-izing a high molecular weight product obtained by polycondensation of aniline and formalin, and is used as a mixture of MDI and those having a number of nuclei higher than that. Normally, as the number of nuclei increases, the hardness of the cured product increases, but the viscosity tends to increase. On the other hand, as the number of nuclei decreases, the compatibility with the polyol component (A) is good and the viscosity is Although it becomes low, it becomes easy to crystallize and is inferior in stability at low temperature. Therefore, in the present invention, it is preferable from the viewpoint of these performance balances to adjust the ratio of the MDI in the polymeric MDI, that is, the ratio of the bifunctional component to a ratio of 50 to 80% by mass. In particular, the amount is preferably 60 to 70% by mass from the viewpoint of excellent balance of physical properties and good so-called finish properties such as prevention of color spots on the coating surface.
なお、ポリイソシアネート成分（Ｂ）として、単独で使用されるＭＤＩ、或いは、ポリメリックＭＤＩにおける核体数の調整の為に使用されるＭＤＩは、２，２’−ジフェニルメタンジイソシアネート（以下、「２，２’−ＭＤＩ」と略記する。）（イ）、２，４’−ジフェニルメタンジイソシアネート（以下、「２，４’−ＭＤＩ」と略記する。）（ロ）及び４，４’−ジフェニルメタンジイソシアネート（以下、「４，４’−ＭＤＩ」と略記する。）（ハ）から構成される。ここで、ＭＤＩ中の２，２’−ＭＤＩ（イ）と２，４’−ＭＤＩ（ロ）の合計質量（（イ）＋（ロ））が少なくなると、低温でポリイソシアネート成分（Ｂ）が結晶化しやすく、逆に、前記合計質量（（イ）＋（ロ））が多くなると、硬化物の硬度が発現し難くなる傾向にある。従って、これら（イ）〜（ハ）の質量比は、（（イ）＋（ロ））：（ハ）＝５：９５〜４０：６０、とりわけ（（イ）＋（ロ））：（ハ）＝１０：９０〜３０：７０の範囲であることが、ポリイソシアネート成分（Ｂ）の低温安定性、及び硬化物硬度の点から好ましい。 As the polyisocyanate component (B), MDI used alone or MDI used for adjusting the number of nuclei in polymeric MDI is 2,2′-diphenylmethane diisocyanate (hereinafter “2,2”). (A), 2,4'-diphenylmethane diisocyanate (hereinafter abbreviated as "2,4'-MDI") (b) and 4,4'-diphenylmethane diisocyanate (hereinafter, "-MDI"). (Abbreviated as “4,4′-MDI”). Here, when the total mass ((b) + (b)) of 2,2′-MDI (b) and 2,4′-MDI (b) in MDI decreases, the polyisocyanate component (B) is reduced at a low temperature. It is easy to crystallize, and conversely, when the total mass ((b) + (b)) increases, the hardness of the cured product tends to be difficult to express. Therefore, the mass ratio of (A) to (C) is ((I) + (B)) :( C) = 5: 95 to 40:60, especially ((A) + (B)) :( C ) = 10: 90 to 30:70 is preferable from the viewpoint of the low temperature stability of the polyisocyanate component (B) and the hardness of the cured product.
また、本発明ではポリイソシアネート成分（Ｂ）として、脂環式炭化水素構造含有ジイソシアネートを用いた場合、その硬化皮膜は硬質であり乍ら、適度な柔軟性を発現し、ひび割れに対する十分な追従性を発現する。また、芳香族系ポリイソシアネートを用いた場合に生じやすい紫外線劣化による黄変を低減させることができ、意匠性に優れた被覆面を形成することができる。 Further, in the present invention, when the diisocyanate containing an alicyclic hydrocarbon structure is used as the polyisocyanate component (B), the cured film is hard but expresses an appropriate flexibility and has sufficient followability to cracks. Is expressed. In addition, yellowing due to ultraviolet degradation that easily occurs when aromatic polyisocyanate is used can be reduced, and a coated surface with excellent design can be formed.
かかる、脂環式炭化水素構造含有ジイソシアネートは、具体的には、イソホロンジイソシアネート、水添キシリレンジイソシアネート、水添ジフェニルメタンジイソシアネート、シクロヘキサンジイソシアネート、ノルボルネンジイソシアネート、ジメタノナフタレンジイソシアネート、及び、これらとポリオールとを反応させて得られるポリイソシアネートが挙げられる。
ここで使用し得るポリオールとしては、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、テトラメチレングリコール、１，３−ブタンジオール、３−メチルペンタンジオール、３，３−ジメチロールヘプタン、トリメチロールプロパン等のアルキレンジオール、或いは、これらのアルキレンジオールに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等のアルキレンオキサイドを重合させたポリアルキレンエーテルポリオールが挙げられる。また、前記アルキレンジオールに、フタル酸、マレイン酸、アジピン酸、ヘット酸、コハク酸、水添ダイマー酸等の二塩基酸とのエステル化反応によって得られるポリエステルポリオール類、前記アルキレンジオールにイプシロンカプロラクトンを共重合させたポリオール等が挙げられる。
これらに中でも特に、硬化被膜の硬度と柔軟性とのバランスが顕著に良好となる点からノルボルネンジイソシアネート、及びジメタノナフタレンジイソシアネートが好ましい。
The alicyclic hydrocarbon structure-containing diisocyanate specifically includes isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, norbornene diisocyanate, dimethanonaphthalene diisocyanate, and these and a polyol. And polyisocyanate obtained.
Examples of polyols that can be used here include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tetramethylene glycol, 1,3-butanediol, 3-methylpentanediol, 3,3-dimethylolheptane, and trimethylolpropane. Or an alkylene diol obtained by polymerizing an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or styrene oxide to the alkylene diol. Further, polyester polyols obtained by esterification reaction with dibasic acids such as phthalic acid, maleic acid, adipic acid, het acid, succinic acid, and hydrogenated dimer acid are added to the alkylene diol, and epsilon caprolactone is added to the alkylene diol. Examples include polyols copolymerized.
Among these, norbornene diisocyanate and dimethanonaphthalene diisocyanate are particularly preferable from the viewpoint that the balance between the hardness and flexibility of the cured coating is remarkably improved.
本発明では、上記した脂環式炭化水素構造含有ジイソシアネートを用いることにより、硬化被膜の硬度がショアーＤ７５以上と硬質であり、かつ伸度が６０％以上と高伸度となる。よって、本発明において脂環式炭化水素構造含有ジイソシアネートを用いたウレタン系樹脂組成物は、下地基材のひび割れに十分に追従し、信頼性の高い被覆性能を得ることができる。また、高い耐候性を有し、優れた黄変防止性を有しているため、意匠性を長期保持することの出来る被覆面を提供することが出来る。 In the present invention, by using the above-described alicyclic hydrocarbon structure-containing diisocyanate, the hardness of the cured film is as hard as Shore D75 or more, and the elongation is as high as 60% or more. Therefore, in the present invention, the urethane-based resin composition using the alicyclic hydrocarbon structure-containing diisocyanate can sufficiently follow the cracks in the base substrate, and can obtain highly reliable coating performance. Moreover, since it has high weather resistance and has excellent yellowing prevention properties, it is possible to provide a coated surface that can maintain design properties for a long period of time.
また、本発明では、ポリイソシアネート成分（Ｂ）として前記脂環式炭化水素構造含有ジイソシアネートを用いる場合、前記した水酸基含有高級脂肪酸アルキルエステルを併用することにより、硬度を保持し乍ら柔軟性をより高めることができる。 Further, in the present invention, when the alicyclic hydrocarbon structure-containing diisocyanate is used as the polyisocyanate component (B), the above-mentioned hydroxyl group-containing higher fatty acid alkyl ester is used in combination, so that the hardness can be maintained while maintaining the hardness. Can be increased.
本発明のウレタン系樹脂組成物を被覆材に用いる場合、前記ポリオール成分（Ａ）及び前記ポリイソシアネート成分（Ｂ）に、更に充填材、及び必要に応じてその他各種の添加剤を加えて目的とする被覆材を調整できる。なお、本発明の組成物から得られる被覆材は、ショアーＤ硬度７０以上の硬質被覆材として、機械強度のみならず低粘度で作業性に優れるという顕著な性能を発現する。即ち、本発明では、ポリオール成分（Ａ）とイソシアネート成分（Ｂ）とを混合した場合の粘度が、ローラー塗布が可能となる１０００ｍＰａ・ｓ以下になるという特長を有する。 When the urethane-based resin composition of the present invention is used as a coating material, the polyol component (A) and the polyisocyanate component (B) are further added with a filler and, if necessary, various other additives. The covering material to be adjusted can be adjusted. In addition, the coating material obtained from the composition of this invention expresses the remarkable performance that it is excellent in workability | operativity not only with mechanical strength but with low viscosity as a hard coating material with a Shore D hardness of 70 or more. That is, the present invention has a feature that the viscosity when the polyol component (A) and the isocyanate component (B) are mixed is 1000 mPa · s or less that enables roller coating.
ここで充填材としては、炭酸カルシウム、表面処理炭酸カルシウム、水酸化アルミニウム、沈降性硫酸バリウム、クレー、シリカ、タルクなどが挙げられる。 Examples of the filler include calcium carbonate, surface-treated calcium carbonate, aluminum hydroxide, precipitated barium sulfate, clay, silica, and talc.
また、他の添加剤成分としては、活性アルミナ粉末、合成ゼオライト、シリカゲル、珪藻土、消石灰、生石灰、水酸化マグネシウム、無水石膏、塩化カルシウム、合成ハイドロタルサイト、活性炭、活性白土の如き吸湿剤、アゾ系、銅フタロシアニン系、弁柄、黄鉛、酸化チタン、亜鉛華またはカーボンブラックの如き有機ないしは無機系の着色顔料、および、鉛丹、鉛白、塩基性クロム酸塩、塩基性硫酸鉛、ジンククロメート、亜鉛末またはＭＩＯの如き防錆顔料、さらには、チキソ付与剤、レベリング剤、吸湿剤、シランあるいはチタネート系カップリング剤などの各種助剤が挙げられる。さらに必要に応じ、ジブチルチンジラウレートまたはジブチルチンジアセテートの如き有機金属化合物や各種アミン類などの硬化触媒を始め、ジオクチルフタレート、アスファルト、またはタールの如き可塑剤成分や、重油または芳香族炭化水素の如き石油系希釈剤成分などを、本発明の効果を損なわない範囲で使用してもよい。 Other additive components include activated alumina powder, synthetic zeolite, silica gel, diatomaceous earth, slaked lime, quicklime, magnesium hydroxide, anhydrous gypsum, calcium chloride, synthetic hydrotalcite, activated carbon, activated clay, moisture absorbents such as azo , Copper phthalocyanine, petal, yellow lead, titanium oxide, zinc white or carbon black, organic or inorganic color pigments, red lead, lead white, basic chromate, basic lead sulfate, zinc Examples include rust preventive pigments such as chromate, zinc dust or MIO, and various auxiliary agents such as thixotropic agents, leveling agents, hygroscopic agents, silane or titanate coupling agents. In addition, if necessary, a curing catalyst such as an organometallic compound such as dibutyltin dilaurate or dibutyltin diacetate or various amines, a plasticizer component such as dioctyl phthalate, asphalt, or tar, or a heavy oil or aromatic hydrocarbon. You may use a petroleum-type diluent component etc. in the range which does not impair the effect of this invention.
上記の充填材、添加物等は、主にポリオール成分（Ａ）に常法により、あらかじめ練り合わせて使用することができる。 The above fillers, additives and the like can be used by kneading in advance with the polyol component (A) by a conventional method.
本発明の組成物から調整された被覆材を用いて塗工する方法は、ポリオール成分（Ａ）、ポリイソシアネート成分（Ｂ）、及び必要に応じて充填材やその他の添加剤成分を所定の混合比で混合（常温）し、可使時間内に下地、例えばコンクリート、金属、プラスチック、ＦＲＰ、木質物等に塗布して硬化させる方法が挙げられる。本発明によれば、低粘度かつ十分な可使時間を発現することから、作業性に優れた被覆材が得られる。よって、熟練を要するコテ塗りのみならず、ローラー塗りまたは刷毛塗りといった、熟練不要の方法により塗工でき、更にスプレー塗装も可能となる。 The coating method using the coating material prepared from the composition of the present invention comprises a predetermined mixing of a polyol component (A), a polyisocyanate component (B), and, if necessary, a filler and other additive components. A method of mixing at a ratio (room temperature), applying to a base, such as concrete, metal, plastic, FRP, woody material, etc. within a pot life and curing. According to the present invention, since a low viscosity and a sufficient pot life are exhibited, a coating material excellent in workability can be obtained. Therefore, not only skillful iron coating but also roller coating or brush coating can be applied by methods that do not require skill, and spray coating is also possible.
以下本発明を実施例によって更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。また本文中「部」とあるのは、質量部を示すものである。
なお、実施例１〜４、及び実施例６中の多分岐ポリエーテルポリオール中の全水酸基数に対する２級水酸基（Ｈ２）の割合は、多分岐ポリエーテルポリオールをトリフロロ酢酸エステルとを反応させた後、１９Ｆ−ＮＭＲによって測定した。
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, “part” in the text indicates a part by mass.
In addition, the ratio of the secondary hydroxyl group (H2) with respect to the total number of hydroxyl groups in the hyperbranched polyether polyols in Examples 1 to 4 and Example 6 is obtained after reacting the hyperbranched polyether polyol with trifluoroacetic acid ester. , 19 F-NMR.
実施例１＜多分岐ポリエーテルポリオールの合成＞
リフラックスコンデンサー、マグネット式攪拌棒、温度計を具備した５００ｍｌ三口フラスコ中で、３−ヒドロキシメチル−３−エチルオキセタン ９２．８ｇ（０．８モル）と、プロピレンオキサイド ４６．４ｇ（０．８モル）とを、乾燥かつ過酸化物フリーの２００ｍｌのジエチルエーテルに溶解し、次いで、このフラスコを−１４℃のアイスバスで冷却した。
次いで、ＨＰＦ６ ９７ｇの６０質量％水溶液を１０分で滴下した。反応混合物は僅かに白濁した。次いで、室温で一晩反応させ、翌朝、透明な反応混合物を３時間還流した。
その後、樹脂溶液からジエチルエーテルを留去し、生成物をＫＯＨ２．８ｇと水４００ｍｌの水溶液で洗浄した。単離した有機層は、次いで、非イオン水４００ｍｌで洗浄し、再度、ジエチルエーテルを除去し、透明で高粘性の多分岐ポリエーテルポリオール１３６ｇを得た。収率９４％であった。
この多分岐ポリエーテルポリオールは、Ｍｎ＝１，３９０ｇ／ｍｏｌ、Ｍｗ＝２，５２０ｇ／ｍｏｌ、ＯＨＶ＝３２０ｍｇ・ＫＯＨ／ｇであり、プロトンＮＭＲから、モル基準で３−ヒドロキシメチル−３−エチルオキセタン：プロピレンオキサイド＝１：１であることが判明した。また、全水酸基数に対する２級水酸基（Ｈ２）の割合は、２７．６％であった。この多分岐ポリエーテルポリオールの１３Ｃ−ＮＭＲのチャート図を第１図に、プロトンＮＭＲのチャート図を第２図に示す。
Example 1 <Synthesis of Multibranched Polyether Polyol>
In a 500 ml three-necked flask equipped with a reflux condenser, a magnetic stirring bar and a thermometer, 92.8 g (0.8 mol) of 3-hydroxymethyl-3-ethyloxetane and 46.4 g (0.8 mol) of propylene oxide Was dissolved in dry and peroxide-free 200 ml of diethyl ether, and the flask was then cooled in a −14 ° C. ice bath.
Next, a 60% by mass aqueous solution of 97 g of HPF 6 was dropped in 10 minutes. The reaction mixture became slightly cloudy. The reaction was then allowed to react overnight at room temperature and the next morning the clear reaction mixture was refluxed for 3 hours.
Thereafter, diethyl ether was distilled off from the resin solution, and the product was washed with an aqueous solution of 2.8 g of KOH and 400 ml of water. The isolated organic layer was then washed with 400 ml of non-ionized water and again diethyl ether was removed to obtain 136 g of a transparent and highly viscous multi-branched polyether polyol. The yield was 94%.
This multi-branched polyether polyol has Mn = 1,390 g / mol, Mw = 2,520 g / mol, OHV = 320 mg · KOH / g, and 3-hydroxymethyl-3-ethyloxetane on a molar basis from proton NMR. : Propylene oxide = 1: 1. The ratio of secondary hydroxyl groups (H2) to the total number of hydroxyl groups was 27.6%. FIG. 1 shows a 13 C-NMR chart of this multi-branched polyether polyol, and FIG. 2 shows a proton NMR chart.
実施例２＜多分岐ポリエーテルポリオールの合成＞
リフラックスコンデンサー、マグネット式攪拌棒、温度計を具備した２リットル三口フラスコ中で、３−ヒドロキシメチル−３−エチルオキセタン ３４８ｇ（３モル）と、プロピレンオキサイド ３４８ｇ（６モル）とを、乾燥かつ過酸化物フリーの１リットルのジエチルエーテルに溶解し、次いで、このフラスコを−１４℃のアイスバスで冷却した。
次いで、ＨＰＦ６ ５．５ｇの６０質量％水溶液を１０分で滴下した。反応混合物は僅かに白濁した。次いで、室温で一晩反応させ、翌朝、透明な反応混合物を３時間還流した。次いで、前記開始剤は、ＮａＯＭｅ９ｇの３０質量％メタノール溶液を加えて失活させた。濾過した後、メンブレンポンプ吸引機でバス温度７５℃でジエチルエーテルを除去した。ジエチルエーテルを完全に除去した後、多分岐ポリエーテルポリオール６６７ｇを得た。収率８９％であった。
この多分岐ポリエーテルポリオールは、Ｍｎ＝１，４４０ｇ／ｍｏｌ、Ｍｗ＝３，３５０ｇ／ｍｏｌ、ＯＨＶ＝２６５ｍｇ・ＫＯＨ／ｇであり、プロトンＮＭＲから、モル基準で３−ヒドロキシメチル−３−エチルオキセタン：プロピレンオキサイド＝１：１．９であることが判明した。また、全水酸基数に対する２級水酸基（Ｈ２）の割合は、３９．０％であった。この多分岐ポリエーテルポリオールの１３Ｃ−ＮＭＲのチャート図を第３図に、プロトンＮＭＲのチャート図を第４図に示す。
Example 2 <Synthesis of Multibranched Polyether Polyol>
In a 2-liter three-necked flask equipped with a reflux condenser, a magnetic stirring bar, and a thermometer, 348 g (3 mol) of 3-hydroxymethyl-3-ethyloxetane and 348 g (6 mol) of propylene oxide were dried and filtered. It was dissolved in 1 liter of diethyl ether free of oxide and then the flask was cooled in a −14 ° C. ice bath.
Then, a 60% by mass aqueous solution of 5.5 g of HPF 6 was dropped in 10 minutes. The reaction mixture became slightly cloudy. The reaction was then allowed to react overnight at room temperature and the next morning the clear reaction mixture was refluxed for 3 hours. Next, the initiator was deactivated by adding a 30 mass% methanol solution of 9 g of NaOMe. After filtration, diethyl ether was removed with a membrane pump suction device at a bath temperature of 75 ° C. After the diethyl ether was completely removed, 667 g of a multi-branched polyether polyol was obtained. The yield was 89%.
This multi-branched polyether polyol has Mn = 1,440 g / mol, Mw = 3,350 g / mol, OHV = 265 mg · KOH / g, and 3-hydroxymethyl-3-ethyloxetane on a molar basis from proton NMR. : Propylene oxide = 1: 1.9. The ratio of secondary hydroxyl groups (H2) to the total number of hydroxyl groups was 39.0%. FIG. 3 shows a 13 C-NMR chart of this multi-branched polyether polyol, and FIG. 4 shows a proton NMR chart.
実施例３＜多分岐ポリエーテルポリオールの合成＞
リフラックスコンデンサー、マグネット式攪拌棒、温度計を具備した５００ｍｌ三口フラスコ中で、３−ヒドロキシメチル−３−エチルオキセタン ６９．６ｇ（０．６モル）と、プロピレンオキサイド １０４．４ｇ（１．８モル）とを、乾燥かつ過酸化物フリーの２５０ｍｌのジエチルエーテルに溶解し、次いで、このフラスコを−１０℃のアイスバスで冷却した。
次いで、ＨＰＦ６ １．４６ｇの６０質量％水溶液を１０分で滴下した。反応混合物は僅かに白濁した。次いで、室温で一晩反応させ、翌朝、透明な反応混合物を４時間還流した。その後、樹脂溶液からジエチルエーテル３００ｍｌを留去し、生成物をＫＯＨ２．８ｇと水４００ｍｌの水溶液で洗浄した。
単離した有機層は、次いで、非イオン水４００ｍｌで２回洗浄し、再度、ジエチルエーテルを除去し、低粘性の透明多分岐ポリエーテルポリオール１６３．２ｇを得た。収率９４％であった。
この多分岐ポリエーテルポリオールは、Ｍｎ＝１，７５０ｇ／ｍｏｌ、Ｍｗ＝３，６３０ｇ／ｍｏｌ、ＯＨＶ＝１９９ｍｇ・ＫＯＨ／ｇであり、プロトンＮＭＲから、モル基準で３−ヒドロキシメチル−３−エチルオキセタン：プロピレンオキサイド＝１：２．９であることが判明した。また、全水酸基数に対する２級水酸基（Ｈ２）の割合は、４６．３％であった。この多分岐ポリエーテルポリオールの１３Ｃ−ＮＭＲのチャート図を第５図に、プロトンＮＭＲのチャート図を第６図に示す。
Example 3 <Synthesis of Multibranched Polyether Polyol>
In a 500 ml three-necked flask equipped with a reflux condenser, a magnetic stirring bar and a thermometer, 69.6 g (0.6 mol) of 3-hydroxymethyl-3-ethyloxetane and 104.4 g (1.8 mol) of propylene oxide Was dissolved in 250 ml of dry and peroxide-free diethyl ether, and the flask was then cooled in an ice bath at -10 ° C.
Then, a 60% by mass aqueous solution of 1.46 g of HPF 6 was added dropwise over 10 minutes. The reaction mixture became slightly cloudy. The reaction was then allowed to react overnight at room temperature and the next morning the clear reaction mixture was refluxed for 4 hours. Thereafter, 300 ml of diethyl ether was distilled off from the resin solution, and the product was washed with an aqueous solution of 2.8 g of KOH and 400 ml of water.
The isolated organic layer was then washed twice with 400 ml of non-ionized water, and diethyl ether was removed again to obtain 163.2 g of a low viscosity transparent multi-branched polyether polyol. The yield was 94%.
This multi-branched polyether polyol has Mn = 1,750 g / mol, Mw = 3,630 g / mol, OHV = 199 mg · KOH / g, and 3-hydroxymethyl-3-ethyloxetane on a molar basis from proton NMR. : Propylene oxide = 1: 2.9. The ratio of secondary hydroxyl groups (H2) to the total number of hydroxyl groups was 46.3%. FIG. 5 shows a 13 C-NMR chart of this multi-branched polyether polyol, and FIG. 6 shows a proton NMR chart.
実施例４＜多分岐ポリエーテルポリオールの合成＞
リフラックスコンデンサー、マグネット式攪拌棒、温度計を具備した５００ｍｌ三口フラスコ中で、３−ヒドロキシメチル−３−エチルオキセタン １３９．２ｇ（１．２モル）と、プロピレンオキサイド ２０８．８ｇ（３．６モル）とを、乾燥かつ過酸化物フリーの５００ｍｌのジエチルエーテルに溶解し、次いで、このフラスコを−１０℃のアイスバスで冷却した。
次いで、ＨＰＦ６ ２．９２ｇの６０質量％水溶液を１０分で滴下した。反応混合物は僅かに白濁した。次いで、室温で一晩反応させ、翌朝、透明な反応混合物を４時間還流した。次いで、前記開始剤は、ＮａＯＭｅ３．２ｇの３０質量％メタノール溶液を加えて失活させた。ジエチルエーテルを完全に除去した後、粘性の多分岐ポリエーテルポリオール３１０ｇを得た。収率８９％であった。
この多分岐ポリエーテルポリオールは、Ｍｎ＝１，５８０ｇ／ｍｏｌ、Ｍｗ＝３，７１０ｇ／ｍｏｌ、ＯＨＶ＝２２４ｍｇ・ＫＯＨ／ｇであり、プロトンＮＭＲから、モル基準で３−ヒドロキシメチル−３−エチルオキセタン：プロピレンオキサイド＝１：３であることが判明した。また、全水酸基数に対する２級水酸基（Ｈ２）の割合は、４５．０％であった。この多分岐ポリエーテルポリオールの１３Ｃ−ＮＭＲのチャート図を第７図に、プロトンＮＭＲのチャート図を第８図に示す。
Example 4 <Synthesis of Multibranched Polyether Polyol>
In a 500 ml three-necked flask equipped with a reflux condenser, a magnetic stirring bar and a thermometer, 139.2 g (1.2 mol) of 3-hydroxymethyl-3-ethyloxetane and 208.8 g (3.6 mol) of propylene oxide Was dissolved in dry and peroxide-free 500 ml of diethyl ether, and the flask was then cooled in an ice bath at -10 ° C.
Next, a 60% by mass aqueous solution of 2.92 g of HPF 6 was added dropwise in 10 minutes. The reaction mixture became slightly cloudy. The reaction was then allowed to react overnight at room temperature and the next morning the clear reaction mixture was refluxed for 4 hours. Subsequently, the initiator was deactivated by adding a 30% by mass methanol solution of NaOMe 3.2 g. After the diethyl ether was completely removed, 310 g of a viscous multi-branched polyether polyol was obtained. The yield was 89%.
This multi-branched polyether polyol has Mn = 1,580 g / mol, Mw = 3,710 g / mol, OHV = 224 mg · KOH / g, and 3-hydroxymethyl-3-ethyloxetane on a molar basis from proton NMR. : Propylene oxide = 1: 3. The ratio of secondary hydroxyl groups (H2) to the total number of hydroxyl groups was 45.0%. FIG. 7 shows a 13 C-NMR chart of this multi-branched polyether polyol, and FIG. 8 shows a proton NMR chart.
実施例５＜多分岐ポリエーテルポリオールの合成＞
リフラックスコンデンサー、マグネット式攪拌棒、温度計を具備した２５０ｍｌ三口フラスコ中で、３−ヒドロキシメチル−３−エチルオキセタン １１．６ｇ（０．１モル）と、プロピレンオキサイド １１．６ｇ（０．２モル）とを、５０ｍｌの乾燥シクロヘキサンに溶解し、次いで、このフラスコを１０℃のアイスバスで冷却した。
次いで、ＨＰＦ６ ０．７６ｇ（モノマー成分に対して０．２５モル％）の６０質量％水溶液を１０ｍｌのジエチルエーテルに溶解し、これを一度にフラスコに加えた。その後、反応混合物は直ちに白濁した。ＨＰＦ６を加えて１時間内に、反応温度は３６℃に上昇した。次いで、該反応混合物はオイルバスで５４〜６０℃に１時間加熱し、更に、室温で一晩攪拌した。
次いで、前記開始剤は、ＮａＯＭｅ０．３ｇの３０質量％メタノール溶液を加えて失活させた。次いで、この白濁した反応混合物をｐＨ６になるまで４時間攪拌した。
反応混合物の下層の白濁層を分離し、シクロヘキサンを完全に除去した後、透明で低粘性の多分岐ポリエーテルポリオール１８．７ｇを得た。収率７９％であった。この多分岐ポリエーテルポリオールは、Ｍｎ＝２，１６０ｇ／ｍｏｌ、Ｍｗ ６，３１０ｇ／ｍｏｌ、ＯＨＶ＝２２４ｍｇＫＯＨ／ｇであり、プロトンＮＭＲから、モル基準で３−ヒドロキシメチル−３−エチルオキセタン：プロピレンオキサイド＝１：１．９であることが判明した。
一方、反応混合物中、透明シクロヘキサン層を乾燥し、低粘性の多分岐ポリエーテルポリオール１．２ｇを得た。この多分岐ポリエーテルポリオールは、Ｍｎ＝５００ｇ／ｍｏｌ、Ｍｗ＝９５０ｇ／ｍｏｌであり、プロトンＮＭＲから、モル基準で３−ヒドロキシメチル−３−エチルオキセタン：プロピレンオキサイド＝１：２．１であることが判明した。この多分岐ポリエーテルポリオールの１３Ｃ−ＮＭＲのチャート図を第９図に、プロトンＮＭＲのチャート図を第１０図に示す。
Example 5 <Synthesis of Multibranched Polyether Polyol>
In a 250 ml three-necked flask equipped with a reflux condenser, a magnetic stirring bar and a thermometer, 11.6 g (0.1 mol) of 3-hydroxymethyl-3-ethyloxetane and 11.6 g (0.2 mol) of propylene oxide Was dissolved in 50 ml of dry cyclohexane and the flask was then cooled in a 10 ° C. ice bath.
Next, 0.76 g of HPF 6 (0.25 mol% based on the monomer component) of a 60% by mass aqueous solution was dissolved in 10 ml of diethyl ether, and this was added to the flask all at once. Thereafter, the reaction mixture immediately became cloudy. Within 1 hour of adding HPF 6 , the reaction temperature rose to 36 ° C. The reaction mixture was then heated in an oil bath to 54-60 ° C. for 1 hour and further stirred overnight at room temperature.
Next, the initiator was deactivated by adding a 30 mass% methanol solution of 0.3 g of NaOMe. The cloudy reaction mixture was then stirred for 4 hours until
The white turbid layer under the reaction mixture was separated and cyclohexane was completely removed, and 18.7 g of a transparent and low-viscosity multi-branched polyether polyol was obtained. The yield was 79%. This multi-branched polyether polyol has Mn = 2,160 g / mol, Mw 6,310 g / mol, OHV = 224 mgKOH / g, and 3-hydroxymethyl-3-ethyloxetane: propylene oxide on a molar basis from proton NMR = 1: 1.9.
On the other hand, in the reaction mixture, the transparent cyclohexane layer was dried to obtain 1.2 g of a low viscosity multi-branched polyether polyol. This multi-branched polyether polyol has Mn = 500 g / mol, Mw = 950 g / mol, and from proton NMR, it is 3-hydroxymethyl-3-ethyloxetane: propylene oxide = 1: 2.1 on a molar basis. There was found. FIG. 9 shows a 13 C-NMR chart of this multi-branched polyether polyol, and FIG. 10 shows a proton NMR chart.
実施例６＜多分岐ポリエーテルポリオールの合成＞
リフラックスコンデンサー、マグネット式攪拌棒、温度計を具備した５００ｍｌ三口フラスコ中で、３−ヒドロキシメチル−３−エチルオキセタン ５８．０ｇ（０．５モル）と、プロピレンオキサイド １０６．０ｇ（１．５モル）とを、乾燥かつ過酸化物フリーの５００ｍｌのジエチルエーテルに溶解し、次いで、このフラスコを−１０℃のアイスバスで冷却した。
次いで、ＨＰＦ６ １．０ｇ（モノマー成分に対して０．２５モル％）の６０質量％水溶液を３０分かけて滴下した。その後、反応混合物は僅かに白濁した。反応混合物を室温で一晩攪拌した。ついで、反応溶液をジエチルエーテル２５０ｍｌで希釈し、次いで、２００ｍｌの水で、エーテル層が透明になるまで３回洗浄した。有機層を分離した後、該有機層をＮａ２ＳＯ４で乾燥し、次いで、エーテルを留去し、目的とするポリエーテルポリオール１４９．３ｇを得た。収率９０％であった。
この多分岐ポリエーテルポリオールは、Ｍｎ＝１，５４０ｇ／モル、Ｍｗ＝３，２００ｇ／モル、ＯＨＶ＝１７８ｍｇ・ＫＯＨ／ｇであり、プロトンＮＭＲから、モル基準で３−ヒドロキシメチル−３−エチルオキセタン：プロピレンオキサイド＝１：３であることが判明した。また、全水酸基数に対する２級水酸基（Ｈ２）の割合は、４７．０％であった。この多分岐ポリエーテルポリオールの１３Ｃ−ＮＭＲのチャート図を第１１図に、プロトンＮＭＲのチャート図を第１２図に示す。
Example 6 <Synthesis of Multibranched Polyether Polyol>
In a 500 ml three-necked flask equipped with a reflux condenser, a magnetic stirring bar and a thermometer, 58.0 g (0.5 mol) of 3-hydroxymethyl-3-ethyloxetane and 106.0 g (1.5 mol) of propylene oxide Was dissolved in dry and peroxide-free 500 ml of diethyl ether, and the flask was then cooled in an ice bath at -10 ° C.
Next, a 60% by mass aqueous solution of 1.0 g of HPF 6 (0.25 mol% relative to the monomer component) was added dropwise over 30 minutes. Thereafter, the reaction mixture became slightly cloudy. The reaction mixture was stirred at room temperature overnight. The reaction solution was then diluted with 250 ml of diethyl ether and then washed 3 times with 200 ml of water until the ether layer became clear. After the organic layer was separated, the organic layer was dried over Na 2 SO 4 and then the ether was distilled off to obtain 149.3 g of the target polyether polyol. The yield was 90%.
This multi-branched polyether polyol has Mn = 1,540 g / mol, Mw = 3,200 g / mol, OHV = 178 mg · KOH / g, and 3-hydroxymethyl-3-ethyloxetane on a molar basis from proton NMR. : Propylene oxide = 1: 3. The ratio of secondary hydroxyl groups (H2) to the total number of hydroxyl groups was 47.0%. FIG. 11 shows a 13 C-NMR chart of this multi-branched polyether polyol, and FIG. 12 shows a proton NMR chart.
参考例１＜ポリオール成分の調製＞
前記実施例２で得られた多分岐ポリエーテルポリオール２１２部と水酸基当量３５０のひまし油７８８部を混合し、平均水酸基当量が３１６のポリオール成分（Ａ−１）を得た。
Reference Example 1 <Preparation of polyol component>
212 parts of the multi-branched polyether polyol obtained in Example 2 and 788 parts of castor oil having a hydroxyl equivalent weight of 350 were mixed to obtain a polyol component (A-1) having an average hydroxyl equivalent weight of 316.
参考例２＜ポリオール成分の調製＞
前記実施例２で得られた多分岐ポリエーテルポリオール１２０部と水酸基当量３５０のひまし油８８０部を混合し、平均水酸基当量が３２５のポリオール成分（Ａ−２）を得た。
Reference Example 2 <Preparation of polyol component>
120 parts of the multi-branched polyether polyol obtained in Example 2 and 880 parts of castor oil having a hydroxyl equivalent weight of 350 were mixed to obtain a polyol component (A-2) having an average hydroxyl equivalent weight of 325.
参考例３＜ポリオール成分の調製＞
前記実施例５の白濁層から抽出された多分岐ポリエーテルポリオール４３８部と水酸基当量３５０のひまし油５６２部を混合し、平均水酸基当量が２５６のポリオール成分（Ａ−３）を得た。
Reference Example 3 <Preparation of polyol component>
438 parts of the hyperbranched polyether polyol extracted from the cloudy layer of Example 5 and 562 parts of castor oil having a hydroxyl equivalent weight of 350 were mixed to obtain a polyol component (A-3) having an average hydroxyl equivalent weight of 256.
参考例４＜ポリオール成分の調製＞
エポキシ当量が１８８なるビスフェノールＡ型エポキシ樹脂の４０重量部と、ひまし油脂肪酸の６０重量部とを、トリフェニルフォスフィンの０．２重量部の存在下に、窒素バブリングしながら１１０℃で１５時間反応させて得られる酸価０．１、水酸基当量２６５のエポキシエステルの３４０重量部と、水酸基当量３５０のひまし油の６６０重量部をブレンドして、平均水酸基当量３１６のポリオール成分（Ａ−４）を得た。
Reference Example 4 <Preparation of polyol component>
Reaction of 40 parts by weight of bisphenol A type epoxy resin having an epoxy equivalent of 188 and 60 parts by weight of castor oil fatty acid in the presence of 0.2 parts by weight of triphenylphosphine at 110 ° C. for 15 hours while bubbling nitrogen. 340 parts by weight of an epoxy ester having an acid value of 0.1 and a hydroxyl group equivalent of 265 obtained by blending 660 parts by weight of castor oil having a hydroxyl group equivalent of 350 to obtain a polyol component (A-4) having an average hydroxyl group equivalent of 316 It was.
参考例５＜ポリオール成分の調製＞
ソルビトールのプロピレンオキサイド付加物である水酸基当量１１２、官能基数６のエクセノール５００ＳＯ（旭硝子（株）社製）３３０部と水酸基当量３５０のひまし油６７０部を混合し、平均水酸基当量２０６のポリオール成分（Ａ−５）を得た。
Reference Example 5 <Preparation of polyol component>
A sorbitol propylene oxide adduct, a hydroxyl group equivalent of 112, a functional group number of Exenol 500SO (manufactured by Asahi Glass Co., Ltd.) (330 parts) and a hydroxyl group equivalent of 350 castor oil were mixed to obtain a polyol component (A- 5) was obtained.
参考例６＜ポリオール成分の調製＞
トリメチロールプロパンのプロピレンオキサイド付加物である水酸基当量１３８、官能基数３のエクセノール４００ＭＰ（旭硝子（株）社製）２４０部と水酸基当量３５０のひまし油７６０部を混合し、平均水酸基当量２５６のポリオール成分（Ａ−６）を得た。
Reference Example 6 <Preparation of polyol component>
A propylene oxide adduct of trimethylolpropane having a hydroxyl group equivalent of 138, 240 functional parts of Exenol 400MP (manufactured by Asahi Glass Co., Ltd.) and 760 parts of castor oil having a hydroxyl group equivalent of 350 are mixed, and a polyol component having an average hydroxyl group equivalent of 256 ( A-6) was obtained.
参考例７＜ポリオール成分の調製＞
芳香環を持つ水酸基当量２００のポリオール型キシレンホルムアルデヒド樹脂ニカノールＫ−１４０（三菱ガス化学（株）社製）４９０部と水酸基当量３５０のひまし油５１０部を混合し、平均水酸基当量２５６のポリオール成分（Ａ−７）を得た。
Reference Example 7 <Preparation of polyol component>
490 parts of a polyol type xylene formaldehyde resin Nikanol K-140 (Mitsubishi Gas Chemical Co., Ltd.) having a hydroxyl group equivalent of 200 having an aromatic ring and 510 parts of castor oil having a hydroxyl group equivalent of 350 are mixed to obtain a polyol component having an average hydroxyl equivalent of 256 (A -7) was obtained.
参考例８＜イソシアネート成分の調製＞
ＭＤＩが４０質量％、ＭＤＩ中の４，４’−ＭＤＩが９７質量％である市販のクルードＭＤＩ（ミリオネートＭＲ２００：日本ポリウレタン工業（株）製）１００重量部、
４，４’−ＭＤＩが５０質量％、２，４’−ＭＤＩが５０質量％であるＭＤＩ（ルプラネートＭＩ：ＢＡＳＦ ＩＮＯＡＣポリウレタン（株）製）を２６重量部、及び、
４，４’−ＭＤＩ（ミリオネートＭＴ：日本ポリウレタン工業（株）製）を２４重量部加え、イソシアネート成分（Ｂ）を得た。
Reference Example 8 <Preparation of Isocyanate Component>
100 parts by weight of a commercially available crude MDI (Millionate MR200: manufactured by Nippon Polyurethane Industry Co., Ltd.) having 40% by mass of MDI and 97% by mass of 4,4′-MDI in MDI,
26 parts by weight of MDI (Lupranate MI: manufactured by BASF INOAC Polyurethane Co., Ltd.) having 50% by mass of 4,4′-MDI and 50% by mass of 2,4′-MDI, and
24 parts by weight of 4,4′-MDI (Millionate MT: manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to obtain an isocyanate component (B).
実施例７
参考例１で得られたポリオール成分（Ａ−１）５００部、炭酸カルシウム４６０部、顔料２５部をプラネタリーミキサーを用い真空脱泡しながら均一混合したコンパウンドと、、参考例８で得られたイソシアネート成分（Ｂ）とをイソシアネート当量と水酸基当量の比率１．１５となる割合で用いて、下記の各種性能試験を行った。結果を第１表に示す。
Example 7
A compound obtained by uniformly mixing 500 parts of the polyol component (A-1) obtained in Reference Example 1, 460 parts of calcium carbonate and 25 parts of pigment while vacuum degassing using a planetary mixer, and obtained in Reference Example 8 The following various performance tests were conducted using the isocyanate component (B) at a ratio of 1.15 of isocyanate equivalent and hydroxyl equivalent. The results are shown in Table 1.
＜混合粘度及び可使時間評価試験＞
（Ａ）成分を含む前記コンパウンドと（Ｂ）成分を混合し、２５℃の恒温水層につけた。ＢＭ型粘度計ローターＮｏ．４、６ｒｐｍにて５分後の粘度を測定し、その値を混合粘度とした。その後測定を続け、５０，０００ｍＰａ・ｓに到達した時間を可使時間とした。
<Mixed viscosity and pot life evaluation test>
The compound containing the component (A) and the component (B) were mixed and applied to a constant temperature water layer at 25 ° C. BM viscometer rotor No. The viscosity after 5 minutes was measured at 4 and 6 rpm, and the value was defined as the mixed viscosity. Thereafter, the measurement was continued, and the time for reaching 50,000 mPa · s was defined as the pot life.
＜塗膜の物性評価試験＞
（Ａ）成分を含む前記コンパウンドと（Ｂ）成分を混合後、２５℃×７日間養生したシートを用いて、ショアーＤ硬度（ＪＩＳ Ｋ−６２５３）、引張強度（ＪＩＳ Ｋ−６２５１）、伸び率（ＪＩＳ Ｋ−６２５１）、引裂強度（ＪＩＳ Ｋ−６２５２）の評価を行った。
<Physical property evaluation test of coating film>
After mixing the compound containing the component (A) and the component (B), a sheet cured at 25 ° C. for 7 days was used for Shore D hardness (JIS K-6253), tensile strength (JIS K-6251), elongation. (JIS K-6251) and tear strength (JIS K-6252) were evaluated.
＜被覆面の表面発泡性の試験＞
スレート板上に湿気硬化型ウレタン系プライマー（プライアデックＴ−１５０−３５、大日本インキ化学工業（株）製）を塗布、乾燥後、（Ａ）成分を含む前記コンパウンドと（Ｂ）成分を混合後、塗布量１．５ｋｇ／ｍ２となるようにプライマー層上にコテ塗りで塗工、３５℃８０％の条件下で硬化させて、その表面に発生する気泡の有無の評価を行った。
<Surface foamability test of coated surface>
Apply moisture-curable urethane primer (Priadec T-150-35, manufactured by Dainippon Ink & Chemicals, Inc.) on the slate plate, and after drying, mix the compound containing component (A) and component (B) Thereafter, the primer layer was coated with a trowel so that the coating amount was 1.5 kg / m 2 and cured under conditions of 35 ° C. and 80%, and the presence or absence of bubbles generated on the surface was evaluated.
実施例８
参考例２のポリオール成分（Ａ−２）を用いた以外は、実施例７と同様にして各種性能試験を行った。結果を第１表に示す。
Example 8
Various performance tests were performed in the same manner as in Example 7 except that the polyol component (A-2) of Reference Example 2 was used. The results are shown in Table 1.
比較例１
参考例３のポリオール成分（Ａ−４）を用いた以外は、実施例７と同様にして各種性能試験を行った。結果を第１表に示す。
Comparative Example 1
Various performance tests were performed in the same manner as in Example 7 except that the polyol component (A-4) of Reference Example 3 was used. The results are shown in Table 1.
比較例２
参考例４のポリオール成分（Ａ−５）を用いた以外は、実施例７と同様にして各種性能試験を行った。結果を第１表に示す。
Comparative Example 2
Various performance tests were performed in the same manner as in Example 7 except that the polyol component (A-5) of Reference Example 4 was used. The results are shown in Table 1.
第１表に示す通り、本発明のウレタン系樹脂組成物は、低粘度であり、かつ、高温、多湿環境下でも発泡せず平滑性に優れ、更に硬質の被覆面を形成する。これに対し、芳香族系ポリオールを含有する硬質ウレタン被覆材の場合（比較例１）、混合粘度が高く、ローラー塗布には適さない。また、線状多官能ポリオールを用いた場合（比較例２）も、混合粘度が高く、さらには、高温多湿下において被覆面に発泡が見られ、平滑性という点においても乏しい。 As shown in Table 1, the urethane-based resin composition of the present invention has a low viscosity, does not foam even under high temperature and high humidity, has excellent smoothness, and forms a hard coating surface. On the other hand, in the case of a hard urethane coating material containing an aromatic polyol (Comparative Example 1), the mixing viscosity is high and is not suitable for roller coating. Further, when a linear polyfunctional polyol is used (Comparative Example 2), the mixing viscosity is high, and further, foaming is observed on the coated surface under high temperature and high humidity, and the smoothness is poor.
実施例９
参考例３で得られたポリオール成分（Ａ−３）５００部、炭酸カルシウム４６０部、顔料２５部、コンパウンド中６２５ｐｐｍとなるジブチル錫ジラウレートをプラネタリーミキサーを用い真空脱泡しながら均一混合したコンパウンドにノルボルネンジイソシアネート（以下、「ＮＢＤＩ」と略記する。）をイソシアネート当量と水酸基当量の比率１．１５となる割合で用いて、実施例７と同様にして混合粘度及び可使時間の評価、並びに塗膜の物性評価試験を行った。更に、下記の方法に従い、ひび割れ追従性評価試験、及び耐候性試験を行った。これらの結果を第２表に示す。
Example 9
A compound obtained by uniformly mixing 500 parts of the polyol component (A-3) obtained in Reference Example 3, 460 parts of calcium carbonate, 25 parts of pigment, and dibutyltin dilaurate having a concentration of 625 ppm in the compound using a planetary mixer while vacuum degassing. Using norbornene diisocyanate (hereinafter abbreviated as “NBDI”) at a ratio of isocyanate equivalent to hydroxyl equivalent of 1.15, evaluation of mixing viscosity and pot life and coating film in the same manner as in Example 7. The physical property evaluation test was conducted. Furthermore, according to the following method, the crack followability evaluation test and the weather resistance test were done. These results are shown in Table 2.
＜ひび割れ追従性評価試験＞
日本道路公団コンクリート塗装材の品質規格試験法に準拠し、ひび割れ追従性試験を実施した。評価結果は、ひび割れ追従性が０．８ｍｍ以上を◎、０．４ｍｍ以上を○、０．４ｍｍ未満を×とした。
<Crack followability evaluation test>
In accordance with the quality standard testing method for Japan Highway Public Corporation concrete coating material, a crack follow-up test was conducted. The evaluation results were as follows: crack followability was 0.8 mm or more, ◎, 0.4 mm or more was ◯, and less than 0.4 mm was x.
＜耐候性試験＞
物性評価方法にて作製したシートから２０ｍｍ×５０ｍｍの試験片を切り出し、耐候試験片を作製した。耐候試験法としては、サンシャインウエザメーター（スガ試験機（株）製ＷＥＬ-ＳＵＮ-ＨＣＨ-Ｂ型）を用いて促進耐候試験を行った。
試験条件：温度 ６３±３℃、 サイクル １２０分中１８分降雨、時間１０００ｈｒｓ
評価項目：色差（ΔＥ）、被覆材はグレー色を使用
<Weather resistance test>
A test piece of 20 mm × 50 mm was cut out from the sheet prepared by the physical property evaluation method to prepare a weather resistance test piece. As a weather resistance test method, an accelerated weather resistance test was performed using a sunshine weather meter (WEL-SUN-HCH-B type manufactured by Suga Test Instruments Co., Ltd.).
Test conditions: temperature 63 ± 3 ° C,
Evaluation item: Color difference (ΔE), Cover material uses gray color
実施例１０
イソシアネート成分として水添ＭＤＩである「デスモジュールＷ」（住友バイエルウレタン（株）製）を用いた以外は、実施例９と同様にして各種の評価を行った。結果を第２表に示す。
Example 10
Various evaluations were performed in the same manner as in Example 9 except that “Desmodur W” (manufactured by Sumitomo Bayer Urethane Co., Ltd.), which is a hydrogenated MDI, was used as the isocyanate component. The results are shown in Table 2.
比較例３
参考例６のポリオール成分（Ａ−６）を用いた以外は、実施例９と同様に各種の評価を行った。結果を第２表に示す。
Comparative Example 3
Various evaluations were performed in the same manner as in Example 9 except that the polyol component (A-6) in Reference Example 6 was used. The results are shown in Table 2.
比較例４
参考例７のポリオール成分（Ａ−７）を用い、イソシアネート成分としてポリメチレンポリフェニルポリイソシアネートであるミリオネートＭＲ２００（日本ポリウレタン（株）製）を使用し、ジブチルチンジラウレートを添加しない以外は、実施例９と同様に各種の評価を行った。結果を第２表に示す。
Comparative Example 4
Example except that the polyol component (A-7) of Reference Example 7 was used, and polymethylene polyphenyl polyisocyanate Millionate MR200 (manufactured by Nippon Polyurethane Co., Ltd.) was used as the isocyanate component, and no dibutyltin dilaurate was added. Various evaluations were performed in the same manner as in Example 9. The results are shown in Table 2.
第２表に示す通り、本発明のウレタン系樹脂組成物は、低粘度であり、硬質の被覆面を形成し、更に、ひび割れ追従性に優れる。また、紫外線劣化による黄変を低減し、意匠性にも優れるという特長を有する。これに対して、多官能ポリオールの官能基数が少ない場合（比較例３）、ひび割れ追従性は優れているものの、硬質化は困難であり、硬質被覆材としての性能を満たさない。また、芳香族イソシアネートを使用した場合（比較例４）、ポリオール成分に問わずひび割れ追従性に乏しく、被覆面が極度に黄変し、意匠性を損なう。
As shown in Table 2, the urethane resin composition of the present invention has a low viscosity, forms a hard coating surface, and is excellent in crack followability. In addition, it has the feature of reducing yellowing due to ultraviolet degradation and being excellent in design. On the other hand, when the number of functional groups of the polyfunctional polyol is small (Comparative Example 3), although the crack followability is excellent, it is difficult to make it hard and the performance as a hard coating material is not satisfied. Moreover, when aromatic isocyanate is used (Comparative Example 4), the crack followability is poor regardless of the polyol component, and the coated surface is extremely yellowed, thereby impairing the design.
Claims (2)
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| JP2005100813A JP4114012B2 (en) | 2005-03-31 | 2005-03-31 | Multi-branched polyether polyol |
| TW095121593A TWI370144B (en) | 2005-03-31 | 2006-06-16 | Hyperbranched polyetherpolyol and urethane resin composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7918976B2 (en) | 1999-11-15 | 2011-04-05 | Abbott Diabetes Care Inc. | Transition metal complexes with bidentate ligand having an imidazole ring |
| US8268143B2 (en) | 1999-11-15 | 2012-09-18 | Abbott Diabetes Care Inc. | Oxygen-effect free analyte sensor |
| US8444834B2 (en) | 1999-11-15 | 2013-05-21 | Abbott Diabetes Care Inc. | Redox polymers for use in analyte monitoring |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101310696B1 (en) * | 2006-09-29 | 2013-09-25 | 디아이씨 가부시끼가이샤 | Cation-polymerizable resin composition containing multi-branched polyether polyol, adhesive agent comprising the composition, and laminate and polarizing plate using the adhesive agent |
| JP5512971B2 (en) * | 2006-10-31 | 2014-06-04 | 三井化学株式会社 | Polyether polyol, rigid polyurethane foam and production method thereof |
| KR100862048B1 (en) | 2007-02-06 | 2008-10-09 | 주식회사 부일건화 | Three-component type polyurethane flooring composition and method for constructing flooring of building using the same |
| JP2009040916A (en) * | 2007-08-09 | 2009-02-26 | Nippon Polyurethane Ind Co Ltd | Composition for forming water-expanded rigid polyisocyanurate foam, method for production of water-expanded rigid polyisocyanurate foam using the composition, and water-expanded rigid polyisocyanurate foam produced by the method |
| JP5145925B2 (en) * | 2007-12-27 | 2013-02-20 | Ｄｉｃ株式会社 | Two-component urethane primer composition, construction method for civil engineering building, and civil engineering building structure |
| US8529377B2 (en) * | 2010-07-01 | 2013-09-10 | Nike, Inc. | Golf ball incorporating thermoplastic polyurethane |
| WO2015098703A1 (en) * | 2013-12-25 | 2015-07-02 | Dic株式会社 | Polyarylene sulfide resin composition, and molded product thereof |
| CN115368550B (en) * | 2021-05-20 | 2024-01-26 | 常州强力先端电子材料有限公司 | Oxetane fluorine-containing polymer and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7918976B2 (en) | 1999-11-15 | 2011-04-05 | Abbott Diabetes Care Inc. | Transition metal complexes with bidentate ligand having an imidazole ring |
| US8092662B2 (en) | 1999-11-15 | 2012-01-10 | Abbott Diabetes Care Inc. | Redox polymers |
| US8268143B2 (en) | 1999-11-15 | 2012-09-18 | Abbott Diabetes Care Inc. | Oxygen-effect free analyte sensor |
| US8444834B2 (en) | 1999-11-15 | 2013-05-21 | Abbott Diabetes Care Inc. | Redox polymers for use in analyte monitoring |
| US8512534B2 (en) | 1999-11-15 | 2013-08-20 | Abbott Diabetes Care Inc. | Redox polymers |
| US8795490B2 (en) | 1999-11-15 | 2014-08-05 | Abbott Diabetes Care Inc. | Redox polymers |
| US8828204B2 (en) | 1999-11-15 | 2014-09-09 | Abbott Diabetes Care Inc. | Redox polymers |
Also Published As
| Publication number | Publication date |
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| TWI370144B (en) | 2012-08-11 |
| TW200801059A (en) | 2008-01-01 |
| JP2006282698A (en) | 2006-10-19 |
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