JP3340962B2 - One-part moisture-curable urethane resin composition - Google Patents
One-part moisture-curable urethane resin compositionInfo
- Publication number
- JP3340962B2 JP3340962B2 JP17314598A JP17314598A JP3340962B2 JP 3340962 B2 JP3340962 B2 JP 3340962B2 JP 17314598 A JP17314598 A JP 17314598A JP 17314598 A JP17314598 A JP 17314598A JP 3340962 B2 JP3340962 B2 JP 3340962B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- resin composition
- urethane resin
- group
- weight
- 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
- 239000011342 resin composition Substances 0.000 title claims description 19
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims description 16
- -1 phosphoric acid silyl ester Chemical class 0.000 claims description 24
- YIKQLNRXIWIZFA-UHFFFAOYSA-N silyl dihydrogen phosphate Chemical compound OP(O)(=O)O[SiH3] YIKQLNRXIWIZFA-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 18
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 29
- 238000003860 storage Methods 0.000 description 22
- 229920005862 polyol Polymers 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000005056 polyisocyanate Substances 0.000 description 13
- 229920001228 polyisocyanate Polymers 0.000 description 13
- 150000003077 polyols Chemical class 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000009974 thixotropic effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004078 waterproofing Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 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 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- UFAPLAOEQMMKJA-UHFFFAOYSA-N hexane-1,2,5-triol Chemical compound CC(O)CCC(O)CO UFAPLAOEQMMKJA-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- 239000004849 latent hardener Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001117 oleyl 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])=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])[H] 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 125000000160 oxazolidinyl group Chemical group 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000015096 spirit Nutrition 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 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
- 150000003673 urethanes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、一液型湿気硬化性
ウレタン樹脂組成物に関する。詳しくは、貯蔵安定性を
保持しながら、硬化性を自由に調節することが可能な一
液型湿気硬化性ウレタン樹脂組成物に関する。[0001] The present invention relates to a one-pack type moisture-curable urethane resin composition. More specifically, the present invention relates to a one-pack type moisture-curable urethane resin composition capable of freely adjusting curability while maintaining storage stability.
【０００２】[0002]
【従来の技術】一液型湿気硬化性ウレタン樹脂組成物
は、シーリング剤、防水剤、目地剤、接着剤、塗料等に
広く利用されている。このような一液型湿気硬化性ウレ
タン樹脂組成物は、使用目的、使用方法、使用季節によ
り異なる硬化性を要求される。しかし、一般に、一液型
湿気硬化性ウレタン樹脂組成物においては、貯蔵安定性
を損なわずに硬化性を高めることは困難とされてきた。
例えば、一液型湿気硬化性ウレタン樹脂組成物を短時間
で硬化させたい場合には、有機金属化合物、アミン化合
物が硬化触媒として添加されるが、このような硬化触媒
が添加された一液型湿気硬化性ウレタン樹脂組成物は、
硬化時間は短縮されるものの、貯蔵安定性が低下してし
まう。このような硬化触媒では貯蔵安定性が低下すると
いう問題に対して、潜在性硬化剤として、オキサゾリジ
ン、エナミンを添加し、あるいはさらにこれらに特定の
酸性を有する酸性化合物を添加するという発明が、特開
平９−２７８８５７号公報、特開平７−２８９９８９号
公報で開示されている。これらの潜在性硬化剤を添加す
ることにより高い硬化性が得られるが、しかし、これら
の化合物はアミンであるため、ある一定以上使用すると
やはり貯蔵安定性は低下するという問題がある。また、
酸性化合物を添加するため、貯蔵中もこれらの潜在性硬
化剤を活性化し、貯蔵安定性も低下する。2. Description of the Related Art One-part moisture-curable urethane resin compositions are widely used as sealing agents, waterproofing agents, jointing agents, adhesives, paints, and the like. Such one-component moisture-curable urethane resin compositions are required to have different curability depending on the purpose of use, method of use, and season of use. However, in general, it has been difficult to increase the curability of a one-component moisture-curable urethane resin composition without impairing the storage stability.
For example, when it is desired to cure a one-component moisture-curable urethane resin composition in a short time, an organometallic compound and an amine compound are added as a curing catalyst. The moisture-curable urethane resin composition is
Although the curing time is shortened, the storage stability is reduced. In order to solve the problem that the storage stability of such a curing catalyst is reduced, the invention of adding oxazolidine or enamine as a latent curing agent, or further adding an acidic compound having a specific acidity thereto, is a special feature. It is disclosed in Japanese Unexamined Patent Publication No. Hei 9-278857 and Japanese Unexamined Patent Publication No. Hei 7-289989. High curability can be obtained by adding these latent curing agents. However, since these compounds are amines, there is a problem that the storage stability also decreases when used over a certain amount. Also,
The addition of the acidic compound activates these latent hardeners during storage and also reduces storage stability.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、貯蔵
安定性が良好で、硬化性が自由に調節できる一液型湿気
硬化性ウレタン樹脂組成物を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a one-pack type moisture-curable urethane resin composition which has good storage stability and whose curability can be freely adjusted.
【０００４】[0004]
【課題を解決するための手段】すなわち、本発明は、ウ
レタンプレポリマーとリン酸シリルエステルを含有し、
リン酸シリルエステル以外の成分１００重量部に対し、
リン酸シリルエステルを０．００１〜３０重量部含有す
る一液型湿気硬化性ウレタン樹脂組成物を提供する。That is, the present invention comprises a urethane prepolymer and a silyl phosphate ester,
For 100 parts by weight of components other than silyl phosphate,
Provided is a one-part moisture-curable urethane resin composition containing 0.001 to 30 parts by weight of a silyl phosphate.
【０００５】前記リン酸シリルエステルが式（１）で表
される化合物であるのが好ましい。It is preferable that the silyl phosphate is a compound represented by the formula (1).
【化２】 （Ｒはアルキル基、Ｘはヘテロ原子を有していてもよい
有機基、ｎは１〜３の整数を表す。）Embedded image (R is an alkyl group, X is an organic group optionally having a hetero atom, and n represents an integer of 1 to 3.)
【０００６】[0006]
【発明の実施の形態】以下に、本発明についてさらに詳
細に説明する。本発明の一液型湿気硬化性ウレタン樹脂
組成物（以下、本発明の組成物と記す）は、ウレタンプ
レポリマーおよび上記式（１）で表されるリン酸シリル
エステルを含有するウレタン組成物である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The one-pack moisture-curable urethane resin composition of the present invention (hereinafter, referred to as the composition of the present invention) is a urethane composition containing a urethane prepolymer and the silyl phosphate represented by the above formula (1). is there.
【０００７】本発明の組成物に配合されるウレタンプレ
ポリマーは、通常の一液型のポリウレタン樹脂組成物と
同様、ポリオール化合物と過剰のポリイソシアネート化
合物（すなわち、ＯＨ基に対して過剰のＮＣＯ基）を反
応させて得られる反応生成物であって、一般に、０．５
〜５重量％のイソシアネート基を分子末端に含有する。The urethane prepolymer blended in the composition of the present invention comprises a polyol compound and an excess of a polyisocyanate compound (ie, an excess of NCO groups with respect to OH groups), as in a normal one-pack type polyurethane resin composition. Is a reaction product obtained by reacting
It contains ５5% by weight of isocyanate groups at the molecular terminals.
【０００８】このようなウレタンプレポリマーを生成す
るポリイソシアネート化合物としては、通常の一液型の
ポリウレタン樹脂組成物の製造に用いられる各種のもの
が使用できる。具体的には、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、ｐ−フェニレンジ
イソシアネート、ポリメチレンポリフェニレンポリイソ
シアネート等の芳香族ポリイソシアネート；ヘキサメチ
レンジイソシアネート等の脂肪族ポリイソシアネート；
イソホロンジイソシアネート等の脂環式ポリイソシアネ
ート；キシリレンジイソシアネート等のアリール脂肪族
ポリイソシアネート；上記各ポリイソシアネートのカル
ボジイミド変性またはイソシアヌレート変性ポリイソシ
アネート；等が好適に例示される。これらは、１種ある
いは２種以上を組み合わせて用いてもよい。As the polyisocyanate compound for producing such a urethane prepolymer, various compounds used in the production of ordinary one-pack type polyurethane resin compositions can be used. Specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4
4'-diphenylmethane diisocyanate, 2,4'-
Aromatic polyisocyanates such as diphenylmethane diisocyanate, p-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate;
Preferred examples include alicyclic polyisocyanates such as isophorone diisocyanate; aryl aliphatic polyisocyanates such as xylylene diisocyanate; carbodiimide-modified or isocyanurate-modified polyisocyanates of the above polyisocyanates. These may be used alone or in combination of two or more.
【０００９】上記ウレタンプレポリマーを生成するポリ
オール化合物としては、通常の一液型のポリウレタン樹
脂組成物と同様に、ポリエーテルポリオール、ポリエス
テルポリオール、その他のポリオール、およびこれらの
混合ポリオールを用いることができる。As the polyol compound for producing the urethane prepolymer, polyether polyols, polyester polyols, other polyols, and mixed polyols thereof can be used as in the case of the usual one-pack type polyurethane resin composition. .
【００１０】ポリエーテルポリオールとしては、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、テトラヒドロフラン等のア
ルキレンオキサイドの１種または２種以上に、２個以上
の活性水素を有する化合物の１種または２種以上を付加
重合させた生成物を挙げることができる。２個以上の活
性水素を有する化合物としては、多価アルコール、アミ
ン類、アルカノールアミン類等が挙げられる。多価アル
コールとしては、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、グリセリン、１，１，１−トリメチロールプロパ
ン、１，２，５−ヘキサントリオール、１，３−ブタン
ジオール、１，４−ブタンジオール、４，４′−ジヒド
ロキシフェニルプロパン、４，４′−ジヒドロキシフェ
ニルメタン、ペンタエリスリトール等が；アミン類とし
ては、エチレンジアミン、プロパノールアミン等が；ア
ルカノールアミン類としては、エタノールアミン、プロ
パノールアミン等；が挙げられる。Examples of the polyether polyol include one or two or more compounds having two or more active hydrogens in one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide and tetrahydrofuran. A product obtained by addition polymerization of the above can be mentioned. Examples of the compound having two or more active hydrogens include polyhydric alcohols, amines, and alkanolamines. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, 1,4- Butanediol, 4,4'-dihydroxyphenylpropane, 4,4'-dihydroxyphenylmethane, pentaerythritol, etc .; amines include ethylenediamine, propanolamine, etc .; alkanolamines include ethanolamine, propanolamine, etc. ;
【００１１】また、ポリエステルポリオールとしては、
エチレングリコール、プロピレングリコール、ブタンジ
オールペンタンジオール、ヘキサンジオール、シクロヘ
キサンジメタノール、グリセリン、１，１，１−トリメ
チロールプロパン、あるいはその他の低分子ポリオール
の１種または２種以上と、グルタル酸、アジピン酸、ピ
メリン酸、スベリン酸、セバシン酸、テレフタル酸、イ
ソフタル酸、ダイマー酸、あるいはその他の低分子カル
ボン酸やオリゴマー酸の１種または２種以上との縮合重
合体；プロピオンラクトン、バレロラクトン等の開環重
合体；等を挙げることが出来る。Further, as the polyester polyol,
One or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, or other low molecular weight polyols, and glutaric acid, adipic acid , Pimelic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, or a condensation polymer with one or more of low molecular carboxylic acids and oligomeric acids; propionyl lactone, valerolactone, etc. Ring polymer; and the like.
【００１２】さらに、その他のポリオールとしては、ポ
リカーボネートポリオール、ポリブタジエンポリオー
ル、水素添加されたポリブタジエンポリオール、アクリ
ルポリオール等や、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、ブタンジオール、ペンタンジオール、ヘキサンジ
オール等の低分子ポリオールを挙げることが出来る。Further, other polyols include polycarbonate polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, acrylic polyols and the like, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol and the like. Of low molecular weight polyols.
【００１３】このような、ポリオール化合物と過剰のポ
リイソシアネート化合物とを用いて生成される分子末端
にイソシアネート基を有するウレタンプレポリマーを得
る際の、ポリオール化合物とポリイソシアネート化合物
との混合割合は、ポリオール化合物１当量（ＯＨ当量）
当たり、ポリイソシアネート化合物１．２〜５当量（Ｎ
ＣＯ当量）が好ましく、１．５〜３当量がより好まし
い。また、このウレタンプレポリマーの製造は、通常の
ウレタンプレポリマーと同様に、所定量比の両化合物を
混合し、通常３０〜１２０℃、好ましくは５０〜１００
℃で加熱撹拌することによって行われる。When a urethane prepolymer having an isocyanate group at a molecular end produced by using such a polyol compound and an excess of a polyisocyanate compound is obtained, the mixing ratio of the polyol compound and the polyisocyanate compound is not limited to the polyol. 1 equivalent of compound (OH equivalent)
Per equivalent of polyisocyanate compound 1.2 to 5 equivalents (N
CO equivalent), and more preferably 1.5 to 3 equivalents. Further, in the production of this urethane prepolymer, as in the case of a normal urethane prepolymer, both compounds are mixed at a predetermined quantitative ratio, usually at 30 to 120 ° C, preferably 50 to 100 ° C.
It is performed by heating and stirring at ℃.
【００１４】本発明の組成物に含有されるリン酸シリル
エステルとは、下記式（１）で表される化学構造を有す
る化合物でモノマー、ポリマー、あるいは、低分子、高
分子を問わない。The silyl phosphate ester contained in the composition of the present invention is a compound having a chemical structure represented by the following formula (1), regardless of a monomer, polymer, low molecular weight, or high molecular weight.
【化３】 式中、Ｒはメチル基、エチル基等のアルキル基等を、Ｘ
はヘテロ原子を有していてもよい有機基、例えば、メチ
ル基、エチル基等のアルキル基；メトキシ基、エトキシ
基、ブトキシ基、ヘキサオキシ基、２−エチルヘキサオ
キシ基、オクタデキルオキシ基（ＣＨ3 （ＣＨ2 ）17Ｏ
−）等のアルコキシ基；トリメチルシリルオキシ基等
を、ｎは１〜３の整数を表す。ｎが２以上の場合、Ｒは
同じ置換基でも異なる置換基でもよい。３−ｎが２以上
の場合、Ｘは同じ置換基でも異なる置換基でもよい。具
体例として、以下の化合物を示すことが出来る。Embedded image In the formula, R represents an alkyl group such as a methyl group or an ethyl group;
Is an organic group optionally having a hetero atom, for example, an alkyl group such as a methyl group or an ethyl group; a methoxy group, an ethoxy group, a butoxy group, a hexaoxy group, a 2-ethylhexaoxy group, an octadecyloxy group (CH 3 (CH 2 ) 17 O
An alkoxy group such as-); a trimethylsilyloxy group or the like, and n represents an integer of 1 to 3. When n is 2 or more, R may be the same or different substituents. When 3-n is 2 or more, X may be the same substituent or different substituents. As specific examples, the following compounds can be shown.
【化４】 式中、Ｒ1 はメチル基、エチル基、ブチル基、ヘキシル
基、２−エチルヘキシル基、ステアリル基、オレイル基
等を表す。ｍは１以上の整数を表す。Embedded image In the formula, R 1 represents a methyl group, an ethyl group, a butyl group, a hexyl group, a 2-ethylhexyl group, a stearyl group, an oleyl group, or the like. m represents an integer of 1 or more.
【００１５】式（１）で表されるリン酸シリルエステル
は、例えば、相当するリン酸類とトリアルキルクロロシ
ランまたはアルキルシラザンとを反応させる方法により
得ることができる。The silyl phosphate represented by the formula (1) can be obtained, for example, by reacting the corresponding phosphoric acid with a trialkylchlorosilane or an alkylsilazane.
【００１６】本発明の組成物は、式（１）で表されるリ
ン酸シリルエステルを含有する。このリン酸シリルエス
テルは空気中の水分により加水分解され、リン酸を生成
する。リン酸は、イソシアネート基の加水分解を促進さ
せ、また、本発明の組成物中にオキサゾリジン系の硬化
剤を配合する場合にはこの加水分解も促進させる。これ
らの反応により本発明の組成物に含有されるリン酸シリ
ルエステルの含有量を増減することで、硬化性を調節す
ることができる。例えば、後述する実施例１と標準例と
の比較からわかるように、上記リン酸シリルエステルの
１例であるジ（２−エチルヘキシル）ホスフェートのト
リメチルシリルエステルを、リン酸シリルエステル以外
の成分の合計１００重量部に対し、０．０１重量部含有
する本発明の組成物は、標準例に示すようにリン酸シリ
ルエステルを全く含有しないウレタンプレポリマーより
硬化時間（タックフリータイム）を短かくすることがで
きる。一方、後述する実施例２と実施例４に示すよう
に、リン酸シリルエステル以外の成分の合計１００重量
部に対し、上記リン酸シリルエステルの配合量を少量、
例えば０．０１重量部とする場合と、多量、例えば０．
１重量部とする場合では、硬化時間を約７倍変えること
ができる。このように、リン酸シリルエステルの含有量
を調節することで、硬化性を自由に調節することがで
き、使用目的、使用方法、使用季節により異なる硬化性
の要求に答えることが出来る。一方、上記リン酸シリル
エステルは、本発明の組成物の貯蔵中は中性であるた
め、貯蔵安定性に悪影響を与えることはない。従って、
本発明の組成物の上記硬化性のコントロールは、本発明
の組成物の貯蔵安定性や揺変性を損なうことなく行うこ
とができる。The composition of the present invention contains a silyl phosphate represented by the formula (1). The silyl phosphate is hydrolyzed by moisture in the air to generate phosphoric acid. Phosphoric acid promotes hydrolysis of isocyanate groups, and when an oxazolidine-based curing agent is added to the composition of the present invention, the hydrolysis is also promoted. The curability can be adjusted by increasing or decreasing the content of the silyl phosphate contained in the composition of the present invention by these reactions. For example, as can be seen from a comparison between Example 1 and a standard example, which will be described later, trimethylsilyl ester of di (2-ethylhexyl) phosphate, which is one example of the above silyl phosphate, is converted to a total of 100 components other than the silyl phosphate. The composition of the present invention containing 0.01 parts by weight with respect to parts by weight can shorten the curing time (tack-free time) compared to the urethane prepolymer containing no silyl phosphate at all, as shown in the standard example. it can. On the other hand, as shown in Example 2 and Example 4 described below, a small amount of the silyl phosphate was added to 100 parts by weight of the components other than the silyl phosphate.
For example, 0.01 parts by weight and a large amount, for example, 0.1 parts by weight.
In the case of 1 part by weight, the curing time can be changed about 7 times. As described above, by adjusting the content of the silyl phosphate, the curability can be freely adjusted, and it is possible to meet the different curability requirements depending on the purpose of use, method of use, and season of use. On the other hand, since the silyl phosphate is neutral during storage of the composition of the present invention, it does not adversely affect storage stability. Therefore,
The curability of the composition of the present invention can be controlled without impairing the storage stability and thixotropic properties of the composition of the present invention.
【００１７】本発明の組成物に含有される上記リン酸シ
リルエステルの含有量は、リン酸シリルエステル以外の
成分の合計１００重量部に対し、０．００１〜３０重量
部、好ましくは、０．００５〜２０重量部である。この
範囲であれば、貯蔵安定性を損なわずに硬化性を高める
ことができる。０．００１重量部未満では、硬化速度を
高めることができない。３０重量部超では、本発明の組
成物の製造の原料コストが高くなり経済的に不利にな
る。The content of the silyl phosphate in the composition of the present invention is 0.001 to 30 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the components other than the silyl phosphate. 005 to 20 parts by weight. Within this range, the curability can be increased without impairing the storage stability. If the amount is less than 0.001 part by weight, the curing speed cannot be increased. If it exceeds 30 parts by weight, the raw material cost for producing the composition of the present invention becomes high, which is economically disadvantageous.
【００１８】本発明の組成物は、上記必須の成分に加え
て、本発明の目的を損なわない範囲で必要に応じて、そ
の他の添加剤、例えば、トルエン、キシレン、ミネラル
スピリッツなどの溶剤；ジオクチルフタレート、ジウン
デシルフタレート、ジブチルフタレート、ジノニルフタ
エート、ジイソデシルアジペート、ジオクチルアジペー
トなどの可塑剤；炭酸カルシウム、カーボンブラック、
タルク、クレー、シリカ、酸化チタンなどのフィラー；
顔料や染料等の着色剤；酸化防止剤；紫外線吸収剤；な
どを添加しても良い。さらに、高級脂肪酸のシリルエス
テル等を脱水剤として使用してもよい。高級脂肪酸のシ
リルエステルはウレタンプレポリマーのイソシアネート
基よりも容易に加水分解してカルボン酸とシラノールと
なるため、ウレタン組成物中に配合されるフィラー等に
吸着した水分によるウレタンプレポリマーの硬化反応を
阻止することができるので、貯蔵安定性の向上に寄与し
うる。さらに、オキサゾリジン系の硬化剤を、貯蔵安定
性を損なわない程度に添加しても良い。オキサゾリジン
系の硬化剤、例えば、水酸基含有オキサゾリジンとポリ
イソシアネートとの反応物、あるいは、前記オキサゾリ
ジンによりウレタンプレポリマーのイソシアネート基を
一部封鎖したものは、イソシアネート基と反応しない
が、オキサゾリジン基が空気中の水分により開環して水
酸基とイミノ基ができイソシアネート基と反応して架橋
反応が起こり硬化性が促進される。The composition of the present invention may further comprise, if necessary, other additives such as a solvent such as toluene, xylene, and mineral spirits, in addition to the above essential components, as long as the object of the present invention is not impaired. Plasticizers such as phthalate, diundecyl phthalate, dibutyl phthalate, dinonyl phthalate, diisodecyl adipate, dioctyl adipate; calcium carbonate, carbon black,
Fillers such as talc, clay, silica, titanium oxide;
Colorants such as pigments and dyes; antioxidants; ultraviolet absorbers; and the like may be added. Further, a silyl ester of a higher fatty acid or the like may be used as a dehydrating agent. Since the silyl ester of a higher fatty acid is more easily hydrolyzed to the carboxylic acid and silanol than the isocyanate group of the urethane prepolymer, the curing reaction of the urethane prepolymer due to the moisture adsorbed on the fillers and the like incorporated in the urethane composition. Since it can be prevented, it can contribute to improvement of storage stability. Further, an oxazolidine-based curing agent may be added to such an extent that storage stability is not impaired. Oxazolidine-based curing agents, for example, a reaction product of a hydroxyl group-containing oxazolidine and a polyisocyanate, or a partially blocked isocyanate group of a urethane prepolymer with the oxazolidine does not react with the isocyanate group, but the oxazolidine group is present in the air. The ring is opened by the water to form a hydroxyl group and an imino group, and reacts with the isocyanate group to cause a crosslinking reaction to promote curability.
【００１９】本発明の組成物の製造方法は特に限定され
ず、通常の一液型ウレタン組成物と同様にして製造すれ
ばよい。例えば、各成分を減圧下で十分に混練し、均一
に分散させる方法が例示される。The method for producing the composition of the present invention is not particularly limited, and the composition may be produced in the same manner as in a usual one-pack type urethane composition. For example, a method in which each component is sufficiently kneaded under reduced pressure and uniformly dispersed is exemplified.
【００２０】本発明の組成物は、上記構成を採ることに
より、貯蔵安定性に優れる。また、本発明の組成物に配
合される前記式（１）で表されるリン酸シリルエステル
の配合量を所定の範囲で調節することにより、本発明の
組成物の硬化性を自由に調節する事ができる。本発明の
組成物は、リン酸シリルエステルを含有することで揺変
性を有し、この揺変性と貯蔵安定性を低下させることな
しに、硬化性を自由にコントロールできる。従って、本
発明の組成物は、シーリング剤、防水剤、目地剤、接着
剤、塗料等に好適に利用することができ、その組成物の
使用目的、使用方法、使用季節に応じた硬化性をもった
組成物とすることができる。The composition of the present invention has excellent storage stability by adopting the above constitution. In addition, the curability of the composition of the present invention can be freely adjusted by adjusting the amount of the silyl phosphate represented by the formula (1) blended in the composition of the present invention within a predetermined range. Can do things. The composition of the present invention has thixotropy by containing the silyl phosphate, and the curability can be freely controlled without lowering the thixotropy and storage stability. Therefore, the composition of the present invention can be suitably used as a sealing agent, a waterproofing agent, a jointing agent, an adhesive, a paint, and the like. It may be a composition having a weight.
【００２１】[0021]
【実施例】以下に実施例をもって本発明を具体的に説明
する。ウレタンプレポリマーの合成例 乾燥した平均分子量３０００のポリプロピレンジオール
（旭硝子社製、エクセノール３０２０）９６０ｇ、平均
分子量５０００のポリプロピレントリオール（旭硝子社
製、プレミノール３００５）１０００ｇ、およびジオク
チルフタレート６６５ｇにジフェニルメタンジイソシア
ネート２５５．５ｇを触媒存在下、窒素気流下、８０℃
で１８時間反応させてＮＣＯ含量が１．１重量％のプレ
ポリマーを得た。The present invention will be described below in detail with reference to examples. Synthesis Example of Urethane Prepolymer 960 g of dried polypropylene diol having an average molecular weight of 3000 (Exenol 3020 manufactured by Asahi Glass Co., Ltd.), 1000 g of polypropylene triol having an average molecular weight of 5000 (Preminol 3005 manufactured by Asahi Glass Co., Ltd.), and 665 g of dioctyl phthalate to 255.5 g of diphenylmethane diisocyanate At 80 ° C. in the presence of a catalyst in a nitrogen stream
For 18 hours to obtain a prepolymer having an NCO content of 1.1% by weight.
【００２２】リン酸シリルエステルの合成例（ ＬＢ５８−ＯＳｉ） ジ（２−エチルヘキシル）ホスフェート（ＬＢ５８）１
００ｇにヘキサメチルジシラザン３０ｇを滴下、室温で
３０分、６０℃で１時間反応させた。アンモニアおよび
過剰のヘキサメチルジシラザンを減圧下で除去し目的の
化合物を得た。得られた化合物を下記表１中では、ＬＢ
５８−ＯＳｉと記す。なお、 1ＨＮＭＲにより得られた
化合物の構造を確認した。 Synthesis Example of Silyl Phosphate ( LB58-OSi) Di (2-ethylhexyl) phosphate (LB58) 1
30 g of hexamethyldisilazane was dropped into 00 g, and reacted at room temperature for 30 minutes and at 60 ° C. for 1 hour. Ammonia and excess hexamethyldisilazane were removed under reduced pressure to obtain the target compound. The obtained compound is shown in Table 1 below as LB
Write 58-OSi. In addition, the structure of the obtained compound was confirmed by 1 HNMR.
【００２３】シーラント組成物の合成 上述のウレタンプレポリマー１３０ｇに１１０℃で２４
時間乾燥させた炭酸カルシウム１００ｇ（丸尾カルシウ
ム社、シーレッツ２００）、酸化チタン１０ｇ（石原産
業、Ｒ８１０）、キシレン５ｇ、ポリ（メチルステアロ
キシシロキサン）３ｇを配合し、高粘度用混合ミキサー
で均一に分散させシーラント組成物を得た。 Synthesis of Sealant Composition 130 g of the above urethane prepolymer was added at 110 ° C. for 24 hours.
100 g of calcium carbonate (Sealed 200, Maruo Calcium Co., Ltd.) dried for 10 hours, 10 g of titanium oxide (R810, Ishihara Sangyo), 5 g of xylene, and 3 g of poly (methyl stearoxy siloxane) are mixed and uniformly dispersed with a high-viscosity mixing mixer. Then, a sealant composition was obtained.
【００２４】（実施例１〜８、比較例１）下記表１に記
載の配合でウレタン樹脂組成物を調整し、得られた組成
物について、粘度、揺変性、硬化性を下記方法により測
定し評価した。表中、化合物の単位は重量部である。試験法 １）粘度（貯蔵安定性） ２０℃で１日、および、７０℃で１日貯蔵した後、Ｂ型
粘度計を用いて測定し、それぞれ、初期粘度、貯蔵後粘
度として評価した。 ２）チクソインデックスＴＩ（揺変性） ２０℃で１日、および、７０℃で１日貯蔵した後、Ｂ型
粘度計を用いて、１ｒｐｍと２ｒｐｍで測定した粘度比
をチクソインデックスとして算出し、それぞれ、初期Ｔ
Ｉ、貯蔵後ＴＩとして評価した。この値が大きいほど、
揺変性が高いことを示す。 ３）タックフリータイム（硬化性） 実施例、比較例で得られた組成物を調整直後と、７０℃
で１日貯蔵後に、ＪＩＳ Ａ ５７５８に記載の方法に
準拠してタックフリータイムを測定した。結果を表１に
示す。(Examples 1 to 8, Comparative Example 1) A urethane resin composition was prepared according to the formulation shown in Table 1 below, and the viscosity, thixotropic property, and curability of the obtained composition were measured by the following methods. evaluated. In the table, the unit of the compound is part by weight. Test Method 1) Viscosity (Storage Stability) After storing at 20 ° C. for 1 day and at 70 ° C. for 1 day, the viscosity was measured using a B-type viscometer and evaluated as the initial viscosity and the viscosity after storage, respectively. 2) Thixo Index TI (Thixotropic) After storing at 20 ° C. for 1 day and at 70 ° C. for 1 day, the viscosity ratio measured at 1 rpm and 2 rpm using a B-type viscometer was calculated as the thixo index. , Initial T
I, evaluated as TI after storage. The higher this value, the more
It shows that thixotropic is high. 3) Tack free time (curability) Immediately after adjusting the compositions obtained in Examples and Comparative Examples,
After storage for one day, the tack-free time was measured according to the method described in JIS A 5758. Table 1 shows the results.
【００２５】[0025]
【表１】 [Table 1]
【００２６】＜表中の各成分＞ ＬＢ５８−ＯＳｉ：ジ（２−エチルヘキシル）ホスフェ
ートのトリメチルシリルエステル ＤＢＰ−ＯＳｉ：ジブチルホスフェートのトリメチルシ
リルエステル ハードナーＯＺ：オキサゾリジン系硬化剤（バイエルン
社製） ＬＢ５８ ：ジ（２−エチルヘキシル）ホスフェー
ト<Each component in the table> LB58-OSi: Trimethylsilyl ester of di (2-ethylhexyl) phosphate DBP-OSi: Trimethylsilyl ester of dibutyl phosphate Hardener OZ: Oxazolidine-based curing agent (manufactured by Bayern) LB58: Di (2) -Ethylhexyl) phosphate
【００２７】[0027]
【発明の効果】本発明の一液型湿気硬化性ウレタン樹脂
組成物は、貯蔵安定性に優れ、貯蔵後の粘度、揺変性を
変化させずに硬化性をコントロールできる。従って、本
発明の一液型湿気硬化性ウレタン樹脂組成物は、シーリ
ング剤、防水剤、目地剤、接着剤、塗料等に好適に利用
することができる。EFFECT OF THE INVENTION The one-pack type moisture-curable urethane resin composition of the present invention has excellent storage stability and can control the curability without changing the viscosity and thixotropic properties after storage. Therefore, the one-component moisture-curable urethane resin composition of the present invention can be suitably used as a sealing agent, a waterproofing agent, a jointing agent, an adhesive, a paint, and the like.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 細田 浩之 神奈川県平塚市追分２番１号 横浜ゴム 株式会社 平塚製造所内 (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 75/04 - 75/12 C08K 5/54 - 5/5415 C09D 175/04 - 175/12 C09K 3/10 ＣＡ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroyuki Hosoda 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Works (58) Field surveyed (Int. Cl. 7 , DB name) C08L 75/04 -75/12 C08K 5/54-5/5415 C09D 175/04-175/12 C09K 3/10 CA (STN)
Claims (2)
テルを含有し、リン酸シリルエステル以外の成分１００
重量部に対して、リン酸シリルエステルを０．００１〜
３０重量部含有する一液型湿気硬化性ウレタン樹脂組成
物。1. A containing urethane prepolymer and phosphoric acid silyl ester, component other than phosphoric acid silyl ester 100
0.001 to 100 parts by weight of silyl phosphate
A one-component moisture-curable urethane resin composition containing 30 parts by weight.
される化合物である請求項１に記載の一液型湿気硬化性
ウレタン樹脂組成物。 【化１】 （Ｒはアルキル基、Ｘはヘテロ原子を有していてもよい
有機基、ｎは１〜３の整数を表す。）2. The one-part moisture-curable urethane resin composition according to claim 1, wherein the silyl phosphate is a compound represented by the formula (1). Embedded image (R is an alkyl group, X is an organic group optionally having a hetero atom, and n represents an integer of 1 to 3.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17314598A JP3340962B2 (en) | 1998-06-19 | 1998-06-19 | One-part moisture-curable urethane resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17314598A JP3340962B2 (en) | 1998-06-19 | 1998-06-19 | One-part moisture-curable urethane resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000007910A JP2000007910A (en) | 2000-01-11 |
| JP3340962B2 true JP3340962B2 (en) | 2002-11-05 |
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ID=15954953
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17314598A Expired - Fee Related JP3340962B2 (en) | 1998-06-19 | 1998-06-19 | One-part moisture-curable urethane resin composition |
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| Country | Link |
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| WO2019035411A1 (en) * | 2017-08-18 | 2019-02-21 | 積水化学工業株式会社 | Moisture curable resin composition, adhesive for electronic components, and adhesive for display elements |
| EP3336117A1 (en) * | 2017-09-20 | 2018-06-20 | Basf Se | Method for the preparation of flocculation stable polyisocyanates of (cyclo)aliphatic diisocyanates in solvents |
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| Publication number | Publication date |
|---|---|
| JP2000007910A (en) | 2000-01-11 |
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