JPH058730B2 - - Google Patents
Info
- Publication number
- JPH058730B2 JPH058730B2 JP59154631A JP15463184A JPH058730B2 JP H058730 B2 JPH058730 B2 JP H058730B2 JP 59154631 A JP59154631 A JP 59154631A JP 15463184 A JP15463184 A JP 15463184A JP H058730 B2 JPH058730 B2 JP H058730B2
- Authority
- JP
- Japan
- Prior art keywords
- nco
- dehydration condensation
- examples
- moisture
- adhesive
- 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 - Lifetime
Links
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920005862 polyol Polymers 0.000 claims description 20
- 230000018044 dehydration Effects 0.000 claims description 19
- 238000006297 dehydration reaction Methods 0.000 claims description 19
- -1 alicyclic diamine Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 150000003077 polyols Chemical class 0.000 claims description 17
- 239000007859 condensation product Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 description 22
- 239000000853 adhesive Substances 0.000 description 21
- 238000005187 foaming Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000001723 curing Methods 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 239000000565 sealant Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 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 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 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 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 3
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 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
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 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
- 150000002576 ketones Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 150000004072 triols Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XPZBNIUWMDJFPW-UHFFFAOYSA-N 2,2,3-trimethylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1(C)C XPZBNIUWMDJFPW-UHFFFAOYSA-N 0.000 description 1
- AVFZQHWFGFKQIG-UHFFFAOYSA-N 2,2,3-trimethylcyclopentan-1-one Chemical compound CC1CCC(=O)C1(C)C AVFZQHWFGFKQIG-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- NMBQBIACXMPEQB-UHFFFAOYSA-N 2-butoxyethyl benzoate Chemical compound CCCCOCCOC(=O)C1=CC=CC=C1 NMBQBIACXMPEQB-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- JJKMIZGENPMJRC-UHFFFAOYSA-N 3-oxo-3-propan-2-yloxypropanoic acid Chemical compound CC(C)OC(=O)CC(O)=O JJKMIZGENPMJRC-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 239000004839 Moisture curing adhesive Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- BWLKKFSDKDJGDZ-UHFFFAOYSA-N [isocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)C1=CC=CC=C1 BWLKKFSDKDJGDZ-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013466 adhesive and sealant Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012962 antiaging additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004359 castor oil Chemical class 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical class OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 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
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Chemical class CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Description
産業上の利用分野
本発明は湿気硬化性ポリウレタン組成物、更に
詳しくは、湿気硬化に伴い発生する炭酸ガスによ
つて惹起する発泡を抑制したシーリング材および
初期硬化過程における粘着特性に優れた粘接着型
の接着剤として有用なポリウレタン組成物に関す
る。
従来技術と解決すべき問題点
ポリウレタン素材はフオーム、プラスチツク成
形体、ゴム製品などの他に、シーリング材や接着
剤など多方面に広く利用され、またポリウレタン
は機能設計が容易であるため、各種の製品開発研
究が多く行われている。就中、湿気硬化性のシー
リング材ではイソシアネート基（以下、NCOと
称す）と水分の反応副生物である炭酸ガスによつ
て惹起する発泡現象があり、また湿気硬化性の接
着剤では初期の硬化反応段階において粘着力が乏
しく、圧締し仮止めを必要とするなどの難点があ
つた。湿気硬化性のシーリング材および接着剤の
いずれにおいても、硬化速度の調整との関係から
上述の問題が惹起する。
ところで、このような状況下、例えばNCOを
有するウレタンプレポリマーとジアミン／ケトン
の反応生成物とから成るポリウレタン組成物にお
いて、特定のジアミンを用いることにより硬化速
度を調整しうることが知られている（特公昭46−
10550号参照）。しかし、この組成物では上記問題
の解決には不満足であつた。
本発明者らは、かかる公知組成物について検討
を加えたところ意外にも、通常反応設計する
NCOに対しアミン当量割合を過少比率の不均衡
にすると、所望の硬化速度が得られること、しか
も一般にNCOと水分の反応硬化の割合が大とな
つて発泡が多発生すると考えられるのに反し、該
ウレタン硬化物の発泡がほとんど皆無であるこ
と、また初期の硬化過程に伴つて強力な粘着力が
得られることを見出した。更にこの知見に基づき
鋭意研究を進めたところ、特定の活性NCOを有
するウレタンプレポリマーに対し、脂環式ジアミ
ンとカルボニル化合物の脱水縮合生成物を配合
し、NCOに対する脱水縮合生成物のアミン当量
の割合を過少比率の不均衡にした場合、湿気硬化
性シーリング材の発泡抑制と接着剤としての粘着
力の向上が計れることを見出し、本発明を完成さ
せるに至つた。
即ち、本発明は、ポリロール類と過剰の芳香族
ポリイソシアネート類との反応により得られる活
性NCOを有するウレタンプレポリマー、および
脂環式ジアミンとカルボニル化合物の脱水縮合生
成物から成り、NCOに対しアミン当量比が0.2〜
0.55であることを特徴とする湿気硬化性ポリウレ
タン組成物に係るものであつて、その目的とする
ところは、発泡を抑制した湿気硬化性のシーリン
グ材および粘接着型接着剤を提供することであ
る。
発明の構成と効果
本発明で用いるウレタンプレポリマーは、ポリ
エーテルポリオール、ポリエステルポリオール、
水酸基含有ポリブタジエンポリオール、アクリル
ポリオール、ヒマシ油の誘導体、トール油誘導体
などのポリオール類と過剰の芳香族ポリイソシア
ネート類との反応により製造される。
ポリエーテルポリオール、すなわちポリオキシ
アルキレンエーテルポリオールは、活性水素２個
以上を有する低分子量活性水素化合物の１種また
は２種以上の存在下にプロピレンオキサイドおよ
びエチレンオキサイドを開環重合させて得られる
ランダムまたはブロツク共重合体のポリオキシエ
チレン−プロピレンポリオールおよびテトラヒド
ロフランの開環重合によつて得られるポリオキシ
テトラメチレングリコールであつて、１分子中に
２〜３個のヒドロキシ基を有する。低分子量活性
水素化合物としては、エチレングリコール、プロ
ピレングリコール、ブチレングリコール、１，６
−ヘキサンジオールなどのジオール類、グリセリ
ン、トリメチロールプロパン、１，２，６−ヘキ
サントリオールなどのトリオール類、アンモニ
ア、メチルアミン、エチルアミン、プロピルアミ
ン、ブチルアミンなどのアミン類がある。このポ
リオキシアルキレンエーテルポリオールは分子量
500〜10000、１分子中のヒドロキシ基含量２〜３
個のものが望ましい。これらは所望の物性により
種々の分子量および官能基数のものが用いられ、
単独でもまた２種以上を併用して用いてもよい。
ポリエステルポリオールは、一般に、多塩基酸
と多価アルコールとの反応あるいは多価アルコー
ルにε−カプロラクトンなどを開環重合して製造
され、末端にヒドロキシ基を有する。その多塩基
酸成分としては、フタル酸、アジピン酸、テレフ
タル酸、イソフタル酸、セバシン酸、二量化リノ
レイン酸、マレイン酸、およびそれらのジ低級ア
ルキルエステルなどが挙げられる。多価アルコー
ルとしては前記と同じジオール類、トリオール類
のほか、ジエチレングリコール、トリエチレング
リコール、ジプロピレングリコール、トリプロピ
レングリコールなども含まれる。本発明のポリウ
レタン組成物を各種接着剤に用いる場合には、こ
のポリエステルポリオールを前記ポリエーテルポ
リオールと併用することも好ましく、また合成樹
脂フイルムなどのラミネーシヨン加工用接着剤と
して用いる場合にはポリエステルポリオールを単
独で用いてもよい。このように、ポリエーテルポ
リオール、ポリエステルポリオール、その他前記
のごときポリオール類は、本発明のポリウレタン
組成物の用途、所望の物性に応じて、それぞれ単
独でまた２種以上を併用して用いる。
上記ポリオール類と反応させる芳香族ポリイソ
シアネート類としては、トリレンジイソシアネー
ト（TDI）、ジフエニルメタンジイソシアネート
（MDI）、ナフチレンジイソシアネートなどが挙
げられ、特にTDIやMDIが好適である。
上記ポリオール類と芳香族ポリイソシアネート
類を、ポリオール成分のヒドロキシ基に対し芳香
族ポリイソシアネート類の活性NCOが１以上と
なるように反応させて所望のウレタンプレポリマ
ーを得る。例えば、両成分の割合を、1.3≦
NCO／OH≦10の割合にて、70〜100℃で数時間
反応させる。この反応に際して、通常の触媒、可
塑剤および溶剤を用いることができる。得られる
ウレタンプレポリマーは活性NCOが0.5〜15％
（重量％、以下同様）の範囲となるように調整し、
この範囲内で所望の物性、用途に応じて最も好ま
しい含量を選択する。例えば、接着剤の用途では
３〜15％、シーリング材には0.5〜5.0％が望まし
い。
本発明で用いる脱水縮合生成物は、脂環式ジア
ミンとカルボニル化合物を脱水縮合反応させるこ
とにより製造される。
脂環式ジアミンとしては、例えば１，８−ｐ−
メンタンジアミン、イソホロンジアミン、ジアミ
ノシクロヘキサン、４，4′−メチレンビス（シク
ロヘキシルアミン）、１，３−ビス（アミノメチ
ル）シクロヘキサン、３−アミノメチル−３，
３，５−トリメチルシクロヘキシルアミン等が挙
げられ、特に１，８−ｐ−メンタンジアミン、イ
ソホロンジアミンが望ましい。
またカルボニル化合物としては、例えばアセト
アルデヒド、プロピオンアルデヒド、ｎ−ブチル
アルデヒド、イソブチルアルデヒド、ジエチルア
セトアルデヒド、２−エチルヘキシルアルデヒ
ド、グリオキサール、ベルブアルデヒドなどのア
ルデヒド化合物、シクロペンタノン、トリメチル
シクロペンタノン、シクロヘキサノン、トリメチ
ルシクロヘキサノンなどの環状ケトン化合物、ア
セトン、メチルエチルケトン、メチルプロピルケ
トン、メチルイソプロピルケトン、メチルイソブ
チルケトン、ジエチルケトン、ジプロピルケト
ン、ジイソプロピルケトン、ジブチルケトン、ジ
イソブチルケトンなどの脂肪族ケトン化合物、ア
セチルアセトン、アセト酢酸メチル、アセト酢酸
エチル、マロン酸ジメチル、マロン酸ジエチル、
マロン酸メチルエチル、ジベンゾインメタンなど
のβ−ジカルボニル化合物が挙げられる。
上記脱水縮合反応は通常、吸水剤の存在下に、
または加熱還流下に水分を留出させながら行う。
具体的には脂環式ジアミンと化学量論的にほぼ当
量または過剰量のカルボニル化合物をトルエン、
キシレン、ベンゼン等の有機溶媒中、加熱還流下
水分を除去しながら脱水縮合を行う。得られる反
応生成物はそのまま、あるいは所望により系中の
有機溶媒を加熱蒸留で完全に除去してから使用に
供する。更に系中の水分による加水分解を抑制す
るため、吸水剤としてモレキユラーシーブ、無水
硫酸マグネシウムなどを添加しておけば、放置期
間中の安定性が向上する。このように脂感式ジア
ミンのアミノ基をカルボニル化合物でブロツクし
た脱水縮合生成物は、脱水状態では安定である
が、水分存在下で加水分解して活性水素基を生成
するので、活性NCOを有するウレタンプレポリ
マーの架橋剤として使用することができる。
本発明に係る湿気硬化性ポリウレタン組成物
は、上記ウレタンプレポリマーと脱水縮合生成物
を必須成分とし、その配合割合は前者のNCOに
対し後者のアミン当量比が0.2〜0.55、好ましく
は0.3〜0.5となるように設定する。かかる配合割
合では、アミノ基がNCOと優先的に反応し、初
期段階のNCOとアミノ基の反応によつてウレタ
ンプレポリマーが高分子量化して物性発現があつ
てから、残余のNCOが水分と反応して完全硬化
する訳であるが、この段階では水分との反応によ
る炭酸ガスの圧力よりも、硬化物の物理的強度が
強いので、発泡を抑制することができるものと考
えられる。また脂環式ジアミンが架橋剤として作
用し、これとウレタンプレポリマーが反応して高
分子量化するので、ウレタンプレポリマーの粘着
力が発現し、接着剤としての初期の接着力が増大
するので、軽い圧締を行つておけば仮止めする手
間を省くこともできる。特に長尺物の床材シート
等の巻き癖がある場合の接着において、端部のは
ねかえろうとする力よりも粘着力が大であれば、
硬化するまで圧締することなく接着作業が完了す
る等の効果がある。
なお、上記アミン当量比はシーリング材として
用いる場合には0.55以下に設定しておくことが望
ましい。0.55を越えると、アミノ基がNCOと反
応しながら、同時にNCOと水分との反応を促進
する触媒として働き、タツクフリー時間が短く、
また貯蔵安定性が悪くなり、シーリング材として
実用化が困難となる。
以上の構成から成る本発明組成物は、必要に応
じ接着剤やシーリング材の用途に合せて通常配合
されている各種の添加剤、例えば充填剤、可塑
剤、溶剤、硬化促進用触媒、老化防止剤、顔料な
どが配合されてよい。
充填剤としては、NCOと反応する官能基を有
しない不活性であることが必要である。例えばカ
ーボブラツク、炭酸カルシウム、クレー、タルク
等が挙げられ、これらの単独または混合物を70％
以下の割合で配合する。可塑剤としては、ジオク
チルフタレート、ブチルベンジルフタレート、ジ
ノニルフタレートなどのフタル酸エステル類、ジ
エチレングリコールジベンゾエート、エチレング
リコールモノブチルエーテルベンゾエートなどの
安息香酸エステル類、部分水素添加ターフエニ
ル、アルキル多環芳香族炭化水素類、塩素化パラ
フイン類が挙げられ、それらは20％以下の量で配
合される。また溶剤としては、トルエン、キシレ
ンなどの芳香族炭化水素類、エステル類、ケトン
類、エーテル類などが含まれる。なお、これら充
填剤、可塑剤および溶剤などはNCOに対して不
活性である必要があるほか、無水のものである必
要があり、そのため、乾燥、脱水処理をほどこす
のが好ましい。
硬化促進用の触媒としては、Ｎ−アルキルベン
ジルアミン、Ｎ−アルキルモルホリン、Ｎ−アル
キル脂肪族ポリアミン、Ｎ−アルキルピペラジ
ン、トリエチレンジアミン、錫、鉛、コバルト、
マンガンおよび鉄などの重金属のナフテン酸また
はオクテン酸塩、ジブチル錫ジラウレート、ジブ
チル錫マレエートなどが挙げられる。
さらに、無水ケイ酸、酸化防止剤、紫外線吸収
剤、タレ止め剤なども適宜配合してもよい。
本発明のポリウレタン組成物はいわゆる二液型
に調製してもよいが、両必須成分を配合したのち
長期間保存した場合でも、脱水縮合生成物の加水
分解による組成物の粘度上昇、ゲル化などを生ず
ることなく安定に保持し得るため、取扱い上の容
易さ、経済的観点などからも一液型に調製するの
が好ましい。この組成物の調製は常法にしたがつ
て行なわれ、例えば、窒素ガスと置換され得る、
保温ジヤケツト付密閉式撹拌混練装置を用いて、
まずポリオール成分とポリイソシアネート化合物
とを加熱反応させてウレタンプレポリマーを生成
させ、これに、予め乾燥した充填剤、顔料、可塑
剤、溶剤、その他の添加剤を順次加え、最後に脱
水縮合生成物を添加して撹拌混練して製品とす
る。
次に製造例、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。
製造例 １
ジフエニルメタン−４，4′−ジイソシアネート
250ｇとポリエステルポリオール（分子量2000、
ジオール）380ｇおよびポリエーテルポリオール
（分子量3000、ジオール）540ｇを窒素ガス還流
下、80℃で加熱撹拌しながら３時間反応させ、活
性NCO含有率4.5％のウレタンプレポリマーを得
る。
製造例 ２
ジフエニルメタン−４，4′−ジイソシアネート
76.6ｇとポリエーテルポリオール（分子量2000、
ジオール）180ｇおよび（分子量3000、トリオー
ル）180ｇを製造例１同様に反応させて、活性
NCO含有率2.4％のウレタンプレポリマーを得
る。
製造例 ３
ジフエニルメタンイソシアネート72ｇとポリエ
ーテルポリオール（分子量2000、ジオール）360
ｇを製造例１と同様に反応させて、活性NCO含
有率2.1％のウレタンプレポリマーを得る。
製造例 ４
１，８−ｐ−メンタンジアミン170ｇと２−エ
チルヘキシルアルデヒド390ｇをベンゼンに溶解
し、水分定量器を用いて加熱還流下、８時間脱水
縮合反応を行い理論反応値の水分を除去し、次い
で溶媒のベンゼンと未反応の２−エチルヘキシル
アルデヒドを加熱減圧下に除去して、脱水縮合生
成物を得る。
製造例 ５
１，８−ｐ−メタンジアミン170ｇとイソブチ
ルアルデヒド260ｇを製造例４と同様に、脱水縮
合反応および溶媒除去を行つて脱水縮合生成物を
得る。
実施例１〜３および比較例１、２
製造例１のウレタンプレポリマーと製造例４の
脱水縮合生成物を表１に示す割合で配合し、接着
剤を調製する。
この接着剤を１インチ巾×20cm長さに裁断した
スレート板にくしごてで塗布し、これに同寸法に
裁断したポリ塩化ビニルシート（ロンシール加工
業社製、ロンリユーム
）を、10分、20分、30
分、60分のオープンタイム（接着剤を塗布してか
ら貼り合せまでの時間）後に重ね合せ、軽く圧締
する。直ちにポリ塩化ビニルシートを裏側とし水
平にした状態で、一端に50ｇの分銅をとりつけ、
シートが落下するまでの時間をストツプウオツチ
で測定するか、または落下しない場合は60秒後の
はくり長さを測定する方法により、初期の粘着力
を評価する。結果を表１に示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a moisture-curable polyurethane composition, and more specifically, a sealant that suppresses foaming caused by carbon dioxide gas generated during moisture curing, and a adhesive that has excellent adhesive properties during the initial curing process. The present invention relates to a polyurethane composition useful as a mold-fitting adhesive. Conventional technology and problems to be solved Polyurethane materials are widely used in various fields such as foams, plastic molded bodies, rubber products, etc., as well as sealants and adhesives, and polyurethane is easy to design functions, so it can be used in various applications. A lot of product development research is being done. In particular, moisture-curing sealants have a foaming phenomenon caused by carbon dioxide gas, which is a byproduct of the reaction between isocyanate groups (hereinafter referred to as NCO) and moisture, and moisture-curing adhesives have a foaming phenomenon that occurs during initial curing. There were drawbacks such as poor adhesive strength during the reaction stage and the need for temporary clamping. In both moisture-curable sealants and adhesives, the above-mentioned problems arise due to their relationship with the adjustment of curing speed. By the way, under such circumstances, it is known that, for example, in a polyurethane composition consisting of a urethane prepolymer having NCO and a reaction product of diamine/ketone, the curing rate can be adjusted by using a specific diamine. (Tokuko Showa 46-
(See No. 10550). However, this composition was unsatisfactory in solving the above problems. The present inventors investigated such known compositions and found that, unexpectedly, reactions are normally designed.
If the ratio of amine equivalent to NCO is too small, the desired curing speed can be obtained.However, contrary to the general belief that the reaction curing ratio of NCO and water increases and foaming occurs frequently. It has been found that the cured urethane product has almost no foaming and that strong adhesive strength is obtained during the initial curing process. Further intensive research based on this knowledge revealed that a dehydration condensation product of an alicyclic diamine and a carbonyl compound was blended into a urethane prepolymer having a specific active NCO, and the amine equivalent of the dehydration condensation product relative to NCO was calculated. The inventors have discovered that when the ratio is too small or unbalanced, the foaming of the moisture-curable sealant can be suppressed and the adhesive strength of the adhesive can be improved, leading to the completion of the present invention. That is, the present invention consists of a urethane prepolymer having active NCO obtained by reacting polyrolls with an excess of aromatic polyisocyanate, and a dehydration condensation product of an alicyclic diamine and a carbonyl compound. Equivalence ratio is 0.2~
0.55, the purpose of which is to provide a moisture-curable sealant and a pressure-sensitive adhesive that suppresses foaming. be. Structure and Effects of the Invention The urethane prepolymer used in the present invention includes polyether polyol, polyester polyol,
It is produced by reacting polyols such as hydroxyl group-containing polybutadiene polyols, acrylic polyols, castor oil derivatives, and tall oil derivatives with an excess of aromatic polyisocyanates. Polyether polyols, that is, polyoxyalkylene ether polyols, are random or polyether polyols obtained by ring-opening polymerization of propylene oxide and ethylene oxide in the presence of one or more low molecular weight active hydrogen compounds having two or more active hydrogen atoms. It is a polyoxytetramethylene glycol obtained by ring-opening polymerization of a block copolymer of polyoxyethylene-propylene polyol and tetrahydrofuran, and has 2 to 3 hydroxy groups in one molecule. Examples of low molecular weight active hydrogen compounds include ethylene glycol, propylene glycol, butylene glycol, 1,6
- Diols such as hexanediol, triols such as glycerin, trimethylolpropane, and 1,2,6-hexanetriol, and amines such as ammonia, methylamine, ethylamine, propylamine, and butylamine. This polyoxyalkylene ether polyol has a molecular weight of
500-10000, hydroxy group content in 1 molecule 2-3
Preferably one. These are used with various molecular weights and numbers of functional groups depending on the desired physical properties.
They may be used alone or in combination of two or more. Polyester polyols are generally produced by reacting a polybasic acid with a polyhydric alcohol or by ring-opening polymerization of ε-caprolactone or the like with a polyhydric alcohol, and have a hydroxyl group at the end. Examples of the polybasic acid component include phthalic acid, adipic acid, terephthalic acid, isophthalic acid, sebacic acid, dimerized linoleic acid, maleic acid, and di-lower alkyl esters thereof. Polyhydric alcohols include the same diols and triols as mentioned above, as well as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and the like. When the polyurethane composition of the present invention is used in various adhesives, it is also preferable to use this polyester polyol in combination with the above-mentioned polyether polyol, and when used as an adhesive for laminating synthetic resin films, the polyester polyol may be used alone. As described above, polyether polyols, polyester polyols, and other polyols such as those mentioned above can be used alone or in combination of two or more types depending on the use and desired physical properties of the polyurethane composition of the present invention. Examples of the aromatic polyisocyanates to be reacted with the above polyols include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and naphthylene diisocyanate, with TDI and MDI being particularly preferred. A desired urethane prepolymer is obtained by reacting the above polyols and aromatic polyisocyanates such that the active NCO of the aromatic polyisocyanates is 1 or more with respect to the hydroxy groups of the polyol component. For example, the ratio of both components is 1.3≦
React at 70-100°C for several hours at a ratio of NCO/OH≦10. In this reaction, conventional catalysts, plasticizers and solvents can be used. The resulting urethane prepolymer has an active NCO of 0.5-15%
(weight%, the same applies hereafter),
The most preferable content is selected within this range depending on the desired physical properties and use. For example, 3 to 15% is desirable for adhesive applications, and 0.5 to 5.0% for sealants. The dehydration condensation product used in the present invention is produced by subjecting an alicyclic diamine and a carbonyl compound to a dehydration condensation reaction. As the alicyclic diamine, for example, 1,8-p-
Menthanediamine, isophoronediamine, diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 3-aminomethyl-3,
Examples include 3,5-trimethylcyclohexylamine, and 1,8-p-menthanediamine and isophoronediamine are particularly preferred. Examples of carbonyl compounds include aldehyde compounds such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, 2-ethylhexylaldehyde, glyoxal, and berubaldehyde, cyclopentanone, trimethylcyclopentanone, cyclohexanone, and trimethylcyclohexanone. Cyclic ketone compounds such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, aliphatic ketone compounds such as diisobutyl ketone, acetylacetone, methyl acetoacetate, Ethyl acetoacetate, dimethyl malonate, diethyl malonate,
Examples include β-dicarbonyl compounds such as methylethyl malonate and dibenzoinmethane. The above dehydration condensation reaction is usually carried out in the presence of a water absorbing agent.
Alternatively, it is carried out while distilling off water under heating and reflux.
Specifically, a stoichiometrically equivalent or excessive amount of the carbonyl compound to the alicyclic diamine was added to toluene,
Dehydration condensation is carried out in an organic solvent such as xylene or benzene while removing moisture under heating under reflux. The resulting reaction product is used as it is, or if desired, after the organic solvent in the system is completely removed by heated distillation. Furthermore, in order to suppress hydrolysis due to moisture in the system, if a water absorbing agent such as molecular sieve or anhydrous magnesium sulfate is added, stability during the standing period will be improved. The dehydration condensation product obtained by blocking the amino group of a fat-sensitive diamine with a carbonyl compound is stable in a dehydrated state, but it hydrolyzes in the presence of water to generate active hydrogen groups, so it has active NCO. It can be used as a crosslinking agent for urethane prepolymers. The moisture-curable polyurethane composition according to the present invention has the above-mentioned urethane prepolymer and dehydration condensation product as essential components, and the blending ratio is such that the amine equivalent ratio of the latter to NCO of the former is 0.2 to 0.55, preferably 0.3 to 0.5. Set it so that At such a blending ratio, amino groups preferentially react with NCO, and after the reaction between NCO and amino groups in the initial stage increases the molecular weight of the urethane prepolymer and develops physical properties, the remaining NCO reacts with moisture. However, at this stage, the physical strength of the cured product is stronger than the pressure of carbon dioxide gas due to the reaction with moisture, so it is thought that foaming can be suppressed. In addition, the alicyclic diamine acts as a crosslinking agent, and the urethane prepolymer reacts with it to increase its molecular weight, which develops the adhesive strength of the urethane prepolymer and increases its initial adhesive strength as an adhesive. If you apply light pressure, you can save yourself the trouble of temporarily fixing. Especially when adhering a long flooring sheet that has a tendency to curl, if the adhesive force is greater than the force that tends to bounce off the end,
This has the effect of completing the adhesion work without having to press it until it hardens. Note that the amine equivalent ratio is desirably set to 0.55 or less when used as a sealing material. When it exceeds 0.55, the amino group reacts with NCO and at the same time acts as a catalyst to promote the reaction between NCO and water, resulting in a short tack-free time.
Furthermore, storage stability deteriorates, making it difficult to put it to practical use as a sealing material. The composition of the present invention having the above-mentioned structure may contain various additives, such as fillers, plasticizers, solvents, catalysts for accelerating curing, and anti-aging additives, which are usually blended according to the application of adhesives and sealants, as necessary. Agents, pigments, etc. may be added. The filler must be inert and do not have a functional group that reacts with NCO. Examples include carbo black, calcium carbonate, clay, talc, etc., and 70% of these alone or in combination.
Mix in the following proportions. Examples of plasticizers include phthalic acid esters such as dioctyl phthalate, butylbenzyl phthalate and dinonyl phthalate, benzoic acid esters such as diethylene glycol dibenzoate and ethylene glycol monobutyl ether benzoate, partially hydrogenated terphenyl, and alkyl polycyclic aromatic hydrocarbons. and chlorinated paraffins, which are incorporated in an amount of 20% or less. Further, examples of the solvent include aromatic hydrocarbons such as toluene and xylene, esters, ketones, and ethers. Note that these fillers, plasticizers, solvents, etc. need to be inert to NCO and also need to be anhydrous, so it is preferable to dry and dehydrate them. As catalysts for accelerating curing, N-alkylbenzylamine, N-alkylmorpholine, N-alkyl aliphatic polyamine, N-alkylpiperazine, triethylenediamine, tin, lead, cobalt,
Examples include naphthenic acid or octenoic acid salts of heavy metals such as manganese and iron, dibutyltin dilaurate, dibutyltin maleate, and the like. Furthermore, silicic anhydride, antioxidants, ultraviolet absorbers, anti-sagging agents, etc. may be added as appropriate. The polyurethane composition of the present invention may be prepared in a so-called two-component type, but even if it is stored for a long time after blending both essential components, the composition may suffer from increased viscosity and gelation due to hydrolysis of the dehydration condensation product. It is preferable to prepare it in a one-component form from the viewpoint of ease of handling and economical aspects, since it can be stably maintained without causing any problems. The preparation of this composition is carried out according to conventional methods, for example, it may be substituted with nitrogen gas,
Using a closed-type stirring and kneading device with a heat-insulating jacket,
First, a polyol component and a polyisocyanate compound are heated and reacted to form a urethane prepolymer. To this, pre-dried fillers, pigments, plasticizers, solvents, and other additives are sequentially added, and finally a dehydration condensation product is formed. is added and stirred and kneaded to form a product. Next, the present invention will be explained in more detail with reference to Production Examples, Examples, and Comparative Examples. Production example 1 Diphenylmethane-4,4'-diisocyanate
250g and polyester polyol (molecular weight 2000,
380 g of diol) and 540 g of polyether polyol (molecular weight 3000, diol) were reacted under nitrogen gas reflux at 80° C. for 3 hours with heating and stirring to obtain a urethane prepolymer with an active NCO content of 4.5%. Production example 2 diphenylmethane-4,4'-diisocyanate
76.6g and polyether polyol (molecular weight 2000,
180 g of diol) and 180 g of triol (molecular weight 3000) were reacted in the same manner as in Production Example 1, and the activity
A urethane prepolymer with an NCO content of 2.4% is obtained. Production example 3 72g of diphenylmethane isocyanate and polyether polyol (molecular weight 2000, diol) 360g
g is reacted in the same manner as in Production Example 1 to obtain a urethane prepolymer with an active NCO content of 2.1%. Production Example 4 170 g of 1,8-p-menthanediamine and 390 g of 2-ethylhexylaldehyde were dissolved in benzene, and a dehydration condensation reaction was performed for 8 hours under heating under reflux using a moisture meter to remove the theoretical reaction value of moisture. Then, benzene as a solvent and unreacted 2-ethylhexylaldehyde are removed under heating and reduced pressure to obtain a dehydration condensation product. Production Example 5 170 g of 1,8-p-methanediamine and 260 g of isobutyraldehyde are subjected to a dehydration condensation reaction and solvent removal in the same manner as in Production Example 4 to obtain a dehydration condensation product. Examples 1 to 3 and Comparative Examples 1 and 2 The urethane prepolymer of Production Example 1 and the dehydration condensation product of Production Example 4 are blended in the proportions shown in Table 1 to prepare an adhesive. Apply this adhesive with a trowel to a slate board cut to 1 inch wide x 20 cm long, and then apply a polyvinyl chloride sheet (Lonlium, manufactured by Ronseal Manufacturing Co., Ltd.) cut to the same size to this for 10 minutes and 20 minutes. minutes, 30
After an open time of 60 minutes (the time from applying the adhesive to pasting), stack them together and lightly press them together. Immediately, with the polyvinyl chloride sheet on the back side and horizontal, attach a 50g weight to one end.
Initial adhesion strength is evaluated by measuring the time until the sheet falls with a stopwatch, or by measuring the peeling length after 60 seconds if the sheet does not fall. The results are shown in Table 1.
【表】
表１の結果から明らかなように、比較例１では
オープタイム60分後でほとんど硬化して接着不能
であつたり、また比較例２では粘着力がほとんど
皆無であつて、50ｇの荷重により落下した。一
方、実施例１〜３ではオープンタイム10分でも５
秒以上保持し、しかも60分後においても充分接着
可能であり、粘着力も増大している。
実施例４〜７および比較例３〜５
製造例２のウレタンプレポリマーと製造例５の
脱水縮合生成物、およびジオクチルフタレート
（DOP）と炭酸カルシウムを表２に示す割合で配
合してシーリング材を調製する。
このシーリング材をポリエチレン板上に約30mm
の厚さに塗布し、20℃雰囲気中での硬化速度の指
標としてタツクフリー（指触により組成物が付着
しなくなるまでの時間）を測定し、また35℃／90
％R.Hの雰囲気中での３日硬化後の中央部切断面
の発泡状態を目視判定する。貯蔵安定性試験は、
組成物が放置期間中に固化したり、粘度上昇する
かどうかの判定であつて、組成物をサンプルビン
に収容し、窒素ガスにより置換密封して40℃の恆
温器に２日間放置して判定する。これらの結果を
表２に示す。[Table] As is clear from the results in Table 1, Comparative Example 1 was almost cured after 60 minutes of open time and could not be bonded, and Comparative Example 2 had almost no adhesive force and had no adhesive force when applied under a load of 50 g. fell due to On the other hand, in Examples 1 to 3, even if the open time was 10 minutes, the
It can be held for more than 2 seconds, and even after 60 minutes, it can be fully bonded, and the adhesive strength has also increased. Examples 4 to 7 and Comparative Examples 3 to 5 A sealant was prepared by blending the urethane prepolymer of Production Example 2, the dehydration condensation product of Production Example 5, and dioctyl phthalate (DOP) and calcium carbonate in the proportions shown in Table 2. Prepare. Apply this sealing material approximately 30mm onto the polyethylene plate.
tack-free (time until the composition stops adhering to the touch) was measured as an indicator of curing speed in an atmosphere of 20°C, and 35°C/90°C.
After curing for 3 days in an atmosphere of %RH, the foaming state of the central cut surface was visually determined. Storage stability test
To determine whether the composition solidifies or increases in viscosity during the standing period, the composition is placed in a sample bottle, sealed with nitrogen gas, and left in an incubator at 40°C for 2 days. do. These results are shown in Table 2.
【表】
△
○
＊＊) ○：ほとんど粘度上昇なし、×：固化。
表２の結果から明らかなように、実施例４〜７
では硬化時間が１時間から15時間であつて、発泡
も皆無乃至少しの発泡であつた。一方、比較例
３、５では発泡は良好であるも、硬化速度が速く
実用上問題で、貯蔵安定性に問題がある。また比
較例４では発泡が多く発生した。
実施例８〜11および比較例６〜８
製造例３のウレタンプレポリマーと製造例４の
脱水縮合生成物、およびDOPと炭酸カルシウム
を表３に示す割合で配合してシーリング材を調製
し、これを実施例４〜７と同様にタツクフリー、
発泡状態、貯蔵安定性を試験する。結果を表３に
示す。[Table] △
○
**) ○: Almost no increase in viscosity, ×: Solidification.
As is clear from the results in Table 2, Examples 4 to 7
The curing time was from 1 hour to 15 hours, and there was no to slight foaming. On the other hand, in Comparative Examples 3 and 5, although the foaming was good, the curing speed was fast, which was a practical problem, and there were problems with storage stability. Further, in Comparative Example 4, a lot of foaming occurred. Examples 8 to 11 and Comparative Examples 6 to 8 A sealing material was prepared by blending the urethane prepolymer of Production Example 3, the dehydration condensation product of Production Example 4, and DOP and calcium carbonate in the proportions shown in Table 3. As in Examples 4 to 7, tack-free,
Test foaming state and storage stability. The results are shown in Table 3.
【表】
△
○ ×
＊＊) ○：粘度上昇なし、×：固化。
表３の結果から明らかなように、実施例８〜11
ではタツクフリータイムが２時間から23時間であ
つて、発泡状態も良好であつた。しかし、比較例
では発泡が著しいか、もしくは硬化不可であり、
貯蔵安定性試験では固化した。[Table] △
○ ×
**) ○: No increase in viscosity, ×: Solidification.
As is clear from the results in Table 3, Examples 8 to 11
The tack-free time was 2 to 23 hours, and the foaming state was good. However, in the comparative examples, foaming was significant or it could not be cured.
It solidified in the storage stability test.
Claims (1)
ート類との反応により得られる活性イソシアネー
ト基を有するウレタンポリマー、および脂環式ジ
アミンとカルボニル化合物の脱水縮合生成物から
成り、イソシアネート基に対しアミン当量比が
0.2〜0.55であることを特徴とする湿気硬化性ポ
リウレタン組成物。1 Consists of a urethane polymer having active isocyanate groups obtained by the reaction of polyols and excess aromatic polyisocyanates, and a dehydration condensation product of an alicyclic diamine and a carbonyl compound, with an equivalent ratio of amines to isocyanate groups.
A moisture-curable polyurethane composition characterized in that the moisture content is 0.2 to 0.55.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59154631A JPS6131418A (en) | 1984-07-24 | 1984-07-24 | Moisture-curing polyurethane composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59154631A JPS6131418A (en) | 1984-07-24 | 1984-07-24 | Moisture-curing polyurethane composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6131418A JPS6131418A (en) | 1986-02-13 |
| JPH058730B2 true JPH058730B2 (en) | 1993-02-03 |
Family
ID=15588414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59154631A Granted JPS6131418A (en) | 1984-07-24 | 1984-07-24 | Moisture-curing polyurethane composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6131418A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439268A (en) * | 2018-10-31 | 2019-03-08 | 烟台德邦科技有限公司 | A kind of photovoltaic imbrication component low Tg, the conducting resinl of low silver content |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH669955A5 (en) * | 1986-08-04 | 1989-04-28 | Sika Ag | |
| WO1988006165A1 (en) * | 1987-02-20 | 1988-08-25 | Teroson Gmbh | Sealants and adhesives and their use |
| ES2208660T3 (en) * | 1994-06-06 | 2004-06-16 | Basf Corporation | COATING COMPOSITIONS CONTAINING ALDIMINE AND ISOCIANATE AND PROCESS FOR PREPARATION. |
| JP4291887B2 (en) * | 1995-12-14 | 2009-07-08 | 横浜ゴム株式会社 | Two-component polyurethane sealant composition |
| DE60135209D1 (en) | 2000-03-29 | 2008-09-18 | Sekisui Chemical Co Ltd | PHOTOREACTIVE ADHESIVE COMPOSITION AND METHOD OF JOINING THE SAME |
| EP2062926A1 (en) * | 2007-11-21 | 2009-05-27 | Sika Technology AG | Polyurethane polymer for reversible adhesive joints |
| JP5370635B2 (en) * | 2008-07-14 | 2013-12-18 | セメダイン株式会社 | Paint base material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60161417A (en) * | 1984-01-11 | 1985-08-23 | アメリカン・サイアナミド・カンパニー | Ketimine-containing coating composition |
-
1984
- 1984-07-24 JP JP59154631A patent/JPS6131418A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60161417A (en) * | 1984-01-11 | 1985-08-23 | アメリカン・サイアナミド・カンパニー | Ketimine-containing coating composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439268A (en) * | 2018-10-31 | 2019-03-08 | 烟台德邦科技有限公司 | A kind of photovoltaic imbrication component low Tg, the conducting resinl of low silver content |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6131418A (en) | 1986-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4694093A (en) | Polyurethane resin composition | |
| US20070004893A1 (en) | Two-constituent polyurethane composition having high early strength | |
| EP1678230B1 (en) | Two-component polyurethane compound exhibiting a high early strength | |
| RU2291162C2 (en) | Polyaldimine-containing polyurethane composition | |
| EP2183294B1 (en) | Two part polyurethane curable composition having substantially consistent g-modulus across the range of use temperatures | |
| US6136942A (en) | Latent amino groups and isocyanate groups comprising polyurethane prepolymers, method for their production and their use | |
| EP3562853B1 (en) | Two-component polyurethane adhesive | |
| CA1315441C (en) | Catalyzed fast cure polyurethane sealant composition | |
| JP4019446B2 (en) | Two-component curable urethane composition for coating materials | |
| JP2020536136A (en) | Isocyanate functional adhesive that binds to coatings based on silanized acrylic polyol without primer | |
| JPH058730B2 (en) | ||
| KR20180016516A (en) | Adhesive composition and method for producing the same | |
| JP3560554B2 (en) | Two-component adhesive and bonding method using the same | |
| JP3608036B2 (en) | Moisture curable urethane resin composition and waterproof material | |
| JPH0251950B2 (en) | ||
| JPH0764907B2 (en) | Urethane-based moisture-curable composition | |
| CN111344324B (en) | Polyurethanes with (5-alkyl-1, 3-dioxolane-2-one-4-yl) end groups and use thereof | |
| JPH0326711B2 (en) | ||
| JPH09278857A (en) | Moisture-curing urethane composition and coating material | |
| WO2022061087A1 (en) | Low free polyurethane prepolymer composition for reactive hot melt adhesives | |
| CN113166349A (en) | Polyurethanes with (2-oxo-1, 3-dioxolane-4-carboxylic acid ester) end groups | |
| JPH01278559A (en) | Urethane-based one-pack moisture-curable composition | |
| MXPA06004180A (en) | Two-component polyurithane compound exhibiting a high early strength | |
| JPH03190916A (en) | One-pack type urethane composition | |
| JPH04220417A (en) | Production of polyurethane |