WO2021140541A1 - Additive for water-curable composition - Google Patents
Additive for water-curable composition Download PDFInfo
- Publication number
- WO2021140541A1 WO2021140541A1 PCT/JP2020/000061 JP2020000061W WO2021140541A1 WO 2021140541 A1 WO2021140541 A1 WO 2021140541A1 JP 2020000061 W JP2020000061 W JP 2020000061W WO 2021140541 A1 WO2021140541 A1 WO 2021140541A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- additive
- carbon atoms
- acid
- rosin
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 239000000654 additive Substances 0.000 title claims abstract description 44
- 230000000996 additive effect Effects 0.000 title claims abstract description 41
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 56
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 52
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 37
- 125000002252 acyl group Chemical group 0.000 claims description 31
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 229920005610 lignin Polymers 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000005086 pumping Methods 0.000 abstract description 25
- -1 oxybutylene group Chemical group 0.000 description 31
- 239000004568 cement Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000011398 Portland cement Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000006353 oxyethylene group Chemical group 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 239000010881 fly ash Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 3
- 239000003784 tall oil Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- YPGLTKHJEQHKSS-ASZLNGMRSA-N (1r,4ar,4bs,7r,8as,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,7,8,8a,9,10,10a-dodecahydrophenanthrene-1-carboxylic acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@H](C(C)C)C[C@@H]2CC1 YPGLTKHJEQHKSS-ASZLNGMRSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical compound OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 2
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 2
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 2
- 229940118781 dehydroabietic acid Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004370 n-butenyl group Chemical group [H]\C([H])=C(/[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 1
- WVUYYXUATWMVIT-UHFFFAOYSA-N 1-bromo-4-ethoxybenzene Chemical compound CCOC1=CC=C(Br)C=C1 WVUYYXUATWMVIT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- CKUJONFLPBQEKM-UHFFFAOYSA-N 2,2,6,6-tetramethylheptanedioic acid Chemical compound OC(=O)C(C)(C)CCCC(C)(C)C(O)=O CKUJONFLPBQEKM-UHFFFAOYSA-N 0.000 description 1
- BTUDGPVTCYNYLK-UHFFFAOYSA-N 2,2-dimethylglutaric acid Chemical compound OC(=O)C(C)(C)CCC(O)=O BTUDGPVTCYNYLK-UHFFFAOYSA-N 0.000 description 1
- GOHPTLYPQCTZSE-UHFFFAOYSA-N 2,2-dimethylsuccinic acid Chemical compound OC(=O)C(C)(C)CC(O)=O GOHPTLYPQCTZSE-UHFFFAOYSA-N 0.000 description 1
- DIRSQLKNZQKDBK-UHFFFAOYSA-N 2,2-dipropylpropanedioic acid Chemical compound CCCC(C(O)=O)(C(O)=O)CCC DIRSQLKNZQKDBK-UHFFFAOYSA-N 0.000 description 1
- VIWYMIDWAOZEAZ-UHFFFAOYSA-N 2,4-dimethylpentanedioic acid Chemical compound OC(=O)C(C)CC(C)C(O)=O VIWYMIDWAOZEAZ-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- DUHQIGLHYXLKAE-UHFFFAOYSA-N 3,3-dimethylglutaric acid Chemical compound OC(=O)CC(C)(C)CC(O)=O DUHQIGLHYXLKAE-UHFFFAOYSA-N 0.000 description 1
- XAWFHZMTJUGGEE-UHFFFAOYSA-N 3-ethyl-3-methylpentanedioic acid Chemical compound OC(=O)CC(C)(CC)CC(O)=O XAWFHZMTJUGGEE-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- GAYWCADKXYCKCG-UHFFFAOYSA-N 5-pyridin-3-yl-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1NC(=S)N=C1C1=CC=CN=C1 GAYWCADKXYCKCG-UHFFFAOYSA-N 0.000 description 1
- JJOJFIHJIRWASH-UHFFFAOYSA-N Eicosanedioic acid Natural products OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- IFAWYXIHOVRGHQ-UHFFFAOYSA-N Nonadecandioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCC(O)=O IFAWYXIHOVRGHQ-UHFFFAOYSA-N 0.000 description 1
- 241000218641 Pinaceae Species 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000001124 arachidoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SYEOWUNSTUDKGM-UHFFFAOYSA-N beta-methyladipic acid Natural products OC(=O)CC(C)CCC(O)=O SYEOWUNSTUDKGM-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 210000004556 brain Anatomy 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
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- OVHKECRARPYFQS-UHFFFAOYSA-N cyclohex-2-ene-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC=C1 OVHKECRARPYFQS-UHFFFAOYSA-N 0.000 description 1
- FDKLLWKMYAMLIF-UHFFFAOYSA-N cyclopropane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CC1 FDKLLWKMYAMLIF-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 150000004141 diterpene derivatives Chemical class 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
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000000628 margaroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001419 myristoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001312 palmitoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000297 undecanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/34—Natural resins, e.g. rosin
Definitions
- the present invention relates to additives for hydraulic compositions. More specifically, the present invention relates to an additive for a hydraulic composition that improves the pumping property of the hydraulic composition.
- Hydraulic compositions such as concrete are widely used for civil engineering and construction. At the time of use, such a hydraulic composition is prepared as a hydraulic composition kneaded product by mixing and stirring cement, water, fine aggregate, coarse aggregate, admixture and the like.
- a method of transporting the prepared hydraulic composition kneaded product to the casting position a method of pumping using a concrete pump is adopted.
- a transport pipe is arranged between the casting position and the concrete pump to form a flow path for the hydraulic composition kneaded material, and the hydraulic composition kneaded material in the transport pipe is subjected to the pressure generated from the concrete pump. It is pumped to the casting position.
- the concrete admixture shown in Patent Document 2 enables pumping by adding a biogum-based thickener to concrete using a lightweight aggregate to increase the viscosity.
- a biogum-based thickener to concrete using a lightweight aggregate to increase the viscosity.
- the thickener is not easy to adjust because the degree of effect varies sensitively depending on the target material. That is, if even a small amount is added in excess of the optimum amount, the pumping property will be lowered. Further, the thickener has a problem that its handling is troublesome and its workability is inferior.
- the additive for hydraulic composition of the present invention can improve the pumping property at the time of pumping by a concrete pump, can obtain a high effect with a small amount, and can also obtain a high effect of the hydraulic composition.
- An object of the present invention is to provide an additive for a hydraulic composition that does not affect the slump and the amount of air.
- an additive for a hydraulic composition containing a specific rosin polyoxyalkylene adduct is particularly suitable. According to the present invention, the following additives for hydraulic composition are provided.
- R 1 indicates an acyl residue of rosin or a hydrogen atom
- R 2 is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, shows the polyhydric alcohol residue obtained by removing hydroxyl groups from an acyl residue of a polyhydric carboxylic acid of the acyl group or 2 to 20 carbon atoms having 1 to 20 carbon atoms having 3 to 20 carbon atoms (provided that the R 1, at least one When one represents a hydrogen atom, R 2 represents a substituent other than the hydrogen atom), AO represents an oxyalkylene group having 2 to 18 carbon atoms, and m is a number from 1 to 200, n is
- R 2 in the general formula (1) is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a number of 3-6 carbon atoms
- the pumping property at the time of pumping by a concrete pump can be improved, and a high effect can be obtained with a small amount (that is, the pumping property can be improved with a small amount of addition). It can be improved) and has the effect of not affecting the slump and air volume of the hydraulic composition.
- the additive for hydraulic composition of the present invention contains a compound represented by the following general formula (1). This compound is also referred to as a rosin polyoxyalkylene adduct.
- R 1 in the general formula (1) is an acyl residue or a hydrogen atom of rosin.
- rosin refers to a diterpene acid-based compound called a resin acid (loginic acid).
- resin acid loginic acid
- examples of such rosins include natural rosins, modified rosins, and polymerized rosins.
- Natural rosin is a mixture of resin acids present in the residue obtained by distilling volatile substances such as essential oils from resin oil obtained from Pinaceae plants, and is classified into gum rosin, wood rosin, and tall oil rosin according to the production method. Will be done.
- Gamrosin is obtained by cutting a pine tree, filtering and refining the raw pine fat flowing out of it, and removing turpentine oil by steam distillation.
- Wood rosin is obtained by solvent-extracting pine stump chips.
- Tall oil rosin is obtained by distilling and refining crude tall oil produced as a by-product in the process of producing pulp from pine wood by the kraft pulp method.
- Login contains abietic acid as the main component resin acid, and neo-avietic acid, dehydroabietic acid, tetrahydroabietic acid, palastolic acid, pimalic acid, isopimalic acid, sandalacopimaric acid, levopimal as the resin acids of other components. Contains acids and the like.
- the modified rosin refers to a modified natural rosin.
- the natural rosin is hydrogenated using a noble metal catalyst such as a nickel catalyst, a platinum catalyst, or a palladium catalyst at high pressure to form a double bond in the molecule.
- a noble metal catalyst such as a nickel catalyst, a platinum catalyst, or a palladium catalyst at high pressure to form a double bond in the molecule.
- examples thereof include hydrogenated rosin in which hydrogenated rosin is eliminated or reduced, and disproportionated rosin in which unstable conjugated double bonds in the molecule are eliminated by heating natural rosin at a high temperature in the presence of a noble metal catalyst or a halogen catalyst.
- the polymerized rosin is a reaction between natural rosins or modified rosins, and refers to these dimers and trimers.
- rosin natural rosin is preferable from the viewpoint of easy availability.
- a natural rosin gum rosin is more preferable.
- Rosin is generally treated as a mixture of various compounds, and the amount of carboxylic acid is quantified by measuring the acid value. The acid value is determined by measuring according to the Japanese Industrial Standards JIS K0070.
- AO is an oxyalkylene group having 2 to 18 carbon atoms.
- the oxyalkylene group having 2 to 18 carbon atoms include an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group, an oxystyrene group, an oxidedecylene group, an oxytetradecylene group and an oxyhexadecylene.
- Examples include a group, an oxyoctadecylene group and the like.
- an oxyalkylene group having 2 to 4 carbon atoms such as an oxyethylene group, an oxypropylene group, an oxybutylene group and an oxytetramethylene group is preferable, and an oxyalkylene group having 2 to 3 carbon atoms such as an oxyethylene group and an oxypropylene group is preferable.
- Groups are more preferred.
- the AO may be one type or two or more types, and in the case of two or more types, the oxyalkylene group may be in any form of a random adduct, a block adduct, or an alternating adduct.
- m represents the average number of added moles
- m is a number of 1 to 200, preferably a number of 1 to 150, and more preferably a number of 5 to 150.
- n represents the number of added moles, which is a number of 1 to 20, preferably 1 to 6.
- the oxyalkylene group having 2 carbon atoms in the AO is 50 mol% or more, preferably 80 mol% or more. It is more preferably 90 mol% or more. If the oxyalkylene group having 2 carbon atoms in the AO is less than 50 mol%, sufficient pumping property cannot be obtained.
- R 1 is an acyl residue of rosin.
- n is 2 or more, of R 1, at least one is an acyl residue of rosin.
- R 2 is a hydroxyl group derived from a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a polyhydric alcohol having 3 to 20 carbon atoms.
- the removed residue is an acyl group having 1 to 20 carbon atoms or an acyl residue of a carboxylic acid having 2 to 20 carbon atoms.
- R 1 represents a hydrogen atom
- R 2 is a substituent other than the hydrogen atom.
- alkyl group having 1 to 20 carbon atoms examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-hexyl group and an n-octyl group.
- Examples thereof include a linear or branched alkyl group such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group and an icosyl group.
- a linear or branched alkyl group such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group and an icosyl group.
- alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group are preferable.
- alkenyl group having 2 to 20 carbon atoms examples include an ethenyl group, an n-propenyl group, an n-butenyl group, an n-pentenyl group, an n-hexenyl group, an n-heptenyl group, an n-octenyl group and an n-nonel group.
- N-decenyl group N-decenyl group, n-undecenyl group, n-dodecenyl group, n-tridecenyl group, n-tetradecenyl group, n-pentadecenyl group, n-hexadecenyl group, n-heptadecenyl group, n-octadecenyl group, n-nonadeceenyl group , N-Icosenyl group and the like.
- an alkenyl group having 2 to 5 carbon atoms such as an ethenyl group, an n-propenyl group, an n-butenyl group, and an n-pentenyl group, is preferable.
- residue obtained by removing the hydroxyl group from the polyhydric alcohol having 3 to 20 carbon atoms for example, the residue obtained by removing the hydroxyl group from the polyhydric alcohol having 3 to 20 carbon atoms such as glycerin, trimethylolpropane, pentaerythritol, sorbitol and sorbitan.
- the group is mentioned.
- residues obtained by removing hydroxyl groups from polyhydric alcohols having 3 to 6 carbon atoms such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sorbitan, are preferable.
- acyl group having 1 to 20 carbon atoms examples include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, a hexanoyl group, a heptanoil group, an octanoyl group, a nonanoyl group, a decanoyyl group, an undecanoyl group and a dodecanoyl group.
- acyl residue of the polyvalent carboxylic acid having 2 to 20 carbon atoms examples include oxalic acid, malonic acid, dipropylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, glutaric acid, and 2-methylglutaric acid.
- Dicyclohexyl-4,4'-dicarboxylic acid succinoic acid and other alicyclic polyvalent carboxylic acids having 6 to 20 carbon atoms minus hydroxyl groups, terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4 , 4'-stillbenzicarboxylic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, orthophthalic acid, diphenoxyetanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, etc.
- Examples thereof include an acyl residue obtained by removing a hydroxyl group from a carboxylic acid. These acyl residues may be linear or branched.
- the method for producing the compound represented by the general formula (1) is not particularly limited.
- a catalyst or the like for rosin which is a mixture of resin acids such as abietic acid, neoavietic acid, dehydroabietic acid, tetrahydroabietic acid, palastolic acid, pimaric acid, isopimalic acid, sandalacopimalic acid, and levopimalic acid.
- An alkylene oxide is added by a conventional method to produce a rosin polyoxyalkylene adduct represented by the general formula (1), or an alkylene oxide is added to R 2 in advance by using a catalyst or the like.
- a method for producing a rosin polyoxyalkylene adduct represented by the general formula (1) by esterifying with rosin can be mentioned.
- the additive for a hydraulic composition according to the present invention is used for a hydraulic composition containing a hydraulic binder used in civil engineering, construction and the like.
- the additive for hydraulic composition according to the present invention can be used in combination with an existing dispersant.
- a dispersant include a lignin sulfonic acid-based dispersant, a polycarboxylic acid-based dispersant, a naphthalene sulfonic acid-based dispersant, an amino sulfonic acid-based dispersant, and the like.
- at least one dispersant selected from the group consisting of a lignin sulfonic acid-based dispersant and a polycarboxylic acid-based dispersant is preferable from the viewpoint of ensuring dispersion retention.
- the additive for hydraulic composition according to the present invention can be further used in combination with an existing admixture as long as it does not impair the pumping property and does not affect the slump and the amount of air.
- an admixture include an AE water reducing agent, a high-performance AE water reducing agent, an AE agent, a defoaming agent, a shrinkage reducing agent, a thickener, a curing accelerator and the like.
- Examples of the hydraulic binder used for preparing the hydraulic composition to which the additive for the hydraulic composition according to the present invention is used include various Portland cements such as ordinary Portland cement, early-strength Portland cement, and moderate heat Portland cement.
- various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement can be mentioned.
- various admixtures such as blast furnace slag fine powder, fly ash, and silica fume may be used in combination with the various cements shown above.
- examples of the aggregate include fine aggregate and coarse aggregate.
- examples of the fine aggregate include river sand, mountain sand, sea sand, crushed sand, slag fine aggregate, and the like
- examples of the coarse aggregate include river gravel, crushed stone, and lightweight aggregate.
- the ratio of the water binder of the hydraulic composition is not particularly limited. It exhibits a high effect in the ratio of commonly used water binders.
- the additive for a water-hard composition according to the present invention is preferably blended in a proportion of 0.00001 to 1 part by mass, preferably 0.0001 to 0.4 parts by mass, per 100 parts by mass of the water-hard binder. It is more preferable that the mixture is blended in a proportion of 0.0005 to 0.1 parts by mass.
- Test category 1 (Synthesis of compound represented by general formula (1)) -Synthesis of compound (A-1)
- X grade (acid value: 171 mgKOH / g) of "gamrosin” produced in the People's Republic of China (hereinafter simply referred to as "produced in China") was 626.
- 9 g and 2.0 g of potassium hydroxide were charged, heated to 120 ° C., and dehydrated under reduced pressure while stirring for 1 hour.
- the pressure was returned to normal pressure with nitrogen, then 1264 g of ethylene oxide was press-fitted under the same conditions at 150 to 160 ° C., and then 107 g of propylene oxide was press-fitted under the same conditions, and the mixture was aged at the same temperature for 1 hour. Then, the mixture was cooled, 20 g of an adsorbent (trade name: Kyoward 600 manufactured by Kyowa Kagaku Kogyo Co., Ltd.) was added, dehydrated under reduced pressure at 120 ° C., and then pressure filtered to obtain compound (A-1). ..
- an adsorbent trade name: Kyoward 600 manufactured by Kyowa Kagaku Kogyo Co., Ltd.
- R-1 and R-2 are shown below. R-1 and R-2 are used as they are.
- R-1 X grade of "Gamrosin” from China
- R-2 Polyethylene glycol as a reagent (molecular weight 1000)
- Test Category 2 (Preparation of Concrete Composition) -Examples 1 to 13 and Comparative Examples 1 to 6 Using a forced twin-screw mixer with a capacity of 60 liters, kneading was performed for 90 seconds with the contents shown in Table 2 to prepare each concrete composition shown in Table 3. For each concrete composition, the target air amount was 4.5 ⁇ 1.5% and the target slump was 18 ⁇ 1 cm. In Example 13 and Comparative Example 6, the mixture was similarly kneaded using a forced twin-screw mixer having a capacity of 2.0 m 3. The temperature of the concrete composition was 20 ° C.
- Water reducing agent AE water reducing agent standard type I (high-performance type) Tupole EX60 (manufactured by Takemoto Oil & Fat Co., Ltd., a complex of a modified lignin sulfonic acid compound and a polycarboxylic acid-based compound) is used at 1.0% based on the cement mass.
- Defoamer AFK-2 (manufactured by Takemoto Oil & Fat Co., Ltd.) is used at 0.0005% of the cement mass
- AE agent: AE-300 (manufactured by Takemoto Oil & Fat Co., Ltd.) is used at 0.0015% of the cement mass
- Water reducing agent High-performance AE water reducing agent Standard type I (high-performance type) Chupol HP-8 (manufactured by Takemoto Oil & Fat Co., Ltd., polycarboxylic acid copolymer) is used at 0.7% of the cement mass Defoaming agent: AFK- 2 (manufactured by Takemoto Oil & Fat Co., Ltd.) 0.0003% of the cement mass AE agent: AE-200 (manufactured by Takemoto Oil & Fat Co., Ltd.) 0.0002% of cement mass
- Water reducing agent AE water reducing agent Delayed type I (high-performance type) Seekament JR (manufactured by Nippon Seeka Co., Ltd., modified polycarboxylic acid polyether polymer and modified polyol) 1.3% of cement mass Defoamer: AFK-2 (manufactured by Takemoto Oil & Fat Co., Ltd.) 0.0005% of cement mass AE agent: Master Air 202 (manufactured by BASF Japan, modified rosin compound-based anionic surfactant) at 0.005% of the cement mass
- Test category 3 (testing and evaluation of concrete composition) For each of the prepared concrete compositions, the air volume, slump, and O-funnel flow time were measured as follows, and the results are summarized in Table 3. In Example 13 and Comparative Example 6, the pump pressure was also measured.
- the hydraulic composition obtained by the present invention improves the pumping property of the obtained hydraulic composition and has a small effect on the slump and the amount of air. It was confirmed that the additive for use can be provided. In Example 13, it was confirmed that the pump pumping pressure at the time of discharging 20 m 3 / hour decreased and the pump pumping property was actually improved as compared with the condition without the additive of Comparative Example 6. ..
- Comparative Examples 1, 4 and 6 in which the additive for the hydraulic composition was not blended, it was confirmed that the O-funnel flow time could not be reduced. Further, in Comparative Examples 2 and 5, a so-called AE agent, which is a compound having no oxyalkylene group, was used, and due to the effect, the pumping property was good, but the amount of air increased. Further, in Comparative Example 3, it was an example in which polyethylene glycol was used as the compound, and in this case, it was confirmed that the O funnel flow time could not be reduced.
- the additive for hydraulic composition of the present invention can be used as an additive when preparing a hydraulic composition.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Polyethers (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The present invention can provide an additive for a water-curable composition. The additive can improve the pumping performance of a concrete pump performing a pumping operation, can provide good results even if only a small amount is used, and does not affect the slump or air entrainment in a water-curable composition. This additive for a water-curable composition contains a specific rosin polyoxyalkylene adduct.
Description
本発明は、水硬性組成物用添加剤に関する。更に詳しくは、水硬性組成物のポンプ圧送性を改善する水硬性組成物用添加剤に関する。
The present invention relates to additives for hydraulic compositions. More specifically, the present invention relates to an additive for a hydraulic composition that improves the pumping property of the hydraulic composition.
コンクリート等の水硬性組成物は、土木用、建築用として広範囲に使用されている。このような水硬性組成物は、使用に際し、セメント、水、細骨材、粗骨材及び混和剤等を混合攪拌し、水硬性組成物混練物として調製される。
Hydraulic compositions such as concrete are widely used for civil engineering and construction. At the time of use, such a hydraulic composition is prepared as a hydraulic composition kneaded product by mixing and stirring cement, water, fine aggregate, coarse aggregate, admixture and the like.
施工現場において、調製された水硬性組成物混練物を打設位置まで搬送する方法としては、コンクリートポンプを使用して圧送する方法が採用されている。この方法は、打設位置とコンクリートポンプとの間に輸送管を配置して水硬性組成物混練物の流路を形成し、輸送管内の水硬性組成物混練物をコンクリートポンプから生み出される圧力によって打設位置まで圧送するものである。
At the construction site, as a method of transporting the prepared hydraulic composition kneaded product to the casting position, a method of pumping using a concrete pump is adopted. In this method, a transport pipe is arranged between the casting position and the concrete pump to form a flow path for the hydraulic composition kneaded material, and the hydraulic composition kneaded material in the transport pipe is subjected to the pressure generated from the concrete pump. It is pumped to the casting position.
しかしながら、コンクリートポンプを使用して圧送する方法では、輸送管内において、水硬性組成物混練物と輸送管表面の抵抗が大きくなり、吐出不良や輸送管内での詰まりが生じることがあった。
However, in the method of pumping using a concrete pump, the resistance between the hydraulic composition kneaded product and the surface of the transport pipe increases in the transport pipe, which may cause discharge failure or clogging in the transport pipe.
従来、コンクリートポンプを使用して水硬性組成物混練物を圧送する際、上記のような吐出不良や輸送管内での詰まりを防止してポンプ圧送性を改善するため、リグニンスルホン酸塩系ＡＥ減水剤とアミノスルホン酸樹脂とが配合された混和剤を水硬性組成物に配合することが提案されている（例えば、特許文献１参照）。また、ポンプ圧送が困難であるとされている軽量骨材を使用したコンクリートの圧送においては、バイオガム系増粘剤を使用することが提案されている（例えば、特許文献２参照）。
Conventionally, when a hydraulic composition kneaded product is pumped using a concrete pump, the lignin sulfonate-based AE water reduction is performed in order to prevent the above-mentioned discharge failure and clogging in the transport pipe and improve the pump pumpability. It has been proposed to add an admixture containing an agent and an aminosulfonic acid resin to a hydraulic composition (see, for example, Patent Document 1). Further, it has been proposed to use a biogum-based thickener in the pumping of concrete using a lightweight aggregate, which is considered to be difficult to pump (see, for example, Patent Document 2).
特許文献１に示される混和剤を使用すると、ポンプ圧送性はある程度改善される。しかしながら、この混和剤に配合されたリグニンスルホン酸塩系ＡＥ減水剤とアミノスルホン酸樹脂は、いずれも、セメント用減水剤として使用されるものであるので、対象とするコンクリートによってはスランプを調整しづらいといった問題がある。
When the admixture shown in Patent Document 1 is used, the pumping property is improved to some extent. However, since both the lignin sulfonate-based AE water reducing agent and the aminosulfonic acid resin contained in this admixture are used as water reducing agents for cement, the slump may be adjusted depending on the target concrete. There is a problem that it is difficult.
また、特許文献２に示されるコンクリート混和剤は、軽量骨材を使用したコンクリートにバイオガム系増粘剤を添加して粘性を高めることにより、ポンプ圧送を可能にしている。しかし、土木工事で想定される相当の長距離での圧送が必要な場合、ある程度まで粘性を高める必要があるが、粘性を高めたことによりポンプ圧送性が低下するといった問題がある。また、増粘剤は、対象とする材料によっては、敏感に効果の程度が変動するため、その調整が容易ではない。つまり、少しでも最適量より過剰に添加すると逆にポンプ圧送性が低下する。更に、増粘剤はそのハンドリングが煩わしく作業性に劣るという問題がある。
Further, the concrete admixture shown in Patent Document 2 enables pumping by adding a biogum-based thickener to concrete using a lightweight aggregate to increase the viscosity. However, when pumping over a considerably long distance, which is expected in civil engineering work, is required, it is necessary to increase the viscosity to some extent, but there is a problem that the pumping property is lowered due to the increased viscosity. Further, the thickener is not easy to adjust because the degree of effect varies sensitively depending on the target material. That is, if even a small amount is added in excess of the optimum amount, the pumping property will be lowered. Further, the thickener has a problem that its handling is troublesome and its workability is inferior.
上記事情に鑑み、本発明の水硬性組成物用添加剤は、コンクリートポンプによる圧送時におけるポンプ圧送性を向上させることができ、少量で高い効果を得ることができ、また、水硬性組成物のスランプと空気量に影響を与えない水硬性組成物用添加剤の提供を課題とするものである。
In view of the above circumstances, the additive for hydraulic composition of the present invention can improve the pumping property at the time of pumping by a concrete pump, can obtain a high effect with a small amount, and can also obtain a high effect of the hydraulic composition. An object of the present invention is to provide an additive for a hydraulic composition that does not affect the slump and the amount of air.
本発明者らは、前記の課題を解決すべく鋭意研究した結果、特定のロジンポリオキシアルキレン付加物を含有する水硬性組成物用添加剤が特に好適であることを見出した。本発明によれば、以下の水硬性組成物用添加剤が提供される。
As a result of diligent research to solve the above problems, the present inventors have found that an additive for a hydraulic composition containing a specific rosin polyoxyalkylene adduct is particularly suitable. According to the present invention, the following additives for hydraulic composition are provided.
［１］ 下記一般式（１）で表される化合物を含有する水硬性組成物用添加剤。
[1] An additive for a hydraulic composition containing a compound represented by the following general formula (1).
ｍは１～２００の数であって、ｎは１～２０の数であって、かつ、前記ｍ、ｎが、ｍ×ｎ＝１～２００となる関係を満たす数であり、ＡＯの内、炭素数２のオキシアルキレン基が５０モル％以上である。）
m is a number from 1 to 200, n is a number from 1 to 20, and m and n satisfy the relationship of m × n = 1 to 200. The oxyalkylene group having 2 carbon atoms is 50 mol% or more. )
［２］ 前記一般式（１）中のＡＯは、炭素数２～４のオキシアルキレン基である、前記［１］に記載の水硬性組成物用添加剤。
[2] The additive for a hydraulic composition according to the above [1], wherein the AO in the general formula (1) is an oxyalkylene group having 2 to 4 carbon atoms.
［３］ 前記一般式（１）中のＡＯは、炭素数２～３のオキシアルキレン基である、前記［１］または［２］に記載の水硬性組成物用添加剤。
[3] The additive for a hydraulic composition according to the above [1] or [2], wherein the AO in the general formula (1) is an oxyalkylene group having 2 to 3 carbon atoms.
［４］ 前記一般式（１）中のｎは、１～６の数であって、かつ、前記ｍ、ｎが、ｍ×ｎ＝１～１５０となる関係を満たす数である、前記［１］～［３］のいずれかに記載の水硬性組成物用添加剤。
[4] n in the general formula (1) is a number from 1 to 6, and m and n are numbers satisfying the relationship of m × n = 1 to 150. ] To [3]. The additive for a hydraulic composition.
［５］ 前記一般式（１）中のＲ２は、水素原子、ロジンのアシル残基、炭素数１～４のアルキル基、炭素数２～５のアルケニル基、又は、炭素数３～６の多価アルコールから水酸基を除いた残基である、前記［１］～［４］のいずれかに記載の水硬性組成物用添加剤。
[5] R 2 in the general formula (1) is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a number of 3-6 carbon atoms The additive for a water-hard composition according to any one of the above [1] to [4], which is a residue obtained by removing a hydroxyl group from a polyhydric alcohol.
［６］ 前記ロジンが天然ロジンである、前記［１］～［５］のいずれかに記載の水硬性組成物用添加剤。
[6] The additive for a hydraulic composition according to any one of the above [1] to [5], wherein the rosin is a natural rosin.
［７］ 前記天然ロジンがガムロジンである、前記［６］に記載の水硬性組成物用添加剤。
[7] The additive for a hydraulic composition according to the above [6], wherein the natural rosin is a gum rosin.
［８］ 前記一般式（１）中の前記ＡＯの内、炭素数２のオキシアルキレン基が９０モル％以上である、前記［１］～［７］のいずれかに記載の水硬性組成物用添加剤。
[8] The hydraulic composition according to any one of the above [1] to [7], wherein the oxyalkylene group having 2 carbon atoms is 90 mol% or more in the AO in the general formula (1). Additive.
［９］ 前記一般式（１）中の前記ｍ、ｎが、ｍ×ｎ＝１０～１００となる関係を満たす数である、前記［１］～［８］のいずれかに記載の水硬性組成物用添加剤。
[9] The hydraulic composition according to any one of [1] to [8], wherein m and n in the general formula (1) are numbers satisfying the relationship of m × n = 10 to 100. Additives for products.
［１０］ 分散剤を含有する、前記［１］～［９］のいずれかに記載の水硬性組成物用添加剤。
[10] The additive for a hydraulic composition according to any one of the above [1] to [9], which contains a dispersant.
［１１］ 前記分散剤が、リグニンスルホン酸系分散剤、及び、ポリカルボン酸系分散剤からなる群から選ばれる少なくとも１種である、前記［１０］に記載の水硬性組成物用添加剤。
[11] The additive for a water-hard composition according to the above [10], wherein the dispersant is at least one selected from the group consisting of a lignin sulfonic acid-based dispersant and a polycarboxylic acid-based dispersant.
本発明の水硬性組成物用添加剤によれば、コンクリートポンプによる圧送時におけるポンプ圧送性を向上させることができ、少量で高い効果を得ることができ（即ち、少ない添加量でポンプ圧送性を向上させることができ）、また、水硬性組成物のスランプと空気量に影響を与えないという効果がある。
According to the additive for hydraulic composition of the present invention, the pumping property at the time of pumping by a concrete pump can be improved, and a high effect can be obtained with a small amount (that is, the pumping property can be improved with a small amount of addition). It can be improved) and has the effect of not affecting the slump and air volume of the hydraulic composition.
以下、本発明の実施形態について説明する。しかし、本発明は以下の実施形態に限定されるものではない。したがって、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施形態に対し適宜変更、改良等が加えられ得ることが理解されるべきである。なお、以下の実施例等において、別に記載しない限り、％は質量％を、また部は質量部を意味する。
Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that the following embodiments can be appropriately modified, improved, or the like based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. In the following examples and the like, unless otherwise specified,% means mass% and parts means parts by mass.
本発明の水硬性組成物用添加剤は、下記一般式（１）で表される化合物を含有する。この化合物は、ロジンポリオキシアルキレン付加物とも称される。
The additive for hydraulic composition of the present invention contains a compound represented by the following general formula (1). This compound is also referred to as a rosin polyoxyalkylene adduct.
一般式（１）中のＲ１は、ロジンのアシル残基又は水素原子である。ここで、ロジンとは、樹脂酸（ロジン酸）と称されるジテルペン酸系化合物をいう。このようなロジンとして、例えば、天然ロジン、変性ロジン、重合ロジンなどが挙げられる。
R 1 in the general formula (1) is an acyl residue or a hydrogen atom of rosin. Here, rosin refers to a diterpene acid-based compound called a resin acid (loginic acid). Examples of such rosins include natural rosins, modified rosins, and polymerized rosins.
天然ロジンは、マツ科植物から得られる樹脂油から、精油等の揮発性物質を留去した残留物中に存在する樹脂酸の混合物であり、製造方法により、ガムロジン、ウッドロジン、トール油ロジンに分類される。
Natural rosin is a mixture of resin acids present in the residue obtained by distilling volatile substances such as essential oils from resin oil obtained from Pinaceae plants, and is classified into gum rosin, wood rosin, and tall oil rosin according to the production method. Will be done.
ガムロジンは、松の木に切り傷をつけ、そこから流出する生松脂をろ過精製し、水蒸気蒸留によりテレビン油を除去して得られる。ウッドロジンは、松の切株のチップを溶剤抽出して得られる。トール油ロジンは、松材からクラフトパルプ法でパルプを製造する工程で副生する粗トール油を蒸留精製して得られる。
Gamrosin is obtained by cutting a pine tree, filtering and refining the raw pine fat flowing out of it, and removing turpentine oil by steam distillation. Wood rosin is obtained by solvent-extracting pine stump chips. Tall oil rosin is obtained by distilling and refining crude tall oil produced as a by-product in the process of producing pulp from pine wood by the kraft pulp method.
ロジンは、主成分の樹脂酸として、アビエチン酸を含み、その他の成分の樹脂酸として、ネオアビエチン酸、デヒドロアビエチン酸、テトラヒドロアビエチン酸、パラストリン酸、ピマール酸、イソピマール酸、サンダラコピマール酸、レボピマール酸等を含む。
Login contains abietic acid as the main component resin acid, and neo-avietic acid, dehydroabietic acid, tetrahydroabietic acid, palastolic acid, pimalic acid, isopimalic acid, sandalacopimaric acid, levopimal as the resin acids of other components. Contains acids and the like.
変性ロジンとは、天然ロジンを変性したものをいい、例えば、天然ロジンを高圧化でニッケル触媒、白金触媒、パラジウム触媒等の貴金属触媒等を使用して水素添加して、分子内の二重結合を消失若しくは減少させた水添ロジン、天然ロジンを貴金属触媒又はハロゲン触媒の存在下に高温加熱することにより分子内の不安定な共役二重結合を消失させた不均化ロジンが挙げられる。
The modified rosin refers to a modified natural rosin. For example, the natural rosin is hydrogenated using a noble metal catalyst such as a nickel catalyst, a platinum catalyst, or a palladium catalyst at high pressure to form a double bond in the molecule. Examples thereof include hydrogenated rosin in which hydrogenated rosin is eliminated or reduced, and disproportionated rosin in which unstable conjugated double bonds in the molecule are eliminated by heating natural rosin at a high temperature in the presence of a noble metal catalyst or a halogen catalyst.
重合ロジンとは、天然ロジン又は変性ロジン同士を反応させたものであり、これらの２量化物、３量化物をいう。
The polymerized rosin is a reaction between natural rosins or modified rosins, and refers to these dimers and trimers.
なお、このようなロジンとして、入手の容易さの観点から、天然ロジンが好ましい。このような天然ロジンとしては、より好ましくは、ガムロジンである。ロジンは、様々な化合物の混合物として扱うことが一般的であり、カルボン酸の量については、酸価を測定することで定量化される。酸価は、日本工業規格ＪＩＳ Ｋ ００７０により測定することで求められる。
As such rosin, natural rosin is preferable from the viewpoint of easy availability. As such a natural rosin, gum rosin is more preferable. Rosin is generally treated as a mixture of various compounds, and the amount of carboxylic acid is quantified by measuring the acid value. The acid value is determined by measuring according to the Japanese Industrial Standards JIS K0070.
一般式（１）において、ＡＯは、炭素数２～１８のオキシアルキレン基である。炭素数２～１８のオキシアルキレン基としては、例えば、オキシエチレン基、オキシプロピレン基、オキシブチレン基、オキシテトラメチレン基、オキシスチレン基、オキシドデシレン基、オキシテトラデシレン基、オキシヘキサデシレン基、オキシオクタデシレン基等が挙げられる。なかでも、オキシエチレン基、オキシプロピレン基、オキシブチレン基、オキシテトラメチレン基等の炭素数２～４のオキシアルキレン基が好ましく、オキシエチレン基、オキシプロピレン基等の炭素数２～３のオキシアルキレン基がより好ましい。なお、ＡＯは、１種又は２種以上でもよく、２種類以上の場合は、オキシアルキレン基はランダム付加体、ブロック付加体、交互付加体のいずれの形態であってもよい。
In the general formula (1), AO is an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group having 2 to 18 carbon atoms include an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group, an oxystyrene group, an oxidedecylene group, an oxytetradecylene group and an oxyhexadecylene. Examples include a group, an oxyoctadecylene group and the like. Of these, an oxyalkylene group having 2 to 4 carbon atoms such as an oxyethylene group, an oxypropylene group, an oxybutylene group and an oxytetramethylene group is preferable, and an oxyalkylene group having 2 to 3 carbon atoms such as an oxyethylene group and an oxypropylene group is preferable. Groups are more preferred. The AO may be one type or two or more types, and in the case of two or more types, the oxyalkylene group may be in any form of a random adduct, a block adduct, or an alternating adduct.
一般式（１）において、ｍは、平均付加モル数を表し、ｍは、１～２００の数であり、好ましくは、１～１５０の数であり、より好ましくは、５～１５０の数であり、更に好ましくは、１０～１００の数である。また、ｎは、付加モル数を表し、１～２０の数であり、好ましくは、１～６の数である。また、同時に、ｍ及びｎは、ｍ×ｎ＝１～２００の関係を満たす数であり、好ましくは、ｍ×ｎ＝１～１５０の関係を満たす数であり、更に好ましくは、ｍ×ｎ＝１０～１００の関係を満たす数である。ｍ及びｎの積が２００を超える場合、製造コストが高くなりすぎることや、水硬性組成物の粘性が大きくなりすぎる。また、ｍ及びｎの積が１に満たない場合、得られる水硬性組成物の空気量が過剰となる。
In the general formula (1), m represents the average number of added moles, and m is a number of 1 to 200, preferably a number of 1 to 150, and more preferably a number of 5 to 150. , More preferably, the number is 10 to 100. Further, n represents the number of added moles, which is a number of 1 to 20, preferably 1 to 6. At the same time, m and n are numbers that satisfy the relationship of m × n = 1 to 200, preferably numbers that satisfy the relationship of m × n = 1 to 150, and more preferably m × n =. It is a number that satisfies the relationship of 10 to 100. If the product of m and n exceeds 200, the production cost becomes too high and the viscosity of the hydraulic composition becomes too high. Further, when the product of m and n is less than 1, the amount of air in the obtained hydraulic composition becomes excessive.
また、優れたポンプ圧送性を得るためには、一般式（１）において、ＡＯの内、炭素数２のオキシアルキレン基が５０モル％以上であることが必要であり、好ましくは８０モル％以上であり、より好ましくは９０モル％以上である。ＡＯの内、炭素数２のオキシアルキレン基が５０モル％未満の場合は、十分なポンプ圧送性が得られない。
Further, in order to obtain excellent pumping property, in the general formula (1), it is necessary that the oxyalkylene group having 2 carbon atoms in the AO is 50 mol% or more, preferably 80 mol% or more. It is more preferably 90 mol% or more. If the oxyalkylene group having 2 carbon atoms in the AO is less than 50 mol%, sufficient pumping property cannot be obtained.
一般式（１）において、ｎが１の場合、Ｒ１はロジンのアシル残基である。ｎが２以上の場合、Ｒ１のうち、少なくとも１つはロジンのアシル残基である。
In the general formula (1), when n is 1, R 1 is an acyl residue of rosin. when n is 2 or more, of R 1, at least one is an acyl residue of rosin.
一般式（１）において、Ｒ２は、水素原子、ロジンのアシル残基、炭素数１～２０のアルキル基、炭素数２～２０のアルケニル基、炭素数３～２０の多価アルコールから水酸基を除いた残基、炭素数１～２０のアシル基又は炭素数２～２０のカルボン酸のアシル残基である。但し、Ｒ１の少なくとも一つが水素原子を示す場合、Ｒ２は、水素原子以外の置換基である。
In the general formula (1), R 2 is a hydroxyl group derived from a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and a polyhydric alcohol having 3 to 20 carbon atoms. The removed residue is an acyl group having 1 to 20 carbon atoms or an acyl residue of a carboxylic acid having 2 to 20 carbon atoms. However, when at least one of R 1 represents a hydrogen atom, R 2 is a substituent other than the hydrogen atom.
炭素数１～２０のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ヘキシル基、ｎ－オクチル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基等の直鎖又は分岐アルキル基が挙げられる。なかでも、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基等の炭素数１～４のアルキル基が好ましい。
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-hexyl group and an n-octyl group. Examples thereof include a linear or branched alkyl group such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group and an icosyl group. Of these, alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group are preferable.
炭素数２～２０のアルケニル基としては、例えば、エテニル基、ｎ－プロペニル基、ｎ－ブテニル基、ｎ－ペンテニル基、ｎ－ヘキセニル基、ｎ－ヘプテニル基、ｎ－オクテニル基、ｎ－ノネル基、ｎ－デセニル基、ｎ－ウンデセニル基、ｎ－ドデセニル基、ｎ－トリデセニル基、ｎ－テトラデセニル基、ｎ－ペンタデセニル基、ｎ－ヘキサデセニル基、ｎ－ヘプタデセニル基、ｎ－オクタデセニル基、ｎ－ノナデセニル基、ｎ－イコセニル基等が挙げられる。なかでも、エテニル基、ｎ－プロペニル基、ｎ－ブテニル基、ｎ－ペンテニル基等の炭素数２～５のアルケニル基が好ましい。
Examples of the alkenyl group having 2 to 20 carbon atoms include an ethenyl group, an n-propenyl group, an n-butenyl group, an n-pentenyl group, an n-hexenyl group, an n-heptenyl group, an n-octenyl group and an n-nonel group. , N-decenyl group, n-undecenyl group, n-dodecenyl group, n-tridecenyl group, n-tetradecenyl group, n-pentadecenyl group, n-hexadecenyl group, n-heptadecenyl group, n-octadecenyl group, n-nonadeceenyl group , N-Icosenyl group and the like. Of these, an alkenyl group having 2 to 5 carbon atoms, such as an ethenyl group, an n-propenyl group, an n-butenyl group, and an n-pentenyl group, is preferable.
炭素数３～２０の多価アルコールから水酸基を除いた残基としては、例えば、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、ソルビトール及びソルビタン等の炭素数３～２０の多価アルコールから水酸基を除いた残基が挙げられる。なかでも、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、ソルビトール及びソルビタン等の炭素数３～６の多価アルコールから水酸基を除いた残基が好ましい。
As the residue obtained by removing the hydroxyl group from the polyhydric alcohol having 3 to 20 carbon atoms, for example, the residue obtained by removing the hydroxyl group from the polyhydric alcohol having 3 to 20 carbon atoms such as glycerin, trimethylolpropane, pentaerythritol, sorbitol and sorbitan. The group is mentioned. Of these, residues obtained by removing hydroxyl groups from polyhydric alcohols having 3 to 6 carbon atoms, such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sorbitan, are preferable.
炭素数１～２０のアシル基としては、例えば、ホルミル基、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、ヘキサノイル基、ヘプタノイル基、オクタノイル基、ノナノイル基、デカノイル基、ウンデカノイル基、ドデカノイル基、トリデカノイル基、テトラデカノイル基、ペンタデカノイル基、ヘキサデカノイル基、ヘプタデカノイル基、オクタデカノイル基、ノナデカノイル基、イコサノイル基、２－エチルヘキサノイル基、３－エチルヘプタノイル基、３－エチルデカノイル基等の直鎖又は分岐アシル基等が挙げられる。
Examples of the acyl group having 1 to 20 carbon atoms include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, a hexanoyl group, a heptanoil group, an octanoyl group, a nonanoyl group, a decanoyyl group, an undecanoyl group and a dodecanoyl group. Group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyyl group, icosanoyl group, 2-ethylhexanoyl group, 3-ethylheptanoil group, 3- Examples thereof include a linear or branched acyl group such as an ethyldecanoyl group.
炭素数２～２０の多価カルボン酸のアシル残基としては、例えば、シュウ酸、マロン酸、ジプロピルマロン酸、コハク酸、２，２－ジメチルコハク酸、グルタル酸、２－メチルグルタル酸、２，２－ジメチルグルタル酸、２，４－ジメチルグルタル酸、３－メチルグルタル酸、３，３－ジメチルグルタル酸、３－エチル－３－メチルグルタル酸、アジピン酸、３－メチルアジピン酸、ピメリン酸、２，２，６，６－テトラメチルピメリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、ペンタデカン二酸、テトラデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸及び１，４－シクロヘキサンジカルボン酸等の炭素数２～２０の脂肪族多価カルボン酸から水酸基を除いたアシル残基、シクロプロパンジカルボン酸、１，４－シクロヘキサンジカルボン酸、シクロヘキセンジカルボン酸、ジシクロヘキシル－４，４’－ジカルボン酸及びショウノウ酸等の炭素数６～２０の脂環式多価カルボン酸から水酸基を除いたアシル残基、テレフタル酸、イソフタル酸、２－メチルテレフタル酸、４，４’－スチルベンジカルボン酸、ナフタレンジカルボン酸、４，４’－ビフェニルジカルボン酸、オルトフタル酸、ジフェノキシエタンジカルボン酸、ジフェニルエーテルジカルボン酸及びジフェニルスルホンジカルボン酸等の炭素数６～２０の芳香族多価カルボン酸から水酸基を除いたアシル残基が挙げられる。これらのアシル残基は、直鎖又は分岐のいずれであってもよい。
Examples of the acyl residue of the polyvalent carboxylic acid having 2 to 20 carbon atoms include oxalic acid, malonic acid, dipropylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, glutaric acid, and 2-methylglutaric acid. 2,2-Dimethylglutaric acid, 2,4-dimethylglutaric acid, 3-methylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, 3-methyladipic acid, pimerin Acids, 2,2,6,6-tetramethylpimelic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, pentadecanedioic acid, tetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecandioic acid, Acyl residues obtained by removing hydroxyl groups from aliphatic polyvalent carboxylic acids having 2 to 20 carbon atoms such as eicosandioic acid and 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexendicarboxylic acid. , Dicyclohexyl-4,4'-dicarboxylic acid, succinoic acid and other alicyclic polyvalent carboxylic acids having 6 to 20 carbon atoms minus hydroxyl groups, terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4 , 4'-stillbenzicarboxylic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, orthophthalic acid, diphenoxyetanedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, etc. Examples thereof include an acyl residue obtained by removing a hydroxyl group from a carboxylic acid. These acyl residues may be linear or branched.
一般式（１）で表される化合物の製造方法は特に限定されない。例えば、アビエチン酸、ネオアビエチン酸、デヒドロアビエチン酸、テトラヒドロアビエチン酸、パラストリン酸、ピマール酸、イソピマール酸、サンダラコピマール酸、レボピマール酸等の樹脂酸の混合物であるロジンに、触媒等を用いることで常法によりアルキレンオキサイドを付加させて、一般式（１）で表されるロジンポリオキシアルキレン付加物を製造する方法や、Ｒ２に予め、触媒等を用いることで常法によりアルキレンオキシドを付加し、その後ロジンとエステル化させることにより、一般式（１）で表されるロジンポリオキシアルキレン付加物を製造する方法等が挙げられる。
The method for producing the compound represented by the general formula (1) is not particularly limited. For example, by using a catalyst or the like for rosin, which is a mixture of resin acids such as abietic acid, neoavietic acid, dehydroabietic acid, tetrahydroabietic acid, palastolic acid, pimaric acid, isopimalic acid, sandalacopimalic acid, and levopimalic acid. An alkylene oxide is added by a conventional method to produce a rosin polyoxyalkylene adduct represented by the general formula (1), or an alkylene oxide is added to R 2 in advance by using a catalyst or the like. After that, a method for producing a rosin polyoxyalkylene adduct represented by the general formula (1) by esterifying with rosin can be mentioned.
本発明に係る水硬性組成物用添加剤は、土木、建築等に用いられる水硬性結合材を含有する水硬性組成物に使用されるものである。
The additive for a hydraulic composition according to the present invention is used for a hydraulic composition containing a hydraulic binder used in civil engineering, construction and the like.
本発明に係る水硬性組成物用添加剤は、既存の分散剤と併用することができる。かかる分散剤としては、例えば、リグニンスルホン酸系分散剤、ポリカルボン酸系分散剤、ナフタレンスルホン酸系分散剤、アミノスルホン酸系分散剤等が挙げられる。なかでも、分散保持性を確保するという観点から、リグニンスルホン酸系分散剤、及び、ポリカルボン酸系分散剤からなる群から選ばれる少なくとも１種の分散剤が好ましい。
The additive for hydraulic composition according to the present invention can be used in combination with an existing dispersant. Examples of such a dispersant include a lignin sulfonic acid-based dispersant, a polycarboxylic acid-based dispersant, a naphthalene sulfonic acid-based dispersant, an amino sulfonic acid-based dispersant, and the like. Among them, at least one dispersant selected from the group consisting of a lignin sulfonic acid-based dispersant and a polycarboxylic acid-based dispersant is preferable from the viewpoint of ensuring dispersion retention.
本発明に係る水硬性組成物用添加剤は、ポンプ圧送性を損なわず、スランプと空気量に影響を与えないのであれば、更に既存の混和剤と併用することができる。かかる混和剤としては、例えば、ＡＥ減水剤、高性能ＡＥ減水剤、ＡＥ剤、消泡剤、収縮低減剤、増粘剤、硬化促進剤等が挙げられる。
The additive for hydraulic composition according to the present invention can be further used in combination with an existing admixture as long as it does not impair the pumping property and does not affect the slump and the amount of air. Examples of such an admixture include an AE water reducing agent, a high-performance AE water reducing agent, an AE agent, a defoaming agent, a shrinkage reducing agent, a thickener, a curing accelerator and the like.
本発明に係る水硬性組成物用添加剤の使用対象となる水硬性組成物の調製に用いる水硬性結合材としては、例えば、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント等の各種ポルトランドセメントの他に、高炉セメント、フライアッシュセメント、シリカフュームセメント等の各種混合セメントが挙げられる。また、高炉スラグ微粉末、フライアッシュ、シリカフュームなどの各種混和材を、先に示した各種セメントと併用してもよい。
Examples of the hydraulic binder used for preparing the hydraulic composition to which the additive for the hydraulic composition according to the present invention is used include various Portland cements such as ordinary Portland cement, early-strength Portland cement, and moderate heat Portland cement. In addition to portland cement, various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement can be mentioned. In addition, various admixtures such as blast furnace slag fine powder, fly ash, and silica fume may be used in combination with the various cements shown above.
また、水硬性組成物の調製に骨材を用いる場合、その骨材としては、例えば、細骨材、粗骨材が挙げられる。細骨材としては、例えば、川砂、山砂、海砂、砕砂、スラグ細骨材等が挙げられ、粗骨材としては、例えば、川砂利、砕石、軽量骨材等が挙げられる。
When an aggregate is used for preparing a hydraulic composition, examples of the aggregate include fine aggregate and coarse aggregate. Examples of the fine aggregate include river sand, mountain sand, sea sand, crushed sand, slag fine aggregate, and the like, and examples of the coarse aggregate include river gravel, crushed stone, and lightweight aggregate.
更に、水硬性組成物の水結合材比は、特に限定されない。一般的に使用される水結合材比において、高い効果を発現する。
Furthermore, the ratio of the water binder of the hydraulic composition is not particularly limited. It exhibits a high effect in the ratio of commonly used water binders.
本発明に係る水硬性組成物用添加剤は、水硬性結合材１００質量部当たり、０．００００１～１質量部の割合で配合されることが好ましく、０．０００１～０．４質量部の割合で配合されることがより好ましく、０．０００５～０．１質量部の割合で配合されることが更に好ましい。
The additive for a water-hard composition according to the present invention is preferably blended in a proportion of 0.00001 to 1 part by mass, preferably 0.0001 to 0.4 parts by mass, per 100 parts by mass of the water-hard binder. It is more preferable that the mixture is blended in a proportion of 0.0005 to 0.1 parts by mass.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。なお、以下の実施例及び比較例において、特に断りのない限り、“部”は質量部、“％”は質量％を意味する。
Hereinafter, examples and the like will be given in order to make the configuration and effect of the present invention more specific, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” means parts by mass and “%” means mass% unless otherwise specified.
試験区分１（一般式（１）で表される化合物の合成）
・化合物（Ａ－１）の合成
２Ｌのステンレス製耐圧容器に、中華人民共和国産（以降、単に「中国産」と記す）の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を６２６．９ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１２６４ｇを０．４ＭＰａの条件圧入し、続いてプロピレンオキサイド１０７ｇを同条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、吸着材（共和化学工業社製の商品名：キョーワード６００）を２０ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ａ－１）を得た。 Test category 1 (Synthesis of compound represented by general formula (1))
-Synthesis of compound (A-1) In a 2 L stainless steel pressure-resistant container, X grade (acid value: 171 mgKOH / g) of "gamrosin" produced in the People's Republic of China (hereinafter simply referred to as "produced in China") was 626. 9 g and 2.0 g of potassium hydroxide were charged, heated to 120 ° C., and dehydrated under reduced pressure while stirring for 1 hour. The pressure was returned to normal pressure with nitrogen, then 1264 g of ethylene oxide was press-fitted under the same conditions at 150 to 160 ° C., and then 107 g of propylene oxide was press-fitted under the same conditions, and the mixture was aged at the same temperature for 1 hour. Then, the mixture was cooled, 20 g of an adsorbent (trade name: Kyoward 600 manufactured by Kyowa Kagaku Kogyo Co., Ltd.) was added, dehydrated under reduced pressure at 120 ° C., and then pressure filtered to obtain compound (A-1). ..
・化合物（Ａ－１）の合成
２Ｌのステンレス製耐圧容器に、中華人民共和国産（以降、単に「中国産」と記す）の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を６２６．９ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１２６４ｇを０．４ＭＰａの条件圧入し、続いてプロピレンオキサイド１０７ｇを同条件で圧入し、そのままの温度で１時間熟成を行った。その後、冷却し、吸着材（共和化学工業社製の商品名：キョーワード６００）を２０ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ａ－１）を得た。 Test category 1 (Synthesis of compound represented by general formula (1))
-Synthesis of compound (A-1) In a 2 L stainless steel pressure-resistant container, X grade (acid value: 171 mgKOH / g) of "gamrosin" produced in the People's Republic of China (hereinafter simply referred to as "produced in China") was 626. 9 g and 2.0 g of potassium hydroxide were charged, heated to 120 ° C., and dehydrated under reduced pressure while stirring for 1 hour. The pressure was returned to normal pressure with nitrogen, then 1264 g of ethylene oxide was press-fitted under the same conditions at 150 to 160 ° C., and then 107 g of propylene oxide was press-fitted under the same conditions, and the mixture was aged at the same temperature for 1 hour. Then, the mixture was cooled, 20 g of an adsorbent (trade name: Kyoward 600 manufactured by Kyowa Kagaku Kogyo Co., Ltd.) was added, dehydrated under reduced pressure at 120 ° C., and then pressure filtered to obtain compound (A-1). ..
・化合物（Ａ－２）の合成
２Ｌのステンレス製耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を５４１．７ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１４５６ｇを０．４ＭＰａの条件圧入し、そのままの温度で１時間熟成を行った。冷却後、８５％リン酸を２．７ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ａ－２）を得た。 -Synthesis of compound (A-2) 541.7 g of Chinese "Gamrosin" X grade (acid value: 171 mgKOH / g) and 2.0 g of potassium hydroxide were placed in a 2 L stainless steel pressure-resistant container, and 120 The mixture was heated to ° C. and dehydrated under reduced pressure while stirring for 1 hour. After returning to normal pressure with nitrogen, 1456 g of ethylene oxide was press-fitted under the condition of 0.4 MPa at 150 to 160 ° C., and aging was carried out at the same temperature for 1 hour. After cooling, 2.7 g of 85% phosphoric acid was added, dehydrated under reduced pressure at 120 ° C., and then pressure-filtered to obtain compound (A-2).
２Ｌのステンレス製耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を５４１．７ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１４５６ｇを０．４ＭＰａの条件圧入し、そのままの温度で１時間熟成を行った。冷却後、８５％リン酸を２．７ｇ添加し、１２０℃にて減圧脱水の後、加圧濾過を行い、化合物（Ａ－２）を得た。 -Synthesis of compound (A-2) 541.7 g of Chinese "Gamrosin" X grade (acid value: 171 mgKOH / g) and 2.0 g of potassium hydroxide were placed in a 2 L stainless steel pressure-resistant container, and 120 The mixture was heated to ° C. and dehydrated under reduced pressure while stirring for 1 hour. After returning to normal pressure with nitrogen, 1456 g of ethylene oxide was press-fitted under the condition of 0.4 MPa at 150 to 160 ° C., and aging was carried out at the same temperature for 1 hour. After cooling, 2.7 g of 85% phosphoric acid was added, dehydrated under reduced pressure at 120 ° C., and then pressure-filtered to obtain compound (A-2).
・化合物（Ａ－３）の合成
２Ｌのステンレス製耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を１９１．９ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１８０６ｇを０．４ＭＰａの条件圧入し、そのままの温度で１時間熟成を行った。冷却後、回収し、化合物（Ａ－３）を得た。 -Synthesis of compound (A-3) In a 2 L stainless steel pressure-resistant container, 191.9 g of X grade (acid value: 171 mgKOH / g) of "Gamrosin" produced in China and 2.0 g of potassium hydroxide were charged and 120. The mixture was heated to ° C. and dehydrated under reduced pressure while stirring for 1 hour. After returning to normal pressure with nitrogen, 1806 g of ethylene oxide was press-fitted under the condition of 0.4 MPa at 150 to 160 ° C., and aging was carried out at the same temperature for 1 hour. After cooling, it was recovered to obtain compound (A-3).
２Ｌのステンレス製耐圧容器に、中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を１９１．９ｇと、水酸化カリウム２．０ｇを仕込み、１２０℃まで加熱し、撹拌しながら減圧脱水を１時間行った。窒素にて常圧に戻し、その後、１５０～１６０℃でエチレンオキサイド１８０６ｇを０．４ＭＰａの条件圧入し、そのままの温度で１時間熟成を行った。冷却後、回収し、化合物（Ａ－３）を得た。 -Synthesis of compound (A-3) In a 2 L stainless steel pressure-resistant container, 191.9 g of X grade (acid value: 171 mgKOH / g) of "Gamrosin" produced in China and 2.0 g of potassium hydroxide were charged and 120. The mixture was heated to ° C. and dehydrated under reduced pressure while stirring for 1 hour. After returning to normal pressure with nitrogen, 1806 g of ethylene oxide was press-fitted under the condition of 0.4 MPa at 150 to 160 ° C., and aging was carried out at the same temperature for 1 hour. After cooling, it was recovered to obtain compound (A-3).
・化合物（Ａ－４）の合成
１Ｌのガラス製反応容器に試薬のα－メトキシ－ω－ヒドロキシ－ポリ（ｎ＝４５）オキシエチレン５００．０ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を８２．０ｇ、メタンスルホン酸７．２ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－４）を得た。 -Synthesis of compound (A-4) In a 1 L glass reaction vessel, 500.0 g of α-methoxy-ω-hydroxy-poly (n = 45) oxyethylene as a reagent and X grade (acid value) of "gamrosin" produced in China 82.0 g of 171 mgKOH / g) and 7.2 g of methanesulfonic acid were charged, and after nitrogen substitution, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-4).
１Ｌのガラス製反応容器に試薬のα－メトキシ－ω－ヒドロキシ－ポリ（ｎ＝４５）オキシエチレン５００．０ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を８２．０ｇ、メタンスルホン酸７．２ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－４）を得た。 -Synthesis of compound (A-4) In a 1 L glass reaction vessel, 500.0 g of α-methoxy-ω-hydroxy-poly (n = 45) oxyethylene as a reagent and X grade (acid value) of "gamrosin" produced in China 82.0 g of 171 mgKOH / g) and 7.2 g of methanesulfonic acid were charged, and after nitrogen substitution, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-4).
・化合物（Ａ－５）の合成
１Ｌのガラス製反応容器に試薬のグリセリン９２．１ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を６５６．２ｇ、メタンスルホン酸１９．２ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－５）を得た。 -Synthesis of compound (A-5) In a 1 L glass reaction vessel, 92.1 g of the reagent glycerin, 656.2 g of X grade (acid value: 171 mgKOH / g) of "gamrosin" produced in China, and 19. methanesulfonic acid 19. After charging 2 g and replacing with nitrogen, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-5).
１Ｌのガラス製反応容器に試薬のグリセリン９２．１ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を６５６．２ｇ、メタンスルホン酸１９．２ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－５）を得た。 -Synthesis of compound (A-5) In a 1 L glass reaction vessel, 92.1 g of the reagent glycerin, 656.2 g of X grade (acid value: 171 mgKOH / g) of "gamrosin" produced in China, and 19. methanesulfonic acid 19. After charging 2 g and replacing with nitrogen, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-5).
・化合物（Ａ－６）の合成
１Ｌのガラス製反応容器に試薬のソルビトール９３．６ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を６５６．２ｇ、メタンスルホン酸１９．２ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－６）を得た。 -Synthesis of compound (A-6) In a 1 L glass reaction vessel, 93.6 g of the reagent sorbitol, 656.2 g of X grade (acid value: 171 mgKOH / g) of "gamrosin" produced in China, and methanesulfonic acid 19. After charging 2 g and replacing with nitrogen, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-6).
１Ｌのガラス製反応容器に試薬のソルビトール９３．６ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を６５６．２ｇ、メタンスルホン酸１９．２ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－６）を得た。 -Synthesis of compound (A-6) In a 1 L glass reaction vessel, 93.6 g of the reagent sorbitol, 656.2 g of X grade (acid value: 171 mgKOH / g) of "gamrosin" produced in China, and methanesulfonic acid 19. After charging 2 g and replacing with nitrogen, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-6).
・化合物（Ａ－７）の合成
１Ｌのガラス製反応容器にポリ（ｎ＝７０）エチレングリコール３０９．８ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を５２．５ｇ、パラトルエンスルホン酸一水和物５．８ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－７）を得た。 -Synthesis of compound (A-7) In a 1 L glass reaction vessel, 309.8 g of poly (n = 70) ethylene glycol and 52.5 g of X grade (acid value: 171 mgKOH / g) of "gamrosin" produced in China, 5.8 g of paratoluenesulfonic acid monohydrate was charged, and after nitrogen substitution, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-7).
１Ｌのガラス製反応容器にポリ（ｎ＝７０）エチレングリコール３０９．８ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を５２．５ｇ、パラトルエンスルホン酸一水和物５．８ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－７）を得た。 -Synthesis of compound (A-7) In a 1 L glass reaction vessel, 309.8 g of poly (n = 70) ethylene glycol and 52.5 g of X grade (acid value: 171 mgKOH / g) of "gamrosin" produced in China, 5.8 g of paratoluenesulfonic acid monohydrate was charged, and after nitrogen substitution, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-7).
・化合物（Ａ－８）の合成
１Ｌのガラス製反応容器にα－メタリル－ω－ヒドロキシ－ポリ（ｎ＝５０）オキシエチレン５００．０ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を７２．２ｇ、パラトルエンスルホン酸一水和物１２．７ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－８）を得た。 -Synthesis of compound (A-8) 500.0 g of α-metharyl-ω-hydroxy-poly (n = 50) oxyethylene and X grade (acid value: 171 mgKOH) of "gamrosin" produced in China in a 1 L glass reaction vessel. 72.2 g of / g) and 12.7 g of p-toluenesulfonic acid monohydrate were charged, and after nitrogen substitution, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-8).
１Ｌのガラス製反応容器にα－メタリル－ω－ヒドロキシ－ポリ（ｎ＝５０）オキシエチレン５００．０ｇと中国産の「ガムロジン」のＸグレード（酸価：１７１ｍｇＫＯＨ／ｇ）を７２．２ｇ、パラトルエンスルホン酸一水和物１２．７ｇを仕込み、窒素置換後、１５０℃、０．５ｋＰａで減圧脱水を行い、エステル化反応を行った。エステル化率が９９％以上となったところで反応を終了し、精製し、化合物（Ａ－８）を得た。 -Synthesis of compound (A-8) 500.0 g of α-metharyl-ω-hydroxy-poly (n = 50) oxyethylene and X grade (acid value: 171 mgKOH) of "gamrosin" produced in China in a 1 L glass reaction vessel. 72.2 g of / g) and 12.7 g of p-toluenesulfonic acid monohydrate were charged, and after nitrogen substitution, dehydration under reduced pressure was carried out at 150 ° C. and 0.5 kPa to carry out an esterification reaction. When the esterification rate was 99% or more, the reaction was terminated and purified to obtain compound (A-8).
・化合物（Ａ－９）の合成
表１に示すように原料の仕込み量を変化させた以外は、化合物（Ａ－１）と同様に合成を行い、化合物（Ａ－９）を得た。 -Synthesis of compound (A-9) Compound (A-9) was obtained by synthesizing in the same manner as compound (A-1) except that the amount of raw materials charged was changed as shown in Table 1.
表１に示すように原料の仕込み量を変化させた以外は、化合物（Ａ－１）と同様に合成を行い、化合物（Ａ－９）を得た。 -Synthesis of compound (A-9) Compound (A-9) was obtained by synthesizing in the same manner as compound (A-1) except that the amount of raw materials charged was changed as shown in Table 1.
以上で合成した化合物（Ａ－１）～（Ａ－９）及び（Ｒ－１）～（Ｒ－２）の内容を表１にまとめて示した。
Table 1 summarizes the contents of the compounds (A-1) to (A-9) and (R-1) to (R-2) synthesized above.
表１において、Ｒ－１、Ｒ－２について以下に示す。Ｒ－１、Ｒ－２をそのまま用いている。
Ｒ－１：中国産の「ガムロジン」のＸグレード
Ｒ－２：試薬のポリエチレングリコール（分子量１０００） In Table 1, R-1 and R-2 are shown below. R-1 and R-2 are used as they are.
R-1: X grade of "Gamrosin" from China R-2: Polyethylene glycol as a reagent (molecular weight 1000)
Ｒ－１：中国産の「ガムロジン」のＸグレード
Ｒ－２：試薬のポリエチレングリコール（分子量１０００） In Table 1, R-1 and R-2 are shown below. R-1 and R-2 are used as they are.
R-1: X grade of "Gamrosin" from China R-2: Polyethylene glycol as a reagent (molecular weight 1000)
表１中のＲ１について以下に示す。
「ガムロジンアシル残基」：ガムロジンのカルボン酸から水酸基を除いたもの
「ガムロジンアシル残基：Ｈ＝２：１」：Ｒ１におけるガムロジンアシル残基と水素原子のモル比率が２：１
「ガムロジンアシル残基：Ｈ＝４：１」：Ｒ１におけるガムロジンアシル残基と水素原子のモル比率が４：１
ＥＯ：オキシエチレン基
ＰＯ：オキシプロピレン基 R 1 in Table 1 is shown below.
"Gum Rosin acyl residue": minus a hydroxyl group from a carboxylic acid of the gum "Gum Rosin acyl residues: H = 2: 1" molar ratio of gum in R 1 rosin acyl residue and hydrogen atoms is 2: 1
"Gum Rosin acyl residues: H = 4: 1" molar ratio of gum in R 1 rosin acyl residue and hydrogen atoms is 4: 1
EO: Oxyethylene group PO: Oxypropylene group
「ガムロジンアシル残基」：ガムロジンのカルボン酸から水酸基を除いたもの
「ガムロジンアシル残基：Ｈ＝２：１」：Ｒ１におけるガムロジンアシル残基と水素原子のモル比率が２：１
「ガムロジンアシル残基：Ｈ＝４：１」：Ｒ１におけるガムロジンアシル残基と水素原子のモル比率が４：１
ＥＯ：オキシエチレン基
ＰＯ：オキシプロピレン基 R 1 in Table 1 is shown below.
"Gum Rosin acyl residue": minus a hydroxyl group from a carboxylic acid of the gum "Gum Rosin acyl residues: H = 2: 1" molar ratio of gum in R 1 rosin acyl residue and hydrogen atoms is 2: 1
"Gum Rosin acyl residues: H = 4: 1" molar ratio of gum in R 1 rosin acyl residue and hydrogen atoms is 4: 1
EO: Oxyethylene group PO: Oxypropylene group
試験区分２（コンクリート組成物の調製）
・実施例１～１３及び比較例１～６
容量６０リットルの強制２軸ミキサーを用い、表２に記載の内容で、９０秒間練混ぜを行い、表３に記載した各コンクリート組成物を調製した。なお、各コンクリート組成物について、目標空気量を４．５±１．５％とし、目標スランプを１８±１ｃｍとした。なお、実施例１３及び比較例６においては、容量２．０ｍ３の強制２軸ミキサーを用いて同様に練り混ぜた。なお、コンクリート組成物の温度は２０℃の条件で行った。 Test Category 2 (Preparation of Concrete Composition)
-Examples 1 to 13 and Comparative Examples 1 to 6
Using a forced twin-screw mixer with a capacity of 60 liters, kneading was performed for 90 seconds with the contents shown in Table 2 to prepare each concrete composition shown in Table 3. For each concrete composition, the target air amount was 4.5 ± 1.5% and the target slump was 18 ± 1 cm. In Example 13 and Comparative Example 6, the mixture was similarly kneaded using a forced twin-screw mixer having a capacity of 2.0 m 3. The temperature of the concrete composition was 20 ° C.
・実施例１～１３及び比較例１～６
容量６０リットルの強制２軸ミキサーを用い、表２に記載の内容で、９０秒間練混ぜを行い、表３に記載した各コンクリート組成物を調製した。なお、各コンクリート組成物について、目標空気量を４．５±１．５％とし、目標スランプを１８±１ｃｍとした。なお、実施例１３及び比較例６においては、容量２．０ｍ３の強制２軸ミキサーを用いて同様に練り混ぜた。なお、コンクリート組成物の温度は２０℃の条件で行った。 Test Category 2 (Preparation of Concrete Composition)
-Examples 1 to 13 and Comparative Examples 1 to 6
Using a forced twin-screw mixer with a capacity of 60 liters, kneading was performed for 90 seconds with the contents shown in Table 2 to prepare each concrete composition shown in Table 3. For each concrete composition, the target air amount was 4.5 ± 1.5% and the target slump was 18 ± 1 cm. In Example 13 and Comparative Example 6, the mixture was similarly kneaded using a forced twin-screw mixer having a capacity of 2.0 m 3. The temperature of the concrete composition was 20 ° C.
表２において、各配合について以下に示す。
In Table 2, each formulation is shown below.
・配合Ｎｏ１
セメント：普通ポルトランドセメント（密度＝３．１６ｇ／ｃｍ３）
細骨材１：陸砂（表乾密度＝２．５８ｇ／ｃｍ３）
粗骨材１：砕石２００５（表乾密度＝２．６６ｇ／ｃｍ３） ・ Formulation No1
Cement: Ordinary Portland cement (density = 3.16 g / cm 3 )
Fine aggregate 1: Land sand (surface dry density = 2.58 g / cm 3 )
Coarse aggregate 1: Crushed stone 2005 (surface dry density = 2.66 g / cm 3 )
セメント：普通ポルトランドセメント（密度＝３．１６ｇ／ｃｍ３）
細骨材１：陸砂（表乾密度＝２．５８ｇ／ｃｍ３）
粗骨材１：砕石２００５（表乾密度＝２．６６ｇ／ｃｍ３） ・ Formulation No1
Cement: Ordinary Portland cement (density = 3.16 g / cm 3 )
Fine aggregate 1: Land sand (surface dry density = 2.58 g / cm 3 )
Coarse aggregate 1: Crushed stone 2005 (surface dry density = 2.66 g / cm 3 )
配合Ｎｏ１では、更に以下の各化合物を使用した。
減水剤：ＡＥ減水剤標準形Ｉ種（高機能タイプ） チューポールＥＸ６０（竹本油脂社製、変性リグニンスルホン酸化合物とポリカルボン酸系化合物の複合体）をセメント質量に対して１．０％使用
消泡剤：ＡＦＫ－２（竹本油脂社製）をセメント質量に対して０．０００５％使用
ＡＥ剤：ＡＥ－３００（竹本油脂社製）をセメント質量に対して０．００１５％使用 In formulation No. 1, the following compounds were further used.
Water reducing agent: AE water reducing agent standard type I (high-performance type) Tupole EX60 (manufactured by Takemoto Oil & Fat Co., Ltd., a complex of a modified lignin sulfonic acid compound and a polycarboxylic acid-based compound) is used at 1.0% based on the cement mass. Defoamer: AFK-2 (manufactured by Takemoto Oil & Fat Co., Ltd.) is used at 0.0005% of the cement mass AE agent: AE-300 (manufactured by Takemoto Oil & Fat Co., Ltd.) is used at 0.0015% of the cement mass
減水剤：ＡＥ減水剤標準形Ｉ種（高機能タイプ） チューポールＥＸ６０（竹本油脂社製、変性リグニンスルホン酸化合物とポリカルボン酸系化合物の複合体）をセメント質量に対して１．０％使用
消泡剤：ＡＦＫ－２（竹本油脂社製）をセメント質量に対して０．０００５％使用
ＡＥ剤：ＡＥ－３００（竹本油脂社製）をセメント質量に対して０．００１５％使用 In formulation No. 1, the following compounds were further used.
Water reducing agent: AE water reducing agent standard type I (high-performance type) Tupole EX60 (manufactured by Takemoto Oil & Fat Co., Ltd., a complex of a modified lignin sulfonic acid compound and a polycarboxylic acid-based compound) is used at 1.0% based on the cement mass. Defoamer: AFK-2 (manufactured by Takemoto Oil & Fat Co., Ltd.) is used at 0.0005% of the cement mass AE agent: AE-300 (manufactured by Takemoto Oil & Fat Co., Ltd.) is used at 0.0015% of the cement mass
・配合Ｎｏ２
セメント：普通ポルトランドセメント（密度＝３．１６ｇ／ｃｍ３）
ＢＦＳ（高炉スラグ微粉末）：高炉スラグ微粉末４０００ブレーン（密度＝２．８９ｇ／ｃｍ３）
ＦＡ（フライアッシュ）：フライアッシュＩＩ種（密度＝２．２１ｇ／ｃｍ３）
細骨材１：陸砂（表乾密度＝２．５７ｇ／ｃｍ３）
粗骨材１：砕石２００５（表乾密度＝２．６８ｇ／ｃｍ３） ・ Formulation No2
Cement: Ordinary Portland cement (density = 3.16 g / cm 3 )
BFS (Blast Furnace Slag Fine Powder): Blast Furnace Slag Fine Powder 4000 Brain (Density = 2.89 g / cm 3 )
FA (fly ash): Fly ash type II (density = 2.21 g / cm 3 )
Fine aggregate 1: Land sand (surface dry density = 2.57 g / cm 3 )
Coarse aggregate 1: Crushed stone 2005 (surface dry density = 2.68 g / cm 3 )
セメント：普通ポルトランドセメント（密度＝３．１６ｇ／ｃｍ３）
ＢＦＳ（高炉スラグ微粉末）：高炉スラグ微粉末４０００ブレーン（密度＝２．８９ｇ／ｃｍ３）
ＦＡ（フライアッシュ）：フライアッシュＩＩ種（密度＝２．２１ｇ／ｃｍ３）
細骨材１：陸砂（表乾密度＝２．５７ｇ／ｃｍ３）
粗骨材１：砕石２００５（表乾密度＝２．６８ｇ／ｃｍ３） ・ Formulation No2
Cement: Ordinary Portland cement (density = 3.16 g / cm 3 )
BFS (Blast Furnace Slag Fine Powder): Blast Furnace Slag Fine Powder 4000 Brain (Density = 2.89 g / cm 3 )
FA (fly ash): Fly ash type II (density = 2.21 g / cm 3 )
Fine aggregate 1: Land sand (surface dry density = 2.57 g / cm 3 )
Coarse aggregate 1: Crushed stone 2005 (surface dry density = 2.68 g / cm 3 )
配合Ｎｏ２では、更に以下の各化合物を使用した。
減水剤：高性能ＡＥ減水剤標準形Ｉ種（高機能タイプ） チューポールＨＰ－８（竹本油脂社製、ポリカルボン酸コポリマー）をセメント質量に対して０．７％使用
消泡剤：ＡＦＫ－２（竹本油脂社製）をセメント質量に対して０．０００３％
ＡＥ剤：ＡＥ－２００（竹本油脂社製）をセメント質量に対して０．０００２％ In Formulation No. 2, the following compounds were further used.
Water reducing agent: High-performance AE water reducing agent Standard type I (high-performance type) Chupol HP-8 (manufactured by Takemoto Oil & Fat Co., Ltd., polycarboxylic acid copolymer) is used at 0.7% of the cement mass Defoaming agent: AFK- 2 (manufactured by Takemoto Oil & Fat Co., Ltd.) 0.0003% of the cement mass
AE agent: AE-200 (manufactured by Takemoto Oil & Fat Co., Ltd.) 0.0002% of cement mass
減水剤：高性能ＡＥ減水剤標準形Ｉ種（高機能タイプ） チューポールＨＰ－８（竹本油脂社製、ポリカルボン酸コポリマー）をセメント質量に対して０．７％使用
消泡剤：ＡＦＫ－２（竹本油脂社製）をセメント質量に対して０．０００３％
ＡＥ剤：ＡＥ－２００（竹本油脂社製）をセメント質量に対して０．０００２％ In Formulation No. 2, the following compounds were further used.
Water reducing agent: High-performance AE water reducing agent Standard type I (high-performance type) Chupol HP-8 (manufactured by Takemoto Oil & Fat Co., Ltd., polycarboxylic acid copolymer) is used at 0.7% of the cement mass Defoaming agent: AFK- 2 (manufactured by Takemoto Oil & Fat Co., Ltd.) 0.0003% of the cement mass
AE agent: AE-200 (manufactured by Takemoto Oil & Fat Co., Ltd.) 0.0002% of cement mass
・配合Ｎｏ３
セメント：普通ポルトランドセメント（密度＝３．１６ｇ／ｃｍ３）
細骨材１：山砂（表乾密度＝２．５７ｇ／ｃｍ３）
細骨材２：砕砂（表乾密度＝２．７４ｇ／ｃｍ３）
粗骨材１：砕石２００５（表乾密度＝２．７５ｇ／ｃｍ３）
粗骨材２：砕石２００５（表乾密度＝２．７１ｇ／ｃｍ３） ・ Formulation No3
Cement: Ordinary Portland cement (density = 3.16 g / cm 3 )
Fine aggregate 1: Mountain sand (surface dry density = 2.57 g / cm 3 )
Fine aggregate 2: Crushed sand (surface dry density = 2.74 g / cm 3 )
Coarse aggregate 1: Crushed stone 2005 (surface dry density = 2.75 g / cm 3 )
Coarse aggregate 2: Crushed stone 2005 (surface dry density = 2.71 g / cm 3 )
セメント：普通ポルトランドセメント（密度＝３．１６ｇ／ｃｍ３）
細骨材１：山砂（表乾密度＝２．５７ｇ／ｃｍ３）
細骨材２：砕砂（表乾密度＝２．７４ｇ／ｃｍ３）
粗骨材１：砕石２００５（表乾密度＝２．７５ｇ／ｃｍ３）
粗骨材２：砕石２００５（表乾密度＝２．７１ｇ／ｃｍ３） ・ Formulation No3
Cement: Ordinary Portland cement (density = 3.16 g / cm 3 )
Fine aggregate 1: Mountain sand (surface dry density = 2.57 g / cm 3 )
Fine aggregate 2: Crushed sand (surface dry density = 2.74 g / cm 3 )
Coarse aggregate 1: Crushed stone 2005 (surface dry density = 2.75 g / cm 3 )
Coarse aggregate 2: Crushed stone 2005 (surface dry density = 2.71 g / cm 3 )
配合Ｎｏ３では、更に以下の各化合物を使用した。
減水剤：ＡＥ減水剤遅延形Ｉ種（高機能タイプ） シーカメントＪＲ（日本シーカ社製、変性ポリカルボン酸ポリエーテルポリマーと変性ポリオール）をセメント質量に対して１．３％
消泡剤：ＡＦＫ－２（竹本油脂社製）をセメント質量に対して０．０００５％
ＡＥ剤：マスターエア２０２（ＢＡＳＦジャパン製、変性ロジン酸化合物系陰イオン界面活性剤）をセメント質量に対して０．００５％ In Formulation No. 3, the following compounds were further used.
Water reducing agent: AE water reducing agent Delayed type I (high-performance type) Seekament JR (manufactured by Nippon Seeka Co., Ltd., modified polycarboxylic acid polyether polymer and modified polyol) 1.3% of cement mass
Defoamer: AFK-2 (manufactured by Takemoto Oil & Fat Co., Ltd.) 0.0005% of cement mass
AE agent: Master Air 202 (manufactured by BASF Japan, modified rosin compound-based anionic surfactant) at 0.005% of the cement mass
減水剤：ＡＥ減水剤遅延形Ｉ種（高機能タイプ） シーカメントＪＲ（日本シーカ社製、変性ポリカルボン酸ポリエーテルポリマーと変性ポリオール）をセメント質量に対して１．３％
消泡剤：ＡＦＫ－２（竹本油脂社製）をセメント質量に対して０．０００５％
ＡＥ剤：マスターエア２０２（ＢＡＳＦジャパン製、変性ロジン酸化合物系陰イオン界面活性剤）をセメント質量に対して０．００５％ In Formulation No. 3, the following compounds were further used.
Water reducing agent: AE water reducing agent Delayed type I (high-performance type) Seekament JR (manufactured by Nippon Seeka Co., Ltd., modified polycarboxylic acid polyether polymer and modified polyol) 1.3% of cement mass
Defoamer: AFK-2 (manufactured by Takemoto Oil & Fat Co., Ltd.) 0.0005% of cement mass
AE agent: Master Air 202 (manufactured by BASF Japan, modified rosin compound-based anionic surfactant) at 0.005% of the cement mass
試験区分３（コンクリート組成物の試験及び評価）
調製した各コンクリート組成物について、空気量、スランプ、Ｏ漏斗流下時間を下記のように測定し、結果を表３にまとめて示した。なお、実施例１３及び比較例６では、ポンプ圧送圧力も測定した。 Test category 3 (testing and evaluation of concrete composition)
For each of the prepared concrete compositions, the air volume, slump, and O-funnel flow time were measured as follows, and the results are summarized in Table 3. In Example 13 and Comparative Example 6, the pump pressure was also measured.
調製した各コンクリート組成物について、空気量、スランプ、Ｏ漏斗流下時間を下記のように測定し、結果を表３にまとめて示した。なお、実施例１３及び比較例６では、ポンプ圧送圧力も測定した。 Test category 3 (testing and evaluation of concrete composition)
For each of the prepared concrete compositions, the air volume, slump, and O-funnel flow time were measured as follows, and the results are summarized in Table 3. In Example 13 and Comparative Example 6, the pump pressure was also measured.
・添加率
水硬性結合材の合計質量に対する、各化合物の質量％を示した。なお、各化合物は、練り混ぜ水の一部として使用した。
・空気量（容量％）：
日本工業規格ＪＩＳ Ａ １１２８に準拠して測定した。
・スランプ（ｃｍ）：
空気量の測定と同時に日本工業規格ＪＩＳ Ａ １１０１に準拠して測定した。
・Ｏ漏斗流下時間（秒）
土木学会規準ＪＳＣＥ－Ｆ５１２－２０１８に準拠してスランプ測定後に測定した。なお、Ｏ漏斗流下時間は、その値が小さい方がポンプ圧送性は良好であると判定した。
・ポンプ圧送圧力（ＭＰａ）
コンクリートポンプ車「ＰＨ５０Ｂ－１７（極東開発社）」を用いて、流速２０ｍ３／時間での圧力計指示値の最大値を読み取り、記録し、コンクリートのポンプ圧送圧力（ＭＰａ）とした。 -Addition rate The mass% of each compound with respect to the total mass of the hydraulic binder is shown. In addition, each compound was used as a part of kneading water.
・ Air volume (capacity%):
Measured according to Japanese Industrial Standard JIS A 1128.
・ Slump (cm):
At the same time as the air volume was measured, it was measured in accordance with Japanese Industrial Standard JIS A 1101.
・ O funnel flow time (seconds)
The measurement was performed after the slump measurement in accordance with the Japan Society of Civil Engineers standard JSCE-F512-2018. It was determined that the smaller the value of the O funnel flow time, the better the pumping performance.
・ Pump pressure feed pressure (MPa)
Using a concrete pump truck "PH50B-17 (Far East Development Co., Ltd.)", the maximum value of the pressure gauge reading at a flow velocity of 20 m 3 / hour was read and recorded, and used as the concrete pump pumping pressure (MPa).
水硬性結合材の合計質量に対する、各化合物の質量％を示した。なお、各化合物は、練り混ぜ水の一部として使用した。
・空気量（容量％）：
日本工業規格ＪＩＳ Ａ １１２８に準拠して測定した。
・スランプ（ｃｍ）：
空気量の測定と同時に日本工業規格ＪＩＳ Ａ １１０１に準拠して測定した。
・Ｏ漏斗流下時間（秒）
土木学会規準ＪＳＣＥ－Ｆ５１２－２０１８に準拠してスランプ測定後に測定した。なお、Ｏ漏斗流下時間は、その値が小さい方がポンプ圧送性は良好であると判定した。
・ポンプ圧送圧力（ＭＰａ）
コンクリートポンプ車「ＰＨ５０Ｂ－１７（極東開発社）」を用いて、流速２０ｍ３／時間での圧力計指示値の最大値を読み取り、記録し、コンクリートのポンプ圧送圧力（ＭＰａ）とした。 -Addition rate The mass% of each compound with respect to the total mass of the hydraulic binder is shown. In addition, each compound was used as a part of kneading water.
・ Air volume (capacity%):
Measured according to Japanese Industrial Standard JIS A 1128.
・ Slump (cm):
At the same time as the air volume was measured, it was measured in accordance with Japanese Industrial Standard JIS A 1101.
・ O funnel flow time (seconds)
The measurement was performed after the slump measurement in accordance with the Japan Society of Civil Engineers standard JSCE-F512-2018. It was determined that the smaller the value of the O funnel flow time, the better the pumping performance.
・ Pump pressure feed pressure (MPa)
Using a concrete pump truck "PH50B-17 (Far East Development Co., Ltd.)", the maximum value of the pressure gauge reading at a flow velocity of 20 m 3 / hour was read and recorded, and used as the concrete pump pumping pressure (MPa).
（結果）
表３の実施例１～１３に示される結果から明らかなように、本発明により、得られる水硬性組成物のポンプ圧送性を向上させるとともに、スランプと空気量への影響が小さい水硬性組成物用添加剤を提供できることが確認された。なお、実施例１３では、比較例６の添加剤なしの条件と比較すると、２０ｍ３／時間の吐出時のポンプ圧送圧力が低下し、実際にポンプ圧送性が改善していることが確認された。 (result)
As is clear from the results shown in Examples 1 to 13 in Table 3, the hydraulic composition obtained by the present invention improves the pumping property of the obtained hydraulic composition and has a small effect on the slump and the amount of air. It was confirmed that the additive for use can be provided. In Example 13, it was confirmed that the pump pumping pressure at the time of discharging 20 m 3 / hour decreased and the pump pumping property was actually improved as compared with the condition without the additive of Comparative Example 6. ..
表３の実施例１～１３に示される結果から明らかなように、本発明により、得られる水硬性組成物のポンプ圧送性を向上させるとともに、スランプと空気量への影響が小さい水硬性組成物用添加剤を提供できることが確認された。なお、実施例１３では、比較例６の添加剤なしの条件と比較すると、２０ｍ３／時間の吐出時のポンプ圧送圧力が低下し、実際にポンプ圧送性が改善していることが確認された。 (result)
As is clear from the results shown in Examples 1 to 13 in Table 3, the hydraulic composition obtained by the present invention improves the pumping property of the obtained hydraulic composition and has a small effect on the slump and the amount of air. It was confirmed that the additive for use can be provided. In Example 13, it was confirmed that the pump pumping pressure at the time of discharging 20 m 3 / hour decreased and the pump pumping property was actually improved as compared with the condition without the additive of Comparative Example 6. ..
一方、水硬性組成物用添加剤が配合されていない比較例１、４、６においては、Ｏ漏斗流下時間を小さくさせることができないことが確認された。また、比較例２、５においては、オキシアルキレン基を有さない化合物である、いわゆるＡＥ剤を使用しており、その効果によって、ポンプ圧送性は良好ではあるが、空気量が増大した。また、比較例３においては、化合物としてポリエチレングリコールを使用した例であり、この場合、Ｏ漏斗流下時間を小さくさせることができないことが確認された。
On the other hand, in Comparative Examples 1, 4 and 6 in which the additive for the hydraulic composition was not blended, it was confirmed that the O-funnel flow time could not be reduced. Further, in Comparative Examples 2 and 5, a so-called AE agent, which is a compound having no oxyalkylene group, was used, and due to the effect, the pumping property was good, but the amount of air increased. Further, in Comparative Example 3, it was an example in which polyethylene glycol was used as the compound, and in this case, it was confirmed that the O funnel flow time could not be reduced.
本発明の水硬性組成物用添加剤は、水硬性組成物を調製する際の添加剤として利用することができる。
The additive for hydraulic composition of the present invention can be used as an additive when preparing a hydraulic composition.
Claims (11)
- 下記一般式（１）で表される化合物を含有する、水硬性組成物用添加剤。
ｍは１～２００の数であって、ｎは１～２０の数であって、かつ、前記ｍ、ｎが、ｍ×ｎ＝１～２００となる関係を満たす数であり、ＡＯの内、炭素数２のオキシアルキレン基が５０モル％以上である。） An additive for a hydraulic composition containing a compound represented by the following general formula (1).
m is a number from 1 to 200, n is a number from 1 to 20, and m and n satisfy the relationship of m × n = 1 to 200. The oxyalkylene group having 2 carbon atoms is 50 mol% or more. ) - 前記一般式（１）中のＡＯは、炭素数２～４のオキシアルキレン基である、請求項１に記載の水硬性組成物用添加剤。 The additive for a hydraulic composition according to claim 1, wherein the AO in the general formula (1) is an oxyalkylene group having 2 to 4 carbon atoms.
- 前記一般式（１）中のＡＯは、炭素数２～３のオキシアルキレン基である、請求項１または２に記載の水硬性組成物用添加剤。 The additive for a hydraulic composition according to claim 1 or 2, wherein the AO in the general formula (1) is an oxyalkylene group having 2 to 3 carbon atoms.
- 前記一般式（１）中のｎは、１～６の数であって、かつ、前記ｍ、ｎが、ｍ×ｎ＝１～１５０となる関係を満たす数である、請求項１～３のいずれか一項に記載の水硬性組成物用添加剤。 The number of claims 1 to 3 in which n in the general formula (1) is a number from 1 to 6 and m and n satisfy the relationship of m × n = 1 to 150. The additive for a hydraulic composition according to any one of the above.
- 前記一般式（１）中のＲ２は、水素原子、ロジンのアシル残基、炭素数１～４のアルキル基、炭素数２～５のアルケニル基、又は、炭素数３～６の多価アルコールから水酸基を除いた残基である、請求項１～４のいずれか一項に記載の水硬性組成物用添加剤。 R 2 in the general formula (1) is a hydrogen atom, an acyl residue of rosin, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a polyhydric alcohol having 3 to 6 carbon atoms. The additive for a water-hard composition according to any one of claims 1 to 4, which is a residue obtained by removing a hydroxyl group from the water.
- 前記ロジンが天然ロジンである、請求項１～５のいずれか一項に記載の水硬性組成物用添加剤。 The additive for a hydraulic composition according to any one of claims 1 to 5, wherein the rosin is a natural rosin.
- 前記天然ロジンがガムロジンである、請求項６に記載の水硬性組成物用添加剤。 The additive for a hydraulic composition according to claim 6, wherein the natural rosin is gum rosin.
- 前記一般式（１）中の前記ＡＯの内、炭素数２のオキシアルキレン基が９０モル％以上である、請求項１～７のいずれか一項に記載の水硬性組成物用添加剤。 The additive for a hydraulic composition according to any one of claims 1 to 7, wherein the oxyalkylene group having 2 carbon atoms is 90 mol% or more in the AO in the general formula (1).
- 前記一般式（１）中の前記ｍ、ｎが、ｍ×ｎ＝１０～１００となる関係を満たす数である、請求項１～８のいずれか一項に記載の水硬性組成物用添加剤。 The additive for a hydraulic composition according to any one of claims 1 to 8, wherein m and n in the general formula (1) are numbers satisfying the relationship of m × n = 10 to 100. ..
- 分散剤を含有する、請求項１～９のいずれか一項に記載の水硬性組成物用添加剤。 The additive for a hydraulic composition according to any one of claims 1 to 9, which contains a dispersant.
- 前記分散剤が、リグニンスルホン酸系分散剤、及び、ポリカルボン酸系分散剤からなる群から選ばれる少なくとも１種である、請求項１０に記載の水硬性組成物用添加剤。 The additive for a water-hard composition according to claim 10, wherein the dispersant is at least one selected from the group consisting of a lignin sulfonic acid-based dispersant and a polycarboxylic acid-based dispersant.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2020/000061 WO2021140541A1 (en) | 2020-01-06 | 2020-01-06 | Additive for water-curable composition |
| JP2021569610A JPWO2021140541A1 (en) | 2020-01-06 | 2020-01-06 | |
| TW109103917A TWI869371B (en) | 2020-01-06 | 2020-02-07 | Additives for hydraulic compositions |
| JP2023077623A JP7456685B2 (en) | 2020-01-06 | 2023-05-10 | Additives for hydraulic compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2020/000061 WO2021140541A1 (en) | 2020-01-06 | 2020-01-06 | Additive for water-curable composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2021140541A1 true WO2021140541A1 (en) | 2021-07-15 |
Family
ID=76787884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2020/000061 WO2021140541A1 (en) | 2020-01-06 | 2020-01-06 | Additive for water-curable composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JPWO2021140541A1 (en) |
| TW (1) | TWI869371B (en) |
| WO (1) | WO2021140541A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01219052A (en) * | 1988-02-27 | 1989-09-01 | Toho Chem Ind Co Ltd | Dispersant composition for cement |
| JP2001002457A (en) * | 1999-06-18 | 2001-01-09 | Denki Kagaku Kogyo Kk | Cement admixture and cement composition |
| CN104591580A (en) * | 2013-10-30 | 2015-05-06 | 青岛德圣泰建筑安装工程有限公司 | Novel concrete cracking-resistant modifier |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4607321B2 (en) * | 1998-08-14 | 2011-01-05 | コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー | Cement dry molding mixture |
| JP5674543B2 (en) | 2011-04-20 | 2015-02-25 | 電気化学工業株式会社 | Spraying method |
-
2020
- 2020-01-06 WO PCT/JP2020/000061 patent/WO2021140541A1/en active Application Filing
- 2020-01-06 JP JP2021569610A patent/JPWO2021140541A1/ja active Pending
- 2020-02-07 TW TW109103917A patent/TWI869371B/en active
-
2023
- 2023-05-10 JP JP2023077623A patent/JP7456685B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01219052A (en) * | 1988-02-27 | 1989-09-01 | Toho Chem Ind Co Ltd | Dispersant composition for cement |
| JP2001002457A (en) * | 1999-06-18 | 2001-01-09 | Denki Kagaku Kogyo Kk | Cement admixture and cement composition |
| CN104591580A (en) * | 2013-10-30 | 2015-05-06 | 青岛德圣泰建筑安装工程有限公司 | Novel concrete cracking-resistant modifier |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023109836A (en) | 2023-08-08 |
| TWI869371B (en) | 2025-01-11 |
| JP7456685B2 (en) | 2024-03-27 |
| TW202126601A (en) | 2021-07-16 |
| JPWO2021140541A1 (en) | 2021-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3563115B2 (en) | Cement mixture | |
| CN105016659B (en) | concrete composition | |
| WO2012113765A1 (en) | Use of hyperbranched polyether surfactant in cementitious systems | |
| TWI714615B (en) | Polycondensation product containing phenolic copolymer and dispersant for hydraulic composition containing the same | |
| TW200517355A (en) | Cement admixture | |
| JP6180783B2 (en) | Hydraulic composition | |
| CN107778418A (en) | A kind of efficiently defoaming type polycarboxylate water-reducer and preparation method thereof | |
| KR102229896B1 (en) | Ultra rapid harding concrete composition having the frost resistance and a repairing method of concrete structure using the same | |
| JP7456685B2 (en) | Additives for hydraulic compositions | |
| JP6830083B2 (en) | Dispersant and its manufacturing method | |
| JP6906265B1 (en) | Additives for hydraulic compositions and hydraulic compositions | |
| JPH08165157A (en) | Cement additive composition | |
| JP7307954B2 (en) | cement composition | |
| JP4330131B2 (en) | Shrinkage reducing agent for cement compound and cement compound containing the same | |
| JP6493869B2 (en) | Lignin derivative | |
| JP7267997B2 (en) | Antifoam composition and admixture for hydraulic composition containing the same | |
| CN1151151A (en) | Cement composition | |
| JP6839557B2 (en) | Dispersant for hydraulic composition | |
| JP6446753B2 (en) | Cement additive | |
| JP6918330B1 (en) | Additives for hydraulic compositions and hydraulic compositions | |
| TWI779048B (en) | Defoamer for hydraulic composition, additive for hydraulic composition, and hydraulic composition | |
| RU2282601C2 (en) | Concrete mixture | |
| JP5875858B2 (en) | Air-entrained stable volume change inhibitor for cement composition and cement composition | |
| JP2014177385A (en) | Glycerol-containing polymer and method of producing the same | |
| JP2001031453A (en) | Admixture composition for concrete containing fly ash |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20912674 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2021569610 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 20912674 Country of ref document: EP Kind code of ref document: A1 |