JP2014237758A - Main agent for polyurethane waterproof coating material and manufacturing method thereof, polyurethane waterproof coating material, polyurethane waterproof coating, and method for reducing content of free tolylene diisocyanate - Google Patents
Main agent for polyurethane waterproof coating material and manufacturing method thereof, polyurethane waterproof coating material, polyurethane waterproof coating, and method for reducing content of free tolylene diisocyanate Download PDFInfo
- Publication number
- JP2014237758A JP2014237758A JP2013120769A JP2013120769A JP2014237758A JP 2014237758 A JP2014237758 A JP 2014237758A JP 2013120769 A JP2013120769 A JP 2013120769A JP 2013120769 A JP2013120769 A JP 2013120769A JP 2014237758 A JP2014237758 A JP 2014237758A
- Authority
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- Japan
- Prior art keywords
- group
- tolylene diisocyanate
- isocyanate
- polyol
- polyurethane
- 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.)
- Granted
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 58
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- 239000004814 polyurethane Substances 0.000 title claims abstract description 27
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 claims abstract description 91
- 229920005862 polyol Polymers 0.000 claims abstract description 86
- 150000003077 polyols Chemical class 0.000 claims abstract description 86
- 239000012948 isocyanate Substances 0.000 claims abstract description 65
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 65
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011527 polyurethane coating Substances 0.000 claims description 40
- 238000004078 waterproofing Methods 0.000 claims description 35
- 239000002075 main ingredient Substances 0.000 claims description 26
- -1 carboxylic acid halide Chemical class 0.000 claims description 25
- 229920000768 polyamine Polymers 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical group ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 5
- 230000001588 bifunctional effect Effects 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 abstract description 6
- 238000004821 distillation Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000004014 plasticizer Substances 0.000 description 11
- 229920001451 polypropylene glycol Polymers 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- HGXVKAPCSIXGAK-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine;4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N.CCC1=CC(C)=C(N)C(CC)=C1N HGXVKAPCSIXGAK-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000012488 sample solution Substances 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- 239000012085 test solution Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241001112258 Moca Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-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
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920006311 Urethane elastomer Polymers 0.000 description 2
- 229940064734 aminobenzoate Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000006866 deterioration 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
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- UCUPHRPMBXOFAU-UHFFFAOYSA-N 2,4,6-tri(propan-2-yl)benzene-1,3-diamine Chemical compound CC(C)C1=CC(C(C)C)=C(N)C(C(C)C)=C1N UCUPHRPMBXOFAU-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JNVMVDZQEAJFTP-UHFFFAOYSA-N 2-ethyl-4,6-di(propan-2-yl)benzene-1,3-diamine Chemical compound CCC1=C(N)C(C(C)C)=CC(C(C)C)=C1N JNVMVDZQEAJFTP-UHFFFAOYSA-N 0.000 description 1
- VXHRHHAEVWHZBK-UHFFFAOYSA-N 2-methyl-4,6-di(propan-2-yl)benzene-1,3-diamine Chemical compound CC(C)C1=CC(C(C)C)=C(N)C(C)=C1N VXHRHHAEVWHZBK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- JOGPHRRMASCZSC-UHFFFAOYSA-N 3-phenylpentan-3-amine Chemical compound CCC(N)(CC)C1=CC=CC=C1 JOGPHRRMASCZSC-UHFFFAOYSA-N 0.000 description 1
- RQEOBXYYEPMCPJ-UHFFFAOYSA-N 4,6-diethyl-2-methylbenzene-1,3-diamine Chemical compound CCC1=CC(CC)=C(N)C(C)=C1N RQEOBXYYEPMCPJ-UHFFFAOYSA-N 0.000 description 1
- OMHOXRVODFQGCA-UHFFFAOYSA-N 4-[(4-amino-3,5-dimethylphenyl)methyl]-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(CC=2C=C(C)C(N)=C(C)C=2)=C1 OMHOXRVODFQGCA-UHFFFAOYSA-N 0.000 description 1
- KZTROCYBPMKGAW-UHFFFAOYSA-N 4-[[4-amino-3,5-di(propan-2-yl)phenyl]methyl]-2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=C(N)C(C(C)C)=CC(CC=2C=C(C(N)=C(C(C)C)C=2)C(C)C)=C1 KZTROCYBPMKGAW-UHFFFAOYSA-N 0.000 description 1
- GOOQVOJZBVFHDJ-UHFFFAOYSA-N 4-ethyl-2,6-di(propan-2-yl)benzene-1,3-diamine Chemical compound CCC1=CC(C(C)C)=C(N)C(C(C)C)=C1N GOOQVOJZBVFHDJ-UHFFFAOYSA-N 0.000 description 1
- AKZOLEPNYXGNEH-UHFFFAOYSA-N 4-methyl-2,6-di(propan-2-yl)benzene-1,3-diamine Chemical compound CC(C)C1=CC(C)=C(N)C(C(C)C)=C1N AKZOLEPNYXGNEH-UHFFFAOYSA-N 0.000 description 1
- KJTZGGMVRFZKOA-UHFFFAOYSA-N 6-(7-methyloctoxy)-6-oxohexanoic acid Chemical compound CC(C)CCCCCCOC(=O)CCCCC(O)=O KJTZGGMVRFZKOA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LOCDPORVFVOGCR-UHFFFAOYSA-N Bis(methylthio)methane Chemical compound CSCSC LOCDPORVFVOGCR-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 108010039491 Ricin Proteins 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WXZOXVVKILCOPG-UHFFFAOYSA-N bis(2-ethylhexyl) benzene-1,3-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC(C(=O)OCC(CC)CCCC)=C1 WXZOXVVKILCOPG-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
- 239000012490 blank solution Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- FSWDLYNGJBGFJH-UHFFFAOYSA-N n,n'-di-2-butyl-1,4-phenylenediamine Chemical compound CCC(C)NC1=CC=C(NC(C)CC)C=C1 FSWDLYNGJBGFJH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、ポリウレタン塗膜防水材用主剤及びその製造方法、ポリウレタン塗膜防水材、ポリウレタン防水塗膜、並びに遊離トリレンジイソシアネート含有量の低減方法に関するものである。 The present invention relates to a main component for a polyurethane coating film waterproof material and a method for producing the same, a polyurethane coating waterproof material, a polyurethane waterproof coating, and a method for reducing the content of free tolylene diisocyanate.
ポリウレタン塗膜材は、ビルディングの屋上、ベランダ、廊下などの防水材や塗床材、またスポーツ施設の弾性舗装などの用途に広く使用されている。このようなポリウレタン塗膜材においては、例えばポリオキシプロピレンポリオール（以下「ＰＰＧ」という。）とトリレンジイソシアネート（以下「ＴＤＩ」という。）との反応によって得られるイソシアネート基末端プレポリマーを含む主剤を、硬化剤と混合して塗工し、硬化させることによって塗膜を得る。 Polyurethane coating materials are widely used in applications such as waterproofing materials and floor coverings for building rooftops, verandas, and corridors, and elastic paving in sports facilities. In such a polyurethane coating material, for example, a main agent containing an isocyanate group-terminated prepolymer obtained by reaction of polyoxypropylene polyol (hereinafter referred to as “PPG”) and tolylene diisocyanate (hereinafter referred to as “TDI”) is used. A coating film is obtained by mixing with a curing agent, coating, and curing.
通常、主剤中には、未反応の遊離ＴＤＩが１〜３質量％ほど含まれている。このため、ＴＤＩの臭気によって、ポリウレタン塗膜材を扱う際の作業環境が悪化するという問題がある。また、ＴＤＩは労働安全衛生法による通知対象物質であるので、遊離ＴＤＩの含有量が多い主剤ほど法的な規制を受け、その取扱いが煩雑となる。このような問題に対し、遊離ＴＤＩの含有量を低減する方法が提案されている（例えば特許文献１、２参照）。 Usually, about 1 to 3% by mass of unreacted free TDI is contained in the main agent. For this reason, there exists a problem that the working environment at the time of handling a polyurethane coating material deteriorates by the odor of TDI. In addition, since TDI is a substance subject to notification under the Occupational Safety and Health Act, the main agent with a higher content of free TDI is subject to legal restrictions, and its handling becomes complicated. In order to solve such a problem, methods for reducing the content of free TDI have been proposed (see, for example, Patent Documents 1 and 2).
しかしながら、特許文献１に記載の方法では、遊離ＴＤＩの含有量を十分に低減するのは困難であり、特許文献２に記載の方法では、遊離ＴＤＩを除去するために蒸留が必要であることから、製造工程が増えてしまうという問題がある。 However, in the method described in Patent Document 1, it is difficult to sufficiently reduce the content of free TDI, and in the method described in Patent Document 2, distillation is necessary to remove free TDI. There is a problem that the manufacturing process increases.
そこで、本発明の目的は、蒸留等の煩雑な工程を必要とすることなく製造でき、遊離ＴＤＩ含有量が、臭気や取り扱いの点で実用上問題とならない程度に十分に低減されたポリウレタン塗膜防水材用主剤及びその製造方法を提供することにある。本発明の目的はまた、この主剤を用いたポリウレタン塗膜防水材及びポリウレタン防水塗膜、並びに遊離トリレンジイソシアネート含有量の低減方法を提供することにある。 Accordingly, an object of the present invention is a polyurethane coating film that can be produced without requiring a complicated process such as distillation, and the free TDI content is sufficiently reduced to such an extent that it does not become a practical problem in terms of odor and handling. An object of the present invention is to provide a base material for waterproof material and a method for producing the same. Another object of the present invention is to provide a polyurethane coating waterproof material and a polyurethane waterproof coating using the main agent, and a method for reducing the content of free tolylene diisocyanate.
本発明は、イソシアネート基末端プレポリマーを含むポリウレタン塗膜防水材用主剤であって、主剤のＮＥＴ．ＣＰＲ値が−３５〜０．３であり、イソシアネート基末端プレポリマーは、ポリオキシアルキレンポリオールを含むポリオール組成物とトリレンジイソシアネートを含むイソシアネート組成物とを、ポリオキシアルキレンポリオールの水酸基（ＯＨ基）に対するトリレンジイソシアネートのイソシアネート基（ＮＣＯ基）の当量比（ＮＣＯ基／ＯＨ基）が１．５０〜１．９０となるように反応させて得ることがでるものであり、トリレンジイソシアネートは、２，４−トリレンジイソシアネートを９０質量％以上含む、ポリウレタン塗膜防水材用主剤を提供する。 The present invention is a main agent for polyurethane film waterproofing material containing an isocyanate group-terminated prepolymer, which is a NET. The CPR value is −35 to 0.3, and the isocyanate group-terminated prepolymer comprises a polyol composition containing a polyoxyalkylene polyol and an isocyanate composition containing tolylene diisocyanate, and the hydroxyl group (OH group) of the polyoxyalkylene polyol. The tolylene diisocyanate has an isocyanate group (NCO group) equivalent ratio (NCO group / OH group) of 1.50 to 1.90. , 4-Tolylene diisocyanate is provided as a main component for polyurethane coating waterproofing material containing 90% by mass or more.
このポリウレタン塗膜防水材用主剤は、蒸留等の煩雑な工程を必要とすることなく製造でき、遊離ＴＤＩ含有量が、臭気や取り扱いの点で実用上問題とならない程度（例えば、０．１質量％未満）に十分に低減される。このポリウレタン塗膜防水材用主剤においては、アロファネートが形成されるような副反応を極力抑えてプレポリマー化が可能となっている。 This polyurethane waterproofing agent main component can be produced without requiring a complicated process such as distillation, and the free TDI content does not cause a practical problem in terms of odor or handling (for example, 0.1 mass) %)). In this main agent for polyurethane coating waterproofing material, it is possible to prepolymerize by suppressing side reactions such as formation of allophanate as much as possible.
主剤は、カルボン酸ハロゲン化物を含んでいてもよく、ポリオール組成物又はイソシアネート組成物は、カルボン酸ハロゲン化物を含んでいてもよい。また、ポリオール組成物は、ポリオキシアルキレンポリオール及びカルボン酸ハロゲン化物からなっていてもよく、イソシアネート組成物は、トリレンジイソシアネート及びカルボン酸ハロゲン化物からなっていてもよい。これらの場合、主剤のＮＥＴ．ＣＰＲ値が−３５〜０．３となりやすい傾向にある。 The main agent may contain a carboxylic acid halide, and the polyol composition or the isocyanate composition may contain a carboxylic acid halide. The polyol composition may be composed of a polyoxyalkylene polyol and a carboxylic acid halide, and the isocyanate composition may be composed of tolylene diisocyanate and a carboxylic acid halide. In these cases, the NET. The CPR value tends to be −35 to 0.3.
カルボン酸ハロゲン化物は、塩化ベンゾイルであってもよい。塩化ベンゾイルは、ポリオールと良く混和し、また中和後の処理が不要であるため取扱いやすい。 The carboxylic acid halide may be benzoyl chloride. Benzoyl chloride is easy to handle because it mixes well with polyols and does not require treatment after neutralization.
イソシアネート基末端プレポリマー及び主剤中の遊離トリレンジイソシアネート含有量が、０．１質量％未満であってもよい。 The free tolylene diisocyanate content in the isocyanate group-terminated prepolymer and the main agent may be less than 0.1% by mass.
ポリオール組成物に含まれるポリオキシアルキレンポリオールに占める２官能ポリオールの割合が３０〜９０質量％であってもよい。この場合、得られるポリウレタン塗膜の特性がより良好になる。 30-90 mass% may be sufficient as the ratio of the bifunctional polyol to the polyoxyalkylene polyol contained in a polyol composition. In this case, the properties of the obtained polyurethane coating film become better.
上述の本発明は、イソシアネート基末端プレポリマーのポリウレタン塗膜防水材用主剤としての使用（又は応用）としても把握できる。すなわち、本発明は、イソシアネート基末端プレポリマーのポリウレタン塗膜防水材用主剤としての使用であって、主剤のＮＥＴ．ＣＰＲ値が−３５〜０．３であり、イソシアネート基末端プレポリマーは、ポリオキシアルキレンポリオールを含むポリオール組成物とトリレンジイソシアネートを含むイソシアネート組成物とを、ポリオキシアルキレンポリオールの水酸基（ＯＨ基）に対するトリレンジイソシアネートのイソシアネート基（ＮＣＯ基）の当量比（ＮＣＯ基／ＯＨ基）が１．５０〜１．９０となるように反応させて得ることができるものであり、トリレンジイソシアネートは、２，４−トリレンジイソシアネートを９０質量％以上含む使用を提供する。 The above-mentioned present invention can also be grasped as the use (or application) of an isocyanate group-terminated prepolymer as a main ingredient for a polyurethane coating waterproof material. That is, the present invention is the use of an isocyanate group-terminated prepolymer as a main agent for a waterproofing material for polyurethane coatings. The CPR value is −35 to 0.3, and the isocyanate group-terminated prepolymer comprises a polyol composition containing a polyoxyalkylene polyol and an isocyanate composition containing tolylene diisocyanate, and the hydroxyl group (OH group) of the polyoxyalkylene polyol. The tolylene diisocyanate can be obtained by reacting so that the equivalent ratio of the isocyanate group (NCO group) of the tolylene diisocyanate (NCO group / OH group) is 1.50 to 1.90. , 4-tolylene diisocyanate is provided for use in an amount of 90% by mass or more.
また、本発明は、ポリオキシアルキレンポリオールを含むポリオール組成物とトリレンジイソシアネートを含むイソシアネート組成物との反応物からなるイソシアネート基末端プレポリマーを含むポリウレタン塗膜防水材用主剤の製造方法であって、トリレンジイソシアネート中の２，４−トリレンジイソシアネート含有量を９０質量％以上とし、ポリオール組成物とイソシアネート組成物とを、ポリオキシアルキレンポリオールの水酸基（ＯＨ基）に対するトリレンジイソシアネートのイソシアネート基（ＮＣＯ基）の当量比（ＮＣＯ基／ＯＨ基）が１．５０〜１．９０となるように反応させ、反応物のＮＥＴ．ＣＰＲ値を−３５〜０．３とする、ポリウレタン塗膜防水材用主剤の製造方法を提供する。 The present invention also provides a method for producing a main component for a waterproofing material for a polyurethane coating film comprising an isocyanate group-terminated prepolymer comprising a reaction product of a polyol composition containing a polyoxyalkylene polyol and an isocyanate composition containing tolylene diisocyanate. The content of 2,4-tolylene diisocyanate in tolylene diisocyanate is 90% by mass or more, and the polyol composition and the isocyanate composition are mixed with the isocyanate group of tolylene diisocyanate with respect to the hydroxyl group (OH group) of the polyoxyalkylene polyol ( NCO group) is reacted so that the equivalent ratio (NCO group / OH group) is 1.50 to 1.90. Provided is a method for producing a base material for a polyurethane coating waterproofing material having a CPR value of −35 to 0.3.
また、本発明は、上述した主剤と、この主剤の硬化剤とを有する、ポリウレタン塗膜防水材を提供する。このポリウレタン塗膜防水材は、主剤と硬化剤が分離された２液性ポリウレタン塗膜防水材であることが好ましい。 Moreover, this invention provides the polyurethane coating-film waterproofing material which has the main ingredient mentioned above and the hardening | curing agent of this main ingredient. This polyurethane waterproof membrane is preferably a two-component polyurethane waterproof membrane in which the main agent and the curing agent are separated.
硬化剤は、芳香族ポリアミン架橋剤を含んでいてもよく、ジエチルトルエンジアミンを含んでいてもよい。特に、硬化剤がジエチルトルエンアミンを含む場合、安全性が高いため製造や使用に際しての制約を受けない。 The curing agent may contain an aromatic polyamine crosslinking agent, and may contain diethyltoluenediamine. In particular, when the curing agent contains diethyltolueneamine, the safety is high, so there are no restrictions on production and use.
ポリウレタン塗膜防水材においては、芳香族ポリアミン架橋剤のアミノ基（ＮＨ２基）に対する、イソシアネート基末端プレポリマーのイソシアネート基（ＮＣＯ基）との当量比（ＮＣＯ基／ＮＨ２基）が１．０〜１．８であることが好ましい。この場合、所望の可使時間が得られ、また、硬化性が良好となる。 In the polyurethane coating waterproof material, the equivalent ratio (NCO group / NH 2 group) of the isocyanate group-terminated prepolymer to the isocyanate group (NCO group) to the amino group (NH 2 group) of the aromatic polyamine crosslinking agent is 1. It is preferable that it is 0-1.8. In this case, a desired pot life can be obtained and the curability is improved.
本発明はまた、上述したポリウレタン塗膜防水材における、主剤と、この主剤の硬化剤とを反応させて得ることのできる、ポリウレタン防水塗膜を提供する。このポリウレタン防水塗膜は、遊離ＴＤＩ含有量が低減された主剤を用いているため、歩行性等の特性に優れている。 The present invention also provides a polyurethane waterproof coating film that can be obtained by reacting the main agent and the curing agent of the main agent in the above-mentioned polyurethane coating waterproof material. Since this polyurethane waterproof coating film uses the main agent with reduced free TDI content, it is excellent in characteristics such as walking.
本発明はさらに、ポリオキシアルキレンポリオールを含むポリオール組成物とトリレンジイソシアネートを含むイソシアネート組成物との反応物における、遊離トリレンジイソシアネート含有量の低減方法であって、トリレンジイソシアネート中の２，４−トリレンジイソシアネート含有量を９０質量％以上とし、ポリオール組成物とイソシアネート組成物とを、ポリオキシアルキレンポリオールの水酸基（ＯＨ基）に対するトリレンジイソシアネートのイソシアネート基（ＮＣＯ基）の当量比（ＮＣＯ基／ＯＨ基）が１．５０〜１．９０となるように反応させ、反応物のＮＥＴ．ＣＰＲ値を−３５〜０．３とする、低減方法を提供する。 The present invention further relates to a method for reducing the content of free tolylene diisocyanate in a reaction product of a polyol composition containing a polyoxyalkylene polyol and an isocyanate composition containing tolylene diisocyanate, which comprises 2,4 in tolylene diisocyanate. -Tolylene diisocyanate content is 90% by mass or more, and the polyol composition and the isocyanate composition have an equivalent ratio of an isocyanate group (NCO group) of tolylene diisocyanate to a hydroxyl group (OH group) of a polyoxyalkylene polyol (NCO group). / OH group) is 1.50 to 1.90, the NET. A reduction method is provided in which the CPR value is −35 to 0.3.
この低減方法において、反応物、ポリオール組成物又はイソシアネート組成物は、塩化ベンゾイル等のカルボン酸ハロゲン化物を含むことができる。また、ポリオール組成物は、ポリオキシアルキレンポリオール及びカルボン酸ハロゲン化物からなり、イソシアネート組成物は、トリレンジイソシアネート及びカルボン酸ハロゲン化物からなることができる。そして、ポリオキシアルキレンポリオールに占める２官能ポリオールの割合は３０〜９０質量％とすることができる。このような低減方法により、反応物中の遊離トリレンジイソシアネート含有量を０．１質量％未満にすることができる。 In this reduction method, the reactant, polyol composition or isocyanate composition can contain a carboxylic acid halide such as benzoyl chloride. The polyol composition can be composed of a polyoxyalkylene polyol and a carboxylic acid halide, and the isocyanate composition can be composed of tolylene diisocyanate and a carboxylic acid halide. And the ratio of the bifunctional polyol to a polyoxyalkylene polyol can be 30-90 mass%. By such a reduction method, the content of free tolylene diisocyanate in the reaction product can be made less than 0.1% by mass.
本発明によれば、蒸留等の煩雑な工程を必要とすることなく製造でき、遊離ＴＤＩ含有量が、臭気や取り扱いの点で実用上問題とならない程度に十分に低減されたポリウレタン塗膜防水材用主剤を提供することができる。特に、この主剤においては、経日安定性が改善されている。また、この主剤を有するポリウレタン塗膜防水材においては、特に手塗り塗工に最適な可使時間を保持でき、塗膜の硬化時間が短縮するため、作業時間が短縮できる。また、このポリウレタン塗膜防水材は、労働安全衛生法（特定化学物質障害予防規則）等の法的制約を受けない安全性の高い、且つ環境に配慮したものとなる。 According to the present invention, a polyurethane coating waterproof material that can be produced without requiring a complicated process such as distillation, and the free TDI content is sufficiently reduced so as not to cause a practical problem in terms of odor and handling. The main agent for use can be provided. In particular, this main ingredient has improved daily stability. Moreover, in the polyurethane paint waterproofing material which has this main ingredient, since the working time optimal for especially hand-painting can be hold | maintained and the hardening time of a paint film is shortened, working time can be shortened. In addition, this polyurethane coating waterproof material is highly safe and environmentally friendly without being subject to legal restrictions such as the Occupational Safety and Health Act (Specific Chemical Substances Prevention Prevention Rules).
［ポリウレタン塗膜防水材用主剤］
本実施形態に係るポリウレタン塗膜防水材用主剤は、イソシアネート基末端プレポリマーを含み、ＮＥＴ．ＣＰＲ値が−３５〜０．３である。ここで、本明細書におけるＣＰＲ（Ｃｏｎｔｒｏｌｌｅｄ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ Ｒａｔｅ）値とは、ＪＩＳ Ｋ１５５７−４：２００７に定義されているものであり、ポリオール３０ｇ中の塩基性物質のマイクロ当量値を意味する。また、本明細書におけるＮＥＴ．ＣＰＲ値とは、イソシアネート基末端プレポリマー又はポリウレタン塗膜防水用主剤を構成する全原料成分中の塩基性物質と酸性物質との差を意味し、具体的には、下記式（１）によって計算される（「ポリウレタン樹脂」岩田敬治著、日刊工業新聞社、第５版、６５頁も参照）。
Ｃｃ＝ＥＢ−ＥＡ ・・・（１）
ただし、
Ｃｃ：ＮＥＴ．ＣＰＲの計算値
ＥＡ：３０ｇの全原料成分中に含まれる酸性物質のマイクロ当量
ＥＢ：３０ｇの全原料成分中に含まれる塩基性物質のマイクロ当量
[Main agent for waterproofing polyurethane film]
The main component for a polyurethane coating film waterproof material according to the present embodiment includes an isocyanate group-terminated prepolymer, and has a NET. The CPR value is −35 to 0.3. Here, the CPR (Controlled Polymerization Rate) value in this specification is defined in JIS K1557-4: 2007, and means a micro equivalent value of a basic substance in 30 g of polyol. In addition, NET. The CPR value means the difference between the basic substance and the acidic substance in all the raw material components constituting the isocyanate group-terminated prepolymer or the main ingredient for waterproofing polyurethane film, and specifically, calculated by the following formula (1). (See also "Polyurethane resin" written by Keiji Iwata, Nikkan Kogyo Shimbun, 5th edition, page 65).
Cc = EB-EA (1)
However,
Cc: NET. Calculated value of CPR EA: micro equivalent of acidic substance contained in 30 g of all raw material components EB: micro equivalent of basic substance contained in all raw material components of 30 g
また、本明細書におけるＮＥＴ．ＣＰＲ値は、実験的には以下の手順に従って測定される。
１）最大容量５ｍＬのビュレットをもつ自動滴定装置を用いて試験を行う。
２）１００ｍＬ滴定フラスコに試料約３０ｇを１ｍｇまで正確に量りとり、これにメタノール（ＩＳＯ６３５３−２に規定する試験級）５０ｍＬを加え、充分に混ざるまで攪拌し試料用溶液とする。また、空試験用溶液として上記メタノール５０ｍＬを用意する。
３）水酸化ナトリウム溶液（０．０１ｍｏｌ／Ｌ）を１ｍＬ用ホールピペットにとり、上記の試料用及び空試験用溶液に加え、十分に混合する。
４）０．０１ｍｏｌ／Ｌ塩酸で上記試料用溶液及び空試験用溶液を滴定し、終点（最後の変曲点）までの滴定量を記録する。なお、ＮＥＴ．ＣＰＲ値が−１０以下の場合は、規定度の高い水酸化ナトリウム溶液を使用する。
５）ＮＥＴ．ＣＰＲ値を、下記式（２）によって算出する。
Ｃ＝（Ｖｓ−Ｖｂ）×Ｍ×１０００×３０／ｍ ・・・（２）
ただし、
Ｃ：ＮＥＴ．ＣＰＲ値
Ｖｓ：試料用溶液の滴定に要した塩酸量（ｍＬ）
Ｖｂ：空試験用溶液の滴定に要した塩酸量（ｍＬ）
Ｍ：塩酸モル濃度（ｍｏｌ／Ｌ）
ｍ：試料の質量（ｇ）
In addition, NET. The CPR value is experimentally measured according to the following procedure.
1) Test using an automatic titrator with a burette with a maximum volume of 5 mL.
2) About 30 g of sample is accurately weighed to 1 mg in a 100 mL titration flask, and 50 mL of methanol (the test grade specified in ISO63553-2) is added to this, and stirred until it is sufficiently mixed to prepare a sample solution. Also, 50 mL of the methanol is prepared as a blank test solution.
3) Take sodium hydroxide solution (0.01 mol / L) into a 1 mL hole pipette, add to the sample solution and blank test solution, and mix well.
4) Titrate the above sample solution and blank test solution with 0.01 mol / L hydrochloric acid, and record the titration amount to the end point (last inflection point). NET. When the CPR value is -10 or less, a sodium hydroxide solution having a high normality is used.
5) NET. The CPR value is calculated by the following formula (2).
C = (Vs−Vb) × M × 1000 × 30 / m (2)
However,
C: NET. CPR value Vs: Amount of hydrochloric acid required for titration of sample solution (mL)
Vb: Amount of hydrochloric acid required for titration of the blank test solution (mL)
M: molar concentration of hydrochloric acid (mol / L)
m: Mass of the sample (g)
主剤のＮＥＴ．ＣＰＲ値は、−３５〜０．３であるが、好ましくは−３０〜０．１であり、より好ましくは−１５〜０である。主剤のＮＥＴ．ＣＰＲ値が上記範囲内であると、主剤中の遊離ＴＤＩ含有量をより低減させることができる。 NET. The CPR value is −35 to 0.3, preferably −30 to 0.1, and more preferably −15 to 0. NET. When the CPR value is within the above range, the free TDI content in the main agent can be further reduced.
主剤のＮＥＴ．ＣＰＲ値は、後述するとおり、酸性物質若しくは塩基性物質の添加によってＣＰＲ値が調整されたポリオール組成物、又は酸性物質若しくは塩基性物質の添加によって酸度が調整されたイソシアネート組成物を適宜用いることで調整される。また、ポリオール組成物とイソシアネート組成物とを反応させた直後に酸性物質又は塩基性物質を添加して反応を完結させることにより、主剤のＮＥＴ．ＣＰＲ値を調整することもできる。 NET. As will be described later, the CPR value is appropriately determined by using a polyol composition whose CPR value is adjusted by adding an acidic substance or basic substance, or an isocyanate composition whose acidity is adjusted by adding an acidic substance or basic substance. Adjusted. Further, immediately after the polyol composition and the isocyanate composition are reacted, an acidic substance or a basic substance is added to complete the reaction, whereby the NET. The CPR value can also be adjusted.
主剤の２３℃における粘度は、硬化剤との混合直後の未硬化液状物が、施工時のレベリングを保持できる程度の主剤粘度を有するために、３０００〜３５０００ｍＰａ・ｓであることが好ましく、４０００〜１５０００ｍＰａ・ｓであることがより好ましく、５０００〜１００００ｍＰａ・ｓであることが更に好ましい。 The viscosity of the main agent at 23 ° C. is preferably 3000 to 35000 mPa · s in order that the uncured liquid material immediately after mixing with the curing agent has a main agent viscosity sufficient to maintain leveling during construction. It is more preferably 15000 mPa · s, and further preferably 5000 to 10000 mPa · s.
主剤中の遊離ＴＤＩ含有量は、主剤全量基準で、０．１質量％未満であることが好ましい。主剤中の遊離ＴＤＩ含有量が多いと、主剤と硬化剤とを反応させてポリウレタン塗膜を得る際に、遊離ＴＤＩがイソシアネート基末端プレポリマーより先に硬化剤と反応して、得られるポリウレタン塗膜防水材の品質や塗膜物性（機械的強度、可使時間等）等に悪影響を及ぼす可能性がある。 The free TDI content in the main agent is preferably less than 0.1% by mass based on the total amount of the main agent. When the content of free TDI in the main agent is large, when a polyurethane coating film is obtained by reacting the main agent with a curing agent, the free TDI reacts with the curing agent prior to the isocyanate group-terminated prepolymer, and the resulting polyurethane coating is obtained. There is a possibility of adversely affecting the quality of the waterproof membrane and the physical properties of the coating (mechanical strength, pot life, etc.).
主剤は、イソシアネート基末端プレポリマー以外に、塗工前の混合攪拌時の粘度調整、手塗り塗工時の粘度調整等のために可塑剤、溶剤等を更に含んでいてもよい。 In addition to the isocyanate group-terminated prepolymer, the main agent may further contain a plasticizer, a solvent, and the like for adjusting the viscosity at the time of mixing and stirring before coating and adjusting the viscosity at the time of hand coating.
イソシアネート基末端プレポリマーは、ポリオキシアルキレンポリオールを含むポリオール組成物とトリレンジイソシアネートを含むイソシアネート組成物とを、ポリオキシアルキレンポリオールの水酸基（ＯＨ基）に対するトリレンジイソシアネートのイソシアネート基（ＮＣＯ基）の当量比（ＮＣＯ基／ＯＨ基）が１．５０〜１．９０となるように反応させて得ることができる。 The isocyanate group-terminated prepolymer comprises a polyol composition containing a polyoxyalkylene polyol and an isocyanate composition containing tolylene diisocyanate. It can obtain by making it react so that an equivalent ratio (NCO group / OH group) may be 1.50-1.90.
上記のポリオキシアルキレンポリオールの水酸基に対するＴＤＩのイソシアネート基の当量比は、１．５０〜１．９０であるが、好ましくは１．６０〜１．８５であり、より好ましくは１．７０〜１．８５である。当量比が１．５０未満になると、引裂強さ（Ｔｔ）等の塗膜の物性値がＪＩＳ規格値を満たさない可能性がある。また、当量比が１．９０を超えると、主剤中の遊離ＴＤＩ含有量が多くなるおそれがある。 The equivalent ratio of the isocyanate group of TDI to the hydroxyl group of the polyoxyalkylene polyol is 1.50 to 1.90, preferably 1.60 to 1.85, and more preferably 1.70 to 1.90. 85. If the equivalent ratio is less than 1.50, the physical properties of the coating such as tear strength (Tt) may not satisfy the JIS standard values. On the other hand, if the equivalent ratio exceeds 1.90, the free TDI content in the main ingredient may be increased.
ポリオール組成物とイソシアネート組成物とを反応させる反応温度は、１００℃以下であることが好ましく、９０℃以下であることがより好ましく、８０℃以下であることが更に好ましい。反応温度を上記の範囲内にすると、副反応を抑制することができ、結果的に主剤中の遊離ＴＤＩ含有量がより低減される。一方、反応温度の下限は特に制限されないが、例えば４０℃以上である。 The reaction temperature for reacting the polyol composition with the isocyanate composition is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and further preferably 80 ° C. or lower. When the reaction temperature is within the above range, side reactions can be suppressed, and as a result, the free TDI content in the main agent is further reduced. On the other hand, the lower limit of the reaction temperature is not particularly limited, but is, for example, 40 ° C. or higher.
イソシアネート基末端プレポリマーのＮＣＯ基含有率は、好ましくは１．５〜５．０質量％、より好ましくは１．８〜４．０質量％、更に好ましくは１．８〜３．５質量％である。なお、ＮＣＯ基含有率が５．０質量％以下であると、所望の可使時間が得られやすくなる。一方、ＮＣＯ基含有率が１．５質量％以上であると、ポリウレタン塗膜防水材としての物性が良好になる。 The NCO group content of the isocyanate group-terminated prepolymer is preferably 1.5 to 5.0% by mass, more preferably 1.8 to 4.0% by mass, and still more preferably 1.8 to 3.5% by mass. is there. When the NCO group content is 5.0% by mass or less, a desired pot life can be easily obtained. On the other hand, when the NCO group content is 1.5% by mass or more, the physical properties as a polyurethane coating film waterproofing material are improved.
イソシアネート基末端プレポリマー中の遊離ＴＤＩ含有量は、プレポリマー全量基準で０．１質量％未満であることが好ましい。このイソシアネート基末端プレポリマー中の遊離ＴＤＩ含有量は主剤中の遊離ＴＤＩ含有量に直結する。 The free TDI content in the isocyanate group-terminated prepolymer is preferably less than 0.1% by mass based on the total amount of the prepolymer. The free TDI content in the isocyanate group-terminated prepolymer is directly linked to the free TDI content in the main agent.
ポリオール組成物は、ポリオキシアルキレンポリオールを含むが、酸を更に含むことが好ましい。酸を含むことによってポリオキシアルキレンポリオール中の微量のアルカリ金属等が中和され、ポリオール組成物のＣＰＲ値が所望の範囲に調整される。また、ポリオール組成物が酸を含むことによって、主剤が酸を含んでいてもよい。 The polyol composition contains a polyoxyalkylene polyol, but preferably further contains an acid. By containing an acid, a trace amount of alkali metal or the like in the polyoxyalkylene polyol is neutralized, and the CPR value of the polyol composition is adjusted to a desired range. Moreover, the main ingredient may contain the acid by the polyol composition containing an acid.
ポリオール組成物中のポリオキシアルキレンポリオールの含有量は、ポリオール組成物全量基準で、７０質量％以上であることが好ましく、９５質量％以上であることがより好ましい。また、ポリオール組成物が酸を含むときは、ポリオール組成物は、ポリオキシアルキレンポリオール及び酸からなっていることが好ましく、酸の含有量は例えば１質量％以下とすることができる。ここで、本明細書において「ポリオール組成物が、ポリオキシアルキレンポリオール及び酸からなる」とは、本発明の効果が奏される程度であれば、ポリオキシアルキレンポリオール及び酸以外の成分を含んでいてもよいことを意味する。 The content of the polyoxyalkylene polyol in the polyol composition is preferably 70% by mass or more and more preferably 95% by mass or more based on the total amount of the polyol composition. Moreover, when a polyol composition contains an acid, it is preferable that a polyol composition consists of a polyoxyalkylene polyol and an acid, and content of an acid can be 1 mass% or less, for example. Here, in this specification, “the polyol composition is composed of a polyoxyalkylene polyol and an acid” includes components other than the polyoxyalkylene polyol and the acid as long as the effects of the present invention are achieved. It means that it may be.
上記の酸としては、無機酸又は有機酸が挙げられる。無機酸としては、例えば、リン酸、亜リン酸、ピロリン酸、塩酸、硫酸、亜硫酸及びそれらの水溶液が用いられる。また、その他にも、リン酸二水素ナトリウム、リン酸二水素カリウム、炭酸水素ナトリウム等の無機酸塩も無機酸として用いられる。有機酸としては、例えば、シュウ酸、コハク酸、酢酸、安息香酸、パラトルエンスルホン酸、カルボン酸ハロゲン化物及びそれらの水溶液が用いられる。 Examples of the acid include inorganic acids and organic acids. Examples of the inorganic acid include phosphoric acid, phosphorous acid, pyrophosphoric acid, hydrochloric acid, sulfuric acid, sulfurous acid, and aqueous solutions thereof. In addition, inorganic acid salts such as sodium dihydrogen phosphate, potassium dihydrogen phosphate, and sodium hydrogen carbonate are also used as inorganic acids. Examples of organic acids that can be used include oxalic acid, succinic acid, acetic acid, benzoic acid, paratoluenesulfonic acid, carboxylic acid halides, and aqueous solutions thereof.
酸の中では、カルボン酸ハロゲン化物が好ましい。その中でも、特に塩化ベンゾイル（ＣＡＳ登録番号：９８−８８−４）は、ポリオールと良く混和し、また中和後の処理が不要で取扱い易いため好ましい。塩化ベンゾイルは、メチルエチルケトン等の有機溶剤に溶解させ、所定の濃度に調整した希釈溶液として使用する。 Of the acids, carboxylic acid halides are preferred. Among them, benzoyl chloride (CAS registration number: 98-88-4) is particularly preferable because it is well mixed with the polyol and does not require treatment after neutralization and is easy to handle. Benzoyl chloride is dissolved in an organic solvent such as methyl ethyl ketone and used as a diluted solution adjusted to a predetermined concentration.
ポリオール組成物のＣＰＲ値は、−３５〜０．３であることが好ましい。なお、市販されている通常のポリオキシアルキレンポリオールを用いる場合は、ＣＰＲ値はおよそ０〜５であるため、ＣＰＲ値を調整してから用いることが好ましい。 The CPR value of the polyol composition is preferably −35 to 0.3. In addition, when using the usual polyoxyalkylene polyol marketed, since CPR value is about 0-5, it is preferable to use, after adjusting CPR value.
ポリオキシアルキレンポリオールは、得られるイソシアネート基末端プレポリマーの高粘度化、結晶化を抑制でき、かつ可使時間を長くできる傾向にあることから、ポリオキシプロピレンポリオール又はポリオキシエチレンプロピレンポリオールであることが好ましい。これらは、例えばエチレングリコール、プロピレングリコール、グリセリン、トリメチロールプロパンなどの低分子ポリオールにプロピレンオキサイド又はプロピレンオキサイドとエチレンオキサイドとを付加重合して得られる。ポリオキシアルキレンポリオールとしては、その他にも例えばポリオキシテトラメチレングリコールを使用できる。 The polyoxyalkylene polyol is a polyoxypropylene polyol or a polyoxyethylene propylene polyol because it tends to increase the viscosity and crystallization of the resulting isocyanate group-terminated prepolymer and to increase the pot life. Is preferred. These are obtained, for example, by addition polymerization of propylene oxide or propylene oxide and ethylene oxide to a low molecular polyol such as ethylene glycol, propylene glycol, glycerin or trimethylolpropane. In addition, for example, polyoxytetramethylene glycol can be used as the polyoxyalkylene polyol.
ポリオール組成物中の全ポリオキシアルキレンポリオールに占める２官能ポリオールの割合は、３０〜９０質量％であることが好ましく、５０〜９０質量％であることがより好ましく、６０〜９０質量％であることが更に好ましい。上記割合が３０質量％以上の場合、引裂強さ（Ｔｔ）等の物性値がＪＩＳ規格値を満たしやすくなり、９０質量％以下の場合、引張強さ（Ｔｂ）等の物性値がＪＩＳ規格値を満たしやすくなる。 The proportion of the bifunctional polyol in the total polyoxyalkylene polyol in the polyol composition is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and 60 to 90% by mass. Is more preferable. When the ratio is 30% by mass or more, the physical property values such as tear strength (Tt) easily satisfy the JIS standard value, and when it is 90% by mass or less, the physical property value such as tensile strength (Tb) is the JIS standard value. It becomes easy to satisfy.
防水材用途に好適な所望のイソシアネート基末端プレポリマーを得るには、ポリオキシアルキレンポリオールの重量平均分子量は１５００〜８０００であることが好ましく、１７００〜６０００であることがより好ましい。 In order to obtain a desired isocyanate group-terminated prepolymer suitable for use as a waterproof material, the weight average molecular weight of the polyoxyalkylene polyol is preferably 1500 to 8000, and more preferably 1700 to 6000.
イソシアネート組成物は、ＴＤＩを含むが、酸を更に含むこともできる。また、イソシアネート組成物は、可塑剤等の添加剤又は溶剤等を更に含むこともできる。イソシアネート組成物中のＴＤＩの含有量は、イソシアネート組成物全量基準で、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましい。なお、イソシアネート組成物が酸を含まないときは、当該含有量は９９質量％以上であることが好ましい。また、イソシアネート組成物が酸を含むときは、イソシアネート組成物は、ＴＤＩ及び酸からなっていることが好ましく、酸の含有量は例えば１質量％以下とすることができる。ここで、本明細書において「イソシアネート組成物が、ＴＤＩ及び酸からなる」とは、本発明の効果が奏される程度であれば、ＴＤＩ及び酸以外の成分を含んでいてもよいことを意味する。 The isocyanate composition includes TDI, but may further include an acid. The isocyanate composition may further contain an additive such as a plasticizer or a solvent. The content of TDI in the isocyanate composition is preferably 50% by mass or more, and more preferably 70% by mass or more, based on the total amount of the isocyanate composition. In addition, when an isocyanate composition does not contain an acid, it is preferable that the said content is 99 mass% or more. Moreover, when an isocyanate composition contains an acid, it is preferable that an isocyanate composition consists of TDI and an acid, and content of an acid can be 1 mass% or less, for example. Here, in the present specification, “the isocyanate composition is composed of TDI and an acid” means that components other than TDI and an acid may be included as long as the effects of the present invention are exhibited. To do.
上記の酸としては、上記ポリオール組成物のＣＰＲ値の調整に用いるものを同様に用いることができる。 As said acid, what is used for adjustment of the CPR value of the said polyol composition can be used similarly.
ＴＤＩは、ＴＤＩ全量基準で、２，４−異性体を９０質量％以上含むが、９５質量％以上含むことが好ましく、９８質量％以上含むことがより好ましい。２，４−異性体の含有量が９０質量％未満であると、得られる主剤中の遊離ＴＤＩ含有量が多くなるおそれがある。 TDI contains 90% by mass or more of the 2,4-isomer, based on the total amount of TDI, preferably 95% by mass or more, and more preferably 98% by mass or more. When the content of the 2,4-isomer is less than 90% by mass, the free TDI content in the obtained main ingredient may be increased.
ポリオール組成物とイソシアネート組成物との反応前の混合物（以下、反応系原料という）のＮＥＴ．ＣＰＲ値は、−３５〜０．３であることが好ましく、−３０〜０．１であることがより好ましく、−１５〜０であることが更に好ましい。ＮＥＴ．ＣＰＲ値が上記範囲内であると、得られるポリウレタン塗膜の劣化処理（酸処理）後の引張強さ比等の物性値がＪＩＳ規格値を満足しやすくなり、また、主剤中の遊離ＴＤＩ含有量を低減させやすくなる。また、ポリオール組成物とイソシアネート組成物との反応後の反応物のＮＥＴ．ＣＰＲ値も、同様の理由により、−３５〜０．３であることが好ましく、−３０〜０．１であることがより好ましく、−１５〜０であることが更に好ましい。 The NET. Of the mixture before the reaction of the polyol composition and the isocyanate composition (hereinafter referred to as reaction system raw material). The CPR value is preferably −35 to 0.3, more preferably −30 to 0.1, and still more preferably −15 to 0. NET. When the CPR value is within the above range, physical properties such as the tensile strength ratio after deterioration treatment (acid treatment) of the obtained polyurethane coating film easily satisfy the JIS standard values, and free TDI is contained in the main agent. It becomes easy to reduce the amount. Further, the NET. Of the reaction product after the reaction between the polyol composition and the isocyanate composition is obtained. For the same reason, the CPR value is preferably −35 to 0.3, more preferably −30 to 0.1, and still more preferably −15 to 0.
［ポリウレタン塗膜防水材］
本実施形態に係るポリウレタン塗膜防水材は、上記主剤と主剤の硬化剤とを有する。このポリウレタン塗膜防水材は、主剤と硬化剤が分離された２液性ポリウレタン塗膜防水材であることが好ましい。
[Polyurethane coating waterproofing material]
The polyurethane coating waterproof material according to the present embodiment has the main agent and a main agent curing agent. This polyurethane waterproof membrane is preferably a two-component polyurethane waterproof membrane in which the main agent and the curing agent are separated.
硬化剤は、芳香族ポリアミン架橋剤を含むことが好ましい。芳香族ポリアミン架橋剤としては、ジエチルトルエンジアミン（以下、ＤＥＴＤＡという）を用いることが好ましい。ＤＥＴＤＡは、通常３，５−ジエチルトルエン−２，４−ジアミンと３，５−ジエチルトルエン−２，６−ジアミンとの混合物であり、異性体含有率の異なるものが市販されている。市販品としては、例えば“エタキュア１００”（商品名、アルベマール・コーポレーション社製、２，４−異性体／２，６−異性体の質量比８０／２０）などがある。また、ＤＥＴＤＡは、従来芳香族ポリアミンとして慣用されていた４，４’−メチレン−ビス（２−クロロアニリン）（以下、ＭＯＣＡという）より安全性が高いため、製造や使用に際しての制約がなく好ましい。 The curing agent preferably contains an aromatic polyamine crosslinking agent. As the aromatic polyamine cross-linking agent, it is preferable to use diethyltoluenediamine (hereinafter referred to as DETDA). DETDA is usually a mixture of 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine, and those having different isomer contents are commercially available. Examples of commercially available products include “Etacure 100” (trade name, manufactured by Albemarle Corporation, mass ratio 80/20 of 2,4-isomer / 2,6-isomer). Further, DETDA is preferable because it is safer than 4,4′-methylene-bis (2-chloroaniline) (hereinafter referred to as MOCA), which has been conventionally used as an aromatic polyamine, and is not restricted in production or use. .
また、ＤＥＴＤＡと他の芳香族ポリアミン架橋剤とを併用することもできる。ＤＥＴＤＡと併用可能な芳香族ポリアミン架橋剤としては、例えば、ＭＯＣＡ系ポリアミン（ＭＯＣＡ及び変性ＭＯＣＡ）、ポリアルキレンエーテルポリオール−ｐ−アミノベンゾエート、ポリテトラメチレングリコールアミノベンゾエート、１，３，５−トリイソプロピル−２，４−ジアミノベンゼン、１−メチル−３,５−ジイソプロピル−２，４−ジアミノベンゼン、１−メチル−３,５−ジイソプロピル−２，６−ジアミノベンゼン、１−エチル−３,５−ジイソプロピル−２，４−ジアミノベンゼン、１−エチル−３,５−ジイソプロピル−２，６−ジアミノベンゼン、メチレンビス（メチルチオ）ベンゼンジアミン、Ｎ，Ｎ’−ジセカンダリーブチル−ｐ−フェニレンジアミン、４，４’−ビス（ｓｅｃ−ブチルアミン）ジフェニルメタン、及び３，３’，５，５’−テトラメチル−４，４’−ジアミノジフェニルメタン、３，３’，５，５’−テトラエチル−４，４’−ジアミノジフェニルメタン、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジアミノジフェニルメタン、３，３’，５，５’−テトライソプロピル−４，４’−ジアミノジフェニルメタン、３，３’−ジメチル−５，５’−ジイソプロピル−４，４’−ジアミノジフェニルメタン、３，３’−ジメチル−５，５’−ジイソブチル−４，４’−ジアミノジフェニルメタン、３，３’−ジエチル−５，５’−ジイソプロピル−４，４’−ジアミノジフェニルメタン、３，３’−ジエチル−５，５’−ジイソブチル−４，４’−ジアミノジフェニルメタン等のテトラアルキルジアミノジフェニルメタンが挙げられる。なお、ＤＥＴＤＡと他の芳香族ポリアミンとを併用する場合、塗膜の硬化速度の調整のために必要に応じて硬化剤に触媒を添加することができる。 Moreover, DETDA and other aromatic polyamine crosslinking agents can be used in combination. Examples of aromatic polyamine crosslinking agents that can be used in combination with DETDA include MOCA-based polyamines (MOCA and modified MOCA), polyalkylene ether polyol-p-aminobenzoate, polytetramethylene glycol aminobenzoate, 1,3,5-triisopropyl -2,4-diaminobenzene, 1-methyl-3,5-diisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diisopropyl-2,6-diaminobenzene, 1-ethyl-3,5- Diisopropyl-2,4-diaminobenzene, 1-ethyl-3,5-diisopropyl-2,6-diaminobenzene, methylenebis (methylthio) benzenediamine, N, N′-disecondarybutyl-p-phenylenediamine, 4,4 '-Bis (sec-butylamine) diphenylme And 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl -5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diisopropyl -4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diisobutyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-diisopropyl-4,4'- Tetraalkyldiaminodiphenylmethane such as diaminodiphenylmethane, 3,3′-diethyl-5,5′-diisobutyl-4,4′-diaminodiphenylmethane And the like. In addition, when using DETDA and another aromatic polyamine together, a catalyst can be added to a hardening | curing agent as needed for adjustment of the hardening rate of a coating film.
硬化剤は、可塑剤を更に含むことができる。可塑剤としては、主剤に含まれるイソシアネート末端プレポリマーのＮＣＯ基との反応性を有さない可塑剤を使用できる。このような可塑剤としては、フタル酸ジブチル、フタル酸ジヘプチル、フタル酸ジオクチル、フタル酸ブチルベンジル、フタル酸ジイソノニル、アジピン酸ジオクチル、アジピン酸イソノニル、イソフタル酸ジ（２−エチルヘキシル）、塩素化パラフィン、トリス・Ｂ−クロロプロピルホスフェート等が挙げられる。 The curing agent can further include a plasticizer. As the plasticizer, a plasticizer having no reactivity with the NCO group of the isocyanate-terminated prepolymer contained in the main agent can be used. Such plasticizers include dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dioctyl adipate, isononyl adipate, di (2-ethylhexyl) isophthalate, chlorinated paraffin, And tris-B-chloropropyl phosphate.
可塑剤の使用量は、手塗り塗工に適した可使時間、塗膜の硬化性、物性等を考慮して適宜決定されるが、例えば、イソシアネート末端プレポリマー１００質量部に対して３０〜１１０質量部である。可塑剤の使用量が、１１０質量部以下であると、塗膜表面に可塑剤がブリードアウトすることを抑制でき、また、３０質量部以上であると、手塗り塗工に適した可使時間が確保しやすくなる。なお、可塑剤は、上記主剤に配合することもできる。 Although the usage-amount of a plasticizer is suitably determined in consideration of the pot life suitable for hand-coating, the sclerosis | hardenability of a coating film, a physical property, etc., for example, it is 30-30 with respect to 100 mass parts of isocyanate terminal prepolymers. 110 parts by mass. When the amount of the plasticizer used is 110 parts by mass or less, the plasticizer can be prevented from bleeding out on the surface of the coating film, and when it is 30 parts by mass or more, the pot life is suitable for hand-painting. Is easier to secure. In addition, a plasticizer can also be mix | blended with the said main ingredient.
硬化剤は、湿潤分散剤；沈降防止剤；光安定剤；消泡剤；炭酸カルシウム、タルク、カオリン、ゼオライト、ケイソウ土等の無機充填材；酸化クロム、ベンガラ、酸化鉄、カーボンブラック、酸化チタン等の顔料などを更に含むことができる。 Curing agents are wet dispersing agents; anti-settling agents; light stabilizers; antifoaming agents; inorganic fillers such as calcium carbonate, talc, kaolin, zeolite, diatomaceous earth; chromium oxide, bengara, iron oxide, carbon black, titanium oxide And the like.
ポリウレタン塗膜防水材においては、主剤に含まれるイソシアネート基末端プレポリマーのＮＣＯ基と硬化剤に含まれる芳香族ポリアミン架橋剤のＮＨ2基との当量比（ＮＣＯ基／ＮＨ2基）が、好ましくは０．８〜２．０、より好ましくは１．０〜１．８、更に好ましくは１．０〜１．６である。当量比（ＮＣＯ基／ＮＨ2基）が上記範囲内であると、所望の可使時間、塗膜の物性を確保しやすくなり、遊離のアミンによる黄変も抑制できる。また、当量比（ＮＣＯ基／ＮＨ2基）が上記範囲内であると、速硬化性、他材料との層間接着性に優れる傾向がある。 In the polyurethane coating waterproof material, the equivalent ratio (NCO group / NH 2 group) of the NCO group of the isocyanate group-terminated prepolymer contained in the main agent and the NH 2 group of the aromatic polyamine crosslinking agent contained in the curing agent is preferred. Is 0.8 to 2.0, more preferably 1.0 to 1.8, and still more preferably 1.0 to 1.6. When the equivalent ratio (NCO group / NH 2 group) is within the above range, it becomes easy to ensure the desired pot life and physical properties of the coating film, and yellowing due to free amine can be suppressed. In addition, when the equivalent ratio (NCO group / NH 2 group) is within the above range, it tends to be excellent in fast curability and interlayer adhesion with other materials.
本実施形態のポリウレタン塗膜防水材は、手塗り塗工に適しているが、可使時間及びレベリング可能時間が長くとれる点から、スタティックミキサー、ダイナミックミキサー等の自動混合装置を使用した、レベリング性を備えた機械塗工にも適用することができる。また、ダレ止め剤を配合して、立面、壁面、曲面等をローラー、リシンガン、エアレスガン等の方法でも塗工することもできる。 The polyurethane waterproof membrane according to the present embodiment is suitable for hand-painting, but it can be leveled using an automatic mixing device such as a static mixer or a dynamic mixer because the pot life and levelable time can be increased. It can also be applied to mechanical coating with In addition, an anti-sagging agent can be blended to coat the vertical surface, wall surface, curved surface, etc. by a method such as a roller, a ricin gun, or an airless gun.
また、本実施形態のポリウレタン塗膜防水材は、従来からの防水材の用途でもある廊下、階段等の発音性低下、モルタル保護、防塵性を目的とした床材、金属等の腐食防止のための防錆材、コーキング材としても使用できる。使用の際には作業性に応じてキシレン等の有機溶剤を加えて施工することも可能である。 In addition, the polyurethane coating waterproof material of the present embodiment is used for conventional waterproofing materials for corridors, staircases, etc. for sound generation deterioration, mortar protection, flooring materials for the purpose of dust prevention, prevention of corrosion of metals, etc. It can also be used as a rust preventive and caulking material. In use, it is possible to add an organic solvent such as xylene according to workability.
本実施形態に係るポリウレタン防水塗膜は、主剤と当該主剤の硬化剤とを反応させて得ることができる。より具体的には、施工現場で所定量の主剤と硬化剤とを容器内で混合攪拌し、その混合液状物をコテ、ヘラ、レーキ等を用いて塗工し、常温で硬化させることにより、ポリウレタン防水塗膜を得ることができる。 The waterproof polyurethane coating film according to this embodiment can be obtained by reacting a main agent and a curing agent of the main agent. More specifically, a predetermined amount of the main agent and curing agent are mixed and stirred in the container at the construction site, and the mixed liquid is applied using a trowel, spatula, rake, etc., and cured at room temperature, A polyurethane waterproof coating can be obtained.
以下、実施例及び比較例に基づき本発明を更に具体的に説明するが、本発明は下記の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to the following Example at all.
まず、実施例及び比較例において用いた主剤及び硬化剤に含まれる成分を以下に示す。また、実施例及び比較例で用いた評価方法についても以下に示す。 First, the components contained in the main agent and the curing agent used in Examples and Comparative Examples are shown below. Moreover, it shows below also about the evaluation method used by the Example and the comparative example.
＜主剤＞
Ｄ−２０００：ポリオキシプロピレンジオール、分子量２０００
（商品名“アクトコール Ｄ−２０００”、三井化学社製）
Ｔ−３０００：ポリオキシプロピレントリオール、分子量３０００
（商品名“アクトコール Ｔ−３０００Ｓ”、三井化学社製）
Ｔ−８０：トリレンジイソシアネート、２，４／２，６異性体比＝８０／２０
（商品名“コロネートＴ−８０”、日本ポリウレタン社製）
Ｔ−１００：トリレンジイソシアネート、２，４／２，６異性体比＝１００／０
（商品名“コロネートＴ−１００”、日本ポリウレタン社製）
<Main agent>
D-2000: Polyoxypropylene diol, molecular weight 2000
(Brand name “Actocol D-2000”, manufactured by Mitsui Chemicals, Inc.)
T-3000: Polyoxypropylene triol, molecular weight 3000
(Brand name "ACTCOL T-3000S", manufactured by Mitsui Chemicals, Inc.)
T-80: Tolylene diisocyanate, 2,4 / 2,6 isomer ratio = 80/20
(Product name "Coronate T-80", manufactured by Nippon Polyurethanes)
T-100: Tolylene diisocyanate, 2,4 / 2,6 isomer ratio = 100/0
(Product name "Coronate T-100", manufactured by Nippon Polyurethanes)
＜硬化剤＞
ＤＥＴＤＡ：ジエチルトルエンジアミン
（商品名“エタキュア１００”、アルベマール・コーポレーション社製）
可塑剤：フタル酸ジオクチル（大八化学工業所製）
無機充填材：炭酸カルシウム（丸尾カルシウム社製）
<Curing agent>
DETDA: Diethyltoluenediamine (trade name “Ecure 100”, manufactured by Albemarle Corporation)
Plasticizer: Dioctyl phthalate (manufactured by Daihachi Chemical Industry)
Inorganic filler: Calcium carbonate (Maruo Calcium Co., Ltd.)
＜粘度の測定方法＞
粘度は、ＪＩＳ Ｋ ７３０１：１９９５の「熱硬化性ウレタンエラストマー用トリレンジイソシアネート型プレポリマー試験方法 ６．２粘度」に準じて、回転粘度計（東機産業（株）ＢＨ ＩＩ形）を用い２３℃で測定した。
<Measurement method of viscosity>
The viscosity was measured using a rotational viscometer (Toki Sangyo Co., Ltd., BH II type) according to “Testing method for tolylene diisocyanate type prepolymer for thermosetting urethane elastomer 6.2 viscosity” of JIS K 7301: 1995. Measured at ° C.
＜遊離ＴＤＩ含有量の測定方法＞
主剤中に残存する遊離ＴＤＩ含有量は、ＪＩＳ Ｋ ７３０１：１９９５の「熱硬化性ウレタンエラストマー用トリレンジイソシアネート型プレポリマー試験方法 ６．４遊離トリレンジイソシアネート含有率」に準じて測定した。
<Measurement method of free TDI content>
The free TDI content remaining in the main agent was measured according to JIS K 7301: 1995 "Testing method for tolylene diisocyanate type prepolymer for thermosetting urethane elastomer 6.4 Free tolylene diisocyanate content".
＜ＮＥＴ．ＣＰＲ値の測定方法＞
以下の手順に従って、ＮＥＴ．ＣＰＲ値を測定した。
１）最大容量５ｍＬのビュレットをもつ自動滴定装置を用いて試験を行った。
２）１００ｍＬ滴定フラスコに試料約３０ｇを１ｍｇまで正確に量りとった。これにメタノール（ＩＳＯ６３５３−２に規定する試験級）５０ｍＬを加え、充分に混ざるまで攪拌し試料用溶液とした。また、空試験用溶液として上記メタノール５０ｍＬを用意した。
３）水酸化ナトリウム溶液（０．０１ｍｏｌ／Ｌ）を１ｍＬ用ホールピペットにとり、上記の試料用及び空試験用溶液に加え、十分に混合した。
４）０．０１ｍｏｌ／Ｌ塩酸で上記試料用溶液及び空試験用溶液を滴定し、終点（最後の変曲点）までの滴定量を記録した。なお、ＮＥＴ．ＣＰＲ値が−１０以下の場合は、規定度の高い水酸化ナトリウム溶液を使用した。
５）ＮＥＴ．ＣＰＲ値を、下記式（２）によって算出した。
Ｃ＝（Ｖｓ−Ｖｂ）×Ｍ×１０００×３０／ｍ ・・・（２）
ただし、
Ｃ：ＮＥＴ．ＣＰＲ値
Ｖｓ：試料用溶液の滴定に要した塩酸量（ｍＬ）
Ｖｂ：空試験用溶液の滴定に要した塩酸量（ｍＬ）
Ｍ：塩酸モル濃度（ｍｏｌ／Ｌ）
ｍ：試料の質量（ｇ）
<NET. Measuring method of CPR value>
According to the following procedure, NET. CPR values were measured.
1) The test was performed using an automatic titrator with a burette with a maximum volume of 5 mL.
2) About 30 g of sample was accurately weighed to 1 mg in a 100 mL titration flask. To this was added 50 mL of methanol (the test grade specified in ISO 6353-2), and the mixture was stirred until it was sufficiently mixed to prepare a sample solution. Further, 50 mL of the methanol was prepared as a blank test solution.
3) A sodium hydroxide solution (0.01 mol / L) was taken into a 1 mL hole pipette, added to the sample solution and the blank test solution, and mixed well.
4) The sample solution and the blank solution were titrated with 0.01 mol / L hydrochloric acid, and the titration amount to the end point (last inflection point) was recorded. NET. When the CPR value was -10 or less, a sodium hydroxide solution having a high normality was used.
5) NET. The CPR value was calculated by the following formula (2).
C = (Vs−Vb) × M × 1000 × 30 / m (2)
However,
C: NET. CPR value Vs: Amount of hydrochloric acid required for titration of sample solution (mL)
Vb: Amount of hydrochloric acid required for titration of the blank test solution (mL)
M: molar concentration of hydrochloric acid (mol / L)
m: Mass of the sample (g)
＜ＮＥＴ．ＣＰＲ値の計算方法＞
下記式（３）によって、ＮＥＴ．ＣＰＲ値の計算値を求めた。
Ｃｃ＝ＥＢ−ＥＡ＝（Ｅｐ−Ｅｔ＋Ｅｂ−Ｅａ） ・・・（３）
ただし、
Ｃｃ：ＮＥＴ．ＣＰＲ値の計算値
ＥＡ：３０ｇの全原料成分中に含まれる酸性物質のマイクロ当量
ＥＢ：３０ｇの全原料成分中に含まれる塩基性物質のマイクロ当量
Ｅｔ：３０ｇの全原料成分中、ＴＤＩ組成物に含まれる酸性物質のマイクロ当量
Ｅｐ：３０ｇの全原料成分中、ＰＰＧ組成物に含まれる塩基性物質のマイクロ当量
Ｅａ：３０ｇの全原料成分中、添加剤に含まれる酸性物質のマイクロ当量
Ｅｂ：３０ｇの全原料成分中、添加剤に含まれる塩基性物質のマイクロ当量
<NET. Calculation method of CPR value>
According to the following formula (3), NET. The calculated value of CPR value was obtained.
Cc = EB−EA = (Ep−Et + Eb−Ea) (3)
However,
Cc: NET. Calculated value of CPR value EA: micro equivalent of acidic substance contained in all raw material components of 30 g EB: micro equivalent of basic substance contained in all raw material components of 30 g Et: TDI composition in all raw material components of 30 g Microequivalent of acidic substance contained in the additive Ep: 30 g of all raw material components, microequivalent of the basic substance contained in the PPG composition Ea: microequivalent of acidic substance contained in the additive in 30 g of all raw material components Eb: In 30g of all raw material components, micro equivalent of basic substance contained in additive
＜歩行性の評価方法＞
主剤と硬化剤とを混合した後ガラス板上に流延し、流延後１６時間経過時点での塗膜の硬化状態を手で触わることにより歩行性を評価した。歩行性が特に良好なものを＋＋、良好なものを＋、やや不良なものを±、不良なものを−とした。
<Evaluation method of walking ability>
The main agent and the curing agent were mixed and cast on a glass plate, and the walking property was evaluated by touching the cured state of the coating film at the point of 16 hours after casting. Those with particularly good walking ability were marked with ++, those with good walking ability were marked with +, those with slightly poor walking ability were marked with ±, and those with poor walking ability were marked with-.
＜可使時間の評価方法＞
主剤と硬化剤とを混合した後、混合液の２３℃での粘度が１０万センチポイズに達するまでの時間（分）を、支障なく塗工できる時間（可使時間）とした。
<Evaluation method of pot life>
After mixing the main agent and the curing agent, the time (minutes) until the viscosity at 23 ° C. of the mixed solution reached 100,000 centipoise was defined as the time during which coating can be performed without any trouble (pot life).
＜硬化塗膜の物性の評価方法＞
塗工後、２３℃で７日経過後にＪＩＳ Ａ ６０２１（建築用塗膜防水材）に準じて硬化塗膜の物性を評価した。本実施例及び比較例においては、引張強さ（Ｔｂ、単位：Ｎ／ｍｍ２）、引裂強さ（Ｔｔ、単位：Ｎ／ｍｍ）、破断時の伸び率（Ｅｂ、単位：％）、及び酸処理後の引張強さ比（Ｔｂ比、単位：％）について評価した。
<Method for evaluating physical properties of cured coating film>
After coating, after 7 days at 23 ° C., the physical properties of the cured coating film were evaluated in accordance with JIS A 6021 (Building waterproofing film). In Examples and Comparative Examples, tensile strength (Tb, unit: N / mm 2 ), tear strength (Tt, unit: N / mm), elongation at break (Eb, unit:%), and The tensile strength ratio after acid treatment (Tb ratio, unit:%) was evaluated.
［実施例１、比較例１］
表１に示す組成の主剤を以下の手順に従って調製した。まず、Ｄ−２０００（ＣＰＲ値：０．５１）とＴ−３０００（ＣＰＲ値：０．５４）とのＰＰＧ混合物（ＣＰＲ値：０．５２）に、塩化ベンゾイル（メチルエチルケトンの希釈溶液）を添加して中和処理を行い、ポリオール組成物を得た。このポリオール組成物のＣＰＲ値（計算値）を表１に示す。なお、表１に示す塩化ベンゾイルの添加量は、反応系原料（ポリオール組成物とイソシアネート組成物との混合物）の全量を基準とした添加量（マイクロ当量）である。続いて、得られたポリオール組成物にＴ−１００を加え（当量比：ＴＤＩのＮＣＯ基／ＰＰＧのＯＨ基＝１．７５）、反応温度９０℃で反応を完結させてイソシアネート基末端プレポリマーを得た。さらに、添加剤（ＣＰＲ値：０）を加えて主剤を得た。なお、反応系原料のＮＥＴ．ＣＰＲ値（計算値）を表１に示す。また、主剤の性状を表１に示す。
[Example 1, Comparative Example 1]
A main agent having the composition shown in Table 1 was prepared according to the following procedure. First, benzoyl chloride (diluted solution of methyl ethyl ketone) was added to a PPG mixture (CPR value: 0.52) of D-2000 (CPR value: 0.51) and T-3000 (CPR value: 0.54). Then, a neutralization treatment was performed to obtain a polyol composition. Table 1 shows the CPR value (calculated value) of this polyol composition. In addition, the addition amount of benzoyl chloride shown in Table 1 is an addition amount (micro equivalent) based on the total amount of the reaction system raw material (mixture of the polyol composition and the isocyanate composition). Subsequently, T-100 was added to the resulting polyol composition (equivalent ratio: NCO group of TDI / OH group of PPG = 1.75), and the reaction was completed at a reaction temperature of 90 ° C. to obtain an isocyanate group-terminated prepolymer. Obtained. Furthermore, an additive (CPR value: 0) was added to obtain a main agent. Note that the NET. CPR values (calculated values) are shown in Table 1. The properties of the main agent are shown in Table 1.
表１のとおり、実施例１−１〜１−６では主剤中の遊離ＴＤＩ含有量が０．１質量％未満であるが、比較例１−１〜１−２では主剤中の遊離ＴＤＩ含有量が０．１質量％以上であった。また、主剤中の遊離ＴＤＩ含有量は、主剤のＮＥＴ．ＣＰＲ値（測定値）が−１．０〜０．０１付近であるときに極小値を有し、ＮＥＴ．ＣＰＲ値が−１．０から低下するにつれて緩やかに増加する傾向が認められた。 As shown in Table 1, in Examples 1-1 to 1-6, the free TDI content in the main agent is less than 0.1% by mass, but in Comparative Examples 1-1 to 1-2, the free TDI content in the main agent is Was 0.1% by mass or more. In addition, the free TDI content in the main agent is determined based on the NET. It has a minimum value when the CPR value (measured value) is around -1.0 to 0.01, and NET. There was a tendency for the CPR value to increase gradually as it decreased from -1.0.
［実施例２、比較例２］
表２に示す組成の硬化剤と、実施例１−１〜１−６及び比較例１−１〜１−２で調製した各主剤とを、上記ＪＩＳ Ａ ６０２１に準じて、それぞれ２３℃で２４時間以上静置した後、２３℃で質量比（主剤／硬化剤）が１／２（当量比＝１．２）となるように混合した。この混合物を、ガラス板上に厚さ約２ｍｍになるように流延し、２３℃で７日間養生して硬化した塗膜を得た。この塗膜の物性を測定した結果を表３に示す。なお、実施例２−１〜２−６、比較例２−１〜２−２が、それぞれ実施例１−１〜１−６、比較例１−１〜１−２で調製した主剤を用いたときに得られた塗膜である。
[Example 2, Comparative Example 2]
The curing agent having the composition shown in Table 2 and the main agents prepared in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-2 were each 24 ° C. at 23 ° C. according to JIS A 6021. After standing for more than an hour, the mixture was mixed at 23 ° C. so that the mass ratio (main agent / curing agent) was ½ (equivalent ratio = 1.2). This mixture was cast on a glass plate to a thickness of about 2 mm, and cured at 23 ° C. for 7 days to obtain a cured coating film. The results of measuring the physical properties of this coating film are shown in Table 3. In addition, Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-2 used the main agents prepared in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-2, respectively. It is a coating film sometimes obtained.
表３から、主剤のＮＥＴ．ＣＰＲ値が低下しすぎると、酸処理後の塗膜物性（Ｔｂ比）が防水材用ＪＩＳ規格値を満たさないことがわかる（比較例２−２）。 From Table 3, the NET. When the CPR value is too low, it can be seen that the physical properties (Tb ratio) of the coating film after acid treatment do not satisfy the JIS standard values for waterproofing materials (Comparative Example 2-2).
［実施例３］
Ｔ−１００（酸度０．０００１０％）に塩化ベンゾイルを３８．０マイクロ当量添加して、酸度の高いイソシアネート組成物を調製した。このイソシアネート組成物の酸度は０．０１１００％であった。また、実施例３−２では、ＰＰＧにも塩化ベンゾイルを９．０マイクロ当量添加した。上記イソシアネート組成物とＰＰＧ（Ｄ−２０００はＣＰＲ＝０．４１）組成物とを用い、その他は実施例１と同様にしてイソシアネート基末端プレポリマー及び主剤を得た。また、得られた主剤を用いて、実施例２と同様にして塗膜を得た。主剤の性状及び塗膜の物性を表４に示す。
[Example 3]
An isocyanate composition having a high acidity was prepared by adding 38.0 micro equivalents of benzoyl chloride to T-100 (acidity 0.00010%). The acidity of this isocyanate composition was 0.01100%. Moreover, in Example 3-2, 9.0 micro equivalent of benzoyl chloride was also added to PPG. An isocyanate group-terminated prepolymer and a main agent were obtained in the same manner as in Example 1 except that the isocyanate composition and the PPG (D-2000 was CPR = 0.41) composition were used. Moreover, the coating film was obtained like Example 2 using the obtained main ingredient. Table 4 shows the properties of the main agent and the physical properties of the coating film.
ＣＰＲ値を調整していないＰＰＧと、酸度を調整したイソシアネート組成物とを反応させて得られた主剤中の遊離ＴＤＩ含有量は０．１質量％未満であった。また、当該主剤を用いて得られた塗膜の物性は、ＪＩＳ規格値を満たしていた。 The free TDI content in the main agent obtained by reacting the PPG whose CPR value was not adjusted with the isocyanate composition whose acidity was adjusted was less than 0.1% by mass. Moreover, the physical property of the coating film obtained using the said main ingredient satisfy | filled the JIS specification value.
［実施例４、比較例４］
表５に示す条件で、実施例１と同様にして各主剤を調製し、得られた主剤を用いて、実施例２と同様にして塗膜を得た。
[Example 4, Comparative Example 4]
Under the conditions shown in Table 5, each main agent was prepared in the same manner as in Example 1, and a coating film was obtained in the same manner as in Example 2 using the obtained main agent.
表５より、実施例４−１〜４−５では、すべて主剤中の遊離ＴＤＩ含有量が０．１質量％未満であり、また塗膜の物性がＪＩＳ規格値を満足していた。一方、比較例４では、主剤中の遊離ＴＤＩ含有量が０．１質量％以上であった。 From Table 5, in Examples 4-1 to 4-5, the free TDI content in the main agent was less than 0.1% by mass, and the physical properties of the coating film satisfied the JIS standard values. On the other hand, in Comparative Example 4, the content of free TDI in the main agent was 0.1% by mass or more.
［実施例５、比較例５］
主剤中の遊離ＴＤＩ含有量の低減に関して、２，４−異性体／２，６−異性体含有率の異なるＴＤＩ使用による効果を検討した。ＴＤＩとしてＴ−１００とＴ−８０とを表６に示す割合で用い、実施例１と同様にして主剤を得た。実施例５においては、ＴＤＩ中の２，４−異性体の含有量は９０％であり、比較例５においては、ＴＤＩ中の２，４−異性体の含有量は８５％であった。また、得られた主剤を用いて、実施例２と同様にして塗膜を得た。主剤の性状及び塗膜の物性を表６に示す。
[Example 5, Comparative Example 5]
Regarding the reduction of the free TDI content in the main agent, the effect of using TDI with different 2,4-isomer / 2,6-isomer content was examined. A main agent was obtained in the same manner as in Example 1 using T-100 and T-80 as TDI in the ratios shown in Table 6. In Example 5, the content of the 2,4-isomer in TDI was 90%, and in Comparative Example 5, the content of the 2,4-isomer in TDI was 85%. Moreover, the coating film was obtained like Example 2 using the obtained main ingredient. Table 6 shows the properties of the main agent and the physical properties of the coating film.
［実施例６］
表６に示す条件で、実施例１と同様にして主剤を調製した。また、得られた主剤と、ポリアミン架橋剤としてポリテトラメチレングリコールアミノベンゾエートを含む硬化剤とを用いて、実施例２と同様にして塗膜を得た。主剤の性状及び塗膜の物性を表６に示す。
[Example 6]
A base agent was prepared in the same manner as in Example 1 under the conditions shown in Table 6. In addition, a coating film was obtained in the same manner as in Example 2 using the obtained main agent and a curing agent containing polytetramethylene glycol aminobenzoate as a polyamine crosslinking agent. Table 6 shows the properties of the main agent and the physical properties of the coating film.
［比較例７］
表７に示す条件で、実施例１と同様にして主剤を調製した。主剤の性状を表７に示す。
[Comparative Example 7]
A base agent was prepared in the same manner as in Example 1 under the conditions shown in Table 7. Table 7 shows the properties of the main agent.
［実施例８］
表８に示す条件で、実施例１と同様に各主剤を調製した。実施例８−１〜８−６では、Ｄ−２０００とＴ−３０００との質量比（Ｄ−２０００／Ｔ−３０００）を９．５／０．５〜２／８の範囲で変更した。また、得られた主剤を用いて、実施例２と同様にして塗膜を得た。主剤の性状及び得られた塗膜の物性を表８に示す。
[Example 8]
Each main agent was prepared in the same manner as in Example 1 under the conditions shown in Table 8. In Examples 8-1 to 8-6, the mass ratio (D-2000 / T-3000) between D-2000 and T-3000 was changed in the range of 9.5 / 0.5 to 2/8. Moreover, the coating film was obtained like Example 2 using the obtained main ingredient. Table 8 shows the properties of the main agent and the properties of the obtained coating film.
［実施例９］
表９に示す条件で、実施例１と同様にして主剤を調製し、実施例２と同様にして塗膜を得た。実施例９−１〜９−６では、主剤と硬化剤との当量比（ＮＣＯ基／ＮＨ２基）が０．９〜１．９の範囲となるように、硬化剤中のＤＥＴＤＡ含有量を変更した。主剤の性状及び塗膜の物性を表９に示す。
[Example 9]
Under the conditions shown in Table 9, the main agent was prepared in the same manner as in Example 1, and a coating film was obtained in the same manner as in Example 2. In Examples 9-1 to 9-6, the DETDA content in the curing agent was adjusted so that the equivalent ratio of the main agent to the curing agent (NCO group / NH 2 group) was in the range of 0.9 to 1.9. changed. Table 9 shows the properties of the main agent and the physical properties of the coating film.
本発明によれば、安全性の高い、且つ優れた品質性能を有するウレタン塗膜防水材が安定して顧客に提供される。 According to the present invention, a waterproof urethane film waterproof material having high safety and excellent quality performance is stably provided to customers.
Claims (16)
前記主剤のＮＥＴ．ＣＰＲ値が−３５〜０．３であり、
前記イソシアネート基末端プレポリマーは、ポリオキシアルキレンポリオールを含むポリオール組成物とトリレンジイソシアネートを含むイソシアネート組成物とを、前記ポリオキシアルキレンポリオールの水酸基（ＯＨ基）に対する前記トリレンジイソシアネートのイソシアネート基（ＮＣＯ基）の当量比（ＮＣＯ基／ＯＨ基）が１．５０〜１．９０となるように反応させて得ることができるものであり、
前記トリレンジイソシアネートは、２，４−トリレンジイソシアネートを９０質量％以上含む、ポリウレタン塗膜防水材用主剤。 A polyurethane coating waterproofing agent containing an isocyanate group-terminated prepolymer,
NET. The CPR value is −35 to 0.3,
The isocyanate group-terminated prepolymer comprises a polyol composition containing polyoxyalkylene polyol and an isocyanate composition containing tolylene diisocyanate, the isocyanate group (NCO) of the tolylene diisocyanate with respect to the hydroxyl group (OH group) of the polyoxyalkylene polyol. Group) equivalent ratio (NCO group / OH group) can be obtained by reacting to be 1.50 to 1.90,
The tolylene diisocyanate is a main ingredient for polyurethane coating waterproofing material containing 90% by mass or more of 2,4-tolylene diisocyanate.
前記トリレンジイソシアネート中の２，４−トリレンジイソシアネート含有量を９０質量％以上とし、
前記ポリオール組成物と前記イソシアネート組成物とを、前記ポリオキシアルキレンポリオールの水酸基（ＯＨ基）に対する前記トリレンジイソシアネートのイソシアネート基（ＮＣＯ基）の当量比（ＮＣＯ基／ＯＨ基）が１．５０〜１．９０となるように反応させ、前記反応物のＮＥＴ．ＣＰＲ値を−３５〜０．３とする、ポリウレタン塗膜防水材用主剤の製造方法。 A process for producing a base material for a polyurethane coating waterproof material comprising an isocyanate group-terminated prepolymer comprising a reaction product of a polyol composition containing a polyoxyalkylene polyol and an isocyanate composition containing tolylene diisocyanate,
The 2,4-tolylene diisocyanate content in the tolylene diisocyanate is 90% by mass or more,
In the polyol composition and the isocyanate composition, the equivalent ratio (NCO group / OH group) of the isocyanate group (NCO group) of the tolylene diisocyanate to the hydroxyl group (OH group) of the polyoxyalkylene polyol is 1.50. The reaction was carried out to give 1.90, and the NET. The manufacturing method of the main ingredient for polyurethane paint waterproofing materials which makes CPR value -35-0.3.
前記トリレンジイソシアネート中の２，４−トリレンジイソシアネート含有量を９０質量％以上とし、
前記ポリオール組成物と前記イソシアネート組成物とを、前記ポリオキシアルキレンポリオールの水酸基（ＯＨ基）に対する前記トリレンジイソシアネートのイソシアネート基（ＮＣＯ基）の当量比（ＮＣＯ基／ＯＨ基）が１．５０〜１．９０となるように反応させ、前記反応物のＮＥＴ．ＣＰＲ値を−３５〜０．３とする、低減方法。 A method for reducing free tolylene diisocyanate content in a reaction product of a polyol composition containing a polyoxyalkylene polyol and an isocyanate composition containing tolylene diisocyanate,
The 2,4-tolylene diisocyanate content in the tolylene diisocyanate is 90% by mass or more,
In the polyol composition and the isocyanate composition, the equivalent ratio (NCO group / OH group) of the isocyanate group (NCO group) of the tolylene diisocyanate to the hydroxyl group (OH group) of the polyoxyalkylene polyol is 1.50. The reaction was carried out to give 1.90, and the NET. A reduction method in which the CPR value is −35 to 0.3.
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Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6341954B2 (en) * | 1979-03-27 | 1988-08-19 | Nippon Polyurethane Kogyo Kk | |
| JPH03294327A (en) * | 1990-04-13 | 1991-12-25 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of urethane prepolymer containing terminal isocyanate group and having excellent storage stability |
| JPH0418415A (en) * | 1989-12-21 | 1992-01-22 | Mobay Corp | Storage-stable solid isocyanate composition, its manufacture, and method of using it |
| JPH08143816A (en) * | 1994-04-21 | 1996-06-04 | Hodogaya Chem Co Ltd | Production of polyurethane coating film-waterproofing material curable rapidly at normal temperature |
| JPH0959342A (en) * | 1995-08-25 | 1997-03-04 | Hodogaya Chem Co Ltd | Production of waterproofing material of quick-curing polyurethane coating film |
| JPH09278859A (en) * | 1996-04-16 | 1997-10-28 | Asahi Glass Co Ltd | Two-pack waterproofing material composition |
| JPH09324025A (en) * | 1996-06-05 | 1997-12-16 | Asahi Glass Co Ltd | Two-package waterproofing composition |
| JPH1036472A (en) * | 1996-07-24 | 1998-02-10 | Asahi Glass Co Ltd | Two-pack water-proofing material composition |
| JPH1087778A (en) * | 1996-09-20 | 1998-04-07 | Asahi Glass Co Ltd | Two-pack curable composition |
| JPH1095826A (en) * | 1996-09-26 | 1998-04-14 | Asahi Glass Co Ltd | Two-component curable composition |
| JPH10195159A (en) * | 1997-01-07 | 1998-07-28 | Mitsui Chem Inc | Isocyanato-terminated prepolymer, its production and curable polyurethane composition |
| JPH10292025A (en) * | 1997-04-17 | 1998-11-04 | Dainippon Ink & Chem Inc | Two-package curable urethane composition, coating material, sealing material and adhesive |
| JP2007000720A (en) * | 2005-06-22 | 2007-01-11 | I C K Kk | Urethane waterproof structure and environment-responsive type topcoat material using therefor |
| WO2008050340A1 (en) * | 2006-10-26 | 2008-05-02 | Mempile Inc. | Recording medium for use in a three-dimensional optical data carrier, and method and system for data recording/reproducing |
| JP2008297338A (en) * | 2007-05-29 | 2008-12-11 | Dyflex Corp | Two-pack type urethane composition for application of urethane rubber-based coated film waterproofing material, and method for applying urethane rubber-based coated film waterproofing material by using the same |
| JP2009046627A (en) * | 2007-08-22 | 2009-03-05 | Dic Corp | Two-component curing type urethane composition and construction method of water-proof structure |
| JP2011516634A (en) * | 2008-03-20 | 2011-05-26 | ダウ グローバル テクノロジーズ リミティド ライアビリティ カンパニー | Prepolymers made from natural oil-based polyols |
| JP2013139559A (en) * | 2011-12-07 | 2013-07-18 | I C K Kk | Two-pack, environmental-responsive urethane waterproof material composition |
-
2013
- 2013-06-07 JP JP2013120769A patent/JP5484620B1/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6341954B2 (en) * | 1979-03-27 | 1988-08-19 | Nippon Polyurethane Kogyo Kk | |
| JPH0418415A (en) * | 1989-12-21 | 1992-01-22 | Mobay Corp | Storage-stable solid isocyanate composition, its manufacture, and method of using it |
| JPH03294327A (en) * | 1990-04-13 | 1991-12-25 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of urethane prepolymer containing terminal isocyanate group and having excellent storage stability |
| JPH08143816A (en) * | 1994-04-21 | 1996-06-04 | Hodogaya Chem Co Ltd | Production of polyurethane coating film-waterproofing material curable rapidly at normal temperature |
| JPH0959342A (en) * | 1995-08-25 | 1997-03-04 | Hodogaya Chem Co Ltd | Production of waterproofing material of quick-curing polyurethane coating film |
| JPH09278859A (en) * | 1996-04-16 | 1997-10-28 | Asahi Glass Co Ltd | Two-pack waterproofing material composition |
| JPH09324025A (en) * | 1996-06-05 | 1997-12-16 | Asahi Glass Co Ltd | Two-package waterproofing composition |
| JPH1036472A (en) * | 1996-07-24 | 1998-02-10 | Asahi Glass Co Ltd | Two-pack water-proofing material composition |
| JPH1087778A (en) * | 1996-09-20 | 1998-04-07 | Asahi Glass Co Ltd | Two-pack curable composition |
| JPH1095826A (en) * | 1996-09-26 | 1998-04-14 | Asahi Glass Co Ltd | Two-component curable composition |
| JPH10195159A (en) * | 1997-01-07 | 1998-07-28 | Mitsui Chem Inc | Isocyanato-terminated prepolymer, its production and curable polyurethane composition |
| JPH10292025A (en) * | 1997-04-17 | 1998-11-04 | Dainippon Ink & Chem Inc | Two-package curable urethane composition, coating material, sealing material and adhesive |
| JP2007000720A (en) * | 2005-06-22 | 2007-01-11 | I C K Kk | Urethane waterproof structure and environment-responsive type topcoat material using therefor |
| WO2008050340A1 (en) * | 2006-10-26 | 2008-05-02 | Mempile Inc. | Recording medium for use in a three-dimensional optical data carrier, and method and system for data recording/reproducing |
| JP2008297338A (en) * | 2007-05-29 | 2008-12-11 | Dyflex Corp | Two-pack type urethane composition for application of urethane rubber-based coated film waterproofing material, and method for applying urethane rubber-based coated film waterproofing material by using the same |
| JP2009046627A (en) * | 2007-08-22 | 2009-03-05 | Dic Corp | Two-component curing type urethane composition and construction method of water-proof structure |
| JP2011516634A (en) * | 2008-03-20 | 2011-05-26 | ダウ グローバル テクノロジーズ リミティド ライアビリティ カンパニー | Prepolymers made from natural oil-based polyols |
| JP2013139559A (en) * | 2011-12-07 | 2013-07-18 | I C K Kk | Two-pack, environmental-responsive urethane waterproof material composition |
Non-Patent Citations (1)
| Title |
|---|
| 岩田敬治著,プラスチック材料講座●ポリウレタン樹脂, vol. ９版,, JPN6013051162, pages 61 - 66, ISSN: 0002656076 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016203053A (en) * | 2015-04-16 | 2016-12-08 | オルガノ株式会社 | Method and apparatus for regenerating ion exchange resin |
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