JP4919078B2 - Topcoat composition for waterproofing urethane coatings - Google Patents
Topcoat composition for waterproofing urethane coatings Download PDFInfo
- Publication number
- JP4919078B2 JP4919078B2 JP2007263976A JP2007263976A JP4919078B2 JP 4919078 B2 JP4919078 B2 JP 4919078B2 JP 2007263976 A JP2007263976 A JP 2007263976A JP 2007263976 A JP2007263976 A JP 2007263976A JP 4919078 B2 JP4919078 B2 JP 4919078B2
- Authority
- JP
- Japan
- Prior art keywords
- polyisocyanate
- waterproofing
- polyol
- urethane
- diisocyanate
- 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.)
- Active
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- 239000000203 mixture Substances 0.000 title claims description 51
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 41
- 238000004078 waterproofing Methods 0.000 title claims description 37
- 238000000576 coating method Methods 0.000 title claims description 34
- 239000005056 polyisocyanate Substances 0.000 claims description 98
- 229920001228 polyisocyanate Polymers 0.000 claims description 98
- 150000003077 polyols Chemical class 0.000 claims description 51
- 229920005862 polyol Polymers 0.000 claims description 48
- -1 aromatic polyol Chemical class 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 15
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- 239000000463 material Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000012948 isocyanate Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000001723 curing Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 150000002513 isocyanates Chemical class 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 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 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 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 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
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- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
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- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical group COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 235000021313 oleic acid Nutrition 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 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 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Description
本発明は、ウレタン塗膜防水用トップコート組成物に関する。 The present invention relates to a top coat composition for waterproofing urethane coatings.
従来、ビルの屋上、ベランダ、バルコニー、開放廊下等の防水施工方法として塗膜防水工法が広く行われている。
この工法では、コンクリートやモルタルなどの基材表面にプライマー層を形成し、その上にウレタン系防水材層を形成し、さらにその上にトップコート層を形成することで、多層防水構造体とすることが一般的である。
Conventionally, a waterproof coating method has been widely used as a waterproofing method for building rooftops, verandas, balconies, open corridors and the like.
In this construction method, a primer layer is formed on the surface of a base material such as concrete or mortar, a urethane waterproof layer is formed thereon, and a top coat layer is further formed thereon to form a multilayer waterproof structure. It is common.
この場合、トップコートは、ウレタン系防水材層の保護と美観向上とを目的として施工さるものであり、アクリルウレタン系塗料が汎用されている（特許文献１〜３参照）。
防水材層を長期に亘って保護するためには、トップコート層の耐候性、および防水材層に対する接着性が重要となる。
しかし、防水材層は可塑剤を含んでいるため、トップコートとの接着性においてしばしば問題が生じている。特に、最近の防水材は、環境負荷の低減のためその成分も限定されており、より一層トップコートとの接着が困難になってきている。
また、超速乾タイプの防水材も、トップコートとの接着性が低いことが知られている。
In this case, the top coat is constructed for the purpose of protecting the urethane waterproof layer and improving aesthetics, and acrylic urethane paints are widely used (see Patent Documents 1 to 3).
In order to protect the waterproof material layer over a long period of time, the weather resistance of the topcoat layer and the adhesion to the waterproof material layer are important.
However, since the waterproof material layer contains a plasticizer, a problem often arises in adhesion to the top coat. In particular, recent waterproofing materials are limited in their components to reduce the environmental burden, and it is becoming more difficult to adhere to the top coat.
In addition, it is known that an ultra-fast dry type waterproof material also has low adhesion to the top coat.
この点に鑑み、トップコートの成分としては、従来、ウレタン防水材との接着性に優れたトリレンジイソシアネート（ＴＤＩ）などをベースとした芳香族系のイソシアネートが使用されているが、この場合は、十分な耐候性が得られない。
一方、耐候性を向上させるためには、ヘキサメチレンジイソシアネート（ＨＤＩ）などの無黄変イソシアネートを用いることが有効であるが、この場合は、下地防水材に対する接着性が不十分となってしまう。
以上のように、ウレタン系防水材に対する接着性および耐候性を両立することは難しく、これら両性能を兼ね備えたトップコートの開発が望まれている。
In view of this point, as a component of the top coat, aromatic isocyanate based on tolylene diisocyanate (TDI) and the like excellent in adhesiveness with a urethane waterproof material has been conventionally used. , Sufficient weather resistance is not obtained.
On the other hand, in order to improve the weather resistance, it is effective to use a non-yellowing isocyanate such as hexamethylene diisocyanate (HDI), but in this case, the adhesiveness to the base waterproofing material becomes insufficient.
As described above, it is difficult to achieve both adhesion and weather resistance to urethane waterproofing materials, and the development of a top coat having both of these performances is desired.
本発明は、上記事情に鑑みてなされたものであり、ウレタン防水材との接着性に優れ、かつ、耐候性の良好なウレタン塗膜防水用トップコート組成物を提供することを目的とする。 This invention is made | formed in view of the said situation, and it aims at providing the topcoat composition for urethane-film waterproofing excellent in adhesiveness with a urethane waterproof material, and favorable in weather resistance.
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、アロファネート結合を含むポリイソシアネートを所定量以上含むポリイソシアネートとポリオールとを反応させて得られたポリイソシアネート樹脂をトップコート用組成物の一成分として用いることで、得られるトップコートのウレタン防水材に対する接着性が著しく向上するとともに、その耐候性も良好になることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have used a polyisocyanate resin obtained by reacting a polyisocyanate containing a polyisocyanate containing an allophanate bond with a predetermined amount or more and a polyol for a top coat. By using it as a component of the composition, the adhesiveness of the resulting top coat to the urethane waterproof material was remarkably improved and the weather resistance was also improved, and the present invention was completed.
すなわち、本発明は、
１． １分子中に１個以上のアロファネート結合および２個以上のイソシアネート基を含むポリイソシアネート（Ａ１−ａ）を３０質量％以上含むポリイソシアネート（Ａ１）を、ポリオール（Ａ２）と反応させて得られたポリイソシアネート樹脂（Ａ）を含み、
前記ポリイソシアネート（Ａ１−ａ）が、脂肪族ポリイソシアネートおよび脂環式ポリイソシアネートから選ばれる少なくとも１種のアロファネート変性体であることを特徴とするウレタン塗膜防水用トップコート組成物、
２． 前記ポリイソシアネート（Ａ１）が、前記ポリイソシアネート（Ａ１−ａ）を４０質量％以上含む１のウレタン塗膜防水用トップコート組成物、
３． 前記ポリイソシアネート（Ａ１）が、非芳香族ポリイソシアネートである１のウレタン塗膜防水用トップコート組成物、
４． 前記脂肪族ポリイソシアネートおよび脂環式ポリイソシアネートが、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水添化キシリレンジイソシアネート、水添化ジフェニルメタンジイソシアネート、およびノルボルナンジイソシアネートから選ばれる少なくとも１種である２のウレタン塗膜防水用トップコート組成物、
５． 前記ポリオール（Ａ２）が、平均官能基数２〜４、数平均分子量２００〜３０００のポリオールである１〜４のいずれかのウレタン塗膜防水用トップコート組成物、
６． 前記ポリオール（Ａ２）が、非芳香族ポリオールである１〜５のいずれかのウレタン塗膜防水用トップコート組成物、
７． 前記ポリイソシアネート（Ａ１）およびポリオール（Ａ２）の反応モル比が、［ＮＣＯ］／［ＯＨ］＝１．２以上である１〜６のいずれかのウレタン塗膜防水用トップコート組成物、
８． ２液型である１〜７のいずれかのウレタン塗膜防水用トップコート組成物、
９． １分子中に１個以上のアロファネート結合および２個以上のイソシアネート基を含むポリイソシアネート（Ａ１−ａ）を３０質量％以上含むポリイソシアネート（Ａ１）を、ポリオール（Ａ２）と反応させて得られたポリイソシアネート樹脂（Ａ）を含み、
前記ポリイソシアネート（Ａ１−ａ）が、脂肪族ポリイソシアネートおよび脂環式ポリイソシアネートから選ばれる少なくとも１種のアロファネート変性体であることを特徴とするウレタン塗膜防水用トップコート組成物用の硬化剤
を提供する。
That is, the present invention
1. Obtained by reacting polyisocyanate (A1) containing 30% by mass or more of polyisocyanate (A1-a) containing one or more allophanate bonds and two or more isocyanate groups in one molecule with polyol (A2). polyisocyanate resin (a) only contains,
A top coat composition for waterproofing urethane coatings, wherein the polyisocyanate (A1-a) is at least one allophanate-modified product selected from aliphatic polyisocyanates and alicyclic polyisocyanates ,
2. The polyisocyanate (A1) is, the polyisocyanate (A1-a) a urethane waterproofing membrane for the top coat composition comprising more than 40 wt%,
3. The urethane coat waterproofing topcoat composition of 1, wherein the polyisocyanate (A1) is a non-aromatic polyisocyanate,
4). 2. Urethane film waterproofing of 2 wherein said aliphatic polyisocyanate and alicyclic polyisocyanate are at least one selected from hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and norbornane diisocyanate For topcoat composition,
5. The urethane coat waterproofing topcoat composition according to any one of 1 to 4, wherein the polyol (A2) is a polyol having an average functional group number of 2 to 4 and a number average molecular weight of 200 to 3000,
6). The topcoat composition for waterproofing a urethane coating film according to any one of 1 to 5, wherein the polyol (A2) is a non-aromatic polyol,
7). The urethane coat waterproofing topcoat composition according to any one of 1 to 6, wherein the reaction molar ratio of the polyisocyanate (A1) and the polyol (A2) is [NCO] / [OH] = 1.2 or more,
8). The topcoat composition for urethane coating waterproofing according to any one of 1 to 7, which is a two-component type ,
9. Obtained by reacting polyisocyanate (A1) containing 30% by mass or more of polyisocyanate (A1-a) containing one or more allophanate bonds and two or more isocyanate groups in one molecule with polyol (A2). Including a polyisocyanate resin (A),
The polyisocyanate (A1-a) is at least one allophanate-modified product selected from aliphatic polyisocyanates and alicyclic polyisocyanates, and a curing agent for a topcoat composition for waterproofing urethane coatings I will provide a.
本発明のウレタン塗膜防水用トップコート組成物は、アロファネート結合を含むポリイソシアネートを所定量以上含むポリイソシアネートを一成分としているため、ウレタン防水材との接着性に優れ、かつ、耐候性も良好である。 The top coat composition for waterproofing a urethane coating film of the present invention has a polyisocyanate containing a predetermined amount or more of a polyisocyanate containing an allophanate bond, so that it has excellent adhesion to a urethane waterproof material and has good weather resistance. It is.
以下、本発明についてさらに詳しく説明する。
本発明に係るウレタン塗膜防水用トップコート組成物は、１分子中に１個以上のアロファネート結合および２個以上のイソシアネート基を含むポリイソシアネート（Ａ１−ａ）を３０質量％以上含むポリイソシアネート（Ａ１）を、ポリオール（Ａ２）と反応させて得られたポリイソシアネート樹脂（Ａ）を含むものである。
Hereinafter, the present invention will be described in more detail.
The topcoat composition for waterproofing a urethane coating film according to the present invention is a polyisocyanate containing 30% by mass or more of polyisocyanate (A1-a) containing one or more allophanate bonds and two or more isocyanate groups in one molecule. The polyisocyanate resin (A) obtained by reacting A1) with polyol (A2) is included.
本発明において、ポリイソシアネート（Ａ１−ａ）は、１分子中に１個以上のアロファネート結合および２個以上のイソシアネート基を含むものであれば任意であり、ポリイソシアネートと、アルコールとを、イソシアネート基が過剰な状態でウレタン化およびアロファネート化させて得ることができる。このウレタン化およびアロファネート化は同時に進行させてもよく、ウレタン化させた後、アロファネート化させてもよい。 In the present invention, the polyisocyanate (A1-a) is arbitrary as long as it contains one or more allophanate bonds and two or more isocyanate groups in one molecule, and the polyisocyanate and alcohol are combined with an isocyanate group. Can be obtained by urethanization and allophanatization in an excessive state. This urethanization and allophanatization may proceed simultaneously, or after urethanization, allophanatization may be performed.
ここで、アロファネート化用のポリイソシアネートとしては、従来公知の各種ポリイソシアネートから適宜選択して用いることができ、例えば、ヘキサメチレンジイソシアネート（ＨＤＩ）、１，４−テトラメチレンジイソシアネート、２−メチルペンタン−１，５−ジイソシアネート、リジンジイソシアネート等の脂肪族イソシアネート；イソホロンジイソシアネート、ノルボルナンジイソシアネート、水添化トリレンジイソシアネート、水添化キシレンジイソシアネート、水添化ジフェニルメタンジイソシアネート、水添化テトラメチルキシレンジイソシアネート等の脂環式ジイソシアネート；２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４′−ジフェニルメタンジイソシアネート、２，４′−ジフェニルメタンジイソシアネート、２，２′−ジフェニルメタンジイソシアネート、４，４′−ジフェニルエーテルジイソシアネート、２−ニトロジフェニル−４，４′−ジイソシアネート、２，２′−ジフェニルプロパン−４，４′−ジイソシアネート、３，３′−ジメチルジフェニルメタン−４，４′−ジイソシアネート、４，４′−ジフェニルプロパンジイソシアネート、ｍ−フェニレンジイソシアネート、ｐ−フェニレンジイソシアネート、ナフチレン−１，４−ジイソシアネート、ナフチレン−１，５−ジイソシアネート、３，３′−ジメトキシジフェニル−４，４′−ジイソシアネート等の芳香族イソシアネート；キシリレン−１，４−ジイソシアネート、キシリレン−１，３−ジイソシアネート等の芳香脂肪族ジイソシアネート等を用いることができる。これらのポリイソシアネートは、単独で用いても、２種以上混合して用いてもよい。
これらの中でも、トップコートの耐候性をより高めることを考慮すると、脂肪族イソシアネート、脂環式ジイソシアネートが好適であり、特に、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、水添化キシリレンジイソシアネート、水添化ジフェニルメタンジイソシアネート、ノルボルナンジイソシアネートが好ましい。
Here, as the polyisocyanate for allophanate formation, it can be appropriately selected from conventionally known various polyisocyanates. For example, hexamethylene diisocyanate (HDI), 1,4-tetramethylene diisocyanate, 2-methylpentane- Aliphatic isocyanates such as 1,5-diisocyanate and lysine diisocyanate; alicyclic rings such as isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphe L-methane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3 '-Dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3 Aromatic isocyanates such as'-dimethoxydiphenyl-4,4'-diisocyanate; aromatic aliphatic diisocyanates such as xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, etc. It can be used. These polyisocyanates may be used alone or in combination of two or more.
Among these, aliphatic isocyanates and cycloaliphatic diisocyanates are preferred in consideration of further improving the weather resistance of the topcoat, and in particular, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane. Diisocyanate and norbornane diisocyanate are preferred.
一方、アルコールとしても特に限定されるものではなく、例えば、メタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブタノール、ｉ−ブタノール、ｔ−ブタノール等のモノオール類；エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、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、２−メチル−１，５−ペンタンジオール、３−メチル−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、１，８−オクタンジオール、１，９−ノナンジオール、２，２−ジエチル−１，３−プロパンジオール、２−ｎ−ブチル−２−エチル−１，３−プロパンジオール、２，２，４−トリメチル−１，３−ペンタンジオール、２−エチル−１，３−ヘキサンジオール、２−ｎ−ヘキサデカン−１，２−エチレングリコール、２−ｎ−エイコサン−１，２−エチレングリコール、２−ｎ−オクタコサン−１，２−エチレングリコール、ジエチレングリコール、ジプロピレングリコール、１，４−シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイドまたはプロピレンオキサイド付加物、水添化ビスフェノールＡ、３−ヒドロキシ−２，２−ジメチルプロピル−３−ヒドロキシ−２，２−ジメチルプロピオネート等のジオール類；トリメチロールプロパン、グリセリン等のトリオール類などが挙げられる。これらは、単独で用いても、２種以上組み合わせて用いてもよい。 On the other hand, the alcohol is not particularly limited. For example, monools such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and t-butanol; ethylene glycol, 1, 2 -Propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, 2,2-diethyl-1,3-propanediol, 2 -N-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-penta Diol, 2-ethyl-1,3-hexanediol, 2-n-hexadecane-1,2-ethylene glycol, 2-n-eicosane-1,2-ethylene glycol, 2-n-octacosane-1,2-ethylene Glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2, Diols such as 2-dimethylpropionate; and triols such as trimethylolpropane and glycerin. These may be used alone or in combination of two or more.
ウレタン化およびアロファネート化反応は、ポリイソシアネートとアルコールとを有機溶剤の存在下または非存在下、５０〜１５０℃程度に加熱して行うことができる。
ウレタン化とアロファネート化とを同時に行う場合、アロファネート化触媒の存在下で反応を行えばよく、ウレタン化後にアロファネート化を行う場合、アロファネート化触媒の非存在下で、所定時間ウレタン化反応を行った後、アロファネート化触媒を添加してアロファネート化反応を行えばよい。
The urethanization and allophanatization reaction can be performed by heating polyisocyanate and alcohol to about 50 to 150 ° C. in the presence or absence of an organic solvent.
When urethanization and allophanatization are performed simultaneously, the reaction may be performed in the presence of an allophanatization catalyst. When allophanatization is performed after urethanization, the urethanization reaction was performed for a predetermined time in the absence of the allophanatization catalyst. Thereafter, an allophanatization catalyst may be added to carry out the allophanatization reaction.
アロファネート化触媒としては、公知の触媒から適宜選択して用いることができ、例えば、有機カルボン酸の金属塩を用いることができる。
有機カルボン酸としては、例えば、酢酸、プロピオン酸、酪酸、カプロン酸、オクチル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、２−エチルヘキサン酸等の飽和脂肪族カルボン酸；シクロヘキサンカルボン酸、シクロペンタンカルボン酸等の飽和脂環式カルボン酸；ビシクロ（４．４．０）デカン−２−カルボン酸等の飽和複環カルボン酸；オレイン酸、リノール酸、リノレン酸、大豆油脂肪酸、トール油脂肪酸等の不飽和脂肪族カルボン酸；ジフェニル酢酸等の芳香脂肪族カルボン酸；安息香酸、トルイル酸等の芳香族カルボン酸等が挙げられる。
また、カルボン酸の金属塩を構成する金属としては、リチウム、ナトリウム、カリウム等のアルカリ金属；マグネシウム、カルシウム、バリウム等のアルカリ土類金属；マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ジルコニウム等の遷移金属等が挙げられる。
中でも、アルキルカルボン酸のジルコニウム、亜鉛、鉛等の金属塩が好ましく、特に、オクチル酸ジルコニウム、２−エチルヘキサン酸ジルコニウム等のアルキルカルボン酸のジルコニウム塩が好ましい。
なお、アロファネート化触媒の使用量は、ポリイソシアネートとアルコールとの合計質量に対して０．０００５〜１質量％が好ましく、０．００１〜０．１質量％がより好ましい。
As the allophanatization catalyst, a known catalyst can be appropriately selected and used. For example, a metal salt of an organic carboxylic acid can be used.
Examples of the organic carboxylic acid include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and 2-ethylhexanoic acid; cyclohexanecarboxylic acid, Saturated cycloaliphatic carboxylic acids such as cyclopentanecarboxylic acid; saturated bicyclic carboxylic acids such as bicyclo (4.4.0) decane-2-carboxylic acid; oleic acid, linoleic acid, linolenic acid, soybean oil fatty acid, tall oil Examples thereof include unsaturated aliphatic carboxylic acids such as fatty acids; aromatic aliphatic carboxylic acids such as diphenylacetic acid; aromatic carboxylic acids such as benzoic acid and toluic acid.
The metal constituting the metal salt of carboxylic acid includes alkali metals such as lithium, sodium and potassium; alkaline earth metals such as magnesium, calcium and barium; manganese, iron, cobalt, nickel, copper, zinc and zirconium Transition metals and the like.
Of these, metal salts of alkylcarboxylic acid such as zirconium, zinc and lead are preferable, and zirconium salts of alkylcarboxylic acid such as zirconium octylate and zirconium 2-ethylhexanoate are particularly preferable.
In addition, 0.0005-1 mass% is preferable with respect to the total mass of polyisocyanate and alcohol, and, as for the usage-amount of an allophanatization catalyst, 0.001-0.1 mass% is more preferable.
有機溶媒の存在下で反応を行う場合、反応に影響を与えない各種有機溶媒、例えば、ｎ−ヘキサン、オクタン等の脂肪族炭化水素類、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル等のエステル類、エチレングリコールエチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、３−メチル−３−メトキシブチルアセテート、エチル−３−エトキシプロピオネート等のグリコールエーテルエステル類、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル類、塩化メチル、塩化メチレン、クロロホルム、四塩化炭素、臭化メチル、ヨウ化メチレン、ジクロロエタン等のハロゲン化炭化水素類、Ｎ−メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホニルアミド等の極性非プロトン溶媒等が挙げられる。これらの溶媒は単独で、または２種以上組み合わせて用いることができる。
反応後は、リン酸、酸性リン酸エステル等の公知の反応停止剤にてアロファネート化反応を停止させ、薄膜蒸留等の公知の手法により未反応成分を除去して目的とするアロファネート結合を有するポリイソシアネート（Ａ１−ａ）を得ることができる。
When the reaction is performed in the presence of an organic solvent, various organic solvents that do not affect the reaction, for example, aliphatic hydrocarbons such as n-hexane and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate , Glycol ether esters such as ethyl-3-ethoxypropionate, ethers such as diethyl ether, tetrahydrofuran, dioxane, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methyl iodide Emissions, halogenated hydrocarbons dichloroethane, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, polar aprotic solvents such as hexamethylphosphoric phosphonyl amides. These solvents can be used alone or in combination of two or more.
After the reaction, the allophanatization reaction is stopped with a known reaction terminator such as phosphoric acid and acidic phosphate ester, and unreacted components are removed by a known technique such as thin-film distillation to obtain the desired allophanate bond. Isocyanate (A1-a) can be obtained.
本発明において、ポリイソシアネート（Ａ１−ａ）の官能基数は、特に限定されるものではないが、ポリオール（Ａ２）との反応時のゲル化の抑制や、主剤との相溶性を良好にするということを考慮すると、２〜４が好ましく、特に２〜２．５が好適である。
また、ポリイソシアネート（Ａ１−ａ）の粘度は特に限定されるものではないが、主剤と硬化剤との混合性等を考慮すると、２５℃で５０〜９００ｍＰａ・ｓが好ましく、１００〜７００ｍＰａ・ｓがより好ましい。
In the present invention, the number of functional groups of the polyisocyanate (A1-a) is not particularly limited, but it is said that the suppression of gelation at the time of reaction with the polyol (A2) and the compatibility with the main agent are improved. Considering this, 2 to 4 is preferable, and 2 to 2.5 is particularly preferable.
Further, the viscosity of the polyisocyanate (A1-a) is not particularly limited, but considering the miscibility of the main agent and the curing agent, 50 to 900 mPa · s is preferable at 25 ° C., and 100 to 700 mPa · s. Is more preferable.
本発明において、ポリイソシアネート（Ａ１）中には、アロファネート結合を有するポリイソシアネート（Ａ１−ａ）が３０質量％以上含まれる。
この値が、３０質量％未満であると、ウレタン防水材に対する接着性が低下する。一方、その上限については、特に制限はないが、上述したアロファネート化反応では、一般的にヌレート体などが副生してくるため、ポリイソシアネート（Ａ１−ａ）１００質量％のポリイソシアネートを得ることは困難であり、通常、９０〜９９質量％程度である。
In the present invention, the polyisocyanate (A1) contains 30% by mass or more of polyisocyanate (A1-a) having an allophanate bond.
The adhesiveness with respect to a urethane waterproof material falls that this value is less than 30 mass%. On the other hand, the upper limit is not particularly limited, but in the above-described allophanatization reaction, a nurate body or the like is generally produced as a by-product, so that a polyisocyanate of 100% by mass of polyisocyanate (A1-a) is obtained. Is usually about 90 to 99% by mass.
上述したアロファネート化反応の結果得られたポリイソシアネートには、アロファネート結合を有するポリイソシアネート（Ａ１−ａ）以外に、ヌレート体やその他のイソシアネート成分が少量含まれているが、通常は３０質量％以上のアロファネート結合を有するポリイソシアネートが含まれているため、アロファネート化反応で得られたポリイソシアネートを、そのままポリイソシアネート（Ａ１）として用いることができる。
また、得られたポリイソシアネートに、上述した各種ポリイソシアネート等のその他のポリイソシアネートを、アロファネート結合を有するポリイソシアネート（Ａ１−ａ）が３０質量％以上となる適宜な量で配合し、ポリイソシアネート（Ａ１）とすることもできる。
The polyisocyanate obtained as a result of the allophanate reaction described above contains a small amount of nurate and other isocyanate components in addition to the polyisocyanate (A1-a) having an allophanate bond, but usually 30% by mass or more. Therefore, the polyisocyanate obtained by the allophanate reaction can be used as it is as the polyisocyanate (A1).
Moreover, other polyisocyanates, such as various polyisocyanates mentioned above, are blended with the obtained polyisocyanate in an appropriate amount such that the polyisocyanate having an allophanate bond (A1-a) is 30% by mass or more, and the polyisocyanate ( A1) can also be used.
ポリオール（Ａ２）としては、特に限定されるものではなく、ポリエステルポリオール、ポリエーテルポリオール等に代表される従来公知の各種ポリオールが挙げられる。
ポリエステルポリオールとしては、コハク酸、アジピン酸、セバシン酸、アゼライン酸、テレフタル酸、イソフタル酸、オルソフタル酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロオルソフタル酸、ナフタレンジカルボン酸、１，４−シクロヘキサンジカルボン酸、トリメット酸等のポリカルボン酸、酸エステル、または酸無水物の１種以上と、エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，２−ブタンジオール、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、１，８−オクタンジオール、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、１，４−シクロヘキサンジメタノール、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等の低分子ポリオール類の１種類以上との脱水縮合で得られるポリエステルポリオール、また、低分子ポリオール、低分子ポリアミン、低分子アミノアルコールを開始剤として、ε−カプロラクトン、γ−バレロラクトン等の環状エステルモノマーの開環重合で得られるラクトン系ポリエステルポリオールが挙げられる。
ポリエーテルポリオールとしては、低分子ポリオール、低分子ポリアミン、低分子アミノアルコールを開始剤として、エチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン等を開環重合して得られる、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グリコール等、およびこれらの共重合体等が挙げられる。
なお、これらのポリオールは、単独で、または２種以上組み合わせて用いることができる。
これらの中でも、耐候性に優れるトップコートを与え得る無黄変（非芳香族）ポリオールが好ましく、特に、ポリテトラメチレングリコールが好適である。
The polyol (A2) is not particularly limited, and various conventionally known polyols represented by polyester polyol, polyether polyol and the like can be mentioned.
Polyester polyols include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, 1,4- One or more of polycarboxylic acids such as cyclohexanedicarboxylic acid and trimetic acid, acid esters, or acid anhydrides, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedi Methanol, Polyester polyol obtained by dehydration condensation with one or more kinds of low molecular polyols such as methylolpropane, glycerin, pentaerythritol, etc., and ε-caprolactone, using low molecular polyol, low molecular polyamine, low molecular amino alcohol as an initiator, Examples thereof include lactone polyester polyols obtained by ring-opening polymerization of cyclic ester monomers such as γ-valerolactone.
Polyether polyols are obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, etc. using low molecular polyols, low molecular polyamines, and low molecular amino alcohols as initiators. Polyethylene glycol, polypropylene glycol, polytetramethylene glycol And their copolymers.
In addition, these polyols can be used individually or in combination of 2 or more types.
Among these, a non-yellowing (non-aromatic) polyol capable of providing a top coat having excellent weather resistance is preferable, and polytetramethylene glycol is particularly preferable.
本発明において、ポリオール（Ａ２）の平均官能基数は、特に限定されるものではないが、ポリイソシアネート（Ａ１）との反応時のゲル化の抑制や、主剤との相溶性を良好にするということを考慮すると、２〜４が好ましい。
また、その数平均分子量も特に限定されるものではないが、適度なウレタン結合間距離を確保してトップコートの硬度を適切にし、耐汚染性などを向上させることを考慮すると、数平均分子量２００〜３０００が好ましい。
なお、数平均分子量は、示差屈折率計検出によるゲルパーミェーションクロマトグラフィー（以下、ＧＰＣと略称する）測定による測定値（ポリスチレン換算値）である。
In the present invention, the average number of functional groups of the polyol (A2) is not particularly limited, but it means that the gelling is suppressed during the reaction with the polyisocyanate (A1) and the compatibility with the main agent is improved. 2 to 4 are preferable.
Further, the number average molecular weight is not particularly limited. However, in consideration of ensuring an appropriate distance between urethane bonds to make the hardness of the top coat appropriate and improving the stain resistance, the number average molecular weight is 200. ~ 3000 is preferred.
The number average molecular weight is a value measured by gel permeation chromatography (hereinafter abbreviated as GPC) by differential refractometer detection (polystyrene conversion value).
ポリイソシアネート樹脂（Ａ）は、上述したポリイソシアネート（Ａ１）と、ポリオール（Ａ２）とを、溶媒の存在下または非存在下で反応させて得ることができる。
ポリイソシアネート（Ａ１）と、ポリオール（Ａ２）との反応条件は特に限定されるものではなく、例えば、必要に応じてウレタン化触媒の存在下、２０〜１５０℃で過剰量のポリイソシアネート（Ａ１）と、ポリオール（Ａ２）とを反応させる手法が挙げられる。
The polyisocyanate resin (A) can be obtained by reacting the above-described polyisocyanate (A1) with the polyol (A2) in the presence or absence of a solvent.
The reaction conditions of the polyisocyanate (A1) and the polyol (A2) are not particularly limited. For example, an excess amount of the polyisocyanate (A1) at 20 to 150 ° C. in the presence of a urethanization catalyst as necessary. And a method of reacting polyol (A2).
この際、ポリイソシアネート（Ａ１）の［ＮＣＯ］と、ポリオール（Ａ２）の［ＯＨ］のモル比は、［ＮＣＯ］が過剰であれば特に限定されるものではないが、主剤との相溶性を高め、かつ、架橋密度を高めて塗膜性能を高めることを考慮すると、［ＮＣＯ］／［ＯＨ］＝１．２以上が好ましく、１．５以上がより好ましく、１．７以上がより一層好ましい。
なお、必要に応じて用いられるウレタン化触媒は公知のものから適宜選択することができ、例えば、ジブチル錫ラウレート、ジオクチル錫ラウレートなどを用いることができる。
At this time, the molar ratio of [NCO] of the polyisocyanate (A1) and [OH] of the polyol (A2) is not particularly limited as long as [NCO] is excessive, but the compatibility with the main agent is not limited. Considering increasing the coating density by increasing the crosslink density, [NCO] / [OH] is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.7 or more. .
In addition, the urethanization catalyst used as needed can be suitably selected from well-known things, for example, dibutyltin laurate, dioctyltin laurate, etc. can be used.
ポリイソシアネート（Ａ１）とポリオール（Ａ２）との反応は、無溶媒でも、溶媒の存在下でも行うことができる。
溶媒としては、反応に悪影響を及ぼさないものであれば任意であり、例えば、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、シクロヘキサン、シクロペンタン等の脂肪族または脂環族炭化水素；トルエン、キシレン、エチルベンゼン、低沸点芳香族ナフサ、高沸点芳香族ナフサ等の芳香族炭化水素；酢酸エチル、酢酸ｎ−ブチル、酢酸ｎ−アミル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、３−メトキシブチルアセテート等のエステル類；メタノール、エタノール、ｉｓｏ−プロパノール、ｎ−ブタノール、ｉｓｏ−ブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノｎ−ブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノｎ−プロピルエーテル、ジエチレングリコールモノブチルエーテル等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルｎ−アミルケトン、シクロヘキサノン等のケトン類；ジメトキシエタン、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル等のエーテル類；Ｎ−メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、エチレンカーボネート等が挙げられる。これらは単独で用いても、２種以上組み合わせて用いてもよい。
The reaction of the polyisocyanate (A1) and the polyol (A2) can be performed without a solvent or in the presence of a solvent.
Any solvent can be used as long as it does not adversely influence the reaction. For example, aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, cyclopentane; toluene, xylene Aromatic hydrocarbons such as ethylbenzene, low-boiling aromatic naphtha, and high-boiling aromatic naphtha; ethyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 3-methyl Esters such as xylbutyl acetate; methanol, ethanol, iso-propanol, n-butanol, iso-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono alcohols such as n-propyl ether and diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone and cyclohexanone; dimethoxyethane, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether , Diethylene glycol Ethers such as dibutyl ether; N- methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate, and the like. These may be used alone or in combination of two or more.
本発明のウレタン塗膜防水用トップコート組成物は、上述したポリイソシアネート成分に特徴があるため、これと反応硬化させるもう一方の成分としては、当該用途に一般に用いられているものから適宜選択すればよい。
具体例としては、アクリル系ポリオール、フッ素系ポリオール等が挙げられ、これらの中でも、耐候性とコスト面のバランスからアクリル系ポリオールが好適である。
The topcoat composition for waterproofing a urethane coating film of the present invention is characterized by the above-mentioned polyisocyanate component, so that the other component to be reactively cured with this is appropriately selected from those generally used for the application. That's fine.
Specific examples include acrylic polyols and fluorine-based polyols. Among these, acrylic polyols are preferred from the balance of weather resistance and cost.
アクリル系ポリオールとしては、水酸基を有するアクリルモノマーと、不飽和二重結合を有するその他の重合性モノマーとをラジカル共重合して得られる各種アクリルポリオールを用いることができる。
水酸基を有するアクリルモノマーの具体例としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、Ｎ−メチロール化アクリルアミド、ε−カプロラクトン変性ヒドロキシ（メタ）アクリレート、カーボネート変性メタクリレート（ダイセル化学工業株式会社製、ＨＥＭＡＣ）等が挙げられ、これらは単独で用いても、２種以上組み合わせて用いてもよい。
As the acrylic polyol, various acrylic polyols obtained by radical copolymerization of an acrylic monomer having a hydroxyl group and another polymerizable monomer having an unsaturated double bond can be used.
Specific examples of the acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxy. Examples include butyl (meth) acrylate, N-methylol acrylamide, ε-caprolactone-modified hydroxy (meth) acrylate, carbonate-modified methacrylate (manufactured by Daicel Chemical Industries, Ltd., HEMAC) and the like. A combination of the above may be used.
不飽和二重結合を有する重合性モノマーの具体例としては、（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸等のカルボン酸基含有モノマー、グリシジル（メタ）アクリレート等のエポキシ基含有モノマー、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート等のアミノ基含有モノマー、メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉｓｏ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、デカニル（メタ）アクリレート、ウンデカニル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等のＣ１〜Ｃ２４のアルキル（メタ）アクリレートモノマー、スチレン、α−メチルスチレン、ビニルトルエン等の芳香族炭化水素系モノマー、メチルビニルエーテル、エチルビニルエーテル等のビニルエーテル系モノマー、酢酸ビニル、プロピオン酸ビニル、（メタ）アクリロニトリル、Ｎ−ビニルピロリドン等が挙げられ、これらは単独で用いても、２種以上組み合わせて用いてもよい。特に、不飽和二重結合を有する重合性モノマーとして、アルキル（メタ）アクリレートモノマーを用いることが好ましい。 Specific examples of the polymerizable monomer having an unsaturated double bond include carboxylic acid group-containing monomers such as (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid, and epoxy group-containing monomers such as glycidyl (meth) acrylate, Amino group-containing monomers such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (Meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, pentyl (meth A) C1-C24 alkyl (meth) acrylate monomers such as relate, hexyl (meth) acrylate, octyl (meth) acrylate, decanyl (meth) acrylate, undecanyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Aromatic hydrocarbon monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether, vinyl acetate, vinyl propionate, (meth) acrylonitrile, N-vinyl pyrrolidone, etc. These may be used alone or in combination of two or more. In particular, an alkyl (meth) acrylate monomer is preferably used as the polymerizable monomer having an unsaturated double bond.
上記ラジカル共重合は、無溶媒または適当な有機溶媒存在下、重合開始剤を用いて行われる。
有機溶媒としては、反応に悪影響を及ぼさないものであれば任意である。その具体例としては、ポリイソシアネート（Ａ１）とポリオール（Ａ２）との反応で例示したものが挙げられる。
重合開始剤としては、公知のラジカル重合開始剤から適宜選択することができ、例えば、２，２′−アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、過酸化ベンゾイル、ｔ−ブチルパーオキシド、クメンハイドロパーオキシド等が挙げられる。これらは単独で用いても、２種以上組み合わせて用いてもよい。
反応温度は、通常、６０〜１５０℃程度である。反応時間は、通常、１〜１２時間程度である。
The radical copolymerization is performed using a polymerization initiator in the absence of a solvent or in the presence of a suitable organic solvent.
Any organic solvent can be used as long as it does not adversely affect the reaction. Specific examples thereof include those exemplified by the reaction of polyisocyanate (A1) and polyol (A2).
The polymerization initiator can be appropriately selected from known radical polymerization initiators, such as 2,2′-azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butyl peroxide, Examples include cumene hydroperoxide. These may be used alone or in combination of two or more.
The reaction temperature is usually about 60 to 150 ° C. The reaction time is usually about 1 to 12 hours.
また、アクリル系ポリオール、フッ素系ポリオールは、それぞれ市販品を用いることもできる。
アクリル系ポリオールの市販品としては、エクセロール２９０、エクセロール１７０（以上、亜細亜工業（株）製）、アクリディックＡ−８０１−Ｐ、アクリディックＡ−８２３（以上、大日本インキ化学工業（株）製）等が挙げられる。
フッ素系ポリオールの市販品としては、ルミフロンＬＦ−１００，ルミフロンＬＦ−２００（以上、旭硝子（株）製）等が挙げられる。
Commercially available products can also be used for the acrylic polyol and fluorine polyol, respectively.
Commercially available acrylic polyols include Excelol 290, Excelol 170 (above, manufactured by Asia Kogyo Co., Ltd.), Acridic A-801-P, Acridic A-823 (above, Dainippon Ink & Chemicals, Inc. )) And the like.
Examples of commercially available fluorine-based polyols include Lumiflon LF-100 and Lumiflon LF-200 (manufactured by Asahi Glass Co., Ltd.).
本発明のウレタン塗膜防水用トップコート組成物において、ポリイソシアネート成分とポリオール成分との配合割合は特に限定されるものではないが、架橋密度を高めてトップコートの塗膜性能を十分に発揮させることを考慮すると、ポリイソシアネート成分中のイソシアネート基およびポリオール成分中の水酸基のモル比が［ＮＣＯ］／［ＯＨ］＝０．８以上となる割合が好ましい。特に、過剰のイソシアネート基と、水分との反応による発泡を考慮すると、好ましくは、［ＮＣＯ］／［ＯＨ］＝０．８〜５．０、より好ましくは、［ＮＣＯ］／［ＯＨ］＝１．０〜３．５である。 In the topcoat composition for waterproofing a urethane coating film of the present invention, the blending ratio of the polyisocyanate component and the polyol component is not particularly limited, but the crosslink density is increased to sufficiently exhibit the topcoat coating film performance. Considering this, a ratio in which the molar ratio of the isocyanate group in the polyisocyanate component and the hydroxyl group in the polyol component is [NCO] / [OH] = 0.8 or more is preferable. In particular, in consideration of foaming due to a reaction between excess isocyanate groups and moisture, [NCO] / [OH] = 0.8 to 5.0, more preferably [NCO] / [OH] = 1. 0.0-3.5.
本発明のウレタン塗膜防水用トップコート組成物には、必要に応じて有機溶剤を配合してもよい。有機溶剤としては、従来、トップコート組成物に用いられる各種溶剤を用いることができ、例えば、トルエン、キシレン等の芳香族炭化水素溶剤、酢酸エチル、酢酸ｎ−ブチル、酢酸ｎ−アミル等のエステル溶剤、メチルエチルケトン、メチルイソブチルケトン等のケトン溶剤、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の脂環式炭化水素溶剤、ミネラルスピリット等の石油系炭化水素溶剤、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルプロピオネート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、グリコールエーテルエステル類溶剤等が挙げられる。これらの溶剤は、単独で用いても、２種以上混合して用いてもよい。
また、本発明のウレタン塗膜防水用トップコート組成物には、必要に応じて、着色顔料、体質顔料、表面調整剤、消泡剤、増粘剤、沈降防止剤、紫外線吸収剤、光安定剤、触媒等の各種添加剤を配合してもよい。２液型の組成物の場合、これらの溶剤、各種添加剤は、ポリイソシアネート成分およびポリオール成分のどちらか一方に配合しても、両者に配合してもよい。
The top coat composition for waterproofing a urethane coating film of the present invention may contain an organic solvent as necessary. As the organic solvent, various solvents conventionally used in topcoat compositions can be used, for example, aromatic hydrocarbon solvents such as toluene and xylene, esters such as ethyl acetate, n-butyl acetate, and n-amyl acetate. Solvents, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, petroleum hydrocarbon solvents such as mineral spirits, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether acetate DOO, diethylene glycol monobutyl ether acetate, glycolate ether esters solvent. These solvents may be used alone or in combination of two or more.
In addition, the urethane coating waterproofing top coat composition of the present invention includes a coloring pigment, an extender pigment, a surface conditioner, an antifoaming agent, a thickener, an anti-settling agent, an ultraviolet absorber, and a light stabilizer, as necessary. You may mix | blend various additives, such as an agent and a catalyst. In the case of a two-component composition, these solvents and various additives may be blended in either or both of the polyisocyanate component and the polyol component.
本発明のウレタン塗膜防水用トップコート組成物は、２成分を現場で調合し、塗装する２液常温硬化型の組成物として好適に用いることができる。
この場合、塗布法は特に限定されるものではなく、刷毛塗り、ローラ塗りなどの公知の手法から適宜選択すればよい。また、塗布量、塗膜の厚み、乾燥時間などは、ウレタン防水材の種類などに応じて適宜設定すればよい。
The topcoat composition for waterproofing a urethane coating film of the present invention can be suitably used as a two-component room temperature curable composition in which two components are prepared and coated on site.
In this case, the coating method is not particularly limited, and may be appropriately selected from known methods such as brush coating and roller coating. Moreover, what is necessary is just to set suitably the coating amount, the thickness of a coating film, drying time, etc. according to the kind etc. of a urethane waterproof material.
以下、合成例、製造例、実施例および比較例を挙げて、本発明をより具体的に説明するが、本発明は、下記の実施例に限定されるものではない。以下の説明において、「部」は質量部を意味する。
なお、以下において、イソシアネート含量は中和滴定により求めた。また、粘度はＢ型回転粘度計（装置：芝浦システム（株）製ＶＧ−Ａ１）を、遊離のヘキサメチレンジイソシアネート（フリーＨＤＩ）はガスクロマトグラフィー（（株）島津製作所製、ＧＣ−１４Ａ、分離カラム：Ｊ＆Ｗ ｓｃｉｅｎｔｉｆｉｃ社製、ＤＢ−１７）を、アロファネート基含有成分量はＦＴ−ＩＲ（日本分光（株）製、ＦＴ／ＩＲ−４６０）、13Ｃ−ＮＭＲ（日本電子（株）製、ＥＣＸ−４００）およびＧＰＣ（装置：東ソー（株）製ＨＬＣ−８１２０ＧＰＣ、分離カラム：東ソーＴＳＫｇｅｌ Ｓｕｐｅｒ ＨＭ−Ｍのミックスカラム）を用いて測定した。
EXAMPLES Hereinafter, although a synthesis example, a manufacture example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example. In the following description, “parts” means parts by mass.
In the following, the isocyanate content was determined by neutralization titration. The viscosity is a B-type rotational viscometer (device: VG-A1 manufactured by Shibaura System Co., Ltd.), and the free hexamethylene diisocyanate (free HDI) is gas chromatograph (manufactured by Shimadzu Corporation, GC-14A, separated. Column: J & W scientific, DB-17), allophanate group-containing component amount is FT-IR (manufactured by JASCO Corporation, FT / IR-460), 13 C-NMR (manufactured by JEOL Ltd., ECX) -400) and GPC (device: HLC-8120GPC manufactured by Tosoh Corporation, separation column: Tosoh TSKgel Super HM-M mix column).
［１］ポリイソシアネートの合成
［合成例１］ポリイソシアネートＰ−１の合成
温度計、攪拌機、冷却管および窒素ガス導入管を備えた反応器に、ヘキサメチレンジイソシアネート９５０部、イソプロパノール５０部、２−エチルヘキサン酸ジルコニウムのミネラルスピリット溶液（ジルコニウム含有量：２０質量％）０．５部を仕込み、攪拌しながら１１０℃まで昇温した。その後、同温度で２時間反応を行った。次いで、リン酸０．１部を仕込み、５０℃で１時間停止反応を行った。停止反応後の反応生成物のイソシアネート含量は４０．５質量％であった。
次に、得られた生成物を１３０℃、０．０４ｋＰａの条件下で薄膜蒸留を行い、イソシアネート含量１９．４質量％、２５℃粘度１５０ｍＰａ・ｓ、フリーＨＤＩ０．２質量％、アロファネート基含有成分９５質量％のアロファネート基含有ポリイソシアネートＰ−１を得た。
[1] Synthesis of polyisocyanate [Synthesis Example 1] Synthesis of polyisocyanate P-1 In a reactor equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen gas introduction pipe, 950 parts of hexamethylene diisocyanate, 50 parts of isopropanol, 2- 0.5 parts of a mineral spirit solution (zirconium content: 20% by mass) of zirconium ethylhexanoate was charged, and the temperature was raised to 110 ° C. with stirring. Then, reaction was performed at the same temperature for 2 hours. Next, 0.1 part of phosphoric acid was charged, and a stop reaction was performed at 50 ° C. for 1 hour. The isocyanate content of the reaction product after the termination reaction was 40.5% by mass.
Next, the obtained product was subjected to thin film distillation under the conditions of 130 ° C. and 0.04 kPa, isocyanate content 19.4% by mass, viscosity at 25 ° C. 150 mPa · s, free HDI 0.2% by mass, allophanate group-containing component 95 mass% allophanate group containing polyisocyanate P-1 was obtained.
［合成例２］ポリイソシアネートＰ−２の合成
表１に示される組成に変更した以外は、合成例１と同様にして、イソシアネート含量１６．６質量％、２５℃粘度２４０ｍＰａ・ｓ、フリーＨＤＩ０．２質量％、アロファネート基含有成分９２質量％のアロファネート基含有ポリイソシアネートＰ−２を得た。
[Synthesis Example 2] Synthesis of Polyisocyanate P-2 Except for changing to the composition shown in Table 1, the same procedure as in Synthesis Example 1 was repeated except that the isocyanate content was 16.6% by mass, the viscosity at 25 ° C was 240 mPa · s, and free HDI was 0. Allophanate group-containing polyisocyanate P-2 having 2% by mass and 92% by mass of the allophanate group-containing component was obtained.
［合成例３］ポリイソシアネートＰ−３の合成
表１に示される組成に変更した以外は、合成例１と同様にして、イソシアネート含量１０．４質量％、２５℃粘度３５０ｍＰａ・ｓ、フリーＨＤＩ０．２質量％、アロファネート基含有成分８９質量％のアロファネート基含有ポリイソシアネートＰ−３を得た。
[Synthesis Example 3] Synthesis of Polyisocyanate P-3 Except that the composition was changed to the composition shown in Table 1, the same procedure as in Synthesis Example 1 was repeated except that the isocyanate content was 10.4% by mass, the 25 ° C viscosity was 350 mPa · s, and free HDI was 0. Allophanate group-containing polyisocyanate P-3 having 2% by mass and 89% by mass of allophanate group-containing component was obtained.
［比較合成例１］ポリイソシアネートＰ−４の合成
温度計、攪拌機、冷却管および窒素ガス導入管を備えた反応器に、ヘキサメチレンジイソシアネート９５０部、１，３−ブタンジオール５０部を仕込み、攪拌しながら８０℃まで昇温した。その後、同温度で６時間反応を行った。反応後の反応生成物のイソシアネート含量は３５．６質量％であった。
次に、得られた生成物を１３０℃、０．０４ｋＰａの条件下で薄膜蒸留を行い、イソシアネート含量１９．７質量％、２５℃粘度７５０ｍＰａ・ｓ、フリーＨＤＩ０．２質量％、アロファネート基含有成分０質量％のポリイソシアネートＰ−４を得た。
上記合成例１〜３および比較合成例１のまとめを表１に示す。
[Comparative Synthesis Example 1] Synthesis of polyisocyanate P-4 950 parts of hexamethylene diisocyanate and 50 parts of 1,3-butanediol were charged in a reactor equipped with a thermometer, a stirrer, a cooling pipe and a nitrogen gas introduction pipe and stirred. The temperature was raised to 80 ° C. Then, reaction was performed at the same temperature for 6 hours. The isocyanate content of the reaction product after the reaction was 35.6% by mass.
Next, the obtained product was subjected to thin film distillation under conditions of 130 ° C. and 0.04 kPa, isocyanate content 19.7% by mass, viscosity at 25 ° C. 750 mPa · s, free HDI 0.2% by mass, allophanate group-containing component 0% by mass of polyisocyanate P-4 was obtained.
A summary of Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 is shown in Table 1.
［２］ポリイソシアネート樹脂（Ａ）の調製
［製造例１］ポリイソシアネート樹脂溶液Ｋ−１ＰＰの調製
攪拌装置、温度計、冷却管および窒素ガス導入管を備えた反応器に、合成例１で得られたポリイソシアネートＰ−１ ３７．８部、ポリテトラメチレングリコール１０００（保土谷化学（株）製、ＰＴＧ１０００ＳＮ、数平均分子量１０００）４２．２部、トルエン２０部を仕込み、攪拌しながら８０℃まで昇温した。同温度で６時間反応させ、固形分８０質量％、イソシアネート含量３．８質量％のポリイソシアネート樹脂溶液Ｋ−１ＰＰを得た。
[2] Preparation of polyisocyanate resin (A) [Production Example 1] Preparation of polyisocyanate resin solution K-1PP Obtained in Synthesis Example 1 in a reactor equipped with a stirrer, thermometer, cooling pipe and nitrogen gas introduction pipe 37.8 parts of polyisocyanate P-1 obtained, polytetramethylene glycol 1000 (manufactured by Hodogaya Chemical Co., Ltd., PTG1000SN, number average molecular weight 1000), 42.2 parts, and toluene 20 parts were charged and stirred up to 80 ° C. The temperature rose. The mixture was reacted at the same temperature for 6 hours to obtain a polyisocyanate resin solution K-1PP having a solid content of 80% by mass and an isocyanate content of 3.8% by mass.
［製造例２〜７，比較製造例１〜５］
表２に示される組成に変更した以外は、製造例１と同様の方法でポリイソシアネート樹脂溶液Ｋ−２ＰＰ〜Ｋ−１２ＰＰを得た。
製造例１〜７，比較製造例１〜５のまとめを表２に示す。
[Production Examples 2-7, Comparative Production Examples 1-5]
Polyisocyanate resin solutions K-2PP to K-12PP were obtained in the same manner as in Production Example 1, except that the composition was changed to the composition shown in Table 2.
A summary of Production Examples 1-7 and Comparative Production Examples 1-5 is shown in Table 2.
［３］ウレタン塗膜防水用トップコート組成物
［実施例１〜７，比較例１〜５］
（１）硬化剤の調製
上記製造例１〜７および比較製造例１〜５で得られたポリイソシアネート樹脂溶液Ｋ−１ＰＰ〜Ｋ−１２ＰＰ １００部に対し、キシレン１００部、酢酸ブチル１００部、ポリプロピレングリコールモノメチルエーテルアセテート１００部を混合し、イソシアネート含量０．９５質量％、固形分２０．０質量％の硬化剤Ｋ−１〜Ｋ−１２を得た。
[3] Topcoat composition for urethane coating waterproofing [Examples 1 to 7, Comparative Examples 1 to 5]
(1) Preparation of curing agent 100 parts of xylene, 100 parts of butyl acetate, polypropylene with respect to 100 parts of polyisocyanate resin solutions K-1PP to K-12PP obtained in Production Examples 1-7 and Comparative Production Examples 1-5 100 parts of glycol monomethyl ether acetate was mixed to obtain curing agents K-1 to K-12 having an isocyanate content of 0.95% by mass and a solid content of 20.0% by mass.
（２）トップコート組成物の調製
上記硬化剤Ｋ−１〜Ｋ−１２と組み合わせる水酸基含有樹脂を使用した主剤は次のように調製した。
攪拌装置、温度計、冷却管および滴下装置を備えた反応器に、キシレン４００部、酢酸ブチル２００部を仕込み、攪拌しながら１１０℃まで昇温した。そこに、２−ヒドロキシエチルメタクリレート８０部、スチレン１００部、メチルメタクリレート３２０部、ｎ−ブチルメタクリレート２５０部、ｎ−ブチルアクリレート２４７部、アクリル酸３部、ｔ−ブチルパーオキシ−２−エチルヘキサノエート１８部、トルエン１００部からなる混合物を４時間かけて滴下した。滴下終了後、同温度で１時間反応させた。さらに、ｔ−ブチルパーオキシ−２−エチルヘキサノエート２部、トルエン１００部からなる混合物を１時間かけて滴下した。滴下終了後、同温度で３時間反応させ、固形分５６．０質量％、粘度４０００ｍＰａ・ｓ（２５℃）、水酸基価３３．９ｍｇＫＯＨ／ｇ（固形分）、数平均分子量１５，０００、平均官能基数９．１の透明なアクリルポリオール樹脂溶液を得た。
続いて、このアクリルポリオール樹脂溶液２５６部、顔料ＣＲ−９５（石原産業（株）製）８８部、キシレン５６部、ガラスビーズ４００部を混合し、ペイントシェイカーで１時間分散を行った。分散終了後、ガラスビーズを取り除くことにより、固形分５７．８質量％、水酸基価１２．１ｍｇＫＯＨ／ｇの白色塗料を調製し、これを主剤とした。
主剤／硬化剤＝１／１（ｗ／ｗ）で調合し、よく混合した（［ＮＣＯ］／［ＯＨ］モル比＝１．０５）。得られたトップコート組成物の性能を、以下の方法に従って測定した。測定結果を表３に示す。
(2) Preparation of Top Coat Composition A main agent using a hydroxyl group-containing resin combined with the curing agents K-1 to K-12 was prepared as follows.
A reactor equipped with a stirrer, a thermometer, a cooling pipe and a dropping device was charged with 400 parts of xylene and 200 parts of butyl acetate and heated to 110 ° C. while stirring. There, 80 parts of 2-hydroxyethyl methacrylate, 100 parts of styrene, 320 parts of methyl methacrylate, 250 parts of n-butyl methacrylate, 247 parts of n-butyl acrylate, 3 parts of acrylic acid, t-butylperoxy-2-ethylhexano A mixture of 18 parts of ate and 100 parts of toluene was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was carried out at the same temperature for 1 hour. Further, a mixture consisting of 2 parts of t-butylperoxy-2-ethylhexanoate and 100 parts of toluene was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was reacted at the same temperature for 3 hours. The solid content was 56.0% by mass, the viscosity was 4000 mPa · s (25 ° C.), the hydroxyl value was 33.9 mgKOH / g (solid content), the number average molecular weight was 15,000, the average functionality. A transparent acrylic polyol resin solution having a base number of 9.1 was obtained.
Subsequently, 256 parts of this acrylic polyol resin solution, 88 parts of pigment CR-95 (manufactured by Ishihara Sangyo Co., Ltd.), 56 parts of xylene and 400 parts of glass beads were mixed and dispersed with a paint shaker for 1 hour. After the completion of dispersion, the glass beads were removed to prepare a white paint having a solid content of 57.8% by mass and a hydroxyl value of 12.1 mgKOH / g, which was used as a main agent.
The main agent / curing agent was blended at 1/1 (w / w) and mixed well ([NCO] / [OH] molar ratio = 1.05). The performance of the obtained top coat composition was measured according to the following method. Table 3 shows the measurement results.
〔耐候性（光沢保持率、色差）〕
耐候性試験は、ＪＩＳ Ｋ５６００−７−７促進耐候性（キセノンランプ法）に準拠し、キセノンウェザーメーター（スガ試験機（株）製、キセノンＸ７５）を用いて行った。
試験片は、１５０×５０×４ｍｍのフレキシブルボードに湿気硬化プライマー（商品名：メンテプライマーＯＣＭ−１０、亜細亜工業（株）製）を乾燥膜厚２０μｍになるように短毛ローラで塗装し、２３℃，５０％ＲＨの条件下で２４時間養生後、さらに乾燥膜厚２ｍｍになるようにウレタン系塗膜防水材（商品名：サラセーヌＫ、ＡＧＣポリマー建材（株）製）をコテで塗布し、２３℃，５０％ＲＨの条件下で２４時間養生を行い、この上に、上記実施例および比較例で調製したトップコート組成物を乾燥膜厚５０μｍになるように、中毛ローラで塗装し、２３℃，５０％ＲＨの条件下で１６８時間養生して作製した。
キセノンウェザーメーターの試験条件としては、ブラックパネル温度を６５℃、１２０分間照射中に水の噴霧時間を１８分間とし、１０００時間の暴露試験を実施した。試験終了後、塗膜の初期６０°鏡面光沢値に対する光沢保持率、および塗膜の初期の色に対する色差を求めた。
[Weather resistance (gloss retention, color difference)]
The weather resistance test was performed using a xenon weather meter (Xenon X75, manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K5600-7-7 accelerated weather resistance (xenon lamp method).
The test piece is a 150 × 50 × 4 mm flexible board coated with a moisture curing primer (trade name: Maintenance Primer OCM-10, manufactured by Aya Kogyo Co., Ltd.) with a short hair roller so that the dry film thickness is 20 μm. After curing for 24 hours under the conditions of ℃ and 50% RH, apply a urethane film waterproofing material (trade name: Saraseine K, manufactured by AGC Polymer Building Materials Co., Ltd.) with a trowel so that the dry film thickness is 2 mm. Curing was carried out for 24 hours under the conditions of 23 ° C. and 50% RH, and the top coat composition prepared in the above Examples and Comparative Examples was applied thereon with a medium hair roller so as to have a dry film thickness of 50 μm, It was prepared by curing for 168 hours under conditions of 23 ° C. and 50% RH.
As a test condition of the xenon weather meter, a black panel temperature was 65 ° C., a water spraying time was 18 minutes during irradiation for 120 minutes, and an exposure test was performed for 1000 hours. After the test, the gloss retention with respect to the initial 60 ° specular gloss value of the coating film and the color difference with respect to the initial color of the coating film were determined.
〔初期接着性〕
初期接着性はＪＩＳ Ｋ５６００−５−６付着性（クロスカット法）に準拠し、隙間間隔２ｍｍのカッターガイドを用いて、碁盤目状（２５マス；縦５分割×横５分割）に切り傷をつけ、この碁盤目の上にセロハン粘着テープをはり、テープの一端を持って塗面に直角方向に瞬間的に引き剥がし、塗膜の剥がれの面積を測定し、下記の分類にて評価した。
なお、試験片は、１５０×５０×４ｍｍのフレキシブルボードに湿気硬化プライマー（商品名：メンテプライマーＯＣＭ−１０、亜細亜工業（株）製）を乾燥膜厚２０μｍになるように短毛ローラで塗装し、２３℃，５０％ＲＨの条件下で２４時間養生後、さらに乾燥膜厚２ｍｍになるようにウレタン系塗膜防水材（商品名：サラセーヌＫ、ＡＧＣポリマー建材（株）製）をコテで塗布し、２３℃，５０％ＲＨの条件下で７２時間養生を行い、この上に、上記実施例および比較例で調製したトップコート組成物を乾燥膜厚５０μｍになるように、中毛ローラで塗装し、２３℃，５０％ＲＨの条件下で１時間養生して作製した。
分類０：どの格子の目にもはがれがない。
分類１：剥離面積５％未満
分類２：剥離面積５％以上１５％未満
分類３：剥離面積１５％以上３５％未満
分類４：剥離面積３５％以上６５％未満
分類５：剥離面積６５％以上
(Initial adhesion)
The initial adhesion is based on JIS K5600-5-6 adhesion (cross-cut method), and using a cutter guide with a gap interval of 2 mm, a grid pattern (25 squares; 5 vertical and 5 horizontal) is cut. Then, a cellophane adhesive tape was put on the grid, and the tape was peeled off instantaneously in the direction perpendicular to the coating surface with one end of the tape, and the peeling area of the coating film was measured and evaluated according to the following classification.
The test piece was coated with a short hair roller on a 150 x 50 x 4 mm flexible board with a moisture curing primer (trade name: Maintenance Primer OCM-10, manufactured by Asia Industries Co., Ltd.) to a dry film thickness of 20 μm. After curing for 24 hours under the conditions of 23 ° C. and 50% RH, a urethane film waterproofing material (trade name: Saraseine K, manufactured by AGC Polymer Building Materials Co., Ltd.) is applied with a trowel so that the dry film thickness becomes 2 mm. Then, curing was carried out for 72 hours under the conditions of 23 ° C. and 50% RH, and the top coat composition prepared in the above-mentioned Examples and Comparative Examples was further coated with a medium hair roller so as to have a dry film thickness of 50 μm. And then cured under conditions of 23 ° C. and 50% RH for 1 hour.
Classification 0: There is no peeling in the eyes of any lattice.
Classification 1: Peeling area less than 5% Classification 2: Peeling area of 5% or more and less than 15% Classification 3: Peeling area of 15% or more and less than 35% Classification 4: Peeling area of 35% or more and less than 65% Classification 5: Peeling area of 65% or more
〔最終接着性〕
合成樹脂製の底板に剥離紙を、その上に不織布を敷き、乾燥膜厚２ｍｍになるようにウレタン系塗膜防水材（商品名：サラセーヌＫ、ＡＧＣポリマー建材（株）製）をコテで塗布し、２３℃，５０％ＲＨの条件下で７２時間養生を行った。この上に、上記実施例および比較例で調製したトップコート組成物を、乾燥膜厚５０μｍになるように、中毛ローラで塗装し、２３℃，５０％ＲＨの条件下で１６８時間養生を行った。さらに、トップコート組成物をしみ込ませた不織布を重ねて３層とし、２３℃，５０％ＲＨの条件下で１６８時間養生を行った。その後、１５０ｍｍ×２０ｍｍサイズに切断し、試験片とした。この試験片について、物性試験機（（株）島津製作所製、オートグラフＡＧＳ−Ｊ）を用いて、剥離角度１８０°、剥離速度２００ｍｍ／分の条件で剥離強度を測定した。
[Final adhesion]
Put a release paper on the bottom plate made of synthetic resin, spread a non-woven fabric on it, and apply a urethane film waterproofing material (trade name: Saraseine K, manufactured by AGC Polymer Building Materials Co., Ltd.) with a trowel so that the dry film thickness is 2 mm. Then, curing was performed for 72 hours under conditions of 23 ° C. and 50% RH. On top of this, the top coat compositions prepared in the above examples and comparative examples were applied with a medium-hair roller so as to have a dry film thickness of 50 μm, and cured for 168 hours under conditions of 23 ° C. and 50% RH. It was. Furthermore, the nonwoven fabric impregnated with the top coat composition was laminated to form three layers, and curing was performed for 168 hours under conditions of 23 ° C. and 50% RH. Then, it cut | disconnected to 150 mm x 20 mm size, and was set as the test piece. About this test piece, peel strength was measured on condition of a peeling angle of 180 degrees and a peeling speed of 200 mm / min using a physical property tester (manufactured by Shimadzu Corporation, Autograph AGS-J).
表３に示されるように、アロファネート結合を含むポリイソシアネート（Ａ１−ａ）を３０質量％以上含むポリイソシアネート（Ａ１）を、ポリオール（Ａ２）と反応させて得られたポリイソシアネート樹脂（Ａ）を含む硬化剤を用いた実施例１〜７で得られた塗膜は、比較例１〜５の塗膜と比較し、耐候性（光沢保持率、色差）およびウレタン防水材との接着性（初期、最終）が良好であり、これら２つの特性が両立できていることがわかる。 As shown in Table 3, polyisocyanate resin (A) obtained by reacting polyisocyanate (A1) containing 30% by mass or more of polyisocyanate (A1-a) containing allophanate bonds with polyol (A2) is used. The coating films obtained in Examples 1 to 7 using the containing curing agent were compared with the coating films of Comparative Examples 1 to 5, and weather resistance (gloss retention, color difference) and adhesion to urethane waterproofing material (initial stage) It is clear that these two characteristics are compatible.
Claims (9)
前記ポリイソシアネート（Ａ１−ａ）が、脂肪族ポリイソシアネートおよび脂環式ポリイソシアネートから選ばれる少なくとも１種のアロファネート変性体であることを特徴とするウレタン塗膜防水用トップコート組成物。 Obtained by reacting polyisocyanate (A1) containing 30% by mass or more of polyisocyanate (A1-a) containing one or more allophanate bonds and two or more isocyanate groups in one molecule with polyol (A2). polyisocyanate resin (a) only contains,
The top coat composition for waterproofing a urethane coating film, wherein the polyisocyanate (A1-a) is at least one allophanate-modified product selected from an aliphatic polyisocyanate and an alicyclic polyisocyanate .
前記ポリイソシアネート（Ａ１−ａ）が、脂肪族ポリイソシアネートおよび脂環式ポリイソシアネートから選ばれる少なくとも１種のアロファネート変性体であることを特徴とするウレタン塗膜防水用トップコート組成物用の硬化剤。 Obtained by reacting polyisocyanate (A1) containing 30% by mass or more of polyisocyanate (A1-a) containing one or more allophanate bonds and two or more isocyanate groups in one molecule with polyol (A2). Including a polyisocyanate resin (A),
The polyisocyanate (A1-a) is at least one allophanate-modified product selected from aliphatic polyisocyanates and alicyclic polyisocyanates, and a curing agent for a topcoat composition for waterproofing urethane coatings .
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| JP5696397B2 (en) * | 2010-08-17 | 2015-04-08 | オート化学工業株式会社 | One-component moisture-curing primer for surface treatment of architectural sealing materials or waterproofing coatings |
| JP5955729B2 (en) * | 2012-10-01 | 2016-07-20 | 横浜ゴム株式会社 | Photo-curable resin composition for top coat |
| KR101604382B1 (en) | 2015-03-04 | 2016-03-17 | 한국신발피혁연구원 | Composition for primerless adhesive cationic polyureathane water having yellowing resistance and adhesion property |
| JP6607269B2 (en) * | 2018-02-01 | 2019-11-20 | 亜細亜工業株式会社 | Paint composition |
| JP7067602B1 (en) | 2020-12-15 | 2022-05-16 | 亜細亜工業株式会社 | Urethane coating waterproof top coat composition |
| JP7315056B1 (en) | 2022-03-18 | 2023-07-26 | 亜細亜工業株式会社 | Top coat composition for waterproofing urethane coating |
| CN118221908B (en) * | 2024-05-27 | 2024-08-20 | 万华化学集团股份有限公司 | Polyisocyanate composition stable in storage under hot environment and preparation method and application thereof |
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