JP6851906B2 - Chemical solution composition for consolidation of ground - Google Patents
Chemical solution composition for consolidation of ground Download PDFInfo
- Publication number
- JP6851906B2 JP6851906B2 JP2017108317A JP2017108317A JP6851906B2 JP 6851906 B2 JP6851906 B2 JP 6851906B2 JP 2017108317 A JP2017108317 A JP 2017108317A JP 2017108317 A JP2017108317 A JP 2017108317A JP 6851906 B2 JP6851906 B2 JP 6851906B2
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- liquid
- parts
- solution
- ground
- mass
- Prior art date
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- 239000000126 substance Substances 0.000 title claims description 59
- 239000000203 mixture Substances 0.000 title claims description 56
- 238000007596 consolidation process Methods 0.000 title claims description 28
- 239000007788 liquid Substances 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 70
- 150000001875 compounds Chemical class 0.000 claims description 67
- 239000003054 catalyst Substances 0.000 claims description 37
- 239000005056 polyisocyanate Substances 0.000 claims description 30
- 229920001228 polyisocyanate Polymers 0.000 claims description 30
- 229920005862 polyol Polymers 0.000 claims description 28
- 150000003077 polyols Chemical class 0.000 claims description 28
- 229920006295 polythiol Polymers 0.000 claims description 26
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 23
- 239000011593 sulfur Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 16
- 239000003063 flame retardant Substances 0.000 claims description 15
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
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- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 125000000101 thioether group Chemical group 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
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- 238000000034 method Methods 0.000 description 21
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- 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 6
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- 230000009471 action Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 2
- FZQMJOOSLXFQSU-UHFFFAOYSA-N 3-[3,5-bis[3-(dimethylamino)propyl]-1,3,5-triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CN(CCCN(C)C)CN(CCCN(C)C)C1 FZQMJOOSLXFQSU-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 2
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- LULCPJWUGUVEFU-UHFFFAOYSA-N Phthiocol Natural products C1=CC=C2C(=O)C(C)=C(O)C(=O)C2=C1 LULCPJWUGUVEFU-UHFFFAOYSA-N 0.000 description 2
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- HECGKCOICWUUJU-UHFFFAOYSA-N bis(diphenylphosphanylmethyl)-phenylphosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 HECGKCOICWUUJU-UHFFFAOYSA-N 0.000 description 2
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
- IYPNRTQAOXLCQW-UHFFFAOYSA-N [4-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C=C1 IYPNRTQAOXLCQW-UHFFFAOYSA-N 0.000 description 1
- OAJHWYJGCSAOTQ-UHFFFAOYSA-N [Zr].CCCCCCCCO.CCCCCCCCO.CCCCCCCCO.CCCCCCCCO Chemical compound [Zr].CCCCCCCCO.CCCCCCCCO.CCCCCCCCO.CCCCCCCCO OAJHWYJGCSAOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- YBGHFLPNIGPGHX-UHFFFAOYSA-N calcium;octan-1-olate Chemical compound [Ca+2].CCCCCCCC[O-].CCCCCCCC[O-] YBGHFLPNIGPGHX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine 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
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products 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
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ALPIESLRVWNLAX-UHFFFAOYSA-N hexane-1,1-dithiol Chemical compound CCCCCC(S)S ALPIESLRVWNLAX-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- DLAPQHBZCAAVPQ-UHFFFAOYSA-N iron;pentane-2,4-dione Chemical compound [Fe].CC(=O)CC(C)=O DLAPQHBZCAAVPQ-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- XFLSMWXCZBIXLV-UHFFFAOYSA-N n,n-dimethyl-2-(4-methylpiperazin-1-yl)ethanamine Chemical compound CN(C)CCN1CCN(C)CC1 XFLSMWXCZBIXLV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FLESAADTDNKLFJ-UHFFFAOYSA-N nickel;pentane-2,4-dione Chemical compound [Ni].CC(=O)CC(C)=O FLESAADTDNKLFJ-UHFFFAOYSA-N 0.000 description 1
- WKVAXZCSIOTXBT-UHFFFAOYSA-N octane-1,1-dithiol Chemical compound CCCCCCCC(S)S WKVAXZCSIOTXBT-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- GCKZNUDNTDWGFM-UHFFFAOYSA-N pentane-2,4-dione;tin Chemical compound [Sn].CC(=O)CC(C)=O GCKZNUDNTDWGFM-UHFFFAOYSA-N 0.000 description 1
- WATYAKBWIQTPDE-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O WATYAKBWIQTPDE-UHFFFAOYSA-N 0.000 description 1
- SGNLDVYVSFANHW-UHFFFAOYSA-N pentane-2,4-dione;zirconium Chemical compound [Zr].CC(=O)CC(C)=O SGNLDVYVSFANHW-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003015 phosphoric acid halides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Description
本発明は、地山固結用薬液組成物に係り、特に、地盤注入用途又は空洞充填用途に有利に用いられる地山固結用薬液組成物に関するものである。 The present invention relates to a chemical solution composition for ground consolidation, and more particularly to a chemical solution composition for ground consolidation which is advantageously used for ground injection or cavity filling.
従来より、不安定な岩盤や地盤の安定強化のための地盤注入用途や、人工構造物のクラックや空隙を充填する空洞充填用途に採用される対策の一つとして、無機乃至有機系グラウトの注入があり、ある程度の効果を上げている。ここで、それら用途において用いられる有機系グラウトとしては、ポリオールを必須成分とするＡ液と、ポリイソシアネートを必須成分とするＢ液とから構成される二液硬化型のウレタン系薬液が広く知られているところ、例えば、特許文献１（特開２００２−２８５１５４号公報）においては、水と、ポリオールと、三級アミン系触媒を必須成分とするＡ液と、イソシアネートを必須成分とするＢ液とを備え、Ａ液に芳香族系界面活性剤を含有させてなる地山固結用薬液が開示されている。 Conventionally, injection of inorganic or organic grout is one of the measures adopted for ground injection for stabilizing and strengthening unstable rocks and ground, and for filling cavities that fill cracks and voids in artificial structures. There is, and it has a certain effect. Here, as an organic grout used in these applications, a two-component curable urethane-based chemical solution composed of a solution A containing a polyol as an essential component and a solution B containing a polyisocyanate as an essential component is widely known. However, for example, in Patent Document 1 (Japanese Unexamined Patent Publication No. 2002-285154), water, a polyol, a solution A containing a tertiary amine-based catalyst as an essential component, and a solution B containing an isocyanate as an essential component are used. Disclosed is a chemical solution for solidifying ground, which comprises a solution A containing an aromatic surfactant.
しかしながら、特許文献１に開示のものを始めとする従来の、ポリオールを主成分とするＡ液とイソシアネートを主成分とするＢ液とから構成される地山固結用薬液にあっては、特に湧水の多い地山で用いると、Ａ液とＢ液との混合による硬化反応が進行する前に、薬液が湧水と接触することによって希釈され、これにより、薬液を注入する際に湧水が白濁する問題や、湧水中に薬液が流出し、水質汚染の原因になるという問題があった。 However, in the conventional chemical solution for solidifying ground, which is composed of a solution A containing a polyol as a main component and a solution B containing an isocyanate as a main component, such as those disclosed in Patent Document 1, in particular. When used in spring-rich grounds, the chemical solution is diluted by contact with the spring water before the curing reaction due to the mixture of solution A and solution B proceeds, which causes the spring water to be injected when the chemical solution is injected. There was a problem that it became cloudy and that the chemical solution flowed out into the spring water, causing water pollution.
ここにおいて、本発明は、上述の如き事情を背景にして為されたものであって、その解決すべき課題とするところは、湧水などの水と接触した際にも、水の白濁を有利に防止し、且つ水に希釈されて流出することを効果的に防止し得る地山固結用薬液組成物を提供することにある。 Here, the present invention has been made in the background of the above-mentioned circumstances, and the problem to be solved is that the white turbidity of water is advantageous even when it comes into contact with water such as spring water. It is an object of the present invention to provide a chemical solution composition for solidification of a ground, which can prevent the problem from flowing out after being diluted with water.
そして、本発明は、上記した課題を解決するために、以下に列挙せる如き各種の態様において、好適に実施され得るものであるが、また、以下に記載の各態様は、任意の組合せにおいて、採用可能である。なお、本発明の態様乃至は技術的特徴は、以下に記載のものに何等限定されることなく、明細書全体の記載から把握される発明思想に基づいて認識され得るものであることが、理解されるべきである。 Then, in order to solve the above-mentioned problems, the present invention can be preferably carried out in various aspects as listed below, and each aspect described below can be carried out in any combination. It can be adopted. It is understood that the aspects or technical features of the present invention are not limited to those described below and can be recognized based on the invention idea grasped from the description of the entire specification. It should be.
（１） ポリオールを主成分とするＡ液と、ポリイソシアネートを主成分とするＢ液とか らなる地山固結用薬液組成物において、前記Ａ液が、チオール基含有化合物からな る含硫黄化合物を含有していることを特徴とする地山固結用薬液組成物。
（２） 前記チオール基含有化合物が、１分子内に２以上のチオール基を有するポリチオ ール化合物である前記態様（１）に記載の地山固結用薬液組成物。
（３） 前記ポリチオールが、アルキルジチオール化合物、エーテル基含有ポリチオール 化合物、カルボニル基含有ポリチオール化合物、チオエーテル基含有ポリチオール 化合物、芳香族基含有ポリチオール化合物の何れかである前記態様（２）に記載の 地山固結用薬液組成物。
（４） 前記チオール基含有化合物からなる含硫黄化合物が、前記ポリオールの１００質 量部に対して、０．１〜３０質量部の割合で含有せしめられている前記態様（１） 乃至前記態様（３）の何れか１つに記載の地山固結用薬液組成物。
（５） 前記Ａ液が、金属触媒又は３級アミン触媒の何れかを更に含有している前記態様 （１）乃至前記態様（４）の何れか１つに記載の地山固結用薬液組成物。
（６） 前記Ａ液及び前記Ｂ液のうちの少なくとも何れかが、難燃剤を更に含有している 前記態様（１）乃至前記態様（５）の何れか１つに記載の地山固結用薬液組成物。
（７） 前記難燃剤が、前記ポリオールの１００質量部に対して、５〜５０質量部の割合 で前記Ａ液に含有せしめられている前記態様（６）に記載の地山固結用薬液組成物 。
（８） 前記難燃剤が、前記ポリイソシアネートの１００質量部に対して、５〜４０質量 部の割合で前記Ｂ液に含有せしめられている前記態様（６）に記載の地山固結用薬 液組成物。
（９） 前記Ａ液及び前記Ｂ液の２５℃での粘度が、それぞれ、５０〜５００ｍＰａ・ｓ である前記態様（１）乃至前記態様（８）の何れか１つに記載の地山固結用薬液 組成物。
（１０） 前記Ａ液と前記Ｂ液との混合比が、体積基準にて、１：０．５〜１：３である 前記態様（１）乃至前記態様（９）の何れか１つに記載の地山固結用薬液組成物 。
（１１） 発泡倍率が１〜５０倍である硬化反応生成物を与える前記態様（１）１乃至前 記態様（１０）の何れか１つに記載の地山固結用薬液組成物。
（１２） 地盤注入用途又は空洞充填用途に用いられる前記態様（１）乃至前記態様（１ １）の何れか１つに記載の地山固結用薬液組成物。
(1) a polyol and A solution mainly composed of, in B solution Toka Ranaru natural ground consolidating chemical compositions based on polyisocyanates, wherein A liquid, sulfur-containing compounds ing thiol group-containing compound A chemical composition for consolidation of a ground, which is characterized by containing.
(2) The chemical composition for consolidation of a ground according to the above aspect (1) , wherein the thiol group-containing compound is a polythiol compound having two or more thiol groups in one molecule.
(3) The ground according to the above aspect (2) , wherein the polythiol is any one of an alkyldithiol compound, an ether group-containing polythiol compound, a carbonyl group-containing polythiol compound, a thioether group-containing polythiol compound, and an aromatic group-containing polythiol compound. Caking chemical composition.
(4) The above- mentioned aspects (1) to the above-mentioned aspects ( 4), wherein the sulfur-containing compound composed of the thiol group-containing compound is contained in a ratio of 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyol. The chemical composition for solidifying the ground according to any one of 3).
(5) The composition of the chemical solution for consolidation of the ground according to any one of the above aspects (1) to (4) , wherein the solution A further contains either a metal catalyst or a tertiary amine catalyst. Stuff.
(6) The ground consolidation according to any one of the above-described embodiments (1) to (5) , wherein at least one of the liquid A and the liquid B further contains a flame retardant. Chemical composition.
(7) The composition of the chemical solution for consolidation of the ground according to the above aspect (6) , wherein the flame retardant is contained in the solution A at a ratio of 5 to 50 parts by mass with respect to 100 parts by mass of the polyol. Stuff .
(8) The ground consolidation agent according to the above aspect (6) , wherein the flame retardant is contained in the liquid B at a ratio of 5 to 40 parts by mass with respect to 100 parts by mass of the polyisocyanate. Liquid composition.
(9) The consolidation of the ground according to any one of the above-described aspects (1) to (8) , wherein the viscosities of the solution A and the solution B at 25 ° C. are 50 to 500 mPa · s, respectively. Medicinal solution composition.
(10) The above-described one of the above-described embodiments (1) to (9) , wherein the mixing ratio of the liquid A and the liquid B is 1: 0.5 to 1: 3 on a volume basis. Chemical solution composition for consolidation of the ground.
(11) The chemical composition for consolidation of a ground according to any one of the above- mentioned aspects (1) 1 to (10) , which gives a curing reaction product having an effervescence ratio of 1 to 50 times.
(12) the used ground injectable use or cavity fill applications aspects (1) to the natural ground consolidating chemical composition according to any one of the aspects (1 1).
そして、このような本発明に従う地山固結用薬液組成物の構成によれば、以下に列挙せる如き各種の効果が奏され得ることとなるのである。
（１）薬液組成物を注入するときに、水と接触しても、水が白濁することなく、有利に施工できる。
（２）薬液組成物が水に希釈されて、流出することが効果的に防止されることとなるため、水質汚染が防止される。
Then, according to the constitution of the chemical solution composition for solidification of the ground according to the present invention, various effects as listed below can be exhibited.
(1) When injecting the chemical solution composition, even if it comes into contact with water, the water does not become cloudy and can be advantageously applied.
(2) Since the chemical composition is diluted with water and effectively prevented from flowing out, water pollution is prevented.
要するに、本発明は、ポリオールを主成分とするＡ液と、ポリイソシアネートを主成分とするＢ液からなる二液型の地山固結用薬液組成物において、かかるＡ液に、含硫黄化合物及び触媒を含有せしめることによって、所期の目的を達成したところに、大きな特徴を有しているのである。 In short, according to the present invention, in a two-component ground consolidation chemical solution composition consisting of a solution A containing a polyol as a main component and a solution B containing a polyisocyanate as a main component, the solution A contains a sulfur-containing compound and a sulfur-containing compound. By incorporating a catalyst, it has a great feature in achieving the intended purpose.
＜Ａ液＞
（ポリオール）
本発明に従う地山固結用薬液組成物を構成する二液のうちの一つであるＡ液において、主成分であるポリオールとしては、特に限定されるものではなく、従来から地山固結用薬液組成物におけるポリオール成分として用いられているものが、同様に使用され得るところであり、例えば、公知のポリエーテルポリオール、ポリエステルポリオール等を挙げることが出来る。ここで、ポリエーテルポリオールとしては、特に限定されるものではなく、例えば、少なくとも２個以上の活性水素基を有する、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、ペンタエリスリトール等の多価アルコール類；エチレンジアミン等のアミン類；エタノールアミン、ジエタノールアミン等のアルカノールアミン類等の化合物を開始剤として、これとエチレンオキサイドやプロピレンオキサイド等のアルキレンオキサイドとの付加反応により製造されたもの等を、挙げることが出来る。また、ポリエステルポリオールにあっても、特に限定されるものではなく、例えば、多価アルコールと、コハク酸、アジピン酸、セバシン酸、マレイン酸、フタル酸、テレフタル酸、トリメリット酸、ダイマー酸等のポリカルボン酸とを反応させて得られるポリカルボン酸系ポリエステルポリオールや、ラクトン等を開環重合させて得られるラクトン系ポリエステルポリオール等を、挙げることが出来る。それらのポリオールは、単独で使用することが出来る他、二種以上のものを適宜に組み合わせて併用することも、可能である。
<Liquid A>
(Polyprethane)
In the liquid A, which is one of the two liquids constituting the chemical liquid composition for ground consolidation according to the present invention, the polyol as the main component is not particularly limited, and has been conventionally used for ground consolidation. Those used as the polyol component in the chemical composition can be used in the same manner, and examples thereof include known polyether polyols and polyester polyols. Here, the polyether polyol is not particularly limited, and for example, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol having at least two or more active hydrogen groups. Amines such as ethylenediamine; those produced by an addition reaction of compounds such as alkanolamines such as ethanolamine and diethanolamine as initiators with alkylene oxides such as ethylene oxide and propylene oxide can be mentioned. You can. Further, the polyester polyol is not particularly limited, and for example, polyvalent alcohol and succinic acid, adipic acid, sebacic acid, maleic acid, phthalic acid, terephthalic acid, trimellitic acid, dimer acid and the like are used. Examples thereof include a polycarboxylic acid-based polyester polyol obtained by reacting with a polycarboxylic acid, a lactone-based polyester polyol obtained by ring-opening polymerization of a lactone or the like, and the like. These polyols can be used alone, or two or more kinds can be used in combination as appropriate.
そして、上述の如きポリオールは、一般に、１００〜１００００程度の分子量を有していることが望ましく、中でも２００〜８０００程度の分子量を有していることがより望ましく、特に２５０〜５０００程度の分子量を有していることがさらに望ましいのである。かかる分子量が１００よりも小さくなると、薬液組成物の硬化（固結）時に強度の発現が困難となる恐れがあり、また分子量が１００００よりも大きくなると、Ａ液の粘度が高くなり過ぎる問題を惹起する恐れがある。 In general, the above-mentioned polyol preferably has a molecular weight of about 100 to 10,000, more preferably about 200 to 8000, and particularly preferably about 250 to 5000. It is even more desirable to have. If the molecular weight is less than 100, it may be difficult to develop the strength when the chemical composition is cured (consolidated), and if the molecular weight is more than 10,000, the viscosity of the liquid A becomes too high. There is a risk of
（含硫黄化合物）
また、本発明にあっては、Ａ液には、上述の如きポリオールと共に、含硫黄化合物が含有せしめられることとなる。ここで、本明細書及び特許請求の範囲における含硫黄化合物とは、硫黄原子を有する化合物の全てを意味するものである。含硫黄化合物は、ポリオールの１００質量部に対して、０．１〜３０質量部の割合において、好ましくは０．１〜１０質量部の割合において、Ａ液に含有せしめられる。含硫黄化合物の含有量が０．１質量部よりも少ないと、水白濁の防止効果を有利に享受することが出来ない恐れがあり、その一方、３０質量部よりも多いと、硬化反応生成物の物性を低下させる恐れがあり、また経済性も悪くなる。
(Sulfur-containing compound)
Further, in the present invention, the solution A contains a sulfur-containing compound together with the above-mentioned polyol. Here, the sulfur-containing compound in the present specification and claims means all compounds having a sulfur atom. The sulfur-containing compound is contained in the liquid A at a ratio of 0.1 to 30 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyol. If the content of the sulfur-containing compound is less than 0.1 parts by mass, the effect of preventing water turbidity may not be advantageously enjoyed, while if it is more than 30 parts by mass, the curing reaction product may not be enjoyed. There is a risk of deteriorating the physical properties of the product, and the economy will also deteriorate.
本発明に用いられる含硫黄化合物としては、具体的に、チオール基含有化合物、チオケトン基含有化合物、スルフィニル基含有化合物、スルフィド基含有化合物、ジスルフィド基含有化合物等を例示することが出来る。それらの中でも、特にイソシアネートとの反応によって環境中への薬液の流出を抑制し得る観点より、チオール基含有化合物が有利に用いられる。なお、これらの含硫黄化合物は、本発明においては、単独で、又は二種以上の化合物を併用して、使用されることとなる。 Specific examples of the sulfur-containing compound used in the present invention include a thiol group-containing compound, a thioketone group-containing compound, a sulfinyl group-containing compound, a sulfide group-containing compound, and a disulfide group-containing compound. Among them, a thiol group-containing compound is preferably used from the viewpoint of suppressing the outflow of the chemical solution into the environment due to the reaction with isocyanate. In the present invention, these sulfur-containing compounds are used alone or in combination of two or more kinds of compounds.
ここで、チオール基含有化合物としては、ヘキサンチオール、オクタンチオール等のアルキルチオール化合物や、アミノエタンチオール等の、分子内にチオール基の他に水酸基やアミノ基等のポリイソシアネートと反応可能な反応基を有する化合物等を、例示することが出来る。また、本発明において用いられるチオール基含有化合物は、１分子内に２以上のチオール基を有するポリチオール化合物であることが、より好ましい。ポリチオール化合物は、ポリイソシアネートとの反応点となるチオール基を複数、有していることから、水中への溶解がより効果的に抑制され、また、一般的に、チオール基含有化合物特有の臭気も低いものが多く、そのような臭気の低いポリチオール化合物を用いることにより、作業環境への影響を低減できるという効果をも享受することが可能となる。 Here, examples of the thiol group-containing compound include alkylthiol compounds such as hexanethiol and octanethiol, and reactive groups such as aminoethanethiol that can react with polyisocyanates such as hydroxyl groups and amino groups in addition to thiol groups in the molecule. Examples of compounds having a thiol can be exemplified. Further, the thiol group-containing compound used in the present invention is more preferably a polythiol compound having two or more thiol groups in one molecule. Since the polythiol compound has a plurality of thiol groups that serve as reaction points with the polyisocyanate, its dissolution in water is more effectively suppressed, and in general, it also has an odor peculiar to the thiol group-containing compound. Many of them have a low odor, and by using such a polythiol compound having a low odor, it is possible to enjoy the effect of reducing the influence on the working environment.
本発明において用いられるポリチオール化合物としては、エタンジチオール、ヘキサンジチオール、オクタンジチオール、ドデシルジチオール等のアルキルジチオール化合物、ビス（２−メルカプトエチル）エーテル、３，６−ジオキサ−１，８−オクタンジチオール等のエーテル基含有ポリチオール化合物、ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、テトラエチレングリコールビス（３−メルカプトプロピオネート）、トリメチロールプロパンビス（３−メルカプトプロピオナート）、ジペンタエリスリトールトリス（メルカプトアセテート）等のカルボニル基含有ポリチオール化合物、３，７−ジチア−１，９−ノナンジチオール等のチオエーテル基含有ポリチオール化合物、１，４−ベンゼンジメタンチオール、４，５−ビス(メルカプトメチル)−ｏ−キシレン等の芳香族基含有ポリチオール化合物等を挙げることが出来る。また、エーテル基、カルボニル基、チオエーテル基及び芳香族基から選ばれる二種以上のものを１分子内に有するポリチオール化合物にあっても、本発明においては使用可能である。 Examples of the polythiol compound used in the present invention include alkyldithiol compounds such as ethanedithiol, hexanedithiol, octanedithiol, and dodecyldithiol, bis (2-mercaptoethyl) ether, and 3,6-dioxa-1,8-octanedithiol. Ether group-containing polythiol compound, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropanis (3-mercaptopropionate), dipentaerythritoltris (mercapto) Carbonyl group-containing polythiol compounds such as acetate), thioether group-containing polythiol compounds such as 3,7-dithia-1,9-nonandithiol, 1,4-benzenedimethanethiol, 4,5-bis (mercaptomethyl) -o Examples thereof include aromatic group-containing polythiol compounds such as xylene. Further, even a polythiol compound having two or more kinds selected from an ether group, a carbonyl group, a thioether group and an aromatic group in one molecule can be used in the present invention.
より具体的に、本発明のポリチオール化合物としては、例えばエポキシ樹脂硬化剤などとして市販されているポリチオール化合物を、有利に用いることが出来る。そのようなポリチオール化合物としては、ＤＰＭＰ（製品名、ジペンタエリスリトール ヘキサキス（３−メルカプトプロピオネート）、ＳＣ有機化学株式会社製）、ＴＭＭＰ（製品名、トリメチロールプロパン トリス（３−メルカプトプロピオネート）、ＳＣ有機化学株式会社製）、ＴＥＭＰＩＣ（製品名、トリス−［（３−メルカプトプロピオニルオキシ）−エチル］−イソシアヌレート、ＳＣ有機化学株式会社製）、ＰＥＭＰ（製品名、ペンタエリスリトール テトラキス（３−メルカプトプロピオネート）、ＳＣ有機化学株式会社製）、ＥＧＭＰ−４（製品名、テトラエチレングリコール ビス（３−メルカプトプロピオネート）、ＳＣ有機化学株式会社製）、カレンズＭＴ ＰＥ１（製品名、ペンタエリスリトール テトラキス（３−メルカプトブチレート）、昭和電工株式会社製）、カレンズＭＴ ＢＤ１（製品名、１，４−ビス（３−メルカプトブチリルオキシ）ブタン、昭和電工株式会社製）、カレンズＭＴ ＮＲ１（製品名、１，３，５−トリス（３−メルカプトブチリルオキシエチル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、昭和電工株式会社製）、ＴＰＭＢ（製品名、トリメチロールプロパン トリス（３−メルカプトブチレート）、昭和電工株式会社製）、ＴＥＭＢ（製品名、トリメチロールエタン トリス（３−メルカプトブチレート）、昭和電工株式会社製）、チオコールＬＰシリーズ（製品名、ジエトキシメタンポリサルファイドポリマー、東レ・ファインケミカル株式会社製）、ポリチオールＱＥ−３４０Ｍ（製品名、チオール基末端ポリエーテルポリマー、東レ・ファインケミカル株式会社製）等を、例示することが出来る。 More specifically, as the polythiol compound of the present invention, for example, a commercially available polythiol compound such as an epoxy resin curing agent can be advantageously used. Examples of such polythiol compounds include DPMP (product name, dipentaerythritol hexakis (3-mercaptopropionate), manufactured by SC Organic Chemical Co., Ltd.), TMMP (product name, trimethylolpropane tris (3-mercaptopropionate)). ), SC Organic Chemical Co., Ltd.), TEMPIC (Product name, Tris-[(3-mercaptopropionyloxy) -ethyl] -Isocyanurate, SC Organic Chemical Co., Ltd.), PEMP (Product name, Pentaerythritol Tetrakiss (3) -Mercaptopropionate), SC Organic Chemical Co., Ltd.), EGFP-4 (Product name, Tetraethylene glycol bis (3-Mercaptopropionate), SC Organic Chemical Co., Ltd.), Karenz MT PE1 (Product name, Pentaerythritol Tetrakiss (3-mercaptobutyrate), Showa Denko Co., Ltd.), Karenz MT BD1 (Product name, 1,4-bis (3-mercaptobutyryloxy) butane, Showa Denko Co., Ltd.), Karenz MT NR1 (Product name, 1,3,5-tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion, manufactured by Showa Denko Co., Ltd.) , TPMB (product name, trimethylolpropane tris (3-mercaptobutyrate), manufactured by Showa Denko Co., Ltd.), TEMB (product name, trimethylolethane tris (3-mercaptobutyrate), manufactured by Showa Denko Co., Ltd.), thiocol LP series (product name, diethoxymethanepolysulfide polymer, manufactured by Toray Fine Chemical Co., Ltd.), polythiol QE-340M (product name, thiol group-terminated polyether polymer, manufactured by Toray Fine Chemical Co., Ltd.) and the like can be exemplified. ..
（触媒）
また、本発明の地山固結用薬液組成物にあっては、Ａ液に触媒が含有されることが望ましい。本発明に使用される触媒としては、金属触媒又は３級アミン触媒の何れかが好ましく、それら両者を併用することがより好ましい。
(catalyst)
Further, in the chemical solution composition for consolidation of the ground of the present invention, it is desirable that the solution A contains a catalyst. As the catalyst used in the present invention, either a metal catalyst or a tertiary amine catalyst is preferable, and it is more preferable to use both of them in combination.
（金属触媒）
本発明において、金属触媒としては、公知のものを特に制限なく用いることが出来、ナトリウム、カリウム、カルシウム、錫、鉛、ビスマス、亜鉛、鉄、ニッケル、ジルコニウム、コバルト等の有機酸金属塩や有機金属錯体を用いることが出来る。その中で、有機酸金属塩としては、酢酸、オクチル酸、ネオデカン酸、ナフテン酸、ロジン酸等と金属との塩が挙げられ、また有機金属錯体としては、アセチルアセトン等と金属との錯体が挙げられる。具体的には、酢酸ナトリウム、酢酸カリウム、オクチル酸カリウム、オクチル酸ビスマス、オクチル酸鉛、オクチル酸鉄、オクチル酸錫、オクチル酸カルシウム、オクチル酸亜鉛、オクチル酸ジルコニウム、ネオデカン酸ビスマス、ネオデカン酸亜鉛、ネオデカン酸鉛、ネオデカン酸コバルト、ジブチル錫ジオクテート、ジブチル錫ジラウリレート、アセチルアセトン鉄、アセチルアセトン亜鉛、アセチルアセトンジルコニウム、アセチルアセトンニッケル、アセチルアセトン錫等が挙げられる。これらの金属塩や金属錯体は、取り扱い性の向上のため、ミネラルスピリット、有機酸、グリコール類、エステル類等の希釈剤に溶解させたものを用いてもよい。また、これらの金属触媒は単体で用いてもよく、２種類以上を併用してもよい。これらの中でも、好ましくは、カリウム、錫、鉛、ビスマス又は亜鉛の酢酸塩、オクチル酸塩、ネオデカン酸塩、ラウリル酸塩や、アセチルアセトン錯体が挙げられ、より好ましくはカリウム触媒が好適に用いられることとなる。
(Metal catalyst)
In the present invention, known metal catalysts can be used without particular limitation, and organic acid metal salts such as sodium, potassium, calcium, tin, lead, bismuth, zinc, iron, nickel, zirconium, and cobalt, and organic. A metal complex can be used. Among them, examples of the organic acid metal salt include salts of acetic acid, octyl acid, neodecanoic acid, naphthenic acid, loginic acid and the like with a metal, and examples of the organic metal complex include a complex of acetylacetone and the like with a metal. Be done. Specifically, sodium acetate, potassium acetate, potassium octylate, bismuth octylate, lead octylate, iron octylate, tin octylate, calcium octylate, zinc octylate, zirconium octylate, bismuth neodecanoate, zinc neodecanoate. , Lead neodecanoate, cobalt neodecanoate, dibutyltin dioctate, dibutyltin dilaurylate, acetylacetone iron, acetylacetone zinc, acetylacetone zirconium, acetylacetone nickel, acetylacetone tin and the like. As these metal salts and metal complexes, those dissolved in a diluent such as mineral spirits, organic acids, glycols, and esters may be used in order to improve the handleability. Further, these metal catalysts may be used alone or in combination of two or more. Among these, preferably, acetates of potassium, tin, lead, bismuth or zinc, octylate, neodecanoate, laurylate and acetylacetone complexes are mentioned, and more preferably, a potassium catalyst is preferably used. It becomes.
なお、そのような金属触媒を使用する際には、ポリオールの１００質量部に対して、０．１〜５質量部の割合において、好ましくは０．５〜３質量部の割合において、Ａ液に含有せしめられる。金属触媒の含有量が０．１質量部よりも少ないと、反応に対する寄与が小さく、強度発現までの時間が長く、また発現強度も小さくなる恐れがあり、一方、５質量部よりも多いと、反応が速くなりすぎて、反応速度の制御が困難となる。 When such a metal catalyst is used, it should be added to the solution A at a ratio of 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the polyol. It is contained. If the content of the metal catalyst is less than 0.1 parts by mass, the contribution to the reaction is small, the time to develop the intensity is long, and the expression intensity may be small, while if it is more than 5 parts by mass, The reaction becomes too fast, making it difficult to control the reaction rate.
（３級アミン触媒）
３級アミン触媒には、薬液組成物内又は外部の水を発泡剤源として用いる場合に、ポリイソシアネートと水との反応を促進する作用を有する泡化触媒、ポリイソシアネートとポリオールとの反応を促進する作用を有する樹脂化触媒、ポリイソシアネートの三量化を促進する作用を有するイソシアヌレート化触媒（三量化触媒）等がある。
(3rd grade amine catalyst)
The tertiary amine catalyst is a foaming catalyst having an action of promoting the reaction between polyisocyanate and water when water inside or outside the chemical composition is used as a foaming agent source, and promotes the reaction between polyisocyanate and polyol. There are a resination catalyst having an action of forming a resin, an isocyanurate-forming catalyst having an action of promoting the trimerization of polyisocyanate (trimerization catalyst), and the like.
具体的には、泡化触媒としては、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’−トリエチルアミノエチルエタノールアミン、ビス（ジメチルアミノエチル）エーテル、Ｎ，Ｎ，Ｎ’−トリメチルアミノエチルピペラジン、Ｎ，Ｎ−ジメチルアミノエトキシエタノール、トリエチルアミン等が挙げられる。また、樹脂化触媒としては、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロパンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサンジアミン、トリエチレンジアミン、３３％トリエチレンジアミン・６７％ジプロピレングリコール、Ｎ，Ｎ−ジメチルアミノヘキサノール、Ｎ，Ｎ−ジメチルアミノエタノール、Ｎ−メチル−Ｎ’−ヒドロキシエチルピペラジン、Ｎ−メチルモルフォリン、１−メチルイミダゾール、１，２−ジメチルイミダゾール等が挙げられる。更に、イソシアヌレート化触媒としては、２，４，６−トリス（ジメチルアミノメチル）フェノール、Ｎ，Ｎ’，Ｎ”−トリス（ジメチルアミノプロピル）−ヘキサヒドロ−ｓ−トリアジン等が挙げられる。これらは、単独で用いてもよく、２種以上を併用しても何等差し支えない。また、これら３級アミン触媒の中でも、好ましくは樹脂化触媒、イソシアヌレート化触媒（三量化触媒）が好適に用いられる。 Specifically, as the foaming catalyst, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N'-triethylaminoethylethanolamine, bis (dimethylaminoethyl) ether, N , N, N'-trimethylaminoethylpiperazine, N, N-dimethylaminoethoxyethanol, triethylamine and the like. Further, as the resinification catalyst, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropanediamine, N, N, N', N'-tetramethylhexane Diamine, Triethylenediamine, 33% Triethylenediamine / 67% Dipropylene Glycol, N, N-Dimethylaminohexanol, N, N-Dimethylaminoethanol, N-Methyl-N'-Hydroxyethyl Piperazine, N-Methylmorpholin, 1 -Methylimidazole, 1,2-dimethylimidazole and the like can be mentioned. Further, examples of the isocyanurate-forming catalyst include 2,4,6-tris (dimethylaminomethyl) phenol, N, N', N "-tris (dimethylaminopropyl) -hexahydro-s-triazine and the like. , It may be used alone, or two or more kinds may be used in combination. Among these tertiary amine catalysts, a resinification catalyst and an isocyanurate-forming catalyst (trimerization catalyst) are preferably used. ..
なお、そのような３級アミン触媒を使用する際には、ポリオールの１００質量部に対して、０．１〜５質量部の割合において、好ましくは０．５〜３質量部の割合において、Ａ液に含有せしめられる。３級アミン触媒の含有量が０．１質量部よりも少ないと、反応に対する寄与が小さく、強度発現までの時間が長く、また発現強度も小さくなる恐れがあり、一方、５質量部よりも多いと、反応が速くなりすぎて、反応速度の制御が困難となる。 When such a tertiary amine catalyst is used, A is used at a ratio of 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the polyol. It is contained in the liquid. When the content of the tertiary amine catalyst is less than 0.1 parts by mass, the contribution to the reaction is small, the time until the intensity is developed is long, and the expression intensity may be small, while it is more than 5 parts by mass. Then, the reaction becomes too fast, and it becomes difficult to control the reaction speed.
＜Ｂ液＞
（ポリイソシアネート）
一方、本発明に従う地山固結用薬液組成物を構成する二液のうちの他の一つであるＢ液は、従来と同様に、ポリイソシアネートを必須成分として調製されてなるものであって、本発明にあっては、そのようなＢ液中におけるポリイソシアネートの含有量が７０〜１００質量％、好ましくは８０〜１００質量％、より好ましくは９０〜１００質量％となるように調製されることが望ましい。かかるポリイソシアネートの含有量が７０質量％よりも少なくなると、硬化反応生成物の強度が低下する問題がある。そのため、Ｂ液におけるポリイソシアネートの割合は高い方が望ましく、Ｂ液をポリイソシアネートのみで形成しても、何等差支えない。
<Liquid B>
(Polyisocyanate)
On the other hand, the liquid B, which is one of the other two liquids constituting the chemical liquid composition for solidifying the ground according to the present invention, is prepared with polyisocyanate as an essential component as in the conventional case. In the present invention, the content of polyisocyanate in such liquid B is adjusted to be 70 to 100% by mass, preferably 80 to 100% by mass, and more preferably 90 to 100% by mass. Is desirable. If the content of such polyisocyanate is less than 70% by mass, there is a problem that the strength of the curing reaction product is lowered. Therefore, it is desirable that the proportion of polyisocyanate in the liquid B is high, and there is no problem even if the liquid B is formed only with the polyisocyanate.
また、本発明においては、かかるＢ液の必須成分であるポリイソシアネートは、分子中に２個以上のイソシアネート基（ＮＣＯ基）を有する有機系イソシアネート化合物であり、例えば、ジフェニルメタンジイソシアネート（ＭＤＩ）、ポリメチレンポリフェニレンポリイソシアネート（クルードＭＤＩ）、トリレンジイソシアネート、ポリトリレンポリイソシアネート、キシリレンジイソシアネート、ナフタレンジイソシアネート等の芳香族ポリイソシアネート、ヘキサメチレンジイソシアネート等の脂肪族ポリイソシアネート、イソホロンジイソシアネート等の脂環式ポリイソシアネートの他、分子末端にイソシアネート基を有するウレタンプレポリマー、ポリイソシアネートのイソシアヌレート変性体、カルボジイミド変性体等を挙げることが出来る。これらのポリイソシアネートは、単独で用いてもよく、２種以上を併用してもよい。一般的には、反応性や経済性、取扱性等の観点から、ＭＤＩやクルードＭＤＩが好適に用いられる。 Further, in the present invention, the polyisocyanate which is an essential component of the liquid B is an organic isocyanate compound having two or more isocyanate groups (NCO groups) in the molecule, for example, diphenylmethane diisocyanate (MDI), poly. Aromatic polyisocyanate such as methylene polyphenylene polyisocyanate (crude MDI), tolylene diisocyanate, polytolylen polyisocyanate, xylylene diisocyanate, naphthalene diisocyanate, aliphatic polyisocyanate such as hexamethylene diisocyanate, alicyclic poly such as isophorone diisocyanate In addition to isocyanates, urethane prepolymers having an isocyanate group at the molecular terminal, isocyanurate-modified polyisocyanates, carbodiimide-modified products and the like can be mentioned. These polyisocyanates may be used alone or in combination of two or more. In general, MDI and crude MDI are preferably used from the viewpoints of reactivity, economy, handleability and the like.
（難燃剤）
ところで、本発明に従う地山固結用薬液組成物を構成する、上述の如きＡ液及びＢ液の少なくとも何れかには、難燃剤が含有せしめられていることが好ましい。難燃剤は、Ａ液に添加される場合においては、ポリオールの１００質量部に対して５〜５０質量部の割合で、好ましくは１０〜４０質量部の割合で含有せしめられることが望ましい。また、Ｂ液に添加される場合においては、ポリイソシアネートの１００質量部に対して５〜４０質量部の割合で、好ましくは１０〜３０質量部の割合で含有せしめられることが望ましい。
(Flame retardants)
By the way, it is preferable that at least one of the above-mentioned solutions A and B, which constitute the chemical solution composition for solidifying the ground according to the present invention, contains a flame retardant. When the flame retardant is added to the liquid A, it is desirable that the flame retardant is contained in a proportion of 5 to 50 parts by mass, preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyol. When added to the liquid B, it is desirable that the polyisocyanate is contained in a proportion of 5 to 40 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polyisocyanate.
また、そのような難燃剤としては、具体的には、臭素系難燃剤、塩素系難燃剤、リン系難燃剤、ハロゲン化リン酸エステル、無機系難燃剤等が挙げられる。これらは、単独で用いられてもよく、また２種以上を併用して用いられてもよい。これらの中でも、環境への負荷が少なく、発泡性組成物の減粘剤としても機能する点で、リン酸エステル及びハロゲン化リン酸エステルが好ましく用いられることとなる。なお、リン酸エステルとしては、例えば、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリキシレニルホスフェート等が挙げられる。また、ハロゲン化リン酸エステルとしては、例えば、トリス（クロロエチル）ホスフェート、トリス（２−クロロプロピル）ホスフェート、トリス（ジクロロプロピル）ホスフェート、テトラキス（２−クロロエチル）ジクロロイソペンチルジホスフェート、ポリオキシアルキレンビス（ジクロロアルキル）ホスフェート等が挙げられる。 Specific examples of such flame retardants include brominated flame retardants, chlorine flame retardants, phosphorus flame retardants, phosphoric acid halides, and inorganic flame retardants. These may be used alone or in combination of two or more. Among these, a phosphoric acid ester and a halide phosphoric acid ester are preferably used because they have a small burden on the environment and also function as a thickener for the effervescent composition. Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, and trixylenyl phosphate. Examples of the halogenated phosphoric acid ester include tris (chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) dichloroisopentyldiphosphate, and polyoxyalkylene bis. (Dichloroalkyl) phosphate and the like can be mentioned.
なお、本発明に従う地山固結用薬液組成物を構成する、上述の如きＡ液及びＢ液には、その使用目的に応じて、従来と同様な各種の添加剤を添加せしめることが可能である。例えば、Ａ液又はＢ液に対する添加剤としては、整泡剤、減粘剤、発泡剤等を挙げることが出来る。これらの添加剤は、Ａ液を構成するポリオールの１００質量部に対して０．１〜３０質量部、好ましくは０．５〜２０質量部の割合において用いられることとなる。また、Ｂ液を構成するポリイソシアネートの１００質量部に対して０．１〜１５質量部、好ましくは０．５〜１０質量部の割合となるように用いられることとなる。 It is possible to add various additives similar to the conventional ones to the above-mentioned solutions A and B, which constitute the chemical solution composition for consolidation of the ground according to the present invention, depending on the purpose of use. is there. For example, as an additive to the liquid A or the liquid B, a foam stabilizer, a thickener, a foaming agent and the like can be mentioned. These additives are used in a ratio of 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the polyol constituting the liquid A. Further, it is used so as to have a ratio of 0.1 to 15 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyisocyanate constituting the liquid B.
それら添加剤の中で、整泡剤は、Ａ液とＢ液との反応によって形成されるフォームのセル構造を均一に整えるために用いられるものである。この整泡剤としては、例えば、シリコーン、非イオン系界面活性剤、ポリオキシアルキレン変性ジメチルポリシロキサン、ポリシロキサンオキシアルキレン共重合体、ポリオキシエチレンソルビタン脂肪酸エステル、ヒマシ油エチレンオキシド付加物、ラウリル脂肪酸エチレンオキシド付加物等が挙げられ、これらの中でも、シリコーン及び非イオン系界面活性剤が好ましく用いられる。これらは、単独で用いられてもよく、２種以上を併用して用いられてもよい。また、整泡剤の中では、シリコーン系整泡剤がより好ましく、ポリオキシアルキレン変性ジメチルポリシロキサン、ポリシロキサンオキシアルキレン共重合体等が好ましい。 Among these additives, the defoaming agent is used to uniformly adjust the cell structure of the foam formed by the reaction of the liquid A and the liquid B. Examples of this defoaming agent include silicone, nonionic surfactant, polyoxyalkylene-modified dimethylpolysiloxane, polysiloxaneoxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, and lauryl fatty acid ethylene oxide. Additives and the like are mentioned, and among these, silicone and nonionic surfactant are preferably used. These may be used alone or in combination of two or more. Further, among the defoaming agents, silicone-based defoaming agents are more preferable, and polyoxyalkylene-modified dimethylpolysiloxane, polysiloxane oxyalkylene copolymer and the like are preferable.
また、減粘剤は、溶剤として用いられ、Ａ液又はＢ液に溶解されて、それらの液を減粘する働きを有するものである。そのため、そのような機能を有するものである限りにおいて、特に限定されるものではなく、例えば、メタノール、エタノール等のアルコール類、エチルセルソルブ、ブチルセルソルブ等のエーテル類、プロピレンカーボネート等の環状エステル類、ジカルボン酸メチルエステル、エチレングリコールモノメチルエーテルアセテート等のエステル類、石油系炭化水素類等が挙げられる。これらは、単独で用いられてもよく、２種以上を併用して用いられてもよい。 Further, the thickener is used as a solvent, is dissolved in the liquid A or the liquid B, and has a function of reducing the thickness of those liquids. Therefore, as long as it has such a function, it is not particularly limited, and for example, alcohols such as methanol and ethanol, ethers such as ethyl cellsolve and butyl cellsolve, and cyclic esters such as propylene carbonate. , Dicarboxylic acid methyl esters, esters such as ethylene glycol monomethyl ether acetate, petroleum hydrocarbons and the like. These may be used alone or in combination of two or more.
さらに、発泡剤についても、特に限定されるものではなく、水、炭化水素、ハイドロフルオロカーボン、ハイドロフルオロオレフィン、ハイドロクロロフルオロオレフィン等を例示することが出来るが、それらの中でも、特に水が好適である。水は、Ｂ液のポリイソシアネートと反応して炭酸ガスを発生することから、発泡剤として作用するものである。発泡剤の添加量は、地山固結用薬液組成物の用途等に応じて適宜に決定されるところ、好ましくは、Ａ液中に、かかるＡ液を構成するポリオール等の総量（但し、発泡剤は含まず。以下、本段落においては単にＡ液という。）の１００質量部に対して０．１〜２０質量部の割合において含有せしめられる。より具体的には、地盤注入用途に用いる場合、発泡剤は、比較的少量の添加に止める（Ａ液の１００質量部に対して０．１〜２質量部程度の割合において添加する）か、若しくは添加しないことが望ましく、その一方、空洞充填用途に用いる場合には、比較的多量とする（Ａ液の１００質量部に対して１〜２０質量部程度の割合において添加する）ことが望ましい。 Further, the foaming agent is not particularly limited, and water, hydrocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins and the like can be exemplified, and among them, water is particularly preferable. .. Water acts as a foaming agent because it reacts with the polyisocyanate of the liquid B to generate carbon dioxide gas. The amount of the foaming agent added is appropriately determined according to the use of the chemical solution composition for solidification of the ground, and preferably, the total amount of the polyols and the like constituting the liquid A in the liquid A (however, foaming). It does not contain an agent. Hereinafter, it is simply referred to as solution A in this paragraph) and is contained in a ratio of 0.1 to 20 parts by mass with respect to 100 parts by mass. More specifically, when used for ground injection, the foaming agent should be added in a relatively small amount (added at a ratio of about 0.1 to 2 parts by mass with respect to 100 parts by mass of solution A). Alternatively, it is desirable not to add it, and on the other hand, when it is used for cavity filling, it is desirable to add a relatively large amount (added at a ratio of about 1 to 20 parts by mass with respect to 100 parts by mass of the liquid A).
ところで、本発明に従って調製されるＡ液及びＢ液は、それぞれ、２５℃の温度下における粘度が５０〜５００ｍＰａ・ｓ、好ましくは６０〜４００ｍＰａ・ｓとなるように、調製されるのが望ましい。この粘度が５００ｍＰａ・ｓよりも高くなると、Ａ液やＢ液が粘調な液となり、混合時の流動性が悪くなる等の問題を惹起するようになる。また、粘度が５０ｍＰａ・ｓよりも低くなると、水に希釈されやすいという問題がある。なお、後述するように、地山固結用薬液組成物は、一般的に、所望とする硬化反応生成物の発泡倍率が、具体的な用途に応じて異なる。従って、所望とする発泡倍率の硬化反応生成物が得られるように、例えば、使用されるポリオール及びポリイソシアネートの種類やそれらの組合せが適宜に選択され、また必要に応じて発泡剤等が使用されること等によって、本発明の地山固結用薬液組成物は調製されることとなる。 By the way, it is desirable that the solutions A and B prepared according to the present invention are prepared so that the viscosities at a temperature of 25 ° C. are 50 to 500 mPa · s, preferably 60 to 400 mPa · s, respectively. When this viscosity is higher than 500 mPa · s, the liquid A and the liquid B become viscous liquids, which causes problems such as poor fluidity during mixing. Further, when the viscosity is lower than 50 mPa · s, there is a problem that it is easily diluted with water. As will be described later, in the ground consolidation chemical solution composition, the desired foaming ratio of the curing reaction product generally differs depending on the specific use. Therefore, for example, the types of polyols and polyisocyanates used and their combinations are appropriately selected so that a curing reaction product having a desired expansion ratio can be obtained, and a foaming agent or the like is used as necessary. As a result, the chemical composition for solidifying the ground of the present invention will be prepared.
また、かくの如きＡ液とＢ液から構成される、本発明に従う地山固結用薬液組成物の使用に際しては、それら両液が、使用時に混合されて、目的とする地盤、岩盤等に対して、注入や流し込み等によって導入され、反応硬化せしめられることにより、基礎を形成することとなる。なお、かかるＡ液とＢ液との混合比（Ａ：Ｂ）は、Ａ液中の水酸基含有量とＢ液中のＮＣＯ基含有量によって適宜に変化せしめられることとなるが、一般に、体積基準にて、Ａ：Ｂ＝１：０．５〜１：３、好ましくは、１：１〜１：２．５の範囲内において、採用されることとなる。また、それらＡ液やＢ液の使用方法についても、それらの使用の直前に、二液の混合が確実に行われ得る手法であれば、特に限定はなく、従来から公知の注入手法や流し込み手法が、適宜に採用されることとなる。 In addition, when using a chemical solution composition for ground consolidation according to the present invention, which is composed of solutions A and B as described above, both solutions are mixed at the time of use to form the target ground, bedrock, etc. On the other hand, it is introduced by injection, pouring, etc., and is reacted and cured to form a foundation. The mixing ratio (A: B) of the liquid A and the liquid B can be appropriately changed depending on the hydroxyl group content in the liquid A and the NCO group content in the liquid B, but is generally based on the volume. In A: B = 1: 0.5 to 1: 3, preferably in the range of 1: 1 to 1: 2.5. Further, the method of using the liquids A and B is not particularly limited as long as the two liquids can be surely mixed immediately before their use, and a conventionally known injection method or pouring method is used. However, it will be adopted as appropriate.
そして、それらＡ液とＢ液とを混合したときの発泡倍率は、１〜５０倍の範囲で用いられることが好ましいが、例えば湧水を止めるような止水用途には発泡倍率が１〜１０倍、好ましくは１〜５倍、より好ましくは１〜１．５倍となるよう設定される。地盤固結用途に用いる場合は発泡倍率が１〜１５倍、好ましくは２〜１０倍に設定される。また、空洞充填用途に用いる場合は発泡倍率が８〜５０倍、好ましくは１０〜４０倍となるように設定される。 The foaming ratio when the liquids A and B are mixed is preferably used in the range of 1 to 50 times, but the foaming ratio is 1 to 10 for water stopping applications such as stopping spring water. It is set to be double, preferably 1 to 5 times, more preferably 1 to 1.5 times. When used for ground consolidation, the foaming ratio is set to 1 to 15 times, preferably 2 to 10 times. When used for cavity filling, the foaming ratio is set to be 8 to 50 times, preferably 10 to 40 times.
以下に、本発明の実施例や比較例を幾つか示し、本発明を更に具体的に明らかにすることとするが、本発明が、そのような実施例の記載によって、何等の制約をも受けるものでないことは、言うまでもないところである。また、本発明には、以下の実施例の他にも、更には上記した具体的記述以外にも、本発明の趣旨を逸脱しない限りにおいて、当業者の知識に基づいて、種々なる変更、修正、改良等を加え得るものであることが、理解されるべきである。 Hereinafter, the present invention will be clarified more specifically by showing some examples and comparative examples of the present invention, but the present invention is subject to any restrictions by the description of such examples. It goes without saying that it is not a thing. Further, in addition to the following examples, various modifications and modifications to the present invention are made based on the knowledge of those skilled in the art, as long as the gist of the present invention is not deviated from the specific description described above. It should be understood that improvements can be made.
なお、以下の実施例及び比較例において得られたＡ液とＢ液の特性（粘度）と共に、Ａ液とＢ液とを混合して反応硬化せしめた時の反応生成物の発泡倍率とその硬化時間、更には、Ａ液とＢ液とを混合して水中で反応及び発泡せしめて、発泡体を得た後の水の濁りや水の光透過率については、それぞれ、以下の手法に従って、測定乃至は評価した。また、以下に示す「％」及び「部」は、何れも、質量基準である。 In addition to the characteristics (viscosities) of the liquid A and the liquid B obtained in the following Examples and Comparative Examples, the foaming ratio of the reaction product when the liquid A and the liquid B were mixed and cured, and the curing thereof. Time, and further, the turbidity of water and the light transmittance of water after the liquid A and the liquid B were mixed and reacted and foamed in water to obtain a foam were measured according to the following methods. Or evaluated. In addition, both "%" and "part" shown below are based on mass.
（１）粘度
実施例及び比較例において得られたＡ液及びＢ液の粘度を、それぞれ、ＪＩＳ−Ｋ−７１１７−１に準拠して、Ｂ型粘度測定装置を用いて粘度を測定した。
(1) Viscosity The viscosities of the solutions A and B obtained in Examples and Comparative Examples were measured using a B-type viscometer measuring device in accordance with JIS-K-7117-1, respectively.
（２）発泡倍率
２５℃の温度に調整されたＡ液とＢ液とを、下記表１乃至表３に示される所定の混合比において、全量が１００ｍｌとなるようにそれぞれ計量して、それら計量液を２Ｌのディスカップに収容した後、充分に混合撹拌して、硬化せしめた。そして、硬化反応終了後の反応生成物について、その発泡高さを測定し、発泡倍率を求めた。
(2) Foaming Magnification Liquid A and liquid B adjusted to a temperature of 25 ° C. are weighed at the predetermined mixing ratios shown in Tables 1 to 3 below so that the total volume is 100 ml, and weighed them. After the liquid was contained in a 2 L disk cup, it was thoroughly mixed and stirred to cure it. Then, the foaming height of the reaction product after the completion of the curing reaction was measured, and the foaming ratio was determined.
（３）硬化時間
２５℃の温度に調整されたＡ液とＢ液とを、下記表１乃至表３に示される所定の混合比で、混合した後、反応生成物からガスが発生し、発泡高さが変化しなくなるまでの時間、及び、反応生成物に串を刺して、内部まで刺さらない状態となるまでの時間を測定し、その何れか遅い方を、硬化時間の終点とした。
(3) Curing time After mixing the liquid A and the liquid B adjusted to a temperature of 25 ° C. at the predetermined mixing ratios shown in Tables 1 to 3 below, gas is generated from the reaction product and foaming occurs. The time until the height did not change and the time until the reaction product was skewered and did not stick to the inside were measured, and the slower of them was defined as the end point of the curing time.
（４）水濁り
２５℃の温度に調整されたＡ液とＢ液とを、下記表１乃至表３に示される混合比で、全量が１００ｍｌとなるよう計量して、混合した。そして、その混合後、直ちに、２Ｌディスカップ中に収容された、撹拌翼にて１００ｒｐｍで撹拌せしめられている２０℃の水１Ｌ中に、Ａ液とＢ液との混合物を投入し、発泡が開始するまでディスカップ内の撹拌を継続した。発泡開始後は、ディスカップ内より撹拌翼を抜き、反応が収まるまで静置した。反応が収まった後、水の濁りを目視で確認し、濁りが認められないものを◎、ほぼ濁りがないものを○、明らかに濁りが認められるものを×として、評価した。
(4) Water turbidity Liquid A and liquid B adjusted to a temperature of 25 ° C. were weighed and mixed at the mixing ratios shown in Tables 1 to 3 below so that the total volume was 100 ml. Immediately after the mixing, the mixture of the liquid A and the liquid B was put into 1 L of water at 20 ° C., which was housed in the 2 L disc cup and stirred at 100 rpm by the stirring blade, to cause foaming. Stirring in the disc cup was continued until the start. After the start of foaming, the stirring blade was removed from the inside of the disc cup, and the mixture was allowed to stand until the reaction subsided. After the reaction had subsided, the turbidity of the water was visually confirmed, and those with no turbidity were evaluated as ⊚, those with almost no turbidity as ◯, and those with clear turbidity as x.
（５）光透過率
上記（４）の水濁り試験で用いられたディスカップ中の水を回収し、それについて、分光光度計（株式会社日立ハイテクノロジーズ社製：Ｕ−２８００型分光光度計）を用いて、波長５００ｎｍでの光透過率を、測定した。
(5) Light transmittance The water in the disc cup used in the water turbidity test in (4) above was recovered, and a spectrophotometer (manufactured by Hitachi High-Technologies Corporation: U-2800 type spectrophotometer) was used for this. The light transmittance at a wavelength of 500 nm was measured using.
（実施例１）
−Ａ液の調製−
ポリオールとして、三洋化成工業株式会社製ＧＰ−４００（開始剤：グリセリン、分子量：４００、官能基数：３、水酸基価：４００ｍｇＫＯＨ／ｇ）を用い、その１００部に、含硫黄化合物として、ＳＣ有機化学株式会社製ＴＭＭＰ［トリメチロールプロパン トリス（３−メルカプトプロピオネート）］の０．５部、３級アミン触媒として、花王株式会社製カオーライザーＮｏ．３１（樹脂化触媒：３３％トリエチレンジアミンのジプロピレングリコール溶液）の１．５部、金属触媒として、日本化学産業株式会社製プキャット１５Ｇ（カリウム触媒：オクチル酸カリウム）の１．５部、難燃剤として、大八化学工業株式会社ＴＭＣＰＰ［トリス（クロロプロピル）ホスフェート］の３０部を添加して、均一に混合せしめることによって、Ａ液を得た。そして、この得られたＡ液の粘度を測定し、その結果を、下記表１に示した。
(Example 1)
-Preparation of solution A-
GP-400 (initiator: glycerin, molecular weight: 400, number of functional groups: 3, hydroxyl value: 400 mgKOH / g) manufactured by Sanyo Kasei Kogyo Co., Ltd. was used as the polyol, and SC organic chemistry was used as a sulfur-containing compound in 100 parts thereof. Kao Riser No. 1 manufactured by Kao Corporation as a tertiary amine catalyst in 0.5 part of TMMP [Trimethylolpropane Tris (3-mercaptopropionate)] manufactured by Kao Corporation. 1.5 parts of 31 (resinization catalyst: dipropylene glycol solution of 33% triethylenediamine), 1.5 parts of Pucat 15G (potassium catalyst: potassium octylate) manufactured by Nippon Chemical Industry Co., Ltd. as a metal catalyst, flame retardant As a result, 30 parts of TMCPP [Tris (chloropropyl) phosphate] of Daihachi Chemical Industry Co., Ltd. was added and mixed uniformly to obtain a solution A. Then, the viscosity of the obtained solution A was measured, and the results are shown in Table 1 below.
−Ｂ液の調製−
ポリイソシアネートとして、万華化学ジャパン株式会社製Ｗａｎｎａｔｅ ＰＭ−２００（ポリメリックＭＤＩ）を用い、その１００部を、Ｂ液として準備した。そして、この準備されたＢ液の粘度を測定し、その結果を、下記表１に示した。
-Preparation of solution B-
Wannate PM-200 (Polymeric MDI) manufactured by Manka Kagaku Japan Co., Ltd. was used as the polyisocyanate, and 100 parts thereof was prepared as liquid B. Then, the viscosity of the prepared liquid B was measured, and the results are shown in Table 1 below.
−Ａ液とＢ液の反応−
上記で得られたＡ液とＢ液とを、体積比にて、１：１の割合で組み合わせて、常温下において、均一に混合し、反応せしめた後、前述の評価手法に従って、各種の評価試験を行い、それらの結果を、下記表１に示した。
-Reaction of liquid A and liquid B-
Liquid A and liquid B obtained above are combined at a volume ratio of 1: 1 and uniformly mixed at room temperature to react, and then various evaluations are performed according to the above-mentioned evaluation method. The tests were performed and the results are shown in Table 1 below.
（実施例２〜４）
実施例１において、含硫黄化合物の使用量を、それぞれ１部、４部、２０部としたこと以外は、実施例１と同様の手法に従って、各々について各評価試験を行った。そして、その得られた結果を、下記表１に示した。
(Examples 2 to 4)
In Example 1, each evaluation test was carried out according to the same method as in Example 1 except that the amounts of the sulfur-containing compounds used were 1, 4, and 20 parts, respectively. The results obtained are shown in Table 1 below.
（実施例５）
実施例３において、含硫黄化合物をＳＣ有機化学株式会社製ＤＰＭＰ［ジペンタエリスリトール ヘキサキス（３−メルカプトプロピオネート）］に代えたこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表１に示した。
(Example 5)
In Example 3, each evaluation test was carried out according to the same method as in Example 3 except that the sulfur-containing compound was replaced with DPMP [dipentaerythritol hexax (3-mercaptopropionate)] manufactured by SC Organic Chemistry Co., Ltd. went. The results obtained are shown in Table 1 below.
（実施例６）
実施例３において、含硫黄化合物をＳＣ有機化学株式会社製ＴＥＭＰＩＣ（トリス−［（３−メルカプトプロピオニルオキシ）−エチル］−イソシアヌレート）に代えたこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表１に示した。
(Example 6)
In Example 3, the same method as in Example 3 was followed, except that the sulfur-containing compound was replaced with TEMPIC (Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate) manufactured by SC Organic Chemistry Co., Ltd. Each evaluation test was conducted. The results obtained are shown in Table 1 below.
（実施例７）
実施例３において、含硫黄化合物を東レ・ファインケミカル株式会社製チオコールＬＰ−３（ジエトキシメタンポリサルファイドポリマー）に代えたこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表１に示した。
(Example 7)
In Example 3, each evaluation test was carried out according to the same method as in Example 3 except that the sulfur-containing compound was replaced with thiocol LP-3 (diethoxymethane polysulfide polymer) manufactured by Toray Fine Chemicals Co., Ltd. The results obtained are shown in Table 1 below.
（実施例８）
実施例７において、含硫黄化合物の使用量を３０部としたこと以外は、実施例７と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表１に示した。
(Example 8)
In Example 7, each evaluation test was carried out according to the same method as in Example 7 except that the amount of the sulfur-containing compound used was 30 parts. The results obtained are shown in Table 1 below.
（実施例９）
実施例３において、含硫黄化合物を東レ・ファインケミカル株式会社製ポリチオールＱＥ−３４０Ｍ（チオール基末端ポリエーテルポリマー）に代えたこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表１に示した。
(Example 9)
In Example 3, each evaluation test was carried out according to the same method as in Example 3 except that the sulfur-containing compound was replaced with a polythiol QE-340M (thiol group-terminated polyether polymer) manufactured by Toray Fine Chemicals Co., Ltd. The results obtained are shown in Table 1 below.
（実施例１０）
実施例３において、３級アミン触媒を花王株式会社製カオーライザーＮｏ．１４（三量化触媒：Ｎ，Ｎ’，Ｎ”−トリス（３−ジメチルアミノプロピル）ヘキサヒドロ−ｓ−トリアジン）に代えたこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表２に示した。
(Example 10)
In Example 3, the tertiary amine catalyst was used in Kao Riser No. 1 manufactured by Kao Corporation. Each evaluation test was carried out according to the same method as in Example 3 except that 14 (trimerization catalyst: N, N', N "-tris (3-dimethylaminopropyl) hexahydro-s-triazine) was replaced. The results obtained are shown in Table 2 below.
（実施例１１）
実施例３において、３級アミン触媒の使用量を２部とし、金属触媒の使用量を２部とし、Ａ液とＢ液とを体積比にて１：２の割合で組み合わせたこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表２に示した。
(Example 11)
In Example 3, except that the amount of the tertiary amine catalyst used was 2 parts, the amount of the metal catalyst used was 2 parts, and the liquid A and the liquid B were combined in a volume ratio of 1: 2. Each evaluation test was carried out according to the same method as in Example 3. The results obtained are shown in Table 2 below.
（実施例１２）
実施例３において、３級アミン触媒の使用量を２部とし、金属触媒としてＴＮ−１２（スズ触媒：ジブチル錫ラウリレート）を用いて、その使用量を０．５部としたこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表２に示した。
(Example 12)
In Example 3, the amount of the tertiary amine catalyst used was 2 parts, and TN-12 (tin catalyst: dibutyltin laurylate) was used as the metal catalyst, and the amount used was 0.5 parts. Each evaluation test was performed according to the same method as in Example 3. The results obtained are shown in Table 2 below.
（実施例１３）
実施例３において、３級アミン触媒を添加せず、金属触媒の使用量を２部としたこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表２に示した。
(Example 13)
In Example 3, each evaluation test was carried out according to the same method as in Example 3 except that the tertiary amine catalyst was not added and the amount of the metal catalyst used was 2 parts. The results obtained are shown in Table 2 below.
（実施例１４）
実施例３において、３級アミン触媒の使用量を３部とし、金属触媒を添加しないこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表２に示した。
(Example 14)
In Example 3, each evaluation test was carried out according to the same method as in Example 3 except that the amount of the tertiary amine catalyst used was 3 parts and no metal catalyst was added. The results obtained are shown in Table 2 below.
（実施例１５）
実施例３において、３級アミン触媒としてカオーライザーＮｏ．１４を用いて、その使用量を３部とし、金属触媒を添加しないこと以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表２に示した。
(Example 15)
In Example 3, Kao Riser No. 3 was used as the tertiary amine catalyst. Each evaluation test was carried out according to the same method as in Example 3 except that 14 was used, the amount used was 3 parts, and no metal catalyst was added. The results obtained are shown in Table 2 below.
（実施例１６）
実施例３において、整泡剤として、シリコーン系整泡剤Ｌ−６９７０（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）の１部と、更に水の１部を添加した以外は、実施例３と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表２に示した。
(Example 16)
In Example 3, except that a part of a silicone-based defoaming agent L-6970 (manufactured by Momentive Performance Materials Japan, Inc.) and a part of water were added as the defoaming agent. Each evaluation test was conducted according to the same method as in. The results obtained are shown in Table 2 below.
（実施例１７）
実施例１６において、整泡剤の使用量を２部とし、また水の使用量を６．５部とし、Ａ液とＢ液とを体積比にて１：２の割合で組み合わせたこと以外は、実施例１６と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表２に示した。
(Example 17)
In Example 16, except that the amount of the foam stabilizer used was 2 parts, the amount of water used was 6.5 parts, and the liquid A and the liquid B were combined in a volume ratio of 1: 2. , Each evaluation test was carried out according to the same method as in Example 16. The results obtained are shown in Table 2 below.
（実施例１８）
実施例１において、ポリオールとして、三洋化成工業株式会社製ＰＰ−４００（開始剤：プロピレングリコール、分子量：４００、官能基数：２、水酸基価：２８０ｍｇＫＯＨ／ｇ）の８０部と、株式会社アデカ製ＢＭ−５４（開始剤：エチレンジアミン、分子量：５００、官能基数：４、ＥＯ付加あり、水酸基価：４５０ｍｇＫＯＨ／ｇ）の２０部とを使用し、含硫黄化合物の使用量を０．７部とし、金属触媒の使用量を０．５部としたこと以外は、実施例１と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表３に示した。
(Example 18)
In Example 1, 80 parts of PP-400 (initiator: propylene glycol, molecular weight: 400, number of functional groups: 2, hydroxyl value: 280 mgKOH / g) manufactured by Sanyo Kasei Kogyo Co., Ltd. and BM manufactured by Adeca Co., Ltd. were used as polyols. Using 20 parts of -54 (initiator: ethylenediamine, molecular weight: 500, number of functional groups: 4, with EO addition, hydroxyl value: 450 mgKOH / g), the amount of sulfur-containing compound used is 0.7 parts, and the metal Each evaluation test was carried out according to the same method as in Example 1 except that the amount of the catalyst used was 0.5 parts. The results obtained are shown in Table 3 below.
（実施例１９）
実施例１において、ポリオールとして、三洋化成工業株式会社製ＰＰ−４００（開始剤：プロピレングリコール、分子量：４００、官能基数：２、水酸基価：２８０ｍｇＫＯＨ／ｇ）の５０部と、三洋化成工業株式会社製ＦＡ−７０３（開始剤：グリセリン、分子量：５０００、ＥＯ付加あり、官能基数：３、水酸基価：３３ｍｇＫＯＨ／ｇ）の５０部とを使用して、金属触媒の使用量を１部としたこと以外は、実施例１と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表３に示した。
(Example 19)
In Example 1, 50 parts of PP-400 (initiator: propylene glycol, molecular weight: 400, number of functional groups: 2, hydroxyl value: 280 mgKOH / g) manufactured by Sanyo Kasei Kogyo Co., Ltd. and Sanyo Kasei Kogyo Co., Ltd. were used as polyols. Using 50 parts of FA-703 (initiator: glycerin, molecular weight: 5000, with EO addition, number of functional groups: 3, hydroxyl value: 33 mgKOH / g), the amount of metal catalyst used was 1 part. Each evaluation test was carried out according to the same method as in Example 1 except for the above. The results obtained are shown in Table 3 below.
（比較例１〜４）
実施例１、実施例１７、実施例１８、実施例１９において、各々、含硫黄化合物を添加しないこと以外は、実施例１と同様の手法に従って、各評価試験を行った。そして、その得られた結果を、下記表３に示した。
(Comparative Examples 1 to 4)
In Example 1, Example 17, Example 18, and Example 19, each evaluation test was carried out according to the same method as in Example 1 except that the sulfur-containing compound was not added. The results obtained are shown in Table 3 below.
かかる表１乃至表３に示される結果より明らかなように、本発明に従う、実施例１〜１９に係るＡ液とＢ液との組合せからなる薬液組成物においては、何れも、反応が終了した後の水の濁りは、全く認められないか、若しくはほぼ認められず、また、波長５００ｎｍでの光透過率も良好であることが確認される。従って、本発明に従う地山固結用薬液組成物を、例えば湧水の多い地山で用いた場合にあっても、湧水が白濁することなく、有利に施工することが可能であると共に、湧水中への薬液組成物の流出が効果的に抑制され、水質汚染を有利に防止し得ることが認められるのである。 As is clear from the results shown in Tables 1 to 3, in all of the chemical liquid compositions comprising the combination of the liquid A and the liquid B according to Examples 1 to 19 according to the present invention, the reaction was completed. It is confirmed that the subsequent turbidity of water is not observed at all or almost not observed, and the light transmittance at a wavelength of 500 nm is also good. Therefore, even when the chemical solution composition for solidifying the ground according to the present invention is used, for example, in a ground with a large amount of spring water, the spring water can be advantageously applied without becoming cloudy. It is recognized that the outflow of the chemical composition into the spring water is effectively suppressed, and water pollution can be advantageously prevented.
これに対して、比較例１〜４に係るＡ液とＢ液との組合せからなる薬液組成物では、Ａ液中に含硫黄化合物が添加されていないことから、何れも、反応が終了した後の水において、薬液組成物と水との接触に起因すると考えられる白濁が認められ、また、波長５００ｎｍでの光透過率も低いことが認められた。従って、そのような薬液組成物は、湧水の多い地山で用いられると、水質汚染の原因となる恐れがあるものと考えられる。 On the other hand, in the chemical liquid composition composed of the combination of the liquid A and the liquid B according to Comparative Examples 1 to 4, since the sulfur-containing compound was not added to the liquid A, all of them were after the reaction was completed. In the water, white turbidity considered to be caused by contact between the chemical composition and water was observed, and the light transmittance at a wavelength of 500 nm was also found to be low. Therefore, it is considered that such a chemical composition may cause water pollution when used in a mountain with a large amount of spring water.
Claims (12)
前記Ａ液が、チオール基含有化合物からなる含硫黄化合物を含有していることを特徴とする地山固結用薬液組成物。 In a chemical solution composition for consolidation of a ground, which comprises a solution A containing a polyol as a main component and a solution B containing a polyisocyanate as a main component.
A chemical solution composition for solidification of a ground, wherein the solution A contains a sulfur-containing compound composed of a thiol group-containing compound.
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| DE3407031A1 (en) * | 1984-02-27 | 1985-09-05 | Gurit-Essex, Freienbach | CHEMICAL-HARDENING TWO-COMPONENT DIMENSIONS BASED ON POLYURETHANES, METHOD FOR THE PRODUCTION OF A HARDENABLE DIMENSIONS BASED ON POLYURETHANE AND USE OF MIXTURES OF TWO COMPONENTS BASED ON POLYURETHANE |
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